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

Research output: Contribution to journalArticlepeer-review


  • Sam Wilkinson
  • L.g.a. Van De Water
  • B. Miller
  • E. Hugh Stitt
  • M.j. Watson

Colleges, School and Institutes


Understanding 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.


Original languageEnglish
Pages (from-to)208-220
JournalJournal of Catalysis
Early online date27 Feb 2016
Publication statusPublished - May 2016


  • Methanol synthesis, Water gas shift, Active site, Micro kinetics, Steady state, Transient