CN114425244B - Preparation method and application of modified super-hydrophobic membrane based on polytetrafluoroethylene - Google Patents
Preparation method and application of modified super-hydrophobic membrane based on polytetrafluoroethylene Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 42
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 32
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 24
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007853 buffer solution Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract 4
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 9
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000008351 acetate buffer Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000011856 silicon-based particle Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明提供一种基于聚四氟乙烯的改性超疏水膜的制备方法，属于膜表面改性技术领域，疏水性聚四氟乙烯滤膜以乙醇预润湿后浸入热的氢氧化钠、十二烷基二甲基苄基氯化铵混合水溶液中，保温浸泡、再依次浸入γ‑氨基丙基三乙氧基硅烷的乙醇溶液、分散有二氧化硅粒子的酸性缓冲溶液和氟硅烷溶液中制得，本发明所述改性提高了聚四氟乙烯膜的疏水性，同时通量并没有降低，甚至还有所改善。
The invention provides a method for preparing a modified superhydrophobic membrane based on polytetrafluoroethylene, which belongs to the technical field of membrane surface modification. The hydrophobic polytetrafluoroethylene filter membrane is pre-wetted with ethanol and immersed in hot sodium hydroxide, ten In the mixed aqueous solution of dialkyldimethylbenzyl ammonium chloride, soak in heat preservation, then immerse in the ethanol solution of γ-aminopropyltriethoxysilane, the acid buffer solution dispersed with silica particles and the fluorosilane solution The modification described in the present invention improves the hydrophobicity of the polytetrafluoroethylene membrane, while the flux does not decrease, or even improves.
Description
技术领域technical field
本发明涉及膜表面改性技术领域，具体涉及一种基于聚四氟乙烯的改性超疏水膜的制备方法及其应用。The invention relates to the technical field of membrane surface modification, in particular to a preparation method and application of a polytetrafluoroethylene-based modified superhydrophobic membrane.
背景技术Background technique
膜蒸馏是以疏水膜材料为分离介质，蒸汽压力差为推动力的膜分离过程。与反渗透脱盐不同，膜蒸馏过程中有相变，能耗高。因此，其应用一般在反渗透无法适用、处理量相对较小的领域，在工业污水零排放、浓盐水深度浓缩和可移动式小型化纯净水制备等方向具有潜在的应用前景。Membrane distillation is a membrane separation process in which the hydrophobic membrane material is used as the separation medium and the vapor pressure difference is the driving force. Unlike reverse osmosis desalination, there is a phase change in the membrane distillation process and the energy consumption is high. Therefore, its application is generally in the fields where reverse osmosis is not applicable and the treatment capacity is relatively small, and it has potential application prospects in the directions of zero discharge of industrial sewage, deep concentration of concentrated brine, and mobile miniaturized pure water preparation.
废水回用是解决水资源紧缺的有效措施之一，以煤化工为例，含有各种有机物和大量盐分的污水需要经过复杂预处理，包括絮凝、氧化、沉淀、膜过滤和浓缩(如超微滤+反渗透)，所形成的浓盐水含盐量达50000-80000mg/L，然后经浓缩得到结晶和纯水。与现有的浓缩技术相比(如自然蒸发、机械压缩蒸发、多效蒸发)，膜蒸馏设备成本相对低、运行压力和温度低、操作条件温和、产水水质高。如果能够利用太阳能、废热、余热等作为热源进行蒸馏处理，将具有强大的竞争优势。膜蒸馏还可作为可移动式水处理设备的核心部件，为很多淡水匮乏地区提供洁净水源的。然而，膜蒸馏过程在处理复杂水体系时，疏水膜材料的污染、结垢、润湿将导致蒸馏过程不稳定，因此在膜蒸馏过程中，膜材料的疏水稳定性以及耐污染性能对于膜蒸馏的稳定运行至关重要。Wastewater reuse is one of the effective measures to solve the shortage of water resources. Taking coal chemical industry as an example, sewage containing various organic matter and a large amount of salt needs to undergo complex pretreatment, including flocculation, oxidation, precipitation, membrane filtration and concentration (such as ultrafine Filtration + reverse osmosis), the salt content of the formed concentrated brine reaches 50000-80000mg/L, and then concentrated to obtain crystals and pure water. Compared with existing concentration technologies (such as natural evaporation, mechanical compression evaporation, and multi-effect evaporation), membrane distillation equipment has relatively low cost, low operating pressure and temperature, mild operating conditions, and high-quality produced water. If it can use solar energy, waste heat, waste heat, etc. as heat sources for distillation, it will have a strong competitive advantage. Membrane distillation can also be used as a core component of mobile water treatment equipment to provide clean water for many freshwater-scarce areas. However, when the membrane distillation process deals with complex water systems, the fouling, scaling, and wetting of the hydrophobic membrane material will lead to instability in the distillation process. stable operation is crucial.
由于具有一定的价格优势，现有技术中多以改性PVDF(聚偏氟乙烯)膜作为疏水膜，PVDF膜改性后的抗污染性和耐盐性虽然会比PVDF原膜更好，但是改性后的PVDF膜的疏水稳定性和持久性则有待加强，还会造成通量的降低，从而降低了蒸馏产水效率。Due to a certain price advantage, modified PVDF (polyvinylidene fluoride) membranes are mostly used as hydrophobic membranes in the prior art. Although the anti-pollution and salt resistance of PVDF membranes after modification are better than those of original PVDF membranes, The hydrophobic stability and durability of the modified PVDF membrane need to be strengthened, and it will also cause a decrease in flux, thereby reducing the efficiency of distillation water production.
发明内容Contents of the invention
针对上述问题，本发明提供一种基于聚四氟乙烯的改性超疏水膜的制备方法及其应用。In view of the above problems, the present invention provides a preparation method and application of a polytetrafluoroethylene-based modified superhydrophobic membrane.
本发明的目的采用以下技术方案来实现：The object of the present invention adopts following technical scheme to realize:
一种基于聚四氟乙烯的改性超疏水膜的制备方法，包括以下步骤：A preparation method of a modified superhydrophobic membrane based on polytetrafluoroethylene, comprising the following steps:
S1、疏水性聚四氟乙烯滤膜以乙醇预润湿后浸入热的氢氧化钠、十二烷基二甲基苄基氯化铵混合水溶液中，保温浸泡完成后以去离子水洗涤，得到第一改性滤膜；S1. The hydrophobic polytetrafluoroethylene filter membrane is pre-wetted with ethanol and immersed in a hot mixed aqueous solution of sodium hydroxide and dodecyldimethylbenzyl ammonium chloride. After soaking in heat preservation, it is washed with deionized water to obtain The first modified filter membrane;
S2、将所述第一改性滤膜浸入γ-氨基丙基三乙氧基硅烷的乙醇溶液中，得到第二改性滤膜；S2, immersing the first modified filter membrane in an ethanol solution of γ-aminopropyltriethoxysilane to obtain a second modified filter membrane;
S3、将所述第二改性滤膜浸入分散有二氧化硅粒子的酸性缓冲溶液中，得到第三改性滤膜；S3, immersing the second modified filter membrane in an acidic buffer solution dispersed with silica particles to obtain a third modified filter membrane;
S4、将所述第三改性滤膜浸入(1H,1H,2H,2H-)全氟癸基三乙氧基硅烷的乙醇溶液中，浸泡完成后干燥，制得所述改性超疏水膜。S4. Immerse the third modified filter membrane in an ethanol solution of (1H,1H,2H,2H-)perfluorodecyltriethoxysilane, dry it after soaking, and prepare the modified superhydrophobic membrane .
在一些优选的实施方式中，所述疏水性聚四氟乙烯滤膜的孔径为0.1μm。In some preferred embodiments, the hydrophobic polytetrafluoroethylene filter membrane has a pore size of 0.1 μm.
在一些优选的实施方式中，步骤S1所述保温浸泡的温度为60℃，浸泡时间3h。In some preferred embodiments, the soaking temperature in step S1 is 60° C., and the soaking time is 3 hours.
在一些优选的实施方式中，步骤S1所述混合水溶液中氢氧化钠与十二烷基二甲基苄基氯化铵的质量比例为5:1，总浓度为总浓度为6mg/mL。In some preferred embodiments, the mass ratio of sodium hydroxide to dodecyldimethylbenzyl ammonium chloride in the mixed aqueous solution described in step S1 is 5:1, and the total concentration is 6 mg/mL.
在一些优选的实施方式中，步骤S2所述γ-氨基丙基三乙氧基硅烷与乙醇的体积比为1:100。In some preferred embodiments, the volume ratio of γ-aminopropyltriethoxysilane to ethanol in step S2 is 1:100.
在一些优选的实施方式中，步骤S3所述酸性缓冲溶液为pH＝4的醋酸盐缓冲溶液，二氧化硅粒子的分散量为0.05wt.％。In some preferred embodiments, the acidic buffer solution in step S3 is an acetate buffer solution with pH=4, and the dispersion amount of silica particles is 0.05 wt.%.
在一些优选的实施方式中，步骤S4所述(1H,1H,2H,2H-)全氟癸基三乙氧基硅烷与乙醇的体积比为1:100。In some preferred embodiments, the volume ratio of (1H,1H,2H,2H-)perfluorodecyltriethoxysilane to ethanol in step S4 is 1:100.
本发明的目的之二在于提供一种基于聚四氟乙烯的改性超疏水膜，所述改性超疏水膜由前述制备方法制备得到。The second object of the present invention is to provide a polytetrafluoroethylene-based modified super-hydrophobic membrane, which is prepared by the aforementioned preparation method.
本发明的目的之三在于提供一种所述改性超疏水膜的应用，具体是应用在膜蒸馏中。The third object of the present invention is to provide an application of the modified superhydrophobic membrane, specifically in membrane distillation.
本发明的有益效果为：The beneficial effects of the present invention are:
针对现有技术中对基底膜改性造成的稳定性和通量难以兼顾的问题，本发明提供了一种基于聚四氟乙烯的改性超疏水膜，改性提高了PTFE膜的疏水性，同时通量并没有降低甚至还得到了改善，具体的，本发明以疏水性聚四氟乙烯滤膜为基底，经NaOH-DDBAC混合液处理，然后通过硅烷偶联剂引入表面氨基，再在酸性条件下，利用静电作用将待负电荷的二氧化硅通过浸渍引入，最后再经氟硅烷处理，干燥制得，本发明改性后的PTFE膜经历三个不同盐度的膜蒸馏循环测试，依旧保持着较好的耐盐性而没有被润湿，其抗污染性和耐盐性对比PTFE膜得到了更好的提高，相比未改性PTFE膜，其对不同浓度的盐溶液具有良好的耐受性，膜通量也有了较大的提升。Aiming at the problem that the stability and flux caused by the modification of the base membrane in the prior art are difficult to balance, the present invention provides a modified super-hydrophobic membrane based on polytetrafluoroethylene, which improves the hydrophobicity of the PTFE membrane. At the same time, the flux has not been reduced or even improved. Specifically, the present invention uses a hydrophobic polytetrafluoroethylene filter membrane as a substrate, treats it with NaOH-DDBAC mixed solution, and then introduces surface amino groups through a silane coupling agent. Under the conditions, the silicon dioxide to be negatively charged is introduced by impregnation by electrostatic interaction, and finally treated with fluorosilane and dried. The modified PTFE membrane of the present invention has undergone three membrane distillation cycles with different salinities. It maintains good salt resistance without being wetted, and its anti-pollution and salt resistance are better improved than PTFE membranes. Compared with unmodified PTFE membranes, it has good resistance to different concentrations of salt solutions Tolerance and membrane flux have also been greatly improved.
附图说明Description of drawings
利用附图对本发明作进一步说明，但附图中的实施例不构成对本发明的任何限制，对于本领域的普通技术人员，在不付出创造性劳动的前提下，还可以根据以下附图获得其它的附图。The present invention is further described by using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. For those of ordinary skill in the art, without paying creative work, other embodiments can also be obtained according to the following accompanying drawings Attached picture.
图1是是水滴与PTFF膜相互作用力的曲线图；Figure 1 is a graph of the interaction force between water droplets and PTFF membranes;
图2是水滴与F-SiO2@PTFE膜相互作用力的曲线图；Figure 2 is a graph of the interaction force between water droplets and F-SiO 2 @PTFE membrane;
图3是水在PTFF膜与F-SiO2@PTFE膜上的接触角对比图；Figure 3 is a comparison diagram of the contact angle of water on PTFF membrane and F-SiO 2 @PTFE membrane;
图4是水在PTFF膜与F-SiO2@PTFE膜上的滚动性对比图；Figure 4 is a comparison diagram of rolling properties of water on PTFF membrane and F-SiO 2 @PTFE membrane;
图5是实验例所述膜蒸馏装置的结构示意图；Fig. 5 is the structural representation of membrane distillation device described in experimental example;
图6是PTFE膜与F-SiO2@PTFE膜分别对热水侧1.5wt.％、3.5wt.％、5.5wt.％NaCl溶液通量随时间变化图。Fig. 6 is a time-varying diagram of fluxes of 1.5wt.%, 3.5wt.%, and 5.5wt.% NaCl solutions on the hot water side of PTFE membrane and F-SiO 2 @PTFE membrane respectively.
具体实施方式Detailed ways
结合以下实施例对本发明作进一步描述。The present invention is further described in conjunction with the following examples.
本发明的实施例涉及一种改性超疏水膜，其制备方法包括以下步骤：Embodiments of the present invention relate to a modified superhydrophobic membrane, the preparation method of which comprises the following steps:
(1)将干燥的疏水PTFE膜用乙醇完全预湿，然后浸入NaOH和DDBAC(十二烷基二甲基苄基氯化铵)的混合液中，一起放入烘箱中，在60℃温度下浸泡3h，滤出并以去离子水洗涤，得到碱性处理的PTFE膜；(1) The dry hydrophobic PTFE membrane is completely pre-wetted with ethanol, then immersed in the mixture of NaOH and DDBAC (dodecyl dimethyl benzyl ammonium chloride), and placed in an oven together at a temperature of 60 ° C. Soak for 3 hours, filter out and wash with deionized water to obtain an alkaline-treated PTFE membrane;
所述混合液中NaOH和DDBAC的浓度分别为5mg/mL、1mg/mL；The concentrations of NaOH and DDBAC in the mixed solution are respectively 5mg/mL and 1mg/mL;
(2)将(1)得到的PTFE膜在1％(v/v)的APTES(γ-氨基丙基三乙氧基硅烷)-乙醇溶液中浸泡1h，使膜表面引入端胺基和正电荷；(2) Soak the PTFE membrane obtained in (1) in 1% (v/v) APTES (γ-aminopropyltriethoxysilane)-ethanol solution for 1h, so that the membrane surface is introduced with terminal amine groups and positive charges;
(3)将(2)得到的带正电荷的PTFE膜浸入分散有SiO2粒子的醋酸盐缓冲溶液(pH＝4)中，浸泡时间2.5h，制得SiO2@PTFE膜；(3) Immerse the positively charged PTFE membrane obtained in (2) in an acetate buffer solution (pH=4) dispersed with SiO 2 particles for 2.5 hours to prepare SiO 2 @PTFE membrane;
所述缓冲溶液中的醋酸含量为0.0375mL/L，SiO2粒子含量为0.5g/L；The acetic acid content in the buffer solution is 0.0375mL/L, and the SiO particle content is 0.5g/L;
(4)将(3)制得的SiO2@PTFE膜浸入1％(v/v)的(1H,1H,2H,2H-)全氟癸基三乙氧基硅烷-乙醇溶液中，浸泡时间10min，取出后在120℃下真空干燥20min，制得所述改性超疏水膜(记为F-SiO2@PTFE)。(4) Immerse the SiO 2 @PTFE membrane prepared in (3) in 1% (v/v) (1H,1H,2H,2H-)perfluorodecyltriethoxysilane-ethanol solution, soaking time After taking it out for 10 minutes, it was vacuum-dried at 120° C. for 20 minutes to prepare the modified superhydrophobic membrane (referred to as F-SiO 2 @PTFE).
实验例Experimental example
1、以未改性的PTEF膜为对比，测定水滴与PTEF膜以及F-SiO2@PTFE膜相互作用力，测定结果参见附图1-2；1. Taking the unmodified PTEF membrane as a comparison, measure the interaction force between water droplet, PTEF membrane and F-SiO 2 @PTFE membrane, see attached drawings 1-2 for the measurement results;
2、以未改性的PTEF膜为对比，测定水在PTEF膜以及F-SiO2@PTFE膜的接触角和滚动性，测定结果参见附图3-4；2. Taking the unmodified PTEF membrane as a comparison, measure the contact angle and rolling property of water on the PTEF membrane and F-SiO 2 @PTFE membrane, and the measurement results are shown in Figure 3-4;
3、以未改性的PTEF膜为对比，在膜蒸馏装置中进行连续测试，膜蒸馏装置结构示意图参见附图5，测定PTFE膜与F-SiO2@PTFE膜分别对热水侧不同浓度的NaCl溶液(冷水侧为纯水)的通量变化，测定结果参见附图6。3. Taking the unmodified PTEF membrane as a comparison, continuous testing was carried out in the membrane distillation device. The schematic diagram of the membrane distillation device is shown in Figure 5, and the PTFE membrane and F-SiO 2 @PTFE membrane were respectively tested for different concentrations on the hot water side. For the flux change of NaCl solution (pure water on the cold water side), refer to accompanying drawing 6 for the measurement results.
最后应当说明的是，以上实施例仅用以说明本发明的技术方案，而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细地说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting the protection scope of the present invention, although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand , the technical solution of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.
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