Box-Behnken Design for Optimization on Esterification of Free Fatty Acids in Waste Cooking Oil Using Modified Smectite Clay Catalyst

Achanai Buasri(1*), Suthita Lertnimit(2), Arnon Nisapruksachart(3), Issara Khunkha(4), Vorrada Loryuenyong(5)

(1) Department of Materials Science and Engineering, Faculty of Engineering and IndustriaTechnology, Silpakorn University, Nakhon Pathom, 73000, Thailand
(2) Department of Materials Science and Engineering, Faculty of Engineering and IndustriaTechnology, Silpakorn University, Nakhon Pathom, 73000, Thailand
(3) Department of Materials Science and Engineering, Faculty of Engineering and IndustriaTechnology, Silpakorn University, Nakhon Pathom, 73000, Thailand
(4) Department of Materials Science and Engineering, Faculty of Engineering and IndustriaTechnology, Silpakorn University, Nakhon Pathom, 73000, Thailand
(5) Department of Materials Science and Engineering, Faculty of Engineering and IndustriaTechnology, Silpakorn University, Nakhon Pathom, 73000, Thailand
(*) Corresponding Author


A potential alternative fuel option is biodiesel, which is produced mostly from natural resources due to the limited availability of petroleum supplies and environmental issues. Waste cooking oil (WCO) containing a high concentration of free fatty acid (FFA) can be transformed into biodiesel, which substantially benefits the environment and for reducing the fuel . The use of smectite clay as a catalyst in the esterification reaction of WCO with methanol was studied. Smectite was chemically activated by sulfuric acid (H2SO4) to obtain the acid-modified smectite. The utilization of an acid-catalyzed esterification procedure as a pre-treatment for WCO for biodiesel synthesis has been studied in some detail. However, there aren't many effective ways to optimize this operation. The process variables used in this study's esterification of FFAs in WCO were optimized using a Box-Behnken design (BBD). At atmospheric pressure, the catalyst amount of 5.03 wt%, the methanol to WCO molar ratio of 22.38, and the reaction time of 3.01 h are the optimal running parameters for accomplishing 97.96% FFA conversion. The catalyst was employed five times in a row without noticeably lowering its catalytic effectiveness. The results showed that smectite clay is an essential, low-cost, and recyclable catalyst for the esterification of FFA in WCO.


Biodiesel; Smectite; Heterogeneous Catalyst; Box-Behnken Design; Esterification

Full Text:



Altalhi, A. A., Mohamed, E. A., Morsy, S. M., Kana, M. T. H. A., and Negm, N. A., 2021. "Catalytic manufacture and characteristic valuation of biodiesel-biojet achieved from Jatropha curcas and waste cooking oils over chemically modified montmorillonite clay," J. Mol. Liq., 340, 117175.

Alves, H. J., Rocha, A. M., Monteiro, M. R., Moretti, C., Cabrelon, M. D., Schwengber, C. A., and Milinsk, M. C., 2014. "Treatment of clay with KF: New solid catalyst for biodiesel production," Appl. Clay Sci., 91-92, 98-104.

Ansori, A., and Mahfud, M., 2022. "Box-Behnken design for optimization on biodiesel production from palm oil and methyl acetate using ultrasound assisted interesterifcation method," Period. Polytech. Chem. Eng., 66, 30-42.

Bailey, L., Lekkerkerker, H. N. W., and Maitland, G. C., 2015. "Smectite clay - inorganic nanoparticle mixed suspensions: Phase behaviour and rheology," Soft Matter, 11, 222-236.

Buasri, A., and Loryuenyong, V., 2015. "The new green catalysts derived from waste razor and surf clam shells for biodiesel production in a continuous reactor," Green Process. Synth., 4, 389-397.

Buasri, A., and Loryuenyong, V., 2018. "Continuous production of biodiesel from rubber seed oil using a packed bed reactor with BaCl2 impregnated CaO as Catalyst," Bull. Chem. React. Eng. Catal., 13, 320-330.

Buasri, A., Lukkanasiri, M., Nernrimnong, R., Tonseeya, S., Rochanakit, K., Wongvitvichot, W., Masa-ard, U., and Loryuenyong, V., 2016. "Rapid transesterification of Jatropha curcas oil to biodiesel using novel catalyst with a microwave heating system," Korean J. Chem. Eng., 33, 3388-3400.

Chumuang, N., and Punsuvon, V., 2017. "Response surface methodology for biodiesel production using calcium methoxide catalyst assisted with tetrahydrofuran as cosolvent," J. Chem., 2017, Article ID 4190818.

Danane, F., Bessah, R., Alloune, R., Tebouche, L., Madjene, F., Kheirani, A. Y., and Bouabibsa, R., 2022. "Experimental optimization of waste cooking oil ethanolysis for biodiesel production using response surface methodology (RSM)," Sci. Tech. Energ. Transition, 77, 14.

Degfie, T. A., Mamo, T. T., and Mekonnen, Y. S., 2019. "Optimized biodiesel production from waste cooking oil (WCO) using calcium oxide (CaO) nanocatalyst," Sci. Rep., 9, 18982.

Diaz-Felix, W., Riley, M. R., Zimmt, W., and Kazz, M., 2009. "Pretreatment of yellow grease for efficient production of fatty acid methyl esters," Biomass Bioenerg., 33, 558-563.

Gonzaga, V. E., Romero, R., Gómez-Espinosa, R. M., Romero, A., Martínez, S. L., and Natividad, R., 2021. "Biodiesel production from waste cooking oil catalyzed by a bifunctional catalyst," ACS Omega, 6, 24092-24105.

Jeenpadiphat, S., and Tungasmita, D. N., 2014. "Esterification of oleic acid and high acid content palm oil over an acid-activated bentonite catalyst," Appl. Clay Sci., 87, 272-277.

Marwaha, A., Rosha, P., Mohapatra, S. K., Sunil Kumar Mahla, S. K., and Dhir, A., 2019. "Biodiesel production from Terminalia bellerica using eggshell-based green catalyst: An optimization study with response surface methodology," Energy Rep., 5, 1580-1588.

Mostafaei, M., Ghobadian, B., Barzegar, M., and Banakar, A., 2015. "Optimization of ultrasonic assisted continuous production of biodiesel using response surface methodology," Ultrason. Sonochem., 27, 54-61.

Moyo, L. B., Iyuke, S. E., Muvhiiwa, R. F., Simate, G. S., and Hlabangana, N., 2021. "Application of response surface methodology for optimization of biodiesel production parameters from waste cooking oil using a membrane reactor," S. Afr. J. Chem. Eng., 35, 1-7.

Munir, M., Ahmad, M., Rehan, M., Saeed, M., Lam, S. S., Nizami, A. S., Waseem, A., Sultana, S., and Zafar, M., 2021. "Production of high quality biodiesel from novel non-edible Raphnus raphanistrum L. seed oil using copper modified montmorillonite clay catalyst," Environ. Res., 193, 110398.

Munir, M., Saeed, M., Ahmad, M., Waseem, A., Sultana, S., Zafar, M., and Srinivasan, G. R., 2022. "Optimization of novel Lepidium perfoliatum Linn. biodiesel using zirconium-modified montmorillonite clay catalyst," Energ. Source Part A, 44, 6632-6647.

Negm, N. A., Sayed, G. H., Yehia, F. Z., Habib, O. I., and Mohamed, E. A., 2017. "Biodiesel production from one-step heterogeneous catalyzed process of Castor oil and Jatropha oil using novel sulphonated phenyl silane montmorillonite catalyst," J. Mol. Liq., 234, 157-163.

Paineau, E., Philippe, A. M., Antonova, K., Bihannic, I., Davidson, P., Dozov, I., Gabriel, J. C. P., Impéror-Clerc, M., Levitz, P., Meneau, F., and Michot, L. J., 2013. "Liquid–crystalline properties of aqueous suspensions of natural clay nanosheets," Liq. Cryst. Rev., 1, 110-126.

Photaworn, S., Tongurai, C., and Kungsanunt, S., 2017. "Process development of two-step esterification plus catalyst solution recycling on waste vegetable oil possessing high free fatty acid," Chem. Eng. Process: Process Intensif., 118, 1-8.

Ramirez-Ortiz, J., Martinez, M., and Flores, H., 2012. "Metakaolinite as a catalyst for biodiesel production from waste cooking oil," Front. Chem. Sci. Eng., 6, 403-409.

Razzaq, L., Abbas, M. M., Miran, S., Asghar, S., Nawaz, S., Soudagar, M. E. E., Shaukat, N., Veza, I., Khalil, S., Abdelrahman, A., and Kalam, M. A., 2022. "Response surface methodology and artificial neural networks-based yield optimization of biodiesel sourced from mixture of palm and cotton seed oil," Sustainability, 14, 6130.

Rezende, M. J. C., and Pinto, A. C., 2016. "Esterification of fatty acids using acid-activated Brazilian smectite natural clay as a catalyst," Renew. Energy, 92, 171-177.

Soetaredjo, F. E., Ayucitra, A., Ismadji, S., and Maukar, A. L., 2011. "KOH/bentonite catalysts for transesterification of palm oil to biodiesel," Appl. Clay Sci., 53, 341-346.

Steudel, A., Friedrich, F., Boháč, P., Lieske, W., Baille, W., König, D., Schuhmann, R., and Emmerich, K., 2020. "Equimolar cation exchange of polyacrylamide in smectite," Appl. Clay Sci., 188, 105501.

Syukri, S., Septioga, K., Arief, S., Putri, Y. E., Efdi, M., and Septiani, U., 2020. "Natural clay of Pasaman Barat enriched by CaO of chicken eggshells as catalyst for biodiesel production," Bull. Chem. React., 15, 662-673.

Thoai, D. N., Hang, P. T. L., and Lan, D. T., 2019. "Pre-treatment of waste cooking oil with high free fatty acids content for biodiesel production: An optimization study via response surface methodology," Vietnam J. Chem., 57, 568-573.

Wang, Y., Muhammad, Y., Yu, S., Fu, T., Liu, K., Tong, Z., Hu, X., and Zhang, H., 2022. "Preparation of Ca- and Na-modified activated clay as a promising heterogeneous catalyst for biodiesel production via transesterification," Appl. Sci., 12, 4667.


Article Metrics

Abstract views : 1417 | views : 1079


  • There are currently no refbacks.

ASEAN Journal of Chemical Engineering  (print ISSN 1655-4418; online ISSN 2655-5409) is published by Chemical Engineering Department, Faculty of Engineering, Universitas Gadjah Mada.