Understanding the generation of methanol synthesis and water gas shift activity over copper-based catalysts – A spatially resolved experimental kinetic study using steady and non-steady state operation under CO/CO₂/H₂ feeds

AbstractUnderstanding the mechanism and generation of activity for methanol synthesis and the water gas shift reactions over copper-based catalysts remains a significant area of study in heterogeneous catalysis. In this work, steady and non-steady state experimental and kinetic modelling methods are presented to demonstrate changes in functionality of a Cu/ZnO/Al2O3 catalyst based on gas composition.Steady-state testing of a Cu/ZnO/Al2O3 catalyst, using experimental spatial discretisation approaches with fixed-bed, integral-operation micro reactors, has generated performance data over a range of PCO/PCO2 ratios (1–10). The data showed a mixture of observations where forward or reverse water gas shift was kinetically favourable, and also where the reaction was significantly limited by thermodynamic equilibrium. A steady state Langmuir–Hinshelwood model based on micro kinetics was most appropriate which includes kinetic descriptions of both directions of the water gas shift reaction. Using this method, the entire dataset could be predicted and an internal consistency within the kinetic model of the key adsorption constants was demonstrated.Non-steady state, ‘reactor start-up’, testing of a Cu/ZnO/Al2O3 catalyst marked a novel approach to further understanding the functionality of the catalyst. Initial changes in surface carbon and oxygen populations were quantified and linked to subsequent dynamic changes in methanol synthesis and water gas shift activity. Cu/ZnO and Cu/Al2O3 formulations were also evaluated and tested using kinetic models, permitting a structural and compositional comparison with Cu/ZnO/Al2O3

Copper Promotion of Chromium-Doped Iron Oxide Water-Gas Shift Catalysts under Industrially Relevant Conditions

Copper promotion of chromium-doped iron oxide prepared via co-precipitation for high-temperature water-gas shift (WGS) catalysis is investigated. Low-temperature Mössbauer spectra demonstrate that copper doping delays hematite (α-Fe2O3) formation in the fresh catalyst, favoring the formation of small crystallites of ferrihydrite (Fe5HO8∙4 H2O). Catalysts are treated under industrial WGS conditions at 360 °C (activity evaluation) and 450 °C (ageing) at 2 and 25 bar. Mössbauer spectra show that chromium is incorporated in octahedral sites of the active magnetite (Fe3O4) phase, resulting in a partially oxidized structure. Copper doping did not affect the bulk magnetite structure of the activated catalyst, which points to the presence of a separate copper phase. Near-ambient pressure XPS shows that copper is in the metallic state. XPS of discharged catalysts evidenced that reaction at elevated pressure resulted in the surface reduction of Fe3+ to Fe2+. Copper promotion enhances CO conversion under high-temperature WGS conditions