SrCo0.4Fe0.4Zr0.2O3-d混合导体中空纤维膜的制备及其氧渗透性能

doi:10.3724/SP.J.1077.2010.00871

无机材料学报 ›› 2010, Vol. 25 ›› Issue (8): 871-876.DOI: 10.3724/SP.J.1077.2010.00871 CSTR: 32189.14.SP.J.1077.2010.00871

SrCo_0.4Fe_0.4Zr_0.2O_3-d混合导体中空纤维膜的制备及其氧渗透性能

戚律, 董学良, 刘郑堃, 张广儒, 金万勤

(南京工业大学化学化工学院材料化学工程国家重点实验室, 南京 210009)

收稿日期:2009-12-10 修回日期:2010-03-05 出版日期:2010-08-20 网络出版日期:2010-07-19
基金资助:
国家973计划项目(2009CB623406); 国家自然科学基金(20990222); 江苏省六大人才高峰项目(2007007)

Preparation and Oxygen Permeation of SrCo_0.4Fe_0.4Zr_0.2O_3-dMixed-conducting Hollow Fibre Membrane

QI Lü, DONG Xue-Liang, LIU Zhen-Kun, ZHANG Guang-Ru, JIN Wan-Qin

(State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China)

Received:2009-12-10 Revised:2010-03-05 Published:2010-08-20 Online:2010-07-19

摘要/Abstract

摘要：

基于相分离理论, 采用干湿法纺丝技术结合后续的烧结工艺, 制备出SrCo_0.4Fe_0.4Zr_0.2O_3-d(SCFZ)混合导体中空纤维膜. 借助于XRD、SEM、热膨胀分析以及氧渗透性能分析等手段, 分别对样品的晶相结构, 膜的微观形貌,中空纤维膜生坯的烧结行为以及膜的氧渗透通量进行了研究. 结果表明, 中空纤维膜晶相结构由钙钛矿主体相、 SrZrO₃相及Co₃O₄相组成, SrZrO₃相含量随烧结温度升高而增大. 膜断面邻近内外皮层均存在指状孔, 膜壁中部区域为海绵孔, 此结构由聚合物溶液沉浸相分离形成. 综合烧结行为, XRD及SEM结果, 再结合气密性和机械强度测试, 确定生坯适宜的烧结温度为1240℃. 在此条件下制备的SCFZ中空纤维膜力学性能优异, 三弯矩断裂强度达到74.19MPa, 在850℃时, 空气/氦气梯度下的氧渗透通量为2.9´10^-7mol/(cm²·s), 并且在160 h的测试周期内保持稳定.

关键词: 干湿法纺丝, 中空纤维膜, 混合导体氧化物, 氧渗透

Abstract:

SrCo_0.4Fe_0.4Zr_0.2O_3-d (SCFZ) mixed conducting hollow fibre membranes were prepared by a dry-wet spinning technology based on the phase separation theory combined with subsequent sintering process. XRD, SEM, thermal expansion technique and oxygen permeation test were utilized to characterize the crystal phase structures, microstructures, sintering behavior and oxygen permeation flux of SCFZ powder and/or hollow fibre membranes. XRD patterns show that the crystal phase of SCFZ hollow fibre membranes are composed of perovskite main phase, SrZrO₃ and Co₃O₄ impurity phases. The content of SrZrO₃ increases with increasing the sintering temperature. The SEM images demonstrate that fingerlike pores exist adjacent to the inner and outer skin layer of membrane wall. Meantime, sponge-like pores appear in the middle zone of wall. This kind of morphology is caused by the immersion phase separation process. From the gastight, mechanical strength, sintering behavior, XRD and SEM results, the optimum sintering temperature of the green membranes is considered to be 1240℃. The SCFZ hollow fibre membranes are obtained under the optimum sintering schedule. The sintered SCFZ membranes exhibit high mechanical strength and the fracture strength reaches 74.19MPa. At 850℃, the oxygen permeation flux of the membrane is 2.9´10^-7mol/(cm²· s) under air/He gradient, and the flux is stable during the test for more than 160h.

Key words: dry-wet spinning, hollow fibre membrane, mixed conducting oxide, oxygen permeation

中图分类号:

TQ174

戚律, 董学良, 刘郑堃, 张广儒, 金万勤. SrCo_0.4Fe_0.4Zr_0.2O_3-d混合导体中空纤维膜的制备及其氧渗透性能[J]. 无机材料学报, 2010, 25(8): 871-876.

QI Lü, DONG Xue-Liang, LIU Zhen-Kun, ZHANG Guang-Ru, JIN Wan-Qin. Preparation and Oxygen Permeation of SrCo_0.4Fe_0.4Zr_0.2O_3-dMixed-conducting Hollow Fibre Membrane[J]. Journal of Inorganic Materials, 2010, 25(8): 871-876.

参考文献

[1]Teraoka Y, Zhang H M, Futukawa S, et al. Oxygen permeation through perovskite-type oxides. Chem. Lett., 1985, 14(11): 1743-1746.
[2]Teraoka Y, Fukada T, Miura N, et al. Preparation of dense film of perovskite-type oxide on porous substrate. J. Ceram. Soc. Jpn. Int. Ed., 1989, 97(5): 533-538.
[3]Jin W Q, Li S G, Huang P, et al. Preparation of an asymmetric perovskite-type membrane and its oxygen permeability.J. Membr. Sci,2001, 185(2):237-243
[4]Okubo T, Haruta K, Kusakabe K, et al. Preparation of a Sol-Gel derived thin membrane on a porous ceramic hollow fiber by the filtration technique.J. Membrane Sci,1991, 59(1):73-80
[5]Luyten J, Buekenhoudt A. Preparation of LaSrCoFeO3-x membranes.Solid State Ionics,2000, 135(1-4):637-642
[6]Tan X Y, Liu Y T, Li K. Preparation of LSCF ceramic hollow-fibre membranes for oxygen production by a phase–inversion/sintering technique.Ind. Eng. Chem. Res,2005, 44(1):61-66
[7]Wang H H, Werth S, Schiestel T, et al. Perovskite hollow-fibre membranes for the production of oxygen-enriched air.Angew. Chem. Int. Ed,2005, 44(42):6906-6909
[8]Wang H H, Werth S, Schiestel T, et al. Simultaneous production of hydrogen and synthesis gas by combining water splitting with partial oxidation of methane in a hollow-fiber membrane reactor.Angew. Chem. Int. Ed,2008, 47(48):9341-9344
[9]Yang L, Tan L, Gu X H, et al. A new series of Sr(Co,Fe,Zr)O3----perovskite-type membrane materials for oxygen permeation. Ind. & Eng. Chem. Res., 2003, 42(11): 2299-2305.
[10]Li S G, Jin W Q, Xu N P, et al. Mechanical strength, and oxygen and electronic transport properties of SrCo0.4Fe0.6O3---YSZ membranes. J. Membr. Sci., 2001, 186(2): 195-204.
[11]Shao Z P, Yang W S, Cong Y, et al. Investigation of the permeation behavior and stability of a Ba0.5Sr0.5Co0.8Fe0.2O3---oxygen membrane. J. Membr. Sci., 2000, 172(1/2): 177-188.
[12]Jin W Q, Zhang C, Zhang P, et al. Thermal decomposition of carbon dioxide coupled with POM in a membrane reactor.AIChE J,2006, 52(7):2545-2550
[13]Takeda Y, Kanno R, Takada T, et al. Phase relation and oxygen- non-stoichiometry of perovskite-like compound SrCoOx (2.29 < x < 2.80). Z. Anorg. Allg. Chem., 1986, 540(9/10): 259-270.
[14]Poulsen F W, van der Puil N . Phase relations and conductivity of Sr- and La-zirconates.Solid State Ionics,1992, 53-56:777-783
[15]Pinnau I, Koros W J. A qualitative skin layer formation mechanism for membrane made by dry/wet phase inversion.J. Polym. Sci., Part B,1993, 31(4):419-427
[16]宁青菊, 谈国强, 史永胜. 无机材料物理性能. 北京: 化学工业出版社, 2005: 74-75.
[17]Schiestel T, Kilgus M, Peter S, et al. Hollow fibre perovskite membranes for oxygen separation.J. Membr. Sci,2005, 258(1/2):1-4
[18]Barbara Z, Wu Z T, Li K. Preparation of ultrathin La0.6Sr0.4Co0.2Fe0.8O3-- hollow fibre membranes for oxygen permeation. Chem. Eng. Sci., 2009, 64(21): 4383-4388.
[19]Chang X F, Zhang C, Dong X L, et al. Effect of sintering atmospheres on sintering behavior, electrical conducivity and oxygen permeability of mixed-conducting membranes.J. Membr. Sci,2008, 316(1/2):128-136

SrCo_0.4Fe_0.4Zr_0.2O_3-d混合导体中空纤维膜的制备及其氧渗透性能

Preparation and Oxygen Permeation of SrCo_0.4Fe_0.4Zr_0.2O_3-dMixed-conducting Hollow Fibre Membrane

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SrCo0.4Fe0.4Zr0.2O3-d混合导体中空纤维膜的制备及其氧渗透性能

Preparation and Oxygen Permeation of SrCo0.4Fe0.4Zr0.2O3-d Mixed-conducting Hollow Fibre Membrane

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SrCo_0.4Fe_0.4Zr_0.2O_3-d混合导体中空纤维膜的制备及其氧渗透性能

Preparation and Oxygen Permeation of SrCo_0.4Fe_0.4Zr_0.2O_3-dMixed-conducting Hollow Fibre Membrane