Fuel Processing Technology 92 (2011) 15431548

Contents lists available at ScienceDirect

Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Kinetics of methyl ester production from mixed crude palm oil by using acid-alkali catalyst
Surachai Jansri a, Sukritthira B. Ratanawilai b, Michael L. Allen c, Gumpon Prateepchaikul c,
a b c

The Joint Graduate School of Energy and Environment, King Mongkut's University of Technology Thonburi, Bangkok, 10140, Thailand Department of Chemical Engineering, Faculty of Engineering, Prince of Songkla University, Had Yai, Songkhla, 90112, Thailand Department of Mechanical Engineering, Faculty of Engineering, Prince of Songkla University, Had Yai, Songkhla, 90112, Thailand

a r t i c l e

i n f o

a b s t r a c t
The production of biodiesel from high free fatty acid mixed crude palm oil using a two-stage process was investigated. The kinetics of the reactions was determined in a batch reactor at various reaction temperatures. It was found that the optimum conditions for reducing high free fatty acid (FFA) in MCPO (812 wt.%/wt oil) using esterication was a 10:1 molar ratio of methanol to FFA and using 10 wt.%/wt of sulfuric acid (based on FFA) as catalyst. The subsequent transesterication reaction to convert triglycerides to the methyl ester was found to be optimal using 6:1 molar ratio of methanol to the triglyceride (TG) in MCPO and using 0.6 wt.%/ volTG sodium hydroxide as catalyst. Both reactions were carried out in a stirred batch reactor over a period of 20 min at 55, 60 and 65 C. The concentration of compounds in each sample was analyzed by Thin Layer Chromatography/Flame Ionization Detector (TLC/FID), Karl Fischer, and titration techniques. The results were used for calculating the rate coefcients by using the curve-tting tool of MATLAB. Optimal reaction rate coefcients for the forward and reverse esterication reactions of FFA were 1.340 and 0.682 l mol1 min1, respectively. The corresponding optimal transesterication, rate coefcients for the forward reactions of TG, diglyceride (DG), and monoglyceride (MG) of transesterication were 2.600, 1.186, and 2.303 l mol1 min1, and for the reverse reactions were 0.248, 0.227, and 0.022 l mol1 min1, respectively. 2011 Elsevier B.V. All rights reserved.

Article history: Received 15 June 2010 Received in revised form 21 February 2011 Accepted 27 March 2011 Available online 20 April 2011 Keywords: Biodiesel Free fatty acid Kinetics Methyl ester Palm oil Two-stage process

1. Introduction Energy is one of the important drivers of the economic growth contributing to the development of Thailand. Fossil fuels provide the majority of Thailand's energy for driving industrial, agriculture, and transportation sectors. That is the reason Thailand continuously increases the import of fossil diesel fuel for supporting high petroleum consumption in Thailand. In addition, the fossil diesel fuel causes signicant pollution problems such as increasing concentrations of green house gasses and sulfur dioxide. Therefore, alternative fuels are being investigated as substitutes for imported petroleum products and to reduce pollution problems in Thailand. Moreover, alternative fuels make a balanced growth on the demand side. Consequently, biodiesel made from vegetable oils and animal fats, is one of the possible alternative fuels for diesel engines in Thailand because it is biodegradable, non-toxic, and produces low emissions of polluting gasses. Furthermore, it also produces a balance between

Corresponding author at: Department of Mechanical Engineering, Faculty of Engineering, Prince of Songkla University, Had Yai, Songkhla, 90112, Thailand. Tel.: + 66 866945670; fax: + 66 212893. E-mail address: gumpon.p@psu.ac.th (G. Prateepchaikul). 0378-3820/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2011.03.017

agriculture, economic, and environmental needs. Accordingly, the biodiesel strategy of Thailand, which was established by the Thailand government in 2004, aims to produce and to use 10% biodiesel in its nationally distributed diesel fuel by 2012 (8.5 million liters per day). There are several plant sources in Thailand, which can be considered for producing biodiesel, such as oil palm, coconut, soybean, ground nut, jatropha, sesame, and sunower seed. However, oil palm is considered to be the most suitable raw material in the production of biodiesel because of the high yield of oil per hectare and the quality of that oil. Hence this study is aimed at producing biodiesel by using palm oil as a raw material. Generally, biodiesel (methyl ester of several fatty acids) is the product of a chemical process between triglycerides and a low molecular weight alcohol in the presence of an alkaline catalyst [13]. This reaction is one of transesterication. Raw materials in this process must be anhydrous and have a low content of free fatty acid (FFA) [1]. This is because moisture and high FFA (more than 1 wt.%/ wt) will cause a saponication (soap formation) reaction, which results in lower yields and washing difculties [3,4]. Acid-catalyzed transesterication, enzyme-catalyzed transesterication, supercritical CO2 techniques and a preceding esterication (two-stage) process can all be used for reducing the problem arising from high moisture and a high FFA content in vegetable oils and animal fats [1,3,5]. In this work, the two-stage process was preferred for the production of biodiesel

1544

S. Jansri et al. / Fuel Processing Technology 92 (2011) 15431548

Nomenclature A [A] AL [AL] a [B] b [C] c [D] DG [DG] d E Ea [E] e FFA [FFA] f GL [GL] kA ka ka k1, k2 k3 to k8 the initial reagents the molar concentration of reagent A alcohol the molar concentration of alcohol the reaction order of reagent A the molar concentration of reagent B the reaction order of reagent B the molar concentration of product C the reaction order of product C the molar concentration of product D diglyceride the molar concentration of diglyceride the reaction order of product D ester activation energy, J/mol or cal/mol the molar concentration of ester the reaction order of ester free fatty acid the concentration of free fatty acid the reaction order of free fatty acid glycerol the molar concentration of glycerol the rate coefcient the rate coefcient of the forward reaction the rate coefcient of the reverse reaction kinetics rate coefcient for the esterication reaction kinetics rate coefcient for the various transesterication reactions l the reaction order of alcohol MeOH methanol MG monoglyceride [MG] the molar concentration of monoglyceride R universal gas constant = 8.314 J/mol K or 1.987 cal/ mol K R, R, R, R alkyl groups ROH alcohol RCOOR ester T temperature, K TG triglyceride [TG] the molar concentration of triglyceride [WT] the molar concentration of water w the reaction order of water

from mixed crude palm oil (MCPO) because of the need to generate biodiesel in a short time, at a low temperature and at a low pressure. The rst stage effectively produces biodiesel from the FFA while reducing its concentration to less than 1 wt.%/wt in an acid-catalyzed esterication. After removal of water, the second stage is able to produce biodiesel from the triglyceride in an alkali-catalyzed transesterication process. Optimal design of a reactor system to carry out the two stages in a batch or a continuous unit requires knowledge of the kinetics of the various reactions taking place. The kinetics of biodiesel production has been investigated by several researchers [610]. Noureddini et al., [6] investigated the transesterication of soybean oil. The overall reaction appears to take place in three stages, each of which involves a reversible reaction. The effect of variations in the mixing intensity (Agitator Reynolds num-

ber = 3100 to 12,400) and temperatures (30 to 70 C) on the rate of reaction were studied while the molar ratio of alcohol to triglyceride [6:1] and the concentration of catalyst [0.20 wt.%] were held constant. Variations in the mixing intensity appeared to affect the reaction in a similar way to the variation in temperature. A reaction mechanism was proposed consisting of an initial mass transfer-controlled region followed by a kinetically controlled region. Experimental data for the latter region appeared to be in good agreement with a second-order kinetic mechanism. Reaction rate constants and activation energies were determined for all forward and reverse reactions. Darnoko et al., [7] studied the kinetics of methyl ester produced by the transesterication of palm oil with methanol using KOH as the catalyst. The rate of transesterication in a batch reactor with temperatures up to 60 C did not reduce the time to reach the maximal conversion. The conversion of TG, DG, and MG appeared to be second order up to 30 min of reaction time. Reaction rate constants for TG, DG, and MG methanolysis reactions were 0.0180.191 wt.%/ wt mol min1 and were higher at higher temperatures and higher MG reaction than for the TG methanolysis. Activation energies for TG, DG, and MG hydrolysis reactions were 14.7, 14.2, and 6.4 kcal/mol, respectively. The optimal catalyst concentration was 1 wt.%/wt of KOH. Foon et al., [8] studied the kinetics of the base-catalyzed transesterication of palm oil based on the molar ratio of methanol to oil, the amount of catalyst, and the reaction temperature to optimize the conversion rate. Their ndings showed that both sodium hydroxide and sodium methoxide catalyzed the fast formation of palm oil methyl esters with conversions exceeding 99%. The rapid formation of palm oil methyl esters (rate constant of 0.163 l mol min1) was obtained when the reaction was carried out at 60 C, using a 1:10 molar ratio of oil to methanol, and catalyzed by 0.125 mol kg1 oil NaOH. Berrios et al. [9] investigated the kinetics of esterication of FFA in sunower oil with methanol using a molar ratio of (1080):1 (methanol to FFA (oleic acid)) and catalyzed by 5 and 10 wt.%/wt of sulfuric acid based on the FFA concentration. The optimal condition for the reduction of FFA in sunower oil was a 60:1 molar ratio of to oleic acid, a 5 wt.%/wt of sulfuric acid concentration at 60 C. The results of the forward reaction were found to t a rst-order reaction kinetic law whereas the reverse reaction appeared to be a secondorder. The rate constants determined at different temperatures were tted to an Arrhenius equation and the activation energies. It was found that the activation energies of the forward reaction decreased from 50.745 to 44.559 kJ/mol when the catalyst concentration was increased. Stamenkovi et al. [10] studied the kinetics of sunower oil methanolysis at low temperatures (1030 C). The sigmodal curve shown by the results indicated that the reaction was controlled by mass transfer. The objective of this work was to investigate the characteristic of the TG conversion and the methyl ester formation by using a simple kinetic model. It was found that the methanolysis reaction was best represented by a fast irreversible second-order reaction followed by a slow reversible second-order reaction. Although there is a number of researches that investigated on the reaction kinetics of transesterication of palm oil, this investigation has presented the kinetics of biodiesel production from palm oil because of the difference in type of palm oil. A raw material of this study is crude palm oil which is from the mixing of palm ber oil and palm kernel oil; however, only palm ber oil is used as feedstock in a previous work. In addition, there has no studies that ever showed the kinetics of the two-stage process from palm oil and formerly, the reversible reaction rate of palm oil was not investigated. Consequently, this investigation proposes to estimate the kinetics of biodiesel production from MCPO via the two-stage process. In addition, the effect of temperature on the two-stages of biodiesel reaction is also investigated.

S. Jansri et al. / Fuel Processing Technology 92 (2011) 15431548

1545

2. Materials and methods 2.1. Materials Mixed crude palm oil (un-degummed and containing FFA around 812 wt.%/wt) was used as the feed stock for biodiesel production. It was obtained from a local palm oil mill in Had Yai, Songkhla, Thailand. Sulfuric acid, sodium hydroxide and methanol of 98% and of purity commercial grade were purchased from a local chemical store in Had Yai, Songkhla, Thailand. Analytical grade sodium hydroxide (pelleted), sodium periodate, potassium hydrogen phthalate, ethanediol, and bromothymol blue were purchased from Ajax Fine Chem., New Zealand. Sulfuric acid, diethyl ether, iso-propanol, and hexane, also of analytical grade, were purchased from Lab-Scan Analytical Science, Thailand. Analytical grade phenolphthalein and formic acid were purchased from Merck KGaA, Germany. Benzene and HYDRANALcoulomat AG No. 34836, also of analytical grade, were purchased from Honeywell, Germany, and Panreac Quimica, E.U., respectively. 2.2. Theories 2.2.1. Rate equation for a reversible reaction A mole balance for a constant volume reactor shows that the net rate of the reversible reaction is the sum of the reaction rate of the forward and the reverse reaction of reactant A [11]. rA = ka C D ka A B rA = dA dt
d a b

the palmityl and stearyl group derived, respectively, from palmitic and stearic acids. However similar derivatives of other fatty acids may also be present. RCOOR + R OH Ester1 Alcohol1

RCOOR + ROH Ester Alcohol

catalyst 2

(8) The overall transesterication reaction (Eq. (8)) takes place in three successive stages [57]. The corresponding rate equations for the disappearance of triglyceride (TG), diglyceride (DG), monoglyceride (MG), alcohol (AL), ester (E) and glycerol (GL) are given in Eqs. (9)(14) [15]. All of the reactions are reversible and are of pseudo-secondary order overall [6]. dTG = k3 TGAL + k4 DGE dt dDG = k3 TGALk4 DGEk5 DGAL + k6 MGE dt dMG = k5 DGALk6 MGEk7 MGAL + k8 GLE dt dGL = k7 MGALk8 GLE dt 9 10 11 12

1 2 3

dA c d a b = ka C D ka A B dt

2.2.2. Esterication In the two-stage process, esterication is used for converting FFA in the oil to biodiesel thus enabling the subsequent conversion of the triglyceride to biodiesel by transesterication [12]. The FFA contained in the oil is converted into ester by reacting it with alcohol in the presence of sulfuric acid as catalyst as shown in Eq. (4) [13]. However, it should be noted that this reaction is reversible: FFA + R OH
0

dE = k3 TGALk4 DGE + k5 DGALk6 MGE + k7 MGAL dt k8 GLE dAL dE = dt dt 13 14

RCOOR + H O:
k1 k2 0 2

4 2.3. Experiment 2.3.1. Esterication to convert free fatty acids to esters A weight amount of MCPO was heated to the desired reaction temperature and methanol was slowly added. The reactants were mixed for about 5 min before the required amount of concentrated sulfuric acid was added slowly and carefully to act as a catalyst. The 2 l-roundbottomed ask used for the reaction vessel was kept at the reaction temperature by the use of a water-bath (1 C). A 10 cm in diameter, six-bladed mechanical stirrer rotating at 300 rpm (NRe = 2520) ensured adequate mixing. In addition, the ask was tted with a coil-condenser, a thermocouple and a sampling port. 2 mL samples were taken from the ask at 0, 0.5, 1, 3, 5, 7, 9, 12, 15, 18, 20 min [16]. Each sample was immediately immersed in cold water (5 C) to stop the reaction [12]. The composition of each sample was determined by TLC/FID (Thin Layer Chromatography/Flame Ionization Detector) [2], and the appearance of water by Karl Fischer titration technique [17]. At the end of reaction time, the stirrer was stopped and the contents of the ask were transferred to a separating funnel. The reaction was allowed to continue in the separating funnel for at least another 2 h. During this 2 h period, much of the sulfuric acid, some of excess methanol and several of the impurities separated out with the

As a consequence, the rate of appearance of free fatty acid (FFA) can be presented as Eq. (5). The rate of appearance of water is similarly presented as Eq. (6). dFFA f 1 e w = k1 FFA AL + k2 E WT dt dWT f 1 e w = k1 FFA AL k2 E WT dt 5 6

2.2.3. Transesterication Transesterication is a chemical process in which an acyl group in an ester is exchanged for a hydroxyl group in an alcohol thus generating a new alcohol and a new ester as shown in Eq. (7) [4,14]. In the production of biodiesel, the various acyl groups in the esters of the tri-hydric alcohol, 1,2,3-propanetriol (glycerol), are replaced with the hydroxyl groups of an alcohol such as methanol (CH3OH) or ethanol (C2H5OH). This reversible reaction is facilitated by a catalyst and produces a new ester (biodiesel) and the tri-hydric alcohol (glycerol) as shown in Eq. (8) [14]. The most common acyl groups in MCPO are

1546

S. Jansri et al. / Fuel Processing Technology 92 (2011) 15431548

water produced in the reaction, as a black phase. The oily phase above it contained some of the excess methanol, the oil and methyl ester. 2.3.2. Transesterication of the oil The oily phase was poured into the 2 l-round-bottomed ask and heated in the water bath to the required reaction temperature. A sample (4 ml) was extracted and titrated against a standard sodium hydroxide solution (0.1 M) to estimate how much additional sodium hydroxide would need to be added as catalyst. This quantity was added slowly to the reaction vessel and the reaction allowed proceeding, with agitation, for the required time. The sodium hydroxide solution had been previously prepared by dissolving a known mass of sodium hydroxide in a known volume of methanol. As in the esterication experiment, 2 ml samples were withdrawn at the identical time intervals and were similarly analyzed. In addition, glycerol content of the sample was estimated by titration [18]. At the conclusion of the reaction run, the agitator was stopped and the vessel contents were poured into a separating funnel. The reaction was allowed to continue in the separating funnel for 1 h. After that, the products had separated into a light reddish-colored, biodiesel-rich phase and a heavy brown, glycerol-rich phase. Finally, crude biodiesel was cleaned by spray and bubble technique and analyzed according to biodiesel standard of Thailand [19]. The effect of temperature on the rate of FFA and TG production from MCPO was determined as 55, 60 and 65 C. The experimental data were used for computing rate coefcients for the two-stage process (esterication and transesterication) utilizing the curve-tting tool of MATLAB in term of rational t type [6]. It was assumed that the overall order of esterication and transesterication were of primary and secondary order, respectively. The curve-tting tool of MALAB determined rate coefcients with a maximum goodness-of-t as indication by the determination coefcient (R2). The predicted outputs (obtained from MATLAB) was recalculated using Polymath and the RungeKutta method was used for determining the percentage mean data error () and of the standard deviation of the error (). Finally, activation energies of the various reactions taking place in the two-stage process were estimated by using the calculated rate coefcients and the temperatures at which they were observed in the Arrhenius equation [6,7,11]. 3. Results The results for the esterication reaction are presented graphically in Fig. 1. They show that, within the limited range studied, the rate of FFA conversion to ME is not affected by temperature. It appears that better than 92% conversion of FFA was achieved within 5 min (standard deviation () = 0.72) of the reaction commencing in

contrast to Prateepchaukul et al. [2]. They reported the effected of temperature on acid-catalyzed esterication for reducing FFA in MCPO. FFA was reduced to less than 2 wt.% in 90 min at 60 C under the condition of 3 wt.%/wt H2SO4 as a catalyst and a 2.5 molar ratio of methanol to oil. In addition, they also concluded that more reaction time was spent in the FFA reduction though the large amount of catalyst was used because the stirred speed of them was used lower than this experiment. Fig. 2 similarly shows that over the temperature range of 5565 C, ten minute reaction time is sufcient to convert more than 95% of the oil to the methyl ester (ME). Although the reaction time was different due to the amount and type of catalyst, the methanol ratio and the speed of stirrer, the reaction temperature for producing biodiesel from palm oil of all researches was similar [2,7,8]. Darnoko et al., [7] and Foon et al., [8] reported that the conversion of TG in palm oil to ME could be reached more than 95% at 60 C in 30 and 3 min under the conversion of a (6 and 10):1 molar ratio of methanol to oil by using 1 wt.%/wt of KOH and 0.125 mol/kg oil of NaOH, respectively. In addition, Prateepchaukul et al. [2] indicated that when a 5:1 molar ratio of methanol to oil and 2 wt.%/wt of NaOH were used as a reagent for produce biodiesel from palm oil at 60 C, more than 95% conversion of TG in palm oil was obtained in 50 min. Furthermore, within the limitations of the experimental method, there is no effect due to temperature. These results indicate that a reaction temperature at 60 C is suitable for producing biodiesel from MCPO containing high FFA by esterication followed by transesterication. The biodiesel production from un-degummed and de-acidied MCPO, which was carried out by the suitable condition of the twostage process, was analyzed and compared its properties with other biodiesel standard as shown in Table 1. It was found that the biodiesel succeeded in the objective with acceptable requirements for biodiesel standards. The rate coefcient of the two-stage process was calculated by using the curve-tting routines. The determination coefcient (R2) obtained were in the range of 0.848 to 0.992. Rate coefcients were then recalculated by using Polymath package and the RungeKutta method. The results were compared with the original experimental data. Agreement between the original experimental data and the calculated results was not good. This is because of the high percentage mean data error () and of the standard deviation () in for the concentrations of FFA, MeOH, ME and WT (esterication), and of the TG, DG, MG, ME, GL and MeOH concentrations (transesterication). The high variability in accuracy is probably due to the inherent experimental error of the analytical methods used in this study. Subsequently, rate coefcients and reaction orders of the twostage process were recalculated using Polymath package and the RungeKutta method in an iterative loop until the percentage mean

100 8 55 degree Celsius

Reductin of FFA (wt%)

Increment of ME (wt%)

60 degree Celsius 6 65 degree Celsius 4

80 60 40 55 degree Celsius 20 0 60 degree Celsius 65 degree Celsius 40 50 60

10

20

30

40

50

60

10

20

30

Time (min)
Fig. 1. The effect of reaction temperature on FFA reduction.

Time (min)
Fig. 2. The effect of temperature on the production of ME.

S. Jansri et al. / Fuel Processing Technology 92 (2011) 15431548 Table 1 The comparison of methyl ester from MCPO with biodiesel standards. Parameter CPOME Biodiesel standard Austria (ON) Methyl ester (wt.%) Density at 15 C (kg/m3) Viscosity at 40 C (cSt) Flash point (C) Sulfur (wt.%) Sulfated Ash (wt.%) Water and Sediment (vol%) Copper strip corrosion Acid value (mg KOH/g) Free glycerin (wt.%) References 98.75 878.7 4.28 167 0.0004 0.0050 b 0.05 Number 1 0.25 Na 850890 3.55.0 100 0.02 0.80 0.02 [2,14] Germany (DIN) 875890 3.55.0 110 0.01 0.03 Number 1 0.50 0.02 [2,14] Italy (UNI) 98 860900 3.55.0 100 0.01 0.07 0.50 0.05 [2,14] Thiland (ASTM and EN) 96.5 860900 1.98 120 0.0015 0.02 0.2 Number 3 0.80 0.02 [19]

1547

USA (ASTM) 1.96.0 130 0.80 0.02 [14]

CPOME is Mixed Crude Palm Oil Methyl Ester.

Table 2 Rate coefcients for esterication and transesterication of the two-stage process. Conditions (molar ratios; C) Esterication 10:1;55 10:1;60 10:1;65 Transesterication 6:1;55 6:1;60 6:1;65 Rate Coefcients (L/mol.min) k1 0.840 1.340 1.899 k2 0.680 0.682 0.684 k3 K4 k5 k6 k7 k8 37 22 37 43 21 32

2.579 2.600 2.620

0.020 0.248 0.700

0.600 1.186 1.210

0.101 0.227 0.400

0.900 2.303 2.360

0.021 0.022 0.028

59 41 44

107 42 80

data error () and the standard deviation () had been reduced to the values shown in Table 2 (whole population: = 35, = 62). The best-t values of the rate coefcients were used for obtaining approximate activation energy (Ea) by seeking a straight line relationship between the logarithm of the rate coefcients and the reciprocal of the absolute temperature. Results for the two stages are presented in Figs. 3 and 4. The slope of line was used for estimating activation energies for the separate reactions and gave the results shown in Table 3. According to kinetic theory [4], if only temperature had impacted on reaction, low activation energies in a short time would be obtained. However, the values of average activation energies of overall reaction as shown in Table 3 were still high even though the retention time of the reaction is lower. Hence, not only reaction temperature but also other parameters were affected on the reaction rate such as the

concentration of reactants (catalyst and alcohol) and the mixing intensity. According to the collision model [4], the concentration of reactants inuenced the values of activation energies of a reaction. The amount of catalyst and alcohol in this process was used less than or equal to one another such as Prateepchaukul et al. [2], Darnoko et al., [7] and Foon et al., [8]. Therefore, the concentration of reagents was also not the main effects on the reaction rate. In the same way, mixing intensity was another effect on the reaction rate. The reaction without mixing occurred only at the interface of the two layers causing the increase of the reaction time because oil and alcohol were insoluble reagents [20]. The study of mixing intensity of Noureddini et al. [6] and Rashid et al. [20] found that the reaction time was decreased when the mixing intensity was

1 0.6 0.4 k1 k2 0

k3 k4 k5 k6 k7

Log(K)

0.2 0

Log (k)

-1 -2 -3

-0.2 -4 2.96 2.98 3 3.02 3.04 x 10-3 2.96 2.98 3 3.02 3.04 x 10-3

k8

1/T

1/T

Fig. 3. The temperature dependency of reaction rate coefcients of esterication at a 10:1 molar ratio of methanol to FFA.

Fig. 4. The temperature dependency of the reaction rate coefcients of transesterication at a 6:1 molar ratio of methanol to TG.

1548

S. Jansri et al. / Fuel Processing Technology 92 (2011) 15431548

Table 3 Activation energies (cal/mol) of the two-stage process at different molar ratios of methanol to oil. Esterication Esterication FFA-WT (k1) WT-FFA (k2) Transesterication TG-DG (k3) DG-TG (k4) DG-MG (k5) MG-DG (k6) MG-GL (k7) GL-MG (k8) Activation energy (cal/mol) 17,997 129 R2 0.9944 0.9999

Acknowledgments The authors acknowledge the Joint Graduate School of Energy and Environment at King Mongkut's University of Technology Thonburi, Thailand, and Ofce of National Research Council of Thailand for providing the scholarship and research grant and Department of Mechanical Engineering, Faculty of Engineering, Prince of Songkla University, Thailand, for facilitating the research location.

348 78,560 15,538 30,372 21,356 6321

0.9999 0.9493 0.7786 0.9914 0.7763 0.8617

References
[1] F. Ma, H.A. Hanna, Biodiesel production: a review1, Bioresour. Technol. 70 (1998) 115. [2] G. Prateepchaikul, M.L. Allen, T. Leevijit, K. Thaveesinsopha, Methyl ester production from high free fatty acid mixed crude palm oil, Songklanakarin J. Sci. Technol. 29 (6) (2007) 15511561. [3] J. van Gerpen, B. Shanks, R. Pruszko, D. Clements, G. Knothe, Biodiesel production technology, NREL (2004) 140. [4] T.L. Brown, E.H. LeMay, J.R. Burdge, Chemistry: the Central Science, ninth ed., Prentice Hall, New Jersey, 2003. [5] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Possible methods for biodiesel production, Renewable and Sustainable Energy Rev. 11 (6) (2005) 13001311. [6] H. Noureddini, D. Zhu, Kinetics of transesterication of soybean oil, JAOCS 74 (11) (1997) 14571461. [7] D. Darnoko, M. Cheryan, Kinetics of palm oil transesterication in a batch reaction, JAOCS 77 (12) (2000) 12631267. [8] C.S. Foon, C.Y. May, M.A. Ngan, C.C. Hock, Kinetics study on transesterication of palm oil, JOPR 16 (2) (2004) 1929. [9] M. Berrios, J. Siles, M.A. Martn, A. Martn, A kinetic study of the esterication of free fatty acids (FFA) in sunower oil, Fuel 86 (2007) 23832388. [10] O.S. Stamenkovi, Z.B. Todorovi, M.L. Lazi, V.B. Veljkovi, D.U. Skala, Kinetics of sunower oil methanolysis at low temperature, Bioresour. Technol. 99 (2008) 11311140. [11] S.H. Fogler, Element of Chemical Reaction Engineering, third ed. Prentice Hall, New Jersey, 2006. [12] S. Jansri, G. Prateepchaikul, S.B. Ratanawilai, Acid-catalyzed esterication: a technique for reducing high free fatty acid in mixed crude palm oil, Kasetsart J. (Nat. Sci.) 41 (3) (2007) 555560. [13] T.A. Peters, N.E. Benes, A. Holmen, J.T.F. Keurentjes, Comparison of commercial solid acid catalysts for the esterication of acetic acid with butanol, Appl. Cat. A: Gen. 297 (2006) 182188. [14] L.C. Meher, S.D. Vidya, S.N. Naik, Technical aspects of biodiesel production by transesterication a review, Renewable and Sustainable Energy Rev. 47 (5) (2004) 353. [15] M. Allen, G. Prateepchaikul, The Modelling of the Biodiesel Reaction, available online:http://journeytoforever.org. 2003. [16] C.Y. May, Transesterication of palm oil: effect of reaction parameters, JOPR 16 (2) (2004) 111. [17] G. Prateepchaikul, S. Jansri, The Reduction of Free Fatty Acid in Mixed Crude Palm Oil via Esterication (in Thai), PEC 6, Faculty of Engineering, Prince of Songkla University, Hat Yai, Songkhla, Thailand, 2008 [May 89, 2008]. [18] Thai Industrial Standards Institute, Standard for Crude Glycerine: BS 26215: 1964 (specication for glycerol (glycerine) in Thailand) (in Thai), 1980, pp. 711. [19] Department of Energy Business, Methyl Ester Quality for Agricultural Engines in Thailand, available online:http://www.doeb.go.th. 2006. [20] U. Rashid, F. Anwar, Production of biodiesel through optimized alkaline-catalyzed transesterication of rapeseed oil, Fuel 87 (2008) 265273.

increased because it supported the mass transfer control in the rst reaction time. Therefore, mixing intensity was necessary to promote the biodiesel reaction which was consistent with the collision model [4]. Mixing intensity was the main effect to reduce the reaction time though the reaction had high activation energy. In addition, the results indicated that the forward reactions of the two-stage process were very fast because the activation energies were lower than their reverse reactions. Except for the conversion of FFA to ME and MG to GL in esterication and transesterication, respectively, the activation energy of forward reaction was higher than the reverse reaction causing the reaction to be reversed easily. At the optimum conditions of the reaction, therefore, the waste of each process (WT and GL) should be immediately separated from the product. 4. Conclusion In the esterication stage of the two-stage process, carried out with excess methanol at 5565 C, reaction rate coefcients for the FFA forward and the reverse reaction were found to be 1.340 and 0.682 l mol1 min1, respectively. In the transesterication stage, rate coefcients for the forward reactions of TG, DG and MG were 2.600, 1.186, and 2.303 l mol1 min1, respectively and for the reverse reactions 0.248, 0.227, and 0.022 l mol1 min1, respectively. Approximate activation energies determined in this investigation ranged from around 120 to 80,000 cal/mol using the simple Arrhenius model. Thus it is able to produce biodiesel from MCPO by using an optimal two-stage process. In addition, esterication process can be used for the pre-treatment of low-cost, highly acidic palm oils to produce an excellent feedstock for the conventional biodiesel production process. In reducing the concentration of free fatty acid in the crude palm oil by turning it into useful ester, the process also eliminates the need for traditional gum removal. Such a two-stage process could therefore provide the basis for the development of a bio-fuel from otherwise unmarketable vegetable oils.