Influences of cation and anion substitutions on oxidative coupling of methane over hydroxyapatite catalysts.

Lead substituted hydroxyapatite (Pb-HAP) has been an active catalyst for oxidative coupling of methane (OCM) reactions. CO 3 2 − substituted HAP (HAP-CO 3 ) has showed enhanced oxide ion conductivity than bare HAP in high temperature solid oxide fuel cells. Substitutions for both cations and anions in HAP structure (Pb-HAP-CO 3 ) are promising to integrate the catalytic property of Pb-HAP and oxide ion conductive property of HAP-CO 3 into one apatite-based ceramic material that can be manufactured into membrane reactors for possessing CH 4 activation and O 2 permeation capabilities for efficient OCM reactions. In this work, the effects of substitutions for both cation (Pb 2+ ) and anion (CO 3 2 − ) in HAP structure on OCM reactions were studied. The composition and physicochemical properties of HAP catalysts were changed by the cation and anion substitutions, respectively, and as consequences, they influenced the catalytic performances of HAP structure in OCM reactions. The selectivity to C 2 (ethylene and ethane) products increased in the order of HAP-CO 3 < HAP < Pb-HAP-CO 3 < Pb-HAP, while Pb-HAP-CO 3 showed the best stability and comparable C 2 yield (under optimized reaction conditions) to Pb-HAP catalyst. Under different reaction temperature and/or CH 4 /O 2 ratio in the OCM reactions, the CH 4 conversion and C 2 or CO x (CO and CO 2 ) selectivity showed a strong dependence on the composition of HAP-based catalysts. The present study forms a basis for understanding of the correlations between the composition, structure, and catalytic performance of HAP and other apatite structured catalysts, which are potential membrane materials for OCM reactions in membrane reactors. [ABSTRACT FROM AUTHOR]