Production of Methanol by CO₂ Hydrogenation Using a Membrane Reactor

The use of e-fuels, such as methanol (MeOH), is considered an alternative for the reduction of carbon emissions. MeOH can be produced from captured CO₂ and green H₂, with the exothermic (equilibrium-limited) reaction favoured at low temperatures and high pressures. However, CO₂ is a very stable molecule and requires high temperature (>200 °C) to overcome the slow activation kinetics. In this study, MeOH was synthesized from CO₂ and H₂ in a packed-bed membrane reactor (PBMR) using a commercial Cu/ZnO/Al₂O₃ catalyst and a tubular-supported, water-selective composite alumina–carbon molecular sieve membrane (Al-CMSM) immersed in the catalytic bed. A mixture of H₂/CO₂ (3/1) was fed into both sides of the membrane to increase the driving force of the gases produced by the reaction. The effect of the temperature of reaction (200, 220, and 240 °C), pressure difference (0 and 3 bar), and the sweep gas/reacting gas ratio (SW = 1, 3, 5) in the CO₂ conversion and products yield was studied. For comparison, the reactions were also carried out in a packed-bed reactor (PBR) configuration where the tubular membrane was replaced by a metallic tube of the same size. CO₂ conversion and MeOH yield are much higher in PBMR than in PBR configuration, showing the benefit of using the water-selective membrane. In PBMR, MeOH yield increases with SW and slightly decreases with the temperature, overcoming the limitation imposed by the thermodynamics.