Selective oxidation and oxidative dehydrogenation of hydrocarbons on bismuth vanadium molybdenum oxide

Zhai, Zheng; Wang, Xuan; Licht, Rachel; Bell, Alexis T.

doi:10.1016/j.jcat.2015.02.015

Selective oxidation and oxidative dehydrogenation of hydrocarbons on bismuth vanadium molybdenum oxide

Journal Article · Thu Mar 19 00:00:00 EDT 2015 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2015.02.015· OSTI ID:1571042

Zhai, Zheng ^[1]; Wang, Xuan ^[1]; Licht, Rachel ^[1]; Bell, Alexis T. ^[1]

The Univ. of California, Berkeley, CA (United States)

A systematic investigation of the oxidative dehydrogenation of propane to propene and 1- and 2-butene to 1,3-butadiene, and the selective oxidation of isobutene to methacrolein was carried out over Bi_1-x/3V_1-xMo_xO₄ (x = 0-1) with the aim of defining the effects of catalyst and reactant composition on the reaction kinetics. This work has revealed that the reaction kinetics can differ significantly depending on the state of catalyst oxidation, which in turn depends on the catalyst composition and the reaction conditions. Under conditions where the catalyst is fully oxidized, the kinetics for the oxidation of propene to acrolein and isobutene to methacrolein, and the oxidative dehydrogenation of propane to propene, 1-butene and trans-2-butene to butadiene are very similar - first order in the partial pressure of the alkane or alkene and zero order in the partial pressure of oxygen. These observations, together with XANES and UV-Vis data, suggest that all these reactions proceed via a Mars van Krevelen mechanism involving oxygen atoms in the catalysts and that the rate-limiting step involves cleavage of the weakest C-H bond in the reactant. Consistent with these findings, the apparent activation energy and pre-exponential factor for both oxidative dehydrogenation and selective oxidation correlate with the dissociation energy of the weakest C-H bond in the reactant. As the reaction temperature is lowered, catalyst reoxidation can become rate-limiting, the transition to this regime depending on ease of catalyst reduction and effectiveness of the reacting hydrocarbons as a reducing agent. Here, a third regime is observed for isobutene oxidation at lower temperatures, in which the catalyst is more severely reduced and oxidation now proceeds via reaction of molecular oxygen, rather than catalyst lattice oxygen, with the reactant.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571042

Alternate ID(s):: OSTI ID: 1244571

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 325; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Bismuth vanadium molybdenum oxide
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