超稀溶液体系中高性能MFI型沸石膜的制备及表征

doi:10.15541/jim20170205

无机材料学报 ›› 2018, Vol. 33 ›› Issue (3): 345-351.DOI: 10.15541/jim20170205 CSTR: 32189.14.10.15541/jim20170205

超稀溶液体系中高性能MFI型沸石膜的制备及表征

黄攀¹, 周亮¹, 李华征¹, 李洪健¹, 杨建华², 王金渠^{1, 2}

大连理工大学1. 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. 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:2017-04-28 修回日期:2017-06-08 出版日期:2018-03-20 网络出版日期:2018-03-12
作者简介:黄攀(1988-), 男, 硕士研究生. E-mail: huangpanchem@sina.com
基金资助:
国家高新技术研究发展计划(863计划) (2015AA03A602)

Preparation and Characterization of High Performance MFI Zeolite Membrane in Ultradilute Solution

HUANG Pan¹, ZHOU Liang¹, LI Hua-Zheng¹, LI Hong-Jian¹, YANG Jian-hua², WANG Jin-Qu^{1, 2}

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, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China

Received:2017-04-28 Revised:2017-06-08 Published:2018-03-20 Online:2018-03-12
About author:HUANG Pan. E-mail: huangpanchem@sina.com
Supported by:
National High Technology Research and Development Program of China (2015AA03A602)

摘要/Abstract

摘要：

以廉价管状大孔α-Al₂O₃作为载体, 采用二次生长法, 在超稀溶液体系(H₂O/SiO₂=1000)中成功制备了高性能MFI型沸石膜, 分别考察晶种尺寸和H₂O/SiO₂对沸石膜的形貌及渗透蒸发性能的影响。结果表明, 尺寸为0.4 μm晶种制备的晶种层具有更大的晶核密度, 能够增加载体表面的成核位点, 因此对沸石膜的生长具有更强的诱导作用。超稀溶液体系中低浓度的模板剂和硅源环境能够控制沸石晶体的生长速率, 从而降低沸石膜厚度, 同时可以抑制晶间缺陷的形成。将制备的沸石膜用于60℃渗透蒸发分离5wt%乙醇/水混合物, 分离因子α_(乙醇/水)和渗透通量分别为47和4.09 kg/(m²·h)。采用超稀的合成液配方和廉价大孔载体, 既可以降低沸石膜制备的原料成本, 又可以提高沸石膜的渗透通量, 显示出MFI型沸石膜在脱除水中低浓度有机物潜在的工业化应用前景。

关键词: MFI型沸石膜, 管状大孔α-Al₂O₃载体;, 超稀溶液, 渗透蒸发

Abstract:

High performance MFI-type zeolite membrane was successfully prepared in ultradilute solution (H₂O/SiO₂= 1000) on inexpensive and macroporous α-Al₂O₃ tubular support by secondary growth. Influences of seed size and H₂O/SiO₂ on morphology and pervaporation performance of the zeolite membranes were investigated. Results showed that the seed layer prepared with 0.4 μm seeds had higher crystal nucleus density which could increase the amount of the nucleation site on the support surface, resulting in a stronger induced effect on the growth of zeolite membrane. The low-concentration template and silicon source in ultradilute solution decreased the growth rate of zeolite crystals, which could reduce the zeolite membrane thickness and effectively inhibited the formation of intercrystalline defects. The flux and separation factor (α_{ethanol/water}) of the resulting MFI zeolite membrane achieved 4.09 kg/(m²·h¹) and 47, respectively, for separation of 5wt% ethanol/water mixture at 60℃. Ultradilute solution and low-cost macroporous α-Al₂O₃ tubular support reduced the preparation cost of MFI zeolite membranes and increased the flux, showing prospect of the potential industrial application of MFI-type zeolite membrane for removal of the low-concentration organic compounds in water.

Key words: MFI zeolite membrane, macroporous α-Al₂O₃ tubular support;, ultradilute solution, pervaporation

中图分类号:

TQ174

黄攀, 周亮, 李华征, 李洪健, 杨建华, 王金渠. 超稀溶液体系中高性能MFI型沸石膜的制备及表征[J]. 无机材料学报, 2018, 33(3): 345-351.

HUANG Pan, ZHOU Liang, LI Hua-Zheng, LI Hong-Jian, YANG Jian-hua, WANG Jin-Qu. Preparation and Characterization of High Performance MFI Zeolite Membrane in Ultradilute Solution[J]. Journal of Inorganic Materials, 2018, 33(3): 345-351.

图/表 11

表1 不同尺寸Silicalite-1晶种的制备

Table 1 Preparation of Silicalite-1 seeds with different sizes

Sample	Precursor	Temp./℃	Average size/μm	Conc./wt%
A	1	96	0.4	0.35
B	2	100	0.8	0.35
C	2	150	1.3	2.5&0.35

图1 α-Al2O3载体(a)和(b), 修饰后的载体(c)和(d)及不同尺寸晶种制备的晶种层表面和截面SEM照片(0.4 μm (e), (f); 0.8 μm (g), (h); 1.3 μm (i), (j))

Fig. 1 Surface and cross-sectional SEM images of the α-Al2O3 support(a)-(b), the support modified by large seeds(c, d) and the seed layers prepared with differently sized seeds (0.4 μm (e, f); 0.8 μm (g, h) and 1.3 μm (i, j))

图2 H2O/SiO2=1000合成液中不同尺寸晶种制备的MFI型沸石膜的SEM照片

Fig. 2 SEM images of MFI zeolite membranes prepared with different-size seeds in H2O/SiO2=1000 synthetic solution (a, b)-M1 0.4 μm; (c, d)-M2 0.8 μm; (e, f)-M3 1.3 μm

表2 不同尺寸晶种制备的MFI型沸石膜的渗透汽化性能

Table 2 Pervaporation performance of MFI zeolite membranes prepared with seeds of different size

No	Seed size/μm	H₂O/SiO₂	Time/h	J/(kg·m^-2·h^-1)	α
M1	0.4	1000	24	4.09	47
M2	0.8	1000	24	4.22	39
M3	1.3	1000	24	4.30	35
M4	0.4	1800	32	4.36	19
M5	0.8	1800	32	-	-
M6	1.3	1800	32	-	-

图3 H2O/SiO2=1800合成液中不同尺寸晶种制备的MFI型沸石膜的SEM照片

Fig. 3 SEM images of MFI zeolite membranes prepared with different-size seeds in H2O/SiO2=1800 synthetic solution (a, b)-M4 0.4 μm; (c, d)-M5 0.8 μm; (e, f)-M6 1.3 μm

图4 不同水硅比条件下制备的MFI型沸石膜的XRD图谱

Fig. 4 XRD patterns of MFI-type zeolite membranes prepared with H2O/SiO2 ratios of 200 (M7), 650 (M8), 1000 (M1), 1400 (M9). and 1800 (M4)

图5 不同水硅比条件下制备的MFI型沸石膜的SEM照片

Fig. 5 SEM images of MFI-type membranes prepared with H2O/SiO2 ratios of 200 (a, b)-M7; 650 (c, d)-M8; 1400 (e, f)-M9

表3 不同水硅比条件下制备的MFI沸石膜的渗透蒸发性能

Table 3 Pervaporation performances of MFI-type zeolite membranes prepared from synthesis solutions with different H2O/SiO2

Sample	H₂O/SiO₂	Time /h	J/(kg·m^-2·h^-1)	α
M7	200	24	2.94	22
M8	650	24	3.60	32
M1	1000	24	4.09	47
M9	1400	24	4.40	43
M10	1800	24	4.90	11
M4	1800	32	4.36	19

图6 不同H2O/SiO2合成液中制备的MFI型沸石膜表面的EDS图谱

Fig. 6 EDS analysis of MFI-type zeolite membranes prepared in synthetic solutions with different H2O/SiO2 ratios

图7 不同H2O/SiO2合成液中制备的MFI型沸石膜的渗透蒸发性能

Fig. 7 Pervaporation performance of MFI zeolite membrane prepared in synthetic solution with different H2O/SiO2 ratios for separation of 5wt% ethanol/water mixtures at 60℃

表4 MFI沸石膜用于乙醇/水混合物分离的渗透汽化性能

Table 4 Pervaporation performance of MFI membranes for ethanol/water mixtures

Membrane/Support	Pore size/μm	H₂O/SiO₂	Feed conc./wt%	Feed temp./℃	J/(kg·m^-2·h^-1)	α_{(ethanol/water)}	Ref.
Si-1/Ml-t	1.0	800	5	60	1.91	66	[22]
MFI/α-d	0.1+3.0	58	10	60	9.00	5	[14]
Si-1/α-t	2.0	120	5	60	1.81	89	[15]
Si-1/Ml-t	1.0	120	5	60	2.23	62	[15]
MFI/α-hf	0.1-0.2	165	3	60	2.90	66	[17]
MFI/α-t	1.0-3.0	165	5	60	1.36	85	[26]
MFI/α-t	3.0-4.0	1000	5	60	4.09	47	This work
MFI/α-t	3.0-4.0	1400	5	60	4.40	43	This work

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超稀溶液体系中高性能MFI型沸石膜的制备及表征

Preparation and Characterization of High Performance MFI Zeolite Membrane in Ultradilute Solution

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