CN116371195A - Composite nanofiltration membrane and preparation method and application thereof - Google Patents
Composite nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- CN116371195A CN116371195A CN202310390113.6A CN202310390113A CN116371195A CN 116371195 A CN116371195 A CN 116371195A CN 202310390113 A CN202310390113 A CN 202310390113A CN 116371195 A CN116371195 A CN 116371195A
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- Prior art keywords
- chloride
- nanofiltration membrane
- composite nanofiltration
- amine
- swelling
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- 239000012528 membrane Substances 0.000 title claims abstract description 124
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 82
- 230000008961 swelling Effects 0.000 claims abstract description 82
- 238000000926 separation method Methods 0.000 claims abstract description 57
- 150000001412 amines Chemical class 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 30
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 23
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 238000004042 decolorization Methods 0.000 claims abstract description 3
- 238000010612 desalination reaction Methods 0.000 claims abstract description 3
- -1 polyethylene Polymers 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 150000003384 small molecules Chemical class 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004952 Polyamide Substances 0.000 claims description 14
- 229920002873 Polyethylenimine Polymers 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 12
- 229960001231 choline Drugs 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- IKRZCYCTPYDXML-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;hydrochloride Chemical compound Cl.OC(=O)CC(O)(C(O)=O)CC(O)=O IKRZCYCTPYDXML-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 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 4
- 230000005496 eutectics Effects 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- ZBJSGOMTEOPTBH-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC(S(Cl)(=O)=O)=CC2=CC(S(=O)(=O)Cl)=CC=C21 ZBJSGOMTEOPTBH-UHFFFAOYSA-N 0.000 claims description 4
- BCXWMIMRDMIJGL-UHFFFAOYSA-N naphthalene-1,5-disulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1S(Cl)(=O)=O BCXWMIMRDMIJGL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- SNBDGFZQPKCZTO-UHFFFAOYSA-N propanedioic acid;hydrochloride Chemical compound Cl.OC(=O)CC(O)=O SNBDGFZQPKCZTO-UHFFFAOYSA-N 0.000 claims description 3
- GIIOFTHZYOBSHL-VFQQELCFSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;hydrochloride Chemical compound Cl.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO GIIOFTHZYOBSHL-VFQQELCFSA-N 0.000 claims description 2
- HUSXNIFVQFHSEA-UHFFFAOYSA-N 2-hydroxypropanoic acid;hydrochloride Chemical compound Cl.CC(O)C(O)=O HUSXNIFVQFHSEA-UHFFFAOYSA-N 0.000 claims description 2
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002643 polyglutamic acid Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 25
- 239000011148 porous material Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 25
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 11
- 229930006000 Sucrose Natural products 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000005720 sucrose Substances 0.000 description 11
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 10
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 10
- 238000000108 ultra-filtration Methods 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 3
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 3
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229940074393 chlorogenic acid Drugs 0.000 description 3
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 3
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 3
- 235000001368 chlorogenic acid Nutrition 0.000 description 3
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- 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
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- 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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a composite nanofiltration membrane, a preparation method and application thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent. The composite nanofiltration membrane has a smooth surface with narrower pore size distribution, higher hydrophilicity and near charge neutrality, realizes high separation selectivity on small molecular organic matters while obviously improving pure water permeation flux, and has excellent pollution resistance and long-term operation stability, and can be used for wastewater decolorization, wastewater desalination, resource recovery or water softening.
Description
Technical Field
The invention belongs to the technical field of nanofiltration membranes, and particularly relates to a composite nanofiltration membrane and a preparation method and application thereof.
Background
Water resource shortage has become a pressing problem due to rapid population growth, rapid industrialization development and serious water pollution worldwide. Nanofiltration is used as a low-energy separation process, and substances with the molecular weight cut-off of 100-2000 Da are generally used, so that the nanofiltration has excellent separation performance on water/salt or water/organic matters, and has great potential in water purification and resource recovery. However, colloids, proteins and small molecule organics in the feed solution tend to cause membrane fouling during operation, resulting in increased transmembrane resistance, reduced permeation flux and selectively variable separation. Therefore, there is a need to design high performance nanofiltration membranes that are resistant to contamination for accurate solute separation.
Interfacial polymerization is widely used in the preparation of nanofiltration membranes, however, the formation of an active separation layer with a wide pore size distribution and a rough surface due to the non-uniformity of mass transfer of aqueous monomers results in poor membrane separation selectivity and contamination resistance. Thus, CN115350598A discloses a method for preparing nanofiltration membrane by using 1-methylimidazole as water phase additive, wherein hydrogen bond formed by 1-methylimidazole and piperazine inhibits piperazine from diffusing deeper into reaction zone, so that the surface of the formed membrane is smoother, and the pollution resistance of the membrane is improved. However, the introduction of the additive can reduce the crosslinking degree of the polyamide separation layer main body, expand the pore diameter of the membrane, and hydrolyze unreacted acyl chloride groups on the surface to form carboxyl groups, so that the membrane has strong electronegativity, and the anti-pollution capability of the membrane to small molecules and positively charged substances is reduced.
For nanofiltration separation systems with complex components, conventional nanofiltration membranes with single chargeability (positively or negatively charged) are difficult to realize pollution resistance. Thus, CN114768561a discloses a preparation method of an anti-pollution composite membrane, which uses acyl chloride groups remained after interfacial polymerization reaction to continuously react with amine groups of polyamine, so that the surface of the membrane is positively charged by polyamine, then part of amine groups on the surface of the membrane and carboxyl groups of polybasic acid are subjected to dehydration condensation reaction, so that the outermost surface of the membrane is negatively charged, and a double-layer charge structure protective layer is formed, so that the organic pollution of the nanofiltration membrane is reduced. CN114259884a discloses a positively charged composite nanofiltration membrane based on in-situ zwitterionic and a preparation method thereof, and polyethylene imine and 1, 4-butanesultone are used for carrying out in-situ zwitterionic on the membrane surface after interfacial polymerization, and the offset of the isoelectric point of the membrane to neutrality improves the anti-pollution performance of the membrane on positively charged or negatively charged pollutants. However, these surface modification methods only improve the separation layer surface properties, and the introduction of additional separation layers increases the water mass transfer resistance, reducing the permeability of the membrane. In addition, the surface modification cannot improve the pore size distribution of the separation layer, and the wide pore size distribution can cause large local permeation flux difference, so that the separation selectivity and the pollution resistance of the nanofiltration membrane are poor.
Therefore, there is a need to develop a composite nanofiltration membrane with a narrower pore size distribution, higher hydrophilicity and near charge neutrality and smooth surface, so as to meet the requirements of improving pure water permeation flux, high separation selectivity of small molecular organic matters, pollution resistance and long-term operation stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite nanofiltration membrane and a preparation method and application thereof. The composite nanofiltration membrane not only improves the pure water permeation flux, but also realizes high separation selectivity on sucrose/xylose, and the smooth surface with narrower pore size distribution, higher hydrophilicity and near charge neutrality can resist pollution of positively charged/negatively charged micromolecules and proteins, so that flux attenuation during separation is avoided, and the problems that the nanofiltration membrane is easy to be polluted and the separation selectivity is poor during material liquid treatment in the prior art can be effectively solved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite nanofiltration membrane comprising a support base membrane and an active separation layer supported on the support base membrane.
The active separation layer comprises an interfacial polymerization product of a post-treatment modified polyamine and a polyacyl chloride.
The post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent.
In the invention, after the polyamide formed at the interface of the polyamine and the polybasic acyl chloride is soaked in the mixed solution composed of the amine-containing solute and the swelling solvent, the swelling solvent can dissolve polyamide fragments with small molecular weight and the swelling polyamide chain segments, so that the membrane pores of the polyamide active layer are enlarged. In addition, the swelling solvent can promote amine-containing solute to enter the membrane pores, reach the inside of polyamide and react with unhydrolyzed acyl chloride to complete deep grafting, as shown in figure 1, so that the structure and the property of the separation layer formed by the polyamine and the polybasic acyl chloride are reformed, the active separation layer has a smooth surface with narrower pore size distribution, higher hydrophilicity and near charge neutrality, and the separation selectivity and the pollution resistance of small molecular organic matters are improved.
Preferably, the polyamine comprises any one or a combination of at least two of piperazine, meta-phenylenediamine, ortho-phenylenediamine, para-phenylenediamine, polyethyleneimine (PEI), polyethyleneamine, or trimellitic amine, wherein typical but non-limiting combinations include: combinations of piperazine and m-phenylenediamine, combinations of m-phenylenediamine, o-phenylenediamine and p-phenylenediamine, polyethyleneimine, polyethyleneamine and trimellitic amine, and the like.
Preferably, the polyacyl chloride comprises any one or a combination of at least two of trimesoyl chloride, phthaloyl chloride, terephthaloyl chloride, 1, 5-naphthalenedisulfonyl chloride, 1,3, 6-naphthalenetrisulfonyl chloride, 1,3, 5-cyclohexanetricacyl chloride, or pyromellitic chloride, wherein typical but non-limiting combinations include: combinations of trimesoyl chloride and phthaloyl chloride, terephthaloyl chloride, 1, 5-naphthalenedisulfonyl chloride and 1,3, 6-naphthalenetrisulfonyl chloride, 1, 5-naphthalenedisulfonyl chloride, 1,3, 6-naphthalenetrisulfonyl chloride, 1,3, 5-cyclohexaneditricarboxyl chloride and pyromellitic chloride, and the like.
Preferably, the amine-containing solute comprises any one or a combination of at least two of diethylenetriamine, tetraethylenepentamine, polyethylenepolyamine, polyethyleneimine, polyvinylamine, or polyglutamic acid.
Preferably, the molecular weight of polyethyleneimine in the amine-containing solute is 600-1000 Da, for example 600Da, 650Da, 700Da, 750Da, 800Da, 850Da, 900Da, 950Da, 1000Da, or the like.
Preferably, the polyethylenimine comprises any one or a combination of at least two of PEI600, PEI800 or PEI 1000.
Wherein the amine-containing solutes typically, but not limitatively, comprise: a combination of PEI600 and diethylenetriamine, PEI1000, diethylenetriamine, a combination of tetraethylenepentamine and PEI600, a combination of diethylenetriamine, tetraethylenepentamine, PEI600 and PEI800, and the like.
Preferably, the swelling solvent comprises a mixture of green solvent and swelling small molecules.
In the present invention, the weak interaction of the amine-containing solute with the green solvent allows the amine-containing solute to enter the interior of the polyamide to react with the unhydrolyzed acid chloride.
Preferably, the green solvent comprises an ionic liquid and/or a eutectic solvent.
Preferably, the ionic liquid comprises any one or a combination of at least two of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-propylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1, 3-dimethylimidazole tetrafluoroborate, 1- (2-hydroxyethyl) -3-methyl-1H-imidazol-3-ium tetrafluoroborate or 1-ethyl-3-methylimidazolium hexafluorophosphate; typical but non-limiting combinations thereof include: a combination of 1-butyl-3-methylimidazole tetrafluoroborate and 1-methyl-3-propylimidazole tetrafluoroborate, a combination of 1-methyl-3-propylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate and 1, 3-dimethylimidazole tetrafluoroborate, 1- (2-hydroxyethyl) -3-methyl-1H-imidazol-3-ium tetrafluoroborate, 1-ethyl-3-methylimidazole hexafluorophosphate, choline chloride-citric acid, and choline chloride-malonic acid, and the like.
Preferably, the eutectic solvent includes any one or a combination of at least two of choline chloride-citric acid, choline chloride-malonic acid, choline chloride-lactic acid, or choline chloride-sorbitol.
Preferably, the swelling small molecule comprises any one or a combination of at least two of methanol, absolute ethanol, acetone, dimethyl sulfoxide or acetonitrile; typical but non-limiting combinations thereof include: a combination of methanol and absolute ethanol, a combination of absolute ethanol, acetone and dimethyl sulfoxide, a combination of absolute ethanol, acetone, dimethyl sulfoxide and acetonitrile, and the like.
Preferably, the mass ratio of the green solvent to the swelling small molecule in the swelling solvent is (0.43-2.3): 1, for example, may be 0.5:1, 0.8:1, 1.0:1, 1.5:1, 0.5:1, 1.8:1, 2.0:1 or 2.3:1, etc., but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In the invention, the dosage of the green solvent is too small, which causes insufficient swelling of the polyamide chain segment, causes less deep grafting of the amine-containing solute, and is difficult to control the charge of the active separation layer; the excessive use of the green solvent causes excessive swelling of the polyamide chain segments, the grafting reaction is difficult to offset the negative influence of the swelling, the aperture and the chargeability of the active separation layer cannot be effectively regulated and controlled, and the separation selectivity and the pollution resistance are reduced.
The amount of the amine-containing solute is preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of the swelling solvent, and may be, for example, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1.0 part, 2.0 parts, 3.0 parts, 4.0 parts, or 5.0 parts, etc., but is not limited to the values listed, and other values not listed in the numerical range are equally applicable, and further preferably 0.1 to 1.5 parts.
In the invention, excessive amine-containing solute is used to cause serious surface grafting and accumulation, so that the positively charged property of the membrane is enhanced, and the electrostatic attraction effect is enhanced, thus the pollution of negatively charged pollutants is difficult to realize; the amine-containing solute is too little in dosage, so that insufficient grafting is caused, the reforming capacity of the active separation layer structure is limited, and high separation selectivity of the solute is difficult to realize.
Preferably, the post-treatment comprises a soaking and crosslinking reaction.
Preferably, the material of the support base film includes any one or a combination of at least two of polysulfone, polyethersulfone, polyimide, polyamide, polyethylene or polyacrylonitrile, wherein typical but non-limiting combinations include: a combination of polysulfone and polyethersulfone, a combination of polyimide, polyamide and polyethylene, a combination of polyimide, polyamide, polyethylene and polyacrylonitrile, and the like.
In a second aspect, the present invention provides a method for preparing a composite nanofiltration membrane as described in the first aspect, the method comprising the steps of:
(1) And mixing the support base film, polyamine and polybasic acyl chloride, and reacting.
(2) And (3) mixing the product obtained in the step (1) with a mixed solution containing an amine solute and a swelling solvent, and performing a crosslinking reaction to obtain the composite nanofiltration membrane.
In the present invention, the purpose of the crosslinking is to further increase the crosslinking degree of the active separation layer, causing the unreacted amino groups and the acid chloride to continue to react.
Preferably, the mixing in step (1) is performed by immersing the support base film in an aqueous solution of polyamine, taking out, drying, and then coating with a solution of polyacyl chloride/n-hexane.
Preferably, the time for immersing in the aqueous polyamine solution is 3 to 20 minutes, for example, 4 minutes, 6 minutes, 8 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or the like.
Preferably, the mass percentage of the polyamine in the aqueous solution of the polyamine is 0.1 to 1%, for example, may be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%.
Preferably, the mass percentage of the polybasic acyl chloride in the polybasic acyl chloride/normal hexane solution is 0.05-0.3%, for example, 0.10%, 0.12%, 0.15%, 0.18%, 0.20%, 0.22%, 0.25% or 0.28% and the like.
Preferably, the reaction time in the step (1) is 10 to 120s, for example, 12s, 20s, 30s, 40s, 50s, 60s, 70s, 90s, 100s or 120s, etc.
Preferably, the reaction of step (1) is followed by drying.
Preferably, the mixing of step (2) is immersing the product of step (1) with a mixed solution comprising an amine-containing solute and a swelling solvent.
Preferably, the soaking time is 3-30 min, for example, 4min, 6min, 8min, 10min, 15min, 20min or 25min, etc.
Preferably, the soaking step further comprises washing with swelling small molecules for 10-30 s, for example, 10s, 12s, 14s, 16s, 18s, 20s, 22s, 24s, 26s, 28s or 30s, etc.
In the present invention, the purpose of the flushing with the swelled small molecules is to remove unreacted amine-containing solutes after the soaking.
The temperature of the crosslinking reaction in the step (2) is preferably 40 to 60℃and may be, for example, 40℃42℃44℃46℃48℃50℃52℃54℃56℃58℃60 ℃.
Preferably, the time of the crosslinking reaction in the step (2) is 1 to 10min, for example, 1min, 2min, 3min, 5min, 8min or 10min, etc.
In a third aspect, the present invention provides a composite nanofiltration membrane as described in the first aspect for use in wastewater decolorization, wastewater desalination, resource recovery or water softening.
Compared with the prior art, the invention has the following beneficial effects:
according to the composite nanofiltration membrane provided by the invention, the interfacial polymerization product of polyamine and polybasic acyl chloride is soaked by the mixed solution consisting of amine-containing solute and swelling solvent, and the interfacial polymerization product is swelled and reformed, and meanwhile, the deep amide reaction is completed to prepare the active separation layer, so that the regulation and control on the internal structure and the surface property of the active separation layer are realized, the composite nanofiltration membrane with narrower pore size distribution, higher hydrophilicity, near charge neutrality and smooth surface is obtained, the separation selectivity and the pollution resistance of the composite nanofiltration membrane to small molecular organic matters are obviously improved, and compared with the traditional polyamide nanofiltration membrane, the flux attenuation rate of the composite nanofiltration membrane is reduced, and the sucrose/xylose separation selectivity is improved.
Drawings
FIG. 1 is a schematic illustration of the swelling solvent facilitating deep grafting of amine-containing solutes.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the present invention, the materials used in the examples and comparative examples are as follows:
supporting a bottom film: polyethersulfone ultrafiltration membrane, 50kDa, hunan Australian technologies Co., ltd
Supporting a bottom film: polysulfone ultrafiltration membrane, 50kDa, andeyice Membrane technologies Co., ltd
Supporting a bottom film: polyethylene ultrafiltration membrane, 50kDa, andeyice film technologies Co., ltd
Piperazine: anhydrous piperazine, 99%, shanghai Ala Biochemical technology Co., ltd
Trimesoyl chloride: 98%, shanghai Ala Biochemical technology Co.Ltd
N-hexane: 97%, shanghai microphone Biochemical technology Co., ltd
Ethanol: absolute ethanol, 99.8%, division Lin Shenghua Corp., shanghai microphone
Polyethyleneimine: PEI600, shanghai Ala Biochemical technology Co., ltd
1-butyl-3-methylimidazole tetrafluoroborate: 97%, shanghai Michel Biochemical technologies Co., ltd
Chlorogenic acid: 95%, shanghai Ala Biochemical technology Co.Ltd
Methylene blue: 98%, shanghai microphone Lin Shenghua Co., ltd
Example 1
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent; based on 100 parts by weight of the swelling solvent, 1.0 part by weight of the amine-containing solute; the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 1:1.
The preparation method comprises the following steps:
(1) Immersing a support base film (polyether sulfone ultrafiltration film) in a polyamine (piperazine) water solution with the mass percentage of 0.5% for 5min, taking out the immersed support base film, drying the immersed support base film at room temperature until no macroscopic water drops are formed on the surface, then coating a polybasic acyl chloride (trimesoyl chloride)/n-hexane solution with the mass percentage of 0.15% on the immersed support base film for interfacial polymerization reaction, and taking out and drying the support base film after 30s of reaction.
(2) And (3) physically blending 50g of green solvent (1-butyl-3-methylimidazolium tetrafluoroborate) and 50g of swelling small molecule (absolute ethyl alcohol), dissolving 1g of amine-containing solute (PEI 600) in the blending solution to obtain a mixed solution of the amine-containing solute and the swelling solvent, soaking the product prepared in the step (1) in the mixed solution for 5min, taking out the product after soaking, flushing the product with the swelling small molecule (absolute ethyl alcohol) for 20s, and carrying out crosslinking reaction for 3min at 50 ℃ to obtain the composite nanofiltration membrane.
Example 2
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent; based on 100 parts by weight of the swelling solvent, 1.5 parts by weight of the amine-containing solute; the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 0.43:1.
The preparation method comprises the following steps:
(1) Immersing a support base film (polyether sulfone ultrafiltration film) in a piperazine water solution with the mass percentage of 0.5% for 5min, taking out the immersed support base film, drying at room temperature until no macroscopic water drops are on the surface, then coating a trimesoyl chloride/n-hexane solution with the mass percentage of 0.15% on the immersed support base film for interfacial polymerization reaction, and taking out and drying after 30s of reaction.
(2) And (3) physically blending 30g of 1-butyl-3-methylimidazole tetrafluoroborate and 70g of absolute ethyl alcohol, dissolving 1.5g of PEI600 in the blending solution to obtain a mixed solution containing an amine solute and a swelling solvent, soaking the product prepared in the step (1) in the mixed solution for 5min, taking out the product after soaking, washing the product with absolute ethyl alcohol for 20s, and carrying out crosslinking reaction for 3min at 50 ℃ to obtain the composite nanofiltration membrane.
Example 3
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent; based on 100 parts by weight of the swelling solvent, 0.1 part by weight of the amine-containing solute; the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 2.3:1.
The preparation method comprises the following steps:
(1) Immersing a support base film (polyether sulfone ultrafiltration film) in a piperazine water solution with the mass percentage of 0.5% for 5min, taking out the immersed support base film, drying at room temperature until no macroscopic water drops are on the surface, then coating a trimesoyl chloride/n-hexane solution with the mass percentage of 0.15% on the immersed support base film for interfacial polymerization reaction, and taking out and drying after 30s of reaction.
(2) And (3) physically blending 30g of 1-butyl-3-methylimidazole tetrafluoroborate and 70g of absolute ethyl alcohol, dissolving 0.1g of PEI600 in the blending solution to obtain a mixed solution containing an amine solute and a swelling solvent, soaking the product prepared in the step (1) in the mixed solution for 5min, taking out the product after soaking, washing the product with absolute ethyl alcohol for 20s, and carrying out crosslinking reaction for 3min at 50 ℃ to obtain the composite nanofiltration membrane.
Example 4
The present embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the amine-containing solute is a combination of PEI600 and diethylenetriamine (the mass ratio of PEI600 to diethylenetriamine is 1:1), and other raw materials, amounts and preparation methods are the same as those of embodiment 1.
Example 5
The present example provides a composite nanofiltration membrane and a preparation method thereof, which are different from example 1 only in that the green solvent is a combination of 1-butyl-3-methylimidazolium tetrafluoroborate and choline chloride-citric acid (the mass ratio of 1-butyl-3-methylimidazolium tetrafluoroborate to choline chloride-citric acid is 1:1), and other raw materials, amounts and preparation methods are the same as example 1.
Example 6
The present embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the swelling small molecules are a combination of methanol and absolute ethanol (the mass ratio of the methanol to the absolute ethanol is 1:1), and other raw materials, amounts and preparation methods are the same as embodiment 1.
Example 7
The present embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the mass part of the amine-containing solute is 0.01 part based on 100 parts of the mass of the swelling solvent;
the mixed solution of the amine-containing solute and the swelling solvent was prepared by physically blending 50g of green solvent (1-butyl-3-methylimidazolium tetrafluoroborate) and 50g of swelling small molecule (absolute ethanol), and then dissolving 0.01g of pei600 in the above blended solution.
Other raw materials, amounts and preparation methods were the same as in example 1.
Example 8
The present embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the mass part of the amine-containing solute is 10 parts based on 100 parts of the mass of the swelling solvent;
the mixed solution of the amine-containing solute and the swelling solvent was prepared by physically blending 50g of green solvent (1-butyl-3-methylimidazolium tetrafluoroborate) and 50g of swelling small molecule (absolute ethanol), and then dissolving 10g of pei600 in the above blended solution.
Other raw materials, amounts and preparation methods were the same as in example 1.
Example 9
The present embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 0.1:1;
the swelling solvent is prepared by physically blending 9.1g of green solvent (1-butyl-3-methylimidazole tetrafluoroborate) and 90.9g of swelling small molecule (absolute ethanol).
Other raw materials, amounts and preparation methods were the same as in example 1.
Example 10
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, which are different from embodiment 1 only in that the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 4:1;
the swelling solvent is prepared by physically blending 80g of green solvent (1-butyl-3-methylimidazole tetrafluoroborate) and 20g of swelling small molecule (absolute ethyl alcohol).
Other raw materials, amounts and preparation methods were the same as in example 1.
Example 11
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent; based on 100 parts by weight of the swelling solvent, 1.0 part by weight of the amine-containing solute; the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 1:1.
The preparation method comprises the following steps:
(1) Immersing a support base film (polysulfone ultrafiltration film) in a polyamine (m-phenylenediamine) water solution with the mass percentage of 0.1% for 20min, taking out the immersed support base film, drying the immersed support base film at room temperature until no water drops are visible on the surface, then coating a polybasic acyl chloride (trimesoyl chloride and phthaloyl chloride in a combination of 1:1 by mass ratio) with the mass percentage of 0.05% on the immersed support base film, carrying out interfacial polymerization reaction, and taking out and drying after 120s of reaction.
(2) And (3) physically blending 50g of green solvent (1, 3-dimethylimidazole tetrafluoroborate) and 50g of swelling small molecule (acetone), dissolving 5g of amine-containing solute (diethylenetriamine) in the blending solution to obtain a mixed solution of the amine-containing solute and the swelling solvent, soaking the product prepared in the step (1) in the mixed solution for 30min, taking out the product after soaking, flushing the product with the swelling small molecule (acetone) for 10s, and carrying out crosslinking reaction at 40 ℃ for 10min to obtain the composite nanofiltration membrane.
Example 12
The embodiment provides a composite nanofiltration membrane and a preparation method thereof, wherein the composite nanofiltration membrane comprises a support bottom membrane and an active separation layer loaded on the support bottom membrane; the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment; the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent; based on 100 parts by weight of the swelling solvent, 1.0 part by weight of the amine-containing solute; the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is 1:1.
The preparation method comprises the following steps:
(1) Immersing a support base film (polyethylene ultrafiltration film) into a polyamine (combination of o-phenylenediamine and p-phenylenediamine according to a mass ratio of 1:0.5) water solution with a mass percentage of 1% for 3min, taking out the immersed support base film, drying at room temperature until no macroscopic water drops are formed on the surface, then coating a polyacyl chloride (terephthaloyl chloride)/n-hexane solution with a mass percentage of 0.3% on the immersed support base film for interfacial polymerization reaction, and taking out and drying after 10s of reaction.
(2) And (3) physically blending 50g of green solvent (1-ethyl-3-methylimidazole hexafluorophosphate) and 50g of swelling small molecule (dimethyl sulfoxide), dissolving 1g of amine-containing solute (PEI 600) in the blending solution to obtain a mixed solution of the amine-containing solute and the swelling solvent, soaking the product prepared in the step (1) in the mixed solution for 3min, taking out the product after soaking, flushing the product with the swelling small molecule (dimethyl sulfoxide) for 20s, and carrying out crosslinking reaction at 60 ℃ for 1min to obtain the composite nanofiltration membrane.
Comparative example 1
The comparative example provides a composite nanofiltration membrane and a preparation method thereof, wherein the preparation method comprises the following steps:
immersing a support base film (polyether sulfone ultrafiltration film) into a polyamine (piperazine) water solution with the mass percentage of 0.5% for 5min, taking out the immersed support base film, drying the immersed support base film at room temperature until no macroscopic water drops are formed on the surface, then coating a polybasic acyl chloride (trimesoyl chloride)/n-hexane solution with the mass percentage of 0.15% on the immersed support base film for interfacial polymerization reaction, taking out and drying after 30s reaction, and obtaining the composite nanofiltration film.
Comparative example 2
The comparative example provides a composite nanofiltration membrane and a preparation method thereof, which are different from example 1 only in that the mixed solution for post-treatment modification is not added with amine-containing solute (PEI 600), and other raw materials, amounts and preparation methods are the same as those of example 1.
Comparative example 3
This comparative example provides a composite nanofiltration membrane and a preparation method thereof, which are different from example 1 only in that a green solvent (1-butyl-3-methylimidazole tetrafluoroborate) is not added to the mixed solution for post-treatment modification, and other raw materials, amounts and preparation methods are the same as example 1.
Comparative example 4
This comparative example provides a composite nanofiltration membrane and a preparation method thereof, which are different from example 1 only in that 50g of green solvent (1-butyl-3-methylimidazolium tetrafluoroborate) and 50g of swelling small molecule (absolute ethyl alcohol) are replaced with 100g of water in the mixed solution for post-treatment modification, and other raw materials, amounts and preparation methods are the same as example 1.
Performance testing
The composite nanofiltration membranes provided in examples 1 to 12 and comparative examples 1 to 4 were tested for pure water permeation flux, sodium sulfate rejection, magnesium chloride rejection, sucrose rejection, xylose rejection and flux decay rate at 25 ℃:
the pure water permeation flux, sodium sulfate retention rate, magnesium chloride retention rate, sucrose retention rate and xylose retention rate of the composite membrane were tested by adopting a self-made dead-end device. The effective volume of the membrane chamber is13mL, effective membrane area 4.52cm 2 The concentration of each solute in the feed solution was 1g L -1 Constant flux washing filtration mode, flux of 39.8Lm -2 h -1 The test temperature was 25 ℃.
(1) The pure water permeation flux was calculated according to the following formula:
wherein the unit of pure water permeation flux is L m -2 h -1 bar -1 ；V p The volume of permeate (L) collected over time t; a is that m Is the effective membrane area (m 2 ) The method comprises the steps of carrying out a first treatment on the surface of the t is the run time (h); TMP is transmembrane pressure (bar).
(2) The rejection rates of sodium sulfate, magnesium chloride, sucrose and xylose were calculated according to the following formula:
wherein C is p ，C f And C r Represents the concentration of solute in permeate, feed and retentate, respectively: the salt concentration was measured by a conductivity meter and the sucrose concentration was measured by high performance liquid chromatography (HPX-87N, 300 mm. Times.7.8 mm column).
(3) The sucrose/xylose separation factor was calculated according to the following formula:
(4) The membrane flux decay rate was tested using a dead-end device.
A constant flux wash filtration mode (flux 39.8L m) -2 h -1 ) Membrane pure water permeate flux (PWP) was first tested at 25 c 0 ) Then at 2g L -1 Chlorogenic acid and 0.8. 0.8g L -1 Methylene blue is used as a feed liquid, pollution is carried out for 60min at 25 ℃, finally deionized water is used for washing the surface of the polluted membrane for 3 times,the contaminated membrane was tested for pure water permeation flux (PWP) at 25 deg.c f ). The membrane flux attenuation rate is used for evaluating the anti-pollution capability of the membrane, and the calculation formula is as follows:
the specific test results are shown in table 1:
TABLE 1
As can be seen from the table, the composite nanofiltration membrane provided by the invention realizes the reforming of the internal structure and the surface property of the active separation layer by using the solvent to induce the active separation layer to swell and the deep grafting of the amine-containing solute after interfacial polymerization, and the obtained composite nanofiltration membrane has smooth surfaces with narrower pore size distribution, higher hydrophilicity and near charge neutrality, realizes high separation selectivity on sucrose/xylose while obviously improving the pure water permeation flux, and also obviously improves the pollution resistance and long-term operation stability of the composite nanofiltration membrane. As can be seen from examples 1 to 6, the pure water permeation flux of the composite nanofiltration membrane is 10.5 to 12.5. 12.5L m - 2 h -1 bar -1 The retention rate of sodium sulfate is 93-95%, the retention rate of magnesium chloride is 65-68%, the sucrose/xylose separation factor is 7-8, and the selectivity of sucrose/xylose separation is excellent; chlorogenic acid and methylene blue are used as feed liquid, and the flux attenuation rate after 60min of pollution at 25 ℃ is 6.5-7.5%, so that the feed liquid has excellent anti-pollution performance.
As is clear from comparison of examples 1 and examples 7 and 8, when the mass fraction of the amine-containing solute is not within the preferred range of 0.1 to 5.0 parts based on 100 parts by mass of the swelling solvent, the composite nanofiltration membrane is off-neutral in charge and the anti-fouling performance is reduced; as is clear from comparison of examples 1 with examples 9 and 10, when the mass ratio of the green solvent to the small swollen molecules in the swelling solvent is not within the preferred range of (0.43 to 2.3): 1, the degree of swelling of the composite nanofiltration membrane does not match the degree of deep grafting, the pore size distribution becomes broad, and the separation selectivity and contamination resistance are lowered.
As is clear from comparison between example 1 and comparative example 1, when the composite nanofiltration membrane is not subjected to post-treatment modification, the pure water permeation flux of the composite nanofiltration membrane is low, the separation selectivity is poor, the anti-pollution performance is poor, the flux attenuation rate after the post-treatment modification (example 1) is reduced by 63.2%, and the sucrose/xylose separation selectivity is improved by 3.3 times.
As is clear from comparison of example 1 and comparative example 2, the composite nanofiltration membrane has wide pore size distribution and poor anti-pollution performance when no amine-containing solute is added to the mixed solution for post-treatment modification.
As is clear from comparison between example 1 and comparative example 3, the composite nanofiltration membrane has limited reforming ability of absolute ethanol and poor anti-pollution performance when no green solvent is added into the mixed solution for post-treatment modification.
As is clear from comparison of example 1 with comparative example 4, when 50g of green solvent and 50g of swelling small molecule were replaced with 100g of water in the mixed solution for post-treatment modification of the composite nanofiltration membrane, the membrane did not have swelling and reforming ability to the active separation layer, and the separation selectivity was poor.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A composite nanofiltration membrane, characterized in that the composite nanofiltration membrane comprises a support base membrane and an active separation layer supported on the support base membrane;
the active separation layer comprises an interfacial polymerization product of a polyamine and a polybasic acyl chloride which are modified by post treatment;
the post-treatment modification comprises post-treatment with a mixed solution of an amine-containing solute and a swelling solvent.
2. The composite nanofiltration membrane of claim 1, wherein the polyamine comprises any one or a combination of at least two of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, polyethylenimine, polyvinylamine, or trimellitic amine.
3. The composite nanofiltration membrane according to claim 1 or 2, wherein the polybasic acyl chloride comprises any one or a combination of at least two of trimesoyl chloride, phthaloyl chloride, terephthaloyl chloride, 1, 5-naphthalenedisulfonyl chloride, 1,3, 6-naphthalenetrisulfonyl chloride, 1,3, 5-cyclohexanetricacyl chloride or pyromellitic chloride.
4. A composite nanofiltration membrane according to any one of claims 1-3, wherein the amine-containing solute comprises any one or a combination of at least two of diethylenetriamine, tetraethylenepentamine, polyethylene polyamine, polyethylene imine, polyethylene amine, or polyglutamic acid;
preferably, the molecular weight of polyethyleneimine in the amine-containing solute is 600-1000 Da;
preferably, the swelling solvent comprises a mixture of a green solvent and a swelling small molecule;
preferably, the green solvent comprises an ionic liquid and/or a eutectic solvent;
preferably, the ionic liquid comprises any one or a combination of at least two of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-propylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1, 3-dimethylimidazole tetrafluoroborate, 1- (2-hydroxyethyl) -3-methyl-1H-imidazol-3-ium tetrafluoroborate or 1-ethyl-3-methylimidazolium hexafluorophosphate;
preferably, the eutectic solvent comprises any one or a combination of at least two of choline chloride-citric acid, choline chloride-malonic acid, choline chloride-lactic acid or choline chloride-sorbitol;
preferably, the swelling small molecule comprises any one or a combination of at least two of methanol, absolute ethanol, acetone, dimethyl sulfoxide or acetonitrile;
preferably, the mass ratio of the green solvent to the swelling small molecules in the swelling solvent is (0.43-2.3): 1.
5. The composite nanofiltration membrane according to any one of claims 1 to 4, wherein the mass fraction of the amine-containing solute is 0.1 to 5.0 parts, more preferably 0.1 to 1.5 parts, based on 100 parts by mass of the swelling solvent;
preferably, the post-treatment comprises a soaking and crosslinking reaction.
6. The composite nanofiltration membrane of any one of claims 1-5, wherein the support base membrane comprises any one or a combination of at least two of polysulfone, polyethersulfone, polyimide, polyamide, polyethylene, or polyacrylonitrile.
7. The method for preparing a composite nanofiltration membrane according to any one of claims 1 to 6, wherein the method comprises the steps of:
(1) Mixing the support base film, polyamine and polybasic acyl chloride for reaction;
(2) And (3) mixing the product obtained in the step (1) with a mixed solution containing an amine solute and a swelling solvent, and performing a crosslinking reaction to obtain the composite nanofiltration membrane.
8. The method of claim 7, wherein the mixing in step (1) is performed by immersing the support base film in an aqueous solution of polyamine, taking out, drying, and then coating with a solution of polyacyl chloride/n-hexane;
preferably, the time for immersing the polyamine aqueous solution is 3-20 min;
preferably, the mass percentage of the polyamine in the polyamine aqueous solution is 0.1-1%;
preferably, the mass percentage of the polybasic acyl chloride in the polybasic acyl chloride/normal hexane solution is 0.05-0.3%;
preferably, the reaction time in the step (1) is 10-120 s;
preferably, the reaction of step (1) is followed by drying.
9. The method of claim 7 or 8, wherein the mixing of step (2) is immersing the product of step (1) with a mixed solution of an amine-containing solute and a swelling solvent;
preferably, the soaking time is 3-30 min;
preferably, the soaking step further comprises washing with swelling small molecules for 10-30 s;
preferably, the temperature of the crosslinking reaction in the step (2) is 40-60 ℃;
preferably, the time of the crosslinking reaction in the step (2) is 1 to 10 minutes.
10. The composite nanofiltration membrane of any one of claims 1-6 for wastewater decolorization, wastewater desalination, resource recovery, or water softening.
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| CN117797665B (en) * | 2024-03-01 | 2024-05-07 | 中山大学 | Glutamic acid modified separation membrane and preparation method and application thereof |
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