CN102029114A - Hydrophilic hollow fiber membrane and preparation method thereof - Google Patents
Hydrophilic hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN102029114A CN102029114A CN2010105517209A CN201010551720A CN102029114A CN 102029114 A CN102029114 A CN 102029114A CN 2010105517209 A CN2010105517209 A CN 2010105517209A CN 201010551720 A CN201010551720 A CN 201010551720A CN 102029114 A CN102029114 A CN 102029114A
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Abstract
The invention relates to a hollow fiber membrane, in particular to a hydrophilic hollow fiber membrane mainly applied to wastewater treatment and a preparation method thereof. The preparation method comprises the following steps of: adding an organic solvent to raw materials and fully mixing to obtain a mixture, stirring the mixture for 3-48h at 30-96 DEG C, then standing and defoaming for 3-48h to obtain a casting solution, preparing the casting solution into a porous membrane at 0-50 DEG C in a coagulating bath medium by adopting a hollow fiber spinning machine or a flat membrane making machine, soaking the prepared porous membrane in a protective solution for 2-50h, and drying for 2-30h under the conditions that the relative humidity is 30-380 percent and the temperature is 20-80 DEG C to obtain the finished product. According to the combination of lithium chloride and a chemical crosslinking agent, the hydrophilic hollow fiber membrane enhances the stability of polyvinylpyrrolidone, greatly increases the filtration speed of the porous membrane and improves the wastewater treatment capacity when being used for wastewater treatment.
Description
Technical field
The present invention is a kind of hollow-fibre membrane, and particularly a kind of mainly is to be used in hydrophilic hollow-fibre membrane and preparation method thereof in the wastewater treatment.
Background technology
Improve the hydrophily of polyvinylidene fluoride in the prior art, be exactly that polyvinylidene fluoride is mixed with other hydrophilic high molecular material, for example polyvinylpyrrolidone, acetate fiber, sulfonation gather sulfanilamide (SN), acetin, glyceryl triacetate or sulfonated polyether ketone.Yet because these hydrophilic macromolecular materials and polyvinylidene fluoride do not have covalent bond, these hydrophilic substances can be lost gradually, thereby cause the performance of film also can fail in time.
Application number is China's invention of CN200910069277.9, a kind of preparation method of doughnut perforated membrane is provided, this preparation method is polymer with the polytetrafluoroethylene (PTFE), comprise following processing step: A. prepares spinning solution, spinning carrier and the concentrated dispersion emulsion of polytetrafluoroethylene (PTFE), inorganic matter micropowder are pressed 5-15: the percentage by weight of 45-80: 8-50 is evenly mixed, and the viscosity modifier of the mixed liquid percentage by weight of adding 0.03-0.06% makes spinning solution; B. preparation mixes doughnut, adopts conventional dry-wet spinning equipment and technology, through the spinning of hollow spinning head, is setting medium with the aqueous sodium persulfate solution of alkalescence, after the drying, promptly makes polytetrafluoroethylene (PTFE) mixing doughnut; C. prepare the doughnut perforated membrane, gained polytetrafluoroethylene (PTFE) mixing doughnut is washed and drawing process through high temperature sintering, collection successively, promptly make described doughnut perforated membrane.It is loaded down with trivial details relatively that this invents described preparation method, and the filterability of perforated membrane is not high, makes disposal ability descend.Summary of the invention
The present invention adopts hydrophilic hollow-fibre membrane and preparation method thereof, hydrophobic macromolecule is mixed with hydrophilic high mol, and strengthen the stability of hydrophilic high mol by adding crosslinking agent, thereby the performance of film is improved.
Above-mentioned technical problem the present invention is mainly solved by following technical proposals:
A kind of hydrophilic hollow-fibre membrane, it is that feedstock production by following mass percent forms: 40～80% hydrophobic polymer material, 5～40% hydrophilic organics hydrophilicity, 1～10% chemical cross-linking agent and 1～15% lithium chloride.
As preferably, described hydrophobic polymer material is a polyvinylidene fluoride.
As preferably, described hydrophilic organics hydrophilicity is a polyvinylpyrrolidone.
As preferably, described chemical cross-linking agent is one or more mixtures in chromium trichloride, alchlor, ferric trichloride or the glycerine.
A kind of preparation method of hydrophilic hollow-fibre membrane:
The described raw material of claim 1 is added organic solvent fully to be mixed; the mixture that obtains stirred under 30～96 ℃ temperature 3～48 hours; standing and defoaming obtained casting solution after 3～48 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 0～50 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 2～50 hours in protection liquid, then relative humidity be 30～380% and temperature be to get final product in dry 2～30 hours under 20～80 ℃ the condition.
As preferably, the mass concentration of organic solvent is 50～95% in the described casting solution.
As preferably, the viscosity of described casting solution is 50～700000 centipoises; Described organic solvent is N, dinethylformamide, N, a kind of or several mixed solution in N-dimethylacetylamide, ethanol, ketone, the N-methyl pyrrolidone.
As preferably, water, N that described coagulating bath medium is 20～80 ℃ of temperature, dinethylformamide, N, a kind of or several mixed solution in N-dimethylacetylamide, ethanol, ketone, the N-methyl pyrrolidone.
As preferably, the mass concentration of described protection liquid is 10～80% glycerine water solution or 1～25% Tween solution.
As preferably, the tween in the described Tween solution is one or more the mixture in Tween-20, Tween-40, Tween-60 or the Tween-80.
Two key oxygen atoms on the carbonyl in the polyvinylpyrrolidone have localized negative charge again.Asymmetric electron motion between the strong electronegativity of oxygen and the oxygen nitrogen on the track produces the concentration of local negative electrical charge.Assemble the part of electronics makes oxygen atom can be used as proton acceptor.Therefore polyvinylpyrrolidone can be connected by hydrogen bond with the material that comprises proton donor, and glycerine comprises proton donor.Glycerine has three hydroxyls, and is distributed with local positive charge on the hydrogen atom of each hydroxyl.These hydrogen bonds provide physical crosslinking or tangle structure for polyvinylpyrrolidone; Therefore can reduce the water-soluble of polyvinylpyrrolidone equally, the strainability of PVDF membrane is improved.
The fracture tensile strength of perforated membrane is 200-700psi, and under the pressure of 20psi, the pure water flux of described perforated membrane is about 100gfd-1200gfd, interception capacity to the 150k glucan is 5%-99.99%, perforated membrane comprises milipore filter, micro-filtration membrane, and NF membrane.
Therefore, a kind of hydrophilic hollow-fibre membrane provided by the invention and preparation method thereof, lithium chloride combines the stability that has strengthened polyvinylpyrrolidone and the rate of filtration that has improved described perforated membrane greatly with chemical cross-linking agent, when being used in wastewater treatment, improve the wastewater treatment ability.
The specific embodiment
Below by embodiment, the technical scheme of inventing is described in further detail.
Embodiment 1:
Get the raw materials ready by table 1 embodiment 1, and prepare hydrophilic hollow-fibre membrane as follows:
Described raw material is added organic solvent fully to be mixed; the mixture that obtains stirred 12 hours under 60 ℃ temperature; standing and defoaming obtains casting solution after 24 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 50 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 24 hours in protection liquid, then air humidity be 75% and temperature be to get final product in dry 12 hours under 45 ℃ the condition.
The testing result of the hydrophilic hollow-fibre membrane of present embodiment preparation sees Table 2.
Embodiment 2:
Get the raw materials ready by table 1 embodiment 1, and prepare hydrophilic hollow-fibre membrane as follows:
Described raw material is added organic solvent fully to be mixed; the mixture that obtains stirred 12 hours under 50 ℃ temperature; standing and defoaming obtains casting solution after 24 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 45 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 24 hours in protection liquid, then air humidity be 75% and temperature be to get final product in dry 24 hours under 45 ℃ the condition.
The testing result of the hydrophilic hollow-fibre membrane of present embodiment preparation sees Table 2.
Embodiment 3:
Get the raw materials ready by table 1 embodiment 1, and prepare hydrophilic hollow-fibre membrane as follows:
Described raw material is added organic solvent fully to be mixed; the mixture that obtains stirred 12 hours under 70 ℃ temperature; standing and defoaming obtains casting solution after 24 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 35 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 24 hours in protection liquid, then air humidity be 75% and 26 ℃ of dryings of normal temperature got final product in 24 hours.
The testing result of the hydrophilic hollow-fibre membrane of present embodiment preparation sees Table 2.
Embodiment 4:
Get the raw materials ready by table 1 embodiment 1, and prepare hydrophilic hollow-fibre membrane as follows:
The described raw material of claim 1 is added organic solvent fully to be mixed; the mixture that obtains stirred 12 hours under 70 ℃ temperature; standing and defoaming obtains casting solution after 24 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 50-60 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 24 hours in protection liquid, then relative humidity be 75% and 26 ℃ of dryings of normal temperature got final product in 24 hours.
The testing result of the hydrophilic hollow-fibre membrane of present embodiment preparation sees Table 2.
Table 1 embodiment 1-4 composition of raw materials (kg)
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Polyvinylidene fluoride | 16 | 16 | 17 | 15 |
| Polyvinylpyrrolidone | 5 | 5 | 8 | 8 |
| Chromium trichloride | ? | ? | ? | ? |
| Alchlor | ? | 0.7 | ? | ? |
| Ferric trichloride | 0.8 | ? | ? | ? |
| Glycerine | 5 | 5 | 3 | 5 |
| Lithium chloride | 0.3 | 0.3 | ? | 0.3 |
The testing result of the hydrophilic hollow-fibre membrane of table 2 embodiment 1-4 preparation
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Fracture tensile strength, psi | 332 | 351 | 311 | 292 |
| Pure water flux, L/m2-h | 290 | 301 | 330 | 360 |
| To the interception capacity of 150k glucan, % | 92 | 95 | 93 | 95 |
Claims (10)
1. hydrophilic hollow-fibre membrane, it is characterized in that it is that feedstock production by following mass percent forms: 40～80% hydrophobic polymer material, 5～40% hydrophilic organics hydrophilicity, 1～10% chemical cross-linking agent and 1～15% lithium chloride.
2. a kind of hydrophilic hollow-fibre membrane according to claim 1 is characterized in that: described hydrophobic polymer material is a polyvinylidene fluoride.
3. a kind of hydrophilic hollow-fibre membrane according to claim 1 is characterized in that: described hydrophilic organics hydrophilicity is a polyvinylpyrrolidone.
4. a kind of hydrophilic hollow-fibre membrane according to claim 1 is characterized in that: described chemical cross-linking agent is one or more mixtures in chromium trichloride, alchlor, ferric trichloride or the glycerine.
5. the preparation method of a hydrophilic hollow-fibre membrane is characterized in that:
The described raw material of claim 1 is added organic solvent fully to be mixed; the mixture that obtains stirred under 30～96 ℃ temperature 3～48 hours; standing and defoaming obtained casting solution after 3～48 hours then; adopting doughnut spinning-drawing machine or flat sheet membrane film-making machine in the coagulating bath medium, to be prepared into perforated membrane under 0～50 ℃ the temperature casting solution; the perforated membrane for preparing was soaked 2～50 hours in protection liquid, then relative humidity be 30～380% and temperature be to get final product in dry 2～30 hours under 20～80 ℃ the condition.
6. the preparation method of a kind of hydrophilic hollow-fibre membrane according to claim 5, it is characterized in that: the mass concentration of organic solvent is 50～95% in the described casting solution.
7. the preparation method of a kind of hydrophilic hollow-fibre membrane according to claim 6, it is characterized in that: the viscosity of described casting solution is 50～700000 centipoises; Described organic solvent is N, dinethylformamide, N, a kind of or several mixed solution in N-dimethylacetylamide, ethanol, ketone, the N-methyl pyrrolidone.
8. the preparation method of a kind of hydrophilic hollow-fibre membrane according to claim 5, it is characterized in that: water, N that described coagulating bath medium is 20～80 ℃ of temperature, dinethylformamide, N, a kind of or several mixed solution in N-dimethylacetylamide, ethanol, ketone, the N-methyl pyrrolidone.
9. the preparation method of a kind of hydrophilic hollow-fibre membrane according to claim 5 is characterized in that: the mass concentration of described protection liquid is 10～80% glycerine water solution or 1～25% Tween solution.
10. the preparation method of a kind of hydrophilic hollow-fibre membrane according to claim 9 is characterized in that: the tween in the described Tween solution is one or more the mixture in Tween-20, Tween-40, Tween-60 or the Tween-80.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302903A (en) * | 2011-08-03 | 2012-01-04 | 济南大学 | Nano silver-polyvinylidene fluoride composite separation membrane and preparation method thereof |
| CN102527250A (en) * | 2011-12-25 | 2012-07-04 | 河北诺恩水净化设备有限公司 | Hollow fibrous membrane and preparation method thereof |
| CN102614786A (en) * | 2012-04-24 | 2012-08-01 | 柳州森淼环保技术开发有限公司 | Preparation method of polyvinylidene fluoride ultramicro-filtration dry membrane for flat-plate MBR (membrane bioreactor) |
| CN109395593A (en) * | 2018-10-31 | 2019-03-01 | 浙江工业大学 | A kind of preparation method of hydrophilic Pvdf Microporous Hollow Fiber Membrane |
| CN113332768A (en) * | 2021-06-07 | 2021-09-03 | 深圳市创裕达电子有限公司 | Filter bag for electroosmotic dehydration of slurry and preparation method thereof |
| CN113368704A (en) * | 2021-05-14 | 2021-09-10 | 科威天使环保科技集团股份有限公司 | High-performance ultrafiltration membrane for wastewater treatment and preparation method thereof |
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| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
| CN101279211A (en) * | 2008-01-11 | 2008-10-08 | 北京工业大学 | Preparation of polyvinylidene fluoride dewatering microporous film |
| CN101733022A (en) * | 2009-03-12 | 2010-06-16 | 北京碧水源膜科技有限公司 | High-strength polyvinylidene fluoride hollow fiber membrane and production method thereof |
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| CN1583232A (en) * | 2003-08-06 | 2005-02-23 | 浙江欧美环境工程有限公司 | Manufacture and products of hollow fiber membrane of outer pressured polyvinylidene fluoride by immersion gelation |
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302903A (en) * | 2011-08-03 | 2012-01-04 | 济南大学 | Nano silver-polyvinylidene fluoride composite separation membrane and preparation method thereof |
| CN102527250A (en) * | 2011-12-25 | 2012-07-04 | 河北诺恩水净化设备有限公司 | Hollow fibrous membrane and preparation method thereof |
| CN102527250B (en) * | 2011-12-25 | 2014-05-14 | 河北诺恩水净化设备有限公司 | Hollow fibrous membrane and preparation method thereof |
| CN102614786A (en) * | 2012-04-24 | 2012-08-01 | 柳州森淼环保技术开发有限公司 | Preparation method of polyvinylidene fluoride ultramicro-filtration dry membrane for flat-plate MBR (membrane bioreactor) |
| CN102614786B (en) * | 2012-04-24 | 2013-11-20 | 柳州森淼环保技术开发有限公司 | Preparation method of polyvinylidene fluoride ultramicro-filtration dry membrane for flat-plate MBR (membrane bioreactor) |
| CN109395593A (en) * | 2018-10-31 | 2019-03-01 | 浙江工业大学 | A kind of preparation method of hydrophilic Pvdf Microporous Hollow Fiber Membrane |
| CN113368704A (en) * | 2021-05-14 | 2021-09-10 | 科威天使环保科技集团股份有限公司 | High-performance ultrafiltration membrane for wastewater treatment and preparation method thereof |
| CN113332768A (en) * | 2021-06-07 | 2021-09-03 | 深圳市创裕达电子有限公司 | Filter bag for electroosmotic dehydration of slurry and preparation method thereof |
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Application publication date: 20110427 |