Aspects of selective oxidation and ammoxidation mechanisms over bismuth molybdate catalysts--2. Allyl alcohol as a probe for the allylic intermediate
Pulse reactor experiments were conducted on the reactions of unlabeled or deuterium- or oxygen-18-labeled allyl alcohols over molybdenum trioxide and various bismuth molybdates in the absence or presence of oxygen and ammonia. The allyl alcohol apparently adsorbed on oxidation sites to form acrolein via allyl molybdates, and on Broensted acid sites to form diallyl ether via an allyl carbonium ion. The bismuth enhanced ..cap alpha..-hydrogen abstraction, which was the rate-determining step in the oxidation. The product distributions provided evidence that the selective oxidation of propylene to acrolein proceeds via a m-allyl molybdate which collapses to an O o-allyl molybdate prior to the second hydrogen abstraction, and that the analogous N o-complex in ammoxidation undergoes two hydrogen abstractions to form acrylonitrile. Detailed reaction schemes are developed.
- Research Organization:
- Stand. Oil Co. (Ohio)
- OSTI ID:
- 6319918
- Journal Information:
- J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 63:1; ISSN JCTLA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALCOHOLS
ALKYL RADICALS
ALLYL RADICALS
BISMUTH COMPOUNDS
BROENSTED ACIDS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INORGANIC ACIDS
ISOTOPE APPLICATIONS
KINETICS
MOLYBDATES
MOLYBDENUM COMPOUNDS
MOLYBDENUM OXIDES
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PULSED REACTORS
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
REACTORS
REFRACTORY METAL COMPOUNDS
TRACER TECHNIQUES
TRANSITION ELEMENT COMPOUNDS