Experimental and modelling studies on the dynamics of the sorption-enhanced methanol synthesis process

CO 2 hydrogenation to methanol is a promising carbon-utilization pathway; however, it is fundamentally constrained by low equilibrium CO 2 conversion, while accumulation of produced water further limits methanol yield and accelerates catalyst deactivation. This work investigates a sorption-enhanced methanol synthesis (SEMES) process using a physical mixture of an industrial Cu/ZnO/Al 2 O 3 catalyst and zeolite 3 A for in situ water removal. A systematic experimental study was conducted to evaluate the effects of pressure, temperature, and weight hourly space velocity on CO 2 conversion, methanol production, yield, and selectivity. Elevated pressure enhanced CO 2 conversion and methanol productivity through combined equilibrium shifting and stronger water adsorption, while temperature exhibited a convex dependence, with optimal performance observed at 230 °C. To capture the evolving reaction–adsorption environment under sorption-enhanced operation, dynamic reactor models incorporating kinetic formulations by Graaf et al. and Seidel et al. were implemented without parameter refitting. Spatial and temporal rate analyses show that the Seidel model more accurately represents the changing reaction environment induced by water removal, particularly the shifting competition between methanol synthesis and the reverse water–gas shift reaction. A breakthrough-based analysis using gas-phase CO and CO 2 signals enabled clear demarcation of pre-breakthrough and post-breakthrough regimes, allowing quantitative evaluation of conversion, yield, and productivity under transient operation. Overall, the sorption-enhanced configuration increased CO 2 conversion and methanol yield by approximately 200–650% and 150–450%, respectively, relative to the conventional process, demonstrating the potential of coupling selective water adsorption with catalytic methanol synthesis for intensified reactor design.