CN106731841A - 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
- Publication number
- CN106731841A CN106731841A CN201611244794.1A CN201611244794A CN106731841A CN 106731841 A CN106731841 A CN 106731841A CN 201611244794 A CN201611244794 A CN 201611244794A CN 106731841 A CN106731841 A CN 106731841A
- Authority
- CN
- China
- Prior art keywords
- monomer
- solution
- cucurbituril
- membrane
- composite nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000001914 filtration Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 58
- 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 42
- 239000000178 monomer Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 28
- 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 21
- 238000000034 method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 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 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000013047 polymeric layer Substances 0.000 claims description 6
- 150000001263 acyl chlorides Chemical group 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 238000005034 decoration Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 210000004379 membrane Anatomy 0.000 abstract description 45
- 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 19
- 238000001728 nano-filtration Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000007654 immersion Methods 0.000 description 8
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 7
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 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
- 230000014759 maintenance of location Effects 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
- 239000000376 reactant Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 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
- 238000001764 infiltration Methods 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
- 241000235342 Saccharomycetes Species 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 238000004134 energy conservation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012467 final product Substances 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
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- -1 saccharide compound Chemical class 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
- 229930003779 Vitamin B12 Natural products 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
- 239000006227 byproduct Substances 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 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 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 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
- 238000009826 distribution Methods 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 230000035622 drinking Effects 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
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229960003276 erythromycin Drugs 0.000 description 1
- 238000000605 extraction 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
- 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
- DNHVXYDGZKWYNU-UHFFFAOYSA-N lead;hydrate Chemical compound O.[Pb] DNHVXYDGZKWYNU-UHFFFAOYSA-N 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
- 150000007524 organic acids Chemical class 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
- 238000007747 plating Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 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
- 239000000725 suspension Substances 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
- 238000000108 ultra-filtration Methods 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin 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)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 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
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 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
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of supermolecule composite nanometer filtering film and its preparation method and application, the decorative layer that the NF membrane is mainly by basic unit and thereon is constituted, and Cucurbituril is distributed with decorative layer.Preparation method is comprised the steps of：Basement membrane solution is prepared, mechanical agitation to whole dissolvings, standing and defoaming spreads to Flat 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 for preparing is placed and preserves stand-by in deionized water.Making feature of the present invention is the preparation process is simple as interfacial polymerization additive using supermolecule, and obtained supermolecule composite nanometer filter membrane flux is big, rejection is high.
Description
Technical field
The present invention relates to a kind of supermolecule composite nanometer filtering film 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 new between counter-infiltration and ultrafiltration
Membrane separation technique, early stage is referred to as " low pressure reverse osmosis " or " loose counter-infiltration ".Nanofiltration is to adapt to industrial softened water
Demand and reduces cost and a kind of novel pressure for growing up drives membrane process.The molecular cut off of NF membrane is in 200-1000
Between.Membrane aperture suitably separates the dissolved constituent that size is about 1nm, therefore be referred to as " nanofiltration " in 1nm or so.Because NF membrane is special
Specially treated when different pore diameter range and preparation（Compound, chargedization）, make it have more special separating property.NF membrane
One is characterized in very much the presence of charged group in film surface or film greatly, therefore nanofiltration UF membrane has two features, i.e. sieve effect
And charge effect.Molecular weight will be rejected by more than the material of the molecular cut off of film, otherwise then pass through, here it is the screening of film
Effect；The charge effect of film, also known as Donnan effects, refers to the electrostatic interaction of ion and the electric charge of film institute band.To uncharged
The filtering of molecule is charge effect mainly by steric effect, can be separated the material of different molecular weight using sieve effect；And
To the filtering of the material with electric charge mainly by charge effect, NF membrane surface separates and is once made up of polyelectrolyte, film surface band
There is the electric charge of a bit, most of NF membrane surfaces carry negative electrical charge, they hinder oozing for multivalent ion by electrostatic interaction
Thoroughly, this be NF membrane under lower pressure still have compared with high desalination performance main cause.
According to the characteristics of 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, and tool, people couple are added with water pollution
Drinking water quality becomes more concerned with.Traditional drinking water treatment is mainly removed by flocculation, sedimentation, sand filtration and chlorination
Suspension and bacterium in water, and very low to the removal efficiency of various soluble chemistry materials, with poor increasingly tight of water resource
High, environmental pollution aggravation and the raising of various countries' drinking water standard, can remove " drinking for various organic matters and harmful chemical
Water depth treatment technology " is increasingly subject to the attention of people.UF membrane experiment shows that NF membrane can remove disinfecting process generation
Micro- toxic byproduct, heavy metal, natural organic matter and sulfate nitrate etc..There is good processed water quality, stabilization, chemical agent simultaneously
Consumption is few, energy-conservation, be easily managed and safeguard, the advantages of can reach zero-emission substantially.
Industrial Wastewater Treatment：
The development of modern industry also generates serious problem of environmental pollution while for social creativity tremendous economic interests,
Increasing ocean, lake and river etc. are contaminated due to a large amount of entering for industrial wastewater, to the life of the mankind and animals and plants
Depositing the characteristics of causing serious threat, membrane separation technique makes it be played an important role in terms of Industrial Wastewater Treatment.NF membrane with
Its special separating property is successfully applied in the treatment of the industry waste water such as papermaking, plating, printing and dyeing.In dyeing wastewater
In, tissue waste water is the characteristics of have CODCr concentration high high and high chroma, especially the difficulty of the removal of colourity always wastewater treatment
Point, most dyestuffs are complicated aromatic ring structure in waste water, not degradable, are difficult to be oxidized, and the difficulty of wastewater treatment is very big；Together
When waste water in contained salt also further reduce the biodegradable of waste water.Theoretically, various physico-chemical processes can
For the desolventing technology 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 cannot 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 country and society are protected to environment
The requirement of shield is increasingly strict, and it is extremely to be necessary to develop effective dye waste water treatment method and technique.Nanofiltration-membrane technique is near
A kind of new separation technology for growing up for several years, is based primarily upon aperture sieve effect and electric charging effect to realize dividing material
From organic matter and high valence ion to relative molecular weight more than 200 have rejection very high, so nanofiltration is especially suitable
Counter-infiltration is far below in the osmotic pressure of the treatment of dyeing waste water, and NF membrane, so the operation of nanofiltration process is pressed relatively low, from
And the purpose of relatively low cost of water treatment can be reached.
Pharmacy：
Using Nanofiltration-membrane technique can purify with concentration biochemical reagent, can not only reduce the consumption of organic solvent and water,
And micro organic contamination and low molecular weight salts can be removed, it is finally reached energy-conservation, the effect of improve product quality.NF membrane
It has been applied successfully in the concentration and purge process of the Multiple Classes of Antibiotics such as erythromycin, aureomycin, vancomycin and penicillin.Dimension
Raw element B12 is obtained by fermenting, traditional complex manufacturing, low yield.Traditional filtering is substituted with micro-filtration, through the fermentation of micro-filtration
Clear liquid NF membrane can concentrate more than 10 times, so as to greatly reduce Solvent quantity, and improve the production capacity of equipment.Quilt
Water after extraction mutually also has a small amount of vitamin B12 and certain solvent, can be retained by nanofiltration, to reduce product
Loss.Solvent used in crude product purge process, it is also possible to reclaimed with nanofiltration membrane treatment and used.
Food processing：
Because NF membrane has contamination resistance higher, bacterium is difficult to be survived on NF membrane surface and multiplies, due to NF membrane energy
A part of salt is removed, corrosion of the salt to evaporator can be reduced.The process of common-use words yeast and cheese.It solves discharge of wastewater
Problem, can also increase economic efficiency, and NF membrane is also beneficial to the recycling of organic acid in fermentation liquid.At solution
When low ph value, these acid are not dissociated, it is easy to pass through NF membrane；And under high pH conditions, due to the acid of dissociation and film
Between mutual repulsive interaction cause that most of acid is rejected by, while film has also retained saccharide compound, be conducive to reclaiming again
Utilize.Therefore, adjust fermentation liquid pH value, make it be in appropriate scope, and with NF membrane remove fermentation liquid in having
Machine acid, these retention materials are again returned to weight in round by retention saccharomycete, unfermentable sugar and other useful components
It is new to utilize, so can not only weaken inhibitory action of the product to fermentation process, while being conducive to recycling saccharomycete and sugar
Class.Yield is not only increased, the expense of high cost raw material is also reduced.
In addition, NF membrane can be also used for the treatment of the field such as weaving, leather processing waste water and the separation of chiral material.
Due to its special separating property, nanofiltration will be applied to more and more widely many fields such as improve drinking water quality, softened water,
Dyestuff, pigment, medicine are separated with the purification of biogenetic products with concentration and profit depth, dyestuff, printing, weaving, chemistry and cure
The fields such as the decolouring of medicine waste water.Solvent resistant, acid and alkali-resistance NF membrane application prospect it is wider.
But, in separation process is applied to, rejection and water flux are required for the demand for improving to NF membrane.
The content of the invention
The present invention is directed to small, low to the small molecule dyes rejection deficiency of current composite nanometer filter membrane flux, in order to improve boundary
The flux and rejection of the thickness of face polymer layer and electrically raising composite nanometer filtering film, propose to be added in interfacial polymerization aqueous phase solution
A kind of new material is modified to 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 basic unit and its surface covering, and described decorative layer refers to distribution
There is the polymeric layer of Cucurbituril；Described basic unit is organic nanofiltration membrane.
Described Cucurbituril refers to Cucurbituril [n] (arbitrary integer in n=5~12) and its derivative.
The material of described basic unit be selected from polyamide, polyimides, cellulose acetate, SPSF, sulfonated polyether sulfone or
Polyvinyl alcohol etc..
Described basic unit can also be covered on supporting layer, and described supporting layer can be selected from non-woven fabrics etc..
In one embodiment, described 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, described second comonomer is acyl chloride monomer.
The second aspect of the invention：
A kind of preparation method of supermolecule composite nanometer filtering film, comprises the following steps：
I) be dissolved in the first solution for the first monomer, Cucurbituril by, obtains the first phase；
Ii) be dissolved in second comonomer in the second solution by, obtains the second phase；
Iii) is mutually put on first in basic unit, then second is mutually put in the first phase, carries out interface polymerization reaction, is obtained
Composite membrane.
Described the 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 first monomer mass concentration 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.
Described application, refers to the filtering or separation of charged species, neutral substance or their mixture.
The fourth aspect of the invention：
A kind of method of area load supermolecule in organic separation membrane, comprises the following steps：
I) puts on organic separation membrane the second solution containing second comonomer；
Ii) is again put on the second solution the first solution containing Cucurbituril and the first monomer, by the first monomer and
The interface polymerization reaction of two monomers, Cucurbituril is carried on organic separation membrane.
Beneficial effect
Described supermolecule Cucurbituril is a kind of melon ring molecule, and inside has rigid hydrophobic cavity, and respectively there are 6 C=O at sub- two ends
Functional group, can be with many positively charged matter interactions, and there is very strong hydrophily outside, can improve the hydrophilic of film surface
Property, molecule average grain diameter is 1~2nm.
The interfacial polymerization on composite nanometer filtering film surface is found after adding Cucurbituril in interfacial polymerization water phase by ESEM
Layer becomes more fine and close, and nodositas projection becomes uniform, and molecular cut off becomes big, and this causes the water flux of composite nanometer filtering film notable
Lifting, can reach 22L/m2Hbar, to molecular weight for the methylene blue rejection of 319g/mol is up to
99.5%。
Brief description of the drawings
Fig. 1 is the polyimides composite nanometer filtering film topographical surface SEM figures of preparation in reference examples of the present invention 1.
Fig. 2 is supermolecule-polyimides composite nanometer filtering film topographical surface SEM figures of preparation in the embodiment of the present invention 5.
Specific embodiment
The present invention is described in further detail below by specific embodiment.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.Unreceipted specific skill in embodiment
Art or condition person, are carried out according to the technology or condition described by document in the art or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, being can buy the conventional products for obtaining by market.
Approximate language used herein can be used to modify any quantity statement in entire disclosure and claims, and it can
Permit being changed under conditions of the basic function for not causing its related changes.Therefore, 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 indicated otherwise in context or sentence, otherwise range limit can be combined and/or exchange, and
And this scope is confirmed as and including all subranges contained herein.Except in embodiment is operated or elsewhere
In indicate outside, amount, reaction condition of all expression compositions used in specification and claims etc. numeral or
Expression shall be construed as being subject in all cases the modification of word " about ".
Should be interpreted as in a flexible way not only including clearly including as scope using the value of range format expression
The numerical value of limit value, but also including covering all single numbers or subinterval within the range, just as 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 to not only include what is clearly included
The concentration of about 0.1% to about 5%, also including alluding in the range of single concentration（Such as, 1%, 2%, 3% and 4%）And subinterval（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 made up of at least two-layer, and one layer is basic unit, can be common nanofiltration membrane material
Matter layer, for example：Polyamide, cellulose acetate, SPSF, sulfonated polyether sulfone and polyvinyl alcohol etc., are not particularly limited, and it is
As the base material of 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（Can preferred Cucurbituril in the present invention）, the decorative layer, can in the present invention also with certain selective penetrated property
It is carried in basic unit with using interfacial polymerization, similarly, also can be carried on for Cucurbituril other organic by the method
On polymer film, such as microfiltration membranes, milipore filter etc..
Cucurbituril in above-mentioned decorative layer is a kind of supermolecule, with big annular space chamber, the tubbiness of both ends open point
Minor structure, going for Cucurbituril of the invention can include：Cucurbituril [n] (arbitrary integer in n=5~12), also may be used
To be its derivative, it is a kind of melon ring molecule, and inside has a rigid hydrophobic cavity, sub- two ends Ge YouC=O functional groups, outward
There is very strong hydrophily in portion, can improve the hydrophily on film surface, and molecule average grain diameter is 1-2nm.
In addition, its preparation method can be prepared by interfacial polymerization, for example：Added first on base material and contained
There is the first solution of Cucurbituril and the first monomer, then by its contact with the second solution containing second comonomer, and the first solution
Mutually immiscible with the second solution, the first monomer can be polymerized with second comonomer in interface, form the decorative layer on surface, by
In Cucurbituril is dissolved in the first solution, and it has cavity structure, therefore the first monomer can be coated in cavity, warp
Cross after interface polymerization reaction, the polymerization decorative layer being cross-linked with each other through Cucurbituril can be formed so that Cucurbituril is distributed in be repaiied
On decorations layer, and then realize load of the Cucurbituril in basic unit.
Can be able to be and the immiscible organic solution of water, no spy for water, the second solution used herein of the first solution
Do 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
, for example：First monomer can use piperazine, m-phenylene diamine (MPD), and second comonomer can be using acyl chloride monomer, such as equal benzene three
Formyl chloride.
The above-mentioned NF membrane for preparing can apply to common nanofiltration process, for example：The separation and retention of electrolyte,
Separation and retention of organic matter etc..In the present invention, due to increased the polymer containing Cucurbituril by 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, the rejection for the material of negative electrical charge increases again.
The preparation of the polyimide base film of embodiment 1
(1) by polyimides（P84）With PEG400 (PEG) 1-METHYLPYRROLIDONE (NMP) is dissolved in by certain mass ratio
In solvent, the mass ratio of P84, PEG and NMP is 20:12:50,25 DEG C of mechanical agitation 20~24 hours at room temperature, treat that its is complete
After CL, 8~12h deaerations treatment, the casting solution for obtaining are stood；
(2) polyester non-woven fabric is fixed on a glass, control blade thickness for 100 μm, by casting solution blade coating in non-woven polyester
On cloth, after 5~10 seconds volatilization time of control, in immersion water coagulating bath, there is phase separation film-forming, immersion is taken out after 5 minutes
Hygrometric state polyimide film is obtained final product, the basement membrane for preparing is preserved in deionized water.
The polyimide filtering membranes basic unit for preparing is used for the preparation of decorative layer in following examples.
The preparation of the polyether sulfone basement membrane of embodiment 2
(1) polyether sulfone and PEG400 (PEG) are dissolved in 1-METHYLPYRROLIDONE (NMP) solvent by certain mass ratio,
The mass ratio of P84, PEG and NMP is 20:12:50,25 DEG C of mechanical agitation 20~24 hours at room temperature, treat that it is completely dissolved
Afterwards, 8~12h deaerations treatment, the casting solution for obtaining are stood；
(2) polyester non-woven fabric is fixed on a glass, control blade thickness for 100 μm, by casting solution blade coating in non-woven polyester
On cloth, after 5~10 seconds volatilization time of control, in immersion water coagulating bath, there is phase separation film-forming, immersion is taken out after 5 minutes
Hygrometric state poly (ether sulfone) film is obtained final product, the basement membrane for preparing is preserved in deionized water.
The polyether sulfone basement membrane for preparing is used for the preparation of decorative layer in following examples.
The preparation of the polyimide composite film of the Cucurbituril of embodiment 3 modification
Prepare the Piperazine anhydrous of 2wt%（PIP）Aqueous phase solution, adds the Cucurbituril 6 of 0.1 wt %（CB6）, stirring, until completely
Dissolving, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0. 1 wt % is prepared, organic solvent is n-hexane, used as the second phase；
Polyimide base film is fixed on interfacial polymerization device, a certain amount of first immersion that mixes is poured into and is not had film surface, make it
Contacted with surface 120 seconds, taken out, then roll polyimide support film with rubber rollers, remove unnecessary solution, pour into equivalent
Second phase, is soaked 60 seconds, and surface is rinsed with hexane solution after the completion of question response, and then the unnecessary reactant of removal is stored in pure
It is stand-by in water.
The preparation of the polyimide composite film of the Cucurbituril of embodiment 4 modification
Prepare the Piperazine anhydrous of 1wt%（PIP）Aqueous phase solution, adds the Cucurbituril 8 of 0.5 wt %（CB8）, stirring, until completely
Dissolving, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0. 3 wt % is prepared, organic solvent is n-hexane, used as the second phase；
Polyimide base film is fixed on interfacial polymerization device, a certain amount of first immersion that mixes is poured into and is not had film surface, make it
Contacted with surface 150 seconds, taken out, then roll polyimide support film with rubber rollers, remove unnecessary solution, pour into equivalent
Second phase, is soaked 80 seconds, and surface is rinsed with hexane solution after the completion of question response, and then the unnecessary reactant of removal is stored in pure
It is stand-by in water.
The preparation of the polyimide composite film of the Cucurbituril of embodiment 5 modification
Prepare the Piperazine anhydrous of 3wt%（PIP）Aqueous phase solution, adds the Cucurbituril 7 of 0.7 wt %（CB7）, stirring, until completely
Dissolving, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0.2 wt % is prepared, organic solvent is n-hexane, used as the second phase；
Polyamide basement membrane is fixed on interfacial polymerization device, a certain amount of first immersion that mixes is poured into and is not had film surface, make its with
Surface contacts 110 seconds, takes out, and then rolls polyimide support film with rubber rollers, removes unnecessary solution, pours into the of equivalent
Two-phase, is soaked 40 seconds, and surface is rinsed with hexane solution after the completion of question response, is removed unnecessary reactant and is then stored in pure water
In it is stand-by.
The preparation of the polyimide composite film of the Cucurbituril of embodiment 6 modification
Prepare the Piperazine anhydrous of 1wt%（PIP）Aqueous phase solution, adds the Cucurbituril 7 of 0.2 wt %（CB7）, stirring, until completely
Dissolving, as the first phase；
The pyromellitic trimethylsilyl chloride organic phase solution of 0.4 wt % is prepared, organic solvent is n-hexane, used as the second phase；
Polyamide basement membrane is fixed on interfacial polymerization device, a certain amount of first immersion that mixes is poured into and is not had film surface, make its with
Surface contacts 150 seconds, takes out, and then rolls polyimide support film with rubber rollers, removes unnecessary solution, pours into the of equivalent
Two-phase, is soaked 60 seconds, and surface is rinsed with hexane solution after the completion of question response, is removed unnecessary reactant and is then stored in pure water
In it is stand-by.
Reference examples 1 are covered with the preparation of the polyimide composite film of polymer layer
Difference with embodiment 5 is：It is sub- in polyamides only by interface polymerization reaction not in the first quite middle addition Cucurbituril
Amine membrane surface covers a bed boundary polymer layer.
The SEM photograph of the polyimide composite film that reference examples 1 and embodiment 5 are prepared as depicted in figs. 1 and 2, from figure
In as can be seen that being modified by adding Cucurbituril in the interfacial polymerisation processes after, superficial film can be made more uniform, have
Help improve resistance tocrocking, rough surface easily fouling membrane occurs in being easily caused membrane filtration processes.
Polyether sulfone basement membrane, the implementation that will be prepared in the polyimide base film prepared in embodiment 1, embodiment 2
The composite membrane and reference examples 1 prepared in example 3~6 prepare be covered with polymer layer polyimide composite film carry out pure water lead to
The sign experiment of amount.
As can be seen from the above table, there is the NF membrane of the Cucurbituril modification for being prepared in the present invention larger water to lead to
Amount.
The cutoff performance tested under 0.6MPa pressure with the methylene blue of 100ppm using the above-mentioned film for preparing, rejection is such as
Under.
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 (10)
1. a kind of supermolecule composite nanometer filtering film, it is characterised in that include the decorative layer of basic unit and its surface covering, described repaiies
Decorations layer refers to the polymeric layer that Cucurbituril is distributed with；Described basic unit is organic film.
2. supermolecule composite nanometer filtering film according to claim 1, it is characterised in that described Cucurbituril refers to Cucurbituril
Arbitrary integer in [n] or derivatives thereof, wherein n=5~12.
3. supermolecule composite nanometer filtering film according to claim 1, it is characterised in that the material of described basic unit is selected from polyamides
Amine, polyimides, cellulose acetate, SPSF, sulfonated polyether sulfone or polyvinyl alcohol etc..
4. supermolecule composite nanometer filtering film according to claim 1, it is characterised in that described basic unit can also be covered in branch
On support layer, described supporting layer can be selected from non-woven fabrics etc..
5. supermolecule composite nanometer filtering film according to claim 1, it is characterised in that described polymeric layer is single by first
Body and second comonomer are mutually polymerized；The first described monomer is piperazines monomer or amino-contained monomer, described second
Monomer is acyl chloride monomer.
6. the preparation method of the supermolecule composite nanometer filtering film described in any one of Claims 1 to 5, it is characterised in that including as follows
Step：
I) be dissolved in the first solution for the first monomer, Cucurbituril by, obtains the first phase；
Ii) be dissolved in second comonomer in the second solution by, obtains the second phase；
Iii) is mutually put on first in basic unit, then second is mutually put in the first phase, carries out interface polymerization reaction, is obtained
Composite membrane.
7. the preparation method of supermolecule composite nanometer filtering film according to claim 6, it is characterised in that the first described solution
It is immiscible with the second solution；First solution is water, and the second solution is n-hexane.
8. the preparation method of supermolecule composite nanometer filtering film according to claim 6, it is characterised in that the first monomer is piperazine
Class monomer or amino-contained monomer, second comonomer are acyl chloride monomers；First monomer mass concentration in the first phase is 0.01
~5%；Mass concentration of the second comonomer in the second phase is 0.01~5%；Cucurbituril mass concentration in the first phase for
0.01~5%.
9. application of the supermolecule composite nanometer filtering film described in any one of Claims 1 to 5 in liquid filtering.
10. a kind of method of area load supermolecule in organic separation membrane, it is characterised in that comprise the following steps：
I) puts on organic separation membrane the second solution containing second comonomer；
Ii) is again put on the second solution the first solution containing Cucurbituril and the first monomer, by the first monomer and
The interface polymerization reaction of two monomers, Cucurbituril is carried on organic separation membrane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244794.1A CN106731841B (en) | 2016-12-29 | 2016-12-29 | A kind of supermolecule composite nanometer filtering film and its preparation method and application |
| PCT/CN2017/078785 WO2018120476A1 (en) | 2016-12-29 | 2017-03-30 | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244794.1A CN106731841B (en) | 2016-12-29 | 2016-12-29 | A kind of supermolecule composite nanometer filtering film and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106731841A true CN106731841A (en) | 2017-05-31 |
| CN106731841B CN106731841B (en) | 2018-08-14 |
Family
ID=58928696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611244794.1A Active CN106731841B (en) | 2016-12-29 | 2016-12-29 | A kind of supermolecule composite nanometer filtering film and its preparation method and application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106731841B (en) |
| WO (1) | WO2018120476A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110201545A (en) * | 2019-06-28 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of preparation method of antibacterial high-flux nanofiltration membrane |
| CN110449049A (en) * | 2019-07-29 | 2019-11-15 | 南京工业大学 | A kind of nanofiltration membrane, preparation method and its purposes in the separation of pigment wastewater monovalence salt-mixture |
| CN111013391A (en) * | 2019-11-28 | 2020-04-17 | 南京工业大学 | Modified nanofiltration membrane and preparation method thereof |
| CN111545083A (en) * | 2020-03-24 | 2020-08-18 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration |
| CN111589308A (en) * | 2020-06-10 | 2020-08-28 | 杨晓飞 | Composite nanofiltration membrane with heavy metal interception capacity |
| CN114247297A (en) * | 2021-12-23 | 2022-03-29 | 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 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN101462388A (en) * | 2009-01-13 | 2009-06-24 | 四川大学 | Compound film enhanced by inclusion complex of ring molecule and polymer and preparation method thereof |
| CN102327746A (en) * | 2011-08-23 | 2012-01-25 | 复旦大学 | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof |
| CN103272486A (en) * | 2013-06-18 | 2013-09-04 | 天津工业大学 | Composite film containing calixarene structure on surface layer |
| CN106178973A (en) * | 2016-08-24 | 2016-12-07 | 杭州易膜环保科技有限公司 | A kind of energy-saving NF membrane for water cleaning systems and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100499275B1 (en) * | 2002-01-03 | 2005-07-01 | 학교법인 포항공과대학교 | Hydroxy cucrubiturils and their derivatives, their preparation methods and uses |
| CN101792115B (en) * | 2010-03-16 | 2012-12-26 | 清华大学 | Cucurbituril subject-object based chemical nano structure membrane and preparation method and application thereof |
| CN104324619A (en) * | 2014-03-12 | 2015-02-04 | 唐山曹妃甸海清源科技有限公司 | Compound nanofiltration membrane with high selectivity, and preparation method thereof |
| CN105435658B (en) * | 2014-08-28 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of preparation method of supermolecule composite separating film |
| CN106178993B (en) * | 2016-08-23 | 2019-07-26 | 东华理工大学 | A kind of supermolecule polymer nanofiltration membrane and preparation method thereof |
-
2016
- 2016-12-29 CN CN201611244794.1A patent/CN106731841B/en active Active
-
2017
- 2017-03-30 WO PCT/CN2017/078785 patent/WO2018120476A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN101462388A (en) * | 2009-01-13 | 2009-06-24 | 四川大学 | Compound film enhanced by inclusion complex of ring molecule and polymer and preparation method thereof |
| CN102327746A (en) * | 2011-08-23 | 2012-01-25 | 复旦大学 | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof |
| CN103272486A (en) * | 2013-06-18 | 2013-09-04 | 天津工业大学 | Composite film containing calixarene structure on surface layer |
| CN106178973A (en) * | 2016-08-24 | 2016-12-07 | 杭州易膜环保科技有限公司 | A kind of energy-saving NF membrane for water cleaning systems and preparation method thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110201545A (en) * | 2019-06-28 | 2019-09-06 | 万华化学集团股份有限公司 | A kind of preparation method of antibacterial high-flux nanofiltration 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 |
| CN110449049A (en) * | 2019-07-29 | 2019-11-15 | 南京工业大学 | A kind of nanofiltration membrane, preparation method and its purposes in the separation of pigment wastewater monovalence salt-mixture |
| 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 |
| CN111013391A (en) * | 2019-11-28 | 2020-04-17 | 南京工业大学 | Modified nanofiltration membrane and preparation method thereof |
| CN111545083A (en) * | 2020-03-24 | 2020-08-18 | 南京工业大学 | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration |
| 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 |
| CN111589308A (en) * | 2020-06-10 | 2020-08-28 | 杨晓飞 | Composite nanofiltration membrane with heavy metal interception capacity |
| 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 |
| CN114247297A (en) * | 2021-12-23 | 2022-03-29 | 天津大学 | Nanofiltration membrane 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106731841B (en) | 2018-08-14 |
| WO2018120476A1 (en) | 2018-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106731841B (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| CN106975371A (en) | A kind of composite nanometer filtering film of polyolefin micropore substrate based on hydrophilic modifying and preparation method thereof | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| EP2857088B1 (en) | Method for manufacturing a reverse osmosis membrane | |
| CN110339724B (en) | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof | |
| KR101487575B1 (en) | Reverse osmosis membrane having a high fouling resistance and manufacturing method thereof | |
| CN110917907B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| CN109304106A (en) | A kind of Janus forward osmosis membrane and the preparation method and application thereof | |
| CN111686592A (en) | Composite nanofiltration membrane and preparation method thereof | |
| CN102580561B (en) | Tubular composite nanofiltration membrane | |
| CN110449049B (en) | Nanofiltration membrane, preparation method and application of nanofiltration membrane in separation of pigment wastewater monovalent mixed salt | |
| JP6642860B2 (en) | Water treatment separation membrane and method for producing the same | |
| CN106040014B (en) | A kind of antioxidant nanofiltration membrane and preparation method thereof that nanocrystalline cellulose is compound | |
| KR20170021798A (en) | Composite semipermeable membrane | |
| CN102423643B (en) | High-flux composite nanofiltration membrane | |
| CN103055715A (en) | Composite nanofiltration membrane and preparation method thereof | |
| CN102133506B (en) | Polyamide composite nanofiltration membrane | |
| CN104801209B (en) | Ultralow-pressure nanofiltration membrane prepared from imidazole sulfonate grafted polyether sulfone and preparation method thereof | |
| CN107362700B (en) | A kind of nanofiltration separation method of dyestuff intermediate | |
| JP2002224546A (en) | Composite semipermeable membrane for sewage disposal and its manufacturing method | |
| CN110354684A (en) | A kind of reverse osmosis membrane of low energy consumption and its preparation method and application | |
| KR101076221B1 (en) | Method for fabricating of reverse osmosis membrane from polyelectrolyte multilayers and reverse osmosis membrane of fabricated using the same | |
| CN115055061A (en) | Preparation method of polyamide composite nanofiltration membrane with high osmotic selectivity | |
| KR100322235B1 (en) | Fabrication of high permeable reverse osmosis membranes | |
| CN111282453B (en) | Preparation method of high-performance seawater desalination membrane and prepared seawater desalination membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171110 Address after: 211808 Jiangsu province Nanjing city Pukou District garden thought 1 Applicant after: NANJING MEMBRANE MATERIALS INDUSTRY TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 210009 Gulou District, Jiangsu, Nanjing new model road, No. 5 Applicant before: Nanjing University of Technology |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221013 Address after: Room 405, Comprehensive Office Building, Jiangsu Membrane Technology Industrial Park, No. 1, Industrial Technology Research and Innovation Park, Jiangbei New District, Nanjing, Jiangsu Province, 211800 Patentee after: Nanjing Weihua Film Technology Co.,Ltd. Address before: No. 1, YuanthingWay, Pukou District, Nanjing, Jiangsu 211808 Patentee before: NANJING MEMBRANE MATERIALS INDUSTRY TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |