CN110575761A - Fiber-reinforced PVDF ultrafiltration membrane and application thereof in municipal sewage and industrial wastewater - Google Patents
Fiber-reinforced PVDF ultrafiltration membrane and application thereof in municipal sewage and industrial wastewater Download PDFInfo
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- CN110575761A CN110575761A CN201910802328.8A CN201910802328A CN110575761A CN 110575761 A CN110575761 A CN 110575761A CN 201910802328 A CN201910802328 A CN 201910802328A CN 110575761 A CN110575761 A CN 110575761A
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 118
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 118
- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 33
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 4
- 239000010865 sewage Substances 0.000 title abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000004907 flux Effects 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 50
- 238000005266 casting Methods 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000004804 winding Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000010841 municipal wastewater Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 4
- 239000012510 hollow fiber Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- 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
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (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 provides a fiber reinforced PVDF ultrafiltration membrane, which is characterized in that at least two monofilament fibers are embedded in a traditional PVDF membrane layer, wherein the monofilament fibers are made of PVDF resin with ultrahigh molecular weight and are subjected to hydrophilic modification by PVA. The PVDF ultrafiltration membrane prepared by the invention improves the strength and the alcohol water flux of the membrane, and has higher application potential in the water treatment fields of municipal sewage, industrial wastewater and the like.
Description
Technical Field
The invention relates to a hollow fiber membrane, in particular to a fiber reinforced PVDF ultrafiltration membrane.
Background
Ultrafiltration is a pressurized membrane separation technique, in which small molecular solutes and solvents are passed through a special membrane with a certain pore size under a certain pressure, while large molecular solutes are not passed through the membrane and remain on one side of the membrane, thus partially purifying the large molecular substances. Ultrafiltration is one of the membrane separation techniques using pressure as the driving force. The purpose is to separate macromolecules from small molecules. The ultrafiltration device is similar to a reverse osmosis device and has the forms of a plate type, a tube type (an inner pressure tube array type and an outer pressure tube bundle type), a roll type, a hollow fiber type and the like. Compared with other forms of membranes such as flat membrane, roll membrane and the like, the hollow fiber membrane has the advantages of large loading density per unit volume and self-support. Among materials for preparing the ultrafiltration membrane again, polyvinylidene fluoride (PVDF) has excellent mechanical strength and chemical stability, can resist the corrosion of hypochlorous acid in municipal sewage, and is widely applied to pure water production and sewage treatment.
In the application process of the PVDF ultrafiltration membrane, particularly in the application of a membrane reactor, the requirement on the strength of the fiber membrane is high, but the PVDF ultrafiltration membrane prepared by the traditional method can not meet the requirement. To ameliorate such conditions, various patents and articles have proposed fiber-reinforced fiber membranes, commonly known as "concrete-type" fiber membranes. Although the strength of the membrane filaments can be improved, the application stability of the membrane is affected by the peeling phenomenon easily generated in the application process of the reinforced fibers and the membrane filaments. In view of the above, CN106731895A proposes that PVDF fiber is used as a reinforcing fiber to reinforce the strength of PVDF ultrafiltration fiber membrane, so as to achieve the purpose of homogeneous reinforcement. However, the inventors have found experimentally that PVDF-based reinforcement fibers are very susceptible to erosion in the casting solution solvent, greatly compromising the reinforcement objectives.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: the fiber reinforced PVDF ultrafiltration membrane is provided to prevent reinforced fibers from being corroded by a solvent, and the problem of low flux of the fiber reinforced PVDF ultrafiltration membrane is solved through hydrophilic modification of the reinforced fibers.
the invention provides a fiber reinforced PVDF ultrafiltration membrane, which comprises a PVDF ultrafiltration membrane layer with non-ultrahigh molecular weight and modified PVDF monofilament fibers with ultrahigh molecular weight, wherein the modified PVDF monofilament fibers are embedded in the PVDF ultrafiltration membrane layer and are formed by extruding a PVDF material with ultrahigh molecular weight and modifying the PVDF material through PVA hydrophilicity.
Preferably, the ultra-high molecular weight PVDF is PVDF having a relative molecular weight of more than 100 ten thousand.
Preferably, the diameter of the supermolecular weight PVDF monofilament fiber is 0.08-0.15 mm.
preferably, the fiber reinforced PVDF ultrafiltration membrane has the breaking strength of 18-27MPa, the breaking elongation of 190-220 percent and the breaking elongation of 980-1500L/m2Pure water flux of h.
Preferably, the film provided by the invention is prepared by the following steps:
(1) Preparing the super-molecular weight PVDF material into super-molecular weight PVDF monofilament fibers through a screw extruder;
(2) Wetting the super-molecular-weight PVDF monofilament supporting fiber by using deionized water, placing the super-molecular-weight PVDF monofilament supporting fiber in a PVA solution with the concentration of 0.005-0.1wt% for 2-3h, taking out the super-molecular-weight PVDF monofilament supporting fiber, drying the super-molecular-weight PVDF monofilament supporting fiber after drying the super-molecular-weight PVDF monofilament supporting fiber, placing the super-molecular-weight PVDF monofilament supporting fiber in a mixed solution of glutaraldehyde and sulfuric acid for 10-20min, washing;
(3) Mixing PVDF resin, an organic solvent and a pore-forming agent in proportion to form a membrane casting solution, and defoaming in vacuum for 3-5 h;
(4) And filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the super-molecular-weight PVDF monofilament fiber into a spinning jet to enable the super-molecular-weight PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a winding wheel after washing to be completely solidified to form the fiber reinforced PVDF ultrafiltration membrane.
Preferably, the organic solvent is one or more of N-methylpyrrolidone, N-dimethylacetamide, dimethylformamide and dimethylsulfoxide.
preferably, the pore-forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol, LiCl and titanium dioxide.
Preferably, in the casting solution, the PVDF content is 15-25wt%, the organic solvent is 50-70 wt%, and the pore-forming agent is 5-15 wt%.
preferably, the concentration of the glutaraldehyde in the mixed solution of the glutaraldehyde and the sulfuric acid is 3-6wt%, and the concentration of the sulfuric acid is 1-3 wt%.
the invention has the beneficial effects that:
The PVDF reinforced fiber in the prior art is replaced by the PVDF monofilament fiber with the ultra-high molecular weight, and the technical problem that the reinforced fiber is dissolved by a solvent is solved by using the insolubility of the PVDF with the ultra-high molecular weight. In order to improve the flux of the fiber membrane, PVA is creatively utilized to carry out PVA hydrophilic modification on the PVDF monofilament fiber with the ultrahigh molecular weight, so that the water flux of the reinforced fiber membrane is obviously improved, and the application potential of the PVDF ultrafiltration membrane is improved.
Detailed Description
the present invention is specifically illustrated below with reference to specific examples.
example 1
This example was prepared using the following method:
(1) Preparing the supramolecular PVDF material into supramolecular PVDF monofilament fibers with the diameter of about 0.1mm by a double-screw extruder;
(2) wetting the super-molecular-weight PVDF monofilament supporting fiber by using deionized water, placing the super-molecular-weight PVDF monofilament supporting fiber in a PVA solution with the concentration of 0.008wt% for 2 hours, taking out the super-molecular-weight PVDF monofilament supporting fiber, drying the super-molecular-weight PVDF monofilament supporting fiber after drying the super-molecular-weight PVDF monofilament supporting fiber, placing the super-molecular-weight PVDF monofilament supporting fiber in a mixed solution of glutaraldehyde (3 wt%)/sulfuric acid (1 wt%) for 15 minutes, washing;
(3) mixing PVDF resin (20 wt%), N-dimethylacetamide (70 wt%) and polyvinylpyrrolidone (10 wt%) to form a casting solution, and defoaming in vacuum for 3 h;
(4) And filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the modified super-molecular-weight PVDF monofilament fiber into a spinning nozzle to enable the super-molecular-weight PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a winding wheel after washing to be completely solidified to form the fiber-reinforced PVDF ultrafiltration membrane.
comparative example 1
This comparative example was prepared using the following method:
(1) Preparing a PVDF monofilament fiber with the diameter of about 0.1mm from a non-supramolecular PVDF material through a double-screw extruder;
(2) Mixing PVDF resin (20 wt%), N-dimethylacetamide (70 wt%) and polyvinylpyrrolidone (10 wt%) to form a casting solution, and defoaming in vacuum for 3 h;
(3) And filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the PVDF monofilament fiber into a spinning jet to enable the PVDF monofilament fiber with super molecular weight and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a wire winding wheel after washing to be completely solidified to form the fiber reinforced PVDF ultrafiltration membrane.
Comparative example 2
This comparative example was prepared using the following method:
(1) preparing a PVDF monofilament fiber with the diameter of about 0.1mm from a non-supramolecular PVDF material through a double-screw extruder;
(2) Wetting PVDF monofilament supporting fibers by using deionized water, placing the PVDF monofilament supporting fibers in a PVA solution with the concentration of 0.008wt% for 2 hours, taking out the PVDF monofilament supporting fibers, drying the PVDF monofilament supporting fibers, placing the PVDF monofilament supporting fibers in a mixed solution of glutaraldehyde (3 wt%)/sulfuric acid (1 wt%) for 15 minutes, washing and soaking the PVDF monofilament supporting fibers by using the deionized water to form modified PVDF monofilament fibers;
(3) Mixing PVDF resin (20 wt%), N-dimethylacetamide (70 wt%) and polyvinylpyrrolidone (10 wt%) to form a casting solution, and defoaming in vacuum for 3 h;
(4) and filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the modified PVDF monofilament fiber into a spinning jet to enable the supermolecule PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a wire winding wheel after washing to be completely solidified to form the fiber reinforced PVDF ultrafiltration membrane.
comparative example 3
This comparative example was prepared using the following method:
(1) preparing the supramolecular PVDF material into supramolecular PVDF monofilament fibers with the diameter of about 0.1mm by a double-screw extruder;
(2) Mixing PVDF resin (20 wt%), N-dimethylacetamide (70 wt%) and polyvinylpyrrolidone (10 wt%) to form a casting solution, and defoaming in vacuum for 3 h;
(3) and filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the super-molecular-weight PVDF monofilament fiber into a spinning jet to enable the super-molecular-weight PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a winding wheel after washing to be completely solidified to form the fiber reinforced PVDF ultrafiltration membrane.
comparative example 4
This comparative example was prepared using the following method:
(1) Preparing the supramolecular PVDF material into supramolecular PVDF monofilament fibers with the diameter of about 0.1mm by a double-screw extruder;
(2) Wetting the super-molecular-weight PVDF monofilament supporting fiber by using deionized water, placing the super-molecular-weight PVDF monofilament supporting fiber in a PVA solution with the concentration of 0.2wt% for 2h, taking out the super-molecular-weight PVDF monofilament supporting fiber, drying the super-molecular-weight PVDF monofilament supporting fiber after drying the super-molecular-weight PVDF monofilament supporting fiber, placing the super-molecular-weight PVDF monofilament supporting fiber in a mixed solution of glutaraldehyde (3 wt%)/sulfuric acid (1 wt%) for 15min, washing;
(3) Mixing PVDF resin (20 wt%), N-dimethylacetamide (70 wt%) and polyvinylpyrrolidone (10 wt%) to form a casting solution, and defoaming in vacuum for 3 h;
(4) And filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the modified super-molecular-weight PVDF monofilament fiber into a spinning nozzle to enable the super-molecular-weight PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a winding wheel after washing to be completely solidified to form the fiber-reinforced PVDF ultrafiltration membrane.
Characterization test: the PVDF ultrafiltration membranes prepared in examples and comparative examples 1 to 4 were subjected to tests of breaking strength, breaking elongation and pure water flux at 25 ℃ under 0.1MPa, and the results were as follows:
| Sample (I) | breaking strength/MPa | Elongation at break/% | flux/(L/m 2h) |
| Examples | 20.7 | 220 | 1029 |
| comparative example 1 | 9.6 | 170 | 549 |
| comparative example 2 | 8.5 | 164 | 890 |
| comparative example 3 | 21.6 | 216 | 517 |
| Comparative example 4 | 17.9 | 172 | 1121 |
The results in the table show that the PVDDF ultrafiltration membrane prepared by the method provided by the invention is obviously improved in strength and pure water flux, and has high application potential.
Other embodiments of the present invention than the preferred embodiments described above will be apparent to those skilled in the art from the present invention, and various changes and modifications can be made therein without departing from the spirit of the present invention as defined in the appended claims.
Claims (10)
1. the fiber-reinforced PVDF ultrafiltration membrane is characterized by comprising a PVDF ultrafiltration membrane layer with non-ultrahigh molecular weight and modified PVDF monofilament fibers with ultrahigh molecular weight, which are embedded in the PVDF ultrafiltration membrane layer, wherein the modified PVDF monofilament fibers with ultrahigh molecular weight are formed by extruding a PVDF material with ultrahigh molecular weight and are formed by hydrophilic modification through PVA.
2. The membrane of claim 1, wherein said ultra-high molecular weight PVDF is one having a relative molecular weight greater than 100 million.
3. The film according to claim 1, characterized in that said supramolecular PVDF monofilament fiber has a diameter of 0.08-0.15 mm.
4. The membrane as claimed in claim 1, wherein the fiber reinforced PVDF ultrafiltration membrane has a break strength of 18-27MPa, an elongation at break of 190-220% and 980-1500L/m2Pure water flux of h.
5. The film according to claim 1, characterized in that it is prepared by the following steps:
Preparing the super-molecular weight PVDF material into super-molecular weight PVDF monofilament fibers through a screw extruder;
Wetting the super-molecular-weight PVDF monofilament supporting fiber by using deionized water, placing the super-molecular-weight PVDF monofilament supporting fiber in a PVA solution with the concentration of 0.005-0.1wt% for 2-3h, taking out the super-molecular-weight PVDF monofilament supporting fiber, drying the super-molecular-weight PVDF monofilament supporting fiber after drying the super-molecular-weight PVDF monofilament supporting fiber, placing the super-molecular-weight PVDF monofilament supporting fiber in a mixed solution of glutaraldehyde and sulfuric acid for 10-20min, washing;
mixing PVDF resin, an organic solvent and a pore-forming agent in proportion to form a membrane casting solution, and defoaming in vacuum for 3-5 h;
And filtering the membrane casting solution by using a filter screen, simultaneously feeding the membrane casting solution and the super-molecular-weight PVDF monofilament fiber into a spinning jet to enable the super-molecular-weight PVDF monofilament fiber and the membrane casting solution to be compounded and formed, feeding the membrane casting solution into a coagulating bath for phase reaction and solidification to form a membrane, and winding the membrane casting solution on a winding wheel after washing to be completely solidified to form the fiber reinforced PVDF ultrafiltration membrane.
6. the membrane of claim 1, wherein the organic solvent is one or more of N-methylpyrrolidone, N-dimethylacetamide, dimethylformamide, and dimethylsulfoxide.
7. the film of claim 1, wherein the pore former is one or more of polyvinylpyrrolidone, polyethylene glycol, LiCl, and titanium dioxide.
8. the membrane according to claim 1, wherein the casting solution comprises 15-25wt% of PVDF, 50-70 wt% of an organic solvent, and 5-15 wt% of a pore forming agent.
9. The membrane of claim 1, wherein the glutaraldehyde/sulfuric acid mixture has a glutaraldehyde concentration of 3-6wt% and a sulfuric acid concentration of 1-3 wt%.
10. use of a fiber reinforced PVDF ultrafiltration membrane according to any of claims 1 to 9 in municipal and industrial wastewater.
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| CN201910802328.8A CN110575761B (en) | 2019-08-28 | 2019-08-28 | Fiber-reinforced PVDF ultrafiltration membrane and application thereof in municipal sewage and industrial wastewater |
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| CN201910802328.8A CN110575761B (en) | 2019-08-28 | 2019-08-28 | Fiber-reinforced PVDF ultrafiltration membrane and application thereof in municipal sewage and industrial wastewater |
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| CN110575761B CN110575761B (en) | 2021-09-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117771945A (en) * | 2024-02-28 | 2024-03-29 | 泰州禾益新材料科技有限公司 | Preparation method of homogeneous blend fiber reinforced PVDF ultrafiltration membrane |
| CN117771945B (en) * | 2024-02-28 | 2024-05-31 | 泰州禾益新材料科技有限公司 | Preparation method of homogeneous blend fiber reinforced PVDF ultrafiltration membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704152A (en) * | 2004-06-04 | 2005-12-07 | 杨虎 | Preparation of hydrophilic polyvinylidene fluoride microporous membrane |
| CN102597024A (en) * | 2009-10-30 | 2012-07-18 | 株式会社吴羽 | Vinylidene fluoride polymer powder and vinylidene fluoride polymer solution |
| CN106731895A (en) * | 2015-11-19 | 2017-05-31 | 浙江省化工研究院有限公司 | A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane |
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Patent Citations (3)
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| CN117771945A (en) * | 2024-02-28 | 2024-03-29 | 泰州禾益新材料科技有限公司 | Preparation method of homogeneous blend fiber reinforced PVDF ultrafiltration membrane |
| CN117771945B (en) * | 2024-02-28 | 2024-05-31 | 泰州禾益新材料科技有限公司 | Preparation method of homogeneous blend fiber reinforced PVDF ultrafiltration membrane |
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