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Catalysts 2016, 6(2), 22; doi:10.3390/catal6020022

Heterogeneous Partial (amm)Oxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

Laboratoire de Réactivité de Surface, UMR-CNRS 1197, Sorbonne Universités, Université P. & M. Curie, 4 Place Jussieu, 75252 Paris Cedex 05, France
Academic Editor: Stuart H. Taylor
Received: 24 November 2015 / Revised: 16 January 2016 / Accepted: 19 January 2016 / Published: 29 January 2016
(This article belongs to the Special Issue Catalysts for Selective Oxidation)
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Abstract

This paper presents an overview of heterogeneous partial (amm)oxidation and oxidative dehydrogenation (ODH) of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms), Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4) oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(Sb)Nb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (amm)oxidation to (acrylonitrile) acrylic acid on MoVTe(Sb)Nb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO)2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features) and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until reaching steady state, which makes characterisation of active and selective surface sites quite difficult. The use of oxidants other than O2, such as H2O2, N2O or CO2, is also briefly discussed. Based on such analysis and recent discoveries and process developments, our perspective is given. View Full-Text
Keywords: hydrocarbon partial oxidation; oxidative dehydrogenation; light alkanes up-grading; metal oxides catalysts; heterogeneous catalysis; acid-base properties; redox and electronic properties hydrocarbon partial oxidation; oxidative dehydrogenation; light alkanes up-grading; metal oxides catalysts; heterogeneous catalysis; acid-base properties; redox and electronic properties
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Védrine, J.C. Heterogeneous Partial (amm)Oxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides. Catalysts 2016, 6, 22.

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