Sintering of nickel particles is a well-known path of deactivation for Ni/Al₂O₃ catalysts. Considering the CO₂ methanation in the context of Power-to-Gas, a sintering study for up to 300 h was performed in a controlled atmosphere between 450 and 600 °C. Since water is a product of the methanation reaction and is known to favor the particle sintering, the H₂O:H₂ molar ratio was varied in the range 0–3.2. Characterization of the post mortem samples showed sintering of both nickel and support particles. The absence of carbon oxides in the gas feed allows us to rule out other causes of deactivation such as carbon deposits. A sintering law is derived from the loss of metallic surface area with time-on-stream according to local temperature and H₂O:H₂ molar ratio. An excellent fit of the experimental data was obtained allowing the prediction of the metallic surface area within 15%.

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.

Editorial: Hierarchical and Multifunctional Materials in Chemical Engineering: Synthesis Strategies and Processing Challenges