CN115888415A - Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same - Google Patents
Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same Download PDFInfo
- Publication number
- CN115888415A CN115888415A CN202211505734.6A CN202211505734A CN115888415A CN 115888415 A CN115888415 A CN 115888415A CN 202211505734 A CN202211505734 A CN 202211505734A CN 115888415 A CN115888415 A CN 115888415A
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- China
- Prior art keywords
- membrane
- polypropylene microporous
- nanofiltration membrane
- chloride
- preparation
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 129
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- 238000005374 membrane filtration Methods 0.000 title description 2
- -1 polypropylene Polymers 0.000 claims abstract description 91
- 239000004743 Polypropylene Substances 0.000 claims abstract description 67
- 229920001155 polypropylene Polymers 0.000 claims abstract description 67
- 239000012982 microporous membrane Substances 0.000 claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 26
- 239000008346 aqueous phase Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 239000004952 Polyamide Substances 0.000 claims abstract description 22
- 229920002647 polyamide Polymers 0.000 claims abstract description 22
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 21
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 239000012304 carboxyl activating agent Substances 0.000 claims abstract description 12
- 230000033444 hydroxylation Effects 0.000 claims abstract description 8
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001046 Nanocellulose Polymers 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 4
- 239000013183 functionalized metal-organic framework Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 3
- IGMWDYQIKLLYQH-UHFFFAOYSA-N cyanomethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC#N IGMWDYQIKLLYQH-UHFFFAOYSA-N 0.000 claims description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 24
- 230000004907 flux Effects 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002585 base Substances 0.000 description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 150000001263 acyl chlorides Chemical class 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 239000003223 protective agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010364 biochemical engineering Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
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- 150000001805 chlorine compounds Chemical class 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 238000011049 filling Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 239000003002 pH adjusting agent Substances 0.000 description 2
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- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 230000005476 size effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a nanofiltration membrane and the nanofiltration membrane prepared by the method. The preparation method comprises the following steps: the method comprises the following steps of oxidizing a polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, sequentially contacting the polypropylene microporous membrane subjected to surface hydroxylation with a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups and a cross-linking agent to perform hydrophilization modification, applying a nano material containing a plurality of hydroxyl groups and/or a plurality of amino groups on the polypropylene microporous membrane subjected to hydrophilization modification, sequentially contacting with an aqueous phase solution and an organic phase solution to perform interfacial polymerization reaction to form a polyamide separation layer, and performing post-treatment to obtain the nanofiltration membrane, wherein the post-treatment comprises treatment by using a carboxyl activating agent. The nanofiltration membrane provided by the invention has a thinner thickness, can bring a higher effective filtration area of a single membrane element, has higher flux and excellent separation performance (separation of salt ions and the like) in the water treatment process, and has stable performance in the long-term operation process.
Description
Technical Field
The invention relates to the technical field of water treatment membranes, in particular to a preparation method of a nanofiltration membrane and the nanofiltration membrane prepared by the method.
Background
Water resources are indispensable natural resources for human life and production at present. At present, along with the rapid development of society, the contradiction between supply and demand of water resources is more and more prominent, on one hand, the over-development of people on surface water and underground water damages the sustainable cycle of water resources, which results in the reduction of fresh water resources, and on the other hand, a large amount of available water resources are polluted due to the difficultly-degradable pollutants discharged in the production of industry, agriculture and the like, which further results in the shortage of available water resources and serious influence on the sustainable development of society.
The existing solution mainly comprises the measures of sewage treatment and reuse, seawater desalination, trans-regional water transfer and the like. In sewage treatment, polluted water is treated to form regenerated usable water, which is proved to be feasible in a plurality of countries and regions in the world, and the contradiction between supply and demand of water resources can be relieved to a certain extent.
The membrane separation technology can be used for the sewage treatment process, has high-efficiency separation performance and lower energy consumption, and is widely applied to the industries of water treatment, medicine, food, biological purification, energy, chemical industry and the like. The membrane separation technology mainly adopts a pressure driving membrane, and comprises microfiltration, ultrafiltration, nanofiltration, reverse osmosis and the like. The nanofiltration membrane has special separation performance, can intercept inorganic salt and micromolecular organic matters in a solution, but has lower interception performance on monovalent salt ions compared with a reverse osmosis membrane, so that the nanofiltration membrane can be used for drinking water treatment and other processes to ensure that partial elements beneficial to human bodies are retained, and the nanofiltration membrane is greatly developed in the field of partial water treatment by combining with lower energy consumption.
How to reduce the cost of water treatment is a key of the practical application of the nanofiltration membrane, and in the current research, the improvement of the water flux and the pollution resistance of the nanofiltration membrane is the main research direction. At present, reducing the thickness of the nanofiltration membrane and preparing a loose polyamide layer structure are considered as a method which can improve the flux of the nanofiltration membrane, on one hand, the permeation resistance of water molecules can be reduced by reducing the thickness, and on the other hand, the permeability of the nanofiltration membrane with the loose polyamide layer structure is increased due to the high relative porosity of the nanofiltration membrane.
In addition, the current nanofiltration membrane mainly adopts a three-layer structure, namely a polyester non-woven fabric, a polysulfone layer and a polyamide separation layer, the overall thickness of the nanofiltration membrane is mostly concentrated on 100-150 micrometers, part of researchers begin to pay attention to preparation of the nanofiltration membrane with the thickness of less than 100 micrometers or even less than 50 micrometers, the thinner nanofiltration membrane can bring a higher filling area for a single membrane element, and the permeability of the single membrane element is improved, namely, under the same water yield condition, the number of the membrane elements can be reduced, the water production cost of the membrane method is further reduced, and the cost of using the nanofiltration membrane for water treatment is further reduced.
The polypropylene microporous membrane for the lithium battery is a diaphragm used in a lithium ion battery, and has higher porosity, higher tear strength, better acid and alkali resistance and good elasticity, the common thickness is 20-60 micrometers, and the pore diameter is 30-120 nanometers, so that if a polyamide nanofiltration membrane with excellent comprehensive performance can be prepared by using the polypropylene microporous membrane as a base membrane, a nanofiltration membrane element with a high filling area can be obtained by combining the thinner characteristic of the nanofiltration membrane element, and the permeability of a single membrane element is greatly improved.
Disclosure of Invention
Problems to be solved by the invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing a nanofiltration membrane using a polypropylene microporous membrane as a base membrane, and a nanofiltration membrane prepared by the method, wherein the method is simple and easy to operate, does not require modification of existing equipment, and has an effective operation cost, and the nanofiltration membrane prepared by the method has a relatively thin thickness, can provide a relatively high effective filtration area of a single membrane element, and has relatively high flux and excellent separation performance (separation of salt ions and the like) in a water treatment process.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and have creatively conceived the following technical solutions: oxidizing the polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, applying a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups, and realizing hydrophilization modification under the action of a cross-linking agent; then, a nano material containing a plurality of hydroxyl groups and/or a plurality of amino groups is applied on the polypropylene microporous membrane subjected to hydrophilization modification so as to provide an advantageous reaction platform for subsequent interfacial polymerization reaction; in the interfacial polymerization reaction, an alcohol additive is added into an aqueous phase solution, so that the diffusion of the nano material can be promoted, and the nano material participates in the interfacial polymerization reaction to construct a polyamide layer containing a nano water channel; in the post-treatment, the nano material can be stably present in the polyamide layer by the treatment with the carboxyl activating agent, so that the performance stability of the nanofiltration membrane in the long-term operation process is ensured.
The invention provides a preparation method of a nanofiltration membrane, which is characterized by comprising the following steps:
carrying out oxidation treatment on the polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, wherein the oxidation treatment is carried out by an aqueous solution containing persulfate compounds;
sequentially contacting the polypropylene microporous membrane subjected to surface hydroxylation with a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups and a crosslinking agent to perform hydrophilization modification;
applying a nanomaterial comprising a plurality of hydroxyl groups and/or a plurality of amino groups on a hydrophilically modified polypropylene microporous membrane, and then sequentially contacting an aqueous phase solution and an organic phase solution to perform interfacial polymerization reaction to form a polyamide separation layer, wherein the aqueous phase solution comprises an alcohol additive and an amine compound as an aqueous phase monomer, and the organic phase solution comprises an acid chloride compound as an organic phase monomer;
and (3) obtaining the nanofiltration membrane through post-treatment, wherein the post-treatment comprises treatment by using a carboxyl activating agent.
The preparation method according to the invention, wherein the persulfate compound is at least one selected from potassium persulfate, sodium persulfate and ammonium persulfate.
The preparation method according to the present invention, wherein the compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from the group consisting of polyvinyl alcohol, polyethylene glycol, tannic acid, polyethyleneimine, carboxylated chitosan, sorbitol, polyacrylic polyol, polyaminopolyether, and polyacrylamide.
The preparation method of the invention is characterized in that the cross-linking agent is at least one selected from aliphatic dialdehyde with 2-6 carbon atoms, N-methylene-bisacrylamide, glycidyl methacrylate, epichlorohydrin and polyethylene glycol glycidyl ether.
The preparation method according to the invention, wherein the nanomaterial containing a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from carboxylated graphene oxide, aminated graphene, aminated multi-wall carbon nanotubes, aminated single-wall carbon nanotubes, carboxylated single-wall carbon nanotubes, amino-functionalized metal organic framework MOF and aminated nanocrystalline cellulose.
The production method according to the present invention is characterized in that the alcohol additive is at least one selected from the group consisting of an aliphatic alcohol having 1 to 6 carbon atoms and an aromatic alcohol having 7 to 12 carbon atoms.
The preparation method according to the present invention, wherein the amine compound is at least one selected from piperazine, homopiperazine, 2-methylpiperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, trimesamine, and polyethyleneimine.
The preparation method of the invention comprises the step of preparing an acyl chloride compound, wherein the acyl chloride compound is at least one selected from isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl chloride, biphenyl tetracoyl chloride, cyanuric chloride, dansyl chloride and benzenesulfonyl chloride.
The production method according to the present invention, wherein the carboxyl activating agent is a combination of N-hydroxysuccinimide with at least one selected from 1, 3-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, diethylcyanomethyl phosphate, 4-dimethylaminopyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
The invention also provides a nanofiltration membrane prepared by the preparation method.
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation method of the nanofiltration membrane provided by the invention is simple, easy to operate, free of the need of modifying the existing equipment, and effective in operation cost, and the nanofiltration membrane prepared by the method has a thinner thickness, can bring a higher effective filtration area of a single membrane element, has higher flux and excellent separation performance (separation of salt ions and the like) in the water treatment process, and has stable performance in the long-term operation process.
Drawings
Fig. 1 shows the results of stability tests performed on the nanofiltration membranes obtained in examples 1 to 4 (abbreviated as example 1, example 2, example 3, and example 4).
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the specification are international standard units unless otherwise specified, and numerical values and numerical ranges appearing in the present invention should be understood to include systematic errors inevitable in industrial production.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
The invention provides a preparation method of a nanofiltration membrane, which comprises the following steps:
carrying out oxidation treatment on the polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, wherein the oxidation treatment is carried out by an aqueous solution containing persulfate compounds;
sequentially contacting the polypropylene microporous membrane subjected to surface hydroxylation with a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups and a crosslinking agent to perform hydrophilization modification;
applying a nanomaterial comprising a plurality of hydroxyl groups and/or a plurality of amino groups on a hydrophilically modified polypropylene microporous membrane, and then sequentially contacting an aqueous phase solution and an organic phase solution to perform interfacial polymerization reaction to form a polyamide separation layer, wherein the aqueous phase solution comprises an alcohol additive and an amine compound as an aqueous phase monomer, and the organic phase solution comprises an acid chloride compound as an organic phase monomer;
and (3) obtaining the nanofiltration membrane through post-treatment, wherein the post-treatment comprises treatment by using a carboxyl activating agent.
The technical idea of the invention is as follows: oxidizing the polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, applying a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups, and realizing hydrophilization modification under the action of a cross-linking agent; then, a nano material containing a plurality of hydroxyl groups and/or a plurality of amino groups is applied on the polypropylene microporous membrane subjected to hydrophilization modification so as to provide an advantageous reaction platform for subsequent interfacial polymerization reaction; in the interfacial polymerization reaction, an alcohol additive is added into an aqueous phase solution, so that the diffusion of the nano material can be promoted, and the nano material participates in the interfacial polymerization reaction to construct a polyamide layer containing a nano water channel; in the post-treatment, the nano material can be stably present in the polyamide layer by the treatment with the carboxyl activating agent, so that the performance stability of the nanofiltration membrane in the long-term operation process is ensured.
Preferably, the polypropylene microporous membrane used in the present invention has a thickness of 20 to 40 μm and a pore size of 30 to 100 nm. If the thickness of the polypropylene microporous membrane is too thick, the permeability of the membrane is not favorable, if the thickness of the polypropylene microporous membrane is too thin, the mechanical property of the prepared nanofiltration membrane is insufficient, and the pore diameter of the membrane within the range can be favorable for ensuring the compactness and uniformity of the prepared polyamide layer.
The preparation method of the invention comprises the step of preparing the persulfate compound by using the method of the invention, wherein the persulfate compound is at least one selected from potassium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the oxidation treatment is carried out as follows: treating the mixture for 30 to 60 minutes at a temperature of between 60 and 80 ℃ by using an aqueous solution of potassium persulfate with the concentration of between 5 and 15 weight percent. The reaction conditions may be adjusted as necessary to provide different degrees of oxidation.
The preparation method of the present invention, wherein the compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from polyvinyl alcohol, polyethylene glycol, tannic acid, polyethyleneimine, carboxylated chitosan, sorbitol, polyacrylic polyol, polyaminopolyether, and polyacrylamide.
Preferably, the polypropylene microporous membrane subjected to surface hydroxylation is immersed into an aqueous solution in which a compound or polymer containing multiple hydroxyl groups and/or multiple amino groups is dissolved, so that the polypropylene microporous membrane (including the membrane surface and the membrane pores) is ensured to be wetted by the aqueous solution of the compound or polymer containing multiple hydroxyl groups and/or multiple amino groups; after wetting, the membrane is immersed into an aqueous solution containing a cross-linking agent, and hydrophilic modification of the polypropylene microporous membrane is realized through self-crosslinking among hydroxyl groups and crosslinking of hydroxyl groups introduced on a polypropylene chain through the oxidation treatment, so that a hydrophilic membrane surface and a pore channel are constructed.
Preferably, the concentration of the compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups in the aqueous solution is 5 to 10wt%, the temperature of the aqueous solution is 30 to 50 ℃, and the soaking time is 20 to 40 minutes.
The preparation method of the invention is characterized in that the cross-linking agent is at least one selected from aliphatic dialdehyde with 2-6 carbon atoms, N-methylene bisacrylamide, glycidyl methacrylate, epichlorohydrin and polyethylene glycol glycidyl ether.
Preferably, the cross-linking agent is at least one selected from glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, N-methylenebisacrylamide.
Preferably, the content of the crosslinking agent is 0.1 to 1wt% based on the total weight of the aqueous solution containing the crosslinking agent; the immersion time in the aqueous solution containing the crosslinking agent is preferably 5 to 10 minutes, and the temperature of the aqueous solution containing the crosslinking agent is 20 to 40 ℃. The main purpose of this process is to ensure the stability of compounds or polymers containing multiple hydroxyl groups and/or multiple amino groups in polypropylene microporous membranes by chemical bonding and intermolecular entanglement.
The preparation method provided by the invention is characterized in that the nanomaterial containing a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from carboxylated graphene oxide, aminated graphene, aminated multi-wall carbon nanotubes, aminated single-wall carbon nanotubes, carboxylated single-wall carbon nanotubes, amino-functionalized metal organic framework MOF and aminated nanocrystalline cellulose.
Preferably, the nanomaterial containing a plurality of hydroxyl groups and/or a plurality of amino groups is applied by spraying a dispersion liquid containing the nanomaterial on a polypropylene microporous membrane modified by hydrophilization so as to construct a platform for subsequent interfacial polymerization reaction, improve the reaction progress of the interfacial polymerization reaction, and the nanomaterial participates in constructing water molecule channels, thereby contributing to the improvement of the permeability of the membrane sheet and ensuring the separation performance of the membrane.
The nano material has a certain amount of hydroxyl and/or amino and can be fixed on the polyamide layer in the interfacial polymerization or subsequent treatment process; preferably, the concentration of the nanomaterial in the dispersion is 0.01 to 1wt%.
Preferably, the hydrophilically modified polypropylene microporous membrane applied with the nanomaterial including a plurality of hydroxyl groups and/or a plurality of amino groups is sequentially immersed in an aqueous phase solution containing an amine-based compound and an organic phase solution containing an acid chloride-based compound to perform an interfacial polymerization reaction to form an initial polyamide layer. In the process, the nano material participates in the interfacial polymerization process along with the diffusion of the amine compound, so that a nano water molecule channel is formed to improve the permeation separation performance of the polyamide layer; furthermore, an alcohol additive is added into the aqueous phase solution containing the amine compound, and the additive can promote the diffusion of the nano material, so that the nano material is promoted to participate in the interfacial polymerization reaction.
The preparation method comprises the step of preparing an amine compound, wherein the amine compound is at least one selected from piperazine, homopiperazine, 2-methylpiperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, trimesamine and polyethyleneimine.
Preferably, the concentration of the amine compound in the aqueous phase solution is 0.5 to 1.5wt%.
The production method of the present invention is characterized in that the alcohol additive is at least one selected from the group consisting of an aliphatic alcohol having 1 to 6 carbon atoms and an aromatic alcohol having 7 to 12 carbon atoms.
The alcohol additives include, but are not limited to, methanol, ethanol, isopropanol, benzyl alcohol, glycerol, ethylene glycol, n-butanol. Preferably, the concentration of the alcohol additive in the aqueous phase solution is 3 to 5wt%.
Preferably, the aqueous phase solution also comprises a pH regulator to regulate the pH value of the solution and promote the solution to form an alkaline environment so as to absorb hydrogen chloride generated in the interfacial polymerization process, thereby promoting the reaction; the pH adjustor is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium carbonate, ammonium bicarbonate, triethanolamine, and triethylamine/camphorsulfonic acid complex solution. Preferably, the pH of the aqueous phase solution is adjusted to 10 to 11 using a pH adjuster.
Preferably, the contact time with the aqueous phase solution is 30 to 60 seconds; the contact temperature is not limited and may be in the range of 15 to 45 ℃.
The preparation method comprises the step of preparing a chloride compound, wherein the chloride compound is at least one selected from isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride, biphenyl tetracoyl chloride, cyanuric chloride, dansyl chloride and benzenesulfonyl chloride.
Preferably, the content of the acyl chloride compound is 0.1 to 0.5wt% based on the total weight of the organic phase solution.
Preferably, the organic phase solution further comprises an organic solvent, and the organic solvent is at least one selected from n-hexane, n-heptane, cyclohexane, isopar M, isopar H, isopar L, isopar E and Isopar G.
Preferably, the contact time with the organic phase solution is 30 to 60 seconds. The contact temperature is not limited and may be in the range of 15 to 45 ℃.
Preferably, after the interfacial polymerization reaction is completed, the nanofiltration membrane is initially heated to promote further crosslinking of the polyamide layer, so as to obtain an initial nanofiltration membrane.
Preferably, the heating temperature is 25-40 ℃, and the heating time is 1-5 minutes; the purpose of the heating is to promote the volatilization of the solvent and the further cross-linking and curing of the polyamide layer, thereby promoting the formation of the nanofiltration membrane.
Preferably, the initial nanofiltration membrane is immersed in an aqueous solution containing a carboxyl activator to crosslink substances remaining between polyamide layers of the initial nanofiltration membrane, thereby ensuring stability of a water channel composed of the nanomaterial.
In the step, through the soaking treatment of the carboxyl activating agent, the chemical reaction between the amino on the nano material and the carboxyl hydrolyzed by the acyl chloride group on the polyamide layer is promoted, so that the nano material is promoted to be fixed in the polyamide layer, the stable construction of a nano water channel is ensured, and the membrane performance change caused by the falling of the nano material in the subsequent water treatment process is prevented.
The preparation method of the present invention, wherein the carboxyl activating agent is a combination of N-hydroxysuccinimide (NHS) and at least one selected from 1, 3-Dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC), diethylcyanomethyl phosphate (DEPC), 4-Dimethylaminopyridine (DMAP), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC).
Preferably, the content of the carboxyl activator is 0.5 to 2wt% based on the total weight of the aqueous solution containing the carboxyl activator; the immersion time is preferably 1 to 3 minutes, and the immersion temperature is preferably 40 to 60 ℃.
The preparation method of the invention, wherein the post-treatment preferably further comprises pure water washing, pore-protecting treatment and drying treatment.
The purpose of pure water washing is to remove unreacted amine compounds, acyl chloride compounds, and unfixed compounds or polymers containing multiple hydroxyl groups and/or multiple amino groups, crosslinking agents and nano materials;
preferably, the washing is carried out by respectively soaking the two sections of pure water at the temperature of 60-80 ℃ and 20-30 ℃, and the main purpose is to wash away residues in the previous process; preferably, the washing time is 10 to 20 minutes, with 5 minutes of hot water washing.
Furthermore, the nano-filtration membrane prepared by the method is thin, and the membrane shrinkage without hole retention is serious in the subsequent drying process, so that the permeability of the nano-filtration membrane is affected, and the hole retention is needed to ensure the stability of the membrane hole in the subsequent drying process and ensure the performance of the membrane; preferably, the pore-protecting agent is one or more of glycerol and sorbitol; preferably, the concentration of the pore-protecting agent is 10-15 wt%, the temperature of the aqueous solution containing the pore-protecting agent is 20-30 ℃, and the treatment time is 5-10 minutes.
And further, heating and drying are carried out to obtain the final nanofiltration membrane so as to prepare the nanofiltration membrane without water, thereby facilitating the subsequent membrane component rolling.
Preferably, the heating and drying temperature range is 50-90 ℃, and the drying time is 1-3 minutes.
The invention also provides the nanofiltration membrane prepared by the preparation method. The nanofiltration membrane has a thin thickness, can bring a higher effective filtration area of a single membrane element, and has a nanometer water channel, so that the nanofiltration membrane has higher flux and excellent separation performance (separation of salt ions and the like) in a water treatment process, and has stable performance in a long-term operation process. The nanofiltration membrane can be applied to separation and concentration technologies in the fields of water treatment, dyes, biochemical engineering, food, environmental protection and the like.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Preparation example 1
Preparing a polypropylene microporous membrane with the thickness of 30 +/-5 microns and the average pore diameter of 40 nanometers, immersing the polypropylene microporous membrane into an aqueous solution of potassium persulfate with the concentration of 10wt%, heating to 80 ℃ to perform oxidation reaction for 40 minutes so as to introduce hydroxyl groups on the surface of the membrane, and washing with water to remove residual substances;
the polypropylene microporous membrane subjected to the surface hydroxylation by the oxidation treatment is immersed in an aqueous solution containing polyvinyl alcohol as a polymer containing a plurality of hydroxyl groups and having a concentration of 8wt%, immersed for 30 minutes at 40 ℃ to ensure that the membrane is wetted with the aqueous solution, and then immersed in an aqueous solution containing glutaraldehyde as a crosslinking agent (the concentration of the crosslinking agent is 0.5wt%, the pH of the aqueous solution is adjusted to 2.5 to 3.5 with sulfuric acid) to perform a crosslinking reaction, and the hydrophilic modified polypropylene microporous membrane is obtained as the polypropylene microporous base membrane 1 by the reaction for 8 minutes at 30 ℃.
Preparation example 2
A polypropylene microporous base film 2 was obtained in the same manner as in production example 1, except that polyethylene glycol was used instead of polyvinyl alcohol.
Preparation example 3
A polypropylene microporous base film 3 was obtained in the same manner as in preparation example 1, except that tannic acid was used instead of polyvinyl alcohol.
Preparation example 4
A polypropylene microporous base film 4 was obtained in the same manner as in production example 1, except that polyethyleneimine was used instead of polyvinyl alcohol.
Preparation example 5
Preparing aqueous dispersion of nano-materials, wherein aminated graphene oxide is used as the nano-materials, and the concentration of the aminated graphene oxide is 0.05wt%;
the dispersion was spray-coated on the polypropylene microporous base film 1 obtained in preparation example 1, thereby obtaining a polypropylene microporous base film 1-1.
Preparation example 6
Except that the dispersion was spray-coated on the polypropylene microporous base film 2 obtained in production example 2, a polypropylene microporous base film 2-1 was obtained in the same manner as in production example 5.
Preparation example 7
Polypropylene microporous base film 3-1 was obtained in the same manner as in preparation example 5, except that the dispersion was spray-coated on polypropylene microporous base film 3 obtained in preparation example 3.
Preparation example 8
Polypropylene microporous base film 4-1 was obtained in the same manner as in preparation example 5, except that the dispersion was spray-coated on polypropylene microporous base film 4 obtained in preparation example 4.
Preparation example 9
Polypropylene microporous base films 1-2 were obtained in the same manner as in preparation example 5, except that carboxylated graphene oxide was used as the nanomaterial instead of aminated graphene oxide.
Preparation example 10
Polypropylene microporous base films 1 to 3 were obtained in the same manner as in preparation example 5, except that amino-functionalized metal organic framework MOF was used instead of aminated graphene oxide as a nanomaterial.
Preparation example 11
Polypropylene microporous base films 1 to 4 were obtained in the same manner as in preparation example 5, except that aminated nanocrystalline cellulose was used instead of aminated graphene oxide as the nanomaterial.
Preparation example 12
Polypropylene microporous base films 1 to 5 were obtained in the same manner as in preparation example 5, except that aminated multiwalled carbon nanotubes were used as the nanomaterial instead of aminated graphene oxide.
For comparison, in the following comparative examples and examples, the following aqueous phase solution, organic phase solution and aqueous solution containing a carboxyl group activator were used, and the contact time and temperature with the aqueous phase solution and organic phase solution were as follows:
aqueous phase solution: piperazine was used as an aqueous phase monomer at a concentration of 1wt%, sodium hydrogen phosphate was added as a pH adjuster to adjust the pH to 10 to 11, isopropyl alcohol was added as an alcohol additive at a concentration of 4wt%, the immersion temperature in the aqueous phase solution was 20 ℃, and the contact time with the aqueous phase solution was 40 seconds.
Organic phase solution: trimesoyl chloride was used as an organic phase monomer at a concentration of 0.2% by weight, and n-heptane was used as a solvent at a reaction temperature of 25 ℃ in the organic phase solution for 40 seconds.
Aqueous solution comprising a carboxyl activator: the weight ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) to N-hydroxysuccinimide (NHS) was 10.
Comparative example 1
Sequentially immersing the microporous polypropylene base membrane 1 obtained in preparation example 1 into an aqueous phase solution and an organic phase solution to perform interfacial polymerization; taking out and then heating in a 30 ℃ oven for 3 minutes; then immersing the mixture into an aqueous solution containing a carboxyl activating agent for reaction for 2 minutes; however, the membrane was immersed in hot water at 65 ℃ for 5 minutes and cold water at 25 ℃ for 10 minutes, respectively, to wash off the residual chemical substances on the membrane; soaking the membrane in an aqueous solution with the concentration of 12wt% of glycerol and the temperature of 25 ℃ for 8 minutes to ensure that the membrane is wetted by the aqueous solution of glycerol and does not shrink pores in the subsequent process; and drying in an oven at the temperature of 85 ℃ for 2 minutes to obtain the final nanofiltration membrane.
Comparative example 2
Comparative example 2 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 2 obtained in preparation example 2 was used.
Comparative example 3
Comparative example 3 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 3 obtained in preparation example 3 was used.
Comparative example 4
Comparative example 4 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 4 obtained in preparation example 4 was used.
Example 1
Example 1 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 1-1 obtained in preparation example 5 was used.
Example 2
Example 2 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 2-1 obtained in preparation example 6 was used.
Example 3
Example 3 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 3-1 obtained in preparation example 7 was used.
Example 4
Example 4 was performed in the same manner as comparative example 1, except that the polypropylene microporous base film 4-1 obtained in preparation example 8 was used.
Example 5
Example 5 was performed in the same manner as example 1, except that the polypropylene microporous base film 1-2 obtained in preparation example 9 was used.
Example 6
Example 6 was performed in the same manner as example 1, except that the polypropylene microporous base films 1 to 3 obtained in preparation example 10 were used.
Example 7
Example 7 was performed in the same manner as in example 1, except that the polypropylene microporous base films 1 to 4 obtained in preparation example 11 were used.
Example 8
Example 8 was performed in the same manner as example 1, except that the polypropylene microporous base films 1 to 5 obtained in preparation example 12 were used.
Comparative example 5
Comparative example 5 was performed in the same manner as example 1, except that the treatment using the aqueous solution containing the carboxyl group activator was not performed.
Performance testing and results
(1) Testing of osmotic separation Performance
The nanofiltration membranes obtained in the above comparative examples and examples were subjected to the following tests.
A cross-flow type membrane test bench is adopted for membrane test, the test solution is 2000mg/L magnesium sulfate aqueous solution, the test pressure is 70psi, the temperature is 25 ℃, the pH value is 7, and the test stabilization time is 40 minutes. The test results are shown in table 1 below:
TABLE 1
From the results of comparative examples 1 to 4, the surface hydroxylation and hydrophilization modification are carried out on the polypropylene microporous membrane, the subsequent interfacial polymerization reaction can be directly carried out, the obtained nanofiltration membrane also has a certain permeability, but the high requirement on the desalination performance of the nanofiltration membrane cannot be met in terms of the desalination performance, and the desalination rate of the obtained nanofiltration membrane is only 90.36% at most.
Comparing the comparative example 1 with the comparative example 5, it can be seen that the flux of the membrane obtained in the comparative example 5 is higher than that of the membrane obtained in the comparative example 1, because the sprayed nano material can play a role of an intermediate layer, on one hand, the existence of the intermediate layer can enable the prepared polyamide layer to be more uniform, and on the other hand, the nano material is diffused to participate in a water molecule transfer channel constructed by interfacial polymerization reaction, so that the prepared nano-filtration membrane has better permeability and the flux is improved.
As can be seen from comparison of comparative example 5 with examples 1 to 8, the salt rejection of the membrane obtained in comparative example 5 is lower than that of the membranes obtained in examples 1 to 8 because the carboxyl group activating agent treatment process is not performed in comparative example 5, and thus the membrane is unstable, and during operation, a part of nanoparticles are carried away by water current impact, resulting in loss of constructed water channels, defects in the membrane surface, and reduced compactness of the membrane surface, and thus, the salt rejection performance is reduced, rather than that of the membranes obtained in examples 1 to 8; the membranes obtained in examples 1 to 8 were slightly lower in flux than the membrane obtained in comparative example 5 because the carboxyl group activator treatment was further performed in examples 1 to 8, and thus, the membrane surface was further crosslinked, and became more stable and dense, and the pore size effect of the membrane was enhanced due to the increase in denseness, and therefore, the desalting performance was increased, and was superior to that of the membrane obtained in comparative example 5, while the permeation performance of the membrane was slightly lowered relative to that of the membrane obtained in comparative example 5.
From the results of examples 1 to 8, on the basis of surface hydroxylation and hydrophilization modification, a nano material containing a plurality of hydroxyl groups and/or a plurality of amino groups is further applied and is treated by a carboxyl activating agent, so that the obtained nanofiltration membrane has excellent comprehensive performance, good permeability and desalination performance, the flux is equivalent to that of the nanofiltration membranes obtained in comparative examples 1 to 4, and the desalination rate is significantly higher than that of the nanofiltration membranes obtained in comparative examples 1 to 4.
(2) Stability test
The nanofiltration membranes obtained in examples 1 to 4 (abbreviated as example 1, example 2, example 3 and example 4) were subjected to a stability test under the following test conditions: the test solution was 2000mg/L magnesium sulfate in water at a test pressure of 70psi, a temperature of 25 deg.C and a pH of 7.
As shown in fig. 1, it can be seen from fig. 1 that the prepared membrane has good stability during 7 days of operation, and the flux and salt rejection rate are slightly attenuated in the initial stage, and remain stable in the subsequent long-term operation without large attenuation.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the market, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The preparation method of the nanofiltration membrane provided by the invention is simple, easy to operate, free of the need of modifying the existing equipment, and effective in operation cost, the nanofiltration membrane prepared by the method has a thinner thickness, and can bring a higher effective filtration area of a single membrane element, and the membrane has a nanometer water channel, so that the nanofiltration membrane has higher flux and excellent separation performance (separation of salt ions and the like) in the water treatment process, and has stable performance in the long-term operation process. The nanofiltration membrane can be applied to separation and concentration technologies in the fields of water treatment, dyes, biochemical engineering, food, environmental protection and the like.
Claims (10)
1. The preparation method of the nanofiltration membrane is characterized by comprising the following steps:
carrying out oxidation treatment on the polypropylene microporous membrane to hydroxylate the surface of the polypropylene microporous membrane, wherein the oxidation treatment is carried out by an aqueous solution containing persulfate compounds;
sequentially contacting the polypropylene microporous membrane subjected to surface hydroxylation with a compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups and a crosslinking agent to perform hydrophilization modification;
applying a nanomaterial comprising a plurality of hydroxyl groups and/or a plurality of amino groups on a hydrophilically modified polypropylene microporous membrane, and then sequentially contacting an aqueous phase solution and an organic phase solution to perform interfacial polymerization reaction to form a polyamide separation layer, wherein the aqueous phase solution comprises an alcohol additive and an amine compound as an aqueous phase monomer, and the organic phase solution comprises an acid chloride compound as an organic phase monomer;
and (3) obtaining the nanofiltration membrane through post-treatment, wherein the post-treatment comprises treatment by using a carboxyl activating agent.
2. The production method according to claim 1, wherein the persulfate-based compound is at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate.
3. The production method according to claim 1 or 2, wherein the compound or polymer containing a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from polyvinyl alcohol, polyethylene glycol, tannic acid, polyethyleneimine, carboxylated chitosan, sorbitol, polyacrylic polyol, polyaminopolyether, polyacrylamide.
4. The production method according to claim 1 or 2, wherein the crosslinking agent is at least one selected from the group consisting of aliphatic dialdehydes having 2 to 6 carbon atoms, N-methylenebisacrylamide, glycidyl methacrylate, epichlorohydrin, and polyethylene glycol glycidyl ether.
5. The preparation method according to claim 1 or 2, wherein the nanomaterial comprising a plurality of hydroxyl groups and/or a plurality of amino groups is at least one selected from the group consisting of carboxylated graphene oxide, aminated graphene, aminated multiwall carbon nanotubes, aminated single wall carbon nanotubes, carboxylated single wall carbon nanotubes, amino functionalized metal organic framework MOF, aminated nanocrystalline cellulose.
6. The production method according to claim 1 or 2, wherein the alcohol additive is at least one selected from the group consisting of an aliphatic alcohol having 1 to 6 carbon atoms and an aromatic alcohol having 7 to 12 carbon atoms.
7. The production method according to claim 1 or 2, wherein the amine-based compound is at least one selected from the group consisting of piperazine, homopiperazine, 2-methylpiperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, trimesamine, and polyethyleneimine.
8. The production method according to claim 1 or 2, wherein the acid chloride-based compound is at least one selected from the group consisting of isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride, biphenyltetracoyl chloride, cyanuric chloride, dansyl chloride and benzenesulfonyl chloride.
9. The production method according to claim 1 or 2, wherein the carboxyl activating agent is a combination of N-hydroxysuccinimide with at least one selected from 1, 3-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, diethylcyanomethyl phosphate, 4-dimethylaminopyridine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
10. A nanofiltration membrane prepared by the preparation method of any one of claims 1 to 9.
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| PCT/CN2023/131574 WO2024114370A1 (en) | 2022-11-28 | 2023-11-14 | Preparation method for nanofiltration membrane and nanofiltration membrane prepared by using same |
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| CN117125864A (en) * | 2023-10-26 | 2023-11-28 | 湘潭电化科技股份有限公司 | Treatment method of ammonia nitrogen industrial wastewater |
| CN117815911A (en) * | 2024-03-04 | 2024-04-05 | 中山大学 | Amphiphilic ultrafiltration membrane and preparation method and application thereof |
| WO2024114370A1 (en) * | 2022-11-28 | 2024-06-06 | 沃顿科技股份有限公司 | Preparation method for nanofiltration membrane and nanofiltration membrane prepared by using same |
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| AU2006261581B2 (en) * | 2005-06-20 | 2012-03-15 | Evoqua Water Technologies Llc | Cross linking treatment of polymer membranes |
| CN105413464A (en) * | 2015-10-22 | 2016-03-23 | 中国海洋大学 | Preparation method for graphene quantum dot added forward osmosis membrane, prepared forward osmosis membrane and application thereof |
| US11235290B2 (en) * | 2017-02-17 | 2022-02-01 | The Research Foundation For The State University Of New York | High-flux thin-film nanocomposite reverse osmosis membrane for desalination |
| WO2020177274A1 (en) * | 2019-03-06 | 2020-09-10 | 中国海洋大学 | Composite membrane, preparation method therefor and application thereof |
| CN109821427B (en) * | 2019-03-22 | 2021-06-08 | 江南大学 | Preparation method of chlorine-resistant aromatic polyamide composite nanofiltration membrane |
| CN114682102B (en) * | 2020-11-11 | 2023-06-27 | 沃顿科技股份有限公司 | Reverse osmosis membrane and preparation method thereof |
| CN114632429B (en) * | 2020-12-15 | 2023-01-20 | 中化(宁波)润沃膜科技有限公司 | Composite nanofiltration membrane containing composite desalting layer and preparation method thereof |
| CN116143234A (en) * | 2021-11-22 | 2023-05-23 | 沃顿科技股份有限公司 | Preparation method of sea water desalination reverse osmosis membrane and reverse osmosis membrane prepared by same |
| CN114849501B (en) * | 2022-05-30 | 2023-05-26 | 沃顿科技股份有限公司 | Nanofiltration membrane preparation method and nanofiltration membrane prepared by same |
| CN114682105B (en) * | 2022-06-02 | 2022-08-23 | 天津大学 | Preparation method and application of strong-polarity-resistant organic solvent nanofiltration membrane |
| CN115888415A (en) * | 2022-11-28 | 2023-04-04 | 沃顿科技股份有限公司 | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same |
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| WO2024114370A1 (en) * | 2022-11-28 | 2024-06-06 | 沃顿科技股份有限公司 | Preparation method for nanofiltration membrane and nanofiltration membrane prepared by using same |
| CN117125864A (en) * | 2023-10-26 | 2023-11-28 | 湘潭电化科技股份有限公司 | Treatment method of ammonia nitrogen industrial wastewater |
| CN117815911A (en) * | 2024-03-04 | 2024-04-05 | 中山大学 | Amphiphilic ultrafiltration membrane and preparation method and application thereof |
| CN117815911B (en) * | 2024-03-04 | 2024-05-17 | 中山大学 | Amphiphilic ultrafiltration membrane and preparation method and application thereof |
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