CO2 Methanation in the Presence of Ce-Promoted Alumina Supported Nickel Catalysts: H2S Deactivation Studies

Abstract

The performance of alumina supported unpromoted and cerium promoted nickel catalysts in CO2 methanation reaction was investigated. It was found that the activity of catalysts in CO2 methanation reaction at low reaction temperatures can be improved by the increase in nickel loading and introduction of cerium promoter. The catalysts showed high resistance for sintering and coking at high reaction temperatures. A few stages of catalysts deactivation by H2S in the methanation reaction carried out at 475 °C with the time on stream were identified. It was found that an introduction of H2S to the stream (8 ppm) did not induce rapid decrease of activity. Slight and then strong drop of CO2 conversion and simultaneously the loss of methane selectivity was observed after specific time, depending on the catalysts composition. Deactivation of catalysts was related to the nickel content and the presence of cerium. X-ray diffraction studies indicated small changes of crystallite size with the time on stream. Raman spectroscopy studies pointed out that deactivation of catalysts was not connected with formation of carbon deposits. An in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy studies showed that exposition of catalysts to the reaction mixture containing the traces of H2S led to the blocking of nickel active sites responsible for CO2 and H2 activation and successive transformation to carbonyl and formate species.