CN116036896A - Composite nanofiltration membrane with low molecular weight cutoff and narrow pore size distribution and preparation method thereof - Google Patents
Composite nanofiltration membrane with low molecular weight cutoff and narrow pore size distribution and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000011148 porous material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000009826 distribution Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 7
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 239000008346 aqueous phase Substances 0.000 claims abstract description 5
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001263 FEMA 3042 Substances 0.000 claims description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 7
- 229920002258 tannic acid Polymers 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
- 229940033123 tannic acid Drugs 0.000 claims description 7
- 235000015523 tannic acid Nutrition 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000004885 piperazines Chemical class 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 230000014759 maintenance of location Effects 0.000 abstract description 15
- 238000000614 phase inversion technique Methods 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 5
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- 238000007654 immersion Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
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- 238000011010 flushing procedure Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Water Supply & Treatment (AREA)
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- Manufacturing & Machinery (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and a preparation method thereof. The method comprises the following steps: mixing a support film material, an amphiphilic polymer and an additive to prepare a film casting solution, taking an aqueous solution containing a hydrophilic polymer as a coagulating bath, and preparing a support film with a hydrophilic coating on the surface by using an immersion precipitation phase inversion method; treating the surface of a support membrane containing a hydrophilic coating by utilizing aqueous phase solution of polyamine and organic phase solution of polybasic acyl chloride in sequence, and further constructing a polyamide selective separation layer on the surface of the support membrane by an interfacial polymerization technology; and obtaining the composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution after heat treatment. The multivalent anions and cations in the water can be removed simultaneously by the interception of the composite nanofiltration membrane prepared by the steps; when the high-concentration multivalent salt solution is treated, the high-concentration multivalent salt solution has excellent retention performance and long-term separation stability, and can be widely applied to the fields of water treatment and material separation.
Description
Technical field:
the invention belongs to the technical field of nanofiltration membranes, and relates to a composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and a preparation method thereof.
The background technology is as follows:
the nanofiltration membrane separation technology has very wide application space and development prospect as an industrial separation and water treatment technology with advancement and competitiveness at present.
The aperture of the nanofiltration membrane is between 0.5 and 2nm, the molecular weight cut-off is 500 to 2000 daltons, the selective screening of water and salt, water and organic matters, high-valence salt and low-valence salt, organic matters and salt can be realized, and the nanofiltration membrane has been widely applied to the fields of water treatment, chemical industry, medicine and the like. The existing composite nanofiltration membrane is mainly prepared by taking polyamine as a water phase monomer and polybasic acyl chloride as an organic phase monomer and performing interfacial polymerization reaction on the surface of a support membrane. The sieving performance of the composite nanofiltration membrane is mainly determined by physicochemical properties (pore size, porosity, hydrophilicity, chargeability and the like) of the polyamide selective layer. The commercial nanofiltration membrane also has the defects: (1) The negatively charged nanofiltration membrane cannot have high interception of multivalent anions and cations, and is not easy to be used for treating high-salt-concentration water; (2) Limited by the balance effect between permeability and selectivity. Therefore, by optimizing the physicochemical properties of the support membrane and regulating the interfacial polymerization process, the development of a composite nanofiltration membrane integrating high permeability, high rejection rate and excellent stability has become the focus of current research.
The invention comprises the following steps:
aiming at the defects of the prior art, the invention aims to provide a composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and a preparation method thereof, so as to solve the problems of low screening precision and poor stability of the composite nanofiltration membrane.
In order to achieve the aim, the invention provides a composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and a preparation method thereof. The method comprises the following steps:
(1) Mixing a support film material, an amphiphilic polymer and an additive to prepare a film casting solution, taking an aqueous solution containing a hydrophilic polymer as a coagulating bath, and preparing a support film with a hydrophilic coating on the surface by using an immersion precipitation phase inversion method;
(2) Treating the surface of the support film containing the hydrophilic coating with aqueous solution of polyamine for 10-300 s to remove redundant aqueous solution on the surface of the support film; then the organic phase solution of polybasic acyl chloride is used for treatment, and the polyamide selective separation layer is further constructed on the surface of the support membrane through the interfacial polymerization technology for 10-300 s;
(3) Removing unreacted organic phase solution, and performing heat treatment on the obtained membrane at the temperature of 50-90 ℃ for 1-60 min to obtain the composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution.
Preferably, the support membrane material is one or a mixture of several of polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polypropylene and other polymers. More preferably polyvinylidene fluoride. In the step (1), the mass fraction of the supporting film material in the film casting liquid is 10-35%.
Preferably, the monomers corresponding to the hydrophobic structural units in the amphiphilic polymer are: one or more of methyl (meth) acrylate, styrene, acrylonitrile, vinylidene fluoride and other monomers; the monomers corresponding to the hydrophilic structural units are: and (3) one or more of N-hydroxyethyl acrylamide, hydroxyethyl (meth) acrylate, vinyl pyrrolidone and other monomers. More preferably N-hydroxyethyl acrylamide. In the step (1), the mass of the amphiphilic polymer is 2-40% of the mass of the supporting membrane material. More preferably 10%.
Preferably, the additive is one or a mixture of more of polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, lithium chloride and the like. More preferably polyethylene glycol. Preferably, the mass fraction of the additive in the casting film liquid is 1-20%. More preferably 3%.
Preferably, the hydrophilic polymer type is one or a mixture of more of tannic acid, polyvinyl alcohol, cellulose, chitosan and starch. More preferably tannic acid. Preferably, the concentration of the hydrophilic polymer coagulation bath is 0.1-10 g/L, and the coagulation bath soaking time is set to be 0.1-24 h. More preferably, the concentration of the coagulation bath is 1.0g/L, and the soaking time of the coagulation bath is 1h.
Preferably, the water-soluble monomer is one or a mixture of more of piperazine, piperazine derivatives, m-phenylenediamine, phenylenediamine and polyethyleneimine. More preferably piperazine. Preferably, the mass percentage of the water-soluble monomer aqueous phase solution is 0.05-5%. More preferably 1.0% by mass.
Preferably, the oil-soluble monomers are trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride. And more preferably trimesoyl chloride. Preferably, the mass percentage of the oil-soluble monomer organic phase solution is 0.01-5%. More preferably 0.15% by mass.
Preferably, the solvent of the organic phase solution is one or a mixture of more solvents selected from ethyl acetate, n-hexane, dichloromethane and the like. More preferably n-hexane.
In the preparation method, the support film containing the hydrophilic coating is prepared by using an immersion precipitation phase inversion method. The pore diameter of the surface of the support membrane is adjustable, and the hydrophilicity is excellent. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution can be prepared by interfacial polymerization, and has high cut-off performance and stable long-term separation performance on multivalent anions and cations.
Compared with the prior art, the invention has the following beneficial effects:
on the basis of the existing membrane preparation process, firstly, the amphiphilic polymer is blended with the support membrane material, and the aqueous solution containing the hydrophilic polymer is used as a coagulation bath to prepare the support membrane with the pore diameter adjustable and excellent hydrophilic coating; in the interfacial polymerization process, the excellent hydrophilicity and pore structure of the surface of the support membrane containing the hydrophilic coating are beneficial to uniform and high-concentration dispersion of the water phase monomer on the surface of the membrane, so that the prepared polyamide composite nanofiltration membrane has higher crosslinking degree, lower molecular weight cut-off and narrower pore size distribution. The polyamide composite nanofiltration membrane prepared by the invention has high separation efficiency on multivalent anions and cations and wide application fields. The preparation method of the invention can regulate and control the pore size and the hydrophilicity of the surface of the support membrane, further optimize the interfacial polymerization condition, and optimize the structure and the performance of the polyamide composite nanofiltration membrane, and the optimized composite nanofiltration membrane has very high retention rate (Na 2 SO 4 ：99.2％，MgCl 2 :96.8 percent) can be widely applied to the fields of water purification, special material separation and the like. And the preparation process is controllable, the technology is mature, the cost is low, and the method has great industrial application prospect.
Description of the drawings:
FIG. 1 is an electron microscopic view of comparative example 2 with only an amphiphilic polymer modified polyvinylidene fluoride support film of the present invention, scale bar 8 μm;
FIG. 2 is an electron microscope image of a polyvinylidene fluoride support film prepared by modifying an amphiphilic polymer according to example 1 of the present invention with a tannic acid aqueous solution as a coagulation bath, with a scale of 8 μm;
FIG. 3 is an electron microscopic image of the polyamide composite nanofiltration membrane prepared in example 1 of the present invention, with a scale of 8. Mu.m.
The specific embodiment is as follows:
the pore size of nanofiltration membranes is not well measured accurately, but neutral molecular polyethylene glycol is used to test the molecular weight cut-off (MWCO) in view of the surface charge of nanofiltration membranes. When a PEG solution of a certain concentration is filtered, the molecular weight of PEG at a retention rate of 90% is referred to as the molecular weight cut-off. The method comprises the following specific steps:the concentration is 1 g.L -1 The PEG solution is used as the test stock solution of the nanofiltration membrane, the retention rate of the membrane on PEG with different molecular weights (200, 400, 600, 800 and 1000) is calculated after filtration test, a molecular weight-retention rate curve of the PEG is given and is synthesized, and the molecular weight of the PEG corresponding to the curve and the retention rate of 90 percent is the retention molecular weight of the nanofiltration membrane. Determination of Stokes radius (r) of PEGs of different molecular weights s ) The calculation formula is as follows:
r s ＝16.73×10 -12 ×M W 0.557 (1)
with Stokes diameter (d) p ) On the abscissa, the retention (R) is on the ordinate, and the diameter-retention curves for different PEGs are made and fitted. The pore size distribution can be expressed as the following density function. The formula is as follows:
μ p defined as the geometric mean diameter, σ, of the solute at r=50% p Is the geometric standard deviation defined as the ratio of the solute radii at r=84.1% and r=50%. Mu (mu) p Sum sigma p The position and width of the pore size distribution curve are determined by the values of (a) and (b), respectively.
And a cross-flow filtration mode is adopted, and a self-made permeability testing device in a laboratory is used for testing the permeability and separation performance of the nanofiltration membrane.
(1) The film was cut into test samples with a radius of 1.5cm and fixed in the device. The membrane was subjected to a water flux test at a pressure of 6bar and a steady pressure of 60min, noted J w (L·m -2 ·h -1 ) The calculation is performed as in the following formula (3).
Wherein V is permeate volume (L); a is the effective filtration area (m 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Δt is the time (h) required for permeation of volume V filtrate.
(2) Preparing a solution: 1g of Na 2 SO 4 、MgCl 2 Dissolved in 1L of water.
(3) After the pure water flux test is finished, deionized water is changed into various solutions, the pressure is stabilized for 60 minutes under the condition of 6bar, and the flux of the solution is tested and is recorded as J w (L·m -2 ·h -1 ). After the flux is stabilized, permeate is collected, and feed liquid is collected at the same time. The conductivity of the salt collection liquid was measured using a conductivity meter for each salt solution, and then the rejection rate (R) of the salt by the membrane was calculated by equation (4) for each salt solution.
Wherein: c (C) p Is the concentration of the permeate (g.L) -1 )，C f Is the concentration of the feed solution (g.L) -1 )。
In order to achieve the object of the present invention, the present experiment will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
example 1 was made using more preferred formulation materials and proportions, with the following specific steps:
an amphiphilic polymer with a hydrophilic chain segment of poly-N-hydroxyethyl acrylamide and a hydrophobic chain segment of poly (methyl) acrylate is selected as a functional modifier. The method comprises the steps of preparing a polyvinylidene fluoride support film containing a hydrophilic coating on the surface of a non-woven fabric by using tannic acid as a hydrophilic polymer and polyvinylidene fluoride as a film forming material through a submerged precipitation phase inversion method, wherein the mass of an amphiphilic polymer additive is 10% of the mass fraction of polyvinylidene fluoride, the concentration of tannic acid is 1.0g/L, and the soaking time of a tannic acid coagulation bath is 60min. Pouring 1.0wt% piperazine aqueous solution on the surface of the prepared hydrophilic polyvinylidene fluoride support film, reacting for 1min, and then removing redundant piperazine aqueous solution on the surface film surface. Then pouring 0.15wt% of trimesoyl chloride organic phase solution into the surface of the membrane, reacting for 1min, pouring out excessive organic phase solution, flushing with n-hexane, airing and then placing into a 60 ℃ oven for 10min. Taking out and putting into water for standby.
Through testing, the preparedThe average pore diameter of the polyamide composite nanofiltration membrane is 0.22nm, the molecular weight cut-off is 307 daltons, and the flux reaches 11.9 L.m 2 ·h 1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 99.2 percent 2 The rejection rate of (2) was 96.8%.
Example 2:
the amphiphilic polymer functional modifier is selected, the hydrophilic chain segment is polyvinylpyrrolidone, and the hydrophobic chain segment is polystyrene. The method comprises the steps of preparing a polyacrylonitrile support film containing a hydrophilic coating on the surface of a non-woven fabric by using chitosan as a hydrophilic polymer and polyacrylonitrile as a film forming material through a submerged precipitation phase inversion method, wherein the mass of an amphiphilic polymer additive is 10% of the mass fraction of the polyacrylonitrile, the concentration of chitosan is 1.0g/L, and the soaking time of a chitosan coagulation bath is 60min. Pouring 1.0wt% piperazine aqueous solution on the surface of the prepared hydrophilic polyvinylidene fluoride support film, reacting for 1min, and then removing redundant piperazine aqueous solution on the surface film surface. Then pouring 0.15wt% of trimesoyl chloride organic phase solution into the surface of the membrane, reacting for 1min, pouring out excessive organic phase solution, flushing with n-hexane, airing and then placing into a 60 ℃ oven for 10min. Taking out and putting into water for standby, wherein the nanofiltration membrane is a flat membrane.
Through test, the average pore diameter of the prepared polyamide composite nanofiltration membrane is 0.35nm, the molecular weight cut-off is 398 daltons, and the flux reaches 15.9 L.m 2 ·h -1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 98.2 percent 2 The retention rate of (2) was 95.1%.
Example 3:
the difference from example 1 is that: the hydrophobic chain segment in the amphiphilic polymer functional modifier is polyvinylidene fluoride, the hydrophilic polymer is changed into polyvinyl alcohol, and the other parts are the same as in the embodiment 1 and are not described in detail herein.
Through test, the average pore diameter of the prepared polyamide composite nanofiltration membrane is 0.21nm, the molecular weight cut-off is 295 daltons, and the flux reaches 17.8 L.m -2 ·h 1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 99.0 percent 2 The rejection rate of (2) was 96.1%.
Example 4:
the difference from example 1 is that: the hydrophilic chain segment in the amphiphilic polymer functional modifier is polyvinylpyrrolidone, and the hydrophobic chain segment is polymethyl (meth) acrylate. The hydrophilic polymer was changed to chitosan, and the other components were the same as in example 1, and will not be described here again.
Through test, the average pore diameter of the prepared polyamide composite nanofiltration membrane is 0.31nm, the molecular weight cut-off is 384 daltons, and the flux reaches 14.2 L.m -2 ·h -1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 98.7 percent 2 The rejection rate of (2) was 96.1%.
Comparative example 1:
polyvinylidene fluoride is selected as a film forming material, and a polyvinylidene fluoride support film is prepared on the surface of the non-woven fabric by a submerged precipitation phase inversion method. Pouring 1.0wt% piperazine aqueous solution on the surface of the prepared hydrophilic polyvinylidene fluoride support film, reacting for 1min, and then removing redundant piperazine aqueous solution on the surface film surface. Then pouring 0.15wt% of trimesoyl chloride organic phase solution into the surface of the membrane, reacting for 1min, pouring out excessive organic phase solution, flushing with n-hexane, airing and then placing into a 60 ℃ oven for 10min. Taking out and putting into water for standby, wherein the nanofiltration membrane is a flat membrane.
Through test, the average pore diameter of the prepared polyamide composite nanofiltration membrane is 0.61nm, the molecular weight cut-off is 811 daltons, and the flux reaches 29.7 L.m -2 ·h -1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 83.2 percent 2 The rejection rate of (2) was 29.7%.
Comparative example 2:
the amphiphilic polymer functional modifier is selected, the hydrophilic chain segment is poly-N-hydroxyethyl acrylamide, and the hydrophobic chain segment is poly (methyl) acrylate. Polyvinylidene fluoride is used as a film forming material, and a polyvinylidene fluoride supporting film containing a hydrophilic coating is prepared on the surface of a non-woven fabric by a submerged precipitation phase inversion method, wherein the mass of the amphiphilic polymer additive is 10% of the mass fraction of the polyvinylidene fluoride. Pouring 1.0wt% piperazine aqueous solution on the surface of the prepared hydrophilic polyvinylidene fluoride support film, reacting for 1min, and then removing redundant piperazine aqueous solution on the surface film surface. Then pouring 0.15wt% of trimesoyl chloride organic phase solution into the surface of the membrane, reacting for 1min, pouring out excessive organic phase solution, flushing with n-hexane, airing and then placing into a 60 ℃ oven for 10min. Taking out and putting into water for standby, wherein the nanofiltration membrane is a flat membrane.
Through test, the average pore diameter of the prepared polyamide composite nanofiltration membrane is 0.52nm, the molecular weight cut-off is 531 daltons, and the flux reaches 21.7 L.m -2 ·h -1 ·bar -1 ，Na 2 SO 4 The retention rate of MgCl is 92.3 percent 2 The retention rate of (2) was 57.2%.
The unmodified polyvinylidene fluoride support membrane material of comparative example 1 cannot uniformly infiltrate the surface of the support membrane due to inherent hydrophobic property of the material, and the prepared composite nanofiltration membrane has large pore diameter and salt rejection rate. In comparative example 2, although amphiphilic polymer modified polyvinylidene fluoride support membrane material is added, the improvement of the hydrophilicity of the support membrane is not obvious, and compared with comparative example 1, the pore diameter of the prepared nanofiltration membrane is reduced, and the salt rejection rate is increased. Compared with the comparative example 2, the embodiment 1 further introduces hydrophilic polymer into the coagulation bath, which obviously changes the film forming process of the support film, increases the aperture of the support film (as shown in figures 1 and 2), enhances the hydrophilicity, and is beneficial to the uniform and high-concentration dispersion of the aqueous phase monomer piperazine on the film surface, so that the aperture and the molecular weight cut-off of the prepared polyamide composite nanofiltration film are reduced, and the divalent cation and anion cut-off rate is increased.
Claims (11)
1. A composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and a preparation method thereof are characterized in that: the method comprises the following steps:
(1) Mixing a support film material, an amphiphilic polymer and an additive to prepare a film casting solution, taking an aqueous solution containing a hydrophilic polymer as a coagulating bath, and preparing a support film with a hydrophilic coating on the surface by utilizing immersed precipitation phase inversion;
(2) Treating the surface of a support membrane containing a hydrophilic coating by utilizing aqueous phase solution of polyamine and organic phase solution of polybasic acyl chloride in sequence, and further constructing a polyamide selective separation layer on the surface of the support membrane by an interfacial polymerization technology;
(3) And obtaining the composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution after heat treatment.
2. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (1), the supporting membrane material is one or a mixture of more than one of polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, polypropylene and other polymers. In the step (1), the mass fraction of the supporting film material in the film casting liquid is 10-35%.
3. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (1), monomers corresponding to the hydrophobic structural unit in the amphiphilic polymer are: one or more of methyl (meth) acrylate, styrene, acrylonitrile, vinylidene fluoride and other monomers; the monomers corresponding to the hydrophilic structural units are: one or more of monomers such as N-hydroxyethyl acrylamide, hydroxyethyl (meth) acrylate and vinylpyrrolidone (PVP) are mixed; in the step (1), the mass of the amphiphilic polymer is 2-40% of the mass of the supporting membrane material.
4. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (1), the additive is one or a mixture of more of polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, lithium chloride and the like; in the step (1), the mass fraction of the additive in the casting film liquid is 1-20%.
5. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (1), the hydrophilic polymer is one or a mixture of more of tannic acid, polyvinyl alcohol, cellulose, chitosan, starch and other polymers, the concentration of the hydrophilic polymer coagulating bath is 0.1-6 g/L, and the coagulating bath soaking time is set to be 0.1-24 h.
6. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (2), the polyamine is one or a mixture of more of piperazine, piperazine derivative, m-phenylenediamine, polyethyleneimine and the like. In the step b), the mass percentage of the aqueous phase solution of the polyamine is 0.05-5%.
7. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (2), the polybasic acyl chloride is one or a mixture of more of trimesoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride and the like. In the step (2), the mass percentage of the organic phase solution of the polybasic acyl chloride is 0.01-5%.
8. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (2), the solvent of the organic phase solution is one or a mixture of more solvents such as ethyl acetate, normal hexane and dichloromethane.
9. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (3), the heat treatment is carried out at the temperature of 50-90 ℃ for 1-120 min.
10. The composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution and the preparation method thereof according to claim 1, wherein the preparation method is characterized in that: in the step (3), the composite nanofiltration membrane is hollow fiber type or flat type.
11. A composite nanofiltration membrane with low molecular weight cut-off and narrow pore size distribution prepared according to any one of claims 1 to 10 and a preparation method thereof.
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