含氟体系下亲水性ZSM-5沸石分子筛膜的制备及其性能

doi:10.15541/jim20150192

无机材料学报 ›› 2015, Vol. 30 ›› Issue (11): 1167-1171.DOI: 10.15541/jim20150192 CSTR: 32189.14.10.15541/jim20150192

含氟体系下亲水性ZSM-5沸石分子筛膜的制备及其性能

李良清, 张闻煦, 杨建华, 鲁金明, 殷德宏, 王金渠

(大连理工大学精细化工国家重点实验室, 吸附与无机膜研究所, 大连116024)

收稿日期:2015-04-22 修回日期:2015-05-27 出版日期:2015-11-20 网络出版日期:2015-10-20
作者简介:李良清(1988–), 男, 博士研究生. E-mail: lilq@mail.dlut.edu.cn
基金资助:
国家高新技术研究发展计划(863计划)(2015AA03A602);国家自然科学基金(21376036)

Preparation and Characterization of Water Perm-selectivity ZSM-5 Zeolite Membrane Using Fluoride Route

LI Liang-Qing, ZHANG Wen-Xu, YANG Jian-Hua, LU Jin-Ming, YIN De-Hong, WANG Jin-Qu

(Institute of Adsorption and Inorganic Membrane, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China)

Received:2015-04-22 Revised:2015-05-27 Published:2015-11-20 Online:2015-10-20
About author:LI Liang-Qing. E-mail: lilq@mail.dlut.edu.cn
Supported by:
National High Technology Research and Development Program of China (2015AA03A602);National Natural Science Foundation of China (21376036)

摘要/Abstract

摘要：

用变温热浸渍法在廉价大孔α-Al₂O₃的载体管上涂覆大小晶种引入平整均匀的晶种层, 随后在无有机模板剂的含氟体系下通过二次水热生长法制备了亲水性ZSM-5沸石分子筛膜。实验考察了小晶种液浓度对形成晶种层及ZSM-5沸石分子筛膜形貌和性能的影响。并将制备的ZSM-5沸石分子筛膜分别用于渗透汽化异丙醇脱水和乙酸脱水体系中。结果显示, 小晶种液浓度为0.2wt%时, 制备的ZSM-5沸石分子筛膜在75℃下对10wt%水/异丙醇和10wt% 水/乙酸混合物体系均具有优良的分离性能, 其渗透通量分别为3.64 kg/(m²·h)和0.61 kg/(m²·h), 分离因子分别达3204和1321。

关键词: ZSM-5沸石分子筛膜, 大孔α-Al2O3载体, 变温热浸渍法, 渗透汽化, 氟体系

Abstract:

Water perm-selectivity ZSM-5 zeolite membranes were prepared from fluoride media without organic template on the low cost macroporous α-Al₂O₃ tubular support by secondary growth. A varying temperature hot dip-coating method with different size of crystal was used to form a flat and continuous perfect seed layer. The effects of concentration of the small seed solution on the surface of seed layer, the morphology and pervaporation property of the ZSM-5 membrane were investigated. The results show that when the concentration of the small seed solution is 0.2wt%, the prepared ZSM-5 zeolite membrane displays high water perm-selectivity properties in the pervaporation dehydration of 10wt% H₂O/IPA and 10wt% H₂O/AcOH mixtures at 75℃, which fluxes are 3.64 kg/(m²·h) and 0.61 kg/(m²·h), separation factor up to 3204 and 1321, respectively.

Key words: ZSM-5 zeolite membrane, macroporous α-Al2O3 tubular support, varying temperature hot dip-coating method, pervaporation, fluoride route

中图分类号:

TQ174

李良清, 张闻煦, 杨建华, 鲁金明, 殷德宏, 王金渠. 含氟体系下亲水性ZSM-5沸石分子筛膜的制备及其性能[J]. 无机材料学报, 2015, 30(11): 1167-1171.

LI Liang-Qing, ZHANG Wen-Xu, YANG Jian-Hua, LU Jin-Ming, YIN De-Hong, WANG Jin-Qu. Preparation and Characterization of Water Perm-selectivity ZSM-5 Zeolite Membrane Using Fluoride Route[J]. Journal of Inorganic Materials, 2015, 30(11): 1167-1171.

图/表 6

表1 不同涂晶浓度所制备的膜M1~M5及其在75℃下的PV性能

Table 1 Seeding conditions and PV performances of membranes M1-M5 at 75℃

Sample	Seeding condition			10wt% H₂O/IPA		10 wt% H₂O/AcOH
Sample	Seed layer	First seed concentration/wt%	Second seed concentration/wt%	Flux /(kg·m^-2·h^-1)	α_W/IPA(-)	Flux /(kg·m^-2·h^-1)	α_W/AcOH(-)
M1	S1	2.00	0	—	<5	—	<5
M2	S2	2.00	0.05	2.91	36	1.65	13
M3	S3	2.00	0.20	3.64	3204	0.61	1321
M4	S4	2.00	0.50	2.31	4770	0.20	2046

图1 α-Al2O3载体及球磨前后ZSM-5晶种的SEM照片

Fig. 1 SEM images of the α-Al2O3 support (a, b) and ZSM-5 crystal particles without (c) and with (d) ball-milling

图2 α-Al2O3载体和ZSM-5晶种的XRD图谱

Fig. 2 XRD patterns of α-Al2O3 support (a) and ZSM-5 crystal particles

图3 晶种层S1~S4的扫描电镜照片

Fig. 3 SEM images of seed layers of S1 (a, b), S2 (c, d), S3 (e, f), and S4 (g, h)

图4 膜M1~M4的XRD图谱

Fig. 4 XRD patterns of membranes M1-M4

图5 膜M1~M4的扫描电镜照片

Fig. 5 SEM images of membranes of M1 (a, b), M2 (c, d), M3 (e, f), and M4 (g, h)

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含氟体系下亲水性ZSM-5沸石分子筛膜的制备及其性能

Preparation and Characterization of Water Perm-selectivity ZSM-5 Zeolite Membrane Using Fluoride Route

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