Determination of kinetics and equilibria of heterogeneously catalyzed gas-phase reactions in gradientless autoclave reactors by using the total pressure method: Methanol synthesis

Rapid methods are very valuable in the determination of the kinetic and mass transfer effects for heterogeneously catalyzed reactions. The total pressure method is a classical tool in the measurement of the kinetics of gas-phase reactions, but it can be successfully applied to the kinetic measurements of gas-phase processes enhanced by solid catalysts. A general theory for the analysis of heterogeneously catalyzed gas-phase kinetics in gradientless batch reactors was presented for the case of intrinsic kinetic control and combined kinetic-diffusion control in porous catalysts. The concept was applied to gas-phase synthesis of methanol from carbon monoxide and hydrogen on a commercial copper-based catalyst (CuO/ZnO/Al₂O₃ R3-12 BASF). The reaction temperature was 180–210 °C and the initial total pressure was varied between 11 and 21 bar in a laboratory-scale autoclave reactor equipped with a rotating basket for the catalyst particles. The initial molar ratios CO-to-H₂ were approximately 1:2, 1:3 and 1:4. The experimental data from methanol synthesis were compared with numerical simulations and a good agreement between the experiments and model simulations was achieved. The predicted equilibrium agrees with previously reported values.