Esterification of Free Fatty Acids in Crude Palm Oil with Sulfated Zirconia: Effect of Calcination Temperature
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 32807
Esterification of Free Fatty Acids in Crude Palm Oil with Sulfated Zirconia: Effect of Calcination Temperature

Authors: Suthat Turapan, Cattareya Yotkamchornkun, Kamchai Nuithitikul

Abstract:

The production of biodiesel from crude palm oil with a homogeneous base catalyst is unlikely owing to considerable formation of soap. Free fatty acids (FFA) in crude palm oil need to be reduced, e.g. by esterification. This study investigated the activity of sulfated zirconia calcined at various temperatures for esterification of FFA in crude palm oil to biodiesel. It was found that under a proper reaction condition, sulfated zirconia well catalyzes esterification. FFA content can be reduced to an acceptable value for typical biodiesel production with a homogeneous base catalyst. Crystallinity and sulfate attachment of sulfated zirconia depend on calcination temperature during the catalyst preparation. Too low temperature of calcination gives amorphous sulfated zirconia which has low activity for esterification of FFA. In contrast, very high temperature of calcination removes sulfate group, consequently, conversion of FFA is reduced. The appropriate temperature range of calcination is 550-650 oC.

Keywords: Biodiesel, Esterification, Free fatty acids, Sulfatedzirconia.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1083057

Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 2796

References:


[1] H. N. Basu and M.E. Norris, "Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst (Patent style)," U.S. Patent 5,525,126, June 11, 1996.
[2] M. Canakci and J. Van-Gerpen, "Biodiesel production from oils and fats with high free fatty acids," Transactions of the ASAE, vol. 44, pp. 1429- 1436, 2001.
[3] I. K. Mbaraka and B. H. Shanks, "Design of multifunctionalized mesoporous silicas for esterification of fatty acid," J. of Catalysis, vol. 229, pp. 365-373, 2005.
[4] J. Ni and F. C. Meunier, "Esterification of free fatty acids in sunflower oil over solid acid catalysts using batch and fixed bed-reactors," Applied Catalysis A: General, vol. 33, pp. 122-130, 2007.
[5] T. A. Peters, N. E. Benes, A. Holmen, and J. T. F. Keurentjes, "Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol," Applied Catalysis A: General, vol. 297, pp. 182-188, 2006.
[6] T. Sejidov, Y. Mansoori, and N. Goodarzi, "Esterification reaction using solid heterogeneous acid catalysts under solvent-less condition," J. of Molecular Catalysis A: Chemical, vol. 240, pp.186-190, 2005.
[7] P. Shah, A. V. Ramaswamy, K. Lazar, and V. Ramaswamy, "Synthesis and characterization of tin oxide-modified mesoporous SBA-15 molecular sieves and catalytic activity in trans-esterification reaction," Applied Catalysis A: General, vol. 273, pp. 239-248, 2004.
[8] G. Kuriakose and N. Nagaraju, "Selective synthesis of phenyl salicylate (salol) by esterification reaction over solid acid catalysts," J. of Molecular Catalysis A: Chemical, vol. 223, pp. 155-159, 2004.
[9] E. Lotero, Y. Liu, D. E. Lopez, K. Suwannakarn, D. A. Bruce, and J. G. Goodwin, "Synthesis of biodiesel via acid catalysis," Industrial & Engineering Chemistry Research, vol. 44, pp. 5353-5363, 2005.
[10] F. Garin, L. Seyfried, P. Girard, G. Maire, A. Abdulsamad, and J. Sommer, "A skeletal rearrangement study of labeled butanes on a solid superacid catalyst: sulfuric acid treated zirconium oxide," J. of Catalysis, vol. 151, pp. 26-32, 1995.
[11] N. Katada, T. Tsubaki, and M. Niwa, "Measurements of number and strength distribution of Bronsted and Lewis acid sites on sulfated zirconia by ammonia IRMS-TPD method," Applied Catalysis A: General., vol. 340, pp.76-86, 2008.
[12] G. D. Yadov and J. Nair, "Sulfated zirconia and its modified versions as promising catalysts for industrial processes," Microporous & Mesoporous Materials, vol. 33, pp. 1-48, 1999
[13] H. Matsuhashi et al., "Characterization of sulfated zirconia prepared using reference catalysts and application to several model reactions," Applied Catalysis A: General, vol. 360, pp. 89-97, 2009.
[14] K. Tanabe and W. F. Holderich, "Industrial application of solid acidbase catalysts," Applied Catalysis A., vol. 181, pp. 399-434, 1999.
[15] S. Furuta, H. Matsuhashi, and K. Arata, "Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure," Catalysis Communications, vol. 5, pp. 721-723, 2004.
[16] C. M. Garcia, S. Teixeira, L. L. Marciniuk, and U. Schuchardt, "Transesterification of soybean oil catalyzed by sulfated zirconia," Bioresource Technology., vol. 99, pp. 6608-6613, 2008.
[17] S. Furuta, H. Matsuhashi, and K. Arata, "Catalytic action of sulfated tin oxide for etherification and esterification in comparison with sulfated zirconia," Applied Catalysis A: General, vol. 269, pp. 187-191, 2004.
[18] R. W. Stevens Jr., S. S. C. Chuang, and B. H. Davis, "Temperatureprogrammed desorption/decomposition with simultaneous DRIFTS analysis: adsorbed pyridine on sulfated ZrO2 and Pt-promoted sulfated ZrO2," Thermochemica Acta, vol. 407, pp. 61-71, 2003.
[19] N. Tangchupong et al., "Effect of calcination temperature on characteristics of sulfated zirconia and its application as catalyst for isosynthesis," Fuel Processing Technology, vol. 91, pp. 121-126, 2010.
[20] S. Ardizzone, C. L. Bianchi, G. Cappelletti, and F. Porta, "Liquid-phase catalytic activity of sulfated zirconia from sol-gel precursors: the role of the surface features," J. of Catalysis, vol. 227, pp. 470-478, 2004.
[21] M. K. Lam, K. T. Lee, and A. R. Mohamed, "Sulfated tin oxide as solid superacid catalyst for transesterification of waste cooking oil: an optimization study," Applied Catalysis B: Environmental, vol. 93, pp. 134-139, 2009.
[22] W. H. Chen et al., "A solid-state NMR, FT-IR and TPD study on acid properties of sulfated and metal-promoted zirconia: Influence of promoter and sulfation treatment," Catalysis Today, vol. 116, pp. 111- 120, 2006.
[23] X. Qi, M. Watanabe, T. M. Aida, and R. L. Smith Jr., "Sulfated zirconia as a solid acid catalyst for the dehydration of fructose to 5- hydroxymethylfurfural," Catalysis Communications, vol. 10, pp. 1771- 1775, 2009.
[24] X. Song and A. Sayari, "Sulfated zirconia-based strong solid acid catalysts: recent progress," Catal. Rev. Sci. Eng., vol. 38, pp. 329-412, 1996.
[25] M. Hino and K. Arata, "Synthesis of esters from acetic acid with methanol, ethanol, propanol, and isobutyl alcohol catalyzed by solid superacid," Chemistry Letters, pp. 1671-1672, 1981.
[26] C. L. Bianchi, S. Ardizonne, G. Cappelletti, "Surface state of sulfated zirconia: the role of the sol-gel reaction parameters," Surf. Interface Anal., vol. 36, pp. 745-748, 2004.
[27] K. M. Parida and S. Mallick, "Silicotungstic acid supported zirconia: an effective catalyst for esterification," J. of Molecular Catalysis A: Chemical, vol. 275, pp. 77-83, 2007.
[28] M. di Serio, M. Cozzolino, M. Giordana, R. Tesser, P. Patrono, and E. Santacesaria, "From homogeneous to heterogeneous catalysts in biodiesel production," Industrial & Engineering Chemistry Research, vol. 46, pp. 6379-6384, 2007.