Determination of kinetic parameters of the oxidehydrogenation of ethane with CO2 on nanosized calcium-doped ceria under fast deactivation processes

Kinetic parameters of the oxidehydrogenation of ethane with CO2 on nanosized Ca-doped CeO2 have been investigated. During reaction, interaction of the reactants with the oxide catalyst causes a fast deactivation process. Overlapping of this fast deactivation with catalytic reaction makes quite difficult the reliable determination of kinetic parameters. This handicap can be overcome by getting sufficient data in a short testing time, thus reducing the degree of deactivation. The kinetics of catalytic reaction and of catalyst deactivation have been studied by conducting a series of consecutive tests at increasing temperatures in steps of 20 °C and monitoring the evolution of the reaction for periods of 30 min on stream at each temperature, with full product analysis every 3 min. At temperatures above 680 °C, catalytic rates decreased linearly with run time at isothermal operation, while deactivation rates increased with increasing temperature. Analysis of the results allows to uncouple catalyst deactivation and catalytic reaction and to obtain the kinetic parameters of both processes (i.e., steady-state and deactivation rates, and their apparent activation energies). Deactivation rate of CO formation is one order of magnitude faster than of ethene formation but both processes show the same apparent activation energy, ca. 47 kcal/mol. The apparent activation energy values for the catalytic reaction are 32 ± 4 and 26 ± 2 kcal/mol for the rates of formation of ethene and CO, respectively.