担载型中空纤维混合导体氧渗透膜的制备与性能研究

doi:10.15541/jim20140645

无机材料学报 ›› 2015, Vol. 30 ›› Issue (6): 621-626.DOI: 10.15541/jim20140645

担载型中空纤维混合导体氧渗透膜的制备与性能研究

刘郑堃, 朱佳伟, 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:2014-12-16 修回日期:2015-02-02 出版日期:2015-06-04 网络出版日期:2015-05-22
作者简介:刘郑堃(1984–), 男, 博士研究生. E-mail: flyice-lzk@163.com
基金资助:
国家 973 计划项目(2009CB623406);教育部创新团队发展计划(IRT13070);江苏高校优势学科建设工程基金(PAPD)

Preparation and Characterization of Mixed-conducting Supported Hollow Fiber Membrane

LIU Zheng-Kun, ZHU Jia-Wei, JIN Wan-Qin

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

Received:2014-12-16 Revised:2015-02-02 Published:2015-06-04 Online:2015-05-22
About author:LIU Zheng-Kun. E-mail: flyice-lzk@163.com
Supported by:
National Basic Research Program of China (2009CB623406);Innovative Research Team Program by the Ministry of Education of China (IRT13070);Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)

摘要/Abstract

摘要：

采用干湿法纺丝技术制备Sr_0.7Ba_0.3Fe_0.9Mo_0.1O_3-_δ(SBFM)中空纤维支撑体, 以Nb₂O₅掺杂的SrCo_0.8Fe_0.2O_3-_δ (SCFNb)为膜材料, 采用旋转喷涂结合共烧结技术制备出担载型SCFNb/SBFM中空纤维氧渗透膜。借助于XRD、SEM、热膨胀分析、透氧及膜反应性能测试等手段, 分别对样品的晶相结构、膜微观结构、支撑体与膜层的烧结行为、膜的氧渗透通量及膜反应性能进行了研究。结果表明, 膜层与支撑体的晶相结构仍保持钙钛矿主体相。支撑体具有单一海绵孔/指状孔结构, 膜厚为5 μm且致密无缺陷, 膜层与支撑体结合良好。在900℃时, 氧渗透通量达到0.74 mL/(cm²·min)。850℃下甲烷部分氧化膜反应稳定操作超过200 h, 稳态下氧渗透通量为4.5 mL/(cm²·min)。研究表明, 担载型SCFNb/SBFM中空纤维氧渗透膜具有较高的氧渗透通量, 同时具有良好的膜反应稳定性。

关键词: 担载型中空纤维膜, 混合导体膜, 透氧, 膜反应

Abstract:

Sr_0.7Ba_0.3Fe_0.9Mo_0.1O_3-_δ (SBFM) hollow fiber supports were prepared by dry-wet spinning technology. SrCo_0.8Fe_0.2O_3-_δ doped Nb₂O₅(SCFNb) was selected as membrane material, SCFNb/SBFM supported hollow fiber membranes were successfully prepared by a combined spin-spraying and co-sintering method. XRD, SEM, thermal expansion technique, oxygen permeability and membrane reaction tests were utilized to characterize the crystal phase structures, microstructure, sintering behavior, oxygen permeation flux, and reaction performance of membranes and/or supports, respectively. XRD patterns show that the membranes and supports are composed of perovskite main phase. SEM images indicate that the support has an asymmetric structure with a sponge-like microporous/finger-like porous structure. The membrane surface is dense and crack-free, and the membrane layer with a thickness of about 5 μm is well bonded with the support. At 900℃, the oxygen permeation flux of the membrane is 0.74 mL/(cm²·min). No degradation of performance is observed in the membrane reactor under partial oxidation of methane during continuously operating for 200 h at 850℃, and the oxygen permeation flux can reach 4.5 mL/(cm²·min). It is demonstrated that the SCFNb/SBFM supported hollow fiber membrane exhibits high oxygen permeation flux and good stability of the membrane reactor.

Key words: supported hollow fiber, mixed-conducting membrane, oxygen permeation, membrane reaction

中图分类号:

TQ174

刘郑堃, 朱佳伟, 金万勤. 担载型中空纤维混合导体氧渗透膜的制备与性能研究[J]. 无机材料学报, 2015, 30(6): 621-626.

LIU Zheng-Kun, ZHU Jia-Wei, JIN Wan-Qin. Preparation and Characterization of Mixed-conducting Supported Hollow Fiber Membrane[J]. Journal of Inorganic Materials, 2015, 30(6): 621-626.

图/表 7

图1 膜组件及膜反应器示意图

Fig. 1 Schematic diagram of membrane module and membrane reactor

图2 SCFNb膜层和SBFM支撑体的XRD图谱

Fig. 2 XRD patterns of SCFNb membrane and SBFM support

图3 膜层与支撑体的烧结收缩曲线和烧结速率曲线

Fig. 3 Shrinkage curves (a) and shrinkage rate curves (b) of SCFNb membrane layer and SBFM support layer

图4 担载型SCFNb/SBFM中空纤维氧渗透膜和支撑体的SEM照片

Fig. 4 SEM images of SCFNb/SBFM supported hollow fiber membrane (a) Cross section; (b) EDX analysis of cross section; (c) Outside surface of membrane; (d) Hollow fiber support

图5 担载型SCFNb/SBFM中空纤维氧渗透膜的氧渗透性能

Fig. 5 Temperature dependence of oxygen fluxes through SCFNb/SBFM supported hollow fiber

图6 担载型中空纤维膜的反应性能与温度关系

Fig. 6 CO selectivity, CH4 conversion, H2 /CO and O2 permeation flux as a function of temperature Reaction side: He = 20 mL/min, CH4 =3 mL/min; Air side: air = 150 mL/min

图7 担载型SCFNb/SBFM中空纤维氧渗透膜稳定性考察

Fig. 7 Long-term performance of reaction in the SCFNb/ SBFM supported hollow fiber membrane reactor at 850℃

参考文献 20

[1]	BOUWMEESTER H J M, BURGGRAAF A J. Fundamentals of Inorganic Membrane Science Technology. Elsevier, Amsterdam, 1996: 435-515.
[2]	JIN W Q, LI S G, HUANG P, et al.Preparation of an asymmetric perovskite-type membrane and its oxygen permeability.Journal of Membrane Science, 2001, 185(2): 237-243.
[3]	ITO W, NAGAI T, SAKON T.Oxygen separation from compressed air using a mixed conducting perovskite-type oxide membrane.Solid State Ionics, 2007, 178(11/12): 809-816.
[4]	KAWAHARA A, TAKAHASHI Y, HIRANO Y, et al.High oxygen permeation rate in La0.6Sr0.4Ti0.3Fe0.7O3-δ thin membrane on a porous support with multichannel structure for CH4 partial oxidation.Industrial & Engineering Chemistry Research, 2010, 49(12): 5511-5516.
[5]	FAN CHUAN-GANG, HUANG XIANG-XIAN, LIU WEI, et al.Preparation and oxygen permeation for SrCo0.8Fe0.2O3-δ tubular asymmetric membrane.Journal of Inorganic Materials, 2008, 23(6): 1221-1224.
[6]	ZYDORCZAK B, WU Z T, LI K.Fabrication of ultrathin La0.6Sr0.4Co0.2Fe0.8O3-δ hollow fibre membranes for oxygen permeation.Chemical Engineering Science, 2009, 64(21): 4383-4388.
[7]	WANG B, ZYDORCZAK B, POULIDI D, et al.A further investigation of the kinetic demixing/decomposition of La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen separation membranes.Journal of Membrane Science, 2011, 369(1/2): 526-535.
[8]	WU Z T, OTHMAN N H, ZHANG G R, et al.Effects of fabrication processes on oxygen permeation of Nb2O5-doped SrCo0.8Fe0.2O3-δ micro-tubular membranes.Journal of Membrane Science, 2013, 442(1): 1-7.
[9]	LIANG F Y, JIANG H Q, SCHIESTEL T, et al.High-purity oxygen production from air using perovskite hollow fiber membranes.Industrial & Engineering Chemistry Research, 2010, 49(19): 9377-9384.
[10]	CHEN XIN-ZHI, YU LING-HUI, LIU QIAO-SHENG, et al.Preparation and application of perovskite hollow fiber oxygen permeable membrane.Journal of Inorganic Materials, 2008, 23(6): 1216-1220.
[11]	LIAO Q, ZHENG Q, XUE J, et al.U-Shaped BaCo0.7Fe0.2Ta0.1O3-δ hollow-fiber membranes with high permeation for oxygen separation.Industrial & Engineering Chemistry Research, 2012, 51(46): 15217-15223.
[12]	TAN XIAO-YAO, MENG BO, YANG NAI-TAO.Preparation and characteristics of ceramic hollow fiber membranes for oxygen permeation.Journal of Inorganic Materials, 2006, 21(1): 245-249.
[13]	LIU N, TAN X Y, MENG B, et al.Honeycomb-structured perovskite hollow fibre membranes with ultra-thin densified layer for oxygen separation.Separation and Purification Technology, 2011, 80(2): 396-401.
[14]	PAN H P, LI L P, DENG X, et al.Improvement of oxygen permeation in perovskite hollow fibre membranes by the enhanced surface exchange kinetics.Journal of Membrane Science, 2013, 428(1): 198-204.
[15]	WANG H H, FELDHOFF A, CARO J, et al.Oxygen selective ceramic hollow fiber membranes for partial oxidation of methane.AIChE Journal, 2009, 55(10): 2657-2664.
[16]	JIANG W, ZHANG G R, LIU Z K, et al.A novel porous-dense dual-layer composite membrane reactor with long-term stability.AIChE Journal, 2013, 59(11): 4355-4363.
[17]	ZHANG G R, LIU Z K, ZHU N, et al.A novel Nb2O5-doped SrCo0.8Fe0.2O3-δ oxide with high permeability and stability for oxygen separation.Journal of Membrane Science, 2012, 405(1): 300-309.
[18]	LIU Z K, ZHANG G R, DONG X L, et al.Fabrication of asymmetric tubular mixed-conducting dense membranes by a combined spin-spraying and co-sintering process.Journal of Membrane Science, 2012, 415(1): 313-319.
[19]	QI LV, DONG XUE-LIANG, LIU ZHENG-KUN, et al.Preparation and oxygen permeation of SrCo0.4Fe0.4Zr0.2O3-δ mixed-conducting hollow fibre membrane.Journal of Inorganic Materials, 2010, 25(8): 871-876.
[20]	LIN Y S, BURGGRAAF A J.Experimental studies on pore size change of porous ceramic membranes after modification.Journal of Membrane Science, 1993, 79(1): 65-82.

担载型中空纤维混合导体氧渗透膜的制备与性能研究

Preparation and Characterization of Mixed-conducting Supported Hollow Fiber Membrane

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 20

相关文章 12

编辑推荐

Metrics

本文评价

[1]	刘雪娇, 何振宇, 吴昊, 骆婷, 孟夑, 陈初升, 占忠亮. 浸渍LaNi_0.6Fe_0.4O_3-_δ纳米颗粒对Zr_0.84Y_0.16O_2-_δ- La_0.8Sr_0.2Cr_0.5Fe_0.5O_3-_δ透氧膜性能的影响[J]. 无机材料学报, 2018, 33(1): 14-18.
[2]	张莉莉, 李可, 于称称, 张玉文, 吴成章, 丁伟中. Ag-Cu钎料与双相陶瓷透氧膜的润湿和界面反应研究[J]. 无机材料学报, 2016, 31(6): 607-612.
[3]	王芳, 梁春生, 徐大亮, 曹慧群, 孙宏元, 罗仲宽. 锂空气电池的研究进展[J]. 无机材料学报, 2012, 27(12): 1233-1242.
[4]	申梓刚，路朋献，胡行. 利用激光刻蚀技术提高Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ膜的透氧能力[J]. 无机材料学报, 2010, 15(2): 221-224.
[5]	张恒,董新法,林维明. Cu、Ti掺杂的SrFeO_3-δ 基混合导体透氧材料的制备与性能研究[J]. 无机材料学报, 2007, 22(1): 97-100.
[6]	谭小耀,孟波,杨乃涛. 陶瓷中空纤维透氧膜的制备与性能[J]. 无机材料学报, 2006, 21(1): 245-249.
[7]	宋红章,杨德林,胡婕,郝好山,胡行. 混合导电体Y_1-xLa_xBa₂Cu₃O_7-δ透氧膜的透氧性能研究[J]. 无机材料学报, 2006, 21(1): 199-203.
[8]	樊传刚,刘卫,江国顺,宋春林,陈初升. La_0.2Ba_0.8(Co_0.2Fe_0.8)_1-xZr_xO_3-δ透氧膜材料的微结构与氧分离性能研究[J]. 无机材料学报, 2004, 19(1): 121-126.
[9]	李光涛,邵宗平,熊国兴,董辉,丛铀,杨维慎. 几种混合导体陶瓷膜反应器的比较研究[J]. 无机材料学报, 2002, 17(5): 1041-1047.
[10]	吴平伟,高濂,郭景坤. 液-液界面上Gibbs膜反应技术制备CuS颗粒膜[J]. 无机材料学报, 2002, 17(4): 792-796.
[11]	张华,金江,余桂郁,杨南如,施剑林,冯景伟. La₂NiO_4+δ透氧膜材料的结构特点与性能[J]. 无机材料学报, 2001, 16(3): 440-446.
[12]	刘卫,章占平,夏长荣,谢津桥,陈初升. 多孔La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ的制备及表征[J]. 无机材料学报, 2000, 15(5): 849-854.