TRANSESTERIFICATION OF EDIBLE

VEGETABLE OIL
(COCONUT OIL)
 CHAPTER – II

TRANSESTERIFICATION OF EDIBLE VEGETABLE OIL

(Coconut oil)

The use of vegetable oils requires certain modifications in their properties to

replace diesel fuel in conventional diesel engines. Considerable efforts have been made
to develop the vegetable oil derivatives that would approximate the properties and
performance equal to the hydrocarbon-based diesel fuels. The problem of substituting
diesel fuel with pure vegetable oils (edible) as fuel is mostly associated with high
viscosity (Tat and Van Gerpen [1999]). Reduction of viscosity can be effected by any of
the processes like Transesterification, Mineralization, Preheating and Pyrolysis. The
process of Mineralization consumes more time and Pyrolysis brings about irregular
molecular break down. Hence transesterification of coconut oil is taken up in this work
to experiment on a laboratory based DI diesel engine with an additive to enhance the
combustion of biodiesel. Experimentation was performed on esterified coconut oil called
Coconut Oil Methyl Ester (COME) at different percentages of selected additive.

The vegetable oil under consideration is coconut oil. The procedure adopted for
the esterification is in two steps, to attain final coconut oil methyl ester. First stage is
acid esterification, in which sulfuric acid and methanol are used to remove free fatty
acid. The second stage is the base esterification (transesterification) in which methanol is
combined with sodium hydroxide to get sodium methoxide. The formed methyl ester was
water washed, to remove soaps and finally heated to get pure COME, which can be used
for experimental work.

2.1 Transesterification of Vegetable Oils

Transesterification is the general term used to describe the important class of

organic reactions, where the esters are transformed into another through interchange of
alkyl groups. This is also called as alcoholysis. The transesterification is an equilibrium
reaction and the transformation occurs by mixing the reactants. However with the
presence of a catalyst, the reaction accelerates considerably the adjustment of
equilibrium condition in reaction. The equation for transesterification is given below:
 RCOOR’ + R" OH RCOOR" + R' OH ------------- Eq. (1)

The basic constituent of vegetable oils is triglyceride. Vegetable oils comprise

of 90-98 percent of triglycerides and small amounts of mono, diglycerides and free fatty
acids. In transesterification of vegetable oils, the triglyceride reacts with alcohol in the
presence of a strong acid or base, produces the mixture of fatty acid alkyl esters and
glycerol. The overall process was the sequence of three consecutive and reversible
reactions in which the di and monoglycerides were formed as intermediates. In the
stoichiometric reaction, one mole of triglyceride requires three moles of alcohol.
However, excess alcohol is used to increase the yield of alkyl esters and to allow the
phase separation from the formed glycerol. Several aspects such as the type of catalyst
(base or acid), vegetable oil molar ratio, temperature, purity of the reactants (mainly
water content in alcohol) and free fatty acid contents have influence in the process of
transesterification. So in this work the reactants of high purity have been used (methyl
alcohol with 99% purity) in the process. In the base-catalyzed process, the
transesterification of vegetable oils proceeds faster than the acid-catalyzed reaction and
the alkaline catalysts, which are less corrosive than acidic compounds.

The mechanism of the base-catalyzed transesterification reaction in vegetable

oil is shown in the Fig. 2.1. In the first step (eqation.1) of reaction the base with alcohol,
produces alkoxide and the protonated catalyst. The nucleophilic attack of an alkoxide
with the carbonyl group of the triglyceride generates a tetrahedral intermediate, from
which an alkyl ester and diglyceride are formed. The latter deprotonates the catalyst and
regenerates the active species, which enables it to react with a second molecule of
alcohol, and then starting another catalytic cycle. Diglycerides and monoglycerides are
converted by the same mechanism to a mixture of alkyl esters and glycerol.

Alkaline metal alkoxides (as CH3ONa for the methanolysis) are the most active
catalysts, since they give very high yield in short reaction times even if they are
produced in lower molar concentrations. However, they require the absence of water,
which makes it inappropriate for typical industrial process. Alkali metal hydroxides
(KOH or NaOH) are cheaper than metal alkoxides and less active. Nevertheless, they are
good alternatives, since they can give the same high conversion of vegetable oils into
methyl esters just by increasing the catalyst concentration by 1 or 2 folds.
 Fig.2.1 Mechanism of the base-catalyzed transesterification process

2.2 Process employed for making methyl esters

2.2.1 Introduction:

In making of biodiesel fuel efficiently from used vegetable oils and animal fats,
the major problem to be avoided is soap formation. Soap is formed during base-catalyzed
transesterification (using lye) when sodium ions combine with free fatty acids present in
used (and some virgin) vegetable oils and animal fats. Soap decreases the yield of methyl
esters because they bond with water. The bonded esters can be washed out in the
washing stage, but this makes water separation more difficult also increases the
consumption of water.

The first-stage process is not transesterification, but pure and simple

esterification (Canakci and Van Gerpen, Jeromin et al. [1999]). Esterification is followed
by transesterification, but under acid conditions, it is much slower than under caustic
conditions and it won't covert complete oil into methyl ester as the conversion reaction is
much more equilibrium sensitive. For the first stage, it forms a compound out of an acid
and alcohol. The alcohol is still methanol, but instead of using lye (sodium hydroxide),
the catalyst in this reaction is sulfuric acid (battery acid). It requires at least 95% pure
sulfuric acid as one of the common chemicals, just like lye. The percentage of biodiesel
yield is depending upon the quantity, quality, type of catalyst used and reaction time,
temperature and stirring speed maintained during the transesterification process
(Freedman et al. [1984], Jaturong Juputti et al. [2006], Tangsathitkulchai et al. [2004],
Gajendra Kumar et al [2010]). The sulfate ion from sulfuric acid combines with the
sodium ion in the lye during the second-stage reaction to form sodium sulfate, which is a
water-soluble salt and is removed in the water wash. With this, no sulfur remains in the
biodiesel fuel product. The step wise biodiesel formation and its process chart are shown
in figures 2.2 and 2.3.

Fig. 2.2 Step-wise process of Biodiesel formation

2.2.2 The process:

1. The edible oil (Raw Coconut Oil) is filtered using surgical cotton to eliminate water
and solid particulate matter.
2. The oil is heated to 1050C temperature and maintained at this temperature for fifteen
minutes to remove all the water content from oil, since for a successful and complete
reaction, the oil must be free of water. After that the oil is allowed to cool.

2.2.3 First Stage (Acid catalyzed):

The free fatty acids can be reduced to esters by Methanol with acid catalyst.
The following is the sequence of process:
1. One liter of cooled oil is heated to 350 C to melt the solid fats present in the oil.
2. Methanol of 99 % pure, 120 ml per liter of oil [CH3OH, Make: Merck Specialties Pvt.
Ltd, Mumbai] is added to the heated oil and stirred for five to ten minutes. Methanol
is a polar compound and oil is strongly non-polar, hence suspension of oil will form in
the process.
3. Two milliliter of 98 % pure sulfuric acid [H2SO4, Make: Merck Specialties Pvt. Ltd,
Mumbai] was added for each liter of oil by using a graduated eye dropper.
4. The mixture is stirred for one hour in a closed conical beaker maintaining at constant
temperature of 550C.
5. Heating is stopped and stirring of the mixture is continued for about one hour.
6. The mixture is allowed to settle for four hours in a decanter to remove the glycerin and
chemical water separated from methyl ester.
PROCESS CHART

Edible Vegetable Oil

(Raw Coconut Oil)

Filtration

0
Edible Vegetable Oil Heating at 105 C to
(Pure Coconut Oil) remove water
Measured One liter of
Coconut Oil content
Heating at 350C to remove
Add 120 ml of 99% pure
methanol per lit. of oil Solid Fats

Constant Heating and Murkey Solution Add 2 ml of 98% pure

Stirring at 500C for 1 hour H2SO4 per lit. of oil

Stop heating & continue Allow to settle for 4 hours

stirring for 1more hour
Two layer
mixture ACID
Remove water & Glycerin
STAGE
(Bottom part)

Heating and stirring for Add ½ of the sodium

one hour methoxide
Heating mixture
BASE
0
STAGE To 55 C
Add remaining ½ of
Stop heating and allow the sodium
settling for 6 hours Methoxide

Straw yellow colour Ester

Preparation of
Remove Glycerin Brown silky Glycerin sodium Methoxide:
(Bottom part)
200 ml of methanol
Crude Biodiesel
Per liter of oil + 6.5
gms. of NaOH
Add Water + 2ml of H3PO4 Drain out water
and bubble wash
0
Heating at 105 C to
remove water content
Pure Biodiesel (COME)

Fig.2.3 Process Chart for Coconut Oil Methyl Ester (COME)

2.2.4 Second Stage (Base catalyzed):

1. For each liter of oil, 200 ml of methanol (20% by volume) and 6.5 grams of 97% pure
lye [Sodium Hydroxide (NaOH), Make: Central Drug House (P) Ltd] is added. The
mixture is stirred thoroughly until it forms a clear solution called ―Sodium
Methoxide‖.
2. Half of the prepared sodium methoxide is poured into the oil and stirred for fifteen
minutes continuously. This will neutralize the sulfuric acid.
3. The mixture is heated to 550C and the whole reaction is maintained at the same
temperature in a closed container.
4. Remaining sodium methoxide is added to the mixture and stirred at 500 to 600 rpm in
the temperature range of 550 to 580C for about one hour. The solution turns into
brown silky in colour which shows that the whole reaction is completed.
5. Now the mixture is poured into a decanter and allowed it to settle for 6 hours. As
glycerin is heavier than the biodiesel, it will settle at the bottom. The settled glycerin
is separated from the biodiesel.

2.2.5 Washing:

1. Bubble wash method is used to remove soaps. Since the process is designed to yield
neutral ester, finally there is no need to monitor pH value of the biodiesel. Two
milliliter of 98% pure Orthophosphoric acid [H3PO4, Make: Qualigens Fine
Chemicals] is added to the biodiesel for first water wash with bubbling.
2. One third of distilled water by volume is added to the biodiesel and bubble washed for
about half an hour.
3. The mixture is allowed to settle in a decanter for one hour then water with soap or
foam can be separated off from the biodiesel.
4. The process of washing is repeated till the biodiesel is separated from clear water.
5. Finally biodiesel is collected from decanter without soaps and heated to 1050C in order
to dispense the traces of water and then preserved for experimental work.

[Figures 2.4 to 2.12 indicate the process in step by step order to convert raw coconut oil
into biodiesel that is Coconut Oil Methyl Ester (COME)].
Fig. 2.4 Raw Coconut Oil Heating Fig.2.5 Separated Glycerin after Acid
treatment

Fig.2.6 Preparation of sodium Fig. 2.7 Base treatment to remove

Methoxide Free Fatty Acids
 Fig. 2.8 Settlement of Glycerin Fig. 2.9 Collected Free Fatty
After base treatment Acids (Glycerin)

Fig. 2.10 COME with soap in water washing Fig. 2.11 COME with clear water

COME


Fig. 2.12 Final stage of (Heating) COME

The above process was used to prepare the required quantity of COME from
coconut oil in Fuels laboratory of Marine Engineering Department, A. U. College of
Engineering. Then the author employed IS test methods (IS: 1448) to establish the
properties of prepared methyl ester as per the standards at HPCL, Visakhapatnam and
Chemical Engineering Department of A. U. College of Engineering. The results of
properties are tabulated as shown in table 2.1.
2.3 Properties of the biodiesel
Table 2.1 Properties of Diesel and Coconut Oil Methyl Ester

S. No. Fuel Property Diesel COME

1 Density at 33oC Kg/m3 862 892

2 Gross Calorific Value, 43000 36000
KJ/Kg
3 Viscosity at 33oC, cSt 3.45 4.38

4 Cetane Number 45 55
5 Ramsbottom Carbon 0.1 0.5
Residue, Wt%
6 Flash Point, oC 50 170
7 Pour Point, oC Winter 3 Max, < -3
Summer 15 Max
8 Acid Number, mg 0.2 Max < 0.2
KOH/gm

2.4 Summary:

In the present study, DI diesel engine from the laboratory is used to test with
prepared COME and Triacetin additive blends at an injector pressure of 200 bar without
changing any other engine parameter. This is an attempt to investigate the application of
Triacetin additive with COME to run the engine for better combustion and reduced
exhaust emissions. This engine performance is compared with that of the engine with
Petro-diesel.

The following chapter (Chapter III) deals with the mathematical modeling for
the computation of Net Heat Release Rate (NHRR) and Cumulative Heat Release Rate
(CHRR) during the combustion on the basis of first law of thermodynamics taking heat
transfer from the combustion gases into consideration. The baseline data used for