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The kinetics of methanol synthesis remains debatable for various reasons, such as the lack of scientifically conclusive agreement about reaction mechanisms. The focus of this paper is on the evaluation of the intrinsic kinetics of the methanol synthesis reaction based on CO2 hydrogenation and the associated reverse water–gas shift as overall reactions. The industrial methanol synthesis catalyst, Cu/ZnO/Al2O3/MgO, was used for performing the kinetic studies. An optimal kinetic model was assessed for its ability to predict the experimental data from differential to integral conditions, contrary to the typical fitting of only the integral conditions' data (common practice, as reported in the literature). The catalyst testing and kinetic evaluations were performed at various temperatures (210–260 °C) and pressures (40–77 bar), and for different stoichiometric numbers (0.9–1.9), H2/CO2 ratios (3.0–4.4) and carbon oxide ratios (0.9–1.0), in an isothermal fixed bed reactor, operated in a plug-flow mode. Experiments with CO in the feed were also generated and fitted. Different literature kinetic models with different assumptions on active sites, rate-determining steps, and hence, model formulations were fitted and compared. The original Seidel model appeared to fit the kinetic data very well, but it has twelve parameters. The modified model (MOD) we propose is derived from this Seidel model, but it has fewer (nine) parameters—it excludes CO hydrogenation, but it takes into consideration the morphological changes of active sites and CO adsorption. This MOD model, with three active sites, gave the best fit to all the data sets. [ABSTRACT FROM AUTHOR]

Kinetics of methanol synthesis from carbon dioxide and hydrogen were studied on two catalysts, a copper–zinc oxide–alumina catalyst (CuZA) and a copper–zinc oxide–zirconia (CuZZ) catalyst. Although both catalysts show similar turnover frequencies for the methanol synthesis reaction, CuZZ is more selective for methanol synthesis because the reverse water gas shift reaction occurs more slowly on this catalyst. The results of the catalytic tests were modeled with power-law equations which highlight the strong positive impact of hydrogen partial pressure on methanol synthesis activity and selectivity. The comparison of the experimental results with thermodynamic equilibrium allows separating thermodynamic and kinetic driving forces. [ABSTRACT FROM AUTHOR]