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CHAPTER 4

BIODIESEL PRODUCTION PROCESS

4.1 INTRODUCTION

Straight vegetable oils used in engine lead to various problems like

fuel filter clogging, poor atomization and incomplete combustion because of
high viscosity, high density and poor non-volatility. Transformation of
vegetable oils into biodiesel can be realized using four technologies:
(i) Heating/pyrolysis, (ii) dilution/blending, (iii) micro-emulsion, and (iv)
transesterification. Among all these techniques, the transesterification is an
extensive, convenient and the most promising method for the reduction of
viscosity, density and other properties of the straight vegetable oils. However,
this adds extra cost of processing because of the transesterification reaction
involving chemical and process heat inputs (Barnwal and Sharma 2005; Bari
et al. 2002).

4.2 METHOD OF BIODIESEL PRODUCTION

There are so many investigations on biodiesel production of non-

conventional feedstock of oils and have reached a faster pace in the last few
years. An adaptation of the vegetable oil as a CI engine fuel can be done by
four methods (1) Pyrolysis; (2) micro-emulsification; (3) dilution; and (4)
transesterification.
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4.2.1 Pyrolysis

The pyrolysis refers to a chemical change caused by the application

of thermal energy in the absence of air or nitrogen. The liquid fractions of the
thermally decomposed vegetable oils are likely to approach diesel fuels. The
pyrolyzate has a lower viscosity, flash point, and pour point than diesel fuel
and equivalent calorific values. The cetane number of the pyrolyzate is lower.
The pyrolyzed vegetable oils contain acceptable amounts of sulfur, water and
sediments and give acceptable copper corrosion values but unacceptable ash,
carbon residual and pour point. Depending on the operating conditions, the
pyrolysis process can be divided into three subclasses: conventional pyrolysis,
fast pyrolysis and flash pyrolysis.

4.2.2 Micro-emulsification

The formation of micro emulsion is one of the potential solutions

for solving the problem of vegetable oil viscosity. Micro-emulsions are
defined as transparent, thermodynamically stable colloidal dispersion. The
droplet diameters in micro-emulsions range from 100 to 1000 Å. Micro-
emulsion can be made of vegetable oils with an ester and dispersant (co
solvent), or of vegetable oils, and alcohol and a surfactant and a cetane
improver, with or without diesel fuels. All micro-emulsions with butanol,
hexanol and octanol met the maximum viscosity requirement for diesel fuel.
The 2-octanol was found to be an effective amphiphile in the micellar
solubilization of methanol in triolein and soybean oil.

4.2.3 Dilution

The dilution of vegetable oils can be accomplished with such

material as diesel fuels, solvent or ethanol. Dilution results in the reduction of
viscosity and density of vegetable oils. The addition of 4% ethanol to diesel
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fuel increases the brake thermal efficiency, brake torque and brake power,
while decreasing the brake specific fuel consumption. Since the boiling point
of ethanol is less than that of diesel fuel, it could assist the development of the
combustion process through an unburned blend spray.

4.2.4 Transesterification

Transesterification is the method of biodiesel production from oils

and fats and can be carried out by two ways.

(a) Catalytic Transesterification.

(b) Supercritical Methanol Transesterification.

4.2.4.1 Catalytic Transesterification

The “Catalytic Transesterification” process is the reaction of a

triglyceride (fat/oil) with an alcohol in the presence of some catalyst to form
esters and glycerol which is shown in Fig. 4.1. A triglyceride has a glycerin
molecule as its base with three long chain fatty acids attached. The
characteristics of the oil/fat are determined by the nature of the fatty acids
attached to the glycerin. The nature of the fatty acids can in turn affect the
characteristics of the biodiesel.

Figure 4.1 The products of the reaction of biodiesel

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A successful transesterification reaction is signified by the

separations of the ester and glycerol layer after the reaction time. The heavier,
co-product, glycerol settles out and may be sold as it is or it may be purified
for use in other industries, e.g. the pharmaceutical, cosmetics etc.

4.2.4.2 Acid Catalyzed Transesterification

The acid catalyzed process is the reaction of a triglyceride (fat/oil)

with an alcohol in the presence of acid catalyst, preferably sulphonic and
sulphuric acids to form esters (biodiesel) and glycerol. These catalysts give
very high yields in alkyl esters, but the reactions are slow, requiring, typically,
temperatures above 100°C. The acid-catalyzed transesterification should be
carried out in the absence of water, in order to avoid the competitive
formation of carboxylic acids which reduce the yields of alkyl esters.

4.2.4.3 Alkaline Catalyzed Transesterification

The alkaline catalyzed transesterification process is the reaction of

a triglyceride (fat/oil) with an alcohol in the presence of an alkaline catalyst
such as alkaline metal alkoxides and hydroxides as well as sodium or
potassium carbonates to form esters (biodiesel) and glycerol. The alkaline
catalyzed transesterification of vegetable oil proceeds faster than the acid
catalyzed reaction. Due to this reason, together with the fact that the alkaline
catalysts are less corrosive than acidic compounds, industrial processes
usually favor alkaline catalysts, such as alkaline metal alkoxides and
hydroxides as well as sodium or potassium carbonates. But the presence of
water and high amount of free acid gives rise to saponification of oil and
therefore, incomplete reaction during the alkaline transesterification process
with subsequent formation of emulsion and difficulty in separations of
glycerol.
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4.2.4.4 Lipase Catalyzed Transesterification

The lipase catalyzed transesterification process is the reaction of a

triglyceride (fat/oil) with an alcohol in the presence of lipase enzyme as a
catalyst to form esters (biodiesel) and glycerol. In lipase catalyzed process no
complex operations are needed not only for the recovery of glycerol but also
in the elimination of catalyst and soap. This is an environmentally more
attractive option to the conventional process. However, the reaction yields as
well as the reaction times are still unfavorable compared to the alkaline
catalyzed reaction systems.

4.2.4.5 Super Critical Transesterification

The simple transesterification processes discussed above are

confronted with two problems, i.e. the processes are relatively time
consuming and needs separations of the catalyst and saponified impurities
from the biodiesel. The first problem is due to the phase separations of the
vegetable oil/ alcohol mixture, which may be dealt with by vigorous stirring.
These problems are not faced in the supercritical method of
transesterification. This is perhaps due to the fact that the tendency of two
phase formation of vegetable oil/alcohol mixture is not encountered and a
single phase is found due to decrease in the dielectric constant of alcohol in
the supercritical state (at 340°C and 43 MPa). As a result, the reaction was
found to be complete in a very short time within 2-4 mins. Further, since no
catalyst is used, the purification of biodiesel is much easier, trouble free and
environment friendly (Demirbas, 2005).
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4.3 BIODIESEL PREPARATIOSNS BY CATALYTIC

TRANSESTERIFICATION METHOD

Refined corn oil, palm oil, waste cooking cotton seed and rice bran
oils were esterified by the transesterification method. Transesterification is
otherwise known as alcoholysis. It is the reaction of fat or oil with alcohol to
yield esters and glycerin. Transesterification of selected oils was carried out
by heating the oil. In this process, alcohol combines with triglyceride
molecule from acid to form glycerol and ester. The glycerol is then removed
by density separations. Simple alcohols are used for transesterification and
this process is usually carried out with a basic catalyst (NaOH, KOH) in the
complete absence of water. Transesterification decreases the viscosity of oil,
making it similar to diesel fuel in characteristics. A catalyst is used to improve
the reaction rate and yield. Transesterification of triglycerides using alcohol is
shown in Figure 4.2.

Figure 4.2 Biodiesel production process by transesterification method

The “catalytic transesterification” process is the reaction of a

triglyceride (fat/oil) with an alcohol in the presence of acidic, alkaline or
lipase as catalyst to form mono alkyl ester (i.e. Biodiesel) and glycerol.
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Alkaline catalyzed transesterification is the fastest and require simple setup

Therefore, in current the study, the SVO of selected oils was transesterified
with methyl alcohol in the presence of strong alkaline sodium hydroxide
catalyst in a batch type transesterification reactor shown in Figure 4.3. Also,
shows Fig. 4.4 the schematic sketch of transesterification process.

Figure 4.3 Schematic sketch of transesterification reactor

Figure 4.4 Transesterification process

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To prepare biodiesel from SVO of selected oils, first, the sodium

hydroxide is added to methyl alcohol to form sodium-methoxide;
simultaneously oil is heated in a separate vessel to remove moisture. Moisture
free oil is kept in the inner vessel of transesterification reactor, and subjected
to heat and stirring. When the temperature of the oil reaches 60°C, then
sodium methoxide is mixed into the oil and the reaction mixture is stirred for
more than one hour until separation of glycerol is started. Separation of
glycerol is checked by taking a small sample of reactant in a test tube. When
separation of glycerol starts then stirring is stopped and the reaction mixture is
transferred to a separate container. After 8 hours the reaction mixture is
separated into the methyl esters in the upper layer and the glycerol in the
lower layer. The methyl esters are decanted and washed three times with
warm distilled water to remove traces of soap and other impurities. The final
product obtained is good quality biodiesel. The values of various variables of
a transesterification reaction of selected oils are given in Table 4.1.

Table 4.1 Variables of transesterification reaction

S.No Reaction Variable POME COME WCRBME WCCSME

1. Amount of NaOH catalyst (g/liter oil) 6.3 6.5 6.25 6
2. Ratios of methyl alcohol/Oil (v/v %) 22 25 33.4 17
3. Reaction temperature (°C) 60 60 60 60
4. Stirring speed (range in RPM) 350-500 350-500 350-500 350-500
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4.4 SUMMARY

1. In this chapter, the methods of biodiesel conversion process

for different types of vegetable oils and waste cooking oils
were studied.

2. From this study, it may be concluded that transesterification is

convenient and the easiest process of biodiesel production.

3. Different type of transesterification methods have been

studied and catalytic type of transesterification is chosen as a
biodiesel conversion process for this research.

4. The amount of biodiesel yield per liter of vegetable and waste

cooking oils are investigated and presented in this study.

The transesterification process is done by bioprocess laboratory and

biodiesel is obtained through this process. This biodiesel easily meets with
ASTM standards. This detailed study of measurement properties will be
discussed in the later chapter of this thesis.