CN108273399B - Enhanced hollow fiber membrane and preparation method and application thereof - Google Patents
Enhanced hollow fiber membrane and preparation method and application thereof Download PDFInfo
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- CN108273399B CN108273399B CN201710683044.2A CN201710683044A CN108273399B CN 108273399 B CN108273399 B CN 108273399B CN 201710683044 A CN201710683044 A CN 201710683044A CN 108273399 B CN108273399 B CN 108273399B
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- membrane
- solution
- hollow fiber
- fiber
- compound
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- 239000012528 membrane Substances 0.000 title claims abstract description 259
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 191
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 241
- 239000000835 fiber Substances 0.000 claims abstract description 200
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 145
- 229910001868 water Inorganic materials 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 86
- 238000009941 weaving Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 82
- 239000002033 PVDF binder Substances 0.000 claims description 71
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 71
- 238000011282 treatment Methods 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 54
- -1 polyphenol compound Chemical class 0.000 claims description 45
- 235000013824 polyphenols Nutrition 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 34
- 239000002202 Polyethylene glycol Substances 0.000 claims description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 31
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 30
- 229920000098 polyolefin Polymers 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000007853 buffer solution Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 19
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 19
- 229920002873 Polyethylenimine Polymers 0.000 claims description 17
- 229920000768 polyamine Polymers 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000004952 Polyamide Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 229940094952 green tea extract Drugs 0.000 claims description 9
- 235000020688 green tea extract Nutrition 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000004676 glycans Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 150000002466 imines Chemical class 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920001282 polysaccharide Polymers 0.000 claims description 7
- 239000005017 polysaccharide Substances 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229920006306 polyurethane fiber Polymers 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000003637 basic solution Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 4
- 239000007974 sodium acetate buffer Substances 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
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- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
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- 150000001868 cobalt Chemical class 0.000 claims description 2
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(III) nitrate Inorganic materials [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Biodiversity & Conservation Biology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to the field of hollow fiber membrane preparation, in particular to an enhanced hollow fiber membrane and a preparation method and application thereof. The method comprises the following steps: in an alkaline solution, activating the cellosilk to obtain activated cellosilk; impregnating the activated filaments with a modifying composition in a modifying solution to obtain modified filaments; in a metal salt solution, carrying out contact reaction on the modified fiber yarn and a metal salt to obtain a fiber yarn with nanoparticles on the surface; mixing the fiber yarn with the surface provided with the nano particles with a membrane preparation solution, and weaving the obtained mixture to obtain a hollow fiber woven tube; and forming the hollow fiber braided tube into a reinforced hollow fiber membrane. The reinforced hollow fiber membrane prepared by the method has higher backwashing membrane rupture pressure; and moreover, the membrane bioreactor also has higher water flux and higher breaking strength, and is suitable for membrane bioreactors.
Description
Technical Field
The invention relates to the field of hollow fiber membrane preparation, in particular to an enhanced hollow fiber membrane and a preparation method and application thereof.
Background
With the economic development and the population increase, the problem of water resource shortage is increasingly highlighted, so the demand for wastewater reuse is higher and higher. The membrane separation technology rises from the 60 th century, and has the advantages of high separation degree, high efficiency, energy conservation, environmental protection, safety, integration and the like, so that the membrane separation technology quickly becomes a new generation separation technology which is most widely applied, and has great economic and social benefits in the fields of food, medicine, biology, environmental protection, chemical industry, metallurgy, energy, petroleum, water treatment, electronics, bionics and the like.
Among them, the Membrane Bioreactor (MBR) has the characteristics of high effluent quality, stable structure, simple operation and the like, is widely applied to the field of recycling municipal water and industrial wastewater, and is one of the wastewater treatment technologies with the most market prospects. Hollow fiber membranes are the core of membrane modules in membrane bioreactors because of their higher specific surface area. However, in practical industrial application environments, aeration and membrane filament backwashing steps are often accompanied in the operation process, and under the scouring of high-speed airflow and water flow, the strength of a single membrane filament is insufficient and the influence of entanglement in a sewage tank can cause the hollow fiber membrane filaments of the module to break, so that the quality of produced water is reduced, and the service life of the membrane in the membrane bioreactor is shortened. Therefore, in order to achieve the stabilization of the quality of the produced water and the improvement of the service life of the membrane filaments of the membrane bioreactor module, the strength of the hollow fiber membrane needs to be further improved. The preparation method is characterized in that hydrophilic fiber yarns with certain strength are used as a supporting material of the hollow fiber membrane, and the preparation of the hollow fiber ultrafiltration membrane and the weaving technology of the supporting tube are combined to prepare the hollow fiber membrane with a weaving structure, so that the problem of compounding an existing inner support weaving tube and a membrane separation layer can be well solved, and the preparation of the reinforced hollow fiber membrane is one of the most common solving means.
The separation layer of the membrane determines the chemical stability, flux, molecular weight cut-off and cut-off efficiency of the reinforced hollow fiber membrane, and at present, the high molecular materials used as the separation layer generally include polyvinylidene fluoride (PVDF), Polyethersulfone (PES), Polyacrylonitrile (PAN), polyvinyl chloride (PVC), Polysulfone (PSF), and the like. The strength of the membrane filaments of the reinforced hollow fiber membrane is mainly determined by the strength of the supporting material; while the service life for reinforced hollow fiber membranes depends to a large extent on the interfacial bond strength of the separating and supporting layers of the membrane. The interface bonding strength is high, the service stability of the membrane yarn is improved, and on the contrary, the membrane separation layer can be separated in the operation process.
CN102512992A discloses a preparation method of a film-coated hollow fiber tube, which takes a fiber braided tube as a reinforcing material, completely coats a reinforcing body in the hollow fiber membrane, namely coats polyvinylidene fluoride and other casting film liquid on the inner wall and the outer wall of a polyethylene terephthalate fiber braided tube by a multi-dipping and multi-rolling method with a plurality of one-dipping and one-rolling processes connected in series, performs circular tube heat setting after each dipping and rolling, and finally obtains the reinforced hollow fiber membrane through phase conversion. However, the fiber membrane of the method needs more operation process steps before solidification, which causes inconvenient operation in the production process, mutual interference of the front and rear padding coatings and reduction of production efficiency.
CN10357303A discloses a preparation method of a vinylidene fluoride hollow fiber composite microporous membrane with strong interface bonding, wherein a fluorine-containing siloxane coupling agent is adopted to treat the surface of a glass fiber, and a transition layer is formed after crosslinking, so that a reinforced polyvinylidene fluoride hollow fiber membrane is prepared. However, the above method is only suitable for the surface of the glass fiber, and the transition layer can form a smooth interface after being crosslinked, and the bonding strength between the separation layer and the transition layer is still unsatisfactory.
The existing preparation methods of the reinforced hollow fiber membrane all focus on the method of forming the hollow fiber membrane by combining a woven hollow fiber woven tube with an upper composite layer, on one hand, the preparation process is complex; on the other hand, the coating degree of the braided tube (namely the supporting layer) and the separating layer is low, and the binding force is poor, so that the requirement of the conventional industrial MBR process cannot be well met.
Disclosure of Invention
The invention aims to provide a simple, effective and widely-applicable reinforced hollow fiber membrane and a preparation method and application thereof.
As a first invention of the present invention, the following are:
in order to achieve the above object, an aspect of the present invention provides a method for preparing a reinforced hollow fiber membrane, the method comprising:
(1) in an alkaline solution, activating the cellosilk to obtain activated cellosilk;
(2) impregnating the activated filaments with a modifying composition in a modifying solution to obtain modified filaments;
(3) in a metal salt solution, carrying out contact reaction on the modified fiber yarn and a metal salt to obtain a fiber yarn with nanoparticles on the surface;
(4) mixing the fiber yarn with the surface provided with the nano particles with a membrane preparation solution, and weaving the obtained mixture to obtain a hollow fiber woven tube;
(5) forming the hollow fiber braided tube into an enhanced hollow fiber membrane;
wherein the modifying composition comprises a first polyphenolic compound and a crosslinking molecule; the membrane preparation liquid contains a membrane forming polymer, a pore-forming agent and a second polyphenol compound;
wherein the first and second polyphenolic compounds are each independently selected from compounds containing at least 2 phenolic hydroxyl groups, and the crosslinking molecule is one or more of polyamine compounds, crosslinked polyolefin amides, polyalcohols, polyolefin pyrrolidones, polysaccharides, and polyolefin imines.
The second aspect of the present invention provides a reinforced hollow fiber membrane obtained by the above method.
In a third aspect, the invention provides a membrane bioreactor comprising the reinforced hollow fiber membrane described above.
The fourth aspect of the present invention provides the use of the above reinforced hollow fiber membrane in membrane separation.
The reinforced hollow fiber membrane prepared by the method has higher rupture pressure of a backwashing membrane, so that the combination capability of the supporting layer and the separation layer is strong; and moreover, the membrane bioreactor also has higher water flux and higher breaking strength, and is suitable for membrane bioreactors.
As a second invention of the present invention, the following are:
in a first aspect of the second invention, a method for modifying a hollow braided tube is provided, which includes modifying the hollow braided tube with a modifying solution containing a polyphenol compound and a cross-linked polymer.
Preferably, the modified solution is prepared from a buffer solution, a polyphenol compound and a cross-linked polymer, and more preferably, the buffer solution is selected from a Tris buffer solution, a PBS buffer solution or an acetic acid/sodium acetate buffer solution.
Preferably, the polyphenol compound is selected from at least one of catechol, tannic acid, dopamine, catechin, gallic acid, and green tea extract, preferably at least one of catechol, tannic acid, and dopamine; the cross-linked polymer is selected from at least one of polyvinyl amide, polyethylene glycol, polyvinylpyrrolidone, chitosan, polyethyleneimine, polyethylene polyamine, tetraethylenepentamine, diethylenetriamine, ethylenediamine and hexamethylenediamine, preferably at least one of polyethyleneimine, polyethylene glycol and diethylenetriamine; the hollow fiber tube is woven by at least one of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polysulfone fibers or glass fibers, and preferably woven by polyester fibers and/or polyamide fibers.
Preferably, the concentration of polyphenolic compound in the modification solution is between 0.5% and 15% by weight, preferably between 3% and 15% by weight; the concentration of the crosslinked polymer is from 5% to 20% by weight, preferably from 8% to 18% by weight.
Preferably, the temperature of the modification treatment is 40 ℃ to 80 ℃, preferably 50 ℃ to 70 ℃, for 10 minutes to 60 minutes.
A second aspect of the second invention provides a method for producing a hollow fiber membrane, comprising:
step A, modifying the hollow braided tube serving as the supporting material by adopting the method;
b, mineralizing the hollow braided tube treated in the step A by using a salt solution;
and C, coating the surface of the hollow braided tube treated in the step B with a membrane preparation solution.
Preferably, before step a, the hollow braided tube is pretreated with a lye, preferably selected from aqueous solutions of alkali metal hydroxides and alkaline earth metal hydroxides, the lye preferably having a concentration of from 5% to 20% by weight.
Preferably, the salt solution is selected from CaCl2Solution, FeCl3Solution, CuCl2Solution and AgNO3At least one of the solutions, the mass concentration of the salt solution is preferably 0.5% -5%, and more preferably 1.5% -5%.
Preferably, the membrane-forming solution contains a polyphenol compound, and the polyphenol compound is preferably at least one selected from catechol, tannic acid, dopamine, catechin, gallic acid and green tea extract, more preferably at least one selected from catechol, tannic acid and dopamine.
Preferably, the membrane preparation liquid also contains polyvinylidene fluoride, an additive and a solvent; preferably, in the membrane-making solution, the concentration of polyvinylidene fluoride is 8 wt% -26 wt%, more preferably 10 wt% -20 wt%; the concentration of the additive is 3 wt% -17.5 wt%, and more preferably 3.5 wt% -10 wt%; the concentration of the polyphenol compound is 3 wt% to 13 wt%, more preferably 3.5 wt% to 10 wt%.
Preferably, the additive is at least one selected from polyvinylpyrrolidone with molecular weight of 3000-50000, polyethylene glycol with molecular weight of 1000-10000, polyethylene oxide with molecular weight of 10000-60000 and polyvinyl alcohol with molecular weight of 8000-50000, and the solvent is at least one selected from N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, in the step B, the soaking temperature is 10-40 ℃, preferably 25-35 ℃; the soaking time is 1 hour to 8 hours, preferably 3 hours to 5 hours.
As a third invention of the present invention, the following are:
a first aspect of the third invention of the present invention provides a method for producing a hollow fiber membrane, comprising:
1) weaving silver-containing fiber bundles and polymer fiber bundles to obtain a silver-containing fiber woven tube;
2) co-extruding the silver-containing fiber braided tube obtained in the step 1) with the membrane casting solution and the core solution, and then carrying out phase separation to obtain the hollow fiber membrane.
Preferably, the polymer fiber bundle consists of 1000 fiber filaments with the number of 100-; the silver-containing fiber bundle consists of 1-10 silver-containing fiber filaments.
Preferably, the fiber filaments are selected from at least one of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polysulfone fibers, or glass fibers, preferably polyester fibers and/or polyamide fibers.
Preferably, the casting solution used in step 2) includes polyvinylidene fluoride, a solvent, a non-solvent and an additive.
Preferably, the polyvinylidene fluoride has a number average molecular weight of 10 to 50 ten thousand; preferably, in the casting solution, the mass content of the polyvinylidene fluoride is 10% -30%, and more preferably 15% -25%.
Preferably, the additive is selected from at least one of polyvinylpyrrolidone with molecular weight of 3000-50000, polyethylene glycol with molecular weight of 1000-10000, polyethylene oxide with molecular weight of 10000-60000 and polyvinyl alcohol with molecular weight of 8000-50000; preferably, the mass content of the additive in the casting solution is 2% -20%, more preferably 5% -15%.
Preferably, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; preferably, in the casting solution, the mass content of the solvent is 50% to 80%, more preferably 60% to 75%.
Preferably, the non-solvent is at least one of propylene glycol, glycerol, triethylene glycol and polyethylene glycol, and the polyethylene glycol is preferably at least one selected from polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600; preferably, the mass content of the non-solvent in the casting solution is 5% to 20%, more preferably 8% to 12%.
Preferably, the temperature of the coagulation bath is controlled at 30-80 ℃, preferably 50-70 ℃; the temperature of the core liquid is controlled to be 20-80 ℃, and preferably 20-60 ℃.
Preferably, the hollow fiber membrane is subjected to a hydrophilization post-treatment after step 2), the hydrophilization post-treatment being: soaking the hollow fiber membrane obtained in the step 2) in water at the temperature of 40-90 ℃ for 2-24 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; drying the hollow fiber membrane subjected to hydrophilization treatment at the temperature of between 20 and 60 ℃ for 2 to 48 hours to obtain the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial property.
Drawings
Fig. 1 is a schematic view of a PVDF-reinforced hollow fiber membrane having a strong interfacial tension according to a preferred embodiment of the second invention.
Fig. 2 is a cross-sectional view of a hollow fiber membrane according to one embodiment of the second invention type.
Fig. 3 is a surface topography configuration diagram of a hollow fiber membrane in accordance with one embodiment of the second class of inventions of the present invention.
Fig. 4 is a schematic view of a hollow fiber membrane obtained by a production method according to an embodiment of the third invention of the present invention.
Fig. 5 is a scanning electron micrograph of a hollow fiber membrane obtained by a manufacturing method according to an embodiment of the third invention of the present invention after being soaked in an escherichia coli solution for 12 hours.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the first invention of the present invention:
the invention provides a preparation method of an enhanced hollow fiber membrane, which comprises the following steps:
(1) in an alkaline solution, activating the cellosilk to obtain activated cellosilk;
(2) impregnating the activated filaments with a modifying composition in a modifying solution to obtain modified filaments;
(3) in a metal salt solution, carrying out contact reaction on the modified fiber yarn and a metal salt to obtain a fiber yarn with nanoparticles on the surface;
(4) mixing the fiber yarn with the surface provided with the nano particles with a membrane preparation solution, and weaving the obtained mixture to obtain a hollow fiber woven tube;
(5) forming the hollow fiber braided tube into an enhanced hollow fiber membrane;
wherein the modifying composition comprises a first polyphenolic compound and a crosslinking molecule; the membrane preparation liquid contains a membrane forming polymer, a pore-forming agent and a second polyphenol compound;
wherein the first and second polyphenolic compounds are each independently selected from compounds containing at least 2 phenolic hydroxyl groups, and the crosslinking molecule is one or more of polyamine compounds, crosslinked polyolefin amides, polyalcohols, polyolefin pyrrolidones, polysaccharides, and polyolefin imines.
According to the invention, in the step (1), the fiber yarn is activated in the alkaline solution, so that oil stains, surfactants and the like on the fiber yarn can be removed, and the treated fiber yarn can be better subjected to subsequent modification treatment. Wherein the fiber filaments may be any fiber filaments that are conventional in the art for forming a hollow braided tube of a support layer when used in the preparation of a reinforced hollow fiber membrane, for example, the fiber filaments are one or more of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polyvinylidene fluoride fibers, polysulfone fibers, and glass fibers. In view of better cooperation of the fiber filaments with the modified composition, the metal salt and the membrane-forming solution, the reinforced hollow fiber membrane with better performance is obtained, and preferably, the fiber filaments are polyester fibers and/or polyamide fibers. The fiber may be a commercially available product or may be prepared by a method generally used in the art, and the present invention is not particularly limited thereto.
Preferably, the titer of the fiber yarn is 10-500D, preferably 50-300D, and more preferably 100-200D. It is preferably a solid filament.
According to the present invention, in the step (1), the alkaline compound in the alkaline solution may be any alkaline compound which achieves an activation effect on the fiber yarn, preferably, the alkaline compound in the alkaline solution is one or more of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkali metal bicarbonate and ammonia, and more preferably, one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate and ammonia.
The content of the basic compound in the basic solution may vary within a wide range, and in order to obtain a better activation effect, the content of the basic compound in the basic solution is preferably 5 to 20% by weight, preferably 5 to 15% by weight.
According to the invention, in step (1), the filaments may be partially, substantially completely or completely immersed in the alkaline solution, preferably completely, in order to enable a more complete activation of the filaments. The amount of the alkaline solution may vary within a wide range, as long as the fiber filaments are partially, substantially completely or completely immersed therein, and is not particularly limited in the present invention.
According to the present invention, preferably, the conditions of the activation treatment include: the temperature is 30-80 deg.C, and the time is 10-50 min. More preferably, the conditions of the activation treatment include: the temperature is 30-70 deg.C, and the time is 15-30 min.
According to the present invention, the step (1) may further comprise washing the activated fiber yarn (e.g., with water), then centrifuging (e.g., at a rotation speed of 3,000-10,000rpm for 5-20min) and drying the resulting fiber yarn (e.g., at 50-100 ℃), thereby obtaining the activated fiber yarn.
According to the invention, in the step (2), the activated fiber filaments are immersed in the modification composition, so that the crosslinking molecules and the first polyphenol compounds can be attached to the surfaces of the fiber filaments, which has a very important effect on enhancing the binding capacity of the support layer and the separation layer.
According to the present invention, the compound having at least 2 phenolic hydroxyl groups is preferably one or more of a compound represented by formula (1), tannic acid, a compound represented by formula (2), and green tea extract;
wherein the content of the first and second substances,
R1-R6at least 2 of which are OH, the remainder being each independently of the other H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6; r7-R10And R13-R17At least 2 of which are OH, the remainder of R7-R10And R13-R17And R11-R12Each independently of the others being H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6; each L is independently selected from C0-C6 alkylene; each M is independently H and an alkali metal element.
Specific examples of the alkyl group having C1 to C6 may be, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl and the like.
Specific examples of the alkoxy group of C1 to C6 may be, for example: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy and the like.
Specific examples of alkylthio groups of C1-C6 may be, for example: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, n-hexylthio and the like.
The halogen may be, for example, F, Cl, Br, I.
The alkali metal element may be, for example, Li, Na, K.
Specific examples of C0-C6 alkylene groups may be, for example: alkylene of C0, -CH2-、-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2-、-CH(CH3)CH2CH2-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-CH2CH(CH3)CH2-、-CH2C(CH3)2-、-CH2CH(CH2CH3)-、-CH2CH2CH(CH3)-、-CH(CH2CH3CH3)-、-CH(CH(CH3)CH3)-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-and the like. Wherein the alkylene group of C0 means that the linking group is absent or represents a linking bond, whereby the groups at both ends of the linking group are directly linked.
Preferably, R1-R6At least 2 of which are OH, the remainder being each independently of the other H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C4, alkoxy of C1-C4 or alkylthio of C1-C4; r7-R10And R13-R17At least 2 of which are OH, the remainder of R7-R10And R13-R17And R11-R12Each independently of the others being H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C4, alkoxy of C1-C4 or alkylthio of C1-C4; each L is independently selected from C0-C4 alkylene; each M is independently H, Na and K.
More preferably, R1-R6At least 2 of which are OH, the remainder being each independently of the other H, F, Cl, Br, -COOM, -CH2-COOM、-CH2CH2-COOM、-CH2CH2CH2-COOM、-CH(CH3)CH2-COOM、-CH2CH(CH3)-COOM、-CH2CH2CH2CH2-COOM、-SO3M、-CH2-SO3M、-CH2CH2-SO3M、-CH2CH2CH2-SO3M、-CH(CH3)CH2-SO3M、-CH2CH(CH3)-SO3M、-CH2CH2CH2CH2-SO3M、-NH2、-CH2-NH2、-CH2CH2-NH2、-CH2CH2CH2-NH2、-CH(CH3)CH2-NH2、-CH2CH(CH3)-NH2、-CH2CH2CH2CH2-NH2、-OH、-CH2-OH、-CH2CH2-OH、-CH2CH2CH2-OH、-CH(CH3)CH2-OH、-CH2CH(CH3)-OH、-CH2CH2CH2CH2-OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio.
According to the present invention, in a preferred embodiment of the present invention, the compound represented by the formula (1) is selected from compounds represented by the following formulae:
in a preferred embodiment of the present invention, the compound represented by formula (2) is selected from compounds represented by the following formulae:
wherein the green tea extract may be a green tea extract extracted by a conventional extraction means in the art, or may be a green tea extract product available from green technologies of Hunan, Inc.
Particularly preferably, the first polyphenol compound is one or more of catechol, tannic acid and dopamine.
According to the invention, the cross-linking molecule is one or more of polyamine compounds, cross-linked polyolefin amides, polyalcohols, polyolefin pyrrolidones, polysaccharides and polyolefin imines.
Among them, the polyamine-based compound having a plurality of active amino groups and capable of undergoing an addition reaction with a phenolic hydroxyl group is preferably used as the crosslinking molecule of the present invention
And NH2-R-NH2N is an integer of 1 to 8, and R is an alkylene group of C1 to C8. The value of n may be, for example, 1, 2, 3, 4, 5, 6, 7 or 8. The C1-C8 alkylene group may be selected from the alkylene groups described above, and may also include-CH2(CH2)5CH2-、-CH2(CH2)6CH2-and the like.
More preferably, the polyamine compound is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, NH2-CH2-NH2、NH2-CH2CH2-NH2、NH2-CH2CH2CH2-NH2、NH2-CH(CH3)CH2-NH2、NH2-CH2(CH2)2CH2-NH2、NH2-CH2(CH2)3CH2-NH2And NH2-CH2(CH2)4CH2-NH2One or more of (a).
Wherein the cross-linked polyolefin amide is an amide group (-C (O) -NH)2) Preferably, the cross-linked polyolefin amide is one or more of cross-linked polyacrylamide, cross-linked polymethacrylamide and polyacrylamide. Preferably, the number average molecular weight of the crosslinked polyolefin amide is 500-5000.
Wherein, preferably, the polyhydric alcohol is one or more of polyethylene glycol, polypropylene glycol, polyglycerol and polyvinyl alcohol. Preferably, the polymeric polyol has a number average molecular weight of 400-4000.
Wherein, the polyolefin pyrrolidone is a polymer formed by unsaturated olefin with pyrrolidone group, preferably, the polyolefin pyrrolidone is polyvinylpyrrolidone and the like. Preferably, the number average molecular weight of the polyolefin pyrrolidone is 2000-20000.
Wherein, preferably, the polysaccharide is chitosan, starch, modified starch, cellulose and modified cellulose. Preferably, the number average molecular weight of the polysaccharide is 800-.
Wherein the polyolefin imine refers to a structural unit of- [ CH2(CH2)m-NH]- (m is 1 or more, for example, 1 to 4), and preferably, the polyalkyleneimine is polyethyleneimine and/or polypropyleneimine. Preferably, theThe number average molecular weight of the polyolefin imine is 360-5000.
Particularly preferably, the crosslinking molecule is one or more of polyethyleneimine, polyethylene glycol and diethylenetriamine.
According to the present invention, although the modification composition containing the above-mentioned first polyphenol compound and the crosslinking molecule is useful for modifying the surface of the fiber yarn, in order to obtain more excellent modification effect, it is preferable that the weight ratio of the first polyphenol compound to the crosslinking molecule is 100: 80-300, preferably 100: 100- "250", for example 100: 150-200.
The content of the modifying composition in the modifying solution may vary within wide limits, preferably the content of the modifying composition is from 5 to 30% by weight, preferably from 8 to 26% by weight, more preferably from 10 to 25% by weight, for example from 15 to 20% by weight. The modifying solution preferably employs a buffer solution as a solvent, in particular a buffer solution having a pH of 5 to 11, preferably a pH of 7 to 10, for example a pH of 8 to 9.5. The buffer solution may be various buffer solutions conventional in the art, and is preferably a Tris buffer solution, a PBS buffer solution, or an acetic acid-sodium acetate buffer solution.
Wherein, the impregnation in the step (2) may be to partially, substantially entirely or entirely immerse the activated fiber filaments in the modification solution as long as the modification composition can be impregnated, preferably entirely, in the modification solution. The amount of the modifying solution may vary within a wide range, as long as the fiber filaments are partially, substantially entirely or entirely immersed therein, and the present invention is not particularly limited thereto.
According to the present invention, preferably, in the step (2), the impregnation conditions include: the temperature is 50-80 deg.C, and the time is 10-80 min. More preferably, in step (2), the impregnation conditions include: the temperature is 60-70 deg.C, and the time is 20-60 min. The step (2) may further comprise washing the modified fiber filaments (for example, with water), and then spin-drying the modified fiber filaments (for example, spin-drying the modified fiber filaments at a rotation speed of 3,000-10,000rpm for 5-20min) to obtain the modified fiber filaments.
According to the invention, in the step (3), the modified fiber yarn and the metal salt are subjected to contact reaction, so that metal ions can be reduced into metal nanoparticles under the reduction action of the first polyphenol compound, the surface of the fiber yarn is further modified, and the fiber yarn with the nanoparticles on the surface is obtained, that is, the fiber yarn can be understood as the fiber yarn with the crosslinked molecular layer on the surface, and the crosslinked molecular layer has the nanoparticles on the surface. The contacting may also be described as a mineralization reaction process.
Preferably, in the metal salt solution, the metal salt is one or more of calcium salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, silver salt, gold salt, platinum salt and magnesium salt, and more preferably CaCl2、Ca(NO3)2、FeCl3、Fe2(SO4)3、Fe(NO3)3、CoCl3、Co(NO3)3、CuCl2、CuSO4、ZnCl2、Zn(NO3)2、AgNO3、HAuCl4、H2PtCl6、PtN2O6And MgCl2More preferably CaCl2、FeCl3、AgNO3And CuCl2One or more of (a).
Wherein the concentration of the metal salt in the metal salt solution may vary within wide limits, preferably the concentration of the metal salt in the metal salt solution is 0.5-8 wt.%, more preferably 2-5 wt.%, in order to obtain filaments modified with nanoparticles having a more suitable grain size and content.
Wherein the contact reaction in the step (3) may be partially, substantially completely or completely immersing the modified fiber filaments in a metal salt solution, as long as the contact reaction with the metal salt is possible. The amount of the metal salt solution may vary within wide limits, as long as the fiber filaments are partially, substantially completely or completely immersed therein, and is not particularly limited in the present invention.
According to the present invention, preferably, in step (3), the contact reaction conditions include: the temperature is 20-50 ℃ and the time is 4-10 h.
According to the present invention, the step (3) may further comprise washing the filaments after the contact reaction (e.g., washing with water), and drying (e.g., drying at 40-80 deg.C)
According to the invention, the membrane-making solution contains a membrane-forming polymer, a pore-forming agent and a second polyphenol compound, and is used for coating the outer surface of the fiber yarn. Wherein the second polyphenolic compound may be the same as or different from the first polyphenolic compound, each of which is independently selected from the group consisting of the compounds containing at least 2 phenolic hydroxyl groups described above. More preferably, the second polyphenol compound is one or more of gallic acid, tannic acid, dopamine and catechol, preferably gallic acid.
Among them, various polymers for forming the separation layer, which are conventional in the art, may be used, but in order to increase the bonding property with the fiber filament having the nanoparticle on the surface obtained in step (3) of the present invention, it is preferable that the film-forming polymer is one or more of polyvinylidene fluoride (PVDF), polyether sulfone (PES), and Polyacrylonitrile (PAN). Preferably, the number average molecular weight of the film-forming polymer is from 10 to 50 ten thousand.
The pore-forming agent can be one or more of polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), polyethylene oxide, polyvinyl alcohol, polymethyl methacrylate and polyvinyl acetate, and is preferably one or more of polyvinyl pyrrolidone with a number average molecular weight of 3,000-50,000, polyethylene glycol with a molecular weight of 1,000-10,000, polyethylene oxide with a molecular weight of 10,000-60,000, polyvinyl alcohol with a molecular weight of 8,000-50,000 and polymethyl methacrylate with a molecular weight of 11,000-85,000. The above molecular weight generally refers to a number average molecular weight.
In a particularly preferred embodiment of the present invention, in the modifying composition, the first polyphenolic compound is tannic acid, and the crosslinking molecule is polyethyleneimine; in the membrane preparation liquid, the membrane forming polymer is polyvinylidene fluoride, the pore-foaming agent is polyvinylpyrrolidone, and the second polyphenol compound is gallic acid. More preferably, the cross-linking molecule is polyethyleneimine with the number average molecular weight of 3000-4000, the film-forming polymer is polyvinylidene fluoride with the molecular weight of 20-21 ten thousand, and the pore-forming agent is polyvinylpyrrolidone with the number average molecular weight of 2.5-3 ten thousand.
According to the present invention, although the film-forming solution contains the film-forming polymer, the pore-forming agent and the second polyphenol compound, that is, the performance of the reinforced hollow fiber membrane can be improved through the coordination among the film-forming polymer, the pore-forming agent and the second polyphenol compound, in order to improve the synergistic effect among the film-forming polymer, the pore-forming agent and the second polyphenol compound, and in order to enable the film-forming solution to have stronger binding capacity with the fiber filaments with the nanoparticles on the surface obtained in step (3), preferably, the weight ratio of the film-forming polymer, the pore-forming agent and the second polyphenol compound in the film-forming solution is 100: 30-100: 10-120, preferably 100: 35-90: 20-100, more preferably 100: 36-80: 30-80, for example 100: 36-60: 40-60.
According to the invention, the solvent in the membrane-forming liquid is preferably a benign solvent of the membrane-forming polymer and the pore-forming agent, preferably one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, triethyl phosphate, sulfolane, dimethylsulfone and benzophenone. Wherein, preferably, the weight ratio of the film-forming polymer to the solvent is 1: 5-10, preferably 1: 5-8.5.
The amount of the film-forming solution used in the present invention may be any amount conventionally used in the art, and is preferably such that the cellulose is completely impregnated with the film-forming solution.
The preparation of the film-forming solution may be carried out by a method for preparing a film-forming solution which is conventional in the art, and for example, the film-forming solution may be prepared by stirring and mixing the above components in an inert atmosphere (nitrogen atmosphere, argon atmosphere, or the like), dissolving, and defoaming.
According to the present invention, the weaving can be performed by a method conventional in the art, for example, the mixture of the fiber yarn with the nanoparticles on the surface and the membrane-forming solution is introduced into a weaving head of a weaving tube weaving machine, spinning weaving is performed through a weaving tube spinning nozzle, and the formed weaving tube is sent to a weaving tube knife coater to scrape off the excess membrane-forming solution adhered to the fiber yarn. And (3) after the braided tube is obtained, the braided tube enters an extrusion nozzle under the traction force of a take-up pulley for coextrusion, wherein the traction speed of the take-up pulley is preferably 0.5-6 m/min.
The method may further comprise: after the step (4), subjecting the hollow fiber braided tube to coagulation and water washing treatment, wherein the temperature of the coagulation and water washing treatment is preferably 30-80 ℃. The resulting hollow fiber woven tube can be formed into a membrane by coagulation and water washing treatment. The coagulation liquid used for the coagulation treatment may be water or an aqueous solvent containing one or more of N, N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), N-methylpyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfone, and benzophenone (the water content is preferably 60% by weight or more). The coagulation and water washing may be performed simultaneously, that is, the coagulation is performed in the coagulation liquid and the water washing is performed, or it may be performed in steps, for example, the fiber filaments coagulated in the coagulation liquid are washed in water. Usually, coagulation and water washing treatments are performed simultaneously in a coagulation liquid in a coagulation tank as it is.
According to the present invention, the process of forming the hollow fiber woven tube into the reinforced hollow fiber membrane of step (5) may be performed by a conventional method of the present invention, and may include, for example, obtaining an antibacterial hollow fiber membrane by phase separation from a coagulation and water washing treatment system.
According to the present invention, preferably, the step (5) further comprises subjecting the resulting reinforced hollow fiber membrane to a hydrophilization treatment under conditions including: soaking in 60-80 deg.C hot water for 4-12 hr.
According to the invention, after the hydrophilization treatment, the obtained membrane can be washed (for example, with water) and dried (for example, dried at 20-60 ℃ for 12-36 h).
The second aspect of the present invention provides a reinforced hollow fiber membrane obtained by the above method.
In the invention, at least part of the surface of the fiber filament is covered with a cross-linked molecular layer, and at least part of the cross-linked molecular layer and/or at least part of the surface of the fiber filament is provided with metal nanoparticles, that is, the fiber filament with nanoparticles on the surface obtained in the step (3) is covered with a film-forming polymer provided by a film-forming solution, that is, a separation layer; the reinforced hollow fiber membrane is formed by combining hollow fiber braided tubes which are formed by braiding fiber yarns with nano particles on the surfaces, wherein the outermost layer of the hollow fiber braided tubes is covered with a membrane forming polymer provided by a membrane making solution.
According to the invention, the reinforced hollow fiber membrane has higher rupture pressure of the backwashing membrane, so that the combination capability of the supporting layer and the separating layer is strong; and moreover, the membrane has higher water flux, higher breaking strength, higher water contact angle, flux recovery rate, interception rate and the like, and is suitable for a membrane bioreactor. Wherein, the rupture pressure of the backwashing membrane of the reinforced hollow fiber membrane can be more than 2.5MPa, preferably 3-7MPa, and more preferably 5-7 MPa; the water flux can be, for example, 150-250L/m2h, preferably 160-2h; the breaking strength may be, for example, 17MPa or more, preferably 20 to 25 MPa; the water contact angle may be, for example, 40 to 70 degrees, preferably 40 to 60 degrees; the flux recovery rate may be, for example, 90% or more, preferably 92% or more; the retention rate may be, for example, 90% or more, preferably 92% or more.
In a third aspect, the invention provides a membrane bioreactor comprising the reinforced hollow fiber membrane described above.
The fourth aspect of the present invention provides the use of the above reinforced hollow fiber membrane in membrane separation.
According to the invention, the enhanced hollow fiber membrane can be applied to membrane separation technologies related to the fields of food, medicine, biology, environmental protection, chemical industry, metallurgy, energy, petroleum, water treatment, electronics, bionics and the like.
In the second invention of the present invention:
the second invention of the invention provides a modification method of a hollow braided tube and a preparation method of a hollow fiber layer, aiming at the conditions of rupture, filament breakage and the like of a hollow fiber membrane in the prior art caused by poor mechanical strength and the like in the application process of a membrane bioreactor and the defects of poor adhesion between a membrane separation layer and a supporting material, easy shedding and the like of the existing reinforced hollow fiber membrane. According to the invention, on one hand, a transition layer with stable cross-linking and rough surface is constructed on the surface of the braided tube, and on the other hand, the hollow fiber membrane with excellent interface strength is prepared by adjusting the components of the membrane-making solution.
In a first aspect of the present invention, there is provided a method of modifying a hollow braided tube, which comprises subjecting the hollow braided tube to a modification treatment with a modification solution containing a polyphenol compound and a crosslinked polymer.
In the present invention, after the modification treatment, a modified coating is formed on the surface of the hollow braided tube. The catechol group in the modified coating forms a hydrophobic effect with the hollow braided tube, the cross-linked structure enhances the bonding strength and stability of the modified coating and the braided tube, and polar groups such as amino, hydroxyl and the like are introduced into the surface of the modified coating, so that the compatibility between the transition layer and the membrane material is improved.
According to a preferred embodiment of the invention, the hollow braided tube is pretreated with an alkaline solution before the modification treatment. Preferably, the lye is selected from aqueous solutions of alkali metal hydroxides and alkaline earth metal hydroxides, more preferably aqueous solutions of sodium hydroxide, such as sodium hydroxide solution. In one embodiment, the concentration of the lye is between 5 wt% and 20 wt%. The pretreatment may be carried out at a temperature of 20 ℃ to 60 ℃ for, for example, 5 minutes to 60 minutes.
In one embodiment, the pretreatment of the hollow braided tube with the alkali solution specifically comprises: immersing the hollow braided tube into 5-20 wt% sodium hydroxide solution, treating for 5-30 minutes at 20-60 ℃, then cleaning with deionized water, and centrifugally spin-drying at 3000-10000 r/min for 5-20 minutes.
According to a preferred embodiment of the present invention, the modifying solution is formulated from a buffer solution and a polyphenol compound and a cross-linked polymer. Preferably, the buffer solution is selected from Tris buffer solution, PBS buffer solution or acetic acid/sodium acetate buffer solution.
According to a preferred embodiment of the present invention, the polyphenol compound is selected from at least one of catechol, tannic acid, dopamine, catechin, gallic acid and green tea extract, preferably at least one of catechol, tannic acid and dopamine. Preferably, the concentration of the polyphenolic compound is between 0.5% and 15% by weight, preferably between 3% and 15% by weight.
In one embodiment, the polyphenolic compound is catechol, preferably at a concentration of 5 wt% to 15 wt%. In another embodiment, the polyphenolic compound is tannic acid, preferably at a concentration of 1 wt% to 10 wt%. In yet another embodiment, the polyphenolic compound is dopamine, preferably at a concentration of 0.5 wt% to 8 wt%.
According to a preferred embodiment of the present invention, the cross-linked polymer is selected from at least one of polyvinyl amide, polyethylene glycol, polyvinyl pyrrolidone, chitosan, polyethylene imine, polyethylene polyamine, tetraethylenepentamine, diethylenetriamine, ethylenediamine and hexamethylenediamine, preferably at least one of polyethylene imine, polyethylene glycol and diethylenetriamine. Preferably, the concentration of the crosslinked polymer is from 5% to 20% by weight, preferably from 8% to 18% by weight.
According to a preferred embodiment of the present invention, the hollow fiber tube is woven from at least one of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polysulfone fibers, or glass fibers, preferably from polyester fibers and/or polyamide fibers.
In some embodiments, the hollow braided tube has an inner diameter of 0.7mm to 1.5mm and an outer diameter of 1.0mm to 2.3 mm. In some embodiments, the hollow braided tube has a braid density of 15.5mm to 17.5mm and a grammage of 1.0g/mm to 1.6 g/mm.
According to a preferred embodiment of the invention, the temperature of the modification treatment is between 40 and 80 ℃, preferably between 50 and 70 ℃ and the time is between 10 and 60 minutes. In one embodiment, the modification treatment comprises: mixing and stirring a polyphenol compound, a cross-linked polymer and a buffer solution at room temperature, soaking a hollow braided tube into the modified solution, treating at the temperature of 50-70 ℃ for 10-60 minutes, then cleaning with deionized water, and centrifugally drying.
In a second aspect of the present invention, there is provided a method for producing a hollow fiber membrane, comprising:
step A, modifying the hollow braided tube by adopting the modification method;
b, carrying out mineralization treatment on the hollow braided tube treated in the step A by using a salt solution; and
and C, coating the surface of the hollow braided tube treated in the step B with a membrane preparation solution.
In the method of the present invention, since the catechol group has reducibility, nanoparticles can be grown on the surface of the braided tube by mineralization treatment with a salt solution. On one hand, the interaction between the formation of the nano particles and the membrane separation layer is further increased, and on the other hand, the increase of the roughness also enables the combination sites to be further improved, which is beneficial to the stability of the transition layer and the separation layer.
According to a preferred embodiment of the invention, the salt solution is selected from CaCl2Solution, FeCl3Solution, CuCl2Solution and AgNO3At least one of the solutions. The mass concentration of the salt solution is 0.5-5%, and preferably 1.5-5%.
According to a preferred embodiment of the invention, the nanoparticles have a particle size of 15nm to 32 nm.
According to a preferred embodiment of the invention, in step B, the soaking temperature is 10-40 ℃, preferably 25-35 ℃; the soaking time is 1 hour to 8 hours, preferably 3 hours to 5 hours.
Preferably, before the step C, the hollow braided tube treated in the step B is washed by deionized water and dried at the temperature of 60-80 ℃.
According to a preferred embodiment of the present invention, the polyvinylidene fluoride in the casting solution has a number average molecular weight of 10 to 50 ten thousand.
According to a preferred embodiment of the present invention, the casting solution contains a polyphenol compound. Preferably, the polyphenol compound is selected from at least one of catechol, tannic acid, dopamine, catechin, gallic acid, and green tea extract, more preferably at least one of catechol, tannic acid, and dopamine.
According to a preferred embodiment of the present invention, the casting solution further contains polyvinylidene fluoride, an additive and a solvent.
In the membrane-forming liquid, the concentration of polyvinylidene fluoride is preferably 8 wt% to 26 wt%, more preferably 10 wt% to 20 wt%.
In the membrane-forming liquid, the concentration of the additive is preferably 3 wt% to 17.5 wt%, more preferably 3.5 wt% to 10 wt%.
In the membrane-forming liquid, the concentration of the polyphenol compound is preferably 3 wt% to 13 wt%, more preferably 3.5 wt% to 10 wt%.
According to a preferred embodiment of the present invention, the additive is at least one of polyvinylpyrrolidone with molecular weight of 3000-50000, polyethylene glycol with molecular weight of 1000-10000, polyethylene oxide with molecular weight of 10000-60000 and polyvinyl alcohol with molecular weight of 8000-50000.
According to a preferred embodiment of the present invention, the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
According to the invention, the polyphenol compound in the membrane preparation liquid can effectively improve the adhesion of the nanoparticles and the polar groups on the separation layer and the transition layer.
In some embodiments, in step C, the surface of the hollow braided tube is coated with the dope solution by passing the hollow braided tube treated in step B through a spinneret, and injecting the dope solution into the spinneret while maintaining a constant pressure, and drawing the hollow braided tube at a fixed winding speed.
Preferably, the hollow woven tube coated with the film-forming solution is sequentially immersed in a gel bath and a rinsing bath to produce the hollow fiber membrane. The hollow fiber membrane is a braided tube reinforced hollow fiber membrane with high adhesion strength.
Preferably, the aperture of the spinneret is 1.7mm-2.3 mm. Preferably, the winding speed of the drawn hollow braided tube is 2m/min to 20 m/min.
Preferably, the coagulating bath is a mixture of water and at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and more preferably, the mass fraction of water is 60% or more.
In the invention, the operation temperature of the gel tank and the rinsing tank is 30-80 ℃.
Preferably, the preparation method of the present invention further comprises subjecting the hollow fiber membrane prepared as described above to a hydrophilization treatment, for example, a hydrophilization treatment by soaking in hot water at a temperature of 60 ℃ to 80 ℃ for 4 hours to 12 hours.
Preferably, the hollow fiber membrane after the hydrophilization treatment is washed with deionized water and dried at 20 to 60 ℃ for 12 to 36 hours.
Compared with the prior art, the second invention has the beneficial effects that:
1. the modification method of the polyphenol compound and the cross-linked polymer can realize the treatment on the surfaces of the braided tubes made of different materials, and the stability of the modified coating is ensured by the specific group and the cross-linked structure in the coating. Meanwhile, the polar group on the modified coating is beneficial to the adhesion of the polyvinylidene fluoride separation layer.
2. The growth of various nano-particles on the surface of the braided tube is realized, the nano-particles are uniformly distributed, and the size and the density of the nano-particles can be adjusted through the immersion time and the solution temperature. The formation of the nano particles effectively improves the interface contact area of the braided tube and the membrane separation layer, and enhances the interface bonding strength.
3. The method can introduce silver nanoparticles, endow the braided tube enhanced hollow fiber membrane prepared by the method with excellent sterilization and degerming characteristics, and effectively prolong the service time of the membrane.
4. The combination of the separation layer and the transition layer is further enhanced by adding the polyphenol compound into the membrane preparation solution, so that the long-time stable operation of the hollow membrane is ensured.
5. The preparation process is simple, the used raw materials are cheap, and the industrial production is facilitated.
In the third invention of the present invention:
in order to solve the above technical problems, the third invention of the present invention provides a novel method for preparing a hollow fiber membrane. The preparation method comprises the following steps:
1) weaving silver-containing fiber bundles and polymer fiber bundles to obtain a silver-containing fiber woven tube;
2) co-extruding the silver-containing fiber braided tube obtained in the step 1) with the membrane casting solution and the core solution, and then carrying out phase separation to obtain the hollow fiber membrane.
According to a preferred embodiment of the present invention, the preparation method further comprises washing the silver-containing fibers and/or the polymer fibers before step 1). According to one embodiment, the silver-containing fibers and/or polymer fibers are washed with a lye and deionized water. Preferably, the alkali liquor is 5% -15% sodium hydroxide solution. Preferably, the temperature for washing with the alkaline solution is 20 minutes to 60 minutes, and the time is 5 minutes to 30 minutes.
According to a preferred embodiment of the present invention, the production method further comprises subjecting the hollow fiber membrane to a hydrophilization post-treatment after step 2). According to a preferred embodiment, the post-hydrophilization treatment is: soaking the hollow fiber membrane obtained in the step 2) in water at the temperature of 40-90 ℃ for 2-24 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; drying the hollow fiber membrane subjected to hydrophilization treatment at the temperature of between 20 and 60 ℃ for 2 to 48 hours to obtain the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial property.
According to a preferred embodiment of the invention, the weaving is: the silver-containing fiber bundles and the polymer fiber bundles are subjected to herringbone cross weaving along the core liquid pipe.
Preferably, the polymer fiber bundle consists of 1000 fiber filaments in the number of 100-. Preferably, the silver-containing fiber bundle is composed of 1 to 10 silver-containing filaments in number.
According to the present invention, the silver-containing fiber bundle may be commercially available or may be self-made.
According to a preferred embodiment of the present invention, the fiber filaments are selected from at least one of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polysulfone fibers or glass fibers, preferably polyester fibers and/or polyamide fibers.
According to a preferred embodiment of the present invention, the casting solution used in step 2) includes polyvinylidene fluoride, a solvent, a non-solvent and an additive.
According to a preferred embodiment of the present invention, the casting solution is prepared by the following steps: mixing polyvinylidene fluoride, a solvent, a non-solvent and an additive, stirring in a reaction kettle at 60-120 ℃ for 12-24 hours, and defoaming in vacuum for 12-24 hours to obtain the casting solution.
Preferably, the polyvinylidene fluoride has a number average molecular weight of 10 to 50 ten thousand. In the casting solution, the mass content of the polyvinylidene fluoride is preferably 10% to 30%, and more preferably 15% to 25%.
Preferably, the additive is selected from at least one of polyvinylpyrrolidone with molecular weight of 3000-50000, polyethylene glycol with molecular weight of 1000-10000, polyethylene oxide with molecular weight of 10000-60000 and polyvinyl alcohol with molecular weight of 8000-50000. In the casting solution, the mass content of the additive is preferably 2% to 20%, and more preferably 5% to 15%.
Preferably, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. In the casting solution, the mass content of the solvent is preferably 50% to 80%, and more preferably 60% to 75%.
Preferably, the non-solvent is at least one of propylene glycol, glycerol, triethylene glycol and polyethylene glycol. The polyethylene glycol is preferably selected from polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600. In the casting solution, the mass content of the non-solvent is preferably 5% to 20%, and more preferably 8% to 12%.
According to a preferred embodiment of the present invention, the bore fluid is a mixed solution of the solvent or a mixed solvent of water and the non-solvent. Preferably, the concentration of water in the bore fluid is 50% to 100% by weight, preferably 70% to 100%.
According to a preferred embodiment of the invention, the temperature of the bore fluid is controlled between 20 ℃ and 80 ℃, preferably between 20 ℃ and 60 DEG C
According to a preferred embodiment of the invention, the phase separation is carried out by immersing the co-extruded product in a coagulation bath and a water bath. The coagulating bath is an aqueous solution of at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the mass concentration of the aqueous solution is preferably 0-40%, and more preferably 0-20%.
According to a preferred embodiment of the invention, the temperature of the coagulation bath is controlled between 30 ℃ and 80 ℃, preferably between 50 ℃ and 70 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the silver-containing fiber bundle and the polymer fiber are woven into a fiber woven reinforcing layer by adopting a fiber weaving-co-extrusion integrated process, and the fiber woven reinforcing layer is embedded into the body of the hollow fiber membrane. Compared with the common hollow fiber membrane, the membrane wire has higher tensile strength reaching 12.5MPa to 50MPa, bursting strength reaching 0.25MPa to 1.5MPa and pure water flux of 120L/m2h-500L/m2h。
2. The hollow fiber membrane obtained by the invention has excellent antibacterial and bactericidal effects due to the introduction of the silver-containing braided tube. Experiments show that the hollow fiber membrane has the inhibition rate of 82.5-93.5% on escherichia coli and the inhibition rate of 75.1-89.7% on staphylococcus aureus, and has excellent antibacterial effect. Meanwhile, the hollow fiber membrane has 95.3% -97.3% of bovine serum albumin retention rate and excellent separation performance.
3. The silver-containing braided tube is wrapped inside the polyvinylidene fluoride hollow membrane, so that the silver particles are not easy to elute and have long antibacterial time in the using process.
4. The invention provides a preparation method of the hollow fiber ultrafiltration membrane with antibacterial and high mechanical strength, which is simple to operate, can be realized by adopting the existing industrial equipment and is beneficial to realizing industrial production.
It should be understood that although the above three inventions of the present invention have been described in close relation, the three inventions are described independently and not limited to each other.
The present invention will be described in detail below by way of examples.
The first class of inventions directed to the present invention provides the following list:
in the following examples and comparative examples:
the water flux is measured by adopting a dead-end external pressure filtering device, namely, the cleaned wet film is pre-pressed for 30min at 0.15MPa, and then the external pressure water flux is measured at 0.1 MPa; the BSA solution was then passed through to determine the retention and the flux recovery after washing with water.
The backwash membrane rupture pressure is responsive to the interfacial bond strength of the braided tube and the separation layer, which is measured using water backwash pressure.
The water contact angle was measured by a contact angle measuring instrument.
Modified solution preparation examples 1 to 6
According to the compositions in table 1 (the kinds of the respective compounds and the concentrations in the modification solution are as listed, wherein the concentrations refer to the net mass of the respective compounds as a percentage of the total weight of the modification solution), the reagents under the respective modification solutions were mixed to obtain the corresponding modification solutions, respectively, in table 1:
polyethyleneimine, available from aldrich, has a number average molecular weight of 3000;
tannic acid was purchased from alatin reagent;
polyethylene glycol was purchased from national pharmaceutical group chemical agents, ltd, and had a number average molecular weight of 1000.
Preparation of modified solution comparative example 1
According to the preparation of modified solution 1, except that polyethyleneimine was not added and an equal amount of dopamine was used instead of polyethyleneimine, modified solution DA1 was obtained.
Preparation of modified solution comparative example 2
According to the preparation of modified solution 1, except that dopamine was not added and an equal amount of polyethyleneimine was used instead of dopamine, modified solution DA2 was obtained.
TABLE 1
film-Forming solution preparation examples 1 to 9
Under the protection of nitrogen, according to the compositions in table 2 (the types of the compounds and the concentration of the film-forming solution are listed, wherein the concentration refers to the percentage of the net mass of each compound in the total weight of the film-forming solution), stirring and mixing the components under specified conditions (the conditions are shown in table 2) until the components are dissolved, and then carrying out vacuum defoaming to obtain the corresponding film-forming solution; in table 2:
PVDF is polyvinylidene fluoride available from the company Akema MG15, having a number average molecular weight of 21 ten thousand;
PVP is polyvinylpyrrolidone of K30 brand available from national drug and reagent company Limited, and the number average molecular weight of the PVP is 3 ten thousand;
PEG is polyethylene glycol available from national pharmaceutical group chemical agents, Inc. and has a number average molecular weight of 2 ten thousand.
PES is a polyethersulfone purchased from national pharmaceutical group chemical agents, Inc. and having a number average molecular weight of 10 ten thousand;
PAN is a polyacrylonitrile available from Chemicals group, Inc., of the national drug group, having a number average molecular weight of 8 ten thousand.
Preparation of film-Forming solution comparative example 1
According to the preparation process of the membrane-forming solution B1, except that dopamine was not used, the amount of PVDF was increased to 15% by weight, and the amount of PVP was increased to 9% by weight, to prepare a membrane-forming solution DB 1.
Comparative example 2 preparation of film-Forming solution
According to the preparation process of the membrane-forming solution B1, except that PVP was not used, the amount of PVDF was increased to 15 wt%, and the amount of dopamine was increased to 9 wt%, to prepare a membrane-forming solution DB 2.
TABLE 2
Examples 1 to 1
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
(1) The filament polyester fiber (solid filament with 50D fineness) was immersed in 5 wt% sodium hydroxide solution and activated at 50 ℃ for 30min, and then the separated fiber was washed with deionized water and centrifuged at 3000rpm for 5min, and the resulting activated fiber was dried at 80 ℃.
(2) Immersing the activated fiber yarn obtained in the step (1) into a modification solution A1, soaking for 30min at 60 ℃, then washing the separated fiber yarn with deionized water, and then centrifugally drying to obtain the modified fiber yarn.
(3) Immersing the modified fiber filaments into 2 wt% of CaCl2And carrying out mineralization reaction for 8 hours at 25 ℃ in an aqueous solution, then washing the separated fiber filaments by using deionized water, drying the obtained fiber filaments at 60 ℃, and showing that the surfaces of the obtained fiber filaments have Ca metal nanoparticles by SEM pictures and related analysis.
(4) Soaking the fiber yarn obtained in the step (3) in membrane-making liquid B1, feeding the obtained mixture into a weaving head of a weaving tube weaving machine for weaving, feeding the woven weaving tube soaked with the membrane-making liquid into a weaving tube blade coater for scraping and coating the redundant membrane-making liquid adhered around the fiber yarn, and feeding the membrane-making liquid into an extrusion nozzle at a forward speed of 2m/min under the traction of a yarn-receiving wheel for coextrusion. And then, after air exposure (air temperature of 30 ℃, relative humidity of 75%, air distance of 10cm), the fiber enters a coagulating bath (i.e., water) at 40 ℃ to obtain a reinforced hollow fiber membrane.
(5) Soaking the reinforced hollow fiber membrane obtained in the step (4) in water at 80 ℃ for 6h to perform hydrophilization treatment; the treated fibrous membrane was washed with deionized water and dried at 30 ℃ for 24 h. Thus, a reinforced hollow fiber membrane M1 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 2
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (1): the fiber yarn is made of filament nylon fiber (solid filament with fineness of 150D); the alkaline solution is a 7.5 weight percent potassium hydroxide solution, and the activation conditions are as follows: the temperature is 45 ℃ and the time is 20 min; the centrifugation conditions were: rotating speed of 5000rpm for 10 min;
step (2): with the modified solution a2, the impregnation conditions were: the temperature is 70 deg.C, and the time is 20 min;
and (3): the metal salt solution used was 3% by weight of AgNO3In aqueous solution, mineralization reaction conditions: the temperature is 20 ℃, and the time is 7 h; the drying temperature is 70 ℃; SEM images and related analysis of the obtained fiber filament show that the surface of the obtained fiber filament has Ag metal nano particles.
And (4): the adopted membrane-making solution is membrane-making solution B2;
and (5): conditions for hydrophilization treatment: the temperature is 80 ℃, and the time is 12 h; the drying condition is drying for 18h at 40 ℃. Thus, a reinforced hollow fiber membrane M2 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 3
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (1): the fiber yarn is made of filament nylon fiber (solid filament with the fineness of 100D); the alkaline solution is 10 weight percent sodium hydroxide solution, and the activation conditions are as follows: the temperature is 50 ℃ and the time is 15 min; the centrifugation conditions were: the rotating speed is 8000rpm, and the time is 10 min;
step (2): with the modified solution a3, the impregnation conditions were: the temperature is 60 ℃, and the time is 40 min;
and (3): the metal salt solution used was 5% by weight FeCl3In aqueous solution, mineralization reaction conditions: the temperature is 20 ℃, and the time is 6 h; SEM images and related analysis of the obtained fiber filament show that the surface of the obtained fiber filament has Fe metal nanoparticles.
And (4): the adopted membrane-making solution is membrane-making solution B3;
and (5): conditions for hydrophilization treatment: the temperature is 70 ℃, and the time is 10 hours; the drying condition is drying for 18h at 40 ℃. Thus, a reinforced hollow fiber membrane M3 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 4
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (2): adopting a modified solution A4;
and (4): the adopted membrane-making solution is membrane-making solution B4;
thus, a reinforced hollow fiber membrane M4 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 5
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (1): the alkaline solution is 8 weight percent sodium hydroxide solution, and the activation conditions are as follows: the temperature is 60 deg.C, and the time is 25 min; the centrifugation conditions were: rotating speed of 5000rpm for 15 min;
step (2): with the modified solution a5, the impregnation conditions were: the temperature is 70 deg.C, and the time is 50 min;
and (3): the metal salt solution used was 3.5% by weight of CaCl2In aqueous solution, mineralization reaction conditions: the temperature is 25 ℃, and the time is 6 h; the drying temperature is 80 ℃; SEM images and related analyses of the resulting filaments showed that the resulting filaments had Ca metal nanoparticles on the surface.
And (4): the adopted membrane-making solution is membrane-making solution B5;
and (5): conditions for hydrophilization treatment: the temperature is 70 ℃, and the time is 10 hours; the drying condition is drying at 40 ℃ for 24 h. Thus, a reinforced hollow fiber membrane M5 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 6
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (1): the alkaline solution is 10 weight percent sodium hydroxide solution, and the activation conditions are as follows: the temperature is 70 deg.C, and the time is 15 min; the centrifugation conditions were: rotating speed of 5000rpm for 15 min;
step (2): the modification solution a6 used, impregnation conditions: the temperature is 70 deg.C, and the time is 40 min;
and (3): the metal salt solution used was 4.5% by weight of CuCl2In aqueous solution, mineralization reaction conditions: the temperature is 25 ℃, and the time is 8 hours; the drying temperature is 80 ℃; SEM images and related analysis of the obtained fiber filament show that the surface of the obtained fiber filament has Cu metal nanoparticles.
And (4): the adopted membrane-making solution is membrane-making solution B6;
and (5): conditions for hydrophilization treatment: the temperature is 70 ℃, and the time is 8 h; the drying condition is drying at 40 ℃ for 24 h. Thus, a reinforced hollow fiber membrane M6 was obtained, and the properties of the membrane are shown in Table 3.
Examples 1 to 7
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that in step (1) glass fiber filaments (solid filaments with 300D denier) were used instead of the filament polyester fibers;
after passing through the respective steps, a reinforced hollow fiber membrane M7 was thus obtained, and the respective properties of the membrane are shown in table 3.
Examples 1 to 8
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (2): the modified solution A7;
after passing through the respective steps, a reinforced hollow fiber membrane M8 was thus obtained, and the respective properties of the membrane are shown in table 3.
Examples 1 to 9
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
step (2): the modified solution A8;
after passing through the respective steps, a reinforced hollow fiber membrane M9 was thus obtained, and the respective properties of the membrane are shown in table 3.
Comparative examples 1 to 1
The method of example 1-1, except that:
step (2): the adopted modified solution DA 1;
after passing through the respective steps, a reinforced hollow fiber membrane DM1 was thus obtained, the properties of which are shown in table 3.
Comparative examples 1 to 2
The method of example 1-1, except that:
step (2): the adopted modified solution DA 2;
after passing through the respective steps, a reinforced hollow fiber membrane DM2 was thus obtained, the properties of which are shown in table 3.
Examples 1 to 10
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
and (4): the adopted membrane-making solution is membrane-making solution B7;
after passing through the respective steps, a reinforced hollow fiber membrane M10 was thus obtained, and the respective properties of the membrane are shown in table 3.
Examples 1 to 11
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
and (4): the adopted membrane-making solution is membrane-making solution B8;
after passing through the respective steps, a reinforced hollow fiber membrane M11 was thus obtained, and the respective properties of the membrane are shown in table 3.
Examples 1 to 12
This example illustrates a reinforced hollow fiber membrane and a method of making the same according to the present invention.
The method of example 1-1, except that:
and (4): the adopted membrane-making solution is membrane-making solution B9;
after passing through the respective steps, a reinforced hollow fiber membrane M12 was thus obtained, and the respective properties of the membrane are shown in table 3.
Comparative examples 1 to 3
The method of example 1-1, except that:
and (4): the adopted membrane-forming liquid is membrane-forming liquid DB 1;
after passing through the respective steps, a reinforced hollow fiber membrane DM3 was thus obtained, the properties of which are shown in table 3.
Comparative examples 1 to 4
The method of example 1-1, except that:
and (4): the adopted membrane-forming liquid is membrane-forming liquid DB 2;
after passing through the respective steps, a reinforced hollow fiber membrane DM4 was thus obtained, the properties of which are shown in table 3.
Comparative examples 1 to 5
The method of example 1-1, except that step (3) is not included and the modified fiber filaments obtained in step (2) are used directly for soaking in the membrane-forming solution in step (4).
After passing through the respective steps, a reinforced hollow fiber membrane DM5 was thus obtained, the properties of which are shown in table 3.
Comparative examples 1 to 6
The process of example 1-1, except that step (2) is not included and the activated filaments from step (1) are used directly for soaking in CaCl in step (3)2In aqueous solution.
After passing through the respective steps, a reinforced hollow fiber membrane DM6 was thus obtained, the properties of which are shown in table 3.
TABLE 3
As can be seen from the results in table 3, the reinforced hollow fiber membrane prepared by the method of the present invention has a high rupture pressure of the backwash membrane, and it can be seen that the bonding capability between the support layer and the separation layer is strong; and moreover, the membrane bioreactor also has higher water flux and higher breaking strength, and is suitable for membrane bioreactors.
The second class of inventions directed to the present invention provides the following examples:
example 2-1
1) A polyester fiber hollow braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in a5 wt% sodium hydroxide solution, treated at a temperature of 50 ℃ for 30min, then washed with deionized water, centrifuged at 3000rpm for 5min, and dried at a temperature of 80 ℃.
2) Preparing a Tris buffer solution with the pH value of 8.5, and uniformly mixing the Tris buffer solution with dopamine and polyethyleneimine to prepare a modified solution with the dopamine concentration of 4.0 wt% and the polyethyleneimine concentration of 10 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 60 ℃ for 30min, washing with deionized water, and centrifugally drying.
3) Soaking the treated braided tube in 2% CaCl2Mineralizing in the solution, and treating at room temperature (25 ℃) for 8 hours to grow nano particles (25.6 +/-3.6 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 60 ℃.
4) Under the protection of nitrogen, mixing polyvinylidene fluoride, additive, dopamine and solvent, stirring for 24 hours at 80 ℃, and defoaming in vacuum to obtain a casting solution, wherein the casting solution comprises the following components in percentage by weight:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105The weight percentage concentration is 10 percent;
the additive is polyvinylpyrrolidone, the number average molecular weight is 30000, and the weight percentage concentration is 8.0%;
the weight percentage concentration of dopamine is 6%;
the solvent is N, N-dimethylacetamide with a weight percentage concentration of 76%.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 6 hours for hydrophilization treatment, wherein the water temperature of the hot water is 80 ℃; then washed with deionized water and dried at 30 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Examples 2 to 2
1) A nylon fiber braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in a 7.5 wt% sodium hydroxide solution, treated at a temperature of 45 ℃ for 20min, then washed with deionized water, centrifuged at 5000rpm for 10min, and dried at a temperature of 80 ℃.
2) Preparing a Tris buffer solution with the pH value of 8.5, and uniformly mixing the Tris buffer solution with dopamine and diethylenetriamine to prepare a modified solution with the dopamine concentration of 8.0 wt% and the diethylenetriamine concentration of 15 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 70 ℃ for 20min, washing with deionized water, and centrifugally drying.
3) Soaking the braided tube in 3 wt% of AgNO3Mineralizing in the solution, and treating at room temperature (25 ℃) for 7 hours to grow nanoparticles (16.4 +/-2.6 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 70 ℃.
4) Under the protection of nitrogen, mixing polyvinylidene fluoride, additive, dopamine and solvent, stirring for 24 hours at 80 ℃, and defoaming in vacuum to obtain a casting solution, wherein the casting solution comprises the following components in percentage by weight:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105The weight percentage concentration is 15 percent;
the additive is polyvinylpyrrolidone (PVP), the number average molecular weight is 30000, and the weight percentage concentration is 5.5%;
the weight percentage concentration of dopamine is 3.5%;
the solvent is N, N-dimethylacetamide, and the weight percentage concentration is 86%.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 12 hours for hydrophilization treatment, wherein the water temperature of the hot water is 80 ℃; then washed with deionized water and dried at 30 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Examples 2 to 3
1) A nylon fiber hollow braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in a 10 wt% sodium hydroxide solution, treated at a temperature of 50 ℃ for 15min, then washed with deionized water, centrifuged at 8000rpm for 10min, and dried at a temperature of 80 ℃.
2) Preparing a Tris buffer solution with the pH value of 8.5, and uniformly mixing the Tris buffer solution with tannic acid and diethylenetriamine to prepare a modified solution with the tannic acid concentration of 5 wt% and the diethylenetriamine concentration of 10 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 60 ℃ for 40min, washing with deionized water, and centrifugally drying.
3) Soaking the treated braided tube in 5 wt% of FeCl2Mineralizing in the solution, and treating at room temperature (25 ℃) for 6 hours to grow nanoparticles (13.8 +/-2.2 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 60 ℃.
4) Under the protection of nitrogen, polyvinylidene fluoride, PEG, tannic acid and N, N-dimethylacetamide are mixed, stirred for 18 hours at 80 ℃, and subjected to vacuum defoaming to obtain a casting solution, wherein the casting solution comprises the following components in percentage by weight:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105The weight percentage concentration is 10 percent;
the number average molecular weight of PEG is 20000, and the weight percentage concentration is 4.5%;
the weight percentage concentration of the tannic acid is 4 percent;
the concentration of N, N-dimethylacetamide was 81.5% by weight.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 10 hours for hydrophilization treatment, wherein the water temperature of the hot water is 70 ℃; then washed with deionized water and dried at 40 ℃ for 18 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Examples 2 to 4
1) Immersing a polyester fiber hollow braided tube with the inner diameter of 1.0mm and the outer diameter of 1.7mm into 8 wt% of sodium hydroxide solution, treating for 15min at the temperature of 60 ℃, then cleaning with deionized water, centrifuging for 10min at the speed of 8000rpm, and drying at the temperature of 80 ℃.
2) Preparing PBS buffer solution, and uniformly mixing the PBS buffer solution with tannic acid and polyethyleneimine to prepare modified solution with tannic acid concentration of 5 wt% and polyethyleneimine concentration of 12 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 60 ℃ for 50min, washing with deionized water, and centrifugally drying.
3) Soaking the treated braided tube in 3.5 wt% of CaCl2Mineralizing in the solution, and treating at room temperature (25 ℃) for 6 hours to grow nano particles (18.6 +/-2.6 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 80 ℃.
4) Under the protection of nitrogen, polyvinylidene fluoride, PVP, tannic acid and N, N-dimethylacetamide are mixed, stirred for 18 hours at 80 ℃, and subjected to vacuum defoaming to obtain a casting solution, wherein the components and the concentration of the casting solution are as follows:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105At a concentration of 1% by weight2％；
Number average molecular weight of PVP 40000, concentration by weight 4%;
the weight percentage concentration of the tannic acid is 4 percent;
the concentration of N, N-dimethylacetamide was 80% by weight.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 8 hours for hydrophilic treatment, wherein the water temperature of the hot water is 70 ℃; then washed with deionized water and dried at 40 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Examples 2 to 5
1) A polyester fiber hollow braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in 8 wt% sodium hydroxide solution, treated at a temperature of 60 ℃ for 25min, then washed with deionized water, centrifuged at 5000rpm for 15min, and dried at a temperature of 80 ℃.
2) Preparing PBS buffer solution, and uniformly mixing the PBS buffer solution with catechol and PEG to prepare modified solution with catechol concentration of 10 wt% and PEG concentration of 15 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 70 ℃ for 50min, washing with deionized water, and centrifugally drying.
3) Soaking the treated braided tube in 3.5 wt% of CaCl2Mineralizing in the solution, and treating at room temperature (25 ℃) for 6 hours to grow nano particles (18.6 +/-2.6 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 80 ℃.
4) Under the protection of nitrogen, polyvinylidene fluoride, PEG, catechol and N, N-dimethylacetamide are mixed, stirred for 20 hours at 80 ℃, and vacuum defoamed to obtain a casting solution, wherein the components and the concentration of the casting solution are as follows:
number average of polyvinylidene fluorideThe quantum is 2.1X 105The weight percentage concentration is 10 percent;
the number average molecular weight of PEG is 20000, and the weight percentage concentration is 5%;
the weight percentage concentration of the catechol is 5 percent;
the concentration of N, N-dimethylacetamide was 80% by weight.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 10 hours for hydrophilization treatment, wherein the water temperature of the hot water is 70 ℃; then washed with deionized water and dried at 40 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Examples 2 to 6
1) A glass fiber hollow braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in a 10 wt% sodium hydroxide solution, treated at a temperature of 70 ℃ for 15min, then washed with deionized water, centrifuged at 5000rpm for 15min, and dried at a temperature of 80 ℃.
2) Preparing PBS buffer solution, and uniformly mixing the PBS buffer solution with catechol and chitosan to prepare modified solution with catechol concentration of 12 wt% and chitosan concentration of 12 wt%; and immersing the treated braided tube into the modified solution for primary coating, treating at 70 ℃ for 40min, washing with deionized water, and centrifugally drying.
3) Soaking the treated braided tube in 4.5 wt% of CuCl2Mineralizing in the solution, and treating at room temperature (25 ℃) for 8 hours to grow nanoparticles (17.2 +/-3.7 nm) on the surface of the braided tube; after being washed by deionized water, the mixture is dried at the temperature of 80 ℃.
4) Under the protection of nitrogen, polyvinylidene fluoride, PVP, catechol and N, N-dimethylacetamide are mixed, stirred for 18h at 80 ℃, and subjected to vacuum defoaming to obtain a casting solution, wherein the components and the concentration of the casting solution are as follows:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105The weight percentage concentration is 10 percent;
the number average molecular weight of PVP is 30000, and the weight percentage concentration is 6%;
the weight percentage concentration of the catechol is 5.5 percent;
the concentration of N, N-dimethylacetamide was 78.5% by weight.
5) And (3) coating the mineralized braided tube for the second time by using a membrane casting solution, and putting the coated braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
6) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 8 hours for hydrophilic treatment, wherein the water temperature of the hot water is 70 ℃; then washed with deionized water and dried at 40 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
Comparative example 2-1
1) A polyester fiber hollow braided tube with an inner diameter of 1.0mm and an outer diameter of 1.7mm is immersed in a5 wt% sodium hydroxide solution, treated at a temperature of 50 ℃ for 30min, then washed with deionized water, centrifuged at 3000rpm for 5min, and dried at a temperature of 80 ℃.
2) Under the protection of nitrogen, mixing polyvinylidene fluoride, additive, dopamine and solvent, stirring for 24 hours at 80 ℃, and defoaming in vacuum to obtain a casting solution, wherein the casting solution comprises the following components in percentage by weight:
the number average molecular weight of the polyvinylidene fluoride is 2.1X 105The weight percentage concentration is 10 percent;
the additive is polyvinylpyrrolidone, the number average molecular weight is 30000, and the weight percentage concentration is 8.0%;
the weight percentage concentration of dopamine is 6%;
the solvent is N, N-dimethylacetamide with a weight percentage concentration of 76%.
3) And (3) coating the braided tube with the membrane casting solution for the second time, and putting the braided tube into a coagulating bath at 40 ℃ to obtain the polyvinylidene fluoride hollow fiber composite microporous membrane, wherein the air temperature is 30 ℃, the relative humidity is 75%, and the air section distance is 10 cm.
The coagulating bath is water.
4) Soaking a polyvinylidene fluoride hollow fiber composite microporous membrane in hot water for 6 hours for hydrophilization treatment, wherein the water temperature of the hot water is 80 ℃; then washed with deionized water and dried at 30 ℃ for 24 h. Obtaining the braided tube reinforced polyvinylidene fluoride hollow fiber membrane with high bonding strength.
The hollow fiber membranes prepared in examples 2-1 to 2-6 and comparative example 2-1 were subjected to the following performance tests: the water flux is measured by adopting a dead-end external pressure filtering device, namely the cleaned wet membrane is pre-pressed for 30min at the present 0.15MPa, and then the external pressure water flux is measured at the pressure of 0.1 MPa; introducing BSA solution, measuring the retention rate, and measuring the flux recovery rate after washing with water; the interface bonding strength of the braided tube and the separating layer is measured by water recoil pressure; the water contact angle of the dry film is measured by a contact angle measuring instrument; the surface and cross-sectional morphology of the dry film was observed by a field emission scanning electron microscope.
The test results are shown in table 4.
Table 4: the structure and performance parameters of the PVDF hollow fiber membrane are as follows:
a third class of inventions directed to the present invention provides the following list:
example 3-1
1. A fiber bundle consisting of 200 polyester filaments of 0.5 denier and a fiber bundle replacing 4 silver nanowires were treated in a5 wt% sodium hydroxide solution at a temperature of 60 ℃ for 30min, followed by washing with deionized water and centrifugal-drying at a speed of 3000rpm for 30 min.
2. Polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, polyethylene glycol 400 and polyvinylpyrrolidone are stirred at a weight ratio of 15:70:10:5 at a temperature of 80 ℃ for 12 hours, and the casting solution is obtained after filtration and vacuum defoaming for 24 hours.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle at the advancing speed of 4m/min under the traction of the friction wheel. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the fiber braided tube in H at 60 DEG C2Phase separation occurs in the O coagulation bath to obtain the silver-containing hollow fiber membrane.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 12 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at 30 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Examples 3 to 2
1. A fiber bundle consisting of 150 glass fiber filaments of 0.7 denier and a fiber bundle replacing 6 silver nanowires were treated in a 10 wt% sodium hydroxide solution at a temperature of 50 ℃ for 25min, followed by washing with deionized water and centrifugal-drying at a speed of 5000rpm for 25 min.
2. Polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, glycerol and polyvinyl alcohol 30000 are stirred for 18 hours at the temperature of 80 ℃ according to the weight ratio of 15:70:10:5, and the casting solution is obtained after filtration and vacuum defoaming for 18 hours.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle at the advancing speed of 3m/min under the traction of the friction wheel. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the fiber braided tube in H at 60 DEG C2Phase separation occurs in the O coagulation bath to obtain the silver-containing hollow fiber membrane.
4. Soaking the obtained hollow fiber membrane in hot water at 70 ℃ for 12 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at 30 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Examples 3 to 3
1. A fiber bundle consisting of 200 nylon filaments of 0.5 denier and a fiber bundle replacing 8 silver nanowires were treated in a 10 wt% sodium hydroxide solution at a temperature of 50 ℃ for 30min, followed by washing with deionized water and centrifugal-drying at a speed of 5000rpm for 25 min.
2. Polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, polyethylene glycol 600 and polyvinyl alcohol 30000 are stirred at the temperature of 80 ℃ for 24 hours according to the weight ratio of 18:68:9:5, and the casting solution is obtained after filtration and vacuum defoaming for 18 hours.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle at the advancing speed of 3m/min under the traction of the friction wheel. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the fiber braided tube in N, N-dimethylacetamide/H at 60 DEG C2Phase separation occurs in the coagulation bath of O (weight ratio 1:4), and the silver-containing hollow fiber membrane is obtained.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 6 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at 25 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Examples 3 to 4
1. A fiber bundle consisting of 300 0.5 denier nylon filaments and a fiber bundle replacing 10 silver nanowires were treated in a 15 wt% sodium hydroxide solution at a temperature of 60 ℃ for 30min, followed by washing with deionized water and centrifugal-drying at a speed of 10000 rpm for 15 min.
2. Stirring polyvinylidene fluoride (molecular weight is 430000), N-dimethylacetamide, glycerol and polyethylene glycol 20000 according to the weight ratio of 20:64:10:6 at the temperature of 90 ℃ for 18 hours, filtering, and defoaming in vacuum for 18 hours to obtain the casting solution.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle under the traction of the friction wheel at the advancing speed of 1.5 m/min. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the fiber braided tube in N, N-dimethylacetamide/H at 60 DEG C2Phase separation occurs in the coagulation bath of O (weight ratio 1:6), and the silver-containing hollow fiber membrane is obtained.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 6 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at the temperature of 2 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Examples 3 to 5
1. A fiber bundle consisting of 300 polyester filaments of 0.5 denier and a fiber bundle replacing 8 silver nanowires were treated in a 15 wt% sodium hydroxide solution at a temperature of 60 ℃ for 15min, followed by washing with deionized water and centrifugal-drying at a speed of 10000 rpm for 15 min.
2. Stirring polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, glycerol and polyethylene glycol 20000 according to the weight ratio of 20:64:10:6 at the temperature of 90 ℃ for 18 hours, filtering, and defoaming in vacuum for 18 hours to obtain the casting solution.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; the fiber bundles on the weaving frame are crosswise woven along the core liquid pipe in a herringbone mode, so that the core liquid pipe is fixed and wovenIn the middle of the prepared fiber braided tube, the fiber braided tube containing silver wires enters the extrusion nozzle under the traction of a friction wheel and at the advancing speed of 1.5 m/min. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the extruded tubes into a water coagulation bath at the temperature of 60 ℃ for phase separation to obtain the silver-containing hollow fiber membrane.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 6 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at 25 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Examples 3 to 6
1. A fiber bundle consisting of 150 polyester filaments of 0.5 denier and a fiber bundle replacing 6 silver nanowires were treated in a 15 wt% sodium hydroxide solution at a temperature of 60 ℃ for 15min, followed by washing with deionized water and centrifugal-drying at a speed of 10000 rpm for 15 min.
2. Stirring polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, glycerol and polyethylene glycol 20000 according to the weight ratio of 15:71:8.5:5.5 at 80 ℃ for 24 hours, filtering, and defoaming in vacuum for 12 hours to obtain the casting solution.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle at the advancing speed of 3m/min under the traction of the friction wheel. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the extruded tubes into a water coagulation bath at the temperature of 60 ℃ for phase separation to obtain the silver-containing hollow fiber membrane.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 12 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; the hollow fiber membrane after hydrophilization treatment is dried for 24 hours at 25 ℃, and the hollow fiber ultrafiltration membrane with high mechanical strength and antibacterial performance is obtained after drying.
Comparative example 3-1
1. A fiber bundle consisting of 200 polyester filaments of 0.5 denier was immersed in a5 wt% sodium hydroxide solution, treated at a temperature of 60 c for 30min, then washed with deionized water, and centrifugally spun at a speed of 3000rpm for 30 min.
2. Polyvinylidene fluoride (molecular weight is 210000), N-dimethylacetamide, polyethylene glycol 400 and polyvinylpyrrolidone are stirred at a weight ratio of 15:70:10:5 at a temperature of 80 ℃ for 12 hours, and the casting solution is obtained after filtration and vacuum defoaming for 24 hours.
3. Extruding the casting solution into a die under the pressure of 0.2MPa, and extruding the casting solution at the temperature of 25 ℃ in H2O is used as core liquid and enters the die through a core liquid pipe under the pressure of 0.01 MPa; and carrying out herringbone cross weaving on the fiber bundles on the weaving frame along the core liquid pipe, so that the core liquid pipe is fixed in the middle of the woven fiber weaving pipe, and the fiber weaving pipe containing the silver wires enters the extrusion nozzle at the advancing speed of 4m/min under the traction of the friction wheel. Co-extruding the casting solution, the core solution and the fiber braided tube through an extrusion die, and immersing the fiber braided tube in H at 60 DEG C2Phase separation occurs in the O coagulation bath to obtain the hollow fiber membrane.
4. Soaking the obtained hollow fiber membrane in hot water at 60 ℃ for 12 hours, and carrying out hydrophilization and membrane pore shaping post-treatment; and drying the hollow fiber membrane subjected to hydrophilization treatment at 30 ℃ for 24 hours to obtain the hollow fiber ultrafiltration membrane.
The hollow fiber ultrafiltration membranes prepared in examples 3-1 to 3-6 and comparative example 3-1 were subjected to a performance test.
The test conditions were as follows: the water flux is measured by adopting a dead-end external pressure filtering device self-made by a laboratory, namely, the cleaned wet film is pre-pressed for 30min at the present 0.15MPa, and then the external pressure water flux is measured at the 0.1 MPa; introducing BSA (molecular weight of 6700) solution, measuring the retention rate, and measuring the flux recovery rate after washing with water; the interface bonding strength of the braided tube and the separating layer is measured by water recoil pressure; the water contact angle of the dry film was measured by a contact angle measuring instrument of OCA20(Dataphysics, germany); the surface and cross-sectional morphology of the dry film was observed by field emission scanning electron microscopy SIRION-100(FEI, Finland). The model bacteria selected in the antibacterial test are escherichia coli and staphylococcus aureus.
The water flux, rejection rate, backwashing membrane rupture pressure, contact angle, rupture strength, escherichia coli sterilization rate and staphylococcus aureus sterilization rate of the prepared fiber woven reinforced hollow fiber ultrafiltration membrane are shown in table 5.
TABLE 5
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (39)
1. A method of making a reinforced hollow fiber membrane, the method comprising:
(1) in an alkaline solution, activating the cellosilk to obtain activated cellosilk;
(2) impregnating the activated filaments with a modifying composition in a modifying solution to obtain modified filaments;
(3) in a metal salt solution, carrying out contact reaction on the modified fiber yarn and a metal salt to obtain a fiber yarn with nanoparticles on the surface;
(4) mixing the fiber yarn with the surface provided with the nano particles with a membrane preparation solution, and weaving the obtained mixture to obtain a hollow fiber woven tube;
(5) forming the hollow fiber braided tube into an enhanced hollow fiber membrane;
wherein the modifying composition comprises a first polyphenolic compound and a crosslinking molecule; the membrane preparation liquid contains a membrane forming polymer, a pore-forming agent and a second polyphenol compound;
wherein the first and second polyphenolic compounds are each independently selected from compounds containing at least 2 phenolic hydroxyl groups, and the crosslinking molecule is one or more of polyamine compounds, crosslinked polyolefin amides, polyalcohols, polyolefin pyrrolidones, polysaccharides, and polyolefin imines.
2. The method of claim 1, wherein the fiber filaments are one or more of polyester fibers, polyamide fibers, polyolefin fibers, polyamine fibers, polyurethane fibers, polyvinylidene fluoride fibers, polysulfone fibers, and glass fibers.
3. The method of claim 2, wherein the fiber filaments are polyester fibers and/or polyamide fibers.
4. The method of claim 2, wherein the fiber filament has a denier of 10-500D.
5. The method of claim 4, wherein the fiber filament has a denier of 50-300D.
6. The process according to any one of claims 1 to 5, wherein in step (1), the basic compound in the basic solution is one or more of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate and ammonia.
7. The method of claim 6, wherein in step (1), the basic compound in the basic solution is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, and ammonia.
8. The method according to claim 6, wherein in the step (1), the content of the basic compound in the basic solution is 5 to 20% by weight.
9. The method of any one of claims 1-5 and 7-8, wherein the compound having at least 2 phenolic hydroxyl groups is one or more of a compound represented by formula (1), tannic acid, a compound represented by formula (2), and green tea extract;
wherein, the formula (1)
Formula (2)
R1-R6At least 2 of which are OH, the remainder being each independently of the other H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6; r7-R10And R13-R17At least 2 of which are OH, the remainder of R7-R10And R13-R17And R11-R12Each independently of the others being H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C6, alkoxy of C1-C6 or alkylthio of C1-C6; each L is independently selected from C0-C6 alkylene; each M is independently H and an alkali metal element.
10. The method of claim 9, wherein R1-R6At least 2 of which are OH, the remainder being each independently of the other H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C4, alkoxy of C1-C4 or alkylthio of C1-C4; r7-R10And R13-R17At least 2 of which are OH, the remainder of R7-R10And R13-R17And R11-R12Each independently of the others being H, halogen, -L-COOM, -L-SO3M、-L-NH2L-OH, alkyl of C1-C4, alkoxy of C1-C4 or alkylthio of C1-C4; each L is independently selected from C0-C4 alkylene; each M is independently H, Na and K.
11. The method of claim 10, wherein R1-R6At least 2 of which are OH, the remainder being each independently of the other H, F, Cl, Br, -COOM, -CH2-COOM、-CH2CH2-COOM、-CH2CH2CH2-COOM、-CH(CH3)CH2-COOM、-CH2CH(CH3)-COOM、-CH2CH2CH2CH2-COOM、-SO3M、-CH2-SO3M、-CH2CH2-SO3M、-CH2CH2CH2-SO3M、-CH(CH3)CH2-SO3M、-CH2CH(CH3)-SO3M、-CH2CH2CH2CH2-SO3M、-NH2、-CH2-NH2、-CH2CH2-NH2、-CH2CH2CH2-NH2、-CH(CH3)CH2-NH2、-CH2CH(CH3)-NH2、-CH2CH2CH2CH2-NH2、-OH、-CH2-OH、-CH2CH2-OH、-CH2CH2CH2-OH、-CH(CH3)CH2-OH、-CH2CH(CH3)-OH、-CH2CH2CH2CH2-OH, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio.
12. The method of claim 9, wherein,
the compound represented by the formula (1) is selected from compounds represented by the following formulae:
the compound represented by the formula (2) is selected from compounds represented by the following formulae:
13. the method according to any one of claims 1 to 5, 7 to 8 and 10 to 12, wherein, in the crosslinking molecule,
the polyamine compound is
And NH2-R-NH2N is an integer of 1 to 8, R is a C1-C8 alkylene group; the cross-linked polyolefin amide is one or more of cross-linked polyacrylamide, cross-linked polymethacrylamide and polyacrylamide;
the polyhydric alcohol is one or more of polyethylene glycol, polypropylene glycol, polyglycerol and polyvinyl alcohol;
the polyolefin pyrrolidone is polyvinylpyrrolidone;
the polysaccharide is one or more of chitosan, starch, modified starch, cellulose and modified cellulose;
the polyolefin imine is polyethylene imine and/or polypropylene imine.
14. The method of any of claims 1-5, 7-8, and 10-12, wherein the weight ratio of the first polyphenolic compound to the crosslinking molecule is 100: 80-300.
15. The method of claim 14, wherein the weight ratio of the first polyphenolic compound to the crosslinking molecule is 100: 100-250.
16. The method of claim 14, wherein the modifying solution comprises 5-30 wt% of the modifying composition.
17. The method of claim 16, wherein the modifying solution comprises from 8 to 26 wt% of the modifying composition.
18. The method of claim 17, wherein the modifying solution comprises 10-25 wt% of the modifying composition.
19. The method of claim 14, wherein the solvent of the modifying solution is provided by a buffer solution, the buffer solution being a buffer solution having a pH of 5-11.
20. The method of claim 19, wherein the buffer solution is Tris buffer solution, PBS buffer solution, or acetic acid-sodium acetate buffer solution.
21. The method of any of claims 1-5, 7-8, 10-12, and 15-20, wherein the metal salt solution is one or more of a calcium salt, an iron salt, a cobalt salt, a nickel salt, a copper salt, a zinc salt, a silver salt, a gold salt, a platinum salt, and a magnesium salt.
22. The method of claim 21, wherein in the metal salt solution, the metal salt is CaCl2、Ca(NO3)2、FeCl3、Fe2(SO4)3、Fe(NO3)3、CoCl3、Co(NO3)3、CuCl2、CuSO4、ZnCl2、Zn(NO3)2、AgNO3、HAuCl4、H2PtCl6、PtN2O6And MgCl2One or more of (a).
23. The method of claim 22, wherein the metal salt solution has a concentration of 0.5-8 wt%.
24. The method of claim 23, wherein the metal salt solution has a concentration of 2-5 wt%.
25. A method according to any one of claims 1-5, 7-8, 10-12, 15-20, and 22-24, wherein the weight ratio of the film-forming polymer, porogen, and second polyphenolic compound in the film-forming liquid is 100: 30-100: 10-120.
26. The method of claim 25, wherein, in the membrane-forming solution, the weight ratio of the membrane-forming polymer, porogen, and second polyphenolic compound is 100: 35-90: 20-100.
27. The method of claim 26, wherein, in the membrane-forming solution, the weight ratio of the membrane-forming polymer, porogen, and second polyphenolic compound is 100: 36-80: 30-80.
28. The method of claim 25, wherein the film forming polymer is one or more of polyvinylidene fluoride, polyethersulfone, and polyacrylonitrile.
29. The method of claim 25, wherein the porogen is one or more of polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, polyvinyl alcohol, polymethyl methacrylate, and polyvinyl acetate.
30. The method as claimed in claim 29, wherein the porogen is one or more of polyvinylpyrrolidone with number average molecular weight of 3,000-50,000, polyethylene glycol with number average molecular weight of 1,000-10,000, polyethylene oxide with number average molecular weight of 10,000-60,000, polyvinyl alcohol with number average molecular weight of 8,000-50,000, and polymethyl methacrylate with molecular weight of 11,000-85,000.
31. A method according to claim 25, wherein the solvent in the dope solution is one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, triethyl phosphate, sulfolane, dimethyl sulfone and benzophenone, and the weight ratio of the film forming polymer to the solvent is 1: 5-10.
32. A method according to claim 31, wherein the weight ratio of film-forming polymer to solvent in the film-forming solution is 1: 5-8.5.
33. The method of any one of claims 1-5, 7-8, 10-12, 15-20, 22-24, and 26-32,
in the step (1), the activating treatment conditions include: the temperature is 30-80 deg.C, and the time is 10-50 min;
in the step (2), the impregnation conditions include: the temperature is 50-80 deg.C, and the time is 10-80 min;
in the step (3), the contact reaction conditions include: the temperature is 20-50 ℃ and the time is 4-10 h.
34. The method of any of claims 1-5, 7-8, 10-12, 15-20, 22-24, and 26-32, wherein the method further comprises: and (4) after the step (4), performing solidification and water washing treatment on the obtained hollow fiber braided tube, wherein the temperature of the solidification and water washing treatment is 30-80 ℃.
35. The method according to any one of claims 1 to 5, 7 to 8, 10 to 12, 15 to 20, 22 to 24 and 26 to 32, wherein the step (5) further comprises subjecting the resulting reinforced hollow fiber membrane to a hydrophilization treatment under conditions comprising: soaking in 60-80 deg.C hot water for 4-12 hr.
36. The method of claim 13, wherein the polyamine-based compound is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, NH2-CH2-NH2、NH2-CH2CH2-NH2、NH2-CH2CH2CH2-NH2、NH2-CH(CH3)CH2-NH2、NH2-CH2(CH2)2CH2-NH2、NH2-CH2(CH2)3CH2-NH2And NH2-CH2(CH2)4CH2-NH2One or more of (a).
37. A reinforced hollow fiber membrane made by the method of any one of claims 1-36.
38. A membrane bioreactor comprising the enhanced hollow fiber membrane of claim 37.
39. Use of the reinforced hollow fiber membrane of claim 37 in membrane separation.
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| CN201710683431.6A Active CN108273392B (en) | 2017-01-05 | 2017-08-11 | Method for modifying hollow braided tube and method for producing hollow fiber membrane |
| CN201710683044.2A Active CN108273399B (en) | 2017-01-05 | 2017-08-11 | Enhanced hollow fiber membrane and preparation method and application thereof |
| CN202311534013.2A Pending CN117619161A (en) | 2017-01-05 | 2017-08-11 | Antibacterial hollow fiber membrane and preparation method and application thereof |
| CN201710683405.3A Pending CN108273386A (en) | 2017-01-05 | 2017-08-11 | A kind of preparation method of hollow-fibre membrane |
| CN201710683102.1A Pending CN108273398A (en) | 2017-01-05 | 2017-08-11 | Antimicrobial form hollow-fibre membrane and its preparation method and application |
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| CN117619161A (en) | 2024-03-01 |
| CN108273398A (en) | 2018-07-13 |
| CN117379992A (en) | 2024-01-12 |
| CN108273399A (en) | 2018-07-13 |
| CN108273386A (en) | 2018-07-13 |
| CN108273392A (en) | 2018-07-13 |
| CN108273392B (en) | 2021-07-30 |
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