清液体系高性能T型分子筛膜的制备及表征

doi:10.15541/jim20150631

无机材料学报 ›› 2016, Vol. 31 ›› Issue (7): 705-710.DOI: 10.15541/jim20150631

清液体系高性能T型分子筛膜的制备及表征

吕尤佳¹, 李华征¹, 杨建华², 王金渠^{1, 2}, 殷德宏², 鲁金明²

(1. 大连理工大学盘锦校区精细化工国家重点实验室, 石油与化学工程学院, 盘锦124221; 2. 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:2015-12-15 修回日期:2016-01-28 出版日期:2016-07-20 网络出版日期:2016-06-22
作者简介:吕尤佳(1990–), 男, 硕士研究生. E-mail: youjiaa1990@sina.com
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 High Performance Zeolite T Membranes from Clear Solutions

LV You-Jia¹, LI Hua-Zheng¹, YANG Jian-Hua², WANG Jin-Qu^1,2, YIN De-Hong², LU Jin-Ming²

(1. School of Petroleum and Chemical Engineering, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Panjin Campus, Panjin 124221, China; 2. Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, Dalian 116024, China)

Received:2015-12-15 Revised:2016-01-28 Published:2016-07-20 Online:2016-06-22
About author:LV You-Jia. E-mail: youjiaa1990@sina.com
Supported by:
National High Technology Research and Development Program of China (2015AA03A602);National Natural Science Foundation of China (21376036)

摘要/Abstract

摘要：

采用二次生长法, 在廉价大孔α-Al₂O₃管状载体上通过变温热浸渍涂晶法获得连续致密的晶种层, 在摩尔配比为1SiO₂:0.05Al₂O₃:0.26Na₂O:0.09K₂O:30H₂O清液体系中120℃水热晶化16 h成功制备出T型分子筛膜。实验考察了小晶种液浓度, 晶化时间对T型沸石分子筛膜的形貌和性能的影响。XRD和SEM结果表明, 晶化过程中晶种的外延生长和新的晶核成核过程同时进行, 晶种的外延生长和新核的诱导作用产生协同作用, 缩短T型沸石膜的生长时间。将制备的T型沸石分子筛膜用于75℃渗透汽化分离10wt%水/异丙醇体系, 其渗透通量和分离系数分别达到2.96 kg/(m²·h)和6400。

关键词: T型沸石分子筛膜, 变温热浸渍法, 二次生长法, 渗透汽化

Abstract:

T-type zeolite membrances with high permeation performance were successfully synthesized on the low cost macroporous α-Al₂O₃ tubular support by secondary growth from clear solutions. The effects of the concentration of seeds and the membrane crystallization time on the morphology and pervaporation properties of zeolite T membrances. When the molar ration of the synthesis solution was 1SiO₂:0.05Al₂O₃:0.26Na₂O:0.09K₂O: 30H₂O, a high quality T zeolite membrane was obtained at crystallization temperature of 120 ℃ for 16 h, with water flux of 2.96 kg/(m²·h) and separation factor of 6400 for dehydration of IPA aqueous solution by pervaporation at 75℃. XRD pattern and SEM observation suggested that the shortened membrane crystallization time resulted from the secondary nucleation induced by the seeds and the seeds epitaxial growth.

Key words: T-type zeolite membrance, varying temperature hot dip-coating method, secondary growth, pervaporation

中图分类号:

TQ174

吕尤佳, 李华征, 杨建华, 王金渠, 殷德宏, 鲁金明. 清液体系高性能T型分子筛膜的制备及表征[J]. 无机材料学报, 2016, 31(7): 705-710.

LV You-Jia, LI Hua-Zheng, YANG Jian-Hua, WANG Jin-Qu, YIN De-Hong, LU Jin-Ming. Preparation and Characterization of High Performance Zeolite T Membranes from Clear Solutions[J]. Journal of Inorganic Materials, 2016, 31(7): 705-710.

图/表 8

图1 α-Al2O3载体(a,b), 修饰后载体管(c,d)及晶种层S1~ S3(e~j)的扫描电镜照片

Fig. 1 SEM images of the α-Al2O3 support (a,b), the support modified by seeds (c,d) and seed layers of S1 (e,f), S2 (g,h) and S3 (i,j)

图2 膜T1~T3的XRD图谱

Fig. 2 XRD patterns of membranes T1-T3

图3 膜T1~T3的扫描电镜照片

Fig. 3 SEM images of zeolite T membranes of T1 (a,b), T2 (c,d), and T3 (e,f)

表1 不同涂晶浓度所制备的T型分子筛膜及其在75℃下渗透蒸发性能

Table 1 Seeding conditions and PV performances of zeolite T membranes at 75℃

Sample	Seed layer	First step coating (2 μm) seed concentration/wt%	Second step coating (400 nm) seed concentration/wt%	Flux/ (kg·m^-2·h^-1)	Separation factor
T1	S1	2.00	0.10	2.31	716
T2	S2	2.00	0.30	2.64	>5700
T3	S3	2.00	0.50	1.17	>10000

图4 T型分子筛晶种层和晶化时间4~20 h合成膜的XRD图谱

Fig. 4 XRD patterns of seed layer (a); as-synthesized membrane crystallized at 120℃for 4 h (b);8 h (c);12 h (d);16 h (e) and 20 h (f)

图5 不同晶化时间的T型分子筛膜SEM照片

Fig. 5 SEM images of zeolite T membranes crystallized for 4 h (a,b); 8 h (c,d); 12 h (e,f); 16 h (g,h) and 20 h (i,j)

表2 不同晶化时间制备T型分子筛膜渗透蒸发性能

Table 2 Pervaporation performances of zeolite T membranes crystallized for different time

Sample	Crystallization time/h	Flux/ (kg·m^-2·h^-1)	Separation factor
T4	12	1.95	1500
T5	16	2.96	6400
T6	20	2.32	2500
T7	24	1.90	1300
T8	28	1.61	1100

表3 在75℃、水/异丙醇(10:90,w/w)体系中T型沸石膜的渗透汽化性能

Table 3 PV performance of zeolite T membranes towards water/isopropanol(10:90,w/w) mixture at 75℃

Support	Seed size/μm	Temperature/℃	Time/h	Flux/(kg·m^-2·h^-1)	Separation factor	Ref.
α-Al₂O₃	0.4-2.0	120	16	2.96	6400	This work
α-Al₂O₃	0.4-2.0	100	30	2.52	10000	[11]
α-Al₂O₃	8.0	100+140	8+1	2.15	10000	[12]
Mullite	0.1	150	20	3.10	3400	[9]
Mullite	4.0	150	35	2.50	13000	[9]
Mullite	﹤1.0	100	30	2.20	8900	[6]

参考文献 15

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清液体系高性能T型分子筛膜的制备及表征

Preparation and Characterization of High Performance Zeolite T Membranes from Clear Solutions

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