OBJECTIVE
❖ To investigate the different
methods of production of
biodiesel from waste and
jatropha
Introduction
1)Biodiesel production is the process of producing
the biofuel, biodiesel, through the chemical
reactions of transesterification and esterification. This
involves vegetable or animal fats and oils being reacted with
short-chain alcohols (typically methanol or ethanol). The
alcohols used should be of low molecular weight. Ethanol is the
most used because of its low cost, however, greater conversions
into biodiesel can be reached using methanol. Although the
transesterification reaction can be catalyzed by either acids or
bases, the base-catalyzed reaction is more common. This path
has lower reaction times and catalyst cost than those acid
catalysis. However, alkaline catalysis has the disadvantage of
high sensitivity to both water and free fatty acids present in the
oils.
2)Biofuel development in India centres mainly around the
cultivation and processing of Jatropha plant seeds which are
very rich in oil (40%). The drivers for this are historic, functional,
economic, environmental, moral and political. Jatropha oil has
been used in India for several decades as biodiesel for the
diesel fuel requirements of remote rural and forest
communities; jatropha oil can be used directly after extraction
(i.e. without refining) in diesel generators and engines. Jatropha
has the potential to provide economic benefits at the local level
since under suitable management it has the potential to grow
in dry marginal non-agricultural lands, thereby allowing
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villagers and farmers to leverage non-farm land for income
generation.
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What is biodiesel ?
Biodiesel is an alternative fuel similar to conventional or
fossil diesel. Biodiesel can be produced from straight
vegetable oil, animal oil/fats, tallow and waste cooking
oil. The process used to convert these oils to Biodiesel is
called transesterification. The largest possible source of
suitable oil comes from oil crops such as rapeseed, palm
or soybean. In the UK rapeseed represents the greatest
potential for biodiesel production. Most biodiesel
produced at present is produced from waste vegetable
oil sourced from restaurants, chip shops, industrial food
producers such as Birdseye etc. Though oil straight from
the agricultural industry represents the greatest
potential source it is not being produced commercially
simply because the raw oil is too expensive. After the
cost of converting it to biodiesel has been added on it is
simply too expensive to complete with fossil diesel.
Waste vegetable oil can often be sourced for free or
sourced already treated for a small price. (The waste oil
must be treated before conversion to biodiesel to
remove impurities). The result is biodiesel produced
from waste vegetable oil can compete with fossil diesel.
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Process
The major steps required to synthesize biodiesel are as follows:
Common feedstock used in biodiesel production include yellow
grease (recycled vegetable oil), "virgin" vegetable oil, and tallow.
Recycled oil is processed to remove impurities from cooking, storage,
and handling, such as dirt, charred food, and water. Virgin oils are
refined, but not to a food-grade level. Degumming to
remove phospholipids and other plant matter is common, though
refinement processes vary. Water is removed because its presence
during base-catalyzed transesterification results in
the saponification (hydrolysis) of the triglycerides,
producing soap instead of biodiesel.
A sample of the cleaned feedstock is then tested via titration against a
standardized base solution, to determine the concentration of free fatty
acids present in the vegetable oil sample.] The acids are then either
removed (typically through neutralization), or are esterified to produce
biodiesel] (or glycerides]).
➢ Reactions
Base-catalyzed transesterification reacts lipids (fats and oils) with alcohol
(typically methanol or ethanol) to produce biodiesel and an impure
coproduct, glycerol. If the feedstock oil is used or has a high acid
content, acid-catalyzed esterification can be used to react fatty acids with
alcohol to produce biodiesel. Other methods, such as fixed-bed reactors,
supercritical reactors, and ultrasonic reactors, forgo or decrease the use
of chemical reaction that reduces the quality of substance in chemistry.
➢ Product purification
Products of the reaction include not only biodiesel, but also the
byproducts soap, glycerol, excess alcohol, and trace amounts of [Link]
of these byproducts must be removed to meet the standards, but the
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order of removal is process-dependent. The density of glycerol is greater
than that of biodiesel, and this property difference is exploited to
separate the bulk of the glycerol coproduct. Residual methanol is
typically recovered by distillation and reused. Soaps can be removed or
converted into acids. Residual water is also removed from the fuel
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Reactions
➢ Transesterification
Animal and plant fats and oils are composed of triglycerides, which
are esters formed by the reactions of three free fatty acids and the
trihydric alcohol, glycerol. In the transesterification process, the added
alcohol (commonly, methanol or ethanol) is deprotonated with a base to
make it a stronger nucleophile. As can be seen, the reaction has no other
inputs than the triglyceride and the alcohol. Under normal conditions,
this reaction will proceed either exceedingly slowly or not at all, so heat,
as well as catalysts (acid and/or base) are used to speed the reaction. It is
important to note that the acid or base are not consumed by the
transesterification reaction, thus they are not reactants, but catalysts.
Common catalysts for transesterification include sodium
hydroxide, potassium hydroxide, and sodium methoxide.
Almost all biodiesel is produced from virgin vegetable oils using the
base-catalyzed technique as it is the most economical process for
treating virgin vegetable oils, requiring only low temperatures and
pressures and producing over 98% conversion yield (provided the
starting oil is low in moisture and free fatty acids). However, biodiesel
produced from other sources or by other methods may require acid
catalysis, which is much slower. Since it is the predominant method for
commercial-scale production, only the base-catalyzed transesterification
process will be described
Triglycerides (1) are reacted with an alcohol such as ethanol (2) to give
ethyl esters of fatty acids (3) and glycerol (4):
R1, R2, R3 : Alkyl group
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The alcohol reacts with the fatty acids to form the mono-alkyl ester
(biodiesel) and crude glycerol. The reaction between the biolipid (fat or
oil) and the alcohol is a reversible reaction so excess alcohol must be
added to ensure complete conversion.
➢ Base-catalysed transesterification mechanism
The transesterification reaction is base catalyzed. Any strong base
capable of deprotonating the alcohol will work (e.g. NaOH, KOH, sodium
methoxide, etc.), but the sodium and potassium hydroxides are often
chosen for their cost. The presence of water causes undesirable
base hydrolysis, so the reaction must be kept dry.
In the transesterification mechanism, the carbonyl carbon of the starting
ester (RCOOR1) undergoes nucleophilic attack by the incoming alkoxide
(R2O−) to give a tetrahedral intermediate, which either reverts to the
starting material, or proceeds to the transesterified product (RCOOR 2).
The various species exist in equilibrium, and the product distribution
depends on the relative energies of the reactant and product.
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Methods
[Link] process
An alternative, catalyst-free method for transesterification
uses supercritical methanol at high temperatures and pressures
in a continuous process. In the supercritical state, the oil and
methanol are in a single phase, and reaction occurs
spontaneously and rapidly. The process can tolerate water in
the feedstock, free fatty acids are converted to methyl esters
instead of soap, so a wide variety of feedstocks can be used.
Also the catalyst removal step is eliminated. High temperatures
and pressures are required, but energy costs of production are
similar or less than catalytic production routes.
[Link]- and high-shear in-line and batch reactors
Ultra- and High Shear in-line or batch reactors allow production
of biodiesel continuously, semi- continuously, and in batch-
mode. This drastically reduces production time and increases
production volume.
The reaction takes place in the high-energetic shear zone of the
Ultra- and High Shear mixer by reducing the droplet size of the
immiscible liquids such as oil or fats and methanol. Therefore,
the smaller the droplet size the larger the surface area the faster
the catalyst can react.
[Link] reactor method
In the ultrasonic reactor method, the ultrasonic waves cause the
reaction mixture to produce and collapse bubbles constantly;
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this cavitation simultaneously provides the mixing and heating
required to carry out the transesterification process. ] Use of an
ultrasonic reactor for biodiesel production can drastically
reduce reaction time and temperatures, and energy
input.] Using such reactors, the process of transesterification
can run inline rather than using the time-consuming batch
processing.] Industrial scale ultrasonic devices allow for
processing of several thousand barrels per day.]
[Link]-catalyzed method
Large amounts of research have focused recently on the use of
enzymes as a catalyst for the transesterification. Researchers
have found that very good yields could be obtained from crude
and used oils using lipases. The use of lipases makes the
reaction less sensitive to high free fatty-acid content, which is a
problem with the standard biodiesel process. One problem with
the lipase reaction is that methanol cannot be used because it
inactivates the lipase catalyst after one batch. However, if
methyl acetate is used instead of methanol, the lipase is not in-
activated and can be used for several batches, making the
lipase system much more cost-effective.
[Link] fatty acids from anaerobic digestion of waste
streams
Lipids have been drawing considerable attention as a substrate
for biodiesel production owing to its sustainability, non-toxicity
and energy efficient properties. However, due to cost reasons,
attention must be focused on the non-edible sources of lipids,
in particular oleaginous microorganisms. Such microbes have
the ability to assimilate the carbon sources from a medium and
convert the carbon into lipid storage materials. The lipids
accumulated by these oleaginous cells can then be
transesterified to form biodiesel.
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Conclusion
Some factors should be consider in the production of biodiesel
such as cost, property, production methodology, required
equipment, etc., will transesterification process will give a better
fuel quality and yield efficiency , it also does not require any
complicated special equipment. The glycerol will obtain as a by-
product of a process. It can be used for some other required
applications which will reduce the overall production cost .
Because of the above reasons the transesterification process
can be the better biodiesel production process than others.
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References
• [Link]
• [Link]
• [Link]
• [Link]
• [Link]
• [Link]
• [Link]
• [Link]
• NCERT textbook
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