Energy & Fuels 2007, 21, 31093112

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Transesterication of Palm Oil with Methanol to Biodiesel over a KF/Al2O3 Heterogeneous Base Catalyst
Xu Bo, Xiao Guomin,* Cui Lingfeng, Wei Ruiping, and Gao Lijing
School of Chemistry and Chemical Engineering, Southeast UniVersity, Nanjing, 211189, Peoples Republic of China ReceiVed August 20, 2007. ReVised Manuscript ReceiVed October 10, 2007

The KF/Al2O3 catalysts were prepared by an impregnation method and characterized by X-ray diffraction and thermogravimetric analysis. Their catalytic performances were evaluated in the transesterication of palm oil with methanol. The effects of the load ratio of KF to Al2O3, molar ratio of methanol/oil, amount of catalyst, reaction time, and temperature on product yields were investigated. The catalytic behavior was examined in relation to physiochemical properties of the catalysts.

1. Introduction For more than 2 centuries, the energy supply of the world has relied heavily on nonrenewable crude oil.1 It is also known that emissions from the combustion of these fuels, such as carbon dioxide (CO2), carbon monoxide (CO), nitrogen oxides (NOx), and sulfur-containing residues are the principal causes of global warming, and many countries have passed legislation to arrest their adverse environmental consequences.2 With populations increasing rapidly and many developing countries expanding their industrial base and output, the worldwide energy demand is bound to increase. On the other hand, known crude oil reserves could be depleted in less than 50 years at the present rate of consumption. This situation initiated and has sustained interest in identifying and channeling renewable (biomass) raw materials into the manufacture of liquid fuel alternatives because the development of such biomass-based power would ensure that new technologies are available to keep pace with the need of society for new renewable power alternatives for the future. Among the different possible resources, diesel fuels derived from triglycerides of vegetable oils and animal fats have shown potential as substitutes for petroleum-based diesel fuels.3 However, their high viscosity, about 10 times that of No. 2 diesel fuel,4 has limited their use in modern direct-injection-type diesel engines because it affects engine performance and, in some cases, engine damage is inevitable. Consequently, considerable efforts have been made to develop alternative diesel fuels that have the same properties and performance as the petroleumbased fuels, with the transesterication of triglycerides and methanol to fatty acid methyl esters (FAMEs) showing the most current promise. These products are referred to as biodiesel5,6 because their fuel properties are comparable to that of No. 2 diesel fuel.3 In comparison to diesel, biodiesel had good
* To whom correspondence should be addressed. Telephone: +86-2552090612. Fax: +86-25-52090612. E-mail: xiaogm@seu.edu.cn. (1) Edward, C.; Cirilo, N. H.; Genta, K.; Kenji, S.; Ayaaki, I. Process Biochem. 2001, 37, 6571. (2) Sheehan, J.; Cambreco, V.; Dufeld, J.; Gabroski, M.; Shapouri, H. A joint study sponsored by U.S. Departments of Agriculture and Energy. 1998; pp 1-35. (3) Hideki, F.; Akihiko, K.; Hideo, N. J. Biosci. Bioeng. 2001, 92, 405 416. (4) Foglia, T. A.; Nelson, L. A.; Marmer, W. N.; Knothe, G. H.; Dunn, R. O.; Bagby, M. O. J. Am. Oil. Chem. Soc. 1996, 73, 121125.

environmental characteristics because of the lower harmful gas emissions. Its high ash point makes it easy for transportation and storage, with the need to not worry about risks. Transesterication can be catalyzed by both acidic and basic catalysts. An acidic catalyst, such as sulfuric acid, slowly catalyzes triglyceride transesterication and produces a large amount of wastewater.1,7 Alkaline metal hydroxides (e.g., KOH8 and NaOH9) are preferred as the basic catalysts. However, in the alkaline-metal-hydroxide-catalyzed transesterication, even if a water-free vegetable oil and methanol are used, a certain amount of water is produced from the reaction of the hydroxide with methanol. The presence of water leads to the hydrolysis of the esters, and as a result, soap is formed. The formation of soap reduces the biodiesel yield and causes signicant difculty in the separation of ester and glycerol. To avoid the problem of products separation, it has been proposed to replace the homogeneous catalysts by a heterogeneous catalyst,10 suggesting that the production of methyl esters will be simplied when heterogeneous catalysts are used. Among the heterogeneous bases, KF/Al2O3 is a most noteworthy catalyst because of its efciency and convenience. KF/Al2O3 owes its basic activity to the formation of potassium hydroxide and potassium hexauoroaluminate (K3AlF6) during preparation.1113 It can be applied in many organic syntheses.12,14 Its efcient and versatile reactivity as a heterogeneous base has been demonstrated in the literature. In addition, it also becomes commercially available. However, while the applications and advantages of KF/Al2O3 reagents as heterogeneous bases for organic synthesis continue to increase, it has thus far not been reported by using it for the oil transesterication to prepare biodiesel.
(5) Freedman, B.; Pryde, E. H. Proceedings of the International Conference on Plant and Vegetable Oils as Fuels, American Society of Agricultural Engineers (ASAE), St. Joseph, MI, 1982; pp 117-122. (6) Schumacher, L. G.; Borgelt, S. C.; Hires, W. G. Appl. Eng. Agric. 1995, 11, 3740. (7) Freedman, B.; Buttereld, R. O.; Pryde, E. H. J. Am. Oil Chem. Soc. 2000, 77 (12), 12631267. (8) Wu, G. Y.; Wu, M. X.; Lin, X. P.; Zhang, Y. C.; Liu, Y. J. Jiangsu Inst. Petrochem. Technol. 2002, 114 (13), 811. (9) Sheng, M.; Guo, D. F.; Zhang, D. H. China Oils Fats 2002, 27 (1), 7072. (10) Gorzawski, H.; Hoelderich, W. F. Appl. Catal., A 1999, 179, 131 137.

10.1021/ef7005035 CCC: $37.00 2007 American Chemical Society Published on Web 11/03/2007

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In this work, the production of biodiesel using KF/Al2O3 as a heterogeneous catalyst, which was prepared and applied for the transesterication of palm oil (PO), was investigated. PO is one of the four leading vegetable oils traded on the world market.1 It has a maximum proportion of saturates in all of the vegetable oils, which makes it less susceptible toward oxidation. Therefore, it can be preserved without any dopings, and there is no need to worry about it going bad and damaging the engine.15 It is also cheaper than canola, rapeseed, or soybean oil, would reduce the overhead cost of biodiesel production, and generate a ready supply of diesel fuel substitute. 2. Experimental Section
2.1. Materials. PO, KF, CH3OH, and -Al2O3 were purchased from Nanjing Runtai market, Guangdong Guanghua Chemical Factory Co., Ltd., Nanjing Chemical Reagent Co., Ltd. And Nanjing Chemical Industry Corporation Chemical Plant, respectively. Fatty acid methyl esters, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, purchased from Fluka were used as the reference standards for gas chromatography (GC) analysis while methyl tridecanoate obtained from Fluka was used as the internal standard. 2.2. Catalyst Preparation and Characterization. The KF catalyst supported on Al2O3 was prepared by the impregnation method. Globular alumina was immersed in a certain volume KF solution with different concentrations at room temperature for 24 h, ltered the redundant solution, dried at 100 C for 2 h, dried at 200 C for 2 h, and nally, calcined at 600 C for 3 h. The catalyst was characterized by powder X-ray diffraction (XRD) and thermogravimetric analysis (TGA). XRD measurements were performed on a Rigaku D/max-A instrument with a Cu KR radiation at 50 kV and 30 mA and a scan speed of 0.02 C/min. Thermal analysis was determined using a SDT Q600 simultaneous differential scanning calorimetry (DSC)-TGA instrument. Samples were heated in a ow of N2 at 20 C/min from room temperature to 900 C. 2.3. Transesterication Reaction. A prescribed amount of PO and methanol was stirred in a 250 mL three-necked ask. When the temperature was raised to the preset degree, a desired amount of catalyst was put into the ask. Then, the reactants were still stirred for the desired reaction time. Reaction conditions were as following: 0.140-0.547 of the load ratio of KF/Al2O3, 6:1-18:1 of methanol/oil, 1-5% of the catalyst amount, 45-75 C of the reaction temperature, and 1-5 h of the transesterication time. After the reaction, the reactor was cooled to room temperature. Then, the catalyst was separated from the product mixture by ltration. The excess methanol was recovered by rotary evaporation under reduced pressure. Phase separation of the ltrate resulted in the isolation of the methyl esters and glycerol. The top layer was the biodiesel phase of the methyl esters. The fatty acid composition of the rened product was then analyzed by gas chromatography (GC)16,17 using an internal standard. The samples were analyzed by a GC 900C gas chromatograph equipped with a ame ionization detector (FID) and a capillary column PEG-2000 (50 m 0.32 mm i.d.). Nitrogen was used as a carrier gas, at a ow rate of 2
(11) Takashi, A.; James, H. C.; David, G. C.; Takahide, K. Bull. Chem. Soc. Jpn. 1986, 59, 32813282. (12) Weinstock, L. M.; Stevenson, J. M.; Tomellini, S. A.; Pan, S. H.; Utne, T.; Jobson, R. B.; Reinhold, D. F. Tetrahedron Lett. 1986, 27 (33), 38453848. (13) Takashi, A.; Clark, J. H.; Cork, D. G.; Terukiyo., H.; Junko, I.; Takahide, K. Tetrahedron Lett. 1987, 28 (13), 14211424. (14) Cheng, S. S.; Zhang, Z. G.; Liu, X. S.; Huang, T. Jiangxi Chem. 2003, 2, 14. (15) Rakesh, S.; Meeta, S.; Sinharay, S.; Malhotra, R. K. Fuel 2006, 3357, 17. (16) Li, C. S.; Yang, H. Y.; Wang, L. Q.; Tian, S. B. Chin. J. Chromatogr. 2006, 24 (5), 524528. (17) Guo, D. F.; Sheng, M.; Luo, S. P. China Oils Fats 2004, 29 (4), 4446.

Figure 1. Effect of the load ratio of KF/Al2O3 on the FAME yield. The reaction mix contained 12:1 molar ratio of methanol/oil and a 4% KF/Al2O3 solid catalyst. The study was carried out at 65 C for 3 h.

Figure 2. Effect of the molar ratio of methanol/oil on the FAME yield. The load ratio of KF/Al2O3 is 0.331 (C) and 0.382 (B). The reaction condition is a 12:1 molar ratio, 4% KF/Al2O3 (wt/wt), and 65 C for 3 h.

mL/min. The inlet pressure was 96.4 kPa. The oven, injector, and detector temperatures were 190, 250, and 250 C, respectively. The FAME yield in each experiment was calculated from its content in the composition as analyzed by GC. The yield was dened as a ratio of the weight of FAMEs, determined by GC, to the weight of FAMEs that PO used in the reaction, which is given in theory.

3. Results and Discussion 3.1. Inuence of Transesterication Parameters. The effect of the load ratio of KF/Al2O3 was investigated in Figure 1. As we can see, The FAME yield increased as the load ratio increased, and the transesterication got the highest FAME yield of 90.93% when the load ratio reached 0.331. When the load ratio increased, the FAME yield decreased. This may be due to the increase of the KF quantity on the surface; it has basically reached the threshold value of a single layer of dispersion. The continuous increase of the KF quantity will form multilayer decentralization, which causes the active sites to get together and is not conducive for them in full play. Therefore, the decline of the catalytic activity appears in the catalysis.

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Figure 3. Effect of the amount of catalyst on the FAME yield. The reaction mix contained a 12:1 molar ratio of methanol/oil and a 0.382 load ratio catalyst. The study was carried out at 65 C for 3 h.

Figure 5. Effect of the transesterication time on the FAME yield using a 0.382 load ratio and a 4% KF/Al2O3 catalyst with a 12:1 molar ratio of methanol/oil for 3 h at 65 C.

Figure 4. Effect of the reaction temperature on the FAME yield using a 0.382 load ratio, a 4% KF/Al2O3 (wt/wt) catalyst, and a 12:1 molar ratio of methanol/oil over a 3 h period.

Figure 6. XRD patterns of the catalyst before and after calcinations. (a) K3AlF6, (b) Al2O3, and (c) KF.

Figure 2 shows the effect of the molar ratio of methanol/oil on the FAME yield. The FAME yield increased as the molar ratio increased. However, after the 12:1 molar ratio of methanol/ oil, the yield decreased rapidly. Also, considering the economic factor, a 12:1 molar ratio of methanol/oil is the optimal condition. Therefore, we adopt this condition for further studies. Figure 3 gives the stabilized FAME yield with a different amount of catalyst in the transesterication. The reaction yield increased with the amount of catalyst increasing. From Figure 3, it can be seen that the FAME yield increased rapidly when the catalyst amount increased from 1 to 4%, whereas from 4 to 5%, it increased slowly. Thus, the optimum condition is 4% KF/Al2O3 for the transesterication, laeding to the high FAME yield of 77.43%. The effect of reaction temperature was investigated at 45, 55, 65, and 75 C. As shown in Figure 4, the yield of the reaction increased as the temperature increased; 77.43% yield was obtained at 65 C. However, when the temperature continued to increase, the rate of the reaction decreased. This indicates that the reaction is in dynamic control when the temperature is lower than 65 C. In this area, raising the temperature can promote the transesterication. However, because methanol has a relatively low boiling point (64.7 C), the volatilizing of

methanol is serious when the temperature is too high. Also, the volatilization of methanol makes the molar ratio of methanol/ oil in the system decline. From Figure 2, we can also see that the decline of the molar ratio of methanol/oil is unfavorable to the transesterication; therefore, it is most suitable to have the reaction at 65 C. Figure 5 shows the effect of the transesterication time on the FAME yield. As shown in Figure 5, the yield of the reaction increased as the time increased and an 82.91% yield was obtained over 5 h. However, after 3 h, the yield increased slowly; therefore, we chose 3 h for the further studies. 3.2. Catalyst Characterization. Figure 6 shows the XRD patterns of the catalyst before and after calcinations. As we can see from the pattern, before the calcinations, mainly diffraction peaks assigned to KF and Al2O3 appear. However, the diffraction peak of KF disappears after calcination, and there is a new K3AlF6 diffraction peak to appear. It implies that KF interacts with the carrier and formed a new phase through a hightemperature calcining process. It is also in good agreement with the literature;1113 that is to say, it has a very important function on the activation of the catalyst with the high-temperature calcinations.

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Figure 9. DSC-TGA proles of Al2O3. Figure 7. XRD patterns of the catalyst with a different load ratio of KF/Al2O3. (A) 0.187, (B) 0.331, (C) 0.382, and (D) 0.458 (load ratio). (a) K3AlF6 and (b) Al2O3.

Figure 10. DSC-TGA proles of KF/Al2O3.

Figure 8. XRD patterns of the catalyst before and after use. (a) K3AlF6.

that the catalyst shows a signicant weight loss in a relatively low-temperature range (75-150, 200-275, and 475-600 C). It is closely related to the interaction of KF and Al2O3, forming a new phase under a high-temperature calcining process. It can also be seen from Figure 10 that, from 750 to 850 C, although no weight changes, there are changes in the heat ow; this also explains that KF interacted with Al2O3 and formed a new phase. 4. Conclusions With the efciency of the KF/Al2O3 solid-base catalyst, the conversion of PO by transesterication to produce FAME is worthy. At the optimal condition, when the load ratio of KF/ Al2O3 was 0.331 (wt/wt), the molar ratio of methanol/oil was 12:1 (mol/mol), the amount of KF/Al2O3 catalyst was 4% (wt/ wt), the reacted temperature was 65 C, and the reaction time was 3 h, the FAME yield reached its maximum value of over 90%. Through the XRD and TGA analyses, a new phase of K3AlF6 was observed when the catalyst was calcined at a high temperature.
Acknowledgment. The authors thank the Program for Hi-Tech Research of the Jiangsu Province for nancial support.
EF7005035

As shown in Figure 7, with the load ratio of KF/Al2O3 increasing, the diffraction peak of K3AlF6 enhanced and the diffraction peak of Al2O3 declined. In addition, there is no diffraction peak of KF in the whole scan area. This also illustrates that the KF interacted with Al2O3 and formed a new phase under a high-temperature calcining process. This interaction played a key role for raising the catalytic activity. Figure 8 shows the XRD patterns of the catalyst before and after use. As shown in the pattern, the diffraction peak of K3AlF6 diminishes after the reaction; that is to say, the interaction between KF and carrier is weakened. It must be regenerated before use again. Therefore, it causes difculties in continuous production and needs further research. The carrier Al2O3 and the catalyst KF/Al2O3 were analyzed by DCS-TGA. As shown in Figures 9 and 10, the carrier loses its weight all of the time during the analysis process. However, from the catalyst weight-loss curve, we can see