Synthesis, characterization and application of [CTA+]MCM-41 in the catalytic conversion of soybean oil to fatty acid methyl esters
DOI:
https://doi.org/10.24297/jac.v12i6.4348Abstract
The transesterification of vegetable oil and/or animal fats in homogeneous alkaline medium is still the most widely used method for the production of biodiesel. However, this process requires raw materials with low acidity and moisture content to prevent undesirable side reactions such as saponification, which leads to emulsification and promotes losses in the reaction yield. Many solid compounds can be used in catalytic processes to reduce these limitations. Heterogeneous catalysts allow easy separation of the reaction media and have the possibility of reuse in several cycles. In this work, [CTA+]MCM-41 molecular sieves were synthesized and characterized by several methods (XRD, SEM, TGA and BET) to be applied in the methanolysis of soybean oil. The resulting materials were characterized as mesoporous solids of type IV with similar textural properties and thermal stability. The catalytic activity of [CTA+]MCM-41 in soybean oil methanolysis was analyzed by gel permeation chromatography (GPC) and the best solid catalyst was applied in a factorial design that was validated by Analysis of Variance (ANOVA). The oil:methanol molar ratio and the catalyst concentration were the variables with the highest statistical effects, with the latter showing a quadratic profile in relation to the response function. The best conversion was achieved at 343 K, 30 min and 3.75 wt % catalyst, which corresponded to a product with 99.2% in fatty acid methyl esters. Calcination caused a total loss in catalytic activity due to the removal of CTA+ cations from the mesoporous solids. Hence, such activity was associated with the formation of (SiO-)(CTA+) ion pairs at the surface of the solid catalystDownloads
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References
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2. Ren, J., Tan, S., Yang, L., Goodsite, M.E., Pang, C., Dong, L. 2015. Optimization of emergy sustainability index for biodiesel supply network design. Energy Conversion and Management. 92:312-321.
3. Shahir, V.K., Jawahar, C.P., Suresh, P.R. 2015. Comparative study of diesel and biodiesel on CI engine with emphasis to emissions - A review. Renewable Sustainable Energy Reviews. 45:686-697.
4. Silva, F.R., Silveira, M.H.L., Cordeiro, C.S., Nakagaki, S., Wypych, F., Ramos, L.P. 2013. Esterification of fatty acids using a bismuth-containing solid acid catalyst. Energy Fuels. 27:2218-2225.
5. Choedkiatsakul, I., Ngaosuwan, K., Assabumrungrat, S., Mantegna, S., Cravotto, G. 2015. Biodiesel production in a novel continuous flow microwave reactor. Renewable Energy. 83:25-29.
6. Ramos, L.P. and Wilhelm, H.M. 2005. Current status of biodiesel development in Brazil. Applied Biochemistry and Biotechnology. 121-124:807-819.
7. Grün, M,. Unger, K.K., Matsumoto, A., Tsutsumi, K. 1999. Novel pathways for the preparation of mesoporous MCM-41 materials: control of porosity and morphology. Microporous and Mesoporous Materials. 27:207-216.
8. Luna, F.J. and Schuchardt, U. 2001. Modificação de zeólitas para uso em catálise. QuÃmica Nova. 24:885-892.
9. Sing, K.S.W., Everett, D.H., Haul, R.A.W., Moscou, L., Pierotti, R.A., Rouquérol, J., Siemieniewska, T. 1985. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure and Applied Chemistry. 57:603-619.
10. Ranucci, C.R., Colpini, L.M.S., Monteiro, M.R., Kothe, V., Gasparrini, L.J., Alves, H.J. 2015. Preparation, characterization and stability of KF/Si-MCM-41 basic catalysts for application in soybean oil transesterification with methanol. Journal of the Environmental Chemical Engineering. 3:703-707.
11. Fabiano, D.P., Hamad, B., Cardoso, D., Essayem, N. 2010. On the understanding of the remarkable activity of template-containing mesoporous molecular sieves in the transesterification of rapeseed oil with ethanol. Journal of Catalysis. 276:190-196.
12. Cheng, C-F., Park, D.H., Klinowski, J. 1997. Optimal parameters for the synthesis of the mesoporous molecular sieve [Si]-MCM-41. Journal of the Chemical Society, Faraday Transactions. 93:193-197. 13. Kresge, C.T., Leonowicz, M.E., Roth, W.J., Vartulli, J.C., Beck, J.S. 1992. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature. 359:710-712.
14. Martins, L. and Cardoso, D. 2007. Influence of surfactant chain length on basic catalytic properties of Si-MCM-41. Microporous and Mesoporous Materials. 106:8-16.
15. Kubota, Y., Nishizaki, Y., Ikeya, H., Saeki, M., Hida, T., Kawazu, S., Yoshida, M., Fujii, H., Sugi, Y. 2004. Organic-silicate hybrid catalysts based on various defined structures for Knoevenagel condensation. Microporous and Mesoporous Materials. 70:135-149.
16. Kubota, Y., Ikeya, H., Sugi, Y., Yamada, T., Tatsumi, T. 2006. Organic–inorganic hybrid catalysts based on ordered porous structures for Michael reaction. Journal of Molecular Catalysis A: Chemical. 249:181-190.
17. Kresge, C.T. and Roth, W.J. 2013. The discovery of mesoporous molecular sieves from the twenty year perspective. Chemical Society Reviews. 42:3663-3670.
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Published
2016-11-12
How to Cite
Kothe, V., Alves, H. J., Silveira, M. H. L., & Pereira, L. (2016). Synthesis, characterization and application of [CTA+]MCM-41 in the catalytic conversion of soybean oil to fatty acid methyl esters. JOURNAL OF ADVANCES IN CHEMISTRY, 12(6), 4117–4126. https://doi.org/10.24297/jac.v12i6.4348
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