CO2 Hydrogenation to Methanol over La2O3-Promoted CuO/ZnO/Al2O3 Catalysts: A Kinetic and Mechanistic Study

The hydrogenation of CO2 to methanol has been investigated over CuO/ZnO/Al2O3 (CZA) catalysts, where a part of the Al2O3 (0, 25, 50, 75, or 100%) was substituted by La2O3. Results of catalytic performance tests obtained at atmospheric pressure showed that the addition of La2O3 generally resulted in a decrease of CO2 conversion and in an increase of methanol selectivity. Optimal results were obtained for the CZA-La50 catalyst, which exhibited a 30% higher yield of methanol, compared to the un-promoted sample. This was attributed to the relatively high specific surface area and porosity of this material, the creation of basic sites of moderate strength, which enhance adsorption of CO2 and intermediates that favor hydrogenation steps, and the ability of the catalyst to maintain a large part of the copper in its metallic form under reaction conditions. The reaction mechanism was studied with the use of in situ infrared spectroscopy (DRIFTS). It was found that the reaction proceeded with the intermediate formation of surface formate and methoxy species and that both methanol and CO were mainly produced via a common formate intermediate species. The kinetic behavior of the best performing CZA-La50 catalyst was investigated in the temperature range 190–230 °C as a function of the partial pressures of H2 (0.3–0.9 atm) and CO2 (0.05–0.20 atm), and a kinetic model was developed, which described the measured reaction rates satisfactorily.