CN110575760A - preparation method of fiber-reinforced PVDF ultrafiltration membrane - Google Patents
preparation method of fiber-reinforced PVDF ultrafiltration membrane Download PDFInfo
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- CN110575760A CN110575760A CN201910802300.4A CN201910802300A CN110575760A CN 110575760 A CN110575760 A CN 110575760A CN 201910802300 A CN201910802300 A CN 201910802300A CN 110575760 A CN110575760 A CN 110575760A
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- 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
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- 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
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Abstract
The invention provides a preparation method of a fiber reinforced PVDF ultrafiltration membrane applied to the field of municipal sewage and industrial wastewater, which is characterized in that PVDF resin with ultra-high molecular weight is prepared into monofilament fiber, the fiber is subjected to hydrophilic modification through PVA, and the monofilament fiber and a membrane casting solution enter a spinning nozzle at the same time to be extruded to form the fiber reinforced PVDF ultrafiltration membrane, so that the strength and the pure water flux of the membrane are improved, and the fiber reinforced PVDF ultrafiltration membrane has higher application potential in the field of water treatment such as municipal sewage and industrial wastewater.
Description
Technical Field
the invention relates to a preparation method of an ultrafiltration membrane, in particular to a preparation method of a fiber reinforced PVDF ultrafiltration membrane applied to the field of municipal sewage and industrial wastewater.
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 preparation method of the fiber reinforced PVDF ultrafiltration membrane is provided to prevent reinforced fibers from being corroded by a solvent and improve the problem of low flux of the fiber reinforced PVDF ultrafiltration membrane through hydrophilic modification of the reinforced fibers.
The invention provides a preparation method of a fiber reinforced PVDF ultrafiltration membrane, which comprises 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 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 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 fiber reinforced PVDF ultrafiltration membrane prepared by the preparation method 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.
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, the invention creatively utilizes PVA to carry out hydrophilic modification on the PVDF monofilament fiber with ultra-high molecular weight, thereby obviously improving the water flux of the reinforced fiber membrane and improving the application potential of the PVDF ultrafiltration membrane.
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 (7)
1. A preparation method of a fiber reinforced PVDF ultrafiltration membrane is characterized by comprising 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.
2. the method according to claim 1, wherein said ultra-high molecular weight PVDF is PVDF having a relative molecular weight greater than 100 ten thousand.
3. the method according to claim 1, characterized in that said supramolecular PVDF monofilament fiber has a diameter of 0.08-0.15 mm.
4. The method according to claim 1, wherein the organic solvent is one or more of N-methylpyrrolidone, N-dimethylacetamide, dimethylformamide, and dimethylsulfoxide.
5. The method of claim 1, wherein the pore forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol, LiCl, and titanium dioxide.
6. the method according to claim 1, characterized in that the casting solution contains 15-25wt% of PVDF, 50-70 wt% of organic solvent, and 5-15 wt% of pore-forming agent.
7. The method according to claim 1, wherein the glutaraldehyde concentration of the mixed solution of glutaraldehyde and sulfuric acid is 3-6wt%, and the sulfuric acid concentration is 1-3 wt%.
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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)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 钱知勉: "《塑料性能应用手册》", 31 March 1987, 上海科学技术文献出版社 * |
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