Methanation of CO2 with the oxygen-deficient Ni(II)-ferrite under dynamic conditions

The continuous methanation of CO₂ has been accomplished over hydrogen-reduced Ni(II)-bearing ferrite (Ni_xFe_3–xO_4–; x=0.39, > 0) in a mixed gas flow of CO₂ and H₂ at 250–375 °C. The yield and the selectivity for the methanation were larger than 50% and 95%, respectively, at the initial stage of the process. They decreased to 31% and 89%, respectively, after 6 h methanation. The innovative results can be ascribed to the use of the new material; hydrogen-reduced Ni(II)-bearing ferrite. Its formation was evinced by chemical analyses and the increase in the lattice constant; the lattice constant of the Ni(II)-bearing ferrite (a₀ 0.8375 nm) was enlarged to 0.8379 nm by hydrogen reduction. The enlarged lattice constant was not changed during the methanation. These findings suggest that the methanation occurs at the oxygen-deficient site of the hydrogen-reduced Ni(II)-bearing ferrite, as well as the formation of water by combination of the incorporated oxygens with hydrogen. The methanation consists of three steps of the elementary reaction. First, the oxygen-deficient sites are formed by hydrogen reduction; second, CO₂ is reduced to elementary carbon and two oxygen ions which are incorporated into the oxygen-deficient sites; and third, the carbon deposited on the surface of the reduced ferrite is selectively hydrogenated to CH₄.