The mechanism of the oxidation of propene to acrolein over antimony - Tin mixed oxide catalysts

Journal Article · Tue May 01 04:00:00 EDT 1990 · Journal of Catalysis; (USA)

DOI:https://doi.org/10.1016/0021-9517(90)90172-G· OSTI ID:6352279

Ono, Takehiko ^[1]; Hillig, II, K W; Kuczkowski, R L ^[2]

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1. Univ. of Osaka (Japan)
2. Univ. of Michigan, Ann Arbor (USA)

The oxidation of propenes such as {sup 13}CH{sub 2}{double bond}CH-CH{sub 3}, CH{sub 2}{double bond}CH-CD{sub 3}, cis-CHD{double bond}CD-CH{sub 3}, and CH{sub 2}{double bond}CH-CH{sub 3} was studied over Sb{sub 6}O{sub 13}, SnO{sub 2}, and Sb-Sn mixed oxide catalysts. The results with {sup 13}CH{sub 2}{double bond}CH-CH{sub 3} and CH{sub 2}{double bond}CH-CD{sub 3} were consistent with a {pi}-allyl intermediate. The isotope effect for allylic hydrogen abstraction was 1/0.55 (k{sub H}/k{sub D}) over the Sb-Sn oxide catalysts, indicating that this is the slowest step in the formation of acrolein as with other catalyst systems. The oxidation of CHD{double bond}CH-CH{sub 3} did not exhibit a marked isotope effect for the second hydrogen abstraction. This is inconsistent with a fast {pi}-allyl to {sigma}-allyl equilibration process or the irreversible {pi}-allyl to {sigma}-allyl conversion observed over other metal oxide catalysts. The absence of an isotope effect is similar to oxidations over rhodium. The roles of Sn and Sb ions in the oxidation are also discussed.

• OSTI ID: 6352279
• Journal Information: Journal of Catalysis; (USA), Journal Name: Journal of Catalysis; (USA) Vol. 123:1; ISSN 0021-9517; ISSN JCTLA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400* -- Petroleum-- Processing
ACROLEIN
ALDEHYDES
ALKENES
ANTIMONY COMPOUNDS
ANTIMONY OXIDES
CATALYTIC EFFECTS
CATALYTIC REFORMING
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
DEUTERATION
DISPERSIONS
ELEMENTS
HYDROCARBONS
ISOTOPE APPLICATIONS
KINETICS
METALS
MIXTURES
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PLATINUM METALS
PROPYLENE
REACTION INTERMEDIATES
REACTION KINETICS
REFORMER PROCESSES
RHODIUM
SYNTHESIS
TIN COMPOUNDS
TIN OXIDES
TRACER TECHNIQUES
TRANSITION ELEMENTS