Methanolysis Optimization of Cottonseed Oil to Biodiesel Using Heterogeneous Catalysts

Document Type : Research Article

Authors

1 Department of Chemical Engineering, Michael Okpara University of Agriculture, Umudike, Umuahia, NIGERIA

2 Department of Chemical Engineering, Nnamdi Azikiwe University (NAU), Awka, NIGERIA

3 Department of Chemical Engineering, Institute of Management & Technology (I.M.T), Enugu, NIGERIA

4 Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, NIGERIA

Abstract

This paper presented the process optimization for heterogeneous catalysts transesterification of refined cottonseed oil catalyzed by calcium oxide (CaO) and magnesium oxide (MgO) impregnated on Saw Dust Ash (SDA) using Response Surface Methodology Central Composite Design (RSMCCD). The five transesterification process variables studied were: catalyst concentration (4-8 wt% oil), methanol/oil molar ratio (4:1-8:1), reaction temperature (45-85oC), reaction time (3-5h), and agitation speed (200-300rpm). It was revealed that the reaction temperature gave the most significant effect on the yield of Fatty Acid Methyl Ester (FAME), followed by methanol/oil molar ratio. There were also significant interaction effects between catalyst concentration and methanol/oil molar ratio, catalyst concentration and agitation speed, methanol/oil molar ratio and reaction temperature, methanol/oil molar ratio and reaction time, methanol/oil molar ratio and agitation speed, reaction time and agitation speed for CaO/SDA transesterified reaction while for MgO/SDA transesterified reaction the significant interaction effect between variable is methanol/oil molar ratio and reaction time. Based on the optimized conditions, the highest yield of 90% for CaO/SDA transesterified reaction and 77% for MgO/SDA transesterified reaction were predicted using the following variables catalyst concentration, CaO/SDA = 6wt% and MgO/SDA = 8wt%, methanol/oil molar ratio = 6:1(CaO/SDA) and 8:1 (MgO/SDA), reaction temperature = 65oC, reaction time = 4h and agitation speed = 250rpm. Experimental validation of the predicted optimum conditions gave an actual yield of 86% (CaO/SDA) and 73.3% (MgO/SDA). The small errors between the predicted and actual optimum yield (4.7% (CaO/SDA) and 5.2% (MgO/SDA)) indicated that the model were valid and accurate in representing the actual experimental values and also in predicting yield at any conditions within the range studied. 

The results proved the efficacy of saw dust ash impregnated with CaO and MgO in transesterification reaction.

Keywords

Main Subjects


[1] Muniyappa P.R., Brammer S.C., Noureddini H., Improved Conversion of Plant Oils and Fats into Biodiesel and Co-product, Bioresour. Technol., 56: 19 -26 (1996).
[2] Fan X., Wang X., Chen F., Biodiesel Production from Crude Cottonseed Oil; An Optimization Process Using Response Surface Methodology, The Open Feuls and Energy Science Journal, 4:1-8 (2011).
[3] Demirbas A., Progress and Recent Trends in Biodiesel Fuels, Energy Convers. Manage., 50: 14-34  (2009).
[4] Kaya C., Hamamei C., Baysal A., Akba O., Erdogan S.,  Sayduct A., Methyl Ester of Peanut (Arachis Hypogeal L.) Seed Oil as Potential Feedstock for Biodiesel Production, Renewable Energy, 34: 1257-1260  (2009).
[5] Ghetsi G. F., De macedo J. L., Parente V. C. I., Dias J. A., Dias S.C.L., Synthesis, Characterisation and Reactivity of Lewis Acid/Surfactant Cerium Frisdodecylsulfate Catalyst for Transesterification and Esterification Reaction, Appl. Cat. A; Gen, 355: 139-147 (2009).
[6] Aderemi B.O., Hameed B. H., Production of Biodiesel from Palm Oil, Nigeria Society of Chemical Engineers Proceedings, 40: 135-143 (2010).
[7] Leng T.y., Mohamed A. R., Bhatia S., Catalytic Conversion of Palm Oil to Fuels and Chemicals, Canad. J. Chem. Eng., 77: 156 (1999).
[8] Li H., Shen B., Jabalu J. C., Nchare M., Enhancing the Production of Biodiesel from Cottonseed Oil
by Fixed-Fluidized Bed Catalytic Cracking
, Renewable Energy, 34: 1033-1039 (2009).
[9] Ramachandran K., Suganya T., Nagendra Gandhi N., Renganathan S., Recent Developments for Biodiesel Production by Ultrasonic Assist Transesterification Using Different Heterogeneous Catalyst: A Review, Renewable Sustainable Energy Rev., 22: 410-418 (2013).
[10] Younis M. N., Saeed M. S., Khan S., Furqan M. U., Khan R. U., Saleem M., Production and Characterization of Biodiesel, from Waste and Vegetable Oils, Journal of Quality and Technology Management, 5(1): 111-121, (2009).
[11] Attanatho L., Magmee S., Jenvanitpanjakul P., Factors Affecting the Synthesis of Biodiesel
from Crude Palm Kernel Oil
. “Proceedings of the Joint International Conference on Sustainable Energy and Environment (SEE)”, December 1-3, 2004. Hua Hin, Thailand; 359-361, (2004).
[12] Fukuda H., Kondo A., Noda H., Biodiesel Fuel Production by Transesterification of Oils, J. Biosci. Bioeng., 92: 405-416 (2001).
[13] Sivakumar P., Sivakumar P., Jay Karen Maria William, Gnanasekaran Mahadevi Keerthana and Sahadevan Renganathan, Enhanced Removal of Free Fatty Acid from Waste Oil for Biodiesel Production, Elixir Chem. Eng., 38: 4113-4117, (2011).
[14] Sivakumar P, Suganya T., Renganathan S., Studies on Customized Carbon Catalyst in Biodiesel Production from Waste Sunflower Oil, Energy Sources, Part A, 35, 595-603 (2013).
[15] Karthikeyan M., Renganathan S., Govindhan P., Production of Biodiesel via Two Step Acid Base Catalysed Transesterification Reaction of Karanja Oil by BaMoO4 as a Catalyst, Energy Sources, Part A, 39(14), 1504-1510 (2017).
[16] Demirbas A., Studies on Cottonseed Oil Biodiesel Prepared in Non-Catalytic SCF Conditions, Bioresour. Technolo., 99: 1125-1130 (2008).
[17] Cui L. F., Xiao G. M., Xu B., Teng G.Y., Transesterification of Cottonseed Oil Biodiesel
by using Heterogeneous Solid Basic Catalysts
, Energy Fuel, 21: 3740-3743 (2007).
 
[18] Kse ., Tter M., Aksoy H. A., Immobilized Candida Antarctica Lipase-Catalyzed Alcoholysis
of Cottonseed Oil in a Solvent-Free Medium
, Bioresour. Technol., 83: 125-129 (2002).
[19] Chen H., Peng B. X., Wang D. Z., Wang J. F., Biodiesel Production by the Transesterification
of Cottonseed Oil by Solid acid Catalysts
, Front. Chem. Eng. China, 1: 11-15 (2007).
[20] Azcan N., Danisman A., Alkali Catalyzed Transesterification of Cottonseed Oil by Microwave Irradiation, Fuel, 86: 2639-2644 (2001).
[21] Ilgen O., Akin A. N., Transesterification of Canola Oil to Biodiesel Using KOH/MgO as a Heterogeneous Catalyst. Energy Fuels, 23: 1786-1789 (2009).
[22] Verziu M., Cojocam B., Hu J., Richards R., Guculescu C., Filip P., Parvulescu V.I.,  Sunflower and Rapeseed Oil Transesterification to Biodiesel over Different Nano-Crystalline MgO Catalysts, Green Chemistry, 10: 373-381 (2008).
[23] Ramachadran K., Sivakumar P., Suganya T., Renganathan S., Production of Biodiesel from Mixed Waste Vegetable Oil Using an Aluminium Hydrogen Sulphate as a Heterogeneous Acid Catalyst, Bioresour. Technol., 102(15): 7289-7293 (2011).
[24] Di Serio M., Ledda M., Cozzolino M., Minutillo G., Tesser R., Santacesaria E., Transesterification of Soybean Oil to Biodiesel by Using Heterogeneous Basic Catalysts, Ind. Eng. Chem. Res., 45(9): 3009-3014 (2006).
[25] Liu X., He H., Wang Y., Zhu S., Ziao X., Transesterification of Soybean Oil to Biodiesel using CaO as a Solid Base Catalyst, Fuel, 87(2): 216–221 (2008).
[26] Granados M.L., Poves M.D.Z., Alonso D.M., Mariscal R., Galisteo F.C., Tost, R.M., Biodiesel from Sunflower Oil by Using Activated Calcium Oxide, Appl. Cat. B, Environ., 73(3-4): 317-326 (2007).
[27] Sivakumar P., Sankaranarayanan S., Renganathan S., Sivakumar P., Studies on Sonochemical Biodiesel Production Using Smoke Deposited Nano MgO Catalyst, Bull. Chem. React. Eng. Catal., 8(2), 89-96 (2013).
[28] Refaat A. A., Biodiesel Production using Solid Metal Oxide Catalysts, Int. J. Environ. Sci. Tech., 8(1): 203-221 (2011).
[29] Bharathi V. F., Sivakumar P., Suganya T., Dharmendira Kumar M., Nagendra Gandhi N., Renganathan S., Biodiesel Production from Waste Vegetable Oil using Calcium Oxide as a Heterogenous Catalyst, Indian J. Environ. Prot., 32(6):441-448 (2012).
[30] Chakraborty R., Bepari S., Banerjee A., Transesterification of Soybean Oil Catalyzed
by Fly Ash and Egg Shell Derived Solid Catalysts
, Chem. Eng. J., 165(3): 798–805 (2010).
[33] Yaakob Z., Sukarman I.S., Narayanan B., Abdullah S.R., Ismail M., Utilization of Palm Empty Fruit
Bunch for the Production of Biodiesel from Jatropha Curcas Oil
, Bioresour. Technol., 104: 695–700 (2012).
[34] Sharma M., Khan A.A., Puri S.K., Tuli D.K., Wood Ash as a Potential Heterogeneous Catalyst for Biodiesel Synthesis, Biomass Bioenergy, 41: 94–106 (2012).
[36] Sivakumar Pandian, Subramanian Karuppiah, Parthiban, Sivakumar Padmanaban, Vinoba,Mari, Sahadevan Renganathan., Optimization of Extraction Process and Kinetics of Sterculia Foetida Seed Oil and Its process Augmentation for Biodiesel Production, Ind. Eng. Chem. Res., 51: 8992-98 (2012).
[37] Sivakumar Pandian, Sathyaseelan Sindhanaiselvan, Nagarajan Nagendra Gandhi, Sureshan Shiyamala Devi and Sahadevan Renganathan, Optimization and Kinetic Studies on Biodiesel Production from Underutilized Ceiba Pentandra Oil, Fuel, 103, 693-698 (2013).
 
[38] Guan-Yin C., Riu S., Jia-Fu S., Bei-Bei Y. Transesterification of Palm Oil to Biodiesel Using Rice Husk Ash-Based Catalysts, Fuel Process. Technol., 133: 8 – 13 (2015).
[39] AOCS, Sampling and Analysis of Commercial Fats and Triglycerides, Official Methods of Analysis of the American Triglyceride Chemist Soc., 800-855 (1996).
[40] Vicente G., Martinez M., Aracil J., Optimisation of Integrate Biodiesel Production, Part I. aA Study of the Biodiesel Purity and Yields, Bioresour. Technol., 98:1724-1733 (2007).