膜科学与技术

异丁基修饰的微孔二氧化硅膜制备及氢气分离性能

作者：张少康，韦奇，李群艳，聂祚仁，刘亚军

单位：北京工业大学材料科学与工程学院，北京100124

关键词：异丁基；有机-无机杂化微孔二氧化硅膜；孔结构；氢气分离

出版年,卷(期):页码： 2016,36(4):46-53

摘要：

以正硅酸乙酯(TEOS)和异丁基三乙氧基硅烷(iTES)为前驱体，通过溶胶-凝胶法在酸性条件下制备了异丁基修饰的二氧化硅溶胶，并采用浸渍提拉法在?-Al2O3/?-Al2O3支撑体上制备了异丁基修饰的微孔二氧化硅膜材料。分别通过动态光散射技术、接触角测量、红外光谱、核磁共振以及N2吸附等测试手段对溶胶的粒径分布、膜材料的疏水性能以及孔结构进行了表征，并深入研究了异丁基修饰膜材料的氢气渗透和分离性能。结果表明，当摩尔比n(iTES)/n(TEOS)=0.6时，溶胶的平均粒径约为5.1nm，膜材料的孔径狭窄分布在0.45~0.8nm，其对水的接触角达到(114.0±0.5)°。H2在膜材料中的渗透率随测试温度的升高而增大，300°C时达到9.07×10-7mol•m-2•s-1•Pa-1，H2/CO2和H2/CO的理想分离系数分别为6.79和15.37，双组份混合气体分离系数分别为7.09和15.72，均高于对应的Knudsen扩散分离因子，H2在膜材料中的输运主要遵循活化扩散机理。在250°C水蒸气物质的量含量为5%的环境中陈化200h后，异丁基修饰的SiO2膜具有良好的水热稳定性。

An isobutyl-modified silica sol was synthesized by the co-hydrolysis and condensation of tetraethyl orthosilicate(TEOS) and isobutyltriethoxysilane(iTES) under acidic condition and the sol was deposited on the ?-Al2O3/?-Al2O3 support by dip-coating in clean room(Grade 100).The particle size distribution of silica sol, the hydrophobic properties and the pore size distribution of the silica membranes were characterized by means of dynamic light scattering(DLS), water contact angle measurement, Fourier translation infrared spectroscopy(FT-IR), solid state 29Si magic-angle spinning nuclear magnetic resonance(29Si MAS NMR) and N2 adsorption-desorption. The hydrogen permeation and separation performance of modified silica membranes were also investigated in detail. The results show that the particle size of silica sol increases with increasing iTES/TEOS molar ratio, reaching 5.1nm at an iTES/TEOS molar ratio of 0.6. Isobutyl groups have been successfully incorporated into silica membranes, leading to an enhanced hydrophobic property with a water contact angle as high as (114.0±0.5)° for the modified membranes. The modified silica membranes possess a microporous structure with a pore size centered at 0.45~0.8nm.The hydrogen permeance increases with increasing temperatures, indicating that the hydrogen transport in modified silica membranes complies predominantly with activated diffusion mechanism. At a temperature of 300°C, the modified membranes exhibit a significantly high H2permeance of 9.07×10-7 mol•m-2•s-1•Pa-1, a H2/CO2 and H2/COpermselectivity of 6.79 and 15.37, a H2/CO2and H2/CObinary gas mixture separation factor of 7.09 and 15.72, respectively, both higher than that of Knudsen diffusion.Under a humid condition with a temperature of 250°C and a water vapor molar ratio of 5% for at least 200 hours, the modified membranes possess an outstanding hydrothermal stability.

第一作者简介：张少康（1988-），男，河北石家庄人，硕士生，从事用于气体分离的二氧化硅膜材料的制备与表征.*通讯作者，E-mail:qiwei@bjut.edu.cn

参考文献：

[1]Li Gang, Kanezashi M, TsuruT. Preparation of organic–inorganic hybrid silica membranes using organoalkoxysilanes: The effect of pendant groups[J]. Journal of Membrane Science,2011, 379: 287-295
[2]QureshiH F, NijmeijerA, WinnubstL. Influence of sol–gel process parameters on the micro-structure and performance of hybrid silica membranes[J]. Journal of Membrane Science, 2013, 446: 19-25
[3] KanezashiM, MiyauchiS, NagasawaH, et al. Pore size control of Al-doping into bis(triethoxysilyl) methane (BTESM)-derived membranes for improved gas permeation properties[J], RSC Advances, 2013, 3: 12080-12083
[4]刘相革,韦奇, 丁元利, 等. 十三氟辛基修饰的疏水有机-无机杂化二氧化硅膜孔结构、氢气分离及水热稳定性[J].无机化学学报, 2014, 30(5): 1111-1118
[5] LiuLiang, Wang D K, MartensD L, et al. Binary gas mixture and hydrothermal stability investigation of cobalt silica membranes[J]. Journal of Membrane Science,2015, 493: 470-477
[6]deVosRM,Verweij H. High-Selectivity, high-flux silica membranes for gas separation[J]. Science, 1998, 279: 1710-1711
[7]Kanezashi M, Yada K, Yoshioka T, et al. Organic-inorganic hybrid silica membranes with controlled silica network size: Preparation and gas permeation characteristics[J]. Journal of Membrane Science, 2010, 348: 310-318
[8]Kanezashi M, Kawano M, Yoshioka T, et al. Organic-inorganic hybrid silica membranes with controlled silica network size for propylene/propane separation[J]. Industrial & Engineering Chemistry Research, 2012, 51(2): 944-953
[9]Castricum H L, Qureshi H F, Nijmeijer A, et al. Hybrid silica membranes with enhanced hydrogen and CO2 separation properties[J]. Journal of Membrane Science,2015, 488: 121-128
[10] 王艳丽, 韦奇, 于春晓, 等. 乙烯基修饰的微孔二氧化硅膜孔结构与疏水性研究[J]. 无机材料学报, 2007, 22(5): 949-953
[11] 李振杰, 韦奇, 魏娜娜, 等. 苯基修饰的疏水微孔二氧化硅膜的制备与表征[J]. 高等学校化学学报, 2010, 31(12): 2482-2487
[12] 宋霖, 韦奇, 郝润秋, 等. 十七氟癸基修饰的有机-无机杂化二氧化硅膜材料的制备及气体分离性能[J]. 高等学校化学学报, 2012, 33(8): 1670-1675
[13] 王学伟, 韦奇, 洪志发, 等. 三氟丙基修饰的有机-无机杂化二氧化硅膜制备、氢气分离及水热稳定性能[J]. 化学学报, 2012,70: 2529-2535
[14]de Vos R M, Maier W F, Verweij H. Hydrophobic silica membranes for gas separation[J]. Journal of Membrane Science,1999, 158: 277-288
[15]洪志发, 韦奇, 李国华, 等.三氟丙基修饰的二氧化硅膜制备、氢气分离及其水热稳定性[J]. 无机化学学报, 2013, 29(5): 941-947
[16] Qi Wei, Yuan-Li Ding, Zuo-Ren Nie, et al. Wettability, pore structure and performance of perfluorodecyl-modified silica membranes[J]. Journal of Membrane Science,2014, 466: 114-122
[17]Kanezashi M, Yada K, Yoshioka T, et al.Design of silica networks for development of highly permeable hydrogen separationmembranes with hydrothermal stability[J]. Journal of the American Chemical Society,2009, 131(2): 414-415
[18] Wang Y Q, Yang C M, Zibrowius B, et al. Directing the formation of vinyl-functionalized silica to the hexagonal SBA-15 or large-pore ia3d structure[J]. Chemistry of Materials,2003, 15: 5029-5035
[19]Chong A S M, Zhao X S, Kustedjo A T, et al. Functionalization of large-pore mesoporous silicas with organosilanes by direct synthesis[J]. Microporous and Mesoporous Materials,2004, 72: 33-42
[20]Wei Qi, Chen Hui Qiao, NieZuo Ren, et al. Preparation and characterization of vinyl-functionalized mesoporousSBA-15 silica by a direct synthesis method[J]. Materials Letters,2007, 61: 1469-1473
[21]Wei Qi, Wang Yan Li, NieZuo Ren, et al. Facile synthesis of hydrophobic microporous silica membranes and their resistance to humid atmosphere[J]. Microporous and Mesoporous Materials,2008, 111: 97-103
[22]Wei Qi, WangFei, NieZuo Ren, et al. Highly hydrothermally stable microporous silica membranes for hydrogen separation[J]. Journal of Physical Chemistry B,2008, 112: 9354-9359
[23]Yang Dong Jiang, Li Jun Ping, Xu Yao, et al. Direct formation of hydrophobic silica-based micro/mesoporous hybrids from polymethylhydrosiloxane and tetraethoxysilane[J]. Microporous and Mesoporous Materials,2006, 95: 180-186
[24] 段小勇, 韦奇, 何俊, 等. 表面修饰的有机-无机杂化微孔SiO2膜的制备及氢气分离性能[J]. 高等学校化学学报, 2011, 32(10): 2256-2261
[25] Dong Jun Hang,Lin Y S,Kanezashi M, et al. Microporous inorganic membranes for high temperature hydrogenpurification[J]. Journal of Applied Physics, 2008, 104: 121301

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com