WO2024255053A1 - 一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法 - Google Patents

一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法 Download PDF

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WO2024255053A1
WO2024255053A1 PCT/CN2023/126375 CN2023126375W WO2024255053A1 WO 2024255053 A1 WO2024255053 A1 WO 2024255053A1 CN 2023126375 W CN2023126375 W CN 2023126375W WO 2024255053 A1 WO2024255053 A1 WO 2024255053A1
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hollow fiber
fiber membrane
composite hollow
conductive
membrane
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French (fr)
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全燮
杜磊
魏高亮
陈硕
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Dalian University of Technology
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Dalian University of Technology
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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
    • B01D71/0212—Carbon nanotubes
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • 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

Definitions

  • the invention belongs to the technical field of separation membrane preparation, and in particular relates to a method for preparing a conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane and an electrochemically coupled membrane separation component.
  • Membrane separation technology is widely used in water treatment, gas separation, food processing, and drug purification because of its simplicity and high efficiency. It is an important technology to solve problems such as resource shortages and environmental pollution. However, traditional membrane separation technology still has problems such as serious membrane pollution and the mutual restriction of membrane permeability and selectivity, and cannot effectively exert its performance.
  • Electrochemical water treatment technology is a technology that removes pollutants from water by applying an external electric field to cause the electric field effect or electrochemical reaction of pollutants at the solid-liquid interface between the electrode and water. Coupling electrochemical technology with membrane separation and utilizing electrostatic repulsion, electrochemical oxidation-reduction, and electrically assisted adsorption is expected to solve the problems of serious membrane pollution and the mutual restriction of membrane permeability and selectivity in membrane separation technology. It is a new membrane separation technology with great practical application potential.
  • Electro-assisted membrane separation technology based on non-conductive membranes requires an external high-voltage electric field to induce polarization of the membrane, and its high energy consumption restricts its application. Electro-assisted membrane separation technology based on conductive membranes can directly apply a lower voltage to the membrane, which is more energy-saving and efficient to achieve the electro-assisted effect.
  • the conductive separation membranes under research mainly include carbon membranes, metal membranes, conductive polymer membranes and conductive ceramic membranes. These conductive separation membranes have poor stability and mechanical strength, and the preparation process is relatively complicated, which is not conducive to practical application.
  • Conductive polymer materials can be divided into composite conductive polymer materials and structural conductive polymer materials.
  • the conductive mechanism of composite conductive polymer materials is different from that of structural conductive polymer materials (polyaniline, polypyrrole, polythiophene, etc.). It is achieved by adding conductive fillers to traditional polymer materials. After the concentration of the conductive material reaches a critical value, a conductive network is formed in the polymer, which can realize the conduction of electrons.
  • the purpose of the present invention is to provide a method for preparing a conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane and an electrochemically coupled membrane separation component.
  • the conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane uses carbon nanotubes as conductive fillers, utilizes a dispersant to enhance the dispersibility of the carbon nanotubes in polyvinylidene fluoride, is prepared by a wet spinning process, and the hollow fiber membrane is conductively packaged and connected to construct an electrochemically coupled membrane separation component that can realize the combination of electrochemical action and membrane separation function, enhance the anti-pollution ability of the separation membrane, and alleviate the contradiction between its permeability and selectivity.
  • the present invention provides the following technical solutions:
  • a method for preparing a conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane comprises the following steps:
  • the preparation process of the self-supporting composite hollow fiber membrane is as follows: the spinning solution is vacuum degassed as the shell liquid, and water is used as the core liquid, and the shell liquid flow rate and the core liquid flow rate are controlled to be spun into the water coagulation bath at a certain speed ratio through the spinneret of the spinning machine to obtain the self-supporting composite hollow fiber membrane;
  • the preparation process of the composite hollow fiber membrane with inner lining is as follows: vacuum degassing the spinning solution as the shell solution, controlling the speed of the spinning solution injection pump and the speed of the winding roller pulling the inner lining, and mixing the spinning solution and the inner lining through the spinneret and spinning them into a water coagulation bath to obtain the composite hollow fiber membrane with inner lining;
  • the initially solidified carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane is wound on a winding roller, and after spinning, it is soaked in water for 24 to 72 hours to remove excess organic solvent and dispersant, and then naturally air-dried and collected.
  • the carboxylated carbon nanotubes in step (1) are single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes; the carboxyl content is 0.5wt% to 5wt%, preferably 2wt% to 3wt%. Too low a carboxyl content will cause the carbon nanotubes to have poor dispersibility, and too high a carboxyl content will cause the composite hollow fiber membrane to have poor conductivity.
  • the dispersant in step (1) is one or a mixture of two or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, commercial TNACPS dispersant, commercial TNDPS dispersant, commercial Disponer983 dispersant, and commercial XFZ33NMP dispersant; carboxylated carbon nanotubes and dispersant
  • the mass ratio is 0.5 to 5:1, and preferably the mass ratio of carboxylated carbon nanotubes to dispersant is 0.5 to 2:1.
  • the solvent in step (1) is one or a mixture of two or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and the mass fraction of the solute (carboxylated carbon nanotubes and dispersant) in the solution is controlled to be 15% to 30%, preferably 20% to 25%.
  • the mass ratio of carboxylated carbon nanotubes to polyvinylidene fluoride is 15 to 100:100, preferably the mass ratio of carboxylated carbon nanotubes to polyvinylidene fluoride is 1:2. Too low a proportion of carboxylated carbon nanotubes will result in poor conductivity of the composite hollow fiber membrane, and too high a proportion of carboxylated carbon nanotubes will result in poor mechanical strength of the composite hollow fiber membrane.
  • step (2) the ratio of the shell liquid flow rate to the core liquid flow rate of the self-supporting composite hollow fiber membrane is 0.5 to 5:1, and preferably the ratio of the shell liquid flow rate to the core liquid flow rate is 1:1.
  • step (2) the speed of the spinning solution injection pump of the lined composite hollow fiber membrane is 10-50 rpm/min, and the speed of the winding roller pulling the lining is 10-30 m/min.
  • the speed of the injection pump is 20-30 rpm/min, and the speed of the winding roller pulling the lining is 13-18 m/min.
  • the lining of the lined composite hollow fiber membrane is a braided tube lining or a crocheted tube lining, and the material of the lining is not limited.
  • Another aspect of the present invention provides a conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane obtained by the above preparation method.
  • the conductivity range of the composite hollow fiber membrane is 0.1S/m to 100S/m.
  • the present invention also provides an electrochemically coupled membrane separation component, wherein the electrochemically coupled membrane separation component contains the composite hollow fiber membrane.
  • the electrochemically coupled membrane separation component includes an immersed electrochemically coupled membrane separation component and an external pressure electrochemically coupled membrane separation component.
  • the submerged electrochemical coupled membrane separation component is a curtain membrane component, which mainly includes a composite hollow fiber membrane, an insulating layer, a counter electrode and a water collecting pipe.
  • the innermost layer of the component is a composite hollow fiber membrane arranged in parallel.
  • the composite hollow fiber membrane serves as a working electrode, and both ends are sealed in the water collecting pipe to keep the hollow holes of the fiber membrane unobstructed.
  • the outermost layer of the component is a layer of counter electrode, which surrounds the entire composite hollow fiber membrane.
  • An insulating layer is arranged between the composite hollow fiber membrane and the counter electrode to prevent short circuit connection between the conductive hollow fiber membrane and the counter electrode.
  • a circle of conductive layer is fixed on the surface of the composite hollow fiber membrane, and the conductive layer and the composite hollow fiber membrane lead out wires to connect to an external power supply to provide electrochemical assistance for the electrochemical coupled membrane separation component.
  • the external pressure electrochemical coupled membrane separation component is a columnar membrane component, which mainly includes a pressure-resistant columnar housing, a counter electrode, an insulating layer, a composite hollow fiber membrane and a water collection pipe, wherein the counter electrode is fixed in the assembly On the inner side of the component shell, an insulating layer is arranged between the counter electrode and the conductive composite hollow fiber membrane, and the insulating layer is fixed on the counter electrode.
  • an auxiliary counter electrode can be optionally built in the center of the component.
  • a porous plastic tube surrounds the outside of the auxiliary counter electrode to isolate the conductive hollow fiber membrane and the auxiliary counter electrode.
  • the two ends of the bundled composite hollow fiber membrane are fixed to the water inlet and outlet of the component with sealing materials, wherein the water inlet is composed of two layers of sealing materials and a layer of conductive glue to encapsulate the hollow fiber membrane port, and the conductive glue is located between the two layers of sealing materials.
  • the water outlet is encapsulated by a layer of sealing material and a layer of conductive glue. After encapsulation, half of the sealing material layer is cut off to keep the hollow holes of the fiber membrane unobstructed for water discharge; the wires connecting the conductive composite hollow fiber membrane and the wires connecting the auxiliary counter electrode and the counter electrode are all connected from the side outlet, and electrochemical assistance is provided for the electrochemically coupled membrane separation component through an external power supply.
  • the insulating layer in the electrochemical coupling membrane separation component is preferably an insulating material such as non-woven fabric, hollow plastic mesh, etc.;
  • the counter electrode is preferably a conductive material such as metal wire mesh, carbon fiber cloth, etc., and the metal wire mesh used has no restrictions on the type of metal, and is preferably titanium metal and its alloys;
  • the sealing material is preferably an adhesive material such as epoxy resin;
  • the conductive layer is preferably a conductive material such as metal strip, metal foil, etc.;
  • the auxiliary counter electrode is preferably a conductive material such as metal column, carbon rod, etc., and the metal column used has no restrictions on the type of metal, and is preferably titanium metal and its alloys;
  • the conductive glue is preferably a conductive silver paste or a conductive carbon paste;
  • the wire is titanium wire, copper wire, stainless steel wire;
  • the external power supply is a DC regulated power supply, an AC regulated power supply or a pulse power supply.
  • the hollow fiber membrane of the present invention has a simple preparation process, excellent electrical conductivity, electrochemical stability and mechanical strength, controllable membrane performance, and the membrane pore size can be regulated in the range of microfiltration to ultrafiltration; the electrochemically coupled membrane separation component has a reasonable and compact structure, is easy to use, can enhance membrane performance under electrochemical assistance, and is suitable for different specifications and different operating modes.
  • Figure 1 is a schematic diagram of the composition of the immersed electrochemical coupled membrane separation component of the present invention, wherein I is a schematic diagram of the hollow fiber membrane packaging of the immersed electrochemical coupled membrane separation component, II is a schematic diagram of the appearance of the immersed electrochemical coupled membrane separation component, and III is a schematic diagram of the cross-section of the immersed electrochemical coupled membrane separation component.
  • the specific parts are: 1 is a water collection pipe, 2 is a conductive layer, 3 is a conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane, 4 is a wire connecting the hollow fiber membrane, 5 is a wire connecting the counter electrode, 6 is the counter electrode, and 7 is an insulating layer.
  • FIG2 is a schematic diagram of the composition of the external pressure type electrochemical coupling membrane separation component of the present invention, wherein I is a schematic diagram of the packaging of a single bundle of hollow fiber membranes in the external pressure type electrochemical coupling membrane separation component, and II is a schematic diagram of the longitudinal section of the external pressure type electrochemical coupling membrane separation component.
  • the specific parts are: 1 is epoxy resin, 2 is conductive glue, 3 is conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane, 4 is the water inlet of the component, 5 is a porous plastic tube, 6 is an auxiliary counter electrode, 7 is the component shell and the inner counter electrode, 8 is the outer shell of the component and the inner counter electrode, and 9 is the outer shell of the component and the inner counter electrode.
  • the water outlet is the water outlet
  • 9 is the cross-flow outlet
  • 10 is the water collecting pipe
  • 11 is the wire outlet for connecting the conductive hollow fiber membrane and the wire outlet for connecting the counter electrode and the auxiliary counter electrode
  • 12 is the wire connecting the counter electrode and the auxiliary counter electrode
  • 13 is the wire connecting the conductive hollow fiber membrane
  • 14 is the hollow fiber membrane packaging pipe.
  • the preparation of a carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane with an inner liner microfiltration pore size comprises the following steps:
  • the spinning solution was vacuum degassed and used as the shell solution.
  • the spinning solution sampling pump speed was controlled to be 30 rpm/min, and the winding roller pulling the liner speed was 18 m/min.
  • the spinning solution and the liner were mixed and spun into a water coagulation bath through a spinneret to obtain a composite hollow fiber membrane with a liner; the initially solidified carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane was wound on the winding roller, and after the spinning was completed, it was immersed in water for 72 hours to remove excess organic solvent and dispersant, and then naturally air-dried and collected.
  • the prepared hollow fiber membrane had an average pore size of 100 nm, a permeation flux of 1000 LMH, and a conductivity of 50 S/m.
  • the prepared carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane is encapsulated into an immersed electrochemically coupled membrane separation component (as shown in FIG1 ).
  • the immersed electrochemically coupled membrane separation component is a curtain membrane component, which includes a hollow fiber membrane body, an insulating layer, a metal mesh and a water collection pipe.
  • the innermost layer of the component is a hollow fiber membrane arranged in parallel.
  • the two ends of the hollow fiber membrane are sealed in the water collection pipe 1 by epoxy resin.
  • the outermost layer of the component is a layer of metal mesh 6.
  • the metal mesh 6 serves as an electrochemically functional counter electrode, surrounding the entire conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane 3.
  • a layer of non-woven fabric is arranged between the hollow fiber membrane 3 and the metal mesh 6 as an insulating layer 7, which plays the role of insulating the conductive hollow fiber membrane and the metal mesh.
  • the hollow fiber membrane 3 is connected by a circle of conductive copper foil (as a conductive layer 2), and an external wire 4 is drawn out as a working electrode.
  • the metal mesh 6 is directly connected to the wire 5 as a counter electrode, and a voltage is provided to the entire electrochemically coupled membrane separation component through an external power supply.
  • the submerged electrochemical coupled membrane separation component was placed in the membrane pool of the membrane bioreactor, and the internal suction filtration method was adopted. During the operation, the component was connected to a DC voltage-stabilized power supply, and the carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane was used as the cathode. A voltage of 1.2V was applied to the membrane.
  • the influent COD was 503mg/L and the effluent COD was 218mg/L.
  • the ethylene composite hollow fiber membrane was used as the anode, and a voltage of 1V was applied to the membrane.
  • the inlet COD was 503mg/L, the ammonia nitrogen was 25mg/L, the effluent COD was 61mg/L, and the effluent ammonia nitrogen concentration was less than 2mg/L.
  • the carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane was used as the anode, and a voltage of 1V was applied to the membrane. During the 60-day operation cycle, the membrane assembly only needed one backwash to restore the membrane flux, and the backwashing could achieve a flux recovery rate of 97.2%.
  • the preparation of a carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane with an inner liner ultrafiltration pore size comprises the following steps:
  • the spinning solution was vacuum degassed and used as the shell solution.
  • the spinning solution sampling pump speed was controlled to be 25rpm/min, and the winding roller pulling the liner speed was 14.5m/min.
  • the spinning solution and the liner were mixed and spun into a water coagulation bath through a spinneret to obtain a composite hollow fiber membrane with a liner; the initially solidified carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane was wound on the winding roller, and after the spinning was completed, it was soaked in water for 72h to remove excess organic solvent and dispersant, and then naturally air-dried and collected.
  • the average pore size of the prepared membrane was 10nm, the permeation flux was 140LMH, and the conductivity was 46S/m.
  • the prepared carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane is packaged into an external pressure type electrochemical coupling membrane separation component (as shown in FIG2).
  • the external pressure type electrochemical coupling membrane separation component is a columnar membrane component, a 5 mm thick metal column 6 is built into the center of the component as an auxiliary counter electrode, a porous plastic tube 5 surrounds the outside of the metal column 6 to isolate the conductive carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane 3 and the metal column 6, a layer of metal wire mesh 7 is fixed on the inside of the component shell as a counter electrode, a layer of non-woven fabric is arranged between the metal wire mesh 7 and the conductive hollow fiber membrane 3 to play an insulating role, the non-woven fabric is fixed on the metal wire mesh, and both ends of the bundled hollow fiber membrane 3 are sealed with epoxy resin.
  • the grease 1 is fixed to the water inlet 4 and the water outlet 8 of the component and is enclosed in the water collecting pipe 10.
  • the water inlet 4 is composed of a layer of epoxy resin 1, a layer of conductive silver paste 2 and a layer of epoxy resin 1 to seal the hollow hole of the entire hollow fiber membrane.
  • the water outlet 8 is fixed with a layer of epoxy resin 1 and a layer of conductive silver paste 2 to keep the hollow hole unobstructed and able to discharge water.
  • the titanium wire 13 connecting the conductive hollow fiber membrane and the wire 12 connecting the metal column and the metal wire mesh are both connected from the side outlet, and the voltage is provided to the entire electrochemical coupled membrane separation component through an external power supply.
  • the cross-flow filtration method is used in the deep treatment of wastewater.
  • the component is connected to a DC regulated power supply, the carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane is used as the cathode, and a 2V voltage is applied to the membrane.
  • the secondary effluent COD of coal chemical wastewater is 84.3mg/L. After being treated by the electrochemical coupled membrane separation component, the effluent COD reaches 51.2mg/L, and the removal rate reaches 39.3%.
  • the preparation of a self-supporting ultrafiltration pore size carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane comprises the following steps:
  • the spinning solution is vacuum degassed as the shell liquid and water as the core liquid, and the shell liquid flow rate and the core liquid flow rate are controlled to be 1:1 and spun into the water coagulation bath to obtain a self-supporting composite hollow fiber membrane; the preliminarily solidified carbon nanotube-polyvinylidene fluoride composite hollow fiber membrane is wound on a winding roller, and after spinning, it is soaked in water for 72 hours to remove excess organic solvent and dispersant, and then naturally air-dried and collected.
  • the average pore size of the prepared membrane is less than 5nm, the permeation flux is 5-10LMH, and the conductivity is 46S/m.

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Abstract

一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜的制备方法，包括步骤如下：(1)纺丝液的配制，向溶剂中加入羧基化碳纳米管和分散剂，在40～80℃下搅拌使碳纳米管分散均匀，然后加入聚偏氟乙烯，再继续搅拌使聚偏氟乙烯完全溶解，得到纺丝液；(2)湿法纺丝制备碳纳米管-聚偏氟乙烯复合中空纤维膜；将所述中空纤维膜进行导电封装和连接，构建能实现电化学作用与膜分离功能结合的电化学耦合膜分离组件，提高分离膜抗污染能力。

Description

一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法 技术领域
本发明属于分离膜制备技术领域，具体涉及一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法。
背景技术
膜分离技术因为其简单高效的特点，被广泛应用于水处理、气体分离、食品加工和药物提纯等领域，是解决资源短缺和环境污染等问题的重要技术。但是传统膜分离技术仍存在着膜污染严重，膜渗透性与选择性互相制约等问题，不能有效发挥其性能。电化学水处理技术是通过外加电场使污染物在电极与水的固液界面处发生的电场作用或电化学反应去除水中污染物的技术。将电化学技术与膜分离耦合，利用静电排斥、电化学氧化还原、电辅助吸附等作用，有望解决膜分离技术存在的严重膜污染和膜渗透性与选择性互相制约的问题，是一种极具实际应用潜力的新型膜分离技术。
虽然电化学作用能减轻膜污染，缓解膜渗透性和选择性之间的矛盾关系，但电化学耦合膜分离技术的相关研究主要集中于理论探索阶段。缺乏适用的分离膜是限制电辅助膜分离技术实际应用的主要原因。电辅助膜分离技术采用的分离膜有导电膜和非导电膜两种，基于非导电膜的电辅助膜分离技术需要外置高压电场对膜进行极化诱导，高能耗制约了其应用，而基于导电膜的电辅助膜分离技术可以直接施加较低电压于膜上，较为节能高效地实现电辅助效果，因此基于导电膜的电辅助膜分离技术具有更大的应用前景。目前，研究中的导电分离膜主要有碳膜、金属膜、导电高分子膜和导电陶瓷膜。这些导电分离膜的稳定性和机械强度较差，制备过程较为复杂，不利于实际应用。
利用碳纳米管和传统高分子材料构建复合型导电高分子材料，能为这一困境带来转机。导电高分子材料可分为复合型导电高分子材料和结构型导电高分子材料，复合型导电高分子材料的导电机理与结构型导电高分子材料(聚苯胺、聚吡咯、聚噻吩等)不同，是通过向传统高分子材料中添加导电填料，导电材料的浓度达到临界值后，在高分子中形成导电网络，能够实现电子的传导。因此，将碳纳米管作为导电填料加入高分子材料制备复合型导电高分子材料，既能赋予传统高分子膜材料导电性，同时还保留了传统高分子膜材料稳定性和机械强度良好的优点，且制备方法简单，有望制备出具有实际应用前景的导电分离膜。
除此之外，市场上的膜组件均是针对传统膜分离过程设计，并不能实现电化学耦合膜分离功能，新型电化学耦合膜分离组件的研发对促进电化学耦合膜分离技术应用与发展具有重 要意义。
发明内容
针对现有技术存在的上述问题，本发明的目的是提供一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法，所述导电的碳纳米管-聚偏氟乙烯复合中空纤维膜采用碳纳米管作为导电填料，利用分散剂增强碳纳米管在聚偏氟乙烯中的分散性，通过湿法纺丝工艺制备，将该中空纤维膜进行导电封装和连接，构建能实现电化学作用与膜分离功能结合的电化学耦合膜分离组件，强化分离膜抗污染能力，缓解其渗透性与选择性之间的矛盾。
为了实现上述目的，本发明提供如下技术方案：
一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜的制备方法，包括步骤如下：
(1)纺丝液的配制
向溶剂中加入羧基化碳纳米管和分散剂，在40～80℃下搅拌6～12h使碳纳米管分散均匀，然后加入聚偏氟乙烯，再继续搅拌4～8h使聚偏氟乙烯完全溶解，得到纺丝液；
(2)湿法纺丝制备碳纳米管-聚偏氟乙烯复合中空纤维膜
湿法纺丝制备碳纳米管-聚偏氟乙烯复合中空纤维膜包括自支撑复合中空纤维膜和带内衬复合中空纤维膜；
自支撑复合中空纤维膜的制备过程为：将纺丝液真空脱泡后作为壳液，水作为芯液，同时通过纺丝机的喷丝板，控制壳液流速与芯液流速按一定速度比纺进水凝固浴中，得到自支撑复合中空纤维膜；
带内衬复合中空纤维膜的制备过程为：将纺丝液真空脱泡后作为壳液，控制纺丝液进样泵速度和绕丝辊牵引内衬速度，将纺丝液和内衬通过喷丝板混合纺进水凝固浴中，得到带内衬复合中空纤维膜；
将初步固化的碳纳米管-聚偏氟乙烯复合中空纤维膜缠绕在绕丝辊上，纺丝结束后放入水中浸泡24～72h去除多余的有机溶剂和分散剂，自然风干并收集。
基于上述技术方案，进一步地，步骤(1)中所述羧基化碳纳米管为单壁碳纳米管、双壁碳纳米管或多壁碳纳米管；羧基含量为0.5wt％～5wt％，优选为2wt％～3wt％，羧基含量太低会造成碳纳米管分散性太差，羧基含量太高会造成复合中空纤维膜导电性太差。
基于上述技术方案，进一步地，步骤(1)中所述分散剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、商业TNACPS分散剂、商业TNDPS分散剂、商业Disponer983分散剂、商业XFZ33NMP分散剂中的一种或两种以上的混合物；羧基化碳纳米管与分散剂 质量比为0.5～5:1，优选羧基化碳纳米管与分散剂质量比为0.5～2:1。
基于上述技术方案，进一步地，步骤(1)中所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮的一种或两种以上的混合物，控制溶质(羧基化碳纳米管和分散剂)占溶液的质量分数为15％～30％，优选为20％～25％。
基于上述技术方案，进一步地，步骤(1)中羧基化碳纳米管与聚偏氟乙烯质量比为15～100:100，优选羧基化碳纳米管与聚偏氟乙烯质量比为1:2。羧基化碳纳米管占比太低会造成复合中空纤维膜导电性太差，羧基化碳纳米管占比太高会造成复合中空纤维膜机械强度太差。
基于上述技术方案，进一步地，步骤(2)中所述自支撑复合中空纤维膜的壳液流速与芯液流速比为0.5～5:1，优选壳液流速与芯液流速比为1:1。
基于上述技术方案，进一步地，步骤(2)中所述带内衬复合中空纤维膜纺丝液进样泵速度为10～50rpm/min，绕丝辊牵引内衬速度为10～30m/min，优选进样泵速度为20～30rpm/min，绕丝辊牵引内衬速度为13～18m/min。
基于上述技术方案，进一步地，所述带内衬复合中空纤维膜的内衬为编织管型内衬或钩织管型内衬，内衬材质无限制。
本发明另一方面提供上述制备方法得到的导电的碳纳米管-聚偏氟乙烯复合中空纤维膜的。
基于上述技术方案，进一步地，所述复合中空纤维膜的电导率范围为0.1S/m～100S/m。
本发明还提供一种电化学耦合膜分离组件，所述的电化学耦合膜分离组件含有上述的复合中空纤维膜。
基于上述技术方案，进一步地，所述的电化学耦合膜分离组件包括浸没式电化学耦合膜分离组件和外压式电化学耦合膜分离组件。
基于上述技术方案，进一步地，所述的浸没式电化学耦合膜分离组件为帘式膜组件，主要包括复合中空纤维膜、绝缘层、对电极和集水管件，组件最内层是平行排列的复合中空纤维膜，复合中空纤维膜作为工作电极，两端被密封在集水管件中，保持纤维膜中空孔通畅，组件最外侧是一层对电极，环绕包围整个复合中空纤维膜，复合中空纤维膜和对电极之间设置一层绝缘层，防止导电中空纤维膜和对电极之间短路连接，为增强中空纤维膜整体的导电均匀性，在复合中空纤维膜表面固定一圈导电层，导电层和复合中空纤维膜引出导线连接外界电源，为电化学耦合膜分离组件提供电化学辅助。
基于上述技术方案，进一步地，所述外压式电化学耦合膜分离组件为柱式膜组件，主要包括耐压柱式外壳、对电极、绝缘层、复合中空纤维膜和集水管件，其中，对电极固定在组 件外壳内侧，对电极与导电复合中空纤维膜之间设置一层绝缘层，绝缘层固定在对电极上，为增强组件的电化学辅助作用，可选择在组件中心内置辅助对电极，辅助对电极外侧环绕一根有孔塑料管隔绝导电中空纤维膜和辅助对电极，捆扎成束的复合中空纤维膜两端用密封材料固定在组件的进水口和出水口，其中进水口由两层密封材料和一层导电胶封装中空纤维膜端口构成，导电胶位于两层密封材料中间，出水口由一层密封材料和一层导电胶封装，封装后切除一半密封材料层保持纤维膜中空孔能通畅出水；连接导电的复合中空纤维膜的导线和连接辅助对电极及对电极的导线均从侧边出口接出，通过外界电源为电化学耦合膜分离组件提供电化学辅助。
基于上述技术方案，进一步地，所述电化学耦合膜分离组件中的绝缘层优选为无纺布、镂空塑料网等绝缘材料；所述的对电极优选为金属丝网、碳纤维布等导电材料，采用的金属丝网对金属种类没有限制，优选为钛金属及其合金；所述密封材料优选为环氧树脂等粘结材料；所述导电层优选为金属带、金属箔等导电材料；所述辅助对电极优选为金属柱、碳棒等导电材料，采用的金属柱对金属种类没有限制，优选为钛金属及其合金；所述导电胶优选为导电银浆或者导电碳浆；所述的导线为钛丝、铜丝、不锈钢丝；所述外界电源为直流稳压电源、交流稳压电源或脉冲式电源。
本发明相对现有技术具有如下有益效果：
本发明的中空纤维膜制备工艺简单，具有优良的导电性能、电化学稳定性和机械强度，膜性能可控，膜孔径能在微滤到超滤范围内调控；电化学耦合膜分离组件结构合理而紧凑，使用方便，能够实现在电化学辅助作用下增强膜性能，适用于不同规格和不同运行模式。
附图说明
为了更清楚地说明本发明实施例，下面将对实施例涉及的附图进行简单地介绍。
图1是本发明的浸没式电化学耦合膜分离组件的组成示意图，其中，I是浸没式电化学耦合膜分离组件中空纤维膜封装示意图，II是浸没式电化学耦合膜分离组件外观示意图，III是浸没式电化学耦合膜分离组件横切截面示意图，具体零部件：1是集水管件，2是导电层，3是导电的碳纳米管-聚偏氟乙烯复合中空纤维膜，4是连接中空纤维膜的导线，5是连接对电极的导线，6是对电极，7是绝缘层。
图2是本发明的外压式电化学耦合膜分离组件的组成示意图，其中，I是外压式电化学耦合膜分离组件中单束中空纤维膜封装示意图，II是外压式电化学耦合膜分离组件纵切截面示意图，具体零部件：1是环氧树脂，2是导电胶，3是导电的碳纳米管-聚偏氟乙烯复合中空纤维膜，4是组件进水口，5是有孔塑料管，6是辅助对电极，7是组件外壳及内侧对电极，8 是出水口，9是错流出口，10是集水管件，11是连接导电中空纤维膜的导线及连接对电极和辅助对电极的导线出口，12是连接对电极和辅助对电极的导线，13是连接导电中空纤维膜的导线，14是中空纤维膜封装管件。
具体实施方式
下面结合技术方案，通过三个实施例进一步介绍本发明的具体实施方式，说明导电的碳纳米管-聚偏氟乙烯复合中空纤维膜的制备方法及电化学耦合膜分离组件应用方法，但本发明并不局限于以下实施例。
实施例1
制备带内衬微滤孔径的碳纳米管-聚偏氟乙烯复合中空纤维膜，包括以下步骤：
(1)向N,N-二甲基甲酰胺中加入一定量的羧基化碳纳米管(羧基含量为2.58％)和分散剂，控制羧基化碳纳米管与分散剂质量比为0.5，采用的分散剂为商业TNACPS分散剂，在60℃下高速搅拌6h使碳纳米管分散均匀，然后加入适量聚偏氟乙烯，控制羧基化碳纳米管与聚偏氟乙烯质量比为0.5，溶质质量分数为20％，再继续搅拌4h使聚偏氟乙烯完全溶解，得到纺丝液；
(2)将纺丝液进行真空脱泡后作为壳液，控制纺丝液进样泵速度为30rpm/min，绕丝辊牵引内衬速度为18m/min，将纺丝液和内衬通过喷丝板混合纺进水凝固浴中，得到带内衬复合中空纤维膜；将初步固化的碳纳米管-聚偏氟乙烯复合中空纤维膜缠绕在绕丝辊上，纺丝结束后放入水中浸泡72h去除多余的有机溶剂和分散剂，自然风干并收集起来。制备的中空纤维膜平均孔径为100nm，渗透通量为1000LMH，电导率为50S/m。
将制备的碳纳米管-聚偏氟乙烯复合中空纤维膜封装成浸没式电化学耦合膜分离组件(如图1所示)。浸没式电化学耦合膜分离组件为帘式膜组件，所述组件包括中空纤维膜主体、绝缘层、金属丝网和集水管件，组件最内层是平行排列的中空纤维膜，利用环氧树脂将中空纤维膜两端封闭在集水管件1中，组件最外侧是一层金属丝网6，金属丝网6作为电化学功能的对电极，环绕包围整个导电的碳纳米管-聚偏氟乙烯复合中空纤维膜3，中空纤维膜3和金属丝网6之间布置了一层无纺布作为绝缘层7，起到绝缘导电中空纤维膜和金属丝网的作用，中空纤维膜3通过一圈导电铜箔(作为导电层2)连接，引出外接导线4作为工作电极，金属丝网6直接连接导线5作为对电极，通过外界电源为整个电化学耦合膜分离组件提供电压。
将浸没式电化学耦合膜分离组件置于膜生物反应器的膜池中，采用内吸式过滤方式，运行过程中，将组件连接到直流稳压电源上，碳纳米管-聚偏氟乙烯复合中空纤维膜作为阴极，施加1.2V电压于膜上，进水COD为503mg/L，出水COD为218mg/L。碳纳米管-聚偏氟乙 烯复合中空纤维膜作为阳极，施加1V电压于膜上，进水COD为503mg/L，氨氮为25mg/L，出水COD为61mg/L，出水氨氮浓度低于2mg/L。
碳纳米管-聚偏氟乙烯复合中空纤维膜作为阳极，施加1V电压于膜上，60天的运行周期中，膜组件仅需一次反清洗恢复膜通量，反冲洗能够实现通量恢复率达到97.2％。
实施例2
制备带内衬超滤孔径的碳纳米管-聚偏氟乙烯复合中空纤维膜，包括以下步骤：
(1)向N,N-二甲基甲酰胺中加入一定量的羧基化碳纳米管(羧基含量为2.58％)和分散剂，控制羧基化碳纳米管与分散剂质量比为2，采用的分散剂为商业TNACPS分散剂，在60℃下高速搅拌12h使碳纳米管分散均匀，然后加入适量聚偏氟乙烯，控制羧基化碳纳米管与聚偏氟乙烯质量比为0.5，溶质质量分数为23％，再继续搅拌8h使聚偏氟乙烯完全溶解，得到纺丝液；
(2)将纺丝液进行真空脱泡后作为壳液，控制纺丝液进样泵速度为25rpm/min，绕丝辊牵引内衬速度为14.5m/min，将纺丝液和内衬通过喷丝板混合纺进水凝固浴中，得到带内衬复合中空纤维膜；将初步固化的碳纳米管-聚偏氟乙烯复合中空纤维膜缠绕在绕丝辊上,纺丝结束后放入水中浸泡72h去除多余的有机溶剂和分散剂，自然风干并收集起来。制备的膜平均孔径为10nm，渗透通量为140LMH，电导率为46S/m。
将制备的碳纳米管-聚偏氟乙烯复合中空纤维膜封装成外压式电化学耦合膜分离组件(如图2所示)。所述外压式电化学耦合膜分离组件为柱式膜组件，组件中心内置一根5mm粗的金属柱6作为辅助对电极，金属柱6外侧环绕一根有孔塑料管5隔绝导电的碳纳米管-聚偏氟乙烯复合中空纤维膜3和金属柱6，组件外壳内侧固定一层金属丝网7作为对电极，金属丝网7与导电的中空纤维膜3之间布置一层无纺布起到绝缘作用，无纺布固定在金属丝网上，捆扎成束的中空纤维膜3两端用环氧树脂1固定在组件的组件进水口4和出水口8，并封闭在集水管件10中，进水口4由一层环氧树脂1、一层导电银浆2和一层环氧树脂1密封整个中空纤维膜的中空孔构成，出水口8用一层环氧树脂1和一层导电银浆2固定，保持中空孔通畅能出水，连接导电中空纤维膜的钛丝13和连接金属柱及金属丝网的导线12均从侧边出口接出，通过外界电源为整个电化学耦合膜分离组件提供电压。
采用错流过滤方式应用于废水深度处理中，运行过程中，将组件连接到直流稳压电源上，碳纳米管-聚偏氟乙烯复合中空纤维膜作为阴极，施加2V电压于膜上。煤化工废水二级出水COD为84.3mg/L，经过电化学耦合膜分离组件处理后，出水COD达到51.2mg/L，去除率达到39.3％。
实施例3
制备自支撑超滤孔径的碳纳米管-聚偏氟乙烯复合中空纤维膜，包括以下步骤：
(1)向N,N-二甲基甲酰胺中加入一定量的羧基化碳纳米管(羧基含量为2.58％)和分散剂，控制羧基化碳纳米管与分散剂质量比为2，采用的分散剂为商业TNDPS分散剂，在60℃下高速搅拌12h使碳纳米管分散均匀，然后加入适量聚偏氟乙烯，控制羧基化碳纳米管与聚偏氟乙烯质量比为0.5，溶质质量分数为23％，再继续搅拌8h使聚偏氟乙烯完全溶解，得到纺丝液；
(2)将纺丝液进行真空脱泡后作为壳液，水作为芯液，同时通过纺丝机的喷丝板，控制壳液流速与芯液流速按1:1速度纺进水凝固浴中，得到自支撑复合中空纤维膜；将初步固化的碳纳米管-聚偏氟乙烯复合中空纤维膜缠绕在绕丝辊上，纺丝结束后放入水中浸泡72h去除多余的有机溶剂和分散剂，自然风干并收集起来。制备的膜平均孔径为小于5nm，渗透通量为5～10LMH，电导率为46S/m。
以上所述实施例，只是本发明中典型的实施例，并不构成对本发明的不当限定，故凡依本发明申请专利范围所述的显而易见的改动，以及其它不脱离本发明实质的改动，均应包括在本发明的保护范围之内。

Claims (10)

  1. 一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜的制备方法，其特征在于，包括步骤如下：
    (1)纺丝液的配制
    向溶剂中加入羧基化碳纳米管和分散剂，在40～80℃下搅拌使碳纳米管分散均匀，然后加入聚偏氟乙烯，再继续搅拌使聚偏氟乙烯完全溶解，得到纺丝液；
    (2)湿法纺丝制备碳纳米管-聚偏氟乙烯复合中空纤维膜
    湿法纺丝制备的碳纳米管-聚偏氟乙烯复合中空纤维膜包括自支撑复合中空纤维膜和带内衬复合中空纤维膜；
    自支撑复合中空纤维膜的制备过程为：将纺丝液真空脱泡后作为壳液、水作为芯液，同时通过纺丝机的喷丝板，控制壳液流速与芯液流速按一定速度比纺进水凝固浴中，得到自支撑复合中空纤维膜；
    带内衬复合中空纤维膜的制备过程为：将纺丝液真空脱泡后作为壳液，控制纺丝液进样泵速度和绕丝辊牵引内衬速度，将纺丝液和内衬通过喷丝板混合纺进水凝固浴中，得到带内衬复合中空纤维膜；
    将初步固化的碳纳米管-聚偏氟乙烯复合中空纤维膜缠绕在绕丝辊上，纺丝结束后放入水中浸泡，去除有机溶剂和分散剂，之后自然风干并收集。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述羧基化碳纳米管为单壁碳纳米管、双壁碳纳米管或多壁碳纳米管；羧基含量为0.5wt％～5wt％；所述分散剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、商业TNACPS分散剂、商业TNDPS分散剂、商业Disponer983分散剂、商业XFZ33 NMP分散剂中的一种或两种以上的混合物；羧基化碳纳米管与分散剂质量比为0.5～5:1。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮的一种或两种以上的混合物，控制溶质占溶液的质量分数为15％～30％；羧基化碳纳米管与聚偏氟乙烯质量比为15～100:100。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述自支撑复合中空纤维膜的壳液流速与芯液流速比为0.5～5:1。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述带内衬复合中空纤维膜纺丝液进样泵速度为10～50rpm/min，绕丝辊牵引内衬速度为10～30m/min。
  6. 权利要求1-5任一项所述制备方法得到的导电的碳纳米管-聚偏氟乙烯复合中空纤维膜。
  7. 一种电化学耦合膜分离组件，其特征在于，所述的电化学耦合膜分离组件含有权利要求6所述的复合中空纤维膜，所述的电化学耦合膜分离组件包括浸没式电化学耦合膜分离组 件和外压式电化学耦合膜分离组件。
  8. 根据权利要求7所述的电化学耦合膜分离组件，其特征在于，所述的浸没式电化学耦合膜分离组件为帘式膜组件，主要包括复合中空纤维膜、绝缘层、对电极和集水管件，组件最内层是平行排列的复合中空纤维膜，复合中空纤维膜作为工作电极，两端被密封在集水管件中，保持纤维膜中空孔通畅，组件最外侧是一层对电极，环绕包围整个复合中空纤维膜，复合中空纤维膜和对电极之间设置一层绝缘层，防止导电中空纤维膜和对电极之间短路连接；在复合中空纤维膜表面固定一圈导电层，导电层和复合中空纤维膜引出导线连接外界电源，为电化学耦合膜分离组件提供电化学辅助。
  9. 根据权利要求7所述的电化学耦合膜分离组件，其特征在于，所述外压式电化学耦合膜分离组件为柱式膜组件，主要包括耐压柱式外壳、对电极、绝缘层、复合中空纤维膜和集水管件，其中，对电极固定在组件外壳内侧，对电极与导电复合中空纤维膜之间设置一层绝缘层，绝缘层固定在对电极上；在组件中心内置辅助对电极，辅助对电极外侧环绕一根有孔塑料管隔绝导电中空纤维膜和辅助对电极；捆扎成束的复合中空纤维膜两端用密封材料固定在组件的进水口和出水口，其中，进水口由两层密封材料和一层导电胶封装中空纤维膜端口构成，导电胶位于两层密封材料中间，出水口由一层密封材料和一层导电胶封装，封装后切除一半密封材料层保持纤维膜中空孔能通畅出水；连接导电的复合中空纤维膜的导线和连接辅助对电极及对电极的导线均从侧边出口接出，通过外界电源为电化学耦合膜分离组件提供电化学辅助。
  10. 根据权利要求8或9所述的电化学耦合膜分离组件，其特征在于，所述电化学耦合膜分离组件中的绝缘层为无纺布、镂空塑料网绝缘材料；所述的对电极为金属丝网、碳纤维布导电材料，金属丝网的材质为钛金属及其合金；所述密封材料为环氧树脂粘结材料；所述导电层为金属带、金属箔导电材料；所述辅助对电极为金属柱、碳棒导电材料，采用的金属柱的材质为钛金属及其合金；所述导电胶为导电银浆或者导电碳浆；所述的导线为钛丝、铜丝、不锈钢丝；所述外界电源为直流稳压电源、交流稳压电源或脉冲式电源。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120771745A (zh) * 2025-09-04 2025-10-14 北京汇天运维技术服务有限责任公司 一种高强度中空纤维复合纳滤膜及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116571101A (zh) * 2023-06-14 2023-08-11 大连理工大学 一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法
CN117665212A (zh) * 2023-12-04 2024-03-08 大连工业大学 实验室用电化学活性膜测试错流式膜组件
CN118272960B (zh) * 2024-04-24 2025-07-08 苏州大学 一种复合压电纤维及其制备方法
CN118179281B (zh) * 2024-04-28 2025-02-14 大连理工大学 一种抗膜污染的导电碳纳米管中空纤维膜制备方法及电化学耦合在水处理中的应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103785305A (zh) * 2014-01-15 2014-05-14 天津工业大学 一种多壁碳纳米管-聚偏氟乙烯复合导电超滤膜及其制备方法
CN104826503A (zh) * 2015-05-27 2015-08-12 天津工业大学 Pvdf/碳纳米管超疏水膜的制膜配方及其制备方法
US20160038885A1 (en) * 2014-08-08 2016-02-11 University Of Southern California High performance membranes for water reclamation using polymeric and nanomaterials
CN109384307A (zh) * 2018-11-21 2019-02-26 大连理工大学 一种以电化学强化碳纳米管中空纤维膜为分离单元的膜生物反应器
CN110170254A (zh) * 2019-05-31 2019-08-27 江南大学 纳米碳纤维增强聚偏氟乙烯自支撑超滤膜的制备方法及其应用
CN111298664A (zh) * 2020-03-16 2020-06-19 中国人民解放军火箭军工程设计研究院 一种中空纤维气体分离复合膜及其制备方法
CN116571101A (zh) * 2023-06-14 2023-08-11 大连理工大学 一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100377369B1 (ko) * 2000-05-13 2003-03-26 이재복 보조전극을 이용한 오폐수 전해처리방법 및 장치
AUPS220302A0 (en) * 2002-05-08 2002-06-06 Chang, Chak Man Thomas A plasma formed within bubbles in an aqueous medium and uses therefore
WO2009035415A1 (en) * 2007-09-10 2009-03-19 National University Of Singapore Polymeric membranes incorporating nanotubes
KR20120100076A (ko) * 2011-03-03 2012-09-12 윤호성 탄소나노튜브를 포함하는 분리막
CN103120902A (zh) * 2012-11-13 2013-05-29 高润宝 碳纳米管、纳米二氧化硅共改性聚乙烯醇复合超滤膜的制备方法
CN104289114B (zh) * 2014-09-10 2016-10-19 同济大学 一种导电滤膜及其应用
CN108483620A (zh) * 2018-04-12 2018-09-04 大连理工大学 一种电强化分离膜缓解膜污染同步促进产甲烷的装置
CN111186961B (zh) * 2020-01-14 2022-04-26 同济大学 一种电化学无泡曝气膜生物反应器及其应用
CN113582299B (zh) * 2021-07-12 2022-12-06 同济大学 低浓度废水中磷回收膜过滤耦合电化学非均相沉淀反应器
KR102688925B1 (ko) * 2021-11-26 2024-07-29 주식회사 케어메디 전기삼투펌프, 전극의 제조방법, 이를 이용한 유체 펌핑 시스템 및 그 시스템의 동작 방법
CN115845636B (zh) * 2022-12-07 2025-08-29 中国科学技术大学苏州高等研究院 一种电化学自清洁导电复合膜的制备方法及水处理应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103785305A (zh) * 2014-01-15 2014-05-14 天津工业大学 一种多壁碳纳米管-聚偏氟乙烯复合导电超滤膜及其制备方法
US20160038885A1 (en) * 2014-08-08 2016-02-11 University Of Southern California High performance membranes for water reclamation using polymeric and nanomaterials
CN104826503A (zh) * 2015-05-27 2015-08-12 天津工业大学 Pvdf/碳纳米管超疏水膜的制膜配方及其制备方法
CN109384307A (zh) * 2018-11-21 2019-02-26 大连理工大学 一种以电化学强化碳纳米管中空纤维膜为分离单元的膜生物反应器
CN110170254A (zh) * 2019-05-31 2019-08-27 江南大学 纳米碳纤维增强聚偏氟乙烯自支撑超滤膜的制备方法及其应用
CN111298664A (zh) * 2020-03-16 2020-06-19 中国人民解放军火箭军工程设计研究院 一种中空纤维气体分离复合膜及其制备方法
CN116571101A (zh) * 2023-06-14 2023-08-11 大连理工大学 一种导电的碳纳米管-聚偏氟乙烯复合中空纤维膜及电化学耦合膜分离组件的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120771745A (zh) * 2025-09-04 2025-10-14 北京汇天运维技术服务有限责任公司 一种高强度中空纤维复合纳滤膜及其制备方法

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