Oxidant-assisted methane pyrolysis.

Methane pyrolysis has been proposed as a cost-competitive route to produce low-CO-emissions hydrogen that can utilize today's infrastructure to supply feedstock and manage waste, and thereby be rapidly scalable. However, this process faces challenges such as catalyst deactivation and carbon build-up that hinder its large-scale implementation. Pyrolysis is usually conducted in the absence of oxidizers to avoid combustion products such as CO. Here, we demonstrate that the addition of small concentrations of an oxidant to a methane pyrolysis reaction on Fe-based catalysts prevented catalyst deactivation and increased the net production of carbon and hydrogen. Methane pyrolysis in the presence of a small amount of CO demonstrated a twofold increase in carbon yield and a 7.5-fold increase in hydrogen concentration in the effluent compared to that of a pure methane feed during 1 h operation in a fluidized bed reactor at 750 °C. A similar beneficial effect was observed by adding small amounts of HO in the feed. We provide evidence that the cyclic formation and decomposition of an iron carbide catalyst phase allowed for increased methane decomposition and significant carbon removal from the catalyst surface, thus increasing carbon and hydrogen yields. A similar result was obtained for Ni- and Co-based catalysts.