CN105435653A - Composite nano filtration membrane with high selectivity on removing divalent ions and preparation method thereof - Google Patents
Composite nano filtration membrane with high selectivity on removing divalent ions and preparation method thereof Download PDFInfo
- Publication number
- CN105435653A CN105435653A CN201510952929.9A CN201510952929A CN105435653A CN 105435653 A CN105435653 A CN 105435653A CN 201510952929 A CN201510952929 A CN 201510952929A CN 105435653 A CN105435653 A CN 105435653A
- Authority
- CN
- China
- Prior art keywords
- layer
- desalination
- amine
- acyl chlorides
- high selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002500 ions Chemical class 0.000 title claims abstract description 44
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001728 nano-filtration Methods 0.000 title abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 90
- 238000010612 desalination reaction Methods 0.000 claims abstract description 48
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 48
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 18
- 239000002346 layers by function Substances 0.000 claims abstract description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 54
- 239000000178 monomer Substances 0.000 claims description 36
- 150000001263 acyl chlorides Chemical class 0.000 claims description 35
- 150000001412 amines Chemical class 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 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
- 238000000034 method Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 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
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010406 interfacial reaction Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 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
- 238000002156 mixing 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
- -1 polymine Chemical compound 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 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
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 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
- 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
- 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
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-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
- 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
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical group NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims 1
- 229940043237 diethanolamine Drugs 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- YLFCXTJHZOZFFI-UHFFFAOYSA-N n'-ethoxyethane-1,2-diamine Chemical compound CCONCCN YLFCXTJHZOZFFI-UHFFFAOYSA-N 0.000 claims 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims 1
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 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
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract 4
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 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
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229960002668 sodium chloride Drugs 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
- 239000001263 FEMA 3042 Substances 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
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 238000011109 contamination Methods 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
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 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
- 239000012530 fluid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 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
- 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 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
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
Abstract
The invention relates to the technical field of nano filtration membrane and preparation thereof, and especially relates to a composite nano filtration membrane with a high selectivity on removing divalent ions and a preparation method thereof. The preparation method is characterized in that a mixedly crosslinking desalination layer and a charged grafted functional layer for enhancing ion selectivity are arranged on a polysulfone porous support layer; through the mixed crosslinking of aromatic amine and aliphatic amine, the molecular crosslinking structure of the desalination layer is adjusted, thus the crosslinking desalination layer has a unique smooth particle accumulation structure, which is better than the structure of a conventional nano filtration membrane desalination layer; and moreover, the introduced charged grafted functional layer enhances the effect of charge density and groups in ion selectivity and ion rejection. So that the sodium chloride desalination rate of the prepared composite nano filtrate membrane is less than 40%, the magnesium chloride desalination rate is more than 97%, the magnesium sulfate desalination rate is more than 98%, the calcium chloride desalination rate is more than 93%; the removal ratio of monovalent ion to divalent ion is high, the monovalent ions and divalent ions can be effectively separated, and the selective removal of divalent ions is improved.
Description
Technical field
The present invention relates to NF membrane and preparing technical field thereof, especially a kind of composite nanometer filtering film with high selectivity and preparation method thereof is removed to divalent ion.
Background technology
Nanofiltration is as one of pressure-driven membrane process.Because it has low energy consumption and macroion optionally feature, be widely used in that material is concentrated, sewage disposal, the field such as salt refining and medicine separation.Solute molecule or the ion transmittance process in NF membrane is usually comparatively complicated, by the control of Donnan effect, stereoeffect, dielectric effect and effect of mass transmitting.Microhydrodynamics involved by nanofiltration process and interface event usually and the charged character of solute molecule size, solute and film, membrane pore structure and residing liquid environment have close contacting.Based on the energy Si Te-Planck equation expanded, above-mentioned influence factor can carry out predicting and judging in theoretical model.The desalination layer of most NF membrane or ion select layer to have charged character, and the charged kind of institute and density are by the character of NF membrane surface or inner entrained the dissociated group of fenestra and density decision.Preparation technology's classification that the group that can dissociate then is controlled by material selected in NF membrane preparation process and acts on.Researcher generally can be with the polymeric material of the group that can dissociate if the material such as sulfonated polyether sulfone and sulfonated polyether-ether-ketone is via the preparation of phase separation casting film by choosing, and also can introduce last handling process by centering film and effectively prepare.Usually, the transfer behavior of solute in NF membrane can by designing the charged character of special film and physics pass structure comes effectively to be controlled.
Up to now, researcher have developed the multiple NF membrane technology of preparing comprising interfacial polymerization, nano combined and ultraviolet process etc.Wherein interfacial polymerization is because it is simple, controllability is got well and be applicable to the advantages such as large-scale industrial production and become one of major technique preparing composite nanometer filtering film.Composite nanometer filtering film is generally made up of ultrafiltration supporting layer and ultra-thin desalination layer.The polycondensation reaction preparation that ultra-thin desalination layer is carried out at oil phase and aqueous phase interface via two kinds of activated monomers.Its thickness is usually at 200 ~ 400nm.Participated in the monomeric species of reaction by adjustment, can flexibly effectively the charged character on controlling diaphragm top layer and other face character as stain resistance, temperature tolerance and resistance to physical damnification ability etc.Desalination layer to the water permeability of NF membrane, solute is separated and the efficiency of overall nanofiltration process has material impact.Therefore, select suitable active reaction set of monomers to merge carrying out derivatization to it is the main path developed high-performance NF membrane at present and solve membrane pollution problem.Aliphatic and aromatic amine monomer such as bisphenol-A, tannic acid, m-phenylene diamine (MPD) and polyvinylamine etc. prepare composite nanometer filter film activity desalination layer for reacting with pyromellitic trimethylsilyl chloride or dimethyl chloride.Wherein the most common and NF membrane that is large-scale commercial often adopts m-phenylene diamine (MPD) or piperazine and pyromellitic trimethylsilyl chloride to be prepared.Research shows, m-phenylene diamine (MPD) and piperazine make to there is larger difference between the NF membrane performance of corresponding preparation due to the difference of molecular structure.As piperazinyl nanofiltration is being higher than the nanofiltration of m-phenylene diamine (MPD) base in selective between divalent ion and monovalent ion, the overall salt rejection rate of m-phenylene diamine (MPD) base nanofiltration is then far above piperazinyl nanofiltration.Difference in this performance may derive from the difference of active desalination layer in dielectric property and pass structure.Difference due to monomer character causes the difference of NF membrane on filtering feature also to make the selection of film application scenario must from respective intrinsic advantage.In addition, surface grafting technology can be applied to exploitation further and design the NF membrane with better contamination resistance and bacteriostasis.Given this, the present invention plans aliphatic and aromatic amine monomer combines the contribution advantage of ion selectivity, salt rejection rate and flux separately, and introduce surface grafting technology to adjust the charged situation of desalination layer, exploitation has high flux and macroion optionally nanofiltration film.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides and a kind of composite nanometer filtering film with high selectivity and preparation method thereof be removed to divalent ion.
Be achieved particular by following technical scheme:
A kind ofly divalent ion is removed to the composite nanometer filtering film with high selectivity, be made up of nonwoven layer, polysulfone porous supporting layer, crosslinked desalination layer and charged grafting functional layer, wherein, polysulfone porous supporting layer is arranged in nonwoven layer, and crosslinked desalination layer and charged grafting functional layer are successively set on polysulfone porous supporting layer; Crosslinked desalination layer is prepared at profit phase interfacial reaction by amine mixture and acyl chlorides monomer mixture; Charged grafting functional layer by chemical grafting treated in crosslinked desalination layer.
Described amine mixture is mixed by aliphatic amine and aromatic amine; Described acyl chlorides monomer mixture by the acyl chlorides monomer of the acyl chlorides monomer and three-functionality-degree with two degrees of functionality arbitrarily than mixing.
Described aliphatic amine is at least one in cyclohexanediamine, piperazine, ethylene glycol amine, ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, monoethanolamine, polymine and triethylamine.
Described aromatic amine is at least one in aniline, m-phenylene diamine (MPD), p-phenylenediamine (PPD), o-phenylenediamine, terephthaldehyde's ammonia and m-xylene diamine.
Described amine mixture, its mass concentration when profit phase interfacial reaction is 1.5-5%.
Described amine mixture, fatty amines accounts for the 0.5-50% of aromatic amine weight; More excellent is 1-10%, and more excellent is 3-7%, and optimum is 5%.
Described acyl chlorides monomer mixture, its mass concentration when profit phase interfacial reaction is 0.07-0.4%; The acyl chlorides monomer of two described degrees of functionality is at least one in terephthalyl chloride, isophthaloyl chloride, phthalyl chlorine and biphenyl dimethyl chloride; Described three-functionality-degree acyl chlorides monomer is pyromellitic trimethylsilyl chloride.
Described charged grafting functional layer is reacted by amino residual in active group molecule and crosslinked desalination layer and/or acyl chlorides and/or carboxylate radical to be prepared, and its surface charge density and kind are by the kind of active group molecule and regulating and controlling of quantities.
Described active group molecule is at least containing a kind of molecule in carboxyl, acid anhydrides, epoxy radicals, acyl chlorides, sulfonic acid chloride, hydroxyl and amino.
Described the preparation method that divalent ion removes the composite nanometer filtering film with high selectivity to be comprised the following steps:
(1) prepare polysulfones casting solution after being mixed with pore former, solvent by polysulfones particle, and polysulfones casting solution is coated in nonwoven layer, and dipping is with water, obtains polysulfone porous supporting layer;
(2) fatty amines is mixed with into amine mixture with aromatic amine, acid binding agent and water, and the polysulfone porous supporting layer that step (1) obtains be impregnated in wherein, after the absorption of polysulfone porous supporting layer is saturated, take out, adopt nitrogen to remove the water droplet of remained on surface;
(3) after the acyl chlorides monomer of two degrees of functionality and the acyl chlorides monomer of three-functionality-degree being mixed into acyl chlorides monomer mixture, the polysulfone porous supporting layer that step (2) process terminates be impregnated in wherein, the crosslinked desalination layer of reaction preparation, after time to be impregnated reaches 15-25s, adopt nitrogen to remove the residual oil phase solvent of face under room temperature, the NF membrane of crosslinked desalination layer must be had;
(4) active group molecule is become after the aqueous solution with catalyst complex, again this aqueous solution be coated in the NF membrane surface with crosslinked desalination layer or the NF membrane with crosslinked desalination layer impregnated in the aqueous solution after 45-55s, be placed on 5-10min in baking oven again, obtain and the composite nanometer filtering film with high selectivity is removed to divalent ion.
Temperature in baking oven in said method is 50-80 DEG C.
Above-mentioned active group molecule is at least one in maleic anhydride, salicylic acid, benzoic acid, acetic acid, polyacrylic acid, epoxy E-51, polyethylene glycol, polyvinyl alcohol, polymine, pyromellitic trimethylsilyl chloride, monoethanolamine, triethylamine, cyclohexylamine, ethylene glycol amine, glycerine, glycerin ether, PPG, tetramethyl dipropyl support group triamine, bisphenol-A and poly (hexamethylene) hydrochloride, cyclohexane etc.
Above-mentioned active group molecule is after becoming the aqueous solution with catalyst complex, and wherein the mass concentration of active group molecule is 0.1-2%, and the mass concentration of catalyst is 0.01 ~ 1%.
Above-mentioned temperature when being coated in the NF membrane surface with crosslinked desalination layer or the NF membrane with crosslinked desalination layer being impregnated in the aqueous solution can also be 40-110 DEG C, and more excellent is 60-80 DEG C, and optimum is 70 DEG C.Processing time can also be 0.5-20min, and optimum is 3-10min.
Above-mentioned catalyst is any one in hydrochloric acid, the concentrated sulfuric acid, DMF, 1-METHYLPYRROLIDONE, oxolane or NaOH, and its mass concentration is 0.01-1%.Described acid binding agent is at least one in sodium carbonate, sodium hydrogen phosphate, NaOH and potassium hydroxide, and mass concentration is 0.01 ~ 1%.
Above-mentioned polysulfones particle and pore former, solvent, the mass ratio of its mixing is 15 ~ 21: 0.5 ~ 5: 74 ~ 84.5.Described pore former is polyvinyl alcohol.Described solvent is the one in DMF or DMA.Be immersed in pure water after described polysulfones casting solution coating.
Described aromatic amine and the addition of fatty amines make described amine mixture, and its mass concentration when profit phase interfacial reaction is 1.5-5%.Described fatty amines accounts for the 0.5-50% of aromatic amine weight; More excellent is 1-10%, and more excellent is 3-7%, and optimum is 5%; The object of acid binding agent makes pH value be 10-12.
Compared with prior art, technique effect of the present invention is embodied in:
By adopting aromatic amine and fatty amine mixing to be cross-linked, the molecule crosslinked structure of desalination layer being adjusted, making crosslinked desalination layer have unique level and smooth build-up of particles structure, being better than traditional NF membrane desalination layer structure; Combine again and introduce charged grafting layer, enhance charged density and the effect of group in ion selective retention, make the composite nanometer filtering film prepared, its to the salt rejection rate of sodium chloride lower than 40%, to the salt rejection rate of magnesium chloride higher than 97%, to the salt rejection rate of magnesium sulfate higher than 98%, to the salt rejection rate of calcium chloride higher than 93%, it is to monovalent ion and bivalent ionsly remove than having obvious superiority, effectively can be separated by monovalence divalent ion, improve bivalent ions selectively removing.
In addition, this researcher removes to divalent ion the contrast experiment that the composite nanometer filtering film with high selectivity carries out flux and different ions salt rejection rate to of the present invention in conjunction with a large amount of experiments, specific as follows:
The preparation of control sample:
(1) 20gPEG1000 is scattered in 800gN, in N-dimethylacetylamide, stirs 30min at 1600 rpm with mechanical agitator, thereafter 180g polysulfones is dispensed into wherein, and heats up, stirring and dissolving under 80 degree and 1400rpm rotating speed, dissolution time 12h.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 10h.Adopt slot coated station to be spread evenly across on non-woven fabrics gained solution, and solidify in the distilled water of 20 degree, setting time 4 minutes, prepared polysulfones ultrafiltration support membrane, wherein polysulfones layer thickness is 50um.
(2) be dissolved in 953g deionized water by 45g m-phenylene diamine (MPD) and 2g NaOH, stirring and dissolving obtains amine monomers solution completely.
(3) be dissolved in cyclohexane by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains solution of acid chloride.
(4) the polysulfones ultrafiltration support membrane of preparation in (1) is soaked 30s in amine aqueous solution, taking-up drains.
(5) the polysulfones ultrafiltration supporting layer having soaked amine aqueous solution in (4) is placed in solution of acid chloride and carries out interfacial reaction, reaction time 20s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Laboratory sample:
Laboratory sample chooses product prepared by embodiment 7-embodiment 10.
Experimental technique:
Get control sample and the selective composite nanometer filtering film of embodiment of the present invention gained macroion, test its separating property, the operating condition of employing is: when testing for monovalent ion, and feed liquor is the sodium-chloride water solution of 4000mg/l; When testing for divalent ion, feed liquor is respectively the magnesium sulfate of 2000mg/l, magnesium chloride and calcium chloride water; Operating pressure is 100psi, and operating temperature is 25 DEG C, and solution ph is 6.8; And obtain salt rejection rate (R) and water flux (F) by the computing formula of salt rejection rate and water flux.Getting supporting layer is polysulfone porous membrane, and desalination layer is Wholly aromatic polyamide (m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride), thickness be 0.18 RO film be comparative example, obtain its salt rejection rate (R) and water flux (F).Salt rejection rate and water flux are two important parameters evaluating reverse osmosis membrane, and the salt rejection rate of reverse osmosis membrane and the size of water permeation flux directly decide the efficiency of reverse osmosis process.Salt rejection rate (R) refers under certain operating conditions, feeding liquid salinity (Cf) and the difference of salinity (Cp) and the ratio of feeding liquid salinity (Cf) in penetrating fluid, and its computing formula is:
Water flux (F) is under certain operating conditions, and through the volume (V) of the water of per membrane area (A) in the unit interval (t), its unit is GFD, and its computing formula is:
F＝V/At
Experimental result:
Experimental result is shown in Table 1:
Table 1
As can be seen from Table 1, within the scope of the present invention, the selective composite nanometer filtering film of the macroion of gained to monovalent ion and bivalent ions discrimination apparently higher than reference substance.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photograph divalent ion being removed to the composite nanometer filtering film with high selectivity of the present invention.
Detailed description of the invention
Below in conjunction with concrete embodiment, further restriction is done to technical scheme of the present invention, but claimed scope is not only confined to done description.
Embodiment 1
A kind ofly divalent ion is removed to the composite nanometer filtering film with high selectivity, be made up of nonwoven layer, polysulfone porous supporting layer, crosslinked desalination layer and charged grafting functional layer, wherein, polysulfone porous supporting layer is arranged in nonwoven layer, and crosslinked desalination layer and charged grafting functional layer are successively set on polysulfone porous supporting layer; Crosslinked desalination layer is prepared at profit phase interfacial reaction by amine mixture and acyl chlorides monomer mixture; Charged grafting functional layer by chemical grafting treated in crosslinked desalination layer.Described amine mixture is mixed by aliphatic amine and aromatic amine; Described acyl chlorides monomer mixture by the acyl chlorides monomer of the acyl chlorides monomer and three-functionality-degree with two degrees of functionality arbitrarily than mixing.Described aliphatic amine is cyclohexanediamine.Described aromatic amine is aniline.Described amine mixture, its mass concentration when profit phase interfacial reaction is 1.5%.Described amine mixture, fatty amines accounts for 0.5% of aromatic amine weight; Described acyl chlorides monomer mixture, its mass concentration when profit phase interfacial reaction is 0.07%; The acyl chlorides monomer of two described degrees of functionality is terephthalyl chloride; Described three-functionality-degree acyl chlorides monomer is pyromellitic trimethylsilyl chloride.Described charged grafting functional layer is reacted by amino residual in active group molecule and crosslinked desalination layer and/or acyl chlorides and/or carboxylate radical to be prepared, and its surface charge density and kind are by the kind of active group molecule and regulating and controlling of quantities.
Its preparation method, comprises the following steps:
(1) prepare polysulfones casting solution after being mixed with pore former, solvent by polysulfones particle, and polysulfones casting solution is coated in nonwoven layer, and dipping is with water, obtains polysulfone porous supporting layer;
(2) fatty amines is mixed with into amine mixture with aromatic amine, acid binding agent and water, and the polysulfone porous supporting layer that step (1) obtains be impregnated in wherein, after the absorption of polysulfone porous supporting layer is saturated, take out, adopt nitrogen to remove the water droplet of remained on surface;
(3) after the acyl chlorides monomer of two degrees of functionality and the acyl chlorides monomer of three-functionality-degree being mixed into acyl chlorides monomer mixture, the polysulfone porous supporting layer that step (2) process terminates be impregnated in wherein, the crosslinked desalination layer of reaction preparation, after time to be impregnated reaches 15s, adopt nitrogen to remove the residual oil phase solvent of face under room temperature, the NF membrane of crosslinked desalination layer must be had;
(4) active group molecule is become after the aqueous solution with catalyst complex, again this aqueous solution be coated in the NF membrane surface with crosslinked desalination layer or the NF membrane with crosslinked desalination layer impregnated in the aqueous solution after 45s, be placed on 5min in baking oven again, obtain and the composite nanometer filtering film with high selectivity is removed to divalent ion.Temperature in baking oven in said method is 50 DEG C.Above-mentioned active group molecule is maleic anhydride.Above-mentioned active group molecule is after becoming the aqueous solution with catalyst complex, and 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, and its mass concentration is 0.01%.Described acid binding agent is sodium carbonate, and mass concentration is 0.01%.Above-mentioned polysulfones particle and pore former, solvent, the mass ratio of its mixing is 15: 0.5: 74.Described pore former is polyvinyl alcohol.Described solvent is DMF.
Embodiment 2-embodiment 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 in actual production and operating process, make brief description to the present invention; the protection domain of technical scheme of the present invention can not be limited to absolutely; and in addition; this researcher is also by operating in laboratory, and the operation scheme concrete to it is presented as in following examples 7-10.
Embodiment 7
Configure 19% polysulfones solution, make porous polymer supporting layer through liquid-solid phase conversion method.Configuration containing the solution of 0.5wt% hexamethylene diamine and 2.0% m-phenylene diamine (MPD), and adds appropriate NaOH and pH value is adjusted to about 11, i.e. obtained mixed amine solution (solution A).Configuration 0.22wt% pyromellitic trimethylsilyl chloride solution (B solution), wherein solvent is cyclohexane.The glycerin ether aqueous solution (C solution) of configuration 0.3%, catalyst is hydrochloric acid, and concentration is 0.05%.Polysulfone porous supporting layer is soaked in solution A, dip time is 30s, after draining the face globule, enter B solution again, dip time is 20s, the cyclohexane of dry removing face at normal temperatures after taking-up, is placed in C solution by going out the diaphragm of cyclohexane, take out after 50s is put in leaching and heat-treat in the baking oven of 80 DEG C, processing time 5min.Diaphragm after process is taken out to be kept in pure water and detects.
Embodiment 8
Configure 19% polysulfones solution, make porous polymer supporting layer through liquid-solid phase conversion method.Configuration containing the solution of 0.1wt% hexamethylene diamine and 3.0% m-phenylene diamine (MPD), and adds appropriate NaOH and pH value is adjusted to about 11, i.e. obtained mixed amine solution (solution A).Configuration 0.22wt% pyromellitic trimethylsilyl chloride solution (B solution), wherein solvent is cyclohexane.The glycerin ether aqueous solution (C solution) of configuration 0.3%, catalyst is hydrochloric acid, and concentration is 0.05%.Polysulfone porous supporting layer is soaked in solution A, dip time is 30s, after draining the face globule, enter B solution again, dip time is 20s, the cyclohexane of dry removing face at normal temperatures after taking-up, is placed in C solution by going out the diaphragm of cyclohexane, take out after 50s is put in leaching and heat-treat in the baking oven of 80 DEG C, processing time 5min.Diaphragm after process is taken out to be kept in pure water and detects.
Embodiment 9
Configure 19% polysulfones solution, make porous polymer supporting layer through liquid-solid phase conversion method.Configuration containing the solution of 0.1wt% hexamethylene diamine and 3.0% m-phenylene diamine (MPD), and adds appropriate NaOH and pH value is adjusted to about 11, i.e. obtained mixed amine solution (solution A).Configuration 0.22wt% pyromellitic trimethylsilyl chloride solution (B solution), wherein solvent is cyclohexane.The glycerin ether aqueous solution (C solution) of configuration 1%, catalyst is hydrochloric acid, and concentration is 0.1%.Polysulfone porous supporting layer is soaked in solution A, dip time is 30s, after draining the face globule, enter B solution again, dip time is 20s, the cyclohexane of dry removing face at normal temperatures after taking-up, is placed in C solution by going out the diaphragm of cyclohexane, take out after 50s is put in leaching and heat-treat in the baking oven of 80 DEG C, processing time 5min.Diaphragm after process is taken out to be kept in pure water and detects.
Embodiment 10
Configure 19% polysulfones solution, make porous polymer supporting layer through liquid-solid phase conversion method.Configuration containing the solution of 0.5wt% hexamethylene diamine and 2.0% m-phenylene diamine (MPD), and adds appropriate NaOH and pH value is adjusted to about 11, i.e. obtained mixed amine solution (solution A).Configuration 0.22wt% pyromellitic trimethylsilyl chloride solution (B solution), wherein solvent is cyclohexane.The glycerin ether aqueous solution (C solution) of configuration 1%, catalyst is hydrochloric acid, and concentration is 0.1%.Polysulfone porous supporting layer is soaked in solution A, dip time is 30s, after draining the face globule, enter B solution again, dip time is 20s, the cyclohexane of dry removing face at normal temperatures after taking-up, is placed in C solution by going out the diaphragm of cyclohexane, take out after 50s is put in leaching and heat-treat in the baking oven of 50 DEG C, processing time 8min.Diaphragm after process is taken out to be kept in pure water and detects.
Claims (10)
1. one kind removes the composite nanometer filtering film with high selectivity to divalent ion, it is characterized in that, be made up of nonwoven layer, polysulfone porous supporting layer, the crosslinked desalination layer of mixing and charged grafting functional layer, wherein, polysulfone porous supporting layer is arranged in nonwoven layer, and crosslinked desalination layer and charged grafting functional layer are successively set on polysulfone porous supporting layer; Crosslinked desalination layer is prepared at profit phase interfacial reaction by amine mixture and acyl chlorides monomer mixture; Charged merit grafting ergosphere by surface physics or chemical graft in crosslinked desalination layer.
2. remove the composite nanometer filtering film with high selectivity to divalent ion as claimed in claim 1, it is characterized in that, described amine mixture is mixed by aliphatic amine and aromatic amine; Described acyl chlorides monomer mixture by the acyl chlorides monomer of the acyl chlorides monomer and three-functionality-degree with two degrees of functionality arbitrarily than mixing.
3. as claimed in claim 2 the composite nanometer filtering film with high selectivity is removed to divalent ion, it is characterized in that, described aliphatic amine is 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, piperazine, ethylene glycol amine, ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, monoethanolamine, polymine, triethylamine, three (2-aminoethyl) amine, diethylenetriamine, N-(2-ethoxy) ethylenediamine, 1, 3-cyclohexanediamine, 1, the two piperidyl propane of 3-, 4-aminomethylpiperazine, monoethanolamine, diethanol amine, hexylene glycol amine, at least one in diglycolamine.
4. as claimed in claim 2 the composite nanometer filtering film with high selectivity is removed to divalent ion, it is characterized in that, described aromatic amine is aniline, m-phenylene diamine (MPD), p-phenylenediamine (PPD), o-phenylenediamine, 1,3,5-tri-amido benzene, 1,2,4-tri-amido benzene, 3, at least one in 5-diaminobenzoic acid, 2,4-diaminotoluenes, 2,4-diamino anisoles, amidol, xylylene diamine.
5. remove the composite nanometer filtering film with high selectivity to divalent ion as claimed in claim 1, it is characterized in that, described amine mixture, its mass concentration when profit phase interfacial reaction is 1.5-5%.
6. as described in claim 1 or 2 or 5, remove the composite nanometer filtering film with high selectivity to divalent ion, it is characterized in that, described amine mixture, fatty amines accounts for the 0.5-50% of aromatic amine weight; More excellent is 1-10%.
7. remove the composite nanometer filtering film with high selectivity to divalent ion as claimed in claim 1 or 2, it is characterized in that, described acyl chlorides monomer mixture, its mass concentration when profit phase interfacial reaction is 0.07-0.4%; The acyl chlorides monomer of two described degrees of functionality is at least one in terephthalyl chloride, isophthaloyl chloride, phthalyl chlorine and biphenyl dimethyl chloride; Described three-functionality-degree acyl chlorides monomer is pyromellitic trimethylsilyl chloride.
8. as claimed in claim 1 the composite nanometer filtering film with high selectivity is removed to divalent ion, it is characterized in that, described charged grafting functional layer is reacted by amino residual in active group molecule and crosslinked desalination layer and/or acyl chlorides and/or carboxylate radical to be prepared, and its surface charge density and kind are by the kind of active group molecule and regulating and controlling of quantities.
9. remove the composite nanometer filtering film with high selectivity to divalent ion as claimed in claim 8, it is characterized in that, described active group molecule is at least containing a kind of molecule in carboxyl, acid anhydrides, epoxy radicals, acyl chlorides, sulfonic acid chloride, hydroxyl and amino.
10. preparation method divalent ion being removed to the composite nanometer filtering film with high selectivity as described in any one of claim 1-9, is characterized in that, comprise the following steps:
(1) prepare polysulfones casting solution after being mixed with pore former, solvent by polysulfones particle, and polysulfones casting solution is coated in nonwoven layer, and dipping is with water, obtains polysulfone porous supporting layer;
(2) fatty amines is mixed with into amine mixture with aromatic amine, acid binding agent and water, and the polysulfone porous supporting layer that step (1) obtains be impregnated in wherein, after the absorption of polysulfone porous supporting layer is saturated, take out, adopt nitrogen to remove the water droplet of remained on surface;
(3) after the acyl chlorides monomer of two degrees of functionality and the acyl chlorides monomer of three-functionality-degree being mixed into acyl chlorides monomer mixture, the polysulfone porous supporting layer that step (2) process terminates be impregnated in wherein, the crosslinked desalination layer of reaction preparation, after time to be impregnated reaches 15-25s, adopt nitrogen to remove the residual oil phase solvent of face under room temperature, the NF membrane of crosslinked desalination layer must be had;
(4) active group molecule is become after the aqueous solution with catalyst complex, again this aqueous solution be coated in the NF membrane surface with crosslinked desalination layer or the NF membrane with crosslinked desalination layer impregnated in the aqueous solution after 45-55s, be placed on 5-10min in baking oven again, obtain and the composite nanometer filtering film with high selectivity is removed to divalent ion.
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