Chapter 5

Biodiesel from Triglycerides

via Transesterification

5.1 Biodiesel from Triglycerides via Transesterification

The possibility of using vegetable oils as fuel has been recognized since the
beginning of diesel engines. Vegetable oil has too high a viscosity for use in most
existing diesel engines as a straight replacement fuel oil. There are a number of
ways to reduce vegetable oils’ viscosity. Dilution, microemulsification, pyrolysis,
and transesterification are the four techniques applied to solve the problems
encountered with high fuel viscosity. One of the most common methods used to
reduce oil viscosity in the biodiesel industry is called transesterification. Chemical
conversion of the oil into its corresponding fatty ester is called transesterification
(Bala, 2005).
Transesterification (also called alcoholysis) is the reaction of a fat or oil
triglyceride with an alcohol to form esters and glycerol. Figure 5.1 shows the
transesterification reaction of triglycerides. A catalyst is usually used to improve
the reaction rate and yield. Because the reaction is reversible, excess alcohol is
used to shift the equilibrium to the product side.
Figure 5.2 shows enzymatic biodiesel production by interesterification with
methyl acetate in the presence of lipase enzyme as catalyst.
The biodiesel reaction requires a catalyst such as sodium hydroxide to split the
oil molecules and an alcohol (methanol or ethanol) to combine with the separated

Fig. 5.1 Transesterification of triglycerides with alcohol

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122 5 Biodiesel from Triglycerides via Transesterification

Fig. 5.2 Enzymatic biodiesel production by interesterification with methyl acetate

esters. The main byproduct is glycerine. The process reduces the viscosity of the
end product. Transesterification is widely used to reduce vegetable oil viscosity
(Pinto et al., 2005). Biodiesel is a renewable fuel source. It can be produced from
oil from plants or from animal fats that are byproducts in meat processing.
One popular process for producing biodiesel from fats/oils is transesterification
of triglyceride by methanol (methanolysis) to make methyl esters of straight-chain
fatty acids. The purpose of the transesterification process is to lower the viscosity
of oil. The transesterification reaction proceeds well in the presence of some ho-
mogeneous catalysts such as potassium hydroxide (KOH) and sodium hydroxide
(NaOH) and sulfuric acid or heterogeneous catalysts such as metal oxides or
carbonates. Sodium hydroxide is very well accepted and widely used because of
its low cost and high product yield (Demirbas, 2003).
Transesterification is the general term used to describe the important class of
organic reactions where one ester is transformed into another through interchange
of the alkoxy moiety. When the original ester is reacted with an alcohol, the trans-
esterification process is called alcoholysis. In this text, the term transesterification
will be used as a synonym of alcoholysis of carboxylic esters, in agreement with
most publications in this field. Transesterification is an equilibrium reaction and
the transformation occurs essentially by mixing the reactants. However, the pre-
sence of a catalyst accelerates considerably the adjustment of the equilibrium. To
achieve a high yield of the ester, the alcohol has to be used in excess. Trans-
esterification is the process of exchanging the alkoxy group of an ester compound
by another alcohol. These reactions are often catalyzed by the addition of a base
and acid. Bases can catalyze the reaction by removing a proton from the alcohol,
thus making it more reactive, while acids can catalyze the reaction by donating
a proton to the carbonyl group, thus making it more reactive (Schuchardt et al.,
1998). The transesterification reaction proceeds with a catalyst or without any
catalyst by using primary or secondary monohydric aliphatic alcohols having one
to eight carbon atoms as follows:
Triglycerides + Monohydric alcohol ' Glycerine + Monoalkyl esters
One of the first uses of transesterified vegetable oil (biodiesel) was for
powering heavy-duty vehicles in South Africa before World War II. The name
“biodiesel” has been given to transesterified vegetable oil to describe its use as
a diesel fuel (Demirbas, 2002).
The physical properties of the primary chemical products of transesterification
are given in Table 5.1. The high viscosity of vegetable oils was the cause of severe