纺织学报 ›› 2025, Vol. 46 ›› Issue (12): 11-18.doi: 10.13475/j.fzxb.20250304901

• 纺织科技新见解学术沙龙专栏:纤维基功能过滤材料 • 上一篇    下一篇

非对称结构聚四氟乙烯中空管式纤维膜的制备及油水分离性能

刘劲扬1, 李成才1,2(), 朱海霖1,3, 郭玉海1, 姜学梁3   

  1. 1.浙江理工大学 纺织科学与工程学院(国际丝绸学院), 浙江 杭州 310018
    2.浙江格尔泰斯环保特材科技股份有限公司, 浙江 湖州 313000
    3.现代纺织技术创新中心(鉴湖实验室), 浙江 柯桥 312030
  • 收稿日期:2025-03-24 修回日期:2025-06-12 出版日期:2025-12-15 发布日期:2026-02-06
  • 通讯作者: 李成才(1990—),男,副研究员,博士。主要研究方向为高分子分离膜材料制备。E-mail:lcc692716700@163.com
  • 作者简介:刘劲扬(2001—),男,硕士生。主要研究方向为PTFE膜材料在废水处理领域中的应用。
  • 基金资助:
    国家自然科学基金青年科学基金项目(52303160);湖州市重点研发计划项目(2024ZD2040)

Preparation and oil-water separation performance of asymmetric structure polytetrafluoroethene empty tube fiber membrane

LIU Jinyang1, LI Chengcai1,2(), ZHU Hailin1,3, GUO Yuhai1, JIANG Xueliang3   

  1. 1. College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou,Zhejiang 310018, China
    2. Zhejiang Kertice Hi-Tech Fluor-Material Co., Ltd., Huzhou, Zhejiang 313000, China
    3. Zhejiang Provincial Innovation Center of Advancced Textile Technology (Jianhu Laboratory), Keqiao,Zhejiang 312030, China
  • Received:2025-03-24 Revised:2025-06-12 Published:2025-12-15 Online:2026-02-06

摘要: 聚四氟乙烯(PTFE)因优异的耐高温和耐化学性而受到广泛关注,单向拉伸法制备的PTFE中空管式纤维膜孔径和孔隙率难以同时有效控制,为提高PTFE中空管式纤维膜应用领域,通过对PTFE中空管式纤维膜外表面包缠不同孔径、不同层数的平板纤维膜,制备了非对称孔道结构PTFE中空管式纤维膜。研究了不同平板膜孔径、包缠层数对非对称结构PTFE中空管式纤维膜结构和性能的影响;同时采用含有亲水性基团材料对膜进行亲水改性后,赋予优异的水通量与表面润湿性能,并将其用于油水乳液分离。结果表明:包缠0.2 μm孔径平板膜且包缠 3层制备的非对称膜分离性能最佳,且具有良好的化学稳定性,赋予管式膜在油水分离领域优异的应用潜力。

关键词: 聚四氟乙烯, 中空管式纤维膜, 非对称结构, 包缠, 油水分离, 废水处理, 膜分离技术

Abstract:

Objective Polytetrafluoroethylene (PTFE) has garnered significant attention due to its exceptional high-temperature resistance and chemical stability. While the structure of PTFE flat-sheet membranes is relatively controllable, PTFE empty tube fiber membranes prepared by uniaxial stretching face challenges in simultaneously controlling pore size and porosity.

Method By wrapping the outer surface of PTFE tubular membranes with flat-sheet membranes of varying pore sizes and layers, an asymmetric pore structure was constructed, resulting in PTFE empty tube fiber membranes with suitable pore sizes and high porosity. After hydrophilic modification using materials containing hydrophilic groups.

Results The membrane with the highest separation efficiency for oil-in-water emulsions was the modified membrane wrapped with a 0.2 μm flat-sheet membrane and three wrapping layers, achieving a separation efficiency of 99.3%, a pure water flux of 38 710.02 L/(m2·h·MPa), and a permeation flux of 13 010.6 L/(m2·h·MPa). For small-aperture membrane wrapping(0.1 μm,0.2 μm), the gradual increase in flux with additional wrapping layers can be attributed to the expanded separation channels resulting from greater membrane thickness, which provides more porous pathways and a larger effective filtration area, thereby enhancing separation efficiency. Conversely, when wrapping large-aperture membranes(0.45 μm), nodule overlap occurs after multilayer wrapping, and the intrusion of hydrophilic coatings further contributes to pore blockage. The chemical stability of the membrane with the optimal configuration was tested by immersing it in 6% sodium hypochlorite solution, 0.1 mol/L NaOH solution, and 0.1 mol/L H2SO4 solution for 12 h. The fluxes were 37 640.33, and 34 950.57 L/(m2·h·MPa), respectively, indicating that the modified membrane exhibited excellent oxidation resistance and strong acid/alkali resistance. Analysis of oil-in-water emulsion separation under different pressures showed that the membrane remained stable at 0.24 MPa.

Conclusion By wrapping different flat-sheet membranes on the outer surface of PTFE empty tube fiber membranes, the maximum pore size was reduced while retaining the original porosity of the tubular membranes. The modified membrane achieved a maximum pure water flux of 45 540.1 L/(m2·h·MPa), while the optimal performance was observed in the tubular membrane wrapped with a 0.2 μm flat-sheet membrane and three layers, exhibiting a water flux of 38 710.02 L/(m2·h·MPa) and a contact angle of 45.2°. At this condition, the membrane demonstrated a separation efficiency of 99.3%, along with excellent resistance to acids, alkalis, and strong oxidants, making it suitable for most wastewater treatment environments. The membrane maintained stable operation under a maximum pressure of 0.22 MPa, indicating broad prospects for applications in oil-water separation.

Key words: polytetrafluoroethylene, empty tube fiber membrane, asymmetric structure, wrapping, oil-water separation, wastewater treatment, membrane separation technology

中图分类号: 

  • TQ342.8

图1

包缠法制备非对称结构PTFE中空管式纤维膜示意图"

图2

亲水性非对称结构PTFE中空管式纤维膜制备机制"

图3

不同膜的表面形貌照片"

图4

平板膜孔径及层数对非对称膜泡点压力的影响"

图5

亲水改性后非对称结构PTFE中空管式纤维乙醇泡点压力"

图6

不同包缠层数的非对称结构PTFE中空管式纤维膜的纯水通量与水接触角"

图7

不同包缠层数的非对称结构PTFE中空管式纤维膜的渗透通量与分离效率"

图8

非对称结构PTFE中空管式纤维膜在不同工作压力下的分离性能"

图9

亲水性非对称结构PTFE中空管式纤维膜的化学稳定性渗透通量"

图10

经过浸泡后非对称结构膜SEM照片"

[1] ZHANG W Q, LIU Y T, TAO F B, et al. An overview of biomass-based Oil/Water separation materials[J]. Separation and Purification Technology, 2023, 316: 123767.
doi: 10.1016/j.seppur.2023.123767
[2] KARUNANITHI A, DE J, SAXENA S, et al. Surface-modified nanoporous membrane for oil-water separation[J]. Water, Air, & Soil Pollution, 2022, 233(1): 30.
[3] DE MEDEIROS A D M, DA SILVA C J G J, DE AMORIM J D P, et al. Oily wastewater treatment: methods, challenges, and trends[J]. Processes, 2022, 10(4): 743.
doi: 10.3390/pr10040743
[4] LIU Y, JING Z F, ZHANG T, et al. Fabrication of functional biomass carbon aerogels derived from sisal fibers for application in selenium extraction[J]. Food and Bioproducts Processing, 2018, 111: 93-103.
doi: 10.1016/j.fbp.2018.07.004
[5] LIU Y, PENG Y X, ZHANG T, et al. Superhydrophobic, ultralight and flexible biomass carbon aerogels derived from sisal fibers for highly efficient oil-water separation[J]. Cellulose, 2018, 25(5): 3067-3078.
doi: 10.1007/s10570-018-1774-7
[6] CHENG X X, PAN F S, WANG M R, et al. Hybrid membranes for pervaporation separations[J]. Journal of Membrane Science, 2017, 541: 329-346.
doi: 10.1016/j.memsci.2017.07.009
[7] LI B F, QI B, GUO Z Y, et al. Recent developments in the application of membrane separation technology and its challenges in oil-water separation: a review[J]. Chemosphere, 2023, 327: 138528.
doi: 10.1016/j.chemosphere.2023.138528
[8] FU C H, YAO L, GUO Z G. Biomass chitosan-based complexes with superwettability for oil-water separa-tion[J]. Materials Today Chemistry, 2024, 40: 102265.
doi: 10.1016/j.mtchem.2024.102265
[9] PANG H L, TIAN K X, LI Y P, et al. Super-hydrophobic PTFE hollow fiber membrane fabricated by electrospinning of Pullulan/PTFE emulsion for membrane deamination[J]. Separation and Purification Technology, 2021, 274: 118186.
doi: 10.1016/j.seppur.2020.118186
[10] DHANUMALAYAN E, JOSHI G M. Performance properties and applications of polytetrafluoroethy-lene(PTFE): a review[J]. Advanced Composites and Hybrid Materials, 2018, 1(2): 247-268.
doi: 10.1007/s42114-018-0023-8
[11] YU Y F, ZHANG L, LI X D, et al. Multifunctionalization of PTFE membrane surface for biofouling resistance and oil/water separation performance improvement[J]. Journal of Environmental Chemical Engineering, 2023, 11(1): 109158.
doi: 10.1016/j.jece.2022.109158
[12] 王峰. 非对称结构PTFE中空纤维膜的制备及分离性能研究[D]. 杭州: 浙江理工大学, 2016:1-54.
WANG Feng. Study on preparation and separation performance of asymmetric PTFE hollow fiber mem-brane[D]. Hangzhou: Zhejiang Sci-Tech University, 2016:1-54.
[13] 梅德俊, 朱海霖, 郭玉海, 等. 聚四氟乙烯平板膜的亲水改性研究[J]. 水处理技术, 2016, 42(4):42-45,50.
MEI Dejun, ZHU Hailin, GUO Yuhai, et al. Hydrophilic Modification of Polytetrafluoroethylene Flat Sheet Membrane[J]. Technology of Water Treatment, 2016, 42(4):42-45,50.
[1] 谢围围, 朱庆鹏, 宋娇娇, 陈志明. 磁性固定化漆酶的制备及其对染料的高效降解[J]. 纺织学报, 2025, 46(12): 163-170.
[2] 季巧, 于清源, 周爱晖, 马博谋, 徐进, 袁久刚. 细菌纤维素及其复合材料的应用研究进展[J]. 纺织学报, 2025, 46(12): 243-250.
[3] 刘青青, 毛晓卉, 姚焰, 孙颖, 陈鱼, 张霄喆, 朱丽萍, 王雪芬. 纤维基分离膜功能改性及应用研究进展[J]. 纺织学报, 2025, 46(12): 39-48.
[4] 高俊, 凌磊, 陈缘, 武丁胜, 林韩蕾, 李振宇, 凤权. 氨基功能化聚丙烯腈纳米纤维膜的制备及其对Cr(Ⅵ)的吸附性能[J]. 纺织学报, 2025, 46(12): 57-65.
[5] 尹文博, 叶帆, 杨瑞华. 基于包芯-包缠结构复合纱的锦纶/棉机织物服用性能[J]. 纺织学报, 2025, 46(11): 77-85.
[6] 王泓力, 张辉, 刘建宇, 尉海泽, 张雅宁, 王丽丽, 许学潮. 棉基生物炭-ZIF-L(Zn)-壳聚糖/聚丙烯复合膜的制备及其吸附-光催化性能[J]. 纺织学报, 2025, 46(09): 84-93.
[7] 左卓帆, 卢凯亮, 李倩雯, 张维. 基于铝镁合金阳极的靛蓝染色废水电絮凝处理效能优化[J]. 纺织学报, 2025, 46(09): 197-204.
[8] 项文龙, 杨静冉, 肖晓珍. 铁钴双金属有机框架/稻谷壳复合材料的制备及其染料脱色性能[J]. 纺织学报, 2025, 46(06): 178-186.
[9] 王薇, 高建南, 裴笑涵, 陆鑫, 孙银银, 吴建兵. 纤维素/甲基三甲氧基硅烷气凝胶的制备及其油水分离效能[J]. 纺织学报, 2025, 46(05): 135-142.
[10] 金汝诗, 陈万明, 刘国金, 刘承海, 戚栋明, 翟世民. 生物炭在印染废水处理中的应用研究进展[J]. 纺织学报, 2025, 46(04): 235-243.
[11] 林伟嘉, 冀大伟, 田徐泳, 王春蕾, 薛昊龙, 肖长发. 增强型聚丙烯中空纤维膜制备及其油水分离性能[J]. 纺织学报, 2025, 46(04): 38-46.
[12] 李逢春, 孙辉, 于斌, 谢有秀, 张德伟. 共价有机框架材料/粘胶水刺非织造布的制备及其染料吸附性能[J]. 纺织学报, 2025, 46(02): 170-179.
[13] 宇平, 王海跃, 汪毅, 孙钦超, 王彦, 胡祖明. 聚酯织物的直接氟修饰疏水改性及其作用机制[J]. 纺织学报, 2024, 45(10): 137-144.
[14] 郭晨宇, 蒋云, 杨瑞华. 基于环锭纺的三组分负泊松比纱制备及其性能[J]. 纺织学报, 2024, 45(10): 55-63.
[15] 杨硕, 赵朋举, 程春祖, 李晨暘, 程博闻. 非对称润湿性纤维复合膜的制备及其油水分离性能[J]. 纺织学报, 2024, 45(08): 10-17.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!