Kinetic modeling of dynamic changing active sites in a Mars-van Krevelen type reaction: Ethylene oxychlorination on K-doped CuCl2/Al2O3

A kinetic model was developed by taking into account the dynamic nature of the active sites in Mars-van Krevelen type catalytic reactions to predict the evolution of the reactant and product composition in the gas phase and the CuCl2 concentration in the solid catalyst. The kinetic model at the steady-state of ethylene oxychlorination was obtained by combining transient experiments of the two half-reactions in the redox cycle, namely CuCl2 reduced to Cud by ethylene and Cud oxidation by oxygen on the K-promoted CuCl2/gamma-Al2O3 catalyst. The dynamic transitions between CuCl2 and Cud of the active sites during the reactions are also modeled, and the contributions of two active sites, namely Cu coordination numbers of 4 and 3 in CuCl2 were distinguished and included in the kinetic model. The kinetic models describe well the transient response of the reduction and oxidation steps as well as the reaction at the steady-state at different reaction conditions. Moreover, by combining the reactor modeling through a steady-state approach, the spatial-time resolved CuCl2 profile and the C2H4 reaction rate can be well predicted in comparison with the experimental results. The approach of both transient and steady-state kinetic modeling and simulation is supposed to have general relevance for a better understanding of Mars-van Krevelen type reactions.

Automated summary

A kinetic model considering the dynamic nature of active sites in Mars-van Krevelen type reactions was developed to predict the evolution of reactant and product composition, as well as CuCl2 concentration in the solid catalyst. By combining transient and steady-state kinetic modeling, the model successfully described the transient response of reduction and oxidation steps, as well as the reaction at steady state under different conditions, providing a better understanding of Mars-van Krevelen type reactions.