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J. of Supercritical Fluids 44 (2008) 356363

Transesterication of RBD palm oil using supercritical methanol

Eun-Seok Song, Jung-won Lim, Hong-Shik Lee, Youn-Woo Lee
School of Chemical and Biological Engineering and Institute of Chemical Processes, Seoul National University, San 56-1 Sillim-dong, Gwanak-gu, Seoul 151-744, Republic of Korea Received 5 March 2007; received in revised form 27 July 2007; accepted 11 September 2007

Abstract In this work, a batch-type reactor system was used to prepare biodiesel from RBD palm oil in supercritical methanol without any catalyst. Experiments were carried out by changing the operation parameters such as temperature (200400 C), the mole ratio of methanol to RBD palm oil (380) and reaction time (0.520 min). The content of fatty acid methyl esters (FAMEs) was analyzed using a gas chromatography by means of British standards. The content of FAMEs increased drastically with temperature above the critical point and with the mole ratio of methanol to RBD palm oil up to 30. However, the content of FAMEs was affected by thermal decomposition of RBD palm oil and FAMEs above 300 C. Irreversible reaction scheme was used to examine the kinetics of transesterication of RBD palm oil. Activation energy calculated by nonlinear regression was agreed well with the published data. 2007 Elsevier B.V. All rights reserved.
Keywords: Biodiesel; Transesterication; Palm oil; Supercritical methanol

1. Introduction Biodiesel is an alternative fuel for diesel engines that is produced by chemical reaction of a vegetable oil or animal fat with an alcohol such as methanol. The product is called as methyl esters or biodiesel, which is receiving increased attention as an alternative, nontoxic, biodegradable, and renewable diesel fuel. Many researchers have shown that promise as an alternative fuel for diesel engines [111]. When biodiesel displaces petroleum diesel, it reduces global warming gas emissions such as carbon dioxide. Biodiesel has no aromatics, almost no sulfur, and contains 11% oxygen by weight. These characteristics of biodiesel reduce the emissions of carbon monoxide, hydrocarbon, and particulate matter in the exhaust gas compared to petroleum-based diesel fuel [1114]. Transesterication, also called alcoholysis, is the displacement of alcohol from an ester by another alcohol in a similar to hydrolysis, except than alcohol is used instead of water. Fig. 1 shows transesterication of triglycerides (TG) with alcohol. Each reaction step is reversible. This process has been widely used to reduce the viscosity of vegetable oils. Methanol and ethanol are utilized most frequently, especially methanol

Corresponding author. Tel.: +82 2 880 1883; fax: +82 2 883 9124. E-mail address: ywlee@snu.ac.kr (Y.-W. Lee).

because of its low cost and its physical and chemical advantages. If methanol is used in this process it is called methanolysis. Thus, fatty acid methyl esters (FAMEs, known as biodiesel fuel) obtained by transesterication is similar to conventional diesel fuel in its main characteristics and can be used as an alternative fuel for diesel engines [16,8]. The reaction can be catalyzed by alkalis, acids or enzymes. For an alkali-catalyzed transesterication, the glycerides and alcohol must be substantially anhydrous because water makes the reaction partially change to saponication, which produces soap. The soap lowers the yield of esters and renders the separation of ester and glycerol and the water washing difcult. Low free fatty acids (FFAs) content in vegetable oil is required for alkali-catalyzed transesterication [1,4,8]. In the acid-catalyzed process, the presence of water and FFAs had a signicant effect on the FAMEs production as well as in the alkali catalysis [15]. Lower-cost feedstocks are needed, in spite of negative effect of water and FFAs, since biodiesel from food-grade oils is not economically competitive with petroleum-based diesel fuel. Unfortunately, many of these feedstocks contain large amounts of FFAs. These FFAs react with alkali catalysts to produce soaps that inhibit the FAMEs formation [10,16]. In the case of the vegetable oils that contain up to about 5% FFAs, the transesterication reaction can still be catalyzed with an alkali catalyst. However, additional catalyst must be added to compensate for

0896-8446/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.supu.2007.09.010

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Nomenclature A C Ea k m M Nexp r R SSQ t T pre-exponential factor (s1 )(mol/dm3 )1 (mol/dm3 ) concentration (mol/dm3 ) activation energy (J/mol) kinetic rate constant mass (g) molecular weight (g/mol) number of experimental data reaction rate (mol/dm3 s) the universal gas constant (8.314 J/mol K) sum of square times (s) temperature (K)

Greek letters reaction order for triglyceride reaction order for methanol reaction time Subscripts 0 initial value exp experimental value FAME fatty acid methyl ester MeOH methanol pred predicted value by tted model TG triglyceride

the catalyst lost to soap. This soap can inhibit the separation of the methyl esters and glycerol and contributes to emulsion formation during the water wash [7]. Therefore, acid catalyst, such as sulfuric acid, is used to esterify the FFAs to FAMEs. This process can be used to reduce the FFAs level of the feedstocks and to decrease the acid value of the reaction mixture. The low FFAs pretreated oil can be transesteried with an alkali catalyst [7,10,16].

To meet the requirements of biodiesel standards such as ASTM D6751 [17] or EN14214 [18], post-reaction processes such as ester/glycerol separation, ester washing, ester drying, other ester treatments and additization are required. Among these processes, ester washing and ester drying are needed due to the use of alkali catalyst. Ester washing is used to neutralize any residual catalyst and remove any soap formed. Ester drying is also required to remove water used for washing [10]. Saka and Kusdiana [1921] prepared biodiesel fuel from rapeseed oil using supercritical methanol. Supercritical methanol can form a single phase in contrast to the two phase nature of oil/methanol mixture at ambient condition. This is due to a decrease in dielectric constant of methanol at supercritical state. No catalyst was used and the reaction was completed in a very short time within 24 min. Due to non-catalytic process, pretreatment or post-reaction processes mentioned above became much simpler and no wastewater was produced, compared with the conventional alkali catalyst process [1921]. Vegetable oils from rapeseed, soybean and oil palm have been mostly used for biodiesel production. Products from 1 ha each of oil palm, soybean and rapeseed acreage and world supply are shown in Table 1. Oil palm can be regarded as a cost-effective vegetable oil crop with average yields of 3.55.0 103 kg of palm oil/ha/year [22]. Since palm oil contains, however, more saturated fatty acids, that is, palmitic acid (16:0), its pour point is higher than biodiesel prepared from soybean or rapeseed oil [1,23]. High petroleum price demands the study of biofuel production. Lower price feedstocks are needed to compete with petroleum diesel since the biodiesel price is highly dependent on the purchasing cost of raw material. Palm oil is the cheapest among the vegetable oils available to Korea due to being close to palm-producing areas such as Malaysia, Indonesia and Thailand. Crude palm oil contains approximately 1% of minor components such as carotenoids, vitamin E, sterols, phospholipids, glycolipids and so on. Rening, bleaching and deodorization are rstly conducted due to separation of these useful constituents. Therefore, rened, bleached and deodorized (RBD) palm oil was used for the biodiesel production. Non-catalytic transesterication or methanolysis of RBD palm oil was carried out using supercritical methanol. Transesterication of vegetable oils consists of a number of consecutive, reversible reactions. Reaction rate and
Table 1 Products from the harvested crops and world supply of vegetable oils Palm 2003/04 World supply of oil (109 kg/year)a 2005/06 World supply of oil (109 kg/year)b Crops harvested (103 kg/ha)c Oil produced (103 kg/ha)c
a

Soybean 29.85 33.87 2.3 0.4

Rapeseed 14.20 16.59 3.0 1.2

29.70 34.80 19.1 4.8

Fig. 1. Transesterication of triglyceride with alcohol. Rs represent alkyl groups.

Data from reference [22]. b Forecasted data [22]. c Data from oil palm in Malaysia, soybean in Brazil, and rapeseed in Sweden [23].

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Fig. 2. The batch reactor system of transesterication of RBD palm oil.

chemical equilibrium are dependent on the experimental variables such as reaction time, temperature, pressure and mole ratio of methanol to RBD palm oil. Therefore, in this work, the effects of each experimental variable on the contents of FAMEs were investigated. 2. Experimental 2.1. Materials RBD (rened, bleached and deodorized) palm oil used in this study was supplied from Dong Nam Oil & Fats Co., Ltd. Methanol (Samchun Chemical Co., Ltd.) was employed as a reaction media. Methyl heptadecanoate (99% pure, SigmaAldrich Korea, Co.) was used for an internal standard of analysis for FAMEs. n-Heptane (99% pure, Kanto Chemical) was used as an analytical solvent. 2.2. Apparatus Fig. 2 shows the batch-type reactor system for transesterication of RBD palm oil using supercritical methanol. Batch reactor was made from SUS 316 tubing (3/8 inch) and had the volume of about 4.7 cm3 . Molten salt bath (Daepung Industry) was used for heating batch reactor up to reaction temperature. Temperature in the bath was measured by K-type thermocouple and controlled by PID controller. Salt used in this study consisted of KNO3 , NaNO3 and Ca(NO3 )2 . 2.3. Procedure RBD palm oil and methanol were loaded into the reactor with prescribed mole ratio. The batch reactor was then quickly immersed into the molten salt bath preheated up to reaction temperature of 200400 C. After the reaction time of transesterication, 0.520 min, the reactor was moved into ice-water

bath and cooled rapidly to terminate the reaction. The batch reactor was shaken up and down by manufactured shaker during reaction time. As shown in Fig. 3, the contents of FAMEs were not affected by pressure above 30 MPa in the previous study [24]. Therefore, the experiments were conducted above 40 MPa. Since the densities of RBD palm oil and FAMEs changed slightly with temperature and pressure, the pressure inside the batch reactor was assumed to be dependent only upon methanol density. The loaded amounts of reactants were calculated from the methanol density that made the system pressure 40 MPa. The densities of methanol were referred to NIST chemistry webbook [25]. Lack of data above 346.9 C was supplemented by linear extrapolation.

Fig. 3. Synthesis of biodiesel at various pressures using RBD palm oil at 350 C for 40 min. Mole ratio of methanol to RBD palm oil was kept at 60 [24].

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2.4. Preparation of samples and analysis Fig. 4 shows the transesterication reaction and followed post-treatment processes of RBD palm oil using supercritical methanol. Pretreatment of feedstock is not indispensable for the supercritical process. Evaporation and layer separation are used for the separation of unreacted methanol and produced glycerol, while conventional alkali process requires additionally the removal of alkali catalyst and biodiesel washing process. Unreacted methanol in the biodiesel sample was evaporated overnight in drying oven at 70 C. In this work, layer separation between biodiesel and glycerol was just performed by gravimetric precipitation since the amount of biodiesel sample was smaller than 1 g after removal of methanol. As described above, BS EN14103 [26] was used for the analysis of biodiesel samples. The contents of FAMEs in crude biodiesel were analyzed by GC (Agilent, HP6890) with a capillary column (Agilent, HP-INNOWAX, 30 m 0.32 mm 0.25 m) and ame ionization detector. Heptadecanoate (17:0) was used for an internal standard. 3. Results and discussion Transesterication of RBD palm oil was carried out at various reaction conditions. Pressure was xed at about 40 MPa based on the density of methanol as mentioned above. Table 2 represents experimental conditions such as temperature, reac-

tion time, loading amount of RBD palm oil and methanol, and the content of FAMEs. 3.1. Effect of temperature Transesterication of RBD palm oil was carried out at various temperatures using supercritical methanol. Mole ratios of methanol to RBD palm oil were 45 and 60, respectively. Reaction time was 5 min. Fig. 5 shows the contents of FAMEs at various temperatures. FAMEs were detected at temperatures above critical point of methanol (239.45 C). The contents of FAMEs increased with temperature up to 350 C. However, the contents of FAMEs decreased above 375 C. Kusdiana and Saka [20] presented similar result for rapeseed oil. They mentioned that decomposition reaction takes place at temperature above 400 C due to the thermal degradation. Wan Nik et al. [27] investigated TGA study of palm oil in nitrogen atmosphere. They pointed out that the 1% weight loss of RBD palm oil occurs around 279 C and the maximum degradation rate at about 381 C. Therefore, 350 C can be considered as an optimum temperature for transesterication of RBD palm oil using supercritical methanol when the operating conditions are those as listed above. 3.2. Effect of mole ratio of methanol to RBD palm oil Mole ratio between methanol and vegetable oil has been considered one of the most important parameters affecting the yield

Table 2 Experimental conditions of transesterication of RBD palm oil (unit: temperature ( C), reaction time (min), loading amount of palm oil and methanol (g)) No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Temperature 351 351 351 351 351 351 349 349 349 349 349 349 348 348 348 348 348 348 350 350 350 350 350 350 350 350 350 350 350 Reaction time 0.5 1 2 3 4 5 6 8 10 12.5 15 20 0.5 1 2 3 4 5 6 8 10 12.5 15 20 5 5 5 5 5 Palm oil 0.9255 0.9275 0.9311 0.9299 0.9331 0.9263 0.9296 0.9302 0.9292 0.9292 0.9273 0.9298 0.7354 0.7353 0.7366 0.7373 0.7343 0.7347 0.7336 0.7382 0.7376 0.7343 0.7333 0.7334 3.4551 2.8943 2.3748 1.6438 1.2577 Methanol 1.5831 1.5830 1.5867 1.5831 1.5838 1.5830 1.5824 1.5823 1.5846 1.5800 1.5842 1.5876 1.6730 1.6747 1.6711 1.6732 1.6756 1.6737 1.6758 1.6744 1.6800 1.6724 1.6711 1.6738 0.3910 0.6557 0.8985 1.2433 1.4272 FAMEs content 0.1332 0.4869 0.8716 0.9265 0.9304 0.9333 0.9322 0.9261 0.9262 0.9337 0.9218 0.9279 0.0998 0.1972 0.6887 0.8325 0.8981 0.9292 0.9368 0.9390 0.9412 0.9392 0.9408 0.9336 0.4559 0.5032 0.7420 0.8370 0.9207 No. 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 Temperature 350 351 350 348 350 350 350 350 350 350 350 349 350 350 350 203 225 251 276 299 325 339 351 203 225 251 276 299 325 Reaction time 5 5 5 5 5 10 10 10 10 10 10 10 10 10 10 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Palm oil 1.1054 0.9236 0.8552 0.7347 0.5773 3.4528 2.8931 2.3755 1.6451 1.2566 1.0182 0.9292 0.8535 0.7376 0.5768 1.2819 1.2350 1.1866 1.1283 1.0623 0.9911 0.9452 0.9263 1.0376 1.0053 0.9578 0.9068 0.8498 0.7882 Methanol 1.5405 1.5830 1.6190 1.6737 1.7501 0.3919 0.6579 0.8984 1.2437 1.4262 1.5400 1.5846 1.6183 1.6800 1.7488 2.1814 2.1087 2.0243 1.9253 1.8157 1.6876 1.6072 1.5830 2.3597 2.2728 2.1726 2.0592 1.9320 1.7932 FAMEs content 0.9313 0.9333 0.9326 0.9292 0.9301 0.5766 0.7040 0.8308 0.9048 0.9355 0.9187 0.9262 0.9359 0.9412 0.9441 0.0118 0.0124 0.0604 0.0734 0.3315 0.5677 0.8319 0.9333 0.0037 0.0057 0.0713 0.1440 0.2997 0.6535

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Fig. 4. Transesterication process of RBD palm oil using supercritical methanol.

of FAMEs between 5 and 10 min became distinct below the mole ratio of 30. The contents of FAMEs were higher when the mole ratio was 60. Then, for complete conversion of RBD palm oil, a reaction time greater than 10 min at a mole ratio below 30 is required. The reaction rate of transesterication of RBD palm oil increased with mole ratio. 3.3. Effect of reaction time Fig. 7 shows the temporal change of the contents of FAMEs. Reaction temperature was xed at 350 C and pressure at 40 MPa. Mole ratios between methanol and RBD palm oil were 45 and 60. Since mole ratios were higher than 30, transesterication reaction was completed at about 5 and 4 min, respectively. The content of FAMEs remained constant or decreased slightly due to thermal decomposition after transesterication reached reaction equilibrium. The difference between each experimental data set for the mole ratio of 45 and 60 became largest at 2 min. Reaction rate increased with mole ratio. In particular, mole ratio had a strong effect on the initial reaction rate. 3.4. Kinetics of transesterication of RBD palm oil
Fig. 5. Contents of FAMEs at various temperatures (pressure = 40 MPa; reaction time = 5 min; mole ratio of methanol to RBD palm oil = 45 ( ) and 60 ( ).

As shown in Fig. 1, transesterication of RBD palm oil is a series reaction. Each step is reversible and produces 1 mol of

of FAMEs. The stoichiometric ratio of the transesterication is 3. As shown in Fig. 1, 3 mol of methanol are required for the production of 3 mol of FAMEs and 1 mol of glycerol from 1 mol of TG. To shift the transesterication reaction to the right, it is necessary to use either a large excess of alcohol or to remove one of the products from the reaction mixture. The second option is preferred wherever feasible, since in this way, the reaction can be driven to completion. Since high mole ratio increase the reaction rate, a mole ratio of 6:1 is normally used in industrial processes. However, higher mole ratio of alcohol to vegetable oil interferes in the separation of glycerol [2]. Fig. 6 shows the effect of mole ratio on the transesterication of RBD palm oil. Reaction temperature was xed at 350 C and pressure at about 40 MPa. Reaction was conducted for 5 and 10 min at various mole ratios, respectively. The contents of FAMEs increased drastically up to the mole ratio of 30 and were kept nearly constant above 30. As mentioned above, excess methanol is used to enhance methanolysis of vegetable oil. However, after methanolysis, unreacted methanol must be separated from products as shown in Fig. 4. This separation process requires energy and its cost. This cost is considered as a key factor of economic feasibility for transesterication of vegetable oil using supercritical methanol. The difference in content

Fig. 6. Contents of FAMEs at various mole ratios of methanol to RBD palm oil (pressure = 40 MPa; temperature = 350 C; reaction time = 5 min ( ) and 10 min ( ).

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the content of FAMEs in the biodiesel sample. X= = mFAME /MFAME CFAME = 3CTG,0 3mTG,0 /MTG mFAME /3MFAME mFAME content of FAMEs mTG,0 /MTG mTG,0 (5)

As mentioned above, the conversion of transesterication reaction can be acquired from the content of FAMEs without analyzing concentration of TG. Meanwhile, as activation energy (Ea ) and pre-exponential factor (A) are introduced, Eq. (2) becomes dCTG Ea = A exp dt RT
0 CTG CMeOH

(6)

Integration of Eq. (6) for the reaction time of gives CTG () = A exp Ea RT
CTG CMeOH dt

(7)

Fig. 7. Temporal changes of the contents of FAMEs (pressure > 40 MPa; temperature = 350 C; mole ratio of methanol to RBD palm oil = 45 ( ) oil and 60 ( ).

Right hand side of Eq. (7) can be integrated with initial conditions as follows: CTG = CTG,0 , CMeOH = CMeOH,0 at t = 0 (8)

FAME. In this work, methanol was used in excess at more than 15 times of the stoichiometric requirement. Therefore, the forward reaction became dominant and each reaction step could be regarded as an irreversible reaction. In addition, if we assumed that methanolysis of TG is controlling rate step of overall reaction, transesterication reaction of TG can be dened as follows: TG + 3MeOH 3FAME + Glycerol rTG = dCTG = kCTG CMeOH dt (1) (2)

As depicted in Figs. 57, concentrations of FAMEs were measured by BS EN14103:2003 [27] at different reaction condition. Experimental variables were temperature, reaction time, and initial concentrations of TG and methanol. From the experimental data set, unknown parameters such as reaction orders, pre-exponential factor, and activation energy can be tted [28]. LevenbergMarquardt algorithm was used to calculate parameters and minimize sum of square of error dened as follows:
Nexp

SSQ
n=1

(Xexp Xpred )2

(9)

where rTG represents consumption rate of TG (mol/dm3 s). As 1 mol of TG reacts with 3 mol of methanol, 3 mol of FAMEs are produced. Production rate of FAMEs by transesterication of TG can be written as follows: rFAME = dCFAME dCTG = 3 = 3kCTG CMeOH dt dt (3)

where Xpred () 1 CTG () CTG,0 (10)

If the loss by pyrolysis or decomposition of RBD palm oil or biodiesel were negligible, the conversion of RBD palm oil would be same as the mole ratio between FAMEs produced and TG loaded. X=1 CTG CTG,0 CFAME /3 CFAME =1 = CTG,0 CTG,0 3CTG,0 (4)

Since the molecular weight of TG is almost same with three times of that of FAMEs, conversion can be related with the mass fraction. As described in Fig. 4, TG and FAMEs remained only in the biodiesel sample after separating methanol and glycerol. In addition, it can be assumed that the weight loss in the separation process in Fig. 4 is negligible. Even if there were much loss of the biodiesel sample, it does not affect on the content of FAMEs in the sample due to single phase nature of FAMEs and TG mixture. Therefore, conversion can be related with the mass fraction or

The conversion of TG was predicted by Eq. (10) after integration of Eq. (7). This value and experimental value listed in Table 2 were used to calculate SSQ in Eq. (9). The mrqmin subroutine was used to minimize SSQ [29]. Integration of Eq. (7) was conducted by Runge-Kutta 4th order scheme with initial conditions (8). As listed in Table 2, 58 experimental data from transesterication of RBD palm oil were used for numerical analysis. Fig. 8 shows a good comparison between the experimental and predicted concentrations of FAMEs. The coefcient of determination, r2 was 0.9578. This indicated that 95.78% of the original uncertainty was explained by the model [30]. Experimental data were tted well with reaction rate equation given as follows: dCTG = (4.3376 105 ) dt exp 1.0527 105 RT
0.9565 1.0493 CTG CMeOH

(11)

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Fig. 8. Comparison of experimental and predicted concentrations of FAMEs.

Kusdiana and Saka [20] calculated the kinetic rate constant for the transesterication of rapeseed oil using supercritical methanol. Integral method [28] was used to calculate the kinetic rate constant. They assumed rst-order reaction for unmethyl ester such as TG, DG, MG and glycerol. Since they did not present the activation energy and pre-exponential factor, we calculated kinetic data from kinetic rate constants listed in the literature [20]. Activation energy was about 20 kJ/mol for the data above 300 C and 16.7 kJ/mol for the data below 270 C. Diasakou et al. [31] investigated the non-catalytic transesterication of soybean oil at 220235 C. They presented two kinds of activation energy for each reaction step as described in Fig. 1(b). The activation energy was 117 kJ/mol for the transformation of TG to DG and 128 kJ/mol for that of DG to MG. Stamenkovic et al. [32] studied the kinetics of sunower oil methanolysis at lower temperatures with alkali catalyst. Two kinds of reaction scheme, irreversible and reversible reaction, were explained. 53.5 kJ/mol was obtained for irreversible reaction scheme. Activation energy was calculated to be 105 kJ/mol for the transesterication of RBD palm oil using supercritical methanol. This is similar with that of Diasakou et al. for non-catalytic methanolysis of soybean oil at subcritical condition and larger than that of Stamenkovic et al. for the catalytic transesterication of sunower oil. Since catalyst was not used in this work, activation energy became larger than that for the catalytic reaction in spite of the single phase nature of the FAMEs and TG mixture. Reaction order for TG and methanol was obtained to be nearly rst-order. Reaction rate was also dependent on the methanol concentration despite high mole ratio of methanol to TG. 4. Conclusions Biodiesel was prepared by transesterication of RBD palm oil using supercritical methanol. Batch reactor system was used. Effects of reaction time, temperature and mole ratio of methanol

to RBD palm oil were investigated. Biodiesel production rate showed a tendency to increase dramatically near critical temperature of methanol. However, contents of FAMEs decreased above 350 C due to thermal decomposition of RBD palm oil or biodiesel. It was the highest at 350 C when the reaction time was 5 min. Biodiesel with high contents of FAMEs could be produced at mole ratio higher than 30:1 at 350 C. When the mole ratio of methanol to RBD palm oil was 45:1 at 350 C, transesterication of RBD palm oil with methanol reached reaction equilibrium after 5 min. The increase of mole ratio by 60:1 decreased time to achieve equilibrium to 4 min. Supercritical methanolysis does not require any kind of catalyst and longer reaction time. In this work, no pretreatment to remove water or FFAs was used. As shown in Fig. 4, two separation processes evaporation and layer separation were used for the purication of biodiesel. Supercritical process is simpler and faster than alkali catalyst method in biodiesel production. In addition, since wastewater is not produced by pretreatment or washing process, the supercritical process is environmental friendly. However, high investment and energy cost are probably required due to high temperature and pressure at supercritical state. Methanol in excess is needed to enhance the forward reaction without catalyst. It is expected that these costs are comparable to these for the pretreatment and separation process of the alkali-catalyst process. Moreover, if the usage of methanol were reduced, economical feasibility would be possible. Acknowledgements The authors gratefully acknowledge the nancial support of the LG Household & Health Care Ltd. and Korea Energy Management Corporation (KEMCO) under New and Renewable Energy Research Development and Demonstration. References
[1] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresour. Technol. 70 (1999) 115. [2] A. Srivastava, R. Prasad, Triglycerides-based diesel fuels, Renew. Sust. Energy Rev. 4 (2000) 111133. [3] G. Knothe, Historical perspectives on vegetable oil-based diesel fuels, Inform 12 (2001) 11031107. [4] H. Fukuda, A. Kondo, H. Noda, Biodiesel fuel production by transesterication of oils, J. Biosci. Bioeng. 92 (5) (2001) 405416. [5] A. Demirbas, Biodiesel fuels from vegetable oils via catalytic and noncatalytic supercritical alcohol transesterications and other methods: a survey, Energy Convers. Manage. 44 (2003) 20932109. [6] A. Demirbas, Biodiesel production from vegetable oils via catalytic and non-catalytic supercritical methanol transesterication methods, Prog. Energ. Combust. 31 (2005) 466487. [7] J.V. Gerpen, Biodiesel processing and production, Fuel Process. Technol. 6 (2005) 10971107. [8] L.C. Meher, D.V. Sagar, S.N. Naik, Technical aspects of biodiesel production by transestericationa review, Renew. Sust. Energy Rev. 10 (2006) 248268. [9] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Possible methods for biodiesel production, Renew. Sust. Energy Rev. 11 (2007) 13001311. [10] J.V. Gerpen, B. Shanks, R. Pruszko, D. Clements, G. Knothe, Biodiesel Production Technology, NREL/SR-510-36244, National Renewable Energy Laboratory, 2004.

E.-S. Song et al. / J. of Supercritical Fluids 44 (2008) 356363 [11] US Department of Energy, Biodiesel Handling and Use Guidelines, DOE/GO-102006-2288, second ed., 2006. [12] C. Peterson, T. Hustrulid, Carbon cycle for rapeseed oil biodiesel fuels, Biomass Bioenerg. 14 (1998) 91101. [13] J. Sheehan, V. Camobreco, J. Dufeld, M. Graboski, H. Shapouri, Life Cycle Inventory of Biodiesel and Petroleum Diesel for Use in an Urban Bus, NREL/SR-580-24089, National Renewable Energy Laboratory, 1998. [14] US Environmental Protection Agency, A comprehensive analysis of biodiesel impacts on exhaust emissions, Draft Technical Report, EPA420P-02-001, 2002. [15] M. Canakci, J.V. Gerpen, Biodiesel production via acid catalysis., Trans. ASAE 42 (5) (2001) 12031210. [16] M. Canakci, J.V. Gerpen, Biodiesel production from oils and fats with high free fatty acids, Trans. ASAE 44 (6) (2001) 14291436. [17] ASTM International, D 6751-06a: standard specication for biodiesel fuel (B100) blend stock for distillate fuels (2006). [18] European Committee for Standardization (CEN), EN 14214:2003, Automotive fuels fatty acid methyl esters (FAME) for diesel engines requirements and test methods (2003). [19] S. Saka, D. Kusdiana, Biodiesel fuel from rapeseed prepared in supercritical methanol, Fuel 80 (2001) 225231. [20] D. Kusdiana, S. Saka, Kinetics of transesterication in rapeseed oil to biodiesel fuels as treated in supercritical methanol, Fuel 80 (2001) 693 698. [21] D. Kusdiana, S. Saka, Effects of water on biodiesel fuel production by supercritical methanol treatment, Bioresour. Technol. 91 (2004) 289 295.

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[22] M. Ash, E. Dohlman, Oil Crops Situation and Outlook Yearbook, United States Department of Agriculture, 2006. [23] B. Mattsson, C. Cederberg, L. Blix, Agricultural land use in life cycle assessment (LCA): case studies of three vegetable oil crops, J. Clean. Prod. 8 (2000) 283292. [24] Jung-won Lim, Joon-hyuk Choi, Hong-Shik Lee, Youn-Woo Lee, Transesterication of RBD Palm Oil using Supercritical Methanol, Super Green 2005, National Taiwan University, Taipei, Taiwan, 2005, p. 41. [25] http://webbook.nist.gov/chemistry/. [26] European Committee for Standardization (CEN), BS EN 14103:2003, Fat and oil derivatives Fatty acid methyl esters (FAME) determination of ester and linolenic acid methyl ester contents (2003). [27] W.B. Wan Nik, F.N. Ani, H.H. Masjuki, Thermal stability evaluation of palm oil as energy transport media, Energy Convers. Manage. 46 (2005) 21982215. [28] H.S. Fogler, Elements of Chemical Reaction Engineering, fourth ed., Prentice-Hall, 2006. [29] W.H. Press, S.A. Teukolsky, W.T. Vetterling, B.P. Flannery, Numerical Recipes in Fortran 77: The Art of Scientic Computing, Cambridge University Press, 1992, ISBN 0-521-43064-X. [30] S.C. Chapra, R.P. Canale, Numerical Methods for Engineers, second ed., McGraw-Hill, 1990. [31] M. Diasakou, A. Louloudi, N. Papyannakos, Kinetics of the non-catalytic transesterication of soybean oil, Fuel 77 (12) (1998) 12971302. [32] O.S. Stamenkovic, Z.B. Todorovic, M.L. Lazic, V.B. Veljkovic, D.U. Skala, Kinetics of sunower oil methanolysis at low temperatures, Bioresour. Technol. 99 (2008) 11311140.