Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM‐5‐Catalyzed Methane Dehydroaromatization

Non-oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H2 /CO ratio close to two is the main side-product of coke combustion. Using 13 C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one-fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons.