CN112044288A - Based on F-TiO2/Fe-g-C3N4Self-cleaning PVDF hollow fiber ultrafiltration membrane and preparation method thereof - Google Patents
Based on F-TiO2/Fe-g-C3N4Self-cleaning PVDF hollow fiber ultrafiltration membrane and preparation method thereof Download PDFInfo
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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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- 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
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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
- B01D69/08—Hollow fibre membranes
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
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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
- B01D71/024—Oxides
Abstract
The invention discloses a catalyst based on F-TiO2/Fe‑g‑C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane and the preparation method belong to the technical field of membrane separation. 12.0-25.0% (w/w) polyvinylidene fluoride (PVDF), 10.0-23.0% (w/w) pore-forming agent and 0.2-3.0% (w/w) F-TiO2/Fe‑g‑C3N4And 49.0-77.8% (w/w) of solvent are added in a certain orderPutting the mixture into a dissolving tank, stirring the mixture for 8 to 16 hours at the temperature of between 45 and 95 ℃ until the mixture is completely dissolved, standing and defoaming the mixture for 12 to 36 hours to prepare a casting solution; the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane is prepared by adopting a traditional dry-wet spinning process. The pure water flux of the ultrafiltration membrane prepared by the invention is more than or equal to 260L/m2Hr.0.1 MPa, bovine serum albumin retention rate is more than or equal to 90%, and degradation removal rate of humic acid is more than or equal to 90% (simulating operation for 1 hour under visible light), and the composite material has good anti-pollution performance and visible light catalytic performance. The product of the invention is particularly suitable for the water treatment of micro-polluted water sources, the pretreatment of chemical engineering, medicine and seawater desalination, the treatment and recycling of wastewater in the biological field, and the like.
Description
Technical Field
The invention relates to a high-molecular mixed matrix ultrafiltration membrane and a preparation method thereof, in particular to a membrane based on F-TiO2/Fe-g-C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane and the preparation method.
Background
The rapid development of economic society and the rapid increase of population lead to the prominent phenomenon of environmental pollution, and the serious water pollution and the shortage of water resources restrict the development of economy and society in China. In order to achieve the social development goal of sustainable development, the social contradiction between the shortage of water resources and the demand of people for water resources must be solved, so that the recycling of water resources becomes a necessary trend, and the recycling of waste water as resources is an effective way to protect the environment and save water resources. Among many sewage recycling technologies, membrane separation technology is one of the best choices.
A mixed matrix membrane, also called a hybrid membrane, is a membrane formed by chemically crosslinking or microscopically mixing organic and inorganic components, also called an organic-inorganic hybrid membrane, and has the advantages of corrosion resistance and heat resistance of an inorganic membrane, high separability and toughness of an organic membrane and the like, so that the mixed matrix membrane becomes one of hot spots for researching the modification of membrane materials. In recent years, scholars at home and abroad adopt a blending method or a sol-gel method to prepare a nano inorganic material/polymer hybrid ultrafiltration membrane responding to ultraviolet light, so that the nano inorganic material/polymer hybrid ultrafiltration membrane has the multiple functions of photocatalysis and membrane separation and has good development and application prospects; for example, chinese patent ZL201410312781.8 adopts a blend of nano inorganic materials and membrane materials to prepare an ultra-filtration membrane responsive to ultraviolet light, so that the ultra-filtration membrane has a degradation property on organic pollutants under the catalytic action of ultraviolet light. The practical application of the ultraviolet light catalyst modified film is severely limited because the light energy of the ultraviolet light only accounts for less than 5% of the solar light energy. Therefore, the visible light catalytic ultrafiltration membrane is prepared by doping or coating the visible light catalyst, the pollution resistance of the ultrafiltration membrane is improved, the visible light catalytic activity of the ultrafiltration membrane is realized, the application range of the ultrafiltration membrane is expanded, and the method is a hotspot of ultrafiltration membrane research in recent years; the research team of the inventor of the King of the Living nations carries out the research of related ultrafiltration membranes and preparation methods based on visible light catalytic nano inorganic materials, but does not relate to the preparation of mixed matrix ultrafiltration membranes and preparation methods based on visible light catalytic nano inorganic composite materials.
Chinese patent CN104383821A adopts graphene oxide loaded magnetic particles @ TiO with core-shell structure2The modified separation membrane is prepared, and the separation membrane is considered to show good photocatalytic degradation performance and protein pollution resistance to bovine serum albumin serving as a target pollutant, but the separation performance and the visible light photocatalytic degradation performance of the prepared membrane are not clarified in the patent application, and the preparation process of the separation membrane is complex; meanwhile, graphene oxide loaded magnetic particles @ TiO with core-shell structure2The preparation method is complex and has high cost. Chinese patent CN104117291A adopts TiO2The polyvinylidene fluoride membrane is prepared by modifying the/C hybrid aerogel, the degradation rate of the prepared membrane to the active bright red X-3B under the irradiation of a xenon lamp (visible light) is only 13.96 percent, and the degradation rate of the prepared membrane to the active bright red X-3B under the irradiation of a mercury lamp (ultraviolet light) is 93.28 percent, so that the prepared membrane is still an ultra-filtration membrane responding to the ultraviolet light instead of a visible light ultra-filtration membraneAnd (3) a photocatalytic ultrafiltration membrane. Chinese patent CN102989329A is prepared by mixing AgNO3、TiO2The ultra-filtration membrane is prepared by blending modification, and actually, AgNO is mainly utilized3The visible light catalytic activity of the composite material is high, the degradation rate is low (the photocatalytic performance characterization is carried out on the degradation rate of methylene blue by adopting illumination for 10 hours in the patent), and a separation membrane for separation and visible light catalysis cannot be prepared; chinese patent CN104383820A discloses Ag3PO4 /TiO2Composite (Ag)3PO4Deposition of nanoparticles to TiO2Surface) and polyvinylidene fluoride material are blended and modified to make the modified film have visible light catalytic antibacterial and antifouling performance, and the modified film is mainly deposited on TiO2Surface Ag3PO4Organic matters adsorbed in the application process of the particle degradation separation membrane are reduced, so that membrane pollution is reduced, and the particle degradation separation membrane is not used for preparing a separation membrane with separation and visible light catalytic performances; also, neither patent utilizes silver salts and TiO by a synergistic effect2By mere blending or deposition, using silver salts or silver salts with TiO2The respective catalytic activity and visible light catalytic efficiency are low. Chinese patent CN102895888A firstly prepares a titanium dioxide/polyvinylidene fluoride film, and then prepares a visible light responsive polyvinylidene fluoride film by adsorbing and reducing silver ions on the surface of the film, wherein the methylene blue degradation rate of the prepared film is 33-51% (visible light irradiation 100 mins); meanwhile, after the preparation of the titanium dioxide/polyvinylidene fluoride film is finished, the preparation of the patent product can be finished through the steps of silver ion adsorption, silver ion reduction into a silver simple substance, vacuum drying and the like, and conditions such as a darkroom, ultraviolet irradiation, vacuum drying and the like are required in the preparation process, so that the preparation method is complex in process, high in preparation cost and large in industrialization difficulty.
Graphite phase carbon nitride (g-C)3N4) The polymer semiconductor with a layered structure can greatly absorb visible light, has good visible light catalytic performance, high chemical stability and acid or alkali environment competes, and is one of novel catalysts with application prospects. However a single g-C3N4Only a small part of visible light can be absorbed by the light source, the absorption to ultraviolet light is poor,thus g-C alone3N4The photocatalytic activity of (a) is not high, which limits its practical use. TiO 22Is also a photocatalytic material with excellent performance, relatively simple preparation, low price and wide research and application, and the non-metallic element F is doped to modify TiO2Optionally adding TiO2The absorption spectrum of (a) extends into the visible region; the doping modification of the metallic element Fe can obviously improve g-C3N4Photocatalytic activity of (1). Thus, F-TiO is added2And Fe-g-C3N4The two are compounded, so that the synergistic effect of the two can be fully exerted, and the visible light catalytic activity of the composite can be obviously improved. Therefore, F-TiO is added2/Fe-g-C3N4The preparation method is used for developing the visible light catalysis mixed matrix ultrafiltration membrane by blending with a high polymer material, and has certain significance for improving the membrane separation efficiency, widening the application field of the separation membrane, reducing the membrane pollution and realizing the self-cleaning function of the membrane.
The invention adopts composite F-TiO2And Fe-g-C3N4To fully play the synergistic effect of the two, further improve the visible light catalytic activity of the two, and adopt F-TiO2And Fe-g-C3N4The visible light catalytic property of the high molecular ultrafiltration membrane is improved, the PVDF hollow fiber mixed matrix ultrafiltration membrane with the self-cleaning function is prepared, the industrialization is realized, the production of similar visible light catalytic hollow fiber ultrafiltration membrane products is not seen at home, and no relevant literature report is seen at home and abroad.
Disclosure of Invention
The invention aims to provide a catalyst based on F-TiO2/Fe-g-C3N4The invention also aims to provide a preparation method of the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane.
In order to achieve the purpose, the invention adopts the technical scheme that:
based on F-TiO2/Fe-g-C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane consists of the following substances in percentage by mass: 12.0-25.0% (w/w) of polymer membrane material, 10.0-23.0% (w/w) of pore-foaming agent and F-TiO2/Fe-g-C3N4 0.2-3.0% (w/w) and 49.0-77.8% (w/w) of solvent;
the polymer film material is polyvinylidene fluoride, and the content is 12.0-25.0% (w/w);
the pore-foaming agent is polyethylene glycol 400, and the content is 10.0-23.0% (w/w);
the F-TiO2/Fe-g-C3N4The nano inorganic composite is a self-made visible light catalytic nano inorganic composite, and the content is 0.2-3.0% (w/w);
the solvent is N, N-dimethylacetamide (DMAc), and the content is 49.0-77.8% (w/w).
Based on F-TiO2/Fe-g-C3N4The preparation method of the self-cleaning PVDF hollow fiber ultrafiltration membrane comprises the following steps:
(1) mixing a certain amount of solvent, pore-forming agent and F-TiO2/Fe-g-C3N4Respectively adding the materials into a dissolving tank according to a certain proportion and sequence, and uniformly stirring at normal temperature;
(2) adding a proper amount of polyvinylidene fluoride into a dissolving tank, stirring at 45-95 ℃ for 8-16 hours until the polyvinylidene fluoride is completely dissolved, standing and defoaming for 12-36 hours to obtain a self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane casting solution;
(3) the method comprises the following steps of (1) adopting a traditional dry-wet spinning process, controlling the flow rate of a casting film liquid to be 5.0-25.0 mL/min, controlling the temperature of the casting film liquid to be 45-95 ℃, the temperature of a coagulation bath to be 20-45 ℃, the height between air to be 2-15 cm, and the coagulation time of a hollow fiber film to be 1.0-5 minutes, and preparing a self-cleaning hollow fiber mixed matrix ultrafiltration membrane;
(4) soaking and washing the prepared hollow fiber ultrafiltration membrane in deionized water for 24 hours to clean the additive and the pore-forming agent; then the mixture is put into the mixed solution of 50 percent of glycerol and 0.5 percent of Tween 80 for treatment for 48 hours, and the F-TiO-based material can be prepared2/Fe-g-C3N4The self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane.
The coagulating bath is deionized water.
The invention provides a catalyst based on F-TiO2/Fe-g-C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane and the preparation method thereof are prepared by mixing F-TiO2/Fe-g-C3N4The visible light catalytic composite material is introduced into the polymer to prepare the mixed matrix ultrafiltration membrane, and the mixed matrix ultrafiltration membrane has good pollution resistance and self-cleaning performance of degrading organic pollutants by visible light catalysis, which is an innovative point of the invention. In order to test the anti-pollution performance and visible light catalytic performance of the prepared ultrafiltration membrane with the self-cleaning mixed matrix, the resistance increase coefficient and the contact angle of the prepared ultrafiltration membrane are tested, and the result shows that the resistance increase coefficient and the contact angle are both obviously reduced, and the anti-pollution performance of the ultrafiltration membrane is greatly improved. Meanwhile, by taking humic acid as a target pollutant, the visible light catalytic degradation removal rate and ultrafiltration membrane flux change test are carried out on the prepared visible light catalytic mixed matrix ultrafiltration membrane, and the result shows that the prepared ultrafiltration membrane shows good photocatalytic degradation performance and pollution resistance performance when running under simulated visible light, and the flux attenuation of the membrane is obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a catalyst based on F-TiO2/Fe-g-C3N4Compared with the traditional polyvinylidene fluoride hollow fiber ultrafiltration membrane, the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane prepared by blending modification has the advantages that the pollution resistance and the visible light catalytic activity are obviously improved, the membrane separation can be carried out, meanwhile, the organic pollutants are catalytically degraded, and the self-cleaning effect of the ultrafiltration membrane is realized.
(2) The invention provides a catalyst based on F-TiO2/Fe-g-C3N4The method for preparing the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane by blending modification has the same equipment as the traditional hollow fiber ultrafiltration membrane spinning equipment, is simple and easy to control, has simple membrane preparation process, endows the prepared ultrafiltration membrane with visible light catalytic activity and pollution resistance while forming a membrane, and is easy to realize industrialization.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
61.5% (w/w) of dimethylacetamide, 16.0% (w/w) of polyethylene glycol 400 and 1.5% (w/w) of F-TiO2/Fe-g-C3N4Respectively adding the materials into a dissolving tank according to a certain sequence, and uniformly stirring; then 21.0% (w/w) polyvinylidene fluoride is added, and stirred and dissolved for 8 hours at the temperature of 80 ℃ until the polyvinylidene fluoride is completely dissolved; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 24 hours to remove air bubbles remaining in the casting solution.
Controlling the flow rate of the casting film liquid to be 11.0 mL/min, the temperature of the casting film liquid to be 60 ℃, the temperature of the coagulating bath to be 35 ℃, the height between the air to be 7cm and the coagulating time of the hollow fiber membrane to be 2.0 minutes, and preparing the hollow fiber mixed matrix ultrafiltration membrane by adopting the traditional dry-wet spinning process. The prepared hollow fiber ultrafiltration membrane is put into deionized water for soaking and washing for 24 hours to clean the additive and the pore-forming agent. Then the mixture is put into a mixed solution of 50 percent of glycerol and 0.5 percent of Tween 80 to be treated for 48 hours, and the F-TiO-based material is prepared2/Fe-g-C3N4The self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane.
The pure water flux of the self-cleaning hollow fiber mixed matrix ultrafiltration membrane prepared by the embodiment is 261.23L/m2Hr.0.1 MPa, bovine serum albumin rejection 95.12%, resistance increase coefficient 1.26, contact angle 72.2 °; the degradation removal rate of humic acid is improved from 53.06% (without illumination, running for 1 hour) to 93.13% (under simulated visible light, running for 1 hour).
Example 2:
F-TiO is mixed with2/Fe-g-C3N4The content was reduced from 1.5% (w/w) to 0.2% (w/w), and the content of dimethylacetamide was increased from 61.5% (w/w) to 62.8% (w/w), the rest being the same as in example 1. The prepared F-TiO-based2/Fe-g-C3N4The pure water flux of the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane is 223.59L/m2Hr · 0.1MPa, bovine serum albumin rejection of 94.36%, resistance increase coefficient of 1.67, contact angle of 81.3 °; the degradation removal rate of humic acid is improved from 35.43 percent (without illumination and running for 1 hour)Up to 48.61% (simulated visible light, run for 1 hour).
Example 3:
F-TiO is mixed with2/Fe-g-C3N4The content was increased from 1.5% (w/w) to 3.0% (w/w), and the content of dimethylacetamide was decreased from 61.5% (w/w) to 60.0% (w/w), the rest being the same as in example 1. The prepared F-TiO-based2/Fe-g-C3N4The pure water flux of the self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane is 239.67L/m2Hr.0.1 MPa, bovine serum albumin rejection 91.94%, resistance increase coefficient 1.25, contact angle 71.9 °; the degradation removal rate of humic acid is improved from 54.69% (without illumination and running for 1 hour) to 93.87% (under simulated visible light, running for 1 hour).
Comparative example 1:
respectively adding 63.0% (w/w) of dimethylacetamide, 16.0% (w/w) of polyethylene glycol 400 and 21.0% (w/w) of polyvinylidene fluoride into a dissolving tank according to a certain sequence, and stirring and dissolving at the temperature of 80 ℃ for 8 hours until the materials are completely dissolved; then, the obtained casting solution was allowed to stand still at the stirring and dissolving temperature for 24 hours to remove air bubbles remaining in the casting solution.
Controlling the flow rate of the casting solution to be 11.0 mL/min, the temperature of the casting solution to be 45 ℃, the temperature of a coagulation bath to be 35 ℃, the height between the air to be 7cm and the coagulation time of the hollow fiber membrane to be 2.0 minutes, and preparing the polyvinylidene fluoride hollow fiber ultrafiltration membrane by adopting the traditional dry-wet spinning process. The prepared PVDF hollow fiber ultrafiltration membrane is put into deionized water for soaking and washing for 24 hours to clean the additive. Then the membrane is put into a mixed solution of 50 percent of glycerol and 0.5 percent of Tween 80 for treatment for 48 hours, and the commercial polyvinylidene fluoride hollow fiber ultrafiltration membrane is prepared.
The pure water flux of the PVDF hollow fiber ultrafiltration membrane prepared in the comparative example is 207.35L/m2Hr · 0.1MPa, bovine serum albumin rejection of 93.41%, resistance increase coefficient of 1.73, contact angle of 83.8 °; the degradation removal rate of humic acid is improved from 32.29 percent (without illumination and running for 1 hour) to 33.45 percent (running for 1 hour under simulated visible light).
Claims (4)
1. A kind ofBased on F-TiO2/Fe-g-C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane is characterized in that the membrane casting solution contains F-TiO2/Fe-g-C3N4And influence the structure and performance of the ultrafiltration membrane; the casting solution consists of the following substances in percentage by mass: 12.0-25.0% (w/w) of polymer membrane material, 10.0-23.0% (w/w) of pore-foaming agent and F-TiO2/Fe-g-C3N4 0.2-3.0% (w/w), and the balance of solvent.
The polymer film material is polyvinylidene fluoride (PVDF); the pore-foaming agent is polyethylene glycol (PEG-400); the F-TiO2/Fe-g-C3N4Is a self-made visible light catalytic nano inorganic compound; the solvent is N, N-dimethylacetamide (DMAc).
2. The F-TiO-based material of claim 12/Fe-g-C3N4The self-cleaning PVDF hollow fiber ultrafiltration membrane is characterized in that: the ultrafiltration membrane is prepared by adopting a traditional phase inversion method, namely a dry-wet method.
3. Based on F-TiO2/Fe-g-C3N4The preparation method of the self-cleaning PVDF hollow fiber ultrafiltration membrane is characterized by comprising the following steps:
step (1) mixing a certain amount of solvent, pore-forming agent and F-TiO2/Fe-g-C3N4Respectively adding the materials into a dissolving tank according to a certain proportion and sequence, and uniformly stirring at normal temperature;
adding a proper amount of polyvinylidene fluoride into a dissolving tank, stirring at 45-95 ℃ for 8-16 hours until the polyvinylidene fluoride is completely dissolved, standing and defoaming for 12-36 hours to obtain a self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane casting solution;
step (3) adopting a traditional dry-wet spinning process, controlling the flow rate of a casting film liquid to be 5.0-25.0 mL/min, controlling the temperature of the casting film liquid to be 45-95 ℃, the temperature of a coagulation bath to be 20-45 ℃, the height between air to be 2-15 cm and the coagulation time of the hollow fiber membrane to be 1.0-5 minutes, and preparing the self-cleaning hollow fiber mixed matrix ultrafiltration membrane;
soaking and washing the prepared hollow fiber ultrafiltration membrane in deionized water for 24 hours to clean the pore-forming agent and the additive; then the mixture is put into the mixed solution of 50 percent of glycerol and 0.5 percent of Tween 80 for treatment for 48 hours, and the F-TiO-based material can be prepared2/Fe-g-C3N4The self-cleaning PVDF hollow fiber mixed matrix ultrafiltration membrane.
4. An F-TiO-based composition according to claim 32/Fe-g-C3N4The preparation method of the self-cleaning PVDF hollow fiber ultrafiltration membrane is characterized by comprising the following steps: the coagulating bath is deionized water.
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