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Biomass Valorization for Fuel and Chemicals

Production -- A Review
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I NTERNATIONAL J OURNAL OF C HEMICAL
R EACTOR E NGINEERING
Volume 6 2008 Review R2
Biomass Valorization for Fuel and

Chemicals Production A Review
Cedric Briens Jan Piskorz
Franco Berruti

University of Western Ontario, cbriens@eng.uwo.ca

Resource Transforms International, jpiskorz@rtiltd.com

University of Western Ontario, berruti.ijcre@eng.uwo.ca
ISSN 1542-6580
Copyright 2008
c The Berkeley Electronic Press. All rights reserved.
Biomass Valorization for Fuel and Chemicals
Production A Review
Cedric Briens, Jan Piskorz, and Franco Berruti
Abstract
The transformation of biomass into fuel and chemicals is becoming increas-
ingly popular as a way to mitigate global warming and diversify energy sources.
Biomass is a renewable, carbon-neutral resource, and fuels derived from biomass
usually burn more cleanly than fossil fuels. It has been estimated that biomass
could provide about 25% of global energy requirements. In addition, biomass can
also be a source of valuable chemicals, pharmaceuticals and food additives. Sev-
eral kinds of biomass can be converted to fuel and chemicals. Examples are wood
and wood waste, agricultural crops, agricultural waste, litter from animal feedlots,
waste from food processing operations and sludge from water treatment plants.
Various processes can be used to convert biomass to energy. The biomass can
be burned, transformed into a fuel gas through partial combustion, into a bio-
gas through fermentation, into bioalcohol through biochemical processes, into
biodiesel, into a bio-oil or into a syngas from which chemicals and fuels can be
synthesized. Wood combustion, bioethanol production from either sugarcane or
corn, and biodiesel production from oilseeds are currently the most economically
significant processes but still need significant improvements. A detailed review
of the many processes that can convert biomass into fuels and chemicals shows
that no individual process is without drawbacks. As a result, it is recommended
that a biorefinery is the best solution to combine and integrate various processes
to maximize economic and environmental benefits, while minimizing waste and
pollution.
KEYWORDS: biomass, combustion, gasification, pyrolysis, bioethanol, biodiesel,

bio-oil, biorefinery
Briens et al.: Biomass Valorization for Fuel and Chemicals Production 1
INTRODUCTION
The transformation of biomass into fuel and chemicals is becoming increasingly

popular, worldwide, as a way to mitigate global warming and diversify energy
sources. Biomass is a renewable, carbon-neutral resource, and fuels derived from
biomass usually burn more cleanly than fossil fuels. Evaluations of the possible
contribution of biomass to global energy supply range from below 100 EJ/year to
above 400 EJ/year (Berndes, 2003). As a reference, the total USA energy
consumption is around 100 EJ/year and, in 2005, the global commercial primary
energy consumption (oil, natural gas, coal, nuclear energy and hydro electricity)
was 440 EJ (B.P., 2007). This means that biomass could contribute between 20%
and 90% of world energy demand.
Several kinds of biomass can be converted to fuel and chemicals.
Examples are wood and wood waste, agricultural crops, agricultural waste, litter
from animal feedlots, waste from food processing operations and sludge from
water treatment plants. Although wood logs may be used directly, most large
scale conversion plants use wood waste, which may be slash from logging
operations, residues from sawmills, demolition and construction wood waste,
municipal wood waste, pallets or flooring plants waste (Falk, 1997). Potentially,
wood could contribute about 40 EJ/year, worldwide (Parikka, 2004), although
some estimates go as high as 115 EJ/year (Berndes, 2003). Plantations
specifically targeted to the production of crops for energy could produce from 120
to 180 EJ/year. A major problem with such plantations is that they would
compete with food crops. The use of agricultural and forestry residues does not
suffer from this problem and could potentially contribute up to 270 EJ/year, of
which about 100 EJ/year would come from crop residues and 50 EJ/year from
forest residues (Berndes, 2003; Yamamoto, 1999).
Various processes can be used to convert biomass to energy. The biomass
can be burned, transformed into a fuel gas through partial combustion,
transformed into a biogas through fermentation, converted to bioalcohol through
biochemical processes, converted to biodiesel, pyrolyzed into a bio-oil or
transformed into a syngas from which chemicals and fuels can be synthesized. A
biorefinery, where several primary conversion processes are combined and
integrated with sophisticated separations and downstream upgrading operations,
would be very attractive because of it would maximize the feed utilization and the
products value. An additional advantage is that by producing valuable chemical
co-products, a biorefinery would be less affected by the vagaries of the price of
energy, which is controlled by the OPEC oil cartel and can be affected by political
upheavals. However, a biorefinery requires a large throughput to be economical
and biomass is a low density feedstock that is expensive to transport.
Published by The Berkeley Electronic Press, 2008

2 International Journal of Chemical Reactor Engineering Vol. 6 [2008], Review R2
Initially, this paper will review the various biomass conversion processes.
It will also provide a brief overview of the processes that could be used in a
biorefinery. It will then take a few examples of agricultural feedstocks and
speculate how they could be converted to fuels and chemicals.
COMBUSTION
For thousands of years, humans have burned wood to generate heat. Nowadays,
wood is used for space heating and, in industrial plants, to generate heat and
electricity. Some agricultural residues are also burned in industrial plants.
Finally, some power generation facilities blend biomass with coal.
Residential applications
Wood is a relatively cheap source of energy for stoves and boilers when it is
available nearby. Otherwise, transportation costs will usually be prohibitive. An
important advantage of wood is that its net emissions of carbon dioxide are very
low, around 8 kg per MWh of useful energy, as compared with 240 kg/MWh for
natural gas and 490 kg/MWh for oil. The main drawback of residential boilers
and stoves is that using wood results in much more pollution than with oil or
natural gas, as shown in Table 1. A study of large scale use of wood pellets for
heating in Sweden, using community boilers, has shown that it is important to
study the dispersion of the pollutants to ensure that their concentration does not
become too high at crucial locations such as school playgrounds (Jonsson and
Hillring, 2006). In a country such as Canada, residential wood combustion is
already responsible for 7% of the anthropogenic VOC (volatile organic carbon)
emissions and 28% of PM 2.5 (particulate matter below 2.5 microns)
anthropogenic particulate emissions (Government of Canada, 2007).
According to Eskilsson et al. (2004), there is an emissions trade-off since
reducing the combustion temperature will reduce the nitrogen oxides (NOx)
emissions but increase emissions of carbon monoxide and unburnt hydrocarbons.
Analysis of particles and hydrocarbon emissions has identified significant levels
of genotoxic and carcinogenic compounds (Danh et al., 2005). Particulate
emissions will increase substantially when combustion conditions are not optimal,
e.g. if the fuel is wet or the excess air is low (Johansson et al., 2003).
As shown by Table 1, both the design of the boiler and the nature of the
wood have an important effect on pollutant emissions (Kjallstand and Olsson,
2004). Pellets, which are made of sawdust to which wood shavings may be
added, provide consistent fuel properties and help maintain a more regular
combustion (Kjallstand and Olsson, 2004). Consistent wood properties are,
therefore, essential to minimize pollution. The European Committee for
http://www.bepress.com/ijcre/vol6/R2
Standardization is preparing technical specifications for woody feedstocks (and

other biomass feedstocks) (Obernberger et al., 2006). Because of the very large
variety of woody feedstocks, however, the classification is kept flexible
(Alakangas et al., 2006).
The combustor design has also a significant impact on the pollutants
emissions (Olsson et al., 2003). An example of modern stove design is shown in
Figure 1. Heat transferred from the combustion chamber dries the pellets, since
wet pellets would greatly increase pollutants emissions, and the screw feeder can
be regulated to feed the pellets as needed. Using well-calibrated pellets instead of
chopped wood pieces makes it easier to maintain a regular feedrate of fuel into the
combustion chamber.
Old wood boiler New pellet boiler Oil boiler
CO 5000 500 5
CH4 700 0.5 0.5
Other VOC 400 2 0.5
Polycyclic aromatic 15 2 0.01

hydrocarbons (PAH)
Particles 100 15 10
Table 1 Emissions from residential boilers (in mg/MJ of produced energy)

(Kjallstand and Olsson, 2004)
An additional problem of residential and community heaters and boilers is

that they do not respond well to fluctuating thermal demand, which results in
much increased pollutants emissions. It is, therefore, important to provide some
kind of heat storage to smooth out the heat load fluctuations (Lundgren et al.,
2004).

Figure 1 - Example of modern residential pellet stove
Industrial applications
One of the problems of residential boilers is that they are not equipped with
particle separators that could recover a large fraction of the particulates, which are
primarily submicron particles (Johansson et al, 2003). Industrial boilers, on the
other hand, provide for much more effective particulate recovery.
A major pollution problem with industrial boilers, however, is the
emission of dioxins, which are present in both the particulate and gas phases.
Dioxins emissions are much larger when burning wood scrap than when burning
fresh forest wood (Lavric et al., 2004). This has implications for the combustion
of wood from construction and demolition sites. The formation of dioxins can be
prevented or reduced by the addition of chemical inhibitors and proper combustor
design (Lavric et al., 2004).
A serious operating problem with industrial wood combustors is fouling,
which results from the low sintering point of wood ash. Reducing the combustor
temperature hurts the thermodynamic efficiency and increases the emission of
most pollutants. Ash from most woods will sinter at around 1000 C, with ash
from bark sintering at 850 C (Ohman et al., 2004). Some wood pellets are
especially formulated to increase the ash sintering temperature to 1100 C
(Ohman et al., 2004).
Some industrial boilers have used biomass fuels other than woody
feedstocks. Typically, combusting agricultural residues increases pollution,
corrosion and fouling. Obernberger et al. (2006) attribute these problems to the
high levels, when compared to wood, of nitrogen, chlorine and sulfur in straws,
cereals, grasses, grains and fruit residues, which result in higher emissions of
nitrogen oxides, hydrogen chloride, dioxins and sulfur oxides. For example, the
combustion of pellets made from crop residues produces much larger emissions of
dioxins and chlorophenols, when compared to wood pellets (Vierle et al., 1999).
Emissions of polycyclic aromatic hydrocarbons are also much higher than with
wood pellets, whether the pellets are made of straw (Hernandez et al., 2001;
Olsson, 2006) or rice husks (Oanh et al., 2005). There are a few exceptions,
however, since the combustion of hazelnut shells, walnut shells, peanut shells,
apricot seeds and corn cobs emits fewer pollutants than the combustion of wood
(Koyncu and Pinar, 2007). The increased fouling observed when agricultural
biomass is burned results from the lower sintering temperate of its ash.
The lower sintering temperature of the ash from most agricultural residues
also causes problems when it is co-fired with coal. The addition of biomass to
coal increases fouling and the risk of slagging. This has been observed with straw
(Alakangas and Flyktman, 2001), sewage sludge, and meat and bone meal
(Pronobis, 2005). To reduce the slagging risk, the combustor temperature has to
be brought down to about 800 C, which reduces the thermodynamic efficiency
(Alakangas and Flyktman, 2001). The higher chlorine content of agricultural
biomass also causes corrosion problems (Hansen et al., 1998; Spliethoff, 2000;
Pronobis, 2005). Although wood ash has generally a higher sintering
temperature, when co-firing wood and coal, the alkali from the wood combines
with sulfur from the coal to increase fouling and the risk of slagging.
Co-firing biomass with coal generally reduces pollutants emissions
(McIlveen-Wright, 2007). For example, co-firing coal with sugar cane bagasse
reduced NOx emissions by 25% and SOx emissions by 50% (Turn et al., 2006).
Carbon monoxide emissions were, however, much higher because the biomass
moisture reduces the combustion efficiency (Turn et al., 2006). Particulate
emissions, which are such a problem when biomass is burned, are not a problem
when co-firing because coal combustors are already equipped with effective
particle collection systems. An unknown factor, however, are dioxin emissions.
PARTIAL COMBUSTION FOR THE PRODUCTION OF LOW ENERGY

GAS
Transforming biomass into a gas is highly endothermic. There are two ways of
providing the required heat of reaction: transferring heat from a external burner
where by-products such as char are combusted, or conducting the combustion
reactions within the gasifier through the direct injection of oxygen. Steam may
also be injected to control the temperature and increase the hydrogen content of
the gas through the water gas shift reaction. Injecting a mixture of pure oxygen
and steam gives a gas with a heating value of 10 to 18 MJ/Nm3 (Schuster et al.,
2001), while natural gas has a heating value of 33 to 42 MJ/Nm3. Because pure

oxygen is expensive, air is often used, instead, but the added nitrogen greatly
reduces the heating value of the product gas, to 4 to 7 MJ/Nm3 (Schuster et al.,
2001). When air is used, the product gas typically contains more than 50 vol% of
nitrogen and about 10 vol% of carbon dioxide, which means that less than 40
vol% are combustible gases, primarily carbon monoxide and hydrogen.
For electrical production from biomass, the cost of oxygen is prohibitive
and air is used. The low heating value gas may then be burned to generate steam,
combusted directly in a turbine or, for smaller scale applications, sent to a
modified diesel generator. Although turbines or engines are more efficient than
applications using steam generation, their reliability and performance are
compromised even by very low concentrations of tars and particulates in the gas.
There are two main types of gasifiers: fixed beds and fluidized beds. The
poor radial heat transfer in fixed beds limits their use to small gasifiers since with
larger gasifiers, maintaining a high enough temperature for gasification
everywhere in the reactor would lead to hot spots where slagging could occur,
especially with biomass feedstocks that are more prone to slagging than coal.
Fluidized bed gasifiers provide a uniform temperature and greatly reduce the risk
of slagging.
Fixed bed gasifiers
The fixed bed gasifiers may be updraft gasifiers, where the gas flows upward
through the fixed bed, or downdraft gasifiers, where the gas flows downward.
Gas from updraft gasifiers contains too much tar that would gum up the engine.
Downdraft gasifiers are designed to break down the tars by using stratified
gasification.
Figure 2 shows an example of downdraft gasifier. Wood flows down from
a storage hopper into a fire tube. As it moves down the fire tube, wood is first
preheated and dried with heat transferred from the exiting hot gas through the fire
tube wall; it then flows through a pyrolysis zone at about 350-500 C, where it
undergoes thermal cracking and partial oxidation; it continues on to an oxidation
zone where the pyrolytic vapors are partially oxidized, reaching a temperature of
about 1100-1200 C, high enough to destroy most tars (because the vapor
reactions are so rapid, little char gets oxidized in this zone); the char finally
moves down to a reduction zone where it reacts with the gas to form low
molecular weight gases such as H2 and CO and where the temperature drops to
about 200-300 C (Dogru et al., 2002). Downstream of the gasifier, the gas goes
through a packed bed of wood chips where particulates and mist are captured, and
then to the engine intake.
Ash and ash agglomerates are removed at the bottom of the fire tube by a
moving grate connected to a shaker. The moving grate is generally controlled
with the pressure drop through the bed: if this pressure drop becomes too high,
this indicates that too much ash has accumulated and the shaker is activated.
Figure 2 Downdraft gasifier (from Dogru et al., 2002)
There is a trade-off between reliability and combustion efficiency: if the

shaker is activated too often, uncombusted char will be lost with the ash but if it is
not activated often enough, there will be large pressure fluctuations that will upset
the engine. This type of problem could be mitigated by storing the gas under
pressure, but this would eliminate one of the most attractive features of the
downdraft gasifier, which, by working under vacuum, prevents emissions of
dangerous carbon monoxide.
Downdraft gasifiers combined with modified diesel generators seem ideal
to generate electricity for isolated communities but suffer from poor reliability.
The generator will frequently hiccup, causing a disruption in power supply.
These disruptions are caused by poor regulation of the grate or by tars that gum
up the engine. Although tars may be removed with a scrubber, this produces large
quantities of waste water contaminated by carcinogenic tars.

Fluidized bed gasifiers
The uniform temperature of fluidized bed gasifiers makes them more suitable for
large scale applications. Many researchers have studied fluidized bed gasifiers
(e.g. Ergudenler and Ghaly, 1992; Corella et al., 1998; Collot et al., 1999; Liu et
al., 2000; Pan et al., 2000; Petersen and Werther, 2005; Radmanesh et al., 2006).
Two types of fluidized beds have been used: bubbling beds and circulating beds.
A drawback of fluidized beds, however, is the poor conversion of the biomass,
which results from the high rates of particle entrainment and the nearly perfectly
backmixed flow of solids (Li et al., 2004). Multistage fluidized beds have been
proposed to increase the biomass conversion (Kersten et al., 2003). Tar emissions
from fluidized bed gasifiers are higher than from downdraft gasifier, which means
that the tar concentration is unacceptable for use in turbines to generate
electricity.
Tars may be eliminated through physical methods or chemical methods
(Devi et al., 2003). The physical methods involve cooling to condense the tars
and then removal by electrostatic precipitators, filters, scrubbers or rotating
particle separators. The chemical methods consist of thermal or catalytic cracking
of the tars, either within the gasifier or in a special dedicated unit downstream of
the gasifier. In downstream units, thermal cracking requires temperatures higher
than 1200 C while catalytic cracking can occur at temperatures between 700 and
900 C, depending on the catalyst (Bridgewater, 1994; Pena et al., 1996; Sutton et
al., 2001). Three types of catalysts can be used: dolomites, nickel-based catalysts
and non-nickel monoliths. Dolomites and other natural catalysts such as
magnesite and calcite are inexpensive but require higher temperatures of 800 to
900 C (Delgado et al., 1997; Olivaris et al., 1997; Perez et al., 1997; Asadulah et
al., 2004). Nickel-based catalysts, which may or may not be used with steam
reforming, require temperatures of only 700 to 800 C (Baker et al., 1987;
Narvaez et al., 1997; Corella et al., 1997, 1998; Aznar et al., 1998; Caballero et
al., 2000; Asadulah et al., 2004; De Filippis et al., 2004). Non-nickel monolith
catalysts required temperatures of 750 C to 900 C (Toledo et al., 2006).
Although deactivation of the catalyst by carbon deposition is more severe
if the catalyst is in the primary gasifier (Baker et al., 1987; Garcia et al., 1999),
the convenience of eliminating an additional downstream unit has spurred the
development of catalysts that can be used in the primary gasifier. Dolomites have
been used (Narvaez et al., 1997; Olivares et al., 1997), but its calcium combines
with chlorine from the biomass to give calcium chloride that deactivates the
catalyst and has a low melting point (782 C) that lead to fouling (Nordgreen et
al., 2006). Olivine sand has the advantage of being more attrition resistant than
dolomite (Rapagna et al., 2000). Nickel-based catalysts are rapidly deactivated in
the primary gasifier (Devi et al., 2003). Char is also a catalyst for tar cracking
(Ekstrom et al., 1985).
Tars may also be minimized by modifying either the design or the
operation of the gasifier. Several two-stage designs have been proposed to
achieve tar reduction; a pyrolytic zone is usually followed by a reduction zone
where secondary air is injected to raise the temperature and thermally crack the
tars (Devi et al., 2003). Raising the temperature in a single zone gasifier,
however, is not possible since it reduces the gas heating value, enhances corrosion
and increases the sintering risk. Consequently, the optimum gasifier temperature
is about 1000 C for coal, 900 C for wood and 800 C for agricultural waste,
which produces ashes with a lower sintering temperature (Devi et al., 2003).
Other methods have, therefore, been proposed to reduce tar formation in the
gasifier. All these methods, unfortunately, also reduce the heating value of the
gas, whether the ratio of steam and air to biomass is increased (Aznar et al.,
1998), the steam to air ratio is reduced or carbon dioxide is added (Minkova et al.,
2000).
BIOGAS
Biogas is recovered from garbage landfills or wastewater treatment plants. It is

also produced in anaerobic digesters installed in farms, which process manure and
other agricultural wastes. In 2006, biogas from all these sources was 0.22 EJ in
Europe, i.e. a very small fraction of the total energy production. About 58% came
from landfills, 24% from digesters, and 18% from wastewater treatment plants.
Biogas has a low heating value, containing only about 50-70% of
methane. When burned in engines, biogas produces more pollutants than natural
gas. Another issue is the presence of siloxanes in the biogas, which, when biogas
is burned, form silica deposits that quickly ruin the engines. An environmental
problem with biogas production and storage facilities is the fugitive emissions of
methane, which is a much stronger greenhouse gas than carbon dioxide.
A problem with biomass digesters is that it typically takes several weeks
to convert waste streams such as manure. This long residence time means that the
digesters occupy large areas. Digesters tend to be used only for very wet waste
streams, such as manure, whose very high water content greatly lowers the energy
efficiency of thermal processes where water would be vaporized, such as
combustion, gasification or pyrolysis.
GASIFICATION IN SUPERCRITICAL WATER
Much faster processes for gasifying biomass are currently being developed, using
supercritical water as first proposed by Modell et al. (1978). These processes,

which have recently been reviewed by Matsumura et al. (2005), are especially
attractive when the biomass is available with a very high water content and the
additional energy required to vaporize the water would penalize standard
pyrolysis processes. A typical example would be the treatment of sewage sludge
or wastewater from the gasification of wood through partial combustion: the
main purpose is, then, to clean the wastewater and any gas produced is an
additional benefit (Di Blasi, 2007). Products gases are primarily hydrogen,
carbon dioxide and methane, with small concentration of higher molecular weight
hydrocarbons and carbon monoxide.
Published studies vary primarily depending on the biomass that was
gasified (Yanik et al., 2007) and on the catalyst that was used (Guo et al., 2007).
Three main types of catalysts have been tested: activated carbon, metal and alkali
based catalysts (Guo et al., 2007). The activated carbon can be attained from coal
or biomass. The metal catalysts are usually based on nickel, although several
noble metals have also been used. Alkali catalysts, such as calcium hydroxide,
have the additional advantage of capturing carbon dioxide. Guo et al. (2007)
found that the most effective catalyst depends on the type of biomass being
gasified.
BIOETHANOL
Ethanol is increasingly used as a transportation fuel. Although it can be used pure

in modified internal combustion engines, it is mostly attractive in 10% or 15%
blends with gasoline, which can be used in regular internal combustion engines.
When added to gasoline, ethanol promotes complete combustion and reduces the
emissions of pollutants such as carbon monoxide. Ethanol is also an effective
octane enhancer. Although other additives can promote combustion and increase
the octane number, ethanol is attractive because of its low toxicity and
biodegradability. Ethanol, however, has lower energy content than gasoline,
resulting in higher fuel consumption, especially when it is used pure.
Bioethanol production has greatly expanded over the past few years, the
largest producers in 2007 being the USA with 20 billion liters per year and Brazil
with 17 billion liters per year. The first generation processes convert food-grade
sugar or starch to ethanol, the second generation processes will increase process
efficiency through the better use of co-products, and the third generation
processes will convert cellulosic plant material, such as waste or grass.
The current, first generation processes are responsible for nearly all the
bioethanol produced around the world. They either directly ferment sugar from
sugarcane (Brazil) or sugar beets (Europe), or first convert starch from corn to
sugar, and then ferment the sugar (USA and Canada). Figure 3 shows a schematic
process diagram for the production of ethanol from corn. Although ethanol can
be produced from other feedstocks, such as wheat, sugarcane and corn are favored
because of their lower conversion costs. It is slightly cheaper to produce ethanol
from sugarcane than from corn and the large expansion in production capacity in
North America has required subsidies and trade barriers. It should be noted,
however, that the processes using sugarcane, which have been used on a large
scale in Brazil for more than 25 years, are much more mature than the processes
using corn, and their optimization has resulted in major reductions in production
costs over the past 25 years (Goldemberg et al., 2004). A variant uses similar
processes to convert corn kernels to butanol, an alcohol that is more compatible
with gasoline than ethanol and, because its lower volatility, can be transported
through pipelines.
Figure 3 - First generation process for the production of ethanol from corn
The problem with first generation bioethanol processes is that they use
only a small fraction of the corn plant, which has also a high value as food. The
expansion of the bioethanol production has, therefore, resulted in large increases
in food prices. Corn kernels are first extracted and the rest of the plant (stover) is
left as field waste, which is roughly equal in weight to the kernels (Figure 3); only
about half of the kernel mass is converted to ethanol, the rest going to a co-
product called distillers grains. About 0.8 kg of distillers grains are produced for
every liter of ethanol. Although distillers grains can be used, to some extent, as
animal feed, the North American market is progressively becoming saturated.

A major controversy has arisen about the energy balance of the ethanol
production from corn with first generation processes. Some researchers (Patzek,
2006; Pimentel and Patzek, 2005) have estimated that it takes more energy to
make bioethanol than is contained in the ethanol, while others have found that the
energy balance is positive (Malca and Freire, 2006; Morey et al., 2006; Shapouri
et al., 2004; Wang, 2005). The consensus seems that the energy balance is
slightly positive, i.e. about 10-15% of the energy contained in the bioethanol
comes from the solar energy captured by corn plants, while the rest comes from
fossil fuels used in the production and processing of the corn kernels (Jacobson et
al., 2007). Nearly 2/3 of the required energy is consumed by the conversion of
the kernels into ethanol, and the subsequent ethanol purification (Jacobson et al.,
2007).
Energy efficiency, however, is not the only way to evaluate the suitability
of bioethanol production. For example, the corn kernels contain about twice as
much energy as the bioethanol (Jacobson et al., 2007). Although the direct
combustion of the solid corn kernels is more attractive from an energy efficiency
standpoint, it would not be very practical.
The objectives of bioethanol use must be clearly identified. For example,
if the objective is to gain independence from foreign sources of fossil fuels, the
use of domestic coal or nuclear energy for processing becomes justified, in spite
of the associated pollution. On the other hand, if the objective is to reduce net
greenhouse gases emissions from transportation fuels, using nuclear energy, waste
wood or distillers grains to generate energy for processing would be very
attractive, and would probably be more effective than generating electricity for
electric cars.
A process that would use distillers grains to generate energy would greatly
improve the energy efficiency of the conversion of corn kernels to bioethanol.
Jacobson et al. (2007) reviewed the various possible uses of distillers grains and
their analysis is summarized in Table 2. Gasification to syngas or electricity
generation would waste too much energy to be effective. The most energy
efficient process is the direct combustion of the distillers grains to generate heat
for bioethanol production. Direct combustion, however, suffers from two
problems: first the bioethanol process requires only half of the energy that can be
provided by burning the distillers grains and, second, existing plants, which are
set up for natural gas combustion, would have to undergo a major retrofit.
Pyrolysis of the distillers grains to bio-oil, while not quite as energy efficient as
direct combustion, may represent the most attractive solution, especially if
fractions of the bio-oil can be converted to transportation fuels and the remainder
used to generate the energy required by the conversion of kernels to ethanol. An
advantage of bio-oil is that natural gas burners could be easily retrofitted to use
bio-oil.
The second generation processes will convert cellulosic plant material to

bioethanol. Possible feedstocks include forestry waste, agricultural waste, such as
corn stover and energy grasses, which could be grown on marginal land. The
main advantages of these processes are that they would not compete with food
applications, would not require additional irrigation and would not induce
pollution from extra applications of fertilizers and pesticides.
Use of distillers % of Comments

grains ethanol
energy
that
comes
from sun
Current process 13% Distillers grains sold as animal feed.
North American market is saturated.
Gasification to 20% Requires a lot of energy.
syngas Syngas may have value as a source of
chemicals, fuels.
Electricity 26% Efficiency of conversion of heat to
generation electricity is poor (about 33%).
Pyrolysis to bio- 42% Bio-oil can be stored, used in natural gas
oil burners in plant.
Can bio-oil be converted to transportation
fuels?
Combustion 56% Excess energy in plant: only about 50% of
distillers grains can be used.
Table 2 - Possible uses of distillers grains (compiled from Jacobson et al., 2007)
Two main types of second generation processes have been proposed.

Biochemical processes use enzymes to convert cellulose to sugars that are then
fermented to ethanol. Thermochemical processes convert the plant material to a
syngas, a mixture of hydrogen, carbon monoxide and carbon dioxide, from which
alcohols can be synthesized using traditional chemical processes. Of 6 plants
funded by the US government in 2007, 3 will use a biochemical process, 2 will
use a thermochemical process and 1 will use a combination of thermochemical
and biochemical processes (Lammers, 2007). The thermochemical processes that

can be used to convert biomass to syngas are reviewed below in the section:
Conversion of biomass to syngas.
The biochemical production of cellulosic ethanol through enzymatic
hydrolysis is very promising (Wyman, 2007). However, it can commercially
produce only 65 to 70 gallons of ethanol per ton of dry biomass, for a yield of
only 20 wt% (Wyman, 2007). The best yields obtained in the laboratory, under
conditions that may not be practical for large scale commercial plants, are 50 to
60 % (Ohgren et al., 2007). It is therefore likely that if biochemical processes for
the production of bioethanol from cellulosic materials become economically
viable, large amounts of waste, unconverted plant material will be produced.
BIODIESEL
Biodiesel is very popular in Europe, where many passenger cars have diesel
engines. The European production of biodiesel has doubled every year for the
past 3 years and was 10 billion liters in 2007. Malaysia is setting up plants to
produce 5 billion liters per year, in part to supply the European market. Although
cars can run on pure biodiesel, blends of 5 to 20% biodiesel with regular diesel
fuel can be used in standard diesel engines.
Biodiesel can be made from most animal and vegetable oils. Although
tallow, animal fat and fish oils are used, there are not available in large amounts
and most new biodiesel production comes from vegetable oils. The most
commonly used oils are edible oils such as rapeseed oil, soybean oil and palm oil,
although non-edible jatropha oil is being considered in tropical countries (Canoira
et al., 2006). Algae grown from sewage have also been investigated as a possible
feedstock for biodiesel plants (Xu et al., 2006). Many other, non-edible, oils and
fats could also be converted to biodiesel but would require processes that are
currently too complex (Canakci and Gerpen, 2001).
Regular oils, as expressed from the oil seeds, cannot be used directly in
modern, high performance diesel engines (Kalam and Masjuki, 2004; Meher et
al., 2006; Nwafor, 2004). They must first be converted to biodiesel through a
process called transesterification, which reacts the triglyceride groups of the oil
with an alcohol, usually methanol or ethanol, to form the esters that constitute
biodiesel (Figure 4). A co-product of the reaction is glycerol, which is produced
at a rate of about 0.1 kg per kg of biodiesel. The reaction must be catalyzed with
an alkaline catalyst, usually sodium or potassium hydroxide. Figure 5 shows a
diagram of a typical biodiesel process, which uses methanol as alcohol and
potassium hydroxide as alkaline catalyst: most of commercially produced
biodiesel uses this type of process. Using ethanol instead of methanol lowers the
reaction yields and makes glycerol recovery harder (Meher et al., 2006).
Research is being conducted to develop solid catalysts to replace the liquid

catalyst which, in current plants, contaminates the glycerol co-product (DCruz et
al., 2007; Furuta et al., 2006; Gryglewicz, 1999). Currrently, two commercial
plants use a solid catalyst to produce biodiesel, with a process developed by
Axens. Immobilized enzymatic catalysts make the process more environmentally
benign and facilitate products recovery, but suffer from the high cost of enzymes
(Fuduka, 2001; Marchetti et al., 2007; Royon et al., 2007). Finally, alternative
processes avoid transesterification and use, instead, catalytic hydrogenation of the
vegetable oils (Kalnes et al., 2007).
Figure 4 - Transesterification reaction
With current processes, nearly 70% of the energy contained in biodiesel

comes from the sun, and only about 30% from the fossil fuels used in the
production of seeds, their processing and their transformation into biodiesel.
Biodiesel production is already much more energy efficient than even the future,
second generation bioethanol production. Biodiesel is, therefore, a more effective
way of cutting net carbon dioxide emissions, especially when one considers the
higher efficiency of diesel engines. Biodiesel also contains much more energy,
since 1 liter of biodiesel provides as much energy as 1.4 liters of bioethanol.
The use of biodiesel reduces the emissions of most pollutants, with the
important exception of nitrogen oxides. First, biodiesel eliminates the fugitive
emissions of such toxic compounds as benzene and formaldehyde that are
associated with the production, storage and distribution of regular diesel fuel.
Pure biodiesel also reduces sulfur emissions, cuts carbon monoxide emissions by
50%, and decreases particulate emissions by about 20%, although there are
indications that the particulates may be more toxic (Swanson et al., 2007). A
major problem, however, is that nitrogen oxides emissions are increased by 10 to
25% (Swanson et al., 2007; Szybist et al., 2007). This is quite serious since
nitrogen oxides are a major precursor of smog. Nitrogen oxides are also a major
greenhouse gas, since a molecule of nitrogen oxide has a global warning potential
of nearly 300 times that of a molecule of carbon dioxide.

Figure 5 - Diagram of biodiesel process (adapted from Marchetti et al., 2007)
Biodiesel suffers from some quality problems. It tends to gel more easily
than regular diesel fuel at low temperatures. Contamination with water can also
lead to serious problems such as engine corrosion, freezing of fuel lines, and poor
combustion, which increases pollution.
When compared to current bioethanol production from corn, biodiesel
production is much more effective at reducing net greenhouse gas emissions.
However, as bioethanol, it competes with food production and generates large
amounts of waste material. Although the current biodiesel plants produce
glycerol contaminated with alkali, the development of effective solid or
enzymatic catalysts would result in the production of clean, more easily
marketable glycerol. The collection of seeds from the original crops leaves large
amounts of field waste while the extraction of oil from the seeds produces waste
seed cake. Little research has been conducted on the valorization of these waste
materials (seed cakes from edible plants are currently used for animal feeds).
As opposed to bioethanol, processes have not been developed to produce
biodiesel from waste materials, or non-food crops that could be grown on
marginal land. Processes that would generate biodiesel from algae, for example,
are still at a very early stage of development.
PYROLYSIS
Pyrolysis is thermal cracking in the absence of oxygen. It produces a solid

byproduct and a gas that contains condensable vapors, from which liquid bio-oil
can be recovered. Fast pyrolysis is required to achieve high yields of valuable
liquid products, which means that heating of the biomass particles must be rapid,
and the residence time of the product gases must be short (Bridgwater and
Peacocke, 2000). The endothermic pyrolysis reaction requires a continuous, high
rate of heat transfer to the reacting particle. As a biomass particle pyrolyzes, its
surface becomes covered with char, which must be stripped to maintain a high
rate of heat transfer. This can either be achieved by frictional ablation of the
biomass particle with a hot surface, or by immersion of the biomass particle in a
fluidized bed of hot, erosive particles. This section reviews ablative, fluidized
bed and other pyrolytic processes, as well as the techniques used to remove fine
droplets of bio-oil from the product gases. Currently, only the bubbling and
circulating fluidized beds processes produce bio-oil on a commercial scale, using
wood or wood waste.
Ablative pyrolysis processes
Ablative processes have been reviewed by Bridgwater and Peacocke (2000), with
updates from Hulet et al. (2005) and Scholl et al. (2006). All these processes
contact biomass particles with a hot metal surface that is externally heated. A
high slip velocity between the particles and the hot surface is required to achieve
good transfer and ablate the char layer.
One type of ablative pyrolysis technology uses a cyclone: a high velocity
gas stream with suspended biomass particles enters a cyclone with a heated wall.
The tangential entry of the gas with the biomass particles creates a vortex that
keeps the particles moving against the hot wall (Soulignac et al., 1986 a,b; Ld et
al., 2000, 2003; Brem, 2001). Brem (2001) used a rotating filter to prevent
contamination of the product vapors with entrained char particles.
Other ablative processes use mechanical means to keep the biomass
particles moving against a heated wall. This can be achieved with a rotating cone
(Wagenaar et al, 1994), rotating hot plates or fixed hot plates with rotating plows.
Finally, a solids grinder with heated stator and rotor can provide the most intense
ablation.
The main advantage of the ablative processes, especially when ablation is
intensive, is that they can achieve fast pyrolysis even with large biomass particles.
They reduce the need for energy-intensive grinding. They also do not require a
fluidization gas and thus avoid product dilution. However, the residence time of
the cyclonic processes is too short for many feedstocks and the processes that rely

on rotating equipment are mechanically complex (Bridgwater and Peacocke,

2000). In addition, their reliance on heat transfer through a heated wall makes
scale-up inherently difficult. To our knowledge, there is currently no large
commercial plant using this technology.
Fluidized bed processes
Fluidized bed processes have been reviewed by Bridgwater and Peacocke (2000),
with updates from Hulet et al. (2005). The biomass particles are injected into a
fluidized bed of hot particles. In most cases, the fluidized particles are an inert
material such as sand, although some studies have been conducted with catalyst
particles. Fluidized beds provide very good heat transfer to the biomass particles.
The fluidized bed particles also help remove the char layer, although ablation is
not as good as in the most intensive ablation processes.
Two types of fluidized beds have been used for biomass pyrolysis:
bubbling beds and circulating beds. A major issue with bubbling beds is how to
transfer to the bed the heat required for preheating and reaction. Heat may be
generated directly inside the fluidized bed by adding air or oxygen to the
fluidization gas. Partial oxidation is, however, usually associated with poor
product quality, since the most valuable pyrolysis products may be among the
first oxidized and all products are diluted. Consequently, indirect heating must be
used to obtain high quality bio-oil. With small laboratory beds, enough heat can
be transferred through the wall. Commercial scale beds require heat exchanger
tubes through which hot gases flow. The hot gases are generated by the
combustion of gaseous or solid byproducts of the pyrolysis reaction. A
commercial bubbling bed pyrolyzer, built by Dynamotive, is currently being used
in West Lorne, (Canada) to convert 30 tonnes/day of wood waste into bio-oil, and
a new plant has been built in Guelph (Canada) to process 200 tonnes/day of wood
waste. It is based on technology licensed from RTI (Piskorz et al., 1996) and its
flow plan is shown in Figure 6.
Although small fluidized bubbling beds can have vapor residence times as
low as 0.5 s, commercial fluidized beds work with vapor residence times larger
than 3 s, and typically 5 to 10 s. The residence time of the particles can be quite
high since internal cyclones recycle entrained particles to the bed and only very
small particles of char can escape past the cyclones. The biomass particles
therefore remain in the bed until they have reacted. This makes it possible to use
relatively large particles of biomass, in the mm range. Although large particles
give slightly lower liquid yields, they are not as costly to grind.
In circulating fluidized beds, hot circulating solids bring the required heat
to the pyrolysis reactor and are then circulated back to a burner where they are
reheated by combustion of gaseous or solid byproducts. The circulating fluidized
technology was originally developed for the cracking of fossil hydrocarbon

feedstocks (fluid catalytic cracking and fluid coking). The company Ensyn has
patented a circulating fluidized bed process where a hot sand carrier provides the
heat required for the pyrolysis of biomass in a riser reactor. After separation from
the product vapors, sand flows to a regular fluidized bed where it is reheated by
burning pyrolysis by-products such as char or non-condensable gases (Figure 7).
The circulating bed technology has been applied to the commercial
conversion of wood into flavoring agents, by Red Arrow. However, it is not clear
whether this process uses a particulate or a gas heat carrier. In some reactors,
called entrained flow reactors, heat is provided by a hot combustion gas.
For a more compact unit, riser and sand reheater may be combined in a
single unit, called internally recirculating fluidized bed (Figure 8). Biomass
particles are introduced with the riser gas and come in contact with the hot
particles that are entrained from the annulus into a very intense mixing zone at the
base of the riser (Milne et al., 1999).
Cyc lones Quenc h Electrostatic

system precipitator
Feedstock conveyor
Feedstoc k
hopper
Biotherm
reac tor
Char pots Produc t
tank
Cooling
Feed water
box
Feeder
Quenc h liquid Bio oil

pump produc t
Combustion
air
Burner
Natural
gas To flare
Figure 6 Flowsheet of Dynamotive pyrolyzer (Hulet et al., 2005)

Air Water Filter
Exhaust
Biomass
feed
Condensers
Nitrogen
Demister
Sand Filter
Reactor
Sand
heater Filter
Propane
Air Product oil
Figure 7 - The Ensyn process flow plan (after Bridgwater and Peacocke, 2000)
Produc t gas
Gas baffle
Solids
disengaging T
Riser
assembly
Riser gas Fluidization gas
Figure 8 Internally Circulating

Fluidized Bed (from Hulet et al., 2005)
Preheated feed
Preheated N2
Vortical
reactor
Reactor
column
Electrostatic
N2 quench precipitator
To filter
gas collection
Quench bags
Cyclonic
chamber
condenser
Figure 9 Thermovortactor downer (from Hulet et al., 2005)
Another type of circulating bed configuration has recently been proposed

by Boukis et al. (2007). The transport gas for the riser, where the biomass
particles are pyrolyzed, is generated by combusting char particles in a lower
bubbling bed.
An alternate recirculating bed process uses a downer reactor, where both
particles and gas move downward. An example is the thermovortactor downer,
shown in Figure 9 (Graham et al., 1986; Shen et al., 1995). In this representation,
the biomass particles were very quickly heated by hot nitrogen gas, but it was also
used with a particulate heat carrier. Because of the high dilution of the product
vapors by the carrier gas, an electrostatic demister was required to recover most of
the bio-oil (Figure 9). Tracer studies confirmed that both the gas and solids
residence time distributions were narrow, indicating a nearly plug flow behavior
(Roques et al., 1993). This can be an advantage in pyrolysis processes where
overcracking of valuable products must be avoided. Another downer pyrolyzer
uses a gaseous heat carrier that enters tangentially with biomass into the reactor
(Diebold and Scahill, 1988). The tangential entry and ribs on the reactor wall

impose a vortical motion that keeps the particles sliding along the hot reactor
wall, favoring direct heat transfer to the particles from the wall and promoting
mild ablation (Diebold and Scahill, 1988).
In circulating bed pyrolysis, the temperature is relatively high, the gas
residence time is around 0.5 to 1 s and the particle residence time is of the order
of 1 s. This means that, to avoid degradation, product vapors exiting the reactor
must be very quickly separated from the hot solids and quenched. The biomass
particles must also be mixed very quickly and effectively with the heat carrier to
achieve high heating rates. Figure 10 shows a mixing chamber or mixor for a
riser that was proposed by Freel and Graham (1998) and that is very similar to the
mixor used by Berg et al. (1986, 1989) for a downer.
When compared to the bubbling bed technology, the circulating bed
technology is more compact, provides more intense ablation and its narrower
residence time distribution reduces undesirable by-products (Freel and Graham,
1999). An additional advantage is that it can tolerate larger density differences
between the inert particles and the biomass particles. Its drawbacks are the need
for more fluidization gas, the requirement for quick separation of the product
vapors from the circulating solids, and the complexity and lack of flexibility
inherent in a circulating system. Particles also need to be ground finer, since they
do not have a long residence time at reaction temperature, and this is even worse
for downer processes, where the particle residence time is even shorter. Boukis et
al. (2007) have found that, when pyrolyzing particles larger than 1 mm in a
circulating bed, the liquid yield dropped quickly with increasing particle size.
When char is a valuable product, its recovery is also more complex than with a
bubbling bed pyrolyzer.
A problem with processes that use a solid heat carrier is that ash particles
can act in the pyrolyzer as a catalyst for the cracking of bio-oil, reducing bio-oil
yields. On the other hand, Freel and Graham (1998) have shown that char is also
a very effective catalyst for the cracking of bio-oil, reducing bio-oil yields. With
bubbling bed pyrolyzers, it is therefore important to adjust the size of the biomass
particles and the fluidization conditions to promote char elutriation while
minimizing the elutriation of unconverted biomass.
Bio-oils form very stable aerosols of sub-micron droplets that must be
recovered to achieve high liquid yields (Piskorz et al., 1998; Bridgwater, 2004).
Mist recovery is a serious problem with pyrolyzers that use a carrier gas, such as
fluidized bed processes and, especially, circulating fluidized bed processes.
Regular impingement or cyclone demisters are not very effective (Bridgwater,
2004). More advanced demisters such as electrostatic demisters or mechanically
rotating demisters are needed.
Piskorz et al. (1996) and Scott et al. (1999) obtained the same liquid yield
with vapor residence times of 0.5 s and about 5 s, by lower the temperature of the
reactor for the higher residence time. They used three different biomass
feedstocks: wood, wheat straw and sugarcane bagasse. They also found that
adjusting the temperature gave bio-oils that had about the same concentration of
hydroacetaldehyde and acetic acid for both residence times. If verified with other
feedstocks, this would have important practical implications, since commercial-
sized pyrolyzers with a residence time of 5 s are much easier to build and operate
than pyrolyzers with a residence time of 0.5 s, and operating at a lower
temperature reduces energy and capital expenditures.
Figure 10 Mixor (from Hulet et al., 2005)
Other Processes
Other processes for the pyrolysis of biomass include vacuum pyrolysis (Garcia-
Perez et al., 2002), a shock wave laboratory unit (Guo et al., 2002) and a twin-
screw reactor (Rafflet et al., 2006). Vacuum pyrolysis has been used to convert
wood and other feedstocks, using molten salt heat exchangers (Roy, 1999;
Boucher et al., 2000). A spouted bed has also been proposed (Aguado et al.,
2000). Screw reactors use an auger to mix the biomass particles with the hot
carrier particles. They are mechanically complex but provide a very good control
of the biomass residence time.
The rotary cone ablative pyrolyzer has been adapted to a larger scale by
introducing a sand heat carrier, transforming it into a mechanically fluidized bed
(Wagenaar et al., 2001; BTG, 2007). Because it no longer relies on heat transfer

from the wall, it can be scaled up. Because very little carrier gas is used, there is
no significant dilution of the products, which makes quenching and condensation
easier. The residence time is very short, which minimizes overcracking.
However, the solids residence time is very short, between 0.05 and 0.3 s
(Wagenaar et al, 1994), which means that the solids will have to be ground fine
and the temperature will have to be high to achieve a high biomass conversion.
APPLICATIONS OF BIO-CHAR
Biomass pyrolysis produces gaseous, liquid and solid products. The product
gases are usually burned to generate energy for the pyrolysis process, and some of
the solid biochar can also be burned if required. Although the most valuable
product is usually the liquid bio-oil, the solid biochar product is also valuable.
Biochar can be used as a fuel. It is also, for some metallurgical processes,
an attractive substitute for coke derived from fossil fuels, since it contains low
concentrations of metals. In such applications, biochar is carbon neutral, i.e. it
releases to the atmosphere the carbon that the biomass from it was derived had
captured from the atmosphere. When used, pyrolysis gases and liquids are also
carbon neutral.
Biochar can also be carbon negative, i.e. it can be used as a carbon sink,
which captures from the atmosphere carbon that will not be released back to the
atmosphere (Lehmann, 2007). Biochar is an excellent fertilizer: it improves soil
texture, it retains and slowly releases nutrients and water and it acts as a support
for beneficial organisms (Glaser, 2007; Lehmann et al., 2006).
UPGRADING OF BIO-OIL
The main application of bio-oils will probably be as fuels. Bio-oils obtained from
the pyrolysis of wood or agricultural waste are mixtures of many compounds so
that, even when valuable chemicals are first extracted from the bio-oil, the
remainder will be used as fuel. Bridgwater (2004) provides a detailed review of
bio-oil properties and applications. Bio-oils have been considered as fuels for
boilers, for car or truck engines and for turbines or modified diesel generators, to
produce electricity.
Bio-oils are complex mixtures of oxygenated hydrocarbons, water from
the original biomass moisture, pyrolytic water, and char particles (Bridgwater,
2004). Depending on the biomass composition and the pyrolysis conditions, the
bio-oil may be a stable emulsion or readily separate into aqueous and oil phases,
although the oil phase contains a significant amount of dissolved water, which
reduces its heating value. Most of the compounds present in bio-oil are
oxygenated, which further reduces its heating value, so that the bio-oil heating
value is usually around 50% of the heating value of diesel fuel (Bridgwater, 2004;
Qi et al., 2007).
When warm, bio-oil can oxygenate quickly and
condensation/polymerization reactions lead to the formation of gums. While bio-
oil stability at ambient temperature should be sufficient for transportation to a
central location, it must be enhanced with additives such as ethanol for long term
storage (Boucher et al., 2000). It is likely that major improvements in the quality
of bio-oil can be achieved through refining; for example, evaporating the
volatiles, which include most of the water, and adding ethanol to the remaining
bio-oil, enhances its stability, reduces its viscosity and makes its filtration easier
(Oasmaa, 2005).
Applications of raw bio-oil
Raw bio-oil is not generally a very suitable fuel. Although bio-oils can be used in
boilers, the equipment must be modified, fossil fuel must be used for startup and
although nitrogen and sulfur oxides emissions are lower than with fossil fuel,
particulate emissions are generally higher (Gust, 1997; Osmaa et al., 2000).
There are also some concerns about long term fouling and corrosion.
Although bio-oils have been successfully tested in diesel engines, there are
concerns about cold weather flowability, corrosion, the formation of gummy
deposits and the need for an auxiliary fuel at startup (Bridgwater, 2004). In all
cases, it seems that the bio-oil cannot be used as sole fuel, but another fuel, which
can be either an alcohol or diesel fuel, must be used either as pilot fuel or blend
(Bridgwater, 2004). Bio-oils are not usually miscible with fossil fuels so that
cofiring with fossil fuels requires the formation of emulsions, which must be
stabilized by expensive surfactants (Qi et al., 2007). Deposits and corrosion of
the injectors prevent the use of bio-oils in advanced diesel engines. When bio-oil
is blended with regular diesel fuel, corrosion rates may either be higher
(Chiaramonti, 2003) or lower (Ikura et al., 2003) than with pure bio-oil. Diesel
engines running on bio-oil usually emit fewer pollutants than engines running on
diesel fuel, with the exception of carbon monoxide (Bridgwater, 2004; Oasmaa,
2005).
When bio-oils are used in turbines, less pollutant is also emitted, with the
exception of carbon monoxide (Bridgwater, 2004; Oasmaa, 2005). A major
concern is the fouling and corrosion of turbine blades. For example, Dynamotive
used a turbine from Orenda Aerospace Corporation to generate electricity with
bio-oil derived from wood. They found that the bio-oil needed to be filtered to
remove particulates and that methods must be put in place to clean deposits from
the blades and, if necessary, quickly replace the blades on-site (Blackady, 2005).

The oil injectors were modified to allow for startup with diesel fuel and to provide
air-assisted atomization.
Table 3 shows that bio-oils emitted much less sulfur and nitrogen oxides
than other biofuels but much more carbon monoxide.
Fuel #2 diesel Bio-oil Bio-oil Ethanol Biodiesel

fuel (Dynamoti (Ensyn)
ve)
SO2 (ppm) 7 2 1 2 1.4
NOx (ppm) 321 57.5 60 101 321
CO (ppm) 1 48.7 55 3 4.1
Table 3 Pollutants from combustion in a turbine (Blackady, 2005)
Raw bio-oil cannot easily be used in modern engines. It must, therefore,

be refined and upgraded before it can be used, especially for transport
applications. Upgrading can take place in dedicated downstream units or within
the actual pyrolysis reactor.
Upgrading of bio-oils to transport fuels
Upgrading of bio-oils can be done through hydrotreating or catalytic cracking

(Bridgwater, 2003). Catalytic cracking of bio-oils is cheaper than hydro treating
and can effectively remove some to the oxygen from the bio-oil molecules.
However, the high rate of coking and the poor quality of the products make it
unattractive (Qi et al., 2007).
Hydrotreating uses hydrogen, must be conducted under high pressure (100
to 200 atm) and requires expensive catalysts. Elliot et al. (2006) found that trace
contaminants in the bio-oil can deactivate the catalyst. Iron contamination can
poison the catalyst (Elliot et al, 2006) and this contamination presumably results
from the interactions of the bio-oils with piping and vessel walls. Qi et al. (2007)
reviewed the various studies and concluded that hydrotreating was not practical.
Because many countries have set targets of a content of 5% or 10% of
biofuels in transport fuels, it may be attractive to blend bio-oil with fossil fuel and
then process the mixture in standard oil refineries. To be practical, this would
probably involve extraction of a fraction of the bio-oil, which would then be
deoxygenated to increase its compatibility with fossil fuels (Solantausta, 2006).
This co-processing would leverage expertise acquired in the refining of fossil
fuels.
Catalytic pyrolysis
Using a catalyst instead of sand in a fluidized pyrolyzer might help improve the
quality of the products and eliminate the need for downstream processing.
Lappas et al. (2002), Olazar et al. (2000), and Willams and Nugranad (2000) used
a zeolite catalyst, Chen et al. (2003) used several metal oxide catalysts mixed with
calcium and sodium carbonate and Adams et al. (2006) used silica alumina
catalysts with copper doping. These studies observed that the catalyst increased
the gas yield, which is not attractive. There was also fast catalyst deactivation by
coke deposition.
Chemicals from bio-oil
The extraction of chemicals from the bio-oil usually starts with the fractionation
of bio-oil into aqueous and oily phases, which can be achieved by adding small
amounts of water to the bio-oil. The aqueous phase of bio-oil obtained from
wood contains meat browning agents and compounds that impart a smoky flavor.
The Red Arrow company produces liquid smoke from bio-oil resulting from the
pyrolysis of wood, using Ensyn technology.
Although the aqueous phase can be used as an environmentally friendly
road de-icer, it is too expensive when compared to alternatives. The oily/tarry
phase has not found high-value commercial applications, although it has been
considered as a replacement for phenol in phenol-formaldehyde resins, which are
used in plywood (Bridgwater, 2004).
Glycolaldehyde, Levoglucosan and Levoglucosenone are present at a high
concentration in some bio-oils from the pyrolysis of carbohydrates such as
cellusoses and starches. They can be used to produce browning agents for foods.
Currently, it is, however, more economical to produce glycolaldehyde from
sugars (Majerski et al., 2001). Levoglucosan can be produced from cellulose
(Scott, 1995; Radlein et al., 2002).
Possible feedstocks and their products
Pyrolysis may be used to produce, from biomass, bio-oils containing a large

variety of valuable chemicals. A few examples are given in Table 4. Other
examples are flavor chemicals such as liquid smoke and browning agents.
Pyrolysis can also be used to produce bio-oils to be used primarily as
fuels. In this case, it is important to select biomass that grows quickly, with a
minimum of care, irrigation, fertilizer and pesticide. Grasses meet these criteria,
since they regrow from their roots and do not require replanting for long periods

of time (decades). Table 5 provides a few examples. Hemp is another example of

a crop that could be grown for energy.
CONVERSION OF BIOMASS TO SYNGAS
Syngas, or synthetic gas, is a mixture of carbon monoxide, carbon dioxide and

hydrogen. It is currently produced from natural gas or coal and can be used to
produce a variety of chemicals such as ammonia or methanol, using well-
established processes. Syngas can also be converted into synthetic petroleum for
use as a fuel or lubricant via Fischer-Tropsch synthesis, using technologies that
were originally developed by Germany during the Second World War and refined
by South Africa when it was embargoed because of its apartheid policies. Syngas
could also be used as an intermediate when the desired product is hydrogen, with
the carbon monoxide component transformed into additional hydrogen through
the water-gas shift reaction. Air gasification cannot be used to produce syngas
because of the high concentration of nitrogen in the product gas.
Syngas can be produced from biomass through direct gasification. It can
also be produced in two steps, converting first the biomass to bio-oil and then
gasifying the bio-oil.
Direct gasification of biomass
There are many processes available for direct gasification of biomass. In all cases,
fine ash must be filtered out of the product gas. Some gasifiers use costly, pure
oxygen to make syngas. Other systems use high temperature pyrolytic
decomposition of biomass without oxygen but their syngas is contaminated by
trace amounts of thermally resistant tars. Syngas must be cleaned thoroughly
before it can be converted to liquid fuels. An example is the commercial plant
being built in Germany to produce 15 000 tonnes of biodiesel per year from wood
chips (Blades, 2007).
The crucial problem appears to be a logistic one. It has been estimated that
a world-class synthetic fuel production facility would require biomass supplies
from an area half the size of Belgium (WBCSD, 2007). Therefore, the most likely
scenarios require the expensive and polluting transport of biomass to a single
central point for conversion and processing.
Conversion to bio-oil followed by bio-oil gasification
Bio-oil is a high density and clean liquid that is both pumpable and storable. Bio-
oil stability at ambient temperature should be sufficient for transportation to a
central location and can be enhanced with additives for longer term storage
(Boucher et al., 2000). It therefore makes sense to convert the biomass to bio-oil
and transport the bio-oil to the synthetic fuel plant. Liquid bio-oil is a much more
suitable feedstock for catalytic processes than raw, solid biomass.
Producing the bio-oil first makes it possible to get full environmental and
economic benefits of the biomass by first recovering valuable co-products and,
then converting the remaining liquid to syngas. Several publications have
proposed converting biomass to bio-oil in many small pyrolysis plants and then
transporting the bio-oil to a central plant for conversion to a syngas (Wang et al.,
1997; Henrich et al., 2006).
Chemical From General classification
Paclitaxel (taxol) Yew, bark, twigs, needles Taxanes
Betulin Birch bark Terpenoids
Maltol Larch bark, Pine and balsam fir needles Carbohydrate
Quinine Calisaya bark Alkaloid
Salicylic acid Willow (salix) bark Beta-hydroxy acid
Nicotine Tobacco leaves Alkaloid
Tetrahydrocannabinol Hemp, marihuana Cannabinoids
Caffeine Coffee waste Alkaloid
Table 4 Chemicals and possible biomass feedstocks

Reported
Common name Latin name height (m) Comments
Giant Reed, Wild Arundo Donu(a)x 6 - 10 Fresh water

cane, Spanish cane, plant, bamboo
Carrizo like
Elephant grass, Pennisetum 3-7 Native of Africa,

Napier grass, purpureum food of
Uganda grass elephants
Miscanthus Miscanthus 3.5 Native of Asia

gigantheus,
Miscanthus Sinensis
Switchgrass Panicum virgatum 1.5 North American

Tall Panic grass Prairie
Kleingrass Panicum coloratum 0.5-1.2 Africa
Buffalograss Buchloe dactyloides 0.3 North American
Prairie
Reed canary grass Phalaris arundeneacea 0.6-1.8 Temperate North

America, Europe
and Asia
Tall fescue Fetusca arundinacea 0.5 - 2 Europe

Big bluestem Andropogon gerardii 1-3 North American
Prairie
Eastern gamagrass Tripsacum 1.2-2.4 Eastern USA

dactyloides
Table 5 Examples of energy grasses
Syngas has been produced with the high pressure (26 bar or 2.6 MPa),
high temperature (1220 1600 C), slagging oxygen gasification process that is
currently used by Sasol to convert coal to syngas (Wang et al., 1997). Although
good results were obtained, this technology requires very expensive equipment
and most studies for the gasification of bio-oil have focused on processes that
require lower temperatures and pressures, using either catalytic cracking or steam
reforming.
In catalytic cracking of bio-oil, the catalyst is quickly de-activated by coke
formation (Gayubo et al., 2004). Regeneration of the catalyst by combustion leads
to its gradual deactivation due to the loss of acid sites (Vitolo, 2001). Successful
production of syngas from bio-oil therefore requires either the development of
new catalysts or the use of catalytic steam reforming. Several studies (Wang et al.,
1997, 1998; Czernik et al., 2002) have used nickel based catalysts for the catalytic
steam reforming of bio-oil. Regular, nickel-based catalysts lack the attrition
resistance required for the industrial implementation of bio-oil steam reforming.
The mineral olivine, however, has the required attrition resistance and has been
successfully used for tar cracking in a fluidized bed biomass gasifier (Rapagna,
2000, 2001) and for the direct steam gasification of biomass (Hofboauer, 1996).
Preliminary experiments (Radlein et al., 2000) indicate that bio-oil can be
catalytically steam-gasified at relatively low temperatures, with total destruction
of tar, to a high quality hydrogen-rich synthesis gas.
THE BIOREFINERY CONCEPT: SPECULATIVE EXAMPLES
The biorefinery concept attempts to apply to biomass conversion, the methods

that have been applied to the refining of petroleum. The goal is to maximize the
value of the products obtained from the biomass. This section considers different
biomasses, tobacco, flax straw and the residues from the production of bioethanol,
and speculates how the processes reviewed in this paper could be applied to
maximize product value.
For crops and agricultural waste, it would be better to convert the biomass
to bio-oil near the farm and transporting the high-density bio-oil to a central
facility for processing rather than transporting the low-density biomass. The gas
and some of the char would be burned to provide the energy required for pyrolysis
(Figure 11). Processing biomass at the source using mobile pyrolysis is
particularly attractive since it can adapt to the seasonal nature of most biomass:
the mobile pyrolyzers can be rotated to various biomass sources as they become
available.
Tobacco
Tobacco farmers face significant hardship as tobacco consumption is dropping

due to health concerns. Pyrolysis can open a new market for tobacco: valuable
chemicals such as nicotine could be extracted from the bio-oil, and the remainder
could either combusted to generate electricity or used to make synthesis gas. A
further advantage is that the pyrolyzer could process the whole tobacco plant,

eliminating waste and saving on the expensive migrant labor currently employed
to collect tobacco leaves. Nicotine is very valuable since it has pharmaceutical
applications and is also a natural insecticide (Isman, 2006). Little work has been
published on the pyrolysis of tobacco for the production of bio-oil. One study
concentrated on the production of fuel gases and did not perform liquid analysis
(Encinar et al., 1997), while another study looked at the pyrolysis of tobacco
stalk, found a maximum liquid yield at 500 C but did not, unfortunately, analyze
the bio-oil for nicotine (Demicirbas, 2002). Another study showed that bio-oil
produced from tobacco leaves in a bubbling bed pyrolyzer contained significant
amounts of nicotine (Scott et al., 1997). It is also likely that the char by-product
would be a valuable fertilizer.
Because it is inherently biosafe and capable of producing up to 25 000
kg/ha of biomass in a four week period, tobacco is now being widely used as a
means of producing a wide range of biopharmaceuticals including antibodies,
cytokines, blood products and vaccine antigens (Rymerson, 2002). The recovery
of these materials can be in the range of 100 grams to 2 kilograms per hectare,
which leaves a large amount of post-processing biomass targeted for waste
disposal. Using this biomass for pyrolysis is an attractive and safe solution. The
resulting bio-oil allows more value to be captured from the tobacco.
Tobacco could be pyrolyzed to a bio-oil in a fluidized bed. Figure 12
shows an example of results obtained by some of us from the pyrolysis of tobacco
leaves (Berruti et al., 2007). Its bio-oil would then be separated into an aqueous
phase and an oily phase, and the nicotine extracted from the aqueous phase.
Because the nicotine concentration in the pyrolytic aqueous phase is much higher
than in the tobacco leave teas that are currently used for nicotine extraction, its
purification would be more economical. There may be other valuable compounds
in both the oily and aqueous phases that could also be extracted. The remainder
of the aqueous phase could be fermented to produce either biogas or alcohol,
while the remainder of the oily phase might either be burned to generate energy or
converted to a syngas.
Flax straw
Flax straw is a major nuisance in the production of flax seed. While a small
percentage of the material is used for the production of high value papers such as
that used for money, the bulk of it must be baled and removed from fields or
burned (Chen et al., 2005). Its resistance to decomposition in soil is a major issue
and burning is an unacceptable agricultural practice, so its conversion to bio-oil
through pyrolysis would be very attractive. There are as yet no reports describing
bio-oils produced using flax straw and, given the availability of up to 250,000
tonnes of feedstock in North America, it could become a significant source of bio-

oil.
heat
Combusted
recovery
for heat
gases
fuels
agricultural P yro lysis U n it Bio-O il liquids food additives

w astes
pyrolysis cracks
Examples: Flax Straw, m olecules
Corn, Tobacco, Dry
Distillers Grains,
Chicken Litter,
Sludge, Grasses,
Fruits..
pharm aceuticals
solid residue
Combusted
heat
for heat
recovery
fertilizer
Figure 11 Mobile Pyrolyzer
There is a lack of studies on the pyrolysis of flax straw, but

Table 6 provides the product yields obtained by Jan Piskorz, by pyrolyzing
fax straw in a small bubbling fluidized bed.
Table 7 provides the corresponding yields of some specific chemicals. As
in the case of tobacco, valuable chemicals would first be extracted. The
remainder of the aqueous phase could be fermented to produce either biogas or
alcohol. The remainder of the oily phase might either be burned to generate
energy or converted to a syngas.

Figure 12 - Liquid yields from the pyrolysis of tobacco leaves (Berruti et al.,
2007)
Wt % as fed basis
Char 15.52
Water 21.33
Gas 15.32
Organics 43.74
Total recovery 95.91
Table 6 - Product yields from the pyrolysis of flax straw (6.8 wt% moisture)
Concentrations, wt % of dry
organic basis
Pyrolytic Lignin 30.72

Water solubles 69.28
Cellobiosan 0.99
Glyoxal 2.17
Hydroxyacetaldehyde 15.36
Formaldehyde 3.64
Formic Acid 4.76
Acetic Acid 4.25
Acetol 3.19
Levoglucosan 2.83
Table 7 - Products identified in bio-oil from flax straw pyrolysis
Residues from the production of bio-ethanol
Distillers grain is a byproduct of bio-ethanol production through the first

generation conversion of corn kernels, which converts starch to sugar that is
fermented. Approximately 0.8 kg of dried distillers grain is produced for every
liter of bio-ethanol. In the United States, the annual production of bio-ethanol is
14 billion liters, with an additional capacity of 6 billion liters under construction.
In 2008, this should result in an annual production of distillers grains of nearly 20
million tonnes in North America. Although distillers grains can be used as animal
feed, the North American market is already saturated and Suncor, for example, is
planning to ship its production to Europe (although there may be problems if it
uses genetically modified corn). Preliminary pyrolysis tests of distillers grains,
conducted in our pilot plant, produced large yields of bio-oil. Using this bio-oil
for fermentation and fuel could radically improve the economics of bio-ethanol
production.
Table 8 shows results from the pyrolysis of distillers grains obtained by
Jan Piskorz. After extraction of valuable chemicals, the aqueous phase could be
fermented to produce more ethanol. The oily phase would either be burned to
generate energy for the bioethanol process or converted to a syngas.
The production of cellulosic ethanol through enzymatic hydrolysis can
commercially produce only 65 to 70 gallons of ethanol per ton of dry biomass, for
a yield of only 20 wt% (Wyman, 2007). The best yields obtained in the
laboratory, under conditions that may not be pratical for large scale commercial
plants, are 50 to 60 % (Ohgren et al., 2007). Pyrolysis could greatly improve the

process efficiency and economics by producing bio-oil from the large amount of
waste material that would be generated by cellulosic ethanol plants. Alternately,
pyrolysis could produce bio-oil directly from the corn stover. The bio-oil would
then be refined to biofuels and chemicals, and some of its fractions could be
converted to ethanol.
Wt % as fed
Organics 41.97
Water 22.39
Solids 19.31
Losses and 16.33
gases
Total above 100.0
Table 8 - Product yields from distillers grains pyrolysis (10.1 wt% moisture)
CONCLUSION
This review has shown that, of the many processes that can convert biomass into
fuels and chemicals, none is without drawbacks. The best solution is likely a
biorefinery that combines various processes to maximize economic and
environmental benefits while minimizing pollution. The biorefinery approach
would make it possible, for example, to extract energy, fuel and valuable
chemicals from the large amount of waste material produced by current processes
for bioethanol and biodiesel. The use of small, local or mobile pyrolyzers could
also make it attractive to transform forestry and agricultural waste materials into a
liquid that can then be shipped and processed in a central biorefinery complex.
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Biomass Valorization for Fuel and

KEYWORDS: biomass, combustion, gasification, pyrolysis, bioethanol, biodiesel,

The transformation of biomass into fuel and chemicals is becoming increasingly

Published by The Berkeley Electronic Press, 2008

Standardization is preparing technical specifications for woody feedstocks (and

Old wood boiler New pellet boiler Oil boiler

Polycyclic aromatic 15 2 0.01

Table 1 Emissions from residential boilers (in mg/MJ of produced energy)

An additional problem of residential and community heaters and boilers is

Published by The Berkeley Electronic Press, 2008

Figure 1 - Example of modern residential pellet stove

PARTIAL COMBUSTION FOR THE PRODUCTION OF LOW ENERGY

Published by The Berkeley Electronic Press, 2008

Fixed bed gasifiers

Figure 2 Downdraft gasifier (from Dogru et al., 2002)

There is a trade-off between reliability and combustion efficiency: if the

Published by The Berkeley Electronic Press, 2008

Fluidized bed gasifiers

Biogas is recovered from garbage landfills or wastewater treatment plants. It is

GASIFICATION IN SUPERCRITICAL WATER

Published by The Berkeley Electronic Press, 2008

Ethanol is increasingly used as a transportation fuel. Although it can be used pure

Published by The Berkeley Electronic Press, 2008

The second generation processes will convert cellulosic plant material to

Use of distillers % of Comments

Two main types of second generation processes have been proposed.

Published by The Berkeley Electronic Press, 2008

Research is being conducted to develop solid catalysts to replace the liquid

Figure 4 - Transesterification reaction

With current processes, nearly 70% of the energy contained in biodiesel

Published by The Berkeley Electronic Press, 2008

Figure 5 - Diagram of biodiesel process (adapted from Marchetti et al., 2007)

Pyrolysis is thermal cracking in the absence of oxygen. It produces a solid

Ablative pyrolysis processes

Published by The Berkeley Electronic Press, 2008

on rotating equipment are mechanically complex (Bridgwater and Peacocke,

Fluidized bed processes

technology was originally developed for the cracking of fossil hydrocarbon

Cyc lones Quenc h Electrostatic

Quenc h liquid Bio oil

Figure 6 Flowsheet of Dynamotive pyrolyzer (Hulet et al., 2005)

Published by The Berkeley Electronic Press, 2008

Air Water Filter

Riser gas Fluidization gas

Figure 8 Internally Circulating

Figure 9 Thermovortactor downer (from Hulet et al., 2005)

Another type of circulating bed configuration has recently been proposed

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Figure 10 Mixor (from Hulet et al., 2005)

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Applications of raw bio-oil

Published by The Berkeley Electronic Press, 2008

Fuel #2 diesel Bio-oil Bio-oil Ethanol Biodiesel

Table 3 Pollutants from combustion in a turbine (Blackady, 2005)

Raw bio-oil cannot easily be used in modern engines. It must, therefore,

Upgrading of bio-oils to transport fuels