Alkaline Earth Metal Oxide Catalysts for Biodiesel Production from Palm Oil: Elucidation of Process Behaviors and Modeling Using Response Surface Methodology

Document Type : Research Article


1 of Chemical Engineering, School of Engineering, Monash University Sunway Campus, Jalan Lagoon Selatan, 46150 Bandar Sunway, Selangor, MALAYSIA

2 School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, MALAYSIA


Four different alkaline earth metal oxides i.e. MgO, CaO, SrO and BaO were used as heterogeneous catalysts for biodiesel production from palm oil. Effects of critical process variables i.e. reaction time, methanol to oil ratio and temperature were investigated. The results were then fitted to a historical design to study the Analysis of Variance (ANOVA), to characterize interactions between variables and to simulate the process. MgO did not show good catalytic activity while  CaO produced undesired products at longer reaction time. BaO showed the best biodiesel result with a yield of up to 95 %, followed by SrO with a yield of 91 %. A methanol to oil ratio of 9:1 and 60 ºC were found to be the optimum conditions. The experimental data were satisfactorily predicted at 99 % confidence level under various conditions with R2 values higher than 0.92. Characterizations of the catalysts before and after the transesterification process were also performed using a surface analyzer, scanning electron microscopy, Hammett indicator and Atomic Absorption Spectrophotometeric (AAS) methods. The catalytic activity was in the order of BaO > SrO > CaO. However, due to lixiviation of BaO in the product, SrO was found to be the most potential catalyst.  


Main Subjects

[1] Zabaniotou A., Ioannidou O, Skoulou V. Rapeseed Residues Utilization for Energy and 2nd Generation Biofuels, Fuel, 87, p. 1492 (2008).
[2] Kim H.J., Kang B.S., Kim M.J., Park Y.M., Kim D.K., Lee J.S., et al., Transesterification of Vegetable Oil to Biodiesel Using Heterogeneous Base Catalyst, Catal. Today, 93-95, p. 315 (2004).
[3] van Gerpen J., Biodiesel Processing and Production, Fuel Proc. Technol., 86, p. 1097 (2005).
[4] Hattori H., Solid Base Catalysts: Generation of Basic Sites and Application to Organic Synthesis, Appl. Catal. A, 222, p. 247 (2001).
[5] Kawashima A., Matsubara .K, Honda K., Development of Heterogeneous Base Catalysts for Biodiesel Production, Bioresour. Technol., 99, p. 3439 (2008).
[6] Khuri A.I., Cornell J.A., "Response Surfaces: Design and Analyses" 2nd ed., Marcel Dekker, New York (1996).
[7] Xie W., Peng H., Chen L., Transesterification of Soybean Oil Catalyzed by Potassium Loaded on Alumina as a Solid-base Catalyst, Appl. Catal. A, 300, p. 67 (2006).
[8] Dossin T.F., Reyniers M..F, Marin G.B., Kinetics of Heterogeneously MgO-catalyzed Transesterification, Appl. Catal. B, 62, p. 35 (2006).
[9] Yang Z., Xie W., Soybean Oil Transesterification Over Zinc Oxide Modified With Alkali Earth Metals, Fuel Proc. Technol., 88, p. 631 (2007).
[10] Arzamendi G., Arguiñarena E., Campo I., Zabala S., Gandía L.M., Alkaline and Alkaline-earth Metals Compounds as Catalysts for the Methanolysis of Sunflower Oil, Catal. Today, 133-135, p. 305 (2008).
[11] Albuquerque M.C.G., Cavalcante C.L., Torres A.E.B., Azevedo D.C.S., Parente E.J.S., Transesterification of Castor Oil Using Ethanol: Effect of Water Removal by Adsorption onto Zeolite 3A, Energ. Fuel., 23, p. 1136 (2009).
[12] Brito A., Garcia F., Borges M.E., Diaztt M.C., Arvelo R., Otero N., Reuse of Fried Oil to Obtain Biodiesel: Zeolites Y as a Catalyst, Int. J. Chem. React. Eng., 5, Art. no. A104 (2007).
[13] Ono Y., Solid Base Catalysts for the Synthesis of Fine Chemicals, J. Catal., 216, p. 406 (2003).
[14] Liu X., He H., Wang Y., Zhu S., Transesterification of Soybean Oil to Biodiesel Using SrO as a Solid Base Catalyst, Catal. Comm., 8, p. 1107 (2007).
[15] Granados M.L., Poves M.D.Z., Alonso D.M., Mariscal R., Galisteo F.C., Moreno-Tost R., et al. Biodiesel from Sunflower Oil by Using Activated Calcium Oxide, Appl. Catal. B, 73, p. 317 (2007).
[16] Shibasaki-Kitakawa N., Honda H., Kuribayashi H., Toda T., Fukumura T., Yonemoto T., Biodiesel Production Using Anionic Ion-exchange Resin as Heterogeneous Catalyst, Bioresour. Technol., 98, p. 416 (2007).
[17] Özbay N., Oktar N., Tapan N.A., Esterification of Free Fatty Acids in Waste Cooking Oils (WCO): Role of Ion-exchange Resins, Fuel, 87, p. 1789 (2008).
[18] Stavarache C., Vinatoru M., Maeda Y., Aspects of Ultrasonically Assisted Transesterification of Various Vegetable Oils with Methanol, Ultrason. Sonochem., 14, p. 380 (2007).
[19] Antolín G., Tinaut F.V., Briceo Y., Castao V.,   Pérez C., Ramírez A.I., Optimisation of Biodiesel Production by Sunflower Oil Transesterification, Bioresour. Technol., 83, p. 111 (2002).
[20] Xie W., Li H., Alumina-supported Potassium Iodide as a Heterogeneous Catalyst for Biodiesel Production from Soybean Oil, J. Molec. Catal. A, 255, p. 1 (2006).
[21] Vyas A.P., Subrahmanyam N., Patel P.A., Production of Biodiesel Through Transesterification of Jatropha Oil Using KNO3/Al2O3 Solid Catalyst, Fuel, 88, p. 625 (2009).
[22] Umdu E.S., Tuncer M., Seker E., Transesterification of Nannochloropsis oculata Microalga's Lipid         to Biodiesel on Al2O3 Supported CaO and MgO Catalysts, Bioresour. Technol., 100, p. 2828 (2009).
[23] Kouzu M., Kasuno T., Tajika M., Sugimoto Y., Yamanaka S., Hidaka J., Calcium Oxide as a Solid Base Catalyst for Transesterification of Soybean Oil and Its Application to Biodiesel Production, Fuel, 87, p. 2798 (2008).
[24] Zhu H., Wu Z., Chen Y., Zhang P., Duan S., Liu X., et al. Preparation of Biodiesel Catalyzed by Solid     Super Base of Calcium Oxide and Its Refining Process, Chinese J. Catal., 27, p. 391 (2006).
[25] Montgomery D.C., "Design and Analysis of Experiments". 5nd ed., John Wiley & Sons, New York (2001).
[26] Wikipedia. Electron Affinity.
In: (accessed on 10 January 2012).
[27] Ngamcharussrivichai C., Totarat P., Bunyakiat K., Ca and Zn Mixed Oxide as a Heterogeneous Base Catalyst for Transesterification of Palm Kernel Oil, Appl. Catal. A, 341, p. 77 (2008).
[28] Meher L.C., Vidya S.D., Naik S.N., Technical Aspects of Biodiesel Production by Transesterification-A Review, Renew. Sust. Energ. Rev., 10, p. 248 (2006).
[29] Ruppert A.M., Meeldijk J.D., Kuipers B.W.M.,  Erné B.H., Weckhuysen B.M., Glycerol Etherification over Highly Active CaO-based Materials: New Mechanistic Aspects and Related Colloidal Particle Formation, Chem.-Eur. J., 14, p. 2016 (2008).