A kinetic model for methanol (MeOH) synthesis over Cu/ZnO/Al2O3/ZrO2 catalyst has been developed and selected to evaluate the effect of carbon dioxide on the reaction rates due to its high activity and stability. Detailed kinetic mechanism, on the basis of different sites on Cu for the adsorption of carbon monoxide and carbon dioxide, is applied, and the water−gas shift (WGS) reaction is included in order to provide the relationship between the hydrogenations of carbon monoxide and carbon dioxide. Parameter estimation results show that, among 48 reaction rates from different combinations of rate determining steps (RDSs) in each reaction, the surface reaction of a methoxy species, the hydrogenation of a formate intermediate HCO2, and the formation of a formate intermediate are the RDS for CO and CO2 hydrogenations and the WGS reaction, respectively. It is shown that the CO2 hydrogenation rate is much lower than the CO hydrogenation rate, and this affects the methanol production rate. However, carbon dioxid...