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Partial oxidation of methane over supported molybdenum

Conference · · Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)
OSTI ID:5998152
Steady-state activity (percent conversion) and selectivity for the Mo/silica gel catalyzed oxidation of methane to CH/sub 3/OH and CH/sub 2/O by N/sub 2/O in the presence of steam at 600/sup 0/C have been measured in order to define reaction kinetics and the mechanism of molybdenum catalysis. Both selective and non-selective oxidation occur in this system, the latter yielding carbon monoxide and carbon dioxide. Conversion yields of CH/sub 2/O are independent of H/sub 2/O partial pressure but selectivity for CH/sub 3/OH formation increases with increasing H/sub 2/O partial pressure. The rate law for CH/sub 4/ consumption is complex, being determined by non-selective oxidation and reduction reactions. Spectroscopic evidence indicates that the catalytic role of molybdenum involves a cyclic oxidation state change from the +5 state and back vial the +6 state. Tritiation occurs by the N/sub 2/O oxidation of Mo/sup V/ to yield (Mo/sup VI/O/sup -/) which either reacts with CH/sub 4/ to yield (Mo/sup V/(OCH/sub 3/)/sup -/) or is further reduced to (Mo/sup VI/O/sup -2/). The latter complex requires CH/sub 4/ for reduction to Mo/sup V/ in a non-selective process yielding CO/sub 2/ and H/sub 2/O.
Research Organization:
Texas A and M Univ., College Station
OSTI ID:
5998152
Report Number(s):
CONF-830303-
Conference Information:
Journal Name: Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States) Journal Volume: 28:3
Country of Publication:
United States
Language:
English