Dual-Phase Oxygen Transport Membranes for Stable Operation in Environments Containing Carbon Dioxide and Sulfur Dioxide.

Dual-phase membranes are appealing candidates for oxygen transport membranes owing to their unique combination of ambipolar electron-ion transport and endurance. However, O2 separation in industrial environments demands very high stability and effectiveness in the presence of CO2- and SO2-bearing process gases. Here, the composition of dual-phase membranes based on NiFe2O4-Ce(0.8) Tb(0.2)O(2-δ) (NFO-CTO) was optimized and the effective performance of catalytically-activated membranes was assessed in presence of CO2 and SO2. Further insight into the limiting mechanisms in the permeation was gained through electrical conductivity studies, permeation testing in several conditions and impedance spectroscopy analysis. The dual-phase membranes were prepared by one-pot sol-gel method and their permeability increases with increasing fluorite content. An O2 flux of 0.25 (ml min(-1)  cm(-2)) mm at 1000 °C was obtained for a thick self-standing membrane with 40:60 NFO/CTO composition. An in-depth study mimicking typical harsh conditions encountered in oxyfuel flue gases was performed on a 50:50 NFO/CTO membrane. CO2 content as well as SO2 presence in the sweep gas stream were evaluated in terms of O2 permeation. O2 fluxes of 0.13 and 0.09 mL min(-1)  cm(-2) at 850 °C were obtained for a 0.59 mm thick membrane under CO2 and 250 ppm SO2 in CO2 sweep conditions, respectively. Extended periods at work under CO2- and SO2-containing atmospheres revealed good permeation stability over time. Additionally, XRD, backscattered electrons detector (BSD)-SEM, and energy-dispersive X-ray spectroscopy (EDS) analysis of the spent membrane confirmed material stability upon prolonged exposure to SO2.