Bio-energy Systems: Design and Applications

Lesson-13
Trans-Esterification of Biodiesel Production

Content
Content
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 Bio-energy Systems: Design and Applications

Course Name Bio-energy Systems: Design and Applications

Lesson 13
Trans-Esterification of Biodiesel Production
Content Creator Name Er. Tilakkumar V. Chavda

University/College Name Navsari Agricultural University, Navsari

Course Reviewer Name Dr. Sandip Hanumansingh Sengar

University/college Name Navsari Agricultural University, Navsari

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Objectives of the Lecture

 To get the knowledge of bio fuel production process
Transesterification
 Transesterification methods
 Biodiesel production from Jatropha
E-Lecture
1. Transesterification
Transesterification is a chemical reaction used for the conversion of
triglycerides (fats) contained in oils, (Feed stocks) into usable
biodiesel. Biodiesel produced by the process of trans-esterification
has a much lower viscosity, making it capable of replacing petroleum
diesel in diesel engines.
Biodiesel is commonly produced by the trans-esterification of the
vegetable oil or animal fat feedstock. The process involves reacting
vegetable oils or animal fats catalytically with a short-chain aliphatic
alcohol (typically methanol or ethanol). During trans-esterification,
long chains of triglycerides transform to monoesters and glycerol.

The biodiesel production method applied worldwide at industrial level

is the alcoholysis (trans-esterification) of triglycerides which are the
main component of vegetable oils and animal fats. The most common

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type of esters is methyl esters, mainly because methanol is usually the

cheapest alcohol.
When methanol is the alcohol used in the trans-esterification process,
the product of the reaction is a mixture of methyl esters; similarly, if
ethanol were used, the reaction product would be a mixture of ethyl
esters. In both cases, glycerine will be the co-product of the reaction.
For every 1 tonne of biodiesel production, around 100 kg of glycerol
are produced as a by product.
The overall trans-esterification process is a sequence of three
consecutive and reversible reactions, in which di and monoglycerides
are formed as intermediates, yielding one ester molecule in each step.
The stoichiometric reaction requires 1 mole of a triglyceride and 3
moles of the alcohol. However, excess amount of alcohol is used to
increase the yields of the alkyl esters by shifting the equilibrium
towards the formation of esters and to allow its phase separation from
the glycerol formed as a by-product. The product of trans-
esterification process is known as “biodiesel”.
There are several methods for carrying out this trans-esterification
reaction including the common batch process, supercritical processes,
ultrasonic methods, and even microwave methods. According to the
catalyst used, trans-esterification can be basic, acidic or enzymatic.
Basic: Most frequently used at all production scales.
Acid: Less frequent in industrial production, sometimes used a first
stage with highly acidic raw materials.
Enzymatic: Less used; the enzymes are usually lipases.
1.1 Different Transesterification methods
1.1.1 Batch process
In batch process specific amount of raw material (i.e. oil or animal fat)
is taken, then below mention step is followed step by step.

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1) Preparation: care must be taken to monitor the amount of water

and free fatty acids in the incoming oil or fat. If the free fatty acid
level or water level is too high, it may cause problems with soap
formation and the separation of the glycerine by-product
downstream.
2) Catalyst is dissolved in the alcohol using a standard agitator or
mixer.
3) The alcohol/catalyst mix is then charged into a closed reaction
vessel and the oil or fat is added. The system from here onward is
totally closed to the atmosphere to prevent the loss of alcohol.
4) The reaction mix is kept just above the boiling point of the alcohol
(around 70 °C) to speed up the reaction. Some systems
recommend the reaction take place anywhere from room
temperature to 55 °C for safety reasons. Reaction time varies from
1 to 8 hours for compete this process; under normal conditions the
reaction rate will double with every 10°C increase in reaction
temperature up to certain limit. Excess alcohol is normally used to
ensure total conversion of the fat or oil to its esters.
5) The glycerine is much denser than biodiesel. Both are separated
by gravity separated method with glycerine simply drawn off the
bottom of the settling vessel due to denser. In some cases, a
centrifuge is used to separate the two materials at a faster rate.
6) Once the glycerine and biodiesel have been separated, the excess
alcohol in each phase is removed with a flash evaporation process
or by distillation. Care must be taken to ensure no water
accumulates in the recovered alcohol stream.
7) The by-product (i.e., glycerine) contains unused catalyst and soaps
that are neutralized with an acid and sent to storage as crude
glycerine.

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8) Once separated from the glycerine, the biodiesel is sometimes

purified by washing gently with warm water to remove residual
catalyst or soaps, dried and sent to storage.

1.1.2 Supercritical process

It is a catalyst-free method and continuous process. In this method,
trans-esterification process uses supercritical methanol at high
temperatures and pressures.
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.
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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.
1.1.3 Ultra- 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 method drastically reduces production time and increases
production volume. Ultra – Shear, up to three sets of rotor and stator
which converts mechanical energy to high tip speed, high shear stress,
high shear-frequencies.
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.
Ultra- and High Shear mixers are used for the pre-treatment of crude
vegetable oil or animal fats such as:
o The dispersion of citric/phosphoric acid and crude oil within the
de-gumming process to remove Phosphatides (Gums)
o The dispersion of caustic and de-gummed oil within the
neutralization process to remove FFA (Free Fatty Acid)
1.1.4 Ultrasonic-reactor method
In the ultrasonic reactor method, the ultrasonic waves cause the
reaction mixture to produce and collapse bubbles constantly.
This cavitation provides simultaneously the mixing and heating
required to carry out the trans-esterification process.
The ultrasonic reactor method for biodiesel production drastically
reduces the reaction time, reaction temperatures, and energy input.

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Industrial scale ultrasonic devices allow for the industrial scale

processing of several thousand barrels per day.
Ultrasound can promote homogenization between the reagents
through acoustic cavitation. Acoustic cavitation is the growth and
violent collapse of cavitations bubbles, which, when exploded,
generate an increase in temperature in the reaction medium. This
phenomenon is able to increase the speed of the reaction, reduce the
amount of catalyst and reduce the reaction time from hours to
minutes.
In most of the cases, the reactions use simple ultrasonic baths or
ultrasonic probes operating in the frequency range between 20 and
50 kHz and high output power (typically over 200 W).
1.1.5 Microwave method
Current research is being directed into using commercial microwave
ovens to provide the heat needed in the trans-esterification process.
The microwaves provide intense localized heating that may be higher
than the recorded temperature of the reaction vessel.
A continuous flow process producing 6 liters/minute at a 99%
conversion rate has been developed and shown to consume only one-
fourth of the energy required in the batch process. Although it is still
in the lab-scale, development stage, the microwave method holds
great potential to be an efficient and cost-competitive method for
commercial-scale biodiesel production.
Here one example is given for production of biodiesel from non edible
oil. Similarly different feed stocks are available for ethanol production
such as, sugar feed stock i.e., sugarcane and sugar beet; starch feed
stock i.e., cereal grains and potato and cellulose feed stock i.e., forest
products and agricultural residues.
2. Biodiesel production from Jatropha curcas

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Process flow chart for Biodiesel production from Jatropha curcas

Among the various vegetable oil sources, non-edible oils are suitable
for biodiesel production. Because edible oils are already in demand
and too expensive than diesel fuel. Among the non-edible oil sources,
Jatropha curcas is identified as potential biodiesel source and
comparing with other sources, which has added advantages as rapid
growth, higher seed productivity, suitable for tropical and subtropical
regions of the world. The Jatropha plant can give seed yield ranges
from 7.5 to 12 tonnes per hectare per year, after five years of growth.

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The oil content of whole Jatropha seed is 30-35 % by weight basis.

Preparation of bio diesel from Jatropha requires a two-step approach;
the extraction of the Jatropha oils from the seed, and the conversion
of the extracted oil to Biodiesel, according to the following trans-
esterification reaction.

References
 Ramesh, D., Samapathrajan, A. and Venkatachalam, P. 2002.
Production of biodiesel from jatropha curcas oil by using pilot biodiesel
plant. Agrl. Engg. College & Research Institute, TNAU, Coimbtur.
 Kothari, D. P., et.al. 2016. Renewable Energy Sources and Emerging
Technologies. PHI learning Private limited, New Delhi.
 Kumar, S. 2017. Renewable Energy. Kalyani Publisher, New Delhi.

Rai, G. D. 2008. Non-Conventional Energy Sources. Khanna Publishers