Abstract
A model of the kinetics of CH4decomposition on supported Co catalysts, at conditions relevant to the two-step CH4homologation reaction (450°C, 101 kPa), is presented. The model includes the decomposition of gas phase CH4on a Co site and migration of the resulting CHxfragment from the Co to the support as the key kinetic steps in the decomposition reaction. The migration step is essential to explain the observed kinetics at long reaction times (2–7 min) or high CH4feed concentrations (5% CH4in Ar). At these conditions, CH4decomposition continues at a low but constant rate despite a nominal Co coverage by CHx>1. The magnitudes of the estimated rate constants for the decomposition and migration steps are used to interpret the observed effects of temperature, catalyst metal loading, support, and K promoter on the CH4decomposition kinetics.
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