Soybean Oil Transesterification Reactions in the Presence of Mussel Shell: Pseudo-First Order Kinetics

Document Type: Research Article


1 Chemical Engineering Department, Faculty of Energy, Kermanshah University of Technology, Kermanshah, I.R. IRAN

2 Catalyst Research Center, Faculty of Chemical and Petroleum Engineering, Razi University, Kermanshah, I.R. IRAN


Calcium oxide is one of the appropriate catalysts for biodiesel production. In this study, cheap and compatible with environment catalyst has been used. Mussel shell of Persian Gulf coast is one of the sources of calcium carbonate that is converted to calcium oxide at calcination temperature up to 950°C. Transesterification reaction was carried out at optimum condition of our previous study (calcination temperature of 1050°C, methanol to oil ratio of 24:1 and catalyst to oil ratio of to 12 wt.%) in a 250mL two-necked flask. In this study, the effects of stirrer speed (250 and 350rpm), the reaction temperature (328.15, 333.15, and 338.15K) and reaction time (1, 3, 5, 7 and 8h) on the methyl ester conversion were investigated. The methyl ester conversion, in stirrer speed of 250rpm, reaction temperatures of 328.15 and 333.15K and reaction times of less than 5h is too low. But at the reaction temperature of 338.15K (near to methanol boiling point), the mixing is increased slightly and the reaction occurs at a higher rate and the methyl ester conversion is increased. These results indicate that diffusion has a significant role in the methyl ester conversion rate in the heterogeneously catalyzed reaction. In stirrer speed of 350rpm, the diffusion problem has been solved somewhat and the reaction in the catalyst surface is the controller of the overall reaction rate. In this stirrer speed (350rpm) the methyl ester conversion versus time in all temperature shows pseudo-first-order kinetics. Firstly, the rate was determined at the various temperatures and then the activation energy for the transesterification reaction of soybean oil with methanol was obtained in the presence of mussel shell as the catalyst. Results demonstrate the high precision of the pseudo-first-order kinetics model regard to methyl esters concentration.


Main Subjects

[1] Semwal S., Arora A.K., Badoni R.P., Tuli D.K., Biodiesel Production Using Heterogeneous Catalysts, Bioresour. Technol., 102(3): 2151–2161 (2011).

[4] Rao G.P.C., Azeez S.A., Krishna R.V., Kumar C.N., Performance & Evaluation of Diesel Engine (4-stroke 1-cylinder) Using Jatropha Oil Blends with Super Charging Method, Int, J, Mod, Trends Sci, Technol., 3(7): 50-59 (2017).

[5] Tang Y., Meng M., Zhang J., Lu Y., Efficient Preparation of Biodiesel from Rapeseed Oil over Modified CaO, Appl. Energy, 88(8): 2735–2739 (2011).

[6] Meher L.C., Sagar D.V., Naik S.N., Technical Aspects of Biodiesel Production by Transesterification—a Review, Renew. Sust. Energy Rev., 10(3): 248–268 (2006). 

[7] Taufiq-Yap Y.H., Lee H.V., Hussein M.Z., Yunus R., Calcium-Based Mixed Oxide Catalysts for Methanolysis of Jatropha Curcas Oil to Biodiesel, Biomass Bioenergy, 35(2): 827-834 (2011).

[8] Chen C.-L., Huang C.-C., Tran D.-T., Chang J.-S., Biodiesel Synthesis via Heterogeneous Catalysis Using Modified Strontium Oxides as the Catalysts, Bioresour. Technol., 113(1): 8-13 (2012).

[9] Tang S., Wang L., Zhang Y., Li S., Tian S., Wang B., Study on Preparation of Ca/Al/Fe3O4 Magnetic Composite Solid Catalyst and its Application in Biodiesel Transesterification, Fuel Process. Technol., 95(1): 84–89 (2012).

[10] Kouzu M., Kasuno T., Tajika M., Yamanaka S., Hidaka J., Active Phase of Calcium Oxide Used as Solid Base Catalyst for Transesterification of Soybean oil with Refluxing Methanol, Appl. Catal., A, 334(1-2): 357–365 (2008).

[11] Dossin T.F., Reyniers M.-F., Berger R.J., Marin G.B., Simulation of Heterogeneously MgO-Catalyzed Transesterification for Fine-Chemical and Biodiesel Industrial Production, Appl. Catal., B, 67(1-2): 136–148 (2006).

[12] Alba-Rubio A.C., Alonso Castillo M.L., Albuquerqu M.C.G., Mariscal R., Cavalcante Jr. C.L., López Granados M., A New and Efficient Procedure for Removing Calcium Soaps in Biodiesel Obtained Using CaO as a Heterogeneous Catalyst, Fuel., 95(1): 464–470 (2012).

[13] 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(12): 2798-2806 (2008).

[14] Reddy B.M., Patil M.K., Organic Synthesis and Transformations Catalyzed by Sulfated Zirconia, Chem. Rev., 109(6): 2185-2208 (2009).

[15] Sasidharam M., Kumar R., Transesterification over Various Zeolites under Liquid-Phase Conditions, J. Mol. Catal. A: Chem., 210(1-2): 93-98 (2004).

[16] Ngamcharussrivichai C., Benjapornkulaphong S., Bunyakiat K., Al2O3-Supported Alkali and Alkali Earth Metal Oxides for Transesterification of Palm Kernel Oil and Coconut Oil, Chem. Eng. J., 145(3): 468-474 (2008).

[18] Salamatinia B., Hashemizadeh I., Zuhairi A.A., Alkaline Earth Metal Oxide Catalysts for Biodiesel Production from Palm Oil: Elucidation of Process Behaviors and Modeling Using Response Surface Methodology, Iran. J. Chem. Chem. Eng. (IJCCE), 32(1): 113-126 (2013).

[19] Boey P.-L., Maniam G.P., Hamid S.A., Performance of Calcium Oxide as a Heterogeneous Catalyst in Biodiesel Production: A Review, Chem. Eng. J., 168(1): 15–22 (2011).

[20] Sivasamy A., Cheah K.Y., Fornasiero P., Kemausuor F., Zinoviev S., Miertus S., Catalytic Applications in the Production of Biodiesel from Vegetable Oils, Chem. Sust. Chem., 2(4):278-300 (2009).

[21] Nakatani N., Takamori H., Takeda K., Sakugawa H., Transesterification of Soybean Oil Using Combusted Oyster Shell Waste as a Catalyst, Bioresour. Technol., 100(3): 1510–1513 (2009).

[22] Boey P.-L., Maniam G.P., Hamid S.A., Biodiesel Production via transesterification of Palm Olein Using Waste Mud Crab (Scylla Serrata) Shell as a Heterogeneous Catalyst, Bioresour. Technol., 100(24): 6362–6368 (2009).

[23] Boey P.-L., Maniam G.P., Hamid S.A., Utilization of Waste Crab Shell (Scyllaserrata) as a Catalyst in Palm Olein Transesterification, J. Oleo. Sci., 58(10): 499-502 (2009).

[24] Viriya-empikul N., Krasae P., Puttasawat B., Yoosuk B., Chollacoop N., Faungnawakij K., Waste Shells of Mollusk and Egg as Biodiesel Production Catalysts, Bioresour. Technol., 101(10): 3765–3767 (2010).

[25] Rezaei R., Mohadesi M., Moradi GR., Optimization of Biodiesel Production Using Waste Mussel Shell Catalyst, Fuel, 109(1): 534–541 (2013).

[26] Dossin T.F., Reyniers M.-F., Marin G.B., Kinetics of Heterogeneously MgO-Catalyzed Transesterification, Appl. Catal., B, 62(1-2): 35-45 (2006).

[27] Veljkovic´ V.B., Stamenkovic´ O.S., Todorovic´ Z.B., Lazic´ M.L., Skala D.U., Kinetics of Sunflower Oil Methanolysis Catalyzed by Calcium Oxide, Fuel, 88(9): 1554-1562 (2009). 

[28] Birla A., Singh B., Upadhyay S.N., Sharma Y.C., Kinetics Studies of Synthesis of Biodiesel From Waste Frying Oil Using a Heterogeneous Catalyst Derived From Snail Shell, Bioresour. Technol., 106(1): 95–100 (2012).

[32] Zhang L., Sheng B., Xin Z., Liu Q., Sun S., Kinetics of Transesterification of Palm Oil and Dimethyl Carbonate for Biodiesel Production at the Catalysis of Heterogeneous Base Catalyst, Bioresour. Technol., 101(21): 8144–8150 (2010).

[33] Vujicic D.J., Comic D., Zarubica A., Micic R., Boskovi G., Kinetics of Biodiesel Synthesis from Sunflower Oil over CaO Heterogeneous Catalyst, Fuel, 89(8): 2054–2061 (2010).

[34] Freedman B., Pryde E.H., Mounts T.L., Variables Affecting the Yields of Fatty Esters from Transesterified Vegetable Oils, J. Am. Oil. Chem. Soc., 61(10): 1638-1643 (1984).

[35] Singh A.K., Fernando S.D., Reaction Kinetics of Soybean Oil Transesterification Using Heterogeneous Metal Oxide Catalysts, Chem. Eng. Technol., 30(12): 1716–1720 (2007).