Enhanced catalytic performance for methane dehydro‐aromatization on Mo/HMCM‐49 prepared with citric acid

Abstract

A simple citric acid (CA)‐ammonium molybdate co‐impregnation method was applied to prepare the Mo‐based MCM‐49 catalyst to ameliorate the dispersion of metallic Mo for methane dehydro‐aromatization reaction (MDA). The newly prepared catalyst has higher crystallinity and maintains the original morphology of zeolite, which proves that the addition of citric acid will not destroy the basic structure of the catalyst. Based on H2‐TPR, UV‐vis, NH3‐TPD and XPS characterization results, it can be corroborated that the introduction of citric acid changes the coordination state of Mo element. Brønsted acid sites can stabilize the monomeric Mo oxide species by increasing MoOx migration into the MCM‐49 zeolite pores channel after calcination, which may affect the distribution of active sites MoCx and thus improve MDA catalytic activity. The experimental results show that the Mo‐based MCM‐49 catalyst with nCA : nMo ratios of 1.0 has higher methane conversion (14.5 %) and aromatics yield (9.8 %). The combination of XPS, TG and Raman tests of the spent catalyst confirms that the newly synthesized catalysts produce less carbon deposition, thus improving the catalytic durability during the MDA reaction.