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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, 60½C.

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 50½C to 70½C with 0.5% to 1% alkaline catalyst.
With the current trend towards the environment- CPO was from the Malaysian Palm Oil Board’s
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

25 mole kg-1 produced only a marginal improvement. The effect immediately as mentioned above to remove the of molar ratio of CPO to methanol in the catalyst and stop the reaction. catalyzed by NaOMe and NaOH conversion with 0. However.125 mole NaOH kg-1 oil as catalyst. the (GC) (Lau et al. an ester conversion and ratio of oil to methanol were conducted to study of above 99% was achieved after 5 min.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. 21.1875 mole kg-1 oil to 0.125 mole kg-1 of oil produced ester conversion achieved using molar ratios of 1:6 and conversion of 99. Ester conversion above 99% after 5 min. instead of transesterification of palm oil was studied using subjecting the samples to a vacuum pump. A RESULTS AND DISCUSSION higher ratio would therefore be wasteful. the molar ratio was important in The effect of catalyst concentration was studied determining the ester conversion. respectively. for reactions 70½C. the ester conversion using molar ratios of 1:6. and thence. Thus. reaction was ascertained by gas chromatography Under the reaction parameters mentioned. 9. sufficed sufficient to employ a molar ratio of 1:6 when 0. NaOH at 0.. 2002). A longer reaction time had no material. The temperatures studied were 50½C. 5. 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. peanut oil and cottonseed oil.125. 25 min. it sufficed to use 0. The same conclusions were drawn from the NaOH catalyzed reactions.5% in 5 min. poor phase separation significant effect on the ester conversion. The detailed results are presented in Figure 3. 18. respectively. 1984). 60½C and increased to 0. observed when a molar ratio of 1:15 was used. The highest ester dosage of 0. The ester using molar ratios of oil to methanol at 1:10.1875 mole NaOH kg-1 oil. Below 5 min reaction time. the NaOMe and NaOH as catalysts (0. while it took only 3 1:8 was 97% (21 min) and 98% (9 min). Therefore. ester conversion kg-1 oil. It took 7 The effect of temperature on the transesterification min to achieve 99% conversion with 0. Furthermore. 1 mole of oil requires 3 moles of alcohol. 15. excess of Aliquots of the sample were taken at reaction alcohol improves the conversion (Freedman et al. times.JOURNAL OF OIL PALM RESEARCH 16 (2) neutral decanted aqueous layer was obtained. A reaction time was extended. 12. reaction temperature reactions. Such high oil. 1:8 and All the reactions using NaOMe achieved ester 1:10 were 93%. The samples were also purified soyabean oil.125 mole NaOH For the reactions using NaOMe. a conversion improved significantly when the molar reaction temperature of 60½C and stirring rate at 350 ratio of oil to methanol was increased. respectively. After 5 min reaction. The effect of the conversion of 99% was not obtained even when the catalyst was obvious within the initial 5 min.125 mole kg-1 of oil) and at a stirring rate of 350 min were required with the catalyst concentration rpm. the ester conversion was increased with the reaction © MPOB 2004 20 . 2. The detailed results are presented in Figure of 99% was obtained for 50½C. This result indicates Thus. transesterification of methanol remained in the product.25 mole kg-1 oil. Catalyst Concentration For the reactions using 0. Catalyst concentration Reaction Temperature was important for short reactions as the ester conversion increased with more catalyst. Thus. 60½C and 70½C after 5. 7.125 mole kg-1 oil) neutral aliquots were dried with anhydrous Na2SO4 at 60½C and a stirring rate of 350 rpm.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. the esters were subjected to a vacuum pump to ensure that no traces of distilled water and Although stoichiometrically.25 mole kg-1 oil. The molar because of their small volumes. In all the experiments. Ratio of Oil to Methanol Finally. 95% and 99%. 1:8 and 1:10 were transesterification during and at completion of the investigated. 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. The degree of ratios of oil to methanol of 1:6. However. above 10 min.1875 mole kg-1 oil. 3. it their effects on the transesterification process. there was no reactions. Only 3 (0.1875 and 0. it can be concluded that 0. 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. t = 1. further improvement with the catalyst concentration A higher molar ratio of oil to methanol of 1:15 increased from 0. 3 and 1 min.5% after 5 min. The reactions were carried out with NaOMe or results are presented in Figure 4. 0.125 mole NaOMe kg-1 oil is used as the higher ratios produced a comparable ester conversion. min using 0. transesterification. The effect between the palm oil methyl esters and glycerol was of concentration of NaOMe is illustrated in Figure 1.. The detailed rpm.

respectively. it is best to carry them out at For reactions using NaOH. for the NaOH The detailed results are illustrated in Figure 5. Figure 2. the effect of 60½C. Ester conversion (%) 120 100 80 60 0. A up to 60 min. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various catalyst concentrations. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various catalyst concentrations. The detailed results are illustrated in Figure 6. there is no need after 5 min.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. 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 .125 mole kg-1 oil 40 0.1875 mole kg-1 oil 0. temperature was more significant.125 mole kg-1 oil 40 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 60½C. The same ester conversion was not to raise the reaction temperature to 70½C as the ester obtained from the reactions at 50½C and 60½C even conversion is comparable to that obtained at 60½C. Thus. Thus. temperature increased from 50½C to 60½C and 70½C. Figure 1. The highest esters conversion (98%) temperature of 50½C can also be used to achieve 99% for the reactions at 50½C and 60½C was achieved after ester conversion if the reaction time is over 7 min. Reaction temperature at 60½C. temperature raised from 50½C to 60½C and 70½C. Stirring rate at 350 rpm. 21 min and 7 min. catalyzed reactions. An There was not much effect when the temperature ester conversion of 99% was only obtained at 70½C was raised from 60½C to 70½C. Stirring rate at 350 rpm. KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL Ester conversion (%) 120 100 80 60 0.1875 mole kg-1 oil 0.

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.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. Reaction temperature at 60½C.125 mole kg-1 oil. Figure 3. Stirring rate at 350 rpm. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various molar ratios. Stirring rate at 350 rpm. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various molar ratios. © MPOB 2004 22 . Reaction temperature at 60½C. Figure 4.

illustrates the typical trend in the glyceride concentrations during the transesterification. diglycerides and triglycerides.125 mole kg-1 oil. Molar ratio of oil to methanol at 1:10. namely. Ester conversion (%) 120 100 80 60 50ºC 40 60ºC 20 70ºC 0 0 5 10 15 20 25 30 Reaction time (min) Note: Reaction conditions: Catalyst concentration at 0. Figure 5. Kinetics of the transesterification of palm oil to methyl esters using sodium hydroxide as catalyst at various temperatures. Molar ratio of oil to methanol at 1:10. Stirring rate at 350 rpm.6½C) and melting point of CPO (55½C). Figure 7 contact with one another. KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL Ester conversion (%) 120 100 80 60 50ºC 60ºC 40 70ºC 20 0 0 2 4 6 8 10 12 14 Reaction time (min) Note: Reaction conditions: Catalyst concentration at 0. Figure 6. Stirring rate at 350 rpm. while the methyl esters increased © MPOB 2004 23 . results. A reaction temperature at 60½C is suitable for Conversion of Glycerides to Methyl Esters both catalysts as it is very near the boiling point of methanol (64. The concentrations of glycerides.125 mole kg-1 oil. Thus. the reaction mixture is monoglycerides. Triglycerides decreased tremendously and rapidly over the reaction. Kinetics of the transesterification of palm oil to methyl esters using sodium methoxide as catalyst at various temperatures. were thoroughly homogenized and the reactants in good monitored throughout the reactions. at the temperature.

monoglycerides. The monoglycerides. such as diglycerides and reaction. Figure 8. while products since transesterification is a reversible the intermediates. Reaction temperature at 60½C. (ii) MG – monoglycerides. 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. Stirring rate at 350 rpm. © MPOB 2004 24 . Figure 7. did observed. This aforementioned product. however. 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.JOURNAL OF OIL PALM RESEARCH 16 (2) rapidly indicating fast formation of the and then methyl esters subsequently (Figure 8). DG – diglycerides and TG – triglycerides. Diglycerides increased. not show any significant fluctuation. Pathway of glyceride conversion to methyl esters. Glyceride composition during transesterification of palm oil using sodium hydroxide. explains the trends in the glyceride compositions then decreased. Molar ratio of oil to methanol at 1:10.125 mole kg-1 oil.

125 mole kg-1 oil. Stirring rate at 350 rpm. an ester conversion of above 99% was alcoholysis catalyst (Freedman et al. Transesterification of palm oil using a catalyst concentration of 0. Transesterification of palm oil using a catalyst concentration of 0. 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 1:10.1875 mole kg-1 oil. For the same result. 10 and 11). NaOMe sufficed. when 0. However. For example. Reaction temperature at 60½C. 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. The achieved in 5 min. 0.125 mole NaOH kg-1 oil exhibited good catalytic performance. 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. Reaction temperature at 60½C. 1984). Stirring rate at 350 rpm. Figure 9. © MPOB 2004 25 .125 mole NaOH kg-1 oil NaOMe has been cited as the most effective was used.. Figure 10. 0.1875 mole results from this study also showed NaOMe to be NaOH kg-1 oil was needed. if the reaction more superior to NaOH although both catalysts was carried out longer.

the reaction parameters. could yield the same ester ––––––– conversion even when the molar ratio of oil to dt k = rate constant methanol was reduced to 1:6. for each of the reaction was water) of the esters to remove the catalyst used. [TG] = concentration of oil [ML] = concentration of methanol ACKNOWLEDGEMENT Integration yields (Smith. as it is available in methanolic 30% solution. however. However. k. Reaction temperature at 60½C. Determination of the Reaction Rate Constant. 1981): Technical assistance from Ms Rohana Maakrof and Mr Abdul Aziz Mahat is gratefully acknowledged. © MPOB 2004 26 . reaction mixture. The NaOMe catalyzed r = -d[TG] = k[TG][ML] where r = rate of reaction reaction.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. The reaction time (t) (Figures 12. 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. Stirring rate at 350 rpm. At a catalyst expression: concentration of 0. less determined from the slope of the plot of f (xTG) versus emulsion was formed with NaOH than NaOMe. Transesterification of palm oil using a catalyst concentration of 0. k CONCLUSION Kinetics data were obtained from the different Both NaOH and NaOMe offered good catalytic sets of transesterification reactions. during purification (washing with The rate constant. 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.125 mole kg -1 oil. 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. 13 and 14). Figure 11. lowering the varied from one reaction to another depending on product yield. The k values for the various Another advantage of NaOMe is easy handling transesterification reactions are tabulated in Table 1. NaOH These kinetics data would be useful for designing a on the other hand.25 mole kg-1 oil. Thanks are also due to MPOB for the Graduate Research Assistantship to Cheng Sit Foon to pursue her postgraduate study. an ester conversion of above 99% can be achieved by Triglycerides [TG] + 3 methanol [ML] 3 methyl esters conducting the reaction at 60½C and a molar ratio of [ME] + Glycerol oil to methanol of 1:10.

Graph of the integration method results for the transesterification reaction using sodium hydroxide as catalyst at various concentrations.9504 1.2 y = 0.0 0.2 0.163x 0.0 0 2 4 6 8 10 12 14 Reaction time (min) Note: Reaction conditions: Catalyst concentration at 0. KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL f (x TG) 1. Figure 12. Graph of integration method results for transesterification reaction using sodium hydroxide as catalyst at the various molar ratios of oil to methanol.9997 y = 0.4 y = 0.6 y = 0.0 y = 0.6 0.4 1:6 1:8 1:10 0. Stirring rate at 350 rpm.125 mole kg-1 oil 0.2 0.8 1. f (xTG) 1.9792 1. Stirring rate at 350 rpm.303x R2 = 0.25 mole kg-1 oil R2 = 0.2 1.0 0 2 4 6 8 10 Reaction time (min) Note: Reaction conditions: Molar ratio of oil to methanol at 1:10. Reaction temperature at 60½C. © MPOB 2004 27 .1875 mole kg-1 oil 0. Figure 13. Reaction temperature at 60½C.125 mole kg-1 oil.8 0.9832 0.8 R2 = 0.6 0.163x 0.9822 1.1466x R2 = 0.0941x R2 = 0.4 R2 = 0.9997 0.4 y = 0.5124x 1.

E H and MOUNTS. Chapter 5.50 0.526 1:6 350 60 0. (UCAO). T (1990). Sheffield Academic Press.10 0. patent No. CHOO.1250 0.00 0 2 4 6 8 10 Reaction time (min) Note: Reaction conditions: Catalyst concentration at 0. vegetable oil and fats. J. 2188057. © MPOB 2004 28 . Gas chromatography method for Oil Chem. ONG. Y M.00 0. G and DUNN. 2.).. k oil:methanol (rpm) (½C) concentration (litre mole-1 min) (mole kg-1 oil) 1:10 350 60 0. Sabah. PRYDE. Stirring rate at 350 rpm. MAO.70 0. S H.20 0.80 y = 0. 61: 1638-1643. Inc.30 0. Soc. LEE.163x R2 = 0. S H (1984). ONG. Figure 14. 19-20 August 2002. U. GOH. United Coconut Association of from transesterified vegetable oils.. A N and CHUAH.9997 0. Refining Technology. T L Palm oil methyl esters as diesel substitute. K Y and BAKAR. CH (2002). KNOTHE. TABLE 1.1250 0. Y M. S K. V. Oil Chem. Y M and GOH. LAU. Coconut (1984). Molar ratio of oil to methanol at 1:10.309 REFERENCES Vegetable Oils and Fats (Gunstone.3089x 0.K.163 1:10 350 60 0. 75: 1167-1172. purity methyl esters from vegetable oils. C and BULIGAN. Production of alkyl esters from oils and fats. Variables affecting the yields of fatty esters Today Vol. Fast formation of high.1250 0. A S H. Philippines.40 60ºC 70ºC 0. CHEAH. Malaysia.147 1:10 350 70 0. S (1998). BOOCOCK. R O (2001). Oleochemical A (1992).1250 0.90 y = 0. KONAR.60 0. Amer. No. CHOO. Transesterification of fats and oils. Manufacture and Applications: Biofuels Derived from Australian patent No. AU 626014. Presented at the 2002 National Seminar on Palm Oil Milling.9988 R2 = 0.. Graph of integration method results for transesterification reaction using sodium hydroxide as catalyst at various reaction temperatures. CHOO.125 mole kg-1 oil. H Quality and Environment.097 1:8 350 60 0.JOURNAL OF OIL PALM RESEARCH 16 (2) f (xTG) 1. J. A S H. ONG. F D and Hamilton. Vol. 2. D G B.313 1:10 350 60 0. Amer. Y M. Vol. R J eds.2500 0. FREEDMAN. the Philippines. Kota Kinabalu. 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. MA.1875 0. CHOO. B. A S H and KHOR. H L N. Soc.

p. U. B (1982). August Company. E H and FREEDMAN. Fargo.S. © MPOB 2004 29 . Presented Third edition. McGraw-Hill International Book at Plant Vegetable Oils as Fuels. KINETICS STUDY ON TRANSESTERIFICATION OF PALM OIL PRYDE. 65.A. Fatty esters SMITH. from soyabean oil for use as a diesel fuel. Chemical Engineering Kinetics. J M (1981). 1982.