Low temperature catalytic activity of hydrothermally synthesised ruthenium promoted ceria-zirconia composites for reforming CO2-rich methane

Abstract

The use of CO2-rich natural gas as feedstock in DRM is an attractive route of carbon dioxide utilisation due to the compositional advantage of these particular resources. The optimal operating conditions would potentially improve the overall thermal efficiency of the DRM process, especially when the temperature is lower than 800 °C. This study reports a catalyst with the demonstrated high performance and high coke-resistance, developed from ruthenium modified ceria-zirconia. Coprecipitation and hydrothermal methods were adopted to prepare the ceria-zirconia supports, and then impregnated with a very small amount of Ru (0.10 wt%). The structure-catalytic activity relationship of the catalyst was further investigated in DRM. High conversions of CH4 and CO2, i.e., 44.0% and 57.4%, respectively, were achieved by using 0.1Ru1CZ5U-180 at low temperature of 600 °C. A significant reduction in the onset reaction temperature was observed from temperature programmed reduction (TPR) and this observation was related to the increased number of exchangeable oxygens in the presence of Ru. Nitrogen adsorption-desorption results suggested that the specific surface area and the total pore volume also improved the exchange of oxygen between adsorbed carbon dioxide molecules and the crystal lattice. It is evident that the presence of ruthenium accelerated the oxygen spillover process on the surface of the catalyst, and facilitated the dynamics of the oxygen exchange between the adsorbed carbon dioxide molecules and the ceria-zirconia, which ultimately contributed to the observed increase in catalytic activity at temperatures below 800 °C. Most importantly, no detectable carbon deposits were formed over the entire experimental period when the ruthenium modified ceria-zirconia catalyst was used.