Interactions between catalytic hydrodesulfurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyridine. [Sulfided cobalt molybdate type]
Interactions which would occur in upgrading some crudes and synthetic fuels from oil shale or coal were studied in a flow microreactor at 200/sup 0/ to 500/sup 0/C and at approximately 4.4 and 11.2 atm on several commercial catalysts. Pyridine severely inhibited the HDS reaction on a sulfided cobalt molybdate type of catalyst, as previously reported. Pyridine HDN was more difficult than thiophene HDS, and there was a thermodynamic limitation to the first step in the HDN reaction mechanism, which occurred, e.g., at 5 to 11 atm and at above approximately 350/sup 0/C. At low temperatures, thiophene inhibited the reaction by competing with pyridine for hydrogenation sites on the catalyst, thereby retarding the hydrogenation of pyridine to piperidine. At high temperatures, the dominant effect was interaction of hydrogen sulfide, an HDS reaction product, with the catalyst to improve the hydrogenolysis activity. This increased the rate of piperidine hydrogenolysis, which was rate-determining at the latter conditions, and enhanced the over-all HDN rate.
- Research Organization:
- Massachusetts Inst. of Tech., Cambridge
- OSTI ID:
- 7102998
- Journal Information:
- AIChE J.; (United States), Journal Name: AIChE J.; (United States) Vol. 21:6; ISSN AICEA
- Country of Publication:
- United States
- Language:
- English
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010405* -- Coal
Lignite
& Peat-- Hydrogenation & Liquefaction
02 PETROLEUM
020400 -- Petroleum-- Processing
04 OIL SHALES AND TAR SANDS
040403 -- Oil Shales & Tar Sands-- Refining
AZINES
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
COAL LIQUIDS
COBALT COMPOUNDS
CRYOGENIC FLUIDS
DENITRIFICATION
DESULFURIZATION
ELEMENTS
ENERGY SOURCES
FLUIDS
FOSSIL FUELS
FUELS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
HYDROGENATION
MINERAL OILS
MOLYBDATES
MOLYBDENUM COMPOUNDS
NITROGEN
NONMETALS
OILS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OTHER ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PETROLEUM
PROCESSING
PYRIDINE
PYRIDINES
REFINING
REMOVAL
SHALE OIL
SULFIDES
SULFUR
SULFUR COMPOUNDS
SYNTHETIC FUELS
SYNTHETIC PETROLEUM
TEMPERATURE DEPENDENCE
THIOPHENE
TRANSITION ELEMENT COMPOUNDS