Highly Active and Stable CeO2-Promoted CuCl2/Al2O3 Oxychlorination Catalysts Developed by Rational Design Using a Rate Diagram of the Catalytic Cycle

Abstract

In this study, we have developed a method to predict the steady-state rate and Cu oxidation state during ethylene oxychlorination from a reaction rate diagram of the individual steps involved in the catalytic oxychlorination cycle. The steady state of the redox cycle is represented by a cross point of the reaction rates of the reduction and oxidation steps as a function of the Cu2+ in the rate diagram. Transient kinetics of elementary reactions and steady-state kinetics of the overall catalytic cycle were investigated in an operando study using combined mass and UV–vis-NIR spectrophotometry. The catalytic consequence of the promoters was then evaluated in terms of reduction and oxidation activity as well as number of active sites, site activity, and the catalyst oxidation state at steady state. Results revealed that the neat CuCl2 catalysts operated at low Cu2+ at the steady-state conditions with stoichiometric feed composition, as a result of relatively low oxidation rate of Cu1+. As a consequence of a h...