Methanol Synthesis by Hydrogenation of Hybrid CO2−CO Feeds

Abstract The impact of carbon monoxide on CO 2 ‐to‐methanol catalysts has been scarcely investigated, although CO will comprise up to half of the carbon feedstock, depending on the origin of CO 2 and process configuration. In this study, copper‐based systems and ZnO−ZrO 2 are assessed in cycling experiments with hybrid CO 2 −CO feeds and their CO sensitivity is compared to In 2 O 3 ‐based materials. All catalysts are found to be promoted upon CO addition. Copper‐based systems are intrinsically more active in CO hydrogenation and profit from exploiting this carbon source for methanol production, whereas CO induces surplus formation of oxygen vacancies (i. e., the catalytic sites) on ZnO−ZrO 2 , as in In 2 O 3 ‐based systems. Mild‐to‐moderate deactivation occurs upon re‐exposure to CO 2 ‐rich streams, owing to water‐induced sintering for all catalysts except ZnO−ZrO 2 , which responds reversibly to feed variations, likely owing to its more hydrophobic nature and the atomic mixing of its metal components. Catalytic systems are categorized for operation in hybrid CO 2 −CO feeds, emphasizing the significance of catalyst and process design to foster advances in CO 2 utilization technologies.