CN103212302B - A kind of chemical reaction induction phase inversion prepares the method for polymeric hollow fiber multihole film - Google Patents
A kind of chemical reaction induction phase inversion prepares the method for polymeric hollow fiber multihole film Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000006698 induction Effects 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 22
- 238000005345 coagulation Methods 0.000 claims abstract description 19
- 230000015271 coagulation Effects 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 238000000578 dry spinning Methods 0.000 claims description 3
- 238000001891 gel spinning Methods 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 15
- 230000004907 flux Effects 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000012993 chemical processing Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- -1 Kynoar Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 230000004927 fusion Effects 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 238000005192 partition Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
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Abstract
The invention discloses the method that a kind of chemical reaction induction phase inversion prepares polymeric hollow fiber multihole film, belong to field of membrane preparation.Comprise the steps: to prepare homogeneous casting solution, casting solution and core liquid are extruded from spinning head, outside film forming in coagulation bath; Chemical processing is carried out to obtained film, thus even aperture distribution, membrane flux is high, antifouling property is strong hollow fiber porous film can be prepared.Feature of the present invention is, by changing core liquid and outer coagulation bath composition, or chemical reaction pore-foaming agent kind, utilize core liquid, reaction between outer coagulation bath and chemical pore-foaming agent, carry out chemical reaction induction pore, thus prepare even aperture distribution, antifouling property is good, flux is high polymeric hollow fiber multihole film.
Description
Technical field
The invention belongs to field of membrane preparation, relate to a kind of method that phase inversion prepares polymeric hollow fiber multihole film, particularly a kind of chemical reaction induction phase inversion prepares the method for polymeric hollow fiber multihole film.
Background technology
High molecular polymer perforated membrane has multiple preparation method, and wherein modal have phase separation method (phase inversion), thermally induced phase separation and fusion drawn method.The form of polymer porous film has flat, hollow fiber form, capillary type and tubular type.Wherein the present invention's design is adopt phase separation legal system for polymeric hollow fiber multihole film.
Phase inversion is a kind of full-fledged method preparing polymer microporous film.This process can be divided into three phases:
First stage, inverse course of dissolution.The casting film liquid film of casting film-forming keeps homogeneous phase, but due to the volatilization of solvent, solvent and non-solvent exchange or absorb non-solvent water, cause in casting solution, forming the concentration gradient along cross-wise direction.
Second stage, phase process.Casting solution is separated, and liquid-liquid phase-splitting or liquid-solid phase-splitting occur.This is the committed step determining membrane pore structure and performance.
Phase III, inversion of phases process.Comprise the rich solidifying of the cohesion of fenestra, alternate flowing and polymer.This stage has a significant impact membrane structure form.
Researcher prepares high performance diffusion barrier often through to the control of phase process.Record in patent CN1817419A, after the aromatic polymer containing sulfuryl, solvent and organic acid being mixed, prepare flat plate ultrafiltration membrane, membrane flux is less, and pore-size distribution is little.Record in patent CN102527262, Kynoar, solvent, additive and chemical pore-foaming agent calcium carbonate are mixed, add acid, prepare hollow fiber ultrafiltration membrane in coagulation bath, concrete reaction is CaCO
3+ 2H
+→ Ca
2++ H
2o+CO
2↑.Record in JournalofMembraneScience Literature (Agas – liquidchemicalreactiontreatmentandphaseinversiontechniqu eforformationofhighpermeabilityPANUFmembranes) and polyacrylonitrile, solvent, calcium chloride and water are mixed, add ammonia again, pass through CO
2+ CaCl
2+ 2NH
3+ H
2o → CaCO
3↓+2NH
4cl chemical reaction prepares milipore filter.
The object of the invention is for the deficiencies in the prior art, propose a kind of chemical reaction induction phase inversion to prepare the method for even aperture distribution, hollow fiber porous film that antifouling property is strong.The CO that the method utilizes chemical reaction induced reaction to produce
2bubble realizes strengthening pore, strengthens the flux of film, prepares the hollow fiber porous film of inner pressed and external-compression type dual-purpose.
Summary of the invention
The present invention adopts a kind of chemical reaction to induce the method for pore to realize the manual control of fenestra, acquisition even aperture distribution, the polymeric hollow fiber multihole film that flux is high, antifouling property is strong.Adopt the general principle of chemical reaction induction strengthening pore substantially similar as follows:
2CH
3COOH+Na
2CO
3→2CH
3COONa+H
2O+CO
2↑
In the above-mentioned course of reaction of generation, weak base generation chemical reaction in film surface or inner partial chemical pore-foaming agent acetic acid and outer coagulation bath or core liquid, the reaction occurred on the one hand can form micropore on film surface with inner, change the exchange velocity of non-solvent and solvent and point phase velocity of film, on the other hand, under the incomplete phase-splitting state of gelation in the early stage, the carbon dioxide that reaction produces also can destroy continuous print gel structure and form the loose structure of some in film inside and surface, be conducive to non-solvent in follow-up phase process surperficial and inner by film smoothly.
The object of the invention is to be realized by following technical proposals.
A kind of chemical reaction induction phase inversion prepares polymeric hollow fiber multihole film, it is characterized in that, comprises the following steps:
1. the preparation of casting solution: by macromolecular material, solvent, additive and chemical pore-foaming agent blended under agitation 6-24h at the temperature of 50-80 DEG C according to a certain percentage, constant temperature standing and defoaming 12-24h at 50-80 DEG C, obtains homogeneous casting solution;
2. the configuration of core liquid: core liquid is a kind of mixture in water or water and acetic acid, dimethylacetylamide, dimethyl formamide, or mixture a kind of in water and sodium carbonate, sodium acid carbonate, potash or saleratus;
3. hollow fiber spinning: utilize dry-wet spinning equipment that core liquid is injected spinning head together with homogeneous casting solution, and extrude from spinning head together, obtained hollow fiber film thread;
4. inversion of phases process: by the hollow fiber film thread of step 3. gained after the dry-spinning path of 0-30cm, enter successively in the first outer coagulation bath and the second outer coagulation bath and carry out gel phase conversion, forms the polymeric hollow fiber multihole film with micropore canals;
5. post processing: step polymeric hollow fiber multihole film soaking and washing to complete phase-splitting in water that 4. gained has a micropore canals is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 10-30wt% and water.
Described casting solution is prepared from according to the raw material of following mass percent:
Macromolecular material 12-30%, chemical pore-foaming agent 1-20%, solvent 50-80%, additive 0-10%.
Described macromolecular material includes, without being limited to polyacrylonitrile, Kynoar, polyvinyl chloride, polymethyl methacrylate, cellulose acetate.
Described chemical pore-foaming agent includes, without being limited to acetic acid, fumaric acid, citric acid, malic acid.
Described solvent includes, without being limited to the combination of dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE etc. and these solvents.
Described additive includes, without being limited to the one or more combination in polyethylene glycol, acetone, PVP, polyvinyl alcohol, polymethyl methacrylate, lithium chloride, zinc chloride.
First outer coagulation bath is the mixture of one or more and water in sodium carbonate, sodium acid carbonate, potash or saleratus, and the second outer coagulation bath is water, coagulation bath temperature 20-60 DEG C.
Core flow quantity 5-15ml/min, core liquid temp is 20-60 DEG C, and wire winding speed is 4-12m/min.
Step 3. hollow fiber spinning time, common employing core liquid and homogeneous casting solution can obtain hollow fiber film thread, the wall thickness that can affect hollow fiber film thread with magnitude relation of core liquid and homogeneous casting solution, thinking conveniently, little on the impact of hollow fiber film thread pore structure, core liquid volume flow and homogeneous casting solution volume flow ratio are 1:2.
Feature of the present invention is, utilizes core liquid, reaction between outer coagulation bath and chemical pore-foaming agent, carries out chemical reaction induction pore, by changing core liquid and outer coagulation bath composition, or chemical reaction pore-foaming agent kind, by the CO produced
2the difference of bubbles volume, carrys out the size in artificial controlling diaphragm hole.Thus prepare even aperture distribution, antifouling property is good, flux is high polymeric hollow fiber multihole film.
The method is suitable for nearly all existing, membrane material of can be used for conventional inversion of phases partition method masking, such as polyacrylonitrile, polyvinyl acetate, Kynoar etc., and greatly promote the performance of these films, make it obtain in fields such as drinking water treatment, Treated sewage reusing, membrane bioreactor wastewater treatment, Industrial Waste Water Treatments and apply widely.
Beneficial effect of the present invention and advantage:
(1) utilize the various inorganic and organic additive added in casting solution, the gel phase transformation time of casting solution in water can be affected to some extent, on film silk, strengthen pore by chemical reaction, form porous or macroporous structure, improve membrane flux.
(2) by regulating kind and the content of acid in casting solution, affecting gel phase conversion rate and the degree of film silk, changing flux and the rejection of film to a certain extent.
(3) by regulating kind and the content of carbonate or bicarbonate in outer coagulation bath and core liquid, make them different from the chemical reaction intensity of acid, the CO of generation
2bubbles volume is different, causes the pore structure of film and the difference of film inside and surface holes quantity, thus realizes the manual control of fenestra.
Detailed description of the invention
It is quite extensive that chemical reaction of the present invention induction phase inversion prepares polymeric material, applicable solvent and additive that high molecular polymer perforated membrane technique is suitable for, different polymer, chemical pore-foaming agent, solvent and additive can obtain very many process conditions, but general principle is constant.For simplicity's sake, following instance is prepared high molecular polymer hollow-fibre membrane technological principle to chemical reaction of the present invention induction phase inversion and is explained.
Embodiment 1
1. the preparation of casting solution: by macromolecular material, solvent, additive and chemical pore-foaming agent blended under agitation 6-24h at the temperature of 50-80 DEG C according to a certain percentage, constant temperature standing and defoaming 12-24h at 50-80 DEG C, obtains homogeneous casting solution.
2. the preparation of core liquid and outer coagulation bath: a certain proportion of deionization water and minerals is mixed, stand-by.
3. hollow fiber spinning: utilize dry-wet spinning equipment under the spinning speed of setting, core liquid is injected spinning head according to the core liquid measure of setting together with homogeneous casting solution, and extrudes from spinning head together, obtained hollow fiber film thread.
4. inversion of phases process: by the hollow fiber film thread of step 3. gained after the dry-spinning path of 0-30cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, forms the polymeric hollow fiber multihole film with microcellular structure.
5. post processing: soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with microcellular structure is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 10-30wt% and water.
The internal diameter of gained hollow fiber porous film is about 1.10mm, and external diameter is about 1.46mm, and the pure water flux under 0.1MPa is 327L/m
2more than s is more than 88% to the rejection of BSA.
Fig. 1 show further the embodiment of the present invention 1 and prepares rear polyacrylonitrile hollow fiber perforated membrane local section morphosis.Shown in Fig. 2, be example 1 film surface morphological structure figure.
Embodiment 2
Step as described in Example 1, shown in table composed as follows.
The internal diameter of gained hollow fiber porous film is about 1.40mm, and external diameter is about 1.84mm, and the pure water flux under 0.1MPa is 44.5L/m
2more than s is more than 98% to the rejection of BSA.
Embodiment 3
Step as described in Example 1, shown in table composed as follows.
The internal diameter of gained hollow fiber porous film is about 1.10mm, and external diameter is about 1.77mm, and the pure water flux under 0.1MPa is 124L/m
2more than s is more than 91% to the rejection of BSA.
Embodiment 4
Step as described in Example 1, shown in table composed as follows.
The internal diameter of gained hollow fiber porous film is about 0.98mm, and external diameter is about 1.38mm, and the pure water flux under 0.1MPa is 680L/m
2more than s is more than 65% to the rejection of BSA.
Claims (1)
1. chemical reaction induction phase inversion prepares a polymeric hollow fiber multihole film, it is characterized in that, comprises the following steps:
1. the preparation of casting solution: by macromolecular material, solvent, additive and chemical pore-foaming agent blended under agitation 6-24h at the temperature of 50-80 DEG C according to a certain percentage, constant temperature standing and defoaming 12-24h at 50-80 DEG C, obtains homogeneous casting solution;
2. the preparation of core liquid and outer coagulation bath: a certain proportion of deionization water and minerals is mixed, stand-by;
3. hollow fiber spinning: utilize dry-wet spinning equipment under the spinning speed of setting, core liquid is injected spinning head according to the core liquid measure of setting together with homogeneous casting solution, and extrudes from spinning head together, obtained hollow fiber film thread;
4. inversion of phases process: by the hollow fiber film thread of step 3. gained after the dry-spinning path of 0-30cm, enter successively in the first coagulation bath and the second coagulation bath and carry out gel phase conversion, forms the polymeric hollow fiber multihole film with microcellular structure;
5. post processing: soaking and washing to the complete phase-splitting in water of the polymeric hollow fiber multihole film with microcellular structure is obtained the hollow fiber porous film of even aperture distribution, and in the protection liquid that forms of the glycerine be immersed in containing 10-30wt% and water;
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| CN104667760B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| CN103464002B (en) * | 2013-09-17 | 2015-01-28 | 宁波江东科海运拓机械科技有限公司 | Preparation method of composite hollow fiber membrane |
| CN104689725B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| CN104667761B (en) * | 2013-09-17 | 2016-08-31 | 殷逢宝 | A kind of preparation method of composite hollow fiber membrane |
| CN104923088B (en) * | 2013-09-17 | 2017-12-15 | 宁波科恩博电子科技有限公司 | A kind of composite hollow fiber membrane |
| CN103521091A (en) * | 2013-10-25 | 2014-01-22 | 滁州品创生物科技有限公司 | Composite hollow fiber membrane |
| CN103521094A (en) * | 2013-10-25 | 2014-01-22 | 滁州品创生物科技有限公司 | Preparation method of composite hollow fiber membrane |
| CN105833741B (en) * | 2016-04-25 | 2018-06-29 | 中国科学院兰州化学物理研究所 | A kind of preparation method of polyvinylidene fluoride porous membrane |
| CN105854641B (en) * | 2016-06-12 | 2018-06-01 | 天津工业大学 | A kind of preparation method of narrower bore footpath distribution polypropylene nitrile NF membrane |
| CN105854642B (en) * | 2016-06-12 | 2018-07-27 | 天津工业大学 | A kind of preparation method of the hydrophilic polypropylene nitrile NF membrane containing polyhydroxy |
| CN108499361B (en) * | 2018-04-10 | 2021-11-12 | 北京工业大学 | Preparation method of nano-porous polymer film with adjustable pore size |
| CN108927002A (en) * | 2018-07-26 | 2018-12-04 | 浙江工业大学 | A method of preparing large pore size ultrafiltration membrane |
| CN113648842A (en) * | 2021-08-23 | 2021-11-16 | 苏州中色德源环保科技有限公司 | Polyether sulfone hollow fiber membrane aperture adjusting method applied to material separation |
| CN114870643B (en) * | 2022-04-27 | 2023-06-16 | 中科南京绿色制造产业创新研究院 | Polymer hollow fiber membrane and preparation method and application thereof |
| CN116371384B (en) * | 2022-12-28 | 2024-04-16 | 北京碧水源膜科技有限公司 | Forming method of titanium-based lithium ion sieve powder |
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|---|---|---|---|---|
| CN102527262A (en) * | 2011-12-09 | 2012-07-04 | 西安建筑科技大学 | Method for preparing chemically perforated polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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