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BIOFUEL AND GREEN BIOTECHNOLOGY

Course Code: BTE2509 Credit Units: 03

Module I: Biomass Sources, Characteristics & Preparation:


 Biomass Sources and Classification-Chemical composition and properties of different biomass materials
 Bio-fuels – Sugar cane molasses for fermentation of ethanol;
 Sources and processing of oils and fats for liquid fuels
 Energy plantations - Preparation of woody biomass
 Drying, Storage and Handling of Biomass.

Module II: Biogas Technology-


 Biodegradable organic matter
 Feedstock for biogas production,
 Operating parameters for biogas production,
 Dry and wet fermentation

Module III: Bio-Ethanol and Bio-Diesel Technology-


 Production of Fuel Ethanol by Fermentation of Sugars.
 Trans-esterification of Oils to Produce Bio-Diesel.

Module IV: Pyrolysis and Gasification of Biomass-


 Thermo-chemical conversion of Ligno-cellulose biomass - Pyrolysis of biomass,
 Thermo-chemical gasification principles

Module V: Combustion of Biomass and Cogeneration Systems-


 Combustion of Woody Biomass,
 Cogeneration in Biomass Processing Industries.
 Use of biogases for cogeneration.

Examination Scheme:
Components CT Attendance Assignment/ EE
Project/Seminar/Quiz
Weightage (%) 15 5 10 70
Text & References:
 Biotechnology and Alternative Technologies for Utilization of Biomass or Agricultural Wastes, A. Chakravarthy, Oxford & IBH
publishing Co., New Delhi, 1989.
 Biogas Systems: Principles and Applications, K.M. Mital, New Age International Publishers (p) Ltd., 1996.
 Biomass Energy Systems, P. Venkata Ramana and S.N. Srinivas, Tata Energy Research Institute, New Delhi, 1996.
 Fuels from Biomass and Wastes, D.L. Klass and G.M. Emert, Ann Arbor Science publ. Inc. Michigan, 1985.
 Bio-gas Technology, Khandelwal K.C. and Mahdi, Tata McGraw-Hill pub. Co. Ltd., New Delhi
 Advances in bio-gas Technology, O.P. Chawla, I.C.A.R., New Delhi. 1970.
1 Biomass Sources, Characteristics & Preparation

BIOMASS
Biomass is organic material that comes from plants and animals, and it is a renewable source of energy. Biomass
most often refers to plants or plant-based materials that are not used for food or feed, and are specifically called
lignocellulosic biomass. Biomass contains stored energy from the sun. Plants absorb the sun's energy in a process
called photosynthesis. When the bonds between adjacent carbon, hydrogen and oxygen molecules are broken by
digestion, combustion, or decomposition, these substances release their stored, chemical energy. Biomass has
always been a major source of energy for mankind and is presently estimated to contribute of the order 10– 14% of
the world’s energy supply. Biomass can be burned directly or converted to liquid biofuels or biogas that can be burned
as fuels.
Examples of biomass and their uses for energy:
 Wood and wood processing wastes—burned to heat buildings, to produce process heat in industry, and to
generate electricity
 Agricultural crops and waste materials—burned as a fuel or converted to liquid biofuels
 Food, yard, and wood waste in garbage—burned to generate electricity in power plants or converted to biogas
in landfills
 Animal manure and human sewage—converted to biogas, which can be burned as a fuel
Biomass occurs in many different forms with widely varying chemical compositions. Biomass can be readily converted
into solid, liquid, and gaseous fuel products. For example, wood is typically chopped into chunks, chipped for easier
handling, or pelletized for pumping.
Biomass can be pyrolyzed into bio-oil liquid fuel as a major product along with the byproducts including solid biochar
and gaseous fuel. Or, biomass can be gasified to generate synthesis gas which is rich in hydrogen. Biomass can also
be burned to generate heat (such as hot water or steam) or to produce electricity (or power). Thus, biomass
combustion can be used in a combined heat and power (CHP) mode. Alternately, some biomass can be co-processed
with other conventional fossil fuels such as lignite coal to generate power.
However, some biomass is too wet to be efficiently burned and instead is fermented to produce liquid fuel such as
bioethanol. In addition, some biomass such as oil crops and microalgae can be processed into biodiesel via both
physical and chemical treatments. Furthermore, bio-oil and bio-syngas can be upgraded for subsequent chemical and
fuel processing as well as for other diverse end uses.

Types of Biomass
Researchers characterize the various types of biomass in different ways but one simple method is to define four main
types, namely;
• Woody plants,
• Herbaceous plants/grasses,
• Aquatic plants,
• Manures.
Within this categorization, herbaceous plants can be further subdivided into those with high- and low-moisture
contents. Apart from specific applications or needs, most commercial activity has been directed towards the lower
moisture-content types, woody plants and herbaceous species. Aquatic plants and manures are intrinsically high-
moisture materials and as such, are more suited to ‘wet’ processing techniques.

Components of Biomass
Biomass contains varying amounts of cellulose, hemicellulose, lignin and a small amount of other extractives. Woody
plant species are typically characterized by slow growth and are composed of tightly bound fibres, giving a hard
external surface, while herbaceous plants are usually perennial, with more loosely bound fibres, indicating a lower
proportion of lignin, which binds together the cellulosic fibres: both materials are examples of polysaccharides; long-
chain natural polymers. The relative proportions of cellulose and lignin is one of the determining factors in identifying
the suitability of plant species for subsequent processing as energy crops.

1. Cellulose: Cellulose is a glucose polymer, consisting of linear chains of (1, 4)-D-glucopyranose units, in which
the units are linked 1–4 in the b-configuration, with an average molecular weight of around 100,000.

2. Hemicellulose: Hemicellulose is a mixture of polysaccharides, composed almost entirely of sugars such as


glucose, mannose, xylose and arabinose and methyl glucuronic and galacturonic acids, with an average
molecular weight of <30,000. In contrast to cellulose, hemicellulose is a heterogeneous branched polysaccharide
that binds tightly, but non-covalently, to the surface of each cellulose micro fibril. Hemicellulose differs from
cellulose, in consisting primarily of xylose and other five-carbon monosaccharides.
3. Lignin: Lignin can be regarded as a group of amorphous, high
molecular-weight, chemically related compounds. The
building blocks of lignin are believed to be a three carbon
chain attached to rings of six carbon atoms, called phenyl-
propanes. These may have zero, one or two methoxyl groups
attached to the rings, giving rise to three structures, termed I,
II and III, respectively. The proportions of each structure
depend on the source of the polymer i.e. structure I is found
in plants such as grasses; structure II in the wood of conifers;
while structure III is found in deciduous wood.

Cellulose is generally the largest fraction, representing about 40–50% of the biomass by weight; the hemicellulose
portion represents 20–40% of the material by weight.
Both woody and herbaceous plant species have specific growing conditions, based on the soil type, soil moisture,
nutrient balances and sunlight, which will determine their suitability and productive growth rates for specific,
geographic locations. Many types of perennial grasses, such as sugarcane and cereals like wheat and maize, have
widely different yields, depending on the growing conditions: thus wheat can be grown in both hot and temperate
climates with a wide range of rainfall, whereas sugarcane can be grown successfully only in warm, moist climatic
conditions.

Properties of Biomass
It is the inherent properties of the biomass source that determines both the choice of conversion process and any
subsequent processing difficulties that may arise. Equally, the choice of biomass source is influenced by the form in
which the energy is required and it is the interplay between these two aspects that enables flexibility to be introduced
into the use of biomass as an energy source.

The main material properties of interest, during subsequent processing as an energy source, relate to:
• Moisture content (intrinsic and extrinsic),
• Calorific value,
• Proportions of fixed carbon and volatiles,
• Ash/residue content,
• Alkali metal content,
• Cellulose/lignin ratio.
For dry biomass conversion processes, the first five properties are of interest, while for wet biomass conversion
processes, the first and last properties are of prime concern.

1. Moisture content
Two forms of moisture content are of interest in biomass:
• Intrinsic moisture: The moisture content of the material without the influence of weather effects,
• Extrinsic moisture: The influence of prevailing weather conditions during harvesting on the overall biomass
moisture content

In practical terms, it is the extrinsic moisture content that is of concern, as the intrinsic moisture content is usually
only achieved, or applicable, under laboratory conditions. Also of importance in respect of the prevailing weather
conditions at the time of harvesting, is the potential contamination of the harvested biomass by soil and other
detritus, which can in turn have a significant deleterious impact on other ‘material’ properties during subsequent
treatment or processing.

2. Calorific value
The calorific value (CV) of a material is an expression of the energy content, or heat value, released when burnt
in air. The CV is usually measured in terms of the energy content per unit mass, or volume; hence MJ/kg for
solids, MJ/l for liquids, or MJ/Nm3 for gases. The CV of a fuel can be expressed in two forms, the gross CV (GCV),
or higher heating value (HHV) and the net CV (NCV), or lower heating value (LHV).The HHV is the total energy
content released when the fuel is burnt in air, including the latent heat contained in the water vapor and therefore
represents the maximum amount of energy potentially recoverable from a given biomass source. The actual
amount of energy recovered will vary with the conversion technology, as will the form of that energy i.e.
combustible gas, oil, steam, etc

3. Proportions of fixed carbon and volatile matter


Fuel analysis has been developed based on solid fuels, such
as coal, which consists of chemical energy stored in two
forms, fixed carbon and volatiles:
• The volatiles content, or volatile matter (VM) of a solid
fuel, is that portion driven-off as a gas (including
moisture) by heating (to 9500C for 7 min)
• The fixed carbon content (FC), is the mass remaining after the releases of volatiles, excluding the ash and
moisture contents.
Laboratory tests are used to determine the VM and FC contents of the biomass fuel. Fuel analysis based upon
the VM content, ash and moisture, with the FC determined by difference, is termed the proximate analysis of a
fuel. Elemental analysis of a fuel, presented as C, N, H, O and S together with the ash content, is termed the
ultimate analysis of a fuel.
The significance of the VM and FC contents is that they provide a measure of the ease with which the biomass
can be ignited and subsequently gasified, or oxidized, depending on how the biomass is to be utilized as an
energy source.

4. Ash/Residue Content
The chemical breakdown of a biomass fuel, by either thermo-chemical or bio-chemical processes, produces a
solid residue. When produced by combustion in air, this solid residue is called ‘ash’ and forms a standard
measurement parameter for solid and liquid fuels. The ash content of biomass affects both the handling and
processing costs of the overall, biomass energy conversion cost. During biochemical conversion, the percentage
of solid residue will be greater than the ash content formed during combustion of the same material.
For a biochemical conversion process, the solid residue represents the quantity of non-biodegradable carbon
present in the biomass. This residue will be greater than the ash content because it represents the recalcitrant
carbon which cannot be degraded further biologically but which could be burnt during thermo-chemical
conversion.
Dependent on the magnitude of the ash content, the available energy of the fuel is reduced proportionately. In a
thermo-chemical conversion process, the chemical composition of the ash can present significant operational
problems. This is especially true for combustion processes, where the ash can react to form a ‘slag’, a liquid
phase formed at elevated temperatures, which can reduce plant throughput and result in increased operating
costs.

5. Alkali metal content


The alkali metal content of biomass i.e. Na, K, Mg, P and Ca, is especially important for any thermo-chemical
conversion processes. The reaction of alkali metals with silica present in the ash produces a sticky, mobile liquid
phase, which can lead to blockages of airways in the furnace and boiler plant. It should be noted that while the
intrinsic silica content of a biomass source may be low, contamination with soil introduced during harvesting can
increase the total silica content significantly, such that while the content of intrinsic silica in the material may not
be a cause for concern, the increased total silica content may lead to operational difficulties.

6. Cellulose/lignin ratio
The proportions of cellulose and lignin in biomass are important only in biochemical conversion processes. The
biodegradability of cellulose is greater than that of lignin, hence the overall conversion of the carbon-containing
plant material present as cellulose is greater than for plants with a higher proportion of lignin, a determining factor
when selecting biomass plant species for biochemical processing.
For the production of ethanol, a biomass feedstock with a high, cellulose/hemi-cellulose content is needed to
provide a high, l/t, and yield. While the lignin content represents a potentially large energy source, current
techniques involving hydrolysis/enzymatic systems cannot convert the lignin to syngas. To illustrate the effect of
cellulose content on yield, up to 280l/t of ethanol can be produced from switchgrass, compared with 205l/t from
wood, an effect largely due to the increased proportion of lignin in wood.
7. Bulk density
An important characteristic of biomass materials is their bulk
density, or volume, both as-produced and as-subsequently
processed. The importance of the as-produced, bulk density is
in relation to transport and storage costs. The density of the
processed product impacts on fuel storage requirements, the
sizing of the materials handling system and how the material is
likely to behave during subsequent thermo-chemical/biological
processing as a fuel/feedstock.

BIOFUELS
Biofuels are fuels that are obtained from organic materials. They include, but are not limited to, wood, straw,
sugarcane residue, animal wastes, landfill gas, biodiesel and ethanol, municipal waste, switchgrass, and a variety of
synthetic gases derived from plant and animal matter. Biofuels are distinct from fossil fuels in that they are, in some
sense, renewable. There are so many biofuels, and they are derived from so many sources, that their description
requires a classification scheme. In fact, biofuels are commonly classified in several ways, three of which are
described here.
The first classification scheme uses three categories:
1. Wood fuels: In addition to fuel wood, the category “wood fuels” include charcoal, which is manufactured by
partially combusting wood in a low-oxygen environment, and black liquor. Black liquor, an energy- rich liquid
derived from wood, is burned by the companies that produce it, in part to obtain the energy needed to continue
manufacturing operations and in part to recover noncombustible materials suspended within it. Wood can also
be used as a feedstock, or raw material, to manufacture a combustible gas through a process called gasification
or to produce ethanol. There is a great deal of interest in both processes. Gaseous and liquid fuels are often
preferred to direct combustion of solid plant matter because they tend to burn more cleanly and can be used in
ways that a solid fuel cannot. Wood fuels are, then, as simple as logs or bark fed directly into a furnace or the
result of sophisticated processing technologies.
2. Agricultural Fuels: Agricultural fuels generally fall into one of two categories: specially grown crops and
agricultural waste. In the specially grown category are fuel crops such as switchgrass, which can be burned
directly to produce heat or, in theory, processed to produce ethanol or a combustible gas. In the agricultural
waste category are animal wastes, corn stoves, which is the part of the plant left behind after the corn kernels
have been harvested, and bagasse, the part of the sugarcane plant remaining after the juice has been removed.
Rice husks, a byproduct of cultivating one of the world’s most widely grown food crops, is another example of
agricultural waste that can be converted to energy.
3. Urban Waste-based Fuels: Urban waste-based fuels consist of various types of municipal wastes, including
construction debris, furniture, yard waste (such as leaves and grass cuttings), old tires, and the methane that is
produced in landfills.

Another useful and common way of classifying biofuels use only two categories, modern and conventional.
 Ethanol, biodiesel, synthetic gas, and black liquor are examples of modern fuels, because they are
manufactured fuels or, in the case of black liquor, the byproduct of a manufacturing process.
 Conventional fuels include unprocessed wood, charcoal, and straw. The use of conventional fuels extends
far back in history, but they remain important.
Many fuels span both the modern and conventional categories, and manure is one of these. In regions where wood
is scarce, some traditional societies continue to burn manure to generate heat. But manure is also a modern fuel
because some farms and feedlots process manure to produce methane gas, which is burned for heat or power
generation.
A third common and useful scheme classifies types of biomass, the raw material from which fuels are created, by the
extent to which the materials have been changed from their original state. This scheme is somewhat similar to the
conventional/modern classification scheme, but uses three categories instead of two. There are
1. Primary resources, which include fuel wood, crop residues such as the stalks and leaves left behind after
harvest, grains such as corn, and specially grown grasses.
2. Secondary resources include manufactured fuels such as ethanol and biodiesel and the byproducts of
manufacturing processes such as black liquor and sawdust.
3. Tertiary resources include the sorts of fuels that would be generated in more urban environments and that
would pose disposal problems were they not burned and converted into energy. Tertiary resources include
construction and demolition debris, municipal wastes, and landfill gases.

Sugarcane Molasses for production of Bioethanol/Biofuel


Molasses, from the Latin word melaceres, meaning honey-like, is a thick dark syrup that is a byproduct of sugar
refining. It results when sugar is crystallized out of sugar cane or sugar beet juice. Sugarcane molasses is a viscous,
dark and sugar-rich by-product of sugar extraction from the sugarcane (Saccharum officinarum L.). It contains about
62% of carbohydrates in the form of 30% un-crystallized sucrose and about 32% of invert sugar which is a mixture of
glucose and fructose. The sugar, which is converted into molasses, is adjusted to 14-16%, which permits an alcohol
content of 8 - 10 volume percentage in the fermented worts. The term ‘molasses’ is applied to the final effluent
obtained in the preparation of sugar by repeated crystallization. The amount of molasses obtained and its quality
(composition) provide information about the nature of the beets (local conditions of growth and effects of the weather)
and the processing in the sugar factory, such as the efficiency of the juice clarification, the method of crystallization
during boiling, and the separation of the sugar crystals from the low-grade massecuite. Sugarcane molasses has
several important roles in livestock feeding, due to the nutritive, appetizing and physical properties of its sugar content.
Molasses is rather difficult to handle because of its viscosity: it is rarely fed directly in its liquid form but instead mixed
to other ingredients. Sugarcane molasses are also used for alcohol (rum or fuel ethanol) production and the distillery
process yields vinasses that can also be used in animal feeding

Ethanol (C2H5OH) known as ethyl alcohol or grain alcohol is a flammable, colorless, mildly toxic chemical compound
with a distinctive perfume–like odour and the ethanol is found in alcoholic beverages. It has been produced and used
in aqueous solutions as an alcoholic beverage for several thousand years. Ethanol also has several industrial
applications and has been used as transportation fuel for more than a century.

Production of Bioethanol from Fermentation of Molasses

(a) Main Reaction


C12H22O11 + H2O ---------------→ 2C6H12O6 (Invertase)
C6H12O6 ---------------→ 2C2H5OH + 2CO2 (Zymase)
ΔH= -31.2 kcal
(b) Side reaction
2 C6H12O6 + H2O ------------→ ROH + R’CHO
Fused oil
 Large volume storage tanks of molasses provide continuous supply of molasses and store the fresh molasses
from sugar processing section during the fermentation process.
 The molasses from the tanks are diluted with water to obtain the sugar concentration around 10-15%.
 The acidic nature of molasses supports the growth of yeast during breaks up of sucrose, for that purpose acids
are added to maintain the pH between 4 and 5. Continuous diluter equipment takes up this task.
 A yeast culture tank, which is provided with nutrition supply of ammonium and magnesium phosphate or sulphate,
is used as nutrient to the yeast.
 The acidic condition favors the yeast to produce catalytic enzymes, invertase and zymase.
 Diluted and treated molasses and the yeast from storage are fed to the fermentation chamber. Modern
fermentation tanks are made with stainless steel material provided with heating coils or jacket provision. The
temperature 20-30 oC is maintained in the tanks by the heating and cooling system. The process of fermentation
takes place around 30-70 hours based on the temperature and sugar concentration to yeast count. Final
temperature 35 oC is attained at the end of the process. During the fermentation process, microorganism yeast
produces carbon dioxide as by-product.
 After the process cycle, the product liquid mixture is fed to beer still to perform distillation.
 Solid and slurry mass is separated leaving the solution of alcohol and water.
 The concentration of alcohol in the liquid mixture would around 8-10%.
 A series of beer still work out to produce different quality of beer products.
 The slurry form of material obtained from bottom of beer still is called as slops. It is used for cattle feed and
fertilizer after some waste treatment operations.
 However, the aldehydes are not allowed in consumable beer so aldehydes present in the solution are removed
by aldehyde column.
 The streams coming out at different section of the column are aldehydes from top, fused oil and ethanol mixture
from middle and bottom stream with water.
 The middle stream is fed to rectification column to produce a product called rectified spirit having 95% ethanol.
 Rectified spirit further made to absolute alcohol by anhydrous still using benzene as third component.
 Absolute alcohol with 100% ethanol concentration is a standard product used as intermediate for producing other
chemical products and blending agent in power fuels.
 The end use of the ethanol would be largely in solvent, acetaldehyde, acetic acid, polyethylene and synthetic
rubber production.
Oils and Fats for production of Biofuels

Oils are organic molecule of carbon, hydrogen, oxygen and sometimes nitrogen and sulfur. It is composed of long
chain fatty acids and esters (glyceride ester) as well as derivative of glycerine, long chain fatty alcohol, sulfate and
sulfonates. Oils like castor oil, linseed oil are non-edible and oils like ground nut oil, coconut oil are edible .The oil
and fat products used for edible purposes can be divided into two distinct classes:

 Liquid oils, such as olive oil, peanut oil, soybean oil, or sunflower oil
 Plastic fats, such as lard, shortening, butter, and margarine.

The physical nature of the fatty material is unimportant for some uses, but the consistency is a matter of
consequence for other products.

Chemically the oil/fats consist of 90–98% triglycerides and small amount of mono and diglycerides. Triglycerides are
esters of three fatty acids and one glycerol. These contain substantial amount of oxygen in their structures. When
three fatty acids are identical, the product is simple triglycerides, when they are dissimilar the product is mixed
triglycerides fatty acids which are fully saturated with hydrogen have no double bonds. Those with one missing
hydrogen molecule have one double bond between carbon atoms and are called mono-saturated. And those with
more than one missing hydrogen have more than one double bond and are called polyunsaturated. Fully saturated
triglycerides lead to excessive carbon deposits in engines. The fatty acids are different in relation to the chain length,
degree of unsaturation or presence of other chemical functions. Chemically, Biodiesel is referred to as the mono-alkyl
esters of long-chain-fatty acids derived from renewable lipid sources. Biodiesel is the name for a variety of ester based
oxygenated fuel from renewable biological sources. It can be used in compression ignition engines with little or no
modifications.

Processing of Oil and Fats

Oil Extraction

Lipid content in an algal cell is about 40% of its total mass, which can be extracted and converted into biodiesel.
However, to extract the oil from algae is a tedious process because of the small size of an algal cell and thickness of
its cell wall. The algal cell wall and cell membrane need to be breached in order to extract this oil. Extraction of oil
from algae can be broadly classified in following ways:

1. Mechanical Method
a. Pressing: This technique is based on the use of high pressure, which is employed to remove cell walls and
cell membranes for the extraction of oil. Pressing dries the algae while still retaining its oil content. The oil can
then be collected from the cells using different types of press arrangements such as a viz, screw, expeller,
piston etc.
b. Bead milling: Bead milling incorporates the agitation of algal biomass in the presence of small steel or glass
beads in a closed vessel. This collision between cells and beads generates high liquid shear gradient, which
helps to breach algal cell walls and allows the extraction of oil. To enhance the fidelity of this method, nowadays
it is coupled with a solvent based extraction method.
c. Ultrasonic based extraction/ Sonication: Sonication is used to create vapor bubbles of a liquid form in a
solvent material that results in cavitation. When these bubbles collapse near algal cells, it results in the
breaching of cell walls.
d. Homogenization: This constitutes rapid pressure drops through an orifi ce generating high shear gradient
and disrupting cell walls.
2. Chemical Method
Chemical based oil extraction methods are based on the use of chemicals for extraction of oil. This method can
be further classified into two parts:
a. Solvent based extraction: Organic solvents such as benzene, ether, hexane, cyclohexane, acetone and
chloroform can be used for oil extraction from an algal biomass by breaching its cell wall. Out of those, hexane
is popularly used for the extraction of oil. Again, this method also requires drying of the algal biomass, which
is an energy intensive process. Combinations of the hexane solvent method with pressing can release about
95% of oil from algae. Concurrent use of solvent extraction with transesterification enhances its efficacy,
involving the direct conversion of triacylglycerides into methyl esters by the addition of alcohol and a catalyst.
b. Supercritical fluid extraction: Carbon dioxide, which acts as a supercritical fluid, works as an organic solvent
when allowed to mix with algal biomass. It penetrates the cell wall and removes oil from algal cell efficiently.
This method does not require any additional organic solvent and hence produces highly purified extracts.
Moreover, supercritical CO2 can be easily removed from the reaction mixture since it is a gas at room
temperature. Also this method helps to maintain algal lipid characteristics at the time of oil extraction since
supercritical CO2 requires low temperatures for reaction. The efficiency of this method is about 100%.
However, the requirement of additional costly instruments reduces its use. Use of supercritical CO2 in
conjunction with methanol modifies its polarity and viscosity, which subsequently enhances solvating power
and ultimately produces a more efficient extraction method.

Processing of Oils

1. Trans-esterification
Extracted oil from algal biomass can be
used to produce biodiesel using a
widely known method of transforming
lipids into biodiesel viz
transesterification. Basically,
transesterification involves the
conversion of an ester form into another by reciprocate implying alkoxy moiety. This reaction is performed by
using a base catalyst that ends by forming an ester product called biodiesel, hence named base catalyzed
transesterification. This process is initiated by providing a suitable temperature to extract oil, followed by the
addition of an alcohol (usually methanol) and a catalyst (usually Sodium ethanolate). The catalyst will
deprotonate methanol and make it suitable for nucleophilic attack on a triglyceride, finally forming biodiesel
(methyl ester) and glycerol as coproduct. Glycerol, being heavier, settles down with soapy material in the
middle while biodiesel remains floating on the top layer.
Transesterification is usually carried out at about 60–66°C, 20 psi pressure. An increase in temperature can
affect the reaction rate since temperature above the boiling point of methanol (680C) vaporizes it, resulting in
the formation of bubbles which ultimately reduces the rate of the reaction.
There are various types of catalysts that can be incorporated into the transesterification process. Viz sodium
hydroxide (NaOH), potassium hydroxide (KOH), sodium methoxide (CH 3ONa), potassium methoxide
(CH3OK) are possible options, each with their own advantages and disadvantages. Furthermore, KOH and
NaOH are also cheap in cost and easy to handle during experiments by workers but KOH and NaOH require
high concentrations (about 0.5%-1.5% of the weight of the oil) in comparison to sodium methoxide (about
0.3%-0.5% of the weight of the oil) for the same yield of biodiesel. Hence, sodium methoxide is used on a
pilot scale, while NaOH or KOH are used on laboratory scale.
Methanol is a frequently used alcohol in transesterification reaction. However, ethanol or butanol can also be
used in this process. Methanol being more accessible, inexpensive and having less steric resistance than
methanol, is mostly used for transesterification reaction. However, ethanol enhances cetane number, can
easily mix with oil compared to methanol and has a renewable source of origin.
During the initial phase of the reaction, there is a requirement of vigorous mixing so that oil and methanol get
evenly mixed with each other, as they are poorly miscible. However, as the process marks the formation of
the product, slight mixing is required to facilitate the settling down of glycerol, so that reactions can continues
in the upper layer of methanol and oil. Another hurdle during the process is the production of emulsion, which
complicates the process of partitioning glycerol and biodiesel. These emulsions are more enduring in the
case of ethanol than in the case of methanol.
One important factor when using alcohol is to use a suitable amount of alcohol since this reaction is reversible;
a high amount of alcohol can shift the reaction equilibrium to the right and can decline productivity.
2. Pyrolysis
Pyrolysis is a combination of two words where pyro specifies “fire” and lysis specifies “breakage”. Pyrolysis
defines the process of using heat to break chemical bonds. Pyrolysis, an alternative tool to relegate viscosity,
works by breaking chemical bonds at a high temperature to produce biodiesel in the absence of air. Extracted
oil is heated to 450–600°C in the absence of air resulting in the crumbling of chemical bonds and the formation
of vapors, gases and char. These vapors undergo the condensation process forming liquid which can be used
as biodiesel after passing through a catalyst viz, zeolites. Pyrolysis is advantageous over transesterification
in following ways:
 Produces a higher yield than transesterification, which is about 70–75%,
 No need to extract oil in the initial steps.
 After the condensation of vapors into liquid and the passage of it over the catalyst, there is no need for
additional washing, drying or distillation.
 Co-products like char and gases can also be reused.
 Char can be used as a fertilizer and gases, being combustible, can be used in the heating step.
 CO2 produced while the fuels are burning in the heating step can be used for other purposes.
However, this method requires high temperatures and vacuum conditions to process biodiesel, which is an
energy intensive step.

3. Hydro processing
Hydro processing, as its name defines, is a technique of processing oil following pyrolysis into fuel or biodiesel
in the presence of hydrogen. The major objective of this process is the removal of oxygen, which is removed
as water. The process is carried out in the presence of a catalyst and the oil obtained is of fuel grade as is
rich in hydrocarbons. During this process glycerol is formed from triacyl glycerides and is transformed into
propane. The alkane mixture obtained in this step is subjected to fractionation. The fractions obtained include
synthetic kerosene jet fuel and hydrogenation derived renewable diesel (HDRD). HDRD has a high cetane
number and can also be obtained from the processing of any other animal or plant derived oil. Also, it is
environmental friendly as it is low in Sulphur content. In January 2009, Continental Airlines tested its
Continental jet 516, a two engine Boeing 737–800 for a two hour flight. One of the Continental jet’s two
engines was powered by 50% of synthetic kerosene obtained from Jatropha and algal oil, and the remaining
50% was from a petroleum based jet fuel
Energy Plantation
Technically speaking, energy plantation means growing select species of trees and shrubs which are
harvestable in a comparably shorter time and are specifically meant for fuel. The fuel wood may be used either
directly in wood burning stoves and boilers or processed into methanol, ethanol and producer gas. These
plantations help provide wood either for cooking in homes or for industrial use, so as to satisfy local energy
needs in a decentralized manner. The energy plantations provide almost inexhaustible renewable sources (with
total time constant of 3-8 years only for each cycle) of energy which are essentially local and independent of
unreliable and finite sources of fuel . The attractive features of energy plantations are:
 Heat content of wood is similar to that of Indian coal,
 Wood is low in Sulphur and not likely to pollute the atmosphere,
 Ash from burnt wood is a valuable fertilizer,
 Utilization of erosion prone land for raising these plantations helps to reduce wind and water erosion, thereby
minimizing hazards from floods, siltation, and loss of nitrogen and minerals from soil
 Help in rural employment generation - it is estimated that a hectare of energy plantation is estimated to
provide employment for at least seven persons regularly.
Selection of multipurpose species provides a number of by-products like oils, organic compounds, fruits, edible
leaves, forage for livestock, etc.

Woody Biomass
Biomass, in its simplest form, is defined as organic matter renewable over time. Woody biomass is the accumulated
mass, above and below ground, of the roots, wood, bark, and leaves of living and dead woody shrubs and trees.
Woody biomass is primarily comprised of carbohydrates and lignin produced through the photosynthetic process.
Woody biomass can be used for generating electricity, producing biofuels, and making biochemical such as
adhesives, solvents, plastics, inks, and lubricants. Rising fuel costs, uncertainty about energy supplies, dependence
on foreign energy sources, and concern about global climate change and air quality make renewable natural energy
alternatives more attractive, such as that produced from woody biomass.

Preprocessing, Drying and Storage of Woody Biomass


Pre-processing and drying woody biomass are important issues to address in every situation. They particularly
affect transportation costs and combustion efficiency at the end-use location. Both should address four critical
characteristics of biomass: particle size, moisture content, grit contamination, and wood quality. Woody biomass
is typically pre-processed during or after a timber harvest operation and may be dried after a harvest but before
transport to facilitate efficient transport, material handling, and utilization. While there are a number of woody
biomass pre-processing and drying method options, optimum treatment of the biomass depends on the
characteristics of the material, the end-use, and site management requirements. This fact sheet provides a brief
description of the various pre-processing and drying technologies. It also discusses advantages and
disadvantages of each technology.

Pre-processing
Comminution. The most common woody biomass pre-processing operation is comminution by chipper, grinder or
shredder. The choice and location of a comminution device in the woody biomass fuel supply chain are among the
most important components of a processing supply system for woody biomass. Factors affecting comminution
choices include customer requirements for the raw material, total woody biomass volume, forest stand
characteristics and nature of the road network, accessibility and equipment at the end-user reception facility, and
feasibility of creating terminals for efficient handling and storage without incurring excessive additional haul
distances.
1. Chippers. Chippers cut woody material with a slicing action. They make up most of the woody biomass size-
reduction equipment in use today and are characterized by high output, high-speed cutting knives. Most
chippers have the capacity to blow chips into transport trailers for hauling. They rely on sharp knives and,
unfortunately, are susceptible to knife wear from high soil content, metal contamination, rocks, and stone.
Chippers are well integrated into existing timber harvesting systems.
2. Grinders. Grinders reduce woody biomass particles in size by repeatedly pounding them into smaller pieces
through a combination of tensile, shear and compressive forces. Most are derivatives of hammer mills and
include horizontal feed grinders. Grinders accept a wider range of piece sizes. They will even accept short,
non-oriented pieces including stumps, tops, brush, and large forked branches. Grinders rely on hitting a piece
of wood often enough to finally break it into the desired size, usually with high speed rotating hammers. They
require more energy than chippers per ton of output. Additionally, excessive soil contamination can increase
internal wear.
3. Shredders. Shredders are slow-speed rip/ shear devices, used widely in comminuting trees removed at
residential and commercial construction sites. Material is pinched between rotating devices and ripped apart
or sheared. Shredders are used where significant contamination is evident because the internal parts are slow
moving. It avoids damage due to metal, rock, or concrete. They are not widely used in woody biomass
operations because their capital cost is high and the particle size is larger and less uniform than a chipper can
achieve. Material from shredders may require further size reduction if used as a biomass product.
4. Bundler and Composite Residue Log (CRL) Operations. Bundlers collect, compress, and bind forest
residues into cylindrical bundles about 2 feet in diameter and 10 feet long (Image 5). This simplifies handling
forest residues by compacting loose slash into a form that resembles a log. The bundling process enables
forest residues to be shipped to conversion centers for more efficient size reduction. Woody residue material
needs to be properly deposited on the ground to allow efficient bundling. While forest residue bundling is an
attractive alternative, it is not currently cost effective.

Drying
After felling, the moisture content found in woody biomass depends largely on post-harvest handling and storage
conditions. Moisture may be lost by transpiration drying, through foliage or open wood surfaces. The rate of woody
biomass drying depends on many factors, including ambient temperature, relative humidity, wind speed, season,
rainfall pattern, tree species, and tree size. In the South, the best season for drying is usually the summer.
Transpiration drying, also known as “leaf seasoning” and “biological drying,” occurs when felled trees are left for
several weeks with the tops, branches, and leaves intact. The foliage continues to pull water out of the bole through
transpiration until it dies and falls completely off the tree. Such drying can be successful with most tree species.
Excessive precipitation or low temperatures may hinder the efficiency of transpiration drying, if on-site storage is
extended to late fall or even until winter in temperate countries. Additionally, there are added costs in allowing woody
biomass to dry before processing. Capital is tied up in the drying material. Moving equipment to the site is expensive
to collect, pre-process, and transport the woody biomass.
An additional step to facilitate faster woody biomass drying is the use of a prototype roller crusher. The machine
crushes smaller diameter stems and facilitates drying by opening the biomass to the transpiration drying effect. This
step is costly financially. Additionally, crushing introduces a significant amount of dirt into woody biomass, which can
affect pre-processing and conversion

Storage

Sufficient storage for biomass is necessary to accommodate seasonality of production and ensure regular supply to
the biomass utilization plant. The type of storage will depend on the properties of the biomass, especially moisture
content. For high moisture biomass intended to be used wet, such as in fermentation and anaerobic digestion
systems, wet storage systems can be used, with storage times closely controlled to avoid excessive degradation of
feedstock. Storage systems typically used with dry agricultural residues should be protected against spontaneous
combustion and excess decomposition, and the maximum storage moisture depends on the type of storage
employed.

Moisture limits must be observed to avoid spontaneous combustion and the emission of regulated compounds. Cost
of storage is important to the overall feasibility of the biomass enterprise. In some cases, the storage can be on the
same site as the source of the feedstock. In others, necessary volumes can only be achieved by combining the
feedstock from a number of relatively close sources. Typically, delivery within about 50 miles is economic, but longer
range transport is sometimes acceptable, especially when disposal fees can be reduced.

Agricultural residues such as wheat straw, rice husk, rice straw and corn stover are usually spread or windrowed
behind the grain harvesters for later baling. Typically these residues are left in the field to air dry to moisture levels
below about 14% preferred for bales in stacks or large piles of loose material. After collection, biomass may be stored
in the open or protected from the elements by tarps or various structures. Pelletizing may be employed to increase
bulk density and reduce storage and transport volume and cost.
Biomass Storage Options

 Feedstock is hauled directly to the plant with no storage at the production site.
 Feedstock is stored at the production site and then transported to the plant as needed.
 Feedstock is stored at a collective storage facility and then transported to the plant from the intermediate
storage location.

Biomass Storage Systems

The type of storage system used at the production site, intermediate site, or plant can greatly affect the cost and
the quality of the fuel. The most expensive storage systems, no doubt, are the most efficient in terms of maintaining
the high fuel quality. Typical storage systems, ranked from highest cost to lowest cost, include:
 Enclosed structure with crushed rock floor
 Open structure with crushed rock floor
 Reusable tarp on crushed rock
 Outside unprotected on crushed rock
 Outside unprotected on ground
 Subterranean

The storage of biomass is often necessary due to its seasonal production versus the need to produce energy all year
round. Therefore to provide a constant and regular supply of fuel for the plant requires either storage or multi-
feedstocks to be used, both of which tend to add cost to the system. Reducing the cost of handling and stable storage
of biomass feedstocks are both critical to developing a sustainable infrastructure capable of supplying large quantities
of biomass to biomass processing plants. Storage and handling of biomass fuels is expensive and increases with
capacity. The most suitable type of fuel store for solid biomass fuel depends on space available and the physical
characteristics of the fuel.

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