CN105435653B - A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof - Google Patents
A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof Download PDFInfo
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- CN105435653B CN105435653B CN201510952929.9A CN201510952929A CN105435653B CN 105435653 B CN105435653 B CN 105435653B CN 201510952929 A CN201510952929 A CN 201510952929A CN 105435653 B CN105435653 B CN 105435653B
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- layer
- amine
- composite nanometer
- filtering film
- high selectivity
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000001914 filtration Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 83
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 48
- 238000010612 desalination reaction Methods 0.000 claims abstract description 41
- 150000002500 ions Chemical class 0.000 claims abstract description 41
- 150000001412 amines Chemical class 0.000 claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 19
- 239000002346 layers by function Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 36
- 150000001263 acyl chlorides Chemical class 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 26
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- 238000010406 interfacial reaction Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- -1 phthalyl chlorine Chemical compound 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 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 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- RWAWMKWJDOUNKY-UHFFFAOYSA-N 1-piperidin-3-ylpiperidine Chemical compound C1CCCCN1C1CNCCC1 RWAWMKWJDOUNKY-UHFFFAOYSA-N 0.000 claims 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical class COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 claims 1
- 150000004999 2,4-diaminotoluenes Chemical class 0.000 claims 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical class NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims 1
- 229940043237 diethanolamine Drugs 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical class NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 abstract description 23
- 150000003839 salts Chemical class 0.000 abstract description 20
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 abstract description 3
- 235000019341 magnesium sulphate Nutrition 0.000 abstract description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 2
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001728 nano-filtration Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 238000000108 ultra-filtration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
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- 238000001223 reverse osmosis Methods 0.000 description 3
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 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 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010889 donnan-equilibrium Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
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- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- 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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Abstract
The present invention relates to NF membrane and its preparing technical field, especially a kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof, it is characterized in that having mixing crosslinking desalination layer and the charged grafting functional layer for further reinforcing ion selectivity successively on polysulfone porous supporting layer；By using aromatic amine and fatty amine mixing crosslinking, the molecule cross-link structure of desalination layer is adjusted so that crosslinking desalination layer has unique smooth build-up of particles structure, better than traditional NF membrane desalination Rotating fields；In conjunction with the charged grafting functional layer of introducing, enhance the effect of charged density and group in ion selective retention, so that the composite nanometer filtering film prepared, its salt rejection rate to sodium chloride is less than 40%, is higher than 97% to the salt rejection rate of magnesium chloride, is higher than 98% to the salt rejection rate of magnesium sulfate, 93% is higher than to the salt rejection rate of calcium chloride, monovalence divalent ion, than having obvious superiority, can effectively be separated, improved to bivalent ions selectively removing to monovalent ion and bivalent ions removing by it.
Description
Technical field
It is especially a kind of that there is high selectivity to divalent ion removing the present invention relates to NF membrane and its preparing technical field
Composite nanometer filtering film and preparation method thereof.
Background technology
Nanofiltration is as one of pressure-driven membrane process.It is the characteristics of there is low energy consumption and macroion selectivity because of it, wide
It is general to be applied to the fields such as material concentration, sewage disposal, salt refining and medicine separation.Solute molecule or ion are in NF membrane
Transmittance process is typically more complicated, is controlled by Donnan effect, stereoeffect, dielectric effect and effect of mass transmitting.Nanofiltration process institute
The microhydrodynamics and interface event being related to generally with solute molecule size, solute and film charge characteristics, membrane pore structure and
Residing liquid environment has close contact.Energy Si Te-Planck equation based on expansion, above-mentioned influence factor can be in theory
It is predicted and judges in model.Desalination layer or ion the selection layer of most NF membrane have a charge characteristics, and institute is electrically charged
Species and density determined by the property and density of the dissociable group entrained by inside NF membrane surface or fenestra.And it can dissociate
Group is then controlled by selected material in NF membrane preparation process and the preparation technology classification adhered to.Researcher typically may be used
With by choosing the materials such as the polymeric material with dissociable group such as sulfonated polyether sulfone and sulfonated polyether-ether-ketone via phase separation
Prepared by process casting film, can also introduce last handling process by centering film effectively to prepare.Usually, solute is in NF membrane
Transmission behavior can effectively be controlled by designing special film charge characteristics and physics pass structure.
So far, researcher is had been developed for including interfacial polymerization, nano combined and ultraviolet processing etc.
A variety of nanofiltration membrane preparation technologies.Wherein interfacial polymerization is because its is simple, controllability is got well and the advantages that being adapted to large-scale industrial production
And turn into and prepare one of major technique of composite nanometer filtering film.Composite nanometer filtering film is typically by ultrafiltration supporting layer and ultra-thin desalination layer group
Into.Ultra-thin desalination layer is prepared via two kinds of activated monomers in the polycondensation reaction that oil phase and aqueous phase interface are carried out.Its thickness generally exists
200~400nm.By adjust participate in reaction monomeric species, can flexibly efficiently control film top layer charge characteristics and
Other film surface properties such as stain resistance, temperature tolerance and resistance to physical damnification ability etc..Water permeability, solute of the desalination layer to NF membrane
The efficiency of separation and overall nanofiltration process has material impact.Therefore, from appropriate active reaction combination of monomers and it is entered
Row derivatization is current exploitation high-performance NF membrane and solves the main path of membrane pollution problem.Aliphatic and aromatic amine
Monomer such as bisphenol-A, tannic acid, m-phenylene diamine (MPD) and polyvinylamine etc. have been used for preparing with pyromellitic trimethylsilyl chloride or dimethyl chloride reaction
Composite nanometer filter film activity desalination layer.Wherein most common and large-scale commercial NF membrane frequently with m-phenylene diamine (MPD) or piperazine with
It is prepared by pyromellitic trimethylsilyl chloride.Research shows that m-phenylene diamine (MPD) and piperazine make corresponding prepare due to the difference of molecular structure
Nanofiltration film properties between larger difference be present.If piperazinyl nanofiltration is to the selectivity between divalent ion and monovalent ion
On be higher than m-phenylene diamine (MPD) base nanofiltration, and the overall salt rejection rate of m-phenylene diamine (MPD) base nanofiltration is then far above piperazinyl nanofiltration.This property
Difference on energy is probably derived from difference of the active desalination layer in dielectric property and pass structure.Due to the difference of monomer property
Cause difference of the NF membrane on filtering feature also so that the selection of film application scenario must be from respective intrinsic advantage.This
Outside, surface grafting technology can further apply the NF membrane of exploitation and design with more preferable contamination resistance and bacteriostasis.
In consideration of it, to plan the contribution of aliphatic and aromatic amine monomer each to ion selectivity, salt rejection rate and flux excellent by the present invention
Gesture combines, and introduces surface grafting technology to adjust the charged situation of desalination layer, and exploitation is selected with high flux and macroion
The nanofiltration film of selecting property.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention, which provides a kind of removed to divalent ion, to be had
Composite nanometer filtering film of high selectivity and preparation method thereof.
It is achieved particular by following technical scheme：
It is a kind of to divalent ion removing with high selectivity composite nanometer filtering film, by nonwoven layer, polysulfone porous supporting layer,
Desalination layer and charged grafting functional layer composition are crosslinked, wherein, polysulfone porous supporting layer is arranged in nonwoven layer, is crosslinked desalination layer
It is successively set on charged grafting functional layer on polysulfone porous supporting layer；Crosslinking desalination layer is mixed by amine mixture and acyl chlorides monomer
Compound is prepared in profit phase interfacial reaction；Charged grafting functional layer be by chemical grafting treated crosslinking desalination layer on.
Described amine mixture is mixed by aliphatic amine with aromatic amine；Described acyl chlorides monomer mixture
Mixed by the acyl chlorides monomer with two degrees of functionality and any ratio of the acyl chlorides monomer of three-functionality-degree.
Described aliphatic amine be cyclohexanediamine, piperazine, ethylene glycol amine, ethylenediamine, propane diamine, butanediamine, hexamethylene diamine,
At least one of monoethanolamine, polyethyleneimine and triethylamine.
Described aromatic amine is aniline, m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, terephthaldehyde's ammonia and isophthalic two
At least one of methylamine.
Described amine mixture, its mass concentration in profit phase interfacial reaction are 1.5-5%.
Described amine mixture, fatty amines account for the 0.5-50% of aromatic amine weight；More excellent is 1-10%, more excellent to be
3-7%, optimal is 5%.
Described acyl chlorides monomer mixture, its mass concentration in profit phase interfacial reaction are 0.07-0.4%；It is described
Two degrees of functionality acyl chlorides monomer be terephthalyl chloride, isophthaloyl chloride, phthalyl chlorine and biphenyl dimethyl chloride at least
It is a kind of；Described three-functionality-degree acyl chlorides monomer is pyromellitic trimethylsilyl chloride.
Described charged grafting functional layer is by active group molecule with being crosslinked the amino and/or acyl chlorides that are remained in desalination layer
And/or prepared by carboxylate radical reaction, its surface charge density and species are regulated and controled by the type and quantity of active group molecule.
Described active group molecule is at least containing in carboxyl, acid anhydrides, epoxy radicals, acyl chlorides, sulfonic acid chloride, hydroxyl and amino
A kind of molecule.
The described preparation method to composite nanometer filtering film of the divalent ion removing with high selectivity comprises the following steps：
(1) polysulfones casting solution is prepared after polysulfones particle is mixed with pore former, solvent, and polysulfones casting solution is coated on nothing
Spin on layer of cloth, and impregnate with water, obtaining polysulfone porous supporting layer；
(2) fatty amines and aromatic amine, acid binding agent and water are prepared by mixing into amine mixture, and step (1) is obtained
The polysulfone porous supporting layer obtained is impregnated in wherein, after polysulfone porous supporting layer adsorption saturation, is taken out, and surface is removed using nitrogen
The water droplet of residual；
(3), will after the acyl chlorides monomer of the acyl chlorides monomer of two degrees of functionality and three-functionality-degree being mixed into acyl chlorides monomer mixture
The polysulfone porous supporting layer that step (2) processing terminates is impregnated in wherein, and reaction prepares crosslinking desalination layer, and the time to be impregnated reaches
After 15-25s, the oil phase solvent of film surface residual is removed using nitrogen at room temperature, obtains the NF membrane with crosslinking desalination layer；
(4) by active group molecule and catalyst complex into after the aqueous solution, then the aqueous solution, which is coated in, has crosslinking de-
NF membrane with crosslinking desalination layer is impregnated in the aqueous solution after 45-55s by the NF membrane surface of salt deposit, then is placed on
5-10min in baking oven, obtain to composite nanometer filtering film of the divalent ion removing with high selectivity.
The temperature in baking oven in the above method is 50-80 DEG C.
Above-mentioned active group molecule is maleic anhydride, salicylic acid, benzoic acid, acetic acid, polyacrylic acid, epoxy E-51, poly-
It is ethylene glycol, polyvinyl alcohol, polyethyleneimine, pyromellitic trimethylsilyl chloride, monoethanolamine, triethylamine, cyclohexylamine, ethylene glycol amine, glycerine, sweet
In oily ether, PPG, tetramethyl dipropyl support group triamine, bisphenol-A and poly (hexamethylene) hydrochloride, hexamethylene etc. at least
It is a kind of.
Above-mentioned active group molecule with catalyst complex into after the aqueous solution, the wherein mass concentration of active group molecule
For 0.1-2%, the mass concentration of catalyst is 0.01~1%.
The above-mentioned NF membrane surface being coated in crosslinking desalination layer will the NF membrane leaching with crosslinking desalination layer
Temperature when stain is in the aqueous solution can also be 40-110 DEG C, and more excellent is 60-80 DEG C, and optimal is 70 DEG C.Processing time can be with
For 0.5-20min, optimal is 3-10min.
Above-mentioned catalyst be hydrochloric acid, the concentrated sulfuric acid, DMF, 1-METHYLPYRROLIDONE, tetrahydrofuran or
Any one in sodium hydroxide, its mass concentration is 0.01-1%.Described acid binding agent is sodium carbonate, disodium hydrogen phosphate, hydrogen
At least one of sodium oxide molybdena and potassium hydroxide, mass concentration are 0.01~1%.
Above-mentioned polysulfones particle and pore former, solvent, its mass ratio mixed are 15~21: 0.5~5: 74~84.5.Institute
The pore former stated is polyvinyl alcohol.Described solvent is one kind in DMF or DMA.
After described polysulfones casting solution coating it is immersed in pure water.
Described aromatic amine and the addition of fatty amines are so that described amine mixture, and it is in profit boundary
Mass concentration during reaction is 1.5-5%.Described fatty amines account for the 0.5-50% of aromatic amine weight；More excellent is 1-
10%, more excellent is 3-7%, and optimal is 5%；The purpose of acid binding agent is so that pH value is 10-12.
Compared with prior art, technique effect of the invention is embodied in：
By using aromatic amine and fatty amine mixing crosslinking, the molecule cross-link structure of desalination layer is adjusted so that hand over
Joining desalination layer has unique smooth build-up of particles structure, better than traditional NF membrane desalination Rotating fields；It is charged in conjunction with introducing
Layer is grafted, enhances the effect of charged density and group in ion selective retention so that the composite nanometer filtering film of preparation, it is to chlorine
The salt rejection rate for changing sodium is less than 40%, is higher than 97% to the salt rejection rate of magnesium chloride, is higher than 98% to the salt rejection rate of magnesium sulfate, to chlorination
The salt rejection rate of calcium be higher than 93%, its to monovalent ion and it is bivalent ions removing than having obvious superiority, can be effective
Monovalence divalent ion is separated, improved to bivalent ions selectively removing.
In addition, this researcher combines substantial amounts of experiment to have high selectivity to divalent ion removing to the present invention
Composite nanometer filtering film carry out the contrast experiment of flux and different ions salt rejection rate, it is specific as follows：
The preparation of control sample：
(1) 20gPEG1000 is scattered in 800g DMAs, with mechanical agitator at 1600 rpm
30min is stirred, is thereafter dispensed into 180g polysulfones wherein, and is heated up, the stirring and dissolving under 80 degree and 1400rpm rotating speeds, dissolving
Time 12h.After thing dissolving completely to be polymerized, resulting solution is placed in standing and defoaming in vacuum drying oven, inclined heated plate 10h.By institute
Obtain solution to be spread evenly across on non-woven fabrics using slot coated station, and solidified in 20 degree of distilled water, setting time 4 is divided
Clock, wherein prepared polysulfones ultrafiltration support membrane, polysulfones thickness degree are 50um.
(2) 45g m-phenylene diamine (MPD)s and 2g sodium hydroxides are dissolved in 953g deionized waters, stirring and dissolving obtains amine completely
Monomer solution.
(3) 2.0g pyromellitic trimethylsilyl chlorides are dissolved in hexamethylene, stirring and dissolving obtains solution of acid chloride.
(4) the polysulfones ultrafiltration support membrane prepared in (1) is soaked into 30s in amine aqueous solution, taking-up drains.
(5) the polysulfones ultrafiltration that amine aqueous solution has been soaked in (4) support is placed in solution of acid chloride and carries out interfacial reaction, reacted
Time 20s, preserved in deionized water after taking out the hexamethylene for air-drying film surface residual.
Laboratory sample：
Laboratory sample chooses product prepared by embodiment 7- embodiments 10.
Experimental method：
Macroion selectivity composite nanometer filtering film obtained by taking control sample and the embodiment of the present invention, is surveyed to its separating property
Examination, the operating condition used for：When being tested for monovalent ion, feed liquor is 4000mg/l sodium-chloride water solution；For divalence
When ion is tested, feed liquor is respectively 2000mg/l magnesium sulfate, magnesium chloride and calcium chloride water；Operating pressure is 100psi,
Operation temperature is 25 DEG C, solution ph 6.8；And obtain salt rejection rate (R) by the calculation formula of salt rejection rate and water flux and water leads to
Measure (F).It is polysulfone porous membrane to take supporting layer, and desalination layer is Wholly aromatic polyamide (m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride), thickness
It is comparative example for 0.18 RO films, obtains its salt rejection rate (R) and water flux (F).Salt rejection rate and water flux are evaluation reverse osmosis membranes
Two important parameters, the salt rejection rate of reverse osmosis membrane and the size of water penetration flux directly decide the efficiency of reverse osmosis process.
Salt rejection rate (R) refers to that under certain operating conditions the difference of salinity (Cp) is with entering in feeding liquid salinity (Cf) and penetrating fluid
The ratio of feed liquid salinity (Cf), its calculation formula are：
Water flux (F) is the body for the water for passing through per membrane area (A) in the unit interval (t) under certain operating conditions
Product (V), its unit is GFD, and its calculation formula is：
F=V/At
Experimental result：
Experimental result is shown in Table 1：
Table 1
From table 1 it follows that within the scope of the present invention, the macroion selectivity composite nanometer filtering film of gained to monovalence from
Sub and bivalent ions discrimination is apparently higher than reference substance.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph to composite nanometer filtering film of the divalent ion removing with high selectivity of the present invention.
Embodiment
Limited with reference to specific embodiment technical scheme is further, but claimed
Scope is not only limited to made description.
Embodiment 1
It is a kind of to divalent ion removing with high selectivity composite nanometer filtering film, by nonwoven layer, polysulfone porous supporting layer,
Desalination layer and charged grafting functional layer composition are crosslinked, wherein, polysulfone porous supporting layer is arranged in nonwoven layer, is crosslinked desalination layer
It is successively set on charged grafting functional layer on polysulfone porous supporting layer；Crosslinking desalination layer is mixed by amine mixture and acyl chlorides monomer
Compound is prepared in profit phase interfacial reaction；Charged grafting functional layer be by chemical grafting treated crosslinking desalination layer on.Institute
The amine mixture stated is mixed by aliphatic amine with aromatic amine；Described acyl chlorides monomer mixture is by with two officials
The acyl chlorides monomer of energy degree and any ratio of the acyl chlorides monomer of three-functionality-degree mix.Described aliphatic amine is cyclohexanediamine.
Described aromatic amine is aniline.Described amine mixture, its mass concentration in profit phase interfacial reaction are
1.5%.Described amine mixture, fatty amines account for the 0.5% of aromatic amine weight；Described acyl chlorides monomer mixture, its
Mass concentration in profit phase interfacial reaction is 0.07%；The acyl chlorides monomer of two described degrees of functionality is terephthalyl chloride；Institute
The three-functionality-degree acyl chlorides monomer stated is pyromellitic trimethylsilyl chloride.Described charged grafting functional layer is de- with crosslinking by active group molecule
Prepared by amino and/or acyl chlorides and/or the carboxylate radical reaction remained in salt deposit, its surface charge density and species are by active group
The type and quantity regulation and control of molecule.
Its preparation method, comprise the following steps：
(1) polysulfones casting solution is prepared after polysulfones particle is mixed with pore former, solvent, and polysulfones casting solution is coated on nothing
Spin on layer of cloth, and impregnate with water, obtaining polysulfone porous supporting layer；
(2) fatty amines and aromatic amine, acid binding agent and water are prepared by mixing into amine mixture, and step (1) is obtained
The polysulfone porous supporting layer obtained is impregnated in wherein, after polysulfone porous supporting layer adsorption saturation, is taken out, and surface is removed using nitrogen
The water droplet of residual；
(3), will after the acyl chlorides monomer of the acyl chlorides monomer of two degrees of functionality and three-functionality-degree being mixed into acyl chlorides monomer mixture
The polysulfone porous supporting layer that step (2) processing terminates is impregnated in wherein, and reaction prepares crosslinking desalination layer, and the time to be impregnated reaches
After 15s, the oil phase solvent of film surface residual is removed using nitrogen at room temperature, obtains the NF membrane with crosslinking desalination layer；
(4) by active group molecule and catalyst complex into after the aqueous solution, then the aqueous solution, which is coated in, has crosslinking de-
NF membrane with crosslinking desalination layer is impregnated in the aqueous solution after 45s by the NF membrane surface of salt deposit, then is placed on baking
5min in case, obtain to composite nanometer filtering film of the divalent ion removing with high selectivity.The temperature in baking oven in the above method
For 50 DEG C.Above-mentioned active group molecule is maleic anhydride.Above-mentioned active group molecule with catalyst complex into the aqueous solution
Afterwards, wherein the mass concentration of active group molecule is 0.1%, and the mass concentration of catalyst is 0.01%.Above-mentioned catalyst is
Hydrochloric acid, its mass concentration are 0.01%.Described acid binding agent is sodium carbonate, mass concentration 0.01%.Above-mentioned polysulfones particle
With pore former, solvent, its mass ratio mixed is 15: 0.5: 74.Described pore former is polyvinyl alcohol.Described solvent is N,
Dinethylformamide.
Embodiment 2- embodiments 6
On the basis of embodiment 1, other changing contents on the basis of embodiment 1 are as follows：
Above-described embodiment is only limitted to make brief description in actual production and operating process to the present invention, can not be exhausted
Be limited to the protection domain of technical scheme, and in addition, this researcher also by being operated in laboratory, and
Its specific operation scheme is presented as in example 7 below -10.
Embodiment 7
19% polysulfones solution is configured, porous polymer supporting layer is made through liquid-solid phase inversion.Configuration containing 0.5wt% oneself
The solution of diamines and 2.0% m-phenylene diamine (MPD), and add appropriate NaOH and pH value is adjusted to 11 or so, that is, mixing amine aqueous solution is made
(solution A).0.22wt% pyromellitic trimethylsilyl chlorides solution (B solution) is configured, wherein solvent is hexamethylene.The glycerine of configuration 0.3%
The ether aqueous solution (C solution), catalyst are hydrochloric acid, concentration 0.05%.Polysulfone porous supporting layer is soaked in solution A, impregnated
Time is 30s, after draining the film surface globule, enters back into B solution, dip time 20s, is dried at normal temperatures after taking-up and remove film surface
Hexamethylene, the diaphragm for hexamethylene of going out is placed in C solution, leaching is put to take out after 50s and is heat-treated in 80 DEG C of baking oven,
Processing time 5min.Diaphragm after processing is taken out to be stored in pure water and detected.
Embodiment 8
19% polysulfones solution is configured, porous polymer supporting layer is made through liquid-solid phase inversion.Configuration containing 0.1wt% oneself
The solution of diamines and 3.0% m-phenylene diamine (MPD), and add appropriate NaOH and pH value is adjusted to 11 or so, that is, mixing amine aqueous solution is made
(solution A).0.22wt% pyromellitic trimethylsilyl chlorides solution (B solution) is configured, wherein solvent is hexamethylene.The glycerine of configuration 0.3%
The ether aqueous solution (C solution), catalyst are hydrochloric acid, concentration 0.05%.Polysulfone porous supporting layer is soaked in solution A, impregnated
Time is 30s, after draining the film surface globule, enters back into B solution, dip time 20s, is dried at normal temperatures after taking-up and remove film surface
Hexamethylene, the diaphragm for hexamethylene of going out is placed in C solution, leaching is put to take out after 50s and is heat-treated in 80 DEG C of baking oven,
Processing time 5min.Diaphragm after processing is taken out to be stored in pure water and detected.
Embodiment 9
19% polysulfones solution is configured, porous polymer supporting layer is made through liquid-solid phase inversion.Configuration containing 0.1wt% oneself
The solution of diamines and 3.0% m-phenylene diamine (MPD), and add appropriate NaOH and pH value is adjusted to 11 or so, that is, mixing amine aqueous solution is made
(solution A).0.22wt% pyromellitic trimethylsilyl chlorides solution (B solution) is configured, wherein solvent is hexamethylene.The glycerin ether of configuration 1%
The aqueous solution (C solution), catalyst are hydrochloric acid, concentration 0.1%.Polysulfone porous supporting layer is soaked in solution A, dip time
For 30s, after draining the film surface globule, B solution is entered back into, dip time 20s, dries the ring for removing film surface after taking-up at normal temperatures
Hexane, the diaphragm for hexamethylene of going out is placed in C solution, leaching is put to take out after 50s and is heat-treated in 80 DEG C of baking oven, is handled
Time 5min.Diaphragm after processing is taken out to be stored in pure water and detected.
Embodiment 10
19% polysulfones solution is configured, porous polymer supporting layer is made through liquid-solid phase inversion.Configuration containing 0.5wt% oneself
The solution of diamines and 2.0% m-phenylene diamine (MPD), and add appropriate NaOH and pH value is adjusted to 11 or so, that is, mixing amine aqueous solution is made
(solution A).0.22wt% pyromellitic trimethylsilyl chlorides solution (B solution) is configured, wherein solvent is hexamethylene.The glycerin ether of configuration 1%
The aqueous solution (C solution), catalyst are hydrochloric acid, concentration 0.1%.Polysulfone porous supporting layer is soaked in solution A, dip time
For 30s, after draining the film surface globule, B solution is entered back into, dip time 20s, dries the ring for removing film surface after taking-up at normal temperatures
Hexane, the diaphragm for hexamethylene of going out is placed in C solution, leaching is put to take out after 50s and is heat-treated in 50 DEG C of baking oven, is handled
Time 8min.Diaphragm after processing is taken out to be stored in pure water and detected.
Claims (10)
- It is 1. a kind of to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that more by nonwoven layer, polysulfones Hole supporting layer, mixing crosslinking desalination layer and charged grafting functional layer composition, wherein, polysulfone porous supporting layer is arranged on nonwoven layer On, it is crosslinked desalination layer and charged grafting functional layer is successively set on polysulfone porous supporting layer；Crosslinking desalination layer is mixed by amine Thing is prepared with acyl chlorides monomer mixture in profit phase interfacial reaction；Charged work(grafting ergosphere is by surface physics or chemical graft In crosslinking desalination layer；Preparation method, comprise the following steps：(1) polysulfones casting solution is prepared after polysulfones particle is mixed with pore former, solvent, and polysulfones casting solution is coated on non-woven fabrics On layer, and it is impregnated in water, obtains polysulfone porous supporting layer；(2) fatty amines and aromatic amine, acid binding agent and water are prepared by mixing into amine mixture, and step (1) is obtained Polysulfone porous supporting layer is impregnated in wherein, after polysulfone porous supporting layer adsorption saturation, is taken out, and remained on surface is removed using nitrogen Water droplet；(3) after the acyl chlorides monomer of the acyl chlorides monomer of two degrees of functionality and three-functionality-degree being mixed into acyl chlorides monomer mixture, by step (2) the polysulfone porous supporting layer that processing terminates is impregnated in wherein, and reaction prepares crosslinking desalination layer, and the time to be impregnated reaches 15-25s Afterwards, the oil phase solvent of film surface residual is removed using nitrogen at room temperature, obtains the NF membrane with crosslinking desalination layer；(4) by active group molecule and catalyst complex into after the aqueous solution, then the aqueous solution is coated in there is crosslinking desalination layer NF membrane surface or will be impregnated in the NF membrane of crosslinking desalination layer in the aqueous solution after 45-55s, then be placed on baking oven Middle 5-10min, obtain to composite nanometer filtering film of the divalent ion removing with high selectivity.
- 2. as claimed in claim 1 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Amine mixture mixed by aliphatic amine with aromatic amine；Described acyl chlorides monomer mixture is by with two functions The acyl chlorides monomer of degree and any ratio of the acyl chlorides monomer of three-functionality-degree mix.
- 3. as claimed in claim 2 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Aliphatic amine for Isosorbide-5-Nitrae-cyclohexanediamine, 1,2- cyclohexanediamine, piperazine, ethylene glycol amine, ethylenediamine, propane diamine, butanediamine, oneself Diamines, monoethanolamine, polyethyleneimine, triethylamine, three (2- aminoethyls) amine, diethylenetriamine, N- (2- ethoxys) ethylenediamine, 1, 3- cyclohexanediamine, 1,3- bipiperidine bases propane, 4- aminomethylpiperazines, monoethanolamine, diethanol amine, hexylene glycol amine, diglycolamine At least one of.
- 4. as claimed in claim 2 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Aromatic amine for aniline, m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 1,3,5- tri- amido benzene, 1,2,4- tri- amido benzene, In 3,5- diaminobenzoic acids, 2,4- diaminotoluenes, 2,4- diamino anisoles, amidol, xylylene diamine at least It is a kind of.
- 5. as claimed in claim 1 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Amine mixture, its mass concentration in profit phase interfacial reaction is 1.5-5%.
- 6. existing to composite nanometer filtering film of the divalent ion removing with high selectivity, its feature as described in claim 1 or 2 or 5 In described amine mixture, fatty amines account for the 0.5-50% of aromatic amine weight.
- 7. as claimed in claim 6 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Amine mixture, fatty amines account for the 1-10% of aromatic amine weight.
- 8. as claimed in claim 1 or 2 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that Described acyl chlorides monomer mixture, its mass concentration in profit phase interfacial reaction are 0.07-0.4%；Two described functions The acyl chlorides monomer of degree is at least one of terephthalyl chloride, isophthaloyl chloride, phthalyl chlorine and biphenyl dimethyl chloride；It is described Three-functionality-degree acyl chlorides monomer be pyromellitic trimethylsilyl chloride.
- 9. as claimed in claim 1 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that described Charged grafting functional layer it is anti-by active group molecule and the amino that remains and/or acyl chlorides and/or carboxylate radical in crosslinking desalination layer It should prepare, its surface charge density and species are regulated and controled by the type and quantity of active group molecule.
- 10. as claimed in claim 9 to composite nanometer filtering film of the divalent ion removing with high selectivity, it is characterised in that institute The active group molecule stated is at least containing a kind of point in carboxyl, acid anhydrides, epoxy radicals, acyl chlorides, sulfonic acid chloride, hydroxyl and amino Son.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510952929.9A CN105435653B (en) | 2015-12-18 | 2015-12-18 | A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510952929.9A CN105435653B (en) | 2015-12-18 | 2015-12-18 | A kind of composite nanometer filtering film to divalent ion removing with high selectivity and preparation method thereof |
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| CN106582315A (en) * | 2016-11-29 | 2017-04-26 | 华中科技大学 | Polyamide composite membrane and preparation method thereof |
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| CN100396627C (en) * | 2006-09-20 | 2008-06-25 | 江南大学 | Clean production method for treating electroplating waste water by nano filtering process |
| CN101462025B (en) * | 2008-08-13 | 2011-09-21 | 贵阳时代汇通膜科技有限公司 | Double-layer polyamide surface layer composite reverse osmosis membrane and preparation method thereof |
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| CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
| CN102139187B (en) * | 2010-01-28 | 2013-04-10 | 中国科学院化学研究所 | Hyperfiltration membrane or nanofiltration membrane with multi-layered composite structure and preparation method thereof |
| CN201832563U (en) * | 2010-10-08 | 2011-05-18 | 北京能泰高科环保技术有限公司 | Vanadium and sodium separating device |
| EP2714225B1 (en) * | 2011-06-03 | 2020-11-11 | Waters Technologies Corporation | Method of separation of lipid and biological molecular species using high purity chromatographic materials |
| CN102921318B (en) * | 2012-11-21 | 2015-01-07 | 海南立昇净水科技实业有限公司 | External-pressure type charged hollow fiber nano-filtration membrane and preparation method therefor |
| CN103480286B (en) * | 2013-07-26 | 2016-02-10 | 北京碧水源膜科技有限公司 | A kind of preparation method of uv photo initiated grafting charged nanofiltration membrane, its product and application |
| CN104941461B (en) * | 2014-03-27 | 2017-05-03 | 贵阳时代沃顿科技有限公司 | Nanofiltration membrane for seawater desalination and preparation method thereof |
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