CN116651221A - Preparation method of hollow fiber composite membrane - Google Patents
Preparation method of hollow fiber composite membrane Download PDFInfo
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- CN116651221A CN116651221A CN202310580438.0A CN202310580438A CN116651221A CN 116651221 A CN116651221 A CN 116651221A CN 202310580438 A CN202310580438 A CN 202310580438A CN 116651221 A CN116651221 A CN 116651221A
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- hollow fiber
- hollow
- membrane
- braided tube
- composite membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 133
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 238000005266 casting Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000009954 braiding Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001112 coagulating effect Effects 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 238000005234 chemical deposition Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims abstract description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002033 PVDF binder Substances 0.000 claims description 30
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 9
- 238000009941 weaving Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 7
- 239000004811 fluoropolymer Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 3
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims 2
- 229920005989 resin Polymers 0.000 claims 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims 1
- 239000003361 porogen Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 20
- 230000004907 flux Effects 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 238000001728 nano-filtration Methods 0.000 description 10
- 238000009940 knitting Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 5
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 5
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009730 filament winding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The application discloses a preparation method of a hollow fiber composite membrane, which comprises the following steps: step 1: braiding fiber filaments into a hollow braided tube by adopting a two-dimensional braiding technology, and performing alkali washing treatment and drying on the hollow braided tube for later use; step 2: fully soaking the hollow braided tube prepared in the step 1 by adopting an aqueous solution of an organic solvent, uniformly coating the casting solution outside the hollow braided tube preferably through a concentric circle spinning spinneret, immersing in a coagulating bath to generate double diffusion, curing and forming, and cleaning to obtain a primary hollow fiber membrane; step 3: and (3) terminating one end of the nascent hollow fiber membrane wire to prepare a component, vacuumizing the hollow fiber, placing the hollow fiber in a closed container containing pyrrole, forming a polypyrrole separation layer after chemical deposition, and cleaning and drying to obtain the hollow fiber membrane composite membrane. The prepared fluorine-containing polymer-based hollow fiber composite membrane has excellent chemical stability, high interface bonding strength, high pressure resistance and stable hydrophilicity and separation performance.
Description
Technical Field
The application relates to the technical field of membranes, in particular to a preparation method of a hollow fiber composite membrane.
Background
The membrane separation technology is used as a novel efficient and environment-friendly separation technology, becomes a high-new technology with supportability, introductory and prospective properties in the aspects of environmental protection, energy conservation and emission reduction, selective and accurate separation of substances with different scales, deep purification and recovery and the like, and is one of key commonality technologies for solving the important problems of energy crisis, water resource crisis, air pollution and the like facing the world at present. The hollow fiber membrane is an important form of a separation membrane, has the characteristics of good self-supporting property, large specific surface area, large filling density of a membrane component, compact equipment, simple operation process during application, high separation efficiency and the like, and has more advantages in industrial application.
Fluorine-containing polymers such as polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyvinylidene fluoride-chlorotrifluoroethylene (PVDF-CTFE) copolymer and the like have excellent chemical corrosion resistance, high temperature resistance, oxidation resistance, good mechanical strength and wide application range, and are ideal film-forming materials. However, in the market at present, most of the micro/ultrafiltration membranes represented by PVDF are required to be further improved in separation precision. Chinese patent CN105617875a and CN201410607043.6 mention that PVDF microporous filter membrane is used as a base membrane, and the nanofiltration membrane is formed by interfacial polymerization process of soaking in water phase and then adding oil phase, however, the surface energy of fluoropolymer material is low, hydrophilicity is poor, and the nano-filtration/loose nanofiltration membrane is prepared as a base membrane, which is easy to cause discontinuous separation layer on the surface of the base membrane, and has insufficient bonding strength with the base membrane, long-term application stability cannot be ensured, and easy to be peeled. The PVDF membrane is combined with hydrophilic polymer in Chinese patent CN101524626, CN111644077B and the like to improve the hydrophilicity of the PVDF and prepare the nanofiltration membrane, but the modified layer has limited temperature resistance and solvent resistance, and the comprehensive performance of the PVDF can be weakened. In addition, the membrane prepared by traditional non-solvent induced phase separation or thermal induced phase separation has poor strength and pressure resistance, and the prepared nanofiltration/loose nanofiltration membrane has poor pressure resistance and insufficient membrane structure stability. Therefore, developing a new method to obtain the PVDF nanofiltration/loose nanofiltration membrane product with high separation precision, good interface stability and high compressive strength has important significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application provides the preparation method of the hollow fiber composite membrane, which is simple and convenient to operate and suitable for industrial production, and the prepared fluorine-containing polymer-based hollow fiber composite membrane has excellent chemical stability, high interface bonding strength, high pressure resistance and stable hydrophilicity and separation performance.
In order to achieve the above purpose, the application adopts the following technical scheme:
the application takes fluorine-containing polymer as film forming polymer, firstly prepares high-strength and pressure-resistant composite hollow braided tube by two-dimensional braiding technology, prepares fluorine-containing polymer base film by concentric circle composite spinning method, and when double diffusion occurs in coagulating bath, oxidant enters into film to form oxidant gradient concentration distribution primary hollow fiber film, and then polymerizes with pyrrole monomer in situ to form fluorine-containing polymer base low pressure nanofiltration film product. The hollow fiber composite membrane comprises a fluoropolymer base membrane and a polypyrrole separation layer formed on the fluoropolymer base membrane in situ, wherein the fluoropolymer base membrane comprises a fluoropolymer layer and a composite fiber woven tube.
As a preferred embodiment, a method for producing a hollow fiber composite membrane, the method comprising the steps of:
step 1: the fiber filaments are woven into a hollow woven tube by adopting a two-dimensional weaving technology, preferably, the weaving parameters are weaving pitch of 0.5-2 mm, the weaving rotating speed is 500-1000 rpm, and the hollow woven tube is subjected to alkali washing treatment and drying for later use;
the fiber filaments are formed by mixing and braiding two kinds of fibers, wherein one of the mixed-braided filaments is one of fluorine-containing polymer, preferably polyvinylidene fluoride (PVDF) and vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) fiber filaments, and the other is one of poly (m-phenylene isophthalamide) (PMIA) and Polyimide (PI) fiber filaments;
step 2: optionally (optionally meaning that the infiltration step may or may not be performed) fully infiltrating the hollow woven tube prepared in step 1 with an aqueous solution of an organic solvent, uniformly coating the casting solution outside the hollow woven tube, preferably through a concentric circular spinning spinneret with a pore diameter of 1.7-2.3 mm, immersing in a coagulation bath for double diffusion, curing and shaping, and cleaning to obtain a nascent hollow fiber membrane;
step 3: and (3) terminating one end of the nascent hollow fiber membrane wire to prepare a component, vacuumizing the hollow fiber, placing the hollow fiber in a closed container containing pyrrole, forming a polypyrrole separation layer after chemical deposition, and cleaning and drying to obtain the hollow fiber membrane composite membrane.
In the application, in the step 1, the mixed weaving ratio of the two fibers is 1-4:4-1. The hollow braided tube is used as a hollow fiber membrane support body, the strength and the pressure resistance of membrane wires are improved, a mixed braiding process is adopted, a second type of high-strength high-modulus fiber filaments are introduced, the braided tube is endowed with more excellent strength, meanwhile, the two types of mixed braided fiber filaments are both soluble in a cosolvent, the technical problems that the interface bonding strength of a heterogeneous reinforced membrane is low, a homogeneous reinforced membrane is easy to form a compact region are solved, and the interface bonding strength of the reinforced membrane is improved.
In the application, step 1, the alkali washing treatment is to draw the braided tube into NaOH with the temperature of 40-90 ℃ and the concentration of 5-15 wt%
And (5) drying the solution in hot air for 10-30 min.
In the application, in the step 2, the casting solution comprises 5 to 22 weight percent of fluorine-containing polymer resin, 5 to 12 weight percent of pore-forming agent, 1 to 5 weight percent of additive and 61 to 89 weight percent of solvent, and the casting solution is prepared according to the total of the components being 100 percent, and is fully dissolved to obtain uniform solution for standby. Preferably, the pore-forming agent is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium chloride (NaCl), lithium chloride (LiCl), glycerin, preferably PEG, PVP or LiCl. The solvent is one or more of triethyl phosphate (TEP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), preferably low toxicity solvents such as TEP, DMSO and the like. The additive is one or more of Tween-20, tween-60 and Tween-80. The addition of the additive in the casting solution plays a role in regulating and controlling the phase separation time and slowing down the solidification rate. The fluorine-containing polymer resin is one or more of PVDF, PVDF-HFP and PVDF-CTFE.
In the application, in the step 2, the organic solvent is one or more of N, N-dimethylacetamide (DMAc) and N, N-Dimethylformamide (DMF), and the concentration is preferably 15-30wt%.
In the application, step 2, the hollow braided tube after the coating liquid is immersed into a coagulating bath at 20-70 ℃ for 0.2-5 min to be solidified and formed under the traction of a filament winding roller at 0.5-5.0 m/min.
Preferably, the coagulation bath comprises water, a solvent, an alcohol, an oxidizing agent and an additive. Further, the alcohol is one or more of ethanol, n-butanol and isopropanol, and the content is 3-15 wt%, preferably ethanol. The oxidant is one or more of ferric trichloride, ferric sulfate, ferric nitrate and ferric perchlorate, and the content of the oxidant is 1-10wt%, preferably ferric trichloride. The additive is one or more of toluene sulfonic acid, sodium benzene sulfonate and camphorsulfonic acid, and the content is 0.05-1 wt%. The solvent is the same as the solvent used in the casting solution, the content of the solvent is 10-30wt% and the rest is water. As a preferable scheme, the oxidant in the coagulating bath enters the membrane when double diffusion occurs between the non-solvent (in the coagulating bath) and the solvent (in the casting solution), is firmly loaded on the membrane after solidification, and forms the gradient reduction distribution of the oxidant from the outer surface to the inner part by the heavy action of the alcohol in the coagulating bath and the additive in the casting solution, thereby improving the dispersion performance of the oxidant, enhancing the loading firmness of the oxidant, and avoiding the problems of uneven dispersion, blocking membrane holes and the like caused by the traditional dipping mode. The hydrophilicity of the preferable additive sulfonate slows down the subsequent pyrrole polymerization reaction, which is beneficial to the uniform distribution of the polypyrrole layer.
Preferably, before the casting solution is coated on the hollow braided tube, the hollow braided tube is pre-infiltrated, the hollow braided tube prepared in the step (1) is fully infiltrated by adopting a solution of DMAc or DMF and water, the infiltration temperature is 50-65 ℃, and the infiltration time is 0.5-10 min. DMAc or DMF can swell and etch two kinds of mixed knitting fiber simultaneously, thereby increasing the roughness thereof, being beneficial to improving the bonding strength of the knitting pipe and the surface coating layer, and the concentration of the solvent is preferably 5-30wt%.
In the step 3, the vacuum degree is 0.05-0.09 MPa, the temperature is 25-90 ℃, and the chemical deposition time is 20-180 min. The drying is that the baking oven is used for drying for 3 to 5 hours at the temperature of between 60 and 80 ℃. The temperature in the closed container is 50-90 ℃. The dosage of the filarian pyrrole is 1-10 ml per 1m membrane.
Compared with the prior art, the application has the following beneficial effects:
(1) The hollow braided tube of the support body is prepared by adopting a mixed braiding process, and is obtained by carrying out two-dimensional braiding on homogeneous fibers with the same film forming material and high-strength, high-temperature-resistant and hydrophilic heterogeneous fibers after the homogeneous fibers are mixed with the high-strength, high-temperature-resistant and hydrophilic heterogeneous fibers, wherein two fiber cosolvents endow the fluorine-containing polymer hollow fiber membrane support body with strong bonding strength with a surface separation layer, the heterogeneous fibers avoid compact region formation, and meanwhile, the strength and the pressure resistance of the membrane are improved, and the hydrophilicity of the membrane is improved.
(2) The polypyrrole layer is uniformly deposited on the surface and the inside of the hollow fiber membrane in a vapor deposition and in-situ growth mode, so that an external compact and internal loose structure is formed, the separation precision is improved, the hydrophilicity is improved, the membrane holes are prevented from being blocked, the separation layer is firmly riveted inside the base membrane, the interface bonding strength is high, the stability is good, and the problem of poor uniformity of the separation layer in the traditional coating mode due to the high curvature radius of the hollow fiber membrane is solved.
(3) The hollow fiber membrane separation layer and the base membrane prepared by the method have good high temperature resistance and corrosion resistance, the separation performance reaches the nanofiltration level, and the application field of the fluorine-containing polymer hollow fiber membrane can be effectively expanded.
Drawings
FIG. 1 is a scanning electron microscope image of the outer surface of the hollow fiber composite membrane prepared in example 1.
FIG. 2 is a scanning electron microscope image of a cross section of the hollow fiber membrane prepared in example 1.
FIG. 3 is a schematic view showing the structural development of the hollow fiber composite membrane of example 1.
FIG. 4 is a graph showing the static water contact angle of the outer surface of the hollow fiber composite membrane prepared in example 1.
FIG. 5 is a scanning electron microscope image of the outer surface of the hollow fiber membrane prepared in comparative example 1.
Detailed Description
The following describes a hollow fiber composite membrane and a method for preparing the same in detail with reference to the accompanying drawings and specific examples, which are only used for further detailed description of the application, and do not limit the scope of the claims.
The raw material sources in the examples and comparative examples are as follows:
polyvinylidene fluoride (PVDF, belgium solvay, 6010));
vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP, vac ma, kynar 2500);
polyvinylidene fluoride-chlorotrifluoroethylene copolymer (PVDF-CTFE, belgium solvay, 31508);
polyvinylpyrrolidone (PVP, ara Ding Shiji (China), M) w ＝30000)；
Polyethylene glycol (PEG, ara Ding Shiji (China), M) n ＝2000)；
Unless otherwise specified, other materials and reagents are commercially available conventional chemical reagents.
The prepared hollow fiber composite membrane is evaluated, and mainly passes through a water contact angle test, a pure water flux and a dye separation performance test.
(1) Water/oil contact angle test:
the static water contact angle of the hollow fiber composite membrane obtained was measured by using an OCA25 type optical contact angle measuring instrument of Dataphysics company, germany. When the hollow fiber composite membrane is tested, the hollow fiber composite membrane is fixed on a glass slide by double-sided adhesive tape, the glass slide is placed on a test platform for testing, the contact time of liquid drops and the surface of the membrane is set to be 30s, and each sample is tested 5 times after the test is stabilized, and the average value is obtained.
(2) Pure water flux and entrapment test
The flux of pure water was measured at 25℃for 10cm filaments by an external pressure method. Firstly, carrying out pre-pressing treatment on the membrane for 30min, then testing different membrane samples under constant pressure, and calculating the pure water flux of the membrane according to the following formula:
J＝V/(A·T)
wherein J is the pure water flux (L.m -2 ·h -1 ) V is the permeate side volume (L), A is the effective area (m 2 ) The method comprises the steps of carrying out a first treatment on the surface of the T is the test time (h).
The membrane interception performance is inspected by testing the dye interception effect of the hollow fiber composite membrane. The films were pre-pressed for 30min before testing. After the flux is stable, the prepared dye solution with concentration of 20mg/L is used as a stock solution, and the filtered solution is collected for testing. The absorbance of the raw material liquid and the permeate liquid was measured by an X-3 ultraviolet spectrophotometer of Shanghai Yuan-Jib, and the retention rate was calculated from the following formula by converting the relationship between absorbance and concentration into concentration:
R(％)＝(1-C p /C f )·100％
wherein R is retention rate, C f And C p Dye concentrations in the raw material liquid and the filtered liquid are respectively.
Example 1
1) Preparing a mixed-knitting fiber hollow knitting pipe:
the PVDF filaments and PMIA filaments were stranded, a two-dimensional braiding machine (model GBJ-90, xuzhou Henghui braiding machinery Co., ltd.) was used for 24 ingots, a braiding pitch of 2mm was set, a rotational speed of 800rpm, a hollow braided tube was braided with the PVDF filaments and PMIA filaments in a ratio of 1:4, the outer diameter of which was 1.8mm, and the obtained braided tube was immersed in 5wt% sodium hydroxide solution, treated at 40℃for 20 minutes, followed by washing with deionized water, and dried at 60 ℃.
2) Preparing a casting film liquid:
PVDF, DMSO, PEG2000 and Tween-80 are mixed according to 15wt%, 79wt%, 5wt% and 1wt%, and heated in a water bath at 70 ℃ and mechanically stirred for 5 hours, and the uniform casting solution is obtained after complete defoaming.
3) Preparation of a nascent hollow fiber membrane:
immersing the hollow braided tube into a 20wt% DMAc aqueous solution at 50 ℃ for 3min, uniformly coating the casting solution on the outer part of the hollow braided tube through a concentric circular spinning spinneret with the aperture of 2.3mm, immersing the hollow braided tube into a coagulating bath with the composition of 12wt% of ethanol, 2wt% of ferric trichloride, 0.5wt% of sodium toluate, 10wt% of DMSO and 75.5wt% of water for 2min for curing and forming under the traction of a 1m/min wire winding roller, and cleaning to obtain a primary hollow fiber membrane;
4) Preparing a hollow fiber membrane composite membrane:
and (3) end-capping one end of the nascent hollow fiber membrane yarn to prepare a component, vacuumizing the hollow fiber to 0.05MPa, placing the component in a sealed container containing pyrrole at 80 ℃, performing chemical deposition for 60min to form a polypyrrole separation layer, wherein the pyrrole dosage per 1m membrane yarn is 5ml, placing the component in a baking oven at 60 ℃ for drying for 5h, and washing and drying the PVDF hollow fiber composite membrane.
Through tests, the surface of the PVDF hollow fiber composite membrane obtained as shown in the attached drawing 1 is uniformly deposited with an pyrrole accumulation layer, the cross section of the membrane is shown in the drawing 2, the bonding state is good, a compact area formed by dissolving a woven tube does not exist, and the structural evolution diagram is shown in the drawing 3. By pullingTensile tester (model JBDL-200N, manufactured by Minibo test machine Co., ltd.) for testing breaking strength of film (film yarn holding length 10cm, tensile rate 5 mm. Min) -1 ) The breaking strength of the tested film is more than 200MPa, the water contact angle test result is shown in figure 4, the water contact angle is 64 degrees, and the flux is 125 L.m under 0.5MPa -2 ·h -1 The membrane silk is not flattened, the interface bonding state is good, the rejection rate of the membrane silk to methyl blue and Congo red is more than 98%, the rejection rate of NaCl is 19%, the separation of dye and salt can be realized, the repeated washing test is carried out, and the membrane flux and the rejection performance are basically unchanged.
Example 2
1) Preparing a mixed-knitting fiber hollow knitting pipe:
the PVDF filaments and the PI filaments are stranded, a two-dimensional braiding machine with 24 ingots is used for setting the braiding pitch to be 1mm and the rotating speed to be 600rpm, the PVDF filaments and the PI filaments are braided into a hollow braided tube according to the proportion of 1:3, the outer diameter of the hollow braided tube is 1.6mm, the obtained braided tube is immersed into 8wt% sodium hydroxide solution, treated for 20min at the temperature of 40 ℃, then washed by deionized water, and dried at the temperature of 60 ℃.
2) Preparing a casting film liquid:
PVDF, TEP, PVP30000 and Tween-80 are mixed according to 17wt%, 73wt%, 8wt% and 2wt%, and heated in a water bath at 70 ℃ and mechanically stirred for 5 hours, and the uniform casting solution is obtained after complete defoaming.
3) Preparation of a nascent hollow fiber membrane:
immersing the hollow braided tube in a 10wt% DMF water solution at 50 ℃ for 3min, uniformly coating the casting solution on the outer part of the hollow braided tube through a concentric circular spinning spinneret with the aperture of 1.7mm, immersing the hollow braided tube in a coagulating bath with the composition of 10wt% ethanol, 2wt% ferric sulfate, 0.1wt% sodium benzenesulfonate, 15wt% TEP and 72.9wt% water at 50 ℃ for 3min under the traction of a filament winding roller at 0.5m/min, solidifying and forming, and cleaning to obtain a nascent hollow fiber membrane;
4) Preparing a hollow fiber composite membrane:
and (3) blocking one end of the nascent hollow fiber membrane yarn to prepare a component, vacuumizing the hollow fiber to 0.09MPa, placing the hollow fiber in a sealed container containing pyrrole at 80 ℃, performing chemical deposition for 80min to form a polypyrrole separation layer, wherein the pyrrole dosage of each 1m of membrane yarn is 10ml, placing the membrane yarn in a baking oven at 60 ℃ for drying for 5h, and washing and drying to obtain the PVDF hollow fiber composite membrane.
Through tests, the surface of the PVDF hollow fiber composite membrane is uniformly deposited with an polypyrrole layer, a compact area formed by dissolving a woven tube does not exist, the breaking strength is greater than 200MPa, the water contact angle is 58 degrees, and the flux is 102L m under 0.5MPa -2 ·h -1 The membrane silk is not flattened, the interface bonding state is good, the rejection rate of the membrane silk to methyl blue and Congo red is more than 97%, the rejection rate of NaCl is 21%, the separation of dye and salt can be realized, the repeated washing test is carried out, and the membrane flux and the rejection performance are basically unchanged.
Example 3
1) Preparing a mixed-knitting fiber hollow knitting pipe:
the PVDF-HFP filaments and PMIA filaments are twisted, a 24-spindle two-dimensional braiding machine is used for setting the braiding pitch to be 2mm and the rotating speed to be 700rpm, a hollow braided tube is braided by the PVDF-HFP filaments and the PMIA filaments according to the proportion of 1:1, the outer diameter of the hollow braided tube is 1.8mm, the obtained braided tube is immersed in 5 weight percent sodium hydroxide solution, treated for 20min at the temperature of 40 ℃, then washed by deionized water and dried at the temperature of 60 ℃.
2) Preparing a casting film liquid:
PVDF-HFP, DMSO, PEG2000 and Tween-20 are mixed according to 15wt%, 79wt%, 5wt% and 1wt%, and the uniform casting solution is obtained after water bath heating at 70 ℃ and mechanical stirring for 5 hours and complete defoaming.
3) Preparation of a nascent hollow fiber membrane:
immersing the hollow braided tube into a 20wt% DMAc aqueous solution at 50 ℃ for 3min, uniformly coating the casting solution on the outer part of the hollow braided tube through a concentric circular spinning spinneret with the aperture of 2.1mm, immersing the hollow braided tube into a coagulating bath with the composition of 12wt% isopropyl alcohol, 2wt% ferric trichloride, 0.5wt% sodium toluate, 10wt% DMSO and 75.5wt% water for 2min under the traction of a filament winding roller at 0.5m/min for curing and forming, and cleaning to obtain a nascent hollow fiber membrane;
4) Preparing a hollow fiber composite membrane:
and (3) blocking one end of the nascent hollow fiber membrane yarn to prepare a component, vacuumizing the hollow fiber to 0.05MPa, placing the hollow fiber in a sealed container containing pyrrole at 80 ℃, performing chemical deposition for 30min to form a polypyrrole separation layer, placing 2ml of pyrrole per 1m of membrane yarn in a baking oven at 60 ℃ for drying for 5h, and washing and drying to obtain the PVDF-HFP hollow fiber composite membrane.
Through tests, the surface of the PVDF-HFP hollow fiber composite membrane is uniformly deposited with an pyrrole accumulation layer, a compact area formed by dissolving a woven tube does not exist, the breaking strength is greater than 200MPa, the water contact angle is 57 degrees, and the flux is 131L m under 0.5MPa -2 ·h -1 The membrane silk is not flattened, the interface bonding state is good, the rejection rate of the membrane silk to methyl blue and Congo red is more than 92%, the rejection rate of NaCl is 16%, the separation of dye and salt can be realized, the repeated washing test is carried out, and the membrane flux and the rejection performance are basically unchanged.
Example 4
11 Preparing a mixed-woven fiber hollow woven tube:
the PVDF-HFP filaments and PI filaments are stranded, a 24-spindle two-dimensional braiding machine is used for setting the braiding pitch to be 2mm and the rotating speed to be 600rpm, a hollow braided tube is braided by the PVDF-HFP filaments and the PI filaments according to the proportion of 1:3, the outer diameter of the hollow braided tube is 2.0mm, the obtained braided tube is immersed in 8 weight percent sodium hydroxide solution, treated for 20min at the temperature of 40 ℃, then washed by deionized water and dried at the temperature of 60 ℃.
2) Preparing a casting film liquid:
PVDF-HFP, TEP, PVP30000 and Tween-80 are mixed according to 17wt%, 73wt%, 8wt% and 2wt%, and the uniform casting solution is obtained after water bath heating at 70 ℃ and mechanical stirring for 5 hours and complete defoaming.
3) Preparation of a nascent hollow fiber membrane:
immersing the hollow braided tube in a 10wt% DMAc aqueous solution at 50 ℃ for 3min, uniformly coating the casting solution on the outer part of the hollow braided tube through a concentric circular spinning spinneret with the aperture of 1.7mm, immersing the hollow braided tube into a coagulating bath with the composition of 10wt% isopropanol, 2wt% ferric sulfate, 0.1wt% camphorsulfonic acid, 15wt% TEP and 72.9wt% water at 50 ℃ for 3min under the traction of a filament winding roller at 0.5m/min, solidifying and forming, and cleaning to obtain a nascent hollow fiber membrane;
4) Preparing a hollow fiber composite membrane:
and (3) end-capping one end of the nascent hollow fiber membrane yarn to prepare a component, vacuumizing the hollow fiber to 0.09MPa, placing the component in a sealed container containing pyrrole at 80 ℃, performing chemical deposition for 120min to form a polypyrrole separation layer, wherein the pyrrole consumption of each 1m membrane yarn is 10ml, placing the component in a baking oven at 60 ℃ for drying for 5h, and washing and drying the PVDF hollow fiber composite membrane.
Through tests, the surface of the PVDF-HFP hollow fiber composite membrane is uniformly deposited with an pyrrole accumulation layer, a compact area formed by dissolving a woven tube does not exist, the breaking strength is greater than 200MPa, the water contact angle is 60 degrees, and the flux is 89 L.m under 0.5MPa -2 ·h -1 The membrane silk is not flattened, the interface bonding state is good, the rejection rate of the membrane silk to methyl blue and Congo red is more than 99%, and the rejection rate of NaCl is 31%, so that the separation of dye and salt can be realized.
Comparative example 1
The PVDF hollow fiber membrane is prepared by adopting the method in the embodiment 1, except that ferric trichloride is not added in the coagulating bath in the step 3, and the step 4 is not performed, so that the PVDF hollow fiber membrane is prepared, the surface appearance of the membrane is shown in the figure 5, a large number of micropore structures are visible on the surface, the water contact angle is 79 degrees, and the membrane filaments have no interception effect on methyl blue and congo red basically.
Comparative example 2
The PVDF hollow fiber composite membrane is prepared by adopting the method in the embodiment 1, and the difference is that the hollow braided tube is made of polyethylene terephthalate (PET), so that the PVDF hollow fiber composite membrane is prepared, membrane wires are flattened under 0.5MPa, and a separation layer is separated from the braided tube.
In summary, the hollow fiber composite membranes prepared in examples 1-4 have better overall performance than the separation membranes prepared in comparative examples 1-2, the hydrophilicity and separation accuracy of the obtained membranes are greatly improved, the stability of membrane interfaces is enhanced, and the service lives of the membranes are effectively prolonged.
While the present application has been described with reference to the foregoing embodiments, those skilled in the art will understand that various specific parameters in the foregoing embodiments may be changed without departing from the spirit of the application, and that the present application is not limited to the specific embodiments, which are common and various changes of the present application.
Claims (10)
1. A method for preparing a hollow fiber composite membrane, which is characterized by comprising the following steps:
step 1: the fiber filaments are woven into a hollow woven tube by adopting a two-dimensional weaving technology, preferably, the weaving parameters are weaving pitch of 0.5-2 mm, the weaving rotating speed is 500-1000 rpm, and the hollow woven tube is subjected to alkali washing treatment and drying for later use;
the fiber filaments are formed by mixing and braiding two kinds of fibers, wherein one of the mixed-braided filaments is one of fluorine-containing polymers, preferably polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer fiber filaments, and the other is one of poly m-phenylene isophthalamide and polyimide fiber filaments;
step 2: optionally, fully soaking the hollow braided tube prepared in the step 1 by adopting an aqueous solution of an organic solvent, uniformly coating the casting solution outside the hollow braided tube preferably through a concentric circular spinning nozzle with the aperture of 1.7-2.3 mm, immersing in a coagulating bath for double diffusion, curing and forming, and cleaning to obtain a primary hollow fiber membrane;
step 3: and (3) terminating one end of the nascent hollow fiber membrane wire to prepare a component, vacuumizing the hollow fiber, placing the hollow fiber in a closed container containing pyrrole, forming a polypyrrole separation layer after chemical deposition, and cleaning and drying to obtain the hollow fiber membrane composite membrane.
2. The method according to claim 1, wherein the two fibers in step 1 are mixed in a ratio of 1-4:4-1; and/or, the alkali washing treatment is to draw the hollow braided tube into NaOH solution with the temperature of 40-90 ℃ and the concentration of 5-15 wt% for 10-30 min.
3. The preparation method according to claim 1 or 2, wherein in step 2, the temperature of the aqueous solution of the organic solvent is 50 to 65 ℃ and the infiltration time is 0.5 to 10min; .
4. A method according to any one of claims 1 to 3, wherein in step 2, the coagulation bath comprises a solvent, an alcohol, an oxidizing agent, an additive and water;
preferably, the alcohol is one or more of ethanol, n-butanol and isopropanol, and the content is 3-15 wt%, preferably ethanol; and/or the number of the groups of groups,
the oxidant is one or more of ferric trichloride, ferric sulfate, ferric nitrate and ferric perchlorate, and the content is 1-10wt%, preferably ferric trichloride; and/or the number of the groups of groups,
the additive is one or more of toluene sulfonic acid, sodium benzene sulfonate and camphorsulfonic acid, and the content is 0.05-1wt%; and/or the number of the groups of groups,
the solvent is the same as the solvent used in the casting film liquid, and the content is 10-30wt%.
5. The method according to any one of claims 1 to 4, wherein in step 2, the casting solution contains 5 to 22wt% of the fluoropolymer resin, 5 to 12wt% of the porogen, 1 to 5wt% of the additive, and 61 to 89wt% of the solvent; preferably, the fluoropolymer resin is one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-chlorotrifluoroethylene.
6. The preparation method according to claim 5, wherein the additive is one or more of tween-20, tween-60 and tween-80; and/or the pore-forming agent is one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, sodium chloride, lithium chloride and glycerin, preferably polyethylene glycol, polyvinylpyrrolidone or lithium chloride.
7. The preparation method according to claim 5 or 6, wherein the solvent is one or more of triethyl phosphate, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, preferably triethyl phosphate and/or dimethyl sulfoxide.
8. The process according to any one of claims 1 to 7, wherein the organic solvent in step 2 is one or more of N, N-dimethylacetamide, N-dimethylformamide, preferably in a concentration of 15 to 30wt%.
9. The method according to any one of claims 1 to 8, wherein in step 2, the hollow woven tube coated with the casting solution is immersed in a coagulation bath at 20 to 70 ℃ for 0.2 to 5 minutes under traction of a wire winding roller at 0.5 to 5.0m/min to perform double diffusion.
10. The method according to any one of claims 1 to 9, wherein in step 3, the degree of vacuum is 0.05 to 0.09MPa and the time for chemical deposition is 20 to 180min; and/or drying in an oven at 60-80 ℃ for 3-5 h; the temperature in the closed container is 50-90 ℃.
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