CN108579466A - The preparation method of high-throughput anti-pollution composite filter membrane - Google Patents
The preparation method of high-throughput anti-pollution composite filter membrane Download PDFInfo
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- CN108579466A CN108579466A CN201810242823.3A CN201810242823A CN108579466A CN 108579466 A CN108579466 A CN 108579466A CN 201810242823 A CN201810242823 A CN 201810242823A CN 108579466 A CN108579466 A CN 108579466A
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- composite filter
- filter membrane
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- pollution
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- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002121 nanofiber Substances 0.000 claims abstract description 41
- 239000000975 dye Substances 0.000 claims abstract description 33
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 210000002469 Basement Membrane Anatomy 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 6
- 230000001054 cortical Effects 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229920001661 Chitosan Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 Kynoar Polymers 0.000 claims description 8
- 229940005550 Sodium alginate Drugs 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M Sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- 229920000447 polyanionic polymer Polymers 0.000 claims description 6
- MSXHSNHNTORCAW-UHFFFAOYSA-M sodium 3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].OC1OC(C([O-])=O)C(O)C(O)C1O MSXHSNHNTORCAW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- KDXHLJMVLXJXCW-UHFFFAOYSA-J Alcian blue stain Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cu+2].[N-]1C(N=C2C3=CC(CSC(N(C)C)=[N+](C)C)=CC=C3C(N=C3C4=CC=C(CSC(N(C)C)=[N+](C)C)C=C4C(=N4)[N-]3)=N2)=C(C=C(CSC(N(C)C)=[N+](C)C)C=C2)C2=C1N=C1C2=CC(CSC(N(C)C)=[N+](C)C)=CC=C2C4=N1 KDXHLJMVLXJXCW-UHFFFAOYSA-J 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229920002496 poly(ether sulfone) Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 240000001592 Amaranthus caudatus Species 0.000 claims description 3
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L Congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 3
- NKLPQNGYXWVELD-UHFFFAOYSA-M Coomassie Brilliant Blue Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=C1 NKLPQNGYXWVELD-UHFFFAOYSA-M 0.000 claims description 3
- FDZZZRQASAIRJF-UHFFFAOYSA-M Malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 3
- MCPLVIGCWWTHFH-UHFFFAOYSA-L Methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 3
- 229940012189 Methyl orange Drugs 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M Methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940042115 Methylene blue Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229940043267 Rhodamine B Drugs 0.000 claims description 3
- 235000012735 amaranth Nutrition 0.000 claims description 3
- 239000004178 amaranth Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N meta-phosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 229920002492 poly(sulfones) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N Rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- TXVRKNUZLYFDTJ-DDVLFWKVSA-L disodium;(5E)-6-oxo-5-[(4-sulfonatophenyl)hydrazinylidene]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1N\N=C\1C2=CC=C(S([O-])(=O)=O)C=C2C=CC/1=O TXVRKNUZLYFDTJ-DDVLFWKVSA-L 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims 1
- 210000004379 Membranes Anatomy 0.000 abstract description 21
- 230000003373 anti-fouling Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001105 regulatory Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 230000004907 flux Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000520 microinjection Methods 0.000 description 3
- 230000000051 modifying Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000003068 static Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LDCKXVAPQFUIOI-ZFLDVXHKSA-H hexasodium;(3E)-4-oxo-7-[[(6E)-5-oxo-7-sulfonato-6-[[2-sulfonato-4-[(4-sulfonatophenyl)diazenyl]phenyl]hydrazinylidene]naphthalen-2-yl]carbamoylamino]-3-[[2-sulfonato-4-[(4-sulfonatophenyl)diazenyl]phenyl]hydrazinylidene]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].C=1C=C2C(=O)\C(=N/NC=3C(=CC(=CC=3)N=NC=3C=CC(=CC=3)S([O-])(=O)=O)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC2=CC=1NC(=O)NC(C=C1C=C2S([O-])(=O)=O)=CC=C1C(=O)\C2=N/NC(C(=C1)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 LDCKXVAPQFUIOI-ZFLDVXHKSA-H 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N N-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003505 mutagenic Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
Abstract
The invention discloses a kind of preparation methods of high-throughput anti-pollution composite filter membrane, and polymer material is dissolved in solvent and is configured to electrostatic spinning solution, then carries out electrostatic spinning, obtains nanofiber, cold pressing treatment is then carried out and obtains nanofiber basement membrane；Polyelectrolyte is dissolved in solvent and obtains coating solution, is then coated on nanofiber basement membrane, places at room temperature, it dries in the shade, have the nanofiber group compound film of complete cortex to surface, be then immersed in in the dyestuff of superficial cortical layers oppositely charged to get high-throughput anti-pollution composite filter membrane.Component part of the present invention using dyestuff " pollution layer " as composite membrane function barrier layer; the composite filter membrane constructed can be made to be provided simultaneously with good antifouling effect and high osmosis; and preparation method is simple, environmental-friendly; it can realize and finely regulating is carried out to the surface apertures of composite membrane function barrier layer, be suitable for the production of scale.
Description
Technical field
The present invention relates to the preparations of composite membrane for separation, and in particular to a kind of preparation method of high throughput anti-pollution composite filter membrane.
Background technology
A large amount of dye wastewater with high concentration of dyeing discharge are one of main sources of industrial wastewater.Most dye properties
Extremely stable, structure is complex, not degradable, has carcinogenic, teratogenesis, mutagenic effect.High-activity treatment of textile dye waste is not only
The life security of the mankind and other biological can be protected, the dyestuff for the water and recycling being cleaned can also be recycled, to alleviate
The serious water shortage crisis in China, walks sustainable development road.But dyeing waste water has, and coloration is big, organic pollution content is high,
The features such as complicated components, change of water quality and bio-toxicity be big and bio-refractory, makes the difficulty of processing waste water from dyestuff increase.Film
Isolation technics is due to the particular advantages such as high, easy to operate with separative efficiency, low energy consumption, chemical addition agent dosage is few and as useless
The research hotspot of water treatment field, it can be optionally sequestered substance in molecule rank, be particularly suitable for useless to printing and dyeing
Recycling of water resource processing.Composite filter membrane is a kind of novel separation film developed in recent years, has that permeance property is good, resistance to pressure is strong, choosing
Select the advantages such as separating property is good.It is combined by the porous basement membrane of very thin and dense barrier layer and high porosity, Ke Yitong
It crosses and chooses different filmogens and filming technology prepares basement membrane and barrier layer respectively, to reach the optimization of film overall performance.
The property of function barrier layer directly determines compound membrane filtration characteristic, and porous basement membrane plays support composite membrane barrier in filter process
Layer and the effect for maintaining its form.Percent of decolourization height, organic removal rate are high when handling waste water from dyestuff using composite filter membrane, but often
There are permeation fluxes it is low, fouling membrane is serious the shortcomings of, greatly reduce membrane separation efficiency, shorten the service life of film, increase
Operating cost constrains the extensive use of composite membrane.
It is the main reason for causing fouling membrane that separated object matter, which is readily adsorbed in film surface and fenestra,.Anti-pollution is developed at present
The film of dye is the fundamental way for solving membrane pollution problem and one of the key scientific problems in UF membrane field, main target
It is the adsorption for inhibiting membrane material.The common method for preparing composite hydrophilic membrane at present has physical blending process, surface cladding process, table
Face graft modification method, bionical Method for bonding etc., but these methods are difficult to make composite membrane while having good antifouling property and Thief zone
Property.
Invention content
Goal of the invention：The present invention provides a kind of preparation method of high-throughput anti-pollution composite filter membrane, and solution prepares composite membrane
Method cannot make composite membrane while have the problem of good antifouling effect and high osmosis.
Technical solution：A kind of preparation method of high-throughput anti-pollution composite filter membrane of the present invention, includes the following steps：
(1) polymer material is dissolved in the electrostatic spinning solution for being configured to that mass fraction is 4~40wt% in solvent, then
Electrostatic spinning is carried out, nanofiber is obtained, then carries out cold pressing treatment up to nanofiber basement membrane；
(2) polyelectrolyte is dissolved in solvent, is configured to the homogeneous solution that total mass fraction is 0.1-10wt%, is applied
Cover solution；
(3) solution that step (2) obtains is coated on the nanofiber basement membrane that step (1) obtains, is placed at room temperature
6-72h, dry in the shade the nanofiber group compound film for having complete cortex to get surface；
(4) the nanofiber group compound film of complete cortex is immersed in and superficial cortical layers oppositely charged on obtained surface
In the dyestuff of a concentration of 10-1000mg/L, 10-360min is impregnated to get high-throughput anti-pollution composite filter membrane.
Wherein, the polymer material in the step (1) is polyacrylonitrile, polyether sulfone, Kynoar, polysulfones, polyphenyl
At least one of ethylene, polyvinyl alcohol and polyethylene glycol oxide.
Polyelectrolyte in the step (2) is polycation electrolyte or polyanion electrolyte.
The polycation electrolyte is chitosan, polyethyleneimine, polyvinylamine, polyvinylpyrrolidone, polyethylene
At least one of pyridine and polydimethyl diallyl ammonium chloride.
The polyanion electrolyte be Sodium Polyacrylate, polymethylacrylic acid, sodium alginate, sodium carboxymethylcellulose,
At least one of poly-metaphosphoric acid, polystyrolsulfon acid and polyvinyl sulfonic acid.
The solvent of the step (1) and (2) is n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, deionization
At least one of the aqueous acetic acid of water and 0.1%~90wt%.
The technological parameter of electrostatic spinning in the step (1) is 8~50kV of voltage, 0.2~3mm of spout aperture, solution
5~100 μ l/min of flow velocity, spinning environment temperature are 10~60 DEG C, and the relative humidity of spinning environment is 30~60%.
Dyestuff is anionic dye or the dye of positive ion in the step (4).
The anionic dye is active black, directly red, Coomassie brilliant blue, methyl orange, fast green, amaranth, Congo red, day
Fall at least one of yellow, methyl blue and magenta.
The dye of positive ion is at least one in alcian blue, rhodamine B, alkaline red, cationic yellow and methylene blue
Kind.
Advantageous effect：The present invention first prepares the nanofiber group compound film with ultra-thin, loose, complete barrier layer, then soaks
Bubble self assembly is carried out in dyestuff so that barrier layer surface apertures become smaller, can effective filter dyes, with dyestuff " pollution layer " make
For the component part of composite membrane function barrier layer, change fouling membrane disadvantage is advantage, avoids the use of traditional chemical crosslinking agent, is saved
Can be environmentally friendly, while the composite membrane prepared has good antifouling effect and high osmosis, and preparation method is simple, environment
Close friend can realize and carry out finely regulating to the surface apertures of composite film surface function barrier layer, be suitable for the production of scale.
Description of the drawings
Fig. 1 is the cross-section photographs of anti-pollution composite membrane prepared by embodiment 1；
Fig. 2 is permeation flux of the anti-pollution composite membrane of the preparation of embodiment 1 to direct red 80 solution in the case where filtering for a long time for 24 hours
With rejection effect figure；
Fig. 3 is the curve graph that chitosan coating liquid concentration influences composite filter membrane strainability in embodiment 1.
Specific implementation mode
With reference to embodiment, invention is further explained.
Embodiment 1
A kind of high throughput anti-pollution chitosan/polyacrylonitrile nanofiber base composite filter membrane preparation method includes：1, by poly- third
Alkene nitrile 8g is dissolved in n,N-Dimethylformamide (DMF) solvent 92g, obtains transparent uniform electrostatic spinning solution；Polypropylene
The manufacturer of nitrile is Kingsoft petrochemical industry, and molal weight score is Mw=120000g/mol；2, mass fraction is dissolved the chitosan in
To be configured to the coating solution that mass fraction is 1.2% in 1% aqueous acetic acid；3, by the electrostatic spinning solution in step 1
It is added in syringe, is controlled and squeezed out by micro-injection pump, the spout of syringe connects high-voltage positive electrode, and Static Spinning state modulator is in electricity
22kv, spout aperture 0.7mm, 18 μ l/min of solution flow rate, 35 DEG C of environment temperature, relative air humidity 35% is pressed to carry out quiet
Electrospun obtains nanofiber, and the average diameter for obtaining nanofiber is 150nm, and deposition thickness is 80 μm, then at 8MPa
30s is cold-pressed up to nanofiber basement membrane；4, the chitosan solution in step 2 is coated on nanofiber basement membrane in step 3,
Then the nanofiber group compound film for drying in the shade have complete cortex to get surface for 24 hours is placed at room temperature.5, it will be made in step 4
Nanofiber group compound film in 100mg/L 30min directly to be impregnated in red 80 dyestuff multiple to get high-throughput anti-pollution nano fiber base
Close filter membrane.
Chitosan/polyacrylonitrile nanofiber base composite filter membrane intersects the anionic dye directly red 80 of 100ppm
Cross-flow filtration is tested：The mass fraction of chitosan solution is followed successively by 0.8wt%, 1.0wt%, 1.2wt%, when 1.4wt%, has served as
Chitosan nano fiber base composite filter membrane prepared when operating pressure is 0.1MPa is filtered to direct red 80 corresponding permeation flux
Respectively 401.7,167.8,139.1,122.8L/m2H, rejection are respectively 61.7%, 94.9%, 99.6%, 99.8%.It can
To find, when the mass fraction of chitosan solution is 1.2wt%, the filtering of the nanofiber-based composite filter membranes of CS/PAN of preparation
Performance is best.And it is dropped by less than 7% by test permeation flux for 24 hours, shows good antifouling property.
Embodiment 2
A kind of high throughput anti-pollution sodium alginate/nanofiber-based composite filter membrane preparation method of polyether sulfone includes：1, by polyethers
Sulfone 26g is dissolved in n,N-Dimethylformamide (DMF) solvent 74g, obtains transparent uniform electrostatic spinning solution；Polyether sulfone is
The production of Su Wei (Shanghai) Co., Ltd., molal weight score is Mw=64000g/mol；2, sodium alginate is dissolved in quality
Score is the coating solution for being configured to mass fraction in deionized water and being 2%；3, the electrostatic spinning solution in step 1 is added to
It in syringe, is controlled and is squeezed out by micro-injection pump, the spout of syringe connects high-voltage positive electrode, and Static Spinning state modulator is in voltage
24kv, spout aperture 0.7mm, 16 μ l/min of solution flow rate, 30 DEG C of environment temperature, relative air humidity 30% carry out electrostatic
Spinning obtains nanofiber, and the average diameter for obtaining nanofiber is 500nm, and deposition thickness is 80 μm, then cold at 8MPa
Press 30s up to nanofiber basement membrane；4, the sodium alginate soln in step 2 is coated on nanofiber basement membrane in step 3,
Then the nanofiber group compound film for drying in the shade have complete cortex to get surface for 24 hours is placed at room temperature.5, it will be made in step 4
Nanofiber group compound film impregnated in the 100mg/L alcian blue dyes of positive ion 30min to get high-throughput anti-pollution nano fibre
Wiki composite filter membrane.
The nanofiber-based composite filter membrane of sodium alginate/polyether sulfone is at 0.2 mpa to the alcian blue dyestuff of 100mg/L
Rejection is 99.9%, permeation flux 105L/m2H, and it is dropped by less than 10% by test permeation flux for 24 hours, it shows
Good antifouling property.
Embodiment 3
A kind of high throughput anti-pollution Sodium Polyacrylate/polyvinylidene fluoride nanometer fiber base composite filter membrane preparation method includes：1、
It is 7 that Kynoar 16g, which is dissolved in 84g n,N-Dimethylformamide (DMF)/acetone quality ratio,：3 in the mixed solvent, is obtained
Obtain transparent uniform electrostatic spinning solution；The supplier of Kynoar is Aldrich, and molal weight score is Mw=
370000g/mol；2, Sodium Polyacrylate is dissolved in and is configured to the coating solution that mass fraction is 2.5% in deionized water；3、
Electrostatic spinning solution in step 1 is added in syringe, is controlled and is squeezed out by micro-injection pump, the spout of syringe connects high pressure
Anode, for Static Spinning state modulator in voltage 18kv, spout aperture 0.3mm, 40 μ l/min of solution flow rate, 50 DEG C of environment temperature is empty
Gas relative humidity is 30%, carries out electrostatic spinning, obtains nanofiber, and the average diameter for obtaining nanofiber is 200nm, deposition
Thickness is 100 μm, and 30s is then cold-pressed at 10MPa up to nanofiber basement membrane；4, by the sodium polyacrylate solution in step 2
On the nanofiber basement membrane of coating in step 3, then place at room temperature for 24 hours, dry in the shade has receiving for complete cortex to get surface
Rice fiber group compound film.5, nanofiber group compound film obtained in step 4 is immersed in 100mg/L rhodamine B cations dye
30min is impregnated in material to get high-throughput anti-pollution nano fiber base composite filter membrane.
Sodium Polyacrylate/polyvinylidene fluoride nanometer fiber base composite filter membrane is at 0.2 mpa to the alcian blue of 100mg/L
The rejection of dyestuff is 98.8%, permeation flux 89.7L/m2H, and it is dropped by less than 10% by test permeation flux for 24 hours,
Show good antifouling property.
Except the raw material that above example uses, the polymer material in step 1 can also be polysulfones, polystyrene, poly- second
At least one of enol and polyethylene glycol oxide.Polyelectrolyte can be polycation electrolyte or polyanion electricity in step 2
Xie Zhi, polycation electrolyte can be polyethyleneimine, polyvinylamine, polyvinylpyrrolidone, polyvinyl pyridine and poly- two
At least one of methyl diallyl ammonium chloride, polyanion electrolyte can also be polymethylacrylic acid, carboxymethyl cellulose
At least one of plain sodium, poly-metaphosphoric acid, polystyrolsulfon acid and polyvinyl sulfonic acid.Dyestuff is anionic dye or cation
Dyestuff.Anionic dye be active black, Coomassie brilliant blue, methyl orange, fast green, amaranth, Congo red, sunset yellow, methyl blue and
At least one of magenta.The dye of positive ion is alkaline at least one of red, cationic yellow and methylene blue.
Claims (10)
1. a kind of preparation method of high throughput anti-pollution composite filter membrane, which is characterized in that include the following steps：
(1) polymer material is dissolved in the electrostatic spinning solution for being configured to mass fraction in solvent as 4~40wt%, then is carried out
Electrostatic spinning obtains nanofiber, then carries out cold pressing treatment up to nanofiber basement membrane；
(2) polyelectrolyte is dissolved in solvent, is configured to the homogeneous solution that total mass fraction is 0.1-10wt%, obtains coating molten
Liquid；
(3) solution that step (2) obtains is coated on the nanofiber basement membrane that step (1) obtains, places 6- at room temperature
72h, dry in the shade the nanofiber group compound film for having complete cortex to get surface；
(4) the nanofiber group compound film of complete cortex is immersed in and superficial cortical layers oppositely charged concentration on obtained surface
In the dyestuff of 10-1000mg/L, to impregnate 10-360min to get high-throughput anti-pollution composite filter membrane.
2. the preparation method of high throughput anti-pollution composite filter membrane according to claim 1, which is characterized in that the step (1)
In polymer material be polyacrylonitrile, polyether sulfone, Kynoar, polysulfones, polystyrene, polyvinyl alcohol and polyethylene glycol oxide
At least one of.
3. the preparation method of high throughput anti-pollution composite filter membrane according to claim 1, which is characterized in that the step (2)
In polyelectrolyte be polycation electrolyte or polyanion electrolyte.
4. the preparation method of high throughput anti-pollution composite filter membrane according to claim 3, which is characterized in that the polycation
Electrolyte is chitosan, polyethyleneimine, polyvinylamine, two allyl of polyvinylpyrrolidone, polyvinyl pyridine and poly dimethyl
At least one of ammonium chloride.
5. the preparation method of high throughput anti-pollution composite filter membrane according to claim 3, which is characterized in that the polyanion
Electrolyte is Sodium Polyacrylate, polymethylacrylic acid, sodium alginate, sodium carboxymethylcellulose, poly-metaphosphoric acid, polystyrolsulfon acid
At least one of with polyvinyl sulfonic acid.
6. the preparation method of high throughput anti-pollution composite filter membrane according to claim 1, which is characterized in that the step (1)
(2) solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, acetone, deionized water and 0.1%~90wt%'s
At least one of aqueous acetic acid.
7. the preparation method of high throughput anti-pollution composite filter membrane according to claim 1, which is characterized in that the step (1)
In electrostatic spinning technological parameter be 8~50kV of voltage, 0.2~3mm of spout aperture, 5~100 μ l/min of solution flow rate, spin
Silk environment temperature is 10~60 DEG C, and the relative humidity of spinning environment is 30~60%.
8. the preparation method of high throughput anti-pollution composite filter membrane according to claim 1, which is characterized in that the step (4)
Middle dyestuff is anionic dye or the dye of positive ion.
9. the preparation method of high throughput anti-pollution composite filter membrane according to claim 8, which is characterized in that the anion dye
Material is in active black, direct red, Coomassie brilliant blue, methyl orange, fast green, amaranth, Congo red, sunset yellow, methyl blue and magenta
At least one.
10. the preparation method of high throughput anti-pollution composite filter membrane according to claim 8, which is characterized in that the cation
Dyestuff is alcian blue, rhodamine B, alkaline at least one of red, cationic yellow and methylene blue.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110270136A (en) * | 2019-07-16 | 2019-09-24 | 黑龙江东方学院 | A kind of preparation method and application of hydrophilic functions film |
| CN110559865A (en) * | 2019-08-14 | 2019-12-13 | 浙江理工大学 | Method for repairing ultrafiltration membrane pollution or membrane damage |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19841404C2 (en) * | 1998-09-10 | 2000-12-21 | Basf Coatings Ag | Solids based on mesomorphic polyelectrolyte complexes, process for their preparation and their use |
| CN1578702A (en) * | 2001-08-28 | 2005-02-09 | 珀雷克斯公司 | Multi-layer coated porous materials and methods of making the same |
| CN101274222A (en) * | 2007-12-12 | 2008-10-01 | 浙江大学 | Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane |
| CN101354374A (en) * | 2008-07-07 | 2009-01-28 | 浙江大学 | Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer |
| CN103551049A (en) * | 2013-10-23 | 2014-02-05 | 北京工业大学 | Layer by layer self-assembly compound nanofiltration membrane based on natural cellulose polyelectrolyte and preparation method |
| CN104353369A (en) * | 2014-10-22 | 2015-02-18 | 东华大学 | Method for preparing nanofiber-based composite filter membrane by hot-pressing incipient fusion method |
| CN105536577A (en) * | 2016-01-25 | 2016-05-04 | 东华大学 | Novel method for preparing chitosan nanofiber-base composite filter membrane |
| CN106310960A (en) * | 2016-09-28 | 2017-01-11 | 东莞市联洲知识产权运营管理有限公司 | Electro-spinning-based self-assembled polylysine nano-filtration membrane and preparation method thereof |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN106362604A (en) * | 2016-11-24 | 2017-02-01 | 陕西聚洁瀚化工有限公司 | Method for preparing polyelectrolyte coating and nanofiber membrane composite filter membrane |
-
2018
- 2018-03-22 CN CN201810242823.3A patent/CN108579466A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19841404C2 (en) * | 1998-09-10 | 2000-12-21 | Basf Coatings Ag | Solids based on mesomorphic polyelectrolyte complexes, process for their preparation and their use |
| CN1578702A (en) * | 2001-08-28 | 2005-02-09 | 珀雷克斯公司 | Multi-layer coated porous materials and methods of making the same |
| CN101274222A (en) * | 2007-12-12 | 2008-10-01 | 浙江大学 | Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane |
| CN101354374A (en) * | 2008-07-07 | 2009-01-28 | 浙江大学 | Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer |
| CN103551049A (en) * | 2013-10-23 | 2014-02-05 | 北京工业大学 | Layer by layer self-assembly compound nanofiltration membrane based on natural cellulose polyelectrolyte and preparation method |
| CN104353369A (en) * | 2014-10-22 | 2015-02-18 | 东华大学 | Method for preparing nanofiber-based composite filter membrane by hot-pressing incipient fusion method |
| CN105536577A (en) * | 2016-01-25 | 2016-05-04 | 东华大学 | Novel method for preparing chitosan nanofiber-base composite filter membrane |
| CN106310960A (en) * | 2016-09-28 | 2017-01-11 | 东莞市联洲知识产权运营管理有限公司 | Electro-spinning-based self-assembled polylysine nano-filtration membrane and preparation method thereof |
| CN106334447A (en) * | 2016-09-28 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Anti-pollution composite nano filtering membrane for direct dye waste liquid treatment |
| CN106362604A (en) * | 2016-11-24 | 2017-02-01 | 陕西聚洁瀚化工有限公司 | Method for preparing polyelectrolyte coating and nanofiber membrane composite filter membrane |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111261913A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN111261913B (en) * | 2018-11-30 | 2021-09-03 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN110270136A (en) * | 2019-07-16 | 2019-09-24 | 黑龙江东方学院 | A kind of preparation method and application of hydrophilic functions film |
| CN110559865A (en) * | 2019-08-14 | 2019-12-13 | 浙江理工大学 | Method for repairing ultrafiltration membrane pollution or membrane damage |
| CN110559865B (en) * | 2019-08-14 | 2022-02-25 | 浙江理工大学 | Method for repairing ultrafiltration membrane pollution or membrane damage |
| CN110975651A (en) * | 2019-12-25 | 2020-04-10 | 中国石油大学(华东) | Multifunctional efficient sewage treatment membrane and preparation method thereof |
| CN110975651B (en) * | 2019-12-25 | 2022-07-26 | 中国石油大学(华东) | Multifunctional efficient sewage treatment membrane and preparation method thereof |
| CN112675717A (en) * | 2020-11-16 | 2021-04-20 | 广西中科鼎新产业技术研究院有限公司 | Nanofiber filter membrane material and preparation method thereof |
| CN113413774A (en) * | 2021-06-23 | 2021-09-21 | 江苏大学 | Multilayer bio-based nanofiber heavy metal filtering membrane, preparation method and application thereof |
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