Strategy in achieving propane selective oxidation over multi-functional Mo-based oxide catalysts

doi:10.1016/j.molcata.2004.01.026

Journal of Molecular Catalysis A: Chemical

Volume 220, Issue 1, 27 September 2004, Pages 67-76

https://doi.org/10.1016/j.molcata.2004.01.026 Get rights and content

Abstract

Based on recent scientific research and industrial approach on the selective oxidation of propane over complex metal oxide catalysts, strategical elements which are necessary for developing complicated oxide catalysts and for achieving industrial processes are summarized and discussed.

Strategical elements for developing complicated oxide catalysts, typically Mo-V-Te(Sb)-Nb-O, and for achieving industrial processes of the selective oxidation of propane to acrylic acid, are discussed on the basis of recent scientific researches and industrial approaches.

Introduction

The selective oxidation of light alkanes (C₂–C₄) into oxygenated products is a very attractive way for the chemical utilization of natural gas resources. Moreover, additional interests in the transformation of such light alkanes into valuable compounds are the lower environmental impact and the lower cost of such processes. In spite of that many works have been carried out in the field of selective oxidation since 1960s [1], [2], the only reaction that has been brought up to industrial scale until now is the well-known butane oxidation to maleic anhydride over V-P-O catalysts [3]. In the other alkane oxidations, the work is still carried on at laboratories or pilot plant scales. The main problems lying in these selective oxidation reactions are: (i) how to activate the highly stable CH bond of light alkanes effectively, (ii) to suppress the further oxidation of the formed products (alkenes or oxygenates) to undesired products, and (iii) to minimize the possibility of CC bond breaking to CO_x. Obviously, the design of active and selective catalysts for the alkane oxidation are difficult tasks.

Therefore, the points that have been considered as key factors determining the alkane transformation to products via catalytic selective oxidation are mainly concerned with the activation of both oxygen and alkane, the reactivity difference between reactants and products, and the reaction mechanism. A better understanding of each of them brings an improved possibility of increasing the catalytic performance. At the same time, process design become highly important for achieving difficult catalytic oxidations such as the selective oxidation of propane to acrylic acid.

The present report summarizes the selective oxidation of propane over various complex metal oxide catalysts, particularly Mo-V-O based mixed oxide catalysts, and deals with several parameters which are necessary to be considered for design a new industrial process of propane selective oxidation.

Section snippets

Oxidative dehydrogenation of propane to propene

Propene is an important starting material in the petrochemical productions. There are several industrial catalytic processes for simple dehydrogenation of propane [4], [5], [6] but their drawbacks are the high temperature due to the endothermic reaction as well as the rapid deactivation of the catalysts by the deposition of C on the active surface (coking). On the other hand, the catalytic oxidative dehydrogenation of propane is thermodynamically favorable (ΔH = −117 kJ/mol) and has been

Design of a new process based on propane selective oxidation

In order to design a new process based on propane selective oxidation, several parameters have to be considered: (1) depending on the desired product, the by-products and the impurities, (2) the location for the new plant, and the source of propane, (3) the kind of process to be used: multi-tubular fixed-bed reactor, fluidised bed reactor or circulating fluid-bed reactor, (4) complete conversion par pass or partial conversion and in the latter case, propane recycle or not, (5) use of air or

Conclusion

Many research for developing the catalytic selective oxidation process of propane to acrylic acid and acrylonitrile are still undertaken in many places in the world. But there must be strategical approaches in the research for designing catalysts and process for the reaction. Since the propane selective oxidation over solid catalysts is a highly difficult reaction, elemental steps of the reaction, alkane and molecular oxygen activation, effective intermediate oxidation, quick desorption of

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