Synthesis of SO42–/ZrO2 Solid Acid and Na2O/ZrO2 Solid Base Catalysts Using Hydrothermal Method for Biodiesel Production from Low-Grade Crude Palm Oil
Sri Setyaningsih(1), Maisari Utami(2), Akhmad Syoufian(3), Eddy Heraldy(4), Nasih Widya Yuwono(5), Karna Wijaya(6*)
(1) Department of Science Education, Faculty of Teacher Training and Education, Universitas Islam Lamongan, Jl. Veteran No. 53A, Lamongan 62211, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Islam Indonesia, Jl. Kaliurang km. 14, Yogyakarta 55584, Indonesia
(3) Department of Chemistry, Faculty Mathematics and Natural Science, Universitas Gadjah Mada, Sekip Utara, PO BOX BLS 21, Yogyakarta 55281, Indonesia
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Jl. Ir. Sutami 36A, Surakarta 57126, Central Java, Indonesia
(5) Department of Soil Science, Faculty of Agriculture, Universitas Gadjah Mada, Jl. Flora, Bulaksumur, Yogyakarta 55281, Indonesia
(6) Department of Chemistry, Faculty Mathematics and Natural Science, Universitas Gadjah Mada, Sekip Utara, PO BOX BLS 21, Yogyakarta 55281, Indonesia
(*) Corresponding Author
Abstract
Biodiesel is a renewable energy source that can be produced through esterification as well as transesterification reactions. This work presents a series of zirconia catalysts synthesized by hydrothermal method on various concentrations in acidic (H2SO4 0.3, 0.5, and 0.7 M) and basic (NaOH 1, 2, 3, and 4 M) solution to get a catalyst with the highest acidity or basicity. Characterizations of the catalysts were performed by FTIR, XRD, SEM-EDX, surface area analysis, acidity, and basicity test. The most active acid catalyst activity was evaluated for the esterification of low-grade crude palm oil (LGCPO), while the solid base catalyst was utilized for the transesterification reaction. The solid acid catalyst of 0.7 M SO42–/ZrO2 60 °C; 24 h was denoted as the most active acid catalyst with a total acidity of 1.86 mmol g–1, while 4 M Na2O/ZrO2 60 °C; 24 h catalyst was considered as the solid base catalyst with the highest total basicity of 3.75 ± 0.12 mmol g–1. The optimized acid catalyst exhibited a 31 times higher acidity than commercial ZrO2. The concentration of free fatty acids (FFA) decreased to 68.87% in the esterification reaction. The solid base catalyst of 4 M Na2O/ZrO2 60 °C; 24 h successfully converted LGCPO into biodiesel by 68.55% through a transesterification reaction.
Keywords
Full Text:
Full Text PDFReferences
[1] Hajjari, M., Tabatabaei, M., Aghbashlo, M., and Ghanavati, H., 2017, A review on the prospects of sustainable biodiesel production: A global scenario with an emphasis on waste-oil biodiesel utilization, Renewable Sustainable Energy Rev., 72, 445–464.
[2] Muanruksa, P., and Kaewkannetra, P., 2020, Combination of fatty acids extraction and enzymatic esterification for biodiesel production using sludge palm oil as a low-cost substrate, Renewable Energy, 146, 901–906.
[3] Atadashi, I.M., Aroua, M.K., Aziz, A.R.A., and Sulaiman, N.M.N., 2013, The effects of catalysts in biodiesel production: A review, J. Ind. Eng. Chem., 19 (1), 14–26.
[4] Li, Y., Ye, B., Shen, J., Tian, Z., Wang, L., Zhu, L., Ma, T., Yang, D., and Qiu, F., 2013, Optimization of biodiesel production process from soybean oil using the sodium potassium tartrate doped zirconia catalyst under Microwave Chemical Reactor, Bioresour. Technol., 137, 220–225.
[5] Hasanudin, H., Rachmat, A., Said, M., and Wijaya, K., 2020, Kinetic model of crude palm oil hydrocracking over Ni/Mo ZrO2–pillared bentonite catalyst, Period. Polytech., Chem. Eng., 64 (2), 238–247.
[6] Hayyan, A., Mjalli, F.S., Hashim, M.A., Hayyan, M., AlNashef, I.M., Al-Wahaibi, T., and Al-Wahaibi, Y.M., 2014, A solid organic acid catalyst for the pretreatment of low-grade crude palm oil and biodiesel production, Int. J. Green Energy, 11 (2), 129–140.
[7] Min Oo, Y., Prateepchaikul, G., and Somnuk, K., 2021, Continuous acid-catalyzed esterification using a 3D printed rotor–stator hydrodynamic cavitation reactor reduces free fatty acid content in mixed crude palm oil, Ultrason. Sonochem., 72, 105419.
[8] Pua, F., Fang, Z., Zakaria, S., Guo, F., and Chia, C., 2011, Direct production of biodiesel from high-acid value Jatropha oil with solid acid catalyst derived from lignin, Biotechnol. Biofuels, 4 (1), 56.
[9] Qu, T., Niu, S., Zhang, X., Han, K., and Lu, C., 2021, Preparation of calcium modified Zn-Ce/Al2O3 heterogeneous catalyst for biodiesel production through transesterification of palm oil with methanol optimized by response surface methodology, Fuel, 284, 118986.
[10] Chuah, L.F., Bokhari, A., Yusup, S., Klemeš, J.J., Abdullah, B., and Akbar, M.M., 2016, Optimisation and kinetic studies of acid esterification of high free fatty acid rubber seed oil, Arabian J. Sci. Eng., 41 (7), 2515–2526.
[11] Rattanaphra, D., Harvey, A.P., Thanapimmetha, A., and Srinophakun, P., 2012, Simultaneous transesterification and esterification for biodiesel production with and without a sulfated zirconia catalyst, Fuel, 97, 467–475.
[12] Ropero-Vega, J.L., Aldana-Pérez, A., Gómez, R., and Niño-Gómez, M.E., 2010, Sulfated titania [TiO2/SO42–]: A very active solid acid catalyst for the esterification of free fatty acids with ethanol, Appl. Catal., A, 379 (1-2), 24–29.
[13] Johnson, M., Ren, J., Lefler, M., Licht, G., Vicini, J., Liu, X., and Licht, S., 2017, Carbon nanotube wools made directly from CO2 by molten electrolysis: Value-driven pathways to carbon dioxide greenhouse gas mitigation, Mater. Today Energy, 5, 230–236.
[14] Chouhan, A.P.S., and Sarma, A.K., 2011, Modern heterogeneous catalysts for biodiesel production: A comprehensive review, Renewable Sustainable Energy Rev., 15 (9), 4378–4399.
[15] Devyatkov, S.Y., Zinnurova, A.A., Aho, A., Kronlund, D., Peltonen, J., Kuzichkin, N.V., Lisitsyn, N.V., and Murzin, D.Y., 2016, Shaping of sulfated zirconia catalysts by extrusion: understanding the role of binders, Ind. Eng. Chem. Res., 55 (23), 6595–6606.
[16] Pan, Y., Zhang, J., Xu, Y., Gao, Y., Chen, Z., and Wang, J., 2016, A facile one-pot hydrothermal process to synthesize sulfonated mesoporous ZrO2, J. Porous Mater., 23 (2), 489–495.
[17] Utami, M., Trisunaryanti, W., Shida, K., Tsushida, M., Kawakita, H., Ohto, K., Wijaya, K., and Tominaga, M., 2019, Hydrothermal preparation of a platinum-loaded sulfated nanozirconia catalyst for the effective conversion of waste low density polyethylene into gasoline-range hydrocarbons, RSC Adv., 9 (71), 41392–41401.
[18] Li, Y., He, D., Zhu, Q., Zhang, X., and Xu, B., 2004, Effects of redox properties and acid-base properties on isosynthesis over ZrO2-based catalysts, J. Catal., 221 (2), 584–593.
[19] Rabee, A.I.M., Manayil, J.C., Isaacs, M.A., Parlett, C.M.A., Durndell, L.J., Zaki, M.I., Lee, A.F., and Wilson, K., 2018, On the impact of the preparation method on the surface basicity of Mg–Zr mixed oxide catalysts for tributyrin transesterification, Catalysts, 8 (6), 228.
[20] Noh, H.J., Seo, D.S., Kim, H., and Lee, J.K., 2003, Synthesis and crystallization of anisotropic shaped ZrO2 nanocrystalline powders by hydrothermal process, Mater. Lett., 57 (16-17), 2425–2431.
[21] Sohn, J.R., Kim, H.W., Park, M.Y., Park, E.H., Kim, J.T., and Park, S.E., 1995, Highly active catalyst of NiO-ZrO2 modified with H2SO4 for ethylene dimerization, Appl. Catal., A, 128 (1), 127–141.
[22] Saravanan, K., Tyagi, B., and Bajaj, H.C., 2012, Esterification of caprylic acid with alcohol over nano-crystalline sulfated zirconia, J. Sol-Gel Sci. Technol., 62 (1), 13–17.
[23] Srinivasan, R., Sparks, D.E., and Davis, B.H., 1996, State of platinum in zirconia and sulfated zirconia catalysts, Catal. Lett., 40 (3), 167–173.
[24] Zhang, C., Miranda, R., and Davis, B.H., 1994, Platinum-sulfated-zirconia. Infrared study of adsorbed pyridine, Catal. Lett., 29 (3), 349–359.
[25] Popova, M., Szegedi, Á., Lazarova, H., Dimitrov, M., Kalvachev, Y., Atanasova, G., Ristić, A., Wilde, N., and Gläser, R., 2017, Influence of the preparation method of sulfated zirconia nanoparticles for levulinic acid esterification, React. Kinet., Mech. Catal., 120 (1), 55–67.
[26] Sayılkan, F., Asiltürk, M., Burunkaya, E., and Arpaç, E., 2009, Hydrothermal synthesis and characterization of nanocrystalline ZrO2 and surface modification with 2-acetoacetoxyethyl methacrylate, J. Sol-Gel Sci. Technol., 51 (2), 182–189.
[27] Devulapelli, V.G., and Weng, H.S., 2009, Esterification of 4-methoxyphenylacetic acid with dimethyl carbonate over mesoporous sulfated zirconia, Catal. Commun., 10 (13), 1711–1717.
[28] Qiu, F., Li, Y., Yang, D., Li, X., and Sun, P., 2011, Heterogeneous solid base nanocatalyst: Preparation, characterization and application in biodiesel production, Bioresour. Technol., 102 (5), 4150–4156.
[29] El-Desouki, D.S., Ibrahim, A.H., Abdelazim, S.M., Aboul-Gheit, N.A.K., and Abdel-Hafizar, D.R., 2021, The optimum conditions for methanol conversion to dimethyl ether over modified sulfated zirconia catalysts prepared by different methods, J. Fuel Chem. Technol., 49 (1), 63–71.
[30] Pratap, S.R., Shamshuddin, S.Z.M., and Shyamprasad, K., 2020, Microwave assisted synthesis of propyl esters over modified versions of zirconia: Kinetic study, Chem. Data Collect., 30, 100579.
[31] Essamlali, Y., Amadine, O., Larzek, M., Len, C., and Zahouily, M., 2017, Sodium modified hydroxyapatite: Highly efficient and stable solid-base catalyst for biodiesel production, Energy Convers. Manage., 149, 355–367.
[32] Abedin, M.A., Kanitkar, S., Bhattar, S., and Spivey, J.J., 2021, Methane dehydroaromatization using Mo supported on sulfated zirconia catalyst: Effect of promoters, Catal. Today, 365, 71–79.
[33] Marinković, D.M., Stanković, M.V., Veličković, A.V., Avramović, J.M., Miladinović, M.R., Stamenković, O.O., Veljković, V.B., and Jovanović, D.M., 2016, Calcium oxide as a promising heterogeneous catalyst for biodiesel production: Current state and perspectives, Renewable Sustainable Energy Rev., 56, 1387–1408.
[34] Helmiyati, H., Budiman, Y., Abbas, G.H., Dini, F.W., and Khalil, M., 2021, Highly efficient synthesis of biodiesel catalyzed by a cellulose@hematite-zirconia nanocomposite, Heliyon, 7 (3), e06622.
[35] dos Santos, L.K., Hatanaka, R.R., de Oliveira, J.E., and Flumignan, D.L., 2019, Production of biodiesel from crude palm oil by a sequential hydrolysis/esterification process using subcritical water, Renewable Energy, 130, 633–640.
[36] Chong, Y.Y., Thangalazhy-Gopakumar, S., Gan, S., Lee, L.Y., and Ng, H.K., 2020, Esterification and neutralization of bio-oil from palm empty fruit bunch fibre with calcium oxide, Bioresour. Technol. Rep., 12, 100560.
[37] Knothe, G., 2000, Monitoring a progressing transesterification reaction by fiber-optic near infrared spectroscopy with correlation to 1H nuclear magnetic resonance spectroscopy, J. Am. Oil Chem. Soc., 77 (5), 489–493.
[38] Shi, G., Yu, F., Wang, Y., Pan, D., Wang, H., and Li, R., 2016, A novel one-pot synthesis of tetragonal sulfated zirconia catalyst with high activity for biodiesel production from the transesterification of soybean oil, Renewable Energy, 92, 22–29.
[39] Pavia, D.L., Lampman, G.M., Kriz, G.S., and Vyvyan, J.A., 2009, Introduction to Spectroscopy, 4th Ed., Brooks/Cole, Cengage Learning, Belmont, CA.
[40] Liu, N., Ma, Z., Wang, S., Shi, L., Hu, X., and Meng, X., 2020, Palladium-doped sulfated zirconia: Deactivation behavior in isomerization of n-hexane, Fuel, 262, 116566.
[41] Navio, J.A., Colón, G., Sánchez-Soto, P.J., and Macias, M., 1997, Effects of H2O2 and SO42– species on the crystalline structure and surface properties of ZrO2 processed by alkaline precipitation, Chem. Mater., 9 (5), 1256–1261.
[42] Tuong, T., Tran, V., Kaiprommarat, S., Kongparakul, S., Reubroycharoen, P., Guan, G., Huan, M., and Samart, C., 2016, Green biodiesel production from waste cooking oil using an environmentally benign acid catalyst, Waste Manage., 52, 367–374.
[43] El-Dafrawy, S.M., Hassan, S.M., and Farag, M., 2020, Kinetics and mechanism of Pechmann condensation reaction over sulphated zirconia-supported zinc oxide, J. Mater. Res. Technol., 9 (1), 13–21.
[44] Vannucci, J.A., Nichio, N.N., and Pompeo, F., 2021, Solketal synthesis from ketalization of glycerol with acetone: A kinetic study over a sulfated zirconia catalyst, Catal. Today, 372, 238–245.
[45] Pirez, C., Reche, M.T., Lee, A.F., Manayil, J.C., dos-Santos, V.C., and Wilson, K., 2015, Hydrothermal saline promoted grafting of periodic mesoporous organic sulfonic acid silicas for sustainable FAME production, Catal. Lett., 145 (7), 1483–1490.
[46] Colombo, K., Ender, L., and Barros, A.A.C., 2017, The study of biodiesel production using CaO as a heterogeneous catalytic reaction, Egypt. J. Pet., 26 (2), 341–349.
[47] Zhang, H., Luo, X., Shi, K., Wu, T., He, F., Yang, H., Zhang, S., and Peng, C., 2019, Nanocarbon-based catalysts for esterification: Effect of carbon dimensionality and synergistic effect of the surface functional groups, Carbon, 147, 134–145.
[48] Chang, A., Pan, J.H., Lai, N.C., Tsai, M.C., Mochizuki, T., Toba, M., Chen, S.Y., and Yang, C.M., 2020, Efficient simultaneous esterification/transesterification of non-edible Jatropha oil for biodiesel fuel production by template-free synthesized nanoporous titanosilicates, Catal. Today, 356, 56–63.
[49] Shah, K.A., Parikh, J.K., and Maheria, K.C., 2014, Optimization studies and chemical kinetics of silica sulfuric acid-catalyzed biodiesel synthesis from waste cooking oil, Bioenergy Res., 7 (1), 206–216.
[50] Saravana Sathiya Prabhahar, R., Benitha, V.S., and Nagarajan, J., 2021, Improved yield of palm oil biodiesel through nano catalytic transesterification, Mater. Today: Proc., 46, 8433–8437.
DOI: https://doi.org/10.22146/ijc.65404
Article Metrics
Abstract views : 4361 | views : 2979Copyright (c) 2022 Indonesian Journal of Chemistry
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.
View The Statistics of Indones. J. Chem.