Kinetic Analysis of Dry Reforming of Methane on Traditional and Membrane Catalysts

Abstract

The article presents an analysis of the results of a kinetic study of dry reforming of methane (UCM) in reactors with traditional (TC) and membrane catalysts (MC). The kinetic experiment in reactors with MC and TC was performed in the temperature range of 820–900°C and the ratio CH4 : CO2 = 1 : 1. In the experiment, an intensification of the process of the methane cracking reaction was established, the rate constant of which increases by an order of magnitude. Such a difference in the results of the DRM on the studied catalysts are due to the intensification of mass transfer on the MC, which is based on the phenomenon of thermal slip. A mathematical description corresponding to the kinetic scheme of DRM process is proposed, and the rates constants of direct and reverse reactions in both reactors are found. In the DRM process, water gas is formed on the TC, and synthesis gas is formed on the MC. At TC, the DRM process is accompanied by the accumulation of carbon deposits (CD), and at MC this accumulation is absent. The DRM process on both catalysts is characterized by three main reactions (methane cracking, gasification of the CD with carbon dioxide and/or water vapor and the reverse water gas shift), which were assumed to be reversible under experimental conditions. It turned out that on TC the gasification of the CD occurs in the reverse reaction of methane cracking, and on the MC—in the reactions of gasification by water vapor (mainly) and carbon dioxide. The process on the MC is characterized by irreversible reactions of methane cracking, gasification of the CD with water vapor and carbon dioxide. The reverse water gas shift reaction on the MC remains reversible, and its rate constants of the direct and inverse reactions turned out to be an order of magnitude lower than similar constants on the TC.