超声辅助溶胶-凝胶法制备中空纤维TiO2超滤膜

doi:10.15541/jim20220185

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1051-1057.DOI: 10.15541/jim20220185 CSTR: 32189.14.10.15541/jim20220185

超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜

吕庆洋(), 张玉亭, 顾学红()

南京工业大学化工学院, 材料化学工程国家重点实验室, 南京 211816

收稿日期:2022-04-03 修回日期:2022-05-15 出版日期:2022-10-20 网络出版日期:2022-05-27
通讯作者: 顾学红, 教授. E-mail: xhgu@njtech.edu.cn
作者简介:吕庆洋(1997-), 男, 硕士研究生. E-mail: 201961204185@njtech.edu.cn
基金资助:
国家自然科学基金(22035002);国家自然科学基金(22008111);国家重点研发计划(2021YFC2101200)

Fabrication of Hollow Fiber Supported TiO₂ Ultrafiltration Membranes via Ultrasound-assisted Sol-Gel Method

LÜ Qingyang(), ZHANG Yuting, GU Xuehong()

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China

Received:2022-04-03 Revised:2022-05-15 Published:2022-10-20 Online:2022-05-27
Contact: GU Xuehong, professor. E-mail: xhgu@njtech.edu.cn
About author:LÜ Qingyang (1997-), male, Master candidate. E-mail: 201961204185@njtech.edu.cn
Supported by:
National Natural Science Foundation of China(22035002);National Natural Science Foundation of China(22008111);National Key Research and Development Program of China(2021YFC2101200)

摘要/Abstract

摘要：

TiO₂膜具有亲水性强和热化学稳定性好等优点而用于超滤分离, 但是TiO₂膜以管式膜为主, 渗透通量低且制备周期长。为了提高TiO₂膜的渗透通量, 并缩短膜的制备周期, 本工作以钛酸四丁酯为前驱体, 采用超声辅助溶胶-凝胶法制备高通量的中空纤维负载型TiO₂超滤膜。系统考察了硝酸与钛酸四丁酯的摩尔比(酸钛比)、超声时间和煅烧温度对TiO₂溶胶粒径及膜截留性能的影响。结果表明：当酸钛比为0.25时, 溶胶的平均粒径为3252 nm, 采用超声处理30 s后, 平均粒径减小至1817 nm。采用超声后的溶胶循环涂膜并在350 ℃煅烧两次后可得到完整无缺陷的中空纤维TiO₂超滤膜, 膜层平均厚度为1 μm, 膜的纯水渗透通量为145 L·m^-2·h^-1·bar^-1(1 bar=0.1 MPa), 葡聚糖截留分子量为2586 Da, 对应的平均孔径为2.5 nm。

关键词: 超滤膜, 溶胶, 凝胶, TiO₂, 超声辅助

Abstract:

TiO₂ membranes have been applied in ultrafiltration (UF) separation due to their strong hydrophilicity and good thermochemical stability, but most of them are tubular membranes with low permeation flux and time-consuming preparation. To improve the flux and save the preparation time of TiO₂ membrane, hollow fiber supported TiO₂ UF membranes were prepared via ultrasound-assisted Sol-Gel method by using tetrabutyl titanate as precursor. Effects of acid/titanium molar ratio, ultrasound time and calcination temperature on TiO₂ sols and UF performance of membranes were investigated extensively. The results showed that when the acid/titanium ratio was 0.25, the obtained TiO₂ sol showed an average particle size of 3252 nm, which would be reduced to 1817 nm after ultrasonic treatment for 30 s. Coating with the above TiO₂ sol, defect-free TiO₂ UF membrane with average thickness of 1 μm can be prepared on hollow fiber support by calcining at 350 ℃ twice. The pure water flux of the obtained membrane was 145 L·m^-2·h^-1·bar^-1, and the dextran molecular weight at 90% rejection of membrane was 2586 Da with corresponding average pore size of 2.5 nm.

Key words: ultrafiltration membrane, sol, gel, TiO₂, ultrasound-assistance

中图分类号:

TQ174

吕庆洋, 张玉亭, 顾学红. 超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜[J]. 无机材料学报, 2022, 37(10): 1051-1057.

LÜ Qingyang, ZHANG Yuting, GU Xuehong. Fabrication of Hollow Fiber Supported TiO₂ Ultrafiltration Membranes via Ultrasound-assisted Sol-Gel Method[J]. Journal of Inorganic Materials, 2022, 37(10): 1051-1057.

图/表 11

图1 不同酸钛比下TiO2溶胶粒径分布图

Fig. 1 Particle size distribution of TiO2 sols prepared with different acid/titanium ratios (x)

图2 不同酸钛比制备的TiO2膜表面和断面SEM照片

Fig. 2 Surface and cross-section SEM images of TiO2 membranes prepared with different acid/titanium ratios (a1, a2) CM0.25-0-350; (b1, b2) CM0.5-0-350; (c1, c2) CM0.75-0-350

图3 TiO2溶胶(S0.25)经不同时间超声后的粒径分布图

Fig. 3 Particle size distribution of TiO2 sols (S0.25) after ultrasound treatment for different periods

图4 不同超声时间制备的TiO2膜表面及断面SEM照片

Fig. 4 Surface and cross-section SEM images of TiO2 membranes prepared by sonication for different periods (a1, a2) UM0.25-15-350; (b1, b2) UM0.25-30-350; (c1, c2) UM0.25-45-350

图5 采用常规和超声辅助溶胶-凝胶法制备的TiO2膜成膜机理图

Fig. 5 Schematic diagram of proposed formation mechanism of TiO2 membranes prepared by conventional and ultrasound-assisted Sol-Gel methods

图6 不同煅烧温度制备的TiO2粉体XRD图谱

Fig. 6 XRD patterns of TiO2 powders calcined at different temperatures

图7 不同温度煅烧得到的TiO2膜表面SEM照片及其3D形貌

Fig. 7 Surface SEM and 3D morphologies of TiO2 membranes calcined at different temperatures (a) UM0.25-30-350; (b) UM0.25-30-400; (c) UM0.25-30-450; (d) UM0.25-30-500

图8 不同酸钛比制备的TiO2膜对葡聚糖截留性能

Fig. 8 Dextran rejection of TiO2 membranes prepared with different acid/titanium ratios

图9 不同超声时间制备的TiO2膜对葡聚糖截留性能

Fig. 9 Dextran rejection of TiO2 membranes prepared by sonication for different periods

图10 不同煅烧温度制备的TiO2膜对葡聚糖截留性能

Fig. 10 Dextran rejection of TiO2 membranes calcined at different temperatures

表1 常规及超声辅助的溶胶-凝胶法与文献中制备的TiO2膜的性能比较

Table 1 Comparison between TiO2 membranes prepared by conventional and ultrasound-assisted sol-gel method

Membrane	Membrane configuration	Calcination temperature/℃	Pore size / nm	Thickness/ μm	Coating number	Water flux/ (L·m^-2·h^-1·bar^-1)	MWCO/ Da	Ref.
P₂₅-TiO₂	Tube	400	3.6	2	4	128	5600	[12]
MXene-TiO₂	Tube	400	6.5	5	1	90	22000	[15]
P123-TiO₂	Tube	400	6.1	2	3	7.16	19000	[19]
CM_0.5-0-350	Hollow fiber	350	4.4	5	3	142	9078	This work
UM_0.25-30-350	Hollow fiber	350	2.5	1	2	145	2586	This work

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超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜

Fabrication of Hollow Fiber Supported TiO₂ Ultrafiltration Membranes via Ultrasound-assisted Sol-Gel Method

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