聚酰胺/聚醚醚酮复合膜的制备及其有机溶剂纳滤性能

doi:10.16085/j.issn.1000-6613.2024-0261

化工进展 ›› 2025, Vol. 44 ›› Issue (2): 1147-1156.DOI: 10.16085/j.issn.1000-6613.2024-0261

• 资源与环境化工 • 上一篇

聚酰胺/聚醚醚酮复合膜的制备及其有机溶剂纳滤性能

闫鹏程¹^,²(), 高卓凡²(), 周志辉¹(), 吴红丹¹, 陈霞², 周显², 范泽宇², 邓闪闪², 鲁麒², 向媛³

^1.武汉科技大学资源与环境工程学院，湖北武汉 430081
^2.长江水利委员会长江科学院，湖北武汉 430012
^3.武汉长江科创科技发展有限公司，湖北武汉 430010

收稿日期:2024-02-04 修回日期:2024-04-27 出版日期:2025-02-25 发布日期:2025-03-10
通讯作者: 高卓凡,周志辉
作者简介:闫鹏程（1999－），男，硕士研究生，研究方向为有机溶剂纳滤膜。E-mail：278600898@qq.com。
基金资助:
武汉市科技局知识创新专项基础研究项目(CKSF2021437);湖北省教育厅科学研究计划指导性项目(B2020119)

Preparation of polyamide/poly ether ether ketone composite membranes and their organic solvents nanofiltration properties

YAN Pengcheng¹^,²(), GAO Zhuofan²(), ZHOU Zhihui¹(), WU Hongdan¹, CHEN Xia², ZHOU Xian², FAN Zeyu², DENG Shanshan², LU Qi², XIANG Yuan³

^1.School of Resources and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
^2.Changjiang River Scientific Research Institute, Changjiang Water Resources Commission, Wuhan 430012, Hubei, China
^3.Wuhan Changjiang Kechuang Technology Development Co. , Ltd. , Wuhan 430010, Hubei, China

Received:2024-02-04 Revised:2024-04-27 Online:2025-02-25 Published:2025-03-10
Contact: GAO Zhuofan, ZHOU Zhihui

摘要/Abstract

摘要：

有机溶剂纳滤（OSN）作为一种新兴的膜分离技术在医药化工等领域得到广泛应用。然而常见的纳滤膜不具备良好的耐溶剂性能，因此选择适合的膜材料是有机溶剂纳滤工业应用的关键。以哌嗪（PIP）为水相单体，均苯三甲酰氯（TMC）为油相单体，通过界面聚合法在聚醚醚酮（PEEK）多孔膜上负载了聚酰胺（PA）功能层，制备了良好耐溶剂性能的PA/PEEK复合纳滤膜，并对其微观结构、亲水性能等进行了研究。探究了PIP浓度对复合膜渗透分离性能的影响，并对性能最优异的膜进行了多种有机溶剂的通量测试以及低价盐离子和小分子有机物截留性能测试。结果表明，0.3%（质量分数）PIP浓度制备的膜具有最优渗透分离性能，其水通量达到(4.81±0.04)L/(h·m²·bar)（1bar=10⁵Pa），Na₂SO₄截留率为98.23%；复合膜对甲醇溶剂通量达到(2.77±0.22)L/(h·m²·bar)，在乙醇溶剂中的截留分子量约为519g/mol。此外，复合膜表现出稳定的长期有机溶剂纳滤性能。

关键词: 聚醚醚酮, 聚酰胺, 有机溶剂纳滤, 复合材料, 膜, 渗透

Abstract:

As a new membrane separation technology, organic solvent nanofiltration (OSN) has been widely used in medical and chemical industries. However, the common nanofiltration membranes do not have good solvent resistance, so the selection of suitable membrane materials is the key to the industrial application of organic solvent nanofiltration. Using piperazine (PIP) as an aqueous monomer and TMC as an organic monomer, PA/PEEK composite nanofiltration membranes with good solvent resistance were prepared by interfacial polymerization. The microstructure and hydrophilicity of the membranes were studied. The microstructure and hydrophilicity of the membrane were also studied. The effect of PIP concentration on the permeation separation performance of the composite membranes was investigated, and the flux of various organic solvents and the retention performance of low salt ions and small molecule organic compounds were tested for the membranes with the best performance. The results showed that the membranes prepared with 0.3%(weight fraction) PIP concentration had the best permeation separation performance. The water flux reached (4.81±0.04)L/(h·m²·bar)(1bar=10⁵Pa) and the retention rate of Na₂SO₄was 98.23%. The flux of the composite film to methanol solvent reached (2.77±0.22)L/(h·m²·bar) and the retained molecular weight in ethanol solvent was about 519g/mol. In addition, the composite membrane exhibited stable long-term organic solvent nanofiltration performance.

Key words: poly ether ether ketone, polyamide, organic solvent nanofiltration, composite materials, membrane, permeate

中图分类号:

TQ31

闫鹏程, 高卓凡, 周志辉, 吴红丹, 陈霞, 周显, 范泽宇, 邓闪闪, 鲁麒, 向媛. 聚酰胺/聚醚醚酮复合膜的制备及其有机溶剂纳滤性能[J]. 化工进展, 2025, 44(2): 1147-1156.

YAN Pengcheng, GAO Zhuofan, ZHOU Zhihui, WU Hongdan, CHEN Xia, ZHOU Xian, FAN Zeyu, DENG Shanshan, LU Qi, XIANG Yuan. Preparation of polyamide/poly ether ether ketone composite membranes and their organic solvents nanofiltration properties[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 1147-1156.

图/表 19

图1 PEEK的分子结构

图2 界面聚合前后PEEK基膜和PA/PEEK复合膜的表面与截面SEM图像

图3 PEEK膜和PA/PEEK膜的FTIR光谱

图4 PEEK膜和PA/PEEK膜的XPS谱图

图5 PEEK膜和PA/PEEK复合膜的渗透分离性能

图6 PA/PEEK复合膜的耐溶剂性能测试

表1 PA/PEEK复合膜与商业有机溶剂纳滤膜的耐溶剂性能

膜样品	乙醇	正己烷	NMP	THF
PA/PEEK	+	+	+	+
Duramem280	+	+	-	-
Puramem900	+	+	+	+

图7 PA/PEEK复合膜的表面粗糙程度

图8 PA/PEEK复合膜的水接触角

图9 PA/PEEK复合膜的C 1s窄谱图

表2 PA/PEEK复合膜不同元素的原子分数

膜样品编号	原子分数/%				O/N
膜样品编号	C	N	O	S	O/N
M1	76.6	1.29	21.57	0.54	16.7
M2	60.6	11.23	24.8	3.37	2.21
M3	63.08	11.27	22.92	2.73	2.03
M4	68.35	11.53	18.31	1.8	1.59
M5	69.81	11.44	17.64	1.12	1.54

图10 PA/PEEK复合膜的渗透分离性能

图11 M3复合膜对四种低价无机盐溶液的截留率（测试压力20bar，进料无机盐浓度2000μg/g）

图12 M3膜对不同有机溶剂的渗透通量

表3 不同有机溶剂的性质参数

溶剂	δ_ps/MPa^1/2	MV_s/cm³	η_s/cP	δ_ps·MV_s^-1·η_s^-1/MPa^1/2·cP^-1·cm^-3
甲醇	12.3	40.7	0.56	0.54
乙醇	8.8	58.2	1.1	0.14
异丙醇	6.1	76.8	2.05	0.04
DMF	13.7	77	0.82	0.22
乙酸乙酯	5.3	97.6	0.45	0.12
丙酮	10.4	73.4	0.32	0.44
正己烷	0	131.4	0.33	0

图13 有机溶剂的渗透通量与δps·MVs-1·ηs-1参数相关性图

表4 测试有机物小分子的性质

测试组分	分子量/g·mol^-1	电荷
虎红（RB）	1017	负电荷
刚果红（CR）	696	负电荷
罗丹明B（RDB）	479	正电荷
四环素（TC）	444	电中性
亚甲基蓝（MB）	320	正电荷

图14 M3膜对不同有机小分子的截留率（测试压力20bar，进料有机小分子浓度50μg/g）

图15 M3膜的长期性测试（测试压力20bar，进料液50μg/g）

参考文献 38

1	ALARDHI Saja M, Nisreen S ALI, SAADY Noori M Cata, et al. Separation techniques in different configurations of hybrid systems via synergetic adsorption and membrane processes for water treatment: A review[J]. Journal of Industrial and Engineering Chemistry, 2024,130: 91-104.
2	MEHRABI Mohammad, VATANPOUR Vahid. Polyimide-based separation membranes for liquid separation: A review on fabrication techniques, applications, and future perspectives[J]. Materials Today Chemistry, 2024, 35: 101895.
3	CHENG Xiquan, ZHANG Yongling, WANG Zhenxing, et al. Recent advances in polymeric solvent-resistant nanofiltration membranes[J]. Advances in polymer technology, 2014, 33: 21455.
4	GAO Zhuofan, LIU Jiangtao, CHUNG T S. Rapid in situ growth of covalent organic frameworks on hollow fiber substrates with Janus-like characteristics for efficient organic solvent nanofiltration[J]. Separation and Purification Technology, 2022, 294: 121166.
5	BIRNIWA Abdullahi Haruna, HABIBU Shehu, ABDULLAHI Shehu Sa’ad, et al. Membrane technologies for heavy metals removal from water and wastewater: A mini review[J]. Case Studies in Chemical and Environmental Engineering, 2024, 9: 100538.
6	SHEN Liang, WANG Fangqian, TIAN Lian, et al. High-performance thin-film composite membranes with surface functionalization by organic phosphonic acids[J]. Journal of Membrane Science, 2018, 563: 284-297.
7	FADIL Abdelhakim EL, VERBEKE Rhea, KYBURZ Markus, et al. From academia to industry: Success criteria for upscaling nanofiltration membranes for water and solvent applications[J]. Journal of Membrane Science, 2023, 675: 121393.
8	SHI Guimin, FENG Yingnan, LI Bofan, et al. Recent progress of organic solvent nanofiltration membranes[J]. Progress in Polymer Science, 2021,123: 101470.
9	BESHAHWORED Siyum Shewakena, HUANG Yueh-Han, ABDI Zelalem Gudeta, et al. Polybenzimidazole (PBI) membranes cross-linked with various cross-linkers and impregnated with 4-sulfocalix[4]arene (SCA4) for organic solvent nanofiltration (OSN)[J]. Journal of Membrane Science, 2022, 663: 121039.
10	LI Shuxuan, LIU Shaoxiao, SU Baowei, et al. Thin film nanocomposite polyamide membrane doped with amino-functionalized graphene quantum dots for organic solvent nanofiltration[J]. Journal of Membrane Science, 2023, 685: 121960.
11	SILVA BURGAL João DA, PEEVA Ludmila G, KUMBHARKAR Santosh, et al. Organic solvent resistant poly(ether-ether-ketone) nanofiltration membranes[J]. Journal of Membrane Science, 2015, 479: 105-116.
12	CUI Chun, LUO Cong, TIAN Tian, et al. Comparative evaluation of acid-resistant nanofiltration membranes for heavy metal removal in acidic wastewater[J]. Desalination, 2024, 576: 117349.
13	SILVA BURGAL João DA, PEEVA Ludmila, LIVINGSTON Andrew. Negligible ageing in poly(ether-ether-ketone) membranes widens application range for solvent processing[J]. Journal of Membrane Science, 2017, 525: 48-56.
14	LING Xuanzhe, JING Xishuang, ZHANG Chengyang, et al. Polyether ether ketone (PEEK) properties and its application status[J]. IOP Conference Series: Earth and Environmental Science, 2020, 453(1): 012080.
15	SUN Yuxuan, ZHOU Shengyang, QIN Guorui, et al. A chemical-induced crystallization strategy to fabricate poly(ether ether ketone) asymmetric membranes for organic solvent nanofiltration[J]. Journal of Membrane Science, 2021, 620: 118899.
16	KASEI Asahi, KAISHA Kabushiki. Process for Preparing ploy ether ether ketone membrane: EP796649(B1)[P]. 2006-03-29.
17	PEEVA L, LIVINGSTON A. Potential of organic solvent nanofiltration in continuous catalytic reactions[J]. Procedia Engineering, 2012, 44: 307-309.
18	YU Jian, ZHANG Ling, SHEN Liguo, et al. In situ grown cyclodextrin metal-organic framework nanoparticles templated stripe nano-wrinkled polyamide nanofiltration membranes for efficient desalination and antibiotic removal[J]. Journal of Membrane Science, 2024, 694: 122413.
19	高蔓彤, 王升欢, 刘继桥, 等. 基膜表面孔隙率对聚酰胺复合纳滤膜性能的影响[J]. 膜科学与技术, 2022, 42(5): 64-69, 78.
	GAO Mantong, WANG Shenghuan, LIU Jiqiao, et al. Effect of surface porosity of support membrane on structure and performance of polyamide composite nanofiltration membrane[J].Membrane Science and Technology, 2022, 42(5): 64-69, 78.
20	GUAN Kecheng, FANG Shang, ZHOU Siyu, et al. Thin film composite membrane with improved permeance for reverse osmosis and organic solvent reverse osmosis[J]. Journal of Membrane Science, 2023, 688: 122104.
21	WANG Yumeng, ZHANG Tonghui, SHEN Ke, et al. Low temperature regulated reverse interfacial polymerization for fabricating thin film composite membranes based on nanofibrous substrates[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 683: 133044.
22	ZHANG Zhiqiang, WU Qiao, XU Shilin, et al. Ultra-stable fully-aromatic microporous polyamide membrane for molecular sieving of nitrogen over volatile organic compound[J]. Journal of Hazardous Materials, 2023,459:132151.
23	ZHANG Xu, FAN Zixuan, XU Wentao, et al. Thin film composite nanofiltration membrane with nanocluster structure mediated by graphene oxide/metal-polyphenol nanonetwork scaffold interlayer[J]. Journal of Membrane Science, 2023, 669: 121330.
24	GUO Shiwei, YUAN Bo, WU Jicheng, et al. Proton sponge catalyzes interfacial polymerization in organic phase to enhance nanofiltration membrane performance[J]. Desalination, 2024, 571: 117112.
25	CHEN Jingjing, LI Ruilong, LIU Siyu, et al. Surfactant-assisted interfacial polymerization towards high-crystallinity COF membranes for organic solvent nanofiltration[J]. Journal of Membrane Science, 2024, 694: 122404.
26	王伟, 陈中海, 潘巧明, 等. 纳滤和反渗透膜形貌结构与膜性能关系探索[J]. 工业水处理, 2016, 36(7): 39-42.
	WANG Wei, CHEN Zhonghai, PAN Qiaoming, et al. Study on the relationship between the morphologies of nanofiltration and reverse osmose membranes and their performances[J].Industrial Water Treatment, 2016, 36(7): 39-42.
27	CHEN Kuo, LI Peng, ZHANG Hongyu, et al. Organic solvent nanofiltration membrane with improved permeability by in situ growth of metal-organic frameworks interlayer on the surface of polyimide substrate[J]. Separation and Purification Technology, 2020,251: 117387.
28	NULENS Ines, PETERS Rasheda, VERBEKE Rhea, et al. MPD and TMC supply as parameters to describe synthesis-morphology-performance relationships of polyamide thin film composite membranes[J]. Journal of Membrane Science, 2023, 667: 121155.
29	常娜, 高曌寰, 荆兆敬, 等. 界面聚合反应有机溶剂对聚酰胺复合纳滤膜结构及性能的影响[J]. 高分子材料科学与工程, 2022, 38(5): 32-42.
	CHANG Na, GAO Zhaohuan, JING Zhaojing, et al. Effect of organic solvents in interfacial polymerization on structure and performance of polyamide composite nanofiltration membrane[J]. Polymer Materials Science & Engineering, 2022, 38(5): 32-42.
30	ZHANG Yuehua, XU Peng, CHEN Xianfu, et al. Preparation of high permeance thin-film composite nanofiltration membrane on macroporous ceramic support[J]. Journal of Membrane Science, 2022, 663: 121076.
31	LI Shi, ZHENG Zhihao, XIA Sijie, et al. Fabrication of bamboo cellulose-based nanofiltration membrane for water purification by cross-linking sodium alginate and carboxymethyl cellulose and its dynamics simulation[J]. Chemical Engineering Journal, 2023, 473: 145403.
32	LI Tianhao, YE Hao, JIN Jiamin, et al. Electric-field strengthening uranium extraction from seawater assisted by nanofiltration membranes with sieving-adsorption properties[J]. Journal of Membrane Science, 2024, 693: 122334.
33	ZHANG Miaomiao, YUAN Jinqiu, YIN Zhuoyu, et al. Organic salt modulated preparation of ultra-thin and loose polyamide nanofiltration membranes with enhanced performance[J]. Journal of Membrane Science, 2023, 680: 121739.
34	王智. 纳滤截留无机离子特性及机理研究[D]. 北京: 清华大学, 2018.
	WANG Zhi.Properties and mechanisms in rejection of mineral ions by nanofiltration[D]. Beijing:Tsinghua University, 2018.
35	ZHANG Yuanyuan, CHEN Yingbo, WANG Meng, et al. Preparation of high temperature resistant polyamide composite nanofiltration membranes by thermally assisted interfacial polymerization[J]. Journal of Membrane Science, 2023, 687: 122020.
36	LI Shuxuan, YANG Fangyuan, LIU Shaoxiao, et al. Effective regulating interfacial polymerization process of OSN membrane via in situ constructed nano-porous interlayer of 2D TpHz covalent organic frameworks[J]. Journal of Membrane Science, 2023, 665: 121101.
37	LI Shuxuan, YIN Yating, LIU Shaoxiao, et al. Interlayered thin-film nanocomposite membrane with synergetic effect of COFs interlayer and GQDs incorporation for organic solvent nanofiltration[J]. Journal of Membrane Science, 2022, 662: 120930.
38	JIN Longming, HU Lijie, LIANG Songmiao, et al. A novel organic solvent nanofiltration (OSN) membrane fabricated by Poly(m-phenylene isophthalamide) (PMIA) under large-scale and continuous process[J]. Journal of Membrane Science, 2022, 647: 120259.

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聚酰胺/聚醚醚酮复合膜的制备及其有机溶剂纳滤性能

Preparation of polyamide/poly ether ether ketone composite membranes and their organic solvents nanofiltration properties

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