Catalytic functionalities of supported sulfides. IV. C-O hydrogenolysis selectivity as a function of promoter type
Two series of ..gamma..-Al/sub 2/O/sub 3/-supported transition metal-containing catalysts were prepared and their functional selectivities for C-O hydrogenolysis determined. These were (a) MMo catalysts (where M = Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Re, or Cr), containing 25 mmol M and 77 mmol Mo/100 g Al/sub 2/O/sub 3/; and (b) M catalysts, without Mo, containing 25 mmol M/100 g Al/sub 2/O/sub 3/. Pseudo-first-order rate constants for two simultaneous competing reactions, i.e., C-O bond hydrogenolysis of diphenyl ether (k/sub 1/) and ring hydrogenation of naphthalene (k/sub 2/) at 350/sup 0/C and 137 atm H/sub 2/ pressure, were determined for the above catalysts in the sulfided form. It was found that the C-O hydrogenolysis selectivity of MMo catalysts, as expressed by the k/sub 1//k/sub 2/ ratio was in the order (Mo omitted): Ru > Co > Cr > Ir > Re > Pd > Fe > Rh > Pt > Ni. MMo catalysts showed generally much higher selectivities compared to the corresponding M catalysts. Lowest selectivities among the latter, due to very high ring hydrogenation activities, were exhibited by the sulfided Pd, Pt, Ir, Re, and Rh catalysts. Comparison of the actual C-O hydrogenolysis activities of MMo catalysts with calculated additive activities for these catalysts reveals that Ru, Co, and Rh cause a strong promotion, while Pd, Pt, and Re cause a decrease in the hydrogenolysis activity of the corresponding MMo catalysts. Similar comparison of actual and additive ring hydrogenation activities shows that Ni and Rh have a significant promoting effect, while Pd, Ir, Pt, and Re exert a strong depressing effect upon the hydrogenation activities of the MMo catalysts.
- Research Organization:
- Univ. of Utah, Salt Lake City
- DOE Contract Number:
- FG22-83PC60812
- OSTI ID:
- 5457680
- Journal Information:
- J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 104:2; ISSN JCTLA
- Country of Publication:
- United States
- Language:
- English
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ALLOYS
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
AROMATICS
BIMETALS
CATALYST SUPPORTS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHROMIUM COMPOUNDS
CHROMIUM SULFIDES
COAL LIQUIDS
COBALT COMPOUNDS
COBALT SULFIDES
COMPARATIVE EVALUATIONS
CONDENSED AROMATICS
ELEMENTS
ETHERS
FLUIDS
HYDROCARBONS
IRIDIUM COMPOUNDS
IRON COMPOUNDS
IRON SULFIDES
KINETICS
LIQUIDS
METALS
MOLYBDENUM
MOLYBDENUM ALLOYS
NAPHTHALENE
NICKEL COMPOUNDS
NICKEL SULFIDES
NONMETALS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PALLADIUM COMPOUNDS
PALLADIUM SULFIDES
PLATINUM COMPOUNDS
PLATINUM SULFIDES
PROCESSING
PROMOTERS
REACTION KINETICS
REFINING
REFRACTORY METAL COMPOUNDS
REMOVAL
RHENIUM COMPOUNDS
RHENIUM SULFIDES
RHODIUM COMPOUNDS
RHODIUM SULFIDES
RUTHENIUM COMPOUNDS
RUTHENIUM SULFIDES
SULFIDES
SULFUR COMPOUNDS
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TRANSITION ELEMENTS