Journal of Oil Palm Research Vol. 16 No. 2, December 2004, p.

19-29 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

KINETICS STUDY ON TRANSESTERIFICATION

OF PALM OIL
CHENG SIT FOON*; CHOO YUEN MAY*; MA AH NGAN* and CHUAH CHENG HOCK**

ABSTRACT
The kinetics of base-catalyzed transesterification of palm oil based on parameters such as oil and alcohol ratio,
catalyst concentration and temperature were investigated to optimize the conversion rate. Our findings
showed that both sodium hydroxide and sodium methoxide had high kinetic constants depicting fast formation
of palm oil methyl esters with conversions above 99%. Fast formation of palm oil methyl esters with a rate
constant of 0.163 litre mole min-1 was obtained when the reaction parameters were: molar ratio of oil to methanol,
1:10; catalyst concentration, 0.125 mole kg-1 oil; and temperature, 60C.

Keywords: transesterification, kinetics, sodium hydroxide, sodium methoxide, crude palm oil.
Date received: 8 October 2003; Sent for revision: 20 October 2003; Received in final form: 27 February 2004; Accepted: 28 February 2004.

INTRODUCTION varying reaction parameters were conducted to

study the kinetics of the formation of palm oil methyl
Transesterification of vegetable oils and fats to esters.
methyl and ethyl esters using different reactants,
reaction conditions and catalysts have been reported
(Freedman et al., 1984; Choo et al., 1990; Goh et al., MATERIALS AND METHODS
1992). The typical conditions in the transesterification
of vegetable oils are generally mild - a temperature Materials
of 50C to 70C with 0.5% to 1% alkaline catalyst.
With the current trend towards the environment- CPO was from the Malaysian Palm Oil Boards
friendly biofuel (Pryde et al., 1982; Ong et al., 1984; Experimental Palm Oil Mill in Labu, Selangor,
Knothe et al., 2001), coupled with financial incentives, Malaysia. Methanol, NaOMe and anhydrous sodium
producers are encouraged to build not only new sulphate (Na2SO4) were of A.R. grade (Merck). The
plants but to improve the existing production plants catalyst, NaOMe (30%), was obtained from Degussa
to produce high quality methyl esters of biodiesel GmbH (Germany).
grade (Boocock et al., 1998).
In the present study, the optimum conditions to Methods
produce palm oil methyl esters by transesterification
of crude palm oil (CPO) with methanol using Transesterification of CPO and methanol was
alkaline catalysts, namely, sodium methoxide catalyzed by either NaOH and NaOMe in a batch
(NaOMe) and sodium hydroxide (NaOH) were system. The reaction set-up included a round bottom
investigated. With the new trend and depth in the flask equipped with a condenser and thermometer.
development in the biofuel industry, it is hoped to The flask was immersed in a water bath on a
establish the optimum reaction conditions for good magnetic stirrer with heating plate. For the NaOH
yields in the minimum reaction time and material catalyzed reactions, the catalyst was dissolved in
consumption. In this context, experiments with methanol and the mixture added to the reaction
mixture at the reaction temperature. For the NaOMe
catalyzed reactions, the methanolic solution at 30%
* Malaysian Palm Oil Board, concentration was added, also at the elevated
P. O. Box 10620,
reaction temperature.
50720 Kuala Lumpur, Malaysia.
E-mail: choo@mpob.gov.my On completion of the reaction, the glycerol layer
** Department of Chemistry, was decanted and the esters purified and dried. The
University Malaya, Lembah Pantai, esters were washed with warm distilled water in
50603 Kuala Lumpur, Malaysia. excess methanol using a separating funnel until a

19
MPOB 2004
JOURNAL OF OIL PALM RESEARCH 16 (2)

neutral decanted aqueous layer was obtained. Ratio of Oil to Methanol

Finally, the esters were subjected to a vacuum pump
to ensure that no traces of distilled water and Although stoichiometrically, transesterification of
methanol remained in the product. 1 mole of oil requires 3 moles of alcohol, excess of
Aliquots of the sample were taken at reaction alcohol improves the conversion (Freedman et al.,
times, t = 1, 3, 5, 7, 9, 12, 15, 18, 21, 25 min, and thence, 1984). A molar ratio oil to alcohol of at least 1:6 was
after every 5 min to study the kinetics of the used for the transesterification of sunflower oil,
transesterification. The samples were also purified soyabean oil, peanut oil and cottonseed oil. The effect
immediately as mentioned above to remove the of molar ratio of CPO to methanol in the
catalyst and stop the reaction. However, instead of transesterification of palm oil was studied using
subjecting the samples to a vacuum pump, the NaOMe and NaOH as catalysts (0.125 mole kg-1 oil)
neutral aliquots were dried with anhydrous Na2SO4 at 60C and a stirring rate of 350 rpm. The molar
because of their small volumes. The degree of ratios of oil to methanol of 1:6, 1:8 and 1:10 were
transesterification during and at completion of the investigated.
reaction was ascertained by gas chromatography Under the reaction parameters mentioned, the
(GC) (Lau et al., 2002). molar ratio of oil to methanol had no significant effect
Experiments with varying reaction parameters on the ester conversion in the NaOMe catalyzed
such as catalyst concentration, reaction temperature reactions. In all the experiments, an ester conversion
and ratio of oil to methanol were conducted to study of above 99% was achieved after 5 min. Thus, it
their effects on the transesterification process. sufficed sufficient to employ a molar ratio of 1:6
when 0.125 mole NaOMe kg-1 oil is used as the higher
ratios produced a comparable ester conversion. A
RESULTS AND DISCUSSION higher ratio would therefore be wasteful. The
detailed results are presented in Figure 3.
Catalyst Concentration For the reactions using 0.125 mole NaOH kg-1 oil
as catalyst, the molar ratio was important in
The effect of catalyst concentration was studied determining the ester conversion. The ester
using molar ratios of oil to methanol at 1:10, a conversion improved significantly when the molar
reaction temperature of 60C and stirring rate at 350 ratio of oil to methanol was increased. The detailed
rpm. The reactions were carried out with NaOMe or results are presented in Figure 4. After 5 min reaction,
NaOH at 0.125, 0.1875 and 0.25 mole kg-1 oil. the ester conversion using molar ratios of 1:6, 1:8 and
All the reactions using NaOMe achieved ester 1:10 were 93%, 95% and 99%, respectively. Ester
conversion above 99% after 5 min. The effect of the conversion of 99% was not obtained even when the
catalyst was obvious within the initial 5 min. A reaction time was extended. The highest ester
dosage of 0.125 mole kg-1 of oil produced ester conversion achieved using molar ratios of 1:6 and
conversion of 99.5% after 5 min, while it took only 3 1:8 was 97% (21 min) and 98% (9 min), respectively.
min using 0.1875 mole kg-1 oil. This result indicates Thus, more excess methanol was needed to push the
that faster ester conversion was obtained with a reaction towards the product for the NaOH catalyzed
higher dosage of catalyst. However, there was no reactions.
further improvement with the catalyst concentration A higher molar ratio of oil to methanol of 1:15
increased from 0.1875 mole kg-1 oil to 0.25 mole kg-1 produced only a marginal improvement. Such high
oil. Thus, it can be concluded that 0.125 mole kg-1 oil excess methanol without significant improvement
sufficed for NaOMe to achieve ester conversion in the ester conversion is clearly a waste of the raw
above 99.5% in 5 min. A longer reaction time had no material. Furthermore, poor phase separation
significant effect on the ester conversion. The effect between the palm oil methyl esters and glycerol was
of concentration of NaOMe is illustrated in Figure 1. observed when a molar ratio of 1:15 was used.
The same conclusions were drawn from the
NaOH catalyzed reactions. Catalyst concentration Reaction Temperature
was important for short reactions as the ester
conversion increased with more catalyst. It took 7 The effect of temperature on the transesterification
min to achieve 99% conversion with 0.125 mole of palm oil was studied using a molar ratio of CPO to
NaOH kg-1 oil but only 5 min to achieve the same methanol of 1:10, catalyzed by NaOMe and NaOH
conversion with 0.1875 mole NaOH kg-1 oil. Only 3 (0.125 mole kg-1 of oil) and at a stirring rate of 350
min were required with the catalyst concentration rpm. The temperatures studied were 50C, 60C and
increased to 0.25 mole kg-1 oil. Therefore, for reactions 70C.
above 10 min, it sufficed to use 0.125 mole NaOH For the reactions using NaOMe, ester conversion
kg-1 oil. The detailed results are presented in Figure of 99% was obtained for 50C, 60C and 70C after 5,
2. 3 and 1 min, respectively. Below 5 min reaction time,
the ester conversion was increased with the reaction

MPOB 2004 20
 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

Ester conversion
(%)
120

100

80

60
0.125 mole kg-1 oil
40 0.1875 mole kg-1 oil
0.25 mole kg-1 oil
20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 1. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various
catalyst concentrations.

Ester conversion
(%)
120

100

80

60
0.125 mole kg-1 oil
40 0.1875 mole kg-1 oil
0.25 mole kg-1 oil
20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 2. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various
catalyst concentrations.

temperature increased from 50C to 60C and 70C. temperature raised from 50C to 60C and 70C. An
There was not much effect when the temperature ester conversion of 99% was only obtained at 70C
was raised from 60C to 70C. Thus, there is no need after 5 min. The same ester conversion was not
to raise the reaction temperature to 70C as the ester obtained from the reactions at 50C and 60C even
conversion is comparable to that obtained at 60C. A up to 60 min. The highest esters conversion (98%)
temperature of 50C can also be used to achieve 99% for the reactions at 50C and 60C was achieved after
ester conversion if the reaction time is over 7 min. 21 min and 7 min, respectively. Thus, for the NaOH
The detailed results are illustrated in Figure 5. catalyzed reactions, it is best to carry them out at
For reactions using NaOH, the effect of 60C. The detailed results are illustrated in Figure 6.
temperature was more significant. There were great The effect of reaction temperature on the
increments in ester conversion with the reaction transesterification palm oil is obvious from these

MPOB 2004 21
JOURNAL OF OIL PALM RESEARCH 16 (2)

Ester conversion
(%)
120

100

80

60
1:6 1:8
40
1 : 10

20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 3. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various
molar ratios.

Ester conversion
(%)
120

100

80

60
1:6
40 1:8
1 : 10
20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 4. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various
molar ratios.

MPOB 2004 22
 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

Ester conversion
(%)
120

100

80

60
50C 60C
40
70C
20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.

Molar ratio of oil to methanol at 1:10.
Stirring rate at 350 rpm.
Figure 5. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various
temperatures.

Ester conversion
(%)
120

100

80

60

50C
40
60C

20 70C

0
0 5 10 15 20 25 30
Reaction time (min)

Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.

Molar ratio of oil to methanol at 1:10.
Stirring rate at 350 rpm.

Figure 6. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various
temperatures.

results. A reaction temperature at 60C is suitable for Conversion of Glycerides to Methyl Esters
both catalysts as it is very near the boiling point of
methanol (64.6C) and melting point of CPO (55C). The concentrations of glycerides, namely,
Thus, at the temperature, the reaction mixture is monoglycerides, diglycerides and triglycerides, were
thoroughly homogenized and the reactants in good monitored throughout the reactions. Figure 7
contact with one another. illustrates the typical trend in the glyceride
concentrations during the transesterification.
Triglycerides decreased tremendously and rapidly
over the reaction, while the methyl esters increased

MPOB 2004 23
JOURNAL OF OIL PALM RESEARCH 16 (2)

rapidly indicating fast formation of the and then methyl esters subsequently (Figure 8). This
aforementioned product. Diglycerides increased, explains the trends in the glyceride compositions
then decreased. The monoglycerides, however, did observed.
not show any significant fluctuation. This indicates The traces of diglycerides and monoglycerides
that the conversion of triglycerides to intermediates in the end product even with high ester conversion
(diglycerides and monoglycerides) and product indicated an equilibrium between the reactants and
(methyl esters) proceeded at the same time, while products since transesterification is a reversible
the intermediates, such as diglycerides and reaction.
monoglycerides, were converted to monoglycerides

Concentration (%)
120

100

80
MG
60 DG
TG
40 Esters

20

0
0 1 2 3 4 5 6 7 8 9 10
Reaction time (min)

Notes: (i) Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.
Molar ratio of oil to methanol at 1:10.
Reaction temperature at 60C.
Stirring rate at 350 rpm.
(ii) MG monoglycerides, DG diglycerides and TG triglycerides.
Figure 7. Glyceride composition during transesterification of palm oil using sodium hydroxide.

Figure 8. Pathway of glyceride conversion to methyl esters.

MPOB 2004 24
 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

Comparison of Sodium Methoxide with Sodium offered a faster and higher ester conversion than
Hydroxide as Catalysts NaOH at the same concentration (Figures 9, 10 and
11). For example, when 0.125 mole NaOH kg-1 oil
NaOMe has been cited as the most effective was used, an ester conversion of above 99% was
alcoholysis catalyst (Freedman et al., 1984). The achieved in 5 min. For the same result, 0.1875 mole
results from this study also showed NaOMe to be NaOH kg-1 oil was needed. However, if the reaction
more superior to NaOH although both catalysts was carried out longer, 0.125 mole NaOH kg-1 oil
exhibited good catalytic performance. NaOMe sufficed.

Ester conversion
(%)
120

100

80

60

NaOH
40
NaOMe
20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 9. Transesterification of palm oil using a catalyst concentration of 0.125 mole kg-1 oil.

Ester conversion
(%)
120

100

80

60 NaOH

40 NaOMe

20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 10. Transesterification of palm oil using a catalyst concentration of 0.1875 mole kg-1 oil.

MPOB 2004 25
JOURNAL OF OIL PALM RESEARCH 16 (2)

Ester conversion
(%)
120

100

80

60
NaOH

40 NaOMe

20

0
0 2 4 6 8 10 12 14
Reaction time (min)

Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.

Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 11. Transesterification of palm oil using a catalyst concentration of 0.25 mole kg-1 oil.

However, during purification (washing with The rate constant, k, for each of the reaction was
water) of the esters to remove the catalyst used, less determined from the slope of the plot of f (xTG) versus
emulsion was formed with NaOH than NaOMe. The reaction time (t) (Figures 12, 13 and 14). Each
formation of emulsion may cause losses in the end transesterification reaction had its own k value which
product if no special care is taken, lowering the varied from one reaction to another depending on
product yield. the reaction parameters. The k values for the various
Another advantage of NaOMe is easy handling transesterification reactions are tabulated in Table 1.
as it is available in methanolic 30% solution. NaOH These kinetics data would be useful for designing a
on the other hand, is available as pellets and needs reactor system for the transesterification of palm oil
to be dissolved in methanol before adding to the to its methyl esters.
reaction mixture.

Determination of the Reaction Rate Constant, k CONCLUSION

Kinetics data were obtained from the different Both NaOH and NaOMe offered good catalytic
sets of transesterification reactions. The data could activity for the transesterification of CPO with the
be described reasonably by a second order rate latter being superior to the former. At a catalyst
expression: concentration of 0.125 mole kg -1 oil, an ester
conversion of above 99% can be achieved by
Triglycerides [TG] + 3 methanol [ML] 3 methyl esters conducting the reaction at 60C and a molar ratio of
[ME] + Glycerol oil to methanol of 1:10. The NaOMe catalyzed
r = -d[TG] = k[TG][ML] where r = rate of reaction
reaction, however, could yield the same ester
conversion even when the molar ratio of oil to
dt k = rate constant methanol was reduced to 1:6.
[TG] = concentration of oil
[ML] = concentration of
methanol
ACKNOWLEDGEMENT
Integration yields (Smith, 1981):
Technical assistance from Ms Rohana Maakrof and
Mr Abdul Aziz Mahat is gratefully acknowledged.
Thanks are also due to MPOB for the Graduate
Research Assistantship to Cheng Sit Foon to pursue
her postgraduate study.

MPOB 2004 26
 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

f (x TG)
1.8
1.6
y = 0.5124x
1.4 R2 = 0.9504
1.2 y = 0.303x
R2 = 0.9792
1.0
0.8
0.125 mole kg-1 oil
0.6 0.1875 mole kg-1 oil
0.4 y = 0.163x 0.25 mole kg-1 oil
R2 = 0.9997
0.2
0.0
0 2 4 6 8 10
Reaction time (min)
Note: Reaction conditions: Molar ratio of oil to methanol at 1:10.
Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 12. Graph of the integration method results for the transesterification reaction using sodium hydroxide as
catalyst at various concentrations.

f (xTG)
1.4
y = 0.1466x
R2 = 0.9822
1.2
1.0
y = 0.163x
0.8 R2 = 0.9997 y = 0.0941x
R2 = 0.9832
0.6
0.4 1:6 1:8 1:10
0.2
0.0
0 2 4 6 8 10 12 14
Reaction time (min)
Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.
Reaction temperature at 60C.
Stirring rate at 350 rpm.
Figure 13. Graph of integration method results for transesterification reaction using sodium hydroxide as catalyst at
the various molar ratios of oil to methanol.

MPOB 2004 27
JOURNAL OF OIL PALM RESEARCH 16 (2)

f (xTG)
1.00
0.90
y = 0.3089x
0.80 y = 0.163x
R2 = 0.9988
R2 = 0.9997
0.70
0.60
0.50
0.40 60C 70C
0.30
0.20
0.10
0.00
0 2 4 6 8 10
Reaction time (min)
Note: Reaction conditions: Catalyst concentration at 0.125 mole kg-1 oil.
Molar ratio of oil to methanol at 1:10.
Stirring rate at 350 rpm.
Figure 14. Graph of integration method results for transesterification reaction using sodium hydroxide as catalyst at
various reaction temperatures.

TABLE 1. REACTION PARAMETERS AND THE RESPECTIVE RATE CONSTANT FOR TRANSESTERIFICATION OF PALM
OIL TO METHYL ESTERS USING SODIUM HYDROXIDE AS CATALYST

Molar ratio Stirring rate Temperature Catalyst Rate constant, k

oil:methanol (rpm) (C) concentration (litre mole-1 min)
(mole kg-1 oil)

1:10 350 60 0.1250 0.163

1:10 350 60 0.1875 0.313
1:10 350 60 0.2500 0.526
1:6 350 60 0.1250 0.097
1:8 350 60 0.1250 0.147
1:10 350 70 0.1250 0.309

REFERENCES Vegetable Oils and Fats (Gunstone, F D and Hamilton,

R J eds.). Sheffield Academic Press, Chapter 5.
BOOCOCK, D G B; KONAR, S K; MAO, V; LEE, C
and BULIGAN, S (1998). Fast formation of high- LAU, H L N; CHOO, Y M; MA, A N and CHUAH,
purity methyl esters from vegetable oils. J. Amer. CH (2002). Gas chromatography method for
Oil Chem. Soc., Vol., 75: 1167-1172. vegetable oil and fats. Presented at the 2002 National
Seminar on Palm Oil Milling, Refining Technology,
CHOO, Y M; GOH, S H; ONG, A S H and KHOR, H Quality and Environment. Kota Kinabalu, Sabah,
T (1990). Transesterification of fats and oils. U.K. Malaysia. 19-20 August 2002.
patent No. 2188057.
ONG, A S H; CHOO, Y M and GOH, S H (1984).
FREEDMAN, B; PRYDE, E H and MOUNTS, T L Palm oil methyl esters as diesel substitute. Coconut
(1984). Variables affecting the yields of fatty esters Today Vol. 2, No. 2. United Coconut Association of
from transesterified vegetable oils. J. Amer. Oil Chem. the Philippines, Inc. (UCAO). Philippines.
Soc. Vol., 61: 1638-1643.
ONG, A S H; CHOO, Y M; CHEAH, K Y and BAKAR,
KNOTHE, G and DUNN, R O (2001). Oleochemical A (1992). Production of alkyl esters from oils and fats.
Manufacture and Applications: Biofuels Derived from Australian patent No. AU 626014.

MPOB 2004 28
 KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL

PRYDE, E H and FREEDMAN, B (1982). Fatty esters SMITH, J M (1981). Chemical Engineering Kinetics.
from soyabean oil for use as a diesel fuel. Presented Third edition. McGraw-Hill International Book
at Plant Vegetable Oils as Fuels. Fargo, U.S.A. August Company. p. 65.
1982.

MPOB 2004 29