不同硅烷修饰的MFI分子筛膜及其H2/CO2分离性能
作者:陈冬冬, 张春, 洪周, 顾学红
单位: 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
关键词: MFI分子筛膜; 硅烷; CVD; H2/CO2分离
出版年,卷(期):页码: 2016,36(1):1-6

摘要:
通过NH4+离子交换的方法获得了HMFI分子筛膜, 采用在线化学气相沉积法(CVD)对其进行晶内孔道修饰, 以提高其对H2的分离选择性. 实验考察了四乙氧基硅烷(TEOS)、甲基二乙氧基硅烷(MDES)和三甲基乙氧基硅烷(TMES)三种不同尺寸修饰源对膜性能的影响. 结果表明, 尺寸较小的TMES更容易扩散进入分子筛膜的晶内孔道, 从而获得了更优的H2/CO2分离性能, 修饰后的膜在500 ℃下H2/CO2的分离因子可达45.9, H2的渗透性为1.43×10-7 mol/(m2?s?Pa). 同时, 通过质谱(MS)分析了TMES在HMFI分子筛孔道中的裂解行为, 探讨了硅烷修饰的的沉积机理。

 
On-stream chemical vapor deposition (CVD) method was carried out to modify HMFI zeolite membranes, which were obtained by NH4+ ion exchange to improve their hydrogen selective separation performance. The influence of silane size on the separation performance was investigated by using tetraethoxysilane (TEOS), methyldiethoxysilane (MDES) and trimethylethoxysilane (TMES). The results indicated that TMES with smaller size could more easily diffuse into zeolitic pores. The membrane modified by TMES achieved much higher H2/CO2 separation factor up to 45.9 with H2 permeance about 1.43×10-7 mol/(m2?s?Pa) at 500 ℃. Mass spectrometry (MS) was used to analyze the cracking products of TMES in HMFI zeolitic pores and deposition mechanism of modification with silane was discussed.
陈冬冬(1989-), 男, 河南商丘人, 在读硕士, 从事膜材料制备与应用. 通讯联系人

参考文献:
 [1] Momirlan M, Veziroglu T N. The properties of hydrogen as fuel tomorrow in sustainable energy system for a cleaner planet [J]. Int J Hydrogen Energy, 2005, 30(7):795 – 802.
[2] 陈长聘. 氢能未来与储氢金属材料技术 [J]. 氯碱工业, 2003, 5:1 – 3.
[3] Ockwig N W, Nenoff T M. Membranes for hydrogen separation [J]. Chem Rev, 2007, 107(10):4078 – 4110.
[4] 袁欣, 王明臣, 孙明峰, 等. 氢气变压吸附提纯单元改造探讨 [J]. 乙烯工业, 2010, 22(3):20 – 23.
[5] Bernhard D P, Rowles H C, Moss J A, et al. Increased olefins production via recovery of refinery gas hydrocarbons [R]. OSTI Identifier: 6533113, No. CONF-880319-, Washington, DC, NPRA, 1988.
[6] Adhikari S, Fernando S. Hydrogen membrane separation techniques [J]. Ind Eng Chem Res, 2006, 45(3):875 – 881.
[7] Masuda T, Fukumota N, Kitamura M, et al. Modification of pore size of MFI-type zeolite by catalytic cracking of silane and application to preparation of H2 separation zeolite membrane [J]. Micropor Mesopor Mater, 2001, 48(1/3):239 – 245.
[8] Hong M, Falconer J L, Noble RD. Modification of zeolite membranes for H2 separation by catalytic cracking of methyldieth oxysilane [J]. Ind Eng Chem Res, 2005, 44(11):4035 – 4041.
[9] Zhu X, Wang H, Lin Y S. Effect of the membrane quality on gas permeation and chemical vapor deposition modification of MFI-type zeolite membranes [J]. Ind Eng Chem Res, 2010, 49(20):10026 – 10033.
[10] Wang H, Lin Y S. Synthesis and modification of ZSM-5/silicalite bilayer membrane with improved hydrogen separation performance [J]. J Membr Sci, 2012, 396:128 – 137.
[11] Wang H, Lin Y S. Effects of synthesis conditions on MFI zeolite membrane quality and catalytic cracking deposition modification results [J]. Micropor Mesopor Mater, 2011, 142(2):481 – 488.
[12] Gu X H, Tang Z, Dong J H. On-stream modification of MFI zeolite membranes for enhancing hydrogen separation at high temperature [J]. Micropor Mesopor Mater, 2008, 111 (1):441 – 448.
[13] Hong Z, Sun F, Chen D D, et al. Improvement of hydrogen-separating performance by on-stream catalytic cracking of silane over hollow fiber MFI zeolite membrane [J]. Int J Hydrogen Energy, 2013, 38 (20):8409 – 8414.
[14] Hong Z, Wu Z J, Zhang Y T, et al. Catalytic cracking deposition of methyldiethoxysilane for modification of  zeolitic pores in MFI/α-Al2O3 zeolite membrane with H+ ion exchange pretreatment [J]. Ind Eng Chem Res, 2013, 52(36), 13113 − 13119.
[15] 吴再娟, 洪周, 张玉亭, 等. MFI型分子筛膜晶内孔道的在线CVD调变 [J]. 南京工业大学学报, 2013, 35(4):43 – 47.
 
 

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