(576d) Influences of Cation and Anion Substitutions on Oxidative Coupling of Methane over Hydroxyapatite Catalysts Conference: AIChE Annual MeetingYear: 2015Proceeding: 2015 AIChE Annual MeetingGroup: Catalysis and Reaction Engineering DivisionSession: Catalytic Hydrocarbon Processing II Time: Wednesday, November 11, 2015 - 4:15pm-4:35pm Authors: Liu, D., University of Maryland Oh, S. C., University of Maryland Wu, Y., Univeristy of Maryland Lead substituted hydroxyapatite (Pb-HAP) has been an active catalyst for oxidative coupling of methane (OCM) reactions. CO32- substituted HAP (HAP-CO3) 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-CO3) are promising to integrate the catalytic property of Pb-HAP and oxide ion conductive property of HAP-CO3 into one apatite-based ceramic material that can be manufactured into membrane reactors for possessing CH4 activation and O2 permeation capabilities for efficient OCM reactions. In this work, the effects of substitutions for both cation (Pb2+) and anion (CO32-) in HAP structure on OCM reactions were studied. The basicity and acidity of HAP catalysts were strengthened by the cation and anion substitutions, respectively, and as consequences, they influenced the catalytic performances of HAP structure in OCM reactions. The selectivity to C2 (ethylene and ethane) products increased in the order of HAP-CO3 < HAP < Pb-HAP-CO3 < Pb-HAP, while Pb-HAP-CO3 showed the best stability and highest C2 yield (under optimized reaction conditions) among these four HAP-based catalysts. Upon varying the reaction temperature and/or CH4/O2 ratios in the reactions, the CH4 conversion and C2 or COx (CO and CO2) formation showed a strong dependence on the composition of HAP-based catalysts.