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Title: Hydrodesulfurization catalysis by Chevrel phase compounds

Abstract

The catalytic activity of Chevrel phase compounds (M/sub x/Mo/sub 6/S/sub 8/) for thiophene hydrodesulfurization at 400/sup 0/C has been found to be comparable to or greater than that of model industrial catalysts (unpromoted and cobalt-promoted MoS/sub 2/). The most active Chevrel phase catalysts were those containing the ''large'' ternary component cations Ho, Pb, Sn; the ''intermediate'' cation materials (M = Ag and In) were less active; the ''small'' cation materials (M = Cu, Fe, Ni, and Co) were the least active catalysts. The 1-butene hydrogenation activities of the Chevrel phase catalysts at 400/sup 0/C were much lower than MoS/sub 2/, with the exception of Ni/sub 1.6/Mo/sub 6/S/sub 8/. X-ray powder diffraction and laser Raman spectroscopy analysis of the used catalysts revealed that the bulk structures were stable under reaction conditions. XPS analysis of the fresh Chevrel phase catalysts showed reduced molybdenum surface oxidation states compared to the Mo/sup +4/ state of MoS/sub 2/ catalysts. After thiophene reaction, various degrees of oxidation of the surface molybdenum states could be detected for the small and intermediate cation materials, with an accompanying loss of the ternary component from the surface. This was not the case for the large cation materials. Using a deuterium-thiophenemore » feed at 400/sup 0/C, the amount of deuterium incorporated into thiophene and into the desulfurization products was determined as a function of reaction time. For all Chevrel phase and MoS/sub 2/ catalysts examined, H/sub 2/S was almost exclusively formed. At the same levels of thiophene conversion, unpromoted MoS/sub 2/ introduced up to 10 times more deuterium into the nondesulfurized thiophene did the ''promoted'' catalysts. A mechanism of thiophene hydrodesulfurization is proposed: butadiene is the initial reaction product and the hydrogen of hydrogen sulfide originates from the hydrogen-exchange of thiophene. 140 refs., 87 figs., 30 tabs.« less

Authors:
Publication Date:
Research Org.:
Ames Lab., IA (USA)
OSTI Identifier:
5911822
Report Number(s):
IS-T-1168
ON: DE85011359
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Technical Report
Resource Relation:
Other Information: Thesis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 02 PETROLEUM; CATALYSTS; BINDING ENERGY; COMPARATIVE EVALUATIONS; PROMOTERS; RAMAN SPECTRA; STRUCTURAL CHEMICAL ANALYSIS; DESULFURIZATION; CHEMICAL REACTION KINETICS; HYDROGEN SULFIDES; CHEMICAL REACTION YIELD; HYDROGENATION; MOLYBDENUM SULFIDES; CATALYTIC EFFECTS; THIOPHENE; COBALT COMPOUNDS; COPPER COMPOUNDS; DEUTERIUM; DEUTERIUM COMPOUNDS; EXPERIMENTAL DATA; HIGH TEMPERATURE; HOLMIUM COMPOUNDS; INDIUM COMPOUNDS; IRON COMPOUNDS; LEAD COMPOUNDS; MASS SPECTROSCOPY; NICKEL COMPOUNDS; PHOTOELECTRON SPECTROSCOPY; SILVER COMPOUNDS; TIN COMPOUNDS; TRACER TECHNIQUES; X-RAY DIFFRACTION; CHALCOGENIDES; CHEMICAL REACTIONS; COHERENT SCATTERING; DATA; DIFFRACTION; ELECTRON SPECTROSCOPY; ENERGY; HETEROCYCLIC COMPOUNDS; HYDROGEN COMPOUNDS; HYDROGEN ISOTOPES; INFORMATION; ISOTOPE APPLICATIONS; ISOTOPES; KINETICS; LIGHT NUCLEI; MOLYBDENUM COMPOUNDS; NUCLEI; NUMERICAL DATA; ODD-ODD NUCLEI; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; RARE EARTH COMPOUNDS; REACTION KINETICS; REFRACTORY METAL COMPOUNDS; SCATTERING; SPECTRA; SPECTROSCOPY; STABLE ISOTOPES; SULFIDES; SULFUR COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; YIELDS; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400201 - Chemical & Physicochemical Properties; 020400 - Petroleum- Processing

Citation Formats

McCarty, K F. Hydrodesulfurization catalysis by Chevrel phase compounds. United States: N. p., 1985. Web.
McCarty, K F. Hydrodesulfurization catalysis by Chevrel phase compounds. United States.
McCarty, K F. 1985. "Hydrodesulfurization catalysis by Chevrel phase compounds". United States.
@article{osti_5911822,
title = {Hydrodesulfurization catalysis by Chevrel phase compounds},
author = {McCarty, K F},
abstractNote = {The catalytic activity of Chevrel phase compounds (M/sub x/Mo/sub 6/S/sub 8/) for thiophene hydrodesulfurization at 400/sup 0/C has been found to be comparable to or greater than that of model industrial catalysts (unpromoted and cobalt-promoted MoS/sub 2/). The most active Chevrel phase catalysts were those containing the ''large'' ternary component cations Ho, Pb, Sn; the ''intermediate'' cation materials (M = Ag and In) were less active; the ''small'' cation materials (M = Cu, Fe, Ni, and Co) were the least active catalysts. The 1-butene hydrogenation activities of the Chevrel phase catalysts at 400/sup 0/C were much lower than MoS/sub 2/, with the exception of Ni/sub 1.6/Mo/sub 6/S/sub 8/. X-ray powder diffraction and laser Raman spectroscopy analysis of the used catalysts revealed that the bulk structures were stable under reaction conditions. XPS analysis of the fresh Chevrel phase catalysts showed reduced molybdenum surface oxidation states compared to the Mo/sup +4/ state of MoS/sub 2/ catalysts. After thiophene reaction, various degrees of oxidation of the surface molybdenum states could be detected for the small and intermediate cation materials, with an accompanying loss of the ternary component from the surface. This was not the case for the large cation materials. Using a deuterium-thiophene feed at 400/sup 0/C, the amount of deuterium incorporated into thiophene and into the desulfurization products was determined as a function of reaction time. For all Chevrel phase and MoS/sub 2/ catalysts examined, H/sub 2/S was almost exclusively formed. At the same levels of thiophene conversion, unpromoted MoS/sub 2/ introduced up to 10 times more deuterium into the nondesulfurized thiophene did the ''promoted'' catalysts. A mechanism of thiophene hydrodesulfurization is proposed: butadiene is the initial reaction product and the hydrogen of hydrogen sulfide originates from the hydrogen-exchange of thiophene. 140 refs., 87 figs., 30 tabs.},
doi = {},
url = {https://www.osti.gov/biblio/5911822}, journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Apr 01 00:00:00 EST 1985},
month = {Mon Apr 01 00:00:00 EST 1985}
}

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