On the role of hydrogen inhibition in gas-phase methane pyrolysis for carbon capture and hydrogen production in a tubular flow reactor

Abstract

The thermal pyrolysis of methane allows an economically competitive hydrogen production without direct CO2 emissions. Although several mechanisms for the process have already been proposed, especially the inhibitory effect of hydrogen as well as the process operation at increased pressure have not yet been fully clarified. In this context, the present work investigates the influence of hydrogen and argon as inert gas on product composition, methane conversion, and hydrogen selectivity as a function of temperature (1000 °C to 1600 °C), residence time (1s to 7s), molar dilution ratio (1:1 to 4:1), and pressure (1bar to 4bar) in a high-temperature reactor. Within the scope of this work, total differences in CH4 conversion of up to 50% could be observed at equal process parameters between an argon and hydrogen dilution, underlining the potential impact of diluents on the overall process. Moreover, increasing the pressure from 1bar to 4bar reduces the formation of byproducts significantly for both H2 and Ar as diluent, however with different mechanistic characteristics. The most remarkable difference is the formation of propylene that exclusively takes place in argon-diluted reaction gas mixtures. This occurrence persists unabated, even under elevated pressures and temperatures reaching as high as 1600 °C. We ascribe this phenomenon to the interaction of methyl and ethyl radicals, establishing it as an impasse to further reactions leading to the formation of solid products. Herewith, the study provides novel insights from a reaction engineering perspective as well as from a process development perspective and clarifies the role of the dilution gases hydrogen and argon on the methane pyrolysis reaction.