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Title: Sulfur deactivation of fatty ester hydrogenolysis catalysts

Abstract

Trace organosulfur compounds present as natural impurities in oleochemical feedstocks may lead to activation of copper-containing catalysts applied for hydrogenolysis of esters toward fatty alcohols. In this paper, the sulfur deactivation of Cu/SiO{sub 2} and Cu/ZnO/SiO{sub 2} catalysts was studied in the liquid-phase hydrogenolysis of methyl palmitate. The rate of deactivation is fast and increases as a function of the sulfur-containing compound present: octadecanethiol {approx} dihexadecyl disulfide < benzyl isothiocyanate < methyl p-toluene sulfonate < dihexadecyl sulfide < dibenzothiophene. The rapid deactivation is caused by the fact that sulfur is quantitatively removed from the reaction mixture and because mainly surface sulfides are formed under hydrogenolysis conditions. The life time of a zinc-promoted catalyst is up to two times higher than that of the Cu/SiO{sub 2} catalyst, most likely due to zinc surface sulfide formation. The maximum sulfur coverage obtained after full catalyst deactivation with dibenzothiophene and dihexadecyl sulfide--the sulfur compounds that cause the fastest deactivation--may be as low as 0.07. This is due to the fact that decomposition of these compounds as well as the hydrogenolysis reaction itself proceeds on ensembles of copper atoms. Catalyst regeneration studies reveal that activity cannot be regained by reduction or combined oxidation/reduction treatments. XRD,more » TPR, and TPO results confirm that no distinct bulk copper or zinc sulfide or sulfate phases are present.« less

Authors:
; ; ;  [1]
  1. Univ. of Amsterdam (Netherlands). Dept. of Chemical Engineering
Publication Date:
OSTI Identifier:
687733
Resource Type:
Journal Article
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 186; Journal Issue: 1; Other Information: PBD: 15 Aug 1999
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; ESTERS; HYDROGENATION; ALCOHOLS; SYNTHESIS; CATALYSTS; DEACTIVATION; ORGANIC SULFUR COMPOUNDS; COPPER; SILICON OXIDES; ZINC OXIDES

Citation Formats

Brands, D.S., U-A-Sai, G., Poels, E.K., and Bliek, A. Sulfur deactivation of fatty ester hydrogenolysis catalysts. United States: N. p., 1999. Web. doi:10.1006/jcat.1999.2553.
Brands, D.S., U-A-Sai, G., Poels, E.K., & Bliek, A. Sulfur deactivation of fatty ester hydrogenolysis catalysts. United States. doi:10.1006/jcat.1999.2553.
Brands, D.S., U-A-Sai, G., Poels, E.K., and Bliek, A. Sun . "Sulfur deactivation of fatty ester hydrogenolysis catalysts". United States. doi:10.1006/jcat.1999.2553.
@article{osti_687733,
title = {Sulfur deactivation of fatty ester hydrogenolysis catalysts},
author = {Brands, D.S. and U-A-Sai, G. and Poels, E.K. and Bliek, A.},
abstractNote = {Trace organosulfur compounds present as natural impurities in oleochemical feedstocks may lead to activation of copper-containing catalysts applied for hydrogenolysis of esters toward fatty alcohols. In this paper, the sulfur deactivation of Cu/SiO{sub 2} and Cu/ZnO/SiO{sub 2} catalysts was studied in the liquid-phase hydrogenolysis of methyl palmitate. The rate of deactivation is fast and increases as a function of the sulfur-containing compound present: octadecanethiol {approx} dihexadecyl disulfide < benzyl isothiocyanate < methyl p-toluene sulfonate < dihexadecyl sulfide < dibenzothiophene. The rapid deactivation is caused by the fact that sulfur is quantitatively removed from the reaction mixture and because mainly surface sulfides are formed under hydrogenolysis conditions. The life time of a zinc-promoted catalyst is up to two times higher than that of the Cu/SiO{sub 2} catalyst, most likely due to zinc surface sulfide formation. The maximum sulfur coverage obtained after full catalyst deactivation with dibenzothiophene and dihexadecyl sulfide--the sulfur compounds that cause the fastest deactivation--may be as low as 0.07. This is due to the fact that decomposition of these compounds as well as the hydrogenolysis reaction itself proceeds on ensembles of copper atoms. Catalyst regeneration studies reveal that activity cannot be regained by reduction or combined oxidation/reduction treatments. XRD, TPR, and TPO results confirm that no distinct bulk copper or zinc sulfide or sulfate phases are present.},
doi = {10.1006/jcat.1999.2553},
journal = {Journal of Catalysis},
number = 1,
volume = 186,
place = {United States},
year = {1999},
month = {8}
}