Carbon Dioxide Reforming of Methane using an Isothermal Redox Membrane Reactor

The continuous production of carbon monoxide (CO) and hydrogen (H(2)) by dry reforming of methane (CH(4)) is demonstrated isothermally using a ceramic redox membrane in absence of additional catalysts. The reactor technology realizes the continuous splitting of CO(2) to CO on the inner side of a tubular membrane and the partial oxidation of CH(4) with the lattice oxygen to form syngas on the outer side. La(0.6)Sr(0.4)Co(0.2)Fe(0.8)O(3‐δ) (LSCF) membranes evaluated at 840–1030 °C yielded up to 1.27 μmol (CO) [Image: see text] s(−1) from CO(2), 3.77 μmol(H₂) g(−1) s(−1) from CH(4) , and CO from CH(4) at approximately the same rate as CO from CO(2). We compute the free energy of the oxygen vacancy formation for La(0.5)Sr(0.5)B(0.5)B′(0.5)O(3−δ) (B, B′=Mn, Fe, Co, Cu) using electronic structure theory to understand how CO(2) reduction limits dry reforming of methane using LSCF and to show how the CO(2) conversion can be increased by using advanced redox materials such as La(0.5)Sr(0.5)MnO(3−δ) and La(0.5)Sr(0.5)Mn(0.5)Co(0.5)O(3−δ).