Direct conversion of syngas into methyl acetate by relay catalysis: From fabrication of active sites to process control

Abstract The direct and selective conversion of syngas into C 2+ oxygenates is challenging due to the complex reaction network. Here, we report a robust relay system for the direct synthesis of methyl acetate (MA) from syngas, which combines CuZnAlO x /H‐ZSM‐5 for syngas to dimethyl ether (DME) with modified H‐MOR for DME carbonylation. The dehydration of methanol to DME on H‐ZSM‐5 significantly enhanced the hydrogenation of CO on CuZnAlO x , because of high DME equilibrium yields. Blocking of Brönsted acid sites with basic molecules or selective dealumination of 12‐membered rings in H‐MOR suppressed the zeolite coking. Besides, reaction temperatures above 240°C avoided H 2 O poisoning of carbonylation sites inside 8‐MR side pockets of H‐MOR, further benefiting the catalytic stability. Eventually, this relay system provided a high MA selectivity of 75% and an acetic acid selectivity of 13% at a CO conversion of 65%, outperforming reported catalysts.