Kinetics and mechanism of desulfurization and denitrogenation of coal-derived liquids. Seventh quarterly report, December 21, 1976--March 20, 1977. [CoO--MoO3 and NiO--MoO3]

Technical Report · Wed Apr 06 04:00:00 EST 1977

DOI:https://doi.org/10.2172/5295310· OSTI ID:5295310

Gates, B. C.; Katzer, J. R.; Olson, J. H.; Kwart, H.; Stiles, A. B.

Three high-pressure flow microreactors and two batch autoclave reactors have been used to study the reaction networks and kinetics of (1) catalytic hydrodesulfurization of dibenzothiophene and methyl-substituted dibenzothiophenes and (2) catalytic hydrodenitrogenation of acridine. The catalysts were commercial, sulfided CoO-MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ and commercial, sulfided NiO-MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/. At 300/sup 0/C and 104 atm, dibenzothiophene reacts to give H/sub 2/S and biphenyl in high yield. Methyl-substituted dibenzothiophenes react similarly, and each reaction is first-order in the sulfur-containing compound. Two methyl groups near the sulfur atom (in the 4 and 6 positions) reduce the reactivity tenfold, whereas methyl groups in positions further removed from the sulfur atom increase reactivity about twofold. These results are consistent with steric and inductive effects. In acridine conversion, a large amount of hydrogenation precedes nitrogen removal. Breaking of the carbon-nitrogen bond is evidently part of the slowest reaction in the network. The Ni-Mo catalyst is about twice as active as the Co-Mo catalyst for ring hydrogenation, and the two catalysts are about equally active for breaking the carbon-nitrogen bond. Aged catalysts taken from the H-Coal process had greatly reduced activity.

• Research Organization: Delaware Univ., Newark (USA)
• Sponsoring Organization: US Energy Research and Development Administration (ERDA)
• DOE Contract Number: EX-76-C-01-2028
• OSTI ID: 5295310
• Report Number(s): FE-2028-8
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010402* -- Coal
Lignite
& Peat-- Purification & Upgrading
ACRIDINES
AROMATICS
AZINES
BIPHENYL
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL REACTORS
COAL LIQUIDS
COBALT COMPOUNDS
COBALT OXIDES
CRYOGENIC FLUIDS
DENITRIFICATION
DESULFURIZATION
ELEMENTS
EVALUATION
FLUIDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
KINETICS
MOLYBDENUM COMPOUNDS
MOLYBDENUM OXIDES
NICKEL COMPOUNDS
NICKEL OXIDES
NITROGEN
NONMETALS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PYRIDINES
REACTION KINETICS
REMOVAL
SULFIDES
SULFUR
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS