Esterification of Free Fatty Acids in Crude Palm Oil with Sulfated Zirconia: Effect of Calcination Temperature
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.
[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.
[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.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:63481", author = "Suthat Turapan and Cattareya Yotkamchornkun and Kamchai Nuithitikul", title = "Esterification of Free Fatty Acids in Crude Palm Oil with Sulfated Zirconia: Effect of Calcination Temperature", 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.", volume = "4", number = "5", pages = "363-5", }
