Reversible Nature of Coke Formation on Mo/ZSM‐5 Methane Dehydroaromatization Catalysts

Non‐oxidative dehydroaromatization of methane over Mo/ZSM‐5 zeolite catalysts is a promising reaction for the direct conversion of abundant natural gas into liquid aromatics. Rapid coking deactivation hinders the practical implementation of this technology. Herein, we show that catalyst productivity can be improved by nearly an order of magnitude by raising the reaction pressure to 15 bar. The beneficial effect of pressure was found for different Mo/ZSM‐5 catalysts and a wide range of reaction temperatures and space velocities. High‐pressure operando X‐ray absorption spectroscopy demonstrated that the structure of the active Mo‐phase was not affected by operation at elevated pressure. Isotope labeling experiments, supported by mass‐spectrometry and 13C nuclear magnetic resonance spectroscopy, indicated the reversible nature of coke formation. The improved performance can be attributed to faster coke hydrogenation at increased pressure, overall resulting in a lower coke selectivity and better utilization of the zeolite micropore space. Under pressure Mo/ZSM‐5 catalysts display much better methane dehydroaromatization performance in a wide range of conditions. An eightfold increase in aromatic productivity is obtained by increasing the reaction pressure from 1 to 15 bar. These findings are rationalized by the reversible growth of coke species and better utilization of the zeolite micropores.