Kinetics and mechanism of desulfurization and denitrogenation of coal-derived liquids. Tenth quarterly report, September 21-December 20, 1977
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 quinoline, methyl-substituted quinolines, acridine and carbazole. The catalysts were commercial, sulfided CoO-MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/, NiO-MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/, and NiO-WO/sub 3//..gamma..-Al/sub 2/O/sub 3/. At the typical conditions of 300/sup 0/C and 104 atm, dibenzothiophene reacts to give H/sub 2/S and biphenyl in high yield, but there is some hydrogenation preceding desulfurization. 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. The results are consistent with steric and inductive effects influencing adsorption. The data indicate competitive adsorption among the sulfur-containing compounds. In quinoline hydrodenitrogenation, both rings are saturated before the C-N bond is broken. Similarly, in acridine conversion a large amount of hydrogenation precedes nitrogen removal. Breaking of the carbon-nitrogen bond is evidently one of the slower reactions 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. Reactivity of carbazole is slightly lower than that of quinoline but higher than that of acridine.
- 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:
- 5957239
- Report Number(s):
- FE-2028-12
- Country of Publication:
- United States
- Language:
- English
Similar Records
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]
Kinetics and mechanism of desulfurization and denitrogenation of coal-derived liquids. Eleventh quarterly report, December 21, 1977-March 20, 1978
Related Subjects
010402* -- Coal
Lignite
& Peat-- Purification & Upgrading
010405 -- Coal
Lignite
& Peat-- Hydrogenation & Liquefaction
ACRIDINES
AZINES
AZOLES
CARBAZOLES
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CLEAVAGE
COAL LIQUEFACTION
COAL LIQUIDS
COBALT
CRYSTAL STRUCTURE
DENITRIFICATION
DESULFURIZATION
ELEMENTS
HETEROCYCLIC COMPOUNDS
HYDROGENATION
KINETICS
LIQUEFACTION
METALS
MICROSTRUCTURE
MOLYBDENUM
NICKEL
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
QUINOLINES
REACTION KINETICS
REFRACTORY METALS
STRUCTURAL MODELS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENTS
TUNGSTEN