CN110652888A - Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof - Google Patents
Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof Download PDFInfo
- Publication number
- CN110652888A CN110652888A CN201911106111.XA CN201911106111A CN110652888A CN 110652888 A CN110652888 A CN 110652888A CN 201911106111 A CN201911106111 A CN 201911106111A CN 110652888 A CN110652888 A CN 110652888A
- Authority
- CN
- China
- Prior art keywords
- polyvinylidene fluoride
- hollow fiber
- membrane
- lining
- fluoride hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with a lining, which is prepared by a nascent state polyvinylidene fluoride hollow fiber membrane with a lining, performing steam-induced phase separation in a wet steam atmosphere, and then entering a coagulating bath for coagulation and forming. The invention also discloses a preparation method of the film. The invention adopts a two-step induction method, namely, the obtained nascent-state membrane is firstly placed in a high-humidity environment or mixed atmosphere of polar organic solvent and water for steam-induced phase separation, and then the membrane is placed in a water bath for further phase separation to prepare the finished membrane. The membrane can run at low pressure, produces water through liquid level difference and siphoning, saves energy consumption, and is particularly suitable for the fields of sterilizing and filtering drinking water in rural areas in remote mountainous areas, treating sewage in rural areas and the like.
Description
Technical Field
The invention relates to a fiber composite membrane and a preparation method thereof, in particular to a low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with a lining and a preparation method thereof.
Background
The membrane bioreactor process (MBR) is a novel high-efficiency sewage treatment process combining a membrane separation technology with a traditional activated sludge process, wherein a membrane component is arranged in an aeration tank, water after aerobic aeration and biological treatment is filtered by a membrane to remove activated sludge and macromolecular organic matters and is pumped out by a pump. The membrane greatly improves the solid-liquid separation capacity of the system, and the Membrane Bioreactor (MBR) has the advantages of high pollutant removal efficiency, strong nitrification capacity, capability of simultaneously performing nitrification and denitrification, good denitrification effect, stable effluent quality, low residual sludge yield, compact equipment, small occupied area, convenient increment and expansion, high automation degree, simple operation and the like.
Polyvinylidene fluoride (PVDF) is one of the most used membrane materials at present due to good film forming property and excellent oxidation resistance. PVDF has an oxidation resistance 10 times or more that of materials such as Polyethersulfone (PES) and polysulfone (PSf). In sewage treatment, microorganism and organic matter pollution are often the important reasons for irreversible fouling and blocking of the membrane, and oxidant cleaning is the most effective means for recovering flux, and the strong oxidation resistance of the polyvinylidene fluoride membrane shows the superiority of the polyvinylidene fluoride membrane. The PVDF film has strong anti-corrosion performance on a plurality of chemical substances, such as strong acid, alkali, oxidant and the like, can show good operation stability in the pH range of 2-10, and has tolerance range on the oxidant exceeding 1,000,000mg L-1h-1。
The PVDF hollow fiber membrane with the lining has the advantages that the PVDF hollow fiber membrane with the lining is provided with the lining of the enhancement layer on the inner side of the PVDF hollow fiber membrane, and the PVDF hollow fiber membrane with the lining has good strength and can bear the impact of frequent aeration and backwashing in the running process of the MBR without filament breakage, so that the PVDF hollow fiber membrane with the lining has absolute advantages in comparison with membrane materials with other structural forms. The PVDF hollow fiber membrane with the lining prepared by the existing method mostly has compact skin layers, the filtering precision is good, but the filtering pressure is high, the operating pressure of the PVDF hollow fiber membrane with the lining in an immersed assembly is generally-0.1 to-0.3 MPa, and the water is pumped and produced by the negative pressure generated by a suction pump, so that certain limitation is brought to the popularization and application of the PVDF hollow fiber membrane with the lining in the drinking water preparation in rural areas in remote mountainous areas and the rural sewage treatment. Chinese patent CN 104043346B discloses a highly asymmetric sponge structureThe preparation method of the strong polyvinylidene fluoride hollow fiber membrane comprises the following steps: dissolving a mixture of a solid high molecular material polyvinylidene fluoride, a hydrophilic second polymer and an organic small molecular additive in an organic solvent to prepare a transparent, uniform and stable casting solution, uniformly coating the casting solution on the outer surface of a hollow reinforcing tube after passing through a spinning device at 30-150 ℃, immersing a nascent-state membrane in a water bath at 0-80 ℃ for solidification and molding to prepare the reinforced polyvinylidene fluoride hollow fiber membrane, wherein the section of the membrane has an asymmetric sponge structure and is provided with a compact separation layer, the aperture of the separation layer is 0.002-0.1 mu m, and the pure water permeation flux of the membrane is not less than 1000L/(m) under the pressure of 0.1MPa2H), the membrane filtration resistance is greater due to the presence of a dense separation layer.
Disclosure of Invention
The invention aims to provide a low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with a lining, which is prepared by a two-step induction method, namely, firstly placing the obtained nascent state membrane in a high-humidity environment or a mixed atmosphere of a polar organic solvent and water for steam-induced phase separation, and then placing the membrane in a water bath for further phase separation.
The technical scheme for realizing one purpose of the invention is as follows:
a low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with a lining is prepared by a nascent-state polyvinylidene fluoride hollow fiber membrane with a lining, performing steam-induced phase separation in a wet steam atmosphere, and then entering a coagulating bath for coagulation and forming.
The steam atmosphere may be air having a humidity of 50% or more, or may be a mixed atmosphere of a polar organic solvent having a humidity of 50% or more and water.
The nascent-state polyvinylidene fluoride hollow fiber membrane with the lining is prepared by preparing transparent and uniform membrane casting liquid from a solid high polymer material polyvinylidene fluoride, an organic high polymer additive, an organic small molecule additive and a polar organic solvent, and then coating the membrane casting liquid on the outer surface of a polyethylene glycol terephthalate hollow crocheted tube through spinning. As an embodiment of the invention, the solid polymer material polyvinylidene fluoride 10-20 wt%, the organic polymer additive 0-20 wt%, the organic micromolecule additive 0-20 wt%, and the polar organic solvent 50-80 wt%.
The invention also aims to provide a preparation method of the low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining.
Specifically, the preparation method of the low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining provided by the invention comprises the following steps:
(1) preparing a nascent-state polyvinylidene fluoride hollow fiber membrane with a lining;
(2) placing the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in a wet steam atmosphere for steam-induced phase separation, then placing the nascent-state polyvinylidene fluoride hollow fiber membrane in a coagulating bath for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining;
(3) the polyvinylidene fluoride hollow fiber composite membrane with the lining is leached and dried to obtain a membrane finished product.
As an embodiment of the present invention, the step (1) is specifically as follows:
1) dissolving 10-20 wt% of solid polymer material polyvinylidene fluoride, 0-20 wt% of organic polymer additive and 0-20 wt% of organic micromolecule additive in 50-80 wt% of polar organic solvent to prepare transparent casting solution;
2) and (2) after the membrane casting solution in the step 1) is kept stand and defoamed, spraying silk to coat the outer surface of the polyethylene glycol terephthalate hollow crocheted pipe to obtain a nascent-state belt lining polyvinylidene fluoride hollow fiber membrane.
The temperature for preparing the casting solution in the step 1) is 50-95 ℃.
Further, the polar organic solvent in the step 1) is at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethyl phosphate and trimethyl phosphate.
Further, the organic polymer additive in step 1) is two or three of polyvinylpyrrolidone, sulfonated polyethersulfone, polymethyl methacrylate, polyoxyethylene-polyoxypropylene block copolymer, polyvinyl alcohol and polyethylene glycol.
Further, the organic small molecule additive in the step 1) is one or a combination of more than two of glycerol, ethylene glycol and diethylene glycol.
In the step (2), the length of a wet steam atmosphere section through which the nascent-state belt lining polyvinylidene fluoride hollow fiber membrane passes is 0-30cm but not zero, and preferably 10-30 cm; and the temperature of the coagulation bath is 0-80 ℃. In the present invention, the wet steam atmosphere may be air having a humidity of 50% or more, or may be a mixed atmosphere of a polar organic solvent having a humidity of 50% or more and water. As an embodiment of the present invention, in the wet steam, the volume fraction of the polar organic solvent is 10 to 70 vol%, and the steam humidity is 50 to 90%; wherein the polar solvent is at least one of ethanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethyl phosphate and trimethyl phosphate.
In the step (3), the polyvinylidene fluoride hollow fiber composite membrane with the lining is soaked in a mixed solution of water and glycerol at the temperature of 20-80 ℃ for 8-12h to remove high-molecular and small-molecular additives, and then the membrane finished product is obtained after drying. As an embodiment of the invention, the volume fraction of glycerol is 5-30 vol%.
The invention has the following beneficial effects:
the invention adopts a two-step induction method, firstly, the membrane is placed in a high humidity environment or the mixed atmosphere of a solvent and water for steam-induced phase separation, so that the cortex has rich openings, the resistance of water permeation is reduced, low-pressure self-flow is achieved, then the membrane is placed in a water bath for further phase separation, and the low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining and without the cortex or with a very thin cortex is prepared, the section is of a sponge structure, the cortex and the section jointly play a role in intercepting pollutants, the membrane can run at low pressure, water is produced through liquid level difference and siphoning, the energy consumption is saved, and the invention is particularly suitable for the fields of sterilizing and filtering drinking water in rural areas in remote mountainous areas, rural sewage.
Drawings
FIG. 1 is a surface SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with inner lining in example 1;
FIG. 2 is a sectional SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with inner lining in example 1;
FIG. 3 is a surface SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with inner lining in example 2;
FIG. 4 is a sectional SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with inner lining in example 2;
FIG. 5 is a surface SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with a lining in example 3;
FIG. 6 is a SEM image of a cross section of the polyvinylidene fluoride hollow fiber composite membrane with a lining in example 3;
FIG. 7 is a surface SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with inner lining in example 4;
FIG. 8 is a sectional SEM photograph of a polyvinylidene fluoride hollow fiber composite membrane with a lining in example 4.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the scope of the invention.
Example 1
(1) Dissolving 15 wt% of solid high polymer material polyvinylidene fluoride FR915, 10 wt% of polyvinylpyrrolidone K30, 7 wt% of polymethyl methacrylate and 10 wt% of ethylene glycol in 58 wt% of dimethylformamide, and uniformly stirring at 80 ℃ to obtain a transparent and uniform casting solution.
(2) And (3) after standing and defoaming the casting solution, extruding the casting solution at the temperature of 80 ℃, coating the casting solution on the outer surface of a polyethylene terephthalate hollow crocheted pipe which is dragged at a constant speed by a spinning device to obtain the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining.
(3) And (3) carrying out first-step phase separation on the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in 30cm ethanol-water mixed steam atmosphere with the concentration of 60 vol% and the humidity of 80%, and then soaking the nascent-state polyvinylidene fluoride hollow fiber membrane into coagulating bath water at the temperature of 60 ℃ for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining.
(4) Soaking the polyvinylidene fluoride hollow fiber composite membrane with the lining in a glycerol water mixed solution with the concentration of 20 vol% at 50 ℃ for 12h to wash out high-molecular and small-molecular additives, and airing to obtain a membrane finished product. The pore diameter of the membrane surface is 0.2-0.6 μm, the section is full-sponge structure,when the liquid level difference above the membrane of the immersed membrane module is 1m, the pure water flux of the membrane is 610L/(m)2H), the thickness of the skin layer is about 1 micron, the skin layer is rich in open pores, and the water permeation resistance is small.
Example 2
(1) Dissolving 17 wt% of solid high polymer material polyvinylidene fluoride FR915, 9 wt% of polyvinylpyrrolidone K17, 6 wt% of polyethylene glycol 200, 5 wt% of ethylene glycol and 5 wt% of diethylene glycol in 58 wt% of dimethylacetamide, and uniformly stirring at 85 ℃ to obtain a transparent and uniform casting solution.
(2) And (3) after standing and defoaming the casting solution, extruding the casting solution at the temperature of 85 ℃ and coating the casting solution on the outer surface of a polyethylene terephthalate hollow crocheted pipe which is dragged at a constant speed by a spinning device to obtain the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining.
(3) And (3) carrying out first-step phase separation on the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in 25cm of dimethylformamide water mixed steam atmosphere with the concentration of 45 vol% and the humidity of 70%, and then soaking the nascent-state polyvinylidene fluoride hollow fiber membrane into 65 ℃ coagulating bath water for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining.
(4) And soaking the polyvinylidene fluoride hollow fiber composite membrane with the lining in 15 vol% glycerol water mixed solution at 45 ℃ for 8h to wash out high-molecular and small-molecular additives, and airing to obtain a membrane finished product. The membrane has a surface pore diameter of 0.1-0.5 μm and a cross section of full-sponge structure, and has a pure water flux of 530L/(m) when the liquid level difference above the membrane is 1m2H), the thickness of the skin layer is about 1 micron, the skin layer is rich in open pores, and the water permeation resistance is small.
Example 3
(1) Dissolving 18 wt% of solid high polymer material polyvinylidene fluoride FR915, 6 wt% of polyvinylpyrrolidone K17, 4 wt% of polymethyl methacrylate, 6 wt% of polyethylene glycol 200 and 6 wt% of glycerol in 60 wt% of N-methyl pyrrolidone, and uniformly stirring at 85 ℃ to obtain a transparent and uniform casting solution.
(2) And (3) after standing and defoaming the casting solution, extruding the casting solution at the temperature of 75 ℃ and coating the casting solution on the outer surface of a polyethylene terephthalate hollow crocheted pipe which is dragged at a constant speed by a spinning device to obtain the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining.
(3) And (3) carrying out first-step phase separation on the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in a dimethylacetamide water mixed steam atmosphere with the concentration of 20cm and the concentration of 40 vol% and controlling the humidity to be 68%, and then soaking the nascent-state polyvinylidene fluoride hollow fiber membrane into coagulation bath water with the temperature of 75 ℃ for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining.
(4) Soaking the polyvinylidene fluoride hollow fiber composite membrane with the lining in glycerol water mixed solution with the concentration of 15 vol% at 40 ℃ for 9h to wash out high-molecular and small-molecular additives, and airing to obtain a membrane finished product. The membrane has a surface pore diameter of 0.08-0.3 μm and a cross section of full-sponge structure, and has a pure water flux of 460L/(m) when the liquid level difference above the membrane is 1m2H), the thickness of the skin layer is about 1 micron, the skin layer is rich in open pores, and the water permeation resistance is small.
Example 4
(1) Dissolving 15 wt% of solid high polymer material polyvinylidene fluoride Solvay6015, 12 wt% of polyvinylpyrrolidone K30, 5 wt% of polymethyl methacrylate and 12 wt% of ethylene glycol in 56 wt% of dimethylformamide, and uniformly stirring at 82 ℃ to obtain a transparent and uniform casting solution.
(2) And (3) after standing and defoaming the casting solution, extruding the casting solution at 82 ℃ and coating the casting solution on the outer surface of a polyethylene terephthalate hollow crocheted pipe which is dragged at a constant speed by a spinning device to obtain the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining.
(3) And (3) carrying out first-step phase separation on the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in a water vapor atmosphere of 30cm under the condition that the humidity is controlled to be 90%, and then soaking the nascent-state polyvinylidene fluoride hollow fiber membrane into coagulating bath water at the temperature of 60 ℃ for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining.
(4) Soaking the polyvinylidene fluoride hollow fiber composite membrane with the lining in a glycerol water mixed solution with the concentration of 20 vol% at 50 ℃ for 12h to wash out high-molecular and small-molecular additives, and airing to obtain a membrane finished product. The membrane has a surface pore diameter of 0.22-0.45 μm and a cross section of full-sponge structure, and is pure when the liquid level difference above the membrane is 1mThe water flux is 700L/(m)2H), the thickness of the skin layer is about 1 micron, the skin layer is rich in open pores, and the water permeation resistance is small.
Claims (10)
1. The low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining is characterized by being prepared by leading a nascent state polyvinylidene fluoride hollow fiber membrane with the lining to be subjected to steam induced phase separation in a wet steam atmosphere and then entering a coagulating bath for coagulation forming.
2. The low-pressure self-flowing polyvinylidene fluoride hollow fiber composite membrane with an inner liner according to claim 1, wherein the wet steam atmosphere is air with humidity of 50% or more, or a mixed atmosphere of a polar organic solvent with humidity of 50% or more and water.
3. The low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 1, wherein the nascent state polyvinylidene fluoride hollow fiber membrane with the lining is prepared by preparing a casting solution from a solid high polymer material polyvinylidene fluoride, an organic high polymer additive, an organic small molecule additive and a polar organic solvent, and then carrying out spinning coating on the outer surface of a polyethylene terephthalate hollow crocheted tube.
4. The low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 3, wherein the raw materials comprise 10-20 wt% of solid polymer material polyvinylidene fluoride, 0-20 wt% of organic polymer additive, 0-20 wt% of organic small molecule additive and 50-80 wt% of polar organic solvent.
5. A preparation method of a low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with a lining is characterized by comprising the following steps:
(1) preparing a nascent-state polyvinylidene fluoride hollow fiber membrane with a lining;
(2) placing the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining in a wet steam atmosphere for steam-induced phase separation, then placing the nascent-state polyvinylidene fluoride hollow fiber membrane in a coagulating bath for further phase separation and coagulation forming to obtain the polyvinylidene fluoride hollow fiber composite membrane with the lining;
(3) the polyvinylidene fluoride hollow fiber composite membrane with the lining is leached and dried to obtain a membrane finished product.
6. The method for preparing the low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 5, wherein in the step (2), the length of a wet steam atmosphere section through which the nascent-state polyvinylidene fluoride hollow fiber membrane with the lining passes is 0-30cm but is not zero; and the temperature of the coagulation bath is 0-80 ℃.
7. The method for preparing the low-pressure self-flowing polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 5 or 6, wherein the wet steam atmosphere is air with humidity of 50% or more, or a mixed atmosphere of a polar organic solvent with humidity of 50% or more and water.
8. The preparation method of the low-pressure self-flowing polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 5, wherein in the step (3), the polyvinylidene fluoride hollow fiber composite membrane with the lining is soaked in a mixed solution of water and glycerol at 20-80 ℃ for 8-12h to remove high-molecular and small-molecular additives, and then the membrane finished product is obtained after drying.
9. The preparation method of the low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with the lining according to claim 5, wherein the step (1) is as follows:
1) dissolving 10-20 wt% of solid polymer material polyvinylidene fluoride, 0-20 wt% of organic polymer additive and 0-20 wt% of organic micromolecule additive in 50-80 wt% of polar organic solvent to prepare membrane casting solution;
2) and (2) after the membrane casting solution in the step 1) is kept stand and defoamed, spraying silk to coat the outer surface of the polyethylene glycol terephthalate hollow crocheted pipe to obtain a nascent-state belt lining polyvinylidene fluoride hollow fiber membrane.
10. The method for preparing a low-pressure self-flowing polyvinylidene fluoride hollow fiber composite membrane with a lining according to claim 9, wherein the polar organic solvent in the step 1) is at least one of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, triethyl phosphate and trimethyl phosphate; the organic polymer additive in the step 1) is two or three of polyvinylpyrrolidone, sulfonated polyether sulfone, polymethyl methacrylate, polyoxyethylene-polyoxypropylene block copolymer, polyvinyl alcohol and polyethylene glycol; the organic small molecular additive in the step 1) is one or a combination of more than two of glycerol, ethylene glycol and diethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911106111.XA CN110652888B (en) | 2019-11-13 | 2019-11-13 | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911106111.XA CN110652888B (en) | 2019-11-13 | 2019-11-13 | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110652888A true CN110652888A (en) | 2020-01-07 |
| CN110652888B CN110652888B (en) | 2021-09-17 |
Family
ID=69043554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911106111.XA Active CN110652888B (en) | 2019-11-13 | 2019-11-13 | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110652888B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452844A (en) * | 2022-01-29 | 2022-05-10 | 杭州科百特过滤器材有限公司 | PES hollow fiber membrane for purifying biomacromolecules and preparation method and application thereof |
| CN117797661A (en) * | 2024-02-23 | 2024-04-02 | 天津工业大学 | Sandwich-structured lined hollow fiber membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059707A1 (en) * | 1998-05-18 | 1999-11-25 | Usf Filtration And Separations Group Inc. | Highly porous polyvinylidene difluoride membranes |
| CN104043346A (en) * | 2014-05-20 | 2014-09-17 | 桐乡市健民过滤材料有限公司 | Enhanced polyvinylidene fluoride hollow fiber film with highly-asymmetric spongy structure |
| CN104826501A (en) * | 2015-04-15 | 2015-08-12 | 江苏超源膜科技有限公司 | High peel strength vinyl polyvinylidene fluoride hollow fiber composite membrane preparation process |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
-
2019
- 2019-11-13 CN CN201911106111.XA patent/CN110652888B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059707A1 (en) * | 1998-05-18 | 1999-11-25 | Usf Filtration And Separations Group Inc. | Highly porous polyvinylidene difluoride membranes |
| CN104043346A (en) * | 2014-05-20 | 2014-09-17 | 桐乡市健民过滤材料有限公司 | Enhanced polyvinylidene fluoride hollow fiber film with highly-asymmetric spongy structure |
| CN104826501A (en) * | 2015-04-15 | 2015-08-12 | 江苏超源膜科技有限公司 | High peel strength vinyl polyvinylidene fluoride hollow fiber composite membrane preparation process |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN108079795A (en) * | 2017-12-13 | 2018-05-29 | 浙江长兴求是膜技术有限公司 | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452844A (en) * | 2022-01-29 | 2022-05-10 | 杭州科百特过滤器材有限公司 | PES hollow fiber membrane for purifying biomacromolecules and preparation method and application thereof |
| CN114452844B (en) * | 2022-01-29 | 2023-12-29 | 杭州科百特过滤器材有限公司 | PES hollow fiber membrane for purifying biomacromolecule, and preparation method and application thereof |
| CN117797661A (en) * | 2024-02-23 | 2024-04-02 | 天津工业大学 | Sandwich-structured lined hollow fiber membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110652888B (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106731841B (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| CN110652888B (en) | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof | |
| CN106237869A (en) | A kind of polyphenol coating modified hydrophobic hydrophilic method of type polymeric membrane | |
| CN101327408B (en) | Method for preparing antimicrobial modified polyvinyl alcohol-nonwoven compound microporous filtering film | |
| CN100404115C (en) | Grafted styrene modified membrane and preparation method and application thereof | |
| CN111013400A (en) | Method for preparing polyvinylidene fluoride tubular membrane by low-temperature thermal induced phase method | |
| CN110713253A (en) | Bioreactor membrane and preparation process | |
| CN109876680B (en) | Preparation method of TB ultrafiltration membrane and treatment method of oily wastewater | |
| CN111974227A (en) | Swelling-resistant sulfonated polyether sulfone nanofiltration membrane and preparation method thereof | |
| CN108854600B (en) | Graphene oxide/polyurethane hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN112473400B (en) | Graphene micro-ultrafiltration membrane and preparation method thereof | |
| CN104587842A (en) | Preparation method of MBR (Meane Biological Reactor) plain filtering film for industrial sewage treatment | |
| CN110975637B (en) | Preparation method of gallic acid-chitosan/polysulfone composite nanofiltration membrane | |
| CN113304629A (en) | Preparation method of composite nanofiltration membrane based on polyether sulfone hollow fiber ultrafiltration membrane | |
| CN110201559B (en) | Large-flux reinforced hollow fiber membrane and preparation method thereof | |
| CN112844077A (en) | Reverse osmosis membrane with PE microporous membrane as base material and preparation method thereof | |
| CN112237843A (en) | Preparation method of ultrafiltration flat membrane | |
| KR102067861B1 (en) | Composition for preparing reverse osmosis membrane, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module | |
| CN109675447A (en) | A kind of enhancement type hollow fiber film and preparation method thereof for being not easy to strip off | |
| CN114570213B (en) | Modified hollow fiber nanofiltration membrane and preparation method thereof | |
| CN113019139B (en) | Composite ultrafiltration membrane and preparation method thereof | |
| CN114345150B (en) | Preparation method of water purification nanofiltration membrane | |
| CN114210213B (en) | Preparation method of hollow nanofiltration membrane | |
| KR20180080425A (en) | Composite porous membrane of acetylated alkyl cellulose and polyolefinketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Low pressure self flow PVDF hollow fiber composite membrane with lining and its preparation method Effective date of registration: 20221017 Granted publication date: 20210917 Pledgee: China Construction Bank Corporation Jiayu Sub-branch Pledgor: HUBEI RUI FILTER FILM TECHNOLOGY Co.,Ltd. Registration number: Y2022980018474 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |