CN101439268B - Method for preparing high-intensity high-throughput polyvinylidene fluoride hollow fiber membrane - Google Patents
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- CN101439268B CN101439268B CN2008102431088A CN200810243108A CN101439268B CN 101439268 B CN101439268 B CN 101439268B CN 2008102431088 A CN2008102431088 A CN 2008102431088A CN 200810243108 A CN200810243108 A CN 200810243108A CN 101439268 B CN101439268 B CN 101439268B
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 40
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 15
- 239000012510 hollow fiber Substances 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000004907 flux Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000003814 drug Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 2
- 150000002433 hydrophilic molecules Chemical class 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 6
- 238000001471 micro-filtration Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 241001466460 Alveolata Species 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 4
- 235000012489 doughnuts Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Abstract
The invention relates to a preparation method for a high-flux high-intensity polyvinylidene fluoride hollow fibrous membrane. In the method, 0.6 to 1.5 million daltons of polyvinylidene fluoride raw materials with super high molecular weight are chemically treated to lead the materials to form active groups and then are acted with hydrophilic compounds like glycidyl methacrylate or acrylic acid, and the like, to form a hydrophilic polyvinylidene fluoride raw material; the hydrophilic polyvinylidene fluoride material is mixed with a solvent and a pore-foaming agent according to a certain proportion to form membrane preparing liquid; then the membrane preparing liquid is woven into a uniformly distributed pollution-resistant polyvinylidene fluoride hollow fibrous membrane with high intensity, small aperture and high water flux by a phase inversion technique. The pollution-resistant polyvinylidene fluoride hollow fibrous membrane can be used for the fields like water processing, medicines, food, and industry by the forms of hyperfiltration, continuous micro-filter or membrane bioreactor according to the size of the millipore thereof.
Description
Technical field
The present invention relates to a kind of preparation method of hollow-fibre membrane, particularly be suitable for the preparation method of the high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane that uses in micro-filtration and the ultrafiltration field.
Background technology
At present, polymeric membranes such as Kynoar (be called for short PVDF) have been widely used in concentrating in the field production processes such as water purification, drinks, fruit juice, medicine, separate, purify and plant, that this membrane separation technique has is simple to operate, power consumption less, advantages such as little, the non-secondary pollution of floor space, great application is arranged aspect water treatment especially.Yet regrettably, these polymeric membranes mostly are hydrophobic material, and face is easy to be subjected to organic pollution in the sewage, water flux is reduced, and the most intensity of existing polymeric membrane is lower, fractures easily, damage, service life is short, can not satisfy the instructions for use of sewage treatment area.
In order further to improve the separating property of pvdf membrane, improve water flux, can use for a long time again, need carry out modification to pvdf membrane, make its possess hydrophilic property.The method of modification mainly contains: physics cladding process, blending method and chemical modification.For example the physics coating process adopt hydrophilizing agent (as alcohol, surfactant, polyelectrolyte complex compound etc.) processing microporous barrier or the microporous barrier direct impregnation in above-mentioned Polymer Solution, evaporating solvent then.Though this technology is simple,, cause surfactant easily to run off, the very fast decline of hydrophily owing to just fix surfactant by physisorption.Blending method is the more method of using at present, concentrated polymer solution blend in same solvent relies on external force effects such as stirring, make between polymer macromolecule interpenetrate, the phase counterdiffusion, and combine, thereby improve the structure and the performance of membrane material with polarity or nonpolar power.
In this regard, publication number is that the patent molecular weight of CN1654531 is that inorganic oxide that the Kynoar of 103-106 and PEO that molecular weight is 103-107 and particle diameter are the 5-100 nanometer waits pvdf membrane is carried out blending and modifying.Publication number is that the patent of CN1669624 and CN1765981 comes PVDF is carried out blending and modifying with polyvinyl chloride and polyether sulfone and PVDF blend respectively.Because the hydrophily of materials such as PEO, polyvinyl chloride and polyether sulfone itself is not strong yet, blending and modifying effect that therefore should series is also not obvious.
Publication number be CN1772359 patent disclosure the surface graft possess hydrophilic property of Kynoar hollow fiber microfiltration membrane or dull and stereotyped micro-filtration membrane can and the chemical modification technique of ion-exchange performance group, adopting reagent such as acrylic acid, polyvinyl alcohol, acrylamide, methylene-bisacrylamide, potassium peroxydisulfate is raw material, by the chemical crosslinking polymerisation, hydroxy-acid group and oh group on the micro-filtration membrane surface graft.This technology has advantage simple to operate, that grafting efficiency is high, has improved the hydrophilicity of conventional microfiltering separation film of polyvinylidene fluoride, has improved the handling property of microfiltering separation film of polyvinylidene fluoride.But because this chemical modification technique is to carry out modification on the surface of microporous barrier, this just is easy to destroy the surface apertures structure of film, changes the molecular cut off and the filter effect of film.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane, it can overcome the defective of above the whole bag of tricks, prepares the fabulous film of hydrophily that sewage treatment industry uses.
The preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane of the present invention is as follows:
With molecular weight is that 600,000-1,500,000 daltonian Kynoar are raw material, adds solvent and makes it dissolving, and dripping alkali liquid is regulated pH to 8-9, makes it to form active group; It is mixed with hydrophilic modifier, and the addition of hydrophilic modifier is 0.25-0.5 a times of Kynoar raw material weight, and stirring reaction gets hydrophilicity kynoar; Add solvent again, stir, and add pore-foaming agent, preparation liquid is made in configuration; By measuring pump preparation liquid is clamp-oned spinneret, core liquid is quantitatively entered the interior pin of spinneret by measuring pump; By the spinneret spinning, go into the coagulating bath cooled and solidified and get hollow-fibre membrane; Said hydrophilic modifier is the organic matter that has hydroxyl or hydrophilic proton group.
The molecular weight of the PVDF optimal seeking of raw and processed materials is elected 1,000,000-1,200,000 dalton as.
Said core liquid is that weight ratio is ethanol and N-methyl pyrrolidone (the calling NMP in the following text) mixture of 2-4:6-8, and wherein preferred weight ratio is 3:7.
Said pore-foaming agent pore-foaming agent accounts for 12-15% of preparation liquid gross weight.
The PVDF raw material accounts for 15～25% of preparation liquid gross weight, is preferably 16-19%.
Said hydrophilic modifier is preferably GMA or acrylic acid.
Said pore-foaming agent is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) or polyethylene glycol (PEG).
Said solvent is N-methyl pyrrolidone or N, N '-dimethylacetylamide.
Said alkali lye is NaOH or potassium hydroxide solution.
The present invention forms active group with super high molecular weight PVDF raw material earlier under alkali condition, with the hydrophilic compounds reaction, form the hydrophilic PVDF raw material again.Through above-mentioned chemical modification, make hydrophilic grafted chain with chemical bond and microporous barrier surface bond, for good and all be connected on the membrane material by chemical bond, thus can be not dissolved when the material permeance film, can not cause the loss of grafted chain, can keep long service life.These hydrophilic PVDF raw material mix formation system preparation liquid by a certain percentage with solvent and pore-foaming agent and prepare hollow-fibre membrane by phase inversion.The present invention adopts the core liquid (promptly supporting liquid) of preparation can make the hollow-fibre membrane that makes become asymmetrical single skin structure, promptly is made up of supporting layer and a filtration cortex.
The comparison of table 1 expression low-molecular-weight and HMW doughnut film-strength; The comparison of table 2 expression single-skin drum tunic and two cortex doughnut membrane fluxs.
The comparison of table 1. low-molecular-weight and HMW doughnut film-strength
| PVDF molecular weight (weight content in the preparation liquid is 18%) | Hot strength | Average pore size | Pure water flux (lmh) |
| 150,000 dalton | 1.3N | 0.05 micron | 1100 |
| 500,000 dalton | 1.9N | 0.05 micron | 1000 |
| 1,000,000 dalton | 3.5N | 0.05 micron | 950 |
The comparison of table 2. single-skin drum tunic and two cortex doughnut membrane fluxs
| The cortex kind | Hot strength | Average pore size | Pure water flux (lmh) |
| The two cortexes of tradition low-molecular-weight | 2.6N | 0.05 micron | 550 |
| This product single skin | 3.5N | 0.05 micron | 900 |
In sum, the inventive method film-forming process is comparatively simple, technology, equipment is required lower, adopts common process just can spin out directly that the aperture is even, the Kynoar hollow-fibre membrane of high water flux; Improved the form of hollow-fibre membrane simultaneously, the hollow-fibre membrane that makes is asymmetric single skin self-supported membrane structure, and its section only comprises two-layer: exodermis and supporting layer, supporting layer are finger-like or spongelike structure, and exodermis is fine and close relatively.Owing to have only one to filter cortex, the hollow-fibre membrane that makes than conventional method has reduced by a filtration cortex, greatly reduces mould difference and operation energy consumption, has improved the water flux of product.The hydrophily that the invention solves existing pvdf membrane existence is owed height or the not high technical problem of intensity, according to its micropore size, with forms such as ultrafiltration, continuous Microfiltration or membrane bioreactors, is widely used in fields such as water treatment, medicine, food, industry.
Embodiment 1
(1) preparation of raw material
Molecular weight is 1,500,000 daltonian PVDF pressed powder 3kg, solvent N, N '-dimethylacetylamide 11.2L, pore-foaming agent (polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol) 1.5kg, hydrophilic modifier 1kg, core liquid are that weight ratio is the ethanol of 3:7 and the mixture of NMP.
(2) preparation of hollow-fibre membrane
The PVDF pressed powder is added partial solvent, stir and make it dissolving, dropping sodium solution is regulated pH 8-9, makes it to form active group; Mix with hydrophilic modifier, stirring reaction gets hydrophilicity kynoar; It is progressively added in the material liquid tank that contains solvent, and solvent temperature is 50 ℃.The limit edged stirs, and makes it dissolving evenly.After stirring half an hour, add pore-foaming agent, continue to stir 4 hours toward this mixed liquor, up to dissolving evenly, stop to stir preparation liquid, the standing over night deaeration.After the deaeration, under nitrogen 0.5MPa pressure, clamp-on spinneret, stir, preparation liquid is clamp-oned spinneret, core liquid is quantitatively entered the interior pin of spinneret by measuring pump by measuring pump by measuring pump, extrude fiber through the 5cm the air gap after, enter coagulating basin and solidify.At last, collect hollow-fibre membrane by rotating cylinder.The hollow-fibre membrane of gained is complete dissymmetrical structure, and its section is divided into two parts: exodermis and supporting layer, supporting layer are alveolate texture.The external diameter of prepared hollow-fibre membrane is 1.5mm, and internal diameter is 0.9mm, and porosity is 75%, and average pore size is 0.03-0.05 μ m, and its hot strength is 3.5N.Other performances see Table 1 and table 2.
Embodiment 2-3:
Prepare hollow-fibre membrane by embodiment 1 identical method and step, different is that embodiment 2 and embodiment 3 adopt the PVDF molecular weight to be respectively 500,000,1,000,000 dalton.The hollow-fibre membrane of gained is complete dissymmetrical structure, and its section is divided into two parts: exodermis and supporting layer, supporting layer are alveolate texture.The external diameter of prepared hollow-fibre membrane is 1.5mm, and internal diameter is 0.9mm, and porosity is about 75%, and average pore size is 0.03-0.05 μ m.
Embodiment 4-6:
Method and the step identical by embodiment 1-3 prepare hollow-fibre membrane.Different is that this example 4,5,6 adopts the molecular weight of PVDF to be respectively 150,000,500,000 and 1,000,000 dalton, and while core liquid is and adopts weight ratio is the NMP of 1:9 and the mixture of water.
The difference of the section of the hollow-fibre membrane that makes and embodiment 1-3 is that the film that makes is two cortexes, and promptly to be divided into be three parts to section structure: exodermis, supporting layer and endodermis, supporting layer are alveolate texture.The external diameter of prepared hollow-fibre membrane is 1.5mm, and internal diameter is 0.9mm, and porosity is about 75%, and average pore size is 0.03-0.05 μ m, and its hot strength is for being respectively 1.3N, 2.1N and 2.8N.
As seen, with the film that low-molecular-weight raw material PVDF makes, its intensity greatly reduces; With the NMP of low proportioning and the mixture of water is that the film that core liquid makes is two cortexes, can not obtain the single-skin drum tunic, and the water flux of film is also smaller.
Embodiment 7-8:
Method and the step identical by embodiment 4-6 prepare hollow-fibre membrane, and the pore-foaming agent addition of different is this embodiment 7,8 is respectively 2.5kg, 3.5kg, and core liquid becomes the NMP of 5:5 and the mixture of water by the NMP of 1:9 and the mixture of water simultaneously.The hollow-fibre membrane of gained is complete dissymmetrical structure, and its section is divided into two parts: exodermis and supporting layer, supporting layer are alveolate texture.The external diameter of prepared hollow-fibre membrane is 1.5mm, and internal diameter is 0.9mm, and porosity is about 80%, and average pore size is 0.08-0.1 μ m.
Claims (9)
1. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane is that 600,000-1,500,000 daltonian Kynoar are raw material with molecular weight, adds solvent and makes it dissolving, and dripping alkali liquid is regulated pH to 8-9, makes it to form active group; It is mixed with hydrophilic modifier, and the addition of hydrophilic modifier is 0.25-0.5 a times of Kynoar raw material weight, and stirring reaction gets hydrophilicity kynoar; Add solvent again, stir, and add pore-foaming agent, preparation liquid is made in configuration; By measuring pump preparation liquid is clamp-oned spinneret, core liquid is quantitatively entered the interior pin of spinneret by measuring pump; By the spinneret spinning, go into the coagulating bath cooled and solidified and get hollow-fibre membrane; Said hydrophilic modifier is GMA or acrylic acid.
2. the preparation method of intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that said core liquid is that weight ratio is ethanol and the N-crassitude alcohol/ketone mixtures of 2-4: 6-8.
3. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 1, said core liquid is 3: 7 ethanol of weight ratio and N-crassitude alcohol/ketone mixtures.
4. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that said pore-foaming agent is polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol.
5. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 4 is characterized in that said pore-foaming agent accounts for the 12-15% of preparation liquid gross weight.
6. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that said solvent is N-methyl-pyrrolidones or N, N '-dimethylacetylamide.
7. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 1 is characterized in that said Kynoar raw material accounts for 15～25% of preparation liquid gross weight.
8. the preparation method of high-intensity high-throughput polyvinylidene fluoride hollow-fibre membrane according to claim 7 is characterized in that said Kynoar raw material accounts for the 16-19% of preparation liquid gross weight.
9. according to claim 1 or 2 or 3 or 4 or 5 or 6 or the preparation method of 7 or 8 described high-intensity high-throughput polyvinylidene fluoride hollow-fibre membranes, it is characterized in that the raw-material molecular weight of Kynoar is 1,000,000-1,200,000 dalton.
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| CN102553464A (en) * | 2011-12-30 | 2012-07-11 | 江苏大孚膜科技有限公司 | Preparation method of modified polyvinylidene fluoride ultrafiltration membrane |
| WO2013180272A1 (en) | 2012-06-01 | 2013-12-05 | 三菱レイヨン株式会社 | Hollow porous film |
| CN103521093B (en) * | 2013-09-30 | 2016-03-02 | 广州超禹膜分离技术有限公司 | A kind of large flux anti-soil polyvinylidene fluoride hollow fiber microfiltration membranes and preparation method thereof |
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| CN106582323B (en) * | 2016-11-29 | 2019-05-24 | 康命源（贵州）科技发展有限公司 | The high-intensitive, preparation method of High-flux polyvinylidene fluoride hollow fiber membrane and product |
| CN106621842B (en) | 2017-01-16 | 2019-03-22 | 南京大学 | A kind of preparation method, regeneration method and application chelating microfiltration membranes |
| CN109966934A (en) * | 2017-12-28 | 2019-07-05 | 苏州信望膜技术有限公司 | A kind of seperation film, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104984667A (en) * | 2015-07-03 | 2015-10-21 | 鞍山中科美清节能环保技术有限公司 | PVDF ultra-filtration membrane |
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