CN106731841B - A kind of supermolecule composite nanometer filtering film and its preparation method and application - Google Patents
A kind of supermolecule composite nanometer filtering film and its preparation method and application Download PDFInfo
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- CN106731841B CN106731841B CN201611244794.1A CN201611244794A CN106731841B CN 106731841 B CN106731841 B CN 106731841B CN 201611244794 A CN201611244794 A CN 201611244794A CN 106731841 B CN106731841 B CN 106731841B
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- cucurbituril
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000001914 filtration Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 51
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 229920001721 polyimide Polymers 0.000 claims description 23
- 239000004642 Polyimide Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 150000001263 acyl chlorides Chemical group 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 150000004885 piperazines Chemical group 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 abstract description 39
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 11
- 210000002469 basement membrane Anatomy 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000013019 agitation Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 23
- 238000001728 nano-filtration Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000003651 drinking water Substances 0.000 description 6
- 235000020188 drinking water Nutrition 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000013047 polymeric layer Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 241000235342 Saccharomycetes Species 0.000 description 2
- 229930003779 Vitamin B12 Natural products 0.000 description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 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 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000011715 vitamin B12 Substances 0.000 description 2
- 235000019163 vitamin B12 Nutrition 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229960003276 erythromycin Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920000867 polyelectrolyte Polymers 0.000 description 1
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- -1 saccharide compound Chemical class 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229960003165 vancomycin Drugs 0.000 description 1
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-O vancomycin(1+) Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C([O-])=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)[NH2+]C)[C@H]1C[C@](C)([NH3+])[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-O 0.000 description 1
- 238000003911 water pollution 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
- 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
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (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 present invention relates to a kind of supermolecule composite nanometer filtering film and its preparation method and application, the decorative layer of the NF membrane mainly by base and thereon is constituted, and Cucurbituril is distributed in decorative layer.Preparation method comprises the steps of：Basement membrane solution is prepared, mechanical agitation to whole dissolvings, standing and defoaming spreads to plate membrane on non-woven fabrics；The aqueous solution of the first monomer and the organic solution of second comonomer are configured, supermolecule stirring and dissolving is added in the first monomer solution, interfacial polymerization is carried out in membrane surface, the film prepared is placed to be preserved for use in deionized water.It is to use supermolecule as interfacial polymerization additive that the present invention, which makes feature, and preparation process is simple, and supermolecule composite nanometer filter membrane flux obtained is big, rejection is high.
Description
Technical field
The present invention relates to a kind of supermolecule composite nanometer filtering films and its preparation method and application, belong to polymer film technology neck
Domain.
Background technology
Nanofiltration（NF）Be that late 1980s Later development gets up is a kind of novel between ultrafiltration between reverse osmosis
Membrane separation technique, early stage are known as " low pressure reverse osmosis " or " loose reverse osmosis ".Nanofiltration is to adapt to industrial softened water
Demand and a kind of novel pressure for reducing cost and growing up drive membrane process.The molecular cut off of NF membrane is in 200-1000
Between.Membrane aperture is known as " nanofiltration " in 1nm or so, the dissolved constituent for being about 1nm suitable for separation size.Due to NF membrane spy
Specially treated when different pore diameter range and preparation（Compound, chargedization）, make it have more special separating property.NF membrane
One is characterized in greatly in film surface or film that there are charged groups very much, therefore nanofiltration UF membrane has two features, i.e. sieve effect
And charge effect.The substance of molecular cut off that molecular weight is more than film will be rejected by, on the contrary then penetrate, and here it is the screenings of film
Effect；The charge effect of film is also known as Donnan effects, refers to the electrostatic interaction of ion and the charge of film institute band.To uncharged
The filtering of molecule can be detached the substance of different molecular weight using sieve effect mainly by steric effect, that is, charge effect；And
To the filtering of the substance with charge mainly by charge effect, the separation of nanofiltration film surface was once made of polyelectrolyte, film surface band
There are the charge of a bit, most of nanofiltration film surfaces to carry negative electrical charge, they hinder oozing for multivalent ion by electrostatic interaction
Thoroughly, this is NF membrane still has the main reason for compared with high desalination performance under lower pressure.
The characteristics of according to NF membrane, NF membrane is mainly used in the following aspects：
The purification of drinking water：
The maximum application field of NF membrane is the softening of drinking water and the removing of organic matter, adds tool, people with water pollution
Drinking water quality is become more concerned with.Traditional drinking water treatment mainly by flocculation, sedimentation, sand filtration and chlorination come
The suspended matter in water removal and bacterium are gone, and it is very low to the removal efficiency of various soluble chemistry substances, with the day that water resource is poor
Beneficial severe, the aggravation of environmental pollution and various countries' drinking water standard raising can remove various organic matters and harmful chemical
" Advanced Treatment of Drinking Water " is increasingly subject to the attention of people.UF membrane experiment shows that NF membrane can remove disinfecting process
Micro- toxic byproduct, heavy metal, natural organic matter and the sulfate nitrate etc. generated.There is good processed water quality, stabilization, change simultaneously
Learn that dosing is few, energy saving, the advantages that being easily managed and safeguard, can reaching zero-emission substantially.
Industrial Wastewater Treatment：
The development of modern industry also produces serious environmental pollution and asks while for social creativity tremendous economic interests
Topic, more and more oceans, lake and river etc. be contaminated due to a large amount of being discharged into for industrial wastewater, gives the mankind and animals and plants
The characteristics of existence causes to seriously threaten, membrane separation technique makes it be played an important role in terms of Industrial Wastewater Treatment.NF membrane
It is successfully applied in the processing of the industries waste water such as papermaking, plating, printing and dyeing with its special separating property.In dyeing wastewater
In, tissue waste water has the characteristics that the difficulty of the removal always wastewater treatment of high CODCr concentration height and high chroma, especially coloration
Point, most dyestuffs are complicated aromatic ring structure in waste water, not degradable, are not easy to be aoxidized, wastewater treatment it is difficult；Together
When waste water contained in salt also further decrease the biodegradable of waste water.Theoretically, a variety of physico-chemical process can
For the decolorization of waste water from dyestuff, such as flocculation sediment, absorption, ion exchange, film process, chemical oxidation, photooxidation, electrolysis
And bioremediation etc., but single processing method all can not be by wastewater treatment to recyclable degree.The print of high concentration
Dye waste water causes serious pollution to environment, directly affects the sustainable development of textile industry, as state and society protects environment
The requirement of shield is increasingly strict, develop effective dye waste water treatment method and technique be very it is necessary to.Nanofiltration-membrane technique is close
A kind of new separation technology to grow up for several years, is based primarily upon aperture sieve effect and electric charging effect divides material to realize
From organic matter and high valence ion to relative molecular weight more than 200 have very high rejection, so nanofiltration is especially suitable
In the processing of dyeing waste water, and the osmotic pressure of NF membrane is far below reverse osmosis, so it is relatively low so that the operation of nanofiltration process is pressed, from
And it can achieve the purpose that relatively low cost of water treatment.
Pharmacy：
Using Nanofiltration-membrane technique can purify with concentration biochemical reagent, can not only reduce the consumption of organic solvent and water
Amount, and micro organic contamination and low molecular weight salts can be removed, it is finally reached effect that is energy saving, improving product quality.It receives
Filter membrane has been applied successfully to concentration and the purification process of the Multiple Classes of Antibiotics such as erythromycin, aureomycin, vancomycin and penicillin
In.Vitamin B12 is obtained by fermenting, and traditional production technology is complicated, low yield.Traditional filtering is substituted with micro-filtration, through micro-filtration
Fermentation clear liquid NF membrane can concentrate 10 times or more, to greatly reduce Solvent quantity, and improve the production of equipment
Ability.Water phase after being extracted also has a small amount of vitamin B12 and certain solvent, can be retained by nanofiltration, to reduce
The loss of product.Solvent used in crude product purification process can also be recycled with nanofiltration membrane treatment and be used.
Food processing：
Since NF membrane has higher contamination resistance, bacterium, which is not easy to survive in nanofiltration film surface, to be multiplied, due to nanofiltration
Film can remove a part of salt, can reduce corrosion of the salt to evaporator.The process of common-use words yeast and cheese.It solves waste water
Economic benefit also can be improved in the problem of discharge, and NF membrane is also beneficial to the recycling of organic acid in fermentation liquid.Molten
When liquid is in low ph value, these acid do not dissociate, it is easy to penetrate NF membrane；And under high pH conditions, due to the acid of dissociation
Mutual repulsive interaction makes most of acid be rejected by between film, while film has also retained saccharide compound, is conducive to back
It receives and recycles.Therefore, the pH value for adjusting fermentation liquid makes it be in range appropriate, and NF membrane is used in combination to remove in fermentation liquid
Organic acid, retention saccharomycete, it is unfermentable sugar and other useful components, by these retention substances again return to round
Middle re-using not only can weaken inhibiting effect of the product to fermentation process, while be conducive to recycle saccharomycete
And carbohydrate.Yield is not only increased, the expense of high cost feedstocks is also reduced.
In addition, NF membrane can be also used for the processing of the fields such as weaving, leather processing waste water and the separation of chiral material.
Due to its special separating property, nanofiltration will more and more widely applied to many fields such as improve drinking water quality, softened water,
Dyestuff, pigment, medicine detached with the purification of biogenetic products with concentration and grease depth, dyestuff, printing, weaving, chemistry and cure
The fields such as the decoloration of medicine waste water.Solvent resistant, the NF membrane application prospect of acid and alkali-resistance are wider.
But NF membrane, in applied to separation process, rejection and water flux are required for the demand improved.
Invention content
The present invention is for small, low to the small molecule dyes rejection deficiency of current composite nanometer filter membrane flux, in order to improve boundary
The thickness of face polymer layer and the flux and rejection for electrically improving composite nanometer filtering film, proposition are added in interfacial polymerization aqueous phase solution
A kind of new material is modified film, i.e., a kind of supermolecule composite nanometer filter membrane preparation method.The present invention is obtained by following steps
To realize：
The first aspect of the invention：
A kind of supermolecule composite nanometer filtering film, includes the decorative layer of base and its surface covering, and the decorative layer refers to
The polymeric layer of Cucurbituril is distributed with；The base is organic nanofiltration membrane.
The Cucurbituril refers to Cucurbituril [n] (arbitrary integer in n=5~12) and its derivative.
The material of the base be selected from polyamide, polyimides, cellulose acetate, sulfonated polysulfone, sulfonated polyether sulfone or
Polyvinyl alcohol etc..
The base can also be covered on supporting layer, and the supporting layer can be selected from non-woven fabrics etc..
In one embodiment, the polymeric layer is mutually polymerized by the first monomer and second comonomer；It is described
The first monomer be piperazines monomer or amino-contained monomer, the second comonomer is acyl chloride monomer.
The second aspect of the invention：
A kind of preparation method of supermolecule composite nanometer filtering film, includes the following steps：
I) the first monomer, Cucurbituril are dissolved in the first solution by, obtain the first phase；
Ii) second comonomer is dissolved in the second solution by, obtains the second phase；
Iii) the first phase is applied in base by, then the second phase is applied in the first phase, carries out interface polymerization reaction,
Obtain composite membrane.
First solution and the second solution is immiscible.
In one embodiment, the first solution is water, and the second solution is n-hexane.
In one embodiment, the first monomer is piperazines monomer or amino-contained monomer, and second comonomer is acyl chloride list
Body.
In one embodiment, the mass concentration of the first monomer in the first phase is 0.01~5%, and Cucurbituril is in the first phase
In mass concentration be 0.01~5%；Mass concentration of the second comonomer in the second phase is 0.01~5%.
The third aspect of the invention：
Application of the supermolecule composite nanometer filtering film in liquid filtering.
The application refers to the filtering or separation of charged species, neutral substance or their mixture.
The fourth aspect of the invention：
A method of in the area load supermolecule of organic separation membrane, include the following steps：
I) the second solution containing second comonomer is applied on organic separation membrane by；
Ii) the first solution containing Cucurbituril and the first monomer is applied on the second solution by again, passes through the first monomer
With the interface polymerization reaction of second comonomer, Cucurbituril is carried on organic separation membrane.
Advantageous effect
The supermolecule Cucurbituril is a kind of melon ring molecule, and inside has rigid hydrophobic cavity, and sub- both ends respectively have 6
C=O functional groups, can be with many positively charged matter interactions, and there is very strong hydrophily in outside, can improve the parent of film surface
Aqueous, molecule average grain diameter is 1~2nm.
Find the interfacial polymerization of composite nanometer filter film surface after addition Cucurbituril by scanning electron microscope in interfacial polymerization water phase
Layer becomes more fine and close, and nodositas protrusion becomes uniform, and molecular cut off becomes larger, this causes the water flux of composite nanometer filtering film notable
It is promoted, can reach 22L/m2Hbar is up to the methylene blue rejection that molecular weight is 319g/mol
99.5%。
Description of the drawings
Fig. 1 is the polyimides composite nanometer filtering film topographical surface SEM figures prepared in reference examples 1 of the present invention.
Fig. 2 is the supermolecule-polyimides composite nanometer filtering film topographical surface SEM figures prepared in the embodiment of the present invention 5.
Specific implementation mode
Below by specific implementation mode, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person carry out according to technology or condition described in document in the art or according to product description.Examination used
Production firm person is not specified in agent or instrument, is that can buy the conventional products obtained by market.
Approximate language used herein can be used for modifying in entire disclosure and claims any quantity statement, can
Permit being changed under conditions of not causing its relevant basic function to change.Therefore, it is repaiied by term such as " about "
The value of decorations is not limited to specified exact value.In at least some cases, approximate language can be with the instrument for measuring the value
Precision it is corresponding.Unless being indicated otherwise in context or sentence, otherwise range limit can be combined and/or exchange, and
And this range is confirmed as and includes all subranges contained herein.In addition in the operation embodiment or elsewhere
In indicate except, the number of the amounts of all expression compositions used in specification and claims, reaction condition etc. or
Expression shall be construed as the modification by word " about " in all cases.
The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range
The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating
The concentration of about 0.1% to about 5% further includes the single concentration in how（Such as, 1%, 2%, 3% and 4%）The subinterval and（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.
NF membrane proposed by the present invention is constituted by least two layers, and one layer is base, can be common nanofiltration membrane material
Matter layer, such as：Polyamide, cellulose acetate, sulfonated polysulfone, sulfonated polyether sulfone and polyvinyl alcohol etc., are not particularly limited, it is
Base material as last layer.Another layer is finishing coat, and decorative layer is also one layer of polymeric layer, is also divided in the polymeric layer
It is furnished with supermolecule（It can preferred Cucurbituril in the present invention）, which, can in of the invention also with certain selective penetrated property
To be carried in base using interfacial polymerization, similarly, Cucurbituril can also be carried on other organic by this method
On polymer film, such as microfiltration membranes, ultrafiltration membrane etc..
Cucurbituril in above-mentioned decorative layer is a kind of supermolecule, point with big annular space chamber, the tubbiness of both ends open
Minor structure, the Cucurbituril that can be adapted for the present invention may include having：Cucurbituril [n] (arbitrary integer in n=5~12), also may be used
It is a kind of melon ring molecule to be its derivative, there is rigid hydrophobic cavity, sub- both ends respectively to have C=O functional groups for inside, outside
There is very strong hydrophily in portion, can improve the hydrophily of film surface, and molecule average grain diameter is 1-2nm.
In addition, its preparation method can be prepared by interfacial polymerization, such as：It adds and contains first on base material
There is the first solution of Cucurbituril and the first monomer, then by the contact of itself and the second solution containing second comonomer, and the first solution
Mutually immiscible with the second solution, the first monomer can polymerize with second comonomer in interface, form the decorative layer on surface, by
It is dissolved in the first solution, and it is with cavity structure, therefore the first monomer can be coated in cavity, passes through in Cucurbituril
It crosses after interface polymerization reaction, the polymerization decorative layer being cross-linked with each other through Cucurbituril can be formed so that Cucurbituril, which is distributed in, to be repaiied
It adorns on layer, and then realizes load of the Cucurbituril in base.
Used herein of the first solution can be water, the second solution can be and the immiscible organic solution of water, without spy
It does not limit, as long as can preferably be dissolved Cucurbituril, the first monomer and second comonomer and carry out interfacial reaction.
Wherein, the first monomer and second comonomer are not particularly limited, as long as can carry out carrying out cross-linking reaction on interface
, such as：Piperazine, m-phenylene diamine (MPD) may be used in first monomer, and acyl chloride monomer, such as equal benzene three may be used in second comonomer
Formyl chloride.
The above-mentioned NF membrane being prepared can be applied to common nanofiltration process, such as：The separation and retention of electrolyte,
The separation of organic matter and retention etc..In the present invention, due to by increasing the polymer containing Cucurbituril on the surface of NF membrane
Decorative layer so that the surface of film is stretched so that water flux and for neutral substance（Such as PEG）Molecular cut off have increase
Trend, simultaneously as its same effects for having, increases for the rejection of the substance of negative electrical charge again.
The preparation of 1 polyimide base film of embodiment
(1) by polyimides（P84）With polyethylene glycol 400 (PEG) N-Methyl pyrrolidone is dissolved in by certain mass ratio
(NMP) in solvent, the mass ratio of P84, PEG and NMP are 20:12:50,25 DEG C of mechanical agitation 20~24 hours at room temperature, wait for
After it is completely dissolved, 8~12h deaerations processing, obtained casting solution are stood；
(2) polyester non-woven fabric is fixed on a glass, control blade thickness is 100 μm, and casting solution is scratched in polyester
It on non-woven fabrics, after control 5~10 seconds time of volatilization, immerses in water coagulating bath, phase separation film-forming occurs, impregnates after five minutes
The basement membrane prepared up to hygrometric state polyimide film is taken out to preserve in deionized water.
The polyimide filtering membranes base being prepared is used for the preparation of decorative layer in following embodiment.
The preparation of 2 polyether sulfone basement membrane of embodiment
(1) it is molten polyether sulfone to be dissolved in N-Methyl pyrrolidone (NMP) with polyethylene glycol 400 (PEG) by certain mass ratio
In agent, the mass ratio of P84, PEG and NMP are 20:12:50,25 DEG C of mechanical agitation 20~24 hours at room temperature, wait for it completely
After dissolving, 8~12h deaerations processing, obtained casting solution are stood；
(2) polyester non-woven fabric is fixed on a glass, control blade thickness is 100 μm, and casting solution is scratched in polyester
It on non-woven fabrics, after control 5~10 seconds time of volatilization, immerses in water coagulating bath, phase separation film-forming occurs, impregnates after five minutes
The basement membrane prepared up to hygrometric state poly (ether sulfone) film is taken out to preserve in deionized water.
The polyether sulfone basement membrane being prepared is used for the preparation of decorative layer in following embodiment.
The preparation of the polyimide composite film of 3 Cucurbituril of embodiment modification
Prepare the Piperazine anhydrous of 2wt%（PIP）The Cucurbituril 6 of 0.1 wt % is added in aqueous phase solution（CB6）, stirring, until
It is completely dissolved, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0. 1 wt % is prepared, organic solvent is n-hexane, as the second phase；
Polyimide base film is fixed on interfacial polymerization device, a certain amount of first phase solution submergence film surface is poured into,
So that it is contacted with surface 120 seconds, take out, then rolls polyimide support film with rubber rollers, remove extra solution, pour into
Second phase of amount is impregnated 60 seconds, is waited rinsing surface with hexane solution after the completion of reacting, is removed extra reactant and then preserve
It is for use in pure water.
The preparation of the polyimide composite film of 4 Cucurbituril of embodiment modification
Prepare the Piperazine anhydrous of 1wt%（PIP）The Cucurbituril 8 of 0.5 wt % is added in aqueous phase solution（CB8）, stirring, until
It is completely dissolved, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0. 3 wt % is prepared, organic solvent is n-hexane, as the second phase；
Polyimide base film is fixed on interfacial polymerization device, a certain amount of first phase solution submergence film surface is poured into,
So that it is contacted with surface 150 seconds, take out, then rolls polyimide support film with rubber rollers, remove extra solution, pour into
Second phase of amount is impregnated 80 seconds, is waited rinsing surface with hexane solution after the completion of reacting, is removed extra reactant and then preserve
It is for use in pure water.
The preparation of the polyimide composite film of 5 Cucurbituril of embodiment modification
Prepare the Piperazine anhydrous of 3wt%（PIP）The Cucurbituril 7 of 0.7 wt % is added in aqueous phase solution（CB7）, stirring, until
It is completely dissolved, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0.2 wt % is prepared, organic solvent is n-hexane, as the second phase；
Polyamide basement membrane is fixed on interfacial polymerization device, a certain amount of first phase solution submergence film surface is poured into, makes
It is contacted 110 seconds with surface, is taken out, and is then rolled polyimide support film with rubber rollers, is removed extra solution, pour into equivalent
The second phase, impregnate 40 seconds, wait rinsing surface with hexane solution after the completion of reacting, remove and extra reactant and then be stored in
It is for use in pure water.
The preparation of the polyimide composite film of 6 Cucurbituril of embodiment modification
Prepare the Piperazine anhydrous of 1wt%（PIP）The Cucurbituril 7 of 0.2 wt % is added in aqueous phase solution（CB7）, stirring, until
It is completely dissolved, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0.4 wt % is prepared, organic solvent is n-hexane, as the second phase；
Polyamide basement membrane is fixed on interfacial polymerization device, a certain amount of first phase solution submergence film surface is poured into, makes
It is contacted 150 seconds with surface, is taken out, and is then rolled polyimide support film with rubber rollers, is removed extra solution, pour into equivalent
The second phase, impregnate 60 seconds, wait rinsing surface with hexane solution after the completion of reacting, remove and extra reactant and then be stored in
It is for use in pure water.
Reference examples 1 are covered with the preparation of the polyimide composite film of polymer layer
With embodiment 5 difference lies in：Not in the first quite middle addition Cucurbituril, only by interface polymerization reaction poly-
Imide film surface covers a bed boundary polymer layer.
The SEM photograph for the polyimide composite film that reference examples 1 and embodiment 5 are prepared is as depicted in figs. 1 and 2, from figure
In as can be seen that by added in interfacial polymerisation processes Cucurbituril modification after, superficial film can be made more uniform, had
Help improve resistance tocrocking, rough surface, which is easy to cause in membrane filtration processes, is susceptible to fouling membrane.
By the polyether sulfone basement membrane being prepared in the polyimide base film being prepared in embodiment 1, embodiment 2, implement
The composite membrane and reference examples 1 being prepared in example 3~6, which are prepared, to be covered with the polyimide composite film of polymer layer to carry out pure water logical
The characterization of amount is tested.
As can be seen from the above table, the NF membrane for the Cucurbituril modification being prepared in the present invention is logical with larger water
Amount.
The cutoff performance tested under 0.6MPa pressure with the methylene blue of 100ppm using the above-mentioned film prepared, retention
Rate is as follows.
By embodiment 5 as can be seen that modifying it by increasing Cucurbituril on polyimide film compared with reference examples 1
Afterwards, the rejection to dyestuff can preferably be improved；And the NF membrane in embodiment 1 and embodiment 2 is non-to the rejection of dyestuff
It is often low.
Claims (3)
1. application of the supermolecule composite nanometer filtering film in liquid filtering；The liquid filtering refers to the mistake to methylene blue solution
Filter；The preparation method of the supermolecule composite nanometer filtering film, includes the following steps：
I) the first monomer, Cucurbituril are dissolved in the first solution by, obtain the first phase；
Ii) second comonomer is dissolved in the second solution by, obtains the second phase；
Iii) the first phase is applied in base by, then the second phase is applied in the first phase, is carried out interface polymerization reaction, is obtained
Composite membrane；
The Cucurbituril refers to Cucurbituril [n] or derivatives thereof, the wherein arbitrary integer in n=5~12；
The material of the base is selected from polyamide, polyimides, cellulose acetate, sulfonated polysulfone, sulfonated polyether sulfone or poly- second
Enol；
First solution is water, and the second solution is n-hexane；
First monomer is piperazines monomer or amino-contained monomer, and second comonomer is acyl chloride monomer；
The mass concentration of first monomer in the first phase is 0.01~5%；
Mass concentration of the second comonomer in the second phase is 0.01~5%；
The mass concentration of Cucurbituril in the first phase is 0.01~5%.
2. application of the supermolecule composite nanometer filtering film according to claim 1 in liquid filtering, which is characterized in that described
Base is also covered on supporting layer.
3. application of the supermolecule composite nanometer filtering film according to claim 2 in liquid filtering, which is characterized in that described
Supporting layer is selected from non-woven fabrics.
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| PCT/CN2017/078785 WO2018120476A1 (en) | 2016-12-29 | 2017-03-30 | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof |
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| CN109758924A (en) * | 2019-03-16 | 2019-05-17 | 浙江清创环保新材料有限公司 | A kind of preparation method of supermolecule hollow-fibre membrane |
| CN110201545B (en) * | 2019-06-28 | 2021-09-03 | 万华化学集团股份有限公司 | Preparation method of antibacterial high-flux nanofiltration membrane |
| CN110449049B (en) * | 2019-07-29 | 2022-01-11 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in separation of pigment wastewater monovalent mixed salt |
| CN111013391B (en) * | 2019-11-28 | 2021-02-26 | 南京工业大学 | Modified nanofiltration membrane and preparation method thereof |
| CN111545083B (en) * | 2020-03-24 | 2022-03-15 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration |
| CN111644081A (en) * | 2020-05-23 | 2020-09-11 | 浙江迪萧环保科技有限公司 | Preparation method of novel high-stability composite nanofiltration membrane |
| CN111589308B (en) * | 2020-06-10 | 2022-03-25 | 中煤（北京）环保工程有限公司 | Composite nanofiltration membrane with heavy metal interception capacity |
| CN112755810B (en) * | 2020-12-18 | 2023-05-12 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
| CN113491955B (en) * | 2021-06-04 | 2023-05-26 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN114247297B (en) * | 2021-12-23 | 2023-10-20 | 天津大学 | Nanofiltration membrane and preparation method thereof |
| CN114471180A (en) * | 2021-12-28 | 2022-05-13 | 南京工业大学 | Nanofiltration membrane based on subject-guest compound, preparation method and characterization test method |
| CN114249463A (en) * | 2021-12-30 | 2022-03-29 | 新疆神邦环境工程有限公司 | Method for efficiently recovering inorganic salt in cotton dyeing residual liquid |
| CN115041026B (en) * | 2022-06-10 | 2023-06-27 | 浙江理工大学 | Preparation method of organic solvent nanofiltration membrane with introduced macrocyclic molecules |
| CN116747715B (en) * | 2023-04-14 | 2024-01-23 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
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