Investigation Of Lauric Acid Conversion With The STA Incorporated Heterogeneous Catalysts In Liquid Phase Reaction

Year 2019, Volume: 6 Issue: 1, 91 - 103, 28.06.2019

Veli Şimşek , Kırali Mürtezaoğlu

https://doi.org/10.35193/bseufbd.553967

Cited By: 3

Abstract

In this study,
firstly the synthesis of acidic catalysts was carried out by loading the active
compound silicotungstic acid(STA) with dry (W/Si:10-50%) and wet (W/Si:10%)
impregnation methods into MCM-41 support material. These synthesized catalysts
were used in the production of mono-di and tri laurin. The amount of active
substance in the synthesized catalysts was determined by the ratios of tungsten
in STA and silicon in MCM-41 structure. Moreover, W/Si: 10% by weight of STA
was applied to the support material after the calcination process was loaded by
dry impregnation method. Brønsted acid (BA) and Lewis acid (LA) regions of synthesized
catalysts were determined by DRIFT analysis. The catalytic activities of the
catalysts were determined by a glycerol-lauric acid esterification reaction in a
batch reactor. The effect of calcination and active compound ratio with
reaction temperature on the lauric acid conversion and mono-di and tri laurin
selectivity was investigated. Furthermore, the esterification reaction of
glycerol with lauric acid was carried out under the same conditions in the
presence of a commercial catalyst Amberlyst-21. The experimental results of the
synthesized catalysts and Amberlyst-21catalyst were compared. The synthesized catalysts
after comparison were observed that have high catalytic activity. Lauric acid conversion and monolaurin selectivity have been obtained with
W/Si: 10% catalyst (dry impregnation method) 3/3/1 molar ratio at383K after 6 hours 95% and 88%, respectively. XRD
analysis was conducted on calcined-uncalcined MCM-41support material. Moreover,
the structural properties of synthesized catalysts after the
esterification reaction were determined by SEM-MAPPING analysis methods.

Keywords

STA, MCM-41, Mono-Di And Tri Laurin, Lauric Acid, Dry-Wet Impregnation

References

• [1] Goyal, H. B, Seal D., Saxena R. C. (2008). Bio-Fuels from Thermo Chemical Conversion of Renewable Resource, A review, Renewable and Sustainable Energy Reviews, 12, 504-517.
• [2] Melero, J. A., Grieken, R., Morales, G., Panioguna, M.(2007) Acidic Mesoporous Silica for the Acetylation of Glycerol Synthesis Bioadditives to Petrol Fuel, Energy and Fuels,21, 1782- 1791.
• [3] Hart, H., Hart, D. J., Craine, L., E.(2008). Organic Chemistry, 8th ed., Palme Publication, Ankara, 164-170,300-310.
• [4] Maki-Arvela, P., Salmi, T., Sundell, M., Ekman, K., Peltonen, R., Lehtonen, J. (1999). Comparison of Polyvinybenzen and Polyolefin Supported Sulphonic Acid Catalysts in the Esterification of Acetic Acid, Applied Catalysis A: General, 184, 25-32.
• [5] Yin, W.L.P., Liu, X., Chen, W., Chen, H., Liu, C., Qu, R., Xu, Q. (2013). Microwave Assisted Esterification of Free Fatty Acid over a Heterogeneous Catalyst for Biodiesel Production, Energy Conversion and Management, 76, 1009-1014.
• [6] Helminen, J., Leppamaki, M., Paatero, E., Minkkinen, P. (1998). Monitoring the Kinetics of the Ion –Exchange Resin Catalysed Esterification of Acetic Acid with Ethanol Using Near Infrared Spectroscopy with PLS Model,Chem. Int. Lab. Sys., 44, 341-352.
• [7] Poonjarersilp, C., Sano, N., Tamon, H.(2014). Hydrothermally Sulfonated Single-Walled Carbon Nano Horns for Use as Solid Catalysts in Biodiesel Production by Esterification of Palmitic acid, Applied Catalysis B: Environmental, 147, 726-732.
• [8] Oliviera, C., F., Dezaneti, L. M., Garcia, F. A. C., DeMacedo, J. L. Dias, J. A., Dias, S. C. L., Alvim, K. S. P. (2010). Esterification of Oleic Acid with Ethanol by 12-Tungstophosphoric Acid Supported on Zirconia, Applied Catalysis A: General, 372, 153-161.
• [9] Şimşek, V., Şahin, S. (2019). Characterization and catalytic performance evaluation of a novel heterogeneous mesoporous catalyst for methanol-acetic acid esterification. Journal of Porous Materials. May (2019) https://doi.org/10.1007/s10934-019-00764-4
• [10] Lilja, J., Murzin, D., Salmi, T., Aumo, J., Makü-Arvela, P., Sundels, M. (2002). Esterification of Different Acids Over Heterogeneous and Homogeneous Catalysts and Correlation with the Teft Equation, Journal of Molecular Catalysis A.Chemical,182-183:555-563.
• [11] Saldamlı, İ. (2007). General Chemistry, 3th ed,Hacettepe University Publications Ankara, 133-175.
• [12] Sakthivel, A., Nakamura, R., Komura, K., Sugi, Y. (2007). Esterification of Glycerol by Lauric Acid over Aluminium and Zirconium Containing Mesoporous Molecular Sieves in Supercritical Carbon Dioxide Medium. J. Supercrit. Fluids, 42, 219–225.
• [13] Diaz, I., Mohino, F., Blasco, T., Sastre, E., Perez-Pariente, J. (2005). Influence of the Alkyl Chain Length of HSO3-R-MCM-41 on the Esterification of Glycerol with Fatty Acids. Microporous Mesoporous Mater., 80, 33-42.
• [14] Diaz, I., Mohino, F., Perez-Pariente, J., Sastre, E. (2003). Synthesis of MCM-41 Materials Functionalized with Dialkylsilane Groups and Their Catalytic Activity in the Esterification of Glycerol with Fatty Acids. Appl.Catal., A., 242, 161-169.
• [15] Gonçalves Valter L.C.,Pinto Bianca P., Silva Joao C., Mota Claudio J.A. (2008). Acetylation of Glycerol Catalyzed by Different Solid Acids. Catalysis Today, 133–135, 673–677.
• [16] Zhou, L., Al-Zaini, E., Adesina A. A. (2013). Catalytic characteristics and parameters optimization of the glycerol acetylation over solid acid catalysts. Fuel, 103, 617–625.
• [17] Simsek, V. (2015). Synthesis, Characterization and Investigation Catalytic Activity in the Glycerol Esterification Reaction of Acidic Catalyst, Ph.D. Thesis, Gazi university graduate school of natural and applied sciences january, Ankara.
• [18] Deraz, N.(2018). The Comparative Jurisprudence of Catalysts Preparation Methods: I. Precipitation and Impregnation Methods. J. Ind. Environ. Chem. 2(1), 19-21.
• [19] Şimşek, V., Avcı, P.( 2018). Characterization and Catalytic Performance of Modified SBA-16 in Liquid Phase Reaction, in International Journal of Chemical Reactor Engineering. 16(8): DOI: https://doi.org/10.1515/ijcre-2017-0246
• [20] Mutlu, V.,N., Yilmaz, S. (2016). Esterification of Cetyl Alcohol with Palmitic Acid over WO3/Zr-SBA-15 and Zr-SBA-15 Catalysts. Applied Catalysis A: General, 522, 194-200.
• [21] Bedard, J., Chiang, H.,Bhan, A. (2012). Kinetics and Mechanism of Acetic Acid Esterification with Ethanol on Zeolites. Journal of Catalysis. 290, 210-219.
• [22] Hykkerud, A., Marchetti, J., M. (2016). Esterificationof Oleic Acid with Ethanol in the Presence of Amberlyst 15. Biomass and Bioenergy. 95, 340-343.
• [23] Torabi, B., Ameri, E. (2016). Methyl Acetate Production by Coupled Esterification-Reaction Process Using Synthesized Cross-Linked PVA/Silica Nanocomposite Membranes. Chemical Engineering Journal. 288, 461-472.
• [24] Simsek, V., Mürtezaoğlu, K. (2018). Characterizations and Catalytic Activities Investigation of Synthesized Solid-Based Heterogeneous Catalysts in the Esterification. Anadolu Univ. J. Sci. Technol. A .Appl. Sci. Eng., 19, 2422-432.
• [25] Øye, G., Sjöblom, J., Stöcker, M. (2001). Synthesis, Characterization and Potential Applications of New Materials in the Mesoporous Range, Advances in colloid and interface science, 89-90: 439-466.
• [26] Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C.,&Beck, J. S. (1992). Ordered Mesoporous Molecular Synthesized by a Liquid-Crystal Template Mechanism, Nature, 359, 710-712.
• [27] Zhang, S., Muratsugu, S., Ishiguro, N., Tada, M.(2013). Ceria-doped Ni/SBA-16 Catalysts for Dry Reforming of Methane. ACS Catalysis. 3(8), 1855-1864.
• [28] Boukoussa, B., Hamacha, R., Morsli, A., Bengueddach, A. (2017). Adsorption of Yellow Dye on Calcined or Uncalcined Al-MCM-41 Mesoporous Materials. Arabian Journal of Chemistry. 10, S2160-S2169.
• [29] Zhao, O., Zhou, X., Li, Y., Li, M., Jiang, T., Yin, H., Li. C. (2009). Effect of the Thermal and Hydrothermal Treatment on Textural Properties of Zr-MCM-41 Mesoporous Molecular Sieve, Applied Surface Science, 255, 6397-6403.
• [30] Şimşek, V., "Investigation of catalytic Sustainability of Silica-Based Mesoporous Acidic Catalysts and Ion-Exchange Resins in Methyl Acetate Synthesis and Characterizations of Synthesized Catalysts, Arabian Journal for Science and Engineering. https://doi.org/10.1007/s13369-018-3570-y (2018).
• [31] Varışlı, D. (2007). Kinetics Studies for Dimethyl Ether and Diethyl Ether Production, Ph.D. Natural and Applied Sciences of Middle East Technical University, Ankara.
• [32] Şimşek, V, Pat, Z, Mürtezaoğlu, K. (2016). Synthesis and Characterization of Silica-Based Acidic Catalysts with the Impregnation Method, 1st International Black Sea Congress on Environmental Sciences.Full paper book, 1, 247-256.
• [33] Varisli, D., Dogu, T., Dogu, G. (2010). Petrochemicals from Ethanol over a W-Si Based Nanocomposite Bidisperse Solid Acid Catalyst, Chemical Engineering Science, 65, 153-159.
• [34] Shanmugam, S., Viswanathan, B., Varadarajan, T.K. (2006). Synthesis and Characterization of Silicotungstic Acid Based Organic–İnorganic Nanocomposite Membrane, Journal of Membrane Science, 275, 105–109.
• [35] Şimşek, V., Değirmenci, L., Mürtezaoğlu, K.(2016). Synthesis of Silicotungstic Acid SBA-15 Catalyst for Selective Monoglyceride Production, Reaction Kinetics, Mechanisms and Catalysis. Vol. 116 No: 2
• [36] Zhu, S., Zhu, Y., Gao, X., Mo, T., Zhu, Y., Li, Y. (2013). Production of Bioadditives from Glycerol Esterification over Zirconia Supported Heteropolyacids. Bioresource Technol., 130, 45–51.
• [37] Oliviera, J.F.G., Lucena, I.L., Saboya, R.M.A., Rodrigues, M.L., Torres, A.R.E.B., Fernandes, F.A.N., C.L. Cavalcante, Jr. (2010). Biodiesel Production from Waste Coconut Oil by Esterification with Ethanol: The Effect of Water Removal by Adsorption. Renewable Energy, 35, 2581–2584.
• [38] Gofferje, G., Stabler, A., Herfellner, T., Schweiggert-Weishz, U., Flöter, E. (2014). Kinetics of Enzymatic Esterification of Glycerol and Free Fatty Acids in Crude Jatropha Oil by Immobilized Lipase From Rhizomucor Miehei. J. Mol. Catal. B Enzym. 107, 1–7.