Hydrodesulfurization catalysis by Chevrel phase compounds

Technical Report · Mon Apr 01 04:00:00 EST 1985

OSTI ID:5911822

McCarty, K F

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.

• Research Organization: Ames Lab., IA (USA)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5911822
• Report Number(s): IS-T-1168; ON: DE85011359
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BINDING ENERGY
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COBALT COMPOUNDS
COHERENT SCATTERING
COMPARATIVE EVALUATIONS
COPPER COMPOUNDS
DATA
DESULFURIZATION
DEUTERIUM
DEUTERIUM COMPOUNDS
DIFFRACTION
ELECTRON SPECTROSCOPY
ENERGY
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HIGH TEMPERATURE
HOLMIUM COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROGEN SULFIDES
HYDROGENATION
INDIUM COMPOUNDS
INFORMATION
IRON COMPOUNDS
ISOTOPE APPLICATIONS
ISOTOPES
KINETICS
LEAD COMPOUNDS
LIGHT NUCLEI
MASS SPECTROSCOPY
MOLYBDENUM COMPOUNDS
MOLYBDENUM SULFIDES
NICKEL COMPOUNDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PROMOTERS
RAMAN SPECTRA
RARE EARTH COMPOUNDS
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SCATTERING
SILVER COMPOUNDS
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SULFIDES
SULFUR COMPOUNDS
THIOPHENE
TIN COMPOUNDS
TRACER TECHNIQUES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
YIELDS