Chemical Bio Refinery Perspectives

Chemical Biorefinery Perspectives
The valorisation of functionalised chemicals from biomass resources

compared to the conventional fossil fuel production route
Ben Brehmer
Dissertation Report
2 © Agrotechnology and Food Sciences Group B.V., member of Wageningen UR
Table of Contents
Chapter 1 5
The Dissertation Report Layout
Chapter 2 11
Energy and Exergy
Chapter 3 37
Life Cycle Assessment vs. Exergy
Chapter 4 75
Crop Output
Chapter 5 115
Prime Energy Input
Chapter 6 217
Secondary Energy Input
Chapter 7 295
Process Energy Input
Chapter 8 389
Fossil Fuel Savings
©Agrotechnology & Food Sciences Group B.V. Member of Wageningen UR 3

4 ©Agrotechnology & Food Sciences Group B.V. Member of Wageningen UR
Chapter 1
The Dissertation Report Layout
Ben Brehmer
Dissertation Report

The Hypothesis
This entire dissertation report is based on the notion that vast amounts of fossil fuel energy can
be mitigated should biomass be utilized as a feedstock for the chemical industry. Biomass has
unique biochemical structures that when employed for the production of existing chemicals
(which have the same functionality) could lead to vast increases of fossil fuel energy savings in
comparison to standard biomass applications (i.e. producing fuels, heat, or power). The final
calorific energy content of these chemical products are identical should existing and not novel
chemicals be produced in the biorefinery. In standard petrochemical refineries, numerous
process steps are required to introduce such chemical functionality into the base structures.
Conversely, many of the biochemical constituents found in biomass often contain similar
functionalities. Therefore, it is attractive to exploit this situation to by-pass many of steps
required to add functionality and thus by utilizing well-suited biomass-based precursors to
possibility eliminate several of these energy intensive processing steps. The following figure
(Figure 1) visually illustrates the idea of producing the different types of functionalized chemicals
(e.g. hydrocarbons, amines, oxides) from both the traditional petrochemical and potential
biorefinery route. Although the final calorific values are equal, the total embedded process energy
involved is expected to be substantially lower for the biomass route.
Figure 1 Petrochemical Refinery and Biorefinery Comparison

Adapted from Johan Sanders – Dissertation mentor
Inclusion of both the feedstock energy and the process energy on a life cycle assessment basis
should reveal major fuel fossil energy savings from biomass. In short, the hypothesis is to argue
that functionality upheaval is something to strive for in industrial biomass applications.

The Book Layout
This book-style report is constructed in such a way to systematically and accurately compile all
the required data to determine the fossil fuel energy and exergy replacement potential of the
conceptualized chemical biorefinery in respect to the existing traditional petrochemical layouts.
The chosen methodology is a comparative energetic and exergetic cradle-to-factory gate assessment. The
following layout is a visual representation of the major aspects in producing the chemicals via the
biorefinery concept; and the respective chapters.
Figure 2 Simplified System Boundaries for Chemical Biorefinery
Chapter 2 – Energy and Exergy

…acts as a documentation for the theoretical differences between energy and exergy while also
describing their practical impact to the matrix calculations. Thermodynamical background is
provided with succinct mathematical formulas to stress the contrast between the two values. It
forms the basis of the calculations and assumptions for the assessment.
Chapter 3 – Life Cycle Assessment versus Exergy

…discusses the various methods and analysis tools available to compare the life cycle of different
processes, production methods and products. It determines the best amalgamation of the various
life cycle analysis tool components for provoking a raw material change in the petrochemical
industry to a biorefinery system. The comparative energetic and exergetic cradle-to-factory gate assessment
methodology is described along with the benefits of exergy inclusion and the reasons fro
excluding common environmental impact factors.

Chapter 4 – Crop Output
…lists the biomass energy crops chosen to be representative and included in the assessment.
Listed in the created crop guide for 16 popular bioenergy crops are all the cultivation dependent
variables required to systematically compare the different energy and exergy inputs. The values
are central to the system layout as illustrated in Figure 2; “crop yields” - it covers the crop
selection, yields, and usable constituents for potential biochemical production. All aspects of the
life cycle revolve around the selected crops and their representative cultivation region.
Chapter 5 – Prime Energy Input

…encapsulates the “prime energy” input box highlighted in Figure 2. It describes and lists in full
detail those inputs directly attributed to biomass growth; namely fertilizers, irrigation, drainage
and crop protection. All the processes and methods are adopted and expanded to include both
energy and exergy values, essentially being related to the primary energy and material use.
Chapter 6 – Secondary Energy Input

…encapsulates the “secondary energy” input box highlighted in Figure 2. It describes and lists in
full detail those inputs indirectly attributed to biomass growth; namely farming procedures,
transportation and storage operations, and pre-processing and drying techniques. All the
processes and methods are adopted and expanded to include both energy and exergy values,
essentially being related to the primary energy and material use. The summation of the prime and
secondary energy input leads to the total biomass acquisition energy input, which provides a biomass
feedstock cost for the chemical biorefinery processing.
Chapter 7 – Process Energy Input

…encapsulates the “process energy” input box highlighted in Figure 2. It describes and lists in
full detail those inputs directly attributed to the internal biorefinery processing. Each biochemical
processing step within the biorefinery involves internal process energy; separated into direct
thermal and electric energy, and indirect energy (plus exergy). All the processes and methods are
adopted and expanded to lead to total bioprocessing energy requirements, essentially being related to the
primary energy and material use. It provides the base data needed for further matrix calculations
of the feedstock dependent biorefinery layouts.
Chapter 8 – Fossil Fuel Energy Savings

…encapsulates the “chemical yields” output box highlighted in Figure 2. It is the summation of
the determined total biomass acquisition energy intensity from Chapter 6 in combination with the total
bioprocessing energy requirements from Chapter 7. Combined they are used to determine the potential
fossil fuel energy and exergy savings for each chemical biorefinery cropping system. Results and
discussion are presented which predominantly used to validate the hypothesis that functionality
upheaval is something to strive for in industrial biomass applications.

Chapter 2
Energy and Exergy
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 2 – Energy and Exergy

Author(s) Ben Brehmer
A&F number -
ISBN-number -
Date o f publication 1. Octob er, 2008
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Agrotechnology & Food Scien ces Group B.V.

P.O. Box 17
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Tel: +31 (0)317 480 150
E-mail: ben.brehmer@wur.nl
Internet: www.afsg.wur.nl
© Agrotechnology & Food Scien ces Group B.V.

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Abstract
The calculation methodology briefly highlighted in the previous chapter and to be conducted in
the succeeding chapters is based on the simplifications and assumptions performed in this
chapter; all relative to energy and exergy determination. It acts as a documentation for the
theoretical differences between energy and exergy and the practical differences for their
calculation. The thermodynamical background is provided with succinct mathematical formulas
to stress the contrast between the two values. It provides all information needed to derive at the
their base values and additional methodology to derive at their cumulative demands. It acts as a
guide for the cumulative fossil fuel energy and exergy demand calculations which may not
necessarily be described in sufficient detail in the succeeding chapters. And lastly, the cumulative
energy and exergy values for the select petrochemicals to be replaced is provided.
Key Words:
Thermodynamics, Energy, Exergy, Fossil Fuels, Base Assumptions

Content
1 Introduction 17
1.1 Chapter Purpose 18
2 Thermodynamics 19
2.1 First Law 19
2.2 Second Law 19
2.3 Difference between energy and exergy 20
2.3.1 Energy 20
2.3.2 Carnot efficiency 20
2.3.3 Exergy 21
2.3.4 Simple Terms: Energy vs. Exergy 22
3 Base Values and Calculations 23
3.1 Solar Radiation Energy and Exergy 23
3.2 Fossil Fuel Source Energy and Exergy 23
3.2.1 Natural Gas 23
3.2.2 Diesel 24
3.3 Energy Carrier Conversions 24
3.3.1 Electric Production 25
3.3.2 Steam 26
3.3.3 Standardized Ratios 28
4 Detailed Processing Values and Calculations 29
4.1 Aspen+ 29
4.2 Process Flow Diagrams 30
4.2.1 Energy - Sankey Diagram 30
4.2.2 Exergy – Grassman Diagram 30
5 Cradle-to-Factory Gate Methodology 31
5.1 Mass and energy balances 31
5.2 Existing Chemical Production Routes 31
6 Conclusion 33

1 Introduction
If someone were to recommend using a chainsaw to cut a piece of butter, the obvious reaction
should be one of bewilderment followed by a complete rejection of the idea. Laconically replying;
why use a chainsaw when a small knife is sufficient? Metaphorically speaking in many industrially
energetic processes, however, this type of action is nearly being conducted on a regular basis.
Vast amounts of energy are being squandered to perform simple tasks that with a more
appropriate technique or process could be drastically reduced.
Manufacturers of hot water boilers, for instance, systematically claim close to 100% energetic
conversion efficiency. Heating 1m³ of water from 15°C to 38°C for the average person to take a
shower requires 2.2m³ of natural gas. From a calorimetric standpoint this is indeed a very
efficient process, as practically all the chemical energy of the natural gas has been converted to an
increase of thermal energy in the water. On the other hand, natural gas has the potential to
combust at temperatures exceeding 2000°C, meaning heating water from 15 to 38°C using
natural gas is analogous to cutting butter with a chainsaw.
This example is an attempt to simply explain what “work potential” is. In many scientific and
applied engineering practices, the traditional “calorimetric” approach to thermodynamics has
dominated energy (or fuel) utilization. It adamantly follows the 1st law of thermodynamics (the
conservation of energy) which proves it to be very successful, at least in the case of the hot water
boiler. Entire process schemes and developmental layouts can be dominated by such studies;
strictly revolving around the 1 st law. Despite the 2nd law (increase of entropy or less order) being
taught in advanced classes, it is classically separated and merely introduced for theoretical merit.
Actually applying its concepts in practice proves difficult and challenging, forcing many to avoid
its principles.
Exergy is the measurable and determinable value of work potential. It is the combination
between both the 1st and 2 nd laws of thermodynamics, incorporating both energy conservation
and maximum conversion potential. When calculated properly it can be a helpful guide to
applying different techniques or processing options to increase the overall energy efficiency for
many energetically intensive processes. And with the current advancements made in computing
power, its determination is no longer as difficult as previously anticipated.
The differences between the 1st and 2 nd law of thermodynamics (i.e. energy and exergy) and their
calculation methods are covered in this chapter. To perform and list these comparative
differences, more detailed knowledge of the process systems are required to enable the correct
determination of enthalpy and entropy flows, in order to finally calculate exergy. At this deeper
level of understanding the process system, energy and exergy flow values can pin-point potential
improvements for an increased overall energy (fuel) efficiency. In many systems however,
processing data is insufficient which can prevent the accurate calculation of exergy flows. In such

situations, there are calculation shortcuts using assumed ratios and relations to standard energy
calculations; enabling the determination of a representative value for exergy.
For an entire process chain-based system, as is the case with chemical biorefineries, the
difference resulting values of energy and exergy illustrate major improvement options.
Regardless, in many situations, the standard calorimetric approach suffices in indicating many
straightforward and large energy efficiency improvement options. But by expanding the
assessment to include exergy other less obvious improvement option should be noticeable.
The entire calculation methodology conducted in the succeeding chapters is based on the
simplifications and assumptions made in this chapter, all related to energy and exergy
determinations. Considering the complexity of the calculation matrix model, these descriptions
primarily provide a systematic approach to convert direct energy streams (heat, power, and fuels)
into cumulative energy and exergy values. The basis of those conversion/calculations are
presented in this chapter to help avoid unnecessary energy squander.
1.1 Chapter Purpose

This chapter is used to document the theoretical differences between energy and exergy and the
practical differences for their calculation. In addition to explaining the thermodynamic theory, it
is also used to list the base values and calculation routes needed to obtain figures for practical
purposes. It is essentially the background piece to the conversion efficiencies and thermodynamic
considerations required to calculate the cumulative energy and exergy demand.

2 Thermodynamics
The entire field of macroscopically analysing the transformation of energy into different forms in
relation to variables, such as temperature and pressure etc., is thermodynamics. The word and study
of thermodynamic originates from the Greek meanings of heat and power; both functional units
of energetic flows to generate work. Heat can be regarded as energy in transit whereas dynamics can
be regarded as a relative motion. In a sense, seeing that the word itself comprising of two parts it is
logical to include both laws needed for the calculation of exergy. There are in fact five laws of
thermodynamics, ranging from the zeroth law to Onsager reciprocal relations law, nonetheless only
two are needed to study energy flows in relation to work potential in the realm of biomass
production chains to determine exergy.
2.1 First Law

“The increase in the internal energy of a system is equal to the amount of energy added by heating the system,
minus the amount lost as a result of the work done by the system on its surroundings.”
The first law can be stated mathematically as:
dU = δQ − δW
dU = a differential (infinitely small) increase in the internal energy of the system

δQ = a differential (infinitely small) amount of heat added to the system
δW = a differential (infinitely small) amount of work done by the system
The first law of thermodynamics is about the conservation of energy; that energy cannot be
created or destroyed, only transformed. In determining useful work within thermodynamical
systems, the quotient enthalpy (denoted as H or h) is primarily used. It expresses the heat content
which can be obtained from a closed system under constant pressure and entropy.
2.2 Second Law

There is no single expression used to describe the second law but one of the succinct
interpretations from Kelvin is fitting and states:
“It is impossible to convert heat completely into work.”
The second law can be stated mathematically as:
dS
≥0
dt
dS = a differential (infinitely small) increase in the entropy of the system

dt = a differential (infinitely small) amount of time

The second law of thermodynamics is about the increase of irreversibility; that while energy
cannot be created or destroyed, its quality is decreased upon each transformation. In determining
useful work within thermodynamical systems, the quotient entropy (denoted as S or s) is
additional considered along with enthalpy. Entropy expresses the unavailability of a system to
perform work. As expressed in the mathematical formula, the total entropy of any isolated
thermodynamic system will increase over time eventually approaching a maximum value or zero
availability of work potential.
2.3 Difference between energy and exergy

Energy calculations are first law-based using only enthalpy and is therefore based on ideal
conditions (simplified assumptions). Exergy calculations are second law-based using both
enthalpy and entropy and is therefore based on real irreversible conditions.
2.3.1 Energy
There are many different interpretations and colloquial meanings of energy, but it is generally
intended to mean the ability to do work. There are many forms of energy ranging from kinetic to
mechanical to nuclear to gravitational, etc. In calculations pertaining to thermodynamic systems
or industrial processes it can be narrowed down to the thermal energy potential…to do work. The
following mathematical formula describes the energy flow of a system:
En = M& ⋅ c p ⋅ (υ i − υ 0 )
M = mass flow, kg/h

cp = heat capacity, kJ/K⋅mol
ϑi = output temperature, °C
ϑ0 = output temperature, °C
It is essentially a summation of mass and heat flows, which can be regarded as enthalpy (H).
2.3.2 Carnot efficiency

The so-called “father of thermodynamics”, Sadi Carnot, took it upon himself to study mass and
heat flows in an engine cycle. Simplified, his study lead to the discovery of the Carnot cycle:
Tc
η carnot = 1 −
Th
Tc = Temperature of cold reservoir (i.e. atmosphere), K

Th = Temperature of hot reservoir (i.e. exhaust), K
It describes the most efficient cycle possible for converting a given amount of thermal energy
(enthalpy) into useable work.

Thermal energy expressed by enthalpy does not have the ability to indicate the sources of or the
magnitude of irreversible energy limitations. It is based on the conjecture that entropy is
constant. Followings the calculations described by Carnot’s cycle, no engine can produce more
work than determined by the thermal limitations of the reservoirs. Furthermore, in practice, work
efficiencies are never able to reach the calculated maximum work potential indicated by the cycle
suggesting the influence of irreversibility within thermodynamic systems. Studying engine systems
was the first step into understanding the limitations of the 1 st law and energy calculations. While
second law considerations were made in determining the cycle’s pathway, the step towards
calculating maximum work potential of reversible energy streams was not performed.
2.3.3 Exergy
Exergy is the quotient for the maximum amount of work that can be extracted from a physical
stream by exchanging mass and energy with reservoirs in a reference state. The reference state
reservoir is the atmospheric conditions of earth, which itself has an exergy content but is zero in
relation to itself. The first law (or enthalpy calculations) states that energy cannot be created or
destroyed only transformed. The second law (or entropy calculations) states that the irreversibility
is increased upon a transformation process. Exergy takes into account both laws; so while energy
cannot be destroyed exergy can and always is within a process destroyed; or while there is a
constant amount of energy in the universe, the amount of exergy is constantly decreasing with
every conversion process.
Since the time of Carnot’s cycle many theorems and mathematical hypothesis have been
developed which can all be considered as exergy. Some famous synonymous terms are:
availability, maximum work content, reversible work, ideal work, etc. The determination of
exergy is broken down into three separate terms; physical, chemical and mixing1:
Ex = Ex ph + Exchem + Exmix
Physical Exergy Flows

The physical exergy flow is a term for the transfer of work potential from one state to another
influenced by the thermal (temperature, T) and mechanical (pressure, p) states.
Ex ph = n& (∆H − T0 ∆S ) or more detailed Ex = M& i ⋅ [( H i − H 0 ) − T0 ⋅ (S i − S0 )]
n& or M& i = molar flow, mol/s

Hi = enthalpy output, cal/mol
H0 = enthalpy reference, cal/mol
Si = entropy output, cal/mol⋅K
S0 = entropy reference, cal/mol⋅K
T0 = reference temperature, °C

Physical exergy is the link between the 1st and 2nd laws for both enthalpy and entropy are
considered in the system dynamics; it is thus the true measure of maximum work potential. In
case where a portion of a process layout (system) is studied, the calculation is performed for both
the input and output conditions of the streams surrounding the process unit; like a black box in
relation to the reference point.
Chemical Exergy
The chemical exergy potential states the work potential of materials in relation to their molecular
composition; i.e. molecular form, orientation, and group formation. Much like chemical energy
potentials, the values are determined by tables and charts2. In most cases, the chemical exergy and
energy do not differ sustainably.
Exchem = ∑i yi ⋅ Exchemi
yi = stoichiometric coefficient of molecular structure i

Exchemi = exergy content or contribution of molecular structure i
It is a summation of each individual molecular group’s contribution to reaction potential in the

whole chemical element, i.e. tabular determination.
Mixing Exergy
Mixing exergy incorporates the effect of dilution or concentration of various elements in relation
to the reference point.
Exmix = n& ⋅ R ⋅ T0 ⋅ ∑i yi ⋅ ln y i
The result is usually negligible. It is only significant for highly energetic minerals such as
radioactive elements; for example the influence of the centrifugal purification (or concentration)
step. In these calculations, however, it is omitted.
2.3.4 Simple Terms: Energy vs. Exergy

In simple terms, energy and exergy can be expressed by the following3:
(1) energy is motion or ability to produce motion and
(2) exergy is work (ordered motion) or ability to produce work.
Basically exergy is a measure of the useable portion of energy for work potential – energy being
quantity and exergy being quality. Differences between exergy versus energy results are mainly
noticeable in thermal processes or those system layouts which rely on the thermal release of
chemical energy: i.e. in cases where the physical exergy flow is greatly different than the enthalpy
flow. As mentioned chemical energy and exergy do not differ substantially.

3 Base Values and Calculations
3.1 Solar Radiation Energy and Exergy
During the early phases of large-scale fossil fuel usage, significant levels of
sulphur was emitted into the atmosphere (otherwise known as smog). The
effects of these large quantities of sulphuric gases in the atmosphere led to so-
called global dimming, wherein the solar radiation is partially blocked and has a
reduced intensity. Traditionally this effect has been limited to volcanic
eruptions. And since the 1980’s stricter environmental laws have pushed for
lower sulphur emission levels. As a direct result sulphur levels in the atmosphere have continually
decreased and the reverse effect of global brightening is occurring, where the solar radiation level
increases4. Global brightening has been attributed to a 2W/m² increase of solar radiation annually
since 1986.
Seeing that solar radiation is the principal source of energy for biomass to create material and
thus lock in chemical energy, any deviations in solar radiation have a direct effect on growth
levels. Here the relationship between the energy content and exergy content of solar radiation
could play a vital role. Following a detailed study pertaining to the maximum work obtainable by
solar radiation, the difference is however only minor: solar exergy is 0.9327 of the energy value5.
Nonetheless the relevance of solar radiation both energetically and exergetically, as described in
Chapter 4, is excluded from consideration. Biomass growth and potential chemical energy/exergy
yields are brought into relation to land use consumption. It should be mentioned, though, that
the chemical exergy of biomass material is slightly higher than the chemical energy and as the
solar radiation exergy is lower than the energy content, plants are actually more exergetically
efficient than energetically efficient. This phenomenon could also be thermodynamically brought
into perspective of thermal-based processes; plants function at near atmospheric conditions,
further proof that nature operates optimally.
3.2 Fossil Fuel Source Energy and Exergy

Fossil fuels are typically combusted to release their chemicals energy and exergy but are also used
as chemical feedstocks. In both situations their cumulative energy and exergy demand is
determined by their chemical energy content and the exergetic ratio. Two examples will be given;
natural gas and diesel to illustrate the procedure.
3.2.1 Natural Gas

Natural gas used for both fuel energy and feedstock requirements and is expressed in
terms of energetic output: lower heating value (LHV - GJ/ton). This correlates to a
stark difference in gas qualities as each natural gas source has varying calorific values.
To calculate the amount of gas (mass) this relates to, the following assumptions and
calculation path has been set up:

Eout
M= ⋅δ
HL
Natural gas source = Groningen

E out = Energetic output/requirement, process dependent
HL = Lower heating value (LHV), 31.65MJ/m³
δ = Natural gas density, 783.6kg/m³ at STP (standard temperature and pressure)
Natural gas can originate from many sources around the world with a large corresponding
deviation of its calorific value (i.e. LHV). At this stage a major assumption is made, that for all
calculations natural gas originates from Groningen6. The chemical energy content of natural gas
directly coming from the Groningse Slochteren is 31.65MJ/m³. The energy content is typically
upgraded through gas purification to a Wobbe-indexed value ranging from 43.5 – 44.4MJ/m³. In
the base calculations the original energy and exergy content of the gas at the point of extraction
will be selected, indicating its original chemical energy content. Natural gas has a chemical energy
and exergy ratio of 1.0:1.05 2.
Therefore:
CED = 40.39GJ/ton, CExD =42.41GJ/ton
3.2.2 Diesel
Diesel and other transportation fuels are used throughout the biomass
chains, primarily as a fuel for internal combustion engines in logistics.
There are two main diesel fuel types for consideration; transport and
industrial variant. Therefore, the first assumption is that diesel
referenced throughout the calculation matrix is transportation
diesel. Little difference is noticeable in the contained chemical energy of transport grade diesel;
according to ACEA it is 45.5MJ/kg7. Diesel is one of the primary fossil fuel products originating
from the crude oil cracker; the allocated process energy involved in its production and ground
extraction will be omitted. This can only be performed when all cracked products embedded in
both the biomass routes and petrochemical routes are treated equally. Thus, in this calculation
matrix a simplification is made: all cracker products are the starting point for replacement and
their cumulative energy and exergy is relative to their chemical energy and exergy. Diesel has a
chemical energy and exergy ratio is 1.0 to 1.02.
Therefore:
CED = 45.5GJ/ton, CExD = 45.5GJ/ton
3.3 Energy Carrier Conversions

In process schematics (process flow diagrams – PFD’s), energy inputs are usually expressed in
heat and power terms; more specifically steam and electricity requirements. Both steam and
electricity are not the original fossil fuel energy (exergy) form. To determine the relative fossil fuel
energy (exergy) involved the actual conditions, production efficiencies and local production mix

of fuels to generate heat and power need to be known. This calls for several assumptions, which
will be listed for electricity and steam:
3.3.1 Electric Production

In nearly all cases, electrical inputs are documented in the kWh terms.
First, these values must be converted to MJ with the easy factor of
3.6MJ/kWh to arrive at the direct energy demand. Secondly, the method
to produce electricity must be set to determine the cumulative energy
demand. In most quick and dirty LCA studies (conducted by non-experts)
this step is frequently overlooked: giving electricity a 1:1 ratio for fossil fuel energy demand. Only
by including the typical electricity production efficiency can the primary fossil fuel energy and
exergy can be proper allocated:
Eel
E prime =
η
E prime = Prime energy, MJ
E el = Electrical energy, MJ
η = Electrical production efficiency, 45%
The electric production efficiency is dependent on many factors from the regional fuel mixture
for power generation to the technological state of the region. In France for instance, they have a
nearly 85% nuclear powered electric grid, which depending on the study has a fossil fuel energy
content 10-50%8. So the first assumption is the power mix, here standard coal will be chosen. In
Holland, its hinterland, and for the large part the rest of the world, coal is still the most used fuel
feedstock for the production of electricity. Secondly, the conversion efficiency of coal to
electricity has greatly increased over the past decades, hereby selecting a 45% energy and 35%
exergy efficiency for a modern coal power plant2, 9. A standard coal power plant (CP) ranges from
35 – 45% with future perspectives at 55%, whereas a gasification clean coal plant (IGCC) range
from 45 – 50% with future perspectives at 60%.
The utilization of off-heat is not considered in this report because typically

CP’s and IGCC’s are on the large grid-based production scales and do not
make adequate use of the off-heat. One often visualizes the large cooling
towers, which is indeed the standard. Only in a few isolated instances is a
portion of the off-heat actually utilized (for example district heating) which
would increase the overall cumulative energy efficiency. Coke (coal) has a
chemical energy and exergy ratio is 1.0:1.0 and electricity as a product has an energy to exergy
ratio of 1.0:1.0 2.
Therefore:
CED = 8.0MJ/kWh, CExD = 10.2MJ/kWh

3.3.2 Steam
In nearly all PFD’s, steam is documented in mass terms of the type of steam. These figures alone
are sufficient in calculating the energy content. Pressure is the main influences of the energy
content of steam; high-pressure steam contains vastly more energy than low-pressure steam. The
correlation between pressure and energy content can be found using steam tables and
consequently related to the total energy content10. The first step is converting the mass figures
(kg, ton, etc.) values into energy figures.
Esteam = hT , p ⋅ M steam
hT,p = Total specific enthalpy (usable heat) at corresponding pressure

Msteam = Steam mass quantity, kg
It is common engineering practice to mention the stream pressure along with the mass flow. The
second step in energy determination is to find the corresponding enthalpies:
hT , p = hl , p + he , p
hl,p = Specific enthalpy of saturated liquid at corresponding pressure

hl,p = Specific enthalpy of saturated vapour at corresponding pressure
The resulting graph depicts the enthalpy content for steam at varying pressures. The formulas are
used to compile a calculative model based on pressure inputs.
Total Steam Specific (Usable) Enthalpy
4250
4000
3750
y = 246.85Ln(x) + 2989.1
Enthalpy /kJ. kg -1
3500
3250
3000
y = 384.4x + 2291
2750
2500
0 20 40 60 80 100 120
Pressure /bar
Figure 1 Steam Chart for Energy

Using the same steam charts and tables the entropy values can also be collected to determine the
exergy content following the physical exergy formula:
Ex = (H − T0 ⋅ S ) − ( H 0 − T0 ⋅ S0 )
H = enthalpy content at corresponding pressure

H0 = enthalpy reference, 104.8kJ/kg
T0 = reference temperature, 298.15K
S = entropy content at corresponding pressure
S0 = entropy reference, 0.367kJ/kg⋅K
The resulting graph depicts the exergy content for steam at varying pressures.
Total Steam Exergy Content
1200
1000
2
y = -0.0165x + 3.3112x + 891.99
800
Exergy /KJ.kg-1
y = 136.46Ln(x) + 499.78
600
400
y = 366.58x - 297.75
200
0 20 40 60 80 100 120
Pressure /bar
Figure 2 Steam Chart for Exergy
The result of these empirical graphical depictions is that steam does not have an energy and
exergy content ratio of 1:1 and is a function of the steam pressure. At standard pressure steam
conditions (11bar and 180° C) the ratio between exergy and energy content in steam is 0.231. The
higher the pressure (and temperature), the higher the energy-to-exergy ratio. The maximum ratio
is 0.26 at pressure of 50 – 75bar (or 260 - 290°C). This translates to means a greatly lower work
potential than energy content of steam.
The third step is determining the cumulative energy and exergy content. It follows the same
procedural steps and assumption as with electricity. Modern steam generation plants are highly
energetically efficient and are fed by the most suitable fossil fuel for the maximum transfer of

chemical energy to heat energy…natural gas. The boiler is the naturally the largest source of
losses; energetically ranges from 80 – 90%, 86.5% for standard conditions. It certain
circumstances it can approach 100% energy transfer with high tech methods, but is usually not
done: 85% will be assumed. Exergetically the work potential transfer is much worse rangingn
between 40 – 50% depending on the system layout. The upper-range value of 50% will be taken
to represent a BAT plant.
Combining the relation between production requirements and the contained output in steam
there is actually more energy necessary than exergy. Following logic, as was the case with
electricity, one could conclude that more exergy is required to produce steam than energy. This is
not the case as is illustrated by the following example:
Example – 1ton of steam at 11bar:

Energy: 1ton of steam = 3.6GJ
- at a production efficiency of 85% yields 4.2GJ of input which in terms of natural gas translates
to 133m³ of natural gas.
Exergy: 1ton of steam = 0.827GJ
- at a production efficiency of 50% yields 1.65GJ of input which in terms of natural gas
(0.03165GJ/m³ and 1.05Ex/En) translates to 49.7m³ natural gas.
3.3.3 Standardized Ratios

The following table lists the standardized ratios for the chemical energy and exergy for the major
fossil fuels present in the calculation matrix.
Table 1 Energy source factor
Facto r Naphtha Natural Gas Coke Fuel Oil Electricity Steam*

Energy 1.0 1.0 1.0 1.0 1/0.45 1.0
Exergy 1.055 1.05 1.0 1/1.07 1/0.35 1/0.231
*At 150°C/4.8bar the energy to exergy ratio is 0.231 (see Section 3.3.2)

4 Detailed Processing Values and Calculations
Many of the bioprocessing steps within the conceptual layout of the biorefinery do not yet exist
necessitating the development of process schematics which are generated from scratch using
process-based assumptions. The process conditions, values and data needed to calculate the
direct energy and exergy and the corresponding cumulative energy and exergy can be determined
using process simulation software.
4.1 Aspen+
There are scores of process simulation software available on the
market for industrial systems. The most popular and powerful in
terms of chemical processes is Aspen+. It does however have a major
drawback; for many of the newer biobased processes it does not have the base chemical
components standard in their database. NREL developed an add-in update for biocomponents
which are related to, in particular, bioethanol processing11. Furthermore, many bioprocesses are
batch processes and also do not necessarily make use of standard chemically-based unit
operations. This fact can lead to difficulties. Aspen+ is still nonetheless the best simulation
program available. Once the process flow diagram has been entered in the program the resulting
streams are used to determine the energy and exergy.
Figure 3 Distillation Unit Cut

Energy is easier to determine as they are included in Aspen as heat and work streams, assuming
the layout has been properly constructed. Exergy is slightly more complex which requires a
detailed look at the individual process unit operations. Take for example the above distillation
unit (Figure 3). The streams of relevance are the input streams (both material and heat) and the
state of the output streams (both material and heat/work). The program calculates the enthalpy
and entropy state of each stream. The physical exergy flow of the bottoms-stream is determined
by using the B-M02 and B-M04A thermodynamical state and subtracted by the work/thermal
stream influence (B-Q05). Each unit operation can be treated like a block box with the details of
minor importance, only the input and output mass and work streams matter. This procedure
calculates the direct energy and exergy flows in the individual unit operations; it must be repeated
throughout the entire process layout. Lastly, the type of energy stream involved in the unit
operation is brought into relation to determine the cumulative energy and exergy demand.

4.2 Process Flow Diagrams
With the detailed knowledge of the entire process dynamics the energy and exergy flows can be
used to construct two graphical diagrams; a Sankey diagram for energy flows and a Grassman
diagram for exergy flows12. They highlight the losses in energy and exergy throughout the entire
system, respectively. It becomes vastly more difficult and complex to construct such a diagram
over an entire life cycle process chains but could in theory be done. They are primary used to
highlight the stark difference between energy and exergy flows in highly thermal processes.
4.2.1 Energy - Sankey Diagram

38kW
Heat Ch ange
28 kW Lo sses
He at Pump
36kW
R290 Com presso r
1kW Tr anspor t Lo sses

29kW
4 0°C
Hea t Str ea m
30 kW
6kW
10kW
111kW Heat Chan ge
2 82kW 273kW 115kW
4kW L osses
70 °C
100kW Loss
1050kW
H eat Str eam
4 35kW
150 °C
H eat Str eam
Dist illatio n
Ga s
Bu rn er
304k W
Losses
Ele ctr icity
166kW
Hea t Ch ange
30kW
Air Comp ressor
36kW
R290 Compr essor
370kW
Elect ricity
Figure 4 Sankey diagram – example power plant with off-heat utilization
4.2.2 Exergy – Grassman Diagram

36 k W
5 0 kW R2 90 Compr es s or
Tra ns por tLos se s
3 0 kW
H ea t Los s e s
1 5 5k W
He a t Tr ans fe r
Heat P ump
40°C
Hea t Stream
1 9 9 kW
2 4k W
3 8 1k W 3 56 k W 3 18 k W
1 0 0 0k W 3 8 1 kW He at Pote ntia l
4 3 5k W
68 k W
150° C H ea t Loss
70°C Greenhouse
H eat Stre am
Heat S tream
Gas
B urner
3 5 6k W
D istil lation
E lectr c
i ity
3 0 kW
Air C ompre ss or
3 6 kW
R2 9 0 C ompre s sor
3 70 k W
Elec tric ity
Figure 5 Grassman diagram – example power plant with off-heat utilization

5 Cradle-to-Factory Gate Methodology
5.1 Mass and energy balances
For those processes that are well documented, the thermodynamic state of the internal heat and
power streams can be studied to accurately determine the cumulative energy and exergy demand.
In other systems, key information may be confidential or simple not present. In such situations,
the simplification of relying on the mass and energy type balances is utilized with the above
conversions table (Table 1) frequently being used. In rare cases, the details pertaining to the
energy type is not mentioned, but instead a total value is provided. Here a comparison between
plausible and similar processes is made to determine the heat and power mix involved to be able
to estimate the relative cumulative energy and exergy demands. Many other inputs streams are
straightforward directly using conversions. It is merely the task of tracing the process chain back
to the original fossil fuel energy input and, in cases of cracker products, to the cracker.
5.2 Existing Chemical Production Routes

The entire purpose of compiling cumulative energy and exergy demand calculations is to
determine the largest fossil fuel replacement potential within the existing petrochemical chain
through systematic comparison. The LCA database and program Boustead (with portions of
BASF internal processing figures) was employed to acquire the direct energy demand of existing
petrochemicals13. Using the detailed information regarding the electric/stream inputs and
feedstock quantities the CED for some major petrochemical products is as follows (Figure 6):
Xyle ne 66. 71
Vinyl Acet ate 74.7
Ur ea 46.38
T olue ne 72.67
Styre ne 83.98
Stea ric Acid 80.02
Prop yle ne 67. 44
Pro pan ioc Acid 44. 16
Pho spho ric Acid 53. 39
Phe nol 76.46
O xalic Acid 128. 2
Nylon Fib er 180. 52
Nylon 66 142.31
Nit ric Acid 19. 65
Naph tha 50.1
Meth yl Met hacr ylate 73.85
M etha nol 36.25
Hydr oge n Cyan ide 73. 57
Hexa ne 59.11
Fo rm aldeh yde 35.69
Et hylene Glycol 54.48
Ethylen diam ine 133. 2
Ethyle ne 67. 03
Dime thylam ine 81. 07
Cyclo hexa ne 93. 51
Capr olactu m 114.7
Bute ne 65. 48
Butan diol 70.81
Buta ne 43.2
Bu tadie ne 45.5
Ben zoic Acid 132.09
Benze ne 68.04
Am mo nium Nitr ate 34.64
Am mo nia 30. 99
Ad ipic Acid 78.43
Acrylon itrile 85.56
Acrylic Est ers 84.29
Acrylic Acid 53. 48
Acrylam ide 61. 58
Aceto ne 70. 52
Ace tic Acid 54.16
0 20 40 60 80 100 1 20 140 160 180 200

Cumulative Fossil Fuel Ener gy Demand GJ/ton P roduct
Figure 6 CED – Cumulative Energy Demand of Major Petrochemicals

With the same detailed process information the cumulative exergy demand can be determined. In
most cases it is only a small factor of 5% higher due to the large influence of the feedstock, i.e.
naphtha and natural gas. Nevertheless, each chemical product is follows an independent process
route and can vary. Presented below is a graph (Figure 7) of the cumulative energy and exergy
demand for those petrochemicals which are envisioned to be replaced by the potential chemical
biorefinery layout presented in this dissertation report:
Relevent Petrochemical Products for Biorefinery

45.7
B iolubricant s 45.5 Exergy
Urea 4 3.2 Energy
4 6.4
Oxalic acid 120.2

128.2
7 3.6
Isopropanolami ne 81.1
Isoprene 68.4
67.4
33 .9
Isobut yraldehyde 35.7
32 .3
Ionic liquids 34.6
g-butyrolactum 84.3
87.3
119.4
Feed grade m ethioni ne 119 .0
119.4
F eed grade cyst ei ne 119 .0
Et hylenediami ne 130 .4
133.2
7 3.6
E thylami ne 81.1
110.7
e-caprolactum 114.7
Amm onia 23.0

31 .0
75 .4
Adipic acid 78.4
A crylami de 6 2.0
61.6
1,4-but andiami ne 110.7

114.7
73.7
Toluene 72.7
St yrene 8 4.5
84.0
75.8
Phenol 76 .5
68.1
Ethylene 67.0
0 20 40 60 80 100 1 20 14 0
Fossil Fuel Demand (GJ /ton)
Figure 7 CED & CExD of Petrochemicals Relevant for a Biorefinery

6 Conclusion
In conducting a comparative energy and exergy life cycle analysis detailed information pertaining
to the individual processes must be known. In some situations, sufficient details are not present
meaning simplifications and assumptions must be taken. A dilemma faced by many professionals
conducting LCA’s (life cycle assessments) is that different forms of energy inputs and different
expressions for these energy types are commonly presented. It is standard practice to list the
energy inputs separately, such as steam or electricity, but also common to simply combine the
inputs as one total figure. Calculation of the cumulative energy demand requires the energy life
cycle to be brought to the cradle. Only then can the extent of the original fossil fuel energy input
be properly assessed. This requires base values and assumptions. Such were listed for their
determination, but solely following the first law of thermodynamics makes no distinction
between the quality of these different energy forms. Therefore, along with the base values and
assumptions for energy calculations the same information was provided for determining the
cumulative exergy demand. Exergy is the thermodynamic measure of the quality of energy flows.
These base data form the guidelines for all the subsequent calculations of the various inputs in
the cradle-to-factory gate matrix. And despite no concrete examples been given on the
importance of exergy, potentially large differences that could emerge between energy and exergy
within the compilation of the calculation matrix will reveal major energy efficiency improvement
options. In the broad field of alternative energy, additionally assessing the quality of energy flows
(read – exergy) can provide the necessary insight to vastly save on the fossil fuel energy
feedstocks throughout the process chain.

References
1. Arons, J. d. S.; Kooi, H. v. d.; Sankaranarayanan, K., Efficiency and Sustainability in the Energy and
Chemical Industries. Marcel Dekker, Inc.: New York, 2004; p 299.
2. Szargut, J.; Morris, D. R.; Steward, F. R., Exergy Analysis of Thermal, Chemical, and Metallurgical
Processes. Springer-Verlag: 1988; p 332.
3. Wall, G. Exergy - A Useful Concept. Chalmers University ofTechnology, Göteborg, 1986.
4. Wild, M.; Ohmura, A.; Makowski, K., Impact of global dimming and brightening on global
warming. Geophysical Research Letters 2008, 34, doi:10.1029/2006GL028031.
5. Petela, R., Exergy of heat radiation. J. Heat Transfer 1964, 86, (1964), 187-192.
6. Gasterra.nl Groningen Natural Gas.
http://www.gasterra.nl/aardgas/Documents/Woordenlijst_140508.pdf (10.2008),
7. ACEA - European Automotive Manufacturers' Association, Diesel versus petrol engines. In
2000.
8. Fthenakis, V. In Nuclear Power - Greenhouse Gas Emissions & Risks A Comparative Life Cycle
Analysis, California Energy Commission Nuclear Issues Workshop, Sacramento, CA, 2007;
Sacramento, CA, 2007.
9. ECN Coal and Climate Change; 2004.
10. Rocchetti, M., Free Engineering Software Website In 2005.
11. Wooley, R. J.; Putsche, V. Development of an ASPEN PLUS Physical Property Database for Biofuels
Components; NREL: Golden, CO, 1996.
12. Yamamoto, M.; Ishida, M., Process vectors both to create functional structures and to
represent characteristics of an entire system. Energy Conversion and Management 2002, 43, (9-12),
1271-1282
13. Boustead Consulting Ltd. Boustead Model 5.0, West Sussex, 2007.

Chapter 3
Life Cycle Assessment vs. Exergy
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 3 – LCA vs. Exergy

A&F number -
ISBN-number -
Date o f publication 1. December, 2004
Confidentiality No
OPD code -
Approved by -
Agrotechnology & Food Innovations B.V.

P.O. Box 17
Tel: +31 (0)317 475 190
Internet: www.agrotechnologyandfood.wur.nl


ISO 9001:2000.

Abstract
Common sense may give the impression that utilising biomass, as a feedstock source for the
petrochemical industry instead of fossil fuels, is an environmentally sound alternative. Looking at
environmental issues alone will not justify or stimulate a change; implementation of biobased
resources must also be a profitable venture for the industry. Proper consideration of both issues
should be based on performing an entire life cycle comparison, from raw material extraction to
production to transport to final end use, a so-called cradle-to-grave approach. There are an
insurmountable amount of different methods and analysis tools available to compare the life
cycle of different processes, production methods and products. A problem is determining which
of these methods and tools is the best for this specific comparison and why. In terms of shifting
the raw material source of an entire industry reliable and incontestable results are more than just
essential, they are a prerequisite.
Over the last several decades, one life cycle analysis tool has dominated the field, namely the life
cycle assessment (LCA). It had expanded from small internal comparisons to large industrial
sector-based comparisons. More recently an ISO standard has been written providing
practitioners with the procedural steps to execute an LCA. From careful review of the inner
workings of the standard it becomes apparent that it is more like a suggestive guideline than an
actual standard. The lack of true standardisation places a greater emphasis on personal
interpretation and raises doubt about the reliability of the results. Therefore, it may not be the
most appropriate tool for this comparison, but many of the methodologies are advantageous.
Other available tools are also unsuitable when followed exclusively, but contain many useful
approach variations. This chapter will determine the best amalgamation of the various life cycle
analysis tool components for the provoking a raw material change in the petrochemical industry.
Key Words:
Life Cycle Analysis, Life Cycle Assessment, LCA, Exergy, ELCA, LLCA, Paradigm Shift

Content
1 Introduction 43
2 Driving Force 45
2.1 Consumers 45
2.2 Industry 45
2.3 Public 46
2.4 Government Bodies 47
2.5 Research Centres 48
2.5.1 Valorisation of plant production chains 49
3 Life Cycle Assessment 51
3.1 Description 51
3.2 Brief History 51
3.2.1 Timeline 52
3.2.2 Application 52
3.3 ISO 14040 53
3.3.1 Recipe 53
3.3.2 Framework 54
3.3.3 Goal and Scope Definition 55
3.3.4 Inventory 55
3.3.4.1 System Boundaries 55
3.3.4.2 Flow Diagram 56
3.3.4.3 Data Collection 58
3.3.4.4 Data Estimation 59
3.3.5 Impact Assessment 60
3.3.5.1 Impact Categories 60
3.3.5.2 Normalisation and Weighting Factors 61
4 Limited Life Cycle Assessment 63
4.1 Overview 63
4.2 Application 64
4.3 Environmental Impact Units 65
5 Exergy 67
5.1 Comparative Exergetic Cradle-to-Factory Gate Analysis 67
6 Paradigm Shift 69
7 Conclusion 73

1 Introduction
Switching from fossil fuels to biomass as a raw material for the petrochemical industry entails a
paradigm shift. Nobody likes change; this holds true for most individuals as for most companies,
corporations and especially entire industries. Many corporate strategies are focused on the short-
term performance (i.e. quarterly profits) and systematically follow the business-as-usual pitch to
appease stakeholders. Declining fossil fuel stocks is an issue to consider and will eventually force
a paradigm shift but is still too far off in the distant future to grant serious acknowledgement by
the petrochemical industry. Government policy and regulations currently have little effect on the
economic freedom that the globalized market is providing. Thus, sparking a pre-depletion raw
material change must be beneficial to the company and stakeholders, which is essentially
expressed in monetary figures or phenomenal environmental benefits.
Life Cycle Assessment (or LCA for short) is a methodology to analyse the ecological
environmental burden of a product from cradle-to-grave. Environmental issues and concerns are
almost entirely used by policy makers. Industry is adjusting to the policies and regulations
becoming more environmentally sound, but the forced developments are still rather minimal. In
regards to the petrochemical industry, all passed policies are symptom treatments and are not
addressing the route cause, i.e. end of tailpipe solutions. It would make little sense to ban the use
of fossil fuel feedstocks in the petrochemical industry. An LCA, and what it basically stands for,
has next to no effect on influencing their strategic planning nor is it being taken all too seriously
by the industry. That is not to say that LCA’s are entirely useless, the framework, procedures and
particular figures can be borrowed to perform a similar cradle-to-grave analysis tool.
Exergy as described earlier (see Chapter 2), relates all energy, materials and services into one
figure; a work potential. The expression could be correlated with how much economic input is
required; the higher difference in input to output exergy the higher the general costs. Following
the guidelines set forth by the ISO-LCA the overall economic representation can be obtained.
Comparing the exergy differences between the petrochemical route and biochemical route from
cradle-to-grave could justify a pre-depletion raw material shift. Some key and less disputed
factors addressed in an LCA can also be beneficial to implement.
1.1 Chapter Purpose

This chapter describes the various life cycle assessment tools, their construct methodology, their
internal workings, and their limitations. As there are many different types and alterations to the
standard environmental LCA. In this chapter, the standard methodology is borrowed to create a
comparative energetic and exergetic cradle-to-factory gate assessment. The advantages of relying on exergy
values and not subjective environmental factors for the impact category is highlighted.

2 Driving Force
Each sector of a society has a different stance on which issues are important and which are not.
When a change does occur their own personal interests stipulate the direction, for the outcome
should not result in a disadvantage. The best interests of one sector may not be compatible with
the interests of another societal sector. For example, a empty spot of land in a city centre;
professionals may want to see it converted into a parking lot, students into a bike stall, the elderly
into a park, families into a playground and so on. By thinking only by about their own benefits
and desires their stance is a selfish one. As Adam Smith hypothesized, self interest in a
competitive environment provides a greater good for society. Yet, the decisions are actually
determined by the city counsel deliberating over the best compromise to satisfy the majority
while satisfying developmental needs. The driving force of change is just that, a balance between
wants and needs. The following subsections relate and extend the analogy of driving force to the
petrochemical industry:
2.1 Consumers
There is not a single consumer good, which does not rely of some form of chemical treatment
and/or material supply. At some stage in the entire production chain, chemicals are required. The
consumer can be anywhere along the chain from the initial purchasers of chemical raw materials
to the end-user of manufactured goods. Yet, their wants and needs are precisely the same:
Needs
• Constant supply
• Consistent quality
• Consistent physical and chemical properties
Wants
• Low and stable prices
The driving force of the consumer is simply lowering the prices without degrading the product.
As an example, it is understandable why bioplastics like Poly Lactic Acid (PLA) have not become
a grand commercial success. They simply do not meet the driving force of consumers. Although
the physical and chemical properties are similar (they are in fact slightly worse), the increased
price does not go over well. Paying more for less.
2.2 Industry
With the progress of a free capitalistic market economy, all industries slowly lose sight of moral
and societal obligations and further focus on revenue and profit. The petrochemical industry is
amongst the largest and most influential in the world, consisting of but a few global corporations.
Such companies are organised much like a hierarchical dictatorship and operate in response to
customer demands and shareholder interests. Their wants and needs are all monetarily motivated:
Needs
• Cheap raw materials
• Continuous supply of raw materials
• To satisfy the consumers driving force

Wants
• Reduce overhead
• Maximize profit
• Continually increase production and areas of activity
• Improve public image
Having a continuous supply of raw materials seems like a contradiction to their apprehension
towards shifting away from fossil fuel resources. However, considering that the majority of the
petrochemical companies are less than 100 years old and the projected worldwide reserves are
anywhere between 50 –100 years, the shift is not yet of major urgency. The current crude oil and
natural gas situation is able to supply the industry with all of its needs for at least several
generations to come. Essentially, the driving force of the petrochemical industry is to further
capitalize and expand while continually meeting the demands of the consumers. In light of the
PLA example, it does indeed comply with the goal of increased activity and improved public
perception, but only that. The raw material and production is more costly than the traditional
chemical route and to be able to satisfy the consumers driving force, the lower properties must
be compensated with an even lower sales price. Overall that would sacrifice profit, increase
overhead and be in contradiction to the industry’s driving force.
2.3 Public
In the developed world, citizens are becoming ever more affluent at a tremendous pace. The
prosperity is shifting the desires of the people from basic necessity to materialism. Simply put, if
they can afford more they want more. To cover these demands nearly everything that can be
mass-produced is. Along side this increase of secular wealth an increase of informational wealth
has come. Public awareness and general knowledge provided by affluence is beginning to address
the indirect problems associated with affluence driven materialism. The environmental burdens
of their lifestyle are becoming apparent and the general consensus would like to see mother earth
and her nature preserved without any serious harm or long-term damage. This warrants an
inconsistency in the needs and wants of the public:
Needs
• Basic survival, i.e. food and shelter
• Extras as stipulated by Maslow’s hierarchy of need
Wants
• More availability and selection of consumer goods
• Increased quality and functionality of consumer goods
• Lower prices for consumer goods
• Preservation of nature
• Lastly, lowered environmental damage impact
Generally speaking the public aspires to further increase their quality of life. In assessing the
public’s view the wants clearly distort the needs. Receiving adequate food and shelter is such a
basic right in the entire developed world that it does not need to be addressed in the driving
force. Thus everything that steers the public driving force are basically wants, and yet even within

these desires are contradicting issues. It places a great uncertainty of what the actual driving force
is. Continuing with the example of PLA, being derived from biomass has the perception of being
environmental sound and less damaging. However, comparing it to the standard fossil derived
plastic it is inferior in the quality-to-price ratio. The lack of public acceptance indicates that the
general populace are not willing to pay additional money for a lesser product solely in the name
of the environment. On one hand they point the finger at industry for polluting the environment
and on the other hand they are not willing to pay for its protection. The driving force of the
public can be paraphrased as thriving for more and better products at cheaper prices with the
environmental issue lingering in the background.
2.4 Government Bodies

In a democratic government the voice of the people and the societal fractions are all represented.
A healthy system provides many different viewpoints, stances, and options of representation
while including many of the grey areas. The majority of the voices are taken into account and are
acted upon with the best intentions of the society as a whole. In many cases, however, the
holistic approach is faced with severe opposition. To maintain power, seat, and the popular vote
they will often side step or completely disregard unfavourable issues. The needs and wants
illustrate the popular voice bias:
Needs
• Voice of the public
• Voice of the industry
• Voice of the consumer
Wants
• Win the popular vote and become re-elected
• Change the system to match their political agenda
Peaceful governments have the power to shift and mould society’s structure through the use of
policies, regulations, guidelines, taxes, subventions and research grants. It is a tedious and
difficult task to govern a society on a holistic approach or even determine what the best
intentions could be. Many governments succumb to their wants and base policies to gain the
popular vote through small gradual changes. Heated issues, which involve a large paradigm shift,
can be proposed by contracting and granting research institutes the finances necessary to
determine a multitude of different alternatives with usable results always the next parliament’s
concern. Decisions are usually based on the popular voice of the public, but also take other
fractions and political agendas into consideration. Therefore, the driving force of government
bodies is to maintain their rule by finding the most popular compromise between the societal
fractions. In regards to the PLA example, government bodies could force their implementation.
Perhaps by placing high tariffs on fossil-based plastics and providing large subsidies for biobased
plastics. The public (representing the popular vote) would be pleased, however, the
petrochemical industry and their consumers would not and they could argue unfair trading
practices which could cause performance losses on the international free market. Losing market
share could spiral down into the local economy and influence the public’s affluence thus

effectively removing the popular vote. The environment an aspect of the driving force, but is a
contradiction within itself. In cases of uncertainty, concerning environmental policy, is it best to
consult outside research groups to gather enough information to properly assess the best
compromise.
2.5 Research Centres

Technology over the last century has reached such a complexity that mere individuals can no
longer contribute to new innovations and breakthroughs. Key historical figures like Gottlieb
Daimler, Karl Benz and Wihlem Maybach were responsible for the invention of the automobile.
Alone they could not make such a significant technological discover today. Presently, horrendous
sums of money and a collective of highly educated personnel are required for even the smallest
contribution. Research centres are just that, institutions with the finances and intellect to perform
minor technological advancements. There are two major types of research centres; progressive
development centres geared towards consumers desires, mainly funded and operated by industry,
and innovative development centres geared towards public desires for example of environmental
concerns, independently operated but funded almost exclusively by government. Paradigm shifts
are the product of the latter but have trouble balancing their own needs or wants:
Needs
• Grants and funding
• To specialize and operate in a niche sector
• To satisfy the public driving force
Wants
• To see full-scale implementation of their research, i.e. acknowledgment
• Additional grants and funding
Being independently operated does not imply an independent choice of research topics. No, to
be eligible for funding they must address issues of public interest deemed worthy of or of interest
by the governmental policy makers. Seeing that governmental grants are limited the centres must
chiefly operate on a specific niche within the two major categories within the biobased economy;
fossil fuel replacement and environmental protection. Their driving force is to expand financial
and operational capabilities by encompassing the concerns of the public. Linking this drive to the
PLA example a blind spot becomes apparent. Research on the PLA alternative is conducted
because it is based on a renewable biomass feedstock and thus should simultaneously tackle the
problem of fossil fuel depletion and environmental destruction. Numerous different areas of
research are possible; plant cultivation, plant modification, logistics, production, enzyme
engineering, synthesis, extraction, applications, policy, environmental benefits, and so on. The list
is nearly infinite; however, there is a standard emerging addressing both fossil fuel use and
environmental factors, the LCA. Once the fundamentals have been determined an LCA can be
employed to fulfil their driving force. It is meant as the final corroboration that the government
bodies are seeking. Yet, by focusing on public concerns and government desires considerations
of the industry are clouded. To overcome this vital flaw reports are written in passive voice to
stress that they are possible long-term alternatives, always 10-years away. PLA may be better for

the environment and require less fossil fuel but it still remains too expensive for acceptance in
the current market. Although not directly foreseeable, but disregard to industrial desires will
prevent research centres from ever obtaining their own wants.
2.5.1 Valorisation of plant production chains

Shifting from a fossil fuel based economy to a renewable fuel based economy is clearly a
challenge. Presently, nearly the entire economy is based on the abundance of cheap fossil fuel
resources; sparking or suggesting a change is bound to generate some opposition. Yet, this does
not have to be. Several technologies and methods are already available to convert some industrial
sectors to renewables without economic concessions. LCA is the valorisation of production
chains following the standard driving force. To entice implementation for the immediate future
an addition need must be added:
Addition needs:
• To satisfy the industrial driving force
To satisfy the interests of industry environmentally-based LCA’s are insufficient and must be
expanded upon. Incorporating exergy, as an additional impact category parameter, can valorize
the production chains following the revised driving force. Alterations and careful consideration
are, however, still necessary as an LCA is littered with inconsistencies, flaws and most
importantly doubts. Ascertaining the shortcomings while preserving the benefits and key
characteristics in combination with an exergetic analysis will create a new tool:
An ELCA, Exergetic Life Cycle Assessment.

3 Life Cycle Assessment
3.1 Description
As with most terms laid out in the English language, life cycle assessment uses esoteric
nomenclature to add a hint of confusion in aims of suggesting more than what is intended.
German on the other hand, is direct and describes more or less exactly what is intended. Before
the term LCA was conjured up, the German term Ökologischerbilanzerung or Ökobilanz had been
assigned. Translated it means ecological balancing or eco-balance. Taking the mathematical
understanding of the word balancing (equality with respect to the net number of reduced
symbolic quantities on each side of an equation) the term is almost self-explanatory. The essence
of an LCA is thus to quantify all factors of a particular product or service completely from the
beginning to end (cradle-to-grave) in light of ecology. It
Cradle-to-grave
will result in assigning all the various ecological and Assessment considers impacts at each
environmental impact categories with numerical figures. stage of a product's lif e-cycle, from the time
natural resources are extracted from the
The English term has focused upon the cradle-to-grave ground and processed through each
subsequent stage of manufacturing,
portion, which has been substituted by the broad term life transportation, product use, and ultimately,
disposal
cycle. Negating the term ecology and using general
terminology suggests a much larger impact and area of Source: EEA
“assessment”. Yet the heart of the assessment remains the same, to balance and quantify the
ecological factors. The first associated problem already appears with the simple naming of the
analysis tool. For even research groups dealing with LCA’s are becoming misled and are starting
to view it as a final corroboration.
3.2 Brief History

Long before the presence of life cycle assessments and analyses, industry had based their process
optimisation on a straightforward energetic reduction approaches. This was achieved by focusing
efforts on optimising existing energy intensive processes and individual production steps.
Towards the latter part of the 20th century industry began to look at other cost saving methods in
a more holistic approach. A transition in reducing energy consumption from individual energy
flows to entire energy flows from raw materials to end products slowly emerged. They were
basically performing an energetic life cycle analysis yet the term of choice was a multiciteria study. It is
rarely disputed that the first was back in 1969, when Coca-Cola had contracted the Midwest
Institute of Kansas City to perform a multiciteria study of their bottle production. The aim of the
study was to determine the lowest energy and environmentally related costs between the option
of using glass or plastic bottles to market their product. In addition, it was discussed whether to
have internal or external production. Afterwards, many other large companies had started using
multiciteria studies to compare different product options. The main focus remained on energy
and material flows, ultimately those streams connected with an economical value. It was not until
decades later when environmental impact took centrefold, see Figure 1.

3.2.1 Timeline
1992
France
NFX30-300
LCA standard
1969 1984 1992 1997-2001

Coca-Cola EMPA EU ISO
Multi citeria First publication “ecol ogical Scheme for ISO14000 to 14050 as
Bottle Producti on report of packaging material” eco-labelling international LCA standard
1965 1970 1975 1980 1985 1990 1995 2000 2005
1974 1991 1996

EMPA SETAC Germany
Methodology for First works DIN33926
eco-balance LCA standard
1992
SPOLD
Data exchange
standard
Figure 1 Developmental Timeline of Life Cycle Assessment
3.2.2 Application
One of the first eco-balance methodologies was created by EMPA (Eidgenössische Materialprüfungs-
und Forschungsanstalt or Swiss Federal Laboratories for Material Testing and Research). Their self-
proclaimed purpose was directed at the internal determination for process optimization based on
ecological considerations for industry. Companies would carry out internal life cycle comparisons
following their methods to help conclude which of the product or process options has the least
environmental burden. At the time focus was on energy, raw material use, and complying with
pollution regulations. Industry was in effect employing (although limited) the eco-balancing based
on fulfilling their own driving force. Partly because of increasing environmental regulations and
fines and partly because of government body interest, the shift became predominately
environmentally based. As more standards and guidelines were created the LCA took shape and
by 1997 the LCA as it is known today was born. Institutionalized standards have made it possible
for outside appraisers to perform analyses for not only comparative purposes of minor changes
but of large scope paradigm shifts. Here the first problem is confronted; the rationale had been
altered. Comparisons were being shifted from internal company issues to entire industrial sector
issues. Due to the shear broadness, a lack of precision emerged questioning the accuracy of such
analyses. Fortunately standards may help overcome this problem, but the standards are in fact
general guidelines. Emphasis of personal interpretation has removed absolute quantitative figures
with subjective quantitative figures.

3.3 ISO 14040
ISO is not an acronym for the International Organisation of Standards as is commonly believed;
it is derived from Greek isos, meaning equal. The organisation has been established to unify other
national standards for worldwide industrial and commercial use. Seen any way ISO represents
efforts towards global standardisation. The ISO 14040 series is meant to be the standard for
executing an LCA study. Unfortunately it is not actually a standard per se and therefore is not a
clear-cut procedure, method, or formulation to follow. The room for personal intervention and
interpretation makes it more like a guideline or even as nebulous as a general recommendation.
3.3.1 Recipe
For those people familiar with the ISO 14040 series, its methodology has been compared to that
of a cookbook recipe. Indeed, there are sequential procedures to follow much like a cooking
recipe. The cookbook analogy has become common LCA terminology that most, if not all
textbooks refer to the recipe format. Again here, the terminology is misleading and
presumptuous in its abilities. Making an analogy between the cooking procedures and the
procedures of a standard like that of an ISO standard is possible and actually quite clever. Both
require specific input figures and precise procedural steps to produce a coherent final result. The
problem with the ISO 14040 series is that it is not an actual standard, so the justification to
continue with the analogy is annulled. A cooking recipe is designed to consistently reproduce the
same culinary product every time should the steps are meticulously followed. For example, when
preparing the internationally renown Dutch pastry, the Spacecake, specific ingredients and
quantities, preparations, oven settings, cooking utensils, etc. are all listed and well documented.
Anyone following the recipe correctly, with adequate knowledge in the fundamentals of cooking,
should bake the exact same cake every time. A guideline does not comply. In terms of cooking a
guideline would be like having a general recommendation of what ingredients to use in baking a
cake while proving the principles of baking. Everyone following the recipe guideline would bake
something slightly different, they may all be cakes but rarely will they be the same. This is
precisely the problem with the ISO14040, for the results will vary with each individual analysis
and is only worsened by the scope size, since broadening the scope will simultaneously broaden
the deviation and uncertainty. A large scope may yield extreme deviations like an Chocolate cake
to a Vanilla cake. Looking back to the origins of the eco-balance system, the scope was much
smaller and kept within the companies’ own knowledge base. Following a guideline, like an LCA
for narrow internal options will reduce the deviance and dilemma of variance. A small scope may
yield minor deviations, like a particular type of icing on a chocolate cake. As ingenious as the
recipe analogy may appear it is completely inappropriate for the new ISO 14040 series and only
increases the doubt surrounding its application.

3.3.2 Framework
The heart of the ISO 14040 series is graphically expressed by the following figure:
Goal and Scope

Definition
Direct Applications
- Product
development and
Inventory improvement
Interpretation
Analysis - Strategic planning
- Public policy
making
- Marketing
- Other
Impact
Assessment
Figure 2 ISO 14040 Life Cycle Assessment framework procedure
The largest box and largest factor in Figure 2 interpretation. All other aspects and steps are
dependent on the interaction of the appraisers interpretation. This is undoubtedly the fatal
problem associated with an LCA; how can anything be concretely determined if the analysis is
entirely based on personal interpretation. In a world of some 6 odd billion people, the amount of
viewpoints, intelligence, education, logic and experience is just as diverse as the population.
Interpretation is a mix of these and other factors of an individuals personal feeling. Who is to say
who is right and who is wrong? Even within the relative fields, different specialists will interpret
the same set of data differently. A classic example of contradicting views of data interpretation is
that of global warming. Most scientists agree that there is enough conclusive evidence available to
deduce that carbon dioxide and other manmade emission gases are responsible, whereas other
scientists interpret the data as being inconclusive. The debate continues to this day and who can
without hindsight really say who is right. General logic is also unreliable, as a global issue will
present a global array of logic. Any capable scientist should be able to draw the conclusions they
want simply by interpreting the data differently. But as before, these problems are relative to the
scope size, for a narrow highly specific topic assessed by relative specialists will bare a strikingly
similar interpretation. This stems back to the issue of application. An internal process or product
option comparison will involve specialists in their own relative field of specialty in a relatively
narrow scope of assessment. For these industrial applications, the problems of interpretation in
the LCA framework is limited and can even be beneficial, should there be a unanimous

agreement. Conversely, as the scope expands and is addressed by various external bodies with
differing stances, the interpretation becomes increasingly subjective. It is best to comment on
each of the framework points separately to comment on their strong and weak points.
3.3.3 Goal and Scope Definition

When starting an analysis of any kind one must raise the questions; what to do and how to do it.
The goal and scope accomplish precisely that and dictate all the procedures and views thereafter.
SETAC, the society of environmental toxicology and chemistry states: “The study goal and scope are
crucial to managing and co-ordinating a life-cycle study by bringing together the LCA information needed to make
an identified decision and an understanding of the reliability and representativeness of the LCA.” Like most
reports and analysis, in a few sentences the goal portion explains the purpose and reasoning for
carrying out such an investigation. The scope on the other hand is slightly more complex in its
execution; the type of LCA and the extent of the investigation are laid out. This step will govern
how the analysis will be handled and what conditions will be considered. Along with it figures
and settings, such as functional units and reference flow, for a correlative comparison are listed.
Expressed in a short text, readers have the opportunity overlook the base assumptions and
simplifications. This is a wise and sound procedure, for should the reader spot any disagreements
or discrepancies they can immediately disregard the study. A similar layout can be adopted for
other analysis tools such as with the ELCA. The only problem is the freedom in the depth of the
scope, which can only really be properly ascertained in the following inventory step.
3.3.4 Inventory
3.3.4.1 System Boundaries

The single most important aspect of any cradle-to-grave analysis is the proper and complete set-
up of the system boundaries. It makes little difference which analysis tool is used this step will
always be filled with doubt, incompleteness, and problems. Where to “draw-the-line” is a question
that can never be properly answered. The scope definition of the analysis is able to reduce the
size of the system boundaries through simplifications. Here the route of the scope problem can
be pinpointed; for the larger the scope, the larger the necessary simplifications and assumptions.
Obviously with a higher demand of simplicity the more inaccurate the results become.
Take again PLA as an example, the entire cradle-to-grave production of the bioplastic must be
determined and compared to the standard plastics. Where to draw the line? At the harvesting
stage, should the production of trackers be accounted for? Should the production of the tires for
the trackers be accounted for? Should the production of the machines for the rubber extraction
for the tires be accounted for? Should the production of steel for the rubber extractors be
accounted for? The list is endless and would eventually cover every aspect of human activity. The
nature of the ISO guideline provides freedom of interpretation to simplify the boundaries as seen
best fit. However, this freedom allows anyone performing an LCA to arbitrarily draw the cut-off
line. It is argued that a sensible cut-off has an error in the range under a single percent. Perhaps

this is true, but as each individual LCA will deviate based on personal choice and further increase
with the scope, a complex LCA could become inconclusive. A smaller comparison like with Coca-
Cola’s bottle choice has much less emphasis on cut-off determination. In contrast to a large
assessment like PLA, many of the chains remain the same or are similar between the two options.
Drawing the few necessary cut-off lines is uncontested in light of the scope. Generally speaking,
the smaller the scope the more accurate and reliable the LCA becomes.
The system boundaries required for an exergetic analysis are slightly different and remarkably
more constricted. Only the steps with an induced change of exergy or require an exergy input will
it be contained and considered within the system. In terms of PLA, the trackers increase the
exergy by collecting the crops to a central location and consume exergy in the form of fuel;
thermodynamically the entropy is increased. How they are made or how much input they require
is practically negligible in exergy terms. The boundaries are clearer, more transparent.
3.3.4.2 Flow Diagram

If a picture says a thousand words than a process flow diagram says ten thousand. Groups of all
processes, inputs and output stream are linked together to illustrate the entire system within the
specified boundaries. It acts as the graphical representation to better describe the entire life cycle
of the process and better develop the process. Errors and inconsistency can be found with
relative ease and while through flow diagram comparison location of gaps or missing streams is
greatly improved. It is a valuable tool and acts more like a true standard than a guideline. The
room for personal intervention is limited to the visual representation and not the content. A
small portion of a flow diagram can easily expand on the comparison of the system boundary
difference between the LCA concept and the exergy concept for PLA:
Harvester rubber
Manufacture
electronics
Cultivation
Botteling electricity
steel
lubricants harve sters

Diesel Tracker
Separation crops
diesel Manufacture
& Purification
trackers
fresh water
waste
Harvesting
Figure 3 LCA flow diagram section

Harvester rubber
Manufacture
electronics
Cultivation
Botteling electricity
steel
lubricants harvesters
Diesel Tracker
Separation crops
diesel Manufacture
& Purification
trackers
fresh water
waste
Harvesting
Figure 4 Exergy flow diagram section
In these flow diagram exurbs, all the steps proceeding and connected to the harvesting step are
depicted. It can be seen that the life cycle components and flows are identical in both procedures.
However, there is a clear and substantial difference regarding the boundaries and thus the cut-off.
The purple dashed line indicates the system boundaries. In the LCA exurb (Figure 3) the
manufacture of the harvester and tracker are considered but could be cut-off at this point. This
may or may not have a large impact on the result, for the chance is present that another appraiser
could incorporate processes further down the line. Incidentally the opposite could also happen
and machinery could be considered as a single input flow without other process considerations.
The freedom for interpreting the system boundary is less with the exergetic flow exurb diagram
(Figure 4). Only those process steps, were an induced exergy change is subjected upon the overall
product chain are contained, are assessed within the system boundaries. The result from cradle-
to-grave will be the total cumulative amount of exergy flow to the product to derive at the final
product. The side chains are not as important as they adhere to their own production chain route,
which is exergy terms are generally negligible. Using a tracker with a harvester is not the only way
to harvest crops; it could very well be performed by manual labour. The result of the product in
question (here PLA) is influenced by the exergy fuelling that choice, but optimising these side
chains does indeed require a separate independent analysis. An LCA should be handled in the
same manner to prevent personal intervention, especially when comparing paradigm shifts.
Unfortunately, this is not the case because the ISO 14040 series calls for personal interpretation
and the process flow diagram merely strengthens the fallacy of scope size.

Limited Scope Large Scope
xx xx x
xx xx
xx xx x x xxx x xxx xx x xxx x xxx xx

xxx x xx xx x xx x x xxx x xx x
xx xx x x xxx x xx xx x
xx xx x xxx xx xx
x xx xx x xx xx xx xx x
x xxx x xxx xxx x
xx xx x xx xx x xx xx x xxx xx x xx xx
xx xx xxx x xx xx x xx x x xx x
xx xx x
xxx x
x xx xx xx xx x xx xx x x xx xx x xxx x xx xx x xxx xx x xxx x
x xx x xx xx xxx x x xx x x xxx xx xx x xx x x xxx
xx xx x xx xx x xxx xx xx xx x
xxx x xx xx x xx x xx xx
xx xx x xxx xx
xxx x x xx x
xx xx x xxx xx
xxx x x xx x
xx xx x xxx xx
xxx x x xx x
Figure 5 Scope size difference illustrated on process flow diagram
With help of the graphical flow diagram (Figure 5) the differences between scope size is clearly
evident. Above is a fictitious process with two different scope sizes definitions, one limited and
the other large. Freedom of definition allows the boundary to be drawn anywhere between the
two extremities. Here the problem of increasingly large scope size is visualised.
3.3.4.3 Data Collection

“Get your facts first, and then you can distort them as much as you please.” – Mark Twain.
To quantify the system and processes within, numerical values are required. An LCA practitioner
must collect data from various sources to fulfil the necessary process information. The
methodology is logical, straightforward, and corresponds with any other form of data collection.
It is suggested to obtain the data how ever possible through an assortment of means like
industrial questioners, interviews, reports, references, articles, databases and so on. To this day
there is still no international standard for data exchange, stressing careful consideration of the
figures and units. Conversion and use of matching nomenclature such as CAS chemical numbers
is strongly advised. Several life cycle inventory (LCI) databases have been created in the last few
years; such as EcoInvent, EcoSpold, APME plastics to name a few. These process values are a
great start but are in no means perfect and must be thoroughly examined before being verified.
The reason is that LCI databases are a collection of independently conducted LCA’s adhering to
their own assumptions and simplifications. Process data can vary from LCI database and for
implementation in another LCA the goal and scope (or base assumptions) must coincide to be
realised. Regardless of how many thousands of processes are registered in the databases they are
still insufficient to complete most LCA’s, especially new biobased production routes. At this
point, an obstacle for the environmental aspects of an LCA appears. Industry has extensive

knowledge and figures regarding their energy (heat and electricity) consumption, raw material use
and their basic pollutant emissions. Many companies are unwilling to relinquish even this limited
information to the public. Eco-balancing in the traditional sense, does not encounter this hurdle
as it based on internal assessments and therefore has access to all values. The term hurdle and
obstacle is a prudent choice as the lack of data can be overcome.
3.3.4.4 Data Estimation

“Where facts are few, experts are many” – Donald R. Gannon
Process data must correspond to several specific specifications for realisation in the system. The
exact specifications are listed in the scope definition and are analogous with where, what, and
when. What is understood with ‘where’ are the locations and local environmental conditions.
What is understood with ‘what’ are the desired emissions and assessment aspects. What is
understood with ‘when’ is the technology status, like state-of-the-art or conventional. No matter
how complicated or elementary the system, the collection of data will never completely satisfy the
specifications. Estimations are inevitably required. Although, it may seem like a reoccurring
theme, data estimation is another form of personal interpretation. Again here an increasingly
large scope puts extra strain on the field of estimation and raises the question of doubt.
The Coca-Cola multiciteria eco-balance is a great example to demonstrate the problems

associated with data estimation through scope size and viewpoint. The small scale and internal
comparison between plastic and glass bottle production must have required little estimation.
Working with specific goals and production specifications internally, they had access to accurate
and directly corresponding data; i.e. the Atlanta glass production plant and the Atlanta plastic
bottle production plant would have readily provided all the required input and output figures.
Other local companies contained within the system boundary must have also provided the
appraisers with complete and actual up-to-date data of the production. Representative data
estimation was kept at a sheer minimum, as the actual production figures were available. An
outsider may not have had access to all the data and may even want to address the entire industry
and not a specific plant. Assumptions, simplifications, and averages are necessary. To the ‘where’
issue, it may be extended to a country, continent or even world averages. Should data from
existing worldwide conventional glass plants be used or the western state-of-the-art facilities? To
the ‘what’ issue, the differences in emissions levels regulations vary from district to district and to
a much larger extent from country to country. Should the regulations of one area be extrapolated
to another? To the ‘when’ issue, the time of data collection and representation is covered. Can
production data from the 1990’s be descriptive enough for a plant proposed for 2010?
Accordingly, considering an outside practitioner following the same ISO guideline, is it wise to
estimate that a conventional Western Canadian glass manufacture of 1983 is representative to a
proposed Atlanta glass manufacturing plant of 2005? Probably not!
The freedom of interpretation expressed in the ISO guideline allows each practitioner to argue
his or her own views on data estimation. Large scope and process boundaries will contain an

insurmountable number of different process steps and require, in cases of insufficient data,
interpreted estimations. The estimation of data is by far the most important and controversial
step. It is not a problem that can be prevented, but can be kept at a minimum. The more specific
the comparison the more accurate the estimations will become. Lack of data availability to the
public places an insurmountable doubt on the data collected and estimated for sector based
paradigm shift LCA’s performed by outside appraisers. It is best to perform a representative LCA
comparison with as much insider data as possible. Deficiency of accurate industrial data places
more strain on data estimation and increases the doubt and lowers the value of the LCA. Data
estimation must be avoided as much as possible.
3.3.5 Impact Assessment

Environmental impacts and societal concerns remain the key focus of any LCA. This is
unmistakably indicted by the procedures listed within the impact assessment step. Because the
collection of system data is considered inadequate in expressing the desired results, the ISO
14042 guideline recommends that a list of specific categories should be defined to “better”
express the results. Some of the categories are solid in their foundation and cannot be contested,
but others are more subjective and may be surrounded by an air of controversy. Those subjective
categories can seem counterproductive to the actual purpose of an LCA execution. From the
start, it has been signified that an LCA is meant to quantify the environmental aspects of
different products or processes. How can subjective personally defined empirical category results
express environmental aspects in concrete numbers? The same problem with interpretation and
ambiguity arises in these procedures.
3.3.5.1 Impact Categories

A list of best practice impact categories has been drawn up by SETAC (see Table 1). They claim
to have created a list of default impact categories, ranging from ‘baseline’ to ‘study-specific’ to
‘other’. It is up to the practitioner to choice between the categories in order to express the most
relevant in correspondence to the initially laid-out goal and scope definition. A slight phrase
modification in the goal and scope can result in a huge deviation in the final result, simply based
on the chosen impact categories. Many of the categories have been set-up following models
specified by environmental organisations and institutes, yet not a single one is universally agreed
upon. Any room for discussion is exploited, especially industries unwilling to change, preventing
the concession of results. Table 1 lists the default categories with the respective subjective doubt
factor:

Table 1 Examples of Best Practice Impact Categories
Catego ry Relative Doubt

Depletion of Abiotic Resources Low
Depletion of Biotic Resources Low
Land Competition High
Loss of Biodiversity Medium
Loss of Life Support Fun ction Very High
Desiccation High
Climate Change Low
Stratospheric Ozone Low
Human Toxicity Very High
Various E cotoxicity High
Photo-oxidant Formation Low
Acidification Medium
Eutrophication Low
Waste Heat Low
Odour Very High
Malodorous Air Very High
Malodorous Water Very High
Noise High
It is hard to characterise the relative doubt properly but some categories are clearly subjective and
are present with large degree of doubt. For example human toxicity; toxic levels for each person
are different and how is it even possible to relate the different effects into one empirical value.
Japanese policy makers refuse to express values in any these categories but present them as
absolutes figures. CO 2, SO 2 and NO x are considered worthy enough topics for individual
categories and are not expressed within the various SETAC categories like Climate Change,
Stratospheric Ozone, Photo-oxidant Formation and so on. The ISO 14042 guideline permits this
expression and actually therefore contains less doubt and allows for better interaction between
different LCA results. This approach presents the data in a much more transparent and
understandable form, if the system produces 400kg of CO 2 and 25kg of CH4 who is to argue. But
if the system produces 500kg of CO2 equivalent there is a potential dispute. These expressions
also conform to other more generally discussed industrial environmental concerns, such as
adhering to the Kyoto protocol. In 2000, the Waste Department of the Dutch Ministry of
Environmental Affairs compiled their OMA project aiming at waste policy options. They are
quoted to say “There is no systematic approach to the use of integral environmental analysis in waste policy”.
This statement can easily be extended to all the environmental impact categories. As long as
doubt and scepticism exists the ISO 14040 series cannot produce a final corroboration.
3.3.5.2 Normalisation and Weighting Factors

To further extend the associated problems and branch further away from compatibility, the
values can be normalised and assigned weighting factors. These steps make perfect sense in
presenting a single final result in a succinct form but make it practicably unusable in transferring
to another LCA. See Table 2 for examples of resulting normalized values:

Table 2 Examples of normalised indicator categories
Normalised Indicator Category Value

Depletion of Abiotic Resources 1.2E-15yr
Depletion of Biotic Resources 5.6E-13yr
Land Competition 4.5E-12yr
The use of esoteric terms is continued in the result expression, for so many negative exponents
of years can only be understood by fellow expert practitioners. The guideline defines the
normalisation step as “calculation of the magnitude of indicator results relative to reference information”. As
with many concepts the praxis never works as well as the theory sounds. Relating the reference
information to one particular community, person or other system is next to impossible with a
broad global scope. Nonetheless, its procedure and execution is strongly recommended. The
values are frequently used as an intermediate for the preparation of further steps, like weighting
factors, further employing personal interpretation. Figure 6 is an illustration of equal results with
different weighting factors for the individual categories:
Impact Assessment
40
Absolute Values
35 Weighting Scale 1
Weighting Scale 2
30
25
Impact Level
20
15
10
0
Clim ate Change Ecotoxicity Huma n Toxicity Loss of Acidifaction Abiotic Biotic Total Eco-
Biod iversity Resource s Resources Indicator
Figure 6 Example of Resulting Weighted Impact Assessment Factors
Although in this hypothetical impact assessment the core data is the same, the weighting scale has
drastically changed the end result. The total eco-indicator presents an either higher or lower value
to the actual absolute value. The room for personal interpretation is capable of shifting the end
figures to whatever result is desired. The ISO 14040 series fails in providing a standard procedure
for LCA practitioners to derive at an unambiguous end result. In fact, its procedures and focus
on interpretation is a catalyst for deviations.

4 Limited Life Cycle Assessment
4.1 Overview
After years of research and work with the allegedly “standardised” LCA, it become apparent to
many practitioners that the scope was simply getting out-of-hand. All the major problems
associated with an LCA are in someway connected to the size of the investigation. A smaller
more concise scope would alleviate the bulk of an LCA’s shortcomings. By 1994 two Swiss
practitioners, Schaltegger und Sturm, had developed a succinct version while preserving the basic
LCA principles. Their aim was to again shift focus back towards economical factors for industry
in light of environmental considerations. They have essentially redefined the old eco-balancing
with the usable portions of the ISO 14040 series through new extensions. Correspondingly to the
original nomenclature, the German term is again more appropriate, Ökonomisch-Ökologischer
Effizienz or Ökoeffizienz (Economical-Ecological Efficiency or Eco-efficiency). In words, an LCA
measures the total environmental impact throughout the life of a product, whereas a limited LCA
measures the relative environmental impacts of various options that may arise for dealing with
issues that can occur anywhere during the life cycle of a product. This definition is sounds cryptic
as the earlier argumentation arrived at a consensus that an LCA is actually very subjective and
thus also relative. It is better to express this definition visually using Figure 7:
Beginning to End
Figure 7 Visual depiction of a process chain and sectional relevance
Depicted above is a representative production chain with all the inter-linked branched
production chains accounted for. An LCA is supposed to address and include the entirety of the
chains from cradle-to-grave within the system boundary. As highlighted in red, a limited LCA can
address a specific section of the production chain. It is a gate-to-gate approach as the inter-linked

branches occurring within the section are completely covered. A limited LCA is essentially a
sectional but more focused LCA with a singularity of dimensions.
4.2 Application
By reducing the span of the scope the systematic procedures of the ISO 14040 series can finally
focus on practical problems. It can investigate specific process alternatives within the grand
product life cycle. Many of the new practitioners of Limited LCA’s regard the scope as being the
vertical assessment and a typical LCA as being horizontal assessment.
Revisiting the PLA example, the difference in directional assessment is apparent. The process
steps joining cultivation to harvesting to storage and so forth is the horizontal chain.
Manufacturing of the trackers from cradle-to-gate is on the vertical path. Another harvesting
alternative could be compared, for instance manual labour, without affecting the horizontal
process chain, visualized by Figure 8:
Harvesting with trackers
Rubber
Extraction
Vertical
Tire Production
Track er
Manufacture
Horizontal
Cultivation Storage
Harvesting
Harvesting with oxen

Feed
Production
Vertic al
Feed Storage
Oxen Feed
Horizontal
Cultivation Storage
Harvesting
Figure 8 Vertical and Horizontal Production Chain Differentiation
In a Limited LCA, the vertical production chain can be isolated without effecting the layout of
the horizontal chain. It can deal with as little as one link in the chain and vertically relate the
cradle-to-grave links thereafter. In this example, different harvesting alternatives can be

compared separately and later incorporated in the grand life cycle chain. By isolating a smaller
portion of the production chain the scope size is greatly reduced effectively solving the vast
majority of the LCA associated problems.
It was stated earlier (in Section 3.3.4.1) that a sensible cut-off would result in a standard deviation
of roughly one percent. If that was in regards to an entire LCA, the nature of an LLCA should
provide a much smaller deviation. Computation of vertical production chains is thus accurate and
concise. It is best suited within the chemical engineering field containing a diversity of minor
production alternatives. Yet, nearly any industry containing a multitude of production steps can
utilise an LLCA to determine the most environmental and economical appealing option. The
Ford Motor Company and Volkswagen AG are amongst the largest corporations currently
working with Limited LCA investigation techniques. Similarly as with the eco-balance
multiciteria, an LLCA is aimed at the internal validation of production options.
4.3 Environmental Impact Units

The ISO 14042 guideline highly recommends the procedure of normalisation and subsequent
weighing factors to express the impact results. Limited LCA’s follow these guidelines but in their
own unique way. All values are to be converted into numerical Pollution Factors (PE) and
similarly weighed based on importance to become expressed in Environmental Impact Units
(EIU). The major difference is that the factors are based on legal pollution regulations and actual
concentration limits. The idea is to provide a precise indicator for policy change based on
economic realities. The room for interpretation and personal intervention nonetheless, still
persists meaning that the procedure while addressed differently, contains the same drawbacks.
This portion is equally as misleading as with the other impact assessment procedures and should
not be taken into account as a usable segment for indicating paradigm shifts. Kept within internal
appraisers and policy makers it can however endorses a transparent data exchange.

5 Exergy
Proposing an exergy analysis to be a sole impact category from an LCA or even an LLCA would
be a tad presumptuous, for flawless would hardly be an appropriate description. Neglecting many
of the life-cycle tree branches required to produce, but not directly part of the product, will
greatly affect the result. Exergy, at least within industry, is a decisive factor in the argumentation
for a production shift. It should be additionally contained in any life cycle comparison to include
the voice of industry.
5.1 Comparative Exergetic Cradle-to-Factory Gate Analysis

Any proficient professional working in the area of life cycle analyses has their own reservations
or praises for the ISO 14040 series. Nobody disagrees with the purpose and need of such analysis
tools but several minor and major disputes are directed at the use. LCA can be considered by
some as incomplete. Adding, and to a lesser extent substituting some impact categories with the
cumulative exergy consumption is one proposal for completing an LCA. The result of the
amalgamation is an Exergetic Life Cycle Analysis or ELCA for short. Many of the guidelines
are followed exactly as written in the ISO 14040 series. For determining the potential fossil fuel
reduction potential of using biomass as a feedstock for the chemical industry requires an
adaptation is required: a comparative exergetic cradle-to-factory gate analysis. Factory gate
implies that the chemicals produced from the traditional fossil fuel route and conceptual biomass
route are identical. This greatly simplifies the assessment by reducing the need to further study
the process chains to the grave, effectively reducing the scope. Figure 9 illustrates the cut-off
point, being labelled as the “functionalized chemical” product:
Fossil Route Functionalized

Chemical
Biomass Route
Figure 9 Chemical Biorefinery Comparative Exergetic Cradle-to-Factory Gate Analysis Layout
The goal and scope is identical. The inventory analysis is identical, however far more elaborate in
its execution. The mass and energy streams of all the different production steps are required. The
streams must be closed or literally speaking balanced. The impact assessment also follows the
ISO guidelines but is limited only to the factors vital in calculating the exergy flows along the
process chains. In this respect, it is contradictory to suggest that the inventory analysis is more
elaborate. Assuming the availability of the data, it is easier to collect detailed data associated with
energy and material streams as opposed to small traces of pollutants because industry is directly

concerned with their function on an economic level. Even though, the inventory is encumbered
with the vision of loop closure, disregard of information not directly connected to exergy fluxes
can greatly reduce the size of the inventory. The goal of an ELCA is to ascertain the levels of
exergetic consumption along the various production processes. Applying a simplified black box
approach to the system boundaries incorporates only the basic inlet and outlet flows of a process.
A further benefit of the chosen tool is the issue of comparison: as all the goal and scope is equal
the base assumptions are also equal meaning that while the resulting data could vary from
practitioner to practitioner the general trend between the two streams will remain. There is a
downfall to the ELCA as well; for because the life cycle is more direct and only concerning the
processes, which have a change of exergy, many side chains are neglected (Figure 4). Finally,
environmental aspects are not taken into account and there is only a heavy interpretation based
extension in relating the cumulative exergy demand to environment emission. All-in-all an ELCA
is an interesting and value tool and is in many fields a serious LCA substitution possibility.

6 Paradigm Shift
Paradigm: A set of assumptions, concepts, values, and practices that constitutes a way of viewing reality for
the community that shares them, especially in an intellectual discip line
Paradigm Shift: Describes the process and result of a change in paradig m - usually total revolution in theory
or worldview. It was orig inally a term referring to science but has become more widely applied to other
realms of human experience as well. The term was first used by Thomas Kuhn in his famous 1962 book The
Structure of Scientific Revolutions.
Examples of parad ig m shifts in science:

The transition from a Ptolemaic cosmology to a Copernican one.
The unification of classic al physics by New ton into a coherent mechanical worldview.
The transition between the Maxwellian Electromagnetic w orldview and the Einsteinian Relativistic worldview.
The development of Quantum Mechanics, whic h overthrew classical mechanics.
The development of Darwin’s theory of evolution by natural selection, which overturned Lamarckian theories of
evolution by inheritance of acquired characteristics.
The acceptance of Plate tectonics as the explanation for large-scale geologic changes.
Switching from fossil fuel resources to biomass resources for the production of chemicals entails
a paradigm shift. The entire industrial name “petrochemicals” is based on the fact that the raw
materials almost exclusively originate from petroleum. Performing a complete life cycle analysis
of the industry is an arduous task and will involve a process tree of immense magnitude.
Comparing the raw material extraction and production with an alternative route of a totally
different nature cannot be taken lightly. It is safe to assume that the process tree of the
alternative will be even larger and more complex than the conventional route. Analysing the two
production routes for a quantitative comparison must be dealt with utmost scrupulousness to
avoid any doubt or confusion. For the whole purpose of carrying out a complete comparative
cradle-to-factory gate is to provide concrete argumentation for the switch. The petrochemical
industry is such an influential and powerful body that adopting a paradigm shift will have to
appeal to their desires. They have two main wants, which following a life cycle analysis do not
necessarily have to be contradictions; improving the public image through environmentally sound
processes and products, and maximising profits and revenues through process optimisation. The
life cycle analysis tool must encompass both desires to a high degree of certainty and precision.
There are many analysis tools to chose from and all possess their own inadequacies. A
combination of the different methodologies and practices from various analysis tools is a logical
approach to minimise the inadequacies and to satisfy the specific goal and scope of a raw material
paradigm shift.
A series of international standards and guidelines for executing a life cycle assessment have been
collected and presented in the ISO 14040 series. From investigating the inner workings of the
ISO standard and the ambitions of those employing it, it becomes apparent that it alone is an
unacceptable tool for this specific paradigm shift. LCA’s derives from internal industrial
comparisons for improvements projects. It is still the best-suited tool for straightforward process
option comparisons of a small nature. Complete, accurate, and reliable data is essential for the

proper execution of an LCA, which is readily available if kept
New Busine ss
internally. With the success of small-scale assessments, practitioners Venture Possibility
voyaged into ever increasingly large-scope sizes. A paradigm shift of a The petrochemical industry
supplies the downstream
raw material feedstock requires a very large and detailed scope size chemical and plastics
industries w ith all their raw
indeed. In the aspects where LCA’s performed superbly within the materials needs. Those
realms of small scopes they fail miserably at larger scopes. Data is no industrial sectors are the
consumers and as consumers
longer complete and personal interpretation dominates the results. their driving force is a steady
supply of those materials at
One large scope LCA can greatly differ from another and increasing the low est possible pric e.
the scope size only worsens the deviation. Deviation fuels doubt and It is common know ledge that
leads to undeceive results and the dependency of personal the companies within the
petrochemical industry are
interpretation does not correspond to a high degree of certainty and notoriously conservative. Old
wealth interests constrict
precision. The ISO guideline is a great tool, but being in its infancy it them to traditional business
practic es and major changes
currently cannot provide the corroboration necessary for a paradigm are virtually unheard of. A lif e
shift of the petrochemical industry. cycle analysis should be
successful in ratifying the
economic feasibility and
environmental benefits of
Another drawback of the LCA is that monetary consideration is non- biobased raw materials. A
paradigm shift can than be
existent, even the energy and raw material flows are insufficient. justified. If the petrochemical
Since the development of the ISO 14040 series the main focus has industry does not act quickly
on efforts to change, another
progressively leaned towards solely assessing the environmental may. From w here or from who
the raw materials originate is
impacts. Proposals and research has gone into altering the LCA to not of importance for the
consumers, just a consist
incorporate exergy and more recently to an extent monetary cost. supply with low costs.
Exergy calculations place a higher demand on material and energy
Many chemical and plastic
flows and compensates for the LCA’s inadequacy. The ELCA is enterprises are already
beginning preliminary
however, also an unacceptable tool for this specific paradigm shift research into alternative
material supplies. The supply
investigation. The process flow diagram is developed with the of chemicals to this sector is
processes containing an exergy consumption or induction as the sole worth billions and does not
necessarily have to be
considerations. Although this does alleviate doubt, it neglects many controlled by the
petrochemical industry. They
secondary side processes. In comparing an option to possibly replace can supply themselves
or change an entire industry “to neglect” is an utterly unacceptable or…whoever!
word phrase.
The other analysis tool previously mentioned was the Limited LCA, the so-called vertically
oriented assessment. It may seem absurd to even acknowledge a tool focused at narrow and
segmented life cycle analyses considering the necessary scope for a paradigm shift, but it does not
have to be applied independently or even singularly. It can be combined with another tool to
mitigate the inadequacies. The ELCA is entirely horizontally oriented with few vertical
considerations; assigning LLCA’s to the secondary side processes will add the extra dimension
and effectively remove the word neglect. The impact categories of the LLCA and ELCA are
however incompatible, but the LCA ISO 14042 provides the practitioner with the freedom to
choose the impact categories almost arbitrarily. As the other tools are derivations of an LCA, the

same liberties can be applied. All the raw material and energy flows (economic flows) are not only
necessary for the calculation of exergy but are also relevant on their own accord. Gathering this
data for the LLCA side production chains would accommodate the possibility of performing
additional exergetic calculations. Combined as assessed for a shift feedstock for the
petrochemical industry the comparative exergetic cradle-to-factory gate assessment provides the best
solution to gather knowledge in regards to the paradigm shift.

7 Conclusion
Justifying a grand paradigm shift, such as converting the type of raw material feedstock for the
petrochemical industrial sector, requires a complete and accurate analysis assessing all the
economical and environmental issues corresponding to their driving force. Expressing those
issues in a life cycle comparison will provide the maximum amount of scope and depth to
address all economical and environmental flows connected to the raw material harnessing. The
flows and processes connected to the production and preparation is immense and must be
represented thoroughly and accurately by the chosen life cycle analysis tool. The so-called
standard and most frequently used tool for calculating a life cycle, the ISO 14040 series LCA, is
not suitable for this large comparison. An LCA is best suited for small-scale internal process
comparison with sufficiently available data. When addressing larger scale issues, like for a raw
material shift, many problems arise which greatly jeopardise the reliability of the results. When in
doubt interpret, is the undisclosed motto of the ISO guideline. Any interpretation relies on
human intervention, personal judgement, meaning the assessors are free to choose what is
important and what it not. In this specific topic all LCA’s are bound to deviate greatly, even with
a small deviation a final corroboration cannot be ascertained. Another life cycle tool expressed
within a detailed collection of international standards does not yet exist. However, there are other
tools that derive from the standard LCA, which can borrow the positive aspects of the guideline
for this specific comparison. One such derivative, the Exergetic LCA, is capable of collecting the
exergy consumed of both raw material production chains from cradle-to-factory gate without any
data being contested, potentially alleviating deviation and doubt. The ELCA is incomplete in
addressing the issues require for the paradigm shift as it is mainly horizontal in its assessment
nature and is only expressed in exergy. Consolidating all the vertical side chains of the larger
Exergetic LCA with Limited LCA’s will cover the grand scope completely and express the
necessary issues to a high degree of precision. Therefore the chosen analysis tool is the
comparative exergetic and energetic cradle-to-factory gate assessment. Through the proper
execution of this assessment tool the best and most realistic raw material alternative can be
compared to the conventional route with the essential certainty and precision. Both the main
environmental and economical issues important for industry are calculated in exergy terms,
providing them with a potentially translucent figure capable of warranting a pre-oil-depletion
paradigm shift to biobased raw resources.

Chapter 4
Crop Output
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 4 – Crop Output

A&F number -
ISBN-number -
Date o f publication 1. June, 2006
Confidentiality No
OPD code -
Approved by -
Agrotechnology & Food Innovations B.V.

P.O. Box 17
Tel: +31 (0)317 475 190


ISO 9001:2000.

Abstract
To assist in the selection process of determining the plants best suited for the production of a
particular biochemical, a large investigation of various crops is needed. A crop guide for 16
popular choice crops has been compiled which lists all the cultivation dependent variables to
systematically compare the different energy inputs. The crops are classified based on their
biochemical constituent yields in hopes of identifying trends, barriers, and opportunities for the
various aspects attributed to the cultivation. The parameters for the biomass cultivation itself are
based on typical regional growth figures for the individual crops along with best practice
operations. Standard yield figures are based (when available) on 5-year average yield trends of
such regions and have all been related to total green dry biomass production. The normalized
yield figures are conversely based on the best agricultural practice for the regionally dependent
cultivated biomass crop. By using the yield figures, chemical composition and cultivation
practices a ten year average yield for the usable constituents for potential biochemical production
is created. Combined with the group contribution method, the output energy and exergy of the
crops is determined. These energetic output figures will prove the basis of many calculations to
follow. Included in this chapter is the chief energy input, solar radiation. It is most dependent on
regional constraints. The total annual solar energy/exergy input has been calculated for each crop
by using the crop specific growth period and monthly solar radiation of the region. Solar
radiation is a large energetic input but is better linked to land use efficiency than energy.
However, the energy/exergy and efficiency analysis used in all preceding chapters are outlined for
the solar input. Finally a list of the Top 3 choice crops for each category is created as the main
findings of the chapter.
Key Words:
Biomass, Crop Guide, Yield, Composition, Solar Radiation, Energy, Exergy, Efficiency

Content
1 Introduction 81
2 Crop Guide 83
2.1 The List 83
2.2 The Classifications 83
2.3 The Crop Guide 85
2.3.1 General Information 85
2.3.2 Growth Details 85
2.3.3 Fertilizer Use 85
2.3.4 Yield and Composition 86
2.3.5 Detailed Information 86
2.4 The Source of Information 87
3 Output 89
3.1 Yields 89
3.1.1 Best Practice 89
3.1.2 Total Crop Yields Explanations 91
3.1.3 Total Crop Yields 93
3.1.4 Growth Cycle 94
3.2 Chemical Composition 95
3.2.1 Unusable components 97
3.3 Energetic Output 98
3.3.1 Calorific Values 98
3.3.2 Group Contribution Formation Energy 98
3.4 Results 99
3.4.1 Total Energetic Output 99
3.4.1.1 Comparative Analysis 100
4 Solar Input 103
4.1 Location 103
4.2 Cultivation Period 104
4.3 Results 105
4.3.1 Total Energetic Input 105
4.3.2 Efficiency 106
4.3.3 Analysis 107
5 Results and Discussion 109

1 Introduction
Arable land will become the raw resource of the future. Today we may be scheming and fighting
over oil deposits in unfavourable lands like deserts, deep seas and even polar ice shields;
tomorrow it may likely be over the lush, green, favourable lands of high arability. Conflicts have
always arisen over territory and land to control natural resources; the biobased economy may just
adjust the emphasis to agricultural production capability. It is our duty and responsibility not to
replace one aspect of scarcity with another, all in the name of energy sustainability.
Many dedicated critics against the biobased economy have a very justified argument; there is not
enough land to go around. That is to say there is not enough fertile land to go around and several
industrial corporations and politicians have begun debates under the motto “fuel for the rich or food
for the poor”1. Although, some studies have concluded that there is sufficient arable land around
the entire world to accommodate our future energy needs2. Hoogwijk suggests that if the total
global surface area were converted to accommodate bioenergy crops a maximum of 3500EJ/y is
possible. And by 2050, following the best scenario including proper technical and socio-
economical development, 657EJ/y is achievable. This is a lot more than current (2000) global
energy demand of 400 – 450EJ/y. If there is enough arable land on a global scale to fulfil our
energy needs is debatable, one thing is clear, that vast and unfathomable amounts of land are
needed for bioenergy.
Proposals for energy production from biomass, bioenergy, are always put into the context of
global proportions. One of the main reasons behind the critique is the high land use intensity in
combination with low solar energy conversion efficiency. Indeed the conversion rate of solar
energy to actual bioenergy stored in the crop is in the magnitude of 1% with figures below 1%
common for many crops. Bioenergy must be able to compete against other solar conversion
device like PV cells which have much higher conversion efficiencies in the range of 15-20%, with
experimental devices surpassing 40%. Additionally such an alternative option does not necessitate
arable land for production, but does have other stipulations. The similarity between the two
forms is solar radiation as the primary energy input. It is regarded as a free source of energy
which may be true, but its cost is land.
Burning biomass for the creation of heat and subsequently energy is the lowest form of
harnessing the exergy of the solar radiation. Biofuels are slightly higher but still do not maximize
the exergy content delivered to the surface. As arable land is undoubtedly the most important
factor in biomass production the goal should be to maximum land use efficiency. Production of
chemicals from biomass, when harnessed properly, will utilize the highest amount of the
incoming solar exergy and thus achieve the highest land use efficiency.
It is common practice in the research field of biomass to mention the yield of particular crops,
for instance in ton dry matter per hectare. The relationship between the calorific value and yield

is used to present energetic terms per land area, i.e. MJ/ha. This is indeed a valuable tool which is
also conducted for the select crops investigated in this study; however it is not enough to
properly address land use efficiency. The additional conjunction to solar energy input provides
the link to relate all factors together in a degree of land utilization. As stated chemicals are of
interest and the biochemical constituent compositions can further shed light into the potential
land requirements for the production of such chemicals. It is paramount to the success of the
biochemical industry that the land use intensity is kept to a minimum. For bioenergy it is even
more vital to strive for maximum land use efficiency.
Maximum land use efficiency, should it be for bioenergy, biofuels or biochemicals may not
necessarily coincide with the highest yielding crop; the relation to solar input is the key. Any
application for biomass will require vast land space and regional dependencies will provide
different levels of solar radiation input. When compiling a cradle-to-factory gate study for
chemicals from a biomass origin the solar input should not be handled as an energy input but as a
factor for the efficient land use. As chemicals, like energy, are commodities replacing them by an
alterative, should it be a renewable, must be sustainable by way of supply. To prevent any land
conflicts that may arise from large-scale biomass cultivation efficient use of the future raw
resource must be foreseen before it can become a conflict.
1.1 Chapter Purpose

By systematically listing a handful of select crops a basis for comparison is created. The crop
guide will provide all the base datasets, values, assumptions and parameters necessary for all
proceeding calculations. The standardization of value expression is essential to create a reference
point. In addition to covering the crop information the resulting output figures are to be covered.
This is understood as yield, composition and energy/exergy content. The output figures will also
serve as a basis for proceeding efficiency relation calculations. As solar radiation is an input but a
special one at that the methodology of the input/output relation will be presented. However
solar radiation will be assessed not as a true energy input but as an indication for land use
efficiency. This chapter essentially forms the heart of the investigation for all following chapters
are dependent on the created reference points and calculation methodology.

2 Crop Guide
Several crops are already considered as classical crops for bioenergy and biomaterials. Two such
examples immediately come into mind (at least mine); the Brazilian sugar cane for bioethanol and
Malaysian palm tree for biodiesel production. Even in the relatively young field of research
several crops have already been sufficiently documented and proposed for a large array of
biomass applications. The exact species of choice are typically based on a maximum yield of the
particular component used for the intended purpose. For example: a high sucrose yield in the
sugar cane to convert to ethanol. To be able to make a subjective comparison of crops a diverse
variety of crops, growing conditions and farming techniques must be evaluated. A list of 16 crops
has been chosen as a starting point for this assessment. They are based on many different
grounds from popularity, to location, to botanical classification, to national development
considerations and as far as gut feeling. By linking the required inputs to the crops a clearer
picture will be created, providing the argumentation necessary to select crops based on energetic
savings and no longer simply on high yielding assumptions.
2.1 The List

The corresponding data in Table 1 are based on typical growing conditions in the main/native
areas of cultivation. All following information and data is related to the mentioned location.
Table 1 Choice of Crops Species
Botanical Nomen clature Common Name Continent Country/State

Beta vulgaris Sugar beet Europe Germany
Brassica napus Rapeseed Europe Belgium
Elaeis guineensis jacq. Oil palm South Pacific Malaysia
Glycine max Soya bean North America Illinois
Helianthus annuus Sunflower Europe Fran ce
Manihot esculenta Cassava Africa Nigeria
Medicago sativa Lu cerne North America South Dakota
Nicotiana tabacum Tobacco Oceania Australia
Lolium perenne Grass Europe Holland
Panicum virgatum Switchgrass North America Iowa
Saccharum officinarum Sugar cane South America Brazil
Salix alba Willow tree Europe Sweden
Solanum tuberosum Potato Europe Holland
Sorghum bicolor Sorghum Africa Kenya
Triticum aestivum Wheat Europe Fran ce
Zea mays Maize North America Iowa
2.2 The Classifications

It is necessary to group the different crops into classification categories to be able to compare the
individual crops within the group as well as create a general group trend. Classifying the crops,
however, becomes a tricky matter as crops used for food and non-food purposes have different
stipulations. Several crops can even fall into different categories. For this reason both the generic

agricultural practices classification and constituent based non-food classification will be
employed. At least two crops must be present in a category to validate the comparison.
Table 2 Classifications of Crops Species
Agricultural (Food) Biomass (Non-Food)

Cereal Crops Simple Carbohydrate Rich
• Maize (Zea mays) • Cassava (Manihot esculenta)
• Sorghum (Sorghum bicolor) • Maize (Zea mays)
• Wheat (Triticum aestivum) • Potato (Solanum tuberosum)
Fibrous/Trees • Sorghum (Sorghum bicolor)
• Oil Palm (Elaeis guineensis jacq.) • Sweet sorghum (Sorghum bicolor)
• White Willow (Salix alba) • Sugar beet (Beta vulgaris)
Grasses/Shrubs • Sugar cane (Sacch arum officin arum)
• Lu cerne (Medicago sativa) • Wheat (Triticum aestivum)
• Ryegrass (Lolium perenne) Complex Carbohydrate Rich
• Switchgrass (Panicum virgatum) • Cassava (Manihot esculenta)
• Tobacco (Nicotian a tab acum) • Maize (Zea mays)
Legumes • Potato (Solanum tuberosum)
• Lu cerne (Medicago sativa) • Sorghum (Sorghum bicolor)
• Soya Beans (Glycine max) • Sweet sorghum (Sorghum bicolor)
Oil Crops • Sugar cane (Sacch arum officin arum)
• Oil Palm (Elaeis guineensis jacq.) • Switchgrass (Panicum virgatum)
• Rapeseed (Brassica napus) • White willow (Salix alba)
• Soya bean (Glycine max) • Wheat (Triticum aestivum)
• Sunflower (Helianthus annuus) Lignin Rich
Root/Tuber Crop • Maize (Zea mays)
• Cassava (Manihot esculenta) • Switchgrass (Panicum virgatum)
• Potato (Solanum tuberosum) • White willow (Salix alba)
Sugar Crops • Oil palm (Elaeis guineensis jacq.)
• Sugar beet (Beta vulgaris) Protein Rich
• Sugar cane (Sacch arum officin arum) • Cassava (Manihot esculenta)
• Sweet sorghum (Sorghum bicolor) • Lu cerne (Medicago sativa)
• Ryegrass (Lolium perenne)
• Soya bean (Glycine max)
• Sunflower (Helianthus annuus)
• Tobacco (Nicotian a tab acum)
Oil/Fat Crops
• Oil Palm (Elaeis guineensis jacq.)
• Rapeseed (Brassica napus)
• Soya bean (Glycine max)
• Sunflower (Helianthus annuus)
The biomass (non-food) classification of Table 2 are grouped into the five main groups of
biochemical constituents present in plants. Naturally, carbohydrates are found in great abundance
in all plants, yet by dubbing them either rich in simple and/or complex carbohydrates can allow
for more specific grouping. Simple carbohydrates are those, which can be fermented relatively
easy, like starches and sugars. Complex carbohydrates are those, which have traditionally been
more difficult, like cellulose and hemicellulose. The other categories are self-explanatory.

Classifying the crops based on their constituents is a far better approach in determining which
chemicals are best suited to be synthesized from a particular crop.
2.3 The Crop Guide

Creating a systematic comparison calls for a standardized listing of the key factors concerning the
various crops. This is essentially the crop guide (found in Chapter 8). Listed are the most
important issues involving the cultivation of the crops (input) and their potential chemical use
(output). The guide itself can be broken down into five sections:
2.3.1 General Information

Along side the visual representation (picture) the basic information regarding the nature of the
plant is listed. Using very short and direct points the reader can build an adequate depiction of
the crop in question, should it not already be known.
2.3.2 Growth Details

Not every plant is capable of growing everywhere. This is what the VOC understood all to well
as they travelled half the world over for coffee and a handful of spices, whilst the tulip was
introduced on native soil. Temperature, climate, participation and soil type are all major factors in
determining the areas of successful growth. Although the locations have been pre-determined
using the current main production sights, the other locations do not differ immensely. Listed are
all the farming details, enabling the determination of the operational input values. The large
variety of farming techniques is equally diverse in energy input. Hand-planting rice stocks in a
shallow basin is much more energy intensive than broadcasting ryegrass seeds. Cultivation and
harvesting times are of particular importance as the utilized solar energy is a function of this
growth period. Rainfall/irrigation is another key value; in areas where rainfall is inadequate
irrigation is the only option, one of the energy input figures. A companion crop can be of
significance should it be of a leguminous order, saving on nitrogenous fertilizers. The values and
terms are for the most part normalized to ensure the transparency in the comparison.
2.3.3 Fertilizer Use

Just as humans require essential amino acids to sustain life, plants require essential nutrients.
They are broken down into 3 types: macro (primary), macro (secondary), and micro. In total
there are 16, yet in the crop guide graphs only 12 are indicated. The reasoning is that carbon (C),
hydrogen (H), and oxygen (O) are not applied in the form of fertilizers or present in the soil as
nutrients. Chlorine (Cl) is never added in its virgin state but frequently linked with potassium in
the molecular form KCl. There are two common practices to interpret the nutrient requirements,
either common fertilizer application rates (i.e. kg/ha) or by nutrient uptake based on the plants
chemical analysis (i.e kg/kg). This report will take into account only the actual nutrient uptake,
for losses occurring on the field (see Chapter 6) can be further reduced as better farming
techniques evolve. Even the specific kind of fertilizer will affect the level of nutrients that can be
taken up or leached. The values expressed in the graphs are thus the amount the crop removes

from the soil and must not to be confused with the amount applied to the field. These values
can, however, be considered (and re-expressed) as the theoretical minimum fertilizer application
rate. Generally the nutrient uptake levels and yield rates respond in a linear proportion with each
other with the slope being unique for each nutrient and crop. The deviation is apparent in the
graphs and some relationships are not linear but follow a logarithmic trend. To ovoid major
errors when extrapolating to specific yields, all figures have been brought into the graph to
determine the exact uptake at the corresponding yield under investigation. Closer attention is
paid to the interrelationship between yield and uptake levels in Chapter 5. Additional crop
specific comments are mentioned only to help in the fertilizer understanding. The graphs have
been broken down into macronutrients and micronutrients as for the large part only trace
amounts of the micronutrients are removed, although in the long-term they must be
reintroduced.
2.3.4 Yield and Composition

To provide a good contrast the normal, optimal and worldwide cultivation figures are listed. They
can quite often have huge deviations. When available, the 5-year averaged and best practice yield
in the region to be assessed is also listed. Furthermore, food application agriculturists are mainly
interested in the yield of the eatable portion of the crop and state such values in a variety of
forms best suited for their food industry. As a clear example, winter wheat, yields are measured in
terms of dry grain. In the odd case that the stalk is even mentioned, documentation is in wet
weight. In tune with standardization all values have been converted into dry weight figures for
the entire plant. Food yield terms are still listed for most crops. As the crops are intended for
biochemical processing the chemical constituents are systematically listed. Practically all of the
crops consist of three main parts: leafs, stem and the fruit/seed. Characteristically these three
components share radically different constituent compositions. In this respect they have been
listed separately with their associated moisture content. The heating values (also known as the
lower calorific value) are also listed for the various crop parts. These are vital for comparing the
calculation method used to determine the resulting output energy.
2.3.5 Detailed Information

Each crop has a specific trait, which can be utilized in sight of biochemical processing. Leafy
plants are particularly well adapted at containing high levels of protein. Protein is a component
that will be investigated in further detail (see Chapter 7). Proteins are a complex of the 20 amino
acids. Listing the free amino acids is a good indication of the actual protein composition.
Quantifying amino acid concentration is a complicated procedure resulting in many “unknown”
levels. In such cases it can be assumed that the levels are or approach zero. Much of the other
information is very crop specific, yet the added information is crucial in justify the final product
processing possibilities.
The complied information contained in the crop guide will act as the source and basis on further
calculations. It is imperative for any sceptical reader to review the crop guide.

2.4 The Source of Information
Several online databases have been used to compile the bulk of the crop guide. They include:
• World Fertilizer Use Manual, IFA (International Fertilizer Association)3
http://www.fertilizer.org/ifa/publicat/html/pubman/namtype.htm#Crop%20index%20-%20Type%20of%20crops
• Crop Index, Center for New Crops & Plant Products, Purdue University4
o James A. Duke. 1983. Handbook of Energy Crops. Unpublished
http://www.hort.purdue.edu/newcrop/Indices/index_ab.html
• Biomass Feedstock Composition and Property Database, Energy Efficiency and
Renewable Energy, DOE (U.S. Department of Energy)5
http://www.eere.energy.gov/biomass/feedstock_databases.html
• Phyllis: database for biomass and waste, ECN (Energy research Centre of the
Netherlands)6
http://www.ecn.nl/phyllis/
• FAO (Food and Agricultural Organization)
o Agricultural Date, FAOSTAT7
http://faostat.fao.org/faostat/collections?subset=agriculture
o Grassland Index8
http://www.fao.org/ag/AGP/AGPC/doc/GBASE/mainmenu.htm
• Index of Top Crops, Leaf for Life9
http://www.leafforlife.org/PAGES/TOPINDEX.HTM
• IENICA (Interactive European Network for Industrial Crops and their Applications)10
http://www.ienica.net/cropsdatabase.htm
• BIOBIB - A Database for biofuels, University of Technology Vienna 11
http://www.vt.tuwien.ac.at/biobib/oxford.html
Even the collective data of these databases is insufficient to complete the demands of the crop
guide. Other crop specific references are listed as they occur.

3 Output
The grass is always greener on the other side of the fence.
This old English phrase translates to: people are
never satisfied with their own situation; they always
think others have it better. Science and geometry
are able to solve this mystery in regards to the
colour of the grass (see adjacent illustration), yet the
perception continues. Except in the case of the
English, where this actually holds true when they
look towards the other side of the Channel. This
expression can also be related to actual farming issues. It is ambitious to set just one figure in one
specific region to represent an entire species. Precise crop yields are affected by a large multitude
of complex factors. Somewhere, someone, on some field, will always have a higher harvested
yield. Cropping experiments are conducted the world over and will always outperform the
average. Most experiments that are performed for maximum yield neglect to mention the input
requirements by shifting focus on the trifling details associated with the great success of increased
yield. Surely an accelerated selectively bred crop in combination with ample water, ample sunlight
and ample nutrients will result in huge yields on a carefully controlled test field. It may be
perceived as greener, but the colour of the grass is not the full story. That is not to say that the
experimental techniques cannot be utilized later in large-scale applications, only that it is a matter
of perception. On the browner side of the fence, figures are readily available for all aspects of
cultivation including typical yields, composition and calorific
Theoretical Maximum values. To mitigate any errors by mixing experimental figures with
typical figures, only the average and best practice figures acquired
from the mentioned locations (see Section 2.1) will be adopted.
This will create a proportional ratio between the inputs and
Experimental/Optimal outputs allowing for an ease of extrapolation; i.e. a location shift
or yield increase. There are two factors that can affect the output,
such as yield, while not directly labelled as inputs: firstly a revised
Best Practice Farmers farming technique and secondly a modified (GMO) species. These
factors will be intentionally left out of the calculations but their
implications will be discussed later in detail (see Chapter 6 and 9).
Higher Regional Average
Natural
Deviation:
3.1 Yields
Regional Average - Year
- Region
Lower Regional Average - Study, etc.
3.1.1 Best Practice
Photosynthetically Active Radiation (PAR) designates the spectral
Poor Practice Farmers
range of solar light from 400 to 700 nanometres that is useful to
terrestrial plants in the process of photosynthesis. Assuming that
Yield: ton/ha
there are no other constraints or restrictions (such as water or

Zero Production nutrients) in plant growth, PAR is used to determine the

theoretical maximum biomass yield of a crop. In practice these yields are by far not obtainable
and only on small test plots carefully monitored with measures to minimize other limitations are
high experimental yields reached. These yields represent the uppermost possible in a region and
are well above the average. Regional average yields are provided yearly by local governmental
bodies for a specific crop. In the figures themselves a natural deviation is present based on the
year of the data collection, the specific region of cultivation and the body conducting the study.
These deviations are indicated on the graph as the higher and lower regional average and can
easily vary by 25%. Several underlining problems exist when applying average figures for non-
food biomass applications. For in the average figures all farms are taking into account including
poor practice farms, small-scale farms, inefficient farms, biologically oriented farms (eco-farms)
and other farms that contribute to lower overall yields. Best practice farms employ currently
available technology and agronomic know-how to obtain significantly higher yields than the
average. As the biomass sector will entail large industrial interest and investment it is foreseeable
that the current best practice will represent the near future standard practice. Furthermore as
quality concerning food regulations is not a major concern (in most production situations) the
eco-farming practices and typical quality over quantity sacrifice practices will not be present in
the biomass sector. The best practice farms are the most logical choice in setting the yield for
near future biomass implementations. Depicted in Figure 1 are the low, 5-year average and best
practice yields of the crops in terms commonly presented in the agricultural industry.
Agricultural Yields
150
Low
Average
Best Practice
125
100
ton/ha/year
75
50
25
0
Dry Biomass
Dry Biomass
Green Biomas s
Green Biomas s
Dry Biomass
Dry Biomass
Dry Biomass
Tuber
Tuber
Tuber
Gr ain
Fruit/Seed
Seed
Seed
Seed
Gr ain
Cassava Gras s Lucer ne Maize Oil P alm Potato Rapes eed Sor ghum Soya bean Sugar beet Sugar cane Sunflower Switchgrass Tobacc o Wheat W illow tree
Figure 1 Various documented agricultural yield figures

For some crops the difference between the average and best practice is large whereas for others it
is marginal. Found in accompanying database spreadsheets are another graphical representations
displaying the ratio between the average and best practice. For all the crops on average the best
practice yields are 192% higher, although have a standard deviation of 106%. Narrowing the
investigation down to only common crops cultivated in prosperous areas with a long tradition of
that particular crop reviles a yield increase of 161% with a standard deviation of only 18.6%.
Thus it can be assumed that the best practice farmers will yield 1.6 times more biomass from
crops cultivated in areas with an advanced and intense agricultural tradition.
3.1.2 Total Crop Yields Explanations

As previously mentioned (see Section 2.3.4) the various plant parts have different yield values and
expressions along with varying moisture content. In conforming to standardization all figures
must be converted into one common term; total dry biomass. This is understood, as above
surface biomass with the clear exception of tuber-based crops, meaning rooting systems are not
included. Roots are indeed a form of biomass and can constitute a considerable quantity of mass
structure. For example, the rooting system of winter wheat can be reach depths of up to 2 meters
and represent slightly less than 10% of the total biomass (dry). But, due to the overwhelmingly
high expenses linked with harvesting and isolating root mass plus the added soil benefits of
leaving the roots in place (e.g. erosion and soil fertility), this biomass portion will not be included.
Although dry weight is occasionally listed, for transparency and unison the table has been
designed to calculate transiting from wet weight to dry weight; meaning that some values have
been calculated backwards. Since there are large discrepancies concerning the actual yield figures,
the lower (or poor practice), average regional conditions and best practice conditions have been
listed together. The source yields figures and explanations behind the yields are as follows:
Cassava
Low = poor conditions: 8ton/ha tuber
Average = poor conditions: Nigeria 5-year average at 9.36ton/ha tuber
Best Practice = high commercial yield: 50ton/ha tuber
Grass
Low = low hay production
Average = EU hay production with 2-3 cuttings per year
Best Practice = upper regions approaching 14.1ton/ha dry weight
Lucerne
Low = USA average of 1.25ton/ha of dry hay
Average = typical US figures when using fertilizers
Best Practice = high range with good soil conditions yielding 15ton/ha dry weight
Maize
Low = lower US yields, based on total crop
Average = good conditions: Iowa 5-year average at 9.35ton/ha grains (cob)
Best Practice = high large scale US yields, 13.8ton/ha grains

Oil Palm
Low = 10ton/ha fruits
Average = normal conditions: Malaysian 5-year average at 19.47ton/ha fruit
Best Practice = good conditions: Malaysian yields of 25ton/ha fruits
Potato
Low = low for temperate regions: 20ton/ha tuber
Average = good conditions: Dutch 5-year average at 43.5ton/ha tuber
Best Practice = optimal Dutch conditions at 65ton/ha tuber
Rapeseed
Low = EU average: 3.0ton/ha seeds
Average = good conditions: Belgian 5-year average at 3.81ton/ha seeds
Best Practice = optimal Belgian conditions at 5.5ton/ha seeds
Sweet Sorghum
Low = poor regions: 25ton/ha green matter
Average = poor conditions: Kenyan 5-year average at 0.74ton/ha grain
Best Practice = good commercial practices: 75ton/ha green matter
Soya Bean
Low = lower levels of normal practice: 1.7ton/ha seeds
Average = good conditions: Illinois 3-year average at 2.61ton/ha seeds
Best Practice = optimal US practices: 4.0ton/ha seeds
Sugar Beet
Low = low for temperate regions: 30ton/ha beet
Average = good conditions: German 5-year average at 57.6ton/ha beets
Best Practices = obtainable high level: 100ton/ha beets
Sugar Cane
Low = lower boundaries: 15ton/ha cane
Average = good conditions: Brazilian 5-year average at 72.3ton/ha cane
Best Practice = upper typical yields: 100ton/ha green matter
Sunflower
Low = world average: 1.23ton/ha seeds
Average = typical: French 5-year average at 2.29ton/ha seeds
Best Practice = optimal conditions: 5.5ton/ha seeds
Switchgrass
Low = low scale of Pacific Northwest
Average = Typical yield for American Alamo species when grown as energy crop
Best Practice = middle range of optimal conditions, 14.0ton/ha
Tobacco
Low = high yield range for smoking tobacco: 4.0ton/ha dry weight
Average = Australian conditions when treated like grass: 24.0ton/ha DW
Best Practice = higher boundary of Australian site: 28.8ton/ha DW

Wheat
Low = low/normal: 6.0ton/ha grains
Average = typical: French 5-year average at 6.98ton/ha grains
Best Practice = optimal average: 10.3ton/ha grains
Willow Tree
Low = low Swedish yield: 3.0ton/ha oven dry wood
Average = typical: Swedish sites 4-5ton/ha oven dry wood
Best Practice = optimal range start: 8ton/ha oven dry wood
3.1.3 Total Crop Yields

In addition, when applicable, the 5-year averaged yield data for the crop in the relevant region of
interest is also listed in detail. The following excel table excerpt (Table 3) clearly plots the
calculation route and input values to acquire the final total dry biomass. The wet weight yields
represent the total green matter yield.
Table 3 Wet Weight and Resulting Dry Weight Yields
Annual Yield Wet Weight Constiguent Distribution Annual Yield

Crop
Low Average High Name Wet Weight Moisture Name Wet Weight Moisture Name Wet Weight Moisture Low Average High
Common Name WW tonnes/ha - % - % - % DW tonnes/ha
Cassava 13.3 15.6 83.4 Tuber 60 69.9 Leafs 15 81.0 Stem 25 15.0 5.6 6.6 35.1
Grass 57.0 71.5 80.5 Whole 100 82.5 10.0 12.5 14.1
Lucerne 5.0 18.1 60.0 Whole 100 75.0 1.3 4.525 15.0
Maize 14.0 46.8 69.0 Ear 20 20.6 Stover 80 75.0 5.0 16.8 24.8
Oil palm 30.0 58.4 72.0 Fruit 33 26.0 Fronds 50 69.9 Trunk 17 50.0 14.4 28.0 34.5
Potato 22.5 48.9 73.1 Tuber 89 78.0 Stover 11 60.0 5.4 11.7 17.5
Rapeseed 48.0 61.0 88.1 Seed 6 10.0 Pod 60 87.4 Stem 34 83.3 8.9 11.4 16.4
Sorghum 25.0 35.0 75.0 Panicle 10 12.5 Leafs 15 80.0 Stalk 75 50.0 12.3 17.2 36.9
Soya bean 9.3 14.5 22.0 Seed 18 10.2 Stover 82 60.0 4.6 7.1 10.8
Sugar beet 42.9 82.3 142.8 Beet 70 76.6 Leafs 30 86.4 8.8 16.8 29.2
Sugar cane 20.0 96.4 140.0 Cane 89 67.5 Leafs 11 80.6 6.2 30.0 43.5
Sunflower 3.5 6.5 15.7 Seed 35 20.0 Husk 15 30.0 Stover 50 70.0 1.9 3.5 8.4
Switchgrass 3.5 9.3 15.9 Whole 100 12.0 3.1 8.1 14.0
Tobacco 33.2 200.0 221.0 Whole 100 88.0 4.0 24.0 26.5
Wheat 36.0 41.9 61.8 Grain 17 20.0 Stover 83 80.0 10.9 12.6 18.7
Willow tree 7.5 11.3 20.0 Whole 100 60.0 3.0 4.5 8.0
In terms of biomass production only dry weight is of interest. The following graph (Figure 2)
illustrates the great differences present between wet and dry weight figures. The calculated
differences between the low and high total dry biomass figures are also present in the form of the
error bars. It is apparent that the water content can lead to some extreme differences in wet and
dry yields. As an example, from a wet weight basis one could assume that the sugar beet is a
much higher yielding crop than maize, where in fact on dry terms is in not. Using wet weight can
be misleading. To alleviate any discrepancies regarding yield, all figures will contain the prefixes
DW (dry weight) and WW (wet weight) alongside the ton/ha term.

Wet Weight and Dry Weight Yields
Total Biomass Production
Best Practice Yields
100
142.8 186.6 240 W et W eight
Dry W eight
90
80
70
60
ton/ha
50
40
30
20
10
0
a
ne
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an
er
s
s
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ee
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ai
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r
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ap
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ga
illo
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ug
y
itc
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So
Su
R
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Figure 2 Wet Weight and Resulting Dry Weight Yields
3.1.4 Growth Cycle

Not every crop is perennial or systematically cultivated on a regular annual cycle. Some crops
require more then one year before harvesting can commence. In the Table 4, it has been dubbed
as establish and growth:
Table 4 Cultivation Figures
Crop Cultivation Figures

Establish Growth Ha rvest Ro tation Years 10-year
Common Name Months Per Cycle Replanting Rotation G ap factor
Cassava 12 12 1 2 0 0 0.50
Grass 0 8 1 1 0 0 1.00
Lucerne 0 7 4 7 8 1 1.00
Maize 0 9 1 1 3 1 1.00
Oil palm 36 12 2 25 0 0 0.88
Potato 0 6 1 1 1 3 1.00
Rapeseed 0 10 1 1 1 2 1.00
Sorghum 0 10 1 1 4 1 1.00
Soya bean 0 6 1 1 3 1 1.00
Sugar beet 0 7 1 1 1 3 1.00
Sugar c ane 8 12 1 3 0 0 0.78
Sunflower 0 6 1 1 1 4 1.00
Switc hgrass 12 7 4 10 0 0 0.90
Tobacco 0 12 4 1 2 1 1.00
Wheat 5 10 1 1 3 1 0.58
Willow tree 24 12 1 30 0 0 0.93
It is common practice to present the yield figures in the form ton/ha. The majority of crops (here
10 out of 16) are indeed annuals and harvested but once a year, so it can be assumed that the unit
ton/ha is analogous with ton/ha/y. For the other crops that have a growth cycle longer than one

year it can be confusing if the figures refer to annual yields or harvestable yields. If the listed yield
figures are indeed in reference to the harvesting period, the actual annual yield for such crops is
substantially less. Frequently the yield of the willow tree, for example, is based on a 3rd or 4th
year harvest. However the figures presented in Table 3 have been adjusted for the most part to
the average yield during an annum. By mentioning the establishment period and replanting
frequency adjustments can be made for those figures that do not refer to consistent yearly yields.
These yield corrections are of particular importance in determining the yields for a 10-year
average to be utilized in the pending efficiency calculations.
Arguably the greatest farming development during the Medieval Ages was the crop rotation
system. It was found that yields improved drastically by rotating different crop species on the
same field. In some instances the fields were even left uncultivated to allow the soil to recover.
Over the generations the best rotation practices were discovered and continue for the most part
to this day. The above table lists, if any, the common rotation periods and gap years. However,
the gap and rotation figures have been mentioned for informational purposes only and are not
included in any subsequent calculations. The replanting periods are on the other hand indeed
utilized in calculating the 10-year average values. The following calculation statement is used in
the excel formulation sheets as the 10-year average adjustment factor:
 months   10 year 
12 ⋅10 year  −   ⋅ establish
 year   replanting 
F10 =
 months 
12 ⋅10 year 
 year 
For crops that require an establishment period and/or have a replanting frequency more than a
year will drop yields significantly over a 10-year period. The cassava, for instance has an
establishment period of a year and a growth period of a year, while requires no rotation.
Following the above calculations the actual cassava yields will be 50% less than previously listed
over a ten-year period. The white willow, in contrast has an establishment period of 2 years while
replanted only every 30 years. In this case, meaning the root structure is left in the ground for
sprout propagation. Again following the above calculations the actual white willow yields will be
93% of the listed yields. The losses connected to establishment time are partly circumvented
because of the long growth/rotation period. These calculations are included for all the crops in
the efficiency sections.
3.2 Chemical Composition

Another misleading aspect of the yield figures is the lack of depth. They say nothing about the
yield of the individual biochemical constituents. Using the crop guide the relationship between
each plant component, the chemical composition, moisture content and weight contribution
were used to calculate the biochemical constituents. Figure 3 depicts the proportional
relationship between the various constituents in the selected crops:

Constituents Proportions
1.0
0.9
0.8
0.7
0.6
k g/k g
0.5
0.4
0.3
0.2 Ash
F at
Protein
0.1 Lignin
Complex Carbohydrates (C5)
Simple Carbohydrate (S.C.)
0.0
va
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ss
s
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Lu
a
or
ga
un
To
o
O
oy
it c
ug
C
il l
Ra
S
Su
W
Sw
S
Figure 3 Crop biochemical constituents proportions
Without words, this visual representation is perfectly capable of explaining the great variety of
composition each crop possesses. It is very important to convey this knowledge when selecting a
crop for industrial biochemical processing. The yield of the individual constituents is far more
useful tool in determining the possible chemical production routes. For an overall low yielding
crop may be a high yielding crop in a constituent of particular interest. Figure 4 displays such.
At a quick glance of all the choice crops, grass has one of the highest levels of protein, yet in
terms of total dry biomass it is on the lower end of the pack. No wonder cows are so big, simply
from eating grass all day. Compared to the soya bean, which is grown especially as a fodder for
rumen husbandry, grass has a noticeably higher yield of protein. One could falsely assume that by
following this graph it would be better to cultivate grass as a feedstock. However the absolute
terms of protein says nothing about to essential amino acids required by cows or other livestock.
The same holds true for the production of the functionalized chemicals, providing the reasoning
into the creation of the detailed information section of the crop guide. Nonetheless this
information is immensely valuable and will provide the basis for many subsequent calculations.

Usable Constituents Yields
15.0
17.3 18.4 Simple Carbohydrate (S .C.)
Lignin
Protein
Fat
12.5
10.0
ton /ha DW
7.5
5.0
2.5
0.0
m
um
va
to
e
er
ss
ss
t
at
ee
ai z
rn
ee
tr e
cc
ta
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w
al
a
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b
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es
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ar
Lu
ya
r
Ca
ap
To
O
So
ga
it c
g
Su
ill
So
Su
Su
W
R
Sw
Figure 4 Crop biochemical constituents yields
3.2.1 Unusable components

The biochemical constituents represent the portion of the plant that can be processed in some
form or another to engineer a viable product. These, however, do not embody the entire plant
mass. Ash, minerals and other trace elements are also present. Yet because these components
cannot be converted into viable products following traditional biochemical pathways, they are
considered unusable. The possible alternative uses (e.g. agricultural nutrients) of these biochemically
unusable components are discussed later in detail (see Chapter 7). In terms of potential yield for
biomass applications the unusable components must be regarded as a material loss. Yield figures
are consequently adjusted for use in further calculations. The following excel excerpt (Table 5)
outlines the material loss values:
Table 5 Unusable biomass portion
(Isolated Minerals, Ash, and Trace Elements)

Crop
Na me Dry W eight Nam e Dry W eig ht Nam e Dry We igh t Total Material Loss
Common Name - Constituent Plant Part - Cons tituent Plant Part - Cons tituent Plant Part Value %
Cassava Tuber 3.9 0.4 Leafs 11.3 0.1 Stem 5.0 0.5 0.050 5.0
Grass Whole 11.4 1.0 - 0.0 - 0.0 0.114 11.4
Lucerne Whole 20.1 1.0 - 0.0 - 0.0 0.201 20.1
Maize Ear 3.0 0.3 Stover 9.9 0.7 - 0.0 0.081 8.1
Oil palm Fruit 1.7 0.5 Fronds 20.1 0.3 T runk 12.0 0.2 0.093 9.3
Potato Tuber 8.5 0.8 Stover 5.0 0.2 - 0.0 0.079 7.9
Rapeseed Seed 6.0 0.3 Pod 11.9 0.4 Stem 4.9 0.3 0.081 8.1
Sorghum Panicle 8.1 0.2 Leafs 5.0 0.1 Stalk 4.9 0.8 0.055 5.5
Soya bean Seed 10.2 0.3 Stover 5.0 0.7 - 0.0 0.067 6.7
Sugar beet Beet 10.7 0.8 Leafs 13.6 0.2 - 0.0 0.113 11.3
Sugar c ane Cane 5.9 0.7 Leafs 10.0 0.3 - 0.0 0.071 7.1
Sunflower Seed 6.1 0.5 Husk 9.3 0.2 Stover 11.1 0.3 0.081 8.1
Switc hgrass Whole 17.8 1.0 - 0.0 - 0.0 0.178 17.8
Tobacco Whole 5.2 1.0 - 0.0 - 0.0 0.052 5.2
Wheat Grain 2.3 0.0 Stover 10.2 0.0 - 0.0 0.000 0.0
Willow tree Whole 2.8 1.0 - 0.0 - 0.0 0.028 2.8

It is remarkable that of the listed crops, the three grass types all have a significantly large portion
of material loss, ranging from 11.4 – 20.1%. This can greatly affect the resulting crop efficiency.
3.3 Energetic Output
3.3.1 Calorific Values

Utilizing biomass to produce energy is by all means
Heating value (or calorific value) is used to define
the amount of heat released during the combustion
nothing new. The first human application, fire, sparked
of a fuel or food. It is measured in units of energy
the genesis of human civilization. For millennia forests
per amount of material. Depending on the context,
heating values may be reported as Btu/m³, kcal/kg,
provided huge reservoirs of accessible burnable material
J/mol, or a variety of other combinations of units.
Heating value in commonly determined by use of a
bomb calorimeter. and formed the bulk of civilizations early energy
The quantity known as higher heating value,
demands. The discovery of coal, and later other fossil
HHV, (or gross calorific value or gross energy) is
determined by bringing all the products offuels, combined with the rapid diminishing rate of
combustion back to the original pre-combustion
forests brought about an energy source shift. In more
temperature. The quantity known as lower heating
value, LHV, (or net calorific value) is determined by
recent years bioenergy has since seen a rebirth, at least in
subtracting the heat of vaporization of the water in
the by-product from the higher heating value results
Source: Wikipedia.org the research sector. Yet, wood is no longer the sole focal
point of investigation, practically all types of biomass are
considered feasible and subjected to analysis. They can range from agricultural waste, to un-
utilized agricultural forage, to the primary cultivated product. The potential energy release during
combustion of each biomass forms can be determined using modern engineering practices (see
Textbox). Such calorific values have since been documented for the vast majority of crops and
crop residues.
Despite the previous sentiment, the current blunt of bioenergy research has focused on utilizing
agricultural residues. This causes precisely the same conflict as with determining the yield figures;
a problem of unison. For example, the calorific values for winter wheat are expressed separately
for the dry grain as for the residual straw. It is desirable to attain a common expression for the
entire crop, a total calorific value. By knowing the moisture content, weight distribution and
calorific values for the individual plant parts the total calorific values can be calculated, higher
and lower heating value.
3.3.2 Group Contribution Formation Energy

The calorific values for a few of the plant parts are absent and have been logically estimated in
large part from comparison amongst the other crops. For instance, the stem/stover (based on the
known crop values for stem/stover) is set at 17000MJ/ton LHV and 17500MJ/ton HHV when
undetermined. This presents a slight uncertainty when using the calorific values and also neglects
the entire aspect of exergy. Another calculation method is readily available that employs more
accurate and abundant data supplied from the crop guide while tackling the notion exergy. The
group contribution method addresses in detail the formation bond energy/exergy required for
the individual biochemicals. In the previous section, biochemical constituents, the yield and
distribution of the biochemicals composed in the crop biomass was calculated. The group

contribution method can be used to calculate the energy and exergy present in all of the
biochemicals, including the ash. Table 6 is an exemplary guide to the method:
Table 6 Group Contribution Method
o o
Component Picture Formula Mole Weight Group b ch H Amount Exergy Enthalpy
Name g/mol kJ/mol # kJ/mol
Glucose C6 H12O 6 180.16
CH 545.27 485.75 6 3271.62 2914.5
OH CH -52.59 -85.11 5 -262.95 -425.55
O -86.52 -131.17
-86.52 -131.17 1
Sum 2922.15 2357.78
(Simple Carbohydrates) Value 16.22 13.09
*Enthalpy of devaluation (Ho ) and standard chemical exergy (bo ch ) are supplied by Szargut12
Listed in the accompanying database spreadsheet are the calculations for the other
biocomponents and further details regarding the method. Protein is a special component as it
consists of a combination of 20 different amino acids. Only for several of the crops (and for that
matter, plant part) is the amino acid distribution of the protein known. For this reason the
average, so-called base amino acid, structure was taken to be representative. The same procedure
has been adapted for the fatty acids (oils), due to lack of detailed oil composition data. Even so
the affect of such simplifications are negligible. It is noticeable that ash has a chemical energy and
exergy of 2.89MJ/kg and 2.43MJ/kg respectively, which is significantly lower than the other
components. Ash, as handled here, is the oxidized (combusted) result of the trace minerals and
biochemicals. The amount of energy/exergy present in such materials while present in the plant
is easy several magnitudes larger, yet since they are regarded as a material loss (as per current
technique) the oxidized values are best suited for biochemical applications.
3.4 Results
3.4.1 Total Energetic Output

Yield figures, calorific values and formation energy alone are not enough to pronounce a final
representative output for a crop species. As the biochemical group contribution method is more
accurate than the calorific value method it will be used henceforth to represent the crop energy
content. A function between the yield and energy content, however, leads to the workable energy
output on the basis of land area:
Total dry biomass yield ⋅ total formation energy = total energetic output [MJ/ha]
Figure 5 has plotted the resulting energetic and exergetic output for the selected crops.

Energetic and Exerg etic Result
Based On Total Gro up Contrib ution Me thod
1 .0E+0 6
9 .0E+0 5
Energy
Exe rgy
8 .0E+0 5
7 .0E+0 5
6 .0E+0 5
MJ/ ha
5 .0E+0 5
4 .0E+0 5
3 .0E+0 5
2 .0E+0 5
1 .0E+0 5
0 .0E+0 0
er
ss
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et
at
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f lo
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Lu
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ap
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un
To
il lo
O
So
tc
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C
y
So
wi
Su
R
W
S
Figure 5 Resulting Crop Energetic Output S
The amount of usable energy (exergy) obtainable per land area is greater than the energy due to
the higher chemical exergy in relation to chemical energy of the biochemicals. A stark difference
between the various crops is apparent, reflecting the land use intensity.
3.4.1.1 Comparative Analysis

Describing and visualising the resulting energy output figures is a very good way to present the
individual crop figures that will compose the basis of all the subsequent efficiency calculations.
Yet, a systematic comparison must be developed for the various categories to help further
judgement in crop choice selection. It is best to create a simple table outlining the main points of
argumentation. Within the output section, resulting energetic output is only one factor of interest.
Even if it is by far the most important, the other categories must be mentioned to provide an
adequate overview. See Table 7 for the resulting dry weight yields and the individual biochemical
constituents as two such important output figures:

Table 7 Comparative Output Overview
Crop Yields Bio chemical Constituents Output

Common Name Total DW Simple C. Complex C. Lignin Protein Fats Energy Exergy
Cassava + + + + + O + +
Grass O O O - + O - O
Lu cerne O - O O + - - -
Maize + + + + + O O +
Oil Palm + - + + - + + +
Potato O + O - O - - O
Rapeseed O - O O + + O O
Sorghum + + + + O - + +
Soya Beans O - O O O O - O
Sugar Beet + + O - O O O O
Sugar Cane + + + O - O O +
Sunflower - - O O O + - -
Switchgrass O - O + - - - O
Tobacco + - + + + - O +
Wheat O O O O + - - O
Willow Tree - - O O - - - -
Total DW: + above 20ton/ha, - below 10ton/ha, O b etween 10 – 20ton/ha
Simple C.: + above 5ton/ha, - below 1ton/ha, O betw een 1 – 5ton/ha
Complex C.: + above 10ton/ha, - below 2.5ton/ha, O b etween 2.5 – 10ton/ha
Lignin: + above 2.5ton/ha, - below 0.5ton/ha, O b etween 0.5 – 2.5ton/ha
Protein: + above 2.5ton/ha, - below 1.5ton/ha, O b etween 1.5 – 2.5ton/ha
Fats: + above 1ton/ha, - below 0.25ton/ha, O b etween 0.25 – 1ton/ha
Total en ergy: + above 5.0⋅105MJ/ha, - below 2.5⋅105MJ/ha, O b etween 2.5⋅105 – 5.0⋅105MJ/ha
Total exergy: + above 5.0⋅105MJ/ha, - below 2.5⋅105MJ/ha, O b etween 2.5⋅105 – 5.0⋅105MJ/ha

4 Solar Input
The major source of energy input in plants is quite obviously the sun. Determining the solar
input is based on two factors, the location and the cultivation period. Common sense suggests
that a plant cultivated in the tropics will have higher yields than one cultivated in Siberia. On a
general stance this is indeed true, yet the solar efficiency is another matter completely. The
amount of energy out (yield ⋅ caloric value) per energy in (solar energy) can widely vary from crop
species regardless of location. Based on these indications, it could be advisable to cultivate some
species in a non-native area, granted it complies with the growth details.
4.1 Location
Solar radiation values are based on a monthly basis over a 10-year average. Data is available for
the entire world over and was obtained from:
• NASA Surface meteorology and Solar Energy: SolarSizer Data 13
The location is stipulated using the global coordinate system and through an
interactive graphical map program (see adjacent picture). A 1x1 deg square
region is set (highlighted in red). The accuracy of the database is 0.1deg
longitude and 0.1deg latitude. Seeing that the world is a sphere the
corresponding distances are different for each specific location. However, an
estimate can be made that regions above the Tropic of Cancer and below the
Tropic of Capricorn are roughly 100x100km. Those regions in between are
closer to 150x150km. In regards to the cultivation areas, these differences are
insignificant.
The location choices listed previously (see Table 1) in many cases span vast land areas. In cases
where hundreds of kilometres scope is present a known cultivation region is selected. Common
sense and well-documented cultivation information dictate the region choice, which are used to
set the exact coordinates. The following excel table excerpt (Table 8) indicates the chosen
location, chosen coordinates and resulting solar monthly solar radiation input:
Table 8 Location Based Solar Radiation Values
Representative Area Solar Radiation Values (Energy)

Crop
Continent Country/Region Latitude Longitude Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Common Name Largest Producer Degrees khW/m²/month
Cassava Africa Nigeria 8 7 188 179 193 180 169 152 146 138 145 164 173 177
Grass Europe Holland 51 5 23 40 78 114 153 147 154 131 85 53 28 19
Lucerne North America South Dakota 44 -103 53 70 106 141 180 192 199 173 128 92 55 44
Maize North America Iowa 41 -91 57 74 108 133 167 180 190 165 128 92 56 46
Oil palm South Pacific Malaysia 2 113 140 137 152 148 152 151 155 159 150 154 141 143
Potato Europe Holland 51 5 23 40 78 114 153 147 154 131 85 53 28 19
Rapeseed Europe Belgium 50 5 25 43 78 112 148 143 155 133 88 56 30 20
Sorghum Africa Kenya 0 35 178 168 190 164 166 154 153 157 171 178 168 174
Soya bean North America Illinois 41 -90 57 75 103 133 167 180 184 161 123 89 50 47
Sugar beet Europe Germany 52 8 22 38 70 109 150 140 145 123 82 50 25 17
Sugar cane South America Brazil -25 -50 173 143 141 119 100 95 104 122 129 157 170 171
Sunflower Europe France 48 0 29 48 83 116 149 150 163 138 100 62 35 25
Switchgrass North America Iowa 41 -91 57 74 108 133 167 180 190 165 128 92 56 46
Tobacco South Pacific Australia -34 145 231 193 171 122 92 74 80 105 145 185 209 222
Wheat Europe France 48 0 29 48 83 116 149 150 163 138 100 62 35 25
Willow tree Europe Sweden 56 13 17 32 69 113 169 165 166 132 84 47 23 16

These figures will be used throughout the rest of the solar radiation calculations. The exergy
values are not displayed, but are a function of solar radiation values (see Chapter 2) and differ
only marginally from the energy terms. It must be stated that there are several possible cultivation
regions for the same crop as mentioned in the crop guide (see Section 2.3.2). The solar radiation
figures will be different for each. As a common example, the potato can and is cultivated in
Holland, Germany and France, which have 154, 145 and 163khW/m² in July respectively. This
represents a standard deviation just over 5%. To circumvent this error the yield figures (see
Section 3.1) correspond to the specified region. In the following efficiency section, this topic will
go into more detail.
4.2 Cultivation Period

It is common mistake applied by most researchers in the field of agriculture and biomass
technology to simply assume an average solar radiation input for all crops. Typically a figure of
1000khW/m²/y is chosen. This is approximately the Northern Hemisphere annual average. It is
also a major fundamental error that should be present in the form of an erratum, but sadly is not.
There are two principal argumentations reasoning against this widespread simplification. The first
is the differences of solar radiation dependent on cultivation location, which has been mentioned
above. The second is the cultivation period.
What is understood by cultivation period is basically the duration of time the crop is actually in
the ground. This starts with propagation (should it be from seed, fruit or re-sprouting) until the
final harvesting. During the periods a crop is not present in the ground the solar radiation cannot
be incorporated as an input. In many cases another crop could be planted in between the
cultivation cycles and could thus theoretically benefit from the otherwise squandered solar
radiation input. Winter wheat is perfect example to illustrate this point:
In the beginning of autumn, around October, the seeds are drilled into place. They remain in the soil until
the following spring. During the autumn the solar radiation is not converted into biomass, yet the crop (in
the form of the seed) is present in the ground. Only in the beginning spring do they begin to sprout. This
facilitates the crop to utilize the maximum amount of springtime solar radiation. In the month of July the
harvesting p ro cedure begins and by mid July the grains are ready for storage. The time b etween mid-July
and October is the p rime months in terms of solar radiation in the Northern Hemisphere. Sin ce th e crop
is not occupying the field at the time, these values must be deducted from the total solar input. If it is
necessary that the field use this time for reco very, b efore the n ext cultivation, then indeed the months
must be included. However, a simple crop like ryegrass or lu cerne could most likely strive during that
period and yield additional biomass; a so-called catch crop.
The various combinations of growth cultivations are best left to the farmers based on regional
circumstances. Success is of course questionable, yet in any case the option does exist. From this
standpoint the solar radiation input is a function of the cultivation period. The following excel
table excerpt (Table 9) indicates the growth period as extracted from the crop guide:

Table 9 Cultivation Period for Solar Radiation Input
Corresponding Growth Period

Crop
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Common Name Occu rrences
Cassava 1 1 1 1 1 1 1 1 1 1 1 1
Grass 0 0 1 1 1 1 1 1 1 1 0 0
Lucerne 0 0 0 1 1 1 1 1 1 1 0 0
Maize 0 0 1 1 1 1 1 1 1 1 1 0
Oil palm 1 1 1 1 1 1 1 1 1 1 1 1
Potato 0 0 0 1 1 1 1 1 1 0 0 0
Rapeseed 1 1 1 1 1 1 1 0 0 1 1 1
Sorghum 1 1 1 0 0 1 1 1 1 1 1 1
Soya bean 0 0 0 0 1 1 1 1 1 1 0 0
Sugar beet 0 0 0 0 1 1 1 1 1 1 1 0
Sugar cane 1 1 1 1 1 1 1 1 1 1 1 1
Sunflower 0 0 0 1 1 1 1 1 1 0 0 0
Switchgrass 0 1 1 1 1 1 1 1 0 0 0 0
Tobacco 1 1 1 1 1 1 1 1 1 1 1 1
W heat 1 1 1 1 1 1 1 0 0 1 1 1
W illow tree 1 1 1 1 1 1 1 1 1 1 1 1
4.3 Results
4.3.1 Total Energetic Input

By combining both the monthly solar radiation values with the cultivation period the amount of
intercepted solar energy can be determined. This is expressed per land area and acts as the
resulting solar radiation input component. Figure 6 illustrates the large differences location and
cultivation practices exert on input solar energy:
Solar Radiation Input

7.5E+07
Annual Growth P eriod (energy)
Annual Growth P eriod (exer gy)
5.0E+07
MJ/ha
2.5E+07
0.0E+00
t
a
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Lu
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Ca
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To
O
So
itc
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Ra
Su
il l
ug
Su
W
Sw
S
Figure 6 Resulting Solar Radiation Input

If one were to average the solar radiation for all the crops, the value of 1000kWh/m²
(3.6 ⋅10 7MJ/ha) would indeed be a good approximate. It is however clear that there are large
differences between the various crops, ranging from roughly 700 to 2000kwh/m² (2.5⋅10 7 to
7.0 ⋅10 7MJ/ha). This represents a deviation of more than 250%. It should now be apparent why
the simplification is unacceptable. When referring to solar radiation the SI-units kWh/m²/y are
generally implied. They can easily be converted into the more workable and transparent SI-units
MJ/ha. Only the latter is indicated on the above graph.
4.3.2 Efficiency
Converting the solar radiation figures from kWh/m² into MJ/ha is preformed because the total
resulting energy output (see Section 3.4.1) is expressed in terms of MJ/ha. Relating the two
figures will result in the solar efficiency as indicated by the simple formula:
Energetic _ Output[ MJ / ha ]
Solar _ Efficiency =
Solar _ Input[MJ / ha ]
Figure 7 displays the resulting solar efficiency for the total yield with 10-year average and the
yield error bars included:
Efficiencies
Based on So la r Radiation I nput E nerg y
1.50
1.90
Energy
Exergy
1.25
1.00
Conve rsion Pe rcent [%]
0.75
0.50
0.25
0.00
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C
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R
Sw
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Figure 7 Resulting Solar Radiation Utilization Efficiency

Solar input, the largest and most significant input factor, when converted into efficiency terms
displays completely different results than the corresponding yield outputs or energetic outputs.
The sugar cane, for example, is a high-yielding, high-energy crop, but fairs rather average in this
respect.
4.3.3 Analysis
Table 10 Comparative Solar Input Overview
Crop Solar Radiation (energy) Solar Radiation (exergy)

Common Name Input Efficien cy Input Efficien cy
Cassava + - + -
Grass - O - O
Lu cerne O O O O
Maize O + O +
Oil Palm + + + +
Potato - O - +
Rapeseed - + - +
Sorghum + O + +
Soya Beans - O - O
Sugar Beet - + - +
Sugar Cane + O + O
Sunflower - O - O
Switchgrass O - - O
Tobacco + O + O
Wheat - - - O
Willow Tree O - - -
Input: 7 7 7
+ above 5.0⋅10 MJ/ha - below 3.6⋅10 MJ/ha, O b etween 3.6 – 5.0⋅10 MJ/ha
Efficien cy: + above 1.0%, - below 0.5%, O b etween 0.5 – 1.0%

5 Results and Discussion
The top 3 choice crops for each category will be handled separately.
Yield is the term to express the mass gained per cultivated area. It is presented in a multitude of
different ways, ranging from the food based component to the entire wet biomass. Both the total
wet weight and dry weight figures were determined. Additionally the total dry weight has been
related to the solar radiation energy to create a land use factor. Table 11 lists the top 3 crop
results from the yield category:
Table 11 Top 3 Crops on total mass premises
Wet Weight Yield Dry Weight Yield Land Use Facto r

Top Crops
ton/ha g/GJ
1. Tobacco: 240 Sorghum: 36.9 Sugar Beet: 1133
2. Sugar Cane: 186.6 Cassava: 35.1 Maize: 711.6
3. Sugar Beet: 142.8 Sugar Cane: 35.0 Potato: 621.5
4.* Rapeseed: 88.1 - -
*A 4th top crop has been added because the tobacco crop is base in large part on experimental data and cannot be taken to properly represent the
yield figures. The experimental data is based on a small plot of 100ha Australian test plot, meaning it is most likely that practical yields will be but
a fraction. Whenever the tobacco crop is present on the list an addition crop will accompany 4th place, should yields not be reproducible when
brought to full-scale applications. For instance, the wet leaf (smoking tobacco) yield in America is 25ton/ha and at 65% moisture is around
9ton/ha DW; about two thirds less.
It is clearly noticeable, also from Figure 2, that the differences between dry weight and wet
weight yields are great. The deviation in weight terms for the select crops ranges from 12% up to
88%. This enormous range clearly stresses the importance of having the yield figures presented in
a standardized term. Dry weight is the most logical term for this task, yet wet weight cannot be
excluded as moisture content will play a deceive role in harvesting techniques and downstream
processing. The ranking positions between the two are also slightly altered with the sorghum
resulting as the leader for yield. The last column has been dubbed “land use factor” and has the unit
g/GJ. It indicates the relationship between the crop productivity and the input of solar radiation.
Assuming that farming practices are to be upheld in a different and compatible region, the yields
will be intrinsically correlated to solar radiation. Temperate crops (like the potato and sugar beet)
are grown in wealthy regions which have highly intensified agriculture. Tropical versions are less
likely to yield the same land use factor, as other agricultural limitations like less intensified
farming and water shortages are present. It could be fathomable that if the crops were properly
adjusted and managed for sunny regions that the yields would be incredible. This aspect is only
one piece of the puzzle as increased energy intensive agriculture will reduce the land use factor.
Those particular topics are covered in the subsequent chapters, yet the solar factor on land use is
quite arguably the largest determinant.
Total yield is a useful tool is displaying general trends for biomass production, but to address the
specific demands of a chemical industry more detailed information is required. The same
procedure is applied to the yield of the individual biocomponents contained in the crop, Table 12

Table 12 Top 3 Crops on Carbohydrate Yields
Simple Complex Total Simple Complex Total

Top Crops
ton/ha (DW) g/GJ
1. Sugar Beet: Tobacco: Sugar Cane: Sugar Beet: Tobacco: Sugar Beet:
18.6 20.4 29.3 713 309 911
2. Sorghum: Sugar Cane: Sorghum: Potato: Sugar Cane: Maize:
17.3 17.5 29.2 368 299 507
3. Sugar Cane: Cassava: Cassava: Sorghum: Maize: Sugar Cane:
11.8 14.4 26.2 285 273 501
4.* - Maize: - - Rapeseed: -
14.3 239
The simple carbohydrates are important for the production of 1 st generation biofuels (ethanol);
the higher the yield of simple carbohydrates the more biofuel per land can be produced. Whereas
complex carbohydrates are becoming more important as they can also be utilized for biofuel
production using so-called 2nd generation technology. In fact, 2nd generation can utilize both
simple and complex forms. What is clear from looking at the list is that both maize and cassava
do not score very well against the competition in the simple carbohydrate section but make the
list for complex. Such crops should thus only be cultivated for biofuels when a 2nd generation
processing plant is available, else the sugar beet, for example, would fair better. The total
carbohydrate yield is conversely a much better indication as 1 st generation is being phased out for
2 nd generation. By the time full-scale implementation is properly realised it would be wasteful to
construct a 1 st generation installation. In the realm of chemical products carbohydrates are also
important for many bulk chemicals, yet of no or low order of functionality. The biochemical
constituents with more functionality and thus a higher energy saving potential are in Table 13:
Table 13 Top 3 Crops on Lignin Yields
Dry Weight Yield Land Use Facto r

Top Crops
ton/ha g/GJ
1. Cassava: 4.2 Maize: 87.8
2. Maize: 3.9 Switchgrass: 67.2
3. Oil Palm: 3.7 Cassava: 58.4
Lignin is the biocomponent associated with aging for strength and stability of crops. Logic would
figure that a fast-growing perennial tree, like the willow, would dominate this category. It does
score above normal, but far below expectations, mainly due to the relatively low Swedish yields.
There is more lignin developed in the stem of the maize than the trunk of the willow.
Table 14 Top 3 Crops on Protein Yields

Top Crops
ton/ha g/GJ
1. Rapeseed: 4.3 Rapeseed: 147
2. Lu cerne: 3.6 Lu cerne: 91.7
3. Tobacco: 3.5 Grass: 83.1
4.* Maize: 3.3 -

Protein contains the highest degree of functionality. All amino acids include an amine group
(nitrogen) and are interrelated to the level of nitrogen fertilization. The following chapter will use
the above table (14) to analysis the relationship between the yield and level of fertilization.
Table 15 Top 3 Crops on Fatty Acid Yields

Top Crops
ton/ha g/GJ
1. Oil Palm: 13.1 Oil Palm: 204
2. Rapeseed: 2.6 Rapeseed: 90.8
3. Sunflower: 2.4 Sunflower: 82.2
As listed in Table 15 it is not surprisingly the crops with the highest fats/oil yield are those
currently employed in biodiesel production. From looking at the yield differences between them
the obvious choice (should land productivity be an issue) is the oil palm. Europe will never be
able to compete against Malaysian imports on an open market. That is, without a biorefinery
producing other high value products.
The amount of weight produced on the fields is only one aspect handled in this chapter, the
energetic output and ratio to incoming solar radiation is the other, Table 16.
Table 16 Top 3 Crops on Energy/Exergy Output
Top Crops Energy Exergy Solar E fficien cy (Input/Output)

GJ/ha Energy Exergy
1. Oil Palm: 833 Oil Palm: 923 Sugar Beet: 1.47% Sugar Beet: 1.90%
2. Cassava: 538 Sorghum: 639 Oil Palm: 1.14% Oil Palm: 1.36%
3. Sorghum: 537 Cassava: 638 Rapeseed: 1.06% Rapeseed: 1.32%
In the context of energy and exergy content the differences between output may be slight but are
noticeable. The underlining reasoning is the difference between the energy and exergy content of
protein, having a deviation of 22.6%. For the production of bioenergy this table is of utmost
importance but is not of terrible significance in the chemical field. Burning protein for its
calorific value is quite different than the potential process energy savings in the chemical industry.
For such considerations the above biochemical yield relations with land use guides are much
better suited. Furthermore the chemical production from biomass will not be a single product
but a multitude as defined by the concept of a biorefinery. Concrete conclusions for the
biochemical industry cannot be drawn from any of these values alone, but will act as a strong
basis in all proceeding calculations.

References
1. Eerste Kamer (Upper House) 10de Vergadering; The Hague, 12 December, 2005, 2005; p 41.
2. Hoogwijk, M. M. On the Global and Regional Potential of Renewable Energy Sources.
University of Utrecht, Utrecht, 2004.
3. International Fertilizer Industry Association (IFA) World Fertilizer Use Manual.
http://www.fertilizer.org/ifa/publicat/html/pubman/manual.htm
4. Duke, J. A. Handbook of Energy Crops.
http://www.hort.purdue.edu/newcrop/Indices/index_ab.html
5. U.S. Department of Energy Biomass Feedstock Composition and Property Database.
http://www1.eere.energy.gov/biomass/feedstock_databases.html
6. Energy research Centre of the Netherlands (ECN) Phyllis: Database for biomass and waste.
http://www.ecn.nl/phyllis/info.asp
7. Food and Agriculture Organization of the United Nations (FAO) FAOSTAT: FAO
Statistical Databases.
http://faostat.fao.org/faostat/default.jsp?language=EN&version=ext&hasbulk=
8. Food and Agriculture Organization of the United Nations (FAO) Grassland Species: Profiles.
http://www.fao.org/ag/AGP/AGPC/doc/GBASE/Default.htm
9. Leaf for Life Index of Top Crops. http://www.leafforlife.org/PAGES/TOPINDEX.HTM
10. Interactive European Network for Industrial Crops and their Applications (IENICA) Crops
Database. http://www.ienica.net/cropsdatabase.htm
11. Reisinger, K.; Haslinger, C.; Herger, M.; Hofbauer, H. BIOBIB - A Database for Biofuels.
http://www.vt.tuwien.ac.at/biobib/oxford.html
12. Szargut, J.; Morris, D. R.; Steward, F. R., Exergy Analysis of Thermal, Chemical, and Metallurgical
Processes. Springer-Verlag: 1988; p 332.
13. NASA Surface meteorology and Solar Energy: SolarSizer Data. http://eosweb.larc.nasa.gov/

Chapter 5
Prime Energy Input
Required energy and exergy input to promote the cultivation of biomass
Ben Brehmer
Dissertation Report

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Abstract
The modern mechanized cultivation of biomass requires significant energy and material inputs
from a multitude of different sources and forms. Seen from the cradle-to-grave they can be
separated into direct (prime) and indirect (secondary) energy and material streams. Those directly
attributed to biomass growth are covered within this chapter; namely fertilizers, irrigation,
drainage and crop protection. Fertilizers per se contain very little usable energy for the crops so
the energy requirements for fertilizers are based on the entire production chain for the nutrients.
Plant nutrients are classified in two groups, primary and secondary; the production processes for
the primary nutrients have been thoroughly investigated. As there are many types and grades of
fertilizers available on the market, those representing the typical and expected market share on
the European market were calculated. The process chains behind those specific fertilizers are
based on logically selected routes from the Best Available Techniques to represent likely near
future averages. Crop nutrient uptake levels were chosen instead of various fertilizer application
rates to avoid discrepancies in farming techniques. Combining the process dependent energy
requirements with the nutrient requirements generates the fertilizer energy and material input
figures. Irrigation is also calculated based on regional rainfall levels versus crop water uptake
levels on a monthly basis. The difference between effective rainfall and crop evapotranspiration
must be supplied via irrigation and drained should it exceed the optimum levels. The process
energy behind typical irrigation systems and water sources were calculated on the regional based
scale for the individual crop. Crop protection measures are performed using agrichemicals called
pesticides. As with the fertilizers the process energy have been tabulated, but as there are more
than 2500 different pesticides on the market only a select few commonly applied chemicals have
been investigated. All the input figures have been set against the resulting energy output of each
crop to determine and compile an overall efficiency comparison as was previously conducted in
Chapter 4. The inefficiencies of fertilizer and pesticide application will be handled in the
following chapter. All the processes and methods were adopted and expanded to include both
energy and exergy values.
Key Words:
Fertilizer, Nutrients, Irrigation, Drainage, Pesticide, Energy, Exergy, Efficiency

Content
Abstract 117
1 Introduction 123
2 Fertilizer Input 125
2.1 Preface 125
2.1.1 Historical Background 125
2.1.2 Industrialization 125
2.1.3 Best Available Techniques 126
2.1.3.1 Assumptions 126
2.2 Nitrogen 129
2.2.1 Brief Description and Nutrient Importance 129
2.2.2 Process Choice and Description 132
2.2.2.1 Ammonia 133
2.2.2.2 Nitric Acid 135
2.2.2.3 Ammonium Nitrate 136
2.2.2.4 Urea 138
2.2.2.5 Urea Ammonium Nitrate 139
2.2.3 Energetic Result 140
2.3 Sulphur 143
2.3.2.1 Hydrogen Sulphide - Sulphur 145
2.3.2.2 Sulphuric Acid 147
2.4 Phosphorous 150
2.4.2.1 Phosphate Rock 152
2.4.2.2 Phosphoric Acid 153
2.5 Potassium 157
2.5.2.1 Potash 158
2.6 Calcium and Magnesium 161
2.6.1.1 Calcium 161

2.6.1.2 Magnesium 162
2.6.2.1 Dolomite Limestone 163
2.7 Micronutrients 164
2.8 Complex Fertilizers 166
2.8.2.1 NPK 167
2.8.2.2 CAN 169
2.9 Nutrient Uptake 173
2.10 Results 176
2.10.3 Analysis 180
3 Water Input 181
3.1 Crop Water Demand 182
3.1.1 Seasonal Amount 182
3.1.2 Relation to Monthly Evapotranspiration 183
3.1.2.1 Growth Stage Factor 183
3.1.2.2 Solar Radiation Factor 185
3.1.2.3 Solar Radiation Factor Assumption Valorization 186
3.1.2.4 Evapotranspiration 188
3.2 Rainfall 189
3.2.1 Regional Figures 189
3.2.2 Effective Rainfall 190
3.3 Irrigation/Drainage Requirements 191
3.3.1 Systems and Sources 191
3.3.1.1 Furrow 191
3.3.1.2 Basin 192
3.3.1.3 Drip 192
3.3.1.4 Sprinkler (travelling gun) 192
3.3.1.5 Sprinkler (center pivot) 192
3.3.1.6 Water body 192
3.3.1.7 Drainage 192
3.3.2 Irrigation Levels 193

3.3.3 Pump 193
3.3.3.1 Fuel Source 194
3.4 Resulting Energy 195
3.4.2 Conversion Efficiency 195
3.4.3 Analysis 196
4 Pesticide Input 197
4.1 Preface 197
4.1.2 Agricultural Applications 197
4.2 Process Energy 199
4.2.1 Source of Data 199
4.2.2 Grouping 200
4.2.3 Calculations 201
4.3 Crop Pesticide Application Rates 202
4.3.1 Crop and Regional Comments 202
4.3.1.1 Cassava – Nigeria 202
4.3.1.2 Grass – Holland 202
4.3.1.3 Lucerne – Wyoming 202
4.3.1.4 Maize – Iowa 202
4.3.1.5 Oil Palm – Malaysia 203
4.3.1.6 Potato – Holland 203
4.3.1.7 Rapeseed – Belgium 203
4.3.1.8 Sorghum – Kenya 203
4.3.1.9 Soya Beans – Illinois 203
4.3.1.10 Sugar Beet – Germany 203
4.3.1.11 Sugar Cane – Brazil 203
4.3.1.12 Sunflower – France 204
4.3.1.13 Switchgrass – Oregon 204
4.3.1.14 Tobacco – Australia 204
4.3.1.15 Wheat – France 204
4.3.1.16 Willow Tree – Sweden 204
4.3.2 Results 204
4.4.3 Analysis 208
References 213

1 Introduction
In basic science books, written for our credulous children, photosynthesis would appear to be the
only system dictating plant growth. Water plus Air plus Solar Radiation will be converted via the
Calvin Cycle into glucose or respectively biomass. The other thousands of biochemical pathways
are ignored for simplification reasons, as they are indeed not the reactions yielding energy for
growth. For the most part this knowledge has remained engraved in the minds that span the
duration of our lives. In the antiquities, this sediment could very well hold true, even amongst the
ranks of the educated. Plant a seed, add some water and during the sunny months a crop will
emerge. This over simplification cannot be used when arguing the entire input requirements for
modern larger scale industrial applications of biomass.
As an interesting tidbit, in Mesopotamia “the cradle of civilization” for example, winter wheat
had an average grain yield of 2ton/ha 1. In Holland, during the medieval period with an arguably
gloomier climate (probably what drove Van Gogh into depression) the average grain yield of
winter wheat was slightly below 1ton/ha. Today, the Dutch yields have increased nearly ten fold.
What can be attributed to this incredible increase of plant growth? Surely global warming has not
yielded ten times more sunny days in Holland. Should that be true, most locals would look like a
typical English tourist visiting Mallorca, lobster red.
Farming techniques, cultivation methods and centuries of experience have given farmers a feeling
of the best spacing and seedling ratio for any particular crop. Mechanization is definitely one of
the major advancements and contributions. Combined they have allowed a near optimum of
ground coverage, timing and speed to maximize the solar radiation component. In fact, seen on
the cradle-to-grave, operating and maintaining farming tools is already a significant required
input. Diesel to drive tractors, harvesters, combines, etc., food to supply the workers on the fields
and so on. However, in comparison to solar energy, this is practically insignificant. Ra, the Sun
God, is clearly more important than the Slaves working the fields.
The Dutch in particular are masters of their lands (God created the world, yet the Dutch created The
Netherlands – Voltaire); generations of their engineers have allowed swamps to be converted into
dry, liveable and more importantly arable land. Redirecting aqua bodies in the form of irrigation
is essential in providing the necessary water for the photosynthesis process. This is another key
component of the optimized farming techniques that can be attributed to the leap in plant
growth (yield). What started off, as those cute picturesque windmill driven channels, has quickly
become an integral part of mechanized farming. Large sprinkler systems, large dam networks,
compressors and pumps are all intertwined with an electrical energy input.
Air, in the sense of photosynthesis, is associated with supplying the necessary carbon dioxide.
Modern greenhouses even utilise the off-gases of power plants to raise the atmospheric CO 2
level. Yields do indeed raise for most (all C-3 species) plants, for instance the widely popular

“Dutch waterbombs” (known on the domestic market as tomatoes). As much as the Kyoto Protocol
is trying to curb emissions of such greenhouse gases (not named for this beneficial effect), the
fractional atmospheric increase cannot be associated with any noteworthy yield increases in
outdoor cultivations.
This is as far as traditional photosynthesis (air, water, sun) optimizations can go; yet these
collective improvements cannot be solely attributed to a ten-fold increase in yield. This is where
the previously ignored biochemical pathways make a loud return. Increasing the metabolic
reaction rates (and adversely photosynthesis) is achieved by systematically applying the necessary
enzymatic and biochemical nutrients. In laymen’s terms these are referred to as fertilizers. On
fertile land, crops produce higher yields, obviously. The lack of this now common farming
knowledge, of what makes a land fertile, is probably what caused the eventual downfall of the
Mesopotamian civilization. It has been hypothesized that over-farming allowed wheat yields to
drop from 2ton/ha down to 0.8ton/ha in a matter of decades and most likely continued to drop
to critical starvation levels. Ironically the single most important nutrient, nitrogen, is abundantly
present in air, yet cannot be easily harnessed by plants. Vast amounts of energy are required to
convert atmospheric air into its useable nutrient constituent, ammonium. Similar trends hold true
for the remaining nutrients.
In fact of all the farming technique improvements, fertilizer technology, is the single most
important factor in increasing yields. As it stands today, with the available arable land and
farming techniques, the world could only sustain circa 3-4 billion human inhabitants without
artificial fertilizers. In as little as 80 years, huge production factories have been constructed
around the world converting ores, minerals, fossil fuels and other components into fertilizers. It
is estimated that more than 3% of the total global energy demand is utilized in fertilizer
production alone1. Yet, again in comparison to the energetic levels of solar radiation these levels
are also negligible. This is an additional reason supporting the choice to handle solar radiation in
land terms.
1.1 Chapter Purpose

In the following chapter all the required primary inputs will be calculated and expressed in a
comparative form for the previously selected crops. The values mentioned herein are based on a
straightforward energy/mass balance in excel and thermodynamic conversion to obtain the
exergy values. This chapter is the first of three energy inputs categories required for the creation
chemicals from biomass. Primary, secondary and process energy inputs comparison will all be
addressed independently from solar energy.

2 Fertilizer Input
2.1 Preface
2.1.1 Historical Background

Guano (from the Quechua 'w anu') “The Netherlands, as any European can tell you, has
Is a collection of droppings of seabirds and bats. It can be
become a land of giants. In just over a century, the Dutch
used as an effective fertilizer due to its high levels of nitrogen.
Soil that is deficient in organic matter can be made much
have gone from being amongst the smallest people in Europe
more productive by addition of this manure. Guano consists
to become the tallest in the world”2. The men now
of ammonia, along with uric, phosphoric, oxalic, and
carbonic acids, as well as some earth salts and impurities. The
average 182cm (18cm taller than in Van Gogh’s
high concentration of nitrates also made guano an important
strategic commodity; in fact, the War of the Pacific between
day) while the women average 176cm. The start of
the Peru-Bolivia alliance and Chile was primarily based upon
Bolivia's attempt to tax Chilean guano harvesters.
this continued growth spout is recorded to have
Guano is harvested on various islands in the Pacific (for
commenced around the 1840’s. Socio-economical
example the Chincha Islands and Nauru) and in other oceans
(for example Juan de Nova Island). These islands have been
issues aside, there is one particular event, which
home to mass seabird colonies for many centuries, and the
guano has collected to a depth of many metres.
plays a decisive factor in this trend. Guano.
Guano has been harvested over several centuries along the
coast of Peru, where islands and rocky shores have been
Beginning in the 1840’s a common load for any
sheltered from humans and predators and administered by
private and state companies European ship returning from a South American
Source: Wikipedia.org
voyage was guano. Chilean guano contained 14%
N and 14% P2O 5, two of the major nutrients required for accelerated plant growth. Previously
local animal manure and crop foliage posed as the only major source to maintain field fertility. By
exploiting guano, an external source of nutrients was available providing the crops with and
resulting in an increased nutritional value of the harvest. This gave rise to the soaring heights of
the aardappeleters.
2.1.2 Industrialization
By 1875 South American sources of guano were basically exhausted, yet the benefits of applying
outside sources of nutrients remained in the minds of the agricultural sector. Other means of
producing (at the time focus was only on nitrogen) nitrate were quickly adopted but could not
maintain with the demand increase for long. In 1898, the English chemist Sir William Crookes
called out to all chemists to find a process to fix nitrogen from the air3. He urged that unless a
new nitrogen source was discovered, famine would be inevitable within several decades. In 1908,
the German professor of chemistry Fritz Haber discovered how to synthesis ammonia from air.
With the help of BASF’s German industrialist Carl Bosch, large-scale production facilities were
erected by 1917. Once the problem of supplying agriculture with enough nitrogen was overcome,
depletion of the other nutrients became apparent.
Fertilizer: Any of a large number of natural and synthetic materials spread on or worked into soil to increase its capacity to support plants.
Since then a wide variety of heavy industrial processes for all the plant nutrients have been
developed and are constantly being improved. Combined they fuel the current fertilizer industry.
Manure and sewage when applied to agricultural fields are also considered as fertilizers, so those
that derive from industrial processing are now referred to as “artificial fertilizers”. The health-

crazed trend of using bio-fertilizers (i.e. manure), amongst other things, for the luxury niche
market of bio-labelled food products represents but a hairline fraction of the current total
worldwide fertilizer market. And in any case for non-food application designs, the cost of such
methods is far too high with no added benefit. The fertilizer market has within 80 years evolved
into one of the core industrial sectors. Many economists even assess the economic growth and
stability of a nation by their fertilizer use/production.
2.1.3 Best Available Techniques

Artificial fertilizers require enormous amounts of energy for a variety of processing requirements
(extraction, pumps/compressors, heat, etc.) and as a raw material source. Today the industry is as
diverse as any other. Every production plant is constructed slightly differently and designed to
produce a final product of a slightly different specification. This is on top of the already huge
array of possible raw materials sources available, all with their own process considerations.
Furthermore, the advancements of traditional processing techniques, development of new
process techniques and the revamping of older production plants are constantly redefining the
energy requirements of the industry. To make matters even more complex, there are practically
countless varieties of final fertilizer products. Each country, each agricultural region, each field,
each farmer, each crop even each season exert a preference to the exact type and form of
fertilizer to be administered. To be able to even fathom the energy input requirements of nutrient
production, a set of carefully laid out assumptions must be listed.
2.1.3.1 Assumptions
For existing commodity products, industry continually strives to maximize profits by reducing
production costs and increase production capacity. On a technological level this is obtained
through maximizing material utilization and energy efficiency. Exploiting cheap labour forces of
impoverished regions (like Poland) is another method to reduce production costs, but usually
does not reflect the newest technological practices. The best available techniques (BAT) found in
the industrial affluent regions (like Germany) reflect the newest technological practices. In 1999,
the European Fertilizer Manufacturers Association (EFMA) had prepared an 8 booklet series
outlining the BAT within the EU fertilizer industry. The IFA has also summarized the processes
in a more compact booklet4. Although they both have focused on conforming to the EU
Directive on integrated pollution prevention and control (IPPC Directive), they describe with
great detail several production options. The EFMA books highlight the industries most widely
used, accepted and technically feasible BAT production routes. Within the described processes
those that achieve the lowest possible material use and energy use will be selected. Thus the
following calculations will represent the highest energy efficiency within the BAT; that is the
European BAT. Therefore the energy/mass balance results will be quite different from world
average estimates, developed world average estimates and even BAT average estimates.
1. Highest energy efficient processes within the EU best available technology from 1999
As briefly mentioned before, there are many different fertilizers, for each region has its own
specific preferences. To conform with the purpose of primarily validating Dutch and European

biochemical production, the common fertilizer forms for those markets will be chosen. The
artificial complex fertilizer, NPK, which can be manufactured to contain all nutrients, is very
popular in Europe. In contrast straight nitrogen fertilizers, primarily urea is a widely used
fertilizer in the developing world in place of the nitrogen component in NPK. CAN, calcium
ammonium nitrite, on the other hand, is a derivative of both AN (ammonium nitrate) and NPK
that is extensively applied on European soils but barely makes it to the developing worlds fields.
2. NPK and CAN are the main artificial fertilizers of interest
NPK and CAN are, however, by far not the only artificial fertilizers on the European market.
The following process flow diagram illustrates the main production route for the most popular
forms of European fertilizers. Those appearing in bold are commonly applied as separate
fertilizers. Yet, they are all linked to the final production of NPK and CAN.
3. The NPK and CAN production route also produces individual fertilizers of interest
Natural Gas
Water
Air
Dolomite
Ammonia
Potash
W ater
Water
Air Micronutri ents
Air
Nitric Acid NPK Sulphuric Acid Sulphur
Hyd ro gen Sul phide

Air
Urea (Super Phosphorous)

(CAN)
Ammonium Phosphoric Acid
Calcium
Nitrate Ammonium W ater
Nitrate
(UAN) Phosphate
Urea Rock
Ammonium
Nitrate
Figure 1 Simplified Artificial Fertilizer Process Flow Diagram
Europe is by all means not autonomous. In regard to the above process flow diagram (Figure 1)
not all of the production routes can be and/or are located in Europe. As an example, potash used
to be big business in Europe, now mines are being phased out. In France the last mines have
already been shut down and plans are underway for the remaining mines in Germany5. In these
cases, the areas with the largest worldwide production and reserves will be chosen. To continue
with the example of potash, that implies Saskatchewan, Canada. Even when selecting a logical
region, there can be a multitude of production options. The first assumption will be extended to
these situations when applicable.
4. When little or no EU production is present then the highest energy efficient processes within the largest area
of world production and reserves will be taken instead

Many of the individual production steps contained within the entire fertilizer industry produce
off-streams (such as heat, steam, electricity, various materials, etc.). In several cases those off-
streams are identical to the input requirements of other production steps. Frequently large
production facilities are constructed manufacturing a multitude of different fertilizers, which are
primarily designed to integrate the off-streams; basically maximizing the material and energy
efficiency. In other occasions, isolated plants do not have this integration. In terms of the
following calculations it will be assumed that the whole production process could be interlinked:
5. Complete energy and material integration is possible
CAN is definitely not the cheapest way to apply the calcium nutrient to the soil. Applying straight
lime is far less expensive and energy intensive, contradicting assumption #1. It is only according
to assumption #2 and now #5 that the CAN production process has such an emphasis. The
production of NPK produces large excess amounts of calcium carbonate. CaCO 3 is the main
input for CAN.
6. When NPK is produced, CAN must be produced

2.2 Nitrogen
2.2.1 Brief Description and Nutrient Importance

Air is all around us and 78.084 volume percent of it is nitrogen. With this vast abundance one
could be lead to believe that nitrogen poses no problems. Atmospheric nitrogen is present in its
diatomic virgin gas form N2, yet only the functionalised forms of nitrogen, such as
hydrides and oxides, can be utilized in the biosphere. Nitrogen gas is considered
inert, so inert that Antoine Lavoiser referred to it as azote (without life). This
inactive reactivity is due to the very high bonding energy between the triple
covalent bond, N≡N = 945.33±0.59 kJ/mol. To transform nitrogen gas into its
biosphere constituents, energy levels exceeding the triple bond enthalpy must be induced to
support functionalization. Nitrogen is indeed in abundance in the atmosphere, but is not readily
available for use in the biosphere. And the problem of availability is strictly determined by energy
accessibility.
There is a naturally occurring mineral nitrate (a functionalized nitrogen

compound) source, potassium nitrate KNO 3 or better known as
saltpetre. Solid combustion will trigger the release of a large bonding
energy, for saltpetre 495 kJ/mol. This high energetic value is primarily
attributed to the functionalised nitrogen component. Saltpetre is a natural
explosive and the understanding of its thermodynamics eventually
blasted way for the synthesis of other nitrogen based chemicals. Quite literally, nitro-glycerine
and trinitrotoluene (TNT) was the dynamite that became the nitrogen-based explosive. TNT has a
heat of explosion of 616.4 kJ/mol.
Although diatomic nitrogen is labelled azote and nitrogen explosives can destroy life, nitrogen is
not only essential but also vital to all forms of life. It is the most important nutrient determining
plant growth and yield. Soils containing low levels of nitrogen are called infertile; this is not the
case with the other nutrients. Nitrogen plays such a key role because amino acids, proteins,
enzymes, chlorophyll and genetic material all contain nitrogen as a functional element. Basically
all metabolic systems are indirectly dependent and limited by nitrogen quantity. For plant uptake
and usage, at some stage diatomic nitrogen must be converted into a functionalised form. Nitrate
and ammonium are the preferred nutrient forms for root uptake. The process by which
atmospheric nitrogen gas is converted into ammonia is called nitrogen fixation. Breaking the
triple covalent bond and reacting it with a hydrogen source (water) is very energy intensive and
proves to be a major limiting factor in plant growth.
Nature is capable of fixing nitrogen in several different ways. The least common, but most
impressive in terms of shear energy intensity, is lightning. Each striking flash wields incredible
temperatures and pressures on the soil and is capable of fixing 0.14kgN on average. During

sunny days the intensity of the solar rays is also able to initiate photochemical reactions on the
topsoil. Combined they represent nearly 10% of naturally fixed nitrogen nutrients1. Many
different forms of bacteria present in the soil are able to fix nitrogen. Their source of energy is
loose organic material present in the soil; they can convert annually 2 kgN/ha. During periods of
abscission, leafs and other remaining foliage supply a recycling of nutrients for following years.
Without external nitrogen nutrient supply, the levels of further growth/yield is limited to the
small amounts of fixed nitrogen added to the soil.
There is another form of natural nitrogen fixation, a true symbiosis. Legumes are a group of plant
species, which can form a symbiotic relationship with the Rhizobium bacteria strain. As illustrated
on the adjacent photo, small nodules are formed on the roots. Most
plants store simple carbohydrates as access energy for reproduction and
transport them within their xylem vessels. The bacteria strains intercept
this source of energy to fix atmospheric nitrogen. It is a trade off for the
plant: carbon-based material (energy) for nitrogen-based material
(nutrients). Legumes will always have a relatively low overall yield as
large amounts of the simple carbohydrates were leached from the
bacteria. However, legumes are generally very high in protein content
and concentration as high levels of ammonia are present for the plant. A
clover, for example, can sustain an average uptake of 200 kgN annually6. This is a striking
contrast to natures other levels of nitrogen fixation.
Nature is able to supply itself with a certain quantity of nitrogen nutrients, but the amount
represents a mere fraction of modern fertilizer application rates. Legumes are appealing because
they reduce the need for external nitrogenous fertilizer applications, yet even under the best
growth conditions their natural fixation is insufficient to obtain good yields. Quite simply
nitrogen-based fertilizers have the largest immediate effect on crop growth, yield and quality.
This fact is best portrayed using world figures:
Worldwide (2001)7: Industrial fixation = 165Mton
Biological fixation = 100-140Mton
Today, crops obtain a larger proportion of their nitrogen-based nutrients through external
synthetic routes than natural.

Maximum Yield
Yield [t/ha]
Nitrogen Fertilizer Application Rate [kgN/ha]
Figure 2 Yield vs. Nitrogen Fertilizer Application Rates Trend
There is a near linear proportional yield gain due to nitrogen fertilizer applications rates.
However, the yield increases will eventually reach a maximum, the highest genetically and
environmentally possible yield. Beyond that it has been noticed that negative trends can occur.
This is most apparent with the potato, where the above graphic (Figure 2) is a reality.
The discovery of the quick and effective benefits exponentially propelled the nitrogenous
fertilizer production. The developing worlds are continually increasing their share of production,
whereas the EU (Western Europe) is capping application rates. This is noticeable in the levelling
off the growth trend in World production and the decreasing/flattening trend of the Western
European production, as seen in Figure 3.
100
Wes t Europe W orld 2000's
Growth stabilization
1970's
75 Large-scale natural gas reformers
1960's
Total [MtN]
Single-line plants
50
1920
1840's First ammonia reformer
Beginning of guano
and nitrate s hipm ents
25
0
1840 1860 1880 1900 1920 1940 1960 1980 2000
Year
Figure 3 Nitrogen Fertilizer Production Rates and Major Developments

Source of Data: EMFA & IFA

There are several motivations for the decrease in applications rates in Europe. Firstly, Europe is a
completely developed continent meaning food production is stabilizing, arable land allocation is
more or less set and population growth is minimal. These factors in combination with the above-
mentioned trend (Figure 2) associating nitrogen application rates have yielded an optimal
nitrogenous fertilizer usage. This however, should result in a very slight increase and not a
decreasing trend. Environmental considerations from the last several decades have resulted in a
set of strict regulations. Around 30% of global N2O emissions are from agriculture; this is
equivalent to 6% total greenhouse gases. That is a clear example of environmental pollution, but
does not influence the regulation decisions. Administering too much nitrogenous fertilizer results
in a disproportional increase of leached nitrates, which can spread to ground water and rivers (see
Chapter 6). These levels are controlled. Ground leaching has been partly remedied by the
development of better forms of nitrogen fertilizers. An additional advantage of the newer forms
of fertilizers is also a more affective uptake by the crops. Along with better farming techniques in
the sense of application timing and location a capping/decreasing trend is understandable.
Nevertheless nitrogenous fertilizers will remain the largest produced, administered and influential
nutrient for as long as it is conceivable to do so.
2.2.2 Process Choice and Description

European farmers have a full range and access to fertilizers. The distribution is relatively even
whereas, in sharp contrast, the developing world focuses mainly on urea. This is attributed to the
extreme variance of soil types, climate conditions, crop specific preferences and superior farming
techniques of Europe. The following pie chart (Figure 4) indicates the types and distribution of
the various nitrogenous fertilizers7.
Other Complex
3%
NPK/NP/NK CAN
21% 26%
Other Straight
6%
UAN
AN
10%
22%
Urea
12%
Figure 4 Western European Nitrogen Fertilizer Distribution, 1997

All of the principle production routes will be described herein. CAN is considered a nitrogenous
fertilizer, yet it will be not mentioned until the calcium section (see Section 2.6). An entire section
will be devoted to NPK and CAN’s (see Section 2.8).
2.2.2.1 Ammonia
Every single nitrogenous fertilizer is based on ammonia. The amount of
energy and fuel (feedstock) required to produce ammonia will
consequently result in the overall energy requirements of the downstream
fertilizers. The discovery of the Haber-Bosch steam reforming process
was a great leap in reducing the energy demand. Compared to the electric arc furnace, which had
an energy consumption of 800MJ/kgN, the initial steam reformer at 100MJ/kgN was a major
improvement. Since then the Haber-Bosch process has been further improved. Figure 5
illustrates the trend of energy reduction8:
Ammonia Producti on
Haber-B osch Proces s
100
Energy Consumtion [MJ/kg]
75
50
25 MJ/kg NH 3
Thoeret ical Minimum
25
1910 1935 1960 1985 2010
Timeline [year]
Figure 5 Energy Consumption for Ammonia Production
The average European energy consumption in 2004 for ammonia was 28.8-31.5MJ/kg NH3,
depending on the feedstock. The theoretically minimum specific energy demand or specific
energy consumption (SEC) of ammonia production is 24.1 GJ/ton N (or 24.8MJ/kg NH3).
Current technology is approaching SEC values meaning any new improvements will have only a
minor effect on the overall energy demand. The BAT outlined herein comes also very close to
SEC values.
Process Choice & Argumentation9

There are several feedstock and processing options; steam reforming light hydrocarbons
(naphtha, natural gas, liquefied petroleum) and partial oxidation of heavy fuel oil and coal. The
most energy efficient is the steam reforming of light hydrocarbons and especially natural gas.

85% of the world ammonia production is based on light hydrocarbon reforming and 90.5% of
that is based on natural gas, so the feedstock choice is easy:
Natural Gas Feedstock
There are three major types of reforming when dealing with natural gas: conventional reforming,
excess air reforming and autothermal reforming. The feedstock requirements are higher for the
excess air and autothermal reforming than for the conventional, yet the reverse is true for the
energy demands. The excess air reformer incorporates a much more efficient second stage
integration. Since only 30-40% of the feed is converted in the primary reformer, this makes for a
significant improvement. The autothermal goes even further, having the absolute best heat
integration. The difference in saved heating value is larger then the increase in feedstock
demands. The autothermal is also the most recently developed reforming system:
Autothermal Reformer Process
Process Results
For transparency the following table lists the major streams only, the material and energy streams.
Minor waste streams and process related streams have been left out intentionally. However, the
minor (trace and waste) streams were also taken in consideration for the final calculations. Refer
to the accompanying database spreadsheets for more detailed in/out flows and the calclations.
Table 1 Ammonia processing figures
Component Symbol Use Quantity Unit Exergy Content

24.8 GJ 26.04GJ/ton
Natural Gas CH4 Carbon Source
(0.607) (ton)
3.6 GJ 3.78GJ/ton
Input Natural Gas CH4 Energy Source
(0.088) (ton)
Water H2O Hydrogen Source 0.700 ton 0.04GJ/ton
Air N2 Nitrogen Source 1.650 ton 0.03GJ/ton
Ammonia NH3 Intermediate 1 ton 19.84GJ/ton
Output
Carbon Dioxid e CO2 Intermediate 1.290 ton 0.58GJ/ton
It can be seen that the material (feedstock) use of natural gas greatly exceeds that of the energy
(fuel) requirements. Yet, because natural gas is a primary energy source, values are better left
expressed in energetic terms:
Total process energy: 28.4 GJ/ton NH3
Exery Input: 29.96GJ/tonNH3
Exery Output: 20.42GJ/tonNH3
Exergetic efficiency: 68.2%
The large amounts of carbon dioxide are used in connected downstream processes (urea and
NPK) and not simply vented into the atmosphere. Justifying the inclusion of the exergetic value
as an output, for typically the waste and side streams are not included as an output, i.e. losses.

2.2.2.2 Nitric Acid
Manufacturing of synthetic ammonia is only half the story behind the
industries mass-producing artificial fertilizers and explosives; nitric acid is
the second half. Also discovered and invented by a German, in 1917
Wilhelm Ostwald had designed the industrial process for manufacturing
nitric acid that would later be named after him, the Ostwald process. Nitric
acid is a strong organic acid. It is useful as an oxidizing agent to yield
nitrates (fertilizers and explosives), digestion of mineral ores (in particular those associated to the
complex fertilizer NPK) and for other industrial organic chemical production (adipic acid). A
nitric acid plant is frequently coupled directly with an ammonia plant, partly because being in
liquid form at room temperature saves on storage and transportation facilities. Those coupled to
fertilizer bound ammonia production plants produce a low concentration of nitric acid, a weak
acid ranging from 30-70% weight. Nitric acid applications in other industries require higher
concentrations (above 70wt%) and thus necessitate additional production steps. These steps will
not be mentioned in this chapter, as they are not related to the fertilizer industry. All following
processes involving nitric acid are based on the 65wt% final product. The BAT outlined herein is
typical of a new 65wt% nitric acid production plant.

The Ostwald process is a rather simple two-step oxidation process. By reacting ammonia with air,
nitric oxide is created. A further oxidation reaction will yield nitrogen dioxide and when absorbed
in water a solution of nitric acid is obtained. The efficiencies of the two steps are however
favoured by contradicting pressures; the first (oxidation) prefers low pressure (below 1.7 bar)
whilst the second (absorption) high (above 13 bar). This had allowed for a variation of pressure
combinations within two main classifications, dual pressure and single pressure plants (original
Ostwald process). Better process control and design has made the single pressure system
obsolete. All new plants are built following the dual pressure system.
Dual pressure process
There are two dual pressure configurations, low/medium and medium/high pressure. The latter
has the disadvantage that the nitric oxide yield is 1% lower, from 97 to 96%, yet has the
advantage that the secondary reaction at high pressure is greatly favoured. Since additional
material, air and water, have been added to the second reaction stream, slight yield gains and
better energy integration in the second stage outweighs the yield loss of the first reaction. This is
in addition to the fact that the most recent plants are all based on the medium/high pressure
configuration.
Medium/high pressure
Process Results
Just as with ammonia, minor waste streams and process related streams have been left out
intentionally. The following table corresponds to a nitric acid concentration of 65wt%.

Table 2 Nitric acid processing figures

Ammonia NH3 Oxidation 0.277 ton 5.50GJ/ton
Air O2 Oxygen Source 1.324 ton 0.16GJ/ton
Input
Water H2O Dilution to 65% 0.536 ton 0.01GJ/ton
Output Nitric Acid HNO3 Intermediate 1 ton 0.69GJ/ton
A modern nitric acid plant is essential energy neutral. The excess heat created by the exothermic
reactions is used to generate steam and drive gas turbines necessary to cover the compressor and
electrical pump duties. Conversely oxidizing ammonia greatly degrades the exergy content.
Total process energy: neutral
Exery Input: 5.87GJ/tonNNO3
Exery Output: 0.69GJ/tonNNO3
2.2.2.3 Ammonium Nitrate

AN is a high-nitrogen, high-oxidative derivative of both ammonia and
nitric acid. It is primarily used as a fertilizer (in its virgin state and as
an intermediate), yet due to the high-energy bonds it is also commonly
connected with the explosives industry. In order to alleviate the need
for farmers to undertake a course in explosives handling, the final
manufacturing process of the two main applications are different. Fertilizer-grade ammonium
nitrate (FGAN) is in a compact form with a low porosity, in order to achieve more stability and
less sensitivity to detonation. On the other hand technical grade ammonium nitrate (TGAN)
granules are louse and porous for better absorption of fuel and exert high reactivity. This
difference does not completely prevent the explosive nature of FGAN, for as recently as
September 21st, 2001 a fertilizer factory in Toulouse, France, was the centre of a disastrous
spectacle11. The huge explosion has been attributed to a warehouse storing large quantities of off-
specification granular AN. Even though it seems apparent that large amounts of energy are
released from the molecule the production, on the contrary, is exothermic. The BAT outlined
herein is typical for a modern AN production plant left in its melt form to be used as an
intermediate:

The exact process route of manufacturing ammonium nitrate is undefined as there are many
explicit end-product specifications. Considerations for production layout are thus greatly
influenced by the final product choice. As ammonium nitrate can be used as an intermediate or
as a final product, this option will have the biggest influence on processing design. As described
in the assumptions section (see Section 2.1.3.1) those final products highlighted in bold will be
used to calculating final production requirements. AN is thus an intermediate, as is urea, to
produce UAN. Both urea and AN when used as virgin fertilizers are converted into their solid

constituents typically through a granulation or less commonly prilling step. This adds a significant
amount of extra process energy, primary by the air circulation fan. There are two possible
feedstock states for UAN manufacturing, solid and liquid, so by leaving AN and urea in their
respective melt/liquid state a great deal of process energy is saved.
Solidification processing is not included
The first step of the process is neutralization and in Europe alone there are at least 10 different
configurations. By inducing an elevated pressure, the resulting steam is at a higher temperature
and can fully cover the steam requirements of the subsequent evaporation stage while producing
a sizeable amount of low-pressure steam for export.
High-pressure neutralization with excess steam production
Since the process information listed in the EFMA booklets includes the solidification options
another source was taken. The ThyssenKrupp Uhde process data for the above mentioned route
was taken instead as it lists the steps leading up to solidification13.
Uhde specific process
Process Results
Table 3 lists only the major streams.
Table 3 Ammonium nitrate (AN) processing figures

Ammonia NH3 Oxidation 0.213 ton 4.23GJ/ton
Nitric Acid (65%) HNO3 Redu ction 1.700 ton 1.17GJ/ton
0.052 ton
Input Steam (10bar) H2O Heating/Synth esis 0.04GJ/ton
(0.179) (GJ)
4.8 kWh
Electricity kWh Utilities 0.02GJ/ton
(0.017) (GJ)
Output Ammonium Nitrate NH4NO3 Intermediate 1 ton 3.68GJ/ton
0.240 ton
Steam (4.5bar) H2O Power/Heat 0.17GJ/ton
(0.770) (GJ)
Water H2O Excess 0.911 ton 0.05GJ/ton
The excess water can be integrated in other processes so is not a waste stream
Since the solidification step is not included the overall energy requirements are negative, meaning
an excess of energy has been produced. The neutralisation step is in fact an exothermic reaction,
yet normally the high solidification energy requirements shadow this gain in steam. The electrical
utilities demand is relatively low because the generated low-pressure steam is integrated in the
down-stream steps; the excess is (or could be) exported.
Total process energy: -0.574GJ/ton NH4NO3
Exery Input: 5.48GJ/tonNH4NO3
Exery Output: 3.90GJ/tonNH4NO3

2.2.2.4 Urea
Chemicals found in the excreted liquid streams of vagrant drunken
individuals are known to decimate public buildings, in particular stone
churches. Yet, when the same waste streams are introduced into the
biosphere, positive affects can be observed such as accelerated plant
growth. The key to this phenomenon is the word urine. The liver
produces urea and supplies the kidneys with this metabolic agent necessary to flush waste
molecules from the body. This high concentration of urea is the origin of the word urine.
Perhaps trees will once again become the main outdoor urinal facilities? In fact probably not, as
many other waste products are contained alongside urea, which may have detrimental effects on
plant life. Pure urea, however, is currently the world’s most popular form of nitrogenous
fertilizer. The methods and materials have changed a lot since the German chemist Friedrich
Wöhler first synthesized urea from inorganic molecules in 1828. That discovery is even attributed
to launching the separate discipline of organic chemistry and today the materials used for the
synthesis are even organic. In reality urea is simply a further reaction step added to the existing
ammonia production. The ammonia by-product carbon dioxide is reintroduced to the system to
yield ammonium carbonate, which is subsequently dewatered to form urea. Market deliverable
urea is sold in its solid concentrated form, which (in the case of urea) is much more affective at
providing nutrients and has less associated leaching problems than the natural liquid product.
However, as mentioned above, urea will be left in its liquid form to be used as an intermediate in
the UAN production. The BAT outlined herein is typical for a modern urea production plant left
in its melt form:

Producing ammonium carbonate is an exothermic reaction, which goes to completion. The
following endothermic dewatering reaction is slow and does not go to completion. The
conversion rate is in the order of 50-80%. Increasing the material utilization stream requires a
recycling stream. What started as a partial recycle system has, through a network of loops,
become a total recycle process. The first option of processing is the choice of stripping agent,
ammonia or carbon dioxide. Of the four available layouts, the two newer and most energy
efficient processes utilize carbon dioxide as a stripping agent.
CO2 as stripping agent
The carbon dioxide stripping process has been further improved, implementing the maximum
amount of material and energy utilization to the point of classifying it as a separate production
layout. The advanced cost & energy (ACES) process employs a serious of strippers and
condensers to minimize the steam and electrical requirements.
ACES process
As with the AN production, the solidification step is not present, leaving the solution in its melt
form, saving on energy requirements.
Solidification processing is not included

Process Results
Table 4 Urea processing figures

Ammonia NH3 Nitrogen Source 0.570 ton 11.3GJ/ton
Carbon Dioxid e CO2 Carbon Source 0.740 ton 0.33GJ/ton
Input 0.700 ton
Steam (98bar) H2O Heating/Synth esis 0.74GJ/ton
(2.905) (GJ)
Electricity kWh Utilities 0.108 GJ 0.11GJ/ton
Output Urea CO(NH2)2 Intermediate 1 ton 11.5GJ/ton
These calculations are based on a 99.7% pure melt concentration of urea, which is quite typical
for a modern plant. Large quantities of low-pressure steam are released from the primary reactor
and are integrated in the secondary dewatering process with no excess. The exergy efficiency is
quite high since synthesis steam has a very low exergy content.
Total process energy: 3.01 GJ/ton CO(NH2)2
Exery Input: 12.5GJ/tonNH4NO3
Exery Output: 11.5GJ/tonNH4NO3
2.2.2.5 Urea Ammonium Nitrate

UAN: Liquid (or solution) fertilizers are rapidly increasing in popularity and with it
their production capabilities. They are particularity common in North
-CO(NH2)2
America, while they currently represent only 12% of the European market7.
-NO3
-NH4 Several various types of liquid nitrogenous fertilizers exist on the market, yet
UAN dominate the sector; arguably applying an analogous connotation for
UAN with solution fertilizers. There are several strong advantages of utilizing solution-based
fertilizers over their solid-based counterpart that have prompted the production increase of
UAN. Urea ammonium nitrate comprises of just that; urea, ammonium and nitrate. Each has a
unique time specific release and uptake time period, giving the fertilizer a unique 3-phase nutrient
release property. This is very attractive for an effective nutrient management and soil/nutrient
efficiency (see Chapter 6). Being in the liquid state also allows a more uniform field distribution,
should it be separately dosed. However, it is commonly fed directly into the water supply (like
sprinkler systems and irrigation cannels) reducing the associated application costs plus adding
other side benefits (also see Chapter 6). On the manufacturing side, there is the even greater
advantage of negating the need for the energy intensive solidifying process. This is even
circumvented three times over as urea and AN are both left in their liquid melt state for UAN
intermediate handling. Liquid UAN has been chosen as the straight nitrogen fertilizer for excess
nitrogen supply simply because it has the lowest energetic production and it is foreseeable that it
will represent a larger share on the European market in the near future. The BAT outlined herein
is typical for a coupled UAN production plant:

Combining urea and ammonium nitrate together with water in a vessel will result in an aqueous
solution. Reaction heating energy is not necessary. The amount of water supplied determines the
overall nitrogen content of the UAN-solution and varies from production site. For instance in
Canada 28%N is typical, America prefers 32%N, where in Europe 30%N is more common.
Process data for 30%N
Many production sites for UAN are based on the solid feedstocks. This method requires an
additional steam-dissolving step and necessitates a batch reactor set-up. By focusing on the liquid
feedstocks the process is not only continuous but requires no addition of steam.
Liquid feedstocks
Process Results
Table 5 Urea-ammonium nitrate (UAN) processing figures

Urea CO(NH2)2 Nitrogen Source 0.328 ton 3.77GJ/ton
Ammonium Nitrate NH4NO3 Nitrogen Source 0.426 ton 1.57GJ/ton
Input Water H2O Dilution 0.245 ton 0.01GJ/ton
10 kWh
(0.036) (GJ)
Output Urea-Ammonium Nitrate UAN Fertilizer 1 ton 5.35GJ/ton
These calculations are based on a 30%N concentration of UAN, which is quite typical for a
modern European plant. The process is a straightforward mixing procedure requiring only the
relatively low associated electrical utilities.
Total process energy: 0.036 GJ/ton UAN
Exery Input: 5.39GJ/tonUAN
Exery Output: 5.35GJ/tonUAN
2.2.3 Energetic Result

Presenting the input in terms of process specific energy demands can be slightly ambiguous, as
they must be coupled with the previous energy requirements of the relative feedstock. The typical
production route for steam and electricity originating from fossil fuels (as specified in Chapter 2)
are included to calculate their cumulative values. By incorporating the feedstock specific demands
the cumulative input is calculated. Furthermore, relating the specific compound with the nitrogen
content presents a clear indication of the actual energy requirements for the nutrient.

Natural Gas
Wa te r
Air
Ener gy: 2 8.4GJ/ton
Ammonia
0.27 7 ton
Water
Ai r
Energy: 0GJ/ton
0.57 0 ton Nitric Acid

0 .7 89 ton
Ener gy: 3 .0 1GJ/ton
0.213 ton
Urea
Water 0.32 8 ton Ammonium
Ener gy: 0 .0 4GJ/ton Nitrate
(UAN) Energy: 0.57GJ /ton
0.426 ton
Urea
Ammonium
Nitrate
Figure 6 Nitrogenous fertilizer simplified mass/energy balance flow diagram
Listed in Table 6 are the conversion factors of the nutrient content in the fertilizers
Table 6 Nutrient Conversion Factors in w/w
The nutrient conversion NH3 N 0.822 N NH 3 1.216 factors are based on the
ratio between the core elements in the molecule.
For example:
HNO3 N 0.222 N HNO3 4.499
H3PO 4 P2O 5 (P is the HNO3 (65%) N 0.145 N HNO3 (65%) 6.921 core element)
H3PO 4 = 3⋅1.00974 + NH4NO3 N 0.350 N NH 4NO3 2.857 1⋅30.97376 + 4⋅15.9994 =
97.99518 (31.61%P) CO(NH2)2 N 0.466 N CO(NH2)2 2.144
P2O 5: 2⋅30.97376 + UAN N 0.300 N UAN 3.333 5⋅15.9994 = 141.9445
(43.64%P)
H3PO 4/P2O 5: S SO3 2.497 SO3 S 0.401 31.61%P/43.64%P =
0.724 H2SO4 SO3 0.816 SO3 H2SO4 1.225
P2O 5/H3PO 4: H2SO4 (78%) SO3 0.636 SO3 H2SO4 (78%) 1.571 43.64%P/31.61%P =
1.381
P P2O5 2.291 P2O5 P 0.436
Ca3(PO4)2 P2O5 0.458 P2O5 Ca3(PO4)2 2.185
H3PO4 P2 O5 0.724 P2O5 H3PO4 1.381
H3PO4 (52%) P2 O5 0.376 P2O5 H3PO4 (52%) 2.656
KCl K 2O 0.631 K2O KCl 1.583
CaCO3 CaO 0.400 CaO CaCO3 2.497
MgCO3 MgO 0.321 MgO MgCO3 3.118

Table 7 Resulting energy requirements for nitrogenous fertilizers
Pro cess Energy Cumulative Energy Nitrogen Content Relative Nutrient Energy
Compound
GJ/ton GJ/ton % GJ/tonN
Ammonia 28.4 28.4 82.2 34.5
Nitric Acid (65%) 0 7.9 14.5 54.5
Ammonium Nitrate
-0.57 19.1 35.0 54.6
(melt)*
Urea
3.01 19.8 46.6 42.5
(melt)*
Urea-Ammonium
0.04 14.7 30.0 49.0
Nitrate
*The results are not representative of the direct fertilizer application as those production processes were left in liquid phase for use as
intermediates. For direct fertilizer use a granulation/prilling process is necessary which requires 25-60kWh electricity and ~50kg steam extra.
Table 8 Resulting exergy requirements for nitrogenous fertilizers
Input Exergy Cumulative Exergy Nitrogen Content Relative Nutrient Exergy

Compound
GJ/ton GJ/ton % GJ/tonN
Ammonia 29.96 30.0 82.2 36.5
Nitric Acid 5.87 8.7 14.5 60.0
Ammonium Nitrate
5.48 21.1 35.0 60.3
(melt)*
Urea
12.5 18.9 46.6 40.6
(melt)*
Urea-Ammonium
5.39 15.3 30.0 50.2
Nitrate
As mentioned these figures represent the most energy efficient choice amongst the best available
technology (BAT) in Europe as of 2002. They are in significantly lower then the commonly
available technology of America from 1982 15. For example, ammonia is listed as 55GJ/tonN or
33.6% more energy intensive. Seeing that ammonia is the base of all subsequent nitrogenous
fertilizers, the rest will approach similar differences. Urea presents the largest variance being
listed at 70GJ/tonN or 42% more energy intensive. A select choice within the most recent BAT
figures can provide a better indication of the energy requirements for the near future.

2.3 Sulphur

Sulphur is the 13 th most abundant element in the
In proper British English (as in the rest of
the commonwealth) the element S is spelt earth’s crust and it is possible to find native sulphur in
S-U-L-P-H-U-R, whereas American its pure elemental form as well as in its simple oxidized
English has opted for S-U-L-F-U-R.
In 1990 the IUPAC announced that it has forms like sulphite and sulphate. These sources are
jurisdiction over the English language and however very scarce or isolated to potentially
adopted the spelling “sulfur” to be the
international norm. However, the IFA and hazardous regions. Investing in extraction practices
EFMA both continue to use the British along side an active volcano may not go over well with
spelling.
As the context of this report is towards workers and deep mine exploration may proof to
fertilizer production “sulphur” will be used. cause a heated affair with unions. In fact, sulphur has
long been associated with volcanic activity and was
first referred to as brimstone, or as “the fuel of hell” in biblical terms. Yet sulphur is not a
scarcity but a commodity, meaning human capabilities are not pushed to the limit.
There are indeed a variety of sulphur sources, all of which share one common attribute; sulphur
is considered as the by-product and occasionally even as the waste stream. This is how abundant
sulphur is. Natural sulphides are most commonly contained in metal ores and are regarded as an
impurity in metal production. Iron ore in particular has a high concentration of sulphur in the
range of 28-32% and is sometimes referred to as sulphur ore. Iron disulfide, FeS2, is called pyrite,
the so-called fool's gold. Striking pyrites upon steel will release a spark and explains why the
Greek word for fire was taken for the ore. Sulphur therefore contains an oxidizing potential
which when combusted can release heat and light (energy). 592,2 kJ/mol is released when
burning pure solid sulphur, which is close to TNT. Sulphur is a key component of gunpowder
and fireworks.
Combusting sulphur for energy production is a very undesirable process as the resulting SO x is
responsible for photochemical smog and acid rain. Besides, sulphur has a vast diversity of
industrial applications and derivatives meaning burning it would make no economical sense.
Fossil fuels also contain large quantities of sulphur, yet
unlike their mineral ore counterparts are present as
hydrogen sulphide. In the last 30 years great lengths have
gone into processes to reduce the sulphur content of
fossil fuels and the SO x of exhaust gases. Transport fuels
above all, employ modern absorption technology to
remove large levels of H2S. Several government bodies
have introduced clean air policies to further reduce the
sulphur content. European Union environmental
regulations are especially stringent having reduced the Shell-Vol ks wagen Trans port F uel Development Predicti on

sulphur content from more than 3000ppm before 1996 to 50ppm by 2005 and are granting
financial incentives to promote a reduction below 10ppm. Certain EU countries are already
transitioning towards the 10ppm limit. The above graph estimates that in less than 10 years all
transport fuels will contain less than 10ppm sulphur. This has two major consequences.
There are three ways in which crop life can utilize sulphur as a nutrient. First, the weathering of
metallic ores will wash sulphate anion (SO 4-2) in the soil. This form is free (or mobile) in the soil
and is very susceptible to leaching. The second and third are from the atmosphere with different
mechanisms and represent the vast majority. Leaves are able to directly absorb SO 2 from the air
and the roots are able to directly absorb the SO 3 constituent from acid rain. These sources are
directly related to the emissions of industry and the transport sector. Until relatively recent times,
agricultural soils have received sufficient sulphur from the deposition in air and rain from such
sources. Now due to the reduction in SOx emissions, sulphur deficiencies are becoming apparent
for the first time since the industrial revolution16. Plus the shift away from ammonia-sulphate
fertilizers towards other nitrogenous fertilizers is also contributing to lower sulphur levels.
Previously little attention was paid to the issue of sulphur; it was free, abundant and in the air.
The first consequence of the sulphur politics in fossil fuels is becoming visible and attention has
been directed towards the effects exerted by sulphur on plant life. It is essential for enzyme and
vitamin production, nodule growth in legumes and for chlorophyll formation. Three amino acids
(cystine, cysteine and methionine) also contain sulphur. As mentioned above sulfates are mobile
and prone to heavy losses though volatization, immobilization and leaching (mentioned further
in Chapter 6). Despite this, natural sulphur deficiencies are mainly isolated to dry sands. Artificial
sulphur nutrient application rates already represent roughly 10% that of the nitrogenous
fertilizers. It is already being considered as the 4 th macronutrient and regarded as a primary
nutrient even though it is a secondary nutrient17. This fact is best portrayed using world figures:
Worldwide (2002)7: Total production = 59Mton
Phosphoric acid production (e.g. NPK) = 27Mton
Sulphur containing fertilizers = 10Mton
Worldwide sulphur reserves are very plentiful and even the economically feasible reserves are
abundant. And as policies regarding the sulphur concentrations in fossil fuels further push the
envelope, even more sulphur will become available. Desulphurisation implementation for crude
oil and natural gas are already so common that only about 5% of elemental sulphur is harnessed
from mining operations18. There is so much sulphur being removed from these fossil fuel sources
that sulphur production is exceeding the demand and is for a large part heavily stockpiled. This is
supplying the sulphur industry. So, the second consequence of the sulphur politics is that prices
are cheap but unstable and start to further spread the notion that sulphur is exceedingly cheap or
even a free resource.

However, it is incorrect to consider the sulphur content of crude oil or natural gas as energy free.
When left in the fuel it would have (although reduced the energetic density) increased the overall
calorific value. Isolating hydrogen sulphide for combustion will release a large quantity of energy.
The overall heat of combustion for hydrogen sulphide is 33.0GJ/ton19. In the article “energetic
and exergetic life cycle analysis to explain the hidden costs of current sulphur utilisation” the
feedstock cost of sulphur was systematically investigated, calculated and assigned: 25.2GJ/ton
energy and 20.9GJ/ton exergy20. This presents large influence on the remaining fertilizers.

Sulphur itself is can be used as a virgin fertilizer when prilled but is primarily altered to a sulphate
(SO 3) to be taken up by the root systems of crops. Sulphuric acid (H2SO 3) is the preferred form.
The majority of the sulphuric acid in the fertilizer industry is used to decompose phosphorous
rock, which when incorporated in the NPK production also yields sulphur nutrients. The
production of sulphuric acid will be based on the liquid sulphur from fossil fuel desulphurisation
and used as a virgin fertilizer and as an intermediate and dissolving agent for NPK production.
2.3.2.1 Hydrogen Sulphide - Sulphur

Today, 98% of the worlds sulphur production is supplied by recovery
methods and are for a large part associated with fossil fuel desulphurisation21.
Of which 25% of worldwide elemental sulphur originates from the
desulphurisation of fossil fuels. It is even more than 63% of the U.S. (1989)
and 38.6% of the EU30 (2002) production21. Although by-products from metallic ores still
constitute the single largest source of sulphur production, its market share is falling, as recovered
sulphur from fossil fuels is continuing to rise. Natural gas can contain up to 28% (volume) of
H2S and must be removed before consumption (theoretically an ammonia plant could be coupled
with a sulphuric acid plant, for optimal process integration). The same holds true for crude oil,
yet the concentrations are significantly lower, typically between 2 – 5%. Removal of hydrogen
sulphide is preformed using an amine extraction absorption system. The residual stream, called
acid gas, also contains small amounts of carbon dioxide. In 1883, the German Carl Friedrich
Claus patented the first catalytic oxidation process to convert hydrogen sulphide (acid gas) into
liquid sulphur. Approximately 90% of all recovered sulphur is produced using the Claus process.
Many improvements have been implemented in the last century, especially in catalyst technology.
Current designs can utilize a great share of the heat energy and have a near complete material
yield conversion. The BAT outlined herein represents the newest desulphurisation process:
Process Choice & Argumentation22, 23

In the original Claus layout, which is still common, the acid gas is sent directly to a series of
catalytic reactors. In newer designs, more energy efficient, the acid gas is first introduced into a
free flame reactor. About 1/3 of the H2S is combusted into sulphur dioxide. In the most modern
heat integration systems, about 80% of that heat energy is converted into high-pressure steam.
Flame reactor with 80% heat conversion to HP steam

The remaining (unreacted) H2S is converted in a series of catalytic reactors to sulphur using the
SO 2 from the burner. Several different alterations to the process have been developed for this
step. Normally a single pass through a catalytic reactor will not go to completion, as the reaction
is an equilibrium chemical reaction. By condensing the stream the sulphur component is liquefied
and can be separated from the gases. The reaction is exothermic and the released heat is used to
generate low-pressure steam. The vast majority of the LP-steam is required to re-heat the
condensed stream back to reaction temperatures. A moderate amount is exported. Typically the
overall recovery is between 95 and 97%, depending on the system. However, Jacobs Comprimo
of The Netherlands has developed a system with a material conversion rate of 99.5 – 99.7%. This
system incorporates 4 stages and has been patented as the Euroclaus system.
Euroclaus process with LP steam
The high sulphur yield also greatly lowers the emission of SO x in the residual stream and reduces
the costs related to tail gas purification. The tail gas is treated to reconvert all sulphur-containing
products back into hydrogen sulphur to be reintroduced in the acid gas stream. The heat energy
required to run the process is also supplied by the LP-stream from the catalytic reactors.
Process Results
Several calculations and assumptions must be made to determine the steam energy levels:
The amount of energy transferred into the HP-steam can be calculated. The heat of combustion is known,
the hydrogen sulphide mass flow is known and the energy efficien cy is known:
EHP-steam = -33.0GJ/tonH2S ⋅ 1.066tonH2S/tonS2 ⋅ 1/ 3 ⋅ 80% = 8.70GJ/tonS2
By setting the pressure o f the HP-steam at 40bar, the amount of steam can b e calculated:
MHP-steam = 2.23ton
It is known that a total of 2.6ton of steam is produced using the Claus pro cess. The differen ce b etween this
value and the calculated HP-steam is the excess LP-steam:
MLP-steam = 0.37ton
By setting the pressure o f the LP-steam at 8bar, the energy contain ed in the steam can be calculated:
ELP-steam = 1.30GJ/ tonS2
Table 9 Liquid sulphur processing figures

1.066 ton
Hydrogen Sulphide H2S Sulphur Source 22.24GJ/ton
(26.9) (GJ)
Input Air O2 Oxidation Source 2.162 ton 0.268GJ/ton
52.8 kWh
(0.19) (GJ)
Sulphur S2 Intermediate 1 ton 19.01GJ/ton
0.370 ton
Steam (8bar) H2O Export (Excess) 0.29GJ/ton
Output (1.30) (GJ)
2.23 ton
Steam (40bar) H2O Export, Power 2.24GJ/ton
(8.70) (GJ)

The calculations are based on 1 ton of liquid sulphur (160 ° C, 16bar), which is a diatomic
molecule. For sulphur as an element (S) the figures identical.
Total process energy: 17.28GJ/ton S2
Exery Input: 22.70GJ/tonS
Exery Output: 21.54GJ/tonS
The exergy efficiency appears high only because the feedstock exergy input is set at 20.9GJ/ton;
pure hydrogen sulphide burning yields a lower efficiency.
2.3.2.2 Sulphuric Acid

Sulphuric acid has many applications; it is included in many chemical reactions
and production processes. It is the most widely used and single most produced
industrial chemical in the world. In fact, sulphuric acid is so extensively exploited
that its consumption rate, like steel production or electric power, can be used to
indicate a nation’s prosperity. Principal applications include chemical synthesis,
wastewater processing, oil refining, ore processing and of course fertilizer
manufacturing. The fertilizer sector is the largest area of practice amounting to more than 70% of
the total market7. It is primarily used for the processing of phosphorous rock to make phosphate
fertilizers, so a large portion of ore processing is related to the fertilizer industry. Virgin sulphuric
acid can also be applied in the agricultural sector without being per se a fertilizer. As a strong acid
is it frequently employed as a soil neutralizer and pH adjuster, while supplying the soil with the
necessary sulphur nutrients. The sulphuric acid industry has reached maturity and little room for
improvements is foreseeable. The BAT outlined herein represents the standard technology from
liquid sulphur:

Being such a large industry there is of course a large diversity of sulphuric acid production
processes, yet the main stipulation is the feedstock choice. Typical sources of sulphur (or SO2)
are from pyrite burning, sulphide roasting, metal sulphate roasting, sulphuric acid regeneration,
combustion of hydrogen sulphide containing gases and pure sulphur burning. For each of the
processes the layouts differ immensely, however for sulphur burning the options are limited.
There are only two options, single or double absorption. Double absorption is with out a doubt
the most energy and material efficient; the conversion rate is increased from 97.5 – 98.5% to
99.6% and along with it the energy generation.
Double catalysis based on sulphur burning
The production of sulphuric acid is a very exothermic process and many energy-harnessing
methods have been implemented. Steam is typically generated at varying pressure to be
implemented within the process; excess steam however is frequently set at 11-bar to be used in a
steam turbine. The listed net energy values are listed for energy content, in this case the steam.
Excess energy in terms of 11-bar steam

Process Results
Table 10 Sulphuric acid processing figures

Sulphur S2 Sulphur Source 0.327 ton 6.83GJ/ton
Air O2 Oxidation Source 7.795 ton 0.97GJ/ton
Input
Water H2O Dilution Source 1.190 ton 0.06GJ/ton
Sulphuric Acid H2SO4 Intermediate 2.19 ton 3.66GJ/ton
Output 0.720 ton
Steam (11bar) H2O Export (Excess) 0.60GJ/ton
(2.50) (GJ)
The mass balances are based on 1ton of 100% sulphuric acid concentration; the water stream is
added to bring it to its final 78% concentration causing a mass dilution of 45.6%.
Total process energy: -1.15 GJ/ton H2SO4 (78%)
Exery Input: 7.89GJ/ton H2SO4 (100%)
Exery Output: 4.26GJ/ton H2SO4 (100%)

As with the nitrogen section, by incorporating the feedstock specific energy demands (H2S) the
cumulative energy input is calculated. In the case of the nutrient sulphur, the element S is not the
nutritional indication figure. The industry prefers sulphate (SO 3) as this is related to the form
taken up by the rooting system of the crop; so all energy production figures will be calculated for
the relative SO 3 content.
Water
Air
Sulphuric Acid Sulphur

0.327 t on
Energy: 1.15GJ/t on Energy: 17.28GJ/t on
Hydrogen Sulphide
Air
Figure 7 Sulphur fertilizer simplified mass/energy balance flow diagram
Table 11 Resulting energy requirements for sulphur fertilizers
Pro cess Energy Cumulative Energy Sulphate Content Relative Nutrient Energy
Compound
GJ/ton GJ/ton % GJ/tonSO3
Sulphur 17.28 17.51 250 7.00
Sulphuric Acid -1.15 1.44 63.6* 2.27
*Dilution to 78%H2SO 4

Table 12 Resulting exergy requirements for sulphur fertilizers
Input Exergy Cumulative Exergy Sulphate Content Relative Nutrient Exergy

Compound
GJ/ton GJ/ton % GJ/tonSO3
Sulphur 22.70 1.16 250 0.61
Sulphuric Acid -3.20 3.28 63.6* 5.16
*Dilution to 78%H2SO 4
All articles (currently known to this author) relating fertilizer nutrients with production energy
requirements are focused solely on the macronutrients; N, P and K. It is understandable using
logic, for the primary macronutrients require large external dose rates and are energy intensive
processes. As sulphur has only recently gained attention as a plant relevant nutrient very little, if
any, data is available. The uptake levels of sulphur are relatively high (see Section 2.9). Previously
these high levels of uptake were free, being available in the atmosphere (see Section 2.3.1), now
being incorporated as an artificially produced nutrient itself, it cannot be regarded as free. These
results indicate that just about 2GJ/tonSO3 is required to manufacture the sulphur nutrient and
over 5GJ/tonSO3 in terms of exergy. The large difference in energy and exergy can be traced
back to the low exergy content in steam. Exothermic reactions used to generate steam typically
have much lower exergy efficiencies then indicated by the energy value alone. Calculating the
sulphur uptake levels as an artificial fertilizer production can provide a better indication of the
energy requirements for the near future. But assigning sulphur a feedstock cost has its greatest
influence on the following nutrient, phosphorous.

2.4 Phosphorous

Phosphorus, P, is the 11th most abundant element in the earths crust. However, unlike the other
key nutrient groups such as hydrogen and oxygen (water), nitrogen and sulphur (air), phosphorus
has no atmospheric component in the biotic cycle. It is so highly reactive that it will
spontaneously combust (i.e. without a spark) in the presence of oxygen to form oxides, typically
P4O 10. Tetraphosphorus decoxide has a heat of formation of –597kJ/mol. Due to this extremely
high reaction potential, pure elemental phosphorus is not present in nature. Vast amounts of
phosphorus are nevertheless present in minerals and sediments, with apatite (Ca5(PO 4)3,OH,Cl,F)
being the most common source. Compounds and molecules
containing an element phosphorus component have been labelled
with the alternative spelling, phosphorous. Since elemental
phosphorus is rare and the spelling difference is so minute, it is a
common mistake to refer to the element P with its adjectival
form of a smaller valency (i.e. reacted P). Sediment and mineral
rock (like apatite) containing P are on the other hand referred to
as phosphate rock.
Phosphate rock acquires its name from the PO4-3 (phosphate) compound contained in the rock
mineral. Mining and extraction operations for phosphate rock are enormous. It is the 4 th largest
bulk mineral currently mined in the world, only slightly behind salt5. In 1999, over 144 million
tonnes were extracted. Roughly 80% of that quantity is directly utilized in the fertilizer industry
with the other 20% going to the detergent, fodder, explosives and other industries. It has become
common practice to couple a phosphate rock mining operation with a phosphorous fertilizer
plant in the form of a phosphoric acid production plant.
Typical concentration of phosphorus in topsoil, without artificial fertilizer applications, range

between 0.005 – 0.15%17. These are very low levels. Lacking an atmospheric component in the
biotic cycle exerts a slow process on nutrient regeneration. Sources of natural phosphorus
components are from the weathering of phosphate minerals and from the remains of mobile
organic species present in the soil. Yet, phosphorus is an essential component in growth and
development of plant life.
All forms of organic life require phosphates. They form the backbone of DNA and RNA, are the
main component of a cell membrane in the form of phospholipids and are used in ATP. The
high reaction speed and potential of phosphorus is exploited in the intercellular energy transfer
molecule adenosine triphosphate (ATP). Phosphorus is obviously a primary macronutrient and
its applications grew along side the development of nitrogenous fertilizers, yet most crops require
an 8:1 ratio of N to P.

Even though phosphate is present in both phosphate rock and phosphoric acid and is the only
form utilized in biology, PO 4-3 it is not the form expressed by the fertilizer industry. Phosphorus
pentoxide P2O 5 has been traditionally chosen. In fact, it and the combustible product P4O 10 are
readily interchangeable and represent the same reaction. There is a history behind this expression
choice. In the 1880’s, basic steel production produced large amounts of by-product waste streams
called slag. Slag is the oxide of many components including phosphorus (i.e. P4O 10) and for
several decades was the main supplier of the phosphorus fertilizer industry. To this day mining
operations still refer to amount or quality of phosphorus in terms of representative P2O 5. All
phosphorous fertilizers are listed as the content of P2O 5. In this sense the ratio of N to P2O 5 is
closer to 3:1. Because the element phosphorus is not expressed as the nutrient form,
phosphorous will be used as the generic term for all phosphorus containing fertilizers.

European farmers have a full range and access to fertilizers. The following pie chart indicates the
types and distribution of the various phosphorous fertilizers7.
TSP
10%
DSP
DAP/MAP
3%
22%
Other Straight
3%
PK
12%
NPK/NP
50%
Figure 8 Western European phosphorous fertilizer distribution, 1997
Unlike with nitrogenous fertilizers, the balance of phosphorous sources is rather uneven. In
Europe the trend is shifting towards a large portion of complex fertilizers, like NPK and NP.
Since phosphorous is produced at about a third of the level of nitrogen, the complex fertilizers
represent a larger portion of the phosphorous market. In contrast, America and other parts of
the world, application of complex fertilizers are less common, so mono- and diammonium
phosphate (MAP and DAP) represents a large portion. TSP, triple superphosphate is analogous
to phosphoric acid and represents the largest single blend application form.

2.4.2.1 Phosphate Rock
Today only a small fraction of the phosphorous fertilizers are still supplied by
the slag of the steel industry. Development of oxygen steel making in the
1960’s crippled the oxidized slag supply. Now, more than 99% originates from
phosphate rock 5. Unprocessed phosphate rock still represents about 2% of
the total phosphorous fertilizers. Yet, such application methods are less
efficient at supplying the nutrient to the crops and contain a smaller
concentration of P2O 5. Phosphate rock is typically extracted and treated using a beneficiation step
to increase the concentration of P2O 5 for further downstream processing. The methods used in
the phosphate rock mining explorations are very dependent on rock quality, quantity, location
and depth. The BAT outlined herein represents the best-practiced technology of an easily
extractable, average quality rock source:
Process Choice & Argumentation5, 25, 26

It is expected that even with the high production of 144Mton, there should be enough phosphate
rock to supply the agricultural sector for thousands of years. That is however not the case with all
mining operation locations, for the reserves in the USA (Florida) are expected to be depleted by
2035. The world’s largest reserves and 2nd largest production site (behind China) is located in
Morocco27. Regrettably very little detailed process information is known (or published) over the
Moroccan production site. The mining techniques and rock composition are known and are very
close to that of the Florida production site.
Table 13 Phosphate rock composition
Lo cation P2O5 CaO SiO2 F CO2 Al2O3 Fe2 O3 MgO Na2O K 2O Rest/Trace
Khouribga 33.4 50.6 1.9 4.0 4.5 0.4 0.2 0.3 0.7 0.1 3.9
Florida 34.3 49.8 3.7 3.9 3.1 1.1 1.1 0.3 0.5 0.1 2.1
The two main constituents, P2O 5 and CaO are both within one percent of each other meaning
such a small deviation in composition is negligible in terms of production energy. Since detailed
information is readily available for Florida from the Florida Institute of Phosphates Research,
their production figures will be used hypothetically for the Moroccan site. It can be safely
assumed that the Florida operations are more advanced and energy efficient than their Moroccan
counterparts. And as production and demand shifts towards the latter, the better production
figures can provide a good indication of near future requirements.
Khouribga site, Florida process figures
Both sites are based on surface opencast dragline mining operations. This is the most energy
efficient mining method, especially compared to underground mining operations employed in
other locations.
Surface opencast dragline
Depending on the quality of the rock one or more beneficiation steps are required to increase the
concentration of P2O 5. A value of 42% is preferred. Major impurities can include organic matter,

clay, siliceous material, carbonates, iron bearing minerals and other trace elements. The Florida
site does indeed perform beneficiation steps, yet since it is coupled to a phosphoric acid plant the
duties are not directly associated to the phosphate rock alone. A calcination step, for example is
not executed, as photogypsum is produced in the down stream process. The beneficiation
process and duties included here are for both production plants.
Included all beneficiation step for phosphate rock processes
Data is available for a 10-year time span, from 1984 to 1994. The 10-year mean figures will be
chosen for the energy input/output values and processing streams.
10-year average figures
Process Results
Table 14 Phosphate rock processing figures

P2O5 0.334 ton
CaO 0.506 ton
SiO2 0.019 ton
Phosphate Ro ck Phosphorus Source 0.06GJ/ton*
F 0.040 ton
Input CO2 0.045 ton
Other 0.056 ton
107.5 kWh
Electricity kWh Utilities 0.39
(0.387) (GJ)
Water H2O Various 5.678 ton 0.28
Output Phosphate Ro ck Ca3(PO4)2 Intermediate 1 ton 0.06
*based on Ca3(PO 4)2 and 1ton extracted rock, waste streams are included in the output. In fact only 840kg Ca3(PO 4)2 per ton is present
The water usage in the mining industry is notably high, however recent recycling initiatives have
reached rates above 88%, so the actual fresh water consumption is closer to 0.680ton.
Total process energy: 0.39 GJ/ton Ca3(PO4)2
Exery Input: 0.73GJ/ton H2SO4 (100%)
Exery Output: 0.06GJ/ton H2SO4 (100%)
2.4.2.2 Phosphoric Acid

Phosphoric acid is a powerful organic growth accelerator. About 10% of the
production is provided to the detergent additive industry to manufacture
water softeners. Phosphorous compounds bind calcium and magnesium ions
present in hard water, thus softening the water. Simple aquatic life (like algae)
in the vicinity of a sewage exit pipes are known to flourish; as a direct reaction
from the phosphorus contained in the sewage water. During the past 30 years the largest
proportion of the net addition to the phosphorous fertilizer production has been in the form of
phosphoric acid based fertilizers. Now, more than two thirds of all phosphorous fertilizers are
currently based on phosphorous acid derived from phosphate rock. The industry is extremely
diversified as it needs to constantly adjust to a wide variety of rock quality, ranging from 5 – 40%
P2O 5. Khouribga sediment is of a relatively high quality, meaning a better selection of processes is

possible. Nevertheless in Europe, the acidulation process with sulphuric acid is preferred. The
BAT outlined herein represents the best-practiced sulphuric acid treatment possible with the
relative phosphate rock composition:

There are three main types of sulphuric acid treatment; dihydrate, hemihydrate and hemihydrate
recrystallization processes. Each has their own advantages and disadvantages, yet only one, in the
sense of maximum energy and material efficiency, stands out. The key advantages of the
hemihydrate process are that it is able to use coarser rocks and produce a purer strong acid
directly. This saves on utilities for crushing and evaporation/concentration. The P2O 5 yield
efficiency is 90 – 94%, which is lower than the 94 – 96% of the dihydrate, but the energy savings
greatly outweigh that slight material yield reduction.
Hemihydrate acidulation process
Since sulphuric acid is used in very high quantities for phosphoric acid production it is becoming
standard practice to also couple those two production plants. The excess steam from the
sulphuric acid plant is, in many cases, able to cover the electric and heating requirements for the
concentration step. Seeing that the hemihydrate process produces 52%mass P2O 5 directly, it does
not require additional concentration steps and can save on that steam energy. In this case, the
clear advantage of coupling the two plants is compromised.
No concentration step, no steam requirements
Process Results
Table 15 Phosphoric acid processing figures

Phosphate Ro ck Ca3(PO4)2 Phosphorus Source 2.600 ton 0.16GJ/ton
Sulphuric Acid H2SO4 Reactant 3.320 ton 5.54GJ/ton
Input 120 kWh
Electricity kWh Crushing, Utilities 0.43GJ/ton
(0.43) (GJ)
Water H2O Dilution 0.770 ton 0.89GJ/ton
Phosphoric Acid H3PO4 Intermediate, Fertilizer 2.656 ton 2.82GJ/ton
Output Photogypsum CaSO4 Waste 4.800 ton 0.24GJ/ton
Fluosilicic Acid H2SiF6 Waste 0.020 ton 0.03GJ/ton
The mass balances are based on a 52%mass P2O 5 relative concentration; 2656kg of phosphoric
acid contains 1 ton of P2O 5. This is the commercial concentration for phosphoric acid for use in
downstream fertilizer production, namely NPK. Virgin phosphoric acid can also be used as a
fertilizer and is nearly identical to triple-superphosphorous (TSP).

Total process energy: 0.43 GJ/ton P2O5
Exery Input: 7.11GJ/ton P2O5
Exery Output: 2.82GJ/ton P2O5

Seen relatively, the extraction and processing of phosphate rock is in itself not all that
energetically demanding. However, by incorporating the cumulative energy input for sulphuric
acid (based on the feedstock specific energy demands of H2S) the resulting energy requirements
are significant. In the case of the nutrient phosphorus, the element P is not the nutritional
indication figure. The industry prefers phosphorus pentoxide (P2O 5) for traditional reasons; so all
energy production figures will be calculated for the relative P2O 5 content.
Figure 9 Phosphorous fertilizer simplified mass/energy balance flow diagram
Ener gy: 1.44GJ/ton
Sulphuric Acid
3.32 0 ton
Ene rgy: 0.39GJ/ton
(Super Phosphorous) Phosphate

Phosphoric Acid 2 .6 0 ton
Rock
Ener gy: 0.43GJ/ton

Water
Table 16 Resulting energy requirements for phosphorous fertilizers
Pro cess Energy Cumulative Energy P2O5 Content Relative Nutrient Energy
Compound
GJ/ton GJ/ton % GJ/tonP2O5
Phosphate Ro ck 0.38 0.86 33.4 2.57
Phosphoric Acid 0.48 3.00 37.6 7.97
Table 17 Resulting exergy requirements for phosphorous fertilizers
Input Exergy Cumulative Exergy P2O5 Content Relative Nutrient Exergy

Compound
GJ/ton GJ/ton % GJ/tonP2O5
Phosphate Ro ck 0.73 1.14 33.4 3.41
Phosphoric Acid 7.11 6.57 37.6 17.48
In the 1987 works published by Mudahar (and sited in many others), regarding the energy
calculations for phosphorous fertilizer production the following assumption was made28:
“For recovered sulfur whether energy is involved in recovering the sulfur in a saleable form is charged to the main product
(natural gas or oil) so the sulfur receives zero energy charge.”
That assumption was also made in this paper (see Section 5.3.1) except that herein sulphur
received a positive energy charge based on the heat of combustion of hydrogen sulphide. This
fundamental difference in analysis results in an enormous deviation in relative nutrient energy
requirements. The straightforward mining and extraction figures, on the other hand, are

comparable, with the progression of time accountable for the reduction. In 1983, the world
average for phosphate rock was 0.963GJ/ton (or 3.01GJ/tonP2O 5). Yet, following the
hemihydrate wet rock fed for phosphoric acid the total energy use is –1.20GJ/ton54%P2O 5.
Included was a sulphuric acid energy use of –6.06GJ/ton P2O 5. That is in stark contrast to the
+7.97GJ/ton P2O 5 when incorporating fossil fuel feedstock energy costs (H2S). More than three
tons of sulphuric acid is needed to convert phosphate rock into phosphoric acid; neglecting one
aspect of its production has a significant affect on many downstream fertilizers. Following these
calculations it is striking that phosphorous fertilizers require about a third of the exergetic input
as their nitrogenous counterparts, whereas traditional calculations indicate a factor of 5 – 10 less.

2.5 Potassium

With the arrival of settlers in the New World more arable land was needed to supply the constant
influx of migrants. The fastest and most effective way of converting the dense wooded area into
agricultural land was “slash and burn” outfits. This being long before the day of environmental
concerns, the only issue was the haste removal of the ash to make the land
quickly available for farming. Through the combustion of plant matter, like
trees, potassium oxide (K2O) is formed and remains in the ash. It was found
that this water-soluble alkali could be harnessed by cooking the ash with
water in a pan or pot. They dubbed it “potash”. Potash is potassium oxide.
Until the 20 th century, potash was one of the most important chemicals in the
European market, used for glassware and earthware (pottery) and to a lesser
extent fertilizer. It was not until 1807 that potassium was discovered and
isolated as a new element. In the English language its name derives from
potash, while the Germanic languages use the Arabic word for “calcined ashes” (kalium). Now
the fertilizer industry refers to all potassium containing fertilizers by the generic term potash and
refers to the nutrient level in terms of K2O.
Despite slash and burn outfits continuing in many parts of the globe, potash is no longer
supplied by the traditional source of ash. Large salt deposits based on potassium chloride, KCl,
provide the industry with the potassium nutrient. The term potash has since become ambiguous,
because potassium chloride salt mines are called potash mines and are even referred to by the
relative quantity of potassium oxide. The plants uptake of potash is in the form of potassium
ions, K+, so even the biological function is speculated by the historical application methods.
The potassium nutrient is one of the three primary macronutrients and has been added to soil
directly and indirectly since antiquity. It is required for many functions and if is often referred to
as the “regulator” in crop production. Potassium does not have one particular function in plant
growth, but works together with scores of basic functions. There are 8 major functions which it
is directly associated with: enzyme activation, efficient use of water, photosynthesis, transport of
sugars, water and nutrient movement, protein synthesis, starch formation and crop quality.
Many soils do contain large amounts of potassium, yet only 0.1 – 2% of these levels are available
for plant uptake17. Various forms of weathering (mainly that of crystalline minerals) provide
potassium to the soil, but also remove it through leaching. The natural cycle of potassium
regeneration is (like phosphorus) a very slow process, which cannot sustain large-scale
agricultural growth. High amounts of potash are thus added to the soil. 36.3Mton of K2O were
applied in the year 1998, with 4.15Mton in Europe alone7.

European farmers have a full range and access to fertilizers. The following pie chart indicates the
types and distribution of the various potassium fertilizers7.
K2SO4
0% Other Straight
6%
KCl
27%
NPK/NK
PK 51%
16%
Figure 10 Western European potassium fertilizer distribution, 1997
Muriate of potash, KCl, can be added to the soil directly and represents the largest proportion of
straight potassium fertilizers. What is noticeable is that the vast majority of the potassium
production is in the form of complex fertilizers, chiefly NPK. However, in both PK and NPK,
the source of potassium is also the muriate of potash. The only problem associated with KCl, is
that some crops are particularly sensitive to high levels of chlorine and is mitigated by using the
other forms of potassium fertilizers, namely potassium sulphate. They however, represent such a
small fraction that only muriate of potash will be included in the following calculations.
2.5.2.1 Potash
In a potash mine there are many types of salts present. Isolated potassium
chloride has been called “muriate of potash” and is used for 95% in the
fertilizers industry. It is by far the cheapest and most effective form of the
potassium nutrient. Compared to the other forms of potassium fertilizers,
muriated potash has the highest plant uptake level and is no coincidence
that it has become the single largest source of the nutrient. The methods used in potash mining
explorations are very dependent on rock quality, quantity, location and depth. The BAT outlined
herein represents the figures from the largest production site with the largest reserve area:
Process Choice & Argumentation5, 29, 30

Canada currently produces one third of the total potash consumed in the world and holds the
world’s largest reserves. There is enough potash available for well over 100 years of continued

exploration. The largest company is the PotashCorp; their 11 mines together represent 23% of
the world capacity. The giant among their production is the Lanigan site, which has a production
rate of 2.34MtonK2O per year. Ore composition for this site is known.
Table 18 Lanigan potash composition
Component Percentage
Potassium Chloride (KCl) 33
Sodium Chloride (NaCl) 56
Insoluble Clay 8
Other Salts 3
Lanigan ore composition

The Canadian Office of Energy Efficiency has composed a detailed analysis of the energy
consumption for the potash industry. The industry in itself can be broken down into two
sections, conventional and solution-based mining operations. Most mines are conventional
relying on electric operated underground cutters and diggers (shaft mining). When the ore
becomes scarce and conventional extraction too difficult, solution-based mining is employed. It
is however, about 2-3 times more energy intensive and still only represents 20% of the industry.
Conventional shaft mining
Data is available for all the conventional potash mining/milling operations for the year 2001. The
average figures for the 8 sites will be chosen for the energy input/output values and processing
streams. There is a deviation of around 50% between the highest and lowest energy consuming
operation. The lowest energy consumption will not be chosen because the ore location, depth
and grade can even within the operational duration of one mine greatly vary.
8 mine average figures
Process Results
Table 19 Potash (potassium) processing figures

KCl 0.33 ton 0.09GJ/ton
NaCl 0.56 ton 0.13GJ/ton
Potash Potassium Source
Clay 0.08 ton 0
Salts 0.03 ton 0
Input
39.6 kWh
Electricity kWh Mining, Utilities 0.14GJ/ton
(0.143) (GJ)
0.29 GJ
Natural Gas CH4 Energy Source 0.30GJ/ton
(0.007) (ton)
Muriated Potash KCl Intermediate 0.300 ton 0.08GJ/ton
Output
Salts NaCl Waste/Table Salt 4.800 ton 0.15GJ/ton
The potassium ratio of KCl in terms of K 2O is 63.1%, meaning that 330kg of muriated
potassium (excluding 30kg loss) is equivalent to 187kg of potash. All process energy and material
streams are listed above as per tonne of product (i.e. 30% of 63.1% K2O equivalent).
Total process energy: 1.42 GJ/ton KCl
Exery Input: 2.20GJ/ton KCL

Exery Output: 0.26GJ/ton KCL

The extraction and beneficiation of potash is straightforward. Since it is a one-step process in the
chain there is no need to display flow diagram interpretation.
Table 20 Resulting energy requirements for potassium fertilizers
Pro cess Energy Cumulative Energy K2O Content Relative Nutrient Energy
Compound
GJ/ton GJ/ton % GJ/tonK 2O
Potash 1.42 2.01 63.1 3.20
Table 21 Resulting exergy requirements for potassium fertilizers
Input Exergy Cumulative Exergy K2O Content Relative Nutrient Exergy

Compound
GJ/ton GJ/ton % GJ/tonK 2O
Potash 2.20 2.59 63.1 4.11
In 1984, the typical world potash production average was considered to be 3.80GJ/ton product
(6.40GJ/ton K2O)28. The energy requirements for North American and European mines are
noticeably lower than the world average. Yet since 1984, a production shift has focused a greater
proportion of production on the Canadian sites. Most European sites are exhausted or simply
being shutdown; France no longer mines potash and Germany is expected to cease production
by 2006 5. The largest stipulation in potash production and energy intensity is the ore grade, the
so-called ore/product ratio. The U.S. and Europe varies between 4 and 6, whereas the Canadian
sites have a higher grade typically ranging from 2 – 3, resulting in less energy intensity. This one
of the major factors explaining why the relative nutrient energy input argued in this case is
3.20GJ/ton K2O compared to 5.0GJ/ton K2O.

2.6 Calcium and Magnesium
2.6.1.1 Calcium
The natural occurrences of calcium are in limestone. Limestone is a
sedimentary rock composing primarily of calcite, calcium carbonate
(CaCO 3). Nearly 10% of all sedimentation worldwide is limestone and
composes of 75% of the crushed rock market31. Surprisingly, calcium was
first discovered and isolated in its oxide from, CaO, better known as lime.
By carefully adding water to limestone at high temperatures the calcite can be oxidized to form
lime, dubbed as the endothermic calcination step. CaO is very reactive with water and will form
calcium hydroxide Ca(OH)2 nearly spontaneously (slaking process), rightfully granting the
alternative name of “quicklime”. In the case of fertilizer it is crushed limestone (CaCO 3) that is
added to the soil but the calcium nutrient is indicated in terms of lime concentration. Although
virgin limestone (calcite) is extensively used as a building material, the ore composition is often
described as the relative CaO concentration, not only due to fertilizers but partly because slaked
lime (Ca(OH)2) is so common.
The Dutch can thank their beautiful big-teethed smiles to the vast quantities of dairy products
they consume. It is calcium that helps humans develop strong teeth and bones. Plants do not
have teeth nor bones but do require calcium nevertheless. They also do not use calcite directly,
but separate the calcium ions out of the limestone. If that were not the case, we too would eat
limestone powder in place of cheese (though a lot less tasty). In plant life, the benefits of calcium
are quite different than that of humans. The main function calcium plays in plant growth is the
development of new points of growth, like root-tips, buds, stems, etc. It also helps in the uptake
of other nutrients, primarily phosphorus and other micronutrients. For legumes it aids in the
inoculation and increases the nitrogen fixation, this can be noticeable with the relative higher
application rates of calcium for legumes17. Calcium also provides cells with elastic properties,
stimulating the elongation and multiplication of cells. Calcium is a secondary macronutrient and
plants can thank their cell develop to the vast quantities of lime they consume.
Application of lime also has another benefit not associated to any nutritional value. Calcium
products are the primary method of pH control. They are frequently added to soils to
counterbalance the acidic properties of the other nutrients. Hydrated lime (or slaked lime) has the
strongest acid neutralization potential, followed by dolomite and limestone. The course texture
also improves the structure of the soils, being the reason why the other nutrients become more
readily available.

2.6.1.2 Magnesium
The last macronutrient to be discussed is magnesium. It too, like calcium,
occurs naturally in sedimentary rock. It occurs in a magnesium containing
limestone variant called dolomite or dolostone. In dolomite, the calcium and
magnesium source are combined together forming the crystal compound
calcium magnesium carbonate, CaMg(CO 3)2. In theory there should be a molar
ratio of magnesium to calcium of 1:1. Pure sources of dolomite are however
rare, more common is a sediment mixture between dolomite and limestone, commonly referred
to as dolomite limestone. A mass percentage of magnesium is in the range of 15-20% to be
classified as dolomite limestone. Plants require more calcium than magnesium; a typical molar
ratio of calcium to magnesium ions supplied by the fertilizer industry is 6:1. The ore composition
can be set based on this specification and with the knowledge that dolomite limestone contains
around 7% impurities32.
Table 22 Dolomite limestone composition
Ore Grade CaCO3 MgCO3 Trace

Pure Dolomite 54.35 45.65 0
Typical Dolomite Limestone 17.5 75.5 7.0
In general magnesium has the smallest uptake figures of the macronutrients, though is fairly close
to sulphur levels and surpasses it in several crop species. Magnesium is utilized in the
photosynthesise process to harness the solar energy and along with calcium acts as a soil
neutralizer.

As with the rest of the fertilizers there are a variety of sources and options to supply the calcium
and magnesium nutrient component. Gypsum, basic slag, different grades of limestone, hydrated
lime and nature manures are common sources for calcium. Hydrated lime is especially preferred
as a neutralizing agent as opposed to strictly being for nutrient supply. The most common source
is the limestones. Dolomite limestone, magnesia, basic slag, Epsom salts and some other
magnesium solutions are common sources for magnesium. The most common however is
dolomite limestone. Since both calcium and magnesium are present and commonly applied in the
form of crushed dolomite, this will be the chosen production path for the nutrients.

2.6.2.1 Dolomite Limestone
Crushed rock, like limestone, is one of the basic raw materials used in countless
numbers of industries. The most obvious is the construction industry with cement,
building stone, plaster and mortar being directly derived from limestone. The metal
industry however, is the single largest consumer of limestone serving as a flux to
remove impurities during the refining processes. In comparison, the agricultural
industry is only a minor player, using around 1% of the total production. The
mining and beneficiation steps are for all industries the same. Limestone is actually
one of the most accessible natural resources in the world. Surface opencast mining with blasting
operations is the commonly practiced; even though several underground operations are
becoming more frequent. The BAT outlined herein represents the average figures for the entire
industry:

The U.S. mining industry has composed a detailed energetic analysis of the crushed rock industry
for the years 1987 to 1997 and the mining and processing sector for the year 2000. Their source
for limestone mining operations is BCS Incorporated using the SHERPA mine cost estimating model.
The hypothetical mine operates for a 10-year period; so the results are a ten year average for the
industry. The energy consumption has been broken down into each operation of the surface
mining and beneficiation step.
Surface limestone mining and beneficiation (2000)
Process Results
Table 23 Limestone dolomite (calcium and magnesium) processing figures

CaCO3 0.755 ton
Calcium &
Dolomite Limestone MgCO3 0.175 ton 0.08GJ/ton
Magnesium Source
Other 0.070 ton
Input 0.056 GJ
Diesel C16+ Mining, Utilities 0.06GJ/ton
(2128) (L)
0.022 GJ
Natural Gas CH4 Energy Source 0.023GJ/ton
(5.4E-4) (ton)
Calcium Carbonate CaCO3 Fertilizer 0.707 ton 0.057GJ/ton
Output Magnesium Carbonate MgCO3 Fertilizer 0.164 ton 0.013GJ/ton
Losses Other Waste 0.133 ton 0.011GJ/ton
Total process energy: 0.078 GJ/ton dolomite CaMg(CO3)2

Exery Input: 0.18GJ/ton CaMg(CO3)2
Exery Output: 0.07GJ/ton CaMg(CO3)2

The extraction and beneficiation of dolomite limestone is straightforward. Since it is a one-step
process in the chain there is no need to display flow diagram interpretation. Calculating the
relative nutrient content is slightly more complicated since two separate nutrients are present. For
each nutrient the relative mass ratio must first be related to the cumulative energy: calcium is
81.2% and magnesium is 18.8% of the fertilizer, i.e. 6:1 Ca to Mg. The resulting relative nutrient
energy is very low for dolomite compared to any of the other macronutrients.
Table 24 Resulting energy requirements for calcium and magnesium fertilizers
Pro cess Energy Cumulative Energy Nutrient Content Relative Nutrient Energy
Compound
GJ/ton GJ/ton CaO MgO GJ/tonCaO GJ/tonMgO
Dolomite 0.078 0.078 39.6 7.8 0.160 0.187
Table 25 Resulting exergy requirements for calcium and magnesium fertilizers
Pro cess Exergy Cumulative Exergy Nutrient Content Relative Nutrient Exergy
Compound
GJ/ton GJ/ton CaO MgO GJ/tonCaO GJ/tonMgO
Dolomite 0.179 0.179 39.6 7.8 0.341 0.400
2.7 Micronutrients

Macronutrients are needed in high quantities and substantial plant growth acceleration is
observable with the application of additional fertilizers. They do not cover all the nutritional
demands of a plant, for there are many essential nutrients, which are only required in very small
quantities. Micronutrients are basically those elements that are vital for normal functionality but
are only needed in minute amounts. To give an indication of the scale between the two
classifications, the macronutrients uptake is in the several hundred kg/ha whereas the
micronutrients uptake is in the couple kg/ha range. That is practically a factor of more than a
hundred.
Essentially any element/compound that is taken up in small amounts by plant life can be
considered as a micronutrient. But despite this, there are several elements that are truly regarded
as micronutrients. They directly affect the growth and function of plant life. Iron (Fe), Copper
(Cu), Zinc (Zn), Molybdenum (Mo), Manganese (Mn), and Boron (B) are the six micronutrients.
They are all metal components of enzymes. It is sometimes disputed whether chlorine (Cl),
silicon (Si) and sodium (Na) should be included in the list, but are frequently left out.
The uptake levels of the metal ions (Cu+2, Mn+2, MoO 4-2, Ni+2, Zn+2) by plants is so low that in
most cases the quantity contained in the soil (and even the regeneration speed) is sufficient to
supply the crop for decades. However, not all soils contain sufficient levels from the beginning of
industrial agricultural exploitation or for prolonged cropping. Two of the micronutrients are

notorious for being the cause of deficiencies; iron and boron. Many soils contain insufficient
levels of those two metal ions and others that can hinder the healthy growth of the crops.
The management of micronutrients is complex and difficult, due to the small quantities involved
and the similar symptoms of macronutrient deficiency. When a micronutrient is determined to be
deficient they are supplied to the soil like any other fertilizer. But since they are metal ions, it is
common practice to bind many of the nutrients with a chelating agent to form a metal complex, a
chelate. This results in a stable compound, more available to the crop without the losses
associated with the loose ions. Another difficult aspect is
the possibility of toxicity. The micronutrients are only
needed in small amounts, too high concentrations can
be just as detrimental as insufficient concentrations (see
adjust illustration.) Deficiency produces a similar trend.
The effect of proper micronutrients management is not
observed growth acceleration, but the continued healthy
growth of the crops.
Source: OSU Dept. of Horticulture. & Crop Science

The micronutrients will not be investigated individually as any deviation in the process energies
will have next to no effect on the total nutrient energy level due to the low quantities involved.
Furthermore they are all metals, meaning their origin is of a similar nature reflecting in only slight
differences in energy and material streams. It will be assumed that all micronutrients will require
equal amounts of process energy to manufacture. The assumed process steps are as follows:
• Mining of metallic ore
• Beneficiation of metallic ore
• Production of metal
• Production of final chelate
For the mining and beneficiation of metallic ore, the previous macronutrients can be of
assistance. Sulphur, or more specifically pyrites, is a metallic ore with data available on extraction
and processing costs (7.38GJ/tonS with 0.2GJ/tonOre). Dolomite is also a type of metallic ore,
although the processing mentioned only covers extraction and crushing. Potassium is not a pure
metal per se, but an alkali metal extracted from ore by analogous methods. Comparing the three
sources can give a rough indication of energy requirements to mine and isolate metal ore:
Mining process energy: 0.5 GJ/ton metal ore
Beneficiation process energy: 3 GJ/ton metal ore
Unlike the other macronutrients, the micronutrients must be further refined into metals. The
most common metal produced worldwide is the ferrous-metal steel. There are two different
production methods for steel, blast furnace and electric arc, with independent energy demands.

The best practice average of both processes from the European steel industry can be used can
give a rough indication of BAT energy requirement to refine metals33:
Refining process energy: 15.5 GJ/ton metal
A typical chelator for stable complex binding is EDTA (ethylenediaminetetraacetic acid). There
are however, many other possibilities including simple salts and even water. The production
energies of course greatly differ when producing a monodentates (low) or a polydentates (high).
It is also neither necessary for all of the micronutrients to be converted into chelates nor is it
always preformed. The following process is just a very rough estimate for the average chelate
production for all the micronutrients:
Chelate process energy: 1 GJ/ton nutrient

The resulting process energy is an average for all micronutrients based on the above assumptions.
Table 26 Resulting energy requirements for micronutrient fertilizers
Compound
GJ/ton GJ/ton % GJ/ton
Micronutrients 20.0 20.0 100 20.0
In terms of exergy, due to the typical trend of being slightly higher, a value of 25GJ/ton is set.
2.8 Complex Fertilizers

Fertilizers that contain more than one particular nutrient are called multi-nutrient fertilizers.
Dolomite limestone can be considered as a multi-nutrient fertilizer, as it contains both calcium
and magnesium. A compound fertilizer is a type of multi-nutrient fertilizer, which underwent
some chemical alteration to incorporate more than one nutrient. Physical mixing is not enough to
constitute a compound; meaning dolomite limestone is a multi-nutrient fertilizer but not a
compound fertilizer. “Complex fertilizer” is the generic term used for all multi-nutrient fertilizers
containing the primary macronutrients regardless if physical or chemically blended. In the case of
actual compound fertilizers (chemically treated), they are designed to contain at least two of the
three primary macronutrients (N, P and K) with supplementary secondary macronutrients.
Complex fertilizers are extremely popular in Europe. They account for 83% of all phosphorus,
67% of all potassium and 25% of all nitrogen consumed in the EU7. In other countries,
particularly in the developing world, complex fertilizers are not as extensively used as in Europe.
The main reason behind this trend is shear economics; it costs more money to produce complex
fertilizers then their straight versions. The advantages, balancing the increased cost, only come
into focus when combined with advanced precision farming (a term unheard of to the average
Chinese peasant farmer). Complex fertilizers maximize nutrient application, use and efficiency.
With knowledge of the exact nutrient requirements of a specific crop in a specific field, the

educated farmer can supply a complex fertilizer costume tailored to meet all its nutritional needs.
That practice has been titled “balanced fertilization”. It can greatly reduce the application costs, by
reducing the frequency and quantity. An added benefit is that the soil is less travelled on,
resulting in less soil compaction, further increasing crop yield. Complex fertilizers do cost more
money (and energy) to produce but are a more efficient form saving in downstream agriculturally
related costs (see following chapter). It is expected that complex fertilizer production will
continue to rise in Europe as in the rest of the world.

There is essentially an infinite array of possible complex
fertilizer combinations and over 200 blends exist on the EU
market alone. The most common are NPK blends containing all
three macronutrients. The number labelling of complex
fertilizers lists the content of the relevant nutrients. On the
adjust illustration a blend of 20-5-10 is indicated, meaning that it
contains 20%N, 5%P2O 5 and 10%K2O in mass percentage.
There are however process limitations to the composition levels.
NPK, for example, can range between 5-24% for the individual primary micronutrients and must
contain less than 8% of the secondary macronutrients34. The process descriptions listed in the
EMFA booklets adhere to a 15-15-15 composition, the average grade. Calcium carbonate is
produced as a waste stream from NPK processing, which is the primarily CAN multi-nutrient
production ingredient.
2.8.2.1 NPK
In Europe, the secondary and micronutrients are frequently added to the NPK
production process to include all plant nutrients. The labelling is thus extended to
mention the all the contained nutrients, usually in brackets or separately listed
underneath. The BAT outlined herein represents the most energy and material
efficient process for the 15-15-15 grade NPK compound fertilizer with typical
levels of added secondary nutrients:

The first industrial process to create a compound fertilizer was the Odda process. It is based on
the acidification of phosphate rock using nitric acid, justifying the other name it is commonly
referred to as – the nitrophosphate process. At the time of its development in 1927, it was
designed to avoid using expensive sulphuric acid. In recent times, sulphuric acid has become one
of the cheapest chemicals, negating the main advantage of the Odda process (see Section 2.3.1).
NPK fertilizers are now produced using four different methods, yet only two are for the
production of the compound NPK’s. They are the Odda process and the mixed-acid process.
The mixed acid process relies on sulphuric acid as the acidification agent to dissolve phosphate
rock. Most European NPK production sites are phasing out the Odda process in favour of the

mixed-acid production method. Both BASF and DSM, which previously employed the Odda
process, already produce NPK’s solely via the mixed-acid process. The transition is for economic
reasons. It is a more flexible process capable of handling a larger variation of material feedstocks,
i.e. lower grades.
Mixed-acid production route
Within the process category of the mixed-acid route there are three different approaches:
granulation with a pipe reactor, drum granulation with ammoniation and sulphuric acid process
with phosphate rock digestion. Mixed-acid routes refer to all processes not based on nitric acid
digestion. The advantages listed above are in fact related only to the sulphuric acid process with
phosphate rock digestion. The other two options require high grades of feedstocks and are not as
flexible in producing various grades of NPK. The sulphuric acid process does require the most
direct energy, but is still considered more energy and material efficient due to upstream savings.
Sulphuric acid process with phosphate digestion
The digestion of phosphate rock can be preformed using various grades. Two examples of 60%
and 80% water solubility were mentioned. The energy intensity of both grades is identical, but
less total material is required for the 80% water solubility.
80% water solubility of phosphates
Process Results
Table 27 NPK processing figures
Exergy
Component Symbol Use Quantity Unit
Content
Phosphate ro ck P2O5 Phosphorus Source 0.148 ton 0.01GJ/ton
Nitric Acid HNO3 Acid Digestion/Nitrogen Source 0.434 ton 0.30GJ/ton
Ammonia NH3 Nitrogen Source 0.111 ton 2.20GJ/ton
Phosphoric Acid H3PO4 Ammoniation 0.200 ton 0.56GJ/ton
Sulphuric Acid H2SO4 Ammoniation/Sulphur Source 0.097 ton 0.16GJ/ton
Potash KCl Potassium Source 0.239 ton 0.02GJ/ton
Input
Dolomite Ca, Mg Calcium & Magn esium Source 0.075 ton 0.002GJ/ton
Carbon Dioxid e CO2 Carbonate 0.148 ton 0.07GJ/ton
50 kWh
(0.18) (GJ)
0.130 ton
Steam (10bar) H2O Heating, Synthesis 0.11GJ/ton
(0.45) (GJ)
N 0.150
P2O5 0.150
K 2O 0.150
NPK Fertilizer ton 0.44GJ/ton
SO3 0.062
Output CaO 0.030
MgO 0.006
Calcium Carbonate CaCO3 Intermediate 0.324 ton 0.00GJ/ton
Quartz Si Waste 0.010 ton 0.00GJ/ton
Hydrogen Fluoride HF Waste 0.006 ton 0.02GJ/ton
Just as with the Odda process, nitric acid is still used as the phosphate rock digestion material.
Differentiation between the nitrophosphorous process and the sulphuric acid process is that the

neutralization and ammoniation agent (creating the resulting compound solution) is sulphuric
acid (along with phosphoric acid); that has the advantage of mixing all the nutrients in one
(flexible) step. For every ton of NPK produced there is 324kg of calcium carbonate produced as
a waste stream. Since it is the main feed stream for CAN, it is not a waste stream but an
intermediate stream. The following section describes the integrated CAN processing choice.
Total process energy: 0.63 GJ/ton NPK

Exery Input: 3.62GJ/ton NPK
Exery Output: 0.44GJ/ton NPK
2.8.2.2 CAN
Ammonium nitrate decomposes in temperatures above 200°C. Pure AN is
CAN:
stable and will stop decomposing once the heat source is removed, but in
-CaCO3
presence of catalysts (or other combustible materials) the reaction can become
-NO3
self-sustaining (known as self-sustaining decomposition, SSD). This is a well-
-NH4
known phenomenon and is responsible for loss of several cargo ships and
production facilities (see Section 2.2.2.3). Calcium ammonium nitrate (CAN) is a blend between
calcium carbonate and ammonium nitrate. The calcium carbonate acts as a filler for AN creating
a more stable fertilizer. The result still contains a relatively high nitrogen content (21-28%) and
represents 30% of free nitrogen share in European soils. With the additional benefit of
containing a calcium component, CAN acts as a nitrogenous fertilizer, calcium fertilizer and as a
soil neutralizer; basically a multi-nutrient fertilizer with soil treatment properties. In the previous
calcium section (see Section 2.6.1.1) it was mentioned that the source for calcium is (dolomite)
limestone, however in the case of process integration with NPK it is the calcium impurities
found in phosphate rock. To utilize all the calcium carbonate by-product from the NPK
production 1.6 ton of CAN must be produced. The BAT outlined herein represents the most
energy efficient process for a 20:80 blend of calcium carbonate to ammonium nitrate:

It is also quite common for CAN to be produced from limestone sources. That feed stock source
will not be calculated because of the vast potential quantities of the NPK related CaCO3.
CaCO3 from NPK production
As mentioned previously it is advantageous to leave AN in its melt form when used as an
intermediate. Final CAN product requires a granulations step to solidify the blended mix. The
lowest available process requirements for the granulation steps are taken.
Includes solidification

Process Results
Table 28 CAN processing figures
Exergy
Component Symbol Use Quantity Unit
Content
Calcium Carbonate CaCO3 Filler/Calcium Source 0.200 ton 0.00GJ/ton
Ammonium Nitrate NH4NO3 Nitrogen Source 0.800 ton 2.94GJ/ton
10 kWh
Input Electricity kWh Utilities 0.04GJ/ton
(0.04) (GJ)
0.150 ton
Steam (10bar) H2O Heating, Granulation 0.12GJ/ton
(0.52) (GJ)
Calcium-Ammonium
Output CAN Fertilizer 1 ton 2.95GJ/ton
Nitrate
The highest nitrogen content of commercially produced CAN is 28%. This 80:20 mix ratio
results in 264kg of N (or 26.4%N) and 112kg of CaO.
Total process energy: 0.548 GJ/ton CAN

Exery Input: 3.10GJ/ton CAN
Exery Output: 2.95GJ/ton CAN

Since CAN must be produced to fully integrate all streams connected to the production of NPK
the overall nutrient content must also include the amount contained in CAN. The figure below
illustrates all the connecting streams. When 1ton of NPK is produced 1.6ton of CAN is also
produced. Meaning the nutrient values correlates to the contents of 38.5%NPK and 61.5%CAN.
The resulting nutrient content is listed in the table below (Table 29) for 1ton total fertilizer
quantity. Calculating the relative nutrient energy requirement for multi-nutrient fertilizers is
complicated. The key assumptions and explanations for the distribution and association of
material and energy streams to the individual nutrients are as follows:

Table 29 NPK+CAN nutrient related energy distribution
Nutrient Stream Proportion Reasoning

100% Ammonia Produ ction Source of Nitrogen
22% Nitric Acid Produ ction Mainly used for digestion, yet 22%N
Nitrogen (N) 33% NPK Pro cess Energy Represents 1/3 of main produ cts
80% CAN Pro cess Energy 80:20 ratio AN:CaCO3
100% AN Production Source of Nitrogen
39.5% Phosphate Ro ck Produ ction Phosphorus to calcium ratio
100% Phosphoric Acid Produ ction Source of Phosphorus
Phosphorous (P2O5)
78% Nitric Acid Produ ction Digestion agent, other 22% fo r N
33% NPK Pro cess Energy Represents 1/3 of main produ cts
100% Potash Production Source of Potassium
Potassium (K2O)
33% NPK Pro cess Energy Represents 1/3 of main produ cts
Sulphur (SO3) 100% Sulphuric Acid Produ ction Source of Sulphur
60.5% Phosphate Ro ck Produ ction Calcium to phosphorus ratio
Calcium (CaO) 54.4% Dolomite Produ ction Calcium to magnesium ratio
20% CAN Pro cess Energy 80:20 ratio AN:CaCO3
Magnesium (MgO) 45.6% Dolomite Produ ction Magnesium to calcium ratio
Potassium Salts
En er gy: 1 .42GJ/ ton
Potash Sulphur
En erg y: 1 7.287GJ /ton
Dolom ite Limest one
0 .239 t on Hydro gen Sulphide
En er gy: 0 .08GJ/ ton
0.327 ton Air
Natur al Gas
Water
Water
Air
En erg y: 28 .4GJ/t on
Dolomite Air
0 .075 t on
Ammonia Sulphuri c Acid

0 .111 t on
0.277 ton 0.09 7 to n 1. 205 to n
Wat er
Air M icronut rients Ene rgy: 0.39 GJ/to n
En erg y: 0GJ /ton En erg y: 0 .63GJ/t on
(Super Phosphorous) Phosphate

Nitric Acid NPK
0 .434 t on
0 .268 t on P hosphoric Acid 0.9 79 to n
Rock
0 .324 t onCaCO3
0.789 ton Ener gy: 0.16GJ /ton
0 .213 t on Water
(CAN)
0 .148 t on
Ammonium Calcium
Nit rat e 1 .298 t on Ammonium
Nitrate
Ene rg y: 0.5 5GJ/to n
Figure 11 NPK+CAN fertilizer simplified mass/energy balance flow diagram
Table 30 Resulting energy requirements for NPK+CAN fertilizers
Compound
NPK 5.08
7.37* - -
CAN 3.10
N - - 22.24 50.9
P2O5 - - 5.77 25.5
K 2O - - 5.77 5.1
SO3 - - 2.38 2.3
CaO - - 8.13 0.9
MgO - - 0.24 0.2
*1ton total (0.385tonNPK and 0.615tonCAN)

Table 31 Resulting exergy requirements for NPK+CAN fertilizers
Input Exergy Cumulative Exergy Nutrient Content Relative Nutrient Exergy

Compound
NPK 0.63
14.86* - -
CAN 0.55
N - - 22.24 54.0
P2O5 - - 5.77 31.6
K 2O - - 5.77 6.3
SO3 - - 2.38 5.2
CaO - - 8.13 0.7
MgO - - 0.24 0.4
*1ton total (0.385tonNPK and 0.615tonCAN)
In the brief description and nutrient importance section for complex fertilizers (see Section 2.8.1) it was
stated that compound fertilizers are more expensive than straight fertilizers. From comparing the
relative nutrient energy results, that statement is debatable. On energetic terms, the compound
fertilizers actually require less and similar process energy for most of the nutrients, providing an
additional plus point for their production and exploitation. Complex fertilizers appear to be the
most energy efficient form of fertilizers, but the alleged higher cost is probably connected by
other factors such as additional investment costs. Phosphorous is the one nutrient that requires
significantly more relative energy then its straight counterpart, superphosphorous. Fully
understandable considering that nearly half a ton of nitric acid is required to digest 150kg of
phosphate rock. And by associating 78% of nitric acids production requirements to phosphorous
the resulting figure is about half that of nitrogen. Through the production of 1ton (NPK+CAN)
385kg of NPK and 615kg of CAN is produced, in which roughly 4-times more available nitrogen
is yielded than any of the other nutrients. That corresponds nicely against typical fertilizer
application trends.

2.9 Nutrient Uptake
Nutrient uptake levels are presented in terms of kg/ha to coincide with the most commonly
adopted term for the fertilizer application industry. Presenting the nutrient requirements based
on mass/area is a desirable from, but can only be compared to other crops when standardized to
a common yield. The similar problem of yield specific terminology again appears in the values
given for nutrient uptake levels. The ambiguities between dry weight, wet weight, total plant or
component specific yield reoccur. As before the values need to be adjusted to one common unit.
Generally the values were presented as kg/ha for a specific wet weight yield, considering that in
chapter 4 wet weight and dry weight absolute figures were both calculated, the nutrient uptake
levels can first easily be related to kg/tonne wet weight for the entire crop.
Several of the selected crops have a bacterial symbiotic relationship or sown together with
leguminous plant material reducing the external nitrogen nutrient demand. The crop guide lists
the inoculation strain and states the inoculation rate. The inoculation rate is essentially the
percentage of nitrogen nutrient demand covered by the nitrogen fixating bacterial strain. In many
cases it is not 100%, meaning that additional nitrogenous fertilizer must be added to satisfy the
uptake demand. The nitrogen requirement levels are adjusted to include those figures.
From the plant analysis data, for the nutrient composition, several elements are in the trace
quantity range and are unknown. As opposed to setting trace elements at zero it will be assumed
that a minimum uptake level of 0.1kg/tonWW for the macronutrients and 0.001kg/tonWW for
the micronutrient is present.
The following table illustrates the resulting uptake levels for the macro- and micronutrients in
terms of kg/tonne wet weight after all the adjustments.
Table 32 Nutrient uptake levels (kg/tonWW)
Bacterial Fixation Macronutrients Micronutrients

Crop
N Inoculation N P2O5 K2 O CaO MgO SO3 Fe Mn B Zn Mo Cu
Common Name kg/ tonne rate kg/tonne WW
Cassava 2.9 0.00 2.9 1.1 4.4 2.5 2.0 0.2 0.015 0.018 0.003 0.011 0.001 0.001
Grass 5.2 0.59 2.1 1.4 5.3 1.5 0.6 0.4 0.018 0.028 0.001 0.007 0.001 0.001
Lucerne 10.0 0.80 2.0 2.3 9.3 4.3 1.8 0.8 0.015 0.013 0.008 0.006 0.000 0.002
Maize 2.6 0.00 2.6 1.4 4.5 0.1 1.4 0.3 0.025 0.013 0.002 0.005 0.000 0.002
Oil palm 2.7 0.00 2.7 0.9 4.5 3.1 1.4 0.0 0.007 0.002 0.003 0.002 0.002 0.003
Potato 2.7 0.00 2.7 0.8 4.5 0.2 0.3 0.4 0.018 0.018 0.002 0.004 0.001 0.002
Rapeseed 4.0 0.00 4.0 0.4 5.8 1.4 0.1 0.3 0.023 0.008 0.004 0.007 0.000 0.001
Sorghum 3.5 0.00 3.5 1.0 3.9 0.3 0.3 0.3 0.001 0.001 0.001 0.001 0.001 0.001
Soya bean 14.8 1.00 0.0 2.6 6.0 4.4 3.3 0.5 0.067 0.016 0.007 0.011 0.001 0.005
Sugar beet 2.7 0.00 2.7 1.0 3.1 1.7 0.8 0.3 0.002 0.014 0.007 0.001 0.000 0.001
Sugar cane 0.6 0.70 0.2 0.2 1.0 0.3 0.4 0.2 0.004 0.004 0.000 0.000 0.000 0.000
Sunflower 13.1 0.00 13.1 8.7 38.5 21.0 7.0 2.0 0.073 0.041 0.040 0.035 0.000 0.006
Switchgrass 22.4 0.30 15.7 5.3 36.2 5.3 4.1 2.0 0.075 0.062 0.018 0.029 0.000 0.006
T obacco 1.5 0.00 1.5 0.3 1.2 1.4 0.3 0.2 0.002 0.008 0.001 0.001 0.000 0.000
Wheat 15.1 0.00 15.1 3.4 24.5 2.5 2.5 1.2 0.032 0.032 0.005 0.003 0.000 0.004
Willow tree 7.5 0.00 7.5 7.5 7.5 0.1 0.1 0.1 0.001 0.001 0.001 0.001 0.001 0.001
The values highlighted in bold are supplied via artificial fertilizers, the rest (not-bold) are currently supplied by sufficient levels in the soil

Due to the great difference in macro- and micronutrient uptake levels, it is best to display the
nutrient classifications in two separate graphs and using dry weight figures as to present a more
comprehensive contrast between each crop and each nutrient.
Macronutrient Requirements
50
72.0
N
P2O5
K2O
CaO
MgO
40
SO3
30
kg/ton DW
20
10
0
a
ze
an
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co
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er
s
s
et
at
lm
um
as
rn
ee
t re
v
t
ta
be
he
w
ai
sa
ra
pa
be
ca
ac
ce
gh
gr
Po
flo
es
M
G
w
as
b
ar
il
h
or
ar
Lu
un
ap
To
illo
O
oy
itc
ug
C
ug
S
S
R
Sw
W
S
Figure 12 Macronutrient uptake levels
One would expect nitrogen to dominate the uptake figures but it is noticeable that for the
majority of crops potassium (K2O) has the highest requirements. The level 25kg/tonDW
represents 2.5% of the total crop biomass and several crops have individual nutrient
requirements approaching and exceeding 25kg/tonDW. Sunflower for example needs
72kg/tonDW of K2O, which is 7.2% of the total dry biomass. It may appear abnormally high,
but considering the high ash and protein content, it is realistic. Potassium is amongst the main
contributing minerals to the ash content. The ash composition for all crops is unique as can be
best described with the grasses. Switchgrass, lucerne and grass are particularly high containing
20.1, 17.8 and 11.4% ash respectively. It can be seen in the above graph that indeed the
potassium uptake in proportion to the other nutrients and in absolute terms is rather high for the
grasses. Potassium and the above nutrients are only one factor determine the ash levels as lucerne
in particular has SiO 2 for the bulk of its ash content 37.

Figure 13 Micronutrient uptake levels
Micronutrient Requ irements
0 .150
0.16 Fe
Mn
B
Zn
0 .125 Mo
Cu
0 .100
kg/ton DW
0 .075
0 .050
0 .025
0 .000
a
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an
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co
e
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s
s
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at
lm
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as
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t re
v
at
be
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ai
sa
ra
pa
se
be
ca
ac
ot
ce
gh
gr
flo
M
G
ow
as
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b
ar
P
il
h
or
ar
Lu
ya
un
To
O
itc
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C
ill
Ra
ug
S
So
W
S
S
As mentioned in the micronutrient explanation (see Section 2.7.1) iron (Fe) and boron (B) are the
two micronutrients commonly prone for deficiencies. On average they along with Manganese
(Mn) do indeed have the highest uptake requirement levels of the micronutrients.
To be able to incorporate the fertilizer production energy, it is more desirable to present the
nutrient uptake levels in terms of kg/ha. As the appropriate yield adjustments have been
considered, the actual “kg/ha” figures are calculated using the wet weight yield figures. The sum
of the entire crop nutrient uptake has also been calculated for display purposes.
Table 33 Nutrient uptake levels (kg/ha)
Macronutrients Micronutrients Total

Crop
N P2 O5 K2 O CaO MgO SO3 Fe Mn B Zn Mo Cu All
Common Name kg/ha kg/ha
Cassava 241.3 88.2 363.4 207.8 166.6 20.4 1.216 1.473 0.270 0.892 0.081 0.108 1092
Grass 170.7 112.8 423.0 118.4 47.7 33.8 1.410 2.256 0.100 0.564 0.100 0.113 911
Lucerne 120.0 135.0 555.0 255.0 105.0 45.0 0.900 0.750 0.450 0.375 0.005 0.105 1218
Maize 228.6 123.9 388.2 5.8 121.0 26.6 2.170 1.104 0.217 0.474 0.016 0.164 898
Oil palm 193.9 63.0 323.7 220.2 98.3 0.0 0.500 0.125 0.250 0.125 0.125 0.188 900
Potato 199.3 61.3 329.1 14.3 21.0 27.6 1.300 1.333 0.130 0.260 0.065 0.127 656
Rapeseed 351.5 34.6 507.7 122.0 10.8 28.3 2.001 0.661 0.374 0.657 0.009 0.071 1059
Sorghum 260.0 76.6 290.0 24.5 24.5 24.5 0.110 0.105 0.100 0.095 0.090 0.085 701
Soya bean 0.0 56.0 132.0 96.0 72.0 12.0 1.464 0.360 0.156 0.244 0.028 0.100 370
Sugar beet 383.3 139.7 443.3 238.3 116.0 38.3 0.300 2.000 1.000 0.150 0.050 0.100 1363
Sugar cane 33.6 42.0 184.8 58.8 70.0 35.0 0.770 0.700 0.070 0.063 0.004 0.001 426
Sunflower 205.9 136.7 605.0 330.0 110.0 31.4 1.150 0.647 0.622 0.547 0.000 0.093 1422
Switchgrass 249.2 84.0 576.0 84.0 65.0 32.0 1.200 0.980 0.280 0.460 0.006 0.098 1093
Tobacco 330.0 75.0 264.0 316.0 66.0 35.0 0.442 1.767 0.177 0.221 0.110 0.088 1089
Wheat 281.9 62.9 459.8 46.4 46.4 23.2 0.608 0.608 0.102 0.050 0.005 0.081 922
Willow tree 150.0 150.0 150.0 2.0 2.0 2.0 0.020 0.020 0.020 0.020 0.020 0.020 456

2.10 Results

By combining both the nutrient uptake levels with the nutrient production requirements the total
energetic input for the individual nutrients can be determined. The calculated NPK+CAN
fertilizer relative nutrient energy requirements will cover the blunt of the energy input flow. But,
due to restrictions in the composition of NPK fertilizers, the relative nutrient energy for several
straight fertilizers will also cover a portion of the energy input flow. The following assumptions
have been made to overcome the NPK composition restriction.
Overvi ew Nutrient input energy assumptions:
Macronutrients
Nutirent Route
Energy Exergy 1. When any of the macronutrients is larger than 25% of the nitrogen
MJ/kg
(N) Nitrogen NPK+CAN 50.90 53.99 level than that nutrients straight route will b e used for the divid end
(N) Nitrogen UAN 49.02 50.22
(P) Phos phor ous NPK+CAN 25.52 31.63 2. When the level of nitrogen is larger than both potassium and
(P) Phos phor ous SuperP 7.97 17.48
(K) Potass ium NPK+CAN 5.10 6.31
phosphorous combined than UAN will b e used fo r the divid end
(K) Potass ium
(S) Sulphur
Potash
NPK+CAN
3.22
2.27
4.11
5.16
3. The adjacent table illustrates the resulting relative nutrient energy
(S) Sulphur H 3 SO4 2.27 5.16 input for each nutrient and chosen production route in terms of
(Ca) Calcium NPK+CAN 0.94 0.74
(Ca) Calcium Dolomite 0.16 0.34 MJ/kg.
(Mg) Magnes ium NPK+CAN 0.19 0.40
(Mg) Magnes ium Dolomite 0.19 0.40
Micronutrients
Nutirent Route Energy Exergy
MJ/kg
Various O re 20.0 25.0
Table 34 Resulting nutrient energy input
Mac ronutrients Micronutrients Tota l

Crop
N P2 O5 K2 O CaO MgO SO3 Fe Mn B Zn Mo Cu Added All
Comm on Na me MJ/h a MJ/h a
Cassava 1228 0 2251 1626 196 31 46 24.3 29. 5 5. 4 17 .8 1 .6 2.2 1 6174 1 6511
Grass 869 0 2879 1685 112 9 77 28.2 45. 1 2. 0 11 .3 2 .0 2.3 1 3253 1 3542
Lucerne 610 8 3445 2015 135 20 102 18.0 15. 0 9. 0 7 .5 0 .1 2.1 6 817 1 1877
Maize 1163 7 3163 1682 5 23 60 43.4 22. 1 4. 3 9 .5 0 .3 3.3 1 6557 1 6653
Oil palm 987 1 1607 1409 208 18 0 10.0 2.5 5. 0 2 .5 2 .5 3.8 1 0632 1 3139
Potato 1014 7 1565 1436 13 4 63 26.0 26. 7 2. 6 5 .2 1 .3 2.5 1 3148 1 3292
Rap eseed 1788 9 882 2298 115 2 64 40.0 13. 2 7. 5 13 .1 0 .2 1.4 2 1069 2 1326
Sorghum 1323 4 1956 1480 23 5 56 2.2 2.1 2. 0 1 .9 1 .8 1.7 1 6728 1 6765
Soya bean 0 446 426 15 13 27 29.3 7.2 3. 1 4 .9 0 .6 2.0 885 975
Sugar beet 1951 1 3564 2263 225 22 87 6.0 40. 0 20 .0 3 .0 1 .0 2.0 2 5645 2 5744
Sugar cane 171 0 1072 659 36 13 79 15.4 14. 0 1. 4 1 .3 0 .1 0.0 1 902 3602
Sunflowe r 1047 8 3489 2338 214 21 71 23.0 12. 9 12 .4 10 .9 0 .0 1.9 1 6317 1 6672
Switchgrass 1268 4 2144 2326 79 12 73 24.0 19. 6 5. 6 9 .2 0 .1 2.0 1 7154 1 7378
Tobacco 1679 6 1914 1348 298 12 79 8.8 35. 3 3. 5 4 .4 2 .2 1.8 2 0436 2 0504
Wh eat 1434 9 1606 2013 44 9 53 12.2 12. 2 2. 0 1 .0 0 .1 1.6 1 8040 1 8101
Willow tre e 763 5 3828 766 2 0 5 0.4 0.4 0. 4 0 .4 0 .4 0.4 0 1 2238
The total “added” represents the summation of the bold figures, thus added through the use of artificial fertilizer

Figure 14 Resulting macronutrient energy input
Ma cronutrie nt Require me nts

Ene rgy Re la tio n
15000
17.9GJ/h 19.5GJ/h 16.8GJ/h
N
P2 O5
K2 O
CaO
12500 M gO
SO3
10000
M J/h a
7500
5000
2500
0
a
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ed
an
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co
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s
s
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at
m
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as
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at
al
be
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w
ai
sa
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ca
ac
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gr
ilp
lo
M
G
W
rg
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as
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b
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P
nf
h
ar
Lu
a
So
To
illo
O
oy
tc
ug
Su
C
Ra
ug
wi
W
S
Average input levels for all the choice crops:

N = 10.8GJ/ha, P2O5 = 2.2GJ/ha, K2O = 1.6GJ/ha, CaO = 0.11GJ/ha, MgO = 0.01GJ/ha, SO3 = 0.06GJ/ha.
This graphic perfectly illustrates the importance of the nitrogen nutrient. The energy input
associated with it is significantly higher than any of the other nutrients. For the legumes the levels
are zero for full inoculation and lower than average for the partly inoculated species. Switchgrass,
however, has such a large demand for nitrogen that even with partial inoculation (AMF) it is
amongst on of the most intense per land area. Phosphorous, although applied in high amounts,
corresponds to only a fraction of the energy input of nitrogen but is significantly higher than the
rest of the nutrients, affectively making it an important nutrient energy input and a major
contributor to the total nutrient energy input.

Figure 15 Resulting macronutrient energy input
Micronutrient Requirements
Energy R elation
50.0
Fe
Mn
B
Zn
Mo
37.5 Cu
MJ/ha
25.0
12.5
0.0
a
o
r
ss
ss
et
t
a lm
um
to
e
we
a
rn
tr e
av
aiz
cc
ta
be
ra
ra
he
se
be
ca
ce
gh
lp
Po
flo
ba
ss
hg
G
ow
pe
r
Lu
ya
or
r
Ca
ga
un
To
Oi
ga
it c
Ra
ill
So
Su
S
Su
W
Sw
Average input levels for all the choice crops:
Fe = 19.5MJ/ha, Mn = 18.6MJ/ha, B = 5.4MJ/ha, Zn = 6.5MJ/ha, Mo = 0.9MJ/ha, Cu = 1.9MJ/ha.
When comparing the energy input requirement of the micronutrients with the macronutrients
they are in terms of MJ/ha as opposed to GJ/ha. Thus their influence is miniscule. The figures
for exergy are very similar and can be found in the Appendix (see Section 5.16 – 5.18)
Figure 16 Total resulting nutrient energy/exergy input
Nutrient Requirements
25000
Energy 25.7GJ/ha
Exergy 28.4GJ/ha
20000
15000
MJ/ha
10000
5000
0
va
ze
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er
ss
ss
et
t
lm
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a
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tr e
cc
at
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sa
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pa
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ca
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gh
ot
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M
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as
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P
Lu
a
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ga
To
ill o
O
it c
C
oy
Ra
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Su
S
Su
W
Sw
S

2.10.2 Efficiency
Displaying the total nutrient input energy in terms of land area is misleading as each crop has
different yields and resulting energy output content. It is preformed because the total resulting
energy output (see Chapter 4) is expressed in terms of land area. Relating the two figures will
result in the nutrient efficiency as indicated by the simple formula:
Energetic _ Output[ MJ / ha]

Nutrient _ Efficiency =
Nutrient _ Input[MJ / ha ]
The following graph displays the resulting nutrient efficiency for the best practice yield:
Figure 17 Resulting nutrient utilization efficiency
Efficiencies
Ba se d on Fe rtilizer Proces In put En erg y
7000
19000 10555
Energy
10677
Exergy
6000
5000
Conversi on Perce nt [%]
4000
3000
2000
1000
0
a
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an
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co
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as
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sa
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ca
tr
ac
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gr
Po
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M
G
W
rg
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Lu
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So
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itc
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C
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Ra
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So
Su
W
S
The same graph format has been chosen as with the solar radiation utilization. The nutrient
energy input involved compared with the solar energy input is not comparable, for this reason
the conversion efficiencies are in the thousands of percent. That basically means that the shear
fertilizer manufacturing energy involved is but a fraction of the resulting output. Displaying the
nutrient efficiencies does however provide a good stance at comparing the individual crops. The
visible difference between energy and exergy for the soya bean, as an example, is attributed to the
leguminous nature of the crops. As little or nitrogen is not required, NPK is cannot be applied,
meaning the large demand of phosphorous is supplied by superphosphorous, which has a clear
deviation between process energy and exergy.

2.10.3 Analysis
Table 35 Comparative nutrient input overview
Crop Nutrient Requirements (energy) Nutrient Requirements (exergy)

Cassava - O - O
Grass O O - O
Lu cerne O O O O
Maize - + - +
Oil Palm O + O +
Potato O O O O
Rapeseed - O - O
Sorghum - + - +
Soya Beans + + + +
Sugar Beet - O - O
Sugar Cane + + + +
Sunflower - - - -
Switchgrass - - - -
Tobacco - O - O
Wheat - - - -
Willow Tree O - O -
Input: + below 5.0GJ/ha, - above 15.0GJ/ha, O betw een 5.0 – 15.0GJ/ha
Efficien cy: + above 2500%, below 1250%, O betw een 1250 – 2500%

3 Water Input
Water is life and without water there is no life. It is the most
W ater
Like sw eat, plants use w ater mainly f or limiting factor in growth. Just as a student is practically
temperature control. Aside from unproductive on a Friday morning due to the previous night’s
temperature control the transport of
nutrients from the soil is of utmost excessive obligations, insufficient water levels will also affect
importance f or the surviv al of plant lif e.
From a biological standpoint, w ater plant productively as badly as a dehydrating hangover. To
has many other distinct properties that
are critical f or the prolif eration of lif e. It attain optimal and projected crop yields it is imperative to
allow s organic compounds to react in constantly regulate the levels of water on the field. Too much
w ays that ultimately provide the
conditions f or replication. It is a good water, like that from a monsoon or flood can be equally as
solvent and has a high surf ace
tension, and thus allow s organic detrimental as a long dry spell or drought. This has resulted in
compounds and living things to be
transported in it.
a wide variety of farming systems developed to regulate water
levels; irrigation to supply and drainage to remove excess
water. Civilizations have been founded upon proper understanding of water management
eventually involving massive engineering undertakings to regulate water flows. Although water
has many other purposes aside from crop production, for instance drinking and washing, globally
seen more than 70% of the freshwater is used for agricultural purposes. It can take more than
500 litres of water to produce just one kg on cereals38. The relation to energy, however, may not
be easy to comprehend as in the Northern regions rain is one thing not in short supply. Dark
humour is even said to have its birth from excessive rain. In fact, with the additional water flows
from rivers, many regions have too much water. In these cases water needs to be pumped out
where in the other cases water needs to be pumped in; pumps being the energy consumer.
Alongside solar radiation and nutrients, it is the third primary energy input for plant growth. The
level of energy required is naturally different being climate, topography and water source
dependent. In many areas the input is next to zero where in some regions it is the most expensive
input. As the biobased economy is realized, the global crop production will further increase
alongside the increased demands of a raising population with higher affluence, consequently
necessitating more water. The process energy input and relative price of water is still (generally
speaking) low but as competition and demand rises, irrigation/drainage capacities need to be
supplemented through expanding existing and by adding new and possibly different systems. The
world over freshwater is being mined faster then it is being regenerated, it is almost certain that
water will become more energy intensive and expensive. Desalination of saltwater is the extreme,
presently costing between 17.3 – 34.2MJ/m³ to purify39.
Understanding the regional and crop based relation towards water
demand can mitigate the looming energy increase or at least
identify possible saving options. The goal being, the most “crop for
the drop.” This section will outline the current irrigation and
drainage requirements for the specified crops in the correlating
regions and relate it to energy and exergy input.

3.1 Crop Water Demand
The amount of water a crop needs has many variables, but is primarily a function of the plant in
question, current growth stage and regional climate factors. A single farm may have sufficient
data to calculate the exact quantity of water needed in a particular week based on the current
seasonal weather and growth developments. Yet to create a model for location-based crop needs,
some estimates and generalizations are necessary. This is mainly due to the insufficient data, but
good estimates are possible by following the steps mentioned.
3.1.1 Seasonal Amount

Specified in the crop guide (Chapter 8) ) is the range of water demand for each crop. The growth
season water need for several popular crops is provided by FAO 40. The following table outlines
the seasonal water uptake for each crop:
Table 36 Seasonal crop water demand
Low Average High Best Practice

Crop
mm
Cassava 50 150 200 175
Grass 210 500 820 660
Lu cerne 800 1030 1600 1315
Maize 500 750 800 775
Oil palm 1750 2000 2300 2150
Potato 500 600 700 650
Rapeseed 100 250 830 540
Sorghum 200 500 750 625
Soya bean 450 600 700 650
Sugar beet 550 600 750 675
Sugar cane 1500 1675 2500 2088
Sunflower 600 900 1000 950
Switchgrass 300 350 400 375
Tobacco 400 500 600 550
Wheat 450 550 650 600
Willow tree 500 600 2000 1300
The maximum water tolerance is also listed in the crop guide for many of the crops, in regards to
flood and heavy rain periods. This is not related to the high mentioned above; the high figures
represent to maximum level of water before negatively affecting plant production. It will be used
for the eventual calculation of drainage. Since the typical growth regions were specially selected
for the various crops, the average water uptake values are representative for those particular
regions. However, as the best practice yields were choice over the regional average it is wise to
compensate, for best practice farmers are more likely to actively regulate irrigation and drainage
levels to obtain the higher yields. And simply by having more biomass the crops will necessitate
more water. The median between the average and high water demand will be used to represent
the best practice water demands, listed in the table.

3.1.2 Relation to Monthly Evapotranspiration
When speaking in terms of irrigation and crop water uptake, figures are mainly presented on a
monthly basis. This corresponds well with the rainfall figures (following section) and the growth
characteristics of the crop, which are also usually expressed in monthly terms. Each crop has a
different growing season and growth development trends. Depending on the stage of
development and the time of the year, the crop will require different levels of water. The amount
of water uptake required by a plant is called evapotranspiration. It is the combined effect of
evaporation and transpiration. Evaporation being the amount of water in the soil converted to
vapour (i.e. climate dependent) and transpiration being the amount of additional water sucked
through the roots and emitted by the leafs (i.e. growth stage dependent). Using those two factors,
growth stage and solar radiation, the seasonal water uptake can be converted to monthly
evapotranspiration.
3.1.2.1 Growth Stage Factor

Each crop has four stages in growth; initial (or emergence), crop development (or rapid growth),
mid-season (or full size), and late season (or maturity). The following picture illustrates the
seasonal growth stages for the various crops types41:
Figure 18 Crop growth stages
A selection of available crop figures was used to calculate the generalized duration percentage for
the three applicable groups of crops over the entire growing season. Figure 19 plots the crops
with known values and is used to create Table 37 for the group types.

Crop Development
90
w hea t 85
80 ma ize 80
p otato
70
so rghu m
so yb ean
60
su garb eet
Duration Perc entage
su nflow er
50
An nua l Ave rag e
40
40 An nua l Cho sen
Pe renn ial Grasse s

30 Pe renn ial Scru bs/Tre es 25
20 20
15 10
10
5 5 5
0
In itial Devel opment Mi d-Season Late Seaso n
Stages
Figure 19 Crop Growth Stages
Table 37 Crop growth stage duration percentage
Initial Development Mid-Season Late Season

Crop Classification
Percentage of growing season (%)
Annual 15 25 40 20
Perennial Grasses 5 10 80 5
Perennial Scrubs/Trees 5 5 85 5
These values essentially relate to the green leaf area index (LAI) or in other words the total
surface area of leafs in relation to the ground coverage. High LAI figures correspond to a higher
leaf mass and therefore a higher respiration rate of the crop and thus more transpiration. At full
growth (i.e. mid-season) the LAI can range from max 3 for succulent leafs (like grass) to 5 – 6 for
thin leafs (like maize). The following graph depicts the LAI development of the maize crop over
the growing season41:
Peak
Average Mid-Season
Initial Development Mid-Season Late-Season
Figure 20 Crop leaf area index development

The actual LAI figures vary for each crop, but are not of importance for the calculation of
evapotranspiration as the curves follow the same trend. It is the relationship that will be used for
calculation. By marking each growth stage alone the curve figures can be generated. Maximum
transpiration occurs during the entire span of the mid-season. As mid-season is reached before
the peak, the 100% LAI in relation to transpiration is set to the stage average allowing the other
growth stage leaf cover percentages to be determined:
• Initial: 12.5%
• Development: 68.8%
• Mid-Season: 100%
• Late Season: 75%
Combing the leaf cover percentage values, the duration in the particular growing stage and the
growing season together will yield the growth stage factor
3.1.2.2 Solar Radiation Factor

The most common and FAO recommended formula for calculating the reference
evapotranspiration is the Penman-Monteith method41. Reference evapotranspiration is more or
less just the soil evaporation of the specific region, as it is based solely on the regional climate and
soil conditions and is accurate for a daily figure:
900
0.408 ⋅ (Rn − G ) + γ ⋅ ⋅ u 2 ⋅ (es − ea )
ETo = T − 273
∆ + γ ⋅ (1 + 0.34u 2 )
Rn : Net radiation (MJ⋅m -2⋅day-1)
G: Soil h eat flux density (MJ⋅m -2⋅day-1)
T: Mean daily air temperature at 2 meter height (°C)
u 2: Wind speed at 2 meter height (m⋅s-1)
es: Saturation vapour pressure (kPa)
ea: Actual vapour pressure (kPa)
∆: Slope vapour pressure cu rve (kPa⋅°C-1)
γ: Psychrometric constant (kPa⋅°C-1)
On the farm scale it is possible to obtain all the necessary data to calculate the actual reference
evapotranspiration for that particular plot over the course of a year. However, on a global scale,
regional climate deviations make it vastly complex to calculate reference evapotranspiration to a
high degree of accuracy. By taking a closer look at the formula it is apparent that the solar (net)
radiation (Rn) has the largest influence in the result. Solar radiation for each month is known for
each crop. The monthly percentage ratio of solar radiation can be calculated by using the total
input over the growing season. It is therefore assumed and simplified that only solar radiation has
an influence on the reference evapotranspiration, effectively becoming the solar radiation factor.
A detailed calculation comparison and description was conducted under Dutch conditions for the
potato crop to validate the simplification.

3.1.2.3 Solar Radiation Factor Assumption Valorization
The Penman-Monteith formula is accurate enough for a single day, but in the calculation path
monthly figures will be used instead. Each factor will be mentioned and handled individually:
• Net Radiation: Same data as in the solar radiation input section
• Soil Heat Flux Density: Typically the figures range from 1-5% of the net radiation. It is the
effect of the soil cooling and emitting heat. A value of 2.5% will be taken
• Mean Temperature: For the region average highs and lows are well documented. The mean
of those two figures will be used for the monthly temperature figures
• Wind Speed: Wind speed data is hard to come across as most studies are designed for wind
turbine applications (i.e at a height of 50m+) or nautical purpose (i.e over water). Wind
speeds of 1-4m/s are typical in most regions of the surface. The reason for choosing
2.25m/s will be discussed later
• Saturation Vapour Pressure and Actual Vapour Pressure: The high and low of the relative
humidity is well known and documented for the region. By adjusting the mean relative
humidity to the saturation vapour pressure of around 2atm, the difference is determined.
• Slope Vapour Pressure: Slope vapour pressure is calculated using a large formula which has
only one variable, mean temperature
• Psychrometric Constant: It is not actually constant as it is a function of pressure and
temperature. It is also calculated for each month
The following table illustrates the calculation path of the reference evapotranspiration:
Formula based ETo
Month - jan feb mar apr may jun jul aug sep oct nov dec
Days/Month day 31 28 31 30 31 30 31 31 30 31 30 31
MJ/m²/month 22.9 39.8 77.5 113.7 152.5 147.0 153.8 131.1 84.9 52.7 27.6 18.6
Net Radiation
MJ/m²/day 0.740 1.420 2.500 3.790 4.920 4.900 4.960 4.230 2.830 1.700 0.920 0.600
Soil Heat Flux Density MJ/m²/day 0.019 0.036 0.063 0.095 0.123 0.123 0.124 0.106 0.071 0.043 0.023 0.015
o
Low ( C) 0 1 3 6 10 13 13 15 13 9 5 2
o
Mean Daily Temperure High ( C) 4 5 8 11 16 17 20 20 17 13 7 5
o
Average ( C) 2.0 3.0 5.5 8.5 13.0 15.0 16.5 17.5 15.0 11.0 6.0 3.5
Wind Speed m/s 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25
Low 60 61 62 64 68 72 76 77 68 71 65 63
Relative Humidity High 94 95 94 93 96 97 97 97 89 97 97 97
Average (%) 77.0 78.0 78.0 78.5 82.0 84.5 86.5 87.0 78.5 84.0 81.0 80.0
Slope vapour pressure kPa/C 0.050 0.054 0.063 0.075 0.098 0.110 0.119 0.126 0.110 0.087 0.065 0.055
Latent Heat of Vapourization MJ/kg 2.496 2.494 2.488 2.481 2.47 2.466 2.462 2.46 2.466 2.475 2.487 2.493
Atmospheric Pressure kPa 101 101 101 101 101 101 101 101 101 101 101 101
Psychrometric Constant kPa/C 0.066 0.066 0.066 0.066 0.067 0.067 0.067 0.067 0.067 0.067 0.066 0.066
mm/day -2.78 -1.22 1.187 3.69 5.13 4.672 4.463 3.109 1.331 -0.92 -2.46 -3.23
Evapotranspiration mm/month -86.3 -34.1 36.78 110.7 159 140.2 138.4 96.37 39.93 -28.4 -73.9 -100
mm/month 0.0 0.0 36.8 110.7 159.0 140.2 138.4 96.4 39.9 0.0 0.0 0.0
Reference evapotranspiration is only the first step in determining the crop specific
evapotranspiration. Each crop has a so-called “crop factor” for each stage of development in
relation to water uptake. The growth stages and duration were already determined as a
prerequisite for the LAI assumption; the same figures will be taken. The crop factor for the
potato is available for several sources and is based on the development stage of the growth
season. The following table illustrates the crop factor and the resulting evapotranspiration:

Potato crop factor
Crop Potato
Growth yes/no 0 0 0 1 1 1 1 1 1 0 0 0
Stage - 0 0 0 I D D M M L 0 0 0
Crop Factor Kc 0 0 0 0.45 0.75 0.75 1.15 1.15 0.85 0 0 0
Water Needs mm 0.0 0.0 0.0 49.8 119.3 105.1 159.1 110.8 33.9 0.0 0.0 0.0
It was mentioned previously that exact wind figures are not available and a best guess was
necessary. It is known that the potato requires 500 – 700mm/year of water with an average of
600mm. Holland is has a mild climate, so the water requirements will tend to be on the low side.
By adjusting the wind figures the total potato evapotranspiration is set to a value just below
600mm. In this case by setting the wind speed at 2.25m/s the resulting total water uptake for the
crop is 578mm.
Comment:
During months were the temperature is below 5° C and/or the solar radiation is below 75MJ/m²
the evapotranspiration is negative, meaning that evaporation does not take place. Any rainfall
occurring at that time is collected and contained in the soil. This correlates well with the other
assumptions of using the rain water during the off-growing seasons.
Comparison
The following graphs represent the comparison between the actual formula, data specific method
and the assumption listed in Chapter 5
Reference Evapotranspiration
Reference Evapotranspiration
175
Penman-Monteith Formula
Adapted Assumption
150
125
100
mm
75
50
25
0
jan feb mar apr may jun jul aug sep oc t nov dec

Crop Water Requirements
Crop Water Requirements
175
Penman-Monteith and Crop Factor
Assumption and LAI
150
125
100
mm
75
50
25
0
jan feb mar apr may jun jul aug sep oc t nov dec
It appears that the differences between the two and more importantly the final crop
evapotranspiration are small, valorizing the assumption.
3.1.2.4 Evapotranspiration
Monthly Evapotranspiration
180
Cassava Africa Nigeria

160
Grass Europe Holland
Lucerne North America Wyoming
140
Maize North America Iowa
Oil palm South Pacific Malaysia
Monthly Water Uptake /mm
120
Potato Europe Holland
100 Rapeseed Europe Belgium

Sorghum Africa Kenya
80 Soya bean North America Illinois

Sugar beet Europe Germany
60 Sugar cane South America Brazil

Sunflower Europe France
40 Switchgras s North America Oregon

Tobac co South Pacific Aus tralia
20 Wheat Europe Franc e

Willow tree Europe Sweden
0
Jan Feb Mar Apr May Jun Jul Aug Sep Oc t Nov Dec
Months
Figure 21 Resulting monthly evapotranspiration

Combing both the growth stage factor and the solar radiation factor will yield the monthly
evapotranspiration (or crop water demand). The Penman-Monteith also contains a factor of
0.408 for the solar radiation. This additional factor will be included to lower the impact of the
solar radiation while placing more stress on the growth stage. The evapotranspiration for all
plants have a bell-curve trend over the course of the growing season. The following graph
illustrates the resulting monthly evapotranspiration for the selected crops. It is noticeable that
indeed bell-curves are present, suggesting the method was successful in converting seasonal water
demand to monthly figures.
3.2 Rainfall
In regions where sufficient rainfall is present for the cultivation of a particular crop, the
agricultural practice is called dryland farming or more appropriately rainfed farming. The previous
term may sound contradictory since these are in fact wet regions, but because no additional water
in the form of irrigation is required; they are kept “dry”. Arid regions have less than 500mm of
rainfall per annum and fundamentally rely on irrigation for crop production40. The level of rainfall
reduces the need for supplementary irrigation and as a result the associated water management
costs. Rainwater (or precipitation) is free as it falls from the sky. And the gravitational potential
energy is too spread out to be utilized or to be assigned an energy charge, save for the large
hydrodams consisting of vast ridges and valleys. However, should too much rain fall and surpass
the high range of monthly evapotranspiration drainage is required, meaning the free source
receives a negative cost. But for the large part, crops have been selected to grow in the best suited
regions keeping drainage and irrigation to a minimum. Rainfall generally reduces the need to
apply water.
3.2.1 Regional Figures

Rainfall values are based on a monthly basis over a 10-year average from the years 1961 to 1990.
Data is available for the entire world over and was obtained from:
• The Deutscher Wetterdienst (National Meteorological Service of Germany)42
The location is stipulated using the global coordinate system and through a formula to derive at
the values listed in the provided excel table.
• Row=((90-Latitude)*360)+1+(180+Longitude)+17
Just as with the solar radiation figures, the accuracy is based on 1deg. This results in a location
grid area of 100x100km for regions above the Tropic of Cancer and below the Tropic of
Capricorn and 150kmx150km for those in between. Likewise in regards to cultivation areas, these
differences are insignificant. Table 38 lists the monthly precipitation values for the corresponding
locations

Table 38 Location based rainfall values
Representative Area GCPP Precipitation Values

Crop Continent Country/Region
Latitude Longitude Grid Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Common Name Largest Producer Degrees 1.0deg mm/month
Cassava Africa Nigeria 8 7 29725 6 12 47 107 179 197 211 219 245 144 11 3
Grass Europe Holland 51 5 14243 66 57 68 59 68 78 75 68 60 66 75 76
Lucerne North America South Dakota 44 -103 16655 9 12 24 49 72 80 59 41 31 24 12 11
Maize North America Iowa 41 -91 17747 39 36 74 98 98 104 104 94 94 74 53 51
Oil palm South Pacific Malaysia 2 113 31991 411 259 278 259 233 232 221 265 274 314 370 404
Potato Europe Holland 51 5 14243 66 57 68 59 68 78 75 68 60 66 75 76
Rapeseed Europe Belgium 50 5 14603 76 64 72 59 71 77 66 64 65 72 83 84
Sorghum Africa Kenya 0 35 32633 68 77 108 176 125 65 63 66 55 57 97 77
Soya bean North America Illinois 41 -90 17748 41 39 76 100 97 104 101 88 90 68 58 57
Sugar beet Europe Germany 52 8 13886 65 43 64 48 68 79 66 63 59 52 63 71
Sugar cane South America Brazil -25 -50 41548 178 162 146 92 104 103 85 80 116 138 118 158
Sunflower Europe France 48 0 15318 63 59 56 50 63 47 46 46 53 59 67 63
Switchgrass North America Iowa 41 -91 17747 39 36 74 98 98 104 104 94 94 74 53 51
T obacco South Pacific Australia -34 145 44983 35 26 34 37 45 30 32 38 34 39 25 30
Wheat Europe France 48 0 15318 63 59 56 50 63 47 46 46 53 59 67 63
Willow tree Europe Sweden 56 13 12451 53 33 43 40 42 53 68 58 61 60 68 60
3.2.2 Effective Rainfall

Not all of the rainfall can be utilized by the crop; there are many limiting factors which prevent
the full use of the rainfall. The actual amount of rainfall that can be utilized by a crop is called the
effective rainfall. 43 It is essentially the rainfall minus runoff, immediate evaporation and deep
percolation (leaching). The factors affecting effective rainfall are: Climate, Soil Moisture Content
Soil Texture, Soil Structure, Depth of Roots and Topography. There are several empirical
formulas available at various levels of detail44. Seeing that the only information available is the
regional rainfall figures a formula pertaining to the relation between actual rainfall and effective
rainfall must be chosen. There are two such methods; the Renfro and the US Bureau of
Reclamation. The following graphic depicts the relationship between actual and effective rainfall:
Figure 22 Effective rainfall
Effective Rainfall
175
US Bureau of Reclamation Renfro
Pe=0.95*P for <25.4mm Pe=0.6*P-10 for under 75
150 Pe=24.1+0.90(P-25.4) for 25.4<P<50.8 Pe=0.8*P-25 for over 75mm
Pe=47.0+0.82(P-50.8) for 50.8<P<76.2
Pe=67.8+0.65(P-76.2) for 76.2<P<101.6
Pe=84.3+0.45(P-101.6) for 101.6<P<127.0
125
Pe=95.8+0.25(P-127.0) for 127.0<P<152.4
Pe=102.1+0.05(P-152.4) for >152.4mm
Effective Rainfall /mm
100
2
y = -0.003x + 1.1743x - 1.7168
75
y = 0.7984x - 24.695
50
25
2
y = 0.0044x + 0.1845x - 1.4167
0
0 50 100 150 200 250
Actual Rainfall /mm

The US Bureau of Reclamation is better suited for arid to temperate regions which do not have
particularly high amounts of rain, whereas the Renfro method is better suited for regions of high
rainfall. The borderline will be drawn at 150mm. Should a location have more than 150mm actual
rainfall in any month the Renfro method will be applied, else the USBR method.
3.3 Irrigation/Drainage Requirements

In cases where the monthly effective rainfall does not meet the level of monthly
evapotranspiration irrigation is required. Moreover, when the monthly effective rainfall exceeds
the high monthly evapotranspiration drainage is required. The water for irrigation has many
sources and systems, which can be generalized for an entire region. In more advanced systems
irrigation can also be used to provide fertilizers, pesticides, herbicides and insecticide, control the
soil temperature and balance the salinity (covered in Chapter 6). Depending on the quality of the
source water and the extent of supplements, it may become necessary to flush more than the
required levels of water to leach salts, acids and alkalis out of the soil45. The maximum height of
the water table is of great importance for drainage systems. In the event that the water table has
risen above the root line, the problem of “wet feet” and water logging can occur, greatly stunting
crop growth.
3.3.1 Systems and Sources

The vast majority of irrigation systems are based on using the gravitational force to redirect large
bodies of water, i.e. rivers and lakes. In these cases the differential height the water needs to be
pumped up and down for control is kept very low, essentially keeping the energy costs at a
minimum. The same source and diversion systems can however have a different application
adding significantly to the energy costs. In Babylon the world could wonder at their great
construction, The Hanging Gardens. It was the first irrigation system in the world to emulate
rainfall. Today sprinklers are common in many parts of the world. They require high pressure to
operate and thus require large amounts of energy input, but are more effective. Each system has a
different rate of water application efficiency. The rate of efficiency stipulates how much
additional water must be supplied to obtain the stipulated irrigation requirement. In several parts
of the world water sources cannot be redirected using gravity, but must employ large pumping
systems. Underground aquifers are a good and ample source of water for many highly productive
regions but require substantial amounts of energy for the extraction; the cost being dependent on
the surface depth of the reservoir. The following outlines the various systems and related
assumptions needed to calculate the level of irrigation, drainage and energy demand46, 47.
3.3.1.1 Furrow
Furrows are small parallel channels made to transport water to and from the
field. The crop is usually grown on the ridges between the furrows. It is
suitable for the largest array of crops.
Circulation/additional height: 2.0m, Efficiency: 50-90% 70%

3.3.1.2 Basin
Basins are large but shallow artificial bodies of water contained within bunds.
They are used to slightly flood the fields. There are also a variant between a
furrow and a basin, called border irrigation, used to guide water down slopes.
Border irrigation has the same properties, so will be classified as basin.
3.3.1.3 Drip
Drip systems consists of a series of thin pipes distributed alone the fields in a
similar configeration as furrows. The heads are places at the base of the plant
to ensure a very high water efficiency and are cheifly utilized in hot regions.
3.3.1.4 Sprinkler (travelling gun)

Sprinklers pressurize water in order to distribute it through a series of pipes
and finally sprayed, simulating natural rainfall. It is sprayed into the air to
reduce the water droplets that fall on the crops. Rotor heads have pressures
between 2.75-9bars. Typical is 4.5bar. It is suitable for all row crops.
3.3.1.5 Sprinkler (center pivot)

Another variant of the sprinkler system is the center pivot, using a series of
tracks to guide the overhead spray in a circular path alone the field. The water
efficiency and energy use is immensely improved. Pressures are reduced to
2.75bar while the air losses are kept to a minimal.
3.3.1.6 Water body

Redirecting a river will require 0m of pumping height. Tapping a lake to allow
it to flow, presumably into a gravitational powered channel, will require about
5m initial pumping height. The surface depth of an aquifer can range from
several meters to several hundred. Of those in question the range more
around 20 – 100mm, so the average will be set at 50m.
3.3.1.7 Drainage
Water collected at the desirable water table must be pumped up and out of
the fields and back into the channels. A system of underground pipes and
porous material are used to divert the water to a central pump. The pipe
depth is slightly below the root length, so a value of 3meters is typical.
Subirrigation works in the same way but reversed with the exception that the
pipes are at more or less at root level close to the surface, so 0.5meters.

3.3.2 Irrigation Levels
The following graph illustrates the resulting irrigation and drainage requirements, the values and
calculations behind the graph are found in the accompanying database spreadsheets:
Figure 23 Irrigation and drainage requirements
Irrigation and Drainage Requirements

3000
Water Uptake
Corrolating Effective Rainf all
I rrigation
Drainage
2500
2000
Water /mm
1500
1000
500
0
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It is clear that most crops require next to no irrigation and drainage, whereas some on the
contrary need large amounts. The cassava in particular needs lots of drainage and the sugar cane
large amounts of supplementary irrigation.
3.3.3 Pump
The most common pump for liquid displacement, like
that of water systems, is the centrifuge pump48. They
deliver high flow rates at comparably low pressures
meaning that the energy consumption is kept fairly low.
The volume displacement efficiency is in the range of
90-98%, with 98% being frequently obtained. The
pressure efficiency (or pressure loss) is slightly worse,
but still high, ranging from 80-90%; 85% being set as typical. The following formula is used to
calculate the power based on the amount of displaced water (irrigation/drainage), the static
height (pump level) and the pump efficiencies:

P = ((V& ⋅η v )⋅ H ⋅ δ ⋅ g )⋅η p
V& : Volume flow (m³⋅s-1)
η v : Volume displacement efficien cy (%)
H: Dynamic height (m)
δ: Fluid density (kg⋅m -3)
g: Gravitational acceleration (9.81m⋅s-2)
η p : Pressure displacement efficien cy (%)
The yearly volume flow (resulting irrigation and drainage requirements) must be converted to
seconds. The resulting power is terms of kW and must be multiplied by the factor 8760 for yearly
kWh and again by 3.6 for MJ.
3.3.3.1 Fuel Source

The sources of energy to fuel the irrigation/drainage pumps are as diverse as the regions where
they are operated. The common three are pure electricity from the grid, natural gas and diesel. In
some rare cases other fuels may be used, for instance fuel oil may be easier and cheaper to
acquire in Africa than diesel, but these minor exceptions have little significance. On the pump
itself the various fuels have negligible influence on the pumping efficiency. However, the major
significance of incorporating the fuel source is for cumulative energy and exergy. The conversion
factors were covered in chapter 2. To increase energy efficiency, in many regions it has been
proposed to switch from electricity to natural gas driven pumps. Subsides have even been
imposed in America to help farms make the switch49. The following table gives an overview of
the systems for the region and crop, resulting dynamic height for both irrigation and drainage and
the fuel type, some this information was already incorporated to determine the irrigation levels:
Table 39 Irrigation system layout for region and crop
Irrigation Dynamic Height Pump Configuration

Crop Producer
Type Source Hir rigation Hdrainage Fuel
Common Name Region - - m type energy exergy
Cassava Nigeria Drip Lake 2 3 Diesel 1 1
Grass Holland Sprinkler-TG River 45 3 Natural Gas 1 1.05
Lucerne South Dakota Sprinkler-CP Aquifer 77.5 3 Electricity 0.45 0.35
Maize Iowa Sprinkler-CP Aquifer 77.5 3 Electricity 0.45 0.35
Oil Palm Malaysia Basin River 1 3 Diesel 1 1
Potato Holland Furrow River 2 3 Natural Gas 1 1.05
Rapeseed Belgium Basin River 1 3 Natural Gas 1 1.05
Sorghum Kenya Drip River 2 3 Diesel 1 1
Soya Beans Illinois Sprinkler-TG Aquifer 95 3 Electricity 0.45 0.35
Sugar Beet Germany Sprinkler-TG River 45 3 Electricity 0.45 0.35
Sugar Cane Brazil Subirrigation River 0.5 3 Diesel 1 1
Sunflower France Sprinkler-TG River 45 3 Electricity 0.45 0.35
Switchgrass Oregon Furrow River 2 3 Electricity 0.45 0.35
Tobacco Australia Drip Aquifer 2 3 Diesel 1 1
Wheat France Sprinkler-TG River 45 3 Electricity 0.45 0.35
Willow Tree Sweden Furrow River 2 3 Electricity 0.45 0.35
Kenya: typically a furrow system is employed but drip systems are advisable for near future developments
Australia: currently a basin-like system is frequent, but tobacco figures based on a system similar to drip
Nigeria: basin is currently used as easy to make, when large scale investments in region drip should be employed
America: centre pivot only employed in mid-west

3.4 Resulting Energy

The difference in quantitive levels of water requirements and the relation to energy demands are
stark. The following graph incorporates all factors mentioned in terms of MJ/ha:
Figure 24 Resulting irrigation/drainage input
Irrigation and Drainage

10000
22.9GJ/ha 10.5GJ/ha Irrigation/Drainage E nergy
29. 4GJ/ha 13.5GJ/ha
Irrigation/Drainage E xergy
9000
8000
7000
6000
MJ/ha
5000
4000
3000
2000
1000
0
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Lucerne (or alfalfa) is grown in a region that requires a high level of irrigation, supplied in
particular from an aquifer via an electric pump control system. It has an input well above
20GJ/ha. Despite the center pivot improvement, irrigation is probably the most expensive input.
The sugar cane had high irrigation requirements, nearly a factor 2 more than the lucerne, but due
to the cost effective system results in a much less energy intense input.
3.4.2 Conversion Efficiency

As opposed to the other energy input streams where all crops in all regions had an energetic
input in many regions crops can be cultivated without the need of an energy intensive water
management system. For this reason it makes little sense to present the figures for those few
crops in a conversion efficiency graph.

3.4.3 Analysis
The water requirements can be seen in two ways; as being the absolute total amount of displaced
water needed or as being the related energy costs. For as technology progresses the costs of
irrigation and drainage could decrease. As an example, several large scale installation in the Great
Plains of America have recently employed low pressure pivot sprinkler systems
and have reduced the energy demand by a substantial amount (see adjustment
picture). This trend could be realized for many of the systems and the different
regions. But, as previously mentioned, the foreseeable increase in water
competition may make water a limited and costly resource to obtain. It is hard
to speculate which direction the relative irrigation and drainage energy cost will
go. This is why the following table is expressed in both absolute terms and in
relative energy terms:
Table 40 Comparative irrigation/drainage input overview
Crop Irrigation and Drain age Requirements

Irrigation Drainage Combined
Common Name
Level Level Energy Exergy
Cassava O - O O
Grass O O - -
Lu cerne - + - -
Maize O O - O
Oil Palm O O O O
Potato - O O O
Rapeseed O O + +
Sorghum O O + +
Soya Beans O O - -
Sugar Beet O O - -
Sugar Cane - + O O
Sunflower - + - -
Switchgrass + O + +
Tobacco O O O O
Wheat O O - -
Willow Tree - + O -
Level: + 0mm, - above 250mm, O between 0 – 250mm
Energy: + 0MJ/ha, - above 500MJ/ha, O betw een 0 – 500MJ/ha
Any crops with a negative sign should be paid special attention to. But, for those crops that have
a negative level and an “O” for energy, already have a good and energy efficiency system.

4 Pesticide Input
4.1 Preface

Connecting the vast oceans of the Pacific with the Atlantic has been an overzealous dream of
world leaders for centuries. It was not until after the success of the Suez Canal, that in 1880, the
French undertook the vast engineering project to construct the Panama Canal. Their failure can
only partly be attributed to natural circumstances and miscalculations; malaria and the yellow
fever had killed over 22000 workers in a span of just 8 years. The route cause of such diseases
was unknown until shortly before the Americans restarted the project in 1904. A theory had been
developed suggesting that mosquitoes harboured and transmitted
the deadly diseases. At the time, the best mitigation and most
ingenious infection prevention system was simply sanitation and
larvae eradication. By providing shielding for the workers dwellings
and hospitals (portable fever cages) and oiling over small water
bodies, mosquito population drastically fell, as did the cases of
malaria and yellow fever. These methods are expensive, time consuming and are a far cry from a
final solution to the problem. In regions were international trade incentives were not important
the diseases continued to spread, killing millions.
Although dichlorodiphenyltrichloroethane (DDT) was first

synthesized in 1873, it was not until the early stages of the
Second World War that Swiss chemist Paul Hermann Müller
discovered its poisoning affects against arthropods like
A mosquito cried out in pain: mosquitoes. DDT was initially and extensively employed by the
“A chemist has poisoned my brain!”
The cause of his sorrow
Allies to regionally control both malaria and typhus. In the 50’s
Was para-dichloro and 60’s DDT was sprayed the world over and is credited for
Diphenyltrichloroethane
- Adam Bernard
the elimination of malaria in Europe and North America. For
his discovery of the high contact poison efficiency of DDT,
Müller was awarded the Nobel Prize in 1948. It is in affect the first pesticide and the transition to
agricultural applications did not take long. The crop related advantages were so great that in the
mean time more than 2500 different pesticides have since been developed (of which more than
1100 have ISO nomenclatures50), creating an entirely new industry…the agrichemical sector.
4.1.2 Agricultural Applications

Sufficient solar radiation, nutrients and water is not enough to guarantee high crop yields. What
Pest: A plant or animal regarded as injurious or unwanted; in agricultural terms competing for or limiting the human supply chain (crops)
are classified as pests can greatly reduce the potential yield of the crop by utilizing the favourable
conditions provided by modern farming techniques; more or less striving from the inputs

intended for the crop. There are four main types of pests hindering the crop growth in
completely different ways that necessitate a unique method/chemical of treatment:
1. Unwanted plants (mainly weeds) will compete against the crop for the
same nutrients, water and ground cover (solar radiation)
o Manual Method: Burning fields, physically removing weeds
o Agrichemical Method: Herbicides
2. Insects and other arthropods will eat at the crop leafs/fruits destroying
or stunting growth
o Manual Method: Screens, generally very little
o Agrichemical Method: Insecticides
3. Fungal infection will decompose the plant matter and use the nutrient
stream to further spread
o Manual Method: Remove the infected section
o Agrichemical Method: Fungicides
4. Roundworms living in the soil can either infect the plant and use its
nutrients or multiply in the soil affectively competing against the crop
o Manual Method: Selective breeding, generally very little
o Agrichemical Method: Nematicides
These four groups represent practically all the crop pests and protection measures. There are of
course other pests, like animals and birds, but chemical prevention is not a socially accepted
method of protection and their influence for the most part is minute. A scarecrow works just
fine. The manual methods of plant protection are hardly carried out in the develop world
anymore as it is very labour intensive with relatively ineffective results compared to the chemical
treatment. In many developing countries, however, pesticides are too expensive to use and is a
major factor why their crop yields are so pathetic.
All crops and thus crop yields are prone to other more serious pests, namely viral infections and
diseases. In worst cases scenarios entire harvests can be lost, lowering the regional yield of such
crops. The manual method sacrifices the entire harvest, by completely disposing of the infected
fields. In food production the yield is affectively zero, yet for industrial applications it is easily
foreseeable that the energy and materials can still be retrieved. Nonetheless the physical yields are
lowered. Much investigation has gone into plant breeding, both in the lab and on the field, to
create protection methods against the pest. However, since agrichemicals (like bactericides and
virucides) are in their infancy and only represent a minor fraction of cure techniques these pests
will not be considered in this section. Furthermore since such pests are fact, the regional yield
figures incorporate these losses.
Some of the amazing crop yields recorded in recent times simply could not have been possible
without the widespread use of pesticides. Water, sun and nutrients can be used by any organism
on the field. Pesticides make sure that it is, to the highest degree, the desired crop. The use of

pesticides can be especially exuberant in highly intensified farming regions like Holland,
exceeding the typical application rates of between 2 – 10 kg active ingredient per hectare51. Yet,
when balanced with the yield benefits still prove very profitable. Since the 1950’s the production
of pesticides has increased more than 50-fold with current worldwide production at more than
2.5 million tonnes annually and the EU alone consuming 0.3 million tonnes52. Due to the many
environmental problems associated with pesticides, like persistent organic pollutants (POP), a
gradual transition on the field level is occurring. For example, Integrated Pest Management is a new
method intended to reduce the level of pesticides applied to a field by making their use more
effective. But more drastic are the chemicals themselves, many older pesticides have been banned
and phased out by newer, more pest specific and less harmful agrichemicals. DDT, the world’s
first pesticide (insecticide), is now completely banned in 98 countries.
4.2 Process Energy

Pesticides are not a primary energy input in the sense of being directly used as a source for crop
growth. They are however, designed to maximize the use of the other primary energy inputs
while requiring a hefty amount of process energy themselves. Compared to fertilizers the
applications rates per field are but a small fraction, yet due to the complex and large chemical
structure of the pesticides, the required production energy is several magnitudes larger. Process
energy range from 50 to 900MJ per kilogram of active ingredient, roughly ten times the amount
required for fertilizers. The deviation correlating to the range of 50 to 900MJ/kg is fairly large as
the chemical structures and associated process energy vary substantially.
Example: 2,4-D has a relatively simple structure consisting of a carboxylic acid attached to a
benzene ring with two straight chlorine functionalities. Cypermethrin has in contrast has a very
large structure with several different forms of functionalities; oxides, amides, chlorides, etc.
2,4-D Cypermethrin
The difference in process energy between the two pesticides is 824 – 115 = 709MJ/kg
Assuming one averaged value for all pesticides can lead to high uncertainties in the calculations
of the pesticide input energy requirements. The calculation path described here within has been
specially chosen to reduce the impact of assumptions by avoiding large averages whenever
possible, thus increasing the certainty. In some cases where data is scarce it is unavoidable to use
such simplifications.
4.2.1 Source of Data

There are currently over 2500 different pesticides on the market and with the high degree of
secrecy over their formulation and process schemes, the availability of information is limited. In
1987, Green compiled an investigation into the process requirements for 38 common and no-

longer patent protected pesticides53. They represent only ~1% of the chemical spectrum but
represent a large proportion of the market share. For instance, Glyphosate (better known as
Roundup) is the world’s most known/used pesticide and even agrichemical. 80% of US Soya
production is been genetically modified for Roundup protection. Information concerning the
pesticide industry is explicitly expressed in terms of active ingredients, those chemicals
responsible for the desired function. Because of their highly toxic and hazardous nature
pesticides are delivered in formulation, either as a liquid, powder or granule form. It is not
exceptional for the formulation to contain as little as 10% of the active ingredient. Although
seemingly large, when related to total process energy, the influence of formulation is minor. In
addition to the process energy flows, Green had also assessed energy costs of formulation,
packaging and distribution of pesticides. Formulation is naturally the largest of the three at
~20MJ/kg for miscible oil, ~30MJ/kg for wettable powder and ~10MJ/kg for granules.
Packaging and distribution combined are only 3MJ/kg. It is even suggested that shipping to the
heart of Africa has roughly the same figure. These aspects will be covered in the following
chapter as they match better with farming practices. More recent process data from the industry
is simply not available and a more detailed investigation would bring little addition benefit in the
scope of further certainty. As with the fertilizer industry the BAT is desirable to best describe the
future trends when the large scale biomass implementation is realized. Pesticides are fine
chemicals with large profit margins, so it is expected that little effort has gone into process
optimization. Therefore, it will be assumed that no significant technological and energy saving
advancements have been made in the agrichemical sector since 1987.
BAT of pesticide production are based solely on Green’s 1987 process energy
4.2.2 Grouping
Since there are well over 2500 different pesticides, the industry has grouped them based on their
working chemical functionalities. Each classification of pesticide works on the same principle
against the pests, but due to industrial proprietary rights each manufacturer produces a slightly
different chemical. In many cases the chemical structural differences between some of the
pesticides are so miniscule that the process energy requirements have next to no difference. As
the agricultural industry has access to the entire spectrum they are free to choice any of the
available pesticides. The accuracy of relating this to the energy input can be increased by using
the given 38 chemicals and grouping them on different degrees of detail available. The grouping
and related accuracy levels are as follows:
Table 41 Pesticide grouping accuracy
Grouping Assumption Example Accuracy Level

Listed, one o f the 38 p esticide Alachlor Very High
Pesticid e Sp ecific Classification Chloroacetanilide Herbicid e High
Pesticid e Type Herbicide Acceptable
Pesticid e Average Pesticid e Low

4.2.3 Calculations
Under the investigation of the required process energies for the 38 pesticides, the various types
of energy origins are listed. They are presented in a cumulative manner including feedstock and
processing costs. However, electricity for instance, is best converted to a fossil origin to
correspond with the other energy inputs. The calculation factors for cumulative energy and
exergy as described in chapter 2 are incorporated.
The resulting calculations for the individual pesticides and the various grouping classifications are
not presented. For sake of visualization the pesticide type herbicide with the individual energy/exergy
values is illustrated:
Herbicides
900
Energ y
800 Exergy
700
600
500
G J/ton
400
300
200
100
0
l
l
ne
ne
ba
in
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D
TC
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or
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at
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Figure 25 Herbicides process energy
The herbicides have a noticeable variation between the different active ingredients. The average
cumulative process energy is 368MJ/kg with a standard deviation of 196MJ/kg, meaning that an
accuracy of 46.7% is present when using the average. It is slightly better in terms of exergy at
385±199MJ/kg. This is a perfect indication of why it is better to strive for the listed values or the
pesticide specific classification. For example, the classification “phenoxyacetic herbicides” has an
average of 158 ±37MJ/kg, yielding an accuracy of 76.6%. The other specific classifications have
similar trends justifying Table 40. The chemicals covered under the assessment for the other
pesticide type groups (insecticide, fungicide and nematicide) are significantly less leading to
higher inaccuracies:
• Nematicide: Energy = 503±159MJ/kg (68.3%) Exergy = 534±150MJ/kg (71.9%)
• Insecticide: Energy = 318±236MJ/kg (25.8%) Exergy = 344±323MJ/kg (32.6%)
• Fungicide: Energy = 244±216MJ/kg (11.6%) Exergy = 256±218MJ/kg (14.8%)

4.3 Crop Pesticide Application Rates
Pesticide application rates are dependent on three factors; the crop, the specific crop pests in the
region and the wealth of the region. The latter is the main factor limiting the availability of data.
In affluent regions, which have strict environmental legislation, the exact pesticide use is carefully
monitored. It is so well documented in some areas that even the exact chemicals, treated area and
typical application ratios are listed, whereas in more impoverished regions specific data is difficult
to acquire. Application rate figures can be presented in a multitude of different manners and level
of detail, yet all figures are converted into kg/ha. By expressing the figures in kg/ha the relation
to energy input is possible. Each crop is strongly dependent on the region and will be assessed
individually; however for the most part, the regional crop-based trend is suggestive of the crop
protection issues as a whole and can be extrapolated. There are of course exceptions and very
regional based problems. These and other comments regarding the crop and region based
pesticide use and information are described by the following:
4.3.1 Crop and Regional Comments

For the calculation tables and more specific data consult the accompanying database spreadsheets
4.3.1.1 Cassava – Nigeria

Nigeria is poor in the sense of agricultural practices. It is suggested that only 3% of the cassava
farmed has access to pesticides and additional detail simply does not exist. These low rates are a
major cause for the low non-commercial yields compared to other regions. This does however
present a large improvement possibility.
4.3.1.2 Grass – Holland

The European Commission had conducted a country based appraisal of the various types of
pesticides used on different types of agricultural fields51. This presents moderately accurate data
for grass. Grass, like that for grazing, requires proportional seen very small amounts of pesticides.
4.3.1.3 Lucerne – Wyoming

In America, state-based data is available on the exact pesticide chemical, the treated area and
average application rates on the treated area 54. These values can be use to calculate the state-based
application rate and relative energy requirements to a high degree of accuracy. Lucerne (for
fodder) in Wyoming is known for having a very small demand of pest control.
4.3.1.4 Maize – Iowa

As with lucerne the level of detail is very high and specific. In some isolated areas of treatment
the application rates can be quite high, exceeding 5kg/ha, yet on a state-based average the
application rate is large but not substantial54.

4.3.1.5 Oil Palm – Malaysia
The availability of specific data is limited and distinctly plantation based55. Typical figures for
pesticides as a whole are present, with suggestions that a large portion of the protection
originates from herbicides use. The rates are not particularly high, quite unlike the uncertainty.
4.3.1.6 Potato – Holland

As with grass a detailed study has been conducted per country and field type51. The potato uses
plenty of pesticides, especially in the form of fungicides and more decisively nematicides.
Throughout Europe but moreover in Northern Netherlands, the problem of Potato Cyst
Nematodes (PCN) is immense requiring excessive amounts of nematicide to control56. However,
since 1993 regulations have been installed that greatly limit the use of nematicides, yet on the
fields that are approved for treatment the levels are enormous. Nematode Control Strategies are
the under experimental phase to reduce the further usage, but are still under investigation. It is
conceivable that within a few years the levels will drop significantly.
4.3.1.7 Rapeseed – Belgium

Information regarding Belgian conditions have not been found, however German and Swedish
conditions have51, 57. As with grass and potato, the German conditions are narrowed to the
national average for the pesticide types regarding the rapeseed fields. It has been mentioned that
German and Belgian practices are analogous. The Swedish conditions are used only to confirm
the trend that herbicide consist the vast majority of applied pesticides. Rates are average.
4.3.1.8 Sorghum – Kenya

Kenya is poor in the sense of agricultural practices and is currently based primarily on small
family farms. There is no recorded data on the use of pesticides for sorghum in Kenya. It is
plausible that they are simply too expensive. Again this is a major cause for the low yields
compared to other regions and presents a large improvement possibility.
4.3.1.9 Soya Beans – Illinois

As with lucerne and maize the level of detail is very high and specific54. On a state-based average
the application rate is moderate.
4.3.1.10 Sugar Beet – Germany

As with other European countries, the German conditions are narrowed to the national average
for the pesticide types regarding the sugar beets plantations51. The application rate of herbicides
in particular is large but not substantial.
4.3.1.11 Sugar Cane – Brazil

The ease of obtaining pesticide information for Brazil is problematic as any available report is
written in Portuguese. However, general data has been collected for the use of herbicides and
insecticides58. The application rate of herbicides is fairly high, but improvement options have

been investigated and already hit the market (Bayer CropScience). All these factors combined
present a large uncertainty.
4.3.1.12 Sunflower – France

Data available for France is based on market share of the various types of pesticides51. This
presented the task of linking total consumption rate and cultivated area together to convert the
information. As it turns out the pesticide use is fairly low with an acceptable accuracy.
4.3.1.13 Switchgrass – Oregon

Switchgrass is one of the recommended bio-energy crops, partly chosen for its low cultivation
intensity. Since it is principally under investigation, broad averages are not yet available. Current
practices in Canada suggest moderately high use of herbicides59. However, precise data based on
fallowland farming in Oregon will be chosen as representative; necessitating low levels54.
4.3.1.14 Tobacco – Australia

Tobacco cultivation in Australia is in its infancy, yielding little valuable information. Cultivation
in America on the other hand is mature. Detailed information was complied to average out the
exact pesticides used on a national level54. It is noticeable that the application rate of insecticides
is very high, well above 10kg/ha. This is due to the fact that tobacco is a value added crop with
highly intense farming practices. When cultivated for biomass production the need for large and
healthy leafs is irrelevant, greatly reducing the pesticide use. However, based on the little
Australian data available it appears to be around 15kg/ha or even higher. The uncertainty of this
crop in the region is very high.
4.3.1.15 Wheat – France

Just as with the sunflower the available data is given as market share and was calculated back to
application rates using production statistics51, 60. What is noticeable is the dominant use of
fungicides, which is typical in Europe as local grains are prone to fungal infection. Rates are
average.
4.3.1.16 Willow Tree – Sweden

A detailed case study on a Swedish bio-energy willow production site was conducted, narrowed
down to specific chemicals indicating a high accuracy61. The application rate of herbicide is
surprisingly higher than expected of a perennial tree.
4.3.2 Results
For ease of comparison, due to the strikingly diverse level of detail, all the various application
rates have been tabulated for all the crops and expressed solely as kg/ha of total pesticides. The
following graphical representation best illustrates the differences amongst the various crops:

Figure 26 Pesticide requirements
Pesticide Requirements
Total
10.0
15.5kg/h 15.0kg/h
a a
7.5
kg/ha
5.0
2.5
0.0
er
s
ss
t
at
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an
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ac
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To
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O
So
tc
g
Ra
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So
Su
wi
W
S
S
There are clearly large deviations amongst the various crops, they range from 0 to just over
6kg/ha. Both the potato and tobacco require larger amounts of pesticide, but the arguments for
why this is the case was mentioned above. For the rest it is best left unsaid until related in terms
of energy input.

Based on the combination of the previous two subsections the calculation of the total energy and
exergy input of pesticides is possible. The following table lists the results:
Table 42 Resulting pesticide input energy
Pesticide Input
Crop Continent Country/Region
Total Energy Exergy
Common Name Largest Producer kg/ha MJ/ha
Cassava Africa Nigeria 0.1 36.4 38.4
Grass Europe Holland 1.0 318.4 338.7
Lucerne North America W yoming 0.2 92.7 97.1
Maize North America Iowa 4.0 1348.0 1423.7
Oil palm South Pacific Malaysia 2.0 715.9 752.7
Potato Europe Holland 15.5 3686.3 3857.2
Rapeseed Europe Belgium 2.9 1017.6 1067.2
Sorghum Africa Kenya 0.0 0.0 0.0
Soya bean North America Illinois 1.3 556.6 593.0
Sugar beet Europe Germany 4.5 1609.4 1691.1
Sugar cane South America Brazil 5.1 1862.7 1954.0
Sunflower Europe France 1.4 523.0 547.6
Switchgrass North America Oregon 0.4 171.9 184.4
Tobacco South Pacific Australia 15.0 6222.4 6600.2
W heat Europe France 3.4 932.1 977.8
W illow tree Europe Sweden 6.4 2103.1 2245.4

A graphical representation of the total energy correlation is better to visualize the figures. It is
noticeable that the relative differences between mass input and energy input do differ if only
slightly, but nevertheless justifying the additional workload necessary to avoid the one averaged
value assumption.
Figure 27 Resulting pesticide input
Pesticide Requirements
250 0
3.67GJ/h 6.22GJ/h
Energy
a
3.86GJ/h 6.60GJ/ha
Exerg y
200 0
150 0
MJ/ha
100 0
50 0
0
a
ze
ed
an
ne
co
e
er
s
s
et
at
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as
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ac
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Po
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M
G
ow
as
pe
ob
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nf
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Lu
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O
itc
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Su
C
ill
Ra
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S
So
Su
Sw
W
S
Cassava and sorghum aside, it is the grasses (grass, lucerne and switchgrass) that require the least
amount of energy input. Not surprising the crops with the highest yield (maize, potato, sugar
beet, sugar cane) require the highest amount of pesticide energy input. Most probably the best
method to boast the production yield for cassava and sorghum is not through primary energy
inputs, but through the use of pesticides. The comparatively high input associated with the
willow tree production perfectly illustrates the affects when large scale biomass production is
implemented, maximized agricultural techniques to accelerate growth/yield, for wild variants
need none.
4.4.2 Efficiency
Precisely as with the other primary energy inputs it is misleading to visualize the total pesticide
input energy in terms of land without relating it to the resulting energy output. Relating the two
figures will result in the pesticide efficiency as indicated by the simple formula:
Energetic _ Output[ MJ / ha ]
Pesticide _ Efficiency =
Pesticide _ Input [MJ / ha ]
The following graph displays the resulting pesticide efficiency for the best practice yield:

Figure 28 Resulting pesticide utilization efficiency
Efficiencies
Based on Pe st icide Proces Inp ut Ene rgy
100000
7.3E5 2.1E5 1.0E5 1.0E5
Energy
8.3E5 2.5E5 1.1E5 1.1E5
Exergy
75000
Conversi on Percent [%]
50000
25000
0
va
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to
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To
illo
O
itc
C
Ra
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So
Su
W
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As the energy input associated with pesticides is quite low compared to the energy output, the
efficiencies are manly above 25000%, meaning that the required pesticide energy only represents
an energy loss of 0.4%. The grasses have even larger conversion efficiencies (well above 60000%)
demonstrating the minor significance and influence of pesticides. This is the leading reason why
pesticides are generally overlooked or greatly simplified using, for example, the one averaged
value assumption. But the insignificance of pesticides does not pertain to all of the crops, as the
influence of the pesticides presents a noticeable energy loss in several of the crops. For instance,
the potato suffers a 1.5% energy loss due to pesticide application, which approaches the losses
associated to its nutrient input. The most extreme case is that of the willow tree, at 5832%
conversion efficiency an energy loss of 1.7% is present. That is only a few magnitudes smaller
than the influence of nutrients.

4.4.3 Analysis
Table 43 Comparative pesticide input overview
Crop Pesticid e Requirements (en ergy) Pesticid e Requirements (exergy)

Cassava + + + +
Grass + + + +
Lu cerne + + + +
Maize O O O O
Oil Palm O + O +
Potato - - - -
Rapeseed O O O O
Sorghum + + + +
Soya Beans O O O O
Sugar Beet - O - O
Sugar Cane - O - O
Sunflower O O O O
Switchgrass + + + +
Tobacco - - - -
Wheat O O O O
Willow Tree - - - -
Input: + below 0.5GJ/ha, - above 1.5GJ/ha, O between 0.5 – 1.5GJ/ha
Efficien cy: + above 50000%, - b elow 10000%, O between 10000 – 50000%
Any crop with a negative sign in the efficiency category should be paid special attention to. Those
crops have a pesticide intensity that can influence the overall positive energy gain.

The top 3 choice crops for each category will be handled separately along with the total result for
the entire group “primary energy inputs” in terms of energy to material production.
Nutrients, in the form of fertilizers, by far constitute the largest portion of the energy demands of
the primary energy inputs. The values expressed in this chapter represent the actual plant uptake
levels and not the typical application levels. The differences between the two are the losses and
being most dependent on farming techniques will be covered in the following chapter.
Table 44 Top 3 crops on low nutrient/fertilizer demand
Energy Exergy Nutrient Efficien cy (Input/Output)

Top Crops
GJ/ha Energy Exergy
1. Soya Bean: 0.98 Soya Bean: 3.48 Soya Bean: 19001 Sugar Cane: 10677
2. Sugar Cane: 3.60 Sugar Cane: 4.26 Sugar Cane: 10555 Soya Bean: 6226
3. Lu cerne: 11.9 Lu cerne: 13.8 Oil Palm: 5580 Oil Palm: 5620
The clear advantage of the legumes requiring less supplementary nitrogen and thus less relative
energy demand can be seen in the list. All the crops, save oil palm, have to various degrees
bacterially fixed nitrogen. For soya bean 100% of the nitrogen demand is covered by inoculation
and sugar cane is up to 90% due to companion species. Generally speaking legumes will always
require less fertilizer input energy as nitrogen is so much more costly to manufacture than the
other nutrients. For point of illustration the top 3 crops of a non-leguminous nature have been
investigated separately. They differ by several magnitudes.
Table 45 Top 3 crops on low nutrient/fertilizer demand (non-leguminous)
Top Energy Exergy Nutrient Efficien cy (Input/Output)

Crops GJ/ha Energy Exergy
1. Willow Tree: 12.2 Willow Tree: 13.8 Oil Palm: 5580 Oil Palm: 5620
2. Oil Palm: 13.1 Oil Palm: 14.5 Sorghum: 3204 Sorghum: 3463
3. Potato: 13.3 Potato: 14.7 Maize: 2831 Maize: 2995
Crops with the best water conditions need neither irrigation nor drainage. There is no placement
for those particular crops as they score equally well, and the best achievable is zero energy/exergy
input. Of the crops investigated 1 has absolutely no and 2 have close to no water requirements:
sorghum, rapeseed and switchgrass. Several other crops also have no or little water requirements
under normal conditions, but when aiming for best practice yields (or water demand) do. They
are: cassava, grass, maize, oil palm, sugar beet, tobacco, wheat and willow. All of these crops are
essentially rainfed crops in the set regions.
Although, as just mentioned, many of the crops have zero energy demand in the form of water
requirements a similar story holds for the pesticide inputs. Cassava and sorghum both have
practically no pesticide requirements, not because they do not need them but because the
particular region of cultivation is impoverished and cannot afford the additional burden of crop

protection measures. This is not realistic when speaking of creating a chemical feedstock. Should
cassava and/or sorghum be realised the yields will dramatically increase with the addition of
pesticides. The other crops however already represent more or less expected figures. In some
particular cases, like that of the potato in Holland, government regulation is the major stipulation
for change and can be expected to swing future application levels. But compared to the nutrients
and water the levels are still quite low, i.e. terms are MJ and not GJ.
Table 46 Top 3 crops on low pesticide demand
Energy Exergy Pesticid e Efficien cy (Input/Output)

Top Crops
MJ/ha Energy Exergy
1. Lu cerne: 92.7 Lu cerne: 97.1 Lu cerne: 2.16⋅105 Lu cerne: 2.46⋅105
2. Switchgrass: 172 Switchgrass: 184 Oil Palm: 1.0⋅105 Oil Palm: 1.08⋅105
3. Grass: 318 Grass: 339 Grass: 6.50⋅104 Grass: 7.29⋅104
It is noticeable that the grasses all require the least amount of pesticides, understandable as they
are low maintenance crops. At those efficiency rates, an energy loss of less than 0.5% is achieved
and is in affect lower than the inaccuracies of the yield figures; basically negligible. This is true for
practically all of the selected crops, yet for some pesticides are a significant input.
In chapter 4 the term land use efficiency was employed to indicate the relationship between the yield
and the incoming solar radiation; affectively compiling the land requirements for material
production. The same procedure can be performed in regards to the primary energy inputs. By
relating the dry weight yields and total primary energy input an “energy use efficiency” is created with
the same unit, g/GJ. This indicates the energy requirements for material production.
Figure 29 Primary energy use efficiency
Energy Use Figures
Based on Dry Weight Figures and Primary Ener gy and Exergy
2.5E+06
Energy 6.3E6
5.5E6
Exergy
2.0E+06
1.5E+06
g/GJ
1.0E+06
5.0E+05
0.0E+00
m
um
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to
e
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et
at
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cc
ta
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a
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lp
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rc
M
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nf
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ga
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ap
So
ga
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itc
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ill
So
Su
Su
R
W
Sw

The crops with a biological symbiosis perform relatively well in terms of low associated nutrient
uptake energy demand. Yet as can be seen in the graph the others factors, primarily water, reduce
the overall benefit to the point of only having one crop in the top 3. And in fact, sugar cane is
not even truly a legume but is sown together with leguminous plant residues. This clearly
illustrates the fact that the benefits of one input, regardless of how large, cannot be used as an
indicator for the whole. Local constraints, in this case water has a large impact of the overall
energy demands but generally the nutrient input dictate the primary input demand.
Table 47 Top 3 crops on energy use efficiency
Energy Exergy
Top Crops
g/GJ
1. Sugar Cane: 6.27⋅106 Sugar Cane: 5.53⋅106
2. Oil Palm: 2.49⋅106 Oil Palm: 2.27⋅106
3. Sorghum: 2.20⋅106 Sorghum: 2.00⋅106
The energy use efficiency term will be transferred to each proceeding section to create the overall
indication of the best choice crop. It will determine the highest exergetically and energetically
efficient crop in relation to material production and finally to chemical production. As solar
radiation is handled in terms of land demand, this energy use factor will present a term for fossil
energy demand. This chapter covered the primary energy inputs and only in combination with
the follow chapters, the secondary (farming procedures) and bioprocessing energy inputs, can
solid conclusions be drawn. Nevertheless, it is noticeable that several crops perform already fairly
bad on this intermediary energy use section, rendering the success of large scale implementation
for those crops highly improbable. They are namely lucerne, rapeseed, sunflower, wheat and
willow. The crops themselves are not necessary poor or unsuitable, for the regional influences are
the route cause. Lucerne (or the Midwest) and the sunflower (or Southern France) both rely a
very costly forms of irrigation. Cultivation in another region might possibility alleviate the stress
on water demand while attention must be paid to the change of the other factors; the potential of
the crops is not yet fully ruled out.
In the realm of primary energy input the distinct leader is the sugar cane. This is mainly attributed
to the common practice of mixing leguminous green manure with the plantation, accounting for
up to 70% nitrogen fixation. This corresponds to 23.5kg/ha and indeed typical Brazilian
application rates are 0-50kg/ha. The blunt of the primary energy inputs are embodied by the
nutrients and legumes are an effective method to reduce the cost. There is a trade off, however,
for absolute yields and thus land use efficiency is sacrificed. Denoting that in areas with limited
land, the cost saving option of using legumes should be avoided or carefully assessed.

References
1. European Fertilizer Manufacturers' Association (EFMA) Understanding Nitrogen and its use in
Agriculture; Brussels, 2004; p 66.
2. Biglar, B., The Height Gap: Why Europeans are getting taller and taller - and American's
aren't. The New Yorker 2004.
3. Trautmann, N. M.; Porter, K. S., Nitrogen: The Essential Element. In Natural Resources
Cornell Cooperative Extension: 1989.http://pmep.cce.cornell.edu/facts-slides-self/facts/nit-
el-grw89.html
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Chapter 6
Secondary Energy Input
Required energy and exergy involved in agricultural practices, storage, pre-processing and
transportation of biomass
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 6 – Secondary Energy Input

A&F number -
ISBN-number -
Date o f publication 6. September, 2007
Confidentiality No
OPD code -
Approved by -

P.O. Box 17
Tel: +31 (0)317 475 190


ISO 9001:2000.

Abstract
The modern mechanized cultivation of biomass requires significant energy and material inputs
from a multitude of different sources and forms. Seen from the cradle-to-grave they can be
separated into direct (prime) and indirect (secondary) energy and material streams. Those
indirectly attributed to biomass growth are covered within this chapter; namely farming
procedures, transportation and storage operations and pre-processing and drying techniques.
Farming is based on the employment of tractors and other self-propelled machinery to perform
one of four basic field procedures; tillage, planting, soil treatment and harvesting. Several of the
most commonly occurring procedures within the groups are investigated based on the implement
parameters, field capacity and diesel consumption. The assessment is separated into two regional
categories, developing and industrialized, to represent the energy intensity differences of the
corresponding crop cultivation practices in the selected regions. The indirect fossil fuel input for
manual labour was also calculated for the two different regions and used to determine the
machinery operation as well as any foreseen separate manual farming procedures. A systematic
approach was used to link the selected procedures for the various regions to the crops under
investigation. The amount of energy and exergy required to transport a certain tonnage of
harvested biomass over a kilometre was calculated for tractor, truck, train, inland barge and sea
vessel transportation systems. As with the farming procedure a differentiation was made between
the regions and their relative requirements. The Port of Rotterdam is chosen as the central
destination point to satisfy the European chemical industry and marks the grave of the LCA
scope. In between each mode of transportation material handling and in many cases storage is
necessary. Storage and transfer energy demands are based on those systems commonly in place to
handle the biomass feedstocks and used between the different transportation modalities. To
reduce transportation and distribution costs densification options were investigated including
cutting, crushing and various forms of drying operations. After careful assessment for each of the
regionally based crops an optimal logistical network system was stipulated using the trade-off
relationship between the transportation and preprocessing procedure requirements. All of the
input figures have been set against the resulting energy output of each crop to determine and
compile an overall efficiency comparison as was previously conducted in the two preceding
chapters. The secondary energy input is the combination of the farming and logistics systems
results and when further combined with the primary energy input leads to the total agricultural
input energy demand. Combined the value represents the total biomass feedstock cost from
cradle-to-chemical factory gate, inducing a total energetic material loss of 15 – 60% of the crops
calorific value.
Key Words:
Biomass, Farming Procedures, Transportation, Logistics, Drying, Energy, Exergy

Content
1 Introduction 225
2 Input Types 227
2.1 Preface 227
2.1.2 Industrial Considerations 227
2.1.3 Regional Considerations 228
2.2 Labour Costs 229
2.3 Farm Equipment Costs 230
2.3.1 Tractor 230
2.3.2 Tillage Implements 232
2.3.2.1 Plough 233
2.3.2.2 Cultivator 233
2.3.2.3 Harrow 233
2.3.3 Planting Implements 234
2.3.3.1 Drill 234
2.3.3.2 Row Crop Planter 235
2.3.3.3 Cuttings Planter 235
2.3.3.4 Tuber Planter 235
2.3.4 Soil Treatment 236
2.3.4.1 Fertilizer Spreader 236
2.3.4.2 Pesticide 236
2.3.5 Harvesting 237
2.3.5.1 Combine Harvester 237
2.3.5.2 Forage Harvester 237
2.3.5.3 Tuber Harvester 239
2.3.6 Trailer Transportation 240
2.4 Transportation Costs 241
2.4.1 Heavy Goods Vehicle (Truck) 242
2.4.2 Train 244
2.4.3 Inland Barge 246
2.4.4 Sea Vessel 247
2.5 Storage and Transfer Costs 249
2.5.1 Storage Description 249
2.5.1.1 Transfer Points 250
2.5.2 Loading/Unloading Equipment 251
2.5.2.1 Wheel Loaders 251
2.5.2.2 Conveyors 251
2.5.2.3 Stacker/Reclaimer 252

2.5.2.4 Crane 253
2.6 Pre-processing and Drying Costs 253
2.6.1 Size-Reduction 254
2.6.1.1 Cutting 255
2.6.1.2 Crushing and Shearing 256
2.6.2 Moisture Reduction 257
2.6.2.1 Natural Air Drying 258
2.6.2.2 Filter Press Dewatering 258
2.6.2.3 Conveyor Belt Drying 259
2.6.2.4 Rotary Drum Drying 259
2.6.2.5 Silo/In-Bin Drying 260
2.6.2.6 Exergy and Energy Efficiency 260
2.6.3 Compaction 261
2.7 Manufacture, Transport and Repairs (MTR) 261
2.7.1 Manufacturing Energy 261
2.7.2 Transport Energy 262
2.7.3 Repair Energy 262
2.7.4 Farm Equipment MTR 263
2.7.5 Transportation and other equipment MTR 263
2.8 Overview Input Type Costs 264
3 Farming Operations 267
3.1 Machinery Employment 267
3.1.1 Operational Labour Requirements 267
3.1.2 Cultivation Practice Factors 268
3.2 Labour Employment 268
3.3.3 Analysis 271
4 Biomass Logistics 273
4.1 Rotterdam 273
4.2 Distance to Rotterdam 274
4.2.1 Starting Point 274
4.2.2 Mode of Transport 275
4.2.2.1 Road 275
4.2.2.2 Rail 275
4.2.2.3 Inland Waterways 275
4.2.2.4 Ocean 275
4.2.3 Topography 276
4.2.4 Resulting Distance and Mode of Transportation 276

4.3 Size and Moisture Reduction 277
4.3.1 Transfer and Storage Systems 278
4.3.2 Balancing Size and Moisture Reduction and Transport Energy Costs 279
4.4.3 Analysis 282
6 Total Agricultural Energy Input 287
6.1 Graphical Overview 287
6.2 Results and Discussion 289
6.3 Individual Regional Crop Explanations and Recommendations 290
References 293

1 Introduction
In the previous chapter much stress was placed on the importance of supplying sufficient
nutrients via artificial fertilizers to promote the high yields associated with modern agricultural
practices. Indeed water, carbon dioxide, solar radiation, pesticides and fertilizers have a direct
impact on the agriculturally harvestable yields. Farming techniques, cultivation methods and
other mechanized agricultural practices on the other hand facilitate the optimal use of those
growth determining inputs. And in many instances the intensity of modern agricultural practices
is visualized by a large combine harvester rather than a sack of fertilizer.
True, diesel is needed to operate tractors and the other agricultural machinery involved in
modern agricultural practices and when related back to the primary fossil fuel energy content
does place a large energy intensity on the overall farming operations. It is especially common in
areas of moderate sunshine for seasonal crops to heavily rely on agricultural machinery to
maximize the yield potential. “Working the land” and “harvesting the fruits of labour” are beginning to
take new meaning as the only manual labour is hooking the proper implements to the tractor. In
newer tractors outfitted with GPS guidance and sensory assistance driving has even become a
quest of programming skills. In fact, all aspects and inputs of modern agriculture have a fossil
fuel source alluding at the notion that the industry is converting oil products into food products.
Achieving the lowest agricultural energy intensity respective to the energy content of the yielded
harvest must be seen as a primary prerogative for supplying feedstocks to the biobased sector.
Many of the potentially highest yielding crops are cultivated in regions of the world that take
advantage of ample and yearly distributed solar radiation and precipitation. These “tropical”
regions have a highly underdevelopment agricultural sector involving manual labour for the bulk
of their harvesting operations. And feeding fieldworkers requires only a minor amount of indirect
fossil fuel energy; operating a combine harvester for one hour is roughly equivalent to
contracting 200 man-hours of developing world fieldworkers. As unmoral as the wide scale
exploitation of underdeveloped workers may appear, it also presents a paradox as those regional
practices and crops promote the potentially highest fossil fuel energy savings. Yet as high as these
local potential energy savings and higher yields are, they must be counterbalanced with the
logistical cost of intercontinental transport.
Fresh biomass is alive and so long as sufficient water is contained in the biomass nature is free to
take its course, reducing the yields through digestion and decomposition. If there is one thing
long-haul transportation of biomass is, it is a time consuming process caused by long travel time
and long layover times. Time enough to promote the decay of fresh biomass. The obvious
solution to preserve the biomass over the entire logistical chain ensuring a high deliverable yield
is to reduce the moisture content. The food industry has done well to market the benefits of
dried foods with the preparation instructions boldly stating “easy - just add water”, despite the
underlining corporate benefits of lower transport costs and longer storage life. Drying biomass,

like food goods, is still an energy intensive process and can for particular systems be the most
energy intensive portion for feedstock acquisition.
Along with biomass moisture reduction, size reduction procedures will increase the net bulk
density of the biomass facilitating less transportation loads. Capacities of the different transport
modalities are limited by either weight or volume but for feedstock material the actual deliverable
weight is all important. A dried and size reduced material will provide more deliverable feedstock
per load than fresh biomass. As many size reduction techniques necessitate a dry input material,
size reduction and moisture reduction procedures are essentially performed in combination.
Combined the procedures are considerably energy intensive and should be balanced to the energy
saved through less frequent transportation shipments.
International shipping has never been so cheap and efficient as it is today, yet it still remains an
energy intensive industry primarily based on fossil fuels, chiefly various grades of diesel. The
chemical industry is comprised of factory clusters situated in areas of high industrial activity with
an accompanying distribution network in a select few locations around in the world. Rotterdam is
the central hub for the European chemical industry. Biomass on the other hand is cultivated and
harvested in areas scattered across the globe; partly grown in the direct hinterland and partly
overseas. Transportation will always be an inevitable and unavoidable energy intensive
component of acquiring a biomass feedstock. Where the locally grown biomass in the temperate
regions may be burdened with high farm related inputs, the imported biomass is burdened with
high logistical inputs.
The summation of the previous chapters primary energy inputs with the inputs related to the
farming procedures, the moisture and size reduction techniques, and the transportation network
results in the total agricultural energy and exergy input to supply a biomass feedstock to the
chemical industry for each crop in the respective region.
1.1 Chapter Purpose

In the following chapter all the secondary inputs will be calculated and expressed in a
comparative form for the previously selected crops. The values mentioned herein are based on a
straightforward energy/mass balance in excel, thermodynamic conversions, and energy relations
to obtain the exergy values. This chapter is the second of three energy input categories required
for the creation of chemicals from biomass. Primary, secondary and process energy inputs will all
be addressed independently from solar energy. The combination of the primary and secondary
energy inputs are used to compile the total agricultural energy input as a feedstock cost.

2 Input Types
2.1 Preface

Although a partly a conjecture it is widely accepted that, as a species,
humans (Homo sapiens) have existed for around 200000years and the
earliest African fossil findings date back to 130000years. In the beginning
humans were nomadic hunter/gatherers struggling to nourish themselves
adequately; life revolved around acquiring food. Between 7000-9000BC
marks the Neolithic Revolution, when in the Fertile Crescent the
domestication of crops and animals is thought to have begun. This first
agricultural revolution was brought on by the depletion of biological
potential (food) through the hunter/gatherer practices for an ever
increasing population. Initially converting forests to pastures by slash-and-burn practices the
population densities flourished leading to an agrarian based life-style. The land cultivation could
continue for 2 years before the nutrients became depleted and needed to be returned as fallow.
Successful systems required a minimum of 2 hectares of cultivated land per person and 10
hectares of land to supply the cultivated land. Land use may have been high but energy input
however was low, being directly coupled to manpower with simple tools. By the point of wide
spread maize cultivation 1144hours of labour (or 60% total adult labour output) was required per
hectare1. This meant that life still revolved around acquiring food. The first major reduction in
energy and land use intensity was by implementing the animal draft. Oxen and horse drawn
ploughing systems reduced the land intensity from 10ha/person to 4. Gradual improvements in
agricultural practices allowed for an ever smaller percentage of the population to labour on the
fields and facilitated the development of a civilization which in turn led to further improvements
on land use efficiency and manpower reduction.
2.1.2 Industrial Considerations

In the 10000 years since the Neolithic Revolution the agricultural sector has seen many changes,
improvements and revolutions that have further reduced the land use intensity (i.e. higher yields)
and manual labour requirements. Probably the single
most important invention in reducing manual labour
was the (steam) tractor. Introduced in 1840, over the
course of 100years the transition from animal draft
to machinery was nearly complete (for the
industrialized world). Currently in a modern highly
intensive maize field less than 10hours of manual
labour is required per hectare2. Agricultural activity is
now located in areas of a low population density.
Steam tractor a nd g ang plou gh, 19 16 And with the advent of low cost international

transport excess biomass/food can be shipped and sold anywhere in the world. All of the
improvements to maximize the crop yields with the least amount of labour and subsequent
distribution to highly populated areas require fossil fuel energy. Along the production and
distribution chains diesel is needed to operate the tractors, fuel the trucks, trains and ships and
other forms of indirect fossil fuel energy is also inherently involved. The agricultural sector has
transformed from a highly labour intense sector to a highly fossil fuel intense sector.
Cultivation practice and biomass logistics are as diverse as the crops and regions where they are
cultivated. Determining the life cycle energy input of the chains first requires a breakdown of the
components involved in the regions of activity. Each secondary input form will be assessed
separately to be able to create a matrix for the 16 choice crops.
2.1.3 Regional Considerations

The selected regions for the crops under investigation are diverse, scattering the world. Yet, they
can be grouped into two general categories, industrialized and developing. The industrialized
world has many names; like developed, rich, western, advanced or
more commonly the 1 st world nations. The OECD (Organisation for
Economic Co-operation and Development) is an international
organisation of those developed countries that accept the principles of representative democracy
and a free market economy. Categorizing the industrialized and developing regions will be based
on OECD membership or not. The following table lists the crops and corresponding regional
category based on OECD membership:
Table 1 Crops choice with regional development category
Botanical Nomen clature Common Name Continent Country/State Development Category

Beta vulgaris Sugar beet Europe Germany Industrialized
Brassica napus Rapeseed Europe Belgium Industrialized
Elaeis guineensis Oil palm South Pacific Malaysia Developing
Glycine max Soya bean North America Illinois Industrialized
Helianthus annuus Sunflower Europe Fran ce Industrialized
Manihot esculenta Cassava Africa Nigeria Developing
Medicago sativa Lu cerne North America South Dakota Industrialized
Nicotiana tabacum Tobacco Oceania Australia Industrialized
Lolium perenne Grass Europe Holland Industrialized
Panicum virgatum Switchgrass North America Iowa Industrialized
Saccharum officinarum Sugar cane South America Brazil Developing
Salix alba Willow tree Europe Sweden Industrialized
Solanum tuberosum Potato Europe Holland Industrialized
Sorghum bicolor Sorghum Africa Kenya Developing
Triticum aestivum Wheat Europe Fran ce Industrialized
Zea mays Maize North America Iowa Industrialized
The agricultural practices and tools/machinery employed differ heavily in the industrialized and
developing world. On a global scale, still 40.7% of the world population is involved directly in

agriculture (i.e. farmers) yet only represent 4.0% of the total GDP. In highly advanced societies,
like Holland, no more than 2% of the population are farmers providing slightly more than 2% of
the GDP3. This illustrates perfectly well the differences in practice and efficiency, especially in
terms of manual labour. For all the individual input types both the common industrialized
representative types with a leaning to best available technology (BAT) and common developing
representative types will be investigated. It is however foreseeable that with large scale financial
investment in biomass cultivation practices adopting efficient industrial practices will be
employed even in the developing world.
2.2 Labour Costs

A worker labouring on a field for biomass production has two sources of energy input. One is
the energy associated with food uptake and the other is the indirect fossil fuel consumption based
on the standard of life. A worker in an industrialized world will both eat more and consume more
luxuriously to sustain the higher quality of life.
Firstly, assigning the calorific food uptake value directly to fossil fuel demands is fundamentally
wrong. For example, the calorific value of a loaf of bread is 10.3MJ/kg whereas following a full
LCA yields between 4.0 – 9.0MJ/kg with 0.01 – 18.6MJ/kg additionally for the mode of
transportation involved in the purchase4. Bread is a simple product. Another detailed LCA study
pertained to the cumulative energy demand (CED) of a typical Swedish meal5. The typical meat-
based meal (containing 100g meatballs (50/50 beef/pork), 160g potatoes, 36g bread, 60g carrots
and 200g milk) requires, regardless on the preparation method involved, around 9.4MJ/meal. The
calorific value of the meal itself is however 3.5MJ, which indicates a factor of nearly 3. For exotic
foods, like fruits and off-season commodities, the CED will further increase. And one of the
oldest studies in the field used a factor of 6.8 to account for the sequestered energy in the food
chain6. The recommended daily food intake as dictated by the EU is 11.4 and 9.1MJ/day for an
adult male and female, respectively. In the modern industrialized societies both men and women
perform for the large part the same occupations and can both work equally well in the
agricultural sector. Sweden’s typical meal will be used as a norm for all industrialized regions,
meaning the total fossil fuel input related to food intake is set at 30MJ/day. The recommended
daily food intake were set for an individual with moderate physical activity and are not
representative of the harsher conditions faced by a developing world farmer. An adult male field
labourer doing highly physical work will require considerably more energy, at 16.8MJ/day. The
fossil fuel energy involved in cultivating, collecting and preparing a typical developing world meal
is lower than that of the industrial region, considering the heavy reliance on man power and
biomass fuel. And as the transportation and acquisition of the food is generally not per truck or
car that relative energy component approaches zero. Simple meals based on the local food
availability (like beans, cassava, jatropha, fruits, etc.) will approach a ratio between input and
calorific output similar to the bread example, meaning around 60%. Thus the total fossil fuel
input related to food intake for a developing region farmer is set at 10MJ/day.

The second aspect revolving around the energy input of a labourer is the indirect energy
associated with the lifestyle. Lifestyle support energy varies considerably per region depending on
the standard of living as measured by products and services consumed in relation to fossil fuel
energy. A farmer in the industrialized regions, being an average member of society, will use the
average amount of fossil energy common for the developed world. A farmer in the developing
regions however, is better described as adhering to the poorest 10% of the world. Following a
recent Science article the average person in the developed (industrialized) world consumes nearly
40barrels of oil equivalent and residents of the poorest 10% consume 1barrel per year7. A single
barrel of crude oil (at 0.853kg/l and 44.9GJ/ton) contains 6.09GJ. Thus an industrialized farmer
and a developing world farmer have an indirect fossil energy cost of 603MJ/day and 16.7MJ/day,
respectively. Compared to the costs attributed to the food consumption, it is clear that
supporting the lifestyle of the industrialized farmer is around 20-fold that of the direct energy
involved in nutrition whereas the developing farmer is less than 2-fold. As no data is available in
terms of exergy for these systems a factor of 5% will be added; the energy-to-exergy ratio of
crude oil. The following depicts the contrast between the labour cost for the industrialized
regions and developing regions both visually and numerically.
Figure 30 Labour costs in developing and industrial regions
Developing Regions Industrialized Regions

- Primarily manual labour farming - Primarily mechanized farming
- Food fossil fuel input: 10MJ/day - Food fossil fuel input: 30MJ/day
- Lifestyle fossil fuel input: 16.7MJ/day - Lifestyle fossil fuel input: 603MJ/day
- Total fossil fuel input costs: 26.7MJ/day - Total fossil fuel input costs: 633MJ/day
2.3 Farm Equipment Costs
2.3.1 Tractor
The primary purpose of agricultural tractors is to perform drawbar work. The origins of the word
tractor reflect this, being a combination between the noun tractus (to pull or draw) and the noun
motor (self-powered movement). Drawbar power is defined by pull (or historically called draft)
and travel speed. The efficient operation of farm tractors has three factors:
1. Maximizing the engine fuel efficiency and mechanical drive train efficiency

2. Maximizing the traction device
3. Optimizing the travel speed
In modern agricultural practices practically all steps in the cultivation and harvesting
of crops is derived from employing tractors. The so-called PTO (Power Take-off)
unit provides power to the specific equipment attached to the tractor both front
and/or back, meaning that the operational costs for each crop specific farm
procedure is a function of the tractor. The sole direct energy input of a tractor is diesel fuel as in
the last 25 years only a select few tractor engines have been outfitted with another fuel type. The
diesel fuel consumption of a tractor is based on several
factors, although mainly engine efficiency, operation
conditions and procedures are influential. Tractor
manufacturers supply two key technical specifications needed
to calculate the fuel consumption, namely the rated power as
a function of rated engine speed (kW/rpm) and the specific
volumetric fuel consumption (SVFC) given in g/kW⋅h. In the
adjacent illustration the rated power versus the rated engine
speed can be seen for a modern tractor. Under low drawbar
power requirements (like positioning or street travel) the grey
trends apply whereas under high drawbar power requirements (like ploughing) the blue/upper
trends apply. For a farmer it is important to have a tractor that can deliver the needed power to
perform the task at hand. Each operational tool/attachment has a tractor power level for the
particular operation, calculated to kW. SVFC for diesel engines typically range from 0.244 –
0.57l/kW⋅h (0.202 – 0.472g/kW⋅h)8. Simply multiplying the tractor power requirements with the
SVFC and the relative field capacity will yield the diesel fuel consumption. The first step is the
selection of representative tractors for the industrialized and developing regions and the
corresponding specifications. Data is based upon two tractor specification sheets9. Take
particular notice to the two graphs outlining the power and the fuel consumption as function of
the rated engine speed (kW/rpm and g/kW⋅h/rpm).
Industrialized Region
To represent the near future best practices a recent (2001)
highly fuel efficient tractor model in the mid/upper power
range was selected.
New Holland TM-16510
- MWD (mechanical front wheel d rive)
- No minal Power & Engine Rotation: 107kW @ 2300rp m
- Maximu m Po wer & Engine Rotation: 110.6kw @ 2160rp m
- Total Weight: 6600kg
- Speed Range: 2.27 – 40km/h, 13.6km/h @ max power
- SVFC: 251g/kW⋅h, 262g/kW⋅h @ max power
- Slip factor: 16.4% under typical soil conditions

Developing Region
Throughout the world one, if not the most popular and most
sold tractors is the Massey-Fergusson MF200 series. It is a
hallmark in p roven strength, quality and low-costs.
Massey-Ferguson MF24011
- 2WD
- No minal Power & Engine Rotation: 32kW @ 2250rp m
- Maximu m Po wer & Engine Rotation: 26.2kW @ 175rp m
- Total Weight: 1730kg
- Speed Range: 1.6 – 30km/h, 5.8km/h @ max power
- SVFC: 273g/kW⋅h, 328g/kW⋅h @ max power
- Slip factor: 18.7% under typical soil conditions
Reports from the Nebraska Tractor Test Laboratory (NTTL) was used to compile an excel
spreadsheet comprising of a database with 700 tractors, 12 major and 7 minor tillage and 12
seeding farm equipment attachments12. Furthermore the German Department of Agriculture
(DLG) has an online database full of tests listing the detailed technical data for essentially all
farming procedures13. In both sources the New Holland TM-165 and Massey Ferguson MF240
(MF340) tractors were included. The NTTL spreadsheet has been developed to calculate the
tractor performance under various conditions and settings for common farm procedures using
the attached equipment (referred to as implementations). Amongst the considerations are tire size,
travelling speed, weight distribution, tractor configuration and terrain conditions. Three different
soil types can be chosen based on the so-called cone index (tear strength measured in pressure).
Good soil (having a cone index of 1725kPa) will be set for industrial regions and medium grade
soil (cone of index of 860kPa) is set for the developing regions. The dimensions and operating
conditions of the implements are calculated for the general tractor settings of the two. Important
resulting estimations are operating depth, operating width, field capacity, draft force, drawbar
power and of course fuel consumption8. For the implements not included in the NTTL
spreadsheet the specific manufacturer and DLG online database will be used to determine the
fuel consumption. The manufacturers of the tractor attachment tools and self-propelled farm
machinery frequently supply the PTO equivalent requirements per set dimension (kW/m width).
Also listed for each implement procedure is the “field efficiency” which, is understood as the
proportion of time actually performing the task. Positioning and turning time, street travel, idle
and general down time all contribute to lower the field efficiency. Field efficiency is found in the
NTTL spreadsheet and in the collection of life cycle assessment data pertaining specifically to
utilities vehicles from the IFEU Institute for Energy and Environment14. As there are a wide
variety of very specific implements they will be grouped together following a generalized
procedural category and calculated for both industrial and developing region capacities.
2.3.2 Tillage Implements

The first step in biomass production systems is the preparation of the land to accommodate the
cultivation of crops, called tillage. There are three major tillage tool classifications, namely
ploughs, cultivators and harrows. The PTO equivalent requirement is used by the farmer to

optimize the size of the ordered attachment tool based on the tractor specifications. Listed are
the parameters and explanation for the three major tillage tools12, 15:
2.3.2.1 Plough
Ploughing has several beneficial effects and is common in almost all agricultural practices.
Originally ploughs were used to break up and turn over the upper layer of the soil adding the
previous crop residue into the soil. Deep ploughing will also mix the subsoil with the topsoil to
promote an even distribution of organic content. The method will reduce the prevalence of
weeds, loosen and aerate the soil creating a porous structure promoting the ease and success of
subsequent planting. Over the long term many disadvantages have arisen including loss of
organic content and erosion. A chisel plough was developed which like the mouldboard plough
will aerate and loosen the soil but will not invert or turn the soil over. This characteristic is a part
of the no-till and limited tillage farming, heading towards more sustainable agricultural practices.
Substantial power requirements are needed for the deep chisel plough:
Chisel Plough
- Specific Type: 2-in straight point
- Operation Speed: 6.5 – 10.5km/h
- Field Efficiency: 70 – 90%, set: 85%
- Capacity: 1.41ha/h (TM165), 0.37ha/h (MF240)
- Fuel Usage: 24.11l/ha (TM 165), 22.03l/ha (M F240)
2.3.2.2 Cultivator
Similar to a plough a field cultivator breaks up, stirs and pulverises the soil. It is common as a
secondary tillage operation, preceding the plough as the depths and forces involved are much
lower. In some cropping layouts it is however employed as the primary tillage unit. It will further
aerate and loosen the soil mitigating the problems associated with compacted soil. It works by
dragging a series of small pikes along the field.
Field Cultivator
- Specific Type: secondary tillage
- Fuel Usage: 6.02l/ha (TM165), 5.87l/ha (MF240)
2.3.2.3 Harrow
A harrow is also a secondary tillage unit used to cultivate the top surface of the soil. It is strictly
employed after a field plough to break up the clods and lumps created by the ploughing. Basically
it provides the fine finish to the top soil, sometime referred to as a “good tilth”. The most
common form of the harrow is the disk harrow and several systems combine a disk harrow and
field cultivator into one implement unit.

Harrow
- Specific Type: single disk gang, secondary tillage
2.3.3 Planting Implements

Upon completion of the tillage operation the seeds can be sown into the land. The starting
material for the propagation of crops is however not always in the direct form of a seed and the
size can also vary considerably, although all forms are referred to as seed material. There are three
major classifications of starting material; a true seed (like grass seeds), a seed covered in a husk or
shell (like sunflower seeds) and a pre-grown stub or cutting of a plant (like cane setts). The
implements for the planting procedure are very crop specific and depend heavily on the form of
plantation and growth system employed. The following implements cover the types required for
the 16 chosen biomass crops.
2.3.3.1 Drill
Carried in a large distribution tank small seeds are sent through a series of tubes to be drilled into
the soil. The distance between injections and row spacing is exact to maximise the seeding rate
with the desired growth conditions. There is a wide variety of seed drill techniques and in many
cases the seeds are mixed or pre-laced with fertilizers and pesticides. Within the drilling
implements there are two major types, those designed especially for grain seeds (like wheat) and
those designed for a more universal application. The grain drill is typically accompanied with
press wheel rollers to cover and compact the soil after seed injection. It is significantly faster than
the pneumatic drill which in turn increases the field capacity and decreases the fuel usage.
Grain Drill
- Specific Type: with press wheel
Drill
- Specific Type: pneumatic (airseeders)

2.3.3.2 Row Crop Planter
Similar to the drill procedures, seeds are injected into the soil based on the desired position. The
depth of the injected seeds is less, being only a few centimetres below the surface, speeding up
the process. Again it is common for the seeds to be mixed with the necessary fertilizers and
pesticides for early emergence. One clear difference however, is the layout of the implement
being much broader allowing for a faster field operation resulting in an even lower fuel usage.
Row Crop Planter

- Specific Type: drawn
2.3.3.3 Cuttings Planter

Several crops are planted not as seeds but as portions of the previous season’s mature crop. The
cuttings are shaved of any branches and leaves and sized to the desired length to include the
largest portion of dormant plant material. The planted biomass can be referred to as setts, whips,
rods, cuttings etc. all depending on the biomass crop, length of the stem and regional terming.
Upon plantation of the stem both roots and shoots will sprout within a few weeks. The most
common and efficient planter is the step planter which requires two personal to feed the stems
into the otherwise fully mechanized implement. A coulter prepares the ground while the stem is
fed and planted into place, 4 rows at a time. These machines are primarily on the European
market as cutting planters in developing areas operate at only two rows at a time.
Cuttings Planter
- Specific Type: step planter
2.3.3.4 Tuber Planter

Crops harvested for tuber production are planted using smaller seed tuber starting material. The
basic concept is the same for all the implement varieties; to pre-form the soil in a series of bed
rows, plant the seed tuber into beds and finalize the bed form. However, forming the soil into
raised beds while injecting the tubers has a high PTO demand restricting the width of the
implement, effectively lowering the field capacity and increasing the fuel consumption compared
to the other planting implements. Like the other seeding operations fertilizers and pesticides can
and are frequently pre-mixed into the bed.

Tuber Planter
- Specific Type: 4-row bed planter
- Fuel Usage: 11.56l/ha (TM 165), 11.52l/ha (M F240)
2.3.4 Soil Treatment

After the planting and throughout the growth and development stages of the crop occasional soil
treatment operations need to be conducted. The fertility of the land will decrease as the crop
consumes the nutrients for biomass production. In some instances the solid fertilizer laced to the
seeds, being time-released, is sufficient in providing the required nutrients throughout the entire
crop cultivation period. In other instances additional fertilization needs to be added, almost
exclusively in the liquid form. Furthermore as the crop matures pesticides need to be supplied.
2.3.4.1 Fertilizer Spreader

In some irrigation systems (sprinklers) the liquid fertilizers can be added with the irrigation water.
With the other systems spraying tanks need to be employed when additional fertilizer demand is
present. The long beam/boom attached with multiple pressure nozzles ensures a quick
application with as little tractor wheel contact on the field as possible.
Fertilizer Spreader
- Specific Type: 20m boom sprayer
2.3.4.2 Pesticide
Pesticides can be added in several methods. In small and precise doses farmers can walk through
the crop fields with a hand-held sprayer applying the pesticides directly on the leaves or close to
the root structure. It can also be combined with the liquid fertilizer and applied via the fertilizer
spreader. Another common route that is able to mitigate large areas of crop plantations prone to
similar pests is a crop duster.
Crop Duster
- Specific Type: small aerial duster
- Operation Speed: 220 – 280km/h
- Capacity: 395ha/h
- Fuel Usage: 2.32l/ha (kerosene)

2.3.5 Harvesting
The last step in biomass cultivation is harvesting; separation and collection of the final desired
product. Several unique machines and implements have been developed for the particular crop to
harvest. As most of the select biomass crops are traditionally eatable crops, the eatable portion
and non-eatable portion are harvested separately. In fact through advances of intensive farming
procedures the separation of the crop components is done on the field whilst harvesting. Food
based agriculture residue, being typically straw, is considered as agricultural waste and frequently
left on the field. In the non-food agricultural sector this residue will also contribute to biomass
production and will require additional harvesting options. The typical machines and implements
used in harvesting and sorting of the components required by the 16 chosen biomass crops will
be investigated. They are split into three broad categories.
2.3.5.1 Combine Harvester

A combine harvester, or simply combine as it is generally referred to, is a stand-alone agricultural
machine that “combines” the task of harvesting, threshing, cleaning and separating grain plants.
It can operate alone or with a tractor pulling a trailer to store the grains in larger volumes. The
desired grain/seed is separated from the rest of the plant through a series of complex mechanical
processing stages with the loose straw discarded to the rear. Combines are used for a wide variety
of crops that produce seeds and grains. Sorghum is the only grain crop located in the developing
regions; however for biomass production purposes it is harvested as sweet sorghum before the
emergence of the grains. Thus combines are strictly for the industrialized regions.
Combine Harvester
- Specific Type: standalone New Ho lland TX6316
- Operation Speed: 3.0 – 6.5km/h, set 5.0km/h
- No minal Power: 175kW
- Operational W idth: 4.57 – 6.10m, set 5.5m
- Capacity: 4.23ha/h
- Fuel Usage: 12.27l/ha
2.3.5.2 Forage Harvester

Forage is described as herbaceous plant matter consumed by grazing animals. It consists mainly
of leafy material and is commonly associated with grasses and hay. Residues from grain
harvesting (straw) can be used and classified as forage. For biomass production the collected
forage material will not be fed to animals but contribute to the overall yields. The collection of
biomass forage material involves several steps before it is delivered to the storage facility. The
precise steps involved are crop type dependent; grasses, stalk green biomass and residues are all
handled slightly differently with a specific series of unit implements.
Mower, cutting unit
Grasses and other plant material grown uniformly over the field and with a limited height must
first be cut loose from the ground. There are many types of cutting units available and one of the
most common and efficient is the rotary mower, also called a drum mower. Mounted on a bar
sharpened edges of rapidly rotating bars or disks will cut the crop. Best practices employ a twin

mounted system, having both a front and rear mounted implement. Combined they are easily
capable of operating at speeds up to 32km/h for young (low-lignin) crops, like ryegrass. More
recent implement systems, called autoswathers, can also combine the task of placing the cuttings
into windrows (densely rowed collection of cuttings) and eliminate the need for rakes.
Mower
- Specific Type: trip le mounted rotary mower conditioner
- Operation Speed: 19.0 – 32.0km/h, set 20km/h
Rake, windrow unit

Not all mowers and cutting units place the biomass in the desired windrow alignment for
subsequent collection. Residues especially from the combines are generally scattered across the
field requiring the rake implement to distribute into the windrow form.
Rake
- Specific Type: side delivery wheel rake
- Operation Speed: 6.5 – 13.0km/h, set 10km/h
Chopper, collection unit

The loose forage that has been positioned in the windrow alignment and left partially to dry is fed
into a chopper that further cuts and blows the material into a large silage collection trailer. The
cutting size is significantly reduced to increase the packing density and the ease of downstream
process handling. The collection trailer is pulled by a secondary tractor and must operate parallel
to one another reducing the field capacity.
Forage Harvester
- Specific Type: drawn forage harvester
- Capacity (2.5:1 row spacing): 4.65ha/h (TM 165), 3.25ha/h (MF240)
- Fuel Usage (2 tractors): 7.00l/ha (TM 165), 3.89l/ha (MF240)
Bailer, collection unit

The power consumption and blade maintenance costs sharply rise with mature forage containing
high levels of lignin, like the crop residue from the combine. In these particular cases it is typical
to gather, compact and press the straw into bails. Bailers can produce either round or rectangular
shaped bails to be collected later. Each bail can weigh 500-700kg and will add transportation
costs to the system over the forage harvester as the bails must be collected from the field.

Bailer
- Specific Type: large rectangular bailer
- Capacity (2.5:1 row spacing): 7.45ha/h (TM 165), 5.20ha/h (MF240)
Self-propelled forage harvester, mower/chopper/collection unit

A large proportion of the grain and seed crops are not cultivated for human consumption but are
strictly dedicated as forage for animals. The separation of the human edible and non-edible
portion is thus redundant. In these cases a so-called self-propelled forage harvester is assigned
the task of harvesting. It cuts, crushes and blows the entire crop into a parallel tractor pulled
silage trailer. For near future biomass applications it would probably be advisable to handle
dedicated non-food biomass crops in a similar manner, although only in cases where it is
beneficial for all the material to be processed in the same reactor. That can save on combine,
mowing, raking and multiple stream handling costs. The self-propelled harvester is very versatile
as practically any crop can be harvested with the proper accompanied head attachment. The
engine size and resulting power of the machine is quite high in comparison to the other machines
and implements as cutting, crushing and blowing are included. Self-propelled forage harvesters
are a relatively recent invention, developed first in 1974, so there is not a developing world
equivalent meaning a new model would apply for both regions.
Self-Propelled Forage Harvester

- Specific Type: New Holland FX4017
- Operational W idth: 3.27 – 6.5m, set 5.5m
- Capacity: 3.03ha/h
- Fuel Usage: 21.6l/ha
2.3.5.3 Tuber Harvester

Universal tuber harvester
Harvesting underground biomass crops requires a very specialized machine, a tuber harvester.
The most state-of-the-art versions are self-propelled and act similar to a self-propelled forage
harvester in the sense that it performs a multitude of tasks feeding a trailer pulled by a paralleling
tractor. First the top portion of the crop is trimmed, crushed and left on the field behind the
harvester. In sugar beet harvesting it is however advisable to first remove the stalks and collect
them before tuber harvests is to commence, whereas with the potato it is optional. This is
performed to maintain higher operational speeds while harvesting and to make use of the high
yielding top portion of the biomass. Next the soil bed row containing the tuber is dug up and
feed along a series of filters and grinding rolls to isolate the tuber. The nearly pure tubers are fed
via a conveyer belt to the trailer and the rests are dumped back onto the field. There is an

operational speed difference between potato harvesting and sugar beet harvesting, which also
includes the extra passage advised for efficient sugar beet harvesting
Self-Propelled Tuber Harvester

- Specific Type: Grimme SF300018
- Operation Speed (Potato): 2.5 – 10.0km/h, set 5.5km/h
- Operation Speed (Beet): 6.5 – 10.0km/h, set 8.0km/h
- Operational W idth: 2 or 4 rows, 4 ro ws at 3.3m
- Capacity: 1.82ha/h (potato), 2.64ha/h (beet)
- Fuel Usage: 45.7l/ha (potato), 31.5l/ha (beet)
Root digger
The cassava roots could be harvested mechanically and are to a degree. Root diggers are a much
simplified version of the tuber harvester. After the removal of the stalk the tractor implement
digs up the entire root structure with the soil and separates the crop with a primitive sieve
conveyor belt. A collection basket or even trailer is possible, but is not yet widely employed.
Stones, vines and undesired solid components are also removed with the rooting structure.
Root Digger
- Specific Type: API cassava root digger
- Capacity: 0.67ha/h (MF240)
- Fuel Usage: 13.1l/ha (MF240)
2.3.6 Trailer Transportation

Directly following the harvest the crop must be brought to a central farm scale storage facility to
await subsequent distribution. Depending on the scale of the farm, storage operations can range
from a small barn to a large silo. For non-food crops intended for industrial biomass production
large-scale silos coupled with crop specific pre-processing procedures, such as drying and
pressing, are foreseen (see Chapter 7). For these relatively short distances of only a few
kilometres tractors using trailer implements are employed. A portion travel occurs on the fields,
whereas the large part of the short haul is on side and rural streets.
Trailer
- Specific Type: 1 axis
- Capacity: 16ton/100m³ (TM 165), 6ton/40m³ (MF240)
- Operation Speed: 5.0 – 22.5km/h (field), 20 – 50km/h (street)
- Travelling Speed: 35km/h (TM 135), 25km/h (MF240)
- Fuel Usage: 25.3MJ/km (TM165), 10.9MJ/km (MF240)
- Fuel Consumption: 2.10MJ/t⋅km (TM 165), 2.42MJ/t⋅km (MF240)

2.4 Transportation Costs
Today anything can be shipped at anytime to anywhere in the entire world. An immensely
complex and efficient logistical infrastructure has facilitated the transportation of goods to no
longer be regarded as regionally bound, but globally free. This proves very advantageous for
industrially grown biomass crops, for biomass production will require vast quantities of arable
land to replace even the smallest portions of current fossil fuel consumption. To obtain a
significant reduction of fossil fuel intensity through biomass implementation can only be
achieved on a global scale. Furthermore, biomass grown regionally and harvested seasonally can
only supply the processing plants with a material feedstock for a limited portion of the
operational year. And as practically all modern processing plants are built on the economical
principle of continuous operation with a constant supply of material, it is imperative to ensure a
constant supply of feedstock. Thus to prevent any operational downtime biomass must be
imported from regions detached from the regional growing season. Although in some regions
perennial crops may suffice in providing enough biomass feedstock for the entire operational
year, the major chemical industries are located in temperate regions consisting of 4 distinct
seasons. The biomass transportation routes and destinations are described in (Section 4).
Raw biomass, pre-processed biomass and first stage biomass products can be separated into two
different categories: dry bulk and liquid bulk cargo. Bulk cargo is unpacked, homogenous and is
usually dropped or poured into a bulk cargo holder. Standard containers are generally not
employed as they are not very well suited for large quantities of biomass transportation.
Containerization has however revolutionized freight handling in the last
century, greatly reducing cost, increasing speed and shipping efficiency.
It is possible to transport dry and wet bulk material in container shaped
and ISO-standardized units. A so-called “bulkcontainer” contains an
open-top and can hold dry bulk goods and a so-called “tankcontainer”
can be used for liquid bulk cargo. As crop harvesting is seasonally based a large quantity of
biomass will be made available in a relatively short period of time, usually over the course of only
a few weeks. To be able to transport these high
volumes of cargo the specialized containers will not be
employed as they are designed for smaller distribution
levels. Two good examples of existing dry and liquid
bulk cargo in the biomass sector are grains and ethanol,
respectively. Dry bulk cargo (like grains) are handled by
conveyer belts, elevators, shovel buckets, etc. Liquid Dry Bulk Cargo: Grains Liquid Bulk Cargo: Chemical
bulk cargo (like ethanol) is handled primarily by piping equipment. The transportation capacity of
the cargo is gauged by two units of measurement; mass (tons) or volume (m³). One of the two
will be the limiting factor in transportation quantity. In case of raw biomass it is possible that
certain untreated crops will have a packing weight density lower than 500kg/m³, meaning that
volume is limiting. The packing densities of the biomass crops and pre-processed material are

listed in (Section 2.6). Aside from a few exceptions mass and not volume is the limiting factor in
transportation quantity. The fossil energy requirement for transportation will thus be presented in
relation to distance and weight, MJ/t⋅km, for the four major modes.
2.4.1 Heavy Goods Vehicle (Truck)

Traffic jams are a constant frustration to anyone travelling on any major
motorway in highly densely populated areas. Peak rush-hour periods congest
the roads for a couple of hours on a daily basis. And seasonal vacation
periods cause a great deal of the prolonged congestion and jams, inflicted in
Germany by the waves of slow moving Dutch caravan drivers, facetiously
dubbed during queues as “eine Campingplatz”. Even when taking the great
deal of social benefits (holidays) of northern countries like the Netherlands
into account the roads should only be congested about a dozen times a year.
And even if that is not taken into account, a more lingering and ever increasing dilemma is
arising…truck traffic. The vast majority of cargo is currently transported by truck. In Germany
alone, 66% of all the cargo is transported via the roads14. This high proportion is synonymous to
any industrialized region and reliance on truck transport is increasing yearly. Economically seen
transporting cargo via trucks makes perfect sense; the goods are delivered directly from A B in
the fastest period of time. And despite the current high prices in diesel, fuel costs contribute to
only a small fraction of the overall transportation costs. Seen purely energetically however poses
a different reality. Out of all the transportation options trucks have the highest energy demand
per distance and weight transported. Even the most energy efficient biomass logistical and
distribution chain options will invariably rely heavily on truck transport, especially in transporting
smaller batches (one truck load) of farm collected biomass to a transfer centre for long haul
distribution. Large scale implementation of biomass for industrial purposes will undoubtedly
further congest motorways, adding an additional socio-economic incentive to foresee and
properly assess biomass chains.
There are a great deal of trucks and manufacturers

Truck vs. Lorry vs. Large Goods Ve hicle
worldwide, with close to half a million being produced The word “truck” comes from the Greek “trochos”,
meaning wheels and during the time of horse drawn
each year. The largest manufacturer with a considerable wagon transport the big wheels were called trucks.
In Britain the word “lorry” was used by the railways
lead is DaimlerChrysler, badged under Mercedes-Benz to describe a long, flat wagon, derived from “lurry”
meaning to pull. With the advent of motorized
and Freightliner, producing 241,500 in 2005 (NTEA). vehicle transport, in America the word “motor-
truck” was adopted and in England “lorry”. Large
Due to the rapid road damage caused by trucks they are Good Vehicle (LGV) is however the official EU term,
but is not used in common speech.
classified and restricted by their maximum allowable
gross weight. In most European countries 40ton is the norm, with the Scandinavian countries
allowing 60ton as the exception, in response to their large logging industry. In other Western
countries, 50ton is the common maximum allowable gross weight, while in Eastern/Orient
countries mid-sized 20ton trucks are popular due to dense urban infrastructure. Other
restrictions and regulations concerning truck transport have also been developed. A clear result
of strict EU directives can be seen in the form, fuel efficiency and emission of gaseous pollutants

of trucks. Most visually apparent are European length restrictions being based on the overall
vehicle length including trailer and cab, where in many non-European OECD countries length
restrictions are either based on the trailer length or allow for longer lengths. This led to the
distinct splitting of truck design in where the Cab Over Engine (COE) “flat-nose” design is
prevalent in Europe and the Conventional “long-nose” design is prevalent in North America. The
long-nose design also facilitates a larger engine block needed to pull the extra 10-20ton of load,
ranging from 300 – 450kW, compared to 200 – 375kW for flat-nose trucks. In 1988, European
measures were taken to regulate the gaseous pollutants from diesel engines chiefly pertaining to
those from large goods vehicles, called 88/77/EEC. The “Euro I” norm placed upper limits on
CO, NO x, HC’s and particle emissions per power unit. Limiting carbon monoxide emission
indirectly affects the fuel efficiency through a higher lambda λ value and the most recent Euro IV
norm (2005) has 3.25 times less CO emission limits than the Euro I norm, at 1.50g/kWh. Thus
trucks constructed in 2005 for the European market are considerably more fuel efficient than a
model from the 1980’s. The separation between industrialized and developing world as
mentioned earlier can no longer hold for truck transport. Here the distinction will be made
between long-nose, full-sized flat-nose and mid-sized flat-nose. The truck classification has a
continental stipulation as opposed to a development stipulation. To date limited effort has gone
into improving the fuel efficiency of long-nosed trucks, meaning that even a new model is
comparable to an outdated flat-nose in terms of energy per distance and tonnage. Three different
truck configurations will be used: for European regions a 40ton gross (28ton net) Euro IV norm
flat-nosed truck will be used, for the Americas a 50ton gross (35ton net) Euro I norm long-nose
will be used and for regions that fall outside of these two categories a 16ton (8ton net) Euro II
flat-nose will be investigated. Much of the data in relation to the Euro norms can be taken from a
recently developed transportation tool (EcoTransIT)19.
Truck transportation in particular has several highly influential factors that can affect the diesel
consumption, namely the road category and characteristics and the transported load. Standard
consumption values are based on motorways in hilly regions, like Germany. Flat regions, like the
Netherlands require less fuel and mountainous regions, like Switzerland require more fuel. A
study by (INFRAS, 1995) found that a deviation of 5-10% occurs based on the regional topology
differences. Thus, like in the EcoTransIT study, flat regions are assumed to consume 5% less and
mountainous regions 5% more. Driving on extra-urban roads (with traffic lights, lower speed
limits and fewer lanes) consumes slightly more fuel than driving on motorways; 12% more on
average14. Wide-spread use of motorways is commonplace only in the originally defined
industrialized regions. Finally, a truck destined for a pick-up will arrive unloaded (empty) and will
consume roughly 1/3 the fuel as when fully loaded. It will be assumed that the trucks used for
biomass transportation are dedicated, meaning that deliveries are made at full load capacity and
returned empty. Both the fully loaded and empty load fuel consumption needs to be addressed.

European Regions (Euro IV)
To represent the near future best practices a recent (2006)
highly fuel efficient 40t flat-nose model was selected.
Mercedes-Benz Actros II14, 19, 20
- Type: 3336 Articulated, Single Cab
- No minal Power: 235 – 350kw, (265kW)
- Net Transportation Size: 28ton/100m³
- Norm: Eu ro V
- Diesel Consumption: 22 – 35l/ 100km
- Energy Requirements (loaded): 0.65MJ/t⋅km
- Energy Requirement (empty): 11.2MJ/km
Americas/Oceanic Regions (Euro I)

To represent the lower fuel efficiency of a Euro I classed
truck a standard, recent 50t long-nose model was selected
Freightliner Century Class
- Type: S/T Art iculated, Fu ll Cab
- No minal Power: 260 - 375kW, (325kW)
- Norm: Eu ro I
- Energy Requirements (loaded): 0.88MJ/t⋅km
Asian/African Regions (Euro II)

To represent the fuel efficiency of a Euro II classed midsized
truck a standard, recent 20t flat-nose model was selected
Mitsubishi FUSO Fighter21
- Type: FM 280M6, Single Cab
- No minal Power: 100 - 210kW, (207kW)
- Norm: Eu ro II
- Energy Requirements (loaded): 1.63 MJ/t⋅km
The compensation factors (like topography and road type) as mentioned above will be taken into
account, as based on the region of transport, in the transportation system layout (Section 3.2).
2.4.2 Train
Before the boom of truck transport the major land-based transportation mode was by freight
train. Today in Germany less than 15.9% of all the cargo is transported by rail14. Though other
countries without good inland waterway systems will have a higher percentage, the general
reliance on railway transport is falling. The major drawback of rail transport is the lack of
flexibility and speed. They must follow the set track routes and wait at transfer points, for

coupling/decoupling of locomotives, wagons, etc. With distances below 100km transport via
train is simply uneconomical and is in many cases even less energetically efficient. Under certain
circumstances, however, transportation via rail is far more economical and energetically efficient
than via road. From a cost standpoint only a few engineers need be occupied versus scores of
truckers and from an energy standpoint far more cargo can be transferred per power demand.
Several governmental bodies are even pushing rail transportation on environmental grounds. The
greatest benefits (economically and environmentally) of rail transportation are achieved with
long-haul bulk cargo. Future large-scale biomass production schemes, being classified as bulk
cargo, should capitalize on the benefits of train transportation. In some foreseen areas of large-
scale biomass cultivation it may be a prerequisite to invest in adequate railway systems. Heavy
initial investment costs in new railway lines are a leading factor in the current decline of rail
transportation reliance. Long term dedicated biomass production schemes and lower operation
costs and energy demand should overcome the initial investment burden.
When assessing the energy input requirements of freight train cargo transport the type of
locomotive plays a decisive role. In vast areas of open space without the option of electrified
railway tracks diesel/electric traction units (an onboard diesel generator powers electric traction
motors) are employed, whereas electric trains
can be employed in areas powered via electric
feed cables. The energy required per tonnage
and distance varies considerably depending on
the traction unit. Following the guidelines of a
limited LCA the electric production will be
traced back to its initial fossil fuel input. As described in Chapter 2 many factors influence the
specific conversion rate, like the grid power mix and power station thermal conversion levels,
45% will be taken. The internal power conversion of a diesel/electric locomotive is 37%.
Transporting bulk cargo involves specially designed wagons tailored to the specific properties of
the material. In Europe self-loading funnel wagons are common for dry bulk cargo whereas in
the rest of the world covered hopper wagons are predominant. Liquids are transported in tanks
for all regions. The size, net weight and volume capacity of each wagon is unique, but total length
and number of wagons is not of terrible importance as the train size capacity is based on total
weight pulled. A typical train load can range anywhere from 500 to a maximum of 2000ton gross
weight. The longer the train (more weight) the more efficient the transportation and a large, long-
haul setup can be expected for dedicated biomass transport, resulting in a gross weight of
1500ton and net weight of 800ton/2400m³. The recent EcoTransIT project/report was
commissioned by the major European railway companies implying a high degree of accuracy for
the rail transportation under different conditions19. Electric range from 23.2 – 90.6Wh/net-t⋅km
(0.18 – 0.72MJ/net-t⋅km) and diesel range from 2.6 – 9.7g/gross-t⋅km (0.22 – 0.83MJ/net-t⋅km).
Topography conditions have a much larger effect on train transport than on truck transport. Flat
regions require 25% less power demand and mountainous regions require 20% more power

demand over the standardized hilly regions. Proportional travelling time empty is incorporated in
the resulting figures for both electric and diesel traction train systems. In many developing
regions the option to transport via rail is not wide spread. Infrastructural investments will be
required to allocate large portions of possible biomass transportation by rail and in such cases
electrified railway lines are not foreseen making the diesel/electric traction units the most likely
choice.
Industrialized Region (Electric)

To represent the best practice, most efficient option, a long
electrified loco motive was chosen19
- Type: Electric
- Gross Pulling Weight: 1500ton
- Net Pu lling Weight: 800ton/2400m³
- Configurat ion: Dedicated, block train
- Cargo Type: Bu lk
- Electric Consumption: 29.0Wh/t⋅km
- Energy Requirements (roundtrip): 0.232MJ/t⋅km
Developing Region (Diesel/Electric)

To represent the areas without electrified railway systems a
long diesel/electric loco motive was chosen14
- Type: Diesel/Electric
- Gross Pulling Weight: 1500ton
- Net Pu lling Weight: 800ton/2400m³
- Configurat ion: Dedicated, block train
- Cargo Type: Bu lk
- Electric Consumption: 0.36Wh/t⋅km
- Diesel Consumption: 0.391M J/t⋅km
- Energy Requirements (roundtrip): 0.394MJ/t⋅km
The topography compensation factors as mentioned above will be taken into account, as based
on the region of transport, in the transportation system layout (Section 4).
2.4.3 Inland Barge

Rivers and canals have always enabled trading between settlements and industries. Before the
onset of rail and truck transport, waterways were the primary method of transport. Historically
industries have been located along bodies of water to supply the factory with process water, a
cooling medium, a reservoir to wash away by-products and as an easy position for transportation.
Inland trading via barge is still today very economically attractive being able to efficiently
transport large quantities of cargo with low associated loading and unloading costs. Many large
processing plants have trading harbours specially constructed to facilitate inland barge transport.
But similarly to rail transport the transportation destinations and flexibility are greatly limited.
Transport via inland waterways is only feasible in areas with large rivers and canals linking the
industries. The European waterways and the current trading volumes are immense and open

many possibilities. The waterway transport options do span for large areas but are not suitable
everywhere. In fact inland barge transportation is limited to only a few regions in North Western
Europe and the Midwest-South of America. Inland barge transport is strictly an industrialized
region mode of transportation, meaning no classification difference will be made.
The energy required to transport cargo over waterways depends on several factors. Firstly, the
trend of inland barges continually growing in size, getting more powerful with an increasingly
large payload reduces the consumption. Typically barges can range from 800 – 2500ton load
carrying capacity with 300 – 750kW engine power. Despite the fuel consumption reduction the
highly powerful barges are chiefly employed in heavy-goods transport, like metals. Biomass and
biomass related products are best suited for modern upper/mid-range capacity, 1750ton. This
still represents more freight than an entire train load. River direction is another major factor, as
travelling upstream requires significantly more fuel than travelling downstream. The form of the
river also affects the fuel consumption. Sluices and slices built along the banks regulate the river
flow velocity and reduce the overall fuel consumption of barges, especially when travelling
upstream. In the areas most reliant on inland transportation sluices are commonplace. Finally,
like with the other modes, dedicated transport implies empty loads.
Industrialized Region
To represent the best practice, most efficient option,
mid/upper sized self-propelled barge was chosen 19
- Type: Self-Propelled River Barge
- Net Cargo Weight: 1750ton
- Energy Requirements (Loaded)
Downstream: 0.17MJ/t⋅km
Upstream: 0.24MJ/t⋅km
- Energy Requirements (Empty)
Downstream: 261MJ/ km
Upstream: 356MJ/km
2.4.4 Sea Vessel

Globalization would not be possible without sea vessel transportation. During the time of the
Dutch East India Trading Company (VOC) a rigged ship manned with a crew of at least a
hundred took several months to complete a journey collecting a couple tonnes of spices. Today
modern bulk carriers can complete a trading journey in a matter of few weeks with less than a
dozen crew collecting on average 40 000 tons of cargo. The newest and largest of the classes can
carry up to 325kton of cargo. Bulk carrier is the general name for dedicated ships transporting
bulk cargo; bulkers describe dry cargo types and tankers for wet cargo types. Bulk carriers
comprise of a large section of the global transport of goods, representing one third of the total
merchant fleet. The bulk carrier fleet includes 6,263 ships with a total capacity of 294million tons
(in 2004)22. Transportation on the open seas is an international business with no clear distinction
between nations. The largest fleet, 1700 bulkers, sail under the Panama flag as they are registered

there for tax reasons. And 41% of the world’s bulkers were built before 1986, meaning regional
discrepancies cannot be made. Classification of sea vessels is thus done by total carrying capacity,
the hulls width, length and draft and type of configuration. The largest proportion of bulk
carriers, 32%, are in the Handysize class having a deadweight tonnage (DWT) of 10 – 35kton, but is
quickly shifting to the larger Handymax class of 35 – 55kton22. Net cargo capacity is 85% dwt for
bulk carriers and 95% for tankers. Nowhere more than in the sea vessel transportation sector is
the economics of scale so apparent and beneficial. Many of the newly built bulkers and tankers
cannot fit through the Panama Canal and Suez Canal called post-panamax and post-suezmax,
respectively. Sailing around Cape Horn and the Cape of Good Hope is simply more economical.
Fuel costs almost represent the entire portion of the operation costs of sea vessels, ranging from
90 – 95%23. The larger the dwt the lower the proportional fuel costs per transported tonnage.
Relating the heavy diesel oil consumption to the transported cargo will be based upon the two
types of cargo, wet and dry. Tankers are considerably more energy efficient than bulkers, simply
due to the higher packing density of liquid cargo. Although the trend of the shipping industry is
to increase ship size, following the economics of scale, the typical sizes will be taken instead. For
it is unlikely that in the biobased economy a single port would process such high levels of
biomass to warrant the employment of supertankers or superbulkers, at least in the initial phases.
Furthermore bulk carriers are strictly dedicated, port-to-port business returning empty. The
option of collecting biomass material on-the-way is not possible or rational as it is with container
ships. A ship returning with empty cargo (but full ballast tanks) holds requires 65% the fuel levels
as during full load conditions. Since most ships are built before 1986 there is not much relevancy
in the age of the sources of information. Borken14, collected shipping information from a wide
variety of international studies reflecting the years 1985 – 1996.
Industrialized and Developing Regions

To represent the expected transport conditions involved in
the biomass sector a typical sized ship was chosen.
- Type: Tanker
- Cargo Type: wet, liquids
- Size Class: Panamax
- No minal Power: 9,760 – 12,200kW
- Cargo Weight (dwt ): 60,000 – 82,000ton
- Diesel Consumption: 0.7 – 2.6g/t⋅km
- Energy Requirements (roundtrip): 0.031 – 0.118MJ/t⋅km
Set: 0.057MJ/t⋅km (1.25g/t⋅km)

Industrialized and Developing Regions
To represent the expected transport conditions involved in
the biomass sector a typical sized ship was chosen.
- Type: Bu lker
- Cargo Type: d ry, loose
- Size Class: Handymax
- No minal Power: 6,730 – 10,600kW
- Cargo Weight (dwt ): 35,000 – 55,000ton
- Diesel Consumption: 2.2 – 4.9g/t⋅km
- Energy Requirements (roundtrip): 0.101 – 0.224MJ/t⋅km
Set: 0.114MJ/t⋅km (2.5g/t⋅km)
2.5 Storage and Transfer Costs
2.5.1 Storage Description

In any logistical chain, simple or complex, storage of material is inherently included and is located
almost exclusively at a transfer point between the different scales and types of modalities. In
terms of large-scale biomass transportation there are two major cause and effects necessitating
storage capacities. Both relate to the fact that each arable piece of cultivated land is independent,
scattered and can only supply moderate quantities of biomass per each harvest period. Tractor
transport will collect the freshly harvested crop and deliver it to a central storage location, such as
a farm-scale barn. Until the collected biomass weighs sufficiently to warrant the next mode and
scale of transportation (such as truck), the material must be stored. The long-haul, high-quantity
transportation types (especially water bound vessels) can transport many hundred-fold the freight
of a tractor and truck load. These differences will result in a bottleneck of delivery flows
mitigated through the use of centralized storage systems. An articulated truck can perform other
tasks during downtimes, whereas the economics and energetics of charting a ship at less than full
capacity is not advantageous. Furthermore biomass being a seasonally dependent commodity
means the time of harvest does not necessarily couple well with the production window. A
limited factory production flow either on the pre-processing or final processing side can create
another bottleneck. Over-sizing of equipment to increase throughput is not economical in light
of cheap storage options. Thus biomass storage facilities follow the simple rule of supply and
demand. As the biomass chain cannot supply a constant flow of material when needed (transfer
point or processing plant) storage is inherent.
Storage of biomass material for non-food purposes does not generally require energy in itself.
Large areas of land are required for its place, which will minutely lower the actually crop yield in
terms of ton/ha. Considering new and large areas of storage facilities must be constructed to
accommodate the near future flows of biomass material, possible arable land is lost. It is however
greatly difficult to place a precise lost yield value considering the different land types and actual
storage positions and sizes. Locations designed for material storage and transfer (i.e. a harbour)
do not classify as arable land. Even on the farmland barns, silos and other agricultural buildings

represent a mere fraction (1-5%) of the arable land. It should only be mentioned that large-scale
biomass production has a relationship on the land requirements. As a land consuming factor,
storage of biomass and related products must be expressed in volume (m³) terms and not weight
(tons), for the dimensions of the storage facilities differ immensely and are very feedstock
dependent. As an example, wet biomass will require a larger surface area than dry biomass, but
dry grains can be stored in high silos (grain elevators) whereas wet grass cannot. In (Section 2.6)
the pre-processing options and types will be investigated. The packing density, moisture content
and particle form determine the storage facility type and land consumption of the biomass
feedstock.
One of the major drawbacks of storage options is the loss of material. Long-term storage can
promote the digestion of the material through bacterial and fungal contamination. The loss of
biomass material is evident by the formation of carbon dioxide, methane, other volatiles and cell
mass from the decomposition of biomass material. It is a function of the type of biomass and of
the degree of moisture, for no decomposition occurs for most biomass feedstocks below 20%
moisture content. Wet materials degrade at a rate of 3% dry mass content per month24. Yet for
example, the first stage of storage being the roadside/farmland can reduce the moisture content
from 50% to 30% purely by the environment without charge or material loss24. Furthermore,
ensiling is a storage technique that can preserve green forage with no notice loss of material.
However in general, pre-processing techniques will need to be implemented to reduce the
moisture content, increase the packing density and lower the particle size/form; all of which will
lower the storage needs, transportation costs and prevent loss of material.
2.5.1.1 Transfer Points

Biomass is stored at a point of logistical transfer. The specific location and feedstock material
properties determine the storage facility and as mentioned, storing biomass does not directly
consume energy. It is the transfer equipment that consumes primary energy. They are determined
by the type of storage facility and the mode of transportation. There are many types of storage
facilities; typically barns, covered halls, and small silos are present for farm based systems and as
collected volumes and masses increase further down the transportation chain large bunkers, silos
and tanks become more apparent. Each of the storage systems relies on a different set of
equipment to perform the unloading, arranging and reloading. Under certain circumstances some
transfer points do not need to rely of any storage systems and can directly transfer the material to
the next mode of transportation, adhering to the just-in-time business model. For example, loading
the funnel wagons of a long-haul train from regional trucks can be immediate given the right
logistical planning. This will avoid one step of unloading, arranging for storage and subsequent
reloading. Akin to storage facilities there are numerous tools and equipment utilized to load,
unload and transfer materials. Figures must be kept in volumetric terms for the operational speed
of transfer equipment is limited by throughput. Bulkier material (lower packing density) will take
more transfer operational time and will thus consume more energy in the process.

Assuming that the material decomposition loss due to inappropriate moisture content levels are
resolved through adequate pre-processing methods, material loss is still present. A minimal loss
of biomass occurs through traditional inefficiencies involving in storage and transferring
operations, namely spillage, being blown away, leaching, leftovers, etc. Typically 1-5% results per
transfer and is system dependent. This material loss is on top of the unavoidable biological
degradation and will be related to the transfer points and the operational equipment involved.
2.5.2 Loading/Unloading Equipment

The major transfer equipment types covering the general expected forms of biomass material
presented by the choice crops will be investigated. Transfer equipment is understood as loading,
unloading and arranging storage facilities. They will be grouped by transfer point stage and
related to feedstock property type. Included in the assessment will be the transfer speed, material
loss and primary energy consumption per volume. Separate grouping of industrialized regions
and developing regions has little effect on the mechanical transfer operations values. The only
true difference in practice is on the farm level and transfer to trucks. For it is commonplace in
the developing regions to heavily rely on manual labour to load outbound vehicles.
2.5.2.1 Wheel Loaders

Wheel loaders are classified as construction equipment fitted with a front movable arm designed
for moving and lifting material and/or freight. A wide variety of front attachments are available
specially fitted for the material to handle, predominantly shovels, buckets and picks. Nearly
anything can be handled with a wheel loader and the operational speed is dependent on the form
of the material handled, the size of the machine and the distances required for transfer. For
agricultural purposes and loading/unloading of trucks a small/mid sized model will be chosen.
Tractors can also be fitted with a front end loading implement and made to operate like a wheel
loader, yet positioning speeds are compromised.
Wheel Loader
- Specific Type: Liebherr L50925
- No minal Power: 52kW, 275g/kWh
- Loading/Unloading Capacity: 10 – 100runs/h, set 30runs/h (assumed)
- Bucket Capacity: 1.0 – 2.0m³, set 1.1m³ (loose material)
- Fork Capacity: 4.0 – 4.4ton, set 3.0m³ (packed material)
- Material Loss: 0.3%26
- Diesel Consumption: 0.39l/ m³ (loose), 0.19l/ m³ (packed)
- Energy Requirements: 14.5MJ/ m³ (loose), 7.3MJ/ m³ (packed)
2.5.2.2 Conveyors
Some of the dry bulk biomass products will be stored in silos; particularly grains are stored in tall
silos, called grain elevators. A system of conveyors is used to transport the material to the top of
the structure for filling. Conveyors operate by a system of electrically powered pulleys with a
looping transport band. Many different configurations are possible with conveyance systems. The

grain elevator for example employs a bucket conveyor track, yet the most common for biomass
applications is the common belt conveyor. They are usually open and capable of transporting
large quantities with very low energy costs. Screw-type conveyors are enclosed and have thus
lower material loss and are best suited for moist biomass material. Conveyors can be utilized in
several transfer points and being coupled with typically large silos are located at major
distribution hubs awaiting transfer. Conveyers are also used to load vessels, called shiploaders.
The energy demand for conveyance has four influencing factors; speed, height, density (weight)
and total rate. It was found that 2.80kWh/t⋅km (+0.2 – 1.0kWh/t⋅km depending on the slope) is
typical for conveyor belts27. 3.0kWh/t⋅km will be used with the following assumptions to relate to
biomass applications, resulting in MJ/ton.
Conveyor
- Specific Type: Belt27
- Electrical Power Demand: 3.0kWh/t⋅km
- Typical Silo Height: 10-100m, set 50m (dry), 10m (wet)
- Set Conveyor Length: 75m (dry), 15m (wet)
- Material Loss: 0.2%26
- Electrical Consumption: 0.23kWh/ton (dry), 0.05kWh/ton (wet)
- Energy Requirements: 1.8MJ/ton (dry), 0.36MJ/ton (wet)
- Add 50m for ship loading: +0.15kWh/ton, +1.2MJ/ton
2.5.2.3 Stacker/Reclaimer
A stacker also operates on the principle of a conveyance system for handling bulk materials. The
difference is that a stacker creates open stockpiles along on a guided track and therefore does not
place them in a silo. Without the benefit of a silo structure gravity cannot be used to further feed
the material to the next transport modality. For this transfer operation a reclaimer distributes the
stockpile affectively reversing the process. Although the height of the stockpile is less than a
common grain elevator, the conveyor belt total length is longer due to the long distribution of
the tracked storage area. Biomass not prone to climatically induced degradation and/or in regions
with minimal rainfall during periods of storage can be stored in stockpiles, preferably in areas
with a high throughput of material. Being stored in the open will nevertheless promote additional
material loss regardless of moisture and weather conditions. Compared to the enclosed silo
storage type an additional factor of 3 will be set for the material loss. The electrical consumption
per ton and distance will be used as was for the conveyor belt.
Stacker/Reclaimer
- Specific Type: Belt/Scope27
- Electrical Power Demand: 3.0kWh/t⋅km
- Stacker Boo m Length: 20 - 40m, set 38m (all)
- Set Conveyor Length: 100 - 500m, set 200m (all)
- Material Loss: 0.6%
- Electrical Consumption: 1.42kWh/ton (pile and reclaim)
- Energy Requirements: 11.4MJ/ton

2.5.2.4 Crane
Unloading of vessels (both sea and inland) is performed by bulk handling port cranes. They come
in many forms and sizes depending on the specific material being transferred and transversely
effect the berthing time. A large bulk carrier can take several days to properly unload taking into
account the dangers of capsizing. Most common is the gantry grab unloaders using a bucket to
scoop dozens of tonnes in one go and place the material via the gantry on the shore in bulk
holders, in stockpiles or directly on feed conveyors. Ports equipped with cranes are close to or
are part of the industrial terrain of the destined chemical factory meaning cranes are the final
phase in long-haul transport. Highly modernized port operations (like in Rotterdam) employ
large continuous suction systems connected to conveyor belt systems; the unloading speed is
enhanced while the energy requirements are comparable.
Crane
- Specific Type: Gantry Bucket28
- Bucket Size: 25 – 63tons/scope
- Unloading Capacity: 800 – 3000ton/h, set 1500ton/h
- Material Loss: 0.1%
- Energy Requirements 29 : 2.32MJ/ m³ (bucket type)
- Energy Requirements 29 : 3.13MJ/ m³ (shovel type)
An older study from 1995 found 10MJ/ton for train transfer points and 40MJ/ton at ship
transfer points26. The EcoTransIT uses the average estimate of 1.3kWh/t (10.4MJ/ton) for all
bulk and general cargo transfer types19. These figures are either lower or higher than the ones
they calculated above with respect to the specific transfer action performed. Depending on the
moisture content, the transported biomass has an energy content of 2 – 20GJ/m³ which when
brought into perspective means that the transfer costs are two orders of magnitude lower. Thus
the exact figures of storage and transfer energy demand do not greatly influence the overall
energy costs, but should nonetheless be included. For transfer options not covered above,
5MJ/m³ energy and 6.4MJ/m³ exergy (since most equipment is electric based) will be taken.
2.6 Pre-processing and Drying Costs

Transportation of bulk materials with a bulk density below
500kg/m³ are considered to be light, volume dependent Bulk Density
materials and are not suitable for cost and energy effective A prop erty o f pa rticulate m ateri als.
long-distance transport. At bulk densities below 500kg/m³, It is the m ass of m any p articles o f
the materi al di vide d by the volum e
more air is being transported than actual material. A classic they occupy. The volum e inclu des
example in the logistics world is the beach ball; inflated or the space b etw een pa rticles as
deflated? Being manufactured in China the balls must be well as th e space i nside th e po res
of in di vi dual particles.
transported across the world to reach their desired markets.
A large inflated beach ball has a bulk density of only a few grams per cubic meter, while a pile of
vacuum packed deflated beach balls can reach nearly 900kg/m³. Practically 100 extra
transportation journeys would be required to transport a shipment of inflated over deflated beach

balls; but than again half the fun of a beach ball is blowing it up. Beach balls are the extreme. In
the biomass sector many crop components are harvested with bulk densities below 500kg/m³.
Biomass has an additional dilemma concerning transportation; high moisture content. Not only
air but water is being transported greatly reducing the net dry biomass material. Thus pre-
processing and drying are a prerequisite before any long distance logistics of biomass can
commence. Processing in the sense of refining biomass to other materials in centralized factories
will be covered in the succeeding chapter. In this section pre-processing and drying is understood
solely as the straightforward, common methods employed to increase the bulk density and lower
the moisture content for longer distance bound biomass; essentially compacting the material and
removing a large portion of the water content.
Sizing and drying are energy intensive steps that can also inflict material loss and degradation.
The higher the desired resulting “dry” bulk density the higher the processing energy costs and
potential for material loss (burning, dust creation, etc.) There is a clear trade-off between the
reduction of transport cost and the increase in processing costs, particularly for short distances.
An optimum must be found to ensure that the least amount of energy and exergy has been lost in
the transportation of biomass material. Little can be done about the required moisture content
for long distance transportation, for as mentioned in (Section 2.5.1) the decomposition of
biomass material ceases at values below 20%. For food-grade grains the moisture content is
brought down to 15% to avoid any decomposition and bacterial infection. Seeing that long-haul
intercontinental transportation can take several weeks and even months, 20% moisture content is
set as a minimum for forage and waste-type biomass feedstocks and 15% moisture content for
grains and seeds. Lower moisture content is not required or advised. Fortunately several of the
crop components already adhere or come close to these levels and require little or no additional
drying procedures. Size reduction is feedstock dependent as there is a multitude of options
available to comply to the specific biomass properties. The demand for and energy intensity of
sizing is a function of the required bulk density and physical feed properties (such as lignin
content and initial size). First the procedures for drying and sizing will be listed and presented in
MJ/ton wet weight, which will later relate to MJ/m³. The optimal settings in combination with
the transport costs will be covered in Section 4. This section will follow the same layout as the
farm equipment costs, systematically listing the equipment options and energy demand as a
general input.
2.6.1 Size-Reduction
Harvesting biomass material inevitably reduces the size and increases the bulk density through
the harvesting techniques. A forage harvester, for example is in fact a crude size-reduction devise
yielding particle sizes between 10 – 25mm. Yet for transportation beyond the regional storage
facility additional size-reduction is necessary to further increase the bulk density. There are three
basic unit operations for biomass size reduction techniques; cutting, crushing and shearing.
Cutting is performed close to the field or initial storage facility to allow for better stockpiling of
bulky material and promote a more effective drying process. After moisture reduction (Section

2.6.2) crushing and shearing further reduce the material into finer particles, usually in the form of
a pulp or course flour. The benefits of employing the final two size-reduction installation options
is only realised for certain logistical operations. System incorporation and the degree of size-
reduction requirements are feedstock, location and destination dependent. In practice, a wide
multitude of installations are custom tailored to the specific needs of the feedstock. Yet, general
installation types follow standard energy demands with only a minor influence of the specific
crop properties. The following size-reduction installations are based on the common parameters
for the three types.
2.6.1.1 Cutting
Initial cutting is already performed for certain crops by the forage harvesting procedures, greatly
increasing the bulk density and facilitating field collection. Grinders, shredders and chippers are
all synonymous as essentially being first stage size-reduction units for those crops and/or crop
components not exposed to the forage harvester or further cutting the material into smaller,
more workable sizes. There are two basic design concepts for cutting units as defined by the
mechanism involved; the drum and the disk chippers. The drum type works by two parallel
rotating steel drums providing the feed and crushing force. This design type can easily take
advantage from the economies of scale and is frequently employed in larger factory installations.
The disk type works by a series of rotating disks mounted with cutting blades. The resulting size
of the material for both types is similar at 5 – 50mm, which lies in the same range as the forage
harvester. The disk type chipper however has been designed primarily for operational safety and
is common for smaller applications and material through-put. Even though being unable to take
much advantage of the economies of scale, the drum chipper has a significantly lower energy
demand per processed amount of material. Currently, drum chippers are primarily employed for
forestry products and are especially useful in sizing of hard and bulky materials. Certain forage
material and other agricultural residues, with their high lignin content, behave similarly to woody
material that has been subjected to forage harvestation.
Several independent studies have investigated the energy demand of drum/roll chippers. A
slightly dated case study for the woodchip industry found a diesel consumption of 6.7l/ton chips
(0.25GJ/ton WW)30. Around the same time a collection of data was presented for the chipping of
various grains at differing moisture contents31. The primary energy consumption ranged from
0.032 – 0.266GJ/ton WW for a roller mill. A more recent study for forestry residue biomass
sizing found considerably lower figures of 0.029 – 0.064GJ/ton DW (0.06 – 0.12GJ/ton WW)32.
While a recent industrial assessment of various chipping machines for woody biomass chips
revealed 0.13 – 0.23GJ/ton DW (0.26 – 0.46GJ/ton WW)23. In summary, these studies show that
the energy requirements for a chipping unit range anywhere from 0.032 – 0.46GJ/ton WW, being
very feedstock dependent. As it is foreseen that even the harder/woody biomass will first be
forage harvested, the energy requirements of employing a cutting unit is on the lower scale:
0.075GJ/ton WW will be assumed to be representative.

Cutting
- Specific Type: dru m/roll ch ipper
- Motor Size: 50 – 1500kW, set as large 1000kW
- Operation Capacity: 10 – 100tonWW/h
- Chipped Size: 15 – 50mm, set 20mm
- Energy Consumption: 0.075GJ/tonWW
2.6.1.2 Crushing and Shearing

Crushing and shearing reduce biomass to even finer particles, typically below 1.0cm in diameter.
In many of the biorefinery plants these units will be invariably foreseen as the first step in
handling the feedstock before subsequent processing. It is essentially a mechanical pre-processing
step. In some logistical systems it may be of advantage to have this step before transportation to
the biorefinery. For these size reduction units a low moisture content is necessary to ensure a
fluid operation, effectively making drying a prerequisite for most of the biomass feedstocks.
Furthermore with the creation of fine particles certain internal crop components become
exposed to the environment and become sensitive to degradation conditions, adding the need for
a possible secondary drying procedure. Fine particle creation is energy intensive and larger scale
industrial units will have a better energy-to-feedstock ratio than smaller scale units while also
reducing or even avoiding the drying steps, being coupled to the biorefinery. Nonetheless many
systems will benefit from localized size reduction steps before long distance transportation.
There are two major types of crushing and shearing units for biomass applications. Hammer mills
are amongst the most common machines in industry to crush coarse material into finer sizes,
particularly in mining operations. They are also used on fibrous and grain biomass to produce
fine feeds and flour. By circulating a beating hammer the material is crushed to size and passed
through a sieve. For even finer particular sizes a burr mill is employed, which grinds the material
into size via two circling plates with jagged surfaces. The energy intensity of a burr mill is
significantly higher as the generated particle sizes are much smaller, in the order under a few
millimetres. A study into the specific energy demand of woody biomass found a general formula
correlated to the final particle size33:
Fine Particles (<1mm) Coarse Particles (>1mm)

E = −0.731 ln(dpm ) + 0.742 E = −203.06 log(dpm ) + 206.11
E: Grinding/Shearing electrical energy [MJ/kg DW] E: Grinding/Shearing electrical energy [kWh/ton DW]
dp m: Middle(average) diameter particles [mm] dp m: Middle(average) diameter particles [mm]
Other studies found the primary energy consumption of a hammer mill to range from 0.032 –
0.263GJ/ton DW23, 31. A recent study into the energy costs of hammer-milling palm-kernel
revealed remarkably low values of 0.0142 – 0.0315GJel/ton DW34, whereas hammering
switchgrass revealed 0.201GJel/ton WW35. As mentioned the burr mill requires significantly
higher energy demands at 0.192 – 0.696GJ/ton WW31, for finer particle sizes. Burr mills are
among of the earliest size reduction machines as is noticeable from the higher energy

consumption, faster wear and will eventually phase out in favour of hammer mill technology.
Furthermore the burr mill advantages are in food processing techniques (i.e small particle size
distribution), which for non-food bares little relevance. Yet, many biomass crops are still based
on the classical food portion of crops warranting its inclusion. Due to the big variations in energy
input and resulting particle size several assumptions will be made based on the above formulae:
for cut and partially dried fibrous residues, forages, the hammer mill will be employed producing
5mm particles and for grains and other dry feedstocks the hammer mill will be employed to yield
1.5mm particles.
Crushing and Shearing

- Specific Type: hammer mill
- Input Moisture Content: 10 - 25%, set 20% forage, 15% g rains
- Chipped Size (forage): 0.5 – 5.0mm, set: 5mm
- Chipped Size (g rains):, 0.1 – 2.5mm, set: 1.5mm
- Energy Consumption (5mm): 0.231GJel /tonDW: 0.44GJ/tonWW
- Energy Consumption (1.5mm): 0.613GJel /tonDW: 1.09GJ/tonWW
2.6.2 Moisture Reduction

In the cereal/grains sector, around 60% of the total process energy demand originates from
water removal. In the forestry sector it is even higher at 70%. Depending on the methodology,
between 9 – 25% of the total industrial energy consumption in developing countries is allocated
for drying operations36. Biomass, especially green biomass, has an inherently high moisture
content in the order of 10 up to 90%. Upon the transportation of wet biomass the embodied
water serves no purpose except to negatively influence the transportation costs and energy
requirements. Long-term storage and long-haul transportation have the additional problem of
accelerated product degradation through increased activity under the presence of water. In the
perishable food industry moisture reduction techniques permit arbitrary harvesting dates reducing
losses attributed to early and late harvestation, for as much as 10 – 15% additional yield is
achieved31. Before the advent of direct crop drying easily 10% of the yield perished in the storage
facilities. Non-food biomass with the intended purpose as a feedstock for chemical biorefineries
have three basic reasons supporting the removal of water. Firstly, it minimizes deterioration of
the product during lengthy logistical systems. Secondary, it enables fully mechanized material
handling in logistical systems. Thirdly and most importantly, it increases the net dry bulk density.
Although quite material dependent, for the large part the biomass structure remains constant
regardless of the moisture content implying that drying in itself has a rather negligible effect on
the resulting volume of the product. Only when coupled with a size reduction step is the net dry
bulk density increased by a significant amount.
Adhering to thermodynamic tables 2.28MJ is required to directly evaporate 1kg of water, which
for thermal drying implies 2.3GJ/ton water removal as a bare minimum, without heat recovery or
integration. Moisture reduction is an energy intensive process further intensified with relatively
low energy/drying efficiencies. Typical energetic drying efficiencies for crop drying installations

lie between 15 – 60% with a strong interdependence on the initial and final moisture levels. For
instance, standard hot air dryers consume 4 – 10GJ per ton of water removed from biomass
materials31. There is an array of dryers and moisture reduction systems available that are highly
specified and effective to the particular biomass feedstock with an equally wide range of energy
demands. The typical systems required for the biomass materials under investigation are
described, listed and calculated for the energy demand in relation to the feedstock and moisture
content.
2.6.2.1 Natural Air Drying

Leaving the harvested crops on the field or under an open-air shelter for a few days can reduce
the moisture content to as low as 30% with no fossil fuel energy charge or loss of material. Many
forage crops in particular are handled this way, being raked into windrows and left to partially dry
before collection. Harvested biomass with a moisture content between 30 and 60% are best
treated in such a fashion to drive drying costs down. Local weather conditions do effect the
speed and extent of moisture reduction, but typically crops are harvested during the warmer and
drier periods of the year. Thus, even in temperate climates drying to 30% with natural
environmental conditions is possible. A moisture content approaching 20% is however generally
not possible with natural air drying alone; additional treatment is necessary for many of
feedstocks. For very wet biomass (>70%) goes to 50%, others (<70%) go to 30%.
Natural Air Drying

- Specific Type: none
- Bio mass Types: green biomass, forages, stems, leaves, etc.
- Input Moisture Content: 30 – 60% and 70 – 90%
- Output Moisture Content: 20 – 40%, set at 30% and 50%
- Energy Consumption: 0GJ/ton
2.6.2.2 Filter Press Dewatering

Extraordinarily wet biomass that upon harvest exceeds 50% moisture cannot be properly air
dried without complications, such as contamination and loss of material. A filter press can speed
up the dewatering process with a moderate addition of electric energy. By applying pressure via a
hydraulic press large amounts of water are forced out of the feedstock through a filter body (belt
or sheets). The filters minimize the permeation of smaller soluble materials but loss is
unavoidable although kept below a few percent when employed as an initial water removal
device. Filter presses are commonplace in wastewater treatment facilities as a first step in
removing large quantities of water. Typically, sludge feedstocks of only a few percent dry matter
are reduced to 50% moisture and in some cases brought to as low as 10%. Particularly wet
biomass that has undergone an initial size reduction treatment can give a moisture reduction to
about 30% with minor energy demand and material loss.

Filter Press Dewatering
- Specific Type: chamber filter press
- Bio mass Types: wet green bio mass, forages, stems, leaves, etc.
- Input Moisture Content: 50 – 90%
- Output Moisture Content: 20 – 40%, set at 30%
- Material Loss: 2% (main ly sugars and free amino acids)
- Energy Consumption: 10 – 30kWh/tonDW, set 0.23GJ/tonWW
2.6.2.3 Conveyor Belt Drying

In the forage industry reducing the moisture content to below 20% is commonly achieved
through the use of a conveyor belt dryer. This is desired when the material is to be converted
into pellets and/or stored for a considerable length of time. The wet feedstock travels along the
conveyer belt and is exposed to hot air (120 - 200° C), either from below or above, which
removes the water in the process. It is a simple yet energy intensive system typically involving a
fuel burner. The energy demand is a direct function of the amount of water removed from the
biomass feedstock. Typically for hot-air belt dryers 4.6 – 7.0GJ/ton water removal is required31.
At temperatures below 150° C driers are considered “low-temp”. These systems have moderately
lower energy demand compared to other system; with other modern improvements the energy
consumption can be further reduced37.
Conveyor Belt Drying

- Specific Type: hot-air conveyor belt
- Bio mass Types: chips, forage, stems, leaves, etc.
- Energy Consumption: 4.5GJ/ton H2 O, for 3020%: 0.56GJ/tonWW
2.6.2.4 Rotary Drum Drying

One of the most straightforward and common dryers for any drying application is the rotary
drum dryer. It works on the exact same principle as the household laundry dryer, rotating the wet
material while injecting a constant flow of warm-air as the drying medium. Industrial rotary drum
dryers for biomass applications use either hot-air (above 130° C) or the direct flue-gas (above
200° C) from the burner. Significant levels of electricity are required to continually rotate the
drum but this still represents less than 0.1 – 2.5% of the total energy demand38. Thus electric
contribution can be disregarded. By rotating the wet material in the drum it is brought into direct
contact with the drying medium and promotes a good air particulate contact and fast mass
transfer. These systems are highly effective for initial moisture content reduction. Early
calculation models for bioenergy applications reduce the moisture content from 50% to below
15% and indicate 1.1 – 3.9GJ/ton final product38. As the initial moisture content was set the
energy demand per water removal can be traced back to 1.3 – 4.7GJ/ton H2O. For most biomass
materials flue-gas cannot be used causing the heat energy demand to lean towards the higher end

of the range, relating to a hot-air medium. For particularly wet biomass feedstocks one should
not use the rotary drum dryer, but opt for the filter press/conveyor belt dryer combination.
Rotary Drum Drying

- Specific Type: hot-air d ru m dryer
- Bio mass Types: any
- Input Moisture Content: 20 – 90%, set below 50%
2.6.2.5 Silo/In-Bin Drying

Grains and other biomass material stored in silos are frequently treated with a drying system to
simultaneously dry and store the product ensuring a safe long-term storage. The most popular
type is the continuous flow system. It works by injecting large volumes of warm-air (60 - 80° C or
120° C) from below or at different layers along the height of the silo. Considering the large air
flows involved and the low temperatures used, the electric power demand of the circulation fan
cannot be neglected. Depending on the layout 5 – 10% of the total energy demand is electric,
which when translated into primary energy requirements can exceed 20%. Yet, compared to the
other drying systems in-bin drying has moderate energy demands ranging from 2.3 – 3.5GJ/ton
H2O 31. It is however only suitable for low-moisture drying. A typical feedstock is shelled corn,
requiring around 1.0GJ/ton WW primary energy to reduce the moisture level from 25% to
15%31. Older values from 1978, indicate similar values for shelled corn brought from 24 to 16%
moisture at 0.94GJ/ton WW. This suggests that for the conventional system, little extra energy
savings can be foreseen.
Silo/In-Bin Drying
- Specific Type: hot-air continuous flow dryer
- Bio mass Types: grains, low moisture content biomass
2.6.2.6 Exergy and Energy Efficiency

Drying procedures are energy intensive, 1 – 3GJ/ton DW correspond to 5 – 15% of the resulting
calorific value of the feedstock. It is suggested that with adequate heat recovery systems up to
65% of the energy could be recovered and used in either a heat recycling system or in other heat
demanding processes. Similarly high energy efficiencies are present with contemporary multistage
cascading evaporators which can reach as low as 1.0GJ/ton water removed. Conversely nearly all
modern dryers are also capable of utilising off-heat and/or district heat from other thermal
sources. Furthermore, in terms of exergy direct drying system are highly inefficient. The exergy
content of hot air (100° C) is below 100kJ/m³, whereas the energy content is around 2500kJ/m³.
A near complete transfer of the fuel energy content to hot air is present suggesting a highly

efficient system, yet the exergy efficiency is closer to 0. This presents ample options to increase
the energy efficiency with better heat integration by using other sources of heat. However, as
beneficial as the mentioned improvement options are, on the rural small-scale they are limited or
completely unfeasible. Since drying operations are best performed in the immediate proximity of
the biomass field to maximize the logistical energy savings, little can be done about the
energy/exergy intense drying options. Only in regions that can properly capitalise on favourable
climate conditions can the external fossil fuel demand for drying be minimized. The energy
required for size and moisture reduction systems must be carefully balanced for the specific
logistical system involved.
2.6.3 Compaction
Currently most biomass is still used for combustion and gasification processes. For these systems
it is common to compact the sized and dried (10% moisture) biomass into pellets. Creating dry
pellets has two advantages for the bioenergy sector; lower logistical costs and a higher heating
value of the feedstock. As this work pertains to biomass as a chemical feedstock pelletization is
not required or even advisable. Additional energy would be involved in opening up the pellet
structure to expose the biomass to the pretreatment steps of a biorefinery.
2.7 Manufacture, Transport and Repairs (MTR)

Large scale cultivation and distribution of non-food biomass requires a considerable amount of
dedicated machinery, both new and old. As they form an integral part of the feedstock
acquisition process the so-called “MTR” for the dedicated machinery must be taken into account.
MTR stands for and connotes the amount of energy sequestered in the manufacturing, delivery
and maintenance of the machinery. Substantial amounts of MTR energy are involved in the
production and continued operation of the machinery involved in the biomass sector. First an
overview, description and general energy requirements of the three components to MTR will be
conducted. This will be followed by considerations and calculations to the dedicated machinery
involved in biomass production and logistical chains.
2.7.1 Manufacturing Energy

Manufacturing of machinery requires vast amounts of the basic raw materials and is associated
with high energy inputs. Despite the advent of high-grade plastics, ceramics and other non-metal
materials steel production and moulding still represents the bulk of the manufacturing cost. As
early as 1973 a simple LCA determined the primary energy demand of the automobile industry to
be 86.77MJ/kg39. Thus, a standard car weighing in at 2000kg relates to an energy demand of
around 175GJ/car. Put in perspective this relates to the energy content of around 100 petrol
fillings or 30000 – 60000km travelled. Catalyzed by the energy crisis a drastic change in raw
material energy efficiency has occurred since the 1970’s. In 1979 USA steel manufacturing cost
was between 22 – 60MJ/kg39. In 1996, the energy demand in the EU dropped by about half to
range between 20 – 30MJ/kg40. Ten years have since transpired which have certainly promoted a
further lowering of the energy intensity. Similar trends are noticeable throughout the raw material

sector; for example aluminium was 214 – 383MJ/kg in 1979 and dropped to 125 – 186MJ/kg by
1996, signifying again a reduction of around 50%. By comparing other manufacturing LCA
studies 86.77GJ/ton was chosen as representative for the farm machine production energy39. The
figures from that study and MTR overview for farm machinery are frequently referenced to, even
in recent publications. Considering the importance and dependence on the steel industry
reducing the manufacturing cost by 50% seems logical to represent recent times. Thus 43.4MJ/kg
is set as the machinery energy demand.
2.7.2 Transport Energy

A elderly study from 1977 determined the energy costs for the transportation and distribution of
manufactured goods to require an additional 8.8MJ/ton39. In the last 30 years the energy
efficiency of transportation has significantly improved. As mentioned and calculated in the heavy
goods vehicle transport section (2.4.1) a reduction of nearly 25% was achieved over 20 years via
the Euro emission norms. The transportation energy portion will be set at 5.9MJ/kg to
implement the assumption of a 33% efficiency improvement over the course of 30 years.
2.7.3 Repair Energy

All machines require servicing and repairs along their lifetime; maintenance is a relatively energy
intense process because of the replacement parts, liquid changes, actual repairing time and
travelling requirements. The replacement parts represent the largest portion at 67.1% of the total
repair energy. In adhering to the simplest approach used to estimate MTR, the repair energy
input is set as a ratio against the manufacturing energy. On average 55% of the initial
manufacturing energy is required for maintaining machinery. The quality and logistics of service
and repairs have improved vastly since the study. Many problems in the manufacturing sector
(like that of rust) have been resolved or minimized. The following table lists the resulting energy
sequestered in repairs of various machines over the course of their lifetime, assuming 50%
reduction achieved since 198539.
Table 2 Repair energy of various farm machinery
Ratio: Ratio:
Equipment
repair-to-manufacturing, old repair-to-manufacturing, new
Tractors 0.49 0.25
Combines 0.24 0.12
Mouldboard Ploughs 0.97 0.49
Row Planters 0.43 0.22
Row Cultivators 0.58 0.29
Field Cultivators 0.51 0.26
Disc Harrow 0.61 0.31
Corn Pickers 0.35 0.18
Stalk Choppers 0.33 0.17
Cutterbar Mowers 1.44 0.72
Balers 0.39 0.20
Forage Harvester 0.39 0.20
Rotary Hoes 0.59 0.30
Sprayers 0.37 0.19
Average 0.55 0.28

2.7.4 Farm Equipment MTR
Expanding the current agricultural systems to incorporate large-scale biomass production for
non-food purposes will require an investment in new farm machinery. In the industrialized
regions this implies new tractors and implement tools, which correspond to a considerable
amount of new materials and energy demand in the form of MTR. It is foreseeable that the
developing world will receive older and used equipment from the industrialized world. This
makes estimates of MTR energy values difficult as the allocation must be performed over the
entire operational lifetime. Placing an MTR cost on older machinery which has not been
dedicated to the production of non-food biomass throughout its entire operational lifetime is
questionable and challenging. However, in many areas of the world older models and smaller
implements are still manufactured. And as biomass propagation will be a long-term activity it will
be assumed that even in the developing world machinery will be strictly dedicated over its
lifetime.
Exam ple: Calculation Method for MTR Energy of a Farming Procedure
Farming procedure: chisel plough in an industrialized region w ith a f ield capacity of 1.4ha/h
Tractor Plough
Manuf acturing: 43.4MJ/kg ⋅ 6600kg = 286.4GJ 43.4MJ/kg ⋅ 1000kg = 43.4GJ
Transport: 5.9MJ/kg ⋅ 6600kg = 38.9GJ 5.9MJ/kg ⋅ 1000kg = 5.9G J
Repairs: 286.4GJ ⋅ 0.25 = 71.6GJ 43.4GJ ⋅ 0.49 = 21.3GJ
Total MTR: 396.9GJ 70.6GJ
Operational Lif e: 12000h 2000h
MTR per time: 33.1MJ/h 35.3MJ/h
MTR per area 33.1MJ/h ÷ 1.4ha/h = 23.6MJ/ha 35.3MJ/h ÷ 1.4ha/h = 16.9MJ/ha
Total MTR for field operation: 40.5MJ/ha
The above text box provides a guideline to the methodology used in calculating the MTR energy
demand for farming procedures. As can be seen it is based on the parameters of the tractor and
field implement (weight and operational lifetime) and brought into relation with the field
capacity. Relating it to the field capacity (ha/h) allows the MTR energy demand to be presented
as a function of time (MJ/h) and regarded as a component of the total energy requirement of the
farming operations. The calculations for the resulting MTR of the different farming operations
are not present but are partially covered in the previous Section 2.3 and the weight and
operational lifetime values12, 39. The resulting farming equipment energy and exergy costs are
presented in the following Section 2.8 which includes the MTR component. Depending on the
region and procedure, MTR costs correspond to 2.5 – 16.0% (7.0% average) of the total farming
operation energy cost.
2.7.5 Transportation and other equipment MTR

MTR should be determined for the transportation machinery for they form an integral part of the
biomass production chains, since they too are dedicated. The MTR will be related to the
transportation distance (MJ/km) and also additionally to the transported tonnage (MJ/t⋅km).
These separate values are calculated because as mentioned in the transportation Section 2.4
dedicated modes of transportation return empty, implying zero transported tonnage for half the

travelled distances. To be able to relate the MTR energy demand to the transportation distance
the operational lifetime is expressed in terms of total travelled distance (km). Transportation
machinery can travel remarkably far distances in their lifetime, for example a modern truck can
cover around 1 million kilometres. Benefiting from near-continuous operation, large and robust
designs, transportation machines require a significantly lower portion of repair energy. The
transportation MTR calculations with the machine weight, lifetime and repair ratio assumptions
have been calculated but due to their small portion are not included in this text. The textbox
below provides a insightful guideline to the methodology used in calculating the MTR energy
demand for transportation operations. The resulting transportation energy and exergy costs is
presented in the following Section 2.8 which includes the MTR component. MTR corresponds to
a rather minor portion of the total transportation operation energy costing being 0.9 – 3.1%
(1.9% average), depending on the region and procedure.
Exam ples: Calculation Method for MTR Energy of a Transportation Procedure
Transportation System: truck and bulker transport in an industrialized region

Truck Bulker
Weight: 8500kg 15% of 45000ton = 6.75⋅10 6kg
Manuf acturing: 43.4MJ/kg ⋅ 8500kg = 368.9GJ 43.4MJ/kg ⋅ 6.8 ⋅10 6kg = 0.293PJ
Transport: 5.9MJ/kg ⋅ 8500kg = 50.1GJ 5.9MJ/kg ⋅ 6.8 ⋅10 6kg = 0.040PJ
Repairs: 368.9GJ ⋅ 0.25 = 92.2GJ 0.293PJ ⋅ 0.063 = 0.018PJ
Total MTR: 511.2GJ 0.351PJ
Operational Lif e: 1.0 ⋅10 6km 25y ⋅ 25knots ⋅ 8000h/y = 9.3⋅10 6km
MTR per distance: 511.2GJ ÷ 1.0 ⋅10 6km = 0.51MJ/km 0.351PJ ÷ 9.3 ⋅10 6km = 46.8 MJ/ km
Transported Tonnage: 28ton 45000ton
Total MTR 0.018MJ/t⋅⋅km 0.001MJ/t⋅⋅km
2.8 Overview Input Type Costs

Table 3 Labour costs
Energy Costs Exergy Costs

Region Type
(MJ/day) (MJ/day)
Developing Manual Labour 20.7 21.7
Industrialized Mechaniz ed Operation 633 665
Table 4 Main tractor specifications
Weight Nominal Power Specific Fuel Consumption

Region Type
(kg) (kW) (g/kW⋅h)
Developing Massey-Ferguson MF240 1730 32 251 – 262
Industrialized New Holland TM-165 6600 107 273 – 328

Table 5 Farm equipment costs
Field Capacity Energy Costs Exergy Costs

Region Tractor Type Implement
(ha/h) (MJ/h) (MJ/h)
Chisel Plough 0.37 894.7 883.2
Field Cultivator 1.40 236.1 233.5
Harrow 2.92 119.5 117.0
Grain Drill 2.01 175.9 171.7
Drill 0.92 384.5 375.4
Row Crop Planter 2.49 136.2 134.0
Cuttings Planter 2.47 196.2 195.2
MF240
Developing Bulb Planter 0.71 477.1 469.3
Fertilizer Sprayer 15.4 11.7 11.5
Mower 4.40 104.1 102.7
Rake 8.00 18.6 18.3
Forage Harvest 3.25 153.1 152.0
Bailer 5.20 116.1 115.6
Root Digger 0.67 550.1 539.7
- Crop Duster 395 85.4 85.4
Chisel Plough 1.41 964.7 955.0
Field Cultivator 5.63 240.0 237.8
Harrow 12.0 116.8 115.0
Grain Drill 9.37 151.6 148.8
Drill 3.95 359.7 353.1
Row Crop Planter 11.73 117.7 116.1
TM165 Cuttings Planter 4.94 97.3 95.4
Tuber Planter 2.93 470.7 464.4
Fertilizer Sprayer 22.4 9.0 8.7
Industrialized
Mower 17.6 72.6 71.6
Rake 10.0 20.7 19.7
Forage Harvest 4.65 279.2 276.6
Bailer 7.45 80.3 78.8
- Crop Duster 395 85.5 85.5
NH - TX63 Combine Harvester 4.23 513.5 504.1
NH – FX40 SP-Forage Harvester 3.03 892.2 878.0
Potato Harvester 1.82 1849.0 1826.6
Grimme SF3000
Beet Harvester 2.64 1274.5 1259.0
Table 6 Transportation costs
Capacity Energy Costs Exergy Costs

Region Method Loaded Empty Return Loaded Empty Return
ton MJ/t⋅km MJ/km MJ/t⋅km MJ/t⋅km MJ/km MJ/t⋅km
Tractor 6 2.46 11.1 - 2.45 11.1 -
Developing Tru ck 8 1.69 6.2 - 1.67 13.9 -
Train 800 - - 0.398 - - 0.398
Tractor 16 2.15 26.1 - 2.14 25.9 -
Tru ck 28 0.67 11.7 - 0.66 11.6 -
Industrialized Tru ck* 35 0.90 14.0 - 0.90 13.9 -
Train 800 - - 0.235 - - 0.301
Barge 1750 0.21 312.1 - 0.21 311.4 -
Tanker 75000 - - 0.057 - - 0.057
Both
Bulker 45000 - - 0.115 - - 0.115
*Used also in South America – Developing World

Table 7 Storage/Transfer costs
Type Material Material Loss Energy Exergy
Loose 3% 14.5MJ/m³ 14.5MJ/m³
Wheel Loader
Packed o r Bagged 3% 7.3MJ/m³ 7.3MJ/m³
Loose, dry 2% 1.8MJ/ton 2.3MJ/ton
Conveyo r Loose, wet 2% 0.36MJ/ton 0.46MJ/ton
All, ship/train bound 1% 1.2MJ/ton 1.5MJ/ton
Stacker/Reclaimer Loose 6% 11.4MJ/ton 14.7MJ/ton
Cran e, Gantry Bu cket Loose 1% 2.32MJ/m³ 2.98MJ/m³
Cran e, Gantry Shovel Loose 1% 3.13MJ/m³ 4.02MJ/m³
General All 2% 5MJ/m³ 6.4MJ/m³
Table 8 Pre-processing costs
Energy Exergy
Method Conditions
GJ/tonWW
Cutting 20mm chipped size 0.075 0.075
Crushing 5mm particle size 0.44 0.66
Shearing 1.5mm particle siz e 1.09 1.75
Table 9 Drying costs
Moisture Conditions Energy Exergy

Method
Input Output GJ/tonH2O Removed
Natural Air <50% 30% 0 0
Filter Press >50% 30% 0.23* 0.35*
Conveyo r Belt <40% 20% 4.5 4.7
Rotary Drum >20% 20% 4.7 4.9
Silo/In-Bin <30% 15% 3.9 4.3
*filter press energy/exergy terms are in GJ/tonWW: no dependence on initial moisture content

3 Farming Operations
The previous section dealt with the collection, investigation and calculation of the core energy
and exergy input costs associated with the operation of the common agricultural machinery for
both the developing world and industrialized world. This section will systematically link those
base calculations to the requirements and typical farming procedures for the selected crops.
3.1 Machinery Employment
3.1.1 Operational Labour Requirements

The energy requirements of an agricultural machine are not defined solely by its diesel
consumption and MTR. To an extent the technology has reached sufficient maturity to enable
fully automated farming machinery, but as public and governmental acceptance is still lacking
humans are required for the operation. This presents a minor but additional factor based on the
labour input and operational hours per cultivated area. By taking the reciprocal value of the field
capacity (ha/h) known for each of the farming procedures, the operational hours per hectare
(h/ha) can be determined. Furthermore, tractor implements must be attached to the tractor and
set-up properly before operated presenting an additional labour hour. Daily field capacity per
shift is thus reduced. Reaping the benefits of intensified and efficient farming practices an
industrialized farmer needs not work more than the standard 8 hours a day whereas it is common
in developing regions that agricultural workers go 12 hours straight.. The total hourly operational
labour input cost is determined by factoring the shift length with the previously listed daily labour
input. The following table lists the total energy/exergy input of farming procedures:
Table 10 Farming procedure energy and exergy cost
Fa rming Proced ure Imp lement Re gio n Tractor Type Capacity Fuel L abour Ene rgy Exergy
Typ e Type OECD Model* ha/h h a/shif t l/h a h/ha MJ/ha
Develo pin g MF2 40 0.4 4 .4 2 2.03 2.93 901.2 89 0.0
Chisel Ploug h
In dustrialized TM1 65 1.4 11 .3 2 4.11 0.80 1027.8 10 21.3
Develo pin g MF2 40 1.4 16 .8 5 .87 0.77 237.9 23 5.3
Tilla ge Field Cu ltivator
In dustrialized TM1 65 5.6 45 .0 6 .02 0.20 255.8 25 4.4
Develo pin g MF2 40 2.9 35 .0 2 .82 0.37 120.3 11 7.9
Harrow
Develo pin g MF2 40 2.0 24 .1 4 .08 0.54 177.1 17 3.0
Gra in Drill
Develo pin g MF2 40 0.9 11 .0 8 .92 1.18 387.2 37 8.2
Drill
Develo pin g MF2 40 2.5 29 .9 3 .29 0.44 137.2 13 5.0
Pla nting Ro w Crop
Develo pin g MF2 40 2.5 29 .6 5 .03 0.44 197.1 19 6.2
Cu ttin gs Plan ter
Develo pin g MF2 40 0.7 8 .5 1 1.52 1.53 480.5 47 2.8
Tuber Plan ter
In dustrialized TM1 65 2.9 23 .4 1 1.56 0.38 501.0 49 6.3
Develo pin g MF2 40 15.4 18 4.8 0 .29 0.07 11.8 1 1.7
Fertiliza tio n
In dustrialized TM1 65 22.4 17 9.2 0 .19 0.05 13.0 1 2.8
Soil Treatme nt
Develo pin g MF2 40 395. 0 474 0.0 2 .32 0.00 88.2 8 8.2
Crop Duster
In dustrialized TM1 65 395. 0 316 0.0 2 .32 0.00 88.5 8 8.5
Combin e In dustrialized TX63 4.2 33 .8 1 2.27 0.27 534.6 52 6.2
Develo pin g MF2 40 4.4 52 .8 2 .56 0.25 104.6 10 3.3
Mower
In dustrialized TM1 65 17.6 14 0.8 1 .78 0.06 77.6 7 6.9
Develo pin g MF2 40 8.0 96 .0 0 .45 0.14 18.9 1 8.7
Rake
Develo pin g MF2 40 3.3 39 .0 3 .89 0.33 153.8 15 2.8
Chopper
Harvestin g In dustrialized TM1 65 4.7 37 .2 7 .00 0.24 298.4 29 6.7
Develo pin g MF2 40 5.2 62 .4 2 .98 0.21 116.6 11 6.0
Bailer
Forage Harvester In dustrialized FX40 3.0 24 .2 2 1.60 0.37 921.6 90 8.8
Beet Harvester In dustrialized SF3000 2.6 21 .1 3 1.50 0.43 1308.2 12 94.4
Po tato Harvester In dustrialized SF3000 1.8 14 .6 4 5.70 0.62 1898.0 18 77.9
Root Digger Develo pin g MF2 40 0.7 8 .0 1 3.10 1.62 553.7 54 3.5

Despite the shorter working day the larger and more powerful tractors of the industrialized
regions greatly increase field capacity and facilitate less operational working hours per cultivated
land. Not a single farming procedure requires a full labour hour per hectare in the industrialized
regions, whereas many of the same procedures cross the 1h/ha mark in the developing regions.
Although the labour requirements are greatly reduced in the industrialized regions, the energy and
exergy requirements are generally higher, further proving the trend of the agricultural sector
transforming from being labour intensive to being fossil fuel intensive.
3.1.2 Cultivation Practice Factors

Listed in Chapter 4, Section 3.1.3 the cropping systems of the choice crops were presented. The
replanting frequency and the harvest cycle rate being crop dependent are needed to determine the
yearly factor for the farming operations. For instance the oil palm is replanted only every 25 years
meaning that on a yearly basis the tillage procedure is 0.04 times the input rate, while an annual
crop like the sunflower, replanted every year, has a tillage factor of 1. This yearly factor is used
for the calculation of the tillage and planting procedures.
For fertilization and pesticide application, a slightly modified yearly factor is used. Fertilizer and
to a lesser extent pesticides are mixed with the seeds before planting. This single application run
is mitigated for seed-based crops only as this option is not possible with cuttings/setts. Nutrients
and crop protection chemicals are required periodically throughout the growing season for many
crops. Called “dressings”, up to half a dozen separate dosing runs can be required over the course
of the growing duration. The yearly factor used for tillage and planting is therefore not
appropriate for soil treatment procedures. Here the establishment and growth duration will be
used for calculating the total growth period. The yearly growth factor is determined by relating
the total growth period to a single year and is set at 1 for crops with a growth period less than 12
months. Calculation of the soil treatment procedures results from combining the total application
frequency over the course of the total growing duration and the yearly growth factor.
Harvesting and collection operations also necessitate a factor. The harvesting cycle rate indicates
the frequency of the harvesting procedures over the course of the growing season. Several crops
are harvested multiple times throughout the year to achieve high crop yields. A perfect example is
sweet sorghum which needs 5 separate harvests to capitalize on the grass-like yield properties.
The yearly factor for harvesting procedures is simply the harvesting cycle rate.
3.2 Labour Employment

Not all the procedures in the cultivation and harvesting of biomass are performed by the
deployment of agricultural machinery; many steps are still carried out by manual labour. This is
especially true in the developing regions where typically entire harvesting operations are
performed by manual labour. A detailed paper has listed and calculated the labour input (h/ha)
for select main crops in a multitude of regions41. Nearly all of the choice crops in their
corresponding regions are covered by the study. Yet for some crops, like the oil palm42,

assessment must be conducted individually or grouped by the crop type and region. The labour
employment has been split into the different farming procedures categories based on expected
portion of the work distribution. The same cultivation practice factors were taken as with the
machinery employment.

The overview of the farming procedure calculations is found in the accompanying database
spreadsheets. It is broken down into the 4 farming procedure sections; tillage, planting, soil
treatment and harvesting. The above mentioned factors and extra manual labour figures are
incorporated. Total energy and exergy values are accumulated for each of the four categories. The
column “use” is meant to denote the employment of that particular agricultural machinery for the
crop. A “1” implies usage and a “0” means not used. A few crops employ no machinery in some
of the farming procedure categories as can be seen by the series of 0’s and the high value for the
labour. This is especially the case for the harvesting section. The following graph incorporates all
factors for the total farming procedure input in MJ/ha terms:
Figure 1 Resulting farming procedure input
Farming Procedu re Input

Based on 10-ye ar a ve rag e
In clud ing Labo ur a nd Ma ch in ery
1 0000
Energy
Exergy
7500
MJ/ha
5000
2500
0
va
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Sweet sorghum in Kenya is unique because to obtain the best yield figures from multiple grass-
like cultivation practices, an “industrialized” self-propelled forage harvester must be employed.

Should this not be done the yields will mirror the national average, being less than half at
35ton/ha WW. In the other developing regions harvesting is conducted almost exclusively by
manual labour with no urgent expansion of machinery exploitation needed to obtain high yields.
Developing region crops are then amongst the lowest for farming procedures, averaging around
2.5GJ/ha. The difference to the industrialized region crops is however not always great. Several
of the industrialized crops fair equally well in low energy intensity. An annual harvest using a
single combine harvester and a rake and bailer implement for straw collection proves highly
efficient, averaging around 3.0GJ/ha for these crops. Multiple harvesting is significantly more
energy intensive (tobacco, and other grasses) and as expected tuber crops (potato, sugar beet) are
amongst the most energy intensive.
3.3.2 Efficiency
Precisely as with all the primary energy inputs (Chapter 5) it is misleading to visualise the total
farming procedure input energy in terms of land without relating it to the resulting energy output.
This can be performed because the total resulting energy output (see Chapter 4) is expressed in
terms of land area as well. The two figures combined give the farming efficiency as indicated by
the simple formula:
Energetic _ Output [ MJ / ha ]
Farming _ Efficiency =
Farming _ Input [MJ / ha ]
The following graph (Figure 2) displays the resulting farming procedure efficiency for the best
practice yields. As one would expect the developing region crops which rely heavily on manual
labour for harvesting are highly energy efficient. At values well above 15000%, reaching 41000%
for the oil palm a loss of a mere 0.67% to 0.25% is found. Even the maize crop with its high
yields and straightforward combine harvester technique yields 14144% energy efficiency which is
equivalent to less than 0.71% energy loss. Other industrial region crops do not fair as well
hovering around 5000% or a loss of 2%. The worst energy efficient crop in terms of farming
procedure is the potato. Despite the high yields of over 65tonWW/ha an energy efficiency of
2780% is found resulting in an energy loss of 3.6%. This approaches the energy losses associated
with the nutrient application/uptake costs. Yet for all the crops the farming procedures remain
several orders of magnitudes below the fertilizer costs. A transition to larger machinery with
higher engine power and the promotion of an increased quality of life for farmers (chiefly in the
developing regions) will not have a drastic lowering effect on the overall energy efficiency of
biomass propagation. None of the investigated crops have an energy loss higher than 5% (or
lower than 2000% efficiency) for the farming procedures, generally signifying that farming does
not have a detrimental influence on the overall energetics and is actually quite efficient. The
subsequent analysis is based on the relative values between the different crops.

Figure 2 Resulting farming procedure efficiency
Eff iciencies
Based o n Fa rm ing Proced ure Energy
25000
2 .5E5 3.8 E5
4.1 E5 Energy
Exergy
20000
Convers ion Perce nt [%]
15000
10000
5000
0
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3.3.3 Analysis
Table 11 Comparative farming input overview
Crop Farming Pro cedure (energy) Farming Pro cedure (exergy)

Cassava + + + +
Grass O - O -
Lu cerne O - O -
Maize + + + +
Oil Palm + + + +
Potato - - - -
Rapeseed + + + +
Sorghum - O - O
Soya Beans + O + O
Sugar Beet O O O O
Sugar Cane + + + +
Sunflower O - O -
Switchgrass O - O -
Tobacco - - - O
Wheat + O + O
Willow Tree + - + -
Input: + below 5.0GJ/ha, - above 7.5GJ/ha, O between 5.0 – 7.5GJ/ha
Efficien cy: + above 10000%, - b elow 5000%, O betw een 5000 – 10000%

4 Biomass Logistics
Location, location, location – the phrase that has become a cliché in the real-estate sector is also
perfectly atoned to the logistics of biomass. Propagation and production of biomass is spread
across great areas of land in diverse and frequently isolated regions of the world. The chemical
industry however, as mentioned in Chapter 1, is concentrated in a select few places of the world.
The top 3 petrochemical cluster areas are Houston (North America), Singapore (Asia) and
Rotterdam (Europe). Being major port cities they have evolved into key distribution and
processing centres of the petrochemical industry and serve the needs of the regional chemical
industries coupled to their hinterland. All biomass that is foreseen as a chemical feedstock must
in one form or another pass through and be treated at such chemical processing hubs. And as the
focus of this entire investigation is on the transition to a biobased chemical industry, above all for
Europe, Rotterdam will be set as the “factory gate”. It is the main location of Europe’s existing
petrochemical sector and it is the best adapted and most logical location for future biomass.
All biomass production and transportation chains will be directed towards reaching the port of
Rotterdam. As the factory gate, no additional transportation considerations need to be made
upon shipment delivery, because the proposed biobased chemicals will match the production and
distribution system of Rotterdam. Logistical planning is required to minimize the energy
requirements of transportation. In this section each of the choice crops in their corresponding
regions will be subjected to the creation of the most fossil fuel energy attractive logistical system.
Location, distances, transportation options, pre-processing and drying options will all be carefully
assessed for each biomass production and transportation chain.
4.1 Rotterdam
Located close to the North Sea on the
banks of the delta created by the merging
Rhine and Maas rivers, Rotterdam is a
world city based on its harbour activities
boasting 0.59 million inhabitants and 1.2
million in the greater metropolitan area. It
is a trading and industrial based economy
forming one of the three pillar cities of the
country. In the Netherlands, there is an
expression illustrating this “Amsterdam to
party, The Hague to live, Rotterdam to work” whereas Rotterdammers prefer a slightly modified
version “In Rotterdam the money is earned, in The Hague it's divided, and in Amsterdam it's spilled”. From
1962 to the late 1990’s the port of Rotterdam was the world’s biggest and busiest harbour. With
the development of containerization and off-shoring practices Rotterdam has fallen to 7th in
containers and 3 rd in total cargo. Having a higher portion of general cargo traffic illustrates the
focus on the heavy industries, like the petrochemical sector. The port covers a surface area of
105km² along 40km and 5.1km² is dedicated to industrial terrain. In 2005, 370Mton of cargo

passed through the port of Rotterdam of which 10.7Mton was agricultural bulk. This suggests
that the know-how and facilities to handle biomass is already present to a degree. The graphic
below highlights the hinterland of Rotterdam; the yellow circles being major trading hubs and
industrial areas and the light-yellow object depicts the regions directly linked to the port. The
port of Rotterdam is the ideal location to receive and process biomass for the chemical industry.
Port of Rotterdam
Rotterdam is Europe’s main port for incoming and outgoing trade in crude oil, oil products, chemicals,
iron ore, coal, metals, foodstuffs and containers. Companies often choose Rotterdam because of its
strategic location in Northwest Europe, the depth of the port (24 metres/75 feet), the many port facilities
and the excellent hinterland connections (the Rhine!). Doing business via Rotterdam brings indisputable
advantages of scale. That is the reason why the German steel industry , for example, imports the majority
of its raw materials – iron ore, coal - via Rotterdam.
Many American and Asian companies use Rotterdam as a base for the distribution of their (consumer)
goods throughout Europe. In the immediate vicinity of the container terminals, there are large European
distribution centres. Not only for the efficient delivery of products on the continent, but also for their
distribution to destinations overseas, such as Great Britain, Scandinavia and the Baltic region.
Rotterdam is among the top three (petro)chemical clusters in the world, with Houston and Singapore. A
large percentage of (petro)chemical production in the port finds its way to industrial centres in the rest of
Europe and on other continents. The port is connected to an extensive underground pipeline network that
cuts right across Western Europe.
www.portofrotterdam.com/en/home
4.2 Distance to Rotterdam

The first step in assessing the energy requirements in biomass logistics is to determine the
distance between the cultivation fields and the port of Rotterdam. In most instances the total
transportation distance is covered by a combination of the different modalities. Determining the
portion and relative distance covered by each of the individual modes of transportation is
achieved by using different navigational sources, whereas determining the most energy efficient
combination of transportation modes and location of transfer hubs is slightly more arduous.
Example: Sin ce both tractor and tru ck transport are the most energy intensive forms of transportation,
demanding at least twice as much as other forms, their employment must be minimized. Switching to the
next larger mode of transportation requires that ample biomass is available to provide for a fully loaded
shipment. At full cap acity, a train fo r example can handle 800tons. Considering the average transportable
wet weight yield to be around 25tonWW/ha, a cultivated area of at least 32h a (0.32km²) would be needed
to satisfy one train load. Using simple geometry that relates to a transportation radius of 0.33km, so even
when taking in constant harvesting dates and multipurpose land utilization the transport distan ce is easily
within the bounds on field tractor delivery. Supplying the larger transportation modalities is thus not
restricted by the volumes of produced biomass in the immediate surroundings but by the infrastru cture.
Train terminals are not lo cated every 0.66km of track (which is th e length of some grand stations), they are
positioned by multiples of 10km. In some rural areas intervals of 50km are easily possible betw een transfer
junctions.
4.2.1 Starting Point

In Chapter 4, Section 4.1 the locations chosen to represent the typical regions of cultivation for
the particular biomass crops were listed. Given in global coordinates, the areas covered are vast,
ranging between 100km² and 150km². To assist in the calculation of the total transportation
distance determination a small village/settlement in the region has been selected. This will be
representative of the first stage collection and temporal storage of biomass; a place where the

farmers will concentrate their harvest for distribution and in many cases expose the biomass to
initial pre-processing options. Tractors are used at this stage with travelling distances ranging
from 5 – 20km depending on the typical farm sizes, density and infrastructure of the region. For
example, densely clustered European farm land will be set at 5km travelling radius whereas the
scattered vast African farm land will be set at 20km. Pick-up is almost exclusively performed by
trucks which, with a given location, enables the use of navigational programs.
4.2.2 Mode of Transport

This sub-section deals with the source of data and calculation methods for determining the
distances involved in logistics for the different modalities.
4.2.2.1 Road
For most areas in the world online navigational programs can
provide a route plan along existing roadways in the region.
ViaMichelin43 and Google maps44 are two good sources for
determining the distance between the set regional starting
point and the next transfer hub along roads. In some regions,
especially in underdeveloped regions, route planners are
currently unavailable and distance determination must be
judged by reading physical maps and the distance legend.
4.2.2.2 Rail
In many instances railways follow the general path of motorways with the major exception that
they are slightly more direct, implying a straighter and shorter path between hubs. The rail
distance will be determined using the road route planners with a 10% distance reduction to
compensate for the infrastructural difference. The EcoTransit model19 will be used for regions in
Europe as it provides accurate distance calculations along the entire European rail system.
4.2.2.3 Inland Waterways

Motorways also have the tendency to follow major rivers and inland waterways. Like the rail
distance calculations the road route planners will be used to determine the inland waterway
distances. But despite many canals and rivers artificially straightened a 10% extra distance will be
added to compensate for the curvy, non-straight nature of rivers.
4.2.2.4 Ocean
Determining the shipping distance between port
cities is performed with the help of the computer
program NetPas45. The optimal shipping route
between the ports is calculated and plotted using
the online database. It provides ample
information relevant to sea logistics, amongst
them the total distance.

4.2.3 Topography
The world, as famously said, “is not flat”. Topography is the broad study of the Earth’s surface
features with terrain relief characteristics covering a major portion. Flat regions, like the
Netherlands, prove to have positive transportation fuel demand reductions. Mountainous
regions, like Malaysia, prove to have transportation fuel demand increases. For tractor, truck, and
train transportation the terrain topography has a significant effect on the fuel consumption. Since
great distances are covered in the logistics of biomass entire regions will be grouped into one of
three gradient types: flat, hilly, or mountainous. Most populated areas in the world have a slightly
hilly terrain which will form the default landscape. The following table lists the compensation
factors for the modalities energy demand.
Table 12 Topography fuel consumption factors
Terrain Type Tractor Tru ck Train

Flat -5% -5% -25%
Hilly (default) 0% 0% 0%
Mountainous +5% +5% +20%
4.2.4 Resulting Distance and Mode of Transportation

Listed in the table below is the resulting distance required to transport each of the harvested
crops from their specific growth region to the Port of Rotterdam. It is broken down into the
different selected modes of transportation.
Table 13 Break down transportation distances
Crop Mode of Transportation

Common Tractor Tru ck Train Barge Vessel Total
Name Distance/km
Cassava 20 100 600 - 4379 5099
Grass 5 23 - 176 - 204
Lu cerne 15 95 - 2750 4822 7682
Maize 10 15 65 1050 4822 5962
Oil palm 40 80 - - 8837 8957
Potato 5 23 - 176 - 204
Rapeseed 5 8 178 - - 191
Sorghum 15 100 650 - 6252 7017
Soya bean 10 40 - 1750 4822 6622
Sugar beet 5 20 - 425 - 450
Sugar cane 15 200 - - 5417 5632
Sunflower 5 38 223 - 458 724
Switchgrass 10 15 65 1050 4822 5962
Tobacco 20 40 340 - 10767 11167
Wheat 5 38 223 - 458 724
Willow tree 5 55 - - 902 963
This is a simplified table, for the detailed calculation to derive at the biomass logistical chains
with all the necessary considerations and transfer hubs is not listed. The base energy and exergy
requirements have also been calculated in wet weight, MJ/tonWW.

4.3 Size and Moisture Reduction
For many of the crops there are two harvestable components; the agriculturally relevant crop
component and the residue (or leftovers) like stover. As these crop components have completely
different properties and process options to reduce size and moisture content they will be handled
and shipped separately. The properties of main interest are the moisture content and bulk
density. Typical harvested bulk densities have a natural range of roughly 10%. Sources listing
crop bulk densities are scattered, which implies that several assumptions based on the similarity
of the crop components are required14, 46, 47. For example, tobacco forage harvested will have the
same bulk density as grass at 640kg/m³ and the stover/Leaves of the cassava will match that of
the potato being 520kg/m³. The “wet” bulk density and moisture content are used to determine
the resulting “net” bulk density, being the amount of actual dry biomass present per volume.
Presented below are two tables listing the moisture content and bulk densities for both crop
components prior to and after sizing and moisture reduction treatment. For the vast majority of
the crop components it is noticeable that the harvested net bulk density is below 500kg/m³
meaning, that when left untreated less biomass material would be transported than water and air.
A break down of the crop specific drying and size reduction procedural steps and the calculations
for the energy costs is highly complex and can be traced in the accompanying database
spreadsheets. The resulting moisture content is based on the previously stated desired levels of
15% and 20% to facilitate long-haul transportation. Several of the harvested crop components
have moisture contents lower than the minimum required level negating any moisture reduction
techniques. Aside from the desired net bulk density increase, an increase of the wet bulk density
is also induced through sizing and moisture reduction techniques. It will be assumed that the bulk
density raises by 20% with treatment and for those crop components resulting in a calculated net
bulk density below 500kg/m³ the bulk density will be set at 520kg/m³.
Table 14 Bulk densities of agricultural crop components before and after treatment
Harvested Conditions Post-Pro cessing Conditions

Crop Component Moisture Bulk Net Bulk Moisture Bulk Net Bulk
Content Density Density Content Density Density
Common Name % kg/m³ % kg/m³
Cassava Tuber 69.9 670 202 20 804 643
Grass Whole 82.5 640 112 50 768 384
Lu cerne Whole 75 640 160 50 768 384
Maize Seeds 20.6 600 476 15 720 612
Oil palm Fruit 26 750 555 20 900 720
Potato Tuber 78 670 147 78 804 643
Rapeseed Seeds 10 640 576 10 768 691
Sorghum Whole 50.8 640 315 20 768 614
Soya bean Seeds 10.2 720 647 10.2 864 776
Sugar beet Beet 76.6 700 164 76.6 700 164
Sugar cane Cane 82.5 300 53 20 360 520
Sunflower Seeds 20 600 480 20 720 576
Switchgrass Whole 12 240 106 12 550 484
Tobacco Whole 88 640 77 20 768 614
Wheat Seeds 20 770 616 15 924 785
Willow tree Whole 60 260 104 20 550 520

Table 15 Bulk densities of residue crop components before and after treatment
Harvested Conditions Post-Pro cessing Conditions

Crop Component Moisture Bulk Net Bulk Moisture Bulk Net Bulk
Content Density Density Content Density Density
Common Name % kg/m³ % kg/m³
Cassava Stover/ Leaves 39.8 520 313 20 624 520
Maize Stover 75 300 75 20 360 520
Oil palm Fronds/Tru ck 64.9 520 183 20 624 520
Potato Stover/ Leaves 60 520 208 50 624 312
Rapeseed Stover/ Pods 85.9 640 90 20 768 614
Soya bean Stover/ Pods 60 640 256 20 768 614
Sugar beet Leaves/Tops 86.4 520 71 50 624 312
Sugar cane Stover/ Leaves 77.5 520 117 20 624 520
Sunflower Stover/Husks 60.8 520 204 20 624 520
Wheat Stover 8 300 276 8 360 520
Sizing and moisture reduction procedures are giving in GJ/tonWW and/or GJ/tonH2O
removed. By knowing the input and setting the output moisture content and determining the
relative wet weight yield, the energy demand per unit operation can be calculated in terms of
GJ/ha and when brought in relation to the net dry weight yield, in terms of GJ/tonDW.
4.3.1 Transfer and Storage Systems

Sizing and drying operations are best performed as close to the field as possible. Considering that
most of the machines require a certain size and continuous feed flow to operate efficiently and
effectively, the first transfer hub (not the farm) will be selected as the location for these
operations. This is understood as the selected “starting point” or central location for a cluster of
agricultural fields. Thus transport via tractors will always be used for untreated, wet and bulky
biomass. And much like the sizing and moisture reduction calculations the moisture contents and
bulk densities heavily influence the transfer and storage system calculation, since the transfer
equipment energy demand is also given in MJ/m³ and MJ/tonWW terms. Relating them to the
bulk density, moisture contents and dry weight yield will result in MJ/ha and MJ/tonDW. The
table below lists the transfer equipment involves for the various logistical systems.
Table 16 Transfer system machine employment
Transport Mode or Lo cation Typ e Transfer E quipment Specific Typ e Biomass Type
from to name name description
Tractor Storage Wheel Loader Loose All freshly h arvested
Storage Tru ck Wheel Loader Packed All freshly h arvested
Tru ck Train Conveyo r Train/Ship Bound Any
Tru ck Barge Conveyo r Train/Ship Bound Any
Tru ck Bulker Stacker/Reclaimer Loose Tropical
Train Vessel Conveyo r Train/Ship Bound Any
Barge Bulker Cran e Bucket Any
Bulker Shore/Storage Cran e Bucket Any
*Storage Silo Conveyo r Wet Forage/Grains
*Silo Tru ck None - Forage/Grains
*Vessel Land Cran e Shovel Delicate
*Exceptions

Each transfer and storage operation is coupled to a loss of material ranging for 0.1 – 0.6% per
transfer. Following each of the transfer and storage calculations a total material loss of 0.70 –
1.29% is present over the entire logistical system.
4.3.2 Balancing Size and Moisture Reduction and Transport Energy Costs
It is a prerequisite for long-haul transportation of biomass to use sizing and moisture reduction
procedures to prevent degradation and lower the associated transportation costs. For shorter
distances, the benefits of reducing the size and moisture content becomes less of a prerequisite
and more of an option. In several cases when the distances are not great, it would actually be
more energy efficient to avoid preprocessing steps. Reducing the size and moisture content to
increase the net bulk density is energy intensive; 0.48 – 3.68GJ/tonDW. To warrant the
preprocessing procedures the total logistics energy with transportation, transfer, sizing and
moisture reduction must be lower than the direct (untreated) logistics system. Several of the
choice crops and logistic systems are confronted with such a trade-off decision. Below is an
example of the tuber portion of the sugar beet.
Figure 3 Logistics and preprocessing energy trade-off
Logistics and Preprocessing Relation

Sug ar B eet Tube r
30
Ba rge - Tre ated
Tru ck - Trea ted
Ba rge - Not Tre ated
Tru ck - No t Trea ted
25
Primary Energy Demand (GJ/tonDW)
20
15
10
100km
75km
1050km
5
0
0 200 400 600 800 1000 1200 1400 1600 1800
425km Dist ance Covered with Modality (k m)
In this particular example 425km is needed to cover the distance from the centralized collection
location in the harvest region to the Port of Rotterdam. Barge transportation has been selected
due to the availability in the region, but for the sake of comparison truck transport is also
included. Preparing the sugar beet tuber for long-haul transport requires 1.26GJ/tonDW. At the

425km marker, untreated barge transport would be the most energy efficient option and only at a
transportation distances beyond 1050km does preprocessing become attractive. The trade-off
distance is much shorter for truck transport at 100km. At distances below 75km untreated truck
transport is even more efficient than treated barge transport. The same can be conducted for the
tops/Leaves of the sugar beet and likewise the untreated barge transportation option is the most
energy efficient. Several other crops in the immediate hinterland of the Port of Rotterdam are
better left untreated before transportation. Furthermore, in the cases of forage and crop residues
components the option of initial natural air drying to reduce the moisture content to 50% is still
possible, advisable and included; being fossil fuel free. The crops and individual crop
components that do not gain from preprocessing are:
• Grass: 176km barge from Raalte, Holland
• Potato: 176km barge from Raalte, Holland
• Rapeseed: 178km train from Hannut, Belgium
• Sugar Beet: 425km barge from Uchte, Germany

The total logistical system and resulting energy demand is determined by combining all the
individual aspects and interrelations of the crops together.
Figure 4 Resulting logistical input energy
Log istical Cost Overview

1 50000
Transfer/Ha ndlin g
Sizing an d Drying
Transportation
Primary Energy Cost (MJ/ha)
1 00000
50000
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The above graph presents the total logistical energy demand separated into the three main
categories; transportation, sizing/drying, and transfer/storage costs. The exergy-base graph is not
presented as there is little noticeable difference. Both represent the total crop as the individually
assessed agricultural and residue components are combined using the common denominator of
land area (MJ/ha). There is clearly a wide variation between the regionally selected crops resulting
in a primary energy input range of 6.1 – 149.2GJ/ha. A generalisation can be made; regional
crops have a low logistical energy intensity and globally distant crops have a high logistical energy
intensity. Long-haul bulker transportation is the least energy intensive transportation mode, but
when required to travel thousands of kilometres becomes a significant factor. Oil palm, tobacco,
sorghum and sugar cane being cultivated halfway around the world (>5000km sea travel) have
very high transportation costs with the greatest portion of the energy demand linked to ocean
transportation. It is also noticeable that the transfer and storage costs are minor, contributing
only a few percent to the total logistical input. Sizing and drying on the other hand, can for some
crops be the largest factor in the entire logistical chain. Rapeseed, wheat and the willow tree all
require sizing and drying to promote an efficient transport which is evident in the relatively high
sizing/drying input and low transportation input.
4.4.2 Efficiency
Precisely as with all the other energy inputs (e.g. farming in Section 3.3.2) it is misleading to
visualise the total logistical systems in terms of land without relating it to the resulting energy
output. As before the same simple formula will be used related the two terms:
Energetic _ Output [ MJ / ha ]
Logistical _ Efficiency =
Logistic _ Input [MJ / ha]
The graph below visualises the resulting energy and exergy efficiency of the crop logistical
systems. This is the section and aspect of the agricultural feedstock (primary + secondary) input
energy cost where regional crops gain in competitiveness over their more lucrative foreign
counterparts. All of the tropical high-yielding crops that have previously ranked amongst the
most efficient in the other sections are now amongst the bottom. A key marker in the graph is
the 500% line corresponding to a 20% crop energy content loss due to the logistical system.
Several of the crops are even below this line. Lucerne, maize, sorghum, sugar cane and tobacco
are 5 examples of high yielding crops that loss more than 20% of their energy content due to the
required long-haul transportation distances to satisfy the European chemical industry. The potato
and grass, both cultivated in Holland, can be transported without the need of preprocessing or
long-haul transportation. As a result they are the most efficient crops in this section.

Figure 5 Resulting logistical efficiency
Eff iciencies
Ba se d on t he Lo gistical Syste ms
2500
3 .4E3 2.8 E3
4 .0E3 Energy
Exergy
2000
Convers ion Perce nt [%]
1500
1000
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4.4.3 Analysis
Table 17 Comparative logistical input overview
Crop Logistical System (energy) Logistical System (exergy)

Cassava - O - O
Grass + + + +
Lu cerne O - O -
Maize - - - -
Oil Palm - O - O
Potato + + + +
Rapeseed + O + O
Sorghum - - - -
Soya Beans O - O O
Sugar Beet O O O +
Sugar Cane - - - -
Sunflower + + + O
Switchgrass O O O O
Tobacco - - - -
Wheat + O + O
Willow Tree O - O -
Input: + below 25.0GJ/ha, - above 75.0GJ/ha, O b etween 25 – 75GJ/ha
Efficien cy: + above 1500%, - b elow 500%, O b etween 500 – 1500%

The top 3 choice crops for each category (farming and logistics) will be discussed separately
along with the total result for the entire group “secondary energy input” in terms of energy to
material production.
Modern farming is highly energy intensive due to the heavy reliance on diesel powered machinery
employed in the tillage, planting, soil treatment and harvesting operations. However, in many
regions of the world, manual labour is still common place especially for the harvesting
operations. The energy requirements “to feed an army” (of harvesters) is much less than the energy
requirements “to fuel a combine” (harvester). This can be seen in the following table listing the top 3
crops with the lowest energy input demand for the farming operations.
Table 18 Top 3 crops on low farming demand
Energy Exergy Farming Efficien cy (Output/Input)

Top Crops
GJ/ha Energy Exergy
1. Oil Palm: 2.19 Oil Palm: 2.23 Oil Palm: 38051 Oil Palm: 41486
2. Cassava: 2.49 Cassava: 2.23 Cassava: 21656 Cassava: 25266
3. Sugar Cane: 2.94 Sugar Cane: 3.02 Sugar Cane: 16616 Sugar Cane: 19364
Between 350 – 750 man-hours are required to harvest one hectare of the top 3 crops in their
respective regions. Even at only ~1 operational hour per hectare for the fully mechanized
operations, the energy intensity is significantly higher. However, it is foreseeable that with an
increased interest and investment in these manually harvested biomass crops the local farmers
may quickly adopt fully mechanized operation practices. This will undoubtedly support the
development of the regions but will negatively influence the energy intensity of the farming
procedures. The following table lists the top 3 crops based on full mechanization.
Table 19 Top 3 crops on low farming demand (fully mechanized)
Energy Exergy Farming Efficien cy (Output/Input)

Top Crops
GJ/ha Energy Exergy
1. Soya Bean: 3.01 Soya Bean: 3.02 Maize: 14144 Maize: 16611
2. Willow Tree: 3.13 Willow Tree: 3.18 Rapeseed: 9629 Rapeseed: 11079
3. Rapeseed: 3.22 Rapeseed: 3.24 Wheat: 7036 Wheat: 8279
Despite being cultivated using fully mechanized operations the maize crop approaches the
efficiencies (85%) achieved by the manually harvested sugar cane fairly closely. This illustrates the
true extent of the cultivation efficiency of the maize crop. The top 3 most efficient crops (in
terms of farming procedures when full mechanization) are all currently employed on a large scale
for bioenergy purposes, suggesting a correlation and not a coincidence.
Yet no matter how energy intense modern farming procedures are, it must be realised that when
brought into the perspective of the yielded crop output energy content, its contribution is in fact

quite low. For all the crops under investigation, the fraction of the potentially yielded output
energy required for farming is 0.26 – 3.53%. It is a mere 0.26 – 0.60% for the top 3 crops.
In retrospect it was determined in Section 4.3.1 that 0.70 – 1.29% material loss occurs over the
storage and transfer operations encountered during the logistical systems. Even when excluding
the material loss the logistical systems are the most energy intensive in the group of secondary
energy input. For many of the chosen crops the requirements for logistics can be several orders
of magnitudes higher than the requirement for farming procedures. As the following table
depicts, the top 3 crops with the lowest logistical input energy cost are in the same (slightly
higher) range than the most intensive farming procedures.
Table 20 Top 3 crops on low logistics demand
Energy Exergy Logistics Efficien cy (Output/Input)

Top Crops
GJ/ha Energy Exergy
1. Grass: 6.13 Grass: 6.15 Grass: 3378 Grass: 4015
2. Potato: 10.3 Potato: 10.4 Potato: 2306 Potato: 2765
3. Sunflower: 12.0 Sunflower: 14.7 Sunflower: 1549 Sugar Beet: 1556
As expected and already mentioned in the previous section, local crops perform best. The shorter
the travel distance the less intense the logistical operations. An other major additional benefit of
local biomass cultivation and collection is the possibility to transport the feedstock without any
sizing or moisture reduction considerations. Local biomass is best! Locally cultivated grass with
the option of partial air drying is by far the most advantageous crop to feed the Port of
Rotterdam. At 3378% logistical efficiency, less than 3% of the collected energy content is
required (and lost) for the logistics. The sunflower, though transported over a seemingly far
distance of 724km, is the 3rd best crop. The reason is twofold. Firstly, the transportation does not
rely heavily on truck/tractor transport and secondly, the harvested seeds require no drying
preparation before transportation. Wheat has also been set to be cultivated and transported using
the same means as the sunflower yet has a logistics efficiency 70% that of the sunflower. The key
difference between the two crops is the pretreatment of the seeds; it is considerably more energy
intensive to grind wheat into flour than sunflower into an oily slurry. This stresses the fact that
each crop in each region is unique and by being handled differently results in regionally crop
specific logistical systems and respective energy demands.
Although it will be covered in the following chapter, it must already be mentioned that as alluring
as local biomass may appear it cannot satisfy the chemical feedstock demands of the Rotterdam
production facilities both continually over the entire year and in total volume flows. Imported
biomass is inherently necessary. Determining the best combination between the domestic and
foreign sources of biomass in respects to energy/exergy efficiency is paramount.
In the previous two chapters the term land use efficiency was employed to indicate the relationship
between the yield and input energy type; effectively compiling the land requirements for material

production. The same procedure can be performed with regards to the secondary energy inputs.
By relating the dry weight yields and total secondary energy input an “energy use efficiency” is created
with the same unit, g/GJ. This indicates the energy requirements for material production.
Figure 6 Secondary energy use efficiency
Energy Use Figures

Based on Dry Weight Figures and Secondary Energy and Exergy
1. 0E+06
1.1 E6
Energy
1.0 E6
Exe rgy
7. 5E+05
g/GJ
5. 0E+05
2. 5E+05
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Three crops clearly stand out as producing vastly more biomass material per energy input than
the others; namely grass, potato and sugar beet making the top 3 crop selection straightforward.
Energy Exergy
Top Crops
g/GJ
1. Grass: 1.05⋅106 Grass: 1.04⋅106
2. Potato: 9.27⋅105 Potato: 9.20⋅105
3. Sugar Beet: 8.18⋅105 Sugar Beet: 8.13⋅105
These three particular crops are rated amongst the lowest in farming procedure efficiency being
heavily reliant on intensive machinery, yet still yield the most material per secondary energy input.
Although this cannot be ignored, the farming procedure energy input is overshadowed by the
significantly higher energy input associated with the logistical systems. Thus transportation and
preprocessing are the most influential aspect for the secondary energy input. This presents
benefits for even the lower yielding crops in temperate regions supplying local chemical industry.

6 Total Agricultural Energy Input
Combining the primary (chapter 5) and secondary (this chapter, 6) energy input results in the
total energy input required to supply the chemical industry (or any other industry) with the
respective biomass feedstock. This summation will be dubbed as “total agricultural energy input”. By
relating the terms once again to the potential crop output figures (chapter 4) and by additionally
including the material lost during the storage and transfer operations (section 4.3.1) the overall
energy and material propagation efficiencies can be determined. This section will be broken
down into three parts. The first part will give a compilation of key graphs, the second will show
the results and the discussion listing the top 3 and bottom 3 choice crops per category, and the
third part will give an individual assessment and suggestions options for the regionally set crops.
Exergy results are only present in the tabular results, not in graphical form.
6.1 Graphical Overview

Four graphs are presented in this section. The first, figure 7, is the total agricultural energy input
brought into relation to the productive land area, MJ/ha. For better clarity the total absolute
value has been broken down into the individual input categories. As repeatedly stressed, the
figures are better presented in relation to the crop yield output figures. Although based on the
same resulting relationships, the second graph is slightly different than the commonly presented
efficiency graphs. Figure 8 depicts the percentage of the potentially yielded crop energy lost,
broken down for each of the major input categories, to create a biomass feedstock. The
subsequent two graphs (figures 9 & 10) present the energy use efficiency for the total material
production and the individual biocomponents of the crops, present in the terms g/GJ.
Figure 7 Total agricultural energy input
Total Energy Input
2.0E+05
Storage
Transportation
1.8E+05 Sizing/Drying
Farming
Irrigation
1.6E+05 Pesticides
Fertilizer
1.4E+05
1.2E+05
MJ/ha
1.0E+05
8.0E+04
6.0E+04
4.0E+04
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Figure 8 Total yielded energy lost through agricultural input
Tot al Energy Loss
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Lo gistic Layou t
Farming
Irrigation
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Fertilize r
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Figure 9 Agricultural energy use efficiency

Energy Use Figures
Based on Dry W eight Figures and Total Agricult ural Energy and Exergy Input
5. 0E+05
Energy
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3. 0E+05
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Figure 10 Agricultural energy use efficiency per crop component
Land Use Figures
Based on Dry Weight Figures and Total Agricultural Energy Input
2.5 E+05
3.1E5 2.9E5 3.8E5 2.8E5 3.5E5 Sim ple CH
Complex C6
Complex C5
Lignin
Protein
Fat
Sum CH
2.0 E+05 2.3E5
1.5 E+05
g/GJ
1.0 E+05
5.0 E+04
0.0 E+00
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6.2 Results and Discussion

The following table lists the top 3 crops corresponding to the graphs figure 8 & 9.
Table 22 Top 3 crops on low total agricultural energy demand
Energy Exergy Agricultural Loss Efficien cy

Top Crops
GJ/ha Energy % Exergy %
1. Grass: 28.4 Grass: 30.2 Grass: 14.7 Grass: 13.1
2. Potato: 36.0 Potato: 37.7 Potato: 16.2 Potato: 14.1
3. Sunflower: 45.4 Sunflower: 53.3 Rapeseed: 17.0 Rapeseed: 16.9
For many of the crops the logistic layout is the largest factor in determining the total agricultural
input energy. Following this, as expected and already mentioned in the previous section, the local
crops perform the best. Grass comes out as the clear leader with less than 15% of the yielded
energy gone into supply the feedstock. On the other scale are the bottom 3 crops, listed in the
following table.
Table 23 Bottom 3 crops on low total agricultural energy demand
Bottom Energy Exergy Agricultural Loss Efficien cy

Crops GJ/ha Energy % Exergy %
1. Tobacco: 181 Tobacco: 192 Lu cerne: 61.7 Lu cerne: 55.4
2. Sorghum: 175 Sorghum: 188 Tobacco: 48.9 Tobacco: 43.6
3. Oil Palm: 163 Oil Palm: 157 Willow Tree: 47.0 Willow Tree: 42.8

Lucerne at an energy loss of 61.7% is a poor crop choice for supplying Rotterdam. Although the
loss is less than 100% suggesting a mitigation potential is possible, it is expected that for most
biomass applications more fossil fuel energy is required than is delivered. Lucerne owes its poor
performance to the high reliance on truck transport, the long overall transportation distance and
local irrigation practices while only yielding a moderate amount of biomass. However judged
solely per land area (GJ/ha) does indicates a high trend, but part of the bottom 3. It is mainly the
relatively low energy-to-material yield that places it well below the other crops. The oil palm, for
instance, is 3 rd in intensive agricultural energy input based on land area but ends up in the middle
of the group (<20% loss) in terms of agricultural loss efficiency. Thus, to compete with a local
crop an imported crop must have a respectable yield potential.
For supplying the chemical industry with a biobased material feedstock it is important to look
into the different components and their respective fossil energy use for material propagation. The
following table lists the 4 most important aspects relevant to the industry; total biomass, total
carbohydrates, protein and fatty acids.
Top Total Biomass Total Carbohydrates Proteins Fatty Acids

Crops Energy Exergy Energy Exergy Energy Exergy Energy Exergy
g/GJ g/GJ g/GJ g/GJ
Grass: Potato: Grass: Oil Palm:
1.
4.96⋅105 4.66⋅105 3.8⋅105 3.6⋅105 9.6⋅104 9.0⋅104 8.1⋅104 8.3⋅104
Potato: Grass: Rapeseed: Rapeseed:
2.
4.87⋅105 4.65⋅105 3.1⋅105 2.9⋅105 8.7⋅104 7.6⋅104 5.4⋅104 4.7⋅104
Sugar Beet: Sugar Beet: Potato: Sunflower:
3.
4.38⋅105 4.13⋅105 3.5⋅105 3.3⋅105 6.5⋅104 6.2⋅104 5.3⋅104 4.5⋅104
Each category corresponds to a different focus on the biorefinery layout. Grass, potato, sugar
beet, rapeseed and the sunflower all score well over all the categories suggesting that they can
become an integral part of any biorefinery dedicated for the European chemical industry. Despite
the high logistic energy demand due to the vast transportation distance, the oil palm is still the
most energy efficient crop for fatty acids production.
6.3 Individual Regional Crop Explanations and Recommendations

The selected crops are regionally based. They may therefore be preferable in one area but not a
good option in another. Several considerations, explanations and recommendations can be made
regarding each of the crops to their respectively selected regions.
Cassava
Cultivated in Nigeria the feedstock must overcome a large transportation input energy cost. The
high yields, especially of simple carbohydrates, overcome this hurdle. It therefore become a
competitive overseas option and is a good option to supply the industry with feedstock during
off-season months. But due to the lack of infrastructure and know-how, intermediary
biorefineries are probably not a feasible option to help reduce the associated transport cost.

Grass
Judging solely from the agricultural input energy it is the most advantageous crop to supply a
feedstock for the set chemical industry. Furthermore, harvested on several separate occasions
over the course of the growing season provides ample feedstock for a good portion of the
operational year. And vast landscapes of grasslands are less intrusive than other crop options.
Lucerne
Of all the investigated crops lucerne shows the poorest performance. Firstly, being cultivated in a
non-rainfed area with irrigation supplied from a deep aquifer is the not very efficient. Locating
the crop in a rainfed area would improve the situation, but would still not make it a viable option
as other crops perform better on such arable lands. Nevertheless the largest factor is the
transportation cost. Seeing that the yield is only marginal, overseas transport is not advisable
being situated so far from a seaport. The lucerne can be competitive in the domestic market
should the irrigation issues be resolved. Even local, small-scale production of half products, like
ethanol and DDGS, with subsequent distribution could not overcome the transport issue.
Maize
Transportation input requirements aside, the maize crop is one of the most advantageous crops
being highly productive relative to its agricultural energy input. Even with the high transportation
cost it can compete with other imported feedstocks. Since it is only grown in the Northern
Hemisphere, its effectiveness is limited: the harvest and deliverable dates coincide with the other
local crop production. The locally existing primitive biorefineries are a practical option to create
half products, lowering the logistical systems input by at least half. Considering the existing
ethanol market and predicted demand increase, the waste from the ethanol plants (distillers
grains) will most certainly be the feedstock coming from the maize in America for the European
chemical industry.
Oil Pal m
The total agricultural energy input demand of the oil palm is almost entirely related to the
overseas transportation. Local preprocessing can reduce the demand only marginally and may
even raise the overall energy costs due to the foreseeable lack of process integration and
efficiency in the region in the coming years
Potato
Behind grass the locally cultivated potato is the 2nd best feedstock option. The only area of
foreseeable improvement would be the promotion of better crop breeding or rotational schemes
to reduce the disproportional high pesticide usage.
Rapeseed
Rapeseed performs rather well overall. The high figure for the agricultural energy input is
associated with the artificial fertilizer requirements. To achieve the high yields significant levels of
nitrogen are needed. A reduction option would be a leguminous cover crop.
Sorghum
Cultivated in Kenya, the feedstock must overcome a high transportation input energy
requirements. The high yields, especially of simple carbohydrates, overcome the hurdle.
Therefore it is a competitive overseas option. It can supply the industry with a feedstock during

off-season months. But due to the lack of infrastructure and know-how, intermediary
biorefineries are probably not a feasible option to help reduce the associated transport cost.
Soya Bean
Transportation input requirements aside, the soya bean crop is one of the most advantageous
crops being highly productive with its agricultural energy input. Even with the high
transportation cost it can still compete with other imported feedstocks, however being situated in
Illinois limits its effectiveness having a harvest and deliverable dates coinciding with other local
crop production. Yet unlike the starch-based maize crop, local processing into half products will
have less of an effect on the oily-based crop. A reduction in transportation costs will be present
but not at the same magnitude. An further option would be to lower the irrigation dependence.
Sugar Beet
Sugar beet performs rather well overall. The agricultural energy input is split between the
associated artificial fertilizer requirements and the logistical system. To achieve the high yields
significant levels of nitrogen are needed. Reduction options would be to use a leguminous cover
crop during the winter months and to locate the cultivation areas closer to the inland waterways.
Sugar Cane
Excluding the large transportation costs, the sugar cane has the lowest agricultural input per
yielded biomass. Using the ethanol production facilities and other local production facilities will
greatly reduce the transportation costs. Considering the existing ethanol market and predicted
demand increase, the waste from the ethanol plants (begasse + stover) will most certainly be an
important feedstock coming from the sugar cane in Brazil for the European chemical industry.
Sunflower
The biggest reduction potential of the French grown sunflower is to better control the irrigation
systems. Integrating a drip system to keep to the bare minimum water demand should bring
down the energy losses.
Switchgrass
Compared to the other American grown crops, switchgrass has the lowest relative logistic system
energy cost which is primarily due to the exclusion of a drying procedure. Yet, its intensive
farming practice and nutrient requirements influence the overall results negatively. Even with
local processing into half products it is unlikely that it can compete to other more efficient local
feedstocks.
Tobacco
Tobacco grown in Australia is simply too far away to efficiently supply the European market,
even with its remarkable yields. Cultivation in a closer region with a suitable climate adapted to
year-round production could be an option.
Wheat
To obtain the high yields associated with best practice conditions, wheat requires vast amounts of
artificial fertilizer. Compared to the other regional simple carbohydrate-based feedstock options,
it is the least efficient. Nitrogen demand can slightly be lowered using a summertime cover crop.
However, its forte is providing an earlier local feedstock source.
Willow Tree
Regardless of the common notion that the willow tree is a fast grower, the actual yields are simply
too low to warrant the sizing and drying procedures for export, let alone for domestic use.

References
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Engineering in Agriculture 2004, 20, (5), 553-561.
9. DLG (German Department of Agriculture), Tractors and Transport Vehicle Tests (in
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Tech: 2006.
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German). In 2006.
14.Borken, J.; Patyk, A.; Reinhardt, G. A., Basisdaten für ökologische Bilanzierungen (core data for life cycle
assessments, In German). Vieweg: 1999; p 223.
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16.New Holland TX Series - Product Specifications.
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23.Suurs, R. Long Distance Bioenergy Logistics: an assessment of costs and energy consumption for various
biomass energy trasnport chains; University of Utrecht: 2002.
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Forestry Wastes; 1989.
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Amsterdam, 1992.
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33.Hotlzapple, M. T.; Humphrey, A. E.; Taylor, J. D., Energy Requirements for the Size
Reduction of Popular and Aspen Wood. Biotechnology and Bioengineering 1989, 33, 207-210.
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Requirements in Palm-Kernel Oil Processing Operations. Journal of Food Engineering 2006, 79,
(1), 322-329.
35.Jannasch, R.; Quan, Y.; Samson, R. A Process and Energy Analysis of Pelletizing Switchgrass;
Resource Efficient Agricultural Production (REAP-Canada): 2001; p 16.
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37.Andritz AG, Drying/Cooling Technologies. In 2007.
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combustion; ECN: Petten, 1995.
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40.Beer, J. d.; Phylipsen, D.; Bates, J. Economic Evaluation of Carbon Dioxide and Nitrous Oxide
Emission Reductions in Industry in the EU; Ecofys Energy and Environment,: 2001; p 82.
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Ensure a Long-Term World Food Supply. Agricultural Engineering International: the CIGR Journal
of Scientific Reaseach and Development. 2002, 4, (Invited Overview Paper).
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http://www.cps.gov.on.ca/english/gs7000/grain.htm

Chapter 7
Process Energy Input
Required energy and exergy involved in processing of biomass within a biorefinery concept
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 7 – Pro cess Energy Input

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ISBN-number -
Date o f publication 1. April, 2008
Confidentiality No
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P.O. Box 17
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ISO 9001:2000.

Abstract
The conversion of biomass feedstocks into chemical products is performed in a biorefinery. Each
of the biochemical constituents as described in Chapter 4 are subjected to a different processing
route to yield a chemical. All of the potential chemical products investigated exist in the current
petrochemical industry as described in Chapter 1. Seen from the cradle-to-grave each biochemical
processing step within the biorefinery involves internal process energy. The process energy is
separated into thermal energy, electric energy and indirect energy (also exergy). These are related
to external fossil fuel energy input requirements. Each potential bioprocessing routes is assessed
systematically and expressed in GJ/ton product for that particular stage of processing. The best
available technologies, recently developments, currently researched and even hypothetical designs
are included to foresee the production of a chemical product from each biochemical constituent.
In those case where it applies, the current average processing routes are also listed alongside the
lowest energy consuming option. This chapter is sectioned in the same sequence as the proposed
steps of a biorefinery. First, receiving biomass to remove soils and other impurities is covered.
Secondly, carbohydrates which, in respects to their large biomass proportion and various forms,
are broken down into three subsections; simple carbohydrates, complex carbohydrates and
further glucose processing. Fatty acids, proteins and lignin are all assessed following the same
methodology to yield chemical products in regards to the required thermal and electric process
energies and indirect fossil fuel energy. Unreacted and unconverted material is gathered and
combusted to yield internal heat and power. The efficiencies of the energy conversion and
potential products is described. While an overview is presented to the extents of various
biorefinery schemes, this chapter essentially provides the base data needed for further matrix
calculations of the feedstock dependent biorefinery layouts.
Key Words:
Biomass, Biorefinery, Fermentation, Separation, Chemicals Processing, Energy, Exergy

Content
1 Introduction 303
2 Handling Procedure 305
2.1 Locations 305
2.2 Preparation 306
2.2.1 Washing 306
2.2.2 Product Isolation 306
2.2.3 Sizing 306
3 Carbohydrates 307
3.1 Simple Carbohydrates 307
3.1.1 Starch 308
3.1.1.1 Description 308
3.1.1.2 Processing 308
3.1.1.3 Energy Input 309
3.1.2 Sucrose 310
3.1.3 Other sugars 312
3.2 Complex Carbohydrates 312
3.2.1 Cellulose 313
3.2.2 Hemicellulose 320
3.2.3 Other Complex Carbohydrates 320
3.2.4 Energy Input 321
3.3 Glucose Chemistry 328
3.3.1 Ethanol production 328
3.3.1.2 Standard Processing 329
3.3.1.3 Recent Processing Improvements 331
3.4 Overall Ethanol Production Cost 334
3.4.1 1 st Generation Bioethanol 334
3.4.2 2 nd Generation Bioethanol 335
3.4.3 Combined generation 336

3.4.4 Ethylene Chemistry 336
4 Fatty Acids 339
4.1 Description 339
4.2 Processing 340
4.2.1 Standard Processing 340
4.2.2 Recent Processing Improvements 342
4.3 Energy Input 343
5 Proteins 347
5.1 Description 347
5.2 Processing 348
5.2.1 Animal feed issue 348
5.2.1.1 General Situation 348
5.2.1.2 Fossil Fuel Mitigation 349
5.2.2 Solubilization 350
5.2.2.1 Chemical Extraction 350
5.2.2.2 Protease 351
5.2.3 Isolation and Purification 352
5.2.3.1 Nanofiltration (NF) 353
5.2.3.2 Electrodialysis (ED) 353
5.2.3.3 Chromatography 354
5.2.3.4 Reverse Osmosis (RO) 356
5.2.3.5 Others 356
5.2.4 Potential synthesis routes 358
5.2.4.1 Process Debriefing (Sources) 360
5.2.4.2 General Process Unit Operations 360
5.3.1 Protease Solubilization 363
5.3.2 Separation and Isolation 364
5.3.3 Drying and Product Preparation 365
5.3.4 Reactions 366
5.3.5 Overall 367
6 Lignin 369
6.1 Description 369
6.2 Processing 370
6.2.1 New Product Options 370
6.2.2 Fungal degradation 370

6.2.3 Gasification 371
6.2.4 Fast-pyrolysis 372
7 Ash 377
7.1 Description 377
7.2 Applications 378
7.2.1 Combustion 378
7.2.2 Post-combustion 378
7.2.2.1 Building Material 378
7.2.2.2 Fertilizers 378
7.2.2.3 Ash Upgrading for Fertilizers 379
7.2.2.4 Land Reclamation 380
8 Biorefinery System 381
8.1 Construction of Facilities 381
8.2 Internal Process Energy 381
8.3 Local Production 381
8.4 Results and Discussion 382
References 383

1 Introduction
In the previous chapters, the various biomass feedstocks were investigated and assigned a
cumulative imbedded fossil fuel value for their propagation; a total agricultural fossil fuel energy
input. Industrially cultivated biomass provides a carbon-based feedstock which has, for the large
part, a significantly lower fossil fuel cost then the contained calorific value. And despite the low
efficiency currently associated with direct combustion of biomass, heat and power generation
usually does yield a moderate reduction in fossil fuel consumption. Investigation into modern
high-tech solutions are already partially implemented which drastically increases this efficiency of
biomass combustion, yet the practice of burning biomass is as old as man himself; archaic in
principle. There are other industrial sectors of high fossil fuel intensity that can make superior
utilization of the carbon-based biomass feedstock, potentially mitigating vast quantities of fossil
fuel energy. The processing of biomass to yield chemical precursors is accompanied with new
and laboratory scale researched technology; cutting edge in principle. While biomass processing is
not void of additional energy input, the field is developing with energy reduction in mind.
Think of the petrochemical industry and images of densely arranged smoke stacks, soaring oil
crackers, towering distillation and rectification columns appear in the mind. Furthermore, in
recent times images used to promote climate change conveniently use these typical scenes as a
backdrop. Throughout the long history of the traditional petrochemical production industry the
technology has been meticulously improved and fine tuned to the point that any additional
efficiency improvements are minimal. Being based on naphtha entails very high temperatures and
pressures to maximize the conversion rates meaning theoretical minimum process energy levels
will remain considerably high. This is where the biorefinery has the prospect to capitalize.
Think of the biobased chemical industry and ones mouth begins to water with the idea of deep
fried food or fresh bread. Indeed the current, limited, applications of biomass processing are
more related to the food processing industry than the naphtha processing industry. Images of hay
stacks, grain silos, fermentation towers and cooking ovens comes into mind when thinking about
the biomass industry. With the envisioned expansion of the facilities into full-scale biorefineries
producing chemical precursors the scene and thought will undoubtedly change, although the
delicious smell will probably linger for some time to come. Grand imposing thermal separation
units and boilers emitting copious amounts of smoke will cover the factory grounds as they do
today in the traditional petrochemical industry. The major difference will be the scale and
intensity. Biomass process technology will be paralleled with the developments and
advancements made particularly in the biotechnology field.
Steps involved in biomass processing employ a combination between time-tested existing

technologies, recently developed biotechnology and upcoming technologies designed especially
for biomass applications. Each product route will encompass an individual internal process
energy demand, partially offset by the initial processing procedures common for other products

and partially derived by the final product’s unique processing requirements. Combined all the
products and relative process energies contribute to the overall biorefinery process energy input.
The more products desired to be produced, the more complex the biorefinery becomes with an
increased leaning towards higher energy intensity. Providing a numerous array of products to
satisfy the chemical industry feedstock needs is mimicking the conceptual ideals of the existing
petrochemical layout. Whereas producing chemical precursors fit for direct application in the
existing chemical sector is about the only similarity between the two types of refineries.
Water is the main component that sets the fossil fuel-based and bio-based feedstocks apart.
Upon harvest biomass is wet with a crop dependent dry weight and regardless of the moisture
reduction precaution for transportation typically the first step in a biorefinery is to add water.
Most processes in a biorefinery will indisputably be dominated by water and the properties
thereof. There will be natural thermodynamic limitations imposed on operation temperatures and
pressures of the processes, even the envisioned thermal units will adhere to the boundaries. Plus
water is a perfect medium to employ novel biotechnological processes. In general the process
conditions will be milder than those of the traditional petrochemical production routes. The
overall process energy of a biorefinery system should be much smaller.
The processing of chemicals from biomass should be less energy intensive than the processing
derived from naphtha. Should be, however the advantage of water by inducing milder conditions
is also the cause of major disadvantages in separation techniques. In addition to separation
technology, low conversion rates and up-scaling experimental systems will be the limiting factors
in the success of the biorefinery layout. Each bioprocess route will be assessed for the best
practice option to minimize process energy, thus maximizing fossil fuel savings potential.
A systematic approach will be taken to describe the possible production routes as grouped by the
biomass chemical compositions. In Chapter 4, the crops were classified to agricultural and
biomass categories. The exact biorefinery layout and processes involved are dependent on the
biomass classification of the crop to be processed. By the end of the chapter the resulting process
energy for the optimal biorefinery system for each of the selected crops will be determined.
1.1 Chapter Purpose

In the following chapter all the process energy inputs pertaining to the proposed biorefinery
options of biomass will be calculated and expressed based on the biochemical composition
groups contained in the biomass. The values mentioned herein are based on a straightforward
energy/mass balance in excel using the thermodynamic conversions and axioms to obtain the
exergy values. This chapter is the final of three energy inputs categories required for the creation
of chemicals from biomass. The combination of total agricultural energy input (primary and
secondary energy inputs) with the internal process energy will be able determine the total
embedded fossil fuel energy in the proposed biorefinery systems.

2 Handling Procedure
Upon receiving biomass at the biorefinery’s “factory gate” the shift from the realms of agriculture
to the realms of engineering is complete; handmade straw hats exchanged for a plastic moulded
hardhats. Biomass material will be treated as any other industrial feedstock and assessed for the
best possible production route to maximize product efficiency. In Chapter 6, Section 4.3, the
procedures to reduce size and moisture content for long-haul biomass transport were covered
with the main motivation of increasing net bulk density. It was based under the pretence that all
process steps concerning the biorefinery would be centralized at the petrochemical cluster areas.
This placed a particularly high logistics energy cost on particular crops located in distant regions.
Some aspects of the biorefinery are technically basic and can be performed closer to the
agricultural production areas, while other processes are not basic and do need the collective
know-how of the cluster. To reduce the logistics portion several aspects of the biorefinery will be
performed close to the feedstock cultivation. Plus stringent criteria to produce final-grade
products are not imperative, so long as they are properly coupled with the clustered biorefineries.
After the detailed explanation of individual biochemical production routes, Section 4.1.1 covers
the aspect of half-products, or semi-processed material designed to optimize logistics and
biorefinery energy efficiency. Yet regardless of the distance, most of the crops will encounter at
least partial onsite processing beyond the sizing and moisture reduction steps. In some
circumstances the sizing and moisture reduction will even be made redundant. Handling and
initial treatment of the biomass material will thus be conducted onsite unless otherwise stipulated.
Handling procedures is understood as the necessary preparation for downstream internal
processing with purification aspects dominating.
2.1 Locations
The most appropriate mood of transportation for each regionally dependent biomass feedstock
has a major influence on the biorefinery upon delivery. Despite being centrally located within the
confides of the petrochemical cluster the feedstocks arrive from all possible corners of the globe
at independent time intervals and quantities. One of the primary success factors for a biorefinery
is to be able to continually operate year-round decoupled from seasonal influences. Locally
cultivated biomass provides the biorefinery with a moderate quantity of feedstock (per truck,
train, barge, etc.) periodically throughout the harvesting season. Cross-continental cultivated
biomass feedstock, although possibly seasonally dependent as well, arrives in enormous quantities
(sea vessel) sporadically during the local off-season period. In addition to continual operation, a
successful biorefinery must also be able to process an acceptable range of similar feedstocks
within the limitations of biomass classifications. This creates a unique cooperation and
integration opportunity for biorefineries based in the petrochemical cluster. Receiving and initial
feedstock handling procedures in particular can be shared or coupled between the different
biorefinery types. The goal being a relatively constant production rate without over-sizing the
equipment. Preprocessing and initial handling close to the agricultural production sites is void
from this benefit, but has the benefit of dedication to one particular feedstock type. This permits

the onsite facilities to operate at optimal levels during periods of harvest. In general, the handling
preparations are identical regardless of location and phase of the refining.
2.2 Preparation
The concept of handling the throughput of biomass feedstock is to prepare it for an efficient
utilization within the biorefinery system. Impurities and unfavourable structures are altered upon
by need. In fact most feedstocks can be directly processed without any preparation requirements,
but for those feedstocks which do require preparation for processing, they are accompanied with
a material loss and minor energy consumption.
2.2.1 Washing
Several of the crop components, especially the agriculturally relevant portions, are impure and
not suitable for direct processing. As a simple precaution the feedstocks are water washed and in
cases of more complex facilities process water is used. Stones, soil, dirt and other minor
impurities are flushed out with minute energy requirements and negligible wastewater treatment.
Even in the extreme cases where more than 3 times water over the biomass feedstock volume the
energy consumption remains minimal: 30MJ heat and 110MJ electricity per ton wet feedstock.
2.2.2 Product Isolation

As will be shortly mentioned in the following section, the effectiveness of processing simple
carbohydrates is dependant on a high feedstock purity. Removal of the outer shell (through
peeling, de-husking, etc.) is performed to isolate to rich core. Existing biomass facilities make
little use of these residues, while recent develops (Section 3.2.1.2) can which greatly lowers the
overall effective biomass loss.
2.2.3 Sizing
Already covered in the previous chapter, the next sequential processing step after washing and
product isolation is size reduction. This justifies the reasoning of handling/preparation occurring
more often onsite then at the biorefinery clusters. Listed in the following table are the feedstocks
which require separate handling before size and (should any be later envisioned) moisture
reduction steps with the resulting loss in biomass material.
Table 1 Initial handling procedures
Crop Component Onsite Pro cessing Initial Handling Steps Biomass loss
Common Name Y/N General classification %
Cassava Tuber Y Soil removal, washing, peeling* 2.0
Maize Seeds Y Silk removal, washing, kern el removal 0.3
Oil palm Fruit Y Fruit bunch separation* 1.0
Potato Tuber N Soil removal, washing, peeling* 2.0
Soya bean Seeds Y Residuals removal, washing, flaking 1.6
Sugar beet Beet N Soil removal, washing, pin ch tops* 2.0
Sugar cane Cane Y Dirt and ash removal, washing† 0.7
Sunflower Seeds Y Husk separation*, washing 0.3
Wheat Seeds Y Kernel isolation*, washing 0.3
†Sugar Cane, is special case as currently washed but with best practice system, no field burning thus no need to be washed; directly feed

3 Carbohydrates
Carbohydrates are the most abundant biomolecules that form
the basis of life. Defined as sugars (or saccharides) and their
derivates, the “hydrates of carbon” are any organic compound
based on aldehydes or ketones with hydroxyl functional groups.
In plant matter, the carbohydrates are typically present in
polymers forming polysaccharides. They have a general formula
of Cn(H2O)n-1 where n is usually a large number between 200 and
2500. Biologically they fulfil numerous functions such as for energy storage, energy
transportation and form structural components. The simplest carbohydrates are the
monosaccharides with glucose being the most common. Nearly all of the proposed applications
for biomass-to-chemicals use glucose as a starting building block material1. Although pure
glucose is not present in vast or accessible quantities in biomass, several particular types of
carbohydrates are present in large quantities which, given the right processing, can be broken
down to glucose or other workable materials (such as xylose). The degree of functionality,
complexity and abundance of these carbohydrates are quite different and vary between crop
species. In this section, two groups (dubbed simple and complex) with several subgroups will be
investigated for saccharification processing (breakdown to glucose). The technologies involved in
processing these carbohydrates, apart from being partially crop dependent, are many and very
type specific. The conditions needed to calculate the direct energy and exergy will be listed along
with modern measures to lower the processing inputs. Relation to the fossil fuel input
(cumulative process energy) will not be conducted in this section as the energy generation of each
biorefinery system is unique and specifies the type of fossil fuel energy generation, if any. Finally
the goal will describe the existing and potential glucose chemistry based on the different
carbohydrate biomass feedstocks in reference to major portion of the biorefining system.
3.1 Simple Carbohydrates

The terminology “simple”, used to describe these particular
carbohydrates was chosen to correlate with the technology
involved. The oldest known and most cherished (by some)
processing of biomass is the fermentation to alcohol. Particular
biomass contains ample quantities of these carbohydrates (starch,
sucrose, fructose, etc.) that can be easily saccharified for
subsequent ethanol fermentation. The technology is easy,
straightforward and has been practiced for millennia. As simple Medieval Monastery Brewery
using starch contained in cereals to fermen t beer
as the processing may be the energy intensity is still remarkably
high allowing for improvements. Heavy consumption of the classical product has possibly lead
process innovation to also remain simple; adhering to the traditional methods. Shifting focus on
biomass utilization for sustainable chemical production places energy efficiency and conversion
rates as paramount. There are many carbohydrates that can be classified as simple, but in this
study the focus will remain on starch and sucrose. Biomass crops containing high levels of these

products are subjected to standard technologies and processing steps, however the specific
conditions vary slightly for each feedstock resulting in minor energy consumption deviations.
3.1.1 Starch
3.1.1.1 Description
Starch is the second most abundant biomolecule in the biosphere. It is used
by plants to store excess energy and is digested upon an energy need. It is
found in high concentrations in the reproductive organs (such as seeds) so
that sufficient energy is available during germination. It consists of two
different α -D-glucose chains configurations; linear chained amylase and
highly branched amylopectin. The ratio between the two forms is plant
source dependent while the typical ratio is 20-amylase:80-amylopectin. The technology use to
break starch down into glucose is similar but also crop dependent. From the select crops two
distinct group classifications can be made: cereal and tuberous. Even though wheat and corn are
both cereal grains corn behaves independently from other grains and must be independently
investigated. Potato and cassava are both tuberous crops and the little difference between them
hardly affects the resulting process energy.
3.1.1.2 Processing
Preparation of starch-rich biomass feedstocks to glucose is called the “mashing process”. Physical
mashing is however only one of three distinct steps; (1) mashing, (2) enzymatic liquefaction and
(3) enzymatic saccharification. Physical mashing is designed to break the cellular walls of the
feedstock to release the inner material largely including starch. Prior to mashing the previously
mentioned size reduction procedures are performed optionally or in some cases cover the
mashing step. Dispersion machines work with a rotor and stator sheering the feedstock material
into a fine pulp with near complete cell wall destruction. It is the most effective system and does
require the handling and size reduction procedures to operate efficiently. Earlier systems rely on
either high pressure (above 6bar) or high temperature (above 100° C) or a combination of both.
The most common of which is the Henze cooker, but is gradually being phased out due its high
energy consumption2. The dispersion mashing system with partial stillage (see Section 3.3.1)
recycling is the most energy efficient. Coming from the down-stream distillation column the
85° C hot stillage promotes a near optimal mashing step with little additional input energy.
Usually following, but also sometimes combined, with the mashing step liquefying enzymes are
added to the reactor under mild temperatures. There exists a wide multitude of enzymes from an
assortment of host bacteria and fungi. Virtually all are α -amylases and are even present to a
degree naturally in the feedstock. Classically malts and autoamylolysis were used for both the
liquefaction and saccharification steps but due to the technical availability of industrially prepared
enzymes have been replaced. TBA, thermostable bacterial α -amylase from bacillus licheniformis, is
the most common liquefying enzyme, although today it is common to add an enzyme cocktail to
ensure complete conversion. Directly following liquefaction the saccharification enzymes are

added under slightly elevated temperatures. The exact temperature is feedstock related and
directly effects the heat demand of the process. Tuberous crops in particular require higher
cooking temperatures in the order of 90° C plus. Glucoamylase hydrolyzes the main glycosidic
linkage (α -1,4; α -1,6;α1,3) between the starch molecules releasing glucose. Like with the other
enzymes a wide assortments exists where Glucoamylase from the fungi aspergillus niger (GAA) is
the most common. The resulting wet product stream is called sugar liquor.
3.1.1.3 Energy Input

Glucose is an intermediary product which when originating from starch is almost exclusively
used in consequent ethanol fermentation. Much information is known regarding ethanol
processing as a whole, whereas isolating the mashing process requires more detailed information.
The overall conversion is the first factor in defining starch processing. Listed in table 2 are all the
relevant figures for each investigated crop type. The first row indicates the slight deviation
between conversion rates, and while all being in the high nineties the tuber crops fair best. Next
the saccharification temperatures play an important role in determining the thermal energy costs.
Steam is used to supply the thermal energy and as discussed in Chapter 2 the difference between
energy content and exergy content is large. The results shown in the table per ton of starch dry
weight elude to this. The mashing process is in particular dominated by enzymatic treatment and
the embedded fossil fuel energy cost of enzyme production is actually quite high. An enzyme
manufacture performed a detailed study for the major enzyme categories3. Liquid α -amylase
originating from bacteria costs 19.5MJ/kg in ingredients and 3.0MJ/kg in direct energy. Liquid
glucoamylase from fungi costs 69.9MJ/kg in ingredients and 35.9MJ/kg in process energy. The
dosing rates are essentially the same for all crop types; between 2.0 – 4.0kg (mean 2.5) per ton
starch of amylase and 0.2 – 0.6kg (mean 0.5) for glucoamylase. Although further optimization in
reducing the enzyme loading rate is foreseeable, as shown in the resulting table the proportional
indirect energy cost is already quite low.
Table 2 Starch Processing Energy/Exergy Input
Crop Cereal Cereal (co rn) Tuberous

Conditions
Conversion Rate (%) 96.2 97.7 99.2
Saccharification Temperature (°C) 65 – 75 80 – 85 92 – 94
Direct Energy
Electric (GJ/ton starch) 0.256 0.260 0.198
Th ermal (GJ/ton starch) 0.52 0.99 2.51
Direct Exergy
Electric (GJ/ton starch) 0.256 0.260 0.198
Th ermal (GJ/ton starch) 0.02 0.10 0.43
Indirect Energy/Exergy Costs
Enzymatic Energy/Exergy* (GJ/ton starch) 0.109 0.109 0.109
*energy=exergy as enzymatic process energy is almost entirely electric based
As a comparison dried granulated corn starch is listed at 34.6GJ/ton in Boustead database4. This
clearly shows the susceptibility of existing biomass and bioprocessing data.

3.1.2 Sucrose
3.1.2.1 Description
Sucrose, sometimes known as saccharose or best as table sugar, is a
disaccharide of glucose and fructose. Held together by the glycoside bond
the resulting molecular formula is C12H22O 11. It can only be formed by plant
life and is regarded as the most important sugar in plants; acting as an
energy transport through the phloem sap. Generally produced seasonally, it
is present in all plant life but at high quantities is a limited to a select few
crops. As with the starch-rich crops there are two distinct biomass feedstock types which contain
high enough quantities of sucrose to be consider sugar-rich crops; namely stems-based (e.g. sugar
cane, sorghum, maple tree) and bulb-based (e.g. sugar beet, onions). Being a disaccharide it has a
much lower order of complexity compared to starch. This allows fermenting bacteria to use
sucrose directly, making the preparation even simpler and less energy intensive than the mashing
process of starch. Essentially the sucrose must be extracted or pressed out of the biomass
feedstock and in this sense the form of biomass determines the applicable technology.
3.1.2.2 Processing
The shape of the two sugar-rich biomass categories dictate the processing steps involved in
extracting the sucrose. Shedding, milling and pressing are involved for the stem-based crops
where slicing, diffusing and pressing are involved for bulb-based crops. Both of these sucrose
processing routes are historically coupled to white table sugar production. Traditionally after the
final pressing procedure the sucrose containing stream is subjected to a clarifier and
concentration step to remove trace chemicals and produce a first molasses. For biorefinery
applications, such as when used directly as a fermentation feedstock, the measures for stream
purification and composition need not be so stringent; sugar liquor containing 10 - 15° Bx (Brix:
sucrose content) is sufficient making the clarification and concentration steps redundant, which
also positively reduces the energy intensity. As sugar-rich crops are directly coupled with the
sugar industry the equipment and technology used in the initial sugar liquor preparation steps
operate at near optimal efficiency. Due to the type dependent processing differences description
will be covered separately for the two sugar-rich crop types.
Stem-based
After the initial handling procedures (cleaning) the stems are subjected to a crude shedder to
break the feedstock down into smaller, easier to handle sizes. Unlike the starch mashing process
the pieces are large and do not require destruction of the plant cells. This significantly reduces the
energy intensity and also means that the size and moisture reduction procedures are not needed.
The shredded stem material in then introduced into the milling train unit which extracts the sugar
juice through a series of rollers. Usually a half-dozen industrial-sized rollers are used to crush the
stems and simultaneously squeeze the sugar containing liquids out. Counter-current water is
sprayed on the milled stems to wash out the residual traces of sucrose. The resulting sugar liquor
stream has sucrose content of 14 - 16° Bx. A total of 94.9% from the biomass contained sucrose

is extracted with 0.6% losses associated to reducing sugars, 3.8% to the extraction degree and
0.8% in the juice treatment (water spraying) step.
Bulb-based
After the initial handing procedures (including top removal) the bulbs are subjected to a drum
slicer to cut the feedstock into thin, long chips called cossettes. This procedure increases the
surface area and exposes the interior of the bulb making sucrose extraction possible; cell wall
destruction and size and moisture reduction procedures are not needed. The cossettes are then
placed in large agitation tanks with a counter-current flow of hot water extracting the sucrose.
The hot water is used as a diffusion medium to produce a sugar liquor stream of 10 - 15° Bx.
Temperature above 80° C additionally extract pectinic material which negatively effect
downstream processing while temperatures below 65° C cause microorganism contamination. At
the optimal 70° C diffusion temperatures5, the associated sucrose losses are only 4.2%. Following
the diffuser step the residual wet solids are placed in a screw presser to extract an extra 1-2%
additional diffusion juices to be added to the sugar liquor stream. In total 95.1% of the sucrose
contained in the biomass feedstock has been extracted.

Sucrose is almost exclusively used for table sugar production with ethanol fermentation gradually
emerging. Much information is known regarding the process energies for both products and
from the various biomass feedstocks types. Without the clarification and concentration steps the
process energy requirements are heavily reduced compared to table sugar production. Sugar cane
processing will be taken as representative for the stem-based crop types6. And for bulb-based
crop types the sugar beet processing is representative5, 7. In the older (and consequently many of
the existing) sugar cane processing plants the use of steam driven machinery is common due to
the high quantities of bagasse (Section 3.6). A modern biorefinery would use electric driven
motors, which relates to the fact that stem-based sucrose has no thermal energy component. Beet
processing on the other hand has several different thermal components; warm water, hot water
and steam. These various thermal sources lead to a considerable difference in direct energy and
exergy consumption as seen in table 3. Energetically the stem-based feedstocks require the least
amount but seen exegetically it is the bulb-based crops that require the least. By comparing table
2 and table 3, in any case sucrose is less energy intensive than starch processing.
Table 3 Starch Processing Energy/Exergy Input
Crop Stem Bulb

Conditions
Conversion Rate (%) 94.9 95.1
Direct Energy
Electric (GJ/ton sucrose) 0.452 0.069
Th ermal (GJ/ton sucrose) 0.0 0.893
Direct Exergy
Electric (GJ/ton sucrose) 0.452 0.069
Th ermal (GJ/ton sucrose) 0.0 0.149
Indirect Energy/Exergy Costs* 0 0
*there are no external uses of chemicals or other materials aside from water

3.1.3 Other sugars
Fructose is another important and common saccharide in plant matter which is present in
relatively high concentrations in the fruit of several crop species. But, due to the low material
yields, high energy intensity and lucrative food consumption market no fruit producing crops
were included in the selection of relevant biomass crops (Chapter 4). Extraction of fructose
would, however, be suitable for direct fermentation. Fermenting microorganisms can directly use
fructose, much like sucrose, meaning little processing would be needed. It is foreseeable that fruit
processing residues or stall waste could be mixed with other simple carbohydrate feedstocks to
increase the fermentable sugar yield. Both the starch and sucrose rich biomass crops contain it
and other sugars in lower quantities. In fact, practically all crops have traces of various
monosaccharides include dextrose, galactose, xylose, ribose and the already mentioned fructose.
They are all intermediaries in the biochemistry of disaccharide and polysaccharide production. In
a biorefinery these trace, or free, sugars will contribute to the downstream fermentation feedstock.
In case of crops with a low quantity of simple carbohydrates, they will contribute to the glucose
creation following the complex carbohydrate technologies.
3.2 Complex Carbohydrates

The terminology “complex”, used to describe these particular carbohydrates was chosen to
correlate with the technology involved. In plant matter these carbohydrates (cellulose,
hemicellulose, pectin, etc.) form the structural integrity and are designed to withstand
environmental stresses. Initial hydrolysis, saccharification and subsequent breakdown into
glucose or other workable monosaccharides is not simple. The resistant structural nature of the
carbohydrates makes it difficult to process necessitating complicated machinery and procedures.
Mark Twain wrote “the secret of getting ahead is getting
started. The secret of getting started is breaking your complex
overwhelming tasks into small manageable tasks, and then
starting on the first one”. This idea can be extrapolated into
the processing of complex carbohydrates. Breaking the
complex structures into small manageable pieces is
done through a process called pretreatment. The adjacent
illustration depicts the pretreatment principle; to
separate the cellulose from the hemicellulose
entanglement and lignin shielding, the lignocellulosic material must be subjected to a harsh
pretreatment. In the industry the complex carbohydrates feedstocks are called lignocellulosic
material while the pretreatment technology is frequently referred to as cellulose technology. In
plant matter cellulose, hemicellulose and lignin are inheritably coupled with one another meaning
they will share many processing steps and as a result the processing energy costs. Lignin,
although a part of the initial lignocellulosic material, is after pretreatment separated from the
saccharide processing route because of its aromatic ring structure; it will be handled separately
(Section 3.6). Cellulose and hemicellulose are processed in parallel with only minor differences
separating their process specifications. All biomass material contains lignocellulosic material while

the ratio between the individual complex carbohydrates is unique, which will dictate to a small
degree the overall processing energy demand. The pretreatment and saccharification technologies
are not yet fully proven with many companies and research institutes racing to develop the new
commercial standard. Several of the most promising, near large-scale implementation and most
energy efficient processes will be covered. Pretreatment chemicals, organisms, operation
temperature and pressure, but primarily conversion rates control the resulting energy demand.
3.2.1 Cellulose
3.2.1.1 Description
Cellulose is the most abundant biomolecule in the biosphere. On a
global scale scientists estimate that combined over one trillion (10 12)
tonnes of cellulose is synthesised by all plant life annually. It is used by
plants as a structural component for the cellular walls. As a
polysaccharide it consists of thousands of linear chained β -D-glucose
units with the general formula (C6H10O 5)n. The name derives from
combining cellular wall and glucose. Because it forms the cellular wall in all plant life, it is
present in all biomass feedstocks. It is however, highly concentrated in woody biomass and in the
stem/stalks portions of non-woody biomass. Fibre and pulp residues from the simple
carbohydrates also provides a rich stream of cellulose material. In fact, all the selected biomass
feedstocks will incorporate cellulose technology at some stage in the biorefinery.
3.2.1.2 Processing
Feedstock Considerations
Harsh pretreatment processing conditions are required to cleave and solubilize the lignin and
hemicellulose matrix isolating cellulose for subsequent saccharification. The severity levels of the
treatments are controlled by elevated temperatures, increased pressures, large deviations in pH
and longer residence times. Under particularly severe conditions a near complete cleavage of the
hemicellulose and lignin appears but simultaneously promotes further degradation of the sugars
into undesired products. In the field of pretreatment technologies these sugar degradation
products are referred to as inhibitors because once formed they lower the downstream enzymatic
saccharification and microbial fermentation processes. The most common inhibitor produced is
caused by xylose (hemicellulose) degradation, 5-hydroxymethyl furfural (HMF). Partial
breakdown of lignin forms phenolic degradation products such as 4-hydroxybenzoic acid,
vanillin, syringaldehyde, etc. And to a smaller degree cellulose degrades for furfurals. There are
process integration and control technologies (discussed in Section 3.3.1) foreseeable to reduce the
influence of the degradation products upon formation, but the most logical step would be to
select the best pretreatment technology and conditions for the particular feedstock to avoid their
formation. Here the ratio of lignin, hemicellulose and cellulose play a decisive role in assigning
the logical pretreatment technology. Furthermore, the actual conversion rates (fermentable sugar
formation) is also a function of the feedstock composition, pretreatment technology, and

severity. All of the selected biomass feedstocks will undergo, at some stage within their proposed
biorefinery system, the cellulose pretreatment processing step to liberate sugars found in the
complex carbohydrates. And aside from the simple carbohydrate rich and oil containing
feedstocks this stage marks the beginning of the biorefinery. Thus for investigating the
performance of the pretreatment technologies the feedstocks will be grouped into three distinct
categories:
1. Agricultural Waste
Characteristic: high proportions of cellulose (30 – 40%) and h emicellulose (20 – 30%) with a slight lean
towards cellulose and moderately low lignin content (<15%)
Examples: stems, stover, leaves
2. Processing Residues
Characteristic: moderate proportions of cellulose (25 – 35%) and h emicellulose (15 – 25%), low lignin
content (<5%) and noticeable protein content (20 – 40%)
Examples: distillers grains, bagasse, press cake
3. Recalcitrant Material
Characteristic: high proportions of cellulose (30 – 50%), moderate levels of hemicellulose (15 – 25%)
and a high lignin content (<15%)
Examples: woods, grasses
Oil press cakes (Section 3.4.1.2) have a considerably high lignin content above 15% but because
the pressing and extraction procedures accommodates for milder and efficient pretreatment they
will be classified as processing residues instead of recalcitrant material. High lignin content limits
the effectiveness of the pretreatment process as lignin affectively shields cellulose. Typically the
yields are lower for these feedstocks yet is entirely technology and condition dependent.
Pretreatment Types and Descriptions

There exist a wide multitude of pretreatment technologies which have been suggested and
partially developed over the course of the last decades. The Oil Crisis of 1973 sparked the initial
interest in using lignocellulosic material. Five year ago, when a renewed interest after the ensuing
crude oil price hike following the 9/11 attacks emerged, this authors Master Thesis investigated
the then recent pretreatment technologies for lignocellulosic material8. Still today, 35 years after
the initial interest none of those technologies have been industrially constructed or are even
commercially ready. There still exist a wide selection of researched and proposed technologies
ranging from physical, chemical, physiochemical, biological to a combination. Some can already
be ruled out while others illustrate a great potential. But perhaps it is wiser to be realistic about
the commercialisation timeframe than maintaining optimism; at least a decade is still needed.
Physical pretreatment technology is the first that can be disregarded for use in a biorefinery;
grinding or milling the feedstock to low enough particle sizes to reach a decent digestibility
requires inordinately high energy costs. Conversely many other technologies have shown sugar
yields above 90% with relatively low energy requirements. Generally for those below 90% there
exists little interest within the biorefinery layout as its basic goal is to maximize product yields;
plus lower yields will directly effect the resulting product process energy needs. Despite the

previous mention of pretreatment technologies types there are three classifications which the
covered options fall under: acidic, alkaline and near neutral. Within each of the classifications are
several leading and state-of-the-art methods which will be described and assessed. As R&D
continues additional efficiency and conversion rates can be expected while herein a synopsis of
the general procedures, working conditions and currently attainable yields will be handled in
regard to the feedstock categories.
Near Neutral
Near neutral is in reference to the pH of the active ingredient, being held close to pH7. To reach
the severities required to pretreat the material high temperatures, high pressures and long
residence times are used. There are two major successful near neutral pretreatment technologies
involving water; liquid hot water and steam. Water will partly solubilize the hemicellulose
releasing acids (like acetic acid and formic acid) which further promotes conversion to monomer
sugars. The conversion rates are however, generally lower than other pretreatment options
necessitating additional hemicellulases in the subsequent enzymatic hydrolysis step.
Liquid Hot Water (LHW)
Technically called hydrothermolysis, but more commonly referred to as liquid hot water (LHW)
treatment this technology is very straight forward involving high temperature water and no
chemicals. Tested water temperatures range from 160 to 230° C with high pressures in the order
of above 30bars necessary to ensure no steam formation. In a plug-flow reactor the biomass
feedstock is subjected to the pressurized hot water stream for a short period of time, typically 2
to 60mins. Tested solids loading are between 10 – 15% meaning there will be a high water
content in the resulting sugar solution which will cause an elevated energy demand in
downstream processing. Within the range of operation temperatures little formation of
degradation products occur as there is no complete hydrolysis to monosaccharides, most stay in
their oligomer form. Temperatures well above 200° C, however, promote a more complete
hydrolysis but cause increased xylose degradation at an expensive associated energy cost. For
certain feedstocks it is possible to achieve a total solubilization of hemicellulose and a partial
hydrolysis of lignin to fully expose the cellulose. The pretreatment works best on agricultural
waste feedstocks, like stover9, below 200 ° C. Processing wastes have not yet been tested using this
technology; so far olive tree pruning residues can give an indication as it contains all the
compositional and partial preprocessing aspects10. Its optimal conditions are indeed at lower
temperatures but the maximum achievable conversion rates are noticeable reduced. Alfalfa can
represent the difficult to process feedstocks as is reflected by the increasingly high temperatures
to achieve moderate conversion rates11. In all investigations it is suggested to include a small
concentration of acid (sulphuric) to increase the sugars yields. An extra 10% is obtainable but
degradation production also increase and in any case adding acid mimics the dilute acid
pretreatment technology (later mentioned). It is common to compare results from LHW to other
technology to validate the research.

Steam
Steam pretreatment is the oldest and still one of the most widely accepted, investigated and to a
limited extent employed technology for processing lignocellulosic feedstocks. It is frequently
associated with sugarcane processing to additionally utilize the bagasse by-product due to an
abundance of available steam. In a pressure reactor high-pressure saturated steam at 6 – 34bar
and 160 - 240 ° C is introduced to the feedstock material with a high solids loading of up to 80%.
The steam largely impregnates and swells the material during a short residence time of 5 – 10
minutes. Upon a quick release of pressure into a flash tank an explosive action is created. It was
previously believed that solely the pressure release mechanism rendered the material more
suitable for hydrolysis. It is now known (as with the LHW) that the water additionally hydrolysed
a part of the hemicellulose into acids. The optimal conditions to yield high cellulose conversion
rates often deviates from those for hemicellulose; a compromise to yield the highest total
converted sugars must be taken. As expected steam pretreatment works best for processing
residues (such as bagasse) although cannot reach values above 90% total yield12. Slightly
unexpected is that higher yields are obtainable from the recalcitrant materials over agricultural
wastes13, 14. High yields, above 90% can be obtained from agricultural wastes but is only possible
under very severe conditions 13. It is hypothesised that the elevated cellulose concentration of the
woody materials positively respond to the swelling despite having a lower hemicellulose content.
Recently studies have began experimenting with the addition of a catalysts before the steam
explosion step to achieve higher overall conversion rates at milder conditions.
Steam with Catalyst
There are two types of catalysts currently tested in combination with steam pretreatment, sulphur
dioxide (SO 2) and sulphuric acid (H2SO 4). In both cases the chemicals are added to the system as
a diluted water soaking step. Low concentrations of between 0.5 – 2.0% are added per feedstock
weight which cannot be recovered and are best neutralized. They act similarly to the dilute acid
process but by being coupled to the steam explosion step greatly reduces the water consumption.
After soaking for several hours the standard steam pretreatment operation is performed. The
catalysts allows for higher conversion rates at lower temperatures and faster residence times, i.e.
milder conditions. As a positive consequence the production of inhibitors are reduced to
practically zero. Like before, the best performances are from the processing residues followed by
woody biomass and trailed by the agricultural wastes14, 15. Minor performance differences is
noticeable between SO2 and H2SO 4, but sulphur dioxide being cheaper, energetically less intense
to produce, and a more workable chemical with no neutralizations precautions is preferred.
Acidic
Acidic pretreatment of lignocellulosic material are very affective at destroying the carbohydrate
matrix shielding the cellulose. At low pH-values and high concentrations the process is fast and
efficient with low energy inputs. Acidity greatly influences the conditional severity promoting a
quick release of sugars including degradation products. The oldest acidic pretreatment technology
of using concentrated sulphuric acid has been prone by hurdles preventing wide spread

implementation. Recovery of the high sugar yields, reduction of degradations products, increased
corrosion protection and recycling of the acid catalysts have caused problems. Few institutes
have remained investigating the option of using concentrated acid and even interest in Arkenol’s
process is a mere footnote. Reducing the concentration while increasing the other process
parameters has proven quite affective, although the presence of degradation products still
remains an issue. Recent work has began in studying the affects of organic acids to reduce the
inhibitor production levels, but come at a product yield reduction cost.
Dilute Acid
Of all the pretreatment technologies dilute sulphuric acid (H2SO 4) technology is by far the closet
to actual commercialisation. Several pilot-scale facilities have been built around the world as
demonstration plants for corn stover and fast-growing tree feedstocks. Biomass feedstock is fed
into a screw conveyor and exposed to low-pressure steam (3 – 5bar) at a temperature of 150 -
160° C. After the short heating and physical treatment the feedstock is fed into a large reactor to
soak in a dilute acid solution for 5 – 60 minutes. High-pressure steam (12 – 14bars) is used to
bring the reactor to temperatures between 140 - 200° C. Low solids loadings of 5% are used.
Studies into increase solid loadings above 10% have proven to drastically reduce the sugars
yields16, 17. Inhibitors including the acid itself must be removed before the enzymatic hydrolysis
step. A slight excess of lime is added to the mixture to precipitate the inhibitors and
simultaneously acts as a neutralization step creating gypsum which is later removed by centrifuge.
Most studies focus on corn stover as a material feedstock because NREL has publically provided
detailed process information and simulations18, 19. These promising results at low economic and
energetic demand have since expanded to other feedstocks20. Best results are found at 160° C, 10
minute residence time, and with an acid concentration of 0.5 vol%. Oddly the recalcitrant materials
perform better than the other feedstock categories reaching nearly 95% sugar yields. This has
sparked the forestry industry to investigate the ethanol option with very promising preliminary
results, sometimes approaching theoretical values. Stover does have a similar performance and
achieves higher sugar yields than the processing residues. Other studies have attempted to
decrease the energy consumption by lowering temperature and increasing residence time and
solids loading through higher concentration; the intentions were good but yielded poor results17.
Maleic Acid
Despite the impressive sugar yields of sulphuric acid treatment it is thought that the inhibitor
production could reach levels that would have a negative overall effect on the process. Following
the same procedure, but in place of sulphuric acid, maleic acid can significantly reduce the
inhibitor production21. Yet to achieve inhibitor levels below influential levels the severity is
reduced by decreasing the tested temperature range from 140 - 170° C. At 150° C no influential
inhibitors are present and the solid loading can be increased to 30% without any detrimental
effect. However, the overall sugar yields are considerably lower than the dilute acid technology.

Alkaline
Alkaline pretreatment works on a different principle than the other categories. By applying and
heating an alkaline solution to the feedstock the pores will swell. Allowed to soak for a sufficient
time or accelerated through pressure changes the swelling will cause an increased internal surface
area and a decrease in the degree of polymerization and crystallinity of the matrix structure. A
rather large fraction of lignin is solubilized along with hemicellulose exposing the cellulose
molecule. Hemicellulose is largely left in tact or recovered as oligomers meaning additional
hemicellulases is required. The quantity of lignin in the feedstock heavily influences the
performance of alkaline pretreatment. Higher lignin levels, as found in the recalcitrant material,
yield low sugar quantities unless the severity of the treatment is increased otherwise. In some
cases of softwoods, which contain large amounts of lignin, no or small effects were observed.
AFEX
Originally dubbed Ammonia Fast EXplosion22, or more recently altered to Ammonia Fibre
EXpansion23 to sound less imposing, it operates analogously to the steam pretreatment process.
The biomass feedstock is placed in a pressurized reactor and ammonia gas or liquid ammonia is
introduced. Over a short residence time of 10 – 60 minutes the temperature is gradually increased
to 80 - 150° C and brought to the corresponding pressures of 5 – 30bars. The material is sent into
a flash tank after a quick release in pressure and while no visible change has occurred the material
has been physically altered. As ammonia is naturally in the gaseous phase at room temperature it
will slowly rise in the flash tank. To accommodate an effective ammonia recycling system it was
initially proposed to use a flash and distillation column achieving 97% recovery. AFEX requires
considerable amounts of ammonia having a 0.5 – 1.5 to dry biomass ratio. Following a detailed
process simulation (as the system is paper-theory) is was concluded that ammonia and its flash
recovery resulted in disproportionally high energy costs24. By focusing on ammonia reduction a
more energy efficiency recovery system was envisioned using a cold water quench25. That system
stipulated ammonia hydroxide be used in place of pure ammonia as the catalyst. Feasibility
testing found positive results at a greatly reduced ammonia consumption; down to a ratio of
0.175:1 ammonia to dry biomass26. AFEX works particularly well on agricultural waste and
processing residues yielding well above 90% free sugars27. Extra xylanase and hemicellulases is
however needed as only a minute portion of the C5 sugars are converted to monosaccharides. A
terrible performance is noticed for the recalcitrant material (i.e. high lignin) feedstocks. To
generalize feedstocks with a lignin content above 15% are not suited for AFEX pretreatment.
ARP
Ammonia Recycle Percolation is another type of process utilizing ammonia. Biomass enters a
packed-bed flow reactor (percolation reactor) and is exposed to aqueous ammonia at elevated
temperatures (150 - 170° C) and pressures (20 – 30bar). A lower solid loading of 20 – 30% over
the AFEX process is present but does compensate by having a lower ammonia ratio demand as
compared to the original AFEX process. Recycling is envisioned by a conventional
evaporation/condensation unit, which does require a considerable amount of steam24, 28.
Nonetheless, ARP is an effective method to attain acceptable levels of digestibility (~90%) but

generally performs slightly worse than the AFEX process accompanied by an increased energy
demand. One particularity of the ARP systems is it ability to have a near complete delignification.
So far only corn stover has been tested (or published) and it is expected that it would follow a
similar trend as AFEX with the exception of possibility having a positive effect on the
recalcitrant materials due to its delignification properties.
Lime
Calcium hydroxide (CaOH) pretreatment is a straight forward, economically cheap, and easy
process to increase the susceptibility of cellulose. In a large continuously stirred batch reactor the
biomass feedstock is soaked in a 5 - 10vol% lime solution at a solid loading level of 10 – 20%. The
mash temperature is raised slightly to 50 - 60° C and allowed to sit for several days. Under these
conditions the severity of the system is rather low meaning one week residence time is a
necessity. As with the other alkaline processes the pretreatment impregnates the biomass swelling
the pores thus increasing the internal surface area without majorly affecting the hemicellulose or
producing inhibitors. A limited number of studies have been conducted using lime. The well
investigated corn stover revealed remarkably high conversion rates when using 7.3 mass% lime in
the magnitude of 90%29. Wheat stover has also been tested using a higher 10 mass% concentration
of lime, but yielded considerably lower sugar levels30. The large difference places doubt on the
reliability of the stover figures. Regardless, of all the alkaline treatments lime does have the best
performance on the recalcitrant materials, but at best cannot surpass 80%31. Furthermore as lime
remains in the liquid phase a neutralization step with an acid is needed after soaking.
Enzymatic hydrolysis
After the above pretreatment processes, the cellulose contained in
the biomass feedstock is converted into fermentable sugars through
enzymatic attack. Enzymes will further hydrolysis and cause a near
complete saccharification of the available complex carbohydrates.
The hydrolysis reaction process for breaking down cellulose into
smaller polysaccharides (cellodextrins) or completely into glucose
units is called cellulolysis. Cellulolysis consists of three distinct steps:
absorption of the cellulase enzymes onto the surface of the cellulose, the biodegradation of
cellulose to fermentable sugars, and finally the desorption of cellulase. Because cellulose
molecules bind strongly to each other, cellulolysis is relatively difficult compared to the break
down of other polysaccharides. Reasonably high enzymatic activities and enzyme concentration
are required to achieve complete cellulolysis. Activity and concentration of cellulase is typically
expressed in filter paper units (FPU) per mass of glucan (all C6-sugars)32. The FPU of the
cellulase formulation mix vary immensely from the manufacturer, supplier, types, formations and
age but can generally be regarded set at 1FPU/g glucan is equal to 0.39mass%. In the laboratory
and experimental phase of the pretreatment technologies an over-dosage of enzymes is applied in
the order of 15 – 25FPU/g; this converts to 6 – 10 mass percentage. Increasing the dosage of
cellulases in the process can, to a certain extent, enhance the yield and rate of cellulolysis.
Cellulose enzymes are however expensive and their indirect energy production cost is

considerable meaning an industrial system would benefit from lower dosages. A dosage of
10FPU/g can be considered representative for industrial maturity, thus around 4.0 mass% of
enzymes is added to the biomass feedstock to promote hydrolysis and saccharification. Most
cellulases is fungi derived with an unspecified formulated mixture of cellobiohydrolases and
endoglucanases supplemented with β -glucosidase (cleaves cellobiose). In a large reactor the
pretreated biomass is mixed with the cellulases and brought to a solid loading of 4 – 6% through
water addition. The solution is adjusted to pH4.0 – 5.0, increased to 45 - 55° C and continuously
mixed for 24 – 168hours. Off-heat from the pretreatment systems is usually more than sufficient
to cover the additional heating requirement of the enzymatic hydrolysis.
3.2.2 Hemicellulose
3.2.2.1 Description
Cellulose and lignin are bonded together in a matrix by the
unsymmetrical form of hemicellulose. It is used as the adhesive by
plants keeping the cell wall structure intact. It is a mixture of several
short, linear and branched heteropolymers (matrix polysaccharides)
formed by the 5-carbon ring sugars xylose and arabinose and (to a
lesser extent) the 6-carbon sugars glucose, mannose and galactose. Formed at random with an
amorphous structure is readily hydrolysed into its sugar monomers, but despite the wide
assortment of components hemicellulose consists mainly of D-pentose sugars with xylose
contributing to the largest amounts of sugar monomers. Meaning that, although a mixture of
components, the general formula of (C5H10O 5)n can be taken.
3.2.2.2 Processing
As already mentioned lignocellulosic material containing cellulose, hemicellulose and lignin share
the same initial pretreatment processing steps. Hemicellulose is broken down into its monomers
(xylose) and oligomers (xylan). Many of the described pretreatment technologies are able to fully
break hemicellulose down to xylose while others continue to degrade it into inhibitors and still
others only provide a partial cleavage. Additional enzymatic hydrolysis is foreseen for those
pretreatment process which have an incomplete hemicellulose depolymerisation (cleavage).
Frequently xylanase or hemicellulases is added to the pretreated biomass feedstock in the same
cellulolysis reactor without any need to alter the conditions. Several cellulase enzyme cocktails
even contain a xylanase activity which can partially lower the addition of separate xylanase
3.2.3 Other Complex Carbohydrates

There are many complex carbohydrates contained lignocellulose feedstocks aside from pure
cellulose (glucose-based) and hemicellulose (xylose-based). Pectin and free sugars contribute to
adding extra trace levels of all the various saccharides. For simplifications 6-carbon based sugars
are allocated to cellulose and 5-sugar based sugars to hemicellulose.

3.2.4 Energy Input
The pretreatment energy input has been broken down into four sections (thermal energy, electric
energy, chemical production energy and enzyme production energy) and individually assessed for
both cellulose (C6-sugars) and hemicellulose (C5-sugars). The reasoning behind assessing C5 and
C6 sugars separately is that each biomass feedstock has a unique compositional ratio which will
lead to different yields and relative process energy costs. And although they have already been
categorized based on their feedstock type the exact compositional ratio will partially influence the
final process energy and exergy result.
Firstly, like with the simple carbohydrates, thermal and electric energy have been kept in their
direct energy form at this stage of assessment. Several of the main pretreatment processes were
simulated using Aspen+ and documented in full detail19, 24. The consumption of low (1.7bar),
medium (4.5bar) and high (13.2bar) pressure steam and net electric demand had been determined
for each process in relation to the total potential ethanol production. The energy and exergy
content of the steam consumption can be calculated by using saturated steam tables (Chapter 2)
and relates to the direct thermal energy/exergy demand. By carefully examining the heat (steam)
and work (electric) streams in the Aspen+ models in relation to the overall sugar yields, inhibitor
production and ethanol production the portion used in the pretreatment stage can be determined.
The values have been set for the standard operation conditions and conversion yield values
(processing residues; corn stover). Listed in the tables (4-6) are all the process conditions and
sugar conversion rates assigned to the pretreatment technologies for three various biomass
feedstocks categories. The listed temperature, pressure, residence time and solids loading directly
influence the process energy streams in the system. They mostly vary for the feedstock materials,
which will affect the steam and electric demand of the process. As the basic procedures remain
consistent for all feedstocks within the pretreatment technology options, it is those conditions
coupled with the conversion efficiency that alter the process energy demand.
Not all the covered processes have been accompanied with a detailed Aspen+ simulation process
file. In these situations new basic simulations must be complied using the known operation
conditions and sugar conversion yields. These are brought in relation to the well documented and
similar functioning procedures and expressed in the corresponding terms. For example, the
consumption level of high steam versus medium steam is dependent on the reactor operating
temperature of the pretreatment. Similar process heat integration options were also taken into
account. In the calculations thermal and electric process energy demand terms are listed as per
ton initial dry feedstock. The sugar conversion rates will thus directly stipulate the associated
product energy requirements; this is true for all systems.
In the tables: AFEX 1= standard flash recycling, AFEX 2 = proposed quench recycling, Lime 1 =
standard procedure, Lime 2 = WUR (Maas) procedure, Dilute 1 = standard sulphuric acid with
low solid loading, Dilute 2 = high solids, Steam 1 = H2SO 4 catalysts, Steam 2 = SO2

Table 4 Pretreatment Optimal Conditions and Conversion Rates – Agricultural Waste
Residen ce Solids Glucose Xylose

Type Temperature Pressure
Time Loading Yield Yield
Short name °C bar min % % %
AFEX 1 90 30 5 63 96.0 77.7
AFEX 2 100 20 5 55.6 94.1 89.1
ARP 170 23 10 23 88.5 76.4
Lime 1 55 1 40320 17.5 93.2 79.4
Lime 2 50 1 40320 12.4 56.0 67.0
Maleic 150 5 30 30 76.0 90.0
Dilute 1 160 12 20 5 91.6 91.2
Dilute 2 120 12 90 10 54.6 100.0
Steam 210 20 5 11 95.9 93.8
Steam 1 190 20 5 11 83.4 80.6
Steam 2 190 20 5 35 90.0 84.0
LHW 195 30 15 16 85.2 81.7
Table 5 Pretreatment Optimal Conditions and Conversion Rates – Processing Residues

AFEX 1 80 30 5 60 98.0 93.0
AFEX 2 100 20 5 55.6 91.3 86.3
ARP 170 23 10 23 88.5 76.4
Lime 1 55 1 40320 17.5 85.9 80.2
Lime 2 50 1 40320 12.4 51.0 62.0
Maleic 150 5 30 30 74.4 83.8
Dilute 1 160 12 20 5 90.0 85.0
Dilute 2 120 12 90 10 50.6 95.0
Steam 190 20 5 80 80.6 72.6
Steam 1 190 20 5 11 88.4 85.6
Steam 2 190 20 5 35 95.0 89.0
LHW 170 30 60 20 76.0 63.0
Table 6 Pretreatment Optimal Conditions and Conversion Rates – Recalcitrant Material

AFEX 1 90 30 5 63 10.0 5.0
AFEX 2 100 20 5 55.6 10.0 5.0
ARP 170 23 10 23 88.5 76.4
Lime 1 55 1 40320 17.5 80.9 75.2
Lime 2 50 1 40320 12.4 51.0 62.0
Maleic 150 5 30 30 78.4 93.8
Dilute 1 160 12 20 5 94.0 95.0
Dilute 2 120 12 90 10 64.6 100.0
Steam 200 20 14 40 88.0 88.4
Steam 1 190 20 5 11 88.4 85.6
Steam 2 195 20 8 40 87.0 68.0
LHW 220 30 2 15 78.3 78.3

Secondly, the chemicals involved in the various pretreatment technologies are related to their
cumulative fossil fuel energy/exergy demand. To determine the associated energy cost the level
of added chemicals and the recovery levels must be documented. Several of the process
technologies with 0% recovery of the active chemical will require an accompanying additional
neutralization chemical in the order of an equal molar ratio. Listed in table 7 are all the basic
figures needed to calculated the chemical energy/exergy requirements and because the
concentrations are not varied for the biomass feedstocks types it is representative for all. In this
regard though, the associated chemical costs will be related to the sugar conversion yields as was
done with the thermal and electric energy demand. So, although the requirements are equal for all
feedstocks the relative chemical demand varies for the monosaccharide products.
Table 7 Pretreatment Chemical Requirements – All Feedstocks
Active Neutralizing
Type Con centration Reco very CED CExD CED CExD
Chemical Chemical
Short name Formula ton/ton feedstock % GJ/ton Formula GJ/ton
AFEX 1 NH3 0.80 97.0 28.40 29.96 - - -
AFEX 2 NH3 0.167 96.0 28.40 29.96 - - -
ARP NH3 0.47 95.0 28.40 29.96 - - -
Lime 1 Ca(OH)2 0.073 0 7.04 7.39 H2SO4 1.44 3.28
Lime 2 Ca(OH)2 0.10 0 7.04 7.39 H2SO4 1.44 3.28
Maleic C4H4O4 0.047 80.0 26.60 27.93 Ca(OH)2 7.04 7.39
Dilute 1 H2SO4 0.093 0 1.44 3.28 Ca(OH)2 7.04 7.39
Dilute 2 H2SO4 0.45 0 1.44 3.28 Ca(OH)2 7.04 7.39
Steam - - - - - - - -
Steam 1 H2SO4 0.055 0 1.44 3.28 Ca(OH)2 7.04 7.39
Steam 2 SO2 0.056 0 13.82 18.16 - - -
LHW - - - - - - - -
Thirdly, the cellulase and hemicellulases enzyme requirements are also related to their cumulative
fossil fuel energy/exergy demand. These particular grades of fungi-based enzymes are
extraordinarily energy intensive to produce. Following the same enzyme producer report3, they
require upwards of 230GJ/ton formulated product. During the early financial investigations
surrounding the lignocellulosic material processing it was acknowledged that the cellulase placed
a major strain on the economical feasibility. These high economic costs can be paralleled with
high energetic production costs. Some years back it was resolved to significantly lower the
associated enzymatic hydrolysis step by 10-fold. This initial 10-fold goal has been reached and
new goals have commenced to extend it to a 20 to 30-fold reduction (Genencor, Novozymes).
Cost reduction was reached by improvements on three different aspects in the chain; fungi strain
engineering, more efficient production methods and an increased activity. The increased activity
has already been incorporated by the proposed industrial loading rate of 10FPU/g as opposed to
the laboratory 15FPU/g glucan. To include the other expected improvements for industrial
applications the CED/CExD for the enzymes are lowered 10-fold to 23.5GJ/ton energy and
28.4GJ/ton exergy. The ammonia based pretreatment technologies require an extra 10FPU/g
hemicellulases, the other alkaline processes 5FPU/g as well as the LHW process. Combined they
form the indirect enzyme energy costs, still a considerable portion of the total.

Finally, the four sections of the pretreatment energy input can be combined. Resulting values are
expressed per ton cellulose and ton hemicellulose as well as the total converted sugars. To
determine the associated process energy input for the two products the conversion ratio and
feedstock composition ratios were used. As can be seen in the following graphs and tables,
cellulose has for all technologies a higher associated process energy input than hemicellulose; due
to a typically higher compositional ratio and conversion rate. The following figures illustrate the
proportion of the four direct and indirect energy costs for each feedstock category; C: Cellulose
or C6-sugars, H: Hemicellulose or C5-sugars. It is noticeable that some technologies may
perform well in having low direct thermal and electric consumption but due to their chemical use
(as a measure of severity) results in a higher overall energy input. The tables below lists the total
process energy and exergy input for cellulose, hemicellulose and the sugars combined. The
pretreatment technology with the lowest overall energy input will be selected for that particular
biomass feedstock type for use in the biorefinery system. Its conversion rates, conditions, and
energy/exergy input will form the basis of all subsequent processing within the biorefinery.
Rather surprisingly the selection is different for each biomass feedstock category.

Figure 1 Pretreatment Energy Costs – Agricultural Waste
Pret reat ment Energy Costs

Agricultural Waste
7.0
En zyme Indire ct Energy
C hem ical Ind irect Energy
Electric Ene rgy
6.0 Thermal En ergy
5.0
GJ/ton product
4.0
3.0
2.0
1.0
0.0
C H C H C H C H C H C H C H C H C H C H C H C H
AFEX 1 AFEX 2 ARP Lime 1 Lime 2 Maleic Dilute 1 Dilute 2 Steam Steam 1 Steam 2 LHW
Table 8 Pretreatment Energy/Exergy Costs – Agricultural Waste
Type Total Energy (GJ/ton product) Total Exergy (GJ/ton product)

Short name Cellulose Hemicellulose All Sugars Cellulose Hemicellulose All Sugars
AFEX 1 3.42 2.23 5.65 2.24 1.71 3.95
AFEX 2 1.82 1.48 3.65 1.55 1.39 2.94
ARP 3.65 2.45 6.10 2.23 1.74 3.97
Lime 1 3.53 1.89 5.42 2.19 1.15 3.34
Lime 2 4.62 3.32 7.94 2.00 1.24 3.24
Maleic 2.32 1.06 3.38 2.01 0.67 2.68
Dilute 1 2.33 0.90 3.23 2.42 0.83 3.25
Dilute 2 4.14 3.79 7.93 4.36 3.82 8.18
Steam 2.31 0.87 3.17 1.52 0.25 1.77
Steam 1 3.22 1.42 4.64 2.11 0.61 2.72
Steam 2 3.25 1.39 4.64 2.43 0.78 3.22
LHW 3.59 2.11 5.70 1.62 0.87 2.48
The lowest energetic cost for agricultural wastes is steam, at 3.17GJ/ton sugar products.
Agricultural waste biomass feedstocks = Steam pretreatment

Figure 2 Pretreatment Energy Costs – Process Residues

Pro ce ssing R esid ues
6.0
Electric Ene rgy
Thermal En ergy
5.0
4.0
GJ/ton product
3.0
2.0
1.0
0.0
Table 9 Pretreatment Energy/Exergy Costs – Process Residues

AFEX 1 3.36 2.49 5.85 2.58 2.06 4.64
AFEX 2 1.89 1.54 3.43 1.64 1.46 3.10
ARP 3.84 2.63 6.47 2.65 2.02 4.66
Lime 1 3.72 2.22 5.94 2.53 1.45 3.99
Lime 2 4.95 3.76 8.71 2.72 1.87 4.58
Maleic 2.47 1.17 3.64 2.30 0.89 3.19
Dilute 1 2.79 1.19 3.98 2.99 1.18 4.17
Dilute 2 5.40 5.67 11.07 6.01 6.19 12.20
Steam 2.80 1.14 3.94 1.62 0.30 1.92
Steam 1 3.23 1.50 4.73 2.53 0.91 3.44
Steam 2 3.42 1.58 5.00 3.01 1.19 4.20
LHW 4.11 2.25 6.36 1.83 0.96 2.79
The lowest energetic cost for agricultural wastes is AFEX 2, at 3.43GJ/ton sugar products.
Process residue biomass feedstocks = AFEX (Quench) pretreatment

Figure 3 Pretreatment Energy Costs – Recalcitrant Material

Recalcitran t Mate rial
7.0
Electric Ene rgy
6.0 Thermal En ergy
5.0
GJ/ton product
4.0
3.0
2.0
1.0
0.0
Table 10 Pretreatment Energy/Exergy Costs – Recalcitrant Material

AFEX 1 43.73 10.11 53.84 12.77 3.63 16.39
AFEX 2 30.02 7.17 37.19 10.13 3.06 13.20
ARP 4.25 2.16 6.42 2.68 1.70 4.38
Lime 1 4.43 1.86 6.28 2.57 1.14 3.71
Lime 2 6.05 3.13 9.18 2.91 1.49 4.40
Maleic 2.66 0.88 3.54 2.41 0.65 3.06
Dilute 1 2.75 0.78 3.53 2.87 0.75 3.63
Dilute 2 6.07 3.41 9.48 6.67 3.67 10.34
Steam 3.81 0.76 4.57 1.89 0.20 2.09
Steam 1 3.61 1.11 4.72 2.54 0.58 3.12
Steam 2 4.22 1.10 5.32 3.00 0.63 3.63
LHW 4.59 2.03 6.62 1.95 0.92 2.86
The lowest energetic cost for recalcitrant material is dilute acid 1, at 3.53GJ/ton sugar products.
Recalcitrant material biomass feedstocks = Dilute sulphuric acid pretreatment

3.3 Glucose Chemistry
Once a solution of sugar liquor has been created the proceeding processing steps for the
conversion into fermentable products (like ethanol) is universal. Sugar liquors from both the
simple and complex carbohydrates could in theory be joined at this stage. Depending on the
biomass source these sugar liquors will either contain C-6 sugars (glucose) or C-5 sugars (xylose).
And the only real difference between these sources is the microorganisms used for fermentation
and the maximum conversion yield. There are a few modern exceptions to this general rule which
are increasing the overall conversion rates and lowering the energy intensity. They will be
discussed after the basic (or standard) processing steps have been described. Glucose chemistry is
essentially a two-step process; fermentation followed by a purification step. The purification step
is typically a thermal liquid-liquid separation unit operation, e.g. a distillation unit. These are
highly energy intensive and research efforts are underway to avoid their use.
Many products deriving from sugars are proposed within the biobased
economy. In a recent EC report 21 different bio-based products, practically
all deriving from glucose chemistry, were investigated in detail33. The entire
basis of investigation was placed on the assessment of only three biomass
sources; dextrose from corn starch, sucrose from sugar cane, and C5/C6
sugars from corn stover. Producing these fermentable sugars has been in part practiced for
centuries in the manufacturing of food-grade syrups with product quantity not energy efficiency
controlling the production method. The most common corn syrup (glucose syrup) is derived
from the wet milling process. As described in Section 3.1.1.2 wet milling not the most energy
efficient method and has no place in the non-food biomass applications. In the BREW project
the non-renewable process energy for the three fermentable sugar sources are based on those
traditional methods and documented as 6.2 – 10.3GJ/ton for dextrose, 1.4 – 1.7GJ/ton sucrose
and 4.9 – 7.6GJ/ton C5/C6 sugars. The documented resulting dry matter content also varies
which makes the evaporation and purification steps difficult to assess. Regardless the sugar liquor
stream does not need to be concentrated for use in fermentation systems, which will reduce
process energy demand. It is however good to note that following this government document
10.3GJ/ton glucose is considered standard for the biochemical sector (from corn). Industrial
improvements and experience over several decades have made ethanol the benchmark for
anaerobic fermentation and will be the only product investigated derived from carbohydrates.
3.3.1 Ethanol production
3.3.1.1 Description
Ethanol is the single most important bio-based chemical product in
the biomass field and forms the basis of any biorefinery concept. It
goes by many names from its scientific term ethyl alcohol to the
common grain ethanol and simply alcohol. At purities above 99.9%,
which is foreseen for downstream utilization in the biorefinery, it is
called absolute ethanol or anhydrous ethanol. Industrial production of

anhydrous ethanol is by far not a new and revolutionary process. Over the last three decades the
ethanol industry has been shaped into a high-tech production process and because industrial
grade ethanol will not follow the time honoured potable alcohol systems it can achieve vast
energy consumption reductions. Industrial ethanol has a few traditional applications in its virgin
state although it would not at all be presumptuous to state that its use as a transportation fuel
replacement option is the most commonly known. Bioethanol use in the transport sector is either
found in its pure form or as a blend with gasoline. The advances made in this sector will be listed
and incorporated in the biorefinery layout. The current standard industrial process layout will be
covered first followed by the recent developments and proposed improvements. Despite the
growing market of bioethanol, within the biorefinery system for chemical replacement ethanol is
regarded as a feedstock for the production of ethylene. In this respect the effective dehydration
step all determining.
3.3.1.2 Standard Processing

Fermentation
In a reactor the sugar liquor is exposed to fermenting enzymes, most commonly contained within
the microorganism yeast. Minute quantities of oxygen will promote the production of carboxylic
acids (like vinegar) and other unwanted by-products which one often associates with cheap
French wine. Anaerobic conditions are imperative and must be upheld to maximize microbial
fermentation yields. Bakers yeast, Saccharomyces cerevisiae, can easily convert the C6-sugars into
ethanol and is employed in nearly all bioethanol facilities worldwide. C5-sugars, however, cannot
be converted very well by standard strains of yeast. As the biorefinery system will incorporate all
sources of carbohydrates, including hemicellulose, standard strains are not acceptable. Modified
yeast strains and other bacterial strains exists that can convert xylose into ethanol, but generally
require a separate fermentation tank as the operating conditions are different; cofermentation
would be preferred. Already in 1994, work began on genetically engineering the Zymomonas mobilis
bacteria organism34. It can effectively ferment both C6 and C5-sugars in one reactor under the
same operation conditions and compared to standard yeast also boosts a 2 – 4% extra conversion
yield. Z. Mobilis is market ready and has an overall sugar conversion rate of 92 – 94%. The
following reactions occur in the fermentation reactor:
Glucose 2Ethanol + 2Carbon Dioxide (96% conversion)
C6H12O6 2C2H5OH + 2CO2
1⋅180.16g/mol (180.16g/mol) 2⋅46.07g/mol (92.14g/mol) + 2⋅44.01g/mol (88.02g/mol)
Stoichiometric Ratio: 92.14 ÷ 180.16 = 0.512g/g
3Xylose 5Ethanol + 5Carbon Dioxide (90% conversion)
3C5H10O 5 5C2H5 OH + 5CO2
3⋅150.13g/mol (450.39g/mol) 2⋅46.07g/mol (230.35g/mol) + 5⋅44.01g/mol (220.05g/mol)
Stoichiometric Ratio: 230.35 ÷ 450.39 = 0.512g/g
The conversion of C5-sugars is slightly lower than C6-sugars but does have the same mass
conversion loss of 0.488g/g through the formation of carbon dioxide. The formed carbon
dioxide is vented and scrubbed to recover any trace ethanol that was diffused into the vapour

phase. In older (existing) open-vat systems this portion is lost. Conventional fermentations are a
batch process reaching completion when the ethanol concentration has achieved 7 – 9vol%.
Rather recent advancements in fermentation technology have allowed the critical concentrations
to raise to 12 – 13 vol%. This significantly reduces the downstream separation energy intensity. It is
also an exothermic reaction requiring cooling to maintain operation temperatures between 25 -
37° C with 38° C being the upper limit; temperatures above 40° C will kill the bacteria. But, before
the microorganisms are even added a sterilization shock is needed to properly prepare the
fermentation medium (broth) to ensure no inhibiting infections and a smooth fermentation.
Nutrients containing nitrogen, phosphorous, potassium and other trace minerals are supplied to
the broth ensuring an optimal bacterial growth. DAP (diammonium phosphate) is employed
industrially and covers the brunt of the nutrient requirements. The final ethanol containing
solution existing the fermentor is called beer.
Separation
During the early industrial applications of ethanol production its separation from the beer stream
was straight forward involving one large standard distillation column. Over the last two decades
thermally integrated distillation technology which encompass separate stripping and rectification
operation units have greatly reduced the energy intensity. Now producing a pure stream of
ethanol from the beer stream involves a multitude of separation steps.
First, the beer is sent to a so-called beer distillation column (type of stripper)
to separate the solid residue partials including microbes and a great deal
of the water. In some layouts the bottoms are partly circulated to the
fermentation reactor or hydrolysis step, but their fate within the
biorefinery will be handled in later sections. This initial distillation step
increases the ethanol concentration from 12.5vol% to 37 – 40 wt%. In the
second distillation column, known as the rectifying unit, the ethanol/water
mixture is brought to the azeotropic point. Due to the azeotropic point this ethanol mixture will
always contain a small percentage of water between 4 – 9 wt%. Third, a dehydration unit is needed to
obtain anhydrous (or water-free) ethanol. Traditionally benzene was the chemical of choice to
lower the azeotropic point from 78.2° C to the 64.9° C needed to make 99.5vol% pure ethanol.
Regulation in many countries has banned the use of benzene in place for cyclohexane.
Nonetheless this azeotropic distillation step is energy and chemically intensive and cannot be
considered standard. Vapour phase pressure swing regeneration systems, or marketed as
molecular sieves, dehydrate the ethanol product to 99.5% through adsorbing water into a fixed
bed of zeolite beads. Desorption is performed at elevated temperatures and under vacuum to
force the water molecules out of the zeolite structural matrix, regenerating it. Praj systems state
energy savings of up to 50% and their EcoMol products dominate the ethanol dehydration
market. All newly constructed and planned bioethanol facilities (in America) include molecular
sieve dehydration units and can be considered the current standard practice. The whole
separation system encounters an ethanol loss of 0.4 – 0.7wt%.

3.3.1.3 Recent Processing Improvements
Fermentation
As previously described hydrolysis requires 24 – 168hours (with 96h being normal) residence
time to achieve a complete conversion to the monosaccharides. The accumulation of these sugars
naturally inhibit the enzyme performance which is overcome by lower solid loadings and longer
residence time. Simultaneous saccharification and fermentation (SSF) offers the potential for reduced
fermentation times, decreased capital costs and a more uniform operation temperature to
decrease process energy demands. It works on the concept of continuously removing the formed
sugars by immediately fermenting them in the same reactor, thus keeping the concentration low
and allowing the enzymes to perform more effectively. The idea was first conceptualized in the
late 1970’s and has been seriously considered for more than two decades and is still being
researched upon to fix the optimum, especially in relation to energy consumption2, 35, 36. The
residence time can be lowered to 72hours but presents other compromises. SSF (as is) is not a
suitable option for converting the simple carbohydrates as the optimal operation temperatures
between the enzymatic hydrolysis (65 – 90° C) and fermentation (37° C) differ too much.
Complex carbohydrate enzymatic hydrolysis, on the other hand, operate at lower temperatures
(50° C) and present only minor operational compromises. Furthermore, the resulting ethanol
concentration is actually very low rarely exceeding 4 wt% (5.1 vol%), placing a particularly high
energetic burden on the standard separation techniques. There are two recent developments that
when integrated can remove the temperature difference issue and turn the lower solids loading
compromise into an energy reduction opportunity.
(1) Genetic modified enzymes and microorganisms have the potential to solve many process
engineering problems through specifically tailoring the desired traits. Thermtolerant yeast and
bacteria strains are able to survive at considerably higher temperatures that would otherwise kill
microorganisms. One such organism is Clostridium thermohydrosulfuricum which can ferment both
C5 and C6-sugars at temperatures of around 60 ° C. Another modified organism which also uses a
wide range of sugars, Bacillus stearothermophilus, can handle temperatures in excess of 75°C. Thus, it
is can be expected that continued progress in GMO strains creation will allow fermentations to
be held at optimal hydrolization operating temperatures. Towards the 65° C range the SSF system
could convert all carbohydrate sources as effectively as the current best organisms. Plus, at these
temperatures cooling requirements would be reduced, even creating an extra low heat integration
option to mitigate a portion of the steam demand.
(2) At about 14wt% ethanol fermentation will stop because beyond those concentrations it is toxic
to the microorganisms. Actively removing ethanol while it is being produced can maintain safe
and optimum concentration levels in the fermentation broth. Several conceptual process layouts
have been recently conceived and investigated to achieve a steady state operation. Sending the
fermentation mash into a column with carbon dioxide as a stripping agent has been proposed37.
It was developed for corn starch achieving a continuous ethanol concentration of 5 – 8 wt% in the

broth and 25 – 27 wt% concentration after the stripping. Removing the carbon dioxide from the
stripped vapour is performed by compression or condensation via cryogenics. Both recycling
options utilize a rather large quantity of electricity in the order of 4.1 – 6.5GJ/ton EtOH (internal
report calculations). The energy intensity also increases with lower fermentable material
concentration which would be the case for complex carbohydrate streams. And despite the
distillation energy savings from an elevated concentration starting point, this layout would be
more energy intense than the standard system. Stripping, however, is still a promising option.
Several bioethanol plants have been constructed in the last decades based on Alfa Laval’s Biostil
process. It was initially plagued by operational and process flow hurdles with design concessions
making it a semi-continuous processes. Many of the problems have since been solved and a new
fully continuous system is available, marketed as the Biostil 2000 process (high performance
ethanol production plant)38. It works by using a portion of the hot ethanol/water vapour mixture
to strip ethanol from the fermentation mash. In the mash stripper 90% of the ethanol contained
in the fermentation mash is removed resulting in a 40 wt% ethanol/water stream. And an ethanol
concentration of 6.5 wt% is upheld in the broth ensuring optimal concentration. Increasing the
SSF system’s resulting ethanol concentration from 4.0 wt% to 6.5 wt% should be feasible to applied
in this concept. Microorganism propagation levels are also reduced due to recycling and longer
vitality brought forth by the system dynamics.
Separation
Pervaporation has been a topic of much discussion and research for many decades. A large array
membrane materials are being developed and tested from complex composites to straight
silicalite polycrystallines to simple polymers. They all work by the same principle under similar
(low temperature) conditions and should be ready for large-scale industrial applications shortly.
Membrane production is slowly approaching economic feasibility and is considered a realistic
possibility to replace the distillation or even the rectifying unit. Several studies have begun
investigating the option of creating a continuous fermentation with pervaporation. The
fermentation mash is passed over a non-porous membrane with a hydrophobic coating where
ethanol travels through the membrane by being brought into the vapour phase. A vacuum pump
on the permeate side of the unit provides the necessary pressure drop (5 – 10bar) to convert the
ethanol (and a large portion of water) from the liquid stream to vapour phase. A cooler
condenses the 20 – 23wt% rich ethanol/water stream back into the liquid phase. Membrane
fouling (clogging) problems and low product through-puts have not yet been solved. The 40wt%
ethanol/water stream coming from the continuous Biostil-SSF system could benefit from using
pervaporation technology without encountering fouling constraints. As intriguing as this may
appear, pervaporation would not be suitable within the system because a portion of the rectifier’s
hot top stream is used to strip the ethanol from the fermentation broth. To substitute the
rectifier the product stream would have to the heated to specification, effectively removing the
energy reduction benefit. Nonetheless, integrating the rectifier product stream in the mash
distillation column does present minor energy reduction over the standard layout. Again as
ethanol stream leaving the rectifier unit is not 100% pure a dehydration step like in the standard

layout is needed. Molecular sieves are effective and efficient but limited to 99.5% purity, whereas
modern nanoporous dehydration membranes can achieve 99.7% at even slightly reduced energy
costs39. Acting as a filter pore sizes of 0.4nm are only permeable to the smaller water molecules
thus separating the larger ethanol molecules. A pressure gradient of 1.5bar is introduce by
pressurizing the feed flow and creating a vacuum of 0.007bar on the permeate side.

Both the “standard” and “select recent” improvement process energy and exergy input for the
glucose to ethanol production route have been handled. Table 11 lists the resulting direct and
indirect energy as well as the relevant conditions. A fermentation unit requires modest agitation
and aeration electric energy based on the medium volume ranging from 3.1 up to 23kWh/m³;
realistic best practices were chosen33. As the broth concentration is lower for the select recent
process and is recycled, its electric consumption is noticeable higher. Microbial indirect
production energy costs are based on the Simapro LCA database for yeast at 8.4MJ/kg. Recycling
is taking into consideration for the select recent process. The nutrient DAP has an energy/exergy
production demand of 3.73/4.63GJ/ton (based on Chapter 5) with 0.044ton/ton ethanol
requires for both system layouts. Distillation is the most energy intensive step in ethanol
production. Old systems (starting at 7 – 8vol%) required 6.3 – 7.6GJ/ton EtOH. Increasing the
broth concentration to 12.5vol% reduced it to 5.4GJ/ton and combining the beer column and
rectifier unit reduce it further to 3.93GJ/ton40. Using a portion of the rectifiers top product as a
stripping agent reduces the thermal energy consumption even lower to 2.80GJ/ton. Azeotropic
dehydration costs between 2.6 – 3.3GJ/ton while modern molecular sieves are only 0.67GJ/ton.
All separation operation require moderate level of circulation electricity, but the nanoporous
dehydration being based on pressure gradients has a higher electric demand explaining the
difference in thermal and electric for the select recent process.
Table 11 Glucose Processing Energy/Exergy Input – Standard and Select Process
Catego ry Unit Standard Pro cess Select Recent Pro cess

Fermentation
Conditions
Broth Con centration wt % EtOH 12.5 6.5
Temperature °C 37 65
Direct Energy (Exergy)
Electric GJ/ton EtOH 0.136 0.194
Thermal GJ/ton EtOH 0.588 (0.058) 0.362 (0.036)
Indirect Energy (Exergy)
Microbial GJ/ton EtOH 0.009 0.005
Ch emicals GJ/ton EtOH 0.164 (0.204) 0.164 (0.204)
Separation
Conditions
Input Concentration wt % EtOH 12.5 40
Output Con centration wt % EtOH 99.5 99.7
Electric GJ/ton EtOH 0.321 1.462
Thermal GJ/ton EtOH 4.603 (0.932) 2.800 (0.097)
Conversion rates for both system layout is 96.0% C6 and 90.0% C5

3.4 Overall Ethanol Production Cost
The overall ethanol production cost is merely a summation of the glucose/xylose preparation and
the ethanol fermentation and separation process energy input. It will be highly crop dependent as
the final values are based on the conversion rates and individual proportion of the simple and
complex carbohydrates. The general biomass feedstocks as covered in the previous sections will
be used as an indication. So, in the following sub-sections the direct process energy (thermal and
electricity) and indirect process energy (chemicals, microorganisms, etc.) are presented for the 1st
generation and 2 nd generation bioethanol technologies. A distinction has been made between the
standard ethanol and the selection of recent improvement process layouts.
3.4.1 1 st Generation Bioethanol

Figure 4 1 st Generation Bioethanol – Overall Process Energy Input
1st Generation Ethanol Production
12.5
Indirect Energy
Electric Energy
Thermal Energy
10.0
7.5
GJ/ton Ethanol
5.0
2.5
0.0
Standard Recent Std. Sel. Std. Sel. Std. Sel. Std. Sel.
Sel ect
Cereals Cereal (Cron) Tuberous Stem-based Bulb-based
Table 12 1 st Generation Bioethanol Production Costs
Feedstock Type Cereals Cereals (corn) Tuberous Stem-based Bulb-based

Overall Conversion
0.473 0.480 0.488 0.466 0.467
(ton EtOH/ton carbohydrates)
Total Energy (GJ/ton) 6.86 7.82 10.76 5.96 7.04
Total Exergy (GJ/ton) 2.81 2.97 3.51 2.97 2.46
Only the recently select improvement ethanol process route, not fully cumulative
As expected the stem-based crops, like sugar cane, have the lowest process energy intensity for
the production of the biofuel. However in terms of exergy it is the bulb-based crops, like sugar

beet, which require the least amount of process exergy. The stark difference between energy and
exergy illustrate the inefficiencies of steam utilization for mild temperature treatments.
3.4.2 2 nd Generation Bioethanol

General indication, but not specific as in Chapter 8 the biorefinery will be based per crop. Here
the three types are developed for both the standard and select.
2nd Generation Ethanol Production

7.5
Indirect Energy
Electric Energy
Thermal Energy
5.0
GJ/ton Ethanol
2.5
0.0
C H C H C H C H C H C H
Standard Recent Select Standard Recent Select Standard Recent Select
Agricultural Wastes Processing Residues Recalcitrant Material
Table 13 2 nd Generation Bioethanol Production Costs
Feedstock Type Agricultural W astes Pro cessing Residues Recalcitrant Material

C6 Conversion 0.471 0.449 0.462
C5 Conversion 0.432 0.398 0.438
Overall Conversion
0.456 0.428 0.438
(ton EtOH/ton carbohydrates)
Total Energy (GJ/ton) 8.75 9.07 8.27
Total Exergy (GJ/ton) 4.17 5.65 4.45
Only the recently select improvement ethanol process route, not fully cumulative
Conversion of lignocellulosic feedstocks are in the same broad range (5.96 – 10.76GJ/ton) as the
1 st generation route, but all have a higher process energy cost than the best biomass feedstock
option. Rather surprisingly the best performance of the 2 nd generation feedstock types is for the
recalcitrant materials, like the willow tree. Like the 1 st generation technologies, there is large room
for energy efficiency improvements as indicated by the difference in energy and exergy, however
as there is a higher reliance on electricity and indirect inputs it is at a lower magnitude.

3.4.3 Combined generation
At this stage it is not possible to combine the 1st and 2 nd generation technology for display
purposes as the results are heavily feedstock dependent. Nearly all biomass feedstocks contain
portions of simple carbohydrates and complex carbohydrates, where several other will first be
processed for their high fatty acid content. In a biorefinery they will be combined into one
system and will be presented in Chapter 8. Besides, ethanol is destined for ethylene production
within the realms of the biorefinery and the above results are more for interest than crucial for
the calculation of the process energy inputs of the biorefinery.
3.4.4 Ethylene Chemistry
3.4.4.1 Description
Originally called olefiant gas its official term is ethene as stipulated by the
1993 IUPAC nomenclature guidelines, but is still most commonly
referred to as ethylene. It is the simplest alkene chemical with the
molecular formula C2H4 and is present in the gaseous phase in its
virgin form at atmospheric conditions. Ethylene is the single most
important primary petrochemical with an annual global production
exceeding 75Mton. It is used in the synthesis of many other chemicals, but especially used as the
base building block for the production of plastics. Polyethylene (PE), Polyethylene Terephthalate
(PET), Polyvinyl Chloride (PVC), and Polystyrene (PS) comprise of at least half the total global
production of plastics and all four derive from ethylene. The conventional production method is
through the thermo-cracking of the naphtha feedstock. Industrial dehydration of ethanol has
been around for more then a century but has only recently, through improved catalysis, achieved
conversions rates that can compete energetically to the highly efficient cracking route.
3.4.4.2 Processing
The dehydration of ethanol into ethylene is an easy and straight forward reaction involving only
moderate energy demands. The basic technological process is well-known and was first proposed
and employed on a limited degree during the early phases of the 1975 Brazilian PróAlcool
program. Typically ethylene production was restrained to solitary ethanol producers and minor
players in the chemical industry but due to the low conversion yields was eventually phased out.
Currently interest in producing ethylene from bioethanol has since re-emerged in Brazil over the
last few years. Braskem and Dow have both announced the construction of full-scale ethylene
factories based on sugar cane ethanol. Anhydrous ethanol is heated to the vapour phase and
passed over a catalyst-lined dehydration column to remove the water The process is a two-step
reaction; firstly, ethylene ion formation by adsorbing the water (H-O-H) side branch of the
ethanol molecule and secondly, proton removal by splitting the hydrogen cation off creating the
double bonded carbon ethylene molecule. The entire reaction occurs at elevated temperatures
(180 - 500° C) and atmospheric pressures with no presence of water vapour. The intermediate
ethylene cation product is highly reactive and will immediately reform into ethanol under the

presence of water molecules. This is why it is imperative that the anhydrous ethanol product
stream be of a maximum purity, for any trace water will lower the ethylene yield. It is also the
function of the catalysts to adsorb and contain the water molecules during the entire process.
Scores of different catalysts have been investigated to maximize the ethanol dehydration
conversion rates. Metal oxide catalysts (Fe2O 3 and Mn2O 3) along with various calcined physical
mixtures of ferric and manganese oxide with alumina and silica gel have been tested41. The
selectivity of the catalysts showed a strong correlation to temperature dependence, particularly at
high temperatures approaching 500° C. Regardless, the best metal oxide catalyst could not surpass
80% ethanol to ethylene conversion rate and at those temperatures would entail high associated
energy demands. These systems represents the failed earlier attempts at industrial production.
More recently investigation has shifted to solid acid catalysts such as pure silica-alumina and
other zeolite configurations at a lower temperature range (180 - 300° C)42. A catalyst mixture of
90%-SiO 2 and 10%-Al2O 3 at a high activity of 25.1g catalyst⋅minute per nmol ethanol can
dehydrate 99.9% of the ethanol at 180° C. These adsorbing zeolites help prevent the reformation
of ethanol and while it is possible to obtain a conversion rate of almost 100% an ethylene carbon
selectivity of more than 99wt% is difficult. Under the best patented solid acid catalysts process a
loss of 1.5% is present, resulting in a product yield of 98.5%43. Steam is foreseen as the thermal
energy source to elevate the column to the absorptive temperature and for regeneration.

Effective and energy efficient dehydration of ethanol for the production of ethanol is a recent
development with corporate propriety restricting the transparency. Depending on the exact
system and configuration the total energy demand ranges from 0.8 – 2.5GJ/ton ethylene. Reverse
calculations from the confidential Shell data used in the EU-BREW report reveal a total energy
consumption of (0.78 – 1.15GJ/ton) with 0.98GJ/ton ethylene being the mean. To avoid its use
the molecular sieve (zeolite) ethanol dehydration unit was used as a guide to determine the actual
electric and thermal energy consumption by relating to the product flow. Ethylene from ethanol
has a stoichiometric yield of 0.609kg/kg or 1.64ton ethanol per ton ethylene. By including the
trace water levels and conversion efficiency the actual ratio becomes 1.67ton ethanol per ton
ethylene. In addition to this higher material adsorption and regeneration requirements the
operation temperatures demand high pressure steam. Here the resulting total direct energy
consumption has been determined to be 1.47GJ/ton. And despite the heavy reliance of catalysts
material the consumption versus the product throughput is so low that its indirect energy
consumption is negligible.
Table 14 Ethylene Processing Energy/Exergy Input
Catego ry Unit Values

Conditions
Temperature °C 180
Overall Conversion Rate ton ethylen e/ton ethanol 0.598
Electric GJ/ton ethylene 0.30
Th ermal GJ/ton ethylene 1.17 (0.26)

4 Fatty Acids
4.1 Description
Although commonly associated with poor human nutrition through high
consumption of animal fats, there are at least 40 distinct plant species
known to produce fatty acids in large quantities and concentrations which
actually represent the bulk of global production. Fatty acids are defined by
having a carboxylic acid molecule linked with a long unbranched aliphatic
tail. They form a major part of the broader chemical classification lipids,
and when present in plant matter are frequently referred to as organic oils,
vegetable oils or merely oil. They are formed through the biosynthesis involving the coenzyme
acetyl-CoA which by carrying a 2-carbon atom group lead to most natural fatty acids composing
of an even number of carbon atoms. In plant matter, they have at least 8 carbon atoms ranging
up to but rarely 24. Furthermore, fatty acids are sub-classified under two categories; saturated and
unsaturated. Those enclosing a carbon-carbon double bond along the aliphatic tail are said to be
unsaturated, while those composed solely of single carbon bonds are known as saturated. Thus a
wide range of fatty acids exists written as CN:M, with N being the number of carbon atoms and
M being the number of carbon double bonds. Palmitic acid (CH3(CH2)14COOH), the most
widespread saturated fatty acid is written C16:0. Oleic acid (CH3(CH2)7CH=CH(CH2)7COOH),
being one of the most widespread unsaturated fatty acids is written C18:1. Practically all fatty
acids, saturated and unsaturated, in plants have the carboxylic acid group bonded to each other
forming a glycerine end chain. These triglyceride molecules are large, diverse, crop dependent and
have a high molecular weight (850 – 950g/mol) leading to oily properties. Vegetable oils and free
fatty acids serve several particular functions in plant matter; they are essential to build and repair
cell structures like the cell wall, form a small proportion of cell membranes, participate in
signalling pathways, but most importantly are concentrated energy sources. Germinating seeds
restricted in size, regardless of the biological grounds, are usually associated with large
concentrations of fatty acids. They typically range from 40 – 50% with some plant species
containing over 70% in the fruit.
Despite the rising health food craze onset by recent obesity trends, within a biorefinery for the
non-food market there exist only a few product options. Hydrolysis or alcoholysis (hydrolysis
with alcohols) of triglyceride fatty acids will form oleochemicals. They are analogous to chemicals
derived from petroleum including fatty acid methyl esters, fatty alcohols, fatty amines and
gycerols. Applications are generally limited to the pharmaceutical, cosmetic and other speciality
industries with restricted production volumes. The transesterification (specific alcoholysis type)
of triglycerides, however, will produce biodiesel and, under strict formulations, biolubricants that
both have bulk production potential. But while most fatty acid-rich crops are currently cultivated
for biodiesel production, it is not a chemical and also has inferior product properties over
conventional fuel diesel, thus biodiesel production (like bioethanol) will not be included in the
biorefinery system layout. Biolubricants, on the other hand, have equal (or even superior)

properties compared to the petroleum-based lubricants and is a chemical with bulk production
potential, reaching 72.7Mton in 200544. The initial processing steps are practically identical to
biodiesel involving pressing, extraction, transesterification and modern solutions for glycerine
production. The true difference is formulation with the exact free fatty acid composition
determining the application and type of biolubricants products, while biodiesel is an unspecified
mixture. Thus, for simplification only one standard blend for each crop type will be chosen to
assess the process energy. In addition, modern and efficient system developments with recycling
and innovative product developments will be covered.
4.2 Processing
The fatty acids of vegetables oils are present in their triglyceride form in relatively high
concentrations in the seeds or fruits of biomass crops. Processing seeds and fruits to obtain free
fatty acids for biolubricants production involves four basic steps; pressing, extracting,
transesterification and purification. These processing steps are identical to standard biodiesel
production methods with industrial and scientific literature information supplying detailed
reports and processing conditions. After the creation of fatty acid esters further separation,
isolation, mixing and/or supplying additives are required to improve performance characteristics
(such as oxidative stability, pour point and viscosity index) of formulated biolubricants. Many
researchers have even gone directly to the biomass production itself genetically altering the fatty
acid compositional distribution in the plant to produce a higher quantity of the desired fatty
acids45. Plus, like the carbohydrate-rich crops, feedstock type influence the process conditions
and energy demands. In the case of fatty acid-rich crops only two categories will be made; seed-
based (40 – 50%) and fruit-based (70 – 80%). The standard processing will be handled first
followed by the recent processing improvements in light of process energy reductions.
4.2.1 Standard Processing

Pressing and Extracting
As a preliminary step to physically force a large portion of the oils out of the feedstock, a
mechanical press is employed. These electrically driven devices are limited to pressing out
between half and three quarters of the contained oil. By heating the feedstock up to 60 - 70° C
(using low pressure steam) the viscosity is lowered increasing the pressing efficiency at a lower
electric demand, but is still limited to 80% maximum yield for the seed-based type feedstocks
while fruits-based types can already achieve 96%46. To maximize the oil yields solvents are used
to extract residual traces of oils and accelerate the entire process. Many types of solvents have
been experimented and tested upon, but none have proved as affective as hexane. Besides, the
main motivation of searching for a suitable substitute for hexane (avoiding toxic levels in the
press cake which are strictly regulated for fodder application) is not of relevance within the
strictly non-food biorefinery. With a large flow of 1.2 – 2.5kg hexane per kg feedstock, 95.4% oil
can be recovered47. At such large material demands recovery methods have been developed and
near perfected to achieve 99.8% recovery for recycling. The hexane in the oil stream is recovered
via a flash column while the hexane in the press cake is sent to a desolventizer to be removed;

using high pressure steam and spread over a large surface area the hexane is boiled off and
collected. Overall a best practice installation requires only 1.0kg fresh hexane solvent per ton
recovered oil. The whole system can be described as a steam heated mechanical presser with
integrated solvent extraction. There are four major types of units available; rotary or deep-bed,
horizontal belt, continuous loop extractors and some miscellaneous like a screw presses. They all
work on the counter-current principle with the extracted oil sent to the next stage of processing.
Press cake will be treated as processing residues and subjected to carbohydrate processing
(Section 3.2) and since is does not need to be dried and prepare as an animal feed a noticeable
portion of process energy will be mitigated.
Transesterification
The general term for hydrolysis with an alcohol is alcoholysis where by in the special case of using
vegetable oils it is known as transesterification. Reacting the triglycerides with an alcohol will split
the molecule apart into free fatty acid esters and a glycerol molecule. The reaction can use any
assortment of alcohols but will result in the formation of functional ester branches at the length
of the alcohol molecule. Methanol will form fatty acid methyl ester; ethanol becomes fatty acid
ethyl ester; propanol, fatty acid propyl ester; butanol, butyl ester; and so forth. At some point the
chain length becomes an obstruction; the most common alcohol currently applied in the industry
is the single carbon methanol derived from natural gas. It is economical cheap but does come at a
high cumulative energy demand as will be highlighted in the next section. The following general
formula depicts the overall reaction with the stoichiometric demand:
Triglyceride + 3Methanol 3 Fatty Acids Methyl Esters (FAME) + Glycerol

C54H104O9 + 3CH3OH 3C18H32 O2 + C3H5(OH)3
1⋅930.27g/mol (930.3) + 3⋅32.04g/mol (96.1) 3⋅279.39g/mol (934.3) + 1⋅92.09g/mol (92.1)
Stoichiometric Ratio (Methanol Demand): 96.1 ÷ 934.3 = 0.103g/g
Each fatty acid-rich feedstock has a different fatty acid composition which will result in a
different molecular weight of its triglycerides, however differences are only apparent between the
previously mentioned separation between seed-based and fruit-based feedstocks. The following
lists the feedstock based molecular weight and methanol demand:
Table 15 Vegetable Oil Molecular Weight for Methanol (g/mol)
Feedstock Triglyceride Free Fatty Acid FAME Methanol Demand

Seed-based 930.27 279.39 934.3 0.103kg/kg
Fruits based 901.50 269.80 905.5 0.106kg/kg
As a general rule of thumb 10 wt% methanol is taken for quick studies and scans; carrying out this
extra calculation step slightly increases the accuracy of the minimum methanol demand for the
feedstock types. In practice the reactive alcohol (methanol) is added in excess, usually at twice the
stoichiometric requirements, to ensure a complete reaction conversion. Transesterification
conversion rates of 98% are systematically achieved48. Over 99.99% of the excess solvent is

recovered and recycled according the purification steps (next sub-section). Commercial facilities
use the well-established alkali-catalysts refining step to catalyze the reaction. And although many
alkali catalyst exist, Na(CH3O) (sodium methoxide), is almost exclusively used at 5 mol% compared
to the ester product.
Purification and Recovery
To prepare for the transesterification reaction step a purification process called degumming is
required because some of the fatty acids in plant matter are not bonded as a triglyceride molecule
but are present as free fatty acids which negatively influence the reaction; they and other non-
triglyceride molecules must be removed. Free fatty acids and the so-called “unsaponifiable” matter
contribute to an additional overall yield loss of 4.0%47. A 9.5 wt% caustic (NaOH) solution is used
to flush out and separate the molecules by their intrinsic behaviour to foam into soap. Resulting
lime demand is 7.5kg per ton product. The methyl ester product is sent to a cascade of hot water
washes columns (70° C) to strip the water-soluble components (glycerol, methanol, etc.) out. The
methyl ester product is then vacuum dried to remove any residual water that entered the aqueous
phase and purified to 98.9%. None of the ester products entered the water wash phase. This
stream is sent to a simple series of evaporator tanks and distillation columns to recovery the
glycerine using thermal steam energy.
4.2.2 Recent Processing Improvements

Pressing and Extracting
Within the pressing and extraction steps little improvements are foreseen aside from general
energy efficiency increases through better steam utilization, production and integration. Minor
decrease in steam usage are already noticed between contemporary European facilities to
conventional American ones. This provides a trend indication for newer plant design49, 50.
Information pertaining to palm oil processing plants are limited and noted as being considerably
inefficient51. Modern steam production and integration options can easily reduce the process
energy intensity by the half or not more.
Transesterification and Recovery
As mentioned earlier any alcohol can be used for the alcoholysis (transesterification) step. It was
also mentioned in Section 3.2.1.2 that oil press cakes will be included as “processing residues” for
ethylene production from complex carbohydrates. A portion of the ethanol could be used as the
transesterification reactant before being converted into ethylene within the biorefinery system.
Fatty acid ethyl ester (FAEE) would be produced in place of fatty acid methyl ester (FAME).
FAEE has slightly different physical and chemical properties, but when applied for the
formulation of biolubricants presents minor, if not negligible, constraints. While in this
biorefinery system the fossil fuel derived methanol is avoided, the calculated stoichiometric ratio
however indicates that more ethanol required. And as with methanol a distinction is made
between the two feedstock types. Following the overall reaction equation for FAEE production
from ethanol the minimum ethanol can be calculated. Presented in the following table are the
corresponding difference in molecular weight of the products.

Triglyceride + 3Ethanol 3 Fatty Acids Ethyl Esters (FAEE) + Glycerol
C54H104O9 + 3C2H5OH 3C19H34 O2 + C3H5(OH)3
1⋅930.27g/mol (930.3) + 3⋅46.07g/mol (138.2) 3⋅325.46g/mol (976.4) + 1⋅92.09g/mol (92.1)
Stoichiometric Ratio (Ethanol Demand): 138.2 ÷ 976.4 = 0.142g/g
Table 16 Vegetable Oil Molecular Weight for Ethanol (g/mol)
Feedstock Triglyceride Free Fatty Acid FAEE Ethanol Demand

Seed-based 930.27 279.39 976.4 0.142kg/kg
Fruits based 901.50 269.80 947.6 0.146kg/kg
Nearly 40% more ethanol is required than methanol to produce the fatty acids ester products. A
recent biotechnological advancement has allowed enzymes to be used in the degumming
preparation step, effectively eliminating the caustic treatment3. Further studies suggest that this
and other lipase enzymes could also be applied to replace the alkali catalyst in the
transesterification step48. There are several key benefits of enzymatic-catalysis, which all relate to
an increased energy efficiency; the reaction temperature is lowered from 80 ° C to 35° C, the
product yields are marginally increased from 98.0% to 98.5%, the recovery of glycerol is possible
without thermal units, and the water-wash product purification step can be completely removed.
In the early days of biodiesel production, glycerol was considered an economically viable by-
product. Due to the production boom (especially in Europe) in recent years it is now treated as a
waste by-product with ever-increasing disposal costs. In 2007, BioMethanol Chemie Holdings
announced their renovation plans to convert the feedstock of an existing methanol chemical
plant from natural gas to glycerol through an undisclosed gasification process. The great
abundance of glycerol has promoted many other investigations into fermentation products in
order to recreate an economic viability of the by-product50. Producing methanol from glycerol
may not be the most logical product, despite the recycling options, as it makes no use of the
highly reduce nature of the C3-carbon structure. In any case, this biorefinery system sees ethanol
fully replacing the need for methanol as a transesterification agent. Particularly in anaerobic
fermentation metabolism glycerol is of special interest and is a viable feedstock for the
production of 1,3-propanedoil (PDO). While PDO is being hyped as a potential fermentation
product from glucose, maintaining the C3-carbon structural integrity results in higher conversion
rates52. Initial studies have found that with 16.2mM glycerol, 11.2mM PDO can be harnessed
leading to a mass yield of 57wt%. The fermentation conditions were held at 58° C, 6.0-6.5pH for
at least 8hours at 10wt% solids loading.
4.3 Energy Input

Both the “standard” and “recent” improvement process energy and exergy input for the fatty
acids to biolubricant production route have been handled. Table 17 lists the resulting direct and
indirect energy as well as the relevant conditions. At the moment there are over 450 different
lubricants on the market with specific compositional formulations for the specific applications.

Biomass derived fatty acid esters offer many replacement opportunities with, in some cases, a
number of performance advantages. Projected biolubricant consists of base fatty acid esters
(usually 75 – 90%) and a fossil based additive package designed to achieve the desired properties.
Hydrogenation and other chemical processes are also proposed to increase the oxidative stability
of fatty acid esters, but are not a necessity. As a simplification, the fatty acid esters will be used at
a 75% formulation mixture with additives. The seed-based standard process is based on a series
of rapeseed and soybean production processes with the lowest energy insensitive figures for each
step chosen to be representative for a new installation. Steam is the primary direct energy source
in all processing steps which can be seen by the large energy and exergy difference. However, in
the standard transesterification process, the fossil-based reactant methanol is the most energy and
exergy intensive component. Using ethanol from the downstream biorefinery streams instead of
methanol from natural gas corresponds to a major reduction in energy intensity. Press cake
derived ethanol costs 9.07GJ/ton and 5.65GJ/ton direct process energy and exergy to produce,
respectively. Although the lipase enzyme requires 105GJ/ton and 173GJ/ton indirect energy and
exergy and ample amounts of citric acid as a growth medium, those extra induced costs are
considerably lower than the mitigated thermal (steam) costs. The large electric consumption in
the transesterification step of the recent improvement process is caused primarily caused by
glycerol fermentation.
Table 17 Fatty Acid Processing Energy/Exergy Input – Standard and Recent Process
Catego ry Unit Standard Pro cess Recent Improvement Pro cess*

Crop Seed-based Fruit-based Seed-based Fruit-based
Pressing & Extracting
Conditions
Temperature °C 60 70 60 60
Oil Yield (pressing) ton/ton 0.954 0.960 0.954 0.960
Oil Yield (degumming) ton/ton 0.96 0.96 1.00 1.00
Electric GJ/ton esters 0.175 0.364 0.175 0.364
Th ermal GJ/ton esters 2.20 (0.22) 8.10 (0.80) 2.18 (0.22) 1.17 (0.40)
Solvent GJ/ton esters 0.059 (0.056) 0.0 0.059 (0.056) 0.0
Transesterification & Recovery
Conditions
Temperature °C 80 80 35 35
Oil Yield ton/ton 0.980 0.980 0.985 0.985
Electric GJ/ton esters 0.001 0.001 0.251 0.251
Th ermal GJ/ton esters 1.21 (0.12) 1.24 (0.12) 0.15 (0.01) 0.16 (0.02)
Reactant GJ/ton esters 3.73 (3.92) 3.84 (4.03) 1.29 (0.80) 1.32 (0.82)
Catalysts/Others GJ/ton esters 0.34 (0.33) 0.35 (0.33) 0.85 (1.04) 0.85 (1.04)
*Also produces PDO: 53.9kg/ton for seed-based, 55.5kg/ton for fruit-based
The (electric) energy and exergy demand to emulsify the fatty acid esters with the necessary
additives for the lubricant formulation are negligible and can be disregarded. Considering the
global interest in biofuels, like biodiesel, and the fact that unformulated biolubricants follow the

same production route, presenting the overall process energy input is worthwhile. Just as with the
biofuel ethanol section a graph is used to show the direct process energy (thermal and electric)
and indirect process energy (chemicals, microbes, etc.) in combination.
Figure 5 1 st Generation Biodiesel – Overall Process Energy Input
Biolub ricant (o r Biodiesel) Pro duction

15. 0
I ndirect C hem ical Ene rgy
D irect Electric Ene rgy
D irect Thermal En ergy
12. 5
10. 0
GJ/ton Biolubrica nt
7. 5
5. 0
2. 5
0. 0
Seed-based Fruit-Based Seed-based Fruit-Based
Standard Rec ent Improvements
Table 18 1 st Generation Biodiesel Production Costs
Catego ry Standard Pro cess Recent Improvement Pro cess*

Crop Seed-based Fruit-based Seed-based Fruit-based
Overall Conversion
0.898 0.903 0.940 0.946
(ton esters/ton fatty acids)
Total Energy (GJ/ton) 7.71 13.89 4.95 7.00
Total Exergy (GJ/ton) 4.82 5.66 2.97 3.67
*Also produces PDO: 53.9kg/ton for seed-based, 55.5kg/ton for fruit-based
Rather unexpectedly the fruit-based feedstocks, which contain a higher concentration of

triglycerides, require more energy to convert into fatty acid esters over the seed-based feedstocks.
The exergetic difference is much less however because the fruit-based feedstocks are heavily
influenced by inefficient thermal energy. A noticeable process energy reduction is attainable by
using the recent improvement process, to the point that the fruit-based crops have a lower energy
consumption then the standard seed-based process. The overall conversion yields are comparable
for both feedstock types with 89.8 – 90.3% reached for the standard process and increased to
94.0 – 94.6% for the recent selection.

5 Proteins
5.1 Description
Of all the various biomolecules forming plant matter, proteins may
not be present in the highest concentration, but as the Greek origin
word προτα “prota” denounces, they are of primary importance.
Proteins perform a large multitude of tasks and functions in biological
life. They are responsible for carrying out the duties specified by gene
encoded information and even form a large portion of the genetic
material itself (RNA, DNA, etc.). In response to the duty assignments,
proteins can be enzymes catalyzing metabolism and catabolism or can act as the main molecules
regulating signalling and ligand (see Ash, Section 7) transportation. Proteins also govern the
physical forces needed for movement in cells (e.g. sunflowers aligning their heads towards the
sun) and can be used as secondary sources of energy. Legumes in particular store proteins instead
of starch for seed germination energy as they exchange simple carbohydrates for nitrates and
nitrates (ligands) with the inoculated symbiotic nitrogen fixating bacteria. Proteins comprise of
any possible combination of the 20 amino acids and can form quite large and complex structures.
Peptide bonds between the carboxyl and amine (nitrogen containing) group of the amino acids
hold the structure together, which are often referred to biochemically as a
polypeptides. In biochemistry, the general formula for amino acids is
C3H6O 2N with a molecular weight of 88.09g/mol; direct to the adjacent
image for the general structure. The protein content of plant matter is
determined by analysing the nitrogen content and multiplying by the
conversional factor 6.25, but actually relates to the amino acid building blocks. Thus amino acids
and their derived proteins are always associated with a nitrogen component.
Existing applications of plant-based proteins hardly make use of the energy intensive nitrogen
functionalization. Even the recently constructed biorefinery systems are limited using the protein-
rich by-products as a source of combustion energy or moderately processed to be suitable as
animal feed. The latter option of using biomass derived protein-rich streams for animal feed
industry applications will be handled in detail to properly allocate the marginal fossil fuel
reduction potential. While the current animal feed industry is profitable enough to industrially
produce certain free amino acids (from both renewable and non-renewable sources) as additives
on a large scale; those production routes for amino acids are energetically intensive. In the early
developmental phases of a full chemical biorefinery, the initial goal should be the extraction,
isolation and any needed purification to yield those amino acids of particular interest for the
animal feed sector. Utilizing the biomass-derived proteins for amine chemical production is still
in its paper hypothesis and initial laboratory experimental phases without a single production
route ready for series industrial consideration. Yet, the first process steps involve protein
separation and purification from the protein-rich by-products to form free amino acids are
somewhat closer. Only with continued research and development into the biotechnological

processing steps within the field of amine chemistry can the nitrogen functionalization be fully
utilized for chemical production. Here no distinction is made between the biomass feedstock
types as all the protein-rich streams originate after the carbohydrate conversion step of the
proposed biorefinery. Each amino acid will be studied for an exemplary functionalized chemical
production route, one with a high existing production volume and associated process energy cost.
As the process routes are hypothesized, the necessary process energy will be determined by
comparison to general processing equipment operated at foreseen conditions. Envisioned
advances in amine chemistry and biotechnology will facilitate the production of many existing
petrochemicals at relatively low process energy intensities without comprising the nitrogen
functionality structure of the amino acids. Finally, this section will exemplify the grand energy
savings potential of using proteins as a feedstock for chemical production within the biorefinery
concept; possibly making protein chemistry, “prota”: of primary importance.
5.2 Processing
5.2.1 Animal feed issue
5.2.1.1 General Situation

Meat production is big global business consuming tremendous quantities of feeding stuffs for
raising livestock. The EU25 alone consumes in excess of 450Mton annually; while most of the
animal fodder originates from farm grown roughages, 142.1Mton of compound feed was
industrially prepared in the EU and an additional 42.5Mton was imported53. It is broken down
into 4 major categories; pigs (swine), poultry (broiler), cattle (beef) and others, with the three
main livestock’s (swine, broiler, beef) all being fairly equally distributed at about a third. The
desired end product is meat with animal fodder serving as an energetic and nutritional input. One
of the industry’s key criteria for efficient production of meat is expressed by the feed to weight
gain ratio, F:G (kg/kg). This ratio is dependent on several factors from animal type, breed, sex,
fodder type, preparation, additives, to the seasonal climate conditions. In the 1980’s, a large cattle
range with locally grown roughages had required a total of 33kg feed per kg beef54. Supplying the
animals with a good-quality pasture (i.e. high digestibility, high protein content) reduces the F:G
ratio by half. Today, by utilizing better compound feeds the modern beef production industry has
significantly lowered the ratio to 7.8kg/kg. Preliminarily testing on genetically improved feed
propagation has further lowered the feed to weight gain ratio to 6.6kg/kg, a full 5-fold lower then
the open system55. Any preachy moral arguments on biological meat production must take into
account this huge boost in land use efficiency. Beef in particular has the largest F:G ratio while
the other two major livestock classifications require considerably less feed. Pork production
ranges from 2.6 – 3.5kg/kg and broiler production ranges from 1.0 – 1.5kg/kg54. In terms of
total feed energy input in relation to the meat energy content the following was found55: beef
40:1; swine 14:1; broiler 4:1. A common method to increase the weight gain ratio (and lower the
energy relation) is to artificially produce and blend in the limiting amino acids. Ruminant animals,
like cattle and sheep, do not have such limitations while the other livestock animals types do. So

despite its gluttonous nature, pork meat production is heavily limited by certain key amino acids,
frequently referred to as the ileal amino acids. To yield the optimal growth rates for swine,
industrial blending of ileal amino acids is in the order of 1.0 lysine, 0.6 methionine + cystine, 0.65
tryptophan, and 0.19 tyrosine. Isoleucine, leucine, valine and phenylalanine are sometimes also
added, but in considerably lower proportions. By far the most limiting amino acid is lysine which
is frequently added at a minimum level of 6.0g/kg pork feed. The same addition of amino acids is
present for all industrially prepared compound feeds, save for the actual blending ratio.
5.2.1.2 Fossil Fuel Mitigation

Animal feed is a tricky co-product in terms of proper allocation within life cycle assessments and
due to this difficulty it has become common to leave it out all together or merely resort to the
energy content56, 57. This is not the proper method when conducting a comparative cradle-to-
factory gate analysis for a biorefinery’s protein-rich by-products because when used as an animal
feed they substitute (or mitigate) the need of producing dedicated animal feeds. A study has
published detailed information regarding the fossil fuel input to produce various animal feeds58.
In general forage animal feeds cost 1 – 3GJ/ton and “concentrated” (compound) feeds cost 6 –
14MJ/kg. Two notable compound feeds are corn gluten meal at 6.1GJ/ton with a protein
content of 47% and soymeal at 6.8GJ/ton with a protein content of 45%. At this stage in the
biorefinery the residue streams could be able to partially replace these two animal feeds.
“Partially” because the most important attribute within the feed industry are the digestion values
coupled with the protein concentration. Therefore, the feed replacement potential must be based
on the protein content relation. Here the protein concentration is very feedstock dependent, and
while only few can match a protein content as high as 45% most of the selected feedstocks result
in a residue stream containing less than 30%. Thus in most cases, the gross feed replacement
potential results in less than 4.0GJ/ton. The net is even lower as extra process energy is required
for drying and fodder preparation. These values are actually several magnitudes below the
mistakenly allocated grass calorific value. Meaning that even bioenergy propagation at low
combustion efficiency yields a higher fossil fuel mitigation potential, therefore animal fodder
production is an inferior option compared to burning. The industrially prepared and blended
amino acid additives can, however, present a promising first step. Take the example of lysine via
fermentative production routes:
Table 19 Cumulative Process Energy for Lysine (GJ/ton)
System Classical System Improved System

Input Type Quantity Energy Cost* CED Quantity Energy Cost* CED
Molasses 5.3 ton 8.3 44.1 2.7 ton 8.3 22.0
Steep Liquor 0.413 ton 34.6 14.3 0.413 ton 3.5 1.4
Ammonia 0.152 ton 34.5 5.2 0.152 ton 34.5 5.2
Sulphuric Acid 0.182 ton 2.3 0.4 0.182 ton 2.3 0.4
Electricity 4.7 MWh 45% conversion 37.3 2.7 MWh 45% conversion 21.7
Steam (Medium) 4.34 ton 85% conversion 17.7 2.53 ton 85% conversion 10.3
*Based on internal calculations, See accompanying database spreadsheets for more details and exergy calculations

The total cumulative process energy is 119.0GJ/ton for the classical system and can be lowered
to 61.2GJ/ton following the proposed improvements59, 60. Similar situations are present for the
other synthesized ileal amino acids which clearly shows a higher fossil fuel mitigation potential
over compound animal fodder. Preparing separate amino acid streams from the biorefinery
protein-rich by-products will follow the same initial processing steps as suggested for the
chemical production; solubilization, separation, isolation and purification. For the essential amino
acids (lysine, methionine, cystine, tryptophan, tyrosine, isoleucine, leucine, valine and
phenylalanine) isolation is a very reasonable first step in producing chemicals. Although they are
not non-food products, they are feasible during the introduction phase. Besides, when destined
as animal feed additives they could be marketed as a mixture, possibly saving in isolation costs.
5.2.2 Solubilization
After the last beer column, which separates the ethanol produced from the fermentation broth
mixture of simple and complex carbohydrates, the bottom stream will act as a protein-rich source
from many of the investigated biomass feedstocks. A considerable portion of the proteins have
already been denatured, destroyed or cleaved into smaller peptides and introduced into the
soluble fraction. Others tend to oligomerize into densely packed fibre-like molecules when
exposed to the high temperatures along the various biorefinery processing steps. The induced
state of the protein structures is not of any particular importance within a biorefinery while the
efficiency and effective ability to separate and isolate their amino acids building blocks is.
Solubilizing the proteins and derived peptides found in the beer column bottom stream is the
first step of many required to form purified amino acids streams. Here the molecular structure of
the proteins and peptides directly effect the solubilization performance. There are two major
types of techniques used and investigated for solubilizing proteins; chemical extraction and
enzymatic cleavage. Both methods will be described and assessed, however enzymatic cleavage is
vastly more promising within the biorefinery concept and will serve as the primary solubilization
technique. As a substantial proportion of the other chemical components in the bottoms stream
are also present in their soluble state, further downstream isolation and purification steps are
required to properly prepare the amino acids. Solubilization is thus the first purification step to
separate proteins and its derived peptides from insoluble and solid material. At this stage in the
biorefinery no distinction is made between the feedstocks, although the absolute concentration
of the proteins contained in the stream (feedstock) will directly effect the process energy.
5.2.2.1 Chemical Extraction

In practically all industrial preparations of proteins from impure sources the first step of
purification is a chemical extraction or some cases a precipitation step. A wide assortment of
alkalis, acids and salts are applied to bring the proteins into solution; in affect a hydrolysis
procedure. The effectiveness is extraordinarily high nearly reaching full separation. However,
these techniques have the structural integrity of the proteins in mind and might not work as well
with dirty biorefinery streams. In addition, a large quantity of extraction chemicals sometimes as
high as 1 to 1 are also required which when coupled with the downstream neutralizing steps place

an inordinately high indirect process energy cost. An option to overcome these high chemical
production costs is to either lower the required concentration, employ recycling options or better
yet integrate it with chemicals required or produced along any of the other biorefinery processing
steps. Ethanol, ammonia and lime were personally tested on AFEX pretreated (Section 3.1.1.2)
processing residues from a cereal-type simple carbohydrate (Section 3.1.1.2) feedstock as
chemical extraction solvents. Even at elevated temperatures (>80° C) and high solvent
concentrations (>50wt%) less than 25% of the total insoluble proteins were brought into solution.
Another option is to use strong organic acids to fully hydrolysis the proteins by chemically
cleaving them into soluble fragmented peptides. Sulphuric acid, which is the desired pretreatment
procedure for recalcitrant materials, can indeed solubilize large quantity of the proteins by
cleaving them into small peptides. However, cleavage into the soluble phase will already occur
within the foreseen pretreatment step, meaning additional post-treatment will hardly promote
additional cleavage and even so would entail extra chemical separation costs. This briefly implies
that using biorefinery chemicals to solubilize the proteins and derivatives is not a feasible option.
5.2.2.2 Protease
Proteolytic enzymes, marketed as protease61, are naturally occurring enzymes
in fungal bacteria that are capable of protein cleavage (degrading
polypeptides) at moderately lower temperatures and concentrations. In
the food and industrial enzyme industry much knowledge has been
accumulated regarding technical applications of proteases. That core
know-how can be transferred to the initial protein separation step
within the biorefinery concept. Preliminary protease digestion experiments have been performed
on several process residue feedstocks as a proof of concept26, 62. Initial solubilization rates are
moderate at 51.7% for corn wet distillers grains and 41.5% for wheat stillage. As those
experiments were an introduction to the novel concept of protease digestion to solubilize
proteins from biorefinery side-streams, the results are clearly sub-optimal. An optimal operation
temperature of 50° C has, however, been determined which is lower than the manufacturers 72° C
guidelines for industrial food applications. Heat generally affects protein solubility, but excessive
temperatures also tend to deactivate the enzymes. Many more improvement options are
foreseeable with continued research, investigation and development into the system dynamics. A
plausible (yet untested) improvement is to create a specified proteases cocktail, as was
successfully developed for saccharification processing. It appears that of the cleaved peptides
most are below the protein spectrum detection range of 6kDa. Free amino acids have an average
molecular diameter of 0.15kDa suggesting that many of the proteins could have been reduced to
their amino acid building block. Using a protease cocktail should not only increase the overall
solubility but under the right conditions fully cleave all the peptides down to their compositional
amino acids. Furthermore, it appears from the experiments that the enzyme activity decreases
with time meaning a feed-batch system could increase the solubilization rate. It can be expected
that with further investigation and conditioning of the parameters a near complete digestion is

foreseeable; 95% is assumed for future cases and 60% is taken as current cases. In both cases a
complete conversion to amino acids is taken to facilitate the proceeding separation steps.
5.2.3 Isolation and Purification

Isolating and purifying amino acids after the protein digestion separation step involves a wide
multitude of biotechnological and biochemical technologies; in short bioseparation technology.
Yet, not a single bioseparation technology or processing scheme is currently available to handle a
mixture of amino acids. In fact, most of the purification technologies that will be discussed and
chosen for the now amino acid-rich stream have been designed for waste water treatment,
specialty chemicals or the food market. Desalination procedures, for instance, are common
within the food industry to recover proteins because frequently the solution is not in the optimal
state for consequent processing caused by the wrong buffer,
too much salt, too many impurities, or simply too dilute.
These negative process attributes are analogous with the
amino acid-rich streams. The closest processing route that
can act as a guideline is enzyme preparation from a
fermentation broth; i.e. lysine production. The adjacent
illustration is an overview of the isolation processing steps
generally involved in enzyme preparation63. It is optimized to
remove salts and metallic ions (desalination) and other
biomass broth impurities (proteins), leaving an enzyme rich
stream. Amino acid isolation and purification steps will
adhere to similar a processing scheme, but can in many cases
be left in solution as governed by the downstream chemical
synthesis. Many separation technologies exist which utilize the interaction mechanisms held by
the various physiochemical properties of the amino acids. They have five distinct physiochemical
properties which might help facilitate affective isolation and purification: (1) molecular size
(weight), (2) hydropathy index (hydrophobic & hydrophilic nature), (3) isoelectric point (charge),
(4) acidity and basicity (pH) and (5) polarity. Depicted in Figure 6 is a personally proposed overall
processing scheme to isolate each of the 20 amino acids into purified streams. It is a multistep
procedure playing on the individual physiochemical properties of the amino acids. The final
industrial layout within a biorefinery can deviate significantly from this isolation and purification
proposal, but will nevertheless encapsulate a multistep procedure. It is a current knowledge gap
in the whole biorefinery concept that needs to be closed. On large industrial scales these
individual isolation and purification technologies are selected solely by economic considerations
and not by energetic issues. And seeing that the associated financial costs for membrane
production continues to place the highest proportional cost factor on the membrane-based
technologies, the energy intense process costs are greatly offset meaning hardly any development
has gone into process energy reduction. Furthermore, several of the technologies are confined to
the laboratory analysis scale due to the current process economics. Nonetheless, each of the
technologies will be described in detail with the process condition brought into relation with the

operation energy costs. There will be a vast difference in the resulting process energy demand
between the various feedstocks because the operation conditions and energy intensity are based
on permeate product flow rate, meaning the amino acid concentration is all determining. At this
stage in calculations, however, the process operations will be expressed in product flow rate (m³)
and simplified to (ton) by setting the average density at 1ton/m³ as the stream is primarily
composed of water. A representative amino acid concentration of 6.5 wt% will be selected prior to
being expanded into the exact feedstock related calculation matrix of Chapter 8. Furthermore,
the exact amino acid weight proportions will also determine the overall individual isolation
values. Again, later in Chapter 8 the exact feedstock composition will be included, while here a
representative simplification of equal amino acid mass distribution is made for presentation
purposes.
5.2.3.1 Nanofiltration (NF)

Nanofiltration is a pressure driven filtration process to separate finer particle
sizes from an aqueous solution. A selective separation layer is formed by an
organic semi-permeable membrane with the pressure difference between the
feed stream (retentate) and the filtrate (permeate) providing the driving force.
Systems are approaching technological maturity and are ready for full-scale
industrial applications. Industrial configurations are typically in the compact
multi-tube cylinder form (see picture). In the biorefinery system nanofiltration
will be used as the first stage in amino acid purification to remove the large soluble particles.
Here the membrane permeation size is set at 1kDa; large enough to allow most molecules to pass
through including salts and unconverted sugars but small enough to block delignified products
and any residual peptides. In many biochemical processing applications the impurities contained
in the retentate are regarded as waster water with disposal provisions64. Here these large soluble
lignin products will join the insoluble solid residue (primarily lignin) and combined will form a
dilute but nearly pure lignin feedstock (Section 6).
5.2.3.2 Electrodialysis (ED)

Electrodialysis is an electrochemical separation process in which
ion exchange membranes are used to remove ions (charged
molecules) from organic solutions65. It can be configured to
produce three separate product streams; positively charged,
negatively charged and the demineralised neutral streams. The
feed stream is passed through a channel with a pair of electrically
charged bipolar membranes and a centre transfer membrane. A slight temperature increase to
40° C and an overpressure of 0.25bar are needed to promote a good separation. Salts in solutions
will act as ions and are attracted to either the cathode or anode. Amino acids also have a
isoelectric point (or charge) and will be separately into one of the three streams. Most are
relatively neutral with an isoelectric range of 5.5 – 7.5 and remain in the demineralised product
stream. Positive (or acidic) amino acids have an isoelectric point below 5.5, while negative (or

basic) amino acids have an isoelectric point above 7.5. ED is a fast and effective process for this
stage of separation. Little investigation have been made on the energy consumption of the
desalination of amino acid containing streams, but some studies will act as guides to the energy
costs66. At moderately high concentrations, starting at above 10 wt%, proton leakage is promoted.
Current experiments are typically kept at much lower concentrations67.
5.2.3.3 Chromatography
Chromatography is the separation process based on using differing component affinities within a
mobile phase when passed through a stationary phase fixed in a column. The chromatographic
separation can occur via various interaction mechanisms, including size exclusion
chromatography (SEC), ion exclusion chromatography (IEC), and reverse phase adsorption
chromatography (ADS). Irrespective of the particular mechanism, the engineering basics of the
process are the same, products will be eluted at differing rates thus separating them. This limits
chromatography to be a slow batch process. Much detailed information is written about
chromatographic separation as analytical measurement techniques but very little is known in
regards to its manufacturing process applications. The slow rate of separation, batch process
nature and relatively high economic and energetic operation costs are preventing the wide-scale
implementations. The sugar industry does use ion exclusion chromatography to separate and
purify particular sugars from each other. In addition, this process is used in purifying single
amino acids and various organic acids streams as well as to separate salt from glycerol. Each type
of chromatography that could potentially use the physiochemical properties of amino acids for
separation will be handled individually with a brief explanation to their operation kinetics.
Size Exclusion Chromatography (SEC)
As the name suggests size exclusion chromatography separates
molecules according to their size; or more accurately according to
their hydrodynamic diameter or hydrodynamic volume. In practice,
the molecular weight provides enough insight into the differing
molecular sizes of the amino acids. When an aqueous solution (as is
the case with amino acid-rich streams) acts as the mobile phase, the
technique is known as gel permeation chromatography (GPC). As the image
depicts, smaller molecules are able to enter the pores of the stationary phase and; therefore, take
longer to elute than the larger molecules which pass through the column unretarded. A wide
multitude of inert porous materials with varying pore sizes are employed with plastic beads like
cross-linked polystyrene being rather common. GPC is generally regarded as a low resolution
technique and is often reserved for the final purification step, dubbed “product polishing”.
Frequently, product polishing is used on a single product, but within the amino acid isolation and
purification scheme a arbitrary maximum of four simultaneous amino acid products can be
produced. It is here also assumed that as long as the molecular mass differ by at least 10% a
separation is possible. Due to the previously mentioned fact that amino acid isolation and
purification remain a knowledge gap within the biorefinery concept, the validity of these
statements are unknown. In analytical applications of chromatography high pressures above

15bar are applied to force a uniform solvent flow, in industrial applications the pressure can be
lowered to around 3.5bar. While in both applications, the organic solutions need to be heated to
80 - 85° C. Resulting that thermal energy for heating contributes to the largest proportion of the
overall process energy, unlike electrodialysis being 78% electricity.
Ion Exchange Chromatography (IEC)
Technically called an “anion exchange gradient elution column”, the ion exchange
chromatography column is the most widely used industrial chromatographic
separation process. IEC is a rather interesting application because the
negatively charged stationary solid phase is not actually performing ion
exchange. The resin serves as a media separating based on the differing
amphoteric characteristics of the mobile phase, the pH in other words. As the
image depicts, positively charged (acidic) molecules are attracted to the negatively charged beads
of the stationary phase and; therefore, take longer to elute than the negatively (basic) and less
positive to neutral molecules which pass through the column relatively unretarded. A wide
multitude of inert resin materials are being studied and marketed with several major industrial
corporations enter the market. Corresponding to this trend is the ever increasing reliance of ion
exchange columns for enzyme and other protein purification steps. Unlike electrodialysis which
separates the streams into positive, negative, and neutral, IEC uses the isoelectric affinity of
amino acids to separate the molecules based on their relative charge. The process conditions and
thus energy demands are analogous to SEC.
Reverse-Phase Adsorption Chromatography (ADS)
ADS has a few name deviations from dry flash chromatography to
expanded bed adsorption (EBA), but all work on the adsorption
principle68, 69. And although it represent one of the most
promising recent developments in biomolecule separation
technologies, only a handful of applications have been studied.
Reverse-phase adsorption chromatography also functions
slightly differently then the other column-based chromatography procedures, for it is a three step
procedure and requires significantly less process energy. It works on the molecular polarity
adsorption affinity difference. Polarity refers to the dipole-dipole intermolecular forces between
the slightly positively-charged end of one molecule to the negative end of another or the same
molecule. Nonpolar molecules have a high affinity and are adsorbed into the packed bed
(stationary phase) adsorbent while the polar molecules having a low affinity are left in solution.
The separation into the two streams, polar and nonpolar as the image depicts, is a three step
process; (1) loading the adsorbent with the nonpolar molecules, (2) washing the polar molecules
away, and (3) eluting the nonpolar molecules by desorbing them with a solvent. Methanol is an
effective solvent with 25 – 50wt% required to fully elute the nonpolar molecules. An additional
standard evaporation step is needed (like in Section 4.2.1) to remove and recycle the solvent. A
conservative 50wt% will be chosen. The ADS separation operates at room temperature negating
any thermal energy in the column and with an overpressure of 1.25bar reduces electric demand.

5.2.3.4 Reverse Osmosis (RO)
Reverse osmosis is best known for the desalination and
purification of water, RO-Water. At this stage along the amino
acid isolation and purification scheme (Figure 6) the solution does
not contain any salts as they were removed earlier. The polar
amino acids do however possess a physiochemical difference that
could facilitate reverse osmosis; a hydrophobic and hydrophilic difference. Under pressures
between 2 – 15bar the hydrophilic amino acids would be forced through the semi-permeable
membrane while the hydrophobic amino acids, acting like salts, would remain. This in effect
further separates the amino acids into two distinct streams. The operation conditions and design
configuration mirrors the nanofiltration unit. In fact, RO is sometime referred to as ultrafiltration
when purifying exceedingly dirty water streams.
5.2.3.5 Others
As research and development shifts towards closing the knowledge gap of amino acid isolation
and purification many new and potentially radical ideas could emerge. Precipitation in itself is one
such example that when studied from a different angle could prove beneficial. Traditionally salts
or chemicals are added to bond to the side-chain groups of protein changing pH or promoting
crystallization. An additional neutralizing chemical step is required involving other separation
procedures. Using enzymes could operate in a similar way, clinging to the various amino acid
chemical structures thereby changing the physiochemical properties. The interaction mechanisms
of the amino acids could be shifted potential promoting more efficient separation from the above
described technologies. Another option with few current applications is lyophilisation or freeze
drying. At high solid loadings the amino acids would all have different freezing points (natural
crystal forming) calling for standard solid/liquid separation techniques. Cryogenics essentially
under vacuum conditions, however, are incredibly energy intense. On the other scale of
temperature manipulations thermal parameter pumping within an ion-exchange resin seems
promising70. It could take advantage of process waste heat as the driving force of separation
significantly lowering the electric demand. It uses dissociation reaction constants to govern the
movement of amino acid towards high or low temperature reservoirs. Current studies are
restricted two amino acid with limited success. Nonetheless, the idea of using amino acids as
building block for the chemical industry is slowly being acknowledged by the academic world
with efforts dedicated towards assessing the current knowledge gap71. In any case the separating,
purifying and isolating amino acids from a biomass based stream will typically entail cascading
multistep procedures. One deviation from this general rule is possible in situ chemical reactions.
The next section lists plausible chemical reactions deriving from amino acids; it is thought that
those conducted in an aqueous solution could change the chemical structure in such way as to
promote an easier and less energetically intense separation step.

Figure 6 Amino Acid Separation Steps
Solubilized
Dis tillation Bottoms
Nanofiltration Lignin Products

(partic le s ize separation)
Aspartic Acid
Gel Chromatography Glutamic Acid

Aci dic Amino Acids (particle s ize separation)
Salts/Ash
Electrodialysis
(hydropathy separation)
Basi c Ami no Acids Lysine

Ion Exchange
(pH influence separation) Arginine
His tidine
Neutra l Amino Acids
Tyr os ine
Glutamine
Hydrophobic Amino Acids
Gel Chromatography
(particle siz e s eparation) Asparagine
Pol ar Ami no Acids Reverse Osmosis
Reverse-Phase (hydropathy separation)
Chromatography Proline
Hydrophil ic Ami no Acids
(Polarity s eparation)
Try ptophan
Threonine
Gel Chromatography
(particle s ize separation) Serine
Glycine
Cys tine
Nonpola r Amin o Acids Ion Exchange
(pH influence separation) Phenylalanine
Methionine
Isoleucine
Leucine
pH6< Amino Aci ds Gel Chromatography
(partic le size separat ion) Valine
Alanine
© Agrotechnology and Food Sciences Group B.V., member of Wageningen UR 357

5.2.4 Potential synthesis routes
Mention the words biotechnology and bioengineering to the average laymen and images of
deformed produce caused by failed genetic engineering experiments quickly materialize in their
minds. Public resistance, especially in Europe, is
always directed at health safety (and more recently
monopoly prevention) of genetically alternating
eatable products within the food chain. Yet,
biotechnology spans far beyond the agricultural
scope of maximizing crop production. It
encompasses a much broader range of procedures
and applications of biological organisms, many of
which are already employed on a vast scale within
the food and non-food industries; from bacterial cultures for cheese, industrial enzymes for
detergents, to biocatalysts for pharmaceuticals. And while
Biotechnology bioengineering is a mere subsection of the wider
According to the UN convention on
bio logical diversity , “Bio technology biotechnology field, it is akin to future improvements,
means “any technological application applications tailoring and optimizing the efficiency of the
that uses biological systems, living
organisms, or derivatives thereof, to operations. Nearly all of the potential amino acid synthesis
make or modify products or processes routes to chemicals embody biotechnology and can benefit
for specific use.”
immensely from bioengineering optimizations. In the
traditional petrochemical industry a premium is placed on low production costs with the
employment of high-temperature and high-pressure reaction systems frequently permitting the
use of relatively inexpensive starting materials at strikingly diminished reaction times. Conversely,
a paradigm shift is needed when adopting biotechnology-based options for the biomass derived
processing of the individually isolated amino acid streams because biotechnological operations
perform best at low temperatures and low pressures at considerably long reaction times. The
premium of low production costs remains but the focus is shifted on finding the optimal trade-
off between using expensive enzymes and fermentation microorganisms over the reduction in
intensive direct process energy. Genetically engineering enzymes and microorganisms to lower
the conversional loading rate while simultaneously decreasing the indirect production costs will
not only facilitate but be imperative to the success of amino acid-based chemical production.
In this section a single potential and speculated process route for each of the individual amino
acids will be investigated. The following Table 20 illustrates an overview of a single chemical
product with in some cases a secondary by-product. There are conceivably a sizeable multitude of
chemical production options available for each amino acid; it is simply a quest of continued and
dedicated research and development. Based on the stoichiometric conversion ratios, the mass
yield (kg/kg) is of key importance to be able to determine the relative process energy. As all of
the process steps are hypothesis, the process description and conditions will be clustered and
generalized.
358 © Agrotechnology and Food Sciences Group B.V., member of Wageningen UR

Table 20 Overview Potential Amino Acid Chemical Derivatives
Amino Acids Products

Nomenclature Symbol Formula Structure Molecular Mass Primary Formula Structure Y ield Secondary Formu la Structure Y ield
Alanine ala C3H7 NO2 89.1 e thylamine C 2H 7N 0.51
Arginine arg C 6H 14N 4 O 2 174.2 1,4-butandiamine C 4H1 2N 2 0.46 urea (NH2 )2CO 0.31
Asparagine asn C 4H 6 NO 4 132.12 acry la mide C3H 5NO 0.54
A spartic acid asp C 4H 7 NO 4 133.1 e thylamine C 2H 7N 0.34
Cysteine cy s C 3 H6 NO 2S 121.16 feed grade cyste ine C 3H 6NO 2S 1.00
Gluta mine g ln C 5H 10 N2 O 3 146.15 1,4-butandiamine C 4H1 2N 2 0.46 ammonia NH 3 0.10
Glut amic a cid g lu C 5H 9 NO 4 147.13 1,4-butandiamine C 4H1 2N 2 0.51
Glycine gly C 2H 5 NO 2 75.07 oxalic acid C 2H 2O 4 0.65 ammonia NH 3 0.12
Hist idine his C 6H 9N 3 O 2 155.16 ionic liquids C2 H5 NH 3NO3 0.62 ammonia NH 3 0.10
Isoleucine ile C 6H 13 NO 2 131.18 isoprene C 5H 8 0.97
Le uc ine leu C 6H 13 NO 2 131.18 isoprene C 5H 8 0.97
Ly sine lys C 6 H14 N2 O2 146.188 e thylamine C 2H 7N 0.62
Methionine met C 5H 1 1NO 2S 149.21 feed grade methionine C 5H 11NO 2 S 1
P he ny la lanine phe C 9H 11 NO 2 165.19 styrene C 8H 8 0.63 ammonia NH 3 0.10
Proline pro C 5H9 NO 2 115.13 g- buty rolactum C 4H 6O 2 0.75
Serine se r C 3H 7 NO 3 105.09 e thylenedia mine C 2H 8N 2 0.45
Thre onine thr C 4H 9 NO 3 119.12 isopropa nolamine C3H 9NO 0.63
Try pt ophan trp C1 1H 12 N 2O 2 204.225 adipic acid C 6H1 0O 4 0.54 ammonia NH 3 0.08
Ty rosine tyr C 9H 11 NO 3 181.19 styrene C 8H 8 0.57 ammonia NH 3 0.09
Valine val C 5H 11 NO 2 117.15 isobut yraldehyde C 4H 8O 0.62 ammonia NH 3 0.15
General AA C3 H6 O2N 88.085 ammonia NH 3 0.19

5.2.4.1 Process Debriefing (Sources)
A general insight into several potential chemical products following the biorefinery concept have
been eluded at, including the impending benefits of incorporating protein-based chemistry72. The
described amino acid chemical synthesis examples were limited and process details were not
sufficiently provided. The basis of the herein chosen amino acid chemical synthesis routes were
taken for a large part from a follow-up mini-review focused on probable process routes73. Here
existing processes and plausible process routes were taken from biochemistry, medical and in
some case metabolic pathways studies. Again details pertaining to the exact processing conditions
are void, it does however provide a good insight into potential research directions and covers
most of the hypothetical synthesis routes. For some of the other hypothetical amino acids
product options, additional studies were taken, namely: arginine to ornithine via enzymatic
hydrolysis74, ornithine to butanediamine via enzymatic decaroxylation75, glutamine to glutamic
acid via enzymatic deamination hydrolysis76, GABA to butanediamine following the reverse
reaction of reductive deamination via standard amination77, histidine to ionic liquids via the idea
of solution dissociation60, leucine and isoleucine to isoprene via the complex biosynthesis
mevalonate pathway and enzymatic synthesis73, 78, lysine to ethylamine via a fermentative
degradation to split the carbon backbone of pentanediamine79, tryptophan to adipic acid via a
hydrogenation step of the intermediary muconic acid product80. Many of these and other
hypothesised process routes are contemplated, internally discussed and partially experimented
upon within the Wageningen UR department chair, valorization of plant production chains.
Nonetheless, consult the database for the exact reference sources adhering to the individually
proposed amino acid chemical synthesis route. At the bottom of both tables is the lowest
chemical product option, for as all amino acids contain a carboxylic acid and amine group they
can always be broken down to yield a single ammonia molecule at 0.19kg/kg.
5.2.4.2 General Process Unit Operations

Decarboxylation
Any chemical reaction involving a carboxyl group being split off in the form of a carbon dioxide
compound, following the general reaction formula, is decarboxylation:
R-COOH R-H + CO2
The reaction can be catalyzed either chemically or ever more frequent by specific decarboxylase
enzymes. Today there are so many enzymes specific to substrates containing carboxyl groups that
they are categorized by EC numbers, under EC4.1.1, and consequently named after the base
molecule. The most commonly studied is pyruvate decarboxylase. A temperature dependent
activation energy is needed to promote the reaction with the optimal between 31 - 45° C81, but the
reaction is exothermic as an ATP is released during the carboxyl group removal. The generated
access thermal energy is in the order of 20 – 35kJ/mol with a medium of 29kJ/mol. Nonetheless,
a small electrical energy input is required to pressurized the tank/column and pump the contents,
in the order of 44kWh/ton82. Also, consider the indirect production energy of the enzymes,
which have a loading rate between 3 – 30g/kg with 5.0g/kg chosen to be representative.

Hydrolysis
Any chemical reaction involving a chemical compound being broken down in the presence of
water forming two new molecules, following the general reaction formula, is hydrolysis:
R′-R″ + H2O R′-OH + R″-H
In biochemical applications an enzyme is used to catalyze the reaction and is very site specific to
direct the exact cleavage position. In this section, there is only one reaction involving enzymatic
hydrolysis; alanine to ornithine with urea as a by-product. The operation conditions are thought
to be similar to the enzymatic saccharification step (section 3.1.12); temperature range 65 - 90° C,
but as the stream is purer a lower demand (60° C) should be feasible, enzyme loading of 25g/kg,
and due to the lower viscosity a reduced electric demand to 0.150GJ/ton product.
Maillard Reaction
Any chemical reaction involving an amino group reacting with the carbonyl group of a sugar
forming two new products, following the general reaction formula, is the Maillard reaction:
Amino Acid + Sugar CO2 + H2O + Product 1 + Product 2
The reactions typically involves high heat and is used extensively within the food industry83. It is
used to produce a variety of odours and flavours, meaning the process conditions also vary. Set
temperatures can range from low (40° C) to high (120 ° C) and pressures from atmospheric to on
occasion as high as 60bars. Conversion rates are positively affected by high process intensities,
thus 120 ° C and 10bar will be set. Sugars are supplied in access, typically at 1:2 – 1:3 weight ratio;
the lower value will be taken. Furthermore, the sugar (glucose) will originate from within the
biorefinery (Section 3.3) and its reactant product will be later combusted (Section 6.2.1) yielding
the calorific value. And, while water is produced via the reaction it is best to hold the reactants at
low aqueous concentrations (>20%).
Amination
Any chemical reaction introducing an amine group (ammonia) into an organic molecule to form
an amine, following the general reaction formula, is reductive amination:
R-COOH + NH3 R-CONH2 + H2O
Reductive amination is typically catalyzed with a metallic oxide occasionally in the presence of
addition hydrogen. There are two distinct systems; the well-defined high pressure (>100bar) and
proposed low pressure (~1bar). For the amino acid-based systems, the high pressure options will
be focused upon and it entails slightly elevated temperature of 80 - 95° C without hydrogen.
Ammonia is added at a one to one stoichiometric ratio, but the indirect fossil fuel production
costs of ammonia will not be considered as many of the other proposed amino acid routes
release ammonia as a by-product. The amination process will thus reduce the yield of ammonia
form the other routes. Electricity is the main input to maintain the high-pressure.
Electrolysis
Any chemical reaction using electric current energy to split a chemical bonded molecule to form
two new products, following the general reaction formula, is electrolysis:
R′-R″ + Eo R′-OH + R″-H
Electrolysis is performed in an aqueous solution, usually only with water, but can be catalyzed by
certain alkaline or acidic mixtures. In many systems a weight ratio of 25% is used. Moderately
elevated temperatures are involved ranging from 30 - 80 ° C, with 70° C used in splitting larger
molecules, like proteins. Of course, the electric component is the most intensive and can reach
up to 140 – 200GJ/ton for hydrogen electrolysis. Vastly lower demands are needed for molecule

degradation in heated aqueous solutions. An electric potential of 6 – 30 volts at 0.01 – 0.2 A/cm²
is suitable for protein splitting84. This relates to a slight over electric capacity of 1.5 – 3.0times;
0.48kWh/mol will be taken.
Fermentative
Fermentation does not follow any general reaction formulas. By splitting the source molecule
into new products these substrate acts as an energy source for microorganisms via the unique
internal biochemical pathway of the organisms. For amino acid-base systems it can be called
fermentative degradation as a portion of the molecule is broken off releasing a new usable product.
Ethanol fermentation can act as a guideline to the reaction kinetics and process conditions, but
because it is highly tailored representing the lower scale of fermentation systems the amino acid
system must be placed on the higher scale of the energy range. In the biochemical pathways
involving amino acid a nitrogen functional group is usually consumed by the organism which
reduces greatly reduced the eternal nutrient requirements in the broth.
Enzymatic Catalysis
As with fermentative degradation, enzymatic catalysis does not follow a general reaction formula.
Otherwise known as biocatalysis, the use of enzymes are designed to lower the process condition
intensity to save on heating and pressurizing energies. A detailed example of this principle was
performed on acrylamide and found a process energy reduction from 1.9GJ/ton to 0.4GJ/ton85.
Enzymatic hydrolysis, decarboxylation and deamination are all classified as biocatalysis, yet here it
is understood as being specific reactions which do not fall under those categories. Evaluation is
thus difficult necessitating some set assumptions; atmospheric conditions, 2.5wt% enzymes, and
reflecting with the acrylamide process.
Deamination
Any chemical reaction in the presence of water which removes an amine group in the form of
ammonia, following the general reaction formula, is deamination:
R-CONH2 + H2O R-COOH + NH3
Removing an ammonia molecule is immensely less energy intense then adding a molecule, but
unlike removing a carbon dioxide molecule (decarboxylation) does not release noticeable levels of
energy despite being slightly exothermic. The reaction is catalyzed either chemically or by using
enzymes, however in the field of oxidative deamination enzymes are becoming the norm. The
process conditions are analogous with enzymatic hydrolysis with one minor different, product
allocation. Unlike water, ammonia is a product and will be collected easily using a flash tank
separation. This means an extra 17.03g/mol of product will reduce the energy demand, or on
average

No Action
For the amino acids that contain a sulphur (cystine and methionine) there is currently no
potential production route that can make adequate use of incorporating this functionality.
Leaving them in their purified form for the animal feed market is the superior option. In fact, as
will be discussed in more detail in Chapter 8, amino acids with a chemical product of less than
2.5% of the amino acid distribution are also best left in their purified form for the animal feed
market at this stage of development. The development focus will commence with the higher
production volumes and gradually transition to a more complete use of the streams. This is the
logical step when addressing technological process gap hurdles in practice, but as the biorefinery
is designed to produce non-food chemical products the lowest form of chemistry is preferred;
conversion into ammonia.
Removal of Water
At some stage, before or after, the proposed reactions water must be removed to produce a pure
chemical stream. To facilitate several of the above mentioned reactions it is already required that
the purified amino acid reactants contain 0% moisture content. Others can be reacted directly in
their aqueous solution, namely those using enzyme technology. In these cases the chemical
product must be lastly separated from the aqueous broth. For simplifications purposes the same
process steps to remove water will be handled. As the products all vary to water in density and in
some cases their physical state, a centrifuge will be used to initially lower the moisture content to
20% (set). Afterwards a single stage evaporation system will further reduce the moisture content
to 95% and finally steam-based drier will fully de-watering the products.
5.3 Energy Input
5.3.1 Protease Solubilization

Initial protease digestion experiments were performed as a proof of concept resulting in
moderate solubilization rates of 51.7% for corn wet distillers grains and 41.5% for wheat stillage
(intermediary of distillers grains)26, 62. These values and process conditions form the basis of the
energy and exergy calculations, direct to Chapter 2 for the procedure to use Aspen+ process flow
diagram constructs. However, it is expected that with continued experimentation and
investigation into the operation kinetics that a near complete digestion (95%) can be obtained at
lower residence times (24hours) representing the future “expected” trends. Table 21 lists the
process conditions for the tested and expected values for corn and wheat processing streams and
additionally the projected conditions for all protein-rich biorefinery streams. “All” feedstock
sources, because at this stage within the biorefinery the post-fermentation streams should all have
similar composition and consistency. A protease loading of 0.1 weight percent in respects to the
protein content is set. Bacterial protease needs 22.3MJ/kg worth of ingredients, 19.6MJ/kg for
processing of which most is electricity, totally to 43.1GJ/ton3. Exergetically the value lead to
45.2GJ/ton. The thermal and electric internal process energy were based upon the Aspen+ model
with the entropy and enthalpy figures revealing the exergy flows, see Table 21 for an exemplary
spreadsheet.

Table 21 Protease Internal Process Energy/Exergy Calculations (DDGS example)
Category Unit D DGS

Solid Portion % 48.4%
Biomass Feed kg/h 484
Water Content kg/h 4356
Total Feed kg/h 4840
Feed Temperature °C 21
Protein Content % 4.1
Protein Flow ton/batch 0.1994
Protease Residence T ime h 6 12 24 120
Protease Temperature °C 40 50 72 40 50 72 40 50 72 40 50 72
Protein Solubility (1.0%) 12.5% 10.0% 15.0% 25.0% 20.4% 22.5% 60.0% 50.0% 47.5% 80.0% 49.9% 82.6%
Small Peptide Proportion (1.0%) 99.0% 98.0% 98.0% 99.0% 98.0% 98.0% 99.0% 98.1% 97.0% 75.0% 90.0% 89.6%
Protein Solubility (0.1%) % 5.0% 4.2% 7.5% 7.5% 5.0% 10.0% 55.0% 49.9% 47.3% 67.8% 57.1% 95.0%
Small Peptide Proportion (0.1%) % 99.0% 97.0% 95.0% 99.0% 98.0% 95.0% 99.0% 98.6% 97.4% 91.6% 89.4% 85.8%
Soluble Protein Yield (1.0%) ton 0.025 0.020 0.030 0.050 0.041 0.045 0.120 0.100 0.095 0.160 0.100 0.165
Soluble Protein Yield (0.1%) ton 0.010 0.008 0.015 0.015 0.010 0.020 0.110 0.099 0.094 0.135 0.114 0.189
Batch R eactor Heat 0.09 0.27 0.69 0.09 0.27 0.69 0.09 0.27 0.69 0.09 0.27 0.69
Heat Integrated GJ/h -0.05 -0.20 -0.56 -0.05 -0.20 -0.56 -0.05 -0.20 -0.56 -0.05 -0.20 -0.56
0.04 0.07 0.13 0.04 0.07 0.13 0.04 0.07 0.13 0.04 0.07 0.13
Batch R eactor Heat C ost
GJ 0.045 0.073 0.137 0.046 0.075 0.140 0.048 0.078 0.145 0.062 0.101 0.188
MJ/h 0.5047 0.50969 0.5211 0.5047 0.50969 0.5211 0.5047 0.50969 0.5211 0.5047 0.50969 0.5211
Stirring Electricity
GJ 0.0030 0.0031 0.0031 0.0061 0.0061 0.0063 0.0121 0.0122 0.0125 0.0606 0.0612 0.0625
Enthalpy In -68538 -68538 -68538 -68538 -68538 -68538 -68538 -68538 -68538 -68538 -68538 -68538
cal/mol
Enthalpy Out -68451 -68273 -67870 -68451 -68273 -67870 -68451 -68273 -67870 -68451 -68273 -67870
Entropy In -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336 -38.336
cal/mol. K
Entropy Out -38.053 -37.492 -36.281 -38.053 -37.492 -36.281 -38.053 -37.492 -36.281 -38.053 -37.492 -36.281
Ref Temp K 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15 293.15
kmol/h 246.3 246.3 246.3 246.3 246.3 246.3 246.3 246.3 246.3 246.3 246.3 246.3
Mass F low
mol/s 68.4 68.4 68.4 68.4 68.4 68.4 68.4 68.4 68.4 68.4 68.4 68.4
Exergy cal/s 284.8 1177.9 4464.8 284.8 1177.9 4464.8 284.8 1177.9 4464.8 284.8 1177.9 4464.8
& i ⋅ [(H i − H 0 ) − T0 (S i − S 0 )]
Ex = M kJ/s 1.2 4.9 18.7 1.2 4.9 18.7 1.2 4.9 18.7 1.2 4.9 18.7
GJ 0.005 0.021 0.081 0.021 0.085 0.323 0.082 0.341 1.292 0.206 0.852 3.230
Total Energy GJ 0.0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.2 0.3
Total Exergy GJ 0.008 0.024 0.084 0.027 0.091 0.329 0.095 0.353 1.304 0.267 0.913 3.292
Operation En ergy (1.0%) GJ/ton 1.9 3.8 4.7 1.0 2.0 3.3 0.5 0.9 1.7 0.8 1.6 1.5
Total Process Energy (0.1%) GJ/ton 4.8 9.1 9.4 3.5 8.1 7.3 0.5 0.9 1.7 0.9 1.4 1.3
Total Process Exerg y (1.0% ) GJ/ton 0.3 1.2 2.8 0.5 2.2 7.3 0.8 3.5 13.8 1.7 9.2 20.0
Total Process Exerg y (0.1% ) GJ/ton 0.8 2.9 5.6 1.8 9.2 16.5 0.9 3.6 13.8 2.0 8.0 17.4
Furthermore, heating efficiency of the digester was incorporated by including a typical insulted
mantel losing about 8% heat energy/exergy per day or 0.333% per hourly operation interval. In
the mentioned articles, the optimal processing conditions were assessed between the protein
solubilization yield in light of potential fossil fuel saving from the downstream product yields to
the internal process energy costs. This is not needed when presuming an expected solubilization
yield of 95%; here the focus is placed upon lower processing conditions. The following table
provides an overview with the projected “all” derived by combining the expected corn and wheat
values:
Table 22 Protease Solubilization Process Energy/Exergy
Crop Corn Wheat All

Unit
Phase Tested Expected Tested Expected Projected
Conditions
Solubilization Rate % 51.7 95 41.5 95 95
Protease Loading g/g protein 0.01 0.01 0.01 0.01 0.01
Temperature °C 40 40 50 50 45
Residen ce Time Hours 120 24 120 24 24
Electric GJ/ton AA 1.97 0.33 1.83 0.45 0.39
Th ermal GJ/ton AA 1.31 (0.98) 1.14 (0.12) 3.41 (1.63) 2.52 (1.11) 1.83 (0.62)
Enzymes GJ/ton AA 0.83 (0.87) 0.45 (0.48) 1.04 (1.09) 0.45 (0.48) 0.45 (0.48)
The total projected processing energy and exergy cost for all of the feedstocks from this stage in
the biorefinery are 2.67GJ/ton and 1.48GJ/ton protein.
5.3.2 Separation and Isolation

The separation and isolation steps as depicted in figure 6 are handled individually with a set
separation/isolation efficiency of 97% (being common) for each step33, 65. And seeing that the

amino acids require between 3 and 4 steps, the overall isolation efficiency is 91 – 94%. Table 22
lists the range of thermal and electric energy required to operate the separation units. As the
resulting product process energy are functions of the flux, all the values are presented per
product flow rate (i.e. cubic meter). Thus for representative purposes the listed “product
relation” is based on the continued arbitrary protein concentration of 6.5 wt%. Lower
concentrations (which will occur, see Chapter 8) directly increase the isolation and purification
operation energy demands. Despite the large thermal component needed for viscosity adjusting,
these procedures are considered to be electric driven. Listed in the appendix are the resulting
exergy figures with a clearly indicates the low thermal proportion. The selected (or chosen) values
within the range are thought to be characteristic of potential amino acid purification steps:
Table 23 Isolation and Purification Operation Energy/Exergy Demands
Type Thermal Energy Electric Energy Produ ct Relation

Nanofiltration - 1 – 7kWh/m³ (3.5) 0.194 GJ/ton
Electrodialysis 24.2 – 74.8kWh/m³ (33.8) 85.8 – 265.2kWh/m³ (119.7) 8.5 GJ/ton
Chromatography 42.9 – 123.2kWh/m³ (97.5) 12.1 – 34.8kWh/m³ (27.5) 6.9 GJ/ton
Reverse-Phase 36.2 – 37.1kWh/m³ (36.4) 15.2 – 32.3kWh/m³ (19.0) 3.1 GJ/ton
Reverse Osmosis - 2.5 – 10kWh/m³ (9.0) 0.498 GJ/ton
value range (brackets chosen): # - # (#)
Figure 7 Amino Acid Purification and Isolation Process Energy
Amino Acid Separation Step Process Energy

3.5
Electric Energy
Thermal Energy
3.0
2.5
GJ/ton Direct Energy
2.0
1.5
1.0
0.5
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5.3.3 Drying and Product Preparation

Either before the chemical reactions or afterwards, the purified amino acids streams or final
product entail a dewatering step; envisioned here by a common three step process:
Table 24 Dewatering and Product Preparation Energy Cost
Dewatering Step Unit Value

Centrifuge
Initial Produ ct Content % 6.5
Final Produ ct Content % 80
Electric GJ/ton product 0.31
Th ermal GJ/ton product 0 (0)
Single Evaporation
Initial Produ ct Content % 80
Th ermal GJ/ton product 0.81 (0.08)
Steam Drying
Initial Produ ct Content % 95
Th ermal GJ/ton product 0.27 (0.03)
6.5% moisture is an example for display purpose, will depend on feedstock amino acid content
The three steps involve a transition from the post-fermentation relative weight content (set here
as 6.5 wt%) to 80% via centrifugation than to 95wt% by single evaporation and finally dewatered to
100 wt% through standard steam drying. There are several other dewatering technologies available;
this particular layout is conventional, straight forward, and can be adapted to all product streams.
And while it may not necessarily represent the single most energy efficient technology it is
amongst the ranks of efficient drying process’s.
5.3.4 Reactions
All the reactions involved in the hypothetical amino acid to chemical product production have
been grouped together. Considering that none of the envisioned reactions have any specific
reactions parameters this grouping generalization is possible and provides a satisfactory
indication of the prospective production routes. The grouped reaction type process energy and
exergy requirements are determined and presented in molar mass terms (i.e. kJ/mol) because
each amino acid and potential chemical product boast unique molecular masses. This also allows
the stoichiometric mass to heavily influence the results, see Appendix 10.6. As seen in the
following figure the process energy requirements differ immensely from each other. The indirect
chemical energy is understood as the enzyme production costs. Being currently rare, site specific
and far from optimized enzymes the most energy intensive route are chosen; namely, 89.3GJ/ton
energy and 136.1GJ/ton exergy. Furthermore, a higher loading in the order of 1.0% is
anticipated.
Figure 8 Process Type Process Energy

Amino Acid Chemical Process Unit Type Energy
450
465 1991
Indirect Chemical Energy
Electric Energy
Thermal Energy
350
250
k J/mol
150
50
En zyma tic En zyma tic Ma illard Rea ct io n Redu ct ive Electro lysis Fe rme ntative En zyma tic Th ermal Enzymatic
Decarboxyla tio n Hyd rolysis Amin ation Catalysis Catalysis De amination
-50
5.3.5 Overall
Figure 9 Overall Amino Acid Process Energy
Amino Acid Overview Chemistry
40 5.0%
Indirect
Electric
Thermal
35 Protein Relation 4.5%
30 4.0%
Process Energ y (GJ/ton)
25 3.5%
Overall Yields
20 3.0%
15 2.5%
10 2.0%
5 1.5%
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Figure 10 Overall Amino Acid Chemical Product Process Energy
Amino Acid Product Process Energy
40 8.0%
Indirect
Electric
Thermal
35 Pro tein Relation
7.0%
30 6.0%
25 5.0%
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Overall Yields
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6 Lignin
6.1 Description
Lignin is the second most abundant biomolecule in the biosphere after
carbohydrates and is the single most abundant source of aromatics.
And unlike the other biomass components, lignin is exceedingly unique;
every plant species, every plant, every section of the plant and every
molecule of lignin is slightly different. Its individual highly complex
polymeric structural layout of aromatic compounds are bonded
together by two major links types; unconcentrated beta-oxygen-4 links
(β -O-4) and concentrated carbon-carbon links (C-C). Three aromatic
monolignol monomers with various degrees of methoxylation form the
basis of lignin formation; p-coumaryl alcohol, coniferyl alcohol, and sinapyl
alcohol. When incorporated into the lignin structure following the two
linkage types they form p-hydroxyphenyl (H), guaiacyl (G), and syringal (S).
The final lignin structure present in biomass material are large cross-linked
recemic macromolecules with a molecular mass exceeding 10000 units, see
the adjacent picture for a likely representation. It can be characterized by
the general empirical formula: C9H8-xO 2[H2 ](<1.0[OCH3]x). This chemical configuration provides
great structural integrity to biomass conferring mechanical strength to the cell wall. In addition to
rigidity, lignin’s structure also reduces digestibility of plant biomass, which aids in the defence
systems against pathogens and pests. Yet lignin, as the derived name lignum (Latin for wood)
suggests, provides structural stability to plants as a whole and being a product of plant aging is
commonly associated with woody biomass. The lignin structure in woody biomass is best broken
down into hardwoods consisting primarily of β -O-4-linkages (>60%) and softwoods consisting
primarily of C-C-linkages (upwards of 90%). Non-woody biomass materials (as is case for the
selected crops) are more characteristic of softwoods, consisting mainly of C-C-links.
Lignin as a by-product stream has been around for more than century since lignin is removed
from wood-based pulp to manufacture “woodfree” paper. In both the sulphite and Kraft processes,
sulphur drives the delignification and separation reactions producing a waste stream of
lignosulfonates. The pulp and paper industry have even adopted their own proverb regarding
lignin or in actuality the lignosulfonates, “you can make anything from lignin…expect money”. In fact,
these lignin by-products are used for around 300 different applications varying from binding
agents (adhesives, acting as a glue) to dispersing agents (preventing clumping and settling of
undissolved particles in suspensions). None of these product applications make particularly good
use of lignin’s aromatic functionality and are essentially inferior products, yielding little profit.
Furthermore, despite these existing efforts to produce products and blends the large majority of
lignosulfonates are currently burnt as a fuel source. A good general formula to represent a section
of lignin is C20H23O 7 resulting with a relatively high calorific value of 25.6GJ/ton. Lignin
originating from within future biorefinery concepts will be present in vast quantities and due to
market saturation are not suitable for the same product array as with the lignosulfonates. Its high
calorific value is already proving alluring as currently all 1 st generation biofuel biorefinery-types
are burning the lignin-rich waste streams for internal heat and power requirements. The lignin-

rich stream originating from within this Chapters’ proposed biorefinery concept is, however,
much purer; essentially composed of lignin, minerals (ash) and traces of un-reacted or separated
biochemical impurities in a water solution. This lignin-rich stream is the last stream that can be
subjected to processing options to yield a chemical product. Plus, to remain dedicated to the
main objective of mitigating the use of fossil fuels from within the petrochemical production
chain, directly burning lignin is not a viable option. New processes are gradually being researched
and developed to make use of its aromatic functionality. Soon lignin will no longer be viewed as a
waste product but as a valuable co-product with the biorefinery concept.
6.2 Processing
6.2.1 New Product Options

To utilize the aromatic functional components of lignin the complex lignin structure must be
degraded to release the so-called oxygenated aromatic compounds (OAC)86. Its unique and
complex structure presents a critical problem to any depolymerisation or degradation process as
the resulting OAC products range in an array of beyond 50 individual chemical products. This
places great difficulties in downstream separation and isolation techniques. Research efforts are
under way to vastly reduce the product array and isolate particularly desirable aromatic products.
Due to the unique structure of lignin and the early stages of investigation, laboratory
experimental testing use simple representative structures to mimic the two types of linkages87.
Phenethyl phenyl ether (PPE) for C-C links and its methoxy derivates for β -O-4 links. Cleavage
of the two linkage types will produce several but distinctly different groups of chemicals:
Carbon-carbon cleavage (α and β aryl-alky-ether bonds)
Yields phenolic compounds: like benzene, p-hydroxyph enyl, phenol hydroxylase, acetophenone
monooxygenase, cresol, styren e, paraderivatives of phenol, etc.
β -O-4 cleavage
Yields guaiacols and syringols: both can be fractionalized to yield synthons (idealized fragment ions) but
are better suited fo r furth er d egrad ation into chemical precursors like straight benzenes
The goal of lignin depolymerisation is to cleavage these links yielding high levels of the simple
aromatics from benzene to benzoic acid, those which exist in the petrochemical industry. This
proves advantageous for the selected biomass crops as their lignin structure is primarily based
upon the C-C-link, which form the more desirable phenolic compounds. Three different
emerging technologies (fungal degradation, gasification and fast-pyrolysis) will be handled in this
section with the equal aim set on creating new potential product options for lignin-rich streams.
Although the success is limited and largely hypothetical, the aromatic-based amino acids might
eventually be better suited for lignin processing routes as opposed to the amine chemistry option.
While currently, processing lignin and/or aromatic-based biomass streams to produce OAC’s is
the least investigated technological option within the biorefinery concept. Research is thus in its
infancy with the yield, more so than the actual process conditions, effecting the overall internal
process energy. Therefore, expected yields based on current experimental figures will be handled.
6.2.2 Fungal degradation

In nature decay of the lignin components of wood occurs through a fungal infection of different
types; brown rot, soft rot or white rot fungi. Laboratory investigations pertaining to
delignification processes have almost exclusively focused upon white rot fungi. White rot fungi
cultivated on woody biomass produces several ligninolytic enzymes; extracellular laccases (EC

1.10.3.2), manganese peroxidase (EC 1.11.1.13), lignin peroxidase (EC 1.11.1.14) and H20 2
producing oxidases. There are dozens of fungi species and sub-species containing ligninolytic
enzymes, while most research on lignin degradation for practical purposes has been performed
using the various strains of the pleurotus species. Investigation to their industrial applications have
been around for several decades88. It has since been determined that manganese peroxidase,
which is excreted from most white rot fungi, plays the crucial role in the delignification
mechanisms by generating oxygen species89. The other enzymes are dependent on incorporating
oxygen in their reaction mechanisms with all the enzymes grouped together and expressed as
containing a total ligninolytic activity, expressed in units per gram wood (IU/g). Typical activities
range from 0.1 – 3.0IU/g with 1.5 being average, which converted, approximates 0.12% gram
enzyme per gram lignin loading rate. The main applications of white rot delignification is for
decreasing the lignin content within the pulping process, known as biopulping. It is an intermediary
step to reduce chemical demand and process energy and the conversion rates are rather low8, 89:
Table 25 Fungal Degradation of Lignin
Enzyme Source P. Eryngii P. Ch ysosporium P. Ostreatus P. Radiata

Delignification Rate 47% 45% 56% 25%
It is not necessarily suitable as a means to produce and yield aromatic chemicals because the
lignin only needs to be (partly) solubilized, meaning an immense array of possible chemical
combinations are naturally present. Furthermore, within the carbohydrate processing sections the
enzymatic hydrolysis and pretreatment steps already degrade a portion of the lignin, solubilizing a
noticeable amount (~1/3). Ligninolytic enzymes could be added at the lignocellulose treatment
stage to accelerate and improve the glucose conversion of, in particular, the recalcitrant materials
(i.e. those containing high levels of lignin). Perhaps future strains and generations of specially
tailored enzymes can target specific linkage and produce a narrow range of chemical products by
adapting enzyme cocktail combinations. Until those routes are investigated there is no real future
of fungal delignification within a biorefinery concept, regardless of it worthiness to mention.
6.2.3 Gasification
Gasification is widely considered to be a very promising biomass processing route and a realistic
alternative to the traditional fermentative routes. It involves the thermal degradation of any
carbonaceous (carbon-containing) raw material to produce syngas (H2 + CO). At temperatures
above 900° C tar formation begins to negatively influence the product yields while at
temperatures below 750° C conversion efficiencies drop. Modern fluidized-bed systems can
however, lower the temperature range to 400 - 500° C at no drop in conversion efficiency.
Nonetheless, gasification is a high-temperature thermal operation with corresponding pressures
approaching 25bar and residence times commonly exceeding an hour. Syngas is a mixture of
hydrogen, carbon monoxide and carbon dioxide with the basic idea is to produce the fuel
hydrogen. As the level of oxygen is regulated gasification does not follow combustion kinetics
but instead follows three separate reactions kinetics designed to maximize the production of
syngas:
(1) C + H2O → CO + H2 (2) C + O2 → CO2 (3) CO2 + C → 2CO
Conversion efficiencies are documented by two terms when referring to biomass feedstocks; (1)
carbon-to-gasification product ratio (CGR) and (2) hydrogen-to-gasification ratio (HGR). The

overall feedstock-to-product ratio of biomass feedstocks are frequently able to reach 80 – 95%.
Lignin contained in biomass, however, has been found to directly reduce these conversion
efficiencies. Investigation into gasification systems based solely on pure lignin feedstocks found
HGR values in the order of only 9 – 26%. It is understandable because the depolymerisation of
lignin induced by the gasification process reacts (consumes) with a portion of the released
hydrogen product, effectively lowering the overall syngas yield90. Researchers in the field of
biomass gasification technology are aware of this restriction and are even promoting the
development of low-lignin biomass crops as sources of new feedstocks (Choren). In this respect
the overall conversion efficiencies are misleading as they often relate to low-lignin feedstocks or
in some scientific studies to pure cellulose, taken as a biomass “model” feedstock91. At this stage
it might be an idea to treat the lignin containing biomass material with the previously mentioned
fungal delignification step to overcome the negative influence of untreated lignin. Suppose that
the lignin issue were to be solved eventually, syngas (or hydrogen) does not make any use of the
aromatic functionality; the energetics of syngas production should be carefully assessed:
Consider: Hydrogen has a lower heating value of 120GJ/ton and a higher heating value of
142GJ/ton. Syngas being w ater-free, HHV can b e taken. Biomass contains 4.5 – 6.0wt% hydrogen
with 5.7% being representative fo r the lignin stru cture. Th erefore at maximum conversion
efficien cy the energetic yield is 142GJ/ton ⋅ 0.057 = 8.1GJ/ton. The HHV of lignin is 25.6GJ/ton
and even with a conservatively low power efficien cy of 35% the yielded energy content is
8.9GJ/ton. And this does not even take into account the energy requirements of gasification or
necessary compression of hydrogen for downstream application which must be deducted.
In all fairness though, syngas is envisioned as an intermediate and in the case on biomass
gasification to produce, via Fischer Tropsch, diesel92. FT-diesel is catalyzed and fully utilizes the
off-heat supplied by the high-temperature gasification unit, greatly increasing the overall energetic
efficiency. Yet still, hydrogen nor FT-diesel make efficient use of the aromatic functionality of
the lignin feedstock, meaning these systems are not appropriate for within the biorefinery
concept.
6.2.4 Fast-pyrolysis
Where gasification begins pyrolysis continues and fast-pyrolysis ends. Fast-pyrolysis is similar to
gasification being a thermal-based process acting upon carbonaceous feedstocks. It involves rapid
heat transfer and short residence times for both the substrates and decomposition products. As
water negatively influences heat transfer rates and can cause secondary reactions in the
decomposition product stream, the feedstock must be completely dry. The following table
outlines the main differences between gasification, conventional pyrolysis and fast-pyrolysis:
Table 26 Thermal Degradation Types
Type Pressure Temperature Residen ce Time Liquids Chars Gases

Gasification 25bar 400 - 900°C Hours 5% 10% 85%
Pyrolysis 10 300-400 Minutes 30 35 35
Fast-Pyrolysis 5 250-450 Seconds 75 12 13
The key difference between gasification and fast-pyrolysis is the decomposition product
distribution; gasification produces mainly gases (syngas) where as fast-pyrolysis yields liquids
(aromatics). Gases from the fast-pyrolysis are the smaller components, broken off as formed
CO 2, H2O, etc. The chars are un-reacted and heavy particles, which will form a valuable fuel

source for further combustion, Section 7, and any simple hydrocarbons in the gas stream can also
contribute. Both conventional pyrolysis and fast-pyrolysis are performed with the absence of
oxygen, however inclusion of minor amounts has shown to slightly increase the proportional
yield of phenolic components over other oxygenated aromatics. Some components begin to
cleavage at temperatures as low as 220° C, while require at least 400° C.
Table 27 General lignin pyrolysis temperature dependent decomposition production
Temperature Bond Cleavage Type Derivatives

150 - 300°C α- and β- ether Oxygenated Aromatics
300 - 350°C Aliphatic side chains Phenolic Compounds
370 - 400°C Carbon-carbon Guaiacyl, Syringyl
400 - 450°C Rest Various OAC
>450°C All Phenol/Benzene + Gases
Most researchers agree that between 425 – 575° C yields the maximum amount of decomposition
products. At moderate temperatures, below 450° C, over 90 different products are detectable
from biomass streams. Temperature exceeding 450° C presents a larger proportion of phenols
and benzenes and begin to form styrene which oddly originates from the carbon-carbon links93.
At temperatures above 500° C, phenol, styrene, and toluene appear to be the main products. Even
on woody biomass phenol production can reach up to 52% of the total product distribution
when temperatures above 600° C are employed94. But generally research and development into
lignin pyrolysis is limited and has so far been unsuccessful in producing pure chemical product
streams and are only able to yield a wider assortment of pyrolytic components and their
corresponding radicals. Most studies into lignin decomposition obtain lignin from the traditional
pulping processes (meaning lignosulfonates) while others rely on fresh biomass streams (meaning
lignocellulose). These are not representative for the lignin-rich stream from within the biorefinery
concept. Other investigations are analysing the reaction kinetics of fast-pyrolysis on lignin by
employing lignin model chemicals. A large variety of dimmer and trimmer molecules mimic the
different chemical bonds and links contained in the lignin structure. Initial studies have found
cleavage rates for phenolic dimmers to be 3.6 – 80.5% and 17.8 – 70.1% for p-substituted
phenols95. Fast heat transfer at high temperatures is still the most influential factor. A recent low
temperature fast-pyrolysis experiment on model chemicals found a high cleavage rate but yielded
a wide assortments of phenolic compounds96. Earlier studies on PPE as a model for C-C-linkages
(β -ether) found an increase in styrene and phenol production (at equal molar distributions) at
temperatures ranging from 500 to 650° C97.
The exact yields of potential aromatic chemicals from lignin at this stage must be presumed and
set as an expectation. Firstly, on the variety of lignin sources 75% total decomposition yields are
already achievable, 95% should be possible and foreseeable with future developments and
optimizations. Secondly, as alluded in table 25, lignin will naturally endure losses as at least 13%
of the lignin structure is not and will no longer be directly attached to the aromatic rings of the
liquid product. The level is dependent on the final chemical products, set here (thirdly) as an
equal molar mix of styrene, phenol and toluene. The highly branched aromatic cinnamic acid
with a molar mass of 148.2g/mol can represent an initial decomposition product. The expected
product mix has a lower average molar mass of 99.1g/mol, meaning 33.1 wt% is unusable product

(i.e. gases). Fourthly and finally, setting the yields of the desirable aromatic product mix. Initial
studies have rarely yielded above 10% of any particular component, yet it is expected that with
additional temperature and process optimizations 90% product yields are achievable.
18.5% phenol, 20.5% styrene, 18.1% toluene of lignin feedstock
Another future potential option to lower the product array to these or other certain select
aromatic chemicals could be to utilize enzymes targeting and cleaving off side branches.
6.3 Energy Input

Gasification systems designed for biomass applications are noted to use 20 – 30wt% of the
supplied feedstock as a source of heat generation. At a calorific value of 25.6GJ/ton for lignin
the gasification unit requires more or less 6.4GJ/ton product. Gasification as mentioned is
designed to produce syngas (hydrogen) and operates at high temperatures (>800° C) for long
residence times (>1hour). The fast-pyrolysis unit operates at lower temperatures (<600° C) for
much shorter residence times (<1minute). The operation energy intensity will also be lower
because the feedstock stream must first be removed of water. So, before the fast-pyrolysis unit
the lignin-rich stream will be subjected to a multistage evaporation system. Process energy
requirements are vastly lower then the single stage evaporation as described in the amino acid
section (Section 5.3.3), largely due to the streams release temperature from the distillation column
(~70 – 80° C). The electric energy demand is set at 5kWh/ton water removed and the thermal
energy and exergy demand is 125kWh/ton and 12.4kWh/ton water removed, respectively. And
analogously to the amino acid-rich stream the initial moisture content of the lignin-rich stream is
feedstock dependent. For representation purposes and being close to the expected values, the
solids loading is set here at 10wt%. To fuel the fast-pyrolysis unit an outside source of process
energy is supplied because the feedstock is destined to maximize aromatic product yields. The
requirements are based on the internal cleaving energies of the various chemical bonds:
Table 28 Lignin Bond Type Energies and Product Relation
Bonding Energy Phenol Relation Benzoic Acid Relation

Bond Type
kJ/mol GJ/ton GJ/ton
Aliphatic C-O 245 2.6 2.0
Aromatic C-O (methoxyl) 356 3.8 2.9
Aromatic C-O (hyd roxyl) 414 4.4 3.4
α-ether 185 2.0 1.5
β-ether 239 2.5 2.0
Relating the bonding energies with these two example products (large and small molecules)
reveals that the thermal process energy ranges from 1.51 – 4.40GJ/ton with an average cleavage
energy of 2.73GJ/ton. At 600° C the exergy-to-energy ratio is 84%, resulting in 2.3GJ/ton. Both
energy and exergy values must be brought into relation with the actual product weight
distribution yields (i.e. 18.5% phenol, 20.5% styrene and 18.1% toluene). Further downstream
separation and isolation of the three main product streams is rather straight forward, relying on
swing adsorption technology. The process energy demand is largely based upon the ethanol
dehydration unit, a swing adsorption type. Combined the overall lignin to several select aromatics
products streams results in the following figure:

Figure 11 Overall Lignin Process Energy
Lignin Product Process Energy

4.0 25. 0%
Electric Energy
T hermal Energy
Lignin Relation
3.0 22. 5%
Process En ergy GJ/ton
Overall Yields
2.0 20. 0%
1.0 17. 5%
0.0 15. 0%
Phenol Styrene Toluene

7 Ash
7.1 Description
Ash is the name assigned to all biological components that cannot
be classified as organics. Generally this refers to metal ions and
metal salts, which while contained in living organisms are frequently
referred to as ligands. The term ash is used because these metal
compounds remain after combustion in the form of metal oxides.
As listed in Chapter 4, ash can constitute between 5 to 20% total
plant biomass. While ash is always included in proximate analysis of
biological materials (like biomass), in this section it is not understood as merely the summation of
all non-organic components. In the crop guide overview, it is presented as the summation of all
components that do not fit into the other biochemical classifications; namely carbohydrates, fatty
acids, proteins and lignin. Following this definition ash can also contain undisclosed trace levels
of other organics. The functional role of these ash components was described in full detail for
each major component in the fertilizer section of Chapter 5. As a synopsis, the non-organics are
required for many highly specific biological roles. The exact composition of ash is feedstock
dependent and cultivation practice dependent, but there is a strong relationship between nutrient
uptake requirements and total ash content. Nonetheless, the following table presents an
acceptable generalization that provides an indication to the main resulting metal oxides:
Table 29 Ash Composition Generalization
Metal Oxide SiO2 K 2O CaO P2O5 MgO SO3 Na2O

Ash Proportion 35 30 15 10 5 2.5 2.5
Ash mainly consists of silicon (oxide), which in the event of large soil removal through harvesting
procedures can lead well over 50%. Explained in the earlier handling procedures (Section 2.2), all
soil contamination will be washed out from the feedstock input stream, meaning the 35% value is
representative of the actual amount contained in the biomass material. This composition
generalization was also employed in Chapter 4 (Appendix 3.1) for determining the energy content
upon combustion, resulting in 2.89GJ/ton and 2.43GJ/ton average energetic and exergetic
output. The energetic output of the metal oxide formation is not particularly high and little
deviation would occur by using the exact feedstock specific composition. However, at this last
stage in the biorefinery concept all the unreacted, unconverted, and unseparated biochemicals
will form the ash-rich stream. Combined they are feed into a combustion unit for the generation
heat and power at much higher calorific values than the ligands alone. The power conversion
efficiencies and process conditions will be handed in the next section. In addition to the
moderate levels of energy that can go towards reducing the internal process energy requirements
of the biorefinery, the residue solid stream will still contain the metal oxides or “ash”. Several
potential applications will be described for the ash that have the possibility to mitigate other fossil
fuel intense production routes, unrelated from those of the petrochemical industry.

7.2 Applications
7.2.1 Combustion
In Section 6.2.4, the fast-pyrolysis unit was described in detail to how the aromatic components
can be yielded from the lignin-rich stream. The char residues (unreacted material) and the vented
gases (small hydrocarbons) will be combined and subjected to combustion. This ash-rich stream
can be directly fired in a furnace yielding the components higher heating value (HHV) because
the stream is completely water-free. The basis for calculating the energetic and exergetic output
of the ash-rich streams is based on the group contribution figures for each component in the
stream as previous determined (Appendix 3.2). Even more so then with the other biochemical
components, this stream is incredibly feedstock dependent. The starting biomass feedstock
biochemical composition in combination with the various biorefinery product yields will present
each ash-rich stream with a very unique chemical composition. The resulting energy output upon
combustion cannot be determined at this stage, see Chapter 8 for the combined biorefinery
results. Here the power production efficiency can be determined. Several biomass power
generation technologies have reached technical maturity. The thermal efficiency range for
modern direct combustion units reveals 75 – 92% with a strong dependency on installation scale.
A similar installation scale factor is present for electric generation with smaller scale units
achieving 30% and 35% for larger operations98. In Europe the state-of-the-art biomass
combustion system can achieve an overall thermal power efficiency of 82%99. A combined heat
and power unit (CHP) is the obvious choice, to produce both a portion of electricity and thermal
energy. The 82% total efficiency can still be maintained, where as a realistic electric efficiency of
33% is possible. At those conditions the exergetic efficiency of the thermal component is 29%.
These efficiencies will from the basis for the internal heat and power production capacities.
7.2.2 Post-combustion
With the rising interest and establishment of biomass gasification and combustion units
worldwide, new solutions and opportunities are being researched to deal with ash100. The ash
from coal combustion has been investigated for many decades with several novel solutions101.
Currently, the fast-paced expansion of coal power plants is leading many sites to simply dump the
ash in a sort landfill or ash pond. The same disposal route should not be performed with ash
originating from biomass.
7.2.2.1 Building Material

The easiest and lowest product option is to blend the ash into the production of building
materials, especially concrete and similar construction materials. They have large production
capacities in the megatons scale and mixing in ash is possible at low blends without any
measurable effects on the structural integrity or physical properties. Ash affectively displaces a
portion of stone mining and production. Concrete as such has a rather low cumulative process
energy (between 1.3 and 1.7GJ/ton) with the portion associated to stone being under 1.0GJ/ton.
This ash product option should be considered the lowest utilization form.
7.2.2.2 Fertilizers
What goes in must come out. In the most ideal situation all the nutrients that were removed by
the biomass crop would be brought back to the field of origin in the form of ash; a closed-loop

system with the eventual input reduction of artificial fertilizers to zero. Sadly this is not possible
nor is it foreseeable in the near future due to the following reasons100, 102:
1. Loss of nitrogen
Nitrogen is the single most important and energy intensive fertilizer. In plant matter it is
fixated as protein and physically removed from the biomass feedstock stream as the
desired functionalized nitrogen-based chemicals. Any residual nitrogen is later emitted as
unusable gas (NO x) from the combustion unit.
2. Insolubility of phosphorous
The second most important and energy intensive fertilizer is rendered ineffective.
Through the thermal combustion process the resulting phosphorous oxide molecule has
a very poor solubility in soil and cannot be effective utilized by crops. Release of the P
nutrient is too slow for dedicated short-rotation bioenergy crops.
3. Heavy metal content
Even when originating from clean, untreated sources of biomass trace levels of heavy
metals like cadmium, lead and zinc are present in the ash. The use of catalysts and the
gradual corrosion of the equipment apparently end up in the ash. And while the
concentrations are fairly low (1-10ppm), these levels have a growth limiting effect on
biomass production.
4. Government legislations
In addition to limiting the biomass yields, the heavy metal content contribute to the
overall level of contaminants and can prevent application approval. Furthermore, while
the EU does permit wood-based ash fertilizers for biological farming, it (and thus the
Netherlands) do not permit the use of other biomass-based ashes for fertilizer
applications in respect to environmental protection.
5. Wealthy Dutch farmers
Situating the biorefineries in the midst of the Rotterdam petrochemical cluster means that
the final ash product stream would enter the local market. Ash has little agronomic value
on the expensive farm lands of Holland and farmers will not accept ash on their fields
unless mandated to do so. Alternatively shipping an ash stream back to the original fields
is economically and energetically ludicrous.
7.2.2.3 Ash Upgrading for Fertilizers

There are several exceptions to the above reasons that can permit ash to be used as a recycled
source of fertilizers. The first generation ethanol biorefineries in Brazil, for example, produce a
co-product stream called vinasse6. Vinasse is the bottoms from the distillations columns and
provide an excellent source of ferti-irrigation water while covering the bulk portion of the
adjacent farms potassium nutrient demand. Although proving effective, it is a temporary solution
as the full chemical biorefinery would no longer produce that particular stream. Still, utilization of
potassium and some of the other nutrients is alluring. Acidic treatment on the ash can be
employed to dissolve and separate out the more useful nutrients and brought directly into the
standard fertilizer production schemes. The downside is the energy intensity, for the operation is
more intense then starting with virgin material. Another option is to simply mix and blend in a
portion of the ash into the complex fertilizer formulations. The level of contaminants would
decrease and blending would contribute to a partial reduction of material and indirect fossil fuel

consumption. As long as the biorefineries are in their introductory phase with limited production
scale fertilizer blending is a feasible short-term option.
7.2.2.4 Land Reclamation

Chemical producing biorefineries for fossil fuel mitigation are a long-term solution for the
sustainable feedstock acquisition within the petrochemical industry. Applications for ash should
be addressed for their long-term solutions. One solution is both long-term and is particularly well
suited to the Rotterdam petrochemical cluster location. Mixed in some soil, sand and Dutch
technology and new land mass (polder) can be created with the eventually large streams of ash.
Managed properly over a 25 year course, the polder will become completely fertile. To keep the
polder stable and provide an organic content to the “soil” a perennial crop species is required. It
has been argued that leguminous species will have specific and beneficial application options
within the biobased economy that make use of their nitrogen fixation properties103. Once the
structural integrity of the polder is stable through adequate root structure of the perennial crop,
leguminous crops could be cultivated at these later stages to naturally fix nitrogen into the soil.
Over a course of several years the eventual nitrogen content of the soil could be brought to the
point where it is considered “fertile”. This land reclamation option would overcome the five
listed drawbacks of immediately and directly using ash for fertilizer applications. Here ash will
eventually be supplied to arable lands as a fertile nutrient-rich soil, a fertilizer replacement option.
It is essentially a large-scale, long-term biorefinery compost hep. The fossil fuel mitigation values
will be taken from Chapter 5 for the nutrients, despite the fact that the energy intensity of the
fertilizer industry will certainly decrease over the next 25 years.

8 Biorefinery System
8.1 Construction of Facilities
Producing chemicals from biomass requires the construction of new biorefinery facilities. The
advantage of producing the same chemicals as already contained in the petrochemical industry is
that the downstream infrastructure will remain unaltered. Nonetheless, the biomass feedstock
processing stages require new facilities and costs indirect fossil fuel energy for their manufacture.
EcoInvent, the LCI database, uses a general construction materials input of 0.11kg/kg product
for chemical production facilities. A biorefinery falls under that category. It requires several key
building materials; concrete, steel and glass. Concrete represents the bulk of the materials
followed by steel and lastly glass. Other construction materials (like paints) are in comparatively
minute quantities.
Table 30 Major construction materials process energy and exergy
Material Proportion CED CExD Energy Exergy

Con crete 95% 1.5 3.2 1.43 3.04
Steel 4.5% 22.5 7.4 1.01 0.33
Glass 0.5% 42.3 28.1 0.21 0.14
The average fossil fuel energy requirements for the construction materials is 2.65GJ/ton4. The
exergy value is estimated to be 3.51GJ/ton, meaning that at 0.11kg/kg an extra 0.27GJ/ton
energy and 0.35GJ/ton exergy must be added to the final biorefinery process energy.
8.2 Internal Process Energy

Throughout this chapter each of the steps along the full chemical biorefinery production route
were assessed for internal process energy and were intentionally expressed in thermal, electric and
indirect energy. In the ash section, the combustion unit was discussed and assessed for the heat
and power conversion efficiency. It will partly displace the internal thermal and electric energy
portion. It is however unlikely that the ash-rich stream will provide enough thermal and electric
energy for the entire biorefinery from any of the biomass feedstocks nor biorefinery layouts.
Furthermore, the high-metal chemical composition of the ash stream can cause internal
combustion problems, therefore co-firing is a likely solution. Coal is the best candidate with the
residual ashes following the same land reclamation route as for the biomass ashes. A coal power
plant has a CHP efficiency of 35% electric and 50% thermal energy (30% exergy). In the case
where more electricity is needed then the coal CHP at 35/50 can provide than electricity from
the grid will be imported via natural gas turbines operating at 45% electric energy efficiency. In
cases where more thermal energy is needed a direct coal furnace operating at 85% thermal
efficiency (50% exergy) will cover the difference. Thus the total internal process energy will be
related to the amount of related by external fossil fuel energy input. The amount produced by the
biorefinery combustion unit will be handled separately as a mitigated fossil fuel product. The
graphics used in Chapter 8 provide the best visual insight to the rational.
8.3 Local Production

In Chapter 6, several of the biomass feedstocks requiring vast transportation distances had
particularly high logistical input energy involved in preparing and shipping fresh biomass over the
long-haul transportation distances. Several aspects of the biorefinery can be performed on-site

(or close to the agricultural lands) essentially on a smaller scale. Figure 12 presents a simplified
overview of the total biorefinery system for a simple carbohydrate-rich feedstock (e.g. sugar
cane); an analogous layout is present with the other feedstocks, such as with fatty acid-rich
biomass. The red dotted line indicates which process steps are better performed locally and those
that are better performed at Rotterdam’s petrochemical cluster on the larger scale. Shipping (in
this case) ethylene and a dehydrated product mixture containing lignin, protein and ashes, will
vastly reduce the logistical input energy and thus the total agricultural energy input. The size and
moisture reduction step can also in several cases be avoided. An additional energy input is
introduced by preparing the dehydrated “half-product” mixture. The best suited dehydration unit
is the filter press and conveyor belt combination as handled in Chapter 6. The resulting impact
on the total agricultural energy input can only be determined once the entire biorefinery system
with the overall biochemical conversion yields has been incorporated, see Chapter 8.
Figure 12 Simplified Total Biorefinery System with Half-Product Separation
Biomass Handl ing Soil

(Simple C arbohydrate Rich) (Si zing/Soi l removal)
Simple
Et han ol
Carbohydrate Sugar Rich Glucose Ethylene Ethylene
Processing Processing Separat ion Processing
Complex
Processing Residues Carbohydrate Dehydration Unit
Pr ocessing
On-site (Small Scale)

Petrochemical Cluster (Large-Scale)
S/L Aromatics
Ligni n Rich Li gnin Aromatics
Separat ion Pr ocessing Separat ion
F ertilizers
Ash/ Residuals Electricity
Processing
Heat
Amino Acid Protein

Protein Rich N- Chemicals
Separation Processing
8.4 Results and Discussion

There are no results to discuss in this chapter, as it was an assessment of the internal and indirect
process energy and exergy required for each stage of the biorefinery for chemical production.

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Chapter 8
Fossil Fuel Savings
Mitigated energy and exergy in producing chemicals via the biorefinery concept
Ben Brehmer
Dissertation Report

Colophon
Title Chapter 8 – Fossil Fuel Savings

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ISBN-number -
Date o f publication 1. Octob er, 2008
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Approved by -

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ISO 9001:2000.

Abstract
The summation of the previously determined total biomass acquisition energy intensity in combination
with the total bioprocessing energy requirements are used to determine to potential fossil fuel energy and
exergy savings for each chemical biorefinery cropping system. The ultimate purpose is to present
the benefits of employing biomass as a feedstock for chemicals by using illustrative and concrete
results derived from the developed methodology. The results are used to validate the notion that
functionality upheaval is something to strive for in industrial biomass applications. The results are
expressed in graphical from, numerical form and accompanied by tables and descriptions for the
16 selected crops alongside the accompanying crop guide. The most important impact
assessment terms: savings per produced chemicals (production efficiency) and savings per arable
land area (land use efficiency), provide the information necessary to determine the optimal
biorefinery cropping system. No single optimum was determine but many improvement options
are present for the chemical biorefinery cropping systems. The main consideration of this chapter
has been to illustrate that nothing is simple or clear-cut but and that chemicals should present a
more attractive conversion option for biomass than energy or fuels.
Key Words:
Fossil fuel, biomass, replacement, results, chemicals, (bio)refinery

Content
1 Introduction 395
2 Compiling Results 397
2.1 Crop Guide 397
2.2 Results 397
2.2.1 Graphs 397
2.2.1.1 General Concept 397
2.2.1.2 Construct Description 397
2.2.1.3 Calculated Values 399
2.3 Production Figures 399
2.3.1 Description 400
2.3.2 Improvement options 400
3 Crop Guide, Results, and Discussion 401
Beta Vulgaris L – Sugar Beet 402
Brassica Napus – Rapeseed 406
Elaeis Guineensis Jacq. – Oil Palm 410
Glycine Max – Soya Bean 414
Helianthus Annuus – Sunflower 418
Manihot Esculenta – Cassava 422
Medicago Sativa – Lucerne 426
Nicotiana Tabacum L. – Tobacco 430
Lolium Perenne – Grass 434
Panicum Virgatum – Switchgrass 438
Saccharum Officinarum L. – Sugar Cane 442
Salix Alba – Willow Tree 446
Solanum Tuberosum – Potato 450
Sorghum Bicolor – Sweet Sorghum 454
Triticum Aestivum – Wheat 458
Zea mays L – Maize 462
4 Optimal Biorefinery Concept 467
4.1 Overall Results 467
4.2 Overall Comparison 467
4.2.1 Energy 467
4.2.2 Exergy 469
4.2.3 Combined Performance 470
4.3 Discussion 470
5 Conclusion 473
5.1 Ben’s Tips 473

1 Introduction
In the previous chapters, information relating to and required for the mass and energy balances
were compiled using the standardized methodology enabling a matrix calculation of energy (and
thereby also exergy) inputs all corresponding to biomass propagation and biomass conversions:
the total biomass acquisition energy intensity and the total bioprocessing energy requirements for the
biorefinery were determined for each potential cropping system. At this stage the various selected
cropping systems can be combined with the appropriate conceptual chemical biorefinery layout.
This chapter is therefore, in effect, the summation of all the previous work to illustrate the
potential fossil fuel energy (and exergy) savings that can be obtained by employing biomass
feedstocks for bulk petrochemical products.
Most industrial biomass application routes focus on the potential calorific values of utilizing the
biomass feedstocks; studying the fossil fuel energy replaced upon combustion. This holds true
for nearly all applications from straight bioenergy to biogas, to biofuels, and even to the most
complex gasification systems. And while an internally combined heat and power combustion
(CHP) unit is envisioned for each of the potential chemical biorefinery layouts, it does not
represent the main goal nor encapsulate the greatest replacement potential. Here the focus has
been on providing an alternative feedstock for existing petrochemicals. True, industrially
cultivated biomass feedstocks yield a carbon-based feedstock which have, for the large part, a
significantly lower fossil fuel energy intensity then the contained calorific value. Yet, in this
chapter the results of the energetic and exergetic cradle-to-factory gate assessment will reveal that vast
enhancements of fossil fuel energy savings potential can, in most cases, be a multiple of several
magnitudes higher when employed for petrochemical production routes.
Naturally chemicals used in our throw away society will eventually end up in land-fills or
increasingly (as is the case in more environmental conscience societies) in incinerators. Heat and
power can be captured upon their combustion, hence expressing their contained potential
calorific value. One cannot include this processing stage along the product’s life cycle because
chemicals originating from biomass and fossil fuels (i.e. naphtha or natural gas) will follow the
same end-of-pipe path. Many previous and current LCA chain-based studies are fixated on the
idea of including calorific values at some stage for the biomass feedstock. In seems the norm is to
allot biomass a calorific value, typically dubbed as biomass energy. This is poor practice and cannot
be performed following the principles of comparative life cycle assessments. In this chapter, the
procedures to assess, visualise, and obtain the resulting fossil fuel energy savings potential should
make it clear that such common practices are contradictory. And while including the traditional
crude oil calorific values must be included, it is not in contradiction. Searching and assessing
potential solutions to replace the fossil fuel component in chemicals must include the fossil fuel
feedstocks. They follow the criteria set by the cradle-to-factory gate (or limited LCA) concepts and
are also included in assessing the total biomass acquisition energy intensity which was determined in
Chapter 6. Additionally calculating a biomass calorific value would be counterproductive and is
just incorrect methodology.
The heart of the results are the chemical biorefinery graphs which are meant to illustrate the
process energy (and in a separate graph, exergy) originating from the traditional feedstock routes

(naphtha and gas) in comparison to the unconventional potential alternative feedstock routes, i.e.
biomass. The busy graphs and scatter of comparative chemical products visualise the cumulative
energy (and exergy) demand of both production routes. It has been chosen to illustrate the logic
and conclusive results of upholding the functionalized groups of biochemicals in biomass.
The graphs are accompanied by numerical results and are separately discussed for the various
biomass cropping system as internal comparisons. Some major conclusions can be drawn
between particular regions and particular types of biomass feedstock streams, in the sense of
advantages and disadvantages. A major aspect of the final objective is to determine the optimal
biorefinery cropping system. Such information can help steer research directions and guide future
development of biomass cropping systems while indicating via strengths and potential weakens
the best chemicals to pursue.
The importance of striving for maximum land use efficiency of biomass employed within the
various alternative energy options has been stressed throughout the previous chapters: energy
consumed (and in this chapter saved) per land area, GJ/ha. Even though this does not solve the
apparent dilemma of the food vs. fuel and additionally vs. chemicals issue, it does provide an
indication of how to best cope with a future of increased land use competition. A portion of the
criteria to assess the optimal biomass cropping system layout relies on land use efficiency as a
indication factor. As important as it is, it is but one aspect, the other being the efficiency or fossil
fuel energy savings potential per chemicals actually being produced. Both resulting factors are
investigated in detail using the compiled and corresponding data.
1.1 Chapter Purpose

In the following chapter, all the previous compiled and calculated data pertaining to energy and
exergy input streams of biomass propagation and biorefinery conversions are brought in relation
to the traditional fossil fuel-based chemical production routes. The total embedded fossil fuel
energy in the proposed biorefinery systems are herein actively compared against the existing
petrochemical refinery to determine the level of potential fossil fuel savings in energy and exergy
terms. The ultimate purpose is to present the benefits of employing biomass as a feedstock for
chemical production by using illustrative and concrete results derived from the developed
methodology. These results validate the notion that functionality upheaval is something to strive
for in industrial biomass applications.

2 Compiling Results
2.1 Crop Guide
In the following section, the crop guide as previously described in full detail within Chapter 4 is
presented. It has been intentionally placed in this section as opposed to Chapter 4 to have the
various results of the biorefinery cropping systems alongside each other. It is insightful having all
the relevant information pertaining to the crop’s agricultural practices and considerations
together with the results and eventual discussion. This is mainly due to the fact that the results
are a direct function of the chosen biomass production systems and location. Any alternation in
the harvesting approach or location will have a direct influence on the results. This implies that
the results are meant as a guide for the crops and their corresponding regions, but are actually
variable and may not represent the best choice in regards to the chemical biorefinery layout for
the maximum potential fossil fuel savings.
2.2 Results
Each of the 16 selected crops in their respective locations have been determined following the
matrix-based calculations for the conceptual biorefinery layout. The results are expressed in
graphical from, numerical form and accompanied by tables and descriptions. Each form of the
results are used to indicate the potential fossil fuel energy and exergy savings of the biomass
cropping system for chemical biorefineries.
2.2.1 Graphs
2.2.1.1 General Concept

Immediately succeeding the crop guide are two pictorial representations illustrating the total
cumulative fossil fuel energy and exergy involved in arriving at an array of chemical products
when considering the various process routes from both the traditional petrochemical and
alternative biomass originating feedstocks. They are meant to visualize the methodological
calculation construct adhering to the work described in the previous chapters. The major results
of the graphs are presented in the brackets: the total CED & CExD (cumulative energy and
exergy demand) involved in processing the resulting array of chemical products from the biomass
feedstock route compared to the equivalent naphtha and gas feedstock route (traditional
petrochemical route). The biomass route is on the right-side and illustrated in green while the
traditional petrochemical route is on the left-side and illustrated in red.
2.2.1.2 Construct Description

With the primary goal focused upon producing chemicals and not
biofuels nor bioenergy there is a noticeable header: “next generation”,
explicitly meant to point out the developmental leap from biofuels
to dedicated chemical biorefineries. Listed below are the main
technologies used to convert the biomass feedstock into the main chemical products. They do
not represent every technology involved in converted biomass, but are the variable technological
options of the biorefinery layout, as described in Chapter 7.

Start with the biomass crop image on the right-hand side. Written beneath are the
regional choice and accompanying best practice yields of the crop in both standard
agricultural terms and total dry weight figures. The first energetic and exergetic
value written below “biomass” is a summation of the agricultural and logistics input
according to Chapter 6 in terms of GJ per ton dry weight, otherwise referred to as
“total biomass acquisition energy and exergy intensity”. Each of the biochemical
constituents is presented as their individually allotted feedstock portion. It is a
calculation functionally related to the original mass proportion and additionally as
the useable mass based on the conversion of the final chemical product. For example, simple
carbohydrates are converted to ethylene: the “GJ/ton” value is
expressed in terms of the final product (ethylene) and not of the
original biochemical constituent (simple carbohydrates). Meaning that
the values do not represent the allotted biochemical constituents
values solely but already as the feedstock proportion of the final
chemical product. For this reason, they are typically several factors
higher than the actual biomass acquisition energy and exergy intensity.
The dotted connecting arrows represent the internal process energy and exergy demand. An
intermediate figure is present for several chemical products routes
which indicate either a chemical product or a feedstock that are in
multiples. For example, ethylene can originate from three different
biochemical constituents: simple-, complex C5- and complex C6-
carbohydrates. Each constituent has an independent process route
with the intermediary indicating their independent process energy and
exergy demand. All the dotted connecting arrows led to a chemical product representing the total
cumulative energy and exergy demand. The resulting cumulative
biorefinery energy demand is determined by a direct mass allocation of
the proportional chemical product yields resulting from the biorefinery.
The same proportional mass ratio was used to determine the
corresponding petrochemical mixture, also indicated by the (red)
parenthesis; following the total cumulative energy and exergy demand of the traditional fossil
fuel-based production routes.
On the biomass chemical product side (left, green) the boiler output is listed
in direct energy and exergy terms. It is used to offset a portion (if not more)
of the internal heat and power processing requirements; this value is already taken into account in
the final biorefinery cumulative fossil fuel energy and exergy value. The offset energy and exergy
potential as described in Chapter 2 is a function of the cumulative fossil fuel energy that would
have otherwise been required. In cases, where the boiler produces more heat than necessary in
the biorefinery, the off-heat could theoretically be used to replace a fuel-oil burner. Similarly for
excess electricity which would replace an energy mix of coal and natural gas at limited production
efficiencies. It is here therefore imperative that any excess energy be brought into the grid – at
this stage this considered to take place.

The production of amine-based chemicals originating from proteins
(and subsequently amino acids) are too many to present individually.
There are 20 independent processing routes leading to 15 unique chemical products. To avoid
the obvious issue of cluttering, the protein processing routes have been grouped together to yield
“amine chemicals”. Ammonia is excluded from this grouping as it is a by-product of the main
amine-based chemicals for it is generally cleaved off as a result of the various chemical reactions.
Therefore, the amine chemicals figure indicated in the pictorial representation is the average of all
the 15 separate products, meaning the potentially heavy deviation of particular chemicals
products cannot be graphical visualized.
2.2.1.3 Calculated Values

Presented in the pictorial representation are several key pieces of information and results
calculated by the biorefinery layout. The following are commonly used in biomass and other
alternative energy production system to express their efficiency.
Net Energy Value & Breeding Factor

Net Energy Value (NEV) is the ratio of the output energy or
replaced energy contained in the products compared to the total
energy invested. It is common in practically all biomass application system to give an indication
of energy in versus energy out. The calculation is straightforward:
NEV =
(Petrorefin ery _ Energy + Boiler _ Ouput )
( Biorefiner y _ Energy − Boiler _ Output )
The breeding factor (BF) is the inverse expressed in a percentage form. It is meant to indicate the
percentage of non-renewable energy contained in the alternative feedstock.
Fossil Fuel Energy Savings

NEV and BF may be useful indication factors for bioenergy
and biofuel systems but are poorly adapted at biorefinery
systems. They have been designed for calorific-based
assessment systems; chemicals do not fall into this category,
yet it is nevertheless advisable to present the values for comparison to illustrate their
shortcomings. The most important impact assessment figures for a chemical biorefinery system
are relative fossil fuel energy savings. The savings can be related to many different base terms; to
amount of chemicals produced, to the amount biomass utilized and to land use consumption.
Alongside the oil barrel image is the “fossil fuel energy and exergy savings”: “GJ/ton chemicals” indicates
how much fossil fuel energy is saved per mix of the chemicals produced, “GJ/ton biomass”
indicates how much fossil fuel energy is saved per ton of dry feedstock, and the “GJ/ha”
indicates how much fossil fuel energy is saved per arable land area. These values are used to
determine the optimal biorefinery cropping system.
2.3 Production Figures

Proceeding the pictorial representations is a table listing an overview of the biorefinery system
and the overall savings. Firstly, all the chemicals and their production volumes are presented: in
terms of quantity per biomass feedstock (ton/ton crop), in terms of quantity per land area
(ton/ha), and in relative production terms of the chemical biorefinery mixture (%). Based on the
production mass relation the contribution to the total biorefinery energy and exergy demand is
listed for each chemical produced. This is one of the key differences as opposed to many other
LCA studies in the field of biomass applications, by using thermodynamics as the basis subjective
economic allocation weightings are avoided.
2.3.1 Description
Beneath the table is a short bulleted list describing interesting and unique aspects relevant to the
biorefinery cropping system. It is highly contextualized for the particular crop and helps guide the
reader to aspects which for that specific crop influence the resulting fossil fuel energy savings.
For many of the cropping system large quantities of minerals (or ash) can greatly decrease the
overall energy savings potential. Considering that the most energy intensive nutrient, nitrogen,
cannot be used as a fertilizer in land reclamation steps and for the most part contributes to the
protein molecules the savings potential of the residual nutrients (or ash) is vastly lowered. The
ash or recycled nutrients are a function of the biomass acquisition energy input as it is destined to
be a chemical product, potentially replacing fertilizer production. For this reason fertilizer
production from biomass can be intense but despite the minor to negative replacement potential,
in a world of foreseeable material and energy scarcity it is imperative to include a recycling step
for the nutrients. This step is necessary for long-term biomass schemes meaning those crops with
high ash output may only temporarily improve their overall biorefinery energy savings.
2.3.2 Improvement options

Many improvement options are present for the biorefinery cropping systems. Should any clear
and straightforward alterations in the biorefinery layout or cultivation practices be present to
further increase the fossil fuel energy saving value, they are listed. For several of the crops a
change in location and/or stressing on a certain chemical product by omitting a portion of the
standard (chosen) chemical products mix is frequent.

3 Crop Guide, Results, and Discussion
Crop Guide,
Results,
& Discussion

Beta Vulgaris L – Sugar Beet
Common Names
Sugar beet, beetroot, chad, mangel, spinach beet
Classification
Annual or biennial herb, C-3
Appearance
Numerous 1.5 – 2m large glabrous dark-green Leaves, oval, tapering to a
petiole, 5 - 10 cm thick conically shaped white bulbs
Varieties
Many available, to tolerate:
Al-ions, disease, frost, fungus, HF, high pH, Mn, salts, nematode, phage,
poor soil, slope, smog, SO2 and high disease resistance
Genetically Modified Varieties
Stringent restrictions, testing only, none grown in Europe
Brief Description
About 1/ 3 of the world sugar production derives from the sugar beet. Through crop selection the sugar
yields have increased from 5 to 20% in the past hundred years.
Growth Details
Native Area: Northwest Europe
Location: Europe, North America and China
Climate: Temperate – cool, best with mild frost periods and good sun exposure
Temperature: 5 - 26°C
Rainfall/Irrigation:
550 – 750mm, usually not above 880mm, can tolerate up to 2300 – 3150mm
Soil Type: Deep, friable well-drained soil with organic matter, poorly on clay
Soil Acidity: 4.2 – 8.2 pH, best between 6.0 – 6.8 pH
Plantation: Drilled at 1.5 – 2cm intervals, 30 – 45cm row spacing and 1.3 cm deep
Shallow seeding to control weed growth competition
Seeding Rate: Existing crops must be cold shock treated to produce a seed
4 – 6 kg/ha, seeds germinate irregularly, seed screening advised
35000 – 90000 plants/ha
Companion Crop: No, but rotated
Weed Control: Seedling stage poor competitor to weeds
Cultivation: Summer plant, May – June, mostly hand work or small tractor cultivators
Must be rotated, not with Brassica crops, i.e. kohl
Harvesting: In first year of growth, autumn to winter, mechanical beet harvester
Nutrient/Fertilizer Requirement
Utilizes nutrients from organic manures (farmyard manure, compost, organic wastes) quite well
The plant takes only half of the nutrients up, common practice to leave the foliage on fields
Over fertilization will reduce the yield of sucrose in the beet
Yiel d Dependent Macronutrient Uptake Yiel d Dependent Micronutrient Uptake
500 2500
N Fe
P2O 5 Mn
450 K2O B
CaO Zn
MgO Mo
400 2000
SO3 Cu
Poly . ( N) Po ly. (Fe)
350 Poly . ( P2O5 )
Total Plant Uptake (kg/ha)
Po ly. (Mn)
Total P lant Uptake (g/ha)
Poly . ( K2O) Po ly. (B)

Poly . ( CaO) Po ly. (Zn )
300 Poly . ( Mg O) 1500 Po ly. (Mo)
Poly . ( SO3) Po ly. (Cu)
250
200 1000
150
100 500
50
0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
T uber Yield (ton/ha) Seed Yield (ton/ha)

Yield
Normal Conditions: 30 – 60 ton tuber/ha (increase with further hybrids)
47.8 ton tuber/ha (EU-15 average), 57.6ton/ha (Germany : 5-year average)
Optimal Conditions: Well beyond 100 ton/ha
Worldwide Cultivation: 5.84 million hectares at 41 ton/ha
Chemical Composition*
(Based on dry weight)
Constituent Beet Leaves
Moisture Content 76.6% 86.4%
Cellulose 3.0 27.1
Hemicellulose 4.0 32.5
Lignin 0.7 3.0
Sucrose 70.0 -
Other Sugars 8.6 -
Protein 1.8 23.5
Fats 1.2 0.3
Minerals 3.3 2.1
Ash 7.4 4
Others - 7.5
Beet/tuber represents 62% of the total dry weight of the plant
*Strongly dependent on all growing factors, location and nutrient levels
Lower Heat Value: 16600 kJ/kg (beet only), 19900 kJ/kg (whole plant)
Higher Heat Value: 17700 kJ/kg (beet only)
Detailed Information
Beet Leaves
Free Amino Acid
g/kg % g/kg %
Alanine Unknown Unknown
Isoleucin e Trace 19.3 16.86
Leu cin e 0.58 11.74 16.9 14.76
Nonpolar & Methionine 0.43 8.70 3.1 2.71
Hydrophobic Phenylalanine 0.40 8.10 14.3 12.49
Proline Unknown Unknown
Tryptophan 0.79 15.99 0.5 0.44
Valine 0.49 9.92 14.3 12.49
Asparagine Unknown Unknown
Cystein e 0.13 2.63 0.7 0.61
Glutamine Unknown Unknown
Polar &
Glycine 0.41 8.30 Trace
Hydrophilic
Serin e Unknown Unknown
Threonine 0.11 2.23 10.8 9.43
Tyrosine 0.22 4.45 Trace
Asparagic Acid Unknown Unknown
Acidic
Glutamic Acid Unknown Unknown
Arginine 1.2 24.29 15.3 13.36
Basic Histidine 0.13 2.63 4.7 4.10
Lysine 0.05 1.01 14.6 12.75
Total 4.90 (27.2% of Protein) 114.4 (48.7% of Protein)
Comments
The yields appear very high, but what must be realised is that it is a rotational-based crop. This means that
the average yields over a longer period of time are significantly lower, yet other crops can be planted in the
field, for example legumes, to naturally restore nitrogen nutrients.

Comparative Graph
Energy
Styrene: 124GJ/ton 112 Lignin: 298GJ/ton

T oluene: 111GJ/ton
Next Generation Phenol: 99.7GJ/to n

Styren e: 83.9GJ/ton
80 Amine Chemicals: 83.2GJ/ton Net Energy Value (NEV): 2.3
Sugar-to-Bioethanol (Mi lli ng) Phenol: 76.5GJ/to n
Breeding Factor: 43%
Lignocellulose-to-Bioethanol (AFEX)
Tolu en e: 72.7GJ/ton
Protein Extraction (Protease ) 70
Ethylene: 67.0GJ/ton
Lignin Aromatics (Fast-Pyrol ysi s)
- Chemical vs. Biomass CED
60
- Raw Fossil Fuel Input 59.1GJ/ton
CRACKER
50
Crude Oil Protein:
45.1 45.8GJ/ton
44.9GJ/ton 42.8 Biomass
F ertilizers: 42.3GJ/to n Ash: 42.3GJ/ton 1.97GJ/ton
40
Complex C6
30 Ammo nia: 31.0GJ/ton Carbohydrates: 29.3GJ/ton Sugar Beet
26.7GJ/ton Ammonia: 28.5GJ/to n Germany
Am in e Ch emicals: 25.1GJ/to n Complex C5
10 0to n/h a b eets
Fossil Fuel Energy Savings Ethylene: 22.5GJ/to n
Carbohydrates: 26.6GJ/ton 29.2tota lDW/ha
20
32.3GJ/ton chemicals 17.2
10.0GJ/ton biomass
10
292GJ/ha
Boi ler: 6.2GJ/ton Simple Carbohydrates: 3.5GJ/ton
Fertilizers: 2.9GJ/ton Un-utilized
Traditional Biochemicals: Potential Chemical
Petrochemical Route 0GJ/ton 0GJ/ton Biorefinery Route
Exergy
T oluene: 113GJ/ton
Next Generation Phenol: 108GJ/to n

80 Amine Chemicals: 80.0GJ/ton Net Exergy Value (NExV): 3.0
Sugar-to-Bioethanol (Mi lli ng) Breeding Factor: 34%
Phenol: 75.8GJ/to n
- Chemical vs. Biomass CExD
60
CRACKER
50 Protein:50.4GJ/ton
Crude Oil Ash: 46.6GJ/ton
44.9GJ/ton F ertilizers: 46.6GJ/to n
Biomass
40 40.5 2.17GJ/ton
37.9
Complex C6
Carbohydrates: 32.2GJ/ton
30 Complex C5 Sugar Beet
Carbohydrates: 29.3GJ/ton Germany
Ammo nia: 23.0GJ/ton 10 0to n/h a b eets
Fossil Fuel Exergy Savings 29.2tota lDW/ha
20
67.6GJ/ton chemicals -7.7GJ/ton
Ammonia: 16.4GJ/to n
20.9GJ/ton biomass Am in e Ch emicals: 15.0GJ/to n
Ethylene: 15.0GJ/to n
10
610GJ/ha 8.9
Fertilizers: 6.0GJ/ton Simple Carbohydrates: 3.8GJ/ton

Boi ler: 5.1GJ/ton
Un-utilized

Overview Savings
Chemicals Biorefinery Production Total Biorefinery

Name ton/ton crop ton/ha % Energy Exergy
Ethylene 0.216 6.32 70.1% 18.72 -5.38
Phenol 0.002 0.06 0.7% 0.19 -0.05
Styrene 0.002 0.07 0.8% 0.21 -0.06
Toluene 0.002 0.06 0.7% 0.18 -0.05
1,4-butandiamine 0.005 0.14 1.6% 0.43 -0.12
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.001 0.04 0.4% 0.10 -0.03
Ammonia 0.002 0.07 0.8% 0.20 -0.06
ε-caprolactum 0.002 0.06 0.7% 0.19 -0.06
Ethylamine 0.003 0.09 1.0% 0.27 -0.08
Ethylenediamine 0.001 0.02 0.2% 0.06 -0.02
Feed grad e cystine 0.001 0.02 0.2% 0.05 -0.01
Feed grad e methionine 0.002 0.07 0.7% 0.20 -0.06
γ-butyrolactum 0.001 0.04 0.5% 0.13 -0.04
Ionic liquids 0.001 0.03 0.3% 0.09 -0.03
Isobutyraldehyde 0.004 0.11 1.3% 0.34 -0.10
Isoprene 0.009 0.26 2.9% 0.76 -0.22
Isopropanolamine 0.003 0.08 0.9% 0.23 -0.07
Oxalic acid 0.001 0.04 0.4% 0.12 -0.03
Urea 0.003 0.07 0.8% 0.22 -0.06
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.047 1.36 15.1% 4.04 -1.16
Description
- The biomass acquitistion energy input is in middle range with farming procudes and
logistic operations having the highest contribution. As diesel is the main source, little can
be done about exergy in relation to energy input, explaining the similar figures.
- The lignin-based components (aromatics) cost significantly more cumultaive energy and
exergy demand than the standard fossil fuel-based production routes. The chemical
composition of lignin is far too low in sugar beet even when including the tops.
- Several products which rely heavily on thermal processes (such as ethylene) have a large
difference between energy and exergy demand.
- Overall a considerable performance increase for exergy vs. energy as the boiler contributes
to a large offset of steam (internal heat demand) otherwise supplied by a coal power
plant.
Improvement Options
- Further decrease lignin content by earlier harvesting and/or do not include its processing
steps therby adding additional fuel to the interal heat and power combustion unit. Earlier
harvests could also have the propitious effect of raising protein content.
- A high soil content in harvested product (due to bulb) is present which results in energy
intense ash/fertilizer. Sacrife a portion of the yield to remove soil from skin.

Brassica Napus – Rapeseed
Common Names
Rape, Canola, Rapeseed, Oilseed Rape, Rapa, Rapaseed
Classification
Annual or biennial, C-3
Appearance
Green with purple-tint base, 1.0 - 1.5meter tall, branched, long, slender
stem, 10-30cm long petioles, horizontal toward base, pale yellow open
flowers, 1.2-1.5cm long petals,
Varieties
Several:
Summer and winter, erucic acid free (Canola) and enriched, high oil
Yes, but none in Europe as used as non-GMO feed.
Brief Description
It is widely cultivated for erucic acid, 2nd largest source of animal (mainly cows) feed, primary source of
vegetable oil and the main source for European biodiesel production.
Growth Details
Native Area: Western Europe
Location: Europe, North America, Australia, China and India (13% total cropped land)
Climate: Cool Temperate
Temperature: 5 – 27°C (sensitive to temperatures above 30°C)
100 – 830mm (average 250mm), can tolerate up to 2800mm
Soil Type: Fertile, sandy loams to light soils, well drained, low water table
Soil Acidity: 4.2 – 8.2pH (6.2pH best)
Plantation: Possible broadcasting or firm seedbed, 2.5mm deep grain drill,
30 – 40cm row spacing (common practice at 17 – 35cm apart)
Seeding Rate: Fertilizer dependent, 10 – 30kg/ha (5 – 6kg/ha little fertilizer use),
50/50 mix with cracked grains to mitigate the small seeds,
350000 - 700000plants/ha
Companion Crop: None
Weed Control: Yes, for early protection Treflan, Roundup ready
Cultivation: Winter type (high yielding in Europe): mid-September sowing, fall ploughing,
Must be rotated with non-oil based plant
Harvesting: Before fruit/seed ripens to protect damage, combine seed harvesting, July
Plant residue is re-ploughed in soil
Sensitive to high levels of fertilizers at time of sowing
Yield Dependent Macronutri ent Uptake Yi eld Dependent Micronutrient Uptake
600 2500
N Fe
P2O 5 Mn
K2O B
CaO Zn
500 MgO
2000 Mo
SO3 Cu
Poly . ( N) Poly. (Fe)
Poly . ( P2O5 )
Poly. (Mn)
Total Plant Uptake (g/ha)
400 Poly . ( K2O) Poly. (B)

Poly . ( CaO) Poly. (Zn)
Poly . ( Mg O)
1500
Poly. (Mo)
Poly . ( SO3) Poly. (Cu )
300
1000
200
500
100
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Seed Y ield (ton /ha) Seed Y ield (ton/ha)

Yield
Normal Conditions: 0.9 – 3.0ton/ha (seeds, total WW: 15 – 48ton/ha)
3.06ton/ha (EU-15 average), 3.8ton/ha (Belgium: 5-year average)
Optimal Conditions: 4.12– 5.5ton/ha (Belgium, seeds, total WW: 88ton/ha)
Worldwide Cultivation: 26.4million hectares at 1.75ton/ha (seeds)
Constituent Seeds Pod Stem/Stover
Moisture Content 10% 87.4% 83.3%
Cellulose 7.1 30.5 36.3
Hemicellulose 4.7 20.3 24.2
Lignin 8.6 - 9.7
Starch 0.4 - -
Sucrose 4.1 - -
Other Sugars 2.0 - -
Protein 25.7 34.1 15.7
Fats 41.5 3.2 9.2
Minerals 0.46 - -
Ash 5.0 11.9 4.9
Others 0.44 - -
Seeds, pods and stem represent 30%, 40% and 30% of the total dry weight respectively
Lower Heat Value: 18040kJ/kg (seeds), 20170kJ/kg (whole crop)
Higher Heat Value: 19330kJ/kg (seeds), 21550kJ/kg (whole crop)
Rapeseed is known for the high concentration of erucic acid (C22:1) there is however a variety that has
been altered to contain no erucic acid, so-called “00” or Canola:
Fatty Acid Carbon Chain Normal Rape Oil “00” Rape Oil
(fraction percent)
Palmitic 16:0 3.8 4
Stearic 18:0 1.6 2
Oleic 18:1 39.2 62
Linoleic 18:2 20.5 22
Linolenic 18:3 9.2 10
Eicosenoic 20:1 11.7 -
Erucic 22:1 14.9 -
Low erucic acid variety is mainly used for animal consumption, is lower yielding and has no benefit for
bio-diesel production
Amino Acid Composition of Seeds
Seed Protein %
Isoleucin e 17.94
Leu cin e 7.47
Nonpolar & Methionine 8.65
Hydrophobic Phenylalanine 9.38
Tryptophan 10.47
Valine 8.01
Polar &
Threonine 10.29
Hydrophilic
Basic Arginine 17.94
Histidine 12.57
Acidic
Lysine 7.65
Total (100%)
Comments
The seeds are 30% of the total dry weight, the rest has a large potential of being used as well.

Comparative Graph
Energy
Lignin: 95.1GJ/ton
Next Generation 80
S tyren e: 83.9G J/t on
Amine Chemicals: 83.2GJ/ton
Fatty Acids-to-Biolubricants (FAEE) Net Energy Value (NEV): 2.9
P henol: 76.5GJ/ton
Lignocellulose-to-Bioethanol (AFEX) Breeding Factor: 35%
Tolu en e: 72.7G J/t on
E thylene: 67.0GJ/ton
60
CRACKER
S tyrene: 50.9GJ/ton
50
Crude Oil T oluene: 47.0GJ/ton
44.9GJ/ton Lubricants: 45.5GJ/ton Biomass
40 44.2 2.45GJ/ton
F ertiliz ers: 37.7GJ/to n Ash: 37.7GJ/ton
34.5
P henol: 33.9GJ/ton
30 Ammo nia: 31.0G J/t on
Rapeseed
E thylene: 29.6GJ/to n 26.7
Belgium
5 .5ton/ha seed s
Fossil Fuel Energy Savings 16.4to ta lDW/ha
20n
FAEE /P DO: 20.9GJ/to
41.9GJ/ton chemicals Complex C5 Carbohy drates: 18.3GJ/ton
16.4GJ/ton Fatty Acids: 16.0GJ/ton
Am monia: 15.4GJ/ton
21.5GJ/ton biomass Protein: 14.3GJ/ton
10 Complex C6 Carbohydrates: 10.8GJ/ton
353GJ/ha
Amine Ch em icals: 9.3GJ/to n
Boil er: 6.0GJ/ton
Un-utiliz ed
Traditional Fertilizers: 2.1GJ/ton Biochemicals: Potential Chemical
Exergy
Lignin: 105GJ/ton
Next Generation 80
Fatty Acids-to-Biolubricants (FAEE) Net Exergy Value (NExV): 3.1
P henol: 75.8GJ/ton Breeding Factor: 32%
Lignocellulose-to-Bioethanol (AFEX) Tolu en e: 73.7G J/t on
60
CRACKER
50
Crude Oil
T oluene: 41.5GJ/ton 2.69GJ/ton
40n
F ertiliz ers: 41.4GJ/to Ash:
41.1
41.4GJ/ton
P henol: 35.4GJ/ton
30 Rapeseed
28.7
Belgium
E thylene: 23.3GJ/to n Ammo nia: 23.0G J/t on 5 .5ton/ha seed s
Fossil Fuel Exergy Savings Complex C5 16.4to ta lDW/ha
20n
FAEE /P DO: 20.9GJ/to 20.2 Carbohydrates: 20.1GJ/ton
44.8GJ/ton chemicals Protein: 17.6GJ/ton
13.3GJ/ton Fatty Acids: 15.7GJ/ton
22.9GJ/ton biomass
377GJ/ha
Boil er: 4.9GJ/ton
Fertilizers: 6.3GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.110 1.81 21.5% 3.53 2.85
Phenol 0.008 0.14 1.6% 0.27 0.22
Styrene 0.009 0.15 1.8% 0.30 0.24
Toluene 0.008 0.13 1.6% 0.26 0.21
1,4-butandiamine 0.021 0.35 4.2% 0.69 0.55
Acrylamide 0.001 0.02 0.2% 0.03 0.03
Adipic acid 0.004 0.06 0.7% 0.12 0.10
Ammonia 0.008 0.13 1.5% 0.25 0.20
ε-caprolactum 0.011 0.18 2.2% 0.36 0.29
Ethylamine 0.020 0.33 3.9% 0.65 0.52
Ethylenediamine 0.005 0.08 1.0% 0.16 0.13
Feed grad e cystine 0.001 0.01 0.2% 0.03 0.02
Feed grad e methionine 0.010 0.16 1.9% 0.31 0.25
γ-butyrolactum 0.007 0.11 1.4% 0.22 0.18
Ionic liquids 0.004 0.07 0.9% 0.14 0.11
Isobutyraldehyde 0.009 0.16 1.9% 0.30 0.25
Isoprene 0.031 0.51 6.0% 0.99 0.80
Isopropanolamine 0.010 0.17 2.0% 0.32 0.26
Oxalic acid 0.009 0.14 1.7% 0.28 0.23
Urea 0.007 0.12 1.4% 0.23 0.19
Biolubricants 0.153 2.51 29.9% 4.91 3.96
Fertilizers 0.065 1.07 12.7% 2.08 1.68
Description
- Sufficient lignin content/concentration to lead to a positive contribution of the convertion
to aromatics
- Relatively low protein content, but due to the high conversion of the other components
the risidual concentration are converted efficiently.
- Judging from the exergy graph alone, rapeseed should be one of the best performers but
due to the high product conversion rates the boiler output is lower and cannot overcome
the relatively high indirect energy/exergy cost associated with fatty acid conversion
(despite ethanol being cheaper than methanol)
- Conversion to FAEE is automatically disadvantaged as the traditional petrochemical
production route is only 45GJ/ton (i.e. calorifc value) wheras functional chemicals are
above the mid-70’s range.
Improvement Options
- Possible GMO tailering to increase protein content and lower oil content.
- Burn the pure plant oil onsite for power generation, increasing boiler output and releaving
need for energy intensive purification, extraction and conversion. Rapeseed is a
protenious crop in any case; use oil crops for oil (biolubricant) processing.

Elaeis Guineensis Jacq. – Oil Palm
Common Names
African palm tree, African oil palm, oil palms
Classification
Perennial, C-3
Appearance
Single stemmed erect tree up to 8 - 20 meters high, 20 – 30 pinnate Leaves,
long 3-5 meter, dense clusters 100 – 200 of fruit with fleshy pericarp, 2 x
3.5cm, maturity every 6 month, weigh 40 – 50kg
Varieties
Three: Psifera, Dura, Tenera (classified by fruit)
None, but Dura/Tenera hybrids for higher yield with lower canopies
Brief Description
Palm has many applications, primarily for the commercial production of oil: palm oil and kernel oil. It can
also be used for nutritious, cosmetic and other trade purposes. Grown in many countries outside its native
home in large plantations it has caused some environmental concern.
Growth Details
Native Area: West Africa, between Angola and Gambia
Location: All throughout the tropics, mainly in South East Asia
Climate: Tropical Rainforest, high sunlight required
Temperature: 22 - 32°C, cannot tolerate major variations
1750 – 2300mm, good annual distribution of rainfall
Soil Type: Wide range of tropical soils, adequate water transport required
Soil Acidity: 4 – 6pH, must be acidic, average 5.7pH
Plantation: Seed nursery production of young palms, one year before field planting
9 x 9 meter grid planting
Seeding Rate: Best: 75 – 150 plants/hectare, yield decreases with higher rates
Average: 143 plant/ha
Companion Crop: Legumes suggested for ground cover, erosion prevention and nutrients
Weed Control: Required for seeding (i.e. at nursery) as slow establishment
Cultivation: 1 year nursery production, 2-3 year additional establishment, after 25 years tree
become to high for production, 5-10 peak yield
Harvesting: Manual cutting of fresh fruit bunches when ripe (highest oil content), twice a year
100-150 bunches/man, after 25 years tree becomes to high, removed
Highly variable, depending mainly on the yield potential determined by the genetic make-up of the
planting material and on the yield limit set by climatic factors.
Yield Dependent Macronutri ent Uptake Yiel d Dependent Micronutrient Uptake
350 600
N Fe
P2O5 Mn
K2O B
300 CaO Zn
Mg O
500 Mo
SO3 Cu
Poly. (N) Po ly. (Fe)
250 Poly. (P2 O5) Po ly. (Mn)
Poly. (K2 O) 400 Po ly. (B)

Poly. (Ca O) Po ly. (Zn )
Poly. (MgO ) Po ly. (Mo)
200
Poly. (SO 3) Po ly. (Cu)
300
150
200
100
100
50
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Fruit Yield (ton/ha) Fruit Y ield (ton/ha)

Yield
Normal Conditions: 10 – 25 ton/ha (fruit, yield 3 – 7.5 ton of oil/ha)
19.5ton/ha (Malaysia: 5-year average)
Optimal Conditions: Malaysian good fresh wet: 25 ton/ha + 9.8(fronds) + 5.6(trunk)
Highest recorded: 46 ton/ha (fruits)
Worldwide Cultivation: 7.3 million hectares at 12.6 ton/ha fruits
Constituent Fruit Leaves Trunk
Moisture Content 26% 69.9% 50%
Cellulose 10.1 47.5 45
Hemicellulose 6.4 9.3 25
Lignin 4.7 16.4 18
Protein 2.6 6.7 -
Oils - -
74.5
Fats - -
Minerals 0.3 - 2
Ash 1.4 8.3 -
Others - 11.8 10
Fruits represent 1/3, fronds (leaves) represent ½ and the trunk represent 1/6 the total annual wet weight
After 25 years the tree trunks can be harvested at around 4 - 7.5 ton/ha WW
Lower Heat Value: 39330 kJ/kg (oil), 22100 kJ/kg (fruit residue), 17000 kJ/kg (trunk),
7100 kJ/kg (fronds, wet)
Higher Heat Value: 39385 kJ/kg (oil), 20650 kJ/kg (fruit residue), 17800 kJ/kg (trunk),
17500 kJ/kg (fronds)
Palm oil is known for the high concentration of palmitic (hence the name) oleic, and stearic acids
Fatty Acid Carbon Chain Palm Oil
(fraction percent)
Myristic 14:0 0.5 - 5.9
Palmitic 16:0 32.3 - 47.0
Stearic 18:0 1.0 - 8.5
Oleic 18:1 39.8 - 52.4
Linoleic 18:2 2.0 - 11.3
Normal Grade Palm Oil: 44.0% Palmitic, 4% Stearic, 40.0% Oleic, 10.0% Linoleic, 2.0% Other
Oleic Grade Palm Oil: 40.0% Palmitic, 4.0% Stearic, 43.0% Oleic, 11.0% Linoleic, 2.0% Other
Stearic Grade Palm Oil: 58.0% Palmitic, >5.0% Stearic, 29.0% Oleic, 6.5% Linoleic, 1.5% Other
Palm kernel oil is a side extractive from the processing of the seeds. It is produced at rate roughly 10-20%
of that of the palm oil production, thus 0.25 – 0.75 ton/ha (normal conditions). The composition is
however entirely based on medium chain fatty acids:
Fatty Acid Carbon Chain Palm Oil
(fraction percent)
Caprylic 8:0 4
Capric 10:0 4
Lauric 12:0 45
Myristic 14:0 18
Palmitic 16:0 9
Stearic 18:0 3
Oleic 18:1 15
Linoleic 18:2 2
Comments
Deli Palms (Dura variety) are low-growing and thick-stemmed hybrids with very high yields in Asia but
perform poorly in other areas.

Comparative Graph
Energy
F ertiliz ers: 92.2GJ/to n Protein: 119GJ/ton
Next Generation 80
Ash: 92.2GJ/ton

P henol: 76.5GJ/ton
60
- Raw Fossil Fuel Input
CRACKER
14.9GJ/ton 50 51.9GJ/ton
Crude Oil 46.5
44.9GJ/ton Lignin:
Lubricants: 45.5GJ/ton 46.4GJ/ton Biomass
40 2.50GJ/ton
Amin e Ch em icals: 39.1GJ/to n
E thylene: 31.5GJ/to n Complex C5
T oluene: 31.5GJ/ton Carbohydrates: 30.3GJ/ton Oil Palm
27.9
Malaysia
26.0 25 .0ton/ha fru its
20
37.0GJ/ton chemicals P henol: 18.1GJ/ton
20.9GJ/ton biomass FAEE /P DO: 13.9GJ/to n

721GJ/ha
Boil er: 7.0GJ/ton
Fatty Acids: 6.9GJ/ton
Un-utiliz ed
Exergy
F ertiliz ers: 96.2GJ/to n Protein: 120GJ/ton
Next Generation 80
Ash: 96.2GJ/ton

P henol: 75.8GJ/ton
60
CRACKER
50 51.9GJ/ton
Crude Oil Lignin:
44.9GJ/ton Lubricants: 45.7GJ/ton 48.4GJ/ton Biomass
40 40.1 2.61GJ/ton
Complex C5
30 Carbohydrates: 31.6GJ/ton Oil Palm
S tyrene: 25.7GJ/ton Malaysia
E thylene: 24.2GJ/to n 25 .0ton/ha fru its
Fossil Fuel Exergy Savings T oluene: 23.7GJ/ton Ammo nia: 23.0G22.3
J/t on 34.5to ta lDW/ha
20
18.9
42.6GJ/ton chemicals 9.6GJ/ton P henol: 17.2GJ/ton
24.0GJ/ton biomass
10n Complex C6 Carbohydrates: 10.6GJ/ton
830GJ/ha FAEE /P DO: 10.1GJ/to
Boil er: 5.6GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.100 3.47 17.8% 2.65 1.72
Phenol 0.017 0.60 3.1% 0.46 0.30
Styrene 0.019 0.67 3.4% 0.51 0.33
Toluene 0.017 0.59 3.0% 0.45 0.29
1,4-butandiamine 0.005 0.19 1.0% 0.14 0.09
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.000 0.00 0.0% 0.00 0.00
Ammonia 0.001 0.03 0.1% 0.02 0.01
ε-caprolactum 0.001 0.02 0.1% 0.02 0.01
Ethylamine 0.002 0.07 0.3% 0.05 0.03
Feed grad e cysteine 0.000 0.02 0.1% 0.01 0.01
γ-butyrolactum 0.001 0.03 0.2% 0.03 0.02
Ionic liquids 0.000 0.02 0.1% 0.01 0.01
Isoprene 0.003 0.12 0.6% 0.09 0.06
Oxalic acid 0.001 0.04 0.2% 0.03 0.02
Urea 0.001 0.05 0.3% 0.04 0.02
Biolubricants 0.363 12.54 64.3% 9.57 6.20
Fertilizers 0.027 0.94 4.8% 0.71 0.46
Description
- Has the best overall performance; extraordinarily high yield and relatively low energy
intensity in acquisition and conversion.
- Very high oil concentration facilitates the conversion to biolubricants at energetically
positive rates. Asian production methods are based on drudgery which inherently has a
low energy intensity. Little improvement is foreseeable using current techniques as exergy
demand for FAEE production is similar to energy.
Improvement Options
- Focus on improving extraction techniques, possibly new systems to reduce energy and
potential exergy demand in oil conversion steps.
- Has no possibility to be mechanized which can prevent the industrial and social
development of Malaysia (and other countries in the region). Else yield and production
costs will be heavily sacrificed leading to more of a loss as opposed to a gain by
improving the cropping system. It is foreseeable that through stronger international
development issues oil palm could loss it top position.

Glycine Max – Soya Bean
Common Names
USA: Soybeans, UK: Soya Beans, Edamame, Japan: shoyu, bean sprout, Asia:
Great Treasure, Brings Happiness, Yellow Jewel
Classification
Annual, Legume, Papilionaceous, C-3
Appearance
Erect hairy stem with trifoliate Leaves, small white or purple flowers, short
pods with 1-4 seeds/beans, Height of 0.6 – 1.5 meters with tapped roots up to
2 meters in length
Varieties
Thousands, named by bean/pod colour
Nearly all, 80% of all commercially sold, leader in research Monsanto
Brief Description
Planted in several large areas of the world, the seeds have become an important substitute of meat
(complete) protein and other minerals. There are many industrial applications and possibilities of soya
beans like soap, resins, plastics, solvents and more recently biodiesel.
Growth Details
Native Area: Southeast Asia
Location: Major producers are USA, China, India, Brazil and Argentina
Climate: Warm – subtropical, full sun to partial shade, wet, cannot tolerate drought
Temperature: 20 - 35°C optimal, breaded varieties for temperate areas
450 – 700mm (average 600mm), tolerate up to 4100mm
Soil Type: Deep, free draining, sandy or medium loam
Soil Acidity: 5.8 – 6.5 pH must be slightly acidic and not exceed 7.0
Plantation: 2.5 – 4 cm, deeper exposes soil-based pathogens, vary row spacing 18 –76cm
Seeding Rate: 30kg/ha for plant density of 100,000 – 133,333 plant/ha
60 kg/ha for plant density of up to 300,000 plants/ha
50 - 100cm between rows and 15-30cm between plants
Companion Crop: No, but rotated
Weed Control: Weed competition is serious, and may reduce yields by 50%, early cultivation
Cultivation: Summer plant, May-June start, 3 – 4 month establishment duration, 2-3 year rotation
and not with all crops for disease control reasons
Harvesting: Single harvesting after leaf abscission, fall months, cylinder speed threshes
Seed or soil applied granular inoculation, soil temperature 25 - 30°C for symbiosis to occur
Inoculation bacteria strain: Bradyrhizobium Japonicum (100% N uptake)
Yield Dependent Macronutri ent Uptake Yi eld Dependent Micronutrient Uptake
350 1600
N Fe
P2 O5 Mn
K2 O B
300 1400 Zn
Ca O
MgO Mo
SO 3 Cu
Po ly. (N) 1200 Poly. (Fe)
250 Po ly. (P2O 5) Poly. (Mn)
Po ly. (K2O ) Poly. (B)

Po ly. (CaO ) 1000 Poly. (Zn)
Po ly. (MgO) Poly. (Mo)
200
Po ly. (SO3 ) Poly. (Cu )
800
150
600
100
400
50 200
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Seed Yield (ton/ha) Seed Yield (ton/ha)

Yield
Normal Conditions: 1.7 – 3.4 ton/ha (seeds), ~5 ton/ha (hay, rest of plant)
2.6ton/ha seeds (USA: 5-year average)
Optimal Conditions: 4 ton/ha (seeds), 6 ton/ha (hay)
Worldwide Cultivation: 91 million hectares at 2.2 ton/ha of seeds
Constituent Seeds‡ Leaf/Stem†
Cellulose 17
65
Hemicellulose 4
Sugars 7 -
Lignin 1 20
Protein 40.8 10
Oils 17.9 -
Fats 2.1 -
Minerals 2.8 -
Ash 6 -
Others 1.4 5
Seeds represent about 1/ 3 of the total dry plant mass, †estimate for leafy matter (hay)
‡ Green seeds (or raw seeds) have a moisture content of 68.2%, yellow seeds (or dry seeds) are harvested

Lower Heat Value: 26000 kJ/kg (seed, estimate), 17000 kJ/kg (stover)
Higher Heat Value: 27000 kJ/kg (seed, estimate), 17500 kJ/kg (stover)
The globular protein, Glycine, account for 80 – 90% of the protein with:
Amino Acid Composition Seeds
for Glycine Protein g/kg %
Alanine 5.8 1.71
Isoleucin e 8.2 2.41
Leu cin e 31.3 9.20
Methionine 6.1 1.79
Nonpolar & Hydrophobic
Phenylalanine 14.6 4.29
Proline 14.6 4.29
Tryptophan 5.8 1.71
Valine 5.4 1.59
Asparagine 19.4 5.70
Cystein e 3.7 1.09
Glutamine 64.6 18.99
Polar & Hydrophilic Glycine 2.4 0.71
Serin e Unknown
Threonine 7.1 2.09
Tyrosine 13.3 3.91
Asparagic Acid 21.1 6.20
Acidic
Glutamic Acid 62.6 18.41
Arginine 28.2 8.29
Basic Histidine 7.5 2.21
Lysine 18.4 5.41
Total 340 (85% of Protein)
Comments
Nearly all information regarding the soybean is toward the seed and possible residues after processing the
seed. A possibility for multiple biorefinery to utilize the hull, also the rest of the plant matter is most likely
completely carbohydrate based.

Comparative Graph
Energy
Simple Carbohydrates: 132GJ/ton
Next Generation 80
P henol: 76.5GJ/ton
Lignin Aromatics (Fast-Pyrol ysi s) 62.4GJ/ton
60
CRACKER
FAEE /P DO: 51.6GJ/to
50n
Crude Oil Fatty Acids:
44.9GJ/ton Lub ricant s: 45.5G J/t on 46.6GJ/ton Biomass
40
42.7GJ/ton
36.3
E thylene: 34.8GJ/to n Lignin: 35.5GJ/ton
Soybean
St yrene: 29.5GJ/to n
T oluene: 28.1GJ/ton 25.8 Illinois
Protein: 22.6GJ/ton 4 .0ton/ha seed s
Fossil Fuel Energy Savings 22.0GJ/ton 24.2 10.8to ta lDW/ha
20 Complex C5
40.3GJ/ton chemicals Carbohydrates: 20.2GJ/ton
P henol: 14.6GJ/ton
18.1GJ/ton biomass Am monia: 14.1GJ/ton
10n
Amin e Ch em icals: 12.2GJ/to Complex C6 Carbohydrates: 9.9GJ/ton
196GJ/ha
Boil er: 7.8GJ/ton
Un-utiliz ed
Exergy
Simple Carbohydrates: 160GJ /ton
Next Generation 80
- Chemical vs. Biomass CExD 62.7GJ/ton
60
FAEE /P DO: 57.4GJ/to n Fatty Acids: 54.9GJ/ton
CRACKER
50n
F ertiliz ers: 50.2GJ/to Ash:
Crude Oil 50.2GJ/ton
40 Lignin: 3.26GJ/ton
41.8GJ/ton
32.3
30n
E thylene: 30.6GJ/to
Soybean
Protein: 26.6GJ/ton Illinois
S tyrene: 23.4GJ/ton 4 .0ton/ha seed s
Ammo nia: 23.0G J/t on Complex C5
Fossil Fuel Exergy Savings Toluene: 21.6GJ/to 10.8to ta lDW/ha
20n 20.1 Carbohydrates: 23.7GJ/ton
42.5GJ/ton chemicals 20.2GJ/ton 20.0
19.1GJ/ton biomass P henol: 15.1GJ/ton

Complex C6 Carbohydrates: 11.7GJ/ton
10
206GJ/ha Am monia: 9.8GJ/to n
Boil er: 6.4GJ/ton
Fertilizers: 2.9GJ/ton Un-utiliz ed

Overview Savings

Ethylene 0.134 1.44 29.8% 6.56 6.01
Phenol 0.025 0.27 5.6% 1.24 1.14
Styrene 0.028 0.30 6.2% 1.37 1.26
Toluene 0.025 0.27 5.5% 1.21 1.11
1,4-butandiamine 0.032 0.35 7.1% 1.57 1.44
Acrylamide 0.005 0.05 1.1% 0.25 0.23
Adipic acid 0.001 0.01 0.3% 0.06 0.06
Ammonia 0.004 0.04 0.8% 0.17 0.16
ε-caprolactum 0.006 0.07 1.4% 0.31 0.29
Ethylamine 0.013 0.14 2.9% 0.65 0.59
γ-butyrolactum 0.008 0.08 1.7% 0.37 0.34
Ionic liquids 0.002 0.03 0.5% 0.12 0.11
Isoprene 0.021 0.22 4.6% 1.00 0.92
Oxalic acid 0.003 0.03 0.6% 0.13 0.12
Urea 0.004 0.04 0.9% 0.20 0.18
Biolubricants 0.059 0.64 13.2% 2.91 2.67
Fertilizers 0.065 0.70 14.4% 3.18 2.91
Description
- It is a very energy intense crop to cultivate despite its leguminous nature as the total dry
weight yield is far too low to offset cultivation practices. Noticeable increase in exergy
demand in biomass acquisition demand is due chiefly to required sizing and drying
operation in feedstock preparation.
- Production of FAEE is more energy and exergy intense than the traditional production
method; soya bean is not a suitable crop for oil production.
- Regardless of the low biolubricant CED the effect of amine chemistry in the biorefinery
layout can be seen by the high equivalent petrorefinery cost, being above 60GJ/ton.
- The conversion of protein to the amine chemicals is very beneficial and efficient; right
concentration and right composition.
Improvement Options
- Abolish ideas of saving nitrogen fertilizer, instead promote drastic increases of yields
through heavy fertilization.
- Possible GMO tailering to increase protein content and lower oil content.
- Might consider to burn straw/stover directly and not convert as it is low yeilding.

Helianthus Annuus – Sunflower
Common Names
Sunflower
Classification
Annual herb, C-3
Appearance
0.7 – 3.5m erect unbranched stem, alternating ovate Leaves, bright yellow
to orange round flower head 10 – 40cm across, clusters of seeds/fruits
from achenes, 3m deep, broad taproot system
Varieties
Several, new species transgenic, others with drooping heads
Yes, mainly for resistance, however non-GMO very popular
Brief Description
The world’s second most important source for oil. The seeds have many applications along with human
consumption. Considered one of the possible energy crops for bio-diesel production.
Growth Details
Native Area: Western North America
Location: Wide spread with North America, Europe and Russia leading
Climate: Temperate – subtropical, intolerant of shade, tolerates drought and frost
Temperature: 18 - 25°C, yearly average around 20°C
Rainfall/Irrigation: 600 – 1000mm (average 900mm), can tolerate up to 4000mm
Soil Type: Wide variety, poor to fertile, moist to dry but must be deep and well drained
Soil Acidity: 4.5 – 8.7pH, can tolerate both extremes, prefers 6.6pH
Plantation: 2.5 – 7.5cm deep, 20cm spacing, 60 – 90cm row distancing,
Seeding Rate: 4 – 10kg/ha for plant density of 62500 plants/ha
Companion Crop: Not recommended
Weed Control: Minor problem, as it is a weed itself
Cultivation: Planted in early spring, frost is not a problem, 4 year rotation break and not to be
rotated with potatoes, 70 – 120days maturity
Harvesting: 120 – 160 days after sown when seeds become lose but before shedding occurs,
mechanized head removal, drying and threshing
Respond well to a balanced fertilization, 1-2-3 NPK is best ratio
The potassium (K2O) demand is extraordinarily high
Yield Dependent Macronutri ent Uptake Yield Dependent Micronutrient Uptake
700 1400
N Fe
P2 O5 Mn
K2 O B
600 Ca O 1200 Zn
MgO Mo
SO 3 Cu
Po ly. (N) Poly. (Fe)
500 1000
Total P lant Uptake (kg/ha)
Poly. (Mn)
Po ly. (P2 O5)

Po ly. (K2 O) Poly. (B)
Po ly. (Ca O) Poly. (Zn)
400 Po ly. (MgO ) 800 Poly. (Mo)
Po ly. (SO 3) Poly. (Cu )
300 600
200 400
100 200
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Seed Y ield (ton/ha) Seed Y ield (ton /ha)

Yield
Normal Conditions: 1 – 3.5 ton/ha (seeds), 2.3ton/ha (France: 5-year average)
5 – 8 ton/ha (straw, factor of two)
Optimal Conditions: 5 – 6 ton/ha (seeds)
Worldwide Cultivation: 21.4 million hectares at 4.1 ton/ha (1.23 ton/ha seeds)
Constituent Seeds Husk/Flower Foliage
Moisture Content 20% 30% 70%
Cellulose 9.0 31.4 38.2
Lignin 4.0 11.0 12.3
Protein 25.2 12.7 12.5
Oils -
49.7 13.7
Fats -
Minerals 1.5 - -
Ash 4.2 9.3 11.1
Others 0.4 - -
Seeds + flower head represent 1/ 2 of total wet weight
Seed consist of 20 – 35% DW husk/shell (30% taken as average)
Higher Heat Value: 26000 kJ/kg (seed), 19300 kJ/kg (husk), 16290 kJ/kg (straw)
Lower Heat Value: 24350 kJ/kg (seed), 20400 kJ/kg (husk), 17410 kJ/kg (straw)
Seed oil is known for the high concentration of linoleic acid and low palmitic and stearic acids
Fatty Acid Carbon Chain Seed Oil
(fraction percent)
Palmitic 16:0 3-8
Stearic 18:0 4-7
Oleic 18:1 15-30
Linoleic 18:2 45-75
Commercial Grade Seed Oil: 6.0% Palmitic, 4.6% Stearic, 17.8% Oleic, 69.2% Linoleic
High Oleic Hybrid Seed Oil: 3.6% Palmitic, 4.8% Stearic, 78.9% Oleic, 10.2% Linoleic
Amino Acid Composition of Seed
Seed Protein (protein fraction)
Alanine Unknown
Isoleucin e 4.1
Leu cin e 5.5
Proline Unknown
Tryptophan -
Valine 4.0
Asparagine Unknown
Cystein e 1.7
Glutamine Unknown
Polar &
Glycine 5.6
Hydrophilic
Serin e Unknown
Threonine 3.4
Tyrosine 1.6
Asparagic Acid Unknown
Acidic
Glutamic Acid Unknown
Arginine 10.0
Basic Histidine 2.3
Lysine 3.6
Total 47.9% of Protein
The protein concentration can range from 13 to 26% of seed dry weight, quality worse than soya

Comparative Graph
Energy
Lignin: 129GJ/ton
Next Generation 80
P henol: 76.5GJ/ton
60 58.1
- Raw Fossil Fuel Input T oluene: 57.9GJ/ton 55.6
CRACKER
50
Crude Oil P henol: 45.0GJ/ton 46.1GJ/ton
44.9GJ/ton Lub ricant s: 45.5G J/t on Protein:
Biomass
41.2 42.4GJ/ton
40 4.85GJ/ton
Complex C5
E thylene: 47.5GJ/to n Carbohydrates: 41.9GJ/ton

Sunflower
Fert ilizers: 28.3G J/t on
Ash: 28.3GJ/ton
France
23.9GJ/ton Complex C6 5 .5ton/ha seed s
FAEE /P DO: 22.5GJ/ton
Fossil Fuel Energy Savings Carbohydrates: 25.3GJ/ton 8.4to tal DW/ha
20
22.2GJ/ton chemicals Fatty Acids: 17.6GJ/ton
15.3GJ/ton biomass Amin e Ch em icals: 14.6GJ/to n
10
128GJ/ha
Boil er: 4.1GJ/ton Un-utiliz ed
Exergy
Lignin: 150GJ/ton
Next Generation 80
- Chemical vs. Biomass CExD S tyrene: 62.0GJ/ton
60
- Raw Fossil Fuel Input 57.0
Toluene: 55.8GJ/to n
CRACKER
56.2
50
P henol: 50.0GJ/ton Protein: 49.0GJ/ton
Crude Oil 46.3GJ/ton Complex C5
E thylene: 44.9GJ/to n Carbohydrates:
40 48.5GJ/ton 5.60GJ/ton
37.6

30 Complex C6 Sunflower
Carbohydrates: 29.3GJ/ton France
23.8GJ/ton
Ammo nia: 23.0G J/t on 5 .5ton/ha seed s
Fossil Fuel Exergy Savings FAEE /P DO: 22.8GJ/to n 8.4to tal DW/ha
20
22.5GJ/ton chemicals
Amin e Ch em icals: 12.2GJ/to
10n
130GJ/ha
Boil er: 3.4GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.094 0.79 13.7% 3.27 3.25
Phenol 0.012 0.10 1.8% 0.42 0.42
Styrene 0.013 0.11 2.0% 0.47 0.46
Toluene 0.012 0.10 1.7% 0.41 0.41
1,4-butandiamine 0.030 0.25 4.4% 1.05 1.04
Acrylamide 0.002 0.02 0.3% 0.08 0.08
Adipic acid 0.003 0.02 0.4% 0.10 0.10
Ammonia 0.005 0.04 0.7% 0.16 0.16
ε-caprolactum 0.004 0.04 0.6% 0.15 0.15
Ethylamine 0.010 0.08 1.4% 0.33 0.33
γ-butyrolactum 0.004 0.04 0.6% 0.15 0.15
Ionic liquids 0.002 0.02 0.3% 0.08 0.08
Isoprene 0.016 0.14 2.4% 0.57 0.57
Oxalic acid 0.006 0.05 0.9% 0.21 0.21
Urea 0.006 0.05 0.9% 0.21 0.21
Biolubricants 0.276 2.32 40.2% 9.61 9.56
Fertilizers 0.172 1.44 25.0% 5.97 5.93
Description
- A very expensive crop to cultivate with a meagre yield, i.e. high GJ/ton.
- Nonetheless, oil concentration is sufficient to promote an efficient conversion to FAEE.
- Practically no difference between resulting energy and exergy as oil production represents
over 40% biorefinery chemical product mixture
- Its exergy improvement is offset by higher exergetic biomass acquisition production costs
and large ash/fertilizer product mixture, being 25%.
- Residual protein content and concentration perfectly suited for downstream processing to
amine-based chemicals despite high associated feedstock costs.
- Carbohydrates conversion has a limited positive factor, ethylene close to break-even point.
Improvement Options
- Search for better cultivation location with significantly lower energy demand in irrigation.
- As it has low yields screen for possibilities to cultivate on exhausted or marginal lands.
- GMO tailoring to infuse bacterial symbiosis as fertilizers are a major input component and
overall yields are nonetheless low.
- Considering that oil is the best product from sunflower, it may be best to cess cultivation
of this cropping system as it is highly unlikely to ever be able to compete with oil palm.

Manihot Esculenta – Cassava
Common Names
Cassava, Manioc, Yucca, Mandioca, Tapioca
Classification
Perennial woody shrub, planted as annual crop, C-3
Appearance
Palmate Leaves on stubby fibrous stems, 5 – 10 root tubers,
Clumps of tapered tubers, 50 – 80 cm long, 5 –10 cm thick, roots reaches 2
meters long, 1mm thick brown skin, white/yellow flesh
Varieties
Cultigens, limited, pest and disease resistant, cyanide reduction
None
Brief Description
Similar to a potato the main purpose is for starchy food. In Africa and Latin America cassava is mostly
used for human consumption but is growing on other starch industries.
Growth Details
Native Area: South America
Location: Latin America and Africa
Climate: Tropical – Subtropical, humid but can tolerate drought
Temperature: At least 25°C, heat loving
Less than 150mm
Soil Type: Possible to grow in marginal lands with low nutrients
Soil Acidity: 4.0 – 8.0 pH, grows in nearly all soil
Plantation: 7 – 30cm of mature stem, 1m by 1m spacing, vertical 5 - 10cm in soil
Mechanical planers are present in Brazil
Seeding Rate: Does not occur
Companion Crop: Often rice, maize and grain legumes for sufficient nitrogen
Weed Control: Necessary in first few months, slow early growth
Pest and Disease: In Africa, combined with poor practice yields can reduce by more than 80%
Cultivation: Stem cuttings for propagation (cloning), start of rainy season,
1.5 – 3 months establishment and 6 - 18 months for crop
Harvesting: Roots can be left in ground up to 24 – 36 months in poor soil conditions
Longer left in ground tubers become more woody, less starchy
Root extraction, labour intensive, highly perishable within days
Yi el d Dependent Macronutri ent Uptake Yield Dependent Micr onu tri entUptake
400 1600
N Fe
P2 O5 Mn
K2 O B
350 1400
Ca O Zn
MgO Mo
SO 3 Cu
300 1200 Poly . ( Fe )
Po ly. (N)
Poly . ( Mn)
Total Plant Up take (g /ha)
Po ly. (P2O 5)
Po ly. (K2O ) Poly . ( B)
250 Po ly. (CaO )
1000 Poly . ( Zn )
Po ly. (MgO ) Poly . ( Mo)
Po ly. (SO 3) Poly . ( Cu)
200 800
150 600
100 400
50 200
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
T uber Y ield (ton/ha) T uber Y ield (t on/ha)

Yield
Normal Conditions: 2 – 12 ton/ha tuber (poor)
9.4 ton/ha (Nigeria, 5-year average)
Optimal Conditions: 25 – 40 ton/ha tuber (good commercial yield), 50ton/ha tuber (best)
90 ton/ha (speculated at utmost favourable conditions)
Worldwide Cultivation: 16.2 million hectares at 10.2 ton/ha
(Based on dry weight and sweet cassava, harvested yearly)
Constituent Tuber Leaves Stem†
Moisture Content 69.9% 81.0% 15%
Cellulose 65
11.7 48.4
Hemicellulose
Lignin 2.7 11.1 20
Sucrose 15.3 - -
Starch 63 - -
Protein 2.8 36.3 10
Fats 0.6 6.8 -
Minerals 1.3 2.9 -
Ash 2.5 8.4 5
Others 0.1 - -
The root is 50 – 70% of the total plant wet weight (60% taken), †estimate and 25% of wet weight
Lower Heat Value: 15500 kJ/kg (tuber alone)
Higher Heat Value: 16500 kJ/kg (tuber, estimate)
Root Leaves
Free Amino Acid
g/kg % g/kg %
Alanine 0.35 5.69 12 5.94
Isoleucin e 0.20 3.25 9 4.46
Leu cin e 0.40 6.50 19 9.41
Nonpolar & Methionine 0.05 0.81 5 2.48
Hydrophobic Phenylalanine 0.20 3.25 12 5.94
Proline 0.20 3.25 10 4.95
Tryptophan Trace Trace
Valine 0.25 4.07 12 5.94
Asparagine Unknown Unknown
Cystein e 0.05 0.81 2 0.99
Glutamine Unknown Unknown
Polar &
Glycine 0.35 5.69 11 5.45
Hydrophilic
Serin e 0.35 11 5.45
Threonine 0.30 4.88 11 5.45
Tyrosine 0.10 1.63 7 3.47
Asparagic Acid 1.05 17.07 22 10.89
Acidic
Glutamic Acid 1.60 26.02 27 13.37
Arginine 0.15 2.44 13 6.44
Basic Histidine 0.40 6.50 5 2.48
Lysine 0.15 2.44 14 6.93
Total 6.15 (22%) 202 (55.6%)
Comments
The longer the growth period and exposure to the surface will create a bitter cassava tuber. This is due to
the partial degradation by naturally occurring enzymes creating HCN, 0.3 – 0.5%DW. Its rooting system is
particularly good at mining the soil to extract even trace nutrients.

Comparative Graph
Energy
Next Generation 80
Amine Chemicals: 83.2GJ/ton Net Energy Value (NEV): 2.5
Sugar-to-Bioethanol (Ma sh ing) P henol: 76.5GJ/ton
60
- Raw Fossil Fuel Input F ertiliz ers: 57.9GJ/to n Ash: 57.9GJ/ton
CRACKER
50
Crude Oil
45.1
44.9GJ/ton 42.8 Lignin: Biomass
Protein:
39.4GJ/ton
St yrene: 31.1GJ/to
30n Ammo nia: 31.0G J/t on
T oluene: 29.4GJ/ton Cassava
27.7GJ/ton Am monia: 28.6GJ/ton Nigeria
Amin e Ch em icals: 26.2GJ/to n 25.6
50 ton /ha tube r
20
E thylene: 25.0GJ/to n
37.1GJ/ton chemicals 17.2
P henol: 16.0GJ/ton Complex C5 Carbohydrates: 13.4GJ/ton
12.5GJ/ton biomass
10
438GJ/ha Complex C6 Carbohydrates: 9.1GJ/ton
Boil er: 7.7GJ/ton Simple Carbohydrates : 5.8GJ/ton
Exergy
Next Generation 80
Amine Chemicals: 80.0GJ/ton Net Exergy Value (NExV): 3.4
Sugar-to-Bioethanol (Ma sh ing) Breeding Factor: 30%
P henol: 75.8GJ/ton
- Chemical vs. Biomass CExD F ertiliz ers: 61.7GJ/to
Ash: 61.7GJ/ton
60n
CRACKER
50
Crude Oil Lignin:
44.9GJ/ton Biomass
42.3GJ/ton
40 Protein: 2.04GJ/ton
42.0GJ/ton
30 Cassava
Nigeria
22.8 50 ton /ha tube r
P henol: 23.6GJ/ton Ammo nia: 23.0G J/t on
Fossil Fuel Exergy Savings T oluene: 21.8GJ/ton 35.1to ta lDW/ha
20 20.3
69.1GJ/ton chemicals Am monia: 18.9GJ/ton
Amin e Ch em icals: 16.4GJ/to n 18.0
23.3GJ/ton biomass E thylene: 16.2GJ/to n Complex C5 Carbohy drates: 14.3GJ/ton
-3.9GJ/ton S tyrene: 15.3GJ/ton
10 Complex C6 Carbohy drates: 9.7GJ/ton
817GJ/ha 12.3
Boi ler: 6.3GJ/ton Simple Carbohydrates: 6.2GJ/ton

Un-utiliz ed

Overview Savings

Ethylene 0.210 7.38 62.4% 17.27 -2.41
Phenol 0.016 0.55 4.7% 1.29 -0.18
Styrene 0.017 0.61 5.1% 1.42 -0.20
Toluene 0.015 0.54 4.6% 1.26 -0.18
1,4-butandiamine 0.007 0.25 2.1% 0.59 -0.08
Acrylamide 0.001 0.04 0.3% 0.08 -0.01
Adipic acid 0.000 0.01 0.0% 0.01 0.00
Ammonia 0.002 0.07 0.6% 0.15 -0.02
ε-caprolactum 0.002 0.09 0.7% 0.20 -0.03
Ethylamine 0.007 0.24 2.0% 0.56 -0.08
Feed grad e cysteine 0.001 0.04 0.3% 0.09 -0.01
γ-butyrolactum 0.004 0.12 1.0% 0.29 -0.04
Ionic liquids 0.001 0.04 0.4% 0.10 -0.01
Isoprene 0.008 0.30 2.5% 0.69 -0.10
Oxalic acid 0.002 0.09 0.7% 0.20 -0.03
Urea 0.001 0.04 0.3% 0.09 -0.01
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.033 1.16 9.8% 2.72 -0.38
Description
- An inexpensive cropping system with its major component being logistics; Africa location.
- Has a very high fossil fuel replacement potential based primarily on ethylene production
and to a degree on ash/fertilizer meaning that the system does not make good use out of
biochemical functionality.
- Large unconverted streams feed to boiler which contribute to a large deviation in energy
and exergy to the point of a negative exergy demand.
- And a large efficiency increase potential in exergy over energy is foreseeable in ethylene
production; here 25 down to 16GJ/ton.
Improvement Options
- Best practices conditions must be upheld calling for major improvements on current
cropping systems.
- Better sizing and drying techniques to further reduce the logistics input component.
- Focus solely on ethylene production; burn the rest.
- Has the potential to be the #1 cropping system, but must ensure that the produced off-
heat and energy production are utilized locally.

Medicago Sativa – Lucerne
Common Names
EU: Lucerne, USA: Alfalfa, Medic, Purple Medic, Medick, Barrelclover,
Burclover and Trefoil
Classification
Perennial, Legume, C-3
Appearance
Clusters of clover-like leaves with purple flowers
Height of 0.5 – 1.0 meter with roots up to 4.5meters in length
Varieties
Over 200
Additional tolerance to herbicide, tolerance to arid climates
Brief Description
Planted all over the world and being high in minerals, vitamins and protein it is one of the most nutritious
crops that can be utilized in any forage situation. It is the highest yielding forage plant.
Growth Details
Native Area: Presumably Iran, Northern Middle East
Location: All around the globe
Climate: Cool - Temperate, dry, cannot survive with high heat and humidity
800 – 1600mm (average 1030mm)
Soil Type: Wide variety, preferably dry lands
Soil Acidity: 6.2 – 7.8 pH, grows poorly below pH 6
Plantation: 1 – 3cm, small seedlings require good seed-to-soil contact
Press or air drill machinery, ploughed or rotated before reseeding
Seeding Rate: Best: 6.5 – 11 kg/ha (favourable and ploughed in rows\ridges)
Worst: 18 – 22 kg/ha (unfavourable and broadcast)
Average: 13 – 17 kg/ha
Companion Crop: Not advised as yield is strongly reduced
Weed Control: Required for seeding; slow establishment and uncompetitive crop
Cultivation: Year-round, with spring most successful, 2 – 3-month establishment duration
Multiple cuttings, 3 – 5 per year, 6 – 8 years before rotation or replanting
Harvesting: Easy and straightforward, upon budding for maximum protein levels
The best time to apply nutrients is before flowering and if possible with seeding, seed inoculation
Inoculation bacteria strain: Rhizobium Meliloti (80% N uptake)
Yi el d Dependent Macronutri ent Uptake Yield Dependent Micronutri ent Uptake
700 1000
N Fe
P2 O5 Mn
K2 O 900 B
600 Ca O Zn
MgO Mo
800
SO 3 Cu
Po ly. (N) Poly . ( Fe )
500 700
Poly . ( Mn )
Total Plant Up take (g /ha)
Po ly. (P2O 5)
Po ly. (CaO ) Poly . ( Zn)

600
400 Po ly. (MgO ) Poly . ( Mo )
Po ly. (SO 3) Poly . ( Cu)
500
300
400
200 300
200
100
100
0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Dry Hay Y ield (ton/ha) Dry Hay Y ield (t on/ha)

Yield
Normal Conditions: 4 – 14 ton (1.0 – 3.5 ton/ha dry) (with no conditioning)
12 – 24 ton/ha (with bacterial and fertilizer conditioning)
Optimal Conditions: 40 – 60 ton/ha (with bacterial and fertilizer conditioning)
80 – 120 ton/ha (experimental figures)
Worldwide Cultivation: 33 million hectares at 4 ton/ha (or 1 ton/ha dry)
Constituent Stem/Tuber Leaves Whole Plant
Moisture Content 69.5% 82.7% 75%
Cellulose 34 28 31
Hemicellulose 12 8 10
Lignin 9 5 7
Protein 11 31 21
Oils - - -
Fats - - -
Minerals - - -
Ash 7 - -
Others 26 28 27
Lower Heat Value: 17691 kJ/kg
Higher Heat Value: 18978 kJ/kg
Whole Plant
Free Amino Acid
g/kg %
Alanine 2.37 6.33
Leu cin e 2.93 7.83
Nonpolar & Methionine 0.32 0.86
Hydrophobic Phenylalanine 1.76 4.70
Proline 3.53 9.43
Tryptophan Unknown
Valine 2.37 6.33
Asparagine Unknown
Cystein e Unknown
Glutamine Unknown
Polar &
Glycine 1.82 4.86
Hydrophilic
Serin e 2.04 5.45
Threonine 1.99 5.32
Tyrosine Unknown
Acidic
Arginine 1.90 5.08
Lysine 2.33 6.23
Total 39.23 (18% of Protein)
Comments
Most information regarding alfalfa is aimed towards the production of fodder in the form of hay and
pellets. USA is the largest producer with 23 million ton per year at 1.25 DW ton/ha.

Comparative Graph
Energy
Lignin: 112GJ/ton
Next Generation 80
Lignocellulose-to-Bioethanol (Dilu te) P henol: 76.5GJ/ton
Protein Extraction (Protease ) Tolu en e: 72.7G J/t on
Lignin Aromatics (Fast-Pyrol ysi s) 70
67.2
- Chemical vs. Biomass Cumulative E thylene: 67.0GJ/ton
Process Energy Demand T oluene: 52.3GJ/ton
60
S tyrene: 56.9GJ/ton 56.9GJ/ton
CRACKER Complex C5
50 49.7 Carbohydrates: 53.1GJ/ton
Crude Oil Ash: 46.5GJ/ton
44.9GJ/ton F ertiliz ers: 46.5GJ/to n
Biomass
40 5.17GJ/ton
P henol: 39.3GJ/ton
33.8 Protein: 35.6GJ/ton

Lucerne
27.7GJ/ton
South Dakota
15.0to n/ha dry ha y
20
Complex C6 Carbohy drates: 16.2GJ/ton
10
186GJ/ha
Boil er: 7.1GJ/ton
Fert iliz ers: 3.4G J/t on Un-utiliz ed

Exergy
Lignin: 127GJ/ton
Next Generation 80
Lignocellulose-to-Bioethanol (Dilu te) Breeding Factor: 54%
P henol: 75.8GJ/ton
66.8
60 Complex C5 Carbohy drates: 60.2GJ/ton
57.0GJ/ton
P henol: 53.8GJ/ton Ash: 52.8GJ/ton
CRACKER
F ertiliz ers: 52.8GJ/to n
50
Crude Oil T oluene: 48.6GJ/ton 48.5
44.9GJ/ton Biomass
S tyrene: 42.6GJ/ton 5.86GJ/ton
40
Protein:
40.4GJ/ton
30 Lucerne
29.2 South Dakota
26.2GJ/ton
Ammo nia: 23.0G J/t on 15.0to n/ha dry ha y
Fossil Fuel Exergy Savings 15.0to ta lDW/ha
20
30.7GJ/ton chemicals Complex C6 Carbohy drates: 18.4GJ/ton
13.0GJ/ton biomass
10n
195GJ/ha
Boi ler: 5.9GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.127 1.91 30.1% 8.33 7.89
Phenol 0.015 0.23 3.5% 0.98 0.93
Styrene 0.017 0.25 3.9% 1.09 1.03
Toluene 0.015 0.22 3.5% 0.96 0.91
1,4-butandiamine 0.016 0.24 3.8% 1.05 0.99
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.000 0.00 0.0% 0.00 0.00
Ammonia 0.005 0.07 1.2% 0.33 0.31
ε-caprolactum 0.009 0.14 2.2% 0.60 0.57
Ethylamine 0.031 0.46 7.3% 2.01 1.90
γ-butyrolactum 0.015 0.23 3.6% 1.00 0.95
Ionic liquids 0.004 0.07 1.0% 0.29 0.27
Isoprene 0.025 0.38 5.9% 1.64 1.55
Oxalic acid 0.007 0.10 1.6% 0.45 0.43
Urea 0.003 0.05 0.8% 0.23 0.21
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.111 1.67 26.2% 7.27 6.88
Description
- It is the most expensive crop to cultivate and harvest. Biomass acquisition energy intensity
is mainly associated with irrigation and logistics.
- The ash content is also abnormally high which greatly reduces the fossil fuel energy and
exergy replacement potential and presents a minimal increase of exergy versus energy in
the overall savings potential.
- The resulting cumulative energy and exergy to produce ethylene is still safely below the
break-even point therfore contributing to a positive savings potential.
- Residual protein content and concentration are perfectly suited for downstream processing
to amine-based chemicals despite the high associated feedstock costs.
Improvement Options
Problem is not processing or biomass composition but solely biomass acquisition energy:
- Relocate to a region without heavy use of aquifer-based irrigation and closer to cluster port
for half-product processing; for example, Eastern Europe (i.e. Poland).
- A harvesting or washing technique with less soil take up and without a yield loss.

Nicotiana Tabacum L. – Tobacco
Common Names
Tobacco, flue-cured tobacco, Virginia tobacco
Classification
Perennial, harvested as annual, nightshade family, C-3
Appearance
0.9 – 2m tall, thick-stemmed shrub, white to purple cluster of flowers,
30 – 40cm long, 15 – 20cm thick spiralling Leaves
Varieties
Several, major types divided by colour and curing methods: Brightleave,
White Burley, Shade, Perique, etc.
Yes, against diseases and for high protein and amino-acid content make it
an ideal plant to develop as a source of limited and specialized nutrients.
Brief Description
Known to natives of the Americas for thousands of years, it was used in various forms to release the
hallucinogenic stimulant nicotine alkaloid. Upon colonization of America major cultivation efforts began
with the success of European introduction and subsequent demand.
Growth Details
Native Area: South and Central America
Location: Worldwide, almost chiefly in the Southern United States
Climate: Currently a wide variety, although mainly warm subtropical, frost-free
400 – 600mm, can withstand 1 month drought, sensitive to over irrigation
Soil Type: Light sands – thick loam, sandy soil best, must be well aerated and drained
Soil Acidity: 5 – 6.5pH, preferable 5.7 – 6.0pH
Plantation: Sown in seedbeds, grown for 40 – 60 days under cover, transplanted to fields at 15cm
tall, field spacing 1.2-0.9m x 0.9-0.6m, pre-dug holes
Seeding Rate: 0.125 – 0.175t/ha, 1800 – 2200seeds/m² of seedbed
Companion Crop: No, rotated every 1-2 years with non eelworm susceptible crops (e.g. maize)
Pest and Disease: Yes (i.e. tobacco beetle), some GMO’s act against
Weed Control: Not problems as plants are transplanted and can compete
Cultivation: Early April seeding, automated late June transplanting, hand suckering (only
important for nicotine uses) end August – early September harvesting
Harvesting: Manual cutting of individual Leaves, several at a time with sickle or mechanical whole
crop pulling operations
Based on published data of the American flue-cured species and Australian biomass species:
Yi eld Dependent Macronutrient Uptake Yield Dependent Mi cronutri ent Uptake
350 2000
N Fe
Mn
P2 O5
1800 B
K2 O
300 Zn
Ca O Mo
1600
MgO Cu
Poly . ( Fe )
250 SO 3
1400
Poly . ( Mn )
L og. (N)
Poly . ( B)
L og. (P2 O5) Poly . ( Zn)
L og. (K2 O)
1200 Poly . ( Mo )
200
L og. (Ca O) Poly . ( Cu)
L og. (MgO )
1000
150 L og. (SO 3)

800
100 600
400
50
200
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Dry Hay Y ield (ton /ha) Dry Hay Yield (ton/ha)

Yield
Normal Conditions: 10 – 20 ton/ha (Leaves, relates to 1.5 – 4.0 ton/ha traditionally cured leaves)
16 – 33.2 ton/ha (total plant)
Optimal Conditions: 200 – 240 ton/ha (year-round, 5 harvests, treated like grass, .au)
24 – 30 ton/ha (dry leafy material, no stalk growth)
Worldwide Cultivation: 4.0 million hectares at 18 ton/ha (1.6 ton/ha of cured leaves)
Constituent Leaves Stalk Whole Plant Whole Plant
(for nicotine) (for biomass)
Moisture Content 88% 35% 65% 88%
Cellulose 36.3 42.4 29.1 36.3
Hemicellulose 34.4 28.2 33.0 34.4
Lignin 12.1 27.0 14.8 12.1
Starch - - 3.0 -
Protein 12.0 - 14.8 12.0
Oils - - - -
Fats - - - -
Minerals - - 1.8 -
Ash 5.2 2.4 - 5.2
Others - - 3.5 -
In air-cured variety leaves represent about 3/ 5 of the total wet plant mass
Higher Heat Value: 19370 kJ/kg (leaf), 19375 kJ/kg (stalk)
Lower Heat Value: 16035 kJ/kg (leaf), 18910 kJ/kg (stalk)
The protein of tobacco can be easily fractionated. Between 30 and 50% of the soluble proteins are of a
high nutritional value that can be crystallized and easily extracted, only 1% of amino acids are free. The
rest of the proteins are group in a second fraction.
Amino Acid Composition of Whole Plant Whole Plant
Plant Protein (Protein Fraction 1) (Protein Fraction 2)
Alanine 7.0 5.1
Isoleucin e 4.3 3.7
Leu cin e 8.8 4.1
Proline 4.6 8.2
Tryptophan 4.9 8.8
Valine 7.2 10.4
Asparagine Trace Trace
Cystein e 3.0 0.8
Glutamine Trace Trace
Polar &
Glycine 9.2 3.5
Hydrophilic
Serin e 3.3 4.0
Threonine 5.2 4.6
Tyrosine 1.5 Trace
Acidic
Arginine 6.1 10.3
Lysine 5.8 3.9
Total 98.9% of Protein 99.9% of Protein
Tobacco is of course cultivated for its nicotine levels. They can vary from 1.5 – 2.5DW% depending on
the crop age, GMO’s up to 4%. 65% is present in the Leaves, rest in the stalk.
Comments
It has been mentioned that 4-5 times more proteins can be harnessed from tobacco than from corn and
even soya beans using existing technology and yields.

Comparative Graph
Energy
Next Generation 80
Process Energy Demand 64.7GJ/ton
60
CRACKER
Crude Oil
44.9GJ/ton Protein: Biomass
44.5GJ/ton 3.43GJ/ton
40
T oluene: 34.6GJ/ton
29.2GJ/ton 28.9 Tobacco
E thylene: 27.1GJ/to n 28.2 Australia
25.9 2 00ton/ha wet ha y
20
P henol: 19.2GJ/ton
10
347GJ/ha Complex C6 Carbohydrates: 10.6GJ/ton
Boil er: 7.6GJ/ton

Exergy
Next Generation 80
P henol: 75.8GJ/ton
65.0GJ/ton
60
CRACKER
Lignin: 52.2GJ/ton
50
Crude Oil Protein:
44.9GJ/ton 46.8GJ/ton Biomass
40 3.61GJ/ton
30 Tobacco
P henol: 27.1GJ/ton Australia
T oluene: 24.9GJ/ton 23.6
Ammo nia: 23.0G J/t on 2 00ton/ha wet ha y
Fossil Fuel Exergy Savings 22.0 26.5to ta lDW/ha
20n
E thylene: 20.6GJ/to 19.1
59.6GJ/ton chemicals 5.31GJ/ton S tyrene: 18.5GJ/ton
21.9GJ/ton biomass Am monia: 12.7GJ/ton Complex C5 Carbohy drates: 12.5GJ/ton

10n Complex C6 Carbohy drates: 11.2GJ/ton
582GJ/ha
Boi ler: 6.2GJ/ton Fertilizers: 6.3GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.187 4.97 50.9% 14.84 2.70
Phenol 0.022 0.59 6.1% 1.77 0.32
Styrene 0.025 0.66 6.7% 1.96 0.36
Toluene 0.022 0.58 6.0% 1.74 0.32
1,4-butandiamine 0.010 0.26 2.7% 0.79 0.14
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.005 0.13 1.4% 0.40 0.07
Ammonia 0.005 0.13 1.4% 0.40 0.07
ε-caprolactum 0.003 0.08 0.8% 0.22 0.04
Ethylamine 0.008 0.21 2.1% 0.61 0.11
γ-butyrolactum 0.007 0.17 1.8% 0.52 0.09
Ionic liquids 0.003 0.09 0.9% 0.27 0.05
Isoprene 0.008 0.21 2.1% 0.63 0.11
Oxalic acid 0.002 0.06 0.7% 0.19 0.04
Urea 0.003 0.09 0.9% 0.27 0.05
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.040 1.06 10.9% 3.17 0.58
Description
- The very high dry biomass yield can offset to a large degree the biomass acquisition energy
intensity including the hefty logistics costs.
- Main biomass component is lignocellulose resulting in a large quantity of ethylene and at a
relatively low process energy intensity.
- Aromatics are also produced in significant quantities at vastly lower cumulative energy as
compared to traditional process routes.
- Those products (ethylene & aromatics) which rely heavily on thermal processes have a
large difference between energy and exergy demand while supplying the boiler with large
unconverted material streams.
Improvement Options
- Relocated to closer location, such as Southern Europe (i.e. Spain), could vastly decrease the
feedstock energy cost and promote tobacco as one of the best cropping system options.
Should be able, with the right conditions, to outperform Dutch ryegrass.
- Focus on lignin separation and conversion techniques.
- Promote an increase in lignin content by allowing the crop to age; propitiously decrease
harvesting costs and inadvertent soil contamination.

Lolium Perenne – Grass
Common Names
Ryegrass, grass, green grass, European grass
Classification
Perennial, tufted grass, C-3
Appearance
8 – 90cm tall green stems, loosely to densely tufted, shinny folded Leaves,
2 – 6mm narrow, 3 – 20cm long, 3 – 31 cm long spikelets, deep rooting
system, 1 – 1.5 meters, most 15cm below topsoil
Varieties
Practically infinite, many natural hybrids
Countless amounts, developed for application purpose type, highly regulated
Brief Description
Grass grows nearly year round, spreads and tills naturally. It has many purposes when manually tilled
including: natural grasslands, lawns, pastures, grazing, hay production, soil erosion prevention and
possibly as a source of biomass.
Growth Details
Native Area: Eurasia and Northern Africa
Location: Eurasia and has spread to the rest of the world in various subspecies
Climate: Temperate, mild and humid (oceanic/rainy)
Temperature: 4.3 – 23.7°C, sensitive to frost and high temperatures
210 – 820mm, 500mm good yields, <400mm poor yields. Tolerate up to 1760mm.
More important than nutrients, cannot tolerate drought or floods
Soil Type: Heavy, nutrient rich, moist soils; dry and wet soils not suitable
Soil Acidity: 4.5 – 8.2pH tolerance, average 6.3 – 6.7pH, slightly acidic
Plantation: Grid drilling or broadcast, 20 – 60cm row spacing, long-lived pasture strains, sown
perennials 10 – 30% higher yielding
Seeding Rate: EU: 10 – 20kg/ha drilling, 6 – 20kg/ha broadcast, combined with 12 – 28 kg/ha
clover seeds, 440 – 585 kseeds/kg, 20 – 50 kplants/ha (tillers)
Companion Crop: Yes, usually the leguminous clover
Pest and Disease: No, highly resistant
Weed Control: Can become a problem during long-term rotations, reseeding prevents (yearly)
Cultivation: Sown in early spring, fast and peak growth during late spring/early summer
Harvesting: Growth decreases in late autumn, 7-8 months growth period, multiple cuttings
possible, increase shout growth and yield
Sown with clovers, inoculation bacteria strain: Rhizobium Trifolii (59% N uptake)
Legume sowing is not sufficient to supply all nitrogen, additional fertilizer added
Yield Dependent Macronutri ent Uptake Yi el d Dependent Micronutrient Uptake
400 2500
N Fe
P2 O5 Mn
K2 O B
350
Ca O Zn
MgO Mo
2000
SO 3 Cu
300 Po ly. (N) Poly . ( Fe )
Po ly. (P2O 5)
Poly . ( Mn )

250 Po ly. (CaO ) Poly . ( Zn)
Po ly. (MgO)
1500
Poly . ( Mo )
Po ly. (SO3 ) Poly . ( Cu)
200
1000
150
100
500
50
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 16
Dry Hay Yield (ton/ha) Dry Hay Y ield (ton/ha)

Yield
Normal Conditions: 18 – 30 ton/ha (5 – 8 ton/ha dry hay)
Optimal Conditions: 55 – 80 ton/ha (10 – 14 ton/ha dry hay, 2-3 cuttings)
European average: 47 ton/ha (12.5 ton/ha dry hay) (2-3 cuttings)
Best Practice NL: 14.1 ton/ha dry hay
60 – 100+ ton/ha fresh weight, GMO tests (8-9 cuttings)
Worldwide Cultivation: 3.5 billion hectares grazing land at less than 10 ton/ha (2.5 ton/ha dry)
(Based on dry weight, common European species)
Constituent Grass White Clover Mix†
Moisture Content 82.4% 82.7% 82.5
Cellulose 30.6 28.3 29.7
Lignin 3.1 2.5 2.9
Protein 17.9 22.1 19.4
Sugars 10.5 12.0 11.1
Oils
4.9 2.9 4.2
Fats
Ash 11.3 11.6 11.4
†typical mix is 37% clover cover over the course of the growing season
The amino acid concentration and constituents are very similar to that of wheat. This can be expected as
they are very closely related within the same botanical species. Higher mixtures of legumes (i.e. clover)
reduce protein content and amino acid concentration.
Ryegrass/clover mix herbage composition of essential amino acids:
Amino Acid Composition of Whole Plant
Protein g/kg %
Leu cin e 10.05 7.58
Tryptophan Trace
Valine 7.81 5.89
Polar &
Threonine 6.09
Hydrophilic 4.59
Arginine 7.78 5.87
Lysine 8.72 6.58
Other amino
72.03 54.33
acids
Total 132.6 g (79.0% of Protein)
Grass is a good source of carotene (4.8 mg/100 g). It contains free fructose, fructosan, mannitol, a
complex mixture of oligosaccharides; oxalic-, citric-, malic-, and shikimic- acids, glycerides, and a wax
containing hexacosanol.
Comments
It has been researched that between 15 – 40% of grown biomass is present in rooting system. Natural
ryegrass is a diploid and no polyploids occur, however, in The Netherlands a tetraploid variety (2n=28)
was developed and employed in the 60’s. These species have a high tiller density, water solubility for
carbohydrates, better yields and are best for large-scale animal production. These properties would be
equally advantageous for biomass production applications.

Comparative Graph
Energy
Lignin: 148GJ/ton
Next Generation 80
Process Energy Demand T oluene: 63.8GJ/ton 61.8
60
CRACKER
50
P henol: 51.1GJ/ton
Crude Oil
44.9GJ/ton Biomass
7.13GJ/ton 58.0GJ/ton 2.45GJ/ton
40
30 Ammo nia: 31.0G J/t on Ash: 30.4GJ/ton

F ertiliz ers: 30.4GJ/to n 27.8 Grass
E thylene: 27.2GJ/to n The Netherlands
26.9
80.5to n/ha wet ha y
Fossil Fuel Energy Savings Protein: 21.3GJ/ton 14.1to ta lDW/ha
20
Am monia: 15.0GJ/ton Complex C5 Carbohy drates: 13.7GJ/ton
17.6GJ/ton biomass Boil er: 14.1GJ/ton
10n Complex C6 Carbohy drates: 9.3GJ/ton
249GJ/ha

Exergy
Lignin: 163GJ/ton
Next Generation 80
P henol: 75.8GJ/to n
P henol: 66.7GJ/ton E thylene: 68.1GJ/ton

60
- Raw Fossil Fuel Input 60.6
58.1GJ/ton
St yrene: 54.3GJ/ton
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 2.70GJ/ton

30 Grass
The Netherlands
80.5ton/ha wet ha y
Fossil Fuel Exergy Savings Ammo nia: 23.0G21.7
J/t on 14.1tota lDW/ha
20n
E thylene: 21.3GJ/to Protein: 19.9GJ/ton
21.1
19.3GJ/ton biomass 2.5GJ/ton
Boil er: 11.0GJ/ton
10n
Ammonia: 10.6GJ/to Complex C6 Carbohydrates: 10.2GJ/ton
272GJ/ha
Amin e Ch em icals: 8.0GJ/to n Fertilizers: 7.4GJ/ton
Un-utilized

Overview Savings

Ethylene 0.136 1.91 39.1% 2.79 0.98
Phenol 0.005 0.08 1.5% 0.11 0.04
Styrene 0.006 0.08 1.7% 0.12 0.04
Toluene 0.005 0.07 1.5% 0.11 0.04
1,4-butandiamine 0.016 0.22 4.5% 0.32 0.11
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.003 0.05 1.0% 0.07 0.02
Ammonia 0.006 0.08 1.7% 0.12 0.04
ε-caprolactum 0.007 0.09 1.9% 0.14 0.05
Ethylamine 0.017 0.24 5.0% 0.36 0.13
γ-butyrolactum 0.009 0.13 2.6% 0.19 0.07
Ionic liquids 0.003 0.05 1.0% 0.07 0.02
Isoprene 0.020 0.28 5.8% 0.41 0.15
Oxalic acid 0.005 0.06 1.3% 0.09 0.03
Urea 0.004 0.06 1.3% 0.09 0.03
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.081 1.13 23.2% 1.65 0.58
Description
- By focusing on local production with a multi-year harvest the biomass acquisition energy
intensity is low providing a good starting point for many of the biomass components.
- Multiple harvests also renders protein at the ideal content and concentration promoting
effective and efficient amine chemistry conversions.
- Large unconverted waste streams are used to generate significant amounts of internal
process energy, however not quite sufficient to achieve a negative exergy value.
- Ash content is simply too high which reduces the potential effectiveness, albeit not as
severe as some of the other grasses, like lucerne.
Improvement Options
- Increase yield; achieving dry weight yield in excess of 20ton/ha should be possible without
placing large increase in energy demand.
- A harvesting technique or washing technique with less soil take up and without yield losses.
- Since amines and ethylene are produced efficiently and effectively the lignin content may
be utilized to increase the internal heat and power generation, especially considering the
ease of incorporating it in the grid.

Panicum Virgatum – Switchgrass
Common Names
Switchgrass, Tall Panic Grass
Classification
Tall-grass prairie, summer rhizomatous perennial, C-4
Appearance
Up to 0.5 - 2.5 meter tall, round stem, reddish tint. Purple flowers, borne
singly at the end of branches, root system up to 3m deep
Varieties
Several wild varieties, two main types: upland and lowland
None thus far
Brief Description
Eating by all grazing animals, many framers plant it as means for forage or erosion control and more
recently thoughts are given toward biomass applications. It is noted for its heavy growth in late spring and
early summer.
Growth Details
Native Area: North America
Location: Various locations, mainly North America, parts of Europe & South America
Climate: Temperate, can tolerate frost and snow cover
Temperature: 5 - 25°C, growth initiated at temperatures above 10°C
300 – 400mm, varies from type
Soil Type: Moderately deep – deep, dry – poorly drained, sandy – clay loam,
Soil Acidity: 4.9 – 7.6pH, neutrality is optimum
Plantation: 2.5 – 10mm depth, mechanized with airflow, drill or no-till drills in rowed rolled
seedbed of 15 – 20cm width
Seeding Rate: 5 – 10kg/ha, very small seeds, 500 – 1000seeds/g, reseeding at 4 – 5kg/h necessary
for frost application or with poor establishment
Companion Crop: None, but clovers are a possibility
Pest and Disease: Resistant to most, grasshoppers and leafhoppers, nothing serious
Weed Control: Controlled by moving lawn when 10cm height reached, not essential
Cultivation: Frost or spring seeding, possible growth cycle more than 10 years, 75% of mass
produced in summer upon flowering
Harvesting: After second year, delayed until winter/early spring for re-growth reasons
Arbuscalar Mycorrhizal Fungi (AMF) symbiosis in Midwest. European soils do not contain the inoculating
strain, yet investigation is underway for others.
Inoculation bacteria strain: Mycorrhizae, more specifically Glomus etunicatum (30% N Uptake)
First year growth will not incorporate nitrogen as to prevent weed growth stimulation
Yi eld Dependent Macronutrient Uptake Yi el d Dependent Micronutrient Uptake
700 1400
N Fe
P2O5 Mn
K2O B
600 CaO 1200 Zn
Mg O Mo
SO3 Cu
500
Total Plant Uptake ( kg /ha)
Poly. (N) 1000 Poly. (Fe)

Total P lant Uptake (g/ha)
Poly. (P2 O5 ) Poly. (Mn)

Poly. (K2 O) Poly. (B)
Poly. (Ca O) Poly. (Zn)
400 Poly. (MgO ) 800 Poly. (Mo)
Poly. (SO 3) Poly. (Cu )
300 600
200 400
100 200
0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Dry Hay Yield ( ton/ha) Dry Hay Yield (ton/ha)

Yield
Normal Conditions: 3.5 – 14 ton/ha (dry, native area of the Midwest)
8 – 10 ton/ha (dry, average, also in Europe)
Optimal Conditions: 6 – 25 ton/ha (dry, Southern European test sties)
Worldwide Cultivation: Unknown as wild species (in excess of 25 million hectares at 5 ton/ha)
(Based on dry weight and the Alamo species)
Constituent Whole Plant
Moisture Content 12%
Cellulose 31.0
Hemicellulose 24.4
Lignin 17.6
Pectin 1.2
Protein 9.0
Oils -
Fats -
Minerals 8.0
Ash 5.8
Others 4.0
Very little investigation is available for the amino acid content of Switchgrass. Generally speaking the
protein (crude protein) content of the crop can reach up to 20% during the summer growth months and
drop to below 4% during the winter senescence. 9.0% is upon biomass harvesting.
Sugar extractives: 32.2 C-6 sugars
0.3% Mannan
0.9% Galactan
31.0% Glucan
23.2 C-5 sugars
2.8% Arabinan
20.4% Xylan
Comments
Alamo species is more directed at warmer temperatures and wetter soil conditions. As a result is continues
to grow longer and has an average yield of 14 t/ha. It should be noted that the moisture content is
remarkably low and in addition to the low nutrient demands makes it the “cheapest energy crop”.

Comparative Graph
Energy
Next Generation 80
Process Energy Demand
60
- Raw Fossil Fuel Input Protein: 57.8GJ/ton
58.4GJ/ton
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 3.11GJ/ton
Ammo nia: 31.0G J/t on Lignin: 31.0GJ/ton

30 28.9 Switchgrass
Toluene: 27.9GJ/to n 28.5 Iowa
S tyren e: 26.6G J/t on 15.9to n/ha wet ha y
22.7
Fossil Fuel Energy Savings Amin e Ch em icals: 21.7GJ/to 14.0to ta lDW/ha
20n
38.5GJ/ton chemicals 19.9GJ/ton
14.8GJ/ton biomass P henol: 13.1GJ/t on
10
208GJ/ha
Boil er: 8.1GJ/ton

Exergy
Next Generation 80
- Chemical vs. Biomass CExD Protein: 62.6GJ/ton

60
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 3.37GJ/ton
Lignin: 33.5GJ/ton
30 Switchgrass
Iowa
23.1 15.9ton/ha wet ha y
Fossil Fuel Exergy Savings E thylene: 22.7GJ/to n Ammo nia: 23.0G J/t on 14.0tota lDW/ha
20
P henol: 20.4GJ/ton 22.3
43.7GJ/ton chemicals 15.3GJ/ton T oluene: 19.0GJ/ton 17.4
Am in e Ch emicals: 15.3GJ/to n
16.9GJ/ton biomass Ammonia: 13.5GJ/to n Complex C6 Carbohydrates: 12.2GJ/ton
10
St yrene: 12.4GJ/ton
236GJ/ha
Boi ler: 6.6GJ/ton Fert iliz ers: 6.1G J/t on
Un-utilized

Overview Savings

Ethylene 0.150 2.10 39.0% 7.75 5.98
Phenol 0.033 0.46 8.4% 1.68 1.30
Styrene 0.036 0.50 9.3% 1.86 1.43
Toluene 0.032 0.45 8.3% 1.64 1.27
1,4-butandiamine 0.008 0.12 2.2% 0.44 0.34
Acrylamide 0.000 0.00 0.0% 0.00 0.00
Adipic acid 0.004 0.05 1.0% 0.20 0.15
Ammonia 0.003 0.04 0.7% 0.14 0.11
ε-caprolactum 0.002 0.03 0.6% 0.11 0.09
Ethylamine 0.008 0.11 2.1% 0.42 0.32
γ-butyrolactum 0.005 0.07 1.2% 0.25 0.19
Ionic liquids 0.001 0.01 0.3% 0.05 0.04
Isoprene 0.007 0.10 1.8% 0.35 0.27
Oxalic acid 0.002 0.03 0.5% 0.10 0.08
Urea 0.002 0.02 0.4% 0.09 0.07
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.084 1.18 21.8% 4.34 3.35
Description
- Regardless of being located in America (Iowa) the overall biomass acquisition energy is low
enough because the crop has sufficient yields.
- Due to the unique composition all the potential chemical products are in the same
generally low range of energy/exergy intensity.
- The lignin conversion to aromatics is particularly effective and efficient and is in large
quantities; combined reach more than a quarter of products.
- As with other grasses the ash/fertilizer in considerable and decreases the overall savings.
Improvement Options
- Is no major improvement options foreseeable: will remain a middle-range cropping system.
- Relocated to closer location

Saccharum Officinarum L. – Sugar Cane
Common Names
Sugar cane, sugarcane, noblecane
Classification
Asian perennial grass, legume, C-4
Appearance
3-5m height, 2-3cm thick panicle stem, tapering from bottom to top. Silky
spikelets. Thin 4-6cm, 20-60cm long, nodule-sprouting green Leaves, roots
span 30 cm at 2 meters depth.
Varieties
6 species origins: S. spontaneum, S. robustum, S. officinarum, S. barberi, S. sinense and
S. edule. Cultivated versions are hybrids!
None, but plant breeding hybrids usually tri- or quadrispecific
Brief Description
The major source of sugar production. With the advent of the European policy changes the market will
must likely collapse and shift to industrial applications, like ethanol. The by-products, bagasse is also used
in the paper industry and energy sector. Sugarcane is the world's largest crop.
Growth Details
Native Area: South Pacific Islands
Location: Throughout the southern tropics, Brazil and India being large producers
Climate: Tropics – subtropics, rainforest areas, hot and humid
Temperature: Above 30°C, growth cesses at temperature below 19°C
1500mm is a minimum; average is 1675mm, partially drought resistant
High water efficiency, 250 parts water for each part of dry matter
Soil Type: Wide variety with drainage a basic requirement
Soil Acidity: 4.3 – 8.4pH, average 6.3
Plantation: Stalk furrowing (stem cuttings), two node length, mechanized with
chopper-planter, 15-30cm deep, 1.3 – 1.4 meters distance
Seeding Rate: 6000 – 7000kg planted stalks/ha create 90 000-150 000 plants/ha.
Companion Crop: Leguminous manure and smaller crops
Weed Control: Heavy use of herbicides, upon proper canopy development no more
Pest and Disease: Susceptible to many viruses and fungi
Cultivation: Deep ploughing and ridging necessary, no rotation required, 3-4 years
continuous growth up to 8, year round plantation possible
Harvesting: Upon stem discolouration, 12 – 20 months upon plantation, cooler periods
Not exactly a leguminous crop but can harness legumes growth, leguminous manure and side field crops
can cover 70% of the nitrogen demand
Yi eld De pe ndent Mac ronutrient Uptake Yield Depe ndent Mi cronutrient Uptake
200 900
N Fe
P2O5 Mn
180 K2O 800 B
CaO Zn
Mg O Mo
160
SO3 700 Cu
Poly. (N) Po ly. ( Fe )
140
Poly. (P2 O5) Po ly. ( Mn )

Poly. (K2 O) 600 Po ly. ( B)

Poly. (Ca O) Po ly. ( Zn)
120
Poly. (M gO ) Po ly. ( Mo )
Poly. (SO 3)
500
Po ly. ( Cu)
100
400
80
300
60
200
40
20 100
0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Green Biomass Y ield (ton/ha) Green Biomass Y ield (ton/ha)

Yield
Normal Conditions: 15 – 100ton/ha, 72.3ton/ha cane (Brazil: 5-year average)
Best Brazilian practice: 140ton/ha green biomass (35ton/ha dry)
Optimal Conditions: The theoretical maximum yield (PAR) is 280 ton/ha/y wet weight
Worldwide Cultivation: 20 million hectares at 65.5 ton/ha
(Based on dry weight: multiple year average)
Constituent Cane/Stem Leaves
Cellulose 22.3 38.7
Hemicellulose 18.5 32.4
Lignin 3.9 7.1
Sucrose 46.2 -
Other Sugars 2.0 -
Protein 0.6 8.0
Fats 0.6 3.6
Oil - -
Minerals 1.4 1.1
Ash 1.7 8.9
Others 2.8 -
Stalk represents ¾ of the total wet weight
It is common practice in Brazil to burn the leaves before harvesting canes, loss of ¼ wet weight
Lower Heat Value: 18990kJ/kg (bagasse), 21500 kJ/kg (cane juice), 16000 kJ/kg (leaves)
Higher Heat Value: 17710kJ/kg (bagasse), 21000 kJ/kg (cane juice), 16500 kJ/kg (leaves)
Sugar cane itself provides negligible amounts of protein, and supplements are needed when used as a
fodder. Stem contains only 0.62 percent in the dry matter. It is the lowest of all other biomass fodder
options on amino acid usage.
Bagasse (the waste of the sugar processing) is usually burned to harness the contained energy. The
industry is autonomous, meaning the bagasse supplied all the heat, steam and electricity to run the sugar
plant.
Comments
Experimental figures can produce yields of over 35 ton/ha cane of dry weight, which is amazingly high.
As the sugar market will shift, investigation should be made on utilizing the existing infrastructure to
produce something else.

Comparative Graph
Energy
Fertilizers: 163GJ/to n
Amin e Ch em icals: 144GJ/to n Protein: 216GJ/ton
Am monia: 126GJ/to n
Next Generation Styren e: 83.9GJ/ton
80 Amine Chemicals: 83.2GJ/ton
Ash: 163GJ/ton
Net Energy Value (NEV): 2.7
Sugar-to-Bioethanol (Mi lli ng) Phenol: 76.5GJ/ton
Ethylene: 67.0GJ/ton 66.4GJ/ton
60
- Raw Fossil Fuel Input Lignin: 56.8GJ/ton
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 1.34GJ/ton
Styrene: 37.2GJ/ton
31.4
30 Ammo nia: 31.0GJ/ton
Sugar Cane
25.2 Brazil
24.4GJ/ton
22.4 125ton/ha cane
Phenol: 21.5GJ/ton
20
42.0GJ/ton chemicals Ethylene: 19.5GJ/to n 15.9
11.3GJ/ton biomass Complex C5 Carbohydrates: 9.0GJ/ton

490GJ/ha Simple Carbohydrates: 3.3GJ/ton
Boil er: 8.2GJ/ton

Exergy
Fertilizers: 172GJ/to n Protein:227GJ/ton

Ash: 172GJ/ton
Next Generation Amin e Ch em icals: 80.7GJ/ton
Sugar-to-Bioethanol (Mi lli ng) Breeding Factor: 27%
Phenol: 75.8GJ/ton
Lignin Aromatics (Fast-Pyrol ysi s) Am monia: 64.7GJ/ton
67.3GJ/ton
- Chemical vs. Biomass CExD Lignin: 59.9GJ/ton
60
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 1.41GJ/ton
30
Styrene: 29.9GJ/ton Sugar Cane
T oluene: 27.4GJ/ton 26.2 Brazil
125ton/ha cane
Fossil Fuel Exergy Savings Ammo nia: 23.0GJ/ton 43.5to ta lDW/ha
20
Phenol: 21.0GJ/ton
84.3GJ/ton chemicals -17.0GJ/ton 18.0
15.2
22.6GJ/ton biomass Ethylene: 12.5GJ/to n Complex C6 Carbohydrates: 7.0GJ/ton
10 Simple Carbohydrates: 3.5GJ/ton
985GJ/ha 9.1
Boi ler: 6.7GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.231 10.05 86.0% 20.98 -14.59
Phenol 0.008 0.33 2.8% 0.69 -0.48
Styrene 0.008 0.37 3.1% 0.77 -0.53
Toluene 0.007 0.32 2.8% 0.68 -0.47
1,4-butandiamine 0.001 0.05 0.5% 0.11 -0.08
Acrylamide 0.001 0.04 0.3% 0.08 -0.06
Adipic acid 0.000 0.00 0.0% 0.01 -0.01
Ammonia 0.000 0.01 0.1% 0.02 -0.01
ε-caprolactum 0.000 0.01 0.1% 0.02 -0.02
Ethylamine 0.001 0.04 0.3% 0.08 -0.06
γ-butyrolactum 0.000 0.01 0.1% 0.02 -0.02
Ionic liquids 0.000 0.01 0.1% 0.02 -0.01
Isoprene 0.001 0.03 0.2% 0.06 -0.04
Oxalic acid 0.000 0.01 0.1% 0.01 -0.01
Urea 0.000 0.01 0.1% 0.02 -0.01
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.008 0.36 3.1% 0.75 -0.52
Description
- Practically unbeatable; in terms of energy and exergy it performs extraordinarily well.
- It has a very low biomass acquisition energy intensity and simultaneously produces
extraordinarily high yields.
- Ethylene dominates the chemical mix, representing more than 85% and is produced very
efficiently with the residuals contributing to the internal CHP.
- Hardly any ash/fertilizers is produced meaning the difference between energy and exergy is
very large when in combination with an efficient boiler.
Improvement Options
- To maintain its top position one must ensure that the produced off-heat and energy
production are utilized locally, which can be an issue in rural Brazil.
- Make only ethylene, nothing else. The amine chemistry and aromatic chemistry are best
directed at contribution to a highly efficient heat and power generation stream.
- It is the best cropping/biorefinery system. (period). Any improvements on yield or
conversion system will only strengthen its position.

Salix Alba – Willow Tree
Common Names
Willow Tree, White willow, Irish Sailach
Classification
Deciduous hardwood tree, C-3
Appearance
20 – 30meters tall, vertical shoots, 5-10cm long, 1-1.5cm wide elongate
and serrate leave, green with silky white hairs
Varieties
Roughly 350 varieties of willow; for alba the difference is between
cultivated and uncultivated, e.g. cricket-bat willow is an English variety
(slightly larger) grown as a specialists timber crop
None, but several hybrids
Brief Description
Native to northern Europe, the willow has been used for timber production for centuries. The fast-
growing nature has put it on the top of lingo-cellulosic biomass applications option list.
Growth Details
Native Area: Europe and Western Asia
Location: Cooler zones of the Northern Hemisphere
Climate: Cool - Temperate
Temperature: 10 - 25°C, above 30 is detrimental, tolerates frost
500 – 2000mm, tolerates floods
Soil Type: Nearly all types, preferably moist, deep loams
Soil Acidity: 5.5 – 8.0pH, can tolerate practically anything, neutrality best
Plantation: 18 – 20cm long stems cuttings, near complete cover
2 – 3meter grid spacing (<5 year), 3 – 5meter grid spacing (>15 year)
Seeding Rate: Propagation from seedlings is not useful in energy silviculture
500 – 1000 plant/ha for long-term rotation (>15 years)
15000 – 35000 plants/ha for short-term rotation (<5 years)
Companion Crop: Legumes highly recommended, grass or mixed with other trees
Weed Control: None, except possibility 1st and 2nd year
Cultivation: Growth period 25 – 30 years, 1st year whip production to stimulate height growth,
also increases yield 10 – 20%, 3 – 4 year harvesting or cutting rotations, can re-sprout
from trunk although not implemented
Harvesting: Immature retrofitted machines, cuttings or logging with direct chipping, after
senescence, later autumn/early winter
The routing systems are capable of leeching traces of nutrients from deep and sometimes far away water
reservoirs, runoffs from other fields and various other sources. This is why deep soils are imperative. The
mentioned average yields (next page) are based on no additional nutrient levels. Information regarding
nutrient uptake is scarce or unavailable: as being not yet truly considered a crop. However, it is suggested
to add sewage sludge to fields as a source of the various nutrients. Results have shown an increase in
yields. On unfertile or exhausted lands, a highly concentrated band of fertilizer is suggested (at max
100kg/ha, 3 source average: 85kg/ha) for lifetime source of nitrogen and potassium. Over fertilizing does
not affect growth.
Assume 7.5kg/tonneWW N, K2O and P2O5, 0.1 for other macronutrients, 0.001 for all micronutrients.

Yield
Normal Conditions: 3 – 10 ton/ha (oven dry, upon 3-4th year harvesting 10 – 30ton/ha)
4 – 5 ton/ha (oven dry, Swedish test sites)
Optimal Conditions: 8 – 10 ton/ha (oven dry, lower latitudes and with fertilization)
Worldwide Cultivation: Wide spread, chiefly wild or planned forest areas, low harvesting
Constituent Trunk Leaves
Moisture Content 60% -
Cellulose 49.6 -
Hemicellulose 22.9 -
Lignin 22.7 -
Protein 2.0 -
Oils - -
Fats - -
Minerals 1.3 -
Ash 1.5 -
Others - -
The Leaves are not harnessed but left to provide a nutrient cycle
Lower Heat Value: 19200 kJ/kg (whole tree), 18500 (trunk)
Higher Heat Value: 19750 kJ/kg (whole tree), 19790 (trunk)
Initial/current practice of harvesting and processing methods is implemented upon leave senescence and
thus only trunk and branches are present. The lignocellulosic material is used for processing (should it be
for burning or fermentation) the rest, residual constituents are at trace levels and practically unusable and
do not need to be mentioned.
Comments
Popular is a common willow hybrid derivate used for the same possible application in warmer climates.
There is a slight difference, harvesting should be held every 4 – 5 years, it has a lower cellulose
concentration and although the yield is comparable due to the warmer climate the actual photosynthetic
conversion is marginally reduced.
An added environmental advantage: provide a year-round habit for forest wildlife.

Comparative Graph
Energy
F ertilizers: 153GJ/to n Protein: 239GJ/ton

As h: 153GJ/ton
Lignocellulose-to-Bioethanol Am in e Ch emicals: 78.0GJ/to n
(Dilu te) Phenol: 76.5GJ/to n Breeding Factor: 42%
Protein Extraction (Protease ) Tolu en e: 72.7GJ/ton
- Chemical vs. Biomass Cumulative Ethylene: 67.0GJ/ton 68.1GJ/ton
Process Energy Demand
60
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 2.98GJ/ton
30 Ammo nia: 31.0GJ/ton

29.6 Willow Tree
Ethylene: 25.9GJ/to n Sweden
24.2GJ/ton Toluene: 25.1GJ/to n 24.3 20.0ton/ha lumbe r
Styren e: 24.1GJ/ton Lignin: 23.0GJ/ton
Fossil Fuel Energy Savings 8.0tota lDW/ha
20 20.1
15.6GJ/ton biomass
10
Phenol: 10.6GJ/ton
125GJ/ha Boi ler: 9.1GJ/ton
Fertilizers: 3.7GJ/ton Un-utilized
Exergy
Fertilizers: 169GJ/to n Protein:264GJ/ton

Ash: 169GJ/ton
Phenol: 75.8GJ/to n
Protein Extraction (Protease ) Tolu en e: 73.7GJ/ton
68.9GJ/ton

60
CRACKER
Ammonia: 51.0GJ/to
50n
Crude Oil
44.9GJ/ton Biomass
40n 3.30GJ/ton
30 Willow Tree
Sweden
23.7
Lignin: 25.5GJ/ton
Ammo nia: 23.0GJ/ton 15.0ton/ha dry ha y
Fossil Fuel Exergy Savings 15.0tota lDW/ha
20
18.4GJ/ton Ethylene: 20.0GJ/to n 18.3
50.5GJ/ton chemicals Phenol: 17.5GJ/ton
14.7
17.9GJ/ton biomass
10
143GJ/ha Styrene: 9.8GJ/ton
Boi ler: 7.3GJ/ton Fertilizers: 7.1GJ/ton
Un-utilized

Overview Savings

Ethylene 0.231 10.05 86.0% 20.98 -14.59
Phenol 0.008 0.33 2.8% 0.69 -0.48
Styrene 0.008 0.37 3.1% 0.77 -0.53
Toluene 0.007 0.32 2.8% 0.68 -0.47
1,4-butandiamine 0.001 0.05 0.5% 0.11 -0.08
Acrylamide 0.001 0.04 0.3% 0.08 -0.06
Adipic acid 0.000 0.00 0.0% 0.01 -0.01
Ammonia 0.000 0.01 0.1% 0.02 -0.01
ε-caprolactum 0.000 0.01 0.1% 0.02 -0.02
Ethylamine 0.001 0.04 0.3% 0.08 -0.06
γ-butyrolactum 0.000 0.01 0.1% 0.02 -0.02
Ionic liquids 0.000 0.01 0.1% 0.02 -0.01
Isoprene 0.001 0.03 0.2% 0.06 -0.04
Oxalic acid 0.000 0.01 0.1% 0.01 -0.01
Urea 0.000 0.01 0.1% 0.02 -0.01
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.008 0.36 3.1% 0.75 -0.52
Description
- The overall dry weight yield is merely too low to compensate for the high biomass
acquisition energy intensity making it a poor starting biomass feedstock. Chipping (sizing)
and fertilizer demand round out the major portion.
- It scores mediocre in its conversion to ethylene compared to other carbohydrate (both
simple and complex) rich crops.
- Due to the high lignin content the conversion to the aromatic components is actually
highly efficient and effective being significantly lower than the traditional process routes.
- There is a minor efficiency improvement noticeable due to the thermally reliant processes
(ethylene and aromatics) but is not nearly adequate to be competitive.
Improvement Options
- Plant in regions without a large demand on fertilizers and allow growth beyond 3-years to
promote a higher lignin content; best to plant in low-value inland areas.
- Do not convert the proteins but use them to contribute to the boiler output.

Solanum Tuberosum – Potato
Common Names
Potato, Irish Potato
Classification
Perennial, harvested as annual, C-3
Appearance
Low-growing herb, 1m, white flowers with yellow stamens, Petiolulate
Leaves, 10–30 cm long, 5–15 cm wide, oval-oblong tubers, 10–20 cm long,
5–15 cm wide covered with spots, eyes,
Varieties
Thousands: brown, yellow, pink, red, purple, blue, etc
Under research, much public pressure
Brief Description
The world’s most important non-cereal crop. Grown for the starchy tuber it produces more food energy
than any other European crop per hectare.
Growth Details
Native Area: Andes, South America
Location: Worldwide
Climate: Cool – temperate, lots of precipitation
Temperature: 15 – 20°C, can tolerate 3.6 – 27.8°C, year round mean around 12°C
500 – 700mm, around 930mm common, can tolerate up to 4100mm
Soil Type: Most soils, for mechanical harvesting light to medium bodied soils
Soil Acidity: 5.5 – 7.0, preferred alkaline, below 4.8 impairs growth, mineral soils 6 – 7 pH
Plantation: Seeds 4 – 5cm diameter, rows, 40 – 120cm spacing, 10 – 20cm deep holes
Seeding Rate: Common varieties are sterile, planted by existing tubers, with 1-2 eyes
1.2 – 1.5 t/ha, as high as 2.5 - 3 t/ha
30000 – 100000 tubers/ha (normal range 30 – 60k tubers/ha, for bulb size)
Companion Crop: No, but can be used as a companion crop for other crops
Weed Control: Field must be root-weed free, up to 3 ploughings needed
Cultivation: Spring to early summer, early maturity 80-100 days, medium maturity 100 – 120days,
late maturity over 120 days, up to 3-4 year rotation break
Harvesting: Large mechanized farms usually defoliate chemically, autumn months
Fertilizers are applied before seedbed preparation and ploughed or cultivated into the soil
Yie ld De pendent Mic ronutrie nt Uptake Yiel d De pe nde nt Micronutrie nt Upta ke
600 2500
N Fe
P2O 5 Mn
K2O B
CaO Zn
500
M gO Mo
2000
SO3 Cu
Lo g. (N) Poly . ( Fe )
Poly . ( P2O5 ) Poly . ( Mn )

400 Lo g. (K2O ) Poly . ( B)

Poly . ( CaO) Poly . ( Zn)
1500
Poly . ( Mg O) Poly . ( Mo )
Poly . ( SO3) Poly . ( Cu)
300
1000
200
500
100
0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Tuber Yield (ton/ha) Tuber Yield (to n/ha)

Yield
Normal Conditions: 20 - 40ton/ha (tubers, native areas of Western Europe)
43.5ton/ha (Holland: 5-year average), 65ton/ha tuber (best practice)
Optimal Conditions: above 100 ton/ha (experimental findings)
Constituent Bud/Tuber Leaf/Stem†
Cellulose 65
7.7
Hemicellulose
Lignin - -
Starch 72.5 20
Protein 10.6 10
Oils - -
Fats 0.7 -
Minerals 0.5 -
Ash 5.4 -
Others 2.6 5
*Strongly dependent on all growing factors, location and nutrient levels, †Estimate,
Tuber represent 60% of total wet weight during growth and upon harvest 89%
Lower Heat Value: 19000 kJ/kg (tuber alone)
Higher Heat Value: 19500 kJ/kg (tuber, estimate)
Starch (70 – 75DW%): 78% amylopectin
22% amylose
Pectin (1.8 – 3.3DW%): 51% Anhydrogalacturonic acid
49% Polysaccharides
- 6% Rhamnose
- 0.6% Fucose
- 5.6% Arobinose
- 1.8% Xylose
- 86% Galactose
Minerals (0.4 – 0.6DW%): rich in K nearly 95% of minerals, poor in Na less than 1% of minerals
Total Amino Acid Tuber
(fraction percent)
Alanine 9.6
Isoleucin e 4.7
Leu cin e 2.9
Proline 4.0
Tryptophan 1.6
Valine 6.1
Asparagine 8.9
Cystein e 2.1
Glutamine 11.0
Polar &
Glycine 0.2
Hydrophilic
Serin e 2.7
Threonine 5.9
Tyrosine 6.9
Asparagic Acid 4.3
Acidic
Glutamic Acid 4.3
Arginine 6.0
Basic Histidine 2.2
Lysine 7.7
Comments
Deficient in sulphur amino acids and probably also histidine. It is relatively rich in lysine

Comparative Graph
Energy

T oluene: 141GJ/ton

Sugar-to-Bioethanol (Ma sh ing) Phenol: 76.5GJ/ton
- Chemical vs. Biomass CED 63.9GJ/ton
60
F ertilizers: 55.5GJ/to n Ash: 55.5GJ/ton
CRACKER
50
Crude Oil
44.9
40 2.04GJ/ton
Complex C5
30 Ammo nia: 31.0GJ/ton Carbohydrates: 28.7GJ/ton Potato
29.5GJ/ton
Protein: 24.8GJ/ton The Netherlands
65 ton /ha tube r
Fossil Fuel Energy Savings 21.1 Complex C6 17.5to ta lDW/ha
20 Carbohydrates : 26.7GJ/ton
10
200GJ/ha
Boil er: 5.9GJ/ton Simple Carbohydrates : 3.7GJ/ton
Exergy
T oluene: 142GJ/ton

Phenol: 75.8GJ/ton
60n Ash: 59.8GJ/ton
F ertilizers: 59.8GJ/to
CRACKER
50
Crude Oil
44.9GJ/ton Biomass
40 39.5 2.21GJ/ton
37.0
Complex C6
30 Complex C5 Potato
Carbohydrates: 28.8GJ/ton The Netherlands
Protein:26.7GJ/ton 65 ton /ha tube r
Fossil Fuel Exergy Savings Ammo nia: 23.0GJ/ton 17.5to ta lDW/ha
20
69.8GJ/ton chemicals -5.6GJ/ton
23.1GJ/ton biomass
10 10.1
405GJ/ha Am monia: 10.0GJ/ton
Fertilizers: 6.3GJ/ton Simple Carbohydrates: 4.0GJ/ton
Boi ler: 4.7GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.215 3.77 65.0% 19.13 -3.61
Phenol 0.002 0.03 0.5% 0.15 -0.03
Styrene 0.002 0.03 0.6% 0.17 -0.03
Toluene 0.002 0.03 0.5% 0.15 -0.03
1,4-butandiamine 0.011 0.20 3.5% 1.02 -0.19
Acrylamide 0.005 0.08 1.4% 0.41 -0.08
Adipic acid 0.001 0.01 0.2% 0.07 -0.01
Ammonia 0.003 0.06 1.0% 0.28 -0.05
ε-caprolactum 0.005 0.09 1.6% 0.48 -0.09
Ethylamine 0.012 0.22 3.7% 1.10 -0.21
γ-butyrolactum 0.005 0.09 1.5% 0.43 -0.08
Ionic liquids 0.002 0.03 0.5% 0.14 -0.03
Isoprene 0.010 0.18 3.2% 0.93 -0.18
Oxalic acid 0.001 0.03 0.5% 0.13 -0.03
Urea 0.002 0.04 0.6% 0.19 -0.03
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.037 0.65 11.1% 3.28 -0.62
Description
- The yield is high enough in relation to the biomass acquisition energy intensity to bring the
overall cropping system in the middle performance range.
- Although the conversion to ethylene via simple carbohydrates is one of most energy
intensive routes there are many efficiency improvement foreseeable as expensed by the
drastic reduction in exergy demand.
- After the carbohydrate conversion the proteins in the residual stream are easily and
efficiently converted, being one of the least energy intensive options.
- The lignin-based components (aromatics) cost significantly more cumultaive energy and
exergy demand than the standard fossil fuel-based production routes. The chemical
composition of lignin is far too low in potato even when including the tops and skins.
Improvement Options
- Little major improvement options foreseeable; an excellent regional choice.
- Do not include lignin’s processing steps and therby add it as additional fuel to the interal
heat and power combustion unit.
- A high soil content in harvested product (due to tuber) and high nutrient uptake is present
which results in energy intense ash/fertilizer. Sacrife a portion of the yield to remove soil
from skin and lower extreme nutrient uptake demands.

Sorghum Bicolor – Sweet Sorghum
Common Names
Sorghum, Sweet Sorghum, Durra, Milo, Shattercane
Classification
Annual (or semi-perennial) grass, C-4
Appearance
0.6 – 5 meter tall, erect, single stemmed, 5 – 30 mm diameter,
panicle 8 – 40cm long, bicolor sorghums are characterized by long, clasping
glumes at least ¾ as long as the broadly elliptical grain
Varieties
>4000, with sorghum types: broom corn, grain, grass and sweet
Several cultivated and hybrid varieties for specific climate conditions.
Reduced lignin composition, easier digestibility and harvesting.
Brief Description
It is the 5th largest cereal crop in the world; major food source in Africa and India. It was extensively used
as a source for sweeteners, however due to heavily labour intensive requirements it has practically been
removed from industrialized worlds. Thrives in arid areas where other cereals do not. Stalks considered as
a bioenergy option.
Growth Details
Native Area: Ethiopia, Eastern Africa
Location: Drier regions of the Southern Hemisphere
Climate: Hot and arid – semiarid, does not do well in shade
Temperature: 20 – 35°C, 30°C optimal for growth period
400 – 650mm, 200mm min, >750mm not economical. Dormant in drought
Soil Type: Wide range, must be deep with good drainage
Soil Acidity: 5.0 – 8.5pH, average 6.7pH
Plantation: 4 – 5cm deep, seedbeds, 75 – 100cm spacing, depends on rainfall/irrigation levels,
developing countries use hand hoe, industrialized maize drills
Seeding Rate: 2 – 12 kg/ha (7 – 8 kg/ha normal conditions), 21800 – 61000 seeds/kg
50000 – 100000 plants/ha normal (extremely dry 5000 – 10000 plants/ha)
Companion Crop: Generally grown as pure crop; forage use legume (cowpea) is advantageous
Weed Control: Spraying of pre-emergence weed killer only at seeding, competes well
Cultivation: May – mid-July, after rain period, 50 – 60 days boot stage, 60 – 70 days flowering,
more than 120 days for maturity
Harvesting: 2 – 5 harvestings per year, first at stem height of 80 – 120cm, 3 – 4 months after
sowing, every 1 – 2 months, 10 – 15 cm stubble left over for re-growth
Deep rooting system can easily leech trace nutrients. Organic fertilizer not recommended.
Yield Depen dent Macronutrient Uptake Yi eld Dependent Mi cronutrient Uptake
350 120
N Fe
P2 O5 Mn
K2 O B
300 Ca O Zn
100
MgO Mo
SO 3 Cu
L og. (N ) Po ly. (Fe)
250
Total Plant Upt ake (kg/ha)
To tal Plant Uptake (g/ha)
Po ly. (P2 O5) Po ly. (Mn)

L og. (K 2O) 80 Po ly. (B)
Po ly. (Ca O) Po ly. (Zn)
200 Po ly. (MgO ) Po ly. (Mo)
Po ly. (SO 3) Po ly. (Cu )
60
150
40
100
20
50
0 0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
Green Biomass Yield (ton/ha) Green Biomass Yield (ton/ha)

Yield
Poor Conditions: 1 – 6 ton/ha (poor in every aspect, developing African nations)
0.7ton/ha Grain (Kenya: 5-year average = 35ton/ha total green matter)
Normal Conditions: 25 – 40 ton/ha (green matter)
30 – 50 ton/ha (good practices, developed nations)
Optimal Conditions: 75 ton/ha (green matter, commercial African yields)
100 – 140 ton/ha (EU demonstration sites)
Constituent Seed/Panicle Stalk Whole Crop†
Moisture Content 12.5% 50.0% 75.5%
Cellulose 22.5 34.6
5.4
Hemicellulose 13.8
Lignin - 11.3 8.7
Starch 74.5 - -
Sucrose - 39.5 45.2
Other Sugars - 4.7
Protein 8.6 3.3 4.0
Oils - -
3.4
Fats - -
Minerals 0.4 - -
Ash 1.7 4.9 2.8
Others 6.0 - 5.0
†Based on EU demonstration practices, harvested just before panicle development
Distribution of dry weight: - Stalk: 75% (82%)
- Leaves: 12.5% (17%)
- Panicle: 7.5% (1%)
- Roots: 10%
Higher Heat Value: 18300 kJ/kg (whole plant)
Lower Heat Value: 17250 kJ/kg (whole plant)
Hardly any additional information of value is available.
However, the proteins contains no Glucan
Comments
Sorghum is considered a possible replacement for maize. It is possible to cultivate in drier, less desirable
conditions and requires less water/irrigation than all other cereals. Some test sites have presented a higher
yield than corn/maize. It has the added advantage of having sucrose, starch and usable bagasse, so can be
classified as a grass, cereal and sugar-yielding crop. For these reasons it is among the leader contenders
for a biobased economy. Sweet sorghum is similar to normal sorghum but cultivated before the panicle
properly develops, sorghum dry weight figures are based on the yield of the panicle.

Comparative Graph
Energy
Fertilizers: 104GJ/to n Ash: 104GJ/ton

Sugar-to-Bioethanol (Ma sh ing) Phenol: 76.5GJ/ton
Lignocellulose-to-Bioethanol (Stea m)
60 Protein: 58.9GJ/ton
CRACKER
50
Crude Oil Lignin: 47.7GJ/ton
40 2.05GJ/ton
Styrene: 33.9GJ/ton
30 Ammo nia: 31.0GJ/ton Complex C6
28.3 Sorghum
27.3GJ/ton 27.0
Kenya
75ton/ha cane
20
39.0GJ/ton chemicals Phenol: 18.6GJ/ton
13.5
12.3GJ/ton biomass
455GJ/ha
Boil er: 6.9GJ/ton
Simple Carbohydrates: 4.5GJ/ton
Exergy
F ertilizers: 109GJ/to n Ash: 109GJ/ton

Phenol: 75.8GJ/to n
Lignocellulose-to-Bioethanol (Stea m)
Ethylene: 68.1GJ/ton 67.1GJ/ton
- Chemical vs. Biomass CExD Protein:62.0GJ/ton
60
CRACKER
Crude Oil
44.9GJ/ton Biomass
40 2.16GJ/ton
37.4
Complex C5
30 Carbohydrates: 32.0GJ/ton Sorghum
Styrene: 26.4GJ/ton Kenya
T oluene: 24.3GJ/ton 22.9 75ton/ha cane
Fossil Fuel Exergy Savings Ammo nia: 23.0GJ/ton 36.9tota lDW/ha
Ammonia: 20.6GJ/to20n
Am in e Ch emicals: 20.5GJ/to n 18.9
73.0GJ/ton chemicals -5.9GJ/ton Phenol: 17.8GJ/to n
23.0GJ/ton biomass Ethylene: 12.1GJ/to n Complex C6 Carbohydrates: 11.1GJ/ton
10
851GJ/ha
5.4 Simple Carbohydrates: 4.7GJ/ton
Boile r: 5.6GJ/to n Fertilizers: 5.6GJ/ton
Un-utilized

Overview Savings

Ethylene 0.221 8.16 69.9% 19.12 -4.14
Phenol 0.014 0.51 4.4% 1.21 -0.26
Styrene 0.015 0.57 4.9% 1.33 -0.29
Toluene 0.014 0.50 4.3% 1.18 -0.26
1,4-butandiamine 0.005 0.20 1.7% 0.46 -0.10
Acrylamide 0.001 0.02 0.2% 0.04 -0.01
Adipic acid 0.000 0.01 0.1% 0.03 -0.01
Ammonia 0.001 0.05 0.4% 0.12 -0.03
ε-caprolactum 0.001 0.05 0.5% 0.13 -0.03
Ethylamine 0.004 0.16 1.4% 0.39 -0.08
γ-butyrolactum 0.003 0.11 0.9% 0.25 -0.05
Ionic liquids 0.001 0.03 0.2% 0.06 -0.01
Isoprene 0.007 0.24 2.1% 0.57 -0.12
Oxalic acid 0.002 0.06 0.5% 0.13 -0.03
Urea 0.001 0.03 0.3% 0.07 -0.02
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.020 0.73 6.3% 1.71 -0.37
Description
- A very successful crop when cultivated as sweet sorghum with extraordinarily high yields.
Cultivation as standard (grain) sorghum would jeopardize benefit.
- Major chemical in the biorefinery mixture is ethylene deriving from the three rich sources
of carbohydrates, nearly 70%.
- Behaves very similar to sugar cane in Brazil and could be dubbed as Africa’s wonder-plant.
The slightly lower yield, however, is replaced by higher amounts of protein which here is
efficiently and effectively converted to amine-based chemicals.
Improvement Options
- Best practices conditions must be upheld calling for major improvements on current
systems.
- Must ensure that the produced off-heat and energy production are utilized locally.
- All chemical conversions can be pursued.

Triticum Aestivum – Wheat
Common Names
Wheat, spring wheat, winter wheat, common wheat, bread wheat
Classification
Annual grass, autumn or spring sown, C-3
Appearance
0.6 – 1.2 m tall erect and hollow grass, 1.3cm narrow 20-38cm long flat hairy
Leaves, thin clumped spikelets, containing the grain
Varieties
Countless: classified by growing season and composition.
Yes, countless amounts
Brief Description
Wheat is the world's most important cereal crop in terms of both area cultivated and amount of grain
produced. It is widely grown throughout the world. It is a food staple for flour production, livestock feed
and more importantly for the brewing of beer. Residue for fodder or biomass use.
Growth Details
Native Area: Middle East, Fertile Crescent
Location: Worldwide, mainly in China, Europe and North America
Climate: Temperate zones (up to 60 °N), tropical/sub-tropical areas at higher altitudes
Temperature: 4.9 – 27.8°C, growth average 13.4°C
450 – 650mm with 550mm average, toleration between 150 – 2500mm
Soil Type: Fertile dark soils rich in nitrogen, prairies with good water retention
Soil Acidity: 4.5 – 8.3pH, worldwide mean 6.5pH
Plantation: (Winter wheat) late summer seed propagation, best when 18°C afternoon temp,
no-till drilled 2.5 – 5cm deep (moisture dependent) 13 – 20cm spacing
Seeding Rate: 90% winter survival rate, limited tilling operations to prevent soil damage,
22 – 100 kg/ha, 33 kg/ha optimum, 5400000 ears/ha at
2.0 – 2.25 ears/plant 2150000 – 2700000 plants/ha
Companion Crop: No, but a 3-year rotation cycle, not to be rotated winter-spring wheat
Weed Control: Agents added to seeds, rare problems because of minimum tillage operations
Pest and Disease: Very susceptible to disease, can suffer from heavy yield losses
Cultivation: Attention to soil hardness, balance between root growth and water retention,
sprouting in early spring, utilizes the most amount of available solar energy
Harvesting: Mid-July, easy, fully mechanized with combiners, drying required for grains
above 14% moisture, average is 20%, one year storage
(Winter wheat) Many added during sowing, however more than 60% used in last shooting phase
Yiel d Dependent Macronutrient Uptake Yiel d Dependent Micronutrient Uptake
500 700
N Fe
P2 O5 Mn
450 K2 O B
Ca O 600 Zn
MgO Mo
400 SO 3 Cu
Po ly. (N) Poly . ( Fe )
350 Po ly. (P2O 5) 500
Poly . ( Mn )

Po ly. (CaO ) Poly . ( Zn)
300 Po ly. (MgO) Poly . ( Mo )
400
Po ly. (SO3 ) Poly . ( Cu)
250
300
200
150 200
100
100
50
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Grain Yield (ton/ha) Grain Yield (ton/ha)

Yield
Normal Conditions: 4.7 – 7.0 ton/ha (dry grain), 8.5 – 12.7ton/ha (whole crop wet)
7.0ton/ha (French: 5-year average)
Optimal Conditions: 9.0 – 14.8 ton/ha (dry grain), testing average 10.3 ton/ha
Correlates to 16.4 – 26.9ton/ha whole crop
Worldwide Cultivation: 217 million hectares at 2.86 ton/ha (dry grain)
(Based on dry weight and winter wheat)
Constituent Grain Stem/Leaves
Moisture Content 20% 8%
Cellulose 32.6
22.3
Hemicellulose 22.6
Lignin 2.4 16.9
Sugars 1.2 -
Starch 56.0 -
Protein 13.4 -
Oils -
2.5
Fats -
Minerals 0.4 -
Ash 1.9 10.2
Others - 17.7
Grains represent a little over ½ of the total wet plant mass (55% taken)
Lower Heat Value: 18600 kJ/kg (straw), 16220 kJ/kg (grain)
Higher Heat Value: 19925 kJ/kg (straw), 17529 kJ/kg (grain)
Wheat germ oil is contained at 8 - 12% in the wheat germ, which is 2% of total grain weight. It is known
for having a high linoleic fatty acid concentration.
Fatty Acid Carbon Chain Germ Oil
(fraction percent)
Palmitic 16:0 11-20
Stearic 18:0 1-6
Oleic 18:1 13-30
Linoleic 18:2 44-65
Alpha Linoleic 18:3 2-13
A large portion of the protein is in the complex water-insoluble form of gluten, around 40%
Free Amino Acid Grain
(fraction percent)
Isoleucin e 6.97
Leu cin e 8.27
Tryptophan 1.03
Valine 4.0
Polar &
Threonine 2.78
Hydrophilic
Arginine 3.81
Basic Histidine 1.65
Lysine 2.80
Total 36.1% of Protein
Comments
In the yield figures, water demand and retention is far more influential than nutrient use.
(T. aestivum) Hexaploid species, most widely cultivated in the world and highest yielding, common wheat.

Comparative Graph
Energy
Next Generation 80
Sugar-to-Bioethanol (Ma sh ing) P henol: 76.5GJ/ton
60
CRACKER
50
Crude Oil
44.9GJ/ton Ash: Biomass
F ertiliz ers: 41.6GJ/to n 41.6GJ/ton 2.04GJ/ton
40
Lignin:
34.2 37.8GJ/ton
30n Ammo nia: 31.0G J/t on

St yrene: 30.4GJ/to
Wheat
25.9 France
10.3ton/ha grain
25.0
Fossil Fuel Energy Savings 21.1 Protein: 21.1GJ/ton 18.6to ta lDW/ha
20
49.1GJ/ton chemicals Am monia: 19.0GJ/ton Complex C5 Carbohydrates: 18.0GJ/ton
16.6GJ/ton
P henol: 15.4GJ/ton
337GJ/ha
Boil er: 8.6GJ/ton
Simple Carbohydrates : 7.6GJ/ton
Exergy
Next Generation 80
P henol: 75.8GJ/ton
60
CRACKER
50
Crude Oil
Ash: 46.4GJ/ton
44.9GJ/ton F ertiliz ers: 46.4GJ/to n Biomass
Lignin:
30
28.7 Wheat
France
P henol: 23.5GJ/ton Ammo nia: 23.0G J/t on Protein: 23.5GJ/ton 10.3ton/ha grain
Fossil Fuel Exergy Savings T oluene: 21.8GJ/ton 18.6to ta lDW/ha
20 20.3 Complex C5
55.0GJ/ton chemicals E thylene: 18.7GJ/to n 19.5 Carbohydrates: 20.1GJ/ton
S tyrene: 15.2GJ/ton 13.9
11.0GJ/ton Complex C6 Carbohy drates: 11.2GJ/ton
10
378GJ/ha Amine Ch em icals: 9.7GJ/to n
Boi ler: 7.0GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.179 3.31 48.2% 8.01 5.30
Phenol 0.017 0.32 4.7% 0.78 0.52
Styrene 0.019 0.36 5.2% 0.87 0.57
Toluene 0.017 0.32 4.6% 0.77 0.51
1,4-butandiamine 0.018 0.33 4.9% 0.81 0.54
Acrylamide 0.002 0.03 0.4% 0.07 0.05
Adipic acid 0.001 0.02 0.2% 0.04 0.02
Ammonia 0.004 0.07 0.9% 0.16 0.10
ε-caprolactum 0.002 0.04 0.5% 0.09 0.06
Ethylamine 0.006 0.11 1.7% 0.28 0.18
γ-butyrolactum 0.011 0.20 2.9% 0.47 0.31
Ionic liquids 0.002 0.04 0.6% 0.09 0.06
Isoprene 0.015 0.28 4.1% 0.68 0.45
Oxalic acid 0.004 0.07 1.1% 0.18 0.12
Urea 0.002 0.03 0.5% 0.08 0.06
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.049 0.91 13.2% 2.20 1.45
Description
- A remarkably high yielding crop of simple carbohydrates for a temperature crop at low
biomass acquisition energy intensity.
- The lignin conversion to aromatics is particularly effective and efficient.
Whereas in this case it is not from soil contamination, but from a high nutrient demand.
Improvement Options
- The biomass feedstock energy demand is mainly attributed to fertilizer demand meaning
few improvements are foreseeable; perhaps general yield increases.
- For this cropping/biorefinery system layout, it may be best to focus on protein conversion
to amine-based chemicals and therefore decrease a portion of the carbohydrate
processing to the less intense options and allocate a larger part of the crop to the boiler.

Zea mays L – Maize
Common Names
EU: Maize, USA: Corn, Mealie, Indian Corn
Classification
Annual grass, C-4
Appearance
2.5m tall, cane-like stem, joints every 30-45cm, 30-90cm long, thin
drooping green Leaves, ears under Leaves covered in sedgy leave
coverings, 15-25cm long, 4-8cm thick, 200-400 kernels/ear
Varieties
6 major types: Flour (soft), Popcorn, Dent, Flint, Pod, Sweetcorn
Practically all, common type BtCorn (against Bt toxin)
Brief Description
The term corn broadly applies to any staple food grain and was originally the term for any crop kernel. It
is primary used for livestock fodder and with an increasingly large portion for ethanol production. Human
consumption is almost negligible.
Growth Details
Native Area: Mexican peninsula, domesticated from the teosinte Zea mays ssp. parviglumis
Location: Worldwide; USA roughly half of harvest
Climate: Subtropical – temperate, frost will destroy crop
Temperature: 21 - 28°C, warm weather crop
500 – 800mm (average 750mm), can tolerate up to 2590mm – 4100mm
Soil Type: Large variety. Prefers deep, naturally rich and easily tilled
Soil Acidity: 4.3 – 8.7pH, average is slightly acidic
Plantation: Only seed propagation, 2.5 – 5cm deep, 3-4 seeds per hill machine drilled,
Spacing 0.8x0.8m – 1.0x1.0m on checker formed rows
Seeding Rate: 11.5 – 16kg/ha for plant density of 40,000 – 50,000 plants/ha
Companion Crop: Dual legume crop (i.e. soybeans) rotation and sometime also 3rd winter wheat
Mixing different variations, i.e. early, medium and late growth
Weed Control: None needed, systematic cultivation and rotation enough
Cultivation: Ploughed before plantation, planted 2 weeks after last winter frost, early spring,
sometimes planted in autumn – early winter and left over the winter
Harvesting: Food consumption usually handpicked, other completely mechanized sorting husk
and ear from stover. Around late-autumn, 80-120 days for maturity and ears
50-75days after ear development
Yields strongly react with organic nutrient sources, companion legumes usually enough
Yield Dependent Macronutri ent Uptake Yiel d Dependent Micronutrient Uptake
450 2500
N Fe
P2 O5 Mn
400 K2 O B
Ca O Zn
MgO Mo
2000
350 SO 3 Cu
Po ly. (N) Po ly. (Fe)
Po ly. (P2O 5) Po ly. (Mn)
300 Po ly. (K2O ) Po ly. (B)

Po ly. (CaO ) Po ly. (Zn )
Po ly. (MgO)
1500 Po ly. (Mo)
250 Po ly. (SO3 ) Po ly. (Cu)
200
1000
150
100
500
50
0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Grain Yield (ton/ha) Grain Y ield (ton/ha)

Yield
Normal Conditions: 3.5 – 11 ton/ha (ear/grain), 9.0 ton/ha (USA: 5-year average)
10 – 50 ton/ha (whole crop), 32.5 ton/ha USA average
Optimal Conditions: 13.8 ton/ha (grain, best practice)
12 – 20 ton/ha (ear, experimental hybrids of grain maize)
Worldwide Cultivation: 145 million hectares at 4.8 ton/ha
Constituent Ear/Cob Stover
Moisture Content 20.6%† 75%
Cellulose 37.3
9.5
Hemicellulose 24.1
Lignin - 17.5
Sugars 2.6 -
Starch 71.7 -
Protein 9.5 11.2
Oils -
4.3
Fats -
Minerals 1.6 1.8
Ash 1.4 6.1
Others - 2.0
Grain (ears/cob) represents about 1/ 5 of the total wet plant mass
†20.6% is mature seedling (upon harvesting), green seeds are 62.5%
Lower Heat Value: 17000 kJ/kg (corncob), 16850 kJ/kg (stover)

Higher Heat Value: 18790 kJ/kg (corncob), 18100 kJ/kg (stover)
There are a number of genetically modified specialty corn varieties that offer several characteristics and
produce value-added properties to the grain:
- Waxy corn: high amylopectin starch content (90-100% of starches)
- High Amylose corn: high amylose starch content (50-94% of starches)
- High lysine corn: increased levels glutelin, i.e. lysine and tryptophan (0.26 - 0.30 up to 0.34 - 0.37%)
- High oil corn: increase oil content to 7-8% DW and increase protein quantity and quality
The globular protein amino acid, Glycine, account for 80 – 90% of the protein. The other amino acids are
at such low levels it is not worth mentioning.
Comments
Corn supplies 75% of the starch industry and not the potato as could be assumed. Additionally the
altitude is greatly confining on the yield, it fairs poorly about 150m. Flat, low lands are ideal. Due to the
small root systems the crop requires large amounts of nutrients in the beginning phases of growth.
Generally speaking the entire crop does need a lot of nutrients and quite a bit more than the actual uptake.
Investigation work is underway in trying to introduce specially designed enzyme to couple with corn, i.e.
like a forced legume feature. So far experiments can achieve 70% of nitrogen requirements.

Comparative Graph
Energy
Next Generation 80
Sugar-to-Bioethanol (Ma sh ing) P henol: 76.5GJ/to n
70 65.3GJ/ton
Protein Extraction (Protease )
Lignin Aromatics (Fast-Pyrol ysi s) Ash: 63.5GJ/ton
- Chemical vs. Biomass CED F ertiliz ers: 63.5GJ/to n
60
CRACKER
50
Crude Oil
44.9GJ/ton Lignin: Biomass
35.9 Protein: 35.0GJ/ton

St yrene: 31.4GJ/to
30n Ammonia: 31.0GJ/to n
T oluene: 29.7GJ/ton Maize
27.0
Iowa
19.9GJ/ton 26.0 13.8ton/ha grain
Fossil Fuel Energy Savings 21.9 24.8tota lDW/ha
45.4GJ/ton chemicals Am in e Ch emicals: 19.1GJ/to n
15.4GJ/ton biomass Complex C6 Carbohydrates: 11.2GJ/ton
10
382GJ/ha Boi ler: 9.4GJ/ton
Fertilizers: 3.0J/t on Un-utilized
Exergy
Next Generation 80
P henol: 75.8GJ/ton
70 Ash: 69.0GJ/ton
Protein Extraction (Protease ) F ertiliz ers: 69.0GJ/to n
60
CRACKER
50
Crude Oil
44.9GJ/ton Lignin: Biomass
Protein: 37.9GJ/ton
30 30.0
Maize
Iowa
P henol: 24.2GJ/ton Ammo nia: 23.0G J/t on 13.8ton/ha grain
Fossil Fuel Exergy Savings T oluene: 22.4GJ/ton 20.9 Complex C5 24.8to ta lDW/ha
20
52.6GJ/ton chemicals E thylene: 18.9GJ/to n 20.5 Carbohydrates: 21.4GJ/ton
13.1GJ/ton S tyrene: 15.9GJ/ton 13.7
Amin e Ch em icals: 12.6GJ/to Complex C6 Carbohy drates: 12.2GJ/ton
10n
444GJ/ha Simple Carbohydrates: 8.1GJ/ton
Boi ler: 7.7GJ/ton
Un-utiliz ed

Overview Savings

Ethylene 0.190 4.70 55.8% 11.11 7.29
Phenol 0.018 0.45 5.3% 1.06 0.69
Styrene 0.020 0.49 5.9% 1.17 0.77
Toluene 0.018 0.44 5.2% 1.03 0.68
1,4-butandiamine 0.009 0.22 2.6% 0.52 0.34
Acrylamide 0.002 0.05 0.6% 0.12 0.08
Adipic acid 0.000 0.00 0.1% 0.01 0.01
Ammonia 0.002 0.06 0.7% 0.14 0.10
ε-caprolactum 0.003 0.07 0.8% 0.15 0.10
Ethylamine 0.007 0.18 2.2% 0.44 0.29
γ-butyrolactum 0.006 0.14 1.6% 0.32 0.21
Ionic liquids 0.001 0.03 0.4% 0.08 0.05
Isoprene 0.012 0.30 3.6% 0.72 0.47
Oxalic acid 0.003 0.08 0.9% 0.18 0.12
Urea 0.001 0.03 0.4% 0.08 0.05
Biolubricants 0.000 0.00 0.0% 0.00 0.00
Fertilizers 0.036 0.88 10.5% 2.08 1.37
Description
- A remarkably high yielding crop of simple carbohydrates for a temperature crop at low
biomass acquisition energy intensity. Actually slightly better than wheat, but not in this
layout due to the logistics penalty of the location, meaning for Europe (i.e. France) corn
would most likely outperform wheat.
- The lignin conversion to aromatics is particularly effective and efficient.
Whereas in this case it is not from soil contamination but from a high nutrient demand.
Improvement Options
- No major improvement options foreseeable: will remain a middle-range cropping system.

4 Optimal Biorefinery Concept
4.1 Overall Results
Table 1 presents the resulting fossil fuels saving (energetically and exergetically) for the select
crops within the calculation matrix:
Table 1 Resulting Overall Fossil Fuels Savings
Lo cation Fossil Fuel Savings (energy) Fossil Fuel Savings (exergy)

Crop
Region /ch emical /biomass /ha /ch emical /biomass /ha
Cassava Nigeria 37.1 12.5 438 69.1 23.3 817
Grass Holland 50.8 17.6 249 55.6 19.3 272
Lu cerne South Dakota 29.2 12.4 186 30.7 13.0 195
Maize Iowa 45.4 15.4 382 52.6 17.9 444
Oil palm Malaysia 37.0 20.9 721 42.6 24.0 830
Potato Holland 34.5 11.4 200 69.8 23.1 405
Rapeseed Belgium 41.9 21.5 353 44.8 22.9 377
Sorghum Kenya 39.0 12.3 455 73.0 23.0 851
Soya bean Illinois 40.3 18.1 196 42.5 19.1 206
Sugar beet Germany 32.3 10.0 292 67.6 20.9 610
Sugar cane Brazil 42.0 11.3 490 84.3 22.6 985
Sunflower Fran ce 22.2 15.3 128 22.5 15.5 130
Switchgrass Iowa 38.5 14.8 208 43.7 16.9 236
Tobacco Australia 35.5 13.1 346 59.6 21.9 582
Wheat Fran ce 49.6 18.5 343 55.5 20.7 383
Willow tree Sweden 44.0 15.6 125 50.5 17.9 143
- /chemical: GJ per ton biorefinery chemical mixture
- /biomass: GJ per ton total dry weight harvested biomass processes
- /ha: GJ per arable cultivated land in hectare
4.2 Overall Comparison
4.2.1 Energy
The most important impact assessment terms: savings per produced chemicals (production
efficiency) and savings per arable land area (land use efficiency), provide the information
necessary to determine the optimal biorefinery cropping system. Their combined results, based
on energy savings, are nominalised and expressed in a single chart, Figure 1. The biorefinery
cropping system option closest to the upper right-hand (green) corner has the “best” overall
performance, whereas the option closet to the lower left-hand (red) corner has the “worst”
overall performance. The blue centre diagonal line separates the (nominally) “good” and “bad”
cropping systems. Grass with the highest per chemical mixture savings is located at the top of the
graph but towards the left due to its lower land use efficiency. Oil palm with the best per land
savings is located at the right of the graph but towards the centre due to its lower chemical
production efficiency. Nevertheless, Malaysian oil palm land use efficiency is so high that it still
scores as the optimal biorefinery cropping system overall from those assessed. Generally those
cropping system located in the “good” area can be regarded as optimal considering their diverse
regions, biomass type and chemicals produced.

Figure 1 Graphical Determination of Optimal Biorefinery Cropping System
Malaysian palm oil and the Dutch ryegrass are two significantly different crops; tropical vs.
temperate, oil-rich vs. protein-rich, half-product processing vs. fresh/direct processing, etc. Of
the selected biorefinery cropping systems, grass has the best energy savings in chemicals terms
(GJ/tonchemical) while oil palm is best in land savings (GJ/ha). They perfectly illustrate the contrast
between generally high yielding crops and those lower yielding crops while still well suited for
chemical biorefineries. It is not surprising that oil palm with its 25.0 tonfruits/ha yield can achieve
the highest savings per arable land. Surprisingly however, grass, at only 40% the total biomass
yield (14.1 tonhay/ha), achieves 1.4-fold more energy savings per chemicals produced than oil
palm (50.8 vs. 37.0GJ/ton). Thus, the overall performance is a combination of yield, biochemical
composition and concentration for downstream processing.

4.2.2 Exergy
A distinctly different pattern emerges with the plotted exergy values (Figure 2). The previous
energy-based savings graph depicts the current situation, i.e. what use is made of the resources.
The exergy based figures depicts the thermodynamic situation, i.e. what use could be made of the
resources. Indicating a possible technologies and integration options for a more efficient use of
the current resources (material and energy) following the outlined biorefinery processes. The
latter graph is therefore a projection of the potential; the former of the current state-of-the-art.
This explains why the exergy-based savings (Table 1) are always noticeably higher than the
energy-based savings.
Figure 2 Graphical Determination of Optimal Biorefinery Cropping System (Exergy)

4.2.3 Combined Performance
The top 5 performing biorefinery cropping systems are listed in Table 2 for both energy and
exergy savings. Exergetically, many other crops outperform palm oil: (German grown) sugar beet,
(Nigerian grown) cassava, (Kenyan grown) sorghum, with (Brazilian grown) sugar cane as the
most optimal in respects to production and land use efficiencies. The influence of the recycled
nutrients (ash) stream become more apparent in exergy terms because the cumulative exergy
demand of the fertilizer chemicals are a function of the acquisition biomass exergy which is
systematically higher than the energy intensity. Furthermore, oil-based crops loss their overall
position as biolubricant (biodiesel) processing is mature with only minor foreseeable work
efficiency improvements on current technologies; completely new processes and technologies are
required to improve their overall performance. Oil palm remains, nonetheless, a major contender
due to it high yields.
Table 2 Top 5 Cropping and Biorefinery System of Energy and Exergy Fossil Fuel Savings
Top 5 Crop/Biorefin ery Nominal Energy Savings Nominal Exergy Savings

1 Oil Palm, MY Sugar Cane, BR
2 Sugar Cane, BR Sorghum, KE
3 Wheat, FR Cassava, NG
4 Maize, US Sugar Beet, DE
5 Grass, NL Oil Palm, MY
4.3 Discussion
In exergy terms the top 4 crops are carbohydrate-based cropping systems producing vast
amounts of ethylene. Should ethanol and not ethylene was produced, practically all the oily and
protein-based crops would outperform. The savings potential from ethylene is very high with the
production costs to break even with savings from ethanol at 47.9GJ/ton ethylene. None of the
crops has such a high production cost for ethylene, which really stresses to benefit.
In both the energy and exergy optimal biorefinery cropping system graphs the French oil-based
crop, sunflower, is consistently indicated as the “worst” performer. The low yield and high
biomass acquisition energy intensity drives the performance of sunflower to be “less good”. In
tune with biofuels as comparison it still, nonetheless has a replacement potential of
21.9GJenergy/tonproduct and 126GJenergy/ha. This is comparable to, if not slightly better than the
current average 1 st generation bioethanol production in Brazil, which mitigates 23.5GJ/ton and
104GJ/ha following the same methodology. As a result even the so-called “worst” biorefinery
cropping system aimed at producing chemicals can be competitive with the “best” system aimed
at producing biofuels.
As a rule of thumb to improve the biorefinery cropping system even further higher the dry
weight yields are desirable, especially with regards to land use efficiency component. Dutch
potato and French wheat are both comparably mid-range yielding crops but are cultivated with a
fairly low agricultural intensity in relation to their total dry weight yield. Wheat therefore
performs high in the energy savings per chemical mixture and overall as did the potato, albeit on
the exergy side. Therefore, even as these are temperate crops, they can approach the overall
savings values of their higher yielding tropical counterparts. There are other some desirable

properties that can steer a cropping system to better performance: like the high yields with an
offset agricultural energy intensity, but also irrigation that is not based on the use of aquifers (as
is the case for lucerne-US), low lignin and high protein content (i.e. frequent harvesting & best
bioprocessing), low harvestable moisture content, cultivation of a crop with minor nutrient
uptake in proportion to total dry weight yield, a convenient location close to a port or waterway,
and so on.
Genetic modification (GM) of crops might assist in increasing the fossil fuel replacement
potential. It could provide incremental yield gains promoting a greater land use efficiency
increase or it could also regulate the biochemical composition promoting a greater production
efficiency increase. GM technology might ultimately drive the cropping systems further into the
upper-right hand corner (green) of the optimal biorefinery cropping system graphs to become
“better”. The crops deemed suitable for genetic modification are those already partially modified
(e.g. soya bean and maize) will naturally have the quickest market entry. More research time is
necessary for the other crops. Conversely, modification is often associated with a sacrifice of
yield or a decrease of many biochemical constituents for the gain of one. The overall balance
could also shift in the wrong direction, consequently it remains to be seen whether these new
GM-crops do indeed contribute positively. In many respects traditional crop breeding systems
along with an altered approach to cultivation and harvesting techniques may have a quicker and
largest beneficial effect in increasing a cropping systems performance. As mentioned in the crop
guide and results, many cropping systems could improve by a simple location change.
One of the bottom-line goals was to determine a singular optimal biorefinery cropping system. If
at this stage a choice must be drawn, it is for the Brazilian sugar cane. Its strength lies solely in
the manufacturing of ethylene and as described the crop guide its only future chemical is
ethylene. That system does not make good use of the functionality of the biochemicals and is
only capable of replacing a single bulk chemical. This approach may face difficulties and hurdles
for market entrance without the help of a full palate of other chemical products. In this sense,
there is no single optimal cropping system currently foreseeable.
Furthermore, biomass is typically harvested at specific time intervals with an irregular production
over the year. Meanwhile it is imperative for the successful forward integration of the large-scale
centralized biorefinery to operate like any other production plant within the petrochemical
cluster. Therefore, it must be able to process biomass constantly throughout the year. Here sugar
cane and other high ethylene dominated cropping systems would not make a contribution, for
example, being dedicated to local production. An overall biorefinery cropping system
combination is consequently only optimal when it has the flexibility to process a variety of
feedstocks (half-products). In this sense, local crops from the hinterland and other temperate
crops can make a contribution, especially during periods of unexpected delays or production
losses of the more favourable variants. Feedstock freedom for continuous operation is imperative
for the success of a chemical biorefinery.

5 Conclusion
Technology is constantly driven to increase efficiency and generate profit in what is coined as
value creation. The first industrial uses of coal (and similar bituminous rocks) were used to
primarily produce steam for motion generation. Its chemical calorific value was converted to
mechanical energy. Later during the industrial revolution coal was being used in the coking
process to produce steel. It become a feedstock for a high value added product. When crude oil
began to flood to market its prime market was to produce kerosene again for motion generation.
Its chemical calorific value was converted to mechanical energy. Later as the industry developed
the field of petro-chemistry saw the emergence of an industry produce a wide range of chemical
products. It become a feedstock for high value added products. The first uses of biomass spread
through the ages of human civilization, it was primarily used to create heat. Its chemical calorific
value was converted to thermal and later mechanical energy for electric generation. Biomass is an
alternative to fossil fuels (like coal and oil), why not already focus higher value added products.
This report merely tried to foresee the eventual change to feedstock applications and provide the
grounds to avoid investing in intermediate technologies.
Currently however, there is no single biomass cropping system nor biorefinery that can be
considered as optimum or the best. They all contribute to fossil fuel energy savings and have up
to several magnitudes saving potential than standard application such as bioenergy or biofuel
conversion, based on calorific values. Employing a biomass crop in a particular region has many
aspects to consider, but the main consideration of this report has been attempted at illustrating
that nothing is simple and that chemicals should present a more attractive conversion option for
biomass than energy or fuels.
Regardless, all biomass and conceptual biorefineries layouts are not equal. In certain situations
conventional applications may outperform the chemical biorefinery concept. The trend
differences between energetic and exergetic results for the chemical biorefinery cropping system
in addition to considerations for a continuous feedstock supply reveal that there is not a single
optimum but a combination. Even with a combination these crop-biorefinery systems should be
able to outperform the conventional applications of biomass concluding that dedicated chemical
biorefineries represent a developmental leap towards achieving maximum fossil fuel replacement.
5.1 Ben’s Tips

Firstly, invest in Brazilian sugar cane while promoting the (bio)ethylene market to maturity.
Secondly, invest in Malaysia palm oil. Potentially sell the oil for biodiesel or cosmetics, but focus
on R&D on upgrading press cakes. Once protein extraction possibilities have been worked out
and some amine-based chemicals can be produced efficiently and cheaply invest in regional
ryegrass cultivations. Thirdly, mix feedstocks by expanding to sweet sorghum in stable regions of
sub-Saharan Africa. Adding additional ethylene and half-product imports. Sugar cane production
should provide a structure for success.

Chemical Bio Refinery Perspectives

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Chemical Bio Refinery Perspectives

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Chemical Biorefinery Perspectives

The valorisation of functionalised chemicals from biomass resources

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Figure 1 Petrochemical Refinery and Biorefinery Comparison

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Figure 2 Simplified System Boundaries for Chemical Biorefinery

Chapter 2 – Energy and Exergy

Chapter 3 – Life Cycle Assessment versus Exergy

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Chapter 5 – Prime Energy Input

Chapter 6 – Secondary Energy Input

Chapter 7 – Process Energy Input

Chapter 8 – Fossil Fuel Energy Savings

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Title Chapter 2 – Energy and Exergy

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1.1 Chapter Purpose

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2.1 First Law

The first law can be stated mathematically as:

dU = a differential (infinitely small) increase in the internal energy of the system

2.2 Second Law

The second law can be stated mathematically as:

dS = a differential (infinitely small) increase in the entropy of the system

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2.3 Difference between energy and exergy

M = mass flow, kg/h

2.3.2 Carnot efficiency

Tc = Temperature of cold reservoir (i.e. atmosphere), K

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Physical Exergy Flows

Ex ph = n& (∆H − T0 ∆S ) or more detailed Ex = M& i ⋅ [( H i − H 0 ) − T0 ⋅ (S i − S0 )]

n& or M& i = molar flow, mol/s

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yi = stoichiometric coefficient of molecular structure i

It is a summation of each individual molecular group’s contribution to reaction potential in the

2.3.4 Simple Terms: Energy vs. Exergy

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3.2 Fossil Fuel Source Energy and Exergy

3.2.1 Natural Gas

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Natural gas source = Groningen

3.3 Energy Carrier Conversions

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3.3.1 Electric Production

The utilization of off-heat is not considered in this report because typically

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hT,p = Total specific enthalpy (usable heat) at corresponding pressure

hl,p = Specific enthalpy of saturated liquid at corresponding pressure

Total Steam Specific (Usable) Enthalpy

Figure 1 Steam Chart for Energy

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H = enthalpy content at corresponding pressure

Total Steam Exergy Content

Figure 2 Steam Chart for Exergy