Redox kinetics of benzene oxidation to maleic anhydride

Steady state kinetics of the oxidation reaction have been determined with the help of a gradientless semi-differential, fixed-bed reactor. The Mars and van Krevelen phenomenological model satisfactorily correlates the experimental data but a modification of the Langmuir-Hinshelwood model taking into account partial coverage of the catalyst surface with reaction intermediates is preferred. Transient kinetics have been studied with a new automated periodic-pulse reactor, directly connected to a gas chromatograph. The response of a catalyst (essentially V₂O₅–MoO₃) to reduction and oxidation has been investigated. The rate of bulk (lattice) oxygen utilization as well as the degree of carbon coverage are estimated by this technique. Selectivity is dependent on the oxidation state of the catalyst: high partial pressure of either benzene or oxyen and high temperatures are detrimental to selectivity.