Selective propylene oxidation and ammoxidation mechanism of bismuth molybdate catalysts

Conference · Mon Jan 01 04:00:00 EST 1979 · Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)

OSTI ID:6821290

Burrington, J D; Kartisek, C T; Grasselli, R K

Selective propylene oxidation and ammoxidation mechanism of bismuth molybdate catalysts was investigated by studying the reactions of labeled allyl alcohol (propylene oxidation intermediate) with fixed beds of Bi/sub 2/O/sub 3/, MoO/sub 3/, ..cap alpha..-Bi/sub 2/O/sub 3/-MoO/sub 3/, ..gamma..-Bi/sub 2/O/sub 3/-3MoO/sub 3/, and a Standard Oil Co. (Ohio) proprietary multicomponent bismuth molybdate catalyst in a pulse microreactor at 320/sup 0/C. MoO/sub 3/ showed up to 90Vertical Bar3< selectivity for acrolein at low allyl alcohol concentrations, but acrolein formation decreased in favor of benzene, diallyl ether, and particularly, 1,5-hexadiene at higher concentrations. With (..cap alpha..)- and (..gamma..)-bismuth molybdates, more propylene and no diallyl ether was formed. The use of pyridine as solvent instead of n-octane reduced diallyl ether yields to almost zero. Pure Bi/sub 2/O/sub 3/ was inactive. A reaction mechanism involving the initial formation of allyl molybdate o-complexes and acrolein formation by hydrogen abstraction from these complexes on Mo sites is suggested with isomerization leading to diallyl ether formation on both Mo and acidic sites. Bi sites enhance hydrogen abstraction by acting as electron sinks.

• Research Organization: Standard Oil Co., Ohio
• OSTI ID: 6821290
• Report Number(s): CONF-790917-
• Conference Information: Journal Name: Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States) Journal Volume: 24:4
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
ALKENES
BISMUTH
CATALYSTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
ELEMENTS
HYDROCARBONS
ISOTOPE APPLICATIONS
KINETICS
METALS
MOLYBDATES
MOLYBDENUM COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
OXIDATION
OXYGEN COMPOUNDS
PROPYLENE
REACTION INTERMEDIATES
REACTION KINETICS
SOLVENTS
TRACER TECHNIQUES
TRANSITION ELEMENT COMPOUNDS
YIELDS