WO2022121102A1 - 多孔聚合物修饰的金属碳纳米管复合膜及其制备方法与应用 - Google Patents

多孔聚合物修饰的金属碳纳米管复合膜及其制备方法与应用 Download PDF

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WO2022121102A1
WO2022121102A1 PCT/CN2021/074576 CN2021074576W WO2022121102A1 WO 2022121102 A1 WO2022121102 A1 WO 2022121102A1 CN 2021074576 W CN2021074576 W CN 2021074576W WO 2022121102 A1 WO2022121102 A1 WO 2022121102A1
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carbon nanotube
porous polymer
modified
nanotube composite
modified metal
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French (fr)
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路建美
陈冬赟
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Suzhou University
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Suzhou University
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    • 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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention belongs to the technical field of functional materials, and specifically relates to a porous polymer modified metal carbon nanotube composite membrane and a preparation method thereof, and is specifically applied to the separation of dye-containing wastewater.
  • the amount of dyes used is very large, so the discharged industrial wastewater often contains a variety of dyes, which has become one of the important reasons for water pollution.
  • the dyes in the wastewater can absorb light, reduce the transparency of the water body, affect the growth of aquatic organisms and microorganisms, are not conducive to the self-purification of the water body, and even seriously affect human health.
  • various water purification processes have been developed, such as chemical oxidation, adsorption, photodegradation, biodegradation and membrane separation, etc.
  • Each of these methods has advantages and disadvantages.
  • the nanofiltration membrane separation method due to its high efficiency, low energy consumption and environmental friendliness, the nanofiltration membrane separation method, which is being widely studied, undoubtedly has very broad application prospects.
  • the purpose of the present invention is to prepare a carbon membrane material with dye separation performance, so as to realize its wide application in the separation of various dyes, specifically the preparation method of the composite membrane and the application in the treatment of dye-containing wastewater.
  • the metal carbon nanotube composite film modified by a porous polymer is prepared by mixing the acidified carbon nanotube film with a modification solution and then heating and reacting to obtain a modified carbon nanotube film; and then coating the surface of the modified carbon nanotube film
  • the polyethylene glycol is then coated with a porous polymer solution and heated to obtain a metal carbon nanotube composite membrane modified by the porous polymer;
  • the modification solution is composed of zirconium salt, terephthalic acid, acetic acid, and a solvent;
  • the porous polymer The preparation method is, in nitrogen, in the presence of anhydrous potassium carbonate, mix 2,3,5,6-tetrafluoroterephthalonitrile with 5,5',6,6'-tetrahydroxy-3,3' ,4,4'-tetramethyl-1,1'-spiral double indane reaction, after the reaction is completed, the product is precipitated in methanol, and the precipitate is sequentially dissolved in chloroform, precipitated in methanol, and boiled to obtain
  • the invention discloses an application of a porous polymer-modified metal carbon nanotube composite membrane in water treatment.
  • the water treatment is to separate dye-containing wastewater; passing the dye-containing wastewater through the porous polymer-modified metal carbon nanotube composite membrane, Complete the separation of dye-containing wastewater; dyes include Congo red, rhodamine B, methyl orange, chrome black T, acid fuchsin, methyl blue or reactive black.
  • dyes include Congo red, rhodamine B, methyl orange, chrome black T, acid fuchsin, methyl blue or reactive black.
  • the separation of dye-containing wastewater is completed under argon pressure.
  • the carbon nanotube film is immersed in aqua regia for acidification to obtain the acidified carbon nanotube film; the carbon nanotube film itself is an existing product.
  • the zirconium salt is zirconium tetrachloride
  • the solvent is N,N-dimethylformamide
  • the dosage ratio of zirconium salt, terephthalic acid and acetic acid is (0.1-0.12) g: (0.08- 0.09) g: (8-8.5) mL, such as 0.112 g: 0.087 g: 8.3 mL.
  • the heating reaction is performed at 115 to 125° C. for 20 to 25 hours; preferably, the heating reaction is performed at 120° C. for 24 hours.
  • the coating is spin coating or spray coating
  • the specific operation is the existing method.
  • anhydrous potassium carbonate 2,3,5,6-tetrafluoroterephthalonitrile, 5,5',6,6'-tetrahydroxy-3,3',4,4'-tetramethyl
  • the weight ratio of base-1,1'-helix double indane is (65 ⁇ 70):12:(20 ⁇ 22).
  • the polymerization reaction is performed at 150-170° C. for 45-60 minutes; preferably, the polymerization reaction is performed at 160° C. for 50 minutes; preferably, during the reaction, toluene is added every 10 minutes.
  • the heat treatment is performed at 110 to 130° C. for 5 to 7 hours, and the heat treatment is preferably performed at 120° C. for 6 hours.
  • polyethylene glycol diglycidyl ether is dissolved in methanol to prepare a polyethylene glycol solution, which is then coated on the surface of the modified carbon nanotube film.
  • concentration of the polyethylene glycol solution is 5wt%;
  • the porous polymer is dissolved in DMF, and then branched polyethyleneimine is added to prepare a porous polymer solution.
  • the weight of the branched polyethyleneimine is 10% of the weight of the porous polymer.
  • the invention successfully prepares the porous polymer-coated metal carbon nanotube composite membrane, and realizes the high-efficiency nanofiltration separation of various dyes. Separation efficiencies of 90% or higher were achieved for many dyes tested.
  • the composite membrane can provide suitable pore size and porosity required for dye separation, in which the polymer coating mainly plays the role of enhancing the stability and durability of the membrane, and solving the crystal defects that may occur during the metal growth process.
  • the membrane material is easy to fabricate, has broad applicability for dye separation, and has great application potential.
  • Figure 1 shows the scanning electron microscope images and atomic force microscope images of the MWCNT films before and after modification.
  • Figure 2 is a comparison chart of the dye separation effect of different membranes.
  • Figure 3 is a graph of the dye separation performance of the modified composite membrane.
  • Figure 4 shows the recycling separation efficiency and flux of chromium black T by the modified composite membrane.
  • the raw materials used in the present invention are all existing commercial products, and the specific preparation operations and testing methods are conventional methods in the field.
  • Example 1 Preparation of the porous polymer-modified metal carbon nanotube composite film, the specific steps are as follows.
  • MWCNT modified multi-walled carbon nanotube
  • a and d are unmodified MWCNT films
  • b and e are metal-loaded modified MWCNT films
  • c and f are MWCNT films (composite films) coated with porous polymer; metal and porous polymer can be seen All have been successfully modified on the MWCNT film.
  • the membrane is fixed in the filter equipment Sterlitech HP4750 high-pressure stirring tank, poured into the corresponding dye solution, and pressurized to 3.0 bar (bar) by passing argon, under the action of pressure, the dye-containing wastewater is completed. separation.
  • Example 2 Comparative test of dye separation effect of metal-loaded modified MWCNT membranes before and after modification of porous polymer Figure 2 carried out a separation experiment of two single-component dye solutions, and compared the membranes before and after coating with porous polymer
  • a is the separation efficiency of the composite membrane modified with porous polymer to Congo red
  • b is the separation efficiency of the modified MWCNT membrane loaded with metal to Congo red
  • c is the composite membrane modified with porous polymer Recirculation separation efficiency of the membrane for Congo red solution
  • d is the separation efficiency of rhodamine B by the composite membrane modified with porous polymer
  • e is the separation efficiency of rhodamine B by the metal-loaded modified MWCNT membrane
  • f is the separation efficiency of rhodamine B Recycling separation efficiency of rhodamine B solution by composite membranes of porous polymers.
  • the separation efficiencies of the metal-loaded modified MWCNT membranes were 95.6% (Congo red) and 61.0% (Rhodamine B), and the separation efficiencies of the composite membranes modified with porous polymers were 97.7% (Congo red) and 91.9% (Rhodamine B), respectively. B), the separation efficiency of the membrane can be significantly improved.
  • Example 1 On the basis of Example 1, the mixed solution 2 was evenly sprayed on the modified MWCNT film loaded with metal, that is, without polyethylene glycol modification, the rest were the same, and the separation efficiency of the obtained composite film for Rhodamine B was: 88.2%, but the second separation dropped to 85.1% and the third separation dropped to 75.9%.
  • Example 1 On the basis of Example 1, the heating at 120 °C for 6 hours was changed to heating at 120 °C for 10 hours, and the rest was the same.
  • the separation efficiency of the obtained composite membrane for Rhodamine B was 85.7%.
  • Example 1 On the basis of Example 1, the preparation of the porous polymer was adjusted from 160°C for 50 minutes to 140°C for 3 hours, and the rest was the same, and the obtained composite membrane had a separation efficiency of 83.1% for Rhodamine B.
  • Example 1 On the basis of Example 1, the heating at 120° C. for 24 hours was adjusted to be heated at 150° C. for 15 hours, and the rest were the same.
  • the separation efficiency of the obtained composite membrane for Rhodamine B was 79.6%.
  • Example 3 Dye separation performance test of the composite membrane modified with porous polymer: The separation efficiency of the composite membrane for dyes with different molecular weights was tested. The results show that the separation efficiency of the membrane for various dyes with molecular weights from 200 to 1300 is over 90%, indicating that the separation performance of the composite membrane has wide applicability.
  • chrome black T was chosen as the dye for the experiments to test the cycle performance of the films. After 10 cycles, the separation efficiency of chrome black T decreased from 98% to 96%, and the separation flux remained above 40 L m -2 s -1 MPa -1 , indicating that the composite membrane modified with porous polymer can effectively perform multiple a separation operation.
  • Figure 3 is the separation efficiency of different molecular weight dyes
  • Figure 4 is the recycling separation efficiency and flux of chrome black T.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

多孔聚合物修饰的金属碳纳米管复合膜及其制备方法与应用，将酸化后的碳纳米管膜与修饰液混合后加热反应，得到修饰碳纳米管膜；然后在修饰碳纳米管膜表面涂覆聚乙二醇后再涂覆多孔聚合物溶液，加热处理，得到多孔聚合物修饰的金属碳纳米管复合膜。成功地制备了涂覆多孔聚合物的金属碳纳米管复合膜，并实现了多种染料的高效纳滤分离，测试的多种染料的分离效率达到90％或更高。另外，该膜材料易于制造，具有广泛的染料分离适用性，具有很大的应用潜力。

Description

多孔聚合物修饰的金属碳纳米管复合膜及其制备方法与应用 技术领域
本发明属于功能材料技术领域，具体涉及到一种多孔聚合物修饰的金属碳纳米管复合膜及其在制备方法，具体应用于含染料废水的分离。
 背景技术
在纺织印染行业中，染料的使用量非常大，因此排放的工业废水中经常含有多种染料，这已成为造成水污染的重要原因之一。废水中的染料可以吸收光，降低水体的透明度，影响水生生物和微生物的生长，不利于水体的自净，甚至严重影响人体健康。目前，为了解决污水中所含的染料，已经开发了多种水净化工艺，例如化学氧化，吸附，光降解，生物降解和膜分离等。这些方法各有优缺点。然而，值得注意的是，由于其高效，低能耗和环境友好的特点，正在被广泛研究的纳滤膜分离方法无疑具有非常广阔的应用前景。
 技术问题
本发明目的是制备出一种具有染料分离性能的碳膜材料，以实现其在多种染料分离方面得到广泛的应用，具体为该复合膜的制备方法与在处理含染料废水中的应用。
 技术解决方案
为了达到上述目的，本发明具体技术方案如下。
多孔聚合物修饰的金属碳纳米管复合膜，其制备方法为，将酸化后的碳纳米管膜与修饰液混合后加热反应，得到修饰碳纳米管膜；然后在修饰碳纳米管膜表面涂覆聚乙二醇后再涂覆多孔聚合物溶液，加热处理，得到多孔聚合物修饰的金属碳纳米管复合膜；修饰液由锆盐、对苯二甲酸、乙酸、溶剂组成；所述多孔聚合物的制备方法为，氮气中，在无水碳酸钾存在下，将2，3,5,6-四氟对苯二甲腈与5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满反应，反应结束后，将产物在甲醇中析出沉淀，所述沉淀依次经过氯仿溶解、甲醇析出、水煮，得到多孔聚合物。
本发明公开了多孔聚合物修饰的金属碳纳米管复合膜在水处理中的应用，水处理为分离含染料废水；将含染料废水通过上述多孔聚合物修饰的金属碳纳米管复合膜，即可完成含染料废水的分离；染料包括刚果红，罗丹明B，甲基橙，铬黑T，酸性品红，甲基蓝或者活性黑。优选的，在氩气加压下，完成含染料废水的分离。
本发明中，将碳纳米管膜浸入王水中进行酸化，得到酸化后的碳纳米管膜；碳纳米管膜本身为现有产品。
本发明中，锆盐为四氯化锆，溶剂为N,N-二甲基甲酰胺；优选的，锆盐、对苯二甲酸、乙酸的用量比例为（0.1～0.12）g∶（0.08～0.09）g∶（8～8.5）mL ，比如0.112g∶0.087g∶8.3mL。
本发明中，加热反应为115～125℃下反应20～25小时；优选加热反应为120℃下反应24小时。
本发明中，涂覆为旋涂或者喷涂，具体操作为现有方法。
本发明中，无水碳酸钾、2，3,5,6-四氟对苯二甲腈、5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满的重量比为（65～70）∶12∶（20～22）。
本发明中，聚合反应为150～170℃反应45～60分钟；优选聚合反应为160℃反应50分钟；优选的，反应过程中，每隔10分钟加入甲苯。
本发明中，加热处理为110～130℃下加热5～7小时，优选加热处理为120℃下加热6小时。
本发明中，将聚乙二醇二缩水甘油醚溶解在甲醇中制备聚乙二醇溶液，再涂覆在修饰碳纳米管膜表面，优选的，聚乙二醇溶液的浓度为5wt%；将多孔聚合物溶解在DMF中，然后添加支链化聚乙烯亚胺制备多孔聚合物溶液，优选的，支链化聚乙烯亚胺的重量为多孔聚合物重量的10%。
 有益效果
本发明成功地制备了涂覆多孔聚合物的金属碳纳米管复合膜，并实现了多种染料的高效纳滤分离。测试的多种染料的分离效率达到90％或更高。复合膜可提供染料分离所需的合适孔径和孔隙率，其中聚合物涂层主要起到增强膜的稳定性和耐久性的作用，并解决了金属生长过程中可能出现的晶体缺陷。另外，该膜材料易于制造，具有广泛的染料分离适用性，具有很大的应用潜力。
 附图说明
图1为修饰前和修饰后的MWCNT膜扫描电镜图与原子力显微镜图。
图2为不同膜的染料分离效果对比图。
图3为修饰后的复合膜的染料分离性能图。
图4为修饰后复合膜对铬黑T的再循环分离效率和通量。
 本发明的实施方式
本发明所用原料都为现有市售产品，具体制备操作以及测试方法都为本领域常规方法。
实施例一 多孔聚合物修饰的金属碳纳米管复合膜的制备, 具体步骤如下。
（1）修饰多壁碳纳米管（MWCNT）薄膜的合成。首先，将30毫升浓盐酸和10毫升浓硝酸以3：1的体积比配制成王水，将现有MWCNT薄膜放入其中并在50℃下浸泡6小时进行酸化，然后，将酸化的MWCNT膜用超纯水洗涤并干燥。
精确称量0.112克四氯化锆和0.087克对苯二甲酸，将它们溶解在60毫升N,N-二甲基甲酰胺（DMF）中，然后超声处理20分钟，随后，向溶液中加入8.3毫升乙酸得到混合物，然后将混合物和酸化后干燥的MWCNT膜（10*10平方厘米）转移到100毫升的不锈钢高压釜中，在120摄氏度下加热24小时；自然冷却后，用DMF和甲醇洗涤，最后在60摄氏度下干燥12小时，得到负载有金属的修饰MWCNT膜。
（2）多孔聚合物的制备。称取 12.0克2，3,5,6-四氟对苯二甲腈，置于干燥的三口烧瓶中，在氮气的气氛中，加入50毫升DMF，再称取20.4克重结晶后的5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满（TTSBI），加入烧瓶中搅拌溶解；然后加入67.0克无水碳酸钾，搅拌均匀，在160摄氏度的油浴中加热反应；期间每隔10分钟向反应中加入5毫升无水甲苯，50分钟后停止反应；冷却至室温，将产物倒入600毫升甲醇中，析出沉淀，随后，将析出的沉淀溶解于100毫升氯仿中，完全溶解后，再倒入500毫升甲醇，使沉淀析出，过滤沉淀，重复溶解/析出操作4次，得到荧光黄色沉淀；最后，将得到的沉淀剪碎，置于超纯水中，煮沸5小时后过滤，用超纯水和乙醇洗涤，反复三次后，置于80摄氏度的真空烘箱中，干燥12小时，得到15.1克黄色固体，为多孔聚合物。
（3）复合膜的制备。将1.0克聚乙二醇二缩水甘油醚（PEGDEG）溶解在19克甲醇中制备质量百分数为5%的溶液1，将溶液1均匀旋涂在负载有金属的修饰MWCNT膜上，常温下干燥，得到聚乙二醇修饰膜。
将1.0克多孔聚合物溶解在20毫升的DMF中，然后添加0.1克的支链化聚乙烯亚胺（PEI）来制备混合溶液2；将混合溶液2均匀喷涂在聚乙二醇修饰膜上，然后将其放入烤箱中，并在120℃下加热6小时，得到产品复合膜。
附图1中a和d是未修饰的MWCNT膜，b和e是负载有金属的修饰MWCNT膜，c和f是涂覆有多孔聚合物的MWCNT膜（复合膜）；可见金属和多孔聚合物均已成功修饰在了MWCNT膜上。
通过常规方法制备七种典型的染料溶液。将刚果红，罗丹明B，甲基橙，铬黑T，酸性品红，甲基蓝，活性黑分别加入100毫升水中分别配制成浓度为100ppm的单组分溶液，即含染料废水；用于以下测试。
根据常规操作，将膜固定在过滤器设备Sterlitech HP4750高压搅拌池中，倒入相应的染料溶液，并通入氩气加压至3.0巴（bar），在压力的作用下，完成含染料废水的分离。
实施例二 修饰多孔聚合物前后的负载有金属的修饰MWCNT膜的染料分离效果对比测试：附图2进行了两种单组分染料溶液的分离实验，比较了用多孔聚合物涂覆前后的膜的分离效果；附图2中a为修饰有多孔聚合物的复合膜对刚果红的分离效率，b为负载有金属的修饰MWCNT膜对刚果红的分离效率，c是修饰有多孔聚合物的复合膜对刚果红溶液的再循环分离效率，d是修饰有多孔聚合物的复合膜对罗丹明B的分离效率，e是负载有金属的修饰MWCNT膜对罗丹明B的分离效率，f是修饰有多孔聚合物的复合膜对罗丹明B溶液的再循环分离效率。
负载有金属的修饰MWCNT膜的分离效率为95.6％（刚果红）和61.0％（罗丹明B），修饰有多孔聚合物的复合膜的分离效率分别为97.7％（刚果红）和91.9％（罗丹明B），膜的分离效率可以显着提高。
另外，酸化的MWCNT膜对罗丹明B的分离效率为42.3%，聚乙二醇修饰膜对罗丹明B的分离效率为63.7%。
同时，测试了两种染料溶液的循环分离效果，一次分离后用水洗涤、烘干后进行再次分离；5个循环后，修饰有多孔聚合物的复合膜对刚果红的分离效率可保持在95％以上，罗丹明B的分离效率保持在90％以上，表明修饰有多孔聚合物的复合膜能够连续分离，用于染料分离的膜材料被成功地制备。
对比例：在实施例一基础上，将混合溶液2均匀喷涂在负载有金属的修饰MWCNT膜上，即不采用聚乙二醇修饰，其余一样，得到的复合膜对罗丹明B的分离效率为88.2%，但第二次分离下降为85.1%，第三次分离下降为75.9%。
在实施例一基础上，将120℃下加热6小时修改为120℃下加热10小时，其余一样，得到的复合膜对罗丹明B的分离效率为85.7%。
在实施例一基础上，将多孔聚合物的制备由160摄氏度50分钟调整为140℃3小时，其余一样，得到的复合膜对罗丹明B的分离效率为83.1%。
在实施例一基础上，将120摄氏度下加热24小时调整为150℃加热15小时，其余一样，得到的复合膜对罗丹明B的分离效率为79.6%。
实施例三 修饰有多孔聚合物的复合膜的染料分离性能测试：测试了复合膜对不同分子量的染料的分离效率。结果表明，膜对分子量为200至1300的各种染料的分离效率均达到90％以上，表明复合膜的分离性能具有广泛的适用性。另外，选择铬黑T作为测试膜循环性能实验的染料。10个循环后，铬黑T的分离效率从98％降至96％，分离通量保持在40 L m -2 s -1 MPa -1以上，表明修饰有多孔聚合物的复合膜可以有效执行多种分离操作。
附图3是不同分子量染料的分离效率；附图4是铬黑T的再循环分离效率和通量。
总结：在这项工作中，成功地制备了修饰有多孔聚合物的复合膜，并实现了多种染料的高效纳滤分离。测试的多种染料的分离效率达到90％或更高，修饰有多孔聚合物的复合膜可提供染料分离所需的合适孔径和孔隙率，且膜的稳定性和耐久性好，并解决了金属生长过程中可能出现的晶体缺陷。另外，该膜材料易于制造，具有广泛的染料分离适用性，具有很大的应用潜力。

Claims (10)

  1. 多孔聚合物修饰的金属碳纳米管复合膜，其特征在于，所述多孔聚合物修饰的金属碳纳米管复合膜的制备方法为，将酸化后的碳纳米管膜与修饰液混合后加热反应，得到修饰碳纳米管膜；然后在修饰碳纳米管膜表面涂覆聚乙二醇后再涂覆多孔聚合物溶液，加热处理，得到多孔聚合物修饰的金属碳纳米管复合膜；修饰液由锆盐、对苯二甲酸、乙酸、溶剂组成；所述多孔聚合物的制备方法为，氮气中，在无水碳酸钾存在下，将2，3,5,6-四氟对苯二甲腈与5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满反应，反应结束后，将产物在甲醇中析出沉淀，所述沉淀依次经过氯仿溶解、甲醇析出、水煮，得到多孔聚合物。
  2. 根据权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜，其特征在于，将碳纳米管膜浸入王水中进行酸化，得到酸化后的碳纳米管膜；涂覆为旋涂或者喷涂。
  3. 根据权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜，其特征在于，锆盐为四氯化锆；锆盐、对苯二甲酸、乙酸的用量比例为（0.1～0.12）g∶（0.08～0.09）g∶（8～8.5）mL。
  4. 根据权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜，其特征在于，加热反应为115～125℃下反应20～25小时；聚合反应为150～170℃反应45～60分钟；加热处理为110～130℃下加热5～7小时。
  5. 根据权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜，其特征在于，无水碳酸钾、2，3,5,6-四氟对苯二甲腈、5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满的重量比为（65～70）∶12∶（20～22）。
  6. 权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜在水处理中的应用。
  7. 根据权利要求6所述的应用，其特征在于，所述水处理为分离含染料废水。
  8. 权利要求1所述多孔聚合物修饰的金属碳纳米管复合膜的制备方法，其特征在于，包括以下步骤：将酸化后的碳纳米管膜与修饰液混合后加热反应，得到修饰碳纳米管膜；然后在修饰碳纳米管膜表面涂覆聚乙二醇后再涂覆多孔聚合物溶液，加热处理，得到多孔聚合物修饰的金属碳纳米管复合膜；修饰液由锆盐、对苯二甲酸、乙酸、溶剂组成；所述多孔聚合物的制备方法为，氮气中，在无水碳酸钾存在下，将2，3,5,6-四氟对苯二甲腈与5,5’,6,6’-四羟基-3,3’,4,4’-四甲基-1,1’-螺旋双茚满进行聚合反应，反应结束后，将产物在甲醇中析出沉淀，所述沉淀依次经过氯仿溶解、甲醇析出、水煮，得到多孔聚合物。
  9. 根据权利要求8所述多孔聚合物修饰的金属碳纳米管复合膜的制备方法，其特征在于，将聚乙二醇二缩水甘油醚溶解在甲醇中制备聚乙二醇溶液，再涂覆在修饰碳纳米管膜表面。
  10. 根据权利要求8所述多孔聚合物修饰的金属碳纳米管复合膜的制备方法，其特征在于，将多孔聚合物溶解在DMF中，然后添加支链化聚乙烯亚胺制备多孔聚合物溶液。
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