直孔三明治结构GDC-LSF双相复合透氧膜制备和性能研究

doi:10.15541/jim20200421

摘要/Abstract

摘要：

致密陶瓷透氧膜因在氧气制备和涉氧化工过程中的潜在重要应用而备受关注。本研究采用相转化流延/叠层/烧结工艺制备了三明治结构Gd_0.1Ce_0.9O_2-_δ-La_0.6Sr_0.4FeO_3-_δ(GDC-LSF)双相复合陶瓷透氧膜, 其中部为起氧分离作用、厚度80 μm的致密功能层, 两侧为厚度420 μm的直孔结构支撑层。采用浸渍法在支撑层内壁修饰Nd₂NiO₄₊_δ(NNO)纳米颗粒。在膜的一侧通入空气, 另一侧通入氦气作为载气, 测得900 ℃时氧渗透通量高达1.53 mL·cm^-2·min^-1。将氦气切换为CO₂, 测得氧渗透通量为0.6 mL·cm^-2·min^-1, 氧渗透在长达90 h的时间内保持稳定。该透氧膜经历70余次热循环(800~900 ℃)后仍保持完好。本研究表明: 直孔三明治结构GDC-LSF透氧膜具有良好的氧渗透性能、化学稳定性和热机械性能, 有望用于氧气分离和富氧燃烧/CO₂捕获。

关键词: 氧分离膜, 双相复合材料, 相转化流延, 浸渍, 直孔, 三明治结构

Abstract:

The dense ceramic oxygen-permeable membrane has attracted much attention due to its potential applications in production of oxygen from air and manipulation of oxygen-consuming industrial chemical processes. In the present study, Gd_0.1Ce_0.9O_2-_δ-La_0.6Sr_0.4FeO_3-_δ (GDC-LSF) dual-phase composite membrane was prepared using the phase-inversion tape casting/lamination/sintering method. The as-prepared membrane consisted of an 80 μm thick dense oxygen separation layer sandwiched between two 420 μm thick finger-like porous support layers. The inner surface of the support layers was further modified with Nd₂NiO₄₊_δ (NNO) nanoparticles using the impregnation method. An oxygen permeation flux of 1.53 mL·cm^-2·min^-1 was measured at 900 ℃ by exposing one side of the membrane to a flowing air stream and the other side to a flowing He stream. When CO₂ was used as sweep gas, an oxygen permeation flux of 0.6 mL·cm^-2·min^-1 was obtained, and no decrease in the flux was observed during 90 h of testing. The membrane remained intact after experiencing over 70 thermal cycles between 800 and 900 ℃. GDC-LSF dual-phase composite membrane with straight pores and sandwich structure has demonstrated satisfactory combination of oxygen permeability, chemical stability and thermal mechanical strength, promising for applications in separation of oxygen from air and oxy-fuel combustion with CO₂ capture.

Key words: oxygen-permeable membrane, dual-phase composite, phase-inversion tape casting, impregnation, straight pores, sandwich structure

中图分类号:

TQ174

郑启凡, 黎超群, 班孝款, 占忠亮, 陈初升. 直孔三明治结构GDC-LSF双相复合透氧膜制备和性能研究[J]. 无机材料学报, 2021, 36(5): 497-501.

ZHENG Qifan, LI Chaoqun, BAN Xiaokuan, ZHAN Zhongliang, CHEN Chusheng. Preparation and Property of GDC-LSF Dual-phase Composite Membrane with Straight Pores and Sandwich Structure[J]. Journal of Inorganic Materials, 2021, 36(5): 497-501.

图/表 9

图1 GDC-LSF透氧膜制备流程图

Fig. 1 Schematic diagram of GDC-LSF membrane preparation process

表1 相转化流延支撑层浆料组成(wt%)

Table 1 Composition of the slurries for the support prepared by phase-inversion tape casting (wt%)

Composition	Slurry 1 (Top)	Slurry 2 (Bottom)
GDC	35.92	-
LSF	20.58	-
Graphite	13.50	60.00
NMP	24.83	33.10
PESf	4.14	5.52
PVP	1.03	1.38

表2 普通流延致密层浆料组成(wt%)

Table 2 Composition of the slurries for the dense layer prepared by conventional tape casting (wt%)

Composition	Weight percentage
GDC	36.33
LSF	20.80
Ethanol	16.80
2-Butanone	12.60
TEOA	1.72
PVB	5.75
PEG-400	3.00
DBP	3.00

图2 氧渗透测量装置示意图

Fig. 2 Experimental setup for oxygen permeation measurements

图3 GDC-LSF透氧膜的XRD图谱

Fig. 3 XRD patterns of GDC-LSF membranes

图4 GDC-LSF透氧膜的SEM照片

Fig. 4 SEM images of GDC-LSF membrane (a) Cross-section of the support green tape; (b) Cross-section of the sintered membrane; (c) Top-view of the support; (d) Magnified view of the NNO nano-particles in the support

图5 氧渗透通量的阿伦尼乌斯曲线

Fig. 5 Oxygen permeation flux as a function of temperature when using He as sweep gas

图6 不同气氛下各样品的归一化的电导弛豫曲线及拟合曲线(850 ℃)(a)和800~900 ℃下表面氧交换系数的阿伦尼乌斯曲线(b)

Fig. 6 Electrical conductivity relaxation curves (normalized conductivity as a function of time) of GDC-LSF bar at 850 ℃ (a) and Arrhenius plots of the surface exchange coefficient at 800-900 ℃ (b) (1 bar=105 Pa)

图7 900 ℃时GDC-LSF氧渗透通量与时间的关系

Fig. 7 Temporal dependence of oxygen permeation flux of GDC-LSF membrane at 900 ℃

参考文献 18

[1]	DYER P N, RICHARDS R E, RUSSEK S L, et al. Ion transport membrane technology for oxygen separation and syngas production. Solid State Ionics, 2000,134(1/2):21-33.
[2]	TONZIELLO J, VELLINI M. Oxygen production technologies for IGCC power plants with CO₂ capture. Energy Procedia, 2011,4:637-644.
[3]	ZENG Q, ZUO Y B, FAN C G, et al. CO₂-tolerant oxygen separation membranes targeting CO₂ capture application. Journal of Membrane Science, 2009,335(1/2):140-144.
[4]	MENG Y Q, HE W, LI X X, et al. Asymmetric La_0.6Sr_0.4Co_0.2Fe_0.8O₃-_δ membrane with reduced concentration polarization prepared by phase-inversion tape casting and warm pressing. Journal of Membrane Science, 2017,533:11-18.
[5]	SHAO Z P, YANG W S, CONG Y, et al. Investigation of the permeation behavior and stability of a Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃-_δ oxygen membrane. Journal of Membrane Science, 2000,172(1/2):177-188.
[6]	YI J X, SCHROEDER M, WEIRICH T, et al. Behavior of Ba(Co, Fe, Nb)O₃-_δ perovskite in CO₂-containing atmospheres: degradation mechanism and materials design. Chemistry of Materials, 2010,22(23):6246-6253.
[7]	LIU J J, LIU T, WANG W D, et al. Zr_0.84Y_0.16O_1.92- La_0.8Sr_0.2Cr_0.5Fe_0.5O₃-_δ dual-phase composite hollow fiber membrane targeting chemical reactor applications. Journal of Membrane Science, 2012,389:435-440.
[8]	KHARTON V V, KOVALEVSKY A V, VISKUP A P, et al. Oxygen transport in Ce_0.8Gd_0.2O₂-_δ-based composite membranes. Solid State Ionics, 2003,160(3/4):247-258.
[9]	KHARTON V V, KOVALEVSKY A V, VISKUP A P, et al. Oxygen permeability of Ce_0.8Gd_0.2O₂-_δ-La_0.7Sr_0.3MnO₃-_δ composite membranes. Journal of The Electrochemical Society, 2000,147(7):2814-2821. DOI URL
[10]	HONG L, CHEN X F, CAO Z D. Preparation of a perovskite La_0.2Sr_0.8CoO₃-_x membrane on a porous MgO substrate. Journal of the European Ceramic Society, 2001,21(12):2207-2215.
[11]	IKEGUCHI M, ISHII K, SEKINE Y, et al. Improving oxygen permeability in SrFeCo_0.5O_x asymmetric membranes by modifying support-layer porous structure. Materials Letters, 2005,59(11):1356-1360. DOI URL
[12]	BÜCHLER O, SERRA J M, MEULENBERG W A, et al. Preparation and properties of thin La₁-_xSr_xCo₁-_yFe_yO₃-_δ perovskitic membranes supported on tailored ceramic substrates. Solid State Ionics, 2017,178(1/2):91-99. DOI URL
[13]	CHANG X F, ZHANG C, JIN W Q, et al. Match of thermal performances between the membrane and the support for supported dense mixed-conducting membranes. Journal of Membrane Science, 2006,285(1):232-238. DOI URL
[14]	FANG W, STEINBACH F, CAO Z W, et al. A highly efficient sandwich-like symmetrical dual-phase oxygen-transporting membrane reactor for hydrogen production by water splitting. Angewandte Chemie International Edition, 2016,55(30):8648-8651. URL PMID
[15]	LIN Q Y, LIN J, LIU T, et al. Solid oxide fuel cells supported on cathodes with large straight open pores and catalyst-decorated surfaces. Solid State Ionics, 2018,323:130-135. DOI URL
[16]	CHENG J G, ZHA S W, HUANG J, et al. Sintering behavior and electrical conductivity of Ce_0.9Gd_0.1O_1.95 powder prepared by the gel-casting process. Materials Chemistry and Physics, 2003,78(3):791-795. DOI URL
[17]	STEELE B C H. Appraisal of Ce₁-_yGd_yO₂-_y_/2 electrolytes for IT-SOFC operation at 500 ℃. Solid State Ionics, 2000,129(1-4):95-110. DOI URL
[18]	LUO H X, EFIMOV K, JIANG H Q, et al. CO₂-stable and cobalt-free dual-phase membrane for oxygen separation. Angewandte Chemie International Edition, 2011,50(3):759-763. URL PMID