Investigation of the permeation behavior and stability of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen membrane

SrCo0.8Fe0.2O3-delta (SCFO) and Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) oxides were successfully prepared, using a combined citrate-EDTA complexing method. The results of O-2-TPD and XRD showed that the introduction of barium into SCFO could effectively suppress the oxidation of Co3+ and Fe3+ to higher valence states of Co4+ and Fe4+ in the lattice, and stabilize the perovskite structure under lower oxygen partial pressures. Oxygen permeation experiment showed that BSCFO membrane also had higher oxygen permeation flux than that of SCFO under air/He oxygen partial pressure gradient. At 950 degrees C, the permeation flux through 1.80 mm BSCFO membrane exposed to flowing predried air (P-O2' = 0.21 atm) and helium (P-O2" = 0.037 atm) is ca. 1.4 ml/cm(2) min and the activation energy for oxygen transportation is 40.9 kJ/mol within the temperature range of 775-950 degrees C. The permeation flux of BSCFO was less sensitive to minor amounts of CO2 and water vapor presented in the air than that of SCFO. Long-term oxygen permeation study of more than 1000 h at 850 degrees C indicated that the BSCFO membrane could operate stably as an oxygen generator at that temperature. A very slow exponential decay in the measured oxygen permeation flux occurred at temperatures lower than 825 degrees C, which was caused by a phase transition. The phase transition was found to be reversible at higher temperatures, but a long time was needed for the equilibration. (C) 2000 Elsevier Science B.V. All rights reserved.

[1]  C. Udovich Ceramic Membrane Reactors for the Conversion of Natural Gas to Syngas , 1998 .

[2]  YamazoeNoboru,et al.  THE EFFECT OF OXYGEN SORPTION ON THE CRYSTAL STRUCTURE OF La1−xSrxCoO3−δ , 1982 .

[3]  B. Steele Oxygen ion conductors and their technological applications , 1992 .

[4]  A. Kovalevsky,et al.  Oxygen permeability of perovskites in the system SrCoO 3 − δ-SrTiO 3 , 1997 .

[5]  R. B. Poeppel,et al.  Failure mechanisms of ceramic membrane reactors in partial oxidation of methane to synthesis gas , 1994 .

[6]  A. Jacobson,et al.  A neutron diffraction study of two strontium cobalt iron oxides , 1995 .

[7]  Zongping Shao,et al.  Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation , 2000 .

[8]  N. Yamazoe,et al.  Effect of Cation Substitution on the Oxygen Semipermeability of Perovskite-type Oxides , 1988 .

[9]  Y. S. Lin,et al.  Catalytic Properties of Oxygen Semipermeable Perovskite-Type Ceramic Membrane Materials for Oxidative Coupling of Methane , 1996 .

[10]  H. Bouwmeester,et al.  Ion and mixed conducting oxides as catalysts , 1992 .

[11]  Roger B. Poeppel,et al.  Dense ceramic membranes for partial oxidation of methane to syngas , 1995 .

[12]  Henricus J.M. Bouwmeester,et al.  Dense Ceramic Membranes for Oxygen Separation , 1997, The CRC Handbook of SOLID STATE Electrochemistry.

[13]  Geert Versteeg,et al.  Current hurdles to the success of high temperature membrane reactorS , 1994 .

[14]  A. Jacobson,et al.  Oxygen permeation studies of SrCo0.8Fe0.2O3 − δ , 1995 .

[15]  H. Bouwmeester,et al.  Chapter 10 Dense ceramic membranes for oxygen separation , 1996 .

[16]  Henricus J.M. Bouwmeester,et al.  Importance of the surface exchange kinetics as rate limiting step in oxygen permeation through mixed-conducting oxides , 1994 .

[17]  Norio Miura,et al.  Influence of constituent metal cations in substituted LaCoO3 on mixed conductivity and oxygen permeability , 1991 .

[18]  Henricus J.M. Bouwmeester,et al.  Influence of order-disorder transitions on oxygen permeability through selected nonstoichiometric perovskite-type oxides , 1993 .

[19]  Noboru Yamazoe,et al.  OXYGEN PERMEATION THROUGH PEROVSKITE-TYPE OXIDES , 1985 .

[20]  V. Kharton,et al.  Materials of high-temperature electrochemical oxygen membranes , 1996 .

[21]  H. Verweij,et al.  Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor , 1995 .

[22]  D. L. Bennett,et al.  Advanced gas-to-liquids processes for syngas and liquid-phase conversion , 1998 .

[23]  William J. Weber,et al.  Electrochemical Properties of Mixed Conducting Perovskites La1 − x M x Co1 − y Fe y O 3 − δ (M = Sr, Ba, Ca) , 1996 .