Nature of the active sites of ferrospheres in the oxidative condensation of methane

The catalytic properties of ferrospheres containing 76–97 wt % Fe2O3 in the oxidative condensation of methane were compared with their phase composition and the distribution of iron cations over the crystallographic positions of iron-containing phases in a steady state. It was established that the reaction route of methane oxidation changed at a Fe2O3 content of 89 wt %. Deep oxidation was the main reaction route on ferrospheres with a Fe2O3 content of <88.8 wt %. At a Fe2O3 content of ≥89 wt %, the yield of C2 hydrocarbons sharply increased and the contribution of deep oxidation decreased. The yield of C2 hydrocarbons correlated with the amount of defects in the structure of iron spinel, which are iron ions with the tetrahedral cation of Ca2+ and the octahedral cation vacancy among the nearest neighbors.