CN113041840B - Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same - Google Patents
Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same Download PDFInfo
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- CN113041840B CN113041840B CN201911387371.9A CN201911387371A CN113041840B CN 113041840 B CN113041840 B CN 113041840B CN 201911387371 A CN201911387371 A CN 201911387371A CN 113041840 B CN113041840 B CN 113041840B
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- 239000012528 membrane Substances 0.000 title claims abstract description 97
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000005374 membrane filtration Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 aliphatic nitrogen-containing heterocyclic compound Chemical class 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 55
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 43
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000008346 aqueous phase Substances 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 16
- 150000004982 aromatic amines Chemical class 0.000 claims description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-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
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 3
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 claims description 3
- WHKWMTXTYKVFLK-UHFFFAOYSA-N 1-propan-2-ylpiperazine Chemical compound CC(C)N1CCNCC1 WHKWMTXTYKVFLK-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 38
- 230000004907 flux Effects 0.000 abstract description 16
- 210000004379 membrane Anatomy 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002202 Polyethylene glycol Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000012695 Interfacial polymerization Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 210000002469 basement membrane Anatomy 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000412 dendrimer Substances 0.000 description 2
- 229920000736 dendritic polymer Polymers 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to a preparation method of a nanofiltration membrane and the nanofiltration membrane prepared by the method. By adopting the preparation method of the application to prepare the nanofiltration membrane, the selective separation of organic matters with different molecular weights can be realized under the condition of keeping the high flux of the nanofiltration membrane.
Description
Technical Field
The application relates to the technical field of water treatment membranes, in particular to the technical field of nanofiltration membranes, and particularly relates to a preparation method of a nanofiltration membrane capable of realizing selective separation of organic matters with different molecular weights under the condition of keeping high flux of the nanofiltration membrane, and the nanofiltration membrane prepared by the preparation method.
Background
With the improvement of the environmental protection requirement, the application range of the nanofiltration membrane is wider and wider. With the development of membrane technology, separation membranes tend to be directed to more challenging feed systems, from separating salts in different valence states to separating organics of different molecular weights and even mixtures thereof. Therefore, the nanofiltration membrane with higher solute selectivity will play an increasingly important role in the field of selective separation.
However, nanofiltration membranes that selectively reject organic substances of different molecular weights are currently under less research. The published patent literature of related research is almost absent at present.
The existing composite nanofiltration membrane technology generally carries out interfacial polymerization reaction of piperazine and trimesoyl chloride on a porous supporting layer of a base membrane. The nanofiltration membrane obtained by the technology has high desalination rate on divalent ion salts and high permeability on monovalent ion salts, so that monovalent salts and divalent salts can be well separated. However, the rejection rate of the conventional nanofiltration membrane to PEG200 is more than 85%, and the rejection rate to PEG400 and PEG600 is more than 95%. The selective separation performance of the organic matters with different molecular weights is poor.
Yan-Li Ji et al prepared a zwp membrane (zcm) by surface-coating Zwitterionic Colloidal Particles (ZCP) on an ultrafiltration membrane having a support layer of polysulfone as a base membrane, and then cross-linked with glutaraldehyde at 50 ℃ for 3 hours. The membrane prepared by the method has good separation performance with organic molecules (polyethylene glycol, PEG). For example, the average retention of PEG1000, PEG600, PEG200 by ZCMP is about 96%, 88%, 60% (Ji Y L, ZHao Q, An Q F, et al. Novel separation membranes based on nonlinear chemical properties: structural selectivity and enhanced chemical property [ J ]. Journal of Materials Chemistry A, 2013, 1(39):12213), respectively).
The research of Yan-Li Ji et al has certain selective separation performance on organic matters with different molecular weights, but the technology is mainly prepared by a coating method, a separation layer obtained by the coating method is physically attached to a base film and lacks a chemical crosslinking effect with the base film, so that the firmness is poor, the stability of the separation layer is poor, the separation layer is easy to fall off, and the excellent selective separation effect is difficult to maintain stably for a long time.
Disclosure of Invention
Problems to be solved by the invention
The method aims to solve the problems that the prior nanofiltration membrane has poor selectivity and separation of organic matters and cannot be industrially produced, improves the application range of the nanofiltration membrane in the field of selective separation, and realizes industrial production. One or more of dendritic PAMAM, aliphatic nitrogen heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) is/are used as a water phase monomer to carry out interfacial polymerization reaction with an acyl chloride compound serving as an organic phase monomer, and a separation layer is formed on a polymer base film, so that the novel nanofiltration membrane is prepared. The novel nanofiltration membrane has high retention rate of different molecular weight organic matters, so that the selective separation of the nanofiltration membrane on the organic matters with different molecular weights can be realized.
Means for solving the problems
In order to achieve the above object, the inventors of the present invention have made intensive studies and have proposed a method for producing a nanofiltration membrane, in which one or more of a dendritic PAMAM, an aliphatic nitrogen-containing heterocyclic compound, or an aromatic amine-based compound-terminated poly (alkylene glycol) is used as an aqueous phase monomer, and an acid chloride compound, which is an organic phase monomer, is subjected to an interfacial polymerization reaction to form a separation layer on a polymer-based membrane.
The dendritic PAMAM has more branched chains and a large number of amino groups which can participate in interfacial polymerization reaction, and the poly (alkylene glycol) terminated by the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine compound has longer straight chain and higher activity of terminated amino groups. One or more of dendritic PAMAM, aliphatic nitrogen heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) is used as an aqueous phase monomer to carry out interfacial polymerization reaction with an organic phase monomer acyl chloride compound, and a separation layer generated by the reaction is loose and has a large pore diameter. Thereby realizing permeation of low molecular weight organic matters and interception of high molecular weight organic matters.
The structure and the performance of the separation layer can be regulated and controlled by regulating the proportion and the concentration of the dendritic PAMAM, the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine compound terminated poly (alkylene glycol), and the retention rate of the nanofiltration membrane on organic matters with different molecular weights can be further regulated, so that the nanofiltration membrane prepared by the method has different selectivity on the organic matters with different molecular weights. Thereby realizing the selective separation of various organic matters with different molecular weights.
One aspect of the application relates to a method for preparing a nanofiltration membrane, which is characterized by comprising the following steps:
dissolving a polymer in a solvent to prepare a polymer solution, and solidifying the polymer solution on a support material to form a base film;
immersing the basement membrane into an aqueous phase solution, wherein the aqueous phase solution contains one or more of dendritic Polyamidoamine (PAMAM), aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol), and then immersing the basement membrane into an organic phase solution containing an acyl chloride compound;
and carrying out post-treatment and drying to obtain the nanofiltration membrane.
The preparation method is characterized in that the polymer is one or more of polyphenylene sulfone PPSU, polyetherimide PEI, polysulfone and polyethersulfone.
The preparation method is characterized in that the solvent in the polymer solution is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and imidazolidinone; preferably, the support material is a nonwoven fabric.
The preparation method is characterized in that the polymer is used in an amount of 15-28 wt%, preferably 15-25 wt%, and more preferably 16-22wt% based on the weight of the polymer solution.
The preparation method is characterized in that the amount of the dendritic polyamidoamine PAMAM is 0.0-3.0 wt%, preferably 0.0-2.5wt%, based on the weight of the aqueous phase solution, and the amount of the poly (alkylene glycol) terminated by the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine compound is 0.0-3.0 wt%, preferably 0.0-2.5wt%, wherein the amount of the dendritic polyamidoamine PAMAM and the amount of the poly (alkylene glycol) terminated by the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine compound are not 0 at the same time.
The preparation method is characterized in that the aliphatic nitrogen-containing heterocyclic compound is one or more of piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-isopropylpiperazine and pyrazole; the aromatic amine compound is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and 4-methyl-m-phenylenediamine.
The production method according to the present invention is characterized in that the poly (alkylene glycol) is poly (ethylene glycol), poly (propylene glycol), poly (butylene glycol); preferably, the poly (alkylene glycol) has a degree of polymerization of 5 to 95, more preferably 5 to 15.
The preparation method is characterized in that the acyl chloride compound is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride and terephthaloyl chloride.
The preparation method is characterized in that the amount of the acyl chloride compound is 0.05-0.5 wt%, preferably 0.1-0.3wt%, and more preferably 0.1-0.25 wt% based on the weight of the organic phase solution.
Another aspect of the present application relates to a nanofiltration membrane prepared by the method for preparing a nanofiltration membrane according to the present application.
ADVANTAGEOUS EFFECTS OF INVENTION
The nanofiltration membrane prepared by the preparation method can increase the difference between the retention rates of organic matters with different molecular weights and improve the selectivity of the separation of the organic matters with different molecular weights under the condition of keeping the high flux of the nanofiltration membrane, thereby realizing the selective separation of the organic matters with different molecular weights, reducing the retention rate of the organic matters with low molecular weights, enabling the organic matters with low molecular weights to be easier to permeate, improving the retention rate of the organic matters with high molecular weights, and enabling the organic matters with high molecular weights to be more difficult to permeate and most of the organic matters to be retained.
The flux of the nanofiltration membrane prepared according to the present invention is higher than that of the nanofiltration membrane in the prior art, and compared to the separation layer obtained by the coating method in the prior art, the separation layer obtained by the interfacial polymerization reaction of the present invention is not physically attached to the surface of the base membrane but is obtained by a chemical reaction on the surface of the base membrane, so that the firmness is more excellent, the stability is more excellent, and the high flux and the excellent selective separation effect can be stably maintained for a long time.
According to the preparation method, the existing industrial production equipment can be directly utilized, an additional coating process is not needed, the existing production equipment and the existing production process are not needed to be adjusted, the production cost is reduced, and the production efficiency is improved.
Detailed Description
The application provides a preparation method of a nanofiltration membrane, which comprises the following steps:
dissolving a polymer in a solvent to prepare a polymer solution, and curing the polymer solution on a support material to form a base film (hereinafter referred to as "base film preparation process");
immersing the base film in an aqueous solution containing one or more of a dendritic polyamidoamine PAMAM, an aliphatic nitrogen-containing heterocyclic compound, or an aromatic amine compound-terminated poly (alkylene glycol), and then immersing the base film in an organic solution containing an acid chloride compound (hereinafter referred to as a "separation layer preparation process"); and carrying out post-treatment and drying to obtain the nanofiltration membrane.
In the preparation process of the basement membrane, the polymer is one or more of polyphenylene sulfone PPSU, polyetherimide PEI, polysulfone and polyethersulfone. The molecular weight of the polymer is not particularly limited, and preferably, the number average molecular weight is 30000 to 50000.
The solvent in the polymer solution is not particularly limited as long as it can sufficiently dissolve the polymer, and preferably the solvent is one or any of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, and imidazolidinone.
The support material is not particularly limited, and preferably, the support material is a nonwoven fabric.
The amount of the polymer is 15-28 wt%, preferably 15-25 wt%, and more preferably 16-22wt% based on the weight of the polymer solution. If the amount of the polymer is less than 15wt%, the pressure resistance of the nanofiltration membrane prepared is reduced. If the amount of the polymer is more than 28wt%, the viscosity of the polymer solution, also called casting solution, increases, and the difficulty and defect of the production of the base film increase.
In the present application, the method of forming the base film by curing is not particularly limited, and the base film is preferably formed by a liquid-solid phase inversion method. Preferably, the phase inversion time is controlled to be 0.5-1 min, the water bath temperature is 15-20 ℃, the thermosetting water bath temperature is 70-85 ℃, and the thickness of the film including the non-woven fabric is 5.0-6.0 mil.
As a non-limiting example, the base film preparation process comprises: 16-22wt% polysulfone or polyethersulfone as polymer was dissolved in Dimethylformamide (DMF) or Dimethylacetamide (DMAC) and stirred at 150 ℃ for 2-3h until the polymer was completely dissolved. Standing and defoaming for 10 h. And (3) forming a base film on the non-woven fabric by a liquid-solid phase conversion method through the polymer solution, wherein the phase conversion generation time is controlled to be 0.5-1 min, the water bath temperature is 15-20 ℃, the thermocuring water bath temperature is 70-85 ℃, and the thickness of the film including the non-woven fabric is 5.0-6.0 mil. And soaking the obtained polymer base membrane in deionized water for storage, and finishing the preparation of the porous supporting layer base membrane.
The dendritic polyamidoamine PAMAM is a three-dimensional, highly branched and monodisperse dendritic polymer. The dendritic polyamidoamine PAMAM is composed of an active center, a surface functional group and a branched chain segment for connecting the active center and the surface functional group, and a series of concentric layers generated by the branched chain segment repeatedly according to geometric rules become generations (G). The dendritic PAMAM is obtained by starting from a core (amine or ethylenediamine) and carrying out molecular construction through repeated stepwise reaction, the molecular surface has high functional group density, meanwhile, the interior of the molecule has wide cavities, the dendritic PAMAM has good reaction activator holding capacity, and a large number of reactive or functional groups can be introduced into the molecular center and the molecular tail end. In the present application, the dendritic polyamidoamine PAMAM has the structure shown below:
dendrimer polyamidoamine PAMAM is commercially available, for example from weaham molecular new materials ltd.
The amount of the dendritic polyamidoamine PAMAM is 0.0-3.0 wt%, preferably 0.0-2.5wt%, based on the weight of the aqueous phase solution. If the amount is more than 3.0wt%, the selectivity and flux of the nanofiltration membrane for organic separation are reduced.
The amount of the aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) is 0.0-3.0 wt%, preferably 0.0-2.5wt% based on the weight of the aqueous phase solution. If the amount is more than 3.0wt%, the selectivity and flux of the nanofiltration membrane for organic separation are reduced.
Preferably, the dosage of the dendritic polyamide amine PAMAM and the dosage of the poly (alkylene glycol) terminated by the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine compound are not 0 at the same time.
Preferably, the ratio of the dendritic polyamidoamine PAMAM to the aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound terminated poly (alkylene glycol) is 0:2.5wt% to 0, preferably 0.5wt% to 1.5wt% to 0.2wt% (i.e., the ratio of the two is in the range of 1:1 to 7.5: 1), more preferably 0.8wt% to 0.5wt% to 0.1wt% (i.e., the ratio of the two is in the range of 2:1 to 5: 1). If the concentration is outside the above range, the selectivity of the nanofiltration membrane for separating organic substances is poor or the nanofiltration membrane may have defects during the membrane formation process.
Optionally adding a pH regulator into the aqueous phase solution, preferably, the pH regulator is one or more of sodium hydroxide, potassium hydroxide, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium citrate and potassium citrate; the addition amount of the pH regulator is 0.01wt% to 0.1wt%, and further, the preferred addition amount of the pH regulator is 0.01wt% to 0.05wt%, based on the total weight of the aqueous phase solution, and the pH regulator is used for absorbing excessive acid generated by interfacial polymerization and promoting the interfacial polymerization to continue a forward reaction.
The aliphatic nitrogen heterocyclic compound is one or more of piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-isopropylpiperazine and pyrazole; the aromatic amine compound is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and 4-methyl-m-phenylenediamine.
The poly (alkylene glycol) is poly (ethylene glycol), poly (propylene glycol), poly (butylene glycol), more preferably poly (ethylene glycol); preferably, the poly (alkylene glycol) has a degree of polymerization of 5 to 95, more preferably 5 to 15. The lower limit of the polymerization degree is preferably 5 from the viewpoint of availability of raw materials; when the polymerization degree is higher than 95, the reaction does not easily proceed.
Preferably, the aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) is piperazine-terminated polyethylene glycol PIP-PEG-PIP.
As a non-limiting example, the process for preparing piperazine terminated polyethylene glycol PIP-PEG-PIP includes: 50g of piperazine is weighed and added into a beaker, 2000mL of pure water is added, 8g of poly (ethylene glycol) diacrylate (AA-PEG-AA, the polymerization degree of PEG is 5) is added, and the mixture is stirred and reacted for 10 minutes at a constant temperature of 25 ℃ to prepare piperazine-terminated polyethylene glycol PIP-PEG-PIP.
Preferably, the prepared piperazine-terminated polyethylene glycol PIP-PEG-PIP is used within one hour.
The acyl chloride compound is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride and terephthaloyl chloride.
The amount of the acyl chloride compound is 0.05 to 0.5wt%, preferably 0.1 to 0.3wt%, and more preferably 0.1 to 0.25wt% based on the weight of the organic phase solution.
As a non-limiting example, the separation layer preparation procedure includes: 1) soaking the base membrane in an aqueous solution containing 0.0-2.5wt% of dendritic PAMAM (polyethylene glycol PIP-PEG-PIP), 0.0-2.5wt% of piperazine end-capped PIP and 0.01-0.05wt% of sodium hydroxide for 0.5-2min, and draining surface water beads, wherein the content of the dendritic PAMAM and the content of the piperazine end-capped polyethylene glycol PIP-PEG-PIP are not 0 at the same time; (2) soaking the basement membrane treated in the step (1) in an organic solvent (n-hexane, ethylcyclohexane, n-octane, n-heptane and the like) containing 0.1-0.3wt% of trimesoyl chloride for reaction for 0.5-2 min;
(3) and (3) carrying out hydrothermal treatment on the membrane subjected to the interface reaction in the step (2) for 1-3min at the temperature of 80-90 ℃, washing with pure water, soaking for 1-3min with a glycerol-containing aqueous solution, and drying to obtain the high-precision selectivity adjustable nanofiltration membrane.
Without being particularly limited, the preparation method is characterized in that the preparation method takes dendritic PAMAM and piperazine-terminated polyethylene glycol PIP-PEG-PIP as an example: one or two of dendritic PAMAM and piperazine-terminated polyethylene glycol PIP-PEG-PIP are used as water phase monomers to perform interfacial polymerization reaction with acyl chloride compounds used as organic phase monomers to form a separation layer on a polymer-based membrane.
The dendritic PAMAM has more branched chains and a large number of amino groups which can participate in interfacial polymerization reaction, and the piperazine-terminated polyethylene glycol PIP-PEG-PIP has longer straight chain and higher activity of terminated amino groups. One or two of dendritic PAMAM and piperazine-terminated polyethylene glycol PIP-PEG-PIP are used as water phase monomers to carry out interfacial polymerization reaction with organic phase monomer acyl chloride compounds, and separation layers generated by the reaction are loose and have large pore diameters. Thereby realizing permeation of low molecular weight organic matters and interception of high molecular weight organic matters.
The structure and the performance of the separation layer can be regulated and controlled by regulating the proportion and the concentration of the dendritic PAMAM and the piperazine-terminated polyethylene glycol PIP-PEG-PIP, so that the rejection rate of the nanofiltration membrane on organic matters with different molecular weights can be regulated, and the nanofiltration membrane prepared by the method has different selectivity on the organic matters with different molecular weights. Thereby realizing the selective separation of various organic matters with different molecular weights.
The application also provides a nanofiltration membrane prepared by the preparation method. The nanofiltration membrane can be applied to selective separation of organic matters with different molecular weights in the fields of water treatment, dyes, biochemical engineering, foods, environmental protection and the like.
ExamplesThe present invention will be described in further detail with reference to specific examples, but the present invention is by no means limited to the following examples. It should be noted that the reagents and raw materials used in the examples of the present invention are commercially available conventional products unless otherwise specified.
Example 1
(1) Preparing a polymer solution: adding 45g of Polysulfone (PS) into 205g N, N-Dimethylformamide (DMF), stirring at a high speed for 6h at 150 ℃ for dissolving, and then carrying out vacuum standing and defoaming on the obtained solution to obtain a polymer solution;
(2) preparing a base film: and (2) preparing the porous polymer supporting layer on the non-woven fabric by the polymer solution obtained in the step (1) through a liquid-solid phase conversion method. The phase inversion time is controlled to be 0.5min, the water bath temperature is 18 ℃, the thermocuring water bath temperature is 80 ℃, and the film thickness is controlled to be 5.5 mil;
(3) soaking the polymer base film obtained in the step (2) in deionized water for storage, and completing the preparation of a high molecular polymer base film;
(4) dissolving 10g of dendritic PAMAM and 0.2g of sodium hydroxide in 989.8g of deionized water, stirring and dissolving completely to obtain an aqueous phase solution, soaking the base membrane prepared in the step (3) in the aqueous phase solution for 2min, and draining water drops on the membrane surface;
(5) dissolving 1.5g of trimesoyl chloride in 998.5g of n-hexane, stirring and dissolving to obtain an organic phase solution, and soaking the base membrane soaked with the aqueous phase solution in the step (4) in the organic phase solution for 0.5 min;
(6) and (3) treating the composite membrane obtained in the step (5) with hot water at the temperature of 80 ℃ for 2min, soaking the composite membrane in glycerol at the temperature of 25 ℃ and the concentration of 18wt% for 15min, and finally drying the composite membrane with hot air at the temperature of 60 ℃ to obtain the nanofiltration membrane.
Example 2 Steps (1) - (3) are the same as in example 1; (4) preparation of piperazine terminated polyethylene glycol PIP-PEG-PIP: weighing 50g of piperazine, adding the piperazine into a beaker, adding 2000mL of pure water, adding 8g of poly (ethylene glycol) diacrylate (AA-PEG-AA, the polymerization degree of PEG is 5), and stirring at the constant temperature of 25 ℃ for reacting for 10 minutes to prepare piperazine-terminated polyethylene glycol PIP-PEG-PIP;
(5) dissolving 10g of piperazine-terminated polyethylene glycol PIP-PEG-PIP and 0.2g of sodium hydroxide in 989.8g of deionized water, and stirring to completely dissolve to obtain an aqueous phase solution; soaking the basement membrane prepared in the step (3) in an aqueous phase solution for 2min, and draining water drops on the membrane surface;
steps (6) to (7) are the same as steps (5) and (6) of example 1.
Example 3
Steps (1) to (4) were the same as in example 2;
(5) dissolving 6g of dendritic PAMAM, 4g of piperazine terminated polyethylene glycol PIP-PEG-PIP and 0.2g of sodium hydroxide in 989.8g of deionized water, and stirring to completely dissolve to obtain an aqueous phase solution; soaking the basement membrane prepared in the step (3) in an aqueous phase solution for 2min, and draining water drops on the membrane surface;
steps (6) to (7) are the same as steps (5) and (6) of example 1.
Example 4 Steps (1) - (4) are the same as in example 2; (5) dissolving 4g of dendritic PAMAM, 1g of piperazine terminated polyethylene glycol PIP-PEG-PIP and 0.2g of sodium hydroxide in 994.8g of deionized water, and stirring to completely dissolve to obtain an aqueous phase solution; and (4) soaking the basement membrane prepared in the step (3) in an aqueous phase solution for 2min, and draining water drops on the membrane surface.
Steps (6) to (7) are the same as steps (5) and (6) of example 1.
Example 5
Steps (1) to (4) were the same as in example 1.
(5) Dissolving 1.0g of trimesoyl chloride in 999g of n-hexane, and stirring and dissolving to obtain an organic phase solution; and (4) soaking the base membrane soaked with the water phase solution in the step (4) in the organic phase solution for 0.5 min.
Step (6) is the same as step (6) of example 1.
Test and result nanofiltration membrane flux and removal test of organic matters with different molecular weights, namely rejection rate test
Taking the composite nanofiltration membranes prepared in examples 1 to 5, performing an organic matter removal test on a membrane detection table, and measuring the water flux and rejection rate of the membrane after running for 30min under the test conditions that the operation pressure is 100psi, the organic matter concentration is 2000ppm of the original water solution, the solution temperature is 25 ℃, and the pH value is 6.5-7.5, wherein the results are shown in tables 1-3, wherein table 1 is a test result for PEG200, table 2 is a test result for PEG400, and table 3 is a test result for PEG 600:
TABLE 1
TABLE 2
TABLE 3
As can be seen from the test results of the composite nanofiltration membranes obtained in examples 1 to 5 listed in tables 1 to 3, the separation layer is prepared by performing interfacial polymerization reaction on the water-phase monomer and the acid chloride compound by using one or two of the dendritic polyamidoamine PAMAM and the piperazine-terminated polyethylene glycol PIP-PEG-PIP, and the obtained nanofiltration membrane realizes that the difference between the retention rates of organic substances with different molecular weights, namely PEG200, PEG400 and PEG600, is increased, the retention rate of PEG200 is reduced, the retention rates of PEG400 and PEG600 are increased, the selectivity of separation of organic substances with different molecular weights is improved, and selective separation of organic substances with different molecular weights is realized while maintaining high flux superior to that of the nanofiltration membrane in the prior art.
The preparation method can directly utilize the existing production equipment, does not need to carry out an additional coating process, does not need to adjust the existing production equipment and production process, reduces the production cost and improves the production efficiency.
In general, by selecting specific water phase monomers and combinations thereof, composite nanofiltration membranes with different retention rates and high fluxes for organic matters with different molecular weights can be obtained, and composite nanofiltration membranes with higher retention rate and flux for organic matters with high molecular weights and capable of allowing organic matters with low molecular weights to pass through (i.e., the retention rate is low and the flux is high for the organic matters with low molecular weights compared with the high retention rate for the organic matters with high molecular weights) can be obtained.
It should be noted that: for the evaluation of the membrane performance, it is not necessarily the case that the higher the molecular weight cut-off is, the better the cut-off is, but it is mainly determined by the application environment of the membrane. For example, in some practical applications, the liquid to be filtered contains organic substances with different molecular weights, and most of the organic substances with high molecular weights need to be intercepted, and when most of the organic substances with low molecular weights need to pass through, the membrane is required to have relatively high interception rate for the organic substances with high molecular weights and relatively low interception rate for the organic substances with low molecular weights; the need to reject a substantial portion of the high molecular weight organics, while passing the appropriate amount of low and medium molecular weight organics, requires the membrane to have a relatively high rejection rate for the high molecular weight organics and an appropriate rejection rate for the low and medium molecular weight organics.
As can be seen from the data of the rejection rate and the flux of the composite nanofiltration membrane obtained in the embodiments 1 to 5 given in the above Table 1, the composite nanofiltration membrane prepared by the method of the present invention meets different application requirements, and the rejection rate and the flux of organic substances with different molecular weights can be adjusted.
Industrial applicabilityBy adopting the preparation method of the application to prepare the nanofiltration membrane, the selective separation of organic matters with different molecular weights can be realized under the condition of keeping the high flux of the nanofiltration membrane.
Claims (15)
1. The preparation method of the nanofiltration membrane is characterized by comprising the following steps:
dissolving a polymer in a solvent to prepare a polymer solution, and solidifying the polymer solution on a support material to form a base film;
immersing the base membrane into an aqueous phase solution, wherein the aqueous phase solution contains one or more of dendritic polyamidoamine PAMAM, aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol), and then immersing the base membrane into an organic phase solution containing an acyl chloride compound, wherein the dosage of the dendritic polyamidoamine PAMAM is 0.0-3.0 wt%, and the dosage of the aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) is 0.0-3.0 wt%, based on the weight of the aqueous phase solution, wherein the dosage of the dendritic polyamidoamine PAMAM and the dosage of the aliphatic nitrogen-containing heterocyclic compound or aromatic amine compound-terminated poly (alkylene glycol) are not 0 at the same time;
obtaining a nanofiltration membrane after post-treatment and drying;
the polymer is one or more of polyphenylene sulfone PPSU, polyetherimide PEI, polysulfone and polyethersulfone;
the aliphatic nitrogen heterocyclic compound is one or more of piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-isopropylpiperazine and pyrazole; the aromatic amine compound is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and 4-methyl-m-phenylenediamine.
2. The preparation method according to claim 1, wherein the solvent in the polymer solution is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, and imidazolidinone.
3. The method of claim 1, wherein the support material is a nonwoven fabric.
4. The method according to claim 1, wherein the polymer is used in an amount of 15 to 28wt% based on the weight of the polymer solution.
5. The method according to claim 4, wherein the polymer is used in an amount of 15 to 25wt% based on the weight of the polymer solution.
6. The method according to claim 5, wherein the polymer is used in an amount of 16 to 22wt% based on the weight of the polymer solution.
7. The method according to claim 1, wherein the amount of the dendritic polyamidoamine PAMAM is 0.0 to 2.5wt% and the amount of the poly (alkylene glycol) terminated with the aliphatic nitrogen-containing heterocyclic compound or the aromatic amine-based compound is 0.0 to 2.5wt% based on the weight of the aqueous solution.
8. The method of claim 1, wherein the poly (alkylene glycol) is poly (ethylene glycol), poly (propylene glycol), poly (butylene glycol).
9. The method according to claim 1, wherein the poly (alkylene glycol) has a degree of polymerization of 5 to 95.
10. The method according to claim 1, wherein the poly (alkylene glycol) has a degree of polymerization of 5 to 15.
11. The preparation method according to claim 1, wherein the acid chloride compound is one or more of trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride and terephthaloyl chloride.
12. The method according to claim 1, wherein the acid chloride compound is used in an amount of 0.05 to 0.5wt% based on the weight of the organic phase solution.
13. The method according to claim 12, wherein the acid chloride compound is used in an amount of 0.1 to 0.3wt% based on the weight of the organic phase solution.
14. The method according to claim 13, wherein the acid chloride compound is used in an amount of 0.1 to 0.25wt% based on the weight of the organic phase solution.
15. A nanofiltration membrane prepared by the preparation method of any one of claims 1 to 13.
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