Esterification of Free Fatty Acids in Crude Palm Oil Using Alumina-Doped Sulfated Tin Oxide as a Catalyst
The conventional production of biodiesel from crude
palm oil which contains large amounts of free fatty acids in the
presence of a homogeneous base catalyst confronts the problems of
soap formation and very low yield of biodiesel. To overcome these
problems, free fatty acids must be esterified to their esters in the
presence of an acid catalyst prior to alkaline-catalyzed
transesterification. Sulfated metal oxides are a promising group of
catalysts due to their very high acidity. In this research, aluminadoped
sulfated tin oxide (SO4
2-/Al2O3-SnO2) catalysts were prepared
and used for esterification of free fatty acids in crude palm oil in a
batch reactor. The SO4
2-/Al2O3-SnO2 catalysts were prepared from
different Al precursors. The results showed that different Al
precursors gave different activities of the SO4
2-/Al2O3-SnO2 catalysts.
The esterification of free fatty acids in crude palm oil with methanol
in the presence of SO4
2-/Al2O3-SnO2 catalysts followed first-order
kinetics.
<p>[1] A. Hayyan, Md. Z. Alam, M. E. S. Mirghani, N. A. Kabbashi, N. I. N.
M. Hakimi, Y. M. Siran, and S. Tahiruddin, “Sludge palm oil as a
renewable raw material for biodiesel production by two-step processes,”
Bioresource Technology, vol. 101, pp. 7804-7811, 2010.
[2] H. Matsuhashi, H. Miyazaki, Y. Kawamura, H. Nakamura, and K. Arata,
“Preparation of a solid superacid of sulfated tin oxide with acidity higher
than that of sulfated zirconia and its applications to aldol condensation
and benzoylation,” Chemistry of Materials, vol. 13, pp. 3038-3042,
2001.
[3] F. T. Sejidov, Y. Mansoori, and N. Goodarzi, “Esterification reaction
using solid heteogeneous acid catalysts under solvent-less condition,”
Journal of Molecular Catalysis A: Chemical, vol. 240, pp. 186-190,
2005.
[4] 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.
[5] J. C. Juan, J. Zhang, Y. Jiang, W. Cao, and M. A. Yarmo, “The
zirconium sulfate microcrystal structure in relation to their activity in the
esterification,” Journal of Molecular Catalysis A: Chemical, vol. 272,
pp. 91-95, 2007.
[6] H. F. Guo, P. Yan, X. Y. Hao, and Z. Z. Wang, “Influences of
introducing Al on the solid super acid SO4
2−/SnO2,” Materials Chemistry
and Physics, vol. 112, pp. 1065-1068, 2008.
[7] A. S. Khder, E. A. El-Sharkawy, S. A. El-Hakam, and A. I. Ahmed,
“Surface characterization and catalytic activity of sulfated tin oxide
catalyst,” Catalysis Communications, vol. 9, pp. 769-777, 2008.
[8] J. I. Moreno, R. Jaimes, R. Gómez, and M. E. Niño-Gómez, “Evaluation
of sulfated tin oxides in the esterification reaction of free fatty acids,”
Catalysis Today, vol. 172, pp. 34-40, 2011.
[9] J., Zhao, Y. Yue, D. Zhai, C. Miao, J. Shen, H. He, W. Hua, and Z. Gao,
“Characterization and catalytic activities of Al2O3-promoted sulfated tin
oxides,” Catalysis Letters, vol. 133, pp. 119-124, 2009.
[10] 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.
[11] Y. M. Park, D. W. Lee, D. K. Kim, J. S. Lee, and K. Y. Lee, “The
heterogeneous catalyst system for the continuous conversion of free fatty
acids in used vegetable oils for the production of biodiesel,” Catalysis
Today, vol. 131, pp. 238-243, 2008
[12] K. Nuithitikul, and J. Limtrakul, “Comparison in catalytic activities of
sulfated zirconia and sulfated tin oxide for converting free fatty acids in
crude pal oil to their methyl esters,” International Journal of Chemical
Reactor Engineering, vol. 10, A.37, pp. 1-27, 2012.
[13] Y. M. Park, S. H. Chung, H. J. Eom, J. S. Lee and K. Y. Lee, “Tungsten
oxide zirconia as solid superacid catalyst for esterification of waste acid
oil (dark oil),” Bioresource Technology, vol. 101, pp. 6589-6593, 2010.
[14] L. A. S. do Nascimento, L. M. Z. Tito, R. S. Angélica, C. E. F. da Costa,
J. R. Zamian, and G. N. da Rocha Filho, “Esterification of oleic acid
over solid acid catalysts prepared from Amazon flint kaolin,” Applied
Catalysis B: Environmental, vol. 101, pp. 495-503, 2011.
[15] B. M. E. Russbueldt and W. F. Hoelderich, “New sulfonic acid ionexchange
resins for the preesterification of different oils and fats with
high content of free fatty acids,” Applied Catalysis A: General, vol. 362,
pp. 47-57, 2009.
[16] 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. 333, pp. 122-130, 2007.
[17] F. Omota, A. C. Dimian, and A. Bliek, “Fatty acid esterification by
reactive distillation: Part 2 – kinetics-based design for sulphated zirconia
catalysts,” Chemical Engineering Science, vol. 58, pp. 3175-3185, 2003.
[18] Y. Wu and S. Liao, “Review of SO4
2-/MxOy solid superacid catalysts,”
Frontiers of Chemical Engineering in China, vol. 3, no. 3, pp. 330-343,
2009.</p>
<p>[1] A. Hayyan, Md. Z. Alam, M. E. S. Mirghani, N. A. Kabbashi, N. I. N.
M. Hakimi, Y. M. Siran, and S. Tahiruddin, “Sludge palm oil as a
renewable raw material for biodiesel production by two-step processes,”
Bioresource Technology, vol. 101, pp. 7804-7811, 2010.
[2] H. Matsuhashi, H. Miyazaki, Y. Kawamura, H. Nakamura, and K. Arata,
“Preparation of a solid superacid of sulfated tin oxide with acidity higher
than that of sulfated zirconia and its applications to aldol condensation
and benzoylation,” Chemistry of Materials, vol. 13, pp. 3038-3042,
2001.
[3] F. T. Sejidov, Y. Mansoori, and N. Goodarzi, “Esterification reaction
using solid heteogeneous acid catalysts under solvent-less condition,”
Journal of Molecular Catalysis A: Chemical, vol. 240, pp. 186-190,
2005.
[4] 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.
[5] J. C. Juan, J. Zhang, Y. Jiang, W. Cao, and M. A. Yarmo, “The
zirconium sulfate microcrystal structure in relation to their activity in the
esterification,” Journal of Molecular Catalysis A: Chemical, vol. 272,
pp. 91-95, 2007.
[6] H. F. Guo, P. Yan, X. Y. Hao, and Z. Z. Wang, “Influences of
introducing Al on the solid super acid SO4
2−/SnO2,” Materials Chemistry
and Physics, vol. 112, pp. 1065-1068, 2008.
[7] A. S. Khder, E. A. El-Sharkawy, S. A. El-Hakam, and A. I. Ahmed,
“Surface characterization and catalytic activity of sulfated tin oxide
catalyst,” Catalysis Communications, vol. 9, pp. 769-777, 2008.
[8] J. I. Moreno, R. Jaimes, R. Gómez, and M. E. Niño-Gómez, “Evaluation
of sulfated tin oxides in the esterification reaction of free fatty acids,”
Catalysis Today, vol. 172, pp. 34-40, 2011.
[9] J., Zhao, Y. Yue, D. Zhai, C. Miao, J. Shen, H. He, W. Hua, and Z. Gao,
“Characterization and catalytic activities of Al2O3-promoted sulfated tin
oxides,” Catalysis Letters, vol. 133, pp. 119-124, 2009.
[10] 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.
[11] Y. M. Park, D. W. Lee, D. K. Kim, J. S. Lee, and K. Y. Lee, “The
heterogeneous catalyst system for the continuous conversion of free fatty
acids in used vegetable oils for the production of biodiesel,” Catalysis
Today, vol. 131, pp. 238-243, 2008
[12] K. Nuithitikul, and J. Limtrakul, “Comparison in catalytic activities of
sulfated zirconia and sulfated tin oxide for converting free fatty acids in
crude pal oil to their methyl esters,” International Journal of Chemical
Reactor Engineering, vol. 10, A.37, pp. 1-27, 2012.
[13] Y. M. Park, S. H. Chung, H. J. Eom, J. S. Lee and K. Y. Lee, “Tungsten
oxide zirconia as solid superacid catalyst for esterification of waste acid
oil (dark oil),” Bioresource Technology, vol. 101, pp. 6589-6593, 2010.
[14] L. A. S. do Nascimento, L. M. Z. Tito, R. S. Angélica, C. E. F. da Costa,
J. R. Zamian, and G. N. da Rocha Filho, “Esterification of oleic acid
over solid acid catalysts prepared from Amazon flint kaolin,” Applied
Catalysis B: Environmental, vol. 101, pp. 495-503, 2011.
[15] B. M. E. Russbueldt and W. F. Hoelderich, “New sulfonic acid ionexchange
resins for the preesterification of different oils and fats with
high content of free fatty acids,” Applied Catalysis A: General, vol. 362,
pp. 47-57, 2009.
[16] 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. 333, pp. 122-130, 2007.
[17] F. Omota, A. C. Dimian, and A. Bliek, “Fatty acid esterification by
reactive distillation: Part 2 – kinetics-based design for sulphated zirconia
catalysts,” Chemical Engineering Science, vol. 58, pp. 3175-3185, 2003.
[18] Y. Wu and S. Liao, “Review of SO4
2-/MxOy solid superacid catalysts,”
Frontiers of Chemical Engineering in China, vol. 3, no. 3, pp. 330-343,
2009.</p>
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:55080", author = "Worawoot Prasitturattanachai and Kamchai Nuithitikul", title = "Esterification of Free Fatty Acids in Crude Palm Oil Using Alumina-Doped Sulfated Tin Oxide as a Catalyst", abstract = "The conventional production of biodiesel from crude
palm oil which contains large amounts of free fatty acids in the
presence of a homogeneous base catalyst confronts the problems of
soap formation and very low yield of biodiesel. To overcome these
problems, free fatty acids must be esterified to their esters in the
presence of an acid catalyst prior to alkaline-catalyzed
transesterification. Sulfated metal oxides are a promising group of
catalysts due to their very high acidity. In this research, aluminadoped
sulfated tin oxide (SO4
2-/Al2O3-SnO2) catalysts were prepared
and used for esterification of free fatty acids in crude palm oil in a
batch reactor. The SO4
2-/Al2O3-SnO2 catalysts were prepared from
different Al precursors. The results showed that different Al
precursors gave different activities of the SO4
2-/Al2O3-SnO2 catalysts.
The esterification of free fatty acids in crude palm oil with methanol
in the presence of SO4
2-/Al2O3-SnO2 catalysts followed first-order
kinetics.
", keywords = "Methyl ester, Biodiesel, Esterification, Sulfated tin
oxide, Fatty acid.", volume = "7", number = "7", pages = "526-5", }
