Microwave-Assisted Conversion Of Methane Over H-(Fe)-Zsm-5: Evidence For Formation Of Hot Metal Sites

Microwave-assisted catalysis offers great promise as an "intensified" technology for chemical processing. The present study investigates microwave-assisted direct conversion of methane with focus on the design and evaluation of microwave-sensitive H-(Fe)ZSM-5 catalysts for the existence of hotspot formation. Isomorphous substituted H-(Fe)ZSM-5 catalysts are tuned to identify key design parameters that control their microwave sensitivity. Increasing the amount of Al and Fe substitution in the zeolite lattice is found to result in higher microwave sensitivity due to improved dielectric properties and hence facilitated microwave heating of the catalyst bed. Comparison between the performance of these catalysts in a conventional thermally-heated (CH) fixed-bed and a microwave (MW) reactor allows identification of the effect of microwave irradiation on the catalyst activity. Methane conversion is drastically enhanced at MW conditions (from 3% at CH conditions to 40% at MW conditions), indicating accelerated methane activation over the metal site and hence suggesting a hot metal site despite much lower catalyst bulk temperature measured in the microwave reactor. The existence of metal hotspot formation is further supported by the reaction product distribution and spent catalyst analysis. At MW conditions, C-2 (ethane and ethylene) and coke (mainly carbon nanotubes and nanofibers) selectivity are much higher at the cost of aromatics make compared to CH conditions. This can be explained by reduced aromatization activity at the Brunsted acid sites of the zeolite due to its lower relative temperature of the zeolite. The much-enhanced metal aggregation observed in the spent catalyst from the MW reactor along with the distribution of coke species further confirms the existence of selective heating (i.e. hotspot formation) occurring at the active metal site in the catalyst at MW conditions.