Langmuir-Blodgett法制备高H2选择性取向ZSM-5分子筛分离膜

doi:10.16085/j.issn.1000-6613.2020-1040

化工进展 ›› 2021, Vol. 40 ›› Issue (4): 2243-2250.DOI: 10.16085/j.issn.1000-6613.2020-1040

Langmuir-Blodgett法制备高H₂选择性取向ZSM-5分子筛分离膜

刘艳¹(), 年佩¹, 张轩¹, 黄锐¹, 王政¹(), 姜男哲²()

^1.省部共建煤炭高效利用与绿色化工国家重点实验室，化学国家级实验教学示范中心，宁夏大学化学化工学院，宁夏银川 750021
^2.延边大学理学院化学系，吉林延吉 133002

收稿日期:2020-06-09 出版日期:2021-04-05 发布日期:2021-04-14
通讯作者: 王政,姜男哲
作者简介:刘艳（1994—），女，硕士研究生，研究方向为沸石分子筛膜的合成与应用。E-mail：ly18395275479@163.com。
基金资助:
国家自然科学基金(21766026);宁夏科技领军人才项目(KJT2016001);宁夏回族自治区国内一流学科建设项目(NXYLXK2017A04);国能宁煤有限责任公司和宁夏煤基合成树脂高值化产业技术协同创新中心项目(2017DC57)

Fabrication of oriented ZSM-5 zeolite membrane with high H₂ selectivity by Langmuir-Blodgett technique

LIU Yan¹(), NIAN Pei¹, ZHANG Xuan¹, HUANG Rui¹, WANG Zheng¹(), JIANG Nanzhe²()

^1.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Department of Chemistry, College of Science, Yanbian University, Yanji 133002, Jilin, China

Received:2020-06-09 Online:2021-04-05 Published:2021-04-14
Contact: WANG Zheng,JIANG Nanzhe

摘要/Abstract

摘要：

利用Langmuir-Blodgett（LB）技术首先在多孔氧化铝载体表面有序组装了单层b-轴取向Silicalite-1分子筛晶种层，再采用二次生长法，以溴化六丙双铵（dimer-TPABr）为结构导向剂配制二次生长合成液，在175℃反应48h制备了高度b-轴取向ZSM-5（Si/Al=120）分子筛膜。扫描电镜（SEM）表征显示ZSM-5分子筛膜致密连续且厚度约为2.6μm。X射线衍射（XRD）表征结果显示，膜的b-轴晶体优先取向值高达0.858。气体分离性能测试结果显示，制备的ZSM-5分子筛膜在高温焙烧脱除有机模板剂过程中会产生缺陷。经硅烷试剂四甲氧基硅烷（TMOS）对缺陷修复后，ZSM-5分子筛膜表现出高的H₂选择性分离性能，H₂/CO₂分离因子高达68 （T=25℃，p=0.1MPa），对应的H₂渗透速率为1.36×10^-8mol/(m²·s·Pa)。

关键词: 取向ZSM-5分子筛膜, 分子筛膜, Langmuir-Blodgett技术, 氢气/二氧化碳分离

Abstract:

Langmuir-Blodgett (LB) technology was used to assemble a highly b-oriented silicalite-1 seed monolayer on porous alumina disk surface. Then, a continuously and highly compact ZSM-5 (Si/Al=120) membrane was fabricated after 48h crystallization at 175℃ by using dimer-TPABr as the structure direct agent during the secondary growth procedure. The SEM results showed that the thickness of ZSM-5 zeolite membrane was about 2.6μm. XRD results revealed that the ZSM-5 zeolite membrane was highly b-oriented and the crystallographic preferred orientation (CPO) indices was 0.858. The gas separation performance test results showed that the prepared ZSM-5 zeolite membrane would produce defects in the calcination process of organic template removal at high temperature. The ZSM-5 membrane showed excellent selective gas separation performance for H₂ after tetramethoxysilane (TMOS) modification for defects. The separation selectivity of H₂/CO₂ mixture was as high as 68 (T=25℃,p=0.1MPa), and the corresponding H₂ permeation rate was 1.36×10^-8mol/(m²·s·Pa).

Key words: oriented ZSM-5 membrane, zeolite membrane, Langmuir-Blodgett technology, H₂/CO₂ separation

中图分类号:

TQ028.8

刘艳, 年佩, 张轩, 黄锐, 王政, 姜男哲. Langmuir-Blodgett法制备高H₂选择性取向ZSM-5分子筛分离膜[J]. 化工进展, 2021, 40(4): 2243-2250.

LIU Yan, NIAN Pei, ZHANG Xuan, HUANG Rui, WANG Zheng, JIANG Nanzhe. Fabrication of oriented ZSM-5 zeolite membrane with high H₂ selectivity by Langmuir-Blodgett technique[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2243-2250.

图/表 7

图1 LB法在α-Al2O3载体表面组装silicalite-1型分子筛晶种层的扫描电镜图和X射线衍射图

图2 未焙烧ZSM-5分子筛膜的表面、截面的扫描电镜图和膜的X射线衍射图

图3 焙烧后ZSM-5分子筛膜的表面扫描电镜图、TMOS修复后ZSM-5分子筛膜的表面及截面扫描电镜图

图4 未修复ZSM-5分子筛膜在0.1MPa和不同压力下的单组分渗透速率

图5 修复后ZSM-5膜在0.1MPa和不同压力下的单组分渗透速率

图6 修复前和修复后ZSM-5分子筛膜的H2/CO2混合气分离性能

表1 ZSM-5分子筛膜与MFI型分子筛膜的H2/CO2分离性能比较

MFI膜类型	测试温度/℃	H₂/CO₂分离因子	H₂渗透速率/mol·m^-2·s^-1·Pa^-1	参考文献
silicalite-1	450	123	2.20×10^-7	[36]
silicalite-1	200	4.6	3.37×10^-5	[37]
silicalite-1	500	45.6	1.00×10^-8	[38]
silicalite-1	500	42.6	2.82×10^-7	[39]
silicalite-1	25	3.5	1.03×10^-6	[40]
ZSM-5	450	17.5	1.86×10^-7	[41]
B-ZSM-5	200	37	3.97×10^-7	[34]
ZSM-5	450	25.3	1.15×10^-7	[42]
ZSM-5	25	15.9	3.43×10^-8	本研究（修复前）
ZSM-5	25	68	1.36×10^-8	本研究（修复后）

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Langmuir-Blodgett法制备高H₂选择性取向ZSM-5分子筛分离膜

Fabrication of oriented ZSM-5 zeolite membrane with high H₂ selectivity by Langmuir-Blodgett technique

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