STUDIES OF THE KINETIC AND THERMODYNAMIC PARAMETERS OF LEVULINIC ACID IN THE CONVERSION TO ETHYL LEVULINATE VIA ESTERIFICATION CATALYSED BY SULFONATED FOOD WASTE CHAR
DOI:
https://doi.org/10.11113/jurnalteknologi.v89.25102Keywords:
Ethyl levulinate, food waste, kinetic study, levulinic acid, thermodynamic studyAbstract
This work investigated the kinetics and thermodynamics of levulinic acid (LA) conversion to ethyl levulinate (EL) catalysed by sulfonated food waste char (SFC) catalyst. The food waste char was derived from the hydrothermal liquefaction of food waste that underwent sulfonation with sulphuric acid to prepare an acid-functionalised catalyst. The esterification reaction was performed by varying the process parameters, including catalyst particle size (300 and 600 μm), agitation speed (100 and 300 rpm), reaction time (1–4 h), and heating temperature (60–80 °C). The EL yield and LA conversion were determined through the concentration of the respective chemicals analysed by gas chromatography-mass spectrometry. Pseudo-homogeneous kinetic models were employed to determine the reaction order and kinetic parameters. Subsequently, the thermodynamic parameters were determined using the Eyring equation. Based on the results, the pseudo-first-order model was identified as the best-fit model to represent the reaction kinetics, yielding an activation energy of 56.1 kJ/mol, an enthalpy of activation of 52.3 kJ/mol, an entropy of activation of -190.9 J/mol·K, and a Gibbs free energy of activation of 84.4 kJ/mol.
References
[1] Badgujar, K.C., Badgujar, V.C., Bhanage, B.M. (2020). A review on catalytic synthesis of energy rich fuel additive levulinate compounds from biomass derived levulinic acid. Fuel Processing Technology. 197, 106213. DOI: https://doi.org/10.1016/j.fuproc.2019.106213.
[2] Oprescu, E.-E., Enascuta, C.-E., Doukeh, R., Calin, C., Lavric, V. (2021). Characterizing and using a new bi-functional catalyst to sustainably synthesize methyl levulinate from biomass carbohydrates. Renewable Energy. 176, 651-662. DOI: https://doi.org/10.1016/j.renene.2021.05.120.
[3] [3] Démolis, A., Essayem, N., Rataboul, F. (2014). Synthesis and applications of alkyl levulinates. ACS Sustainable Chemistry & Engineering. 2, 1338-1352. DOI: https://doi.org/10.1021/sc500082n.
[4] Ramli, N.A.S., Hisham, N.I., Amin, N.A.S. (2018). Esterification of levulinic acid to levulinate esters in the presence of sulfated silica catalyst. Sains Malaysiana. 47, 1131-1138. DOI: http://dx.doi.org/10.17576/jsm-2018-4706-08.
[5] Nandiwale, K.Y., Sonar, S.K., Niphadkar, P.S., Joshi, P.N., Deshpande, S.S., Patil, V.S., Bokade, V.V. (2013). Catalytic upgrading of renewable levulinic acid to ethyl levulinate biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst. Applied Catalysis A: General. 460, 90-98. DOI: https://doi.org/10.1016/j.apcata.2013.04.024.
[6] Peng, L., Li, H., Xi, L., Chen, K., Chen, H. (2014). Facile and efficient conversion of furfuryl alcohol into n-butyl levulinate catalyzed by extremely low acid concentration. BioResources. 9, 3825-3834. DOI: https://doi.org/10.15376/biores.9.3.3825-3834.
[7] Gupta, P., Paul, S. (2014). Solid acids: Green alternatives for acid catalysis. Catalysis Today. 236, 153-170. DOI: https://doi.org/10.1016/j.cattod.2014.04.010.
[8] Bakhtiari, B., Najafi Chermahini, A., Babaei, Z. (2021). Design of an acidic sulfonated mesoporous carbon catalyst for the synthesis of butyl levulinate from levulinic acid. Environmental Progress & Sustainable Energy. 40, e13721. DOI: https://doi.org/10.1002/ep.13721.
[9] Guo, H., Hirosaki, Y., Qi, X., Smith Jr, R.L. (2020). Synthesis of ethyl levulinate over amino-sulfonated functional carbon materials. Renewable Energy. 157, 951-958. DOI: https://doi.org/10.1016/j.renene.2020.05.103.
[10] Kitano, M., Arai, K., Kodama, A., Kousaka, T., Nakajima, K., Hayashi, S., Hara, M. (2009). Preparation of a sulfonated porous carbon catalyst with high specific surface area. Catalysis letters. 131, 242-249. DOI: https://doi.org/10.1007/s10562-009-0062-4.
[11] Hassan, A.H., Zainol, M.M., Samion, M.A., Azlan, M.A.q., Asmadi, M., Mohamad Daud, A.R., Saad, I., Mohd Nor Azman, N.A.N. (2023). Synthesis of ethyl levulinate over sulfonated lignin-based carbon catalyst as a fuel additive to biodiesel-diesel blends towards engine emissions. Journal of Cleaner Production. 418, 138101. DOI: https://doi.org/10.1016/j.jclepro.2023.138101.
[12] Mahssin, Z.Y., Zainol, M.M., Hassan, N.A., Yaacob, H., Puteh, M.H., Amin, N.A.S. (2021). Hydrothermal liquefaction bioproduct of food waste conversion as an alternative composite of asphalt binder. Journal of Cleaner Production. 282, 125422. DOI: https://doi.org/10.1016/j.jclepro.2020.125422.
[13] Kajdas, C., Kulczycki, A., Kurzydłowski, K., Molina, G.J. (2010). Activation energy of tribochemical and heterogeneous catalytic reactions. Materials Science-Poland. 28, 523-533.
[14] Zainol, M.M., Asmadi, M., Amin, N.A.S. (2022). Bio-fuel additive synthesized from levulinic acid using ionic liquid-furfural based carbon catalyst: Kinetic, thermodynamic and mechanism studies. Chemical Engineering Science. 247, 117079. DOI: https://doi.org/10.1016/j.ces.2021.117079.
[15] Zainol, M.M., Amin, N.A.S., Asmadi, M. (2019). Kinetics and thermodynamic analysis of levulinic acid esterification using lignin-furfural carbon cryogel catalyst. Renewable Energy. 130, 547-557. DOI: https://doi.org/10.1016/j.renene.2018.06.085.
[16] Tiong, Y.W., Yap, C.L., Gan, S., Yap, W.S.P. (2020). Kinetic and thermodynamic studies of oil palm mesocarp fiber cellulose conversion to levulinic acid and upgrading to ethyl levulinate via indium trichloride-ionic liquids. Renewable Energy. 146, 932-943. DOI: https://doi.org/10.1016/j.renene.2019.07.024.
[17] Yadav, G.D., Yadav, A.R. (2014). Synthesis of ethyl levulinate as fuel additives using heterogeneous solid superacidic catalysts: Efficacy and kinetic modeling. Chemical Engineering Journal. 243, 556-563. DOI: https://doi.org/10.1016/j.cej.2014.01.013.
[18] Hassan, A.H., Zainol, M.M., Zainuddin, K.R., Saperi, N.Q., Yussuf, M.A.M., Abd Rahman, N., Azman, N.A.N.M.N. (2022). Sulfonated Carbon Catalyst Prepared from Calcination of Lignin for Ethyl Levulinate Synthesis via Ethanolysis of Levulinic Acid. Chemical Engineering Transactions. 97, 307-312. DOI: https://doi.org/10.3303/CET2297052.
[19] Hassan, A.H., Zainol, M.M., Samion, M.A., Asmadi, M., Daud, A.R.M., Saad, I., Azman, N.A.N.M.N. (2023). Synthesis of ethyl levulinate over sulfonated lignin-based carbon catalyst as a fuel additive to biodiesel-diesel blends towards engine emissions. Journal of Cleaner Production. 418, 138101. DOI: https://doi.org/10.1016/j.jclepro.2023.138101
[20] Andreo-Martínez, P., García-Martínez, N., del Mar Durán-del-Amor, M., Quesada-Medina, J. (2018). Advances on kinetics and thermodynamics of non-catalytic supercritical methanol transesterification of some vegetable oils to biodiesel. Energy Conversion and Management. 173, 187-196. DOI: https://doi.org/10.1016/j.enconman.2018.07.069
[21] Hoo, P., Abdullah, A.Z. (2015). Kinetics modeling and mechanism study for selective esterification of glycerol with lauric acid using 12-tungstophosphoric acid post-impregnated SBA-15. Industrial & Engineering Chemistry Research. 54, 7852-7858. DOI: https://doi.org/10.1021/acs.iecr.5b02304.
[22] Nda-Umar, U.I., Ramli, I., Muhamad, E.N., Taufiq-Yap, Y.H., Azri, N. (2020). Synthesis and characterization of sulfonated carbon catalysts derived from biomass waste and its evaluation in glycerol acetylation. Biomass Conversion and Biorefinery. 1-16. DOI: https://doi.org/10.1007/s13399-020-00784-0.
[23] Kastner, J., R., Miller, J., Geller, D.P., Locklin, J., Keith, L.H., Johnson, T. (2012). Catalytic esterification of fatty acids using solid acid catalysts generated from biochar and activated carbon. Catalysis Today. 190, 122-132. DOI: https://doi.org/10.1016/j.cattod.2012.02.006.
[24] Hara, M. (2010). Biodiesel Production by Amorphous Carbon Bearing SO3H, COOH and Phenolic OH Groups, a Solid Brønsted Acid Catalyst. Topics in Catalysis. 53, 805-810. DOI: https://doi.org/10.1007/s11244-010-9458-z
[25] Zainol, M.M., Asmadi, M., Iskandar, P., Wan Ahmad, W.A.N., Amin, N.A.S., Hoe, T.T. (2021). Ethyl levulinate synthesis from biomass derivative chemicals using iron doped sulfonated carbon cryogel catalyst. Journal of Cleaner Production. 281, 124686. DOI: https://doi.org/10.1016/j.jclepro.2020.124686.
[26] Ren, J., Cao, J.-P., Zhao, X.-Y., Liu, Y.-L. (2021). Fundamentals and applications of char in biomass tar reforming. Fuel Processing Technology. 216, 106782. DOI: https://doi.org/10.1016/j.fuproc.2021.106782.
[27] Rocha, P.D., Oliveira, L.S., Franca, A.S. (2019). Sulfonated activated carbon from corn cobs as heterogeneous catalysts for biodiesel production using microwave-assisted transesterification. Renewable Energy. 143, 1710-1716. DOI: https://doi.org/10.1016/j.renene.2019.05.070.
[28] Singare, P.U., Lokhande, R.S., Madyal, R.S. (2011). Thermal degradation studies of some strongly acidic ca-tion exchange resins. Open Journal of Physical Chemistry. 1, 45. DOI: https://doi.org/10.4236/ojpc.2011.12007.
[29] Zailan, Z., Tahir, M., Jusoh, M., Zakaria, Z.Y. (2021). A review of sulfonic group bearing porous carbon catalyst for biodiesel production. Renewable Energy. 175, 430-452. DOI: https://doi.org/10.1016/j.renene.2021.05.030.
[30] Nandiwale, K.Y., Niphadkar, P.S., Deshpande, S.S., Bokade, V.V. (2014). Esterification of renewable levulinic acid to ethyl levulinate biodiesel catalyzed by highly active and reusable desilicated H‐ZSM‐5. Journal of Chemical Technology & Biotechnology. 89, 1507-1515. DOI: https://doi.org/10.1002/jctb.4228.
[31] Ramli, N.A.S., Amin, N.A.S. (2016). Kinetic study of glucose conversion to levulinic acid over Fe/HY zeolite catalyst. Chemical Engineering Journal. 283, 150-159. DOI: https://doi.org/10.1016/j.cej.2015.07.044.
[32] Sert, M. (2020). Catalytic effect of acidic deep eutectic solvents for the conversion of levulinic acid to ethyl levulinate. Renewable Energy. 153, 1155-1162. DOI: https://doi.org/10.1016/j.renene.2020.02.070.
[33] Tian, L., Zhang, L., Liu, Y., He, Y., Zhu, Y., Sun, R., Yi, S., Xiang, J. (2020). Clean production of ethyl levulinate from kitchen waste. Journal of Cleaner Production. 268, 122296. DOI: https://doi.org/10.1016/j.jclepro.2020.122296.
[34] Mthembu, L., Lokhat, D., Deenadayalu, N. (2021). Esterification of levulinic acid to ethyl levulinate: optimization of process conditions using commercial levulinic acid and extension to the use of levulinic acid derived from depithed sugarcane bagasse. Biomass Conversion and Biorefinery. 1-10. DOI: https://doi.org/10.1007/s13399-021-01632-5.
[35] Kokare, M.B., Ranjani, V., Mathpati, C. (2018). Response surface optimization, kinetic study and process design of n-butyl levulinate synthesis. Chemical Engineering Research and Design. 137, 577-588. DOI: https://doi.org/10.1016/j.cherd.2018.07.036.
[36] Fernandes, D., Rocha, A., Mai, E., Mota, C.J., Da Silva, V.T. (2012). Levulinic acid esterification with ethanol to ethyl levulinate production over solid acid catalysts. Applied Catalysis A: General. 425, 199-204. DOI: https://doi.org/10.1016/j.apcata.2012.03.020.
[37] Dhawane, S.H., Al-Sakkari, E., Kumar, T., Halder, G. (2021). Comprehensive elucidation of the apparent kinetics and mass transfer resistances for biodiesel production via in-house developed carbonaceous catalyst. Chemical Engineering Research and Design. 165, 192-206. DOI: https://doi.org/10.1016/j.cherd.2020.11.003
[38] Nandiwale, K.Y., Bokade, V.V. (2015). Environmentally benign catalytic process for esterification of renewable levulinic acid to various alkyl levulinates biodiesel. Environmental Progress & Sustainable Energy. 34, 795-801. DOI: https://doi.org/10.1002/ep.12042.
Downloads
Published
Issue
Section
License
Copyright of articles that appear in Jurnal Teknologi belongs exclusively to Penerbit Universiti Teknologi Malaysia (Penerbit UTM Press). This copyright covers the rights to reproduce the article, including reprints, electronic reproductions, or any other reproductions of similar nature.














