F-Si-PCPA-PVDF超疏水膜的制备及其膜蒸馏性能研究

doi:10.19964/j.issn.1006-4990.2025-0111

摘要/Abstract

摘要：

膜蒸馏技术在水处理领域具有广阔的应用前景，但当长期处理含多种污染物的复杂体系时，常规膜难以避免膜污染和润湿等问题。为提高疏水聚偏氟乙烯（PVDF）膜的膜蒸馏性能，利用贻贝仿生涂层（PCPA）辅助负载氟化二氧化硅（F-SiO₂）纳米粒子，制备F-Si-PCPA-PVDF超疏水改性膜，对其形貌结构、化学组成和润湿性质进行表征，并通过直接接触式膜蒸馏（DCMD）装置考察其膜蒸馏性能。研究结果表明，F-Si-PCPA-PVDF膜具有高水接触角［（168.8±0.6）°］和低水滚动角（2.8°）。同时，在添加碳酸钙（CaCO₃）、腐殖酸（HA）、矿物油（MO）和十二烷基硫酸钠（SDS）等典型污染物的模拟海水体系下，表现出优异的抗污染和抗润湿能力。以含有浓度为0.05 mmol/L SDS的模拟海水体系为代表，PVDF膜的通量在8 h连续膜蒸馏过程中下降24.27%，相比之下，F-Si-PCPA-PVDF膜保持（26.97±0.49） kg/（m²·h）的稳定通量，且截盐率始终维持在99.99%以上。

关键词: 膜蒸馏, 超疏水, 喷涂改性, 贻贝仿生涂层

Abstract:

Membrane distillation technology has broad application prospects in the field of water treatment.However，in the long-term treatment of complex systems containing multiple pollutants，it is difficult for conventional membranes to avoid membrane fouling and wetting.In order to improve the membrane distillation performance of hydrophobic polyvinylidene fluoride（PVDF） membrane，the superhydrophobic modified membrane of F-Si-PCPA-PVDF was prepared by mussel-inspired coating（PCPA） assisting loading of fluorinated silica（F-SiO₂） nanoparticles.The morphology，chemical composition and wetting properties of the modified membrane were characterized，and its membrane distillation performance was investigated by direct contact membrane distillation（DCMD） device.The results demonstrated that the F-Si-PCPA-PVDF membrane exhibited superior hydrophobicity with a high water contact angle of（168.8±0.6）° and low water sliding angle of 2.8°，along with exceptional anti-fouling and anti-wetting capabilities in simulated seawater systems containing typical contaminants such as calcium carbonate（CaCO₃），humic acid（HA），mineral oil（MO），and sodium dodecyl sulfate（SDS）.In the system containing 0.05 mmol/L SDS，the flux of PVDF membranes was declined by 24.27% during the 8 h membrane distillation process.In contrast，the modified membrane maintained a stable flux of （26.97±0.49） kg/（m²·h） while sustaining salt rejection rates above 99.99% throughout the process.

Key words: membrane distillation, superhydrophobic, coating modification, mussel-inspired coating

中图分类号:

TQ051.893

马全, 孟昕, 金央, 李军, 王文. F-Si-PCPA-PVDF超疏水膜的制备及其膜蒸馏性能研究[J]. 无机盐工业, 2026, 58(2): 28-35.

MA Quan, MENG Xin, JIN Yang, LI Jun, WANG Wen. Study on preparation of F-Si-PCPA-PVDF superhydrophobic membrane and its membrane distillation performance[J]. Inorganic Chemicals Industry, 2026, 58(2): 28-35.

图/表 13

图1

表1

图2

图3

图4

图5

表2

图6

图7

表3

表4

图8

图9

参考文献 29

[1]	OMAR N M A， OTHMAN M H D， TAI ZHONG sheng，et al.A review of superhydrophobic and omniphobic membranes as innovative solutions for enhancing water desalination performance through membrane distillation［J］.Surfaces and Interfaces，2024，46：104035.
[2]	许正，李泽华，苏铭晗，等.海水淡化膜蒸馏膜的研究现状与展望［J］.河北科技大学学报，2024，45（1）：15-25.
	XU Zheng， LI Zehua， SU Minghan，et al.Research status and prospect of seawater desalination membrane distillation membrane［J］.Journal of Hebei University of Science and Technology，2024，45（1）：15-25.
[3]	KARANASIOU A， KOSTOGLOU M， KARABELAS A.An experimental and theoretical study on separations by vacuum membrane di-stillation employing hollow-fiber modules［J］.Water，2018，10（7）： 947.
[4]	申静，毛鑫，张冰，等.膜蒸馏过程中膜污染问题及其缓解策略研究［J］.中国给水排水，2024，40（24）：24-32.
	SHEN Jing， MAO Xin， ZHANG Bing，et al.Study on membrane fouling in membrane distillation process and its mitigation strate-gy［J］.China Water & Wastewater，2024，40（24）：24-32.
[5]	王超，赵一， Mujahid Muhammad，等.面向膜蒸馏的抗润湿、抗污染、抗结垢新型膜研究进展［J］.膜科学与技术，2024，44（1）：157-167.
	WANG Chao， ZHAO Yi， MUJAHID M，et al.Research progress of novel membranes for membrane distillation against wetting，fouling and scaling［J］.Membrane Science and Technology，2024，44（1）：157-167.
[6]	CHEN Y， LU KANG jia， CHUNG T S.An omniphobic slippery membrane with simultaneous anti-wetting and anti-scaling properties for robust membrane distillation［J］.Journal of Membrane Science，2020，595：117572.
[7]	YAN Xiaoju， LIN Xinping， MA Cong，et al.Hydrophobic C60-modified PVDF membrane with micro-nano structures for mitigating CaSO₄ scaling in direct contact membrane distillation （DCMD）［J］.Journal of Environmental Chemical Engineering，2024，12（5）：113605.
[8]	阎安，郭寒雨，史乐，等.膜蒸馏脱盐用超疏水复合膜的研制［J］.膜科学与技术，2021，41（4）：8-14.
	YAN An， GUO Hanyu， SHI Le，et al.Preparation of superhydrophobic composite membrane for membrane distillation desalinati-on［J］.Membrane Science and Technology，2021，41（4）：8-14.
[9]	ZHOU Xiaodong， ZANG Hongxin， GUAN Yong，et al.Superhydrophobic flexible strain sensors constructed using nanomaterials：Their fabrications and sustainable applications［J］.Nanomaterials，2023，13（19）：2639.
[10]	UEDA E， LEVKIN P A.Emerging applications of superhydrophilic-superhydrophobic micropatterns［J］.Advanced Materials，2013，25（9）：1234-1247.
[11]	刘大朋，郑俊芝，周学良，等.特殊浸润性多孔膜及其在膜蒸馏中的抗污染特性研究进展［J］.化工进展，2024，43（12）：6769-6779.
	LIU Dapeng， ZHENG Junzhi， ZHOU Xueliang，et al.Research progress of antifouling properties for special wettable porous membranes in membrane distillation［J］.Chemical Industry and Engineering Progress，2024，43（12）：6769-6779.
[12]	SABZI M， MOUSAVI ANIJDAN S H， SHAMSODIN M，et al.A review on sustainable manufacturing of ceramic-based thin films by chemical vapor deposition（CVD）：Reactions kinetics and the deposition mechanisms［J］.Coatings，2023，13（1）：188.
[13]	TWIBI M F， OTHMAN M H D， MOHD SOKRI M N，et al.Novel approach to surface functionalization of mullite-kaolinite hollow fiber membrane using organosilane-functionalized Co₃O₄ spider web-like layer deposition for desalination using direct contact membrane distillation［J］.Ceramics International，2022，48（14）：21025-21036.
[14]	AZIZ M H ABD， PAUZAN M A B， MOHD HISAM N A S，et al.Superhydrophobic ball clay based ceramic hollow fibre membrane via universal spray coating method for membrane distillation［J］.Separation and Purification Technology，2022，288：120574.
[15]	马忠，陈晓蓉，彭艳，等.蒸汽诱导相分离法制备PVDF多孔膜及其膜蒸馏性能研究［J］.膜科学与技术，2024，44（1）：56-62.
	MA Zhong， CHEN Xiaorong， PENG Yan，et al.Study on the preparation of PVDF porous membranes by vapor-induced phase separation and its membrane distillation performance［J］.Membrane Science and Technology，2024，44（1）：56-62.
[16]	赵宇嵘，邢兴，杨辰，等.膜蒸馏脱盐过程中膜润湿控制的研究进展［J］.化工环保，2022，42（6）：669-677.
	ZHAO Yurong， XING Xing， YANG Chen，et al.Research advances in wetting control of membranes used for membrane distillation［J］.Environmental Protection of Chemical Industry，2022，42（6）：669-677.
[17]	LI Xipeng， SHAN Huiting， CAO Min，et al.Facile fabrication of omniphobic PVDF composite membrane via a waterborne coating for anti-wetting and anti-fouling membrane distillation［J］.Journal of Membrane Science，2019，589：117262.
[18]	HOU Deyin， CHRISTIE K S S， WANG Kai，et al.Biomimetic superhydrophobic membrane for membrane distillation with robust wetting and fouling resistance［J］.Journal of Membrane Science，2020，599：117708.
[19]	WEI Zhizhen， JIN Yang， LI Jun，et al.Preparation of superhydrophobic PVDF composite membrane via catechol/polyamine co-deposition and Ag nanoparticles in situ growth for membrane distillation［J］.Desalination，2022，529：115649.
[20]	KUMAR V， PULPYTEL J， RAUSCHER H，et al.Fluorocarbon coatings via plasma enhanced chemical vapor deposition of 1H，1H，2H，2H-perfluorodecyl acrylate-2，morphology，wettability and antifouling characterization［J］.Plasma Processes and Polymers，2010，7（11）：926-938.
[21]	SHI M K， SELMANI A， MARTINU L，et al.Fluoropolymer surface modification for enhanced evaporated metal adhesion［J］.Journal of Adhesion Science and Technology，1994，8（10）：1129-1141.
[22]	LIN Yinyin， LIU Qin， TANG Tingao，et al.XPS analysis of Pb（Zr_0.52Ti_0.48）O₃ thin film after dry-etching by CHF₃ plasma［J］.Applied Surface Science，2000，165（1）：34-37.
[23]	GOLUB M A， LOPATA E S， FINNEY L S.X-ray photoelectron spectroscopy study of argon plasma-treated fluoropolymers［J］.Langmuir，1994，10（10）：3629-3634.
[24]	TIJING L D， WOO Y C， SHIM W G，et al.Superhydrophobic nanofiber membrane containing carbon nanotubes for high-perfor-mance direct contact membrane distillation［J］.Journal of Membrane Science，2016，502：158-170.
[25]	REN Longfei， XIA Fan， SHAO Jiahui，et al.Experimental investigation of the effect of electrospinning parameters on properties of superhydrophobic PDMS/PMMA membrane and its application in membrane distillation［J］.Desalination，2017，404：155-166.
[26]	SU Chunlei， LI Yuping， DAI Youzhi，et al.Fabrication of three-dimensional superhydrophobic membranes with high porosity via simultaneous electrospraying and electrospinning［J］.Materials Letters，2016，170：67-71.
[27]	TOLOMAN D， STEFAN M， MACAVEI S，et al.Photocatalytic self-cleaning PVDF membrane blended with MWCNT-ZnO nanocomposites for RhB removal［J］.Coatings，2023，13（3）：594.
[28]	LIN Jiuyang， DU Jiale， XIE Shuangling，et al.Durable superhydrophobic polyvinylidene fluoride membranes via facile spray-coating for effective membrane distillation［J］.Desalination，2022，538：115925.
[29]	XIE Yahong， ZHOU Xiaofeng， MI Hongyu，et al.High efficiency ZnO-based dye-sensitized solar cells with a 1H，1H，2H，2H-perfluorodecyltriethoxysilane chain barrier for cutting on interfacial recombination［J］.Applied Surface Science，2018，434：1144-1152.

改性前后SiO₂	原子数分数/%
改性前后SiO₂	Si 2p	O 1s	C 1s	F 1s
SiO₂	36.80	62.02	1.18	0
F-SiO₂	27.73	43.90	15.01	13.36

膜	原子数分数/%
膜	C 1s	F 1s	O 1s	N 1s	Si 2p
PVDF	53.52	46.48
PCPA-PVDF	60.86	11.60	16.32	11.22
F-Si-PCPA-PVDF	20.96	16.08	38.32		24.64

膜	粗糙度/nm
膜	R_a	R_q	R_max
PVDF	267±65	331±68	2 015±245
F-Si-PCPA-PVDF	343±37	433±50	3 086±449

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会