Investigation of ideal zirconium-doped perovskite-type ceramic membrane materials for oxygen separation

Zirconium-doped perovskite-type membrane materials of BaCo0.4Fe0.6−xZrxO3−δ (x=0–0.4) with mixed oxygen ion and electron conductivity were synthesized through a method of combining citric and EDTA acid complexes. The results of X-ray diffraction (XRD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) showed that the incorporation of proper amount of zirconium into BaCo0.4Fe0.6O3−δ could stabilize the ideal and cubic structure of perovskite. Studies on the oxygen permeability of the as-synthesized membrane disks under air/He gradient indicated that the content of zirconium in these materials had great effects on oxygen permeation flux, activation energy for oxygen permeation and operation stability. The high oxygen permeation flux of 0.90 ml cm−2 min−1 at 950 °C, the single activation energy for oxygen permeation in the range of 600–950 °C and the long-term operation stability at a relatively lower operational temperature of 800 °C under air/He gradient were achieved for the BaCo0.4Fe0.4Zr0.2O3−δ material. Meanwhile, the effect of carbon dioxide on structural stability and oxygen permeability of this material was also studied in detail, which revealed that the reversible stability could be attained for it.