Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

Performance of a mixed-conducting ceramic membrane reactor with high oxygen permeability for methane conversion

A mixed-conducting perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) ceramic membrane reactor with high oxygen permeability was applied for the activation of methane. The membrane reactor has intrinsic catalytic activities for methane conversion to ethane and ethylene. C-2 selectivity up to 40-70% was achieved, albeit that conversion rate were low, typically 0.5-3.5% at 800-900 degreesC with a 50% helium diluted methane inlet stream at a flow rate of 34 ml/min. Large amount of unreacted molecular oxygen was detected in the eluted gas and the oxygen permeation flux improved only slightly compared with that under non-reactive air/He experiments. The partial oxidation of methane to syngas in a BSCFO membrane reactor was also performed by packing LiLaNiO/gamma -Al2O3 with 10% Ni loading as the catalyst. At the initial stage, oxygen permeation flux, methane conversion and CO selectivity were closely related with the state of the catalyst. Less than 21 h was needed for the oxygen permeation flux to reach its steady state. 98.5% CH4 conversion, 93.0% CO selectivity and 10.45 ml/cm(2) min oxygen permeation flux were achieved under steady state at 850 degreesC. Methane conversion and oxygen permeation flux increased with increasing temperature, No fracture of the membrane reactor was observed during syngas production. However, H-2-TPR investigation demonstrated that the BSCFO was unstable under reducing atmosphere, yet the material was found to have excellent phase reversibility. A membrane reactor made from BSCFO was successfully operated for the POM reaction at 875 degreesC for more than 500h without failure, with a stable oxygen permeation flux of about 11.5 ml/cm(2) min. (C) 2001 Elsevier Science B.V. All rights reserved.

A novel zirconium-based perovskite-type membrane material for oxygen permeation

A novel zirconium-based membrane material of BaCo0.4Fe0.4Zr0.2O3-6 with cubic perovskite structure was synthesized for the first time through a method of citric and EDTA acid combined complexes. The structural stability was characterized by XRD, O-2-TPD and H-2-TPR techniques respectively. The high oxygen permeation flux of 0.873 mL/cm(2) min at 950 degreesC was obtained under He/Air gradient. Meanwhile, the single activation energy for oxygen permeation and the long-term steady operation of 200 h at 800 degreesC were achieved.

Novel porous metal/ceramic membrane materials

During the past 22 months, the preparation and application of novel porous metal/ceramic membrane materials have been extensively explored in the area of membrane science and catalysis. Thus, new preparation methods and new application concepts in membrane catalysis have been developed.