膜科学与技术

钯复合膜表面缺陷修饰材料的研究

作者：徐天莹，俞佳枫，张继新，徐恒泳

单位：中科院大连化学物理研究所，大连，116023

关键词：金属钯复合膜；透氢性能；分子筛；氧化铝；缺陷

出版年,卷(期):页码： 2015,35(2):30-35

摘要：

利用钯膜分离氢是高纯或超纯氢气生产的主要方式，然而，钯膜表面缺陷是影响氢分离纯度的主要因素。本文选择NaA分子筛和γ-Al2O3两种缺陷填充材料对初镀后的钯膜表面缺陷进行修饰，发现两种材料修饰后钯膜透氮量分别下降了57和2倍，NaA分子筛材料修饰后钯膜的透氮量为未修饰钯膜的1/2500。经过补镀和活化后，在相同钯膜厚度（2.5µm）条件下，三种钯膜透氮量分别为1.91×10-2、6.12×10-3和4.89×10-3 m3/h·m2·bar[改成标准单位mPa]。不同修饰材料修饰的钯膜的氢氮分离因子顺序为NaA分子筛 > γ-Al2O3 > 无修饰，说明通过修饰钯膜缺陷的方法可提高钯膜的氢分离选择性，且用NaA分子筛材料要优于γ-Al2O3材料，因为NaA分子筛在缺陷中可根据缺陷形状原位生长，更能有效填补缺陷。NaA分子筛材料修饰后的钯膜经过20次300-400℃以及0.1-1.0MPa的温度和压力循环仍保持性能不变，具有较高的稳定性。

were used to modify the defects of palladium membrane. The performances of unmodified ultra-thin palladium membrane and those modified by NaA zeolite and γ-Al2O3 were investigated. The results showed that, the nitrogen permeations decreased 57 and 2 times after modified by NaA zeolite and γ-Al2O3, respectively. After second electroless plating and activation, the nitrogen permeations of palladium membrane with the same thickness modified by NaA zeolite was 1/2500 of the unmodified membrane. The nitrogen permeations of these three palladium membranes were 1.9108×10-2 , 6.115×10-3 and 4.892×10-3m3/h·m2·bar. The H2/N2 selectivity of palladium membranes followed the order of NaA zeolite-modified > γ-Al2O3-modified > unmodified. It was indicated that the performance of palladium membrane can be improved by modification. And the performances of palladium membrane modified by NaA zeolite were better than γ-Al2O3. In the stability tests of NaA zeolite modified palladium membrane, the purity of hydrogen remained stable during 20 cycles of temperature and pressure changes in the range of 300-400°C and 0.1-1.0 MPa.

徐天莹（1988-），女，黑龙江省哈尔滨人，硕士，从事钯膜制备及钯膜性能评价研究.

参考文献：

[1] Nong Xu, Shinkun Ryi, Anwu Li., Improved pre-treatment of porous stainless steel substrate for preparation of Pd-based composite membrane.[J]. The Canadian Journal of Chemical Engineering, 2013, 91(10):1695~1701.
[2] Cornaglia Carolina A，Tosti Silvano，Sansovini Mirko et al., Novel catalyst for the WGS reaction in a Pd-membrane reactor .[J]. Applied Catalysis A General, 2013, 462:278~286.
[3] Garcia-Garcia F. R., Soria M. A., Mateos-Pedrero C. et al., Dry reforming of methane using Pd-based membrane reactors fabricated from different substrates.[J]. Journal of Membrane Science, 2013, 435:218~225.
[4] Hwang Kyung-Ran, Lee Sung-Wook, Ryi Shin-Kun et al., Water-gas shift reaction in a plate-type Pd-membrane reactor over a nickel metal catalyst.[J]. Fuel Processing Technology, 2013, 106:133~140.
[5] Chen Wei-Hsin, Hsia Ming-Hsien, Lin Yu-Li et al., Hydrogen permeation and recovery from H2-N2 gas mixtures by Pd membranes with high permeance.[J]. International Journal of Hydrogen Energy, 2013, 38(34):14730~14742.
[6] Tanczyk Marek, Gosiewski Krzysztof, Separation properties of membranes in membrane reactors for conversion of CO with simultaneous H2 recovery.[J]. Przemysl Chemiczny, 2012, 91(12):2419~2421.
[7] 李安武，熊国兴，R Hughes，致密钯膜中缺陷的修补.[J]. 中国科学B辑, 1999, 29(2):169~173.
[8] Uemiya S, Sato N., Ando H. et al., Separation of hydrogen through palladium thin film supported on a porous glass tube.[J]. Journal of Membrane Science, 1991, 56:303~313.
[9]胡小娟，魏娟，黄彦，Pd(OH)2 胶体预处理及化学镀法修补复合Pd膜.[J]. 南京工业大学学报， 2011 (3):43~48.
[10] Li Anwu, Liang Weiqiang, Hughes Ronald, Repair of a Pd/α-Al2O3 composite membrane containing defects. [J]. Separation and Purification Technology, 1999,15(2):113~119.
[11] Li Anwu, Liang Weiqiang, Hughes Ronald, Fabrication of defect-free Pd/γ-Al2O3 composite membranes for hydrogen separation.[J]. Thin Solid Films, 1999, 359(1-2):106~112.
[12] 徐恒泳，袁立祥，一种修饰补钯及钯合金复合膜缺陷的方法[P].中国，申请号：200810104368.7
[13] Zeng Gaofeng, Goldbach Andreas, Xu Hengyong, Defect sealing in Pd membranes via point-plating .[J]. Journal of Membrane Science, 2009, 328:6~10.
[14] Bosko M.L., Múnera J.F., Lombardo E.A. et al., Dry reforming of methane in membrane reactors using Pd and Pd–Ag composite membranes on a NaA zeolite modified porous stainless steel support.[J]. Journal of Membrane Science, 2010, 364(1-2): 17~26.
[15] 唐春华，邵炜，徐恒泳，超薄金属钯复合膜表面缺陷修饰的研究.[J]. 天然气化工， 2009(34) :10~16.
[16] 徐恒泳，侯守福，李文钊等，一种复合金属钯膜或合金钯膜及其制备方法[P].中国，专利号：200410021025.6
[17] 徐恒泳，唐春华，李春林，葛庆杰.一种高透氢选择性金属钯复合膜的制备方法[P].中国，专利号：200810013153.4.2014.10.01.
[18] Tong J. H., Matsumura Y., Thin Pd membrane prepared on macroporous stainless steel tube filter by an in-situ multi-dimensional plating mechanism.[J]. Chemical Communications, 2004, 21: 2460~2461.

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