两步晶化制备高性能a&b取向T型沸石膜

doi:10.15541/jim20190469

摘要/Abstract

摘要：

采用廉价的大孔α-Al₂O₃作为载体, 通过二次晶种诱导+两步变温水热合成工艺, 成功制备出薄而致密的高性能T型沸石膜。该方法能够充分发挥晶种的诱导成核作用, 通过改变两阶段水热晶化温度和时间来控制晶种外延生长和晶体生长方向, 最终获得了连续、无缺陷的a&b取向T型沸石膜。实验过程中详细考察了第一阶段的晶化温度、晶化时间以及第二阶段的晶化温度对沸石膜表面结构和性能的影响, 并将最优两步晶化条件下制备的膜用于90wt%的异丙醇/水渗透汽化分离, 在75 ℃下膜的通量为3.84 kg·m ^-2·h ^-1, 分离因子大于10000。

关键词: T型沸石膜, 两步晶化, a&b取向, 渗透汽化

Abstract:

A thin and dense high-performance T-type zeolite membrane was successfully prepared by a two-step seed crystal induction plus two-step temperature-varied hydrothermal synthesis on inexpensive and macroporous α-Al₂O₃ support. This method can fully perform nucleation of seed crystal, regulate the epitaxial growth and crystal growth direction by changing the hydrothermal crystallization temperature and time during the two-stage. Finally a continuous and defect-free a&b oriented zeolite T membrane was obtained. Effects of crystallization temperature and crystallization time of the first-stage and crystallization temperature of the second-stage on the surface structure and properties of zeolite membranes were investigated. The T-type zeolite membrane prepared under the optimal two-step crystallization condition displayed high pervaporation performance with flux over 3.84 kg·m ^-2·h ^-1 and separation factor higher than 10000 for separation of 90wt% isopropanol/water at 75 ℃.

Key words: T zeolite membrane, two-stage crystallization, a&b orientation, pervaporation

中图分类号:

TQ174

张博,张宁,杨建华,兰建成,王金渠. 两步晶化制备高性能a&b取向T型沸石膜[J]. 无机材料学报, 2020, 35(8): 939-946.

ZHANG Bo,ZHANG Ning,YANG Jianhua,LAN Jiancheng,WANG Jinqu. High Performance a&b Oriented T Zeolite Membrane by a Two-stage Crystallization Synthesis[J]. Journal of Inorganic Materials, 2020, 35(8): 939-946.

图/表 12

图1 α-Al2O3载体((a)-表面, (b)-截面)、大晶种(c)、小晶种(d)、大晶种修饰后的载体((e)-表面, (f)-截面)以及小晶种层((g)-表面, (h)-截面)的SEM照片

Fig. 1 SEM images of α-Al2O3 support photographed from surface (a) and cross section (b), large seeds (c), small seeds (d), modified by large seeds photographed from surface (e) and cross section (f), and the small seed layer photographed from surface (g) and cross section (h)

图2 大晶种(a)和小晶种(b)的XRD图谱

Fig. 2 XRD patterns of large seeds (a) and small seeds (b)

图3 不同的第一步晶化温度下第一步晶化后的T型沸石膜的SEM照片

Fig. 3 SEM images of T-type zeolite membranes after first-step crystallization prepared at different first-step crystallization temperatures (a, b) M1-1, 110 ℃; (c, d) M2-1, 120 ℃; (e, f) M3-1, 130 ℃; (g, h) M4-1, 135 ℃; (i, j) M5-1, 150 ℃

图4 不同的第一步晶化温度下两步晶化后的T型沸石膜的SEM照片

Fig. 4 SEM images of T-type zeolite membranes after two-step crystallizations prepared at different first-step crystallization temperature (a, b) M1, 110 ℃; (c, d) M2, 120 ℃; (e, f) M3, 130 ℃; (g, h) M4, 135 ℃; (i, j) M5, 150 ℃

图5 T沸石膜M4(a)和T沸石小晶种(b)的XRD图谱

Fig. 5 XRD patterns of zeolite T membrane M4 (a) and small zeolite T seeds (b)

表1 不同的第一步晶化温度制备的T型沸石膜的渗透汽化性能

Table 1 Pervaporation performance of T zeolite membranes prepared under different first-step crystallization temperatures

No.	First-step crystallization		Second-step crystallization		J/ (kg·m^-2·h^-1)	α
No.	Temp./℃	Time/h	Temp./℃	Time/h	J/ (kg·m^-2·h^-1)	α
M1	110	4	110	6	-	-
M2	120	4	110	6	4.19	968
M3	130	4	110	6	3.87	5219
M4	135	4	110	6	3.84	>10000
M5	150	4	110	6	3.53	2918

图6 不同的第一步晶化时间下第一步晶化后的T型沸石膜的SEM照片

Fig. 6 SEM images of T-type zeolite membranes after first-step crystallization prepared with varying first-step crystallization time (a, b) M6-1, 2 h; (c, d) M7-1, 3 h; (e, f) M8-1, 5 h; (g, h) M9-1, 6 h

图7 不同的第一步晶化时间下两步晶化后的T型沸石膜的SEM照片

Fig. 7 SEM images of T-type zeolite membranes after two-step crystallizations prepared with different first-step crystallization time (a, b) M6, 2 h; (c, d) M7, 3 h; (e, f) M8, 5 h; (g, h) M9, 6 h

表2 不同的第一步晶化时间制备的T型沸石膜的渗透汽化性能

Table 2 Pervaporation performance of T zeolite membranes prepared with different first-step crystallization time

No.	First-step crystallization		Second-step crystallization		J/ (kg ·m^-2·h^-1)	α
No.	Temp./℃	Time/h	Temp./℃	Time/h	J/ (kg ·m^-2·h^-1)	α
M6	135	2	110	6	-	-
M7	135	3	110	6	4.04	915
M4	135	4	110	6	3.84	>10000
M8	135	5	110	6	4.2	2371
M9	135	6	110	6	4.97	697

图8 不同第二步晶化温度下两步晶化后的T型沸石膜的SEM照片

Fig. 8 SEM images of T-type zeolite membranes after two-step crystallizations prepared at different second-step crystallization temperatures (a, b) M10, 90 ℃; (c, d) M11, 100 ℃; (e, f) M12, 120 ℃; (g, h) M13, 130 ℃

表3 不同的第二步晶化温度制备的T型沸石膜的渗透汽化性能

Table 3 Pervaporation performance of T zeolite membranes prepared under different second-step crystallization temperatures

No	First-step crystallization		Second-step crystallization		J/ (kg·m^-2·h^-1)	α
No	Temp./℃	Time/h	Temp./℃	Time/h	J/ (kg·m^-2·h^-1)	α
M10	135	4	90	6	-	-
M11	135	4	100	6	3.94	2646
M4	135	4	110	6	3.84	>10000
M12	135	4	120	6	3.97	5867
M13	135	4	130	6	3.41	5594

表4 T型沸石膜用于75 ℃、90wt%异丙醇/水体系分离的渗透蒸发性能

Table 4 Pervaporation performance of zeolite T membranes for 90wt% isopropanol/water mixture at 75 ℃

Support	Temp./ ℃	Time/ h	J/ (kg·m^-2·h^-1)	α	Ref.
α-Al₂O₃ disc	120	24	2.24	10000	[29]
α-Al₂O₃ tube	100	30	2.52	10000	[21]
α-Al₂O₃ tube	120	16	2.96	6400	[23]
α-Al₂O₃ tube	100+140^a	8+1^a	2.15	10000	[19]
α-Al₂O₃ tube	150+120^b	4+8^b	2.04	2874	[30]
α-Al₂O₃ tube	135+110^c	4+6^c	3.84	>10000	This work

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