CN118059695A - Method for producing reverse osmosis membrane and reverse osmosis membrane produced thereby - Google Patents
Method for producing reverse osmosis membrane and reverse osmosis membrane produced thereby Download PDFInfo
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- CN118059695A CN118059695A CN202211484612.3A CN202211484612A CN118059695A CN 118059695 A CN118059695 A CN 118059695A CN 202211484612 A CN202211484612 A CN 202211484612A CN 118059695 A CN118059695 A CN 118059695A
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- Prior art keywords
- reverse osmosis
- osmosis membrane
- mesoporous
- preparation
- temperature
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- 239000012528 membrane Substances 0.000 title claims abstract description 101
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 51
- 239000013335 mesoporous material Substances 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 10
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical class O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 44
- 239000008346 aqueous phase Substances 0.000 claims description 41
- -1 amine compound Chemical class 0.000 claims description 38
- 239000012074 organic phase Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 32
- 238000005266 casting Methods 0.000 claims description 22
- 239000004745 nonwoven fabric Substances 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 14
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 13
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 229920006393 polyether sulfone Polymers 0.000 claims description 8
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 6
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 150000008624 imidazolidinones Chemical class 0.000 claims description 4
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 4
- LRFWYBZWRQWZIM-UHFFFAOYSA-N (2-fluorophenyl)methanamine Chemical compound NCC1=CC=CC=C1F LRFWYBZWRQWZIM-UHFFFAOYSA-N 0.000 claims description 3
- QVSVMNXRLWSNGS-UHFFFAOYSA-N (3-fluorophenyl)methanamine Chemical compound NCC1=CC=CC(F)=C1 QVSVMNXRLWSNGS-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- JJWACYUTERPMBM-UHFFFAOYSA-N 1-acetylimidazolidin-2-one Chemical compound CC(=O)N1CCNC1=O JJWACYUTERPMBM-UHFFFAOYSA-N 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- BODVSESPBZOELC-UHFFFAOYSA-N 2-(2-phenylethyl)-1h-imidazole Chemical compound N=1C=CNC=1CCC1=CC=CC=C1 BODVSESPBZOELC-UHFFFAOYSA-N 0.000 claims description 3
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 3
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 claims description 3
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims description 3
- NXJZQSRAFBHNLI-UHFFFAOYSA-N 2-oxoimidazolidine-1-carbonyl chloride Chemical compound ClC(=O)N1CCNC1=O NXJZQSRAFBHNLI-UHFFFAOYSA-N 0.000 claims description 3
- ZWTPALHHEULAPI-UHFFFAOYSA-N 3-methylsulfonyl-2-oxoimidazolidine-1-carbonyl chloride Chemical compound CS(=O)(=O)N1CCN(C(Cl)=O)C1=O ZWTPALHHEULAPI-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 3
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- VIHYIVKEECZGOU-UHFFFAOYSA-N N-acetylimidazole Chemical compound CC(=O)N1C=CN=C1 VIHYIVKEECZGOU-UHFFFAOYSA-N 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 3
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims description 3
- MYIGUVWXDJBPEV-UHFFFAOYSA-N piperazin-2-amine Chemical compound NC1CNCCN1 MYIGUVWXDJBPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 238000000926 separation method Methods 0.000 abstract description 16
- 230000004907 flux Effects 0.000 abstract description 14
- 239000012752 auxiliary agent Substances 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract description 12
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 239000012530 fluid Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 64
- 239000000243 solution Substances 0.000 description 63
- 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 18
- 239000010410 layer Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 230000001112 coagulating effect Effects 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 238000010612 desalination reaction Methods 0.000 description 8
- 238000012695 Interfacial polymerization Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 238000007790 scraping Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011033 desalting Methods 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000004840 phenethylimidazoles Chemical group 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical group NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to a preparation method of a reverse osmosis membrane and the reverse osmosis membrane prepared by the method. According to the preparation method, the mesoporous material is introduced into the base film by utilizing the silane coupling agent, so that the mechanical strength and the heat resistance of the base film are improved, and in addition, at least one selected from the imidazole compounds and the imidazolidone compounds is introduced as a high-temperature resistant auxiliary agent, so that the purposes of optimizing the structure of the compact separation layer and increasing the mechanical strength and the heat resistance of the reverse osmosis film are achieved. The reverse osmosis membrane obtained by the preparation method disclosed by the application not only has high water flux, but also can resist high temperature, can stably operate at high temperature, and meanwhile, still maintains excellent retention rate when operating at high temperature, and can be favorably applied to the fields of separation and purification of high-temperature fluid, high-temperature disinfection and cleaning and the like.
Description
Technical Field
The application relates to the technical field of water treatment films, in particular to the technical field of reverse osmosis films, and particularly relates to a preparation method of a reverse osmosis film capable of being used for high-temperature disinfection and a reverse osmosis film prepared by the same.
Background
The commercial reverse osmosis membrane prepared by taking polysulfone and polyethersulfone as the base membrane (also called as a base membrane) has low temperature resistance and usually runs below 50 ℃, so that the use requirements in application fields such as separation and purification of high-temperature fluid, high-temperature disinfection and cleaning are difficult to meet. Therefore, the improvement of the high temperature resistance of the reverse osmosis membrane has very important significance.
Patent document 1 (CN 101205308B) discloses a method for preparing a sulfonated polyphenylsulfone terephthalamide proton exchange membrane, wherein sulfonic acid groups are introduced into a polymer main chain, so that the molecule has better high temperature resistance and chemical stability than the traditional polyamide material, and is suitable for preparing proton exchange membranes, ultrafiltration membranes and reverse osmosis membranes. The invention mainly carries out modification optimization on the base film.
Patent document 2 (CN 110385046B) discloses a method for preparing a large flux reverse osmosis membrane by substituting cyclic macromolecules with polyacyl chloride, wherein the mesh or pore structure in the desalting layer is regulated and controlled by regulating the number of carbon atoms on the substituted ring, so that the purposes of controlling flux and desalination rate are achieved, and the prepared reverse osmosis membrane has the characteristics of good high temperature resistance, acid and alkali resistance and the like.
Patent document 3 (CN 106334457 a) discloses a method for producing a high temperature-resistant reverse osmosis membrane, which is mainly based on improvement of cellulose acetate membrane, however, the temperature resistance of the membrane is not tested herein.
Patent document 4 (CN 107596929 a) discloses a method for preparing a high-temperature-resistant high-flux composite reverse osmosis membrane, which uses fluorine-containing polyaryletherketone as a supporting layer and is doped with a graphene material to prepare a high-temperature-resistant supporting base membrane, and prepares the composite reverse osmosis membrane on the basis, wherein the operation temperature of the prepared composite reverse osmosis membrane is only 40 ℃, and the requirements for high-temperature disinfection and high-temperature fluid separation cannot be met.
Pages 238-245 of non-patent literature 1(Preparation,characterization and application in wastewater treatment of a novel thermal stable composite membrane,Journal of Membrane Science,2006(279),) by using a isophthalonitrile-biphenyl polyaryletheramide ultrafiltration membrane as a support base membrane and m-phenylenediamine and trimesoyl chloride as reaction monomers, a novel heat-stable reverse osmosis membrane is prepared, and when the membrane is used at a temperature ranging from 25 ℃ to 95 ℃, the flux is increased from 22.9 to 76.0 L.m -2·h-1, and the desalination rate is basically unchanged.
From the existing data, the current research on the temperature resistance of reverse osmosis membranes is mainly focused on the preparation of high-temperature-resistant base membrane polymers, the structural modification of a desalting layer and the modification of a high-temperature-resistant ultrafiltration base membrane. Although the preparation of high temperature resistant polymers can improve the high temperature stability of the base membrane, the hydrophilicity, hydrophobicity, pore size and porosity of the surface of the base membrane prepared from such polymers may all be different from those of the existing polysulfone membranes and are not necessarily suitable for the preparation of the temperature resistant reverse osmosis membrane; annealing phenomenon can occur in the high-temperature sterilization process of the common reverse osmosis membrane, the base membrane and the separation layer can be changed in a certain range of molecular chain arrangement configuration, so that the crystallinity is improved, and as a result, the water yield of the membrane is reduced, and the desalination rate is increased. The change of the desalination layer structure of the reverse osmosis membrane can improve the temperature resistance stability of the membrane, but the temperature resistance of the reverse osmosis membrane is closely related to the property of the base membrane. In the prior art, there is little research on the temperature resistance of the desalination layer itself of reverse osmosis membranes.
Disclosure of Invention
Problems to be solved by the invention
The application aims to solve the problem of insufficient temperature resistance of the traditional reverse osmosis membrane, overcome the defect of the traditional reverse osmosis membrane, and provide the reverse osmosis membrane with excellent temperature resistance, thereby widening the application of the reverse osmosis membrane in the fields of separation and purification of high-temperature fluid, high-temperature disinfection, cleaning and the like.
Solution for solving the problem
The inventors of the present application have found through intensive studies that the temperature resistance of a composite reverse osmosis membrane is closely related to the structure of a desalination layer (also called a separation layer or a functional layer) as well as to a base membrane, and that when the membrane is operated at a relatively high temperature, the resistance to solutes and solvents is reduced, resulting in an increase in permeation flux and a decrease in rejection. The preparation of a temperature-resistant reverse osmosis membrane requires both a temperature-resistant base membrane and a temperature-resistant desalting layer.
The inventor creatively provides a preparation method of a reverse osmosis membrane, in the method, mesoporous materials are introduced into a base membrane by using a silane coupling agent, so that the mechanical strength and the temperature resistance of the base membrane are improved, the adsorption quantity of water phase monomers is increased, and the crosslinking degree of a polyamide functional layer formed by subsequent interfacial polymerization reaction is improved; in addition, at least one selected from imidazole compounds and imidazolidone compounds is introduced as a high-temperature resistant auxiliary agent, so that the solubility of the aqueous phase monomer in the organic phase can be increased in the interfacial polymerization reaction stage, and the reactivity of the organic phase monomer can be increased, thereby achieving the purposes of optimizing the structure of the compact separation layer and increasing the mechanical strength and heat resistance of the reverse osmosis membrane.
One aspect of the present application relates to a method for preparing a reverse osmosis membrane comprising the steps of:
Preparing a casting solution, and solidifying the casting solution on a support material to form a base film, wherein the casting solution comprises a polymer, a solvent, a silane coupling agent and a mesoporous material;
Immersing the base film in an aqueous phase solution containing at least one selected from the group consisting of imidazole compounds and imidazolidinones and an amine compound as an aqueous phase monomer, and an organic phase solution containing an acyl chloride compound as an organic phase monomer in this order;
And (5) post-treating and drying to obtain the reverse osmosis membrane.
The preparation method of the application, wherein the polymer is at least one of bisphenol A type PSF, polyarylsulfone, polyethersulfone, sulfonated polyethersulfone, polydiazanaphthalene ether sulfone ketone, polyarylethersulfone ketone, phthalazinone polyarylethernitrile ketone and polyacrylonitrile.
The preparation method of the application, wherein the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; preferably, the support material is a nonwoven fabric.
The preparation method comprises the following steps of preparing a silane coupling agent, wherein the silane coupling agent is at least one of vinyl trimethoxy silane, 3-aminopropyl-triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and N-beta-aminoethyl-gamma-aminopropyl methyl dimethoxy silane; preferably, the content of the silane coupling agent is 0.1 to 5.0wt% based on the total weight of the casting solution.
The preparation method of the application, wherein the mesoporous material is at least one of mesoporous SiO 2, mesoporous Al 2O3, mesoporous nano TiO 2, mesoporous SnO 2, mesoporous VO 2, mesoporous MnO 2 and mesoporous ZrO 2; preferably, the content of the mesoporous material is 0.01 to 0.5 weight percent based on the total weight of the casting solution.
The preparation method of the application, wherein the imidazole compound is at least one of 1-methylimidazole, 2-methylimidazole, 1-propylimidazole, imidazole-2-formaldehyde, 1-acetylimidazole, imidazoline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, phenethylimidazole and benzimidazole; preferably, the imidazole compound is contained in an amount of 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
The preparation method of the application, wherein the imidazolidone compound is at least one of 2-imidazolidone, 1-chloroformyl-2-imidazolidone, 1, 3-dimethyl-2-imidazolidone, 1-acetyl-2-imidazolidone and 1-chloroformyl-3-methylsulfonyl-2-imidazolidone; preferably, the content of the imidazolidinone compound is 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
The preparation method of the application comprises the steps of preparing an amine compound, wherein the amine compound is at least one of aniline, diphenylamine, 2-ethylaniline, 4-ethylaniline, p-propylaniline, p-chloroaniline, o-nitroaniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, N-dimethyl m-phenylenediamine, 2-fluorobenzylamine, 3-fluorobenzylamine, ethylamine, ethylenediamine, propylamine, di-N-propylamine, N-butylamine, isobutylamine, diisobutylamine, piperazine, 3-aminopiperazine, diethanolamine, triethanolamine, cyclobutylamine, N-hexylamine and polyether amine; preferably, the amine compound is contained in an amount of 3.0wt% to 9.0wt% based on the total weight of the aqueous phase solution.
The preparation method of the application, wherein the acyl chloride compound is at least one of trimesoyl chloride, pyromellitic chloride, terephthaloyl chloride, o-chlorobenzoyl chloride and isophthaloyl chloride; preferably, the content of the acid chloride compound is 0.01wt% to 5.0wt% based on the total weight of the organic phase solution.
Another aspect of the present application relates to a reverse osmosis membrane made according to the method of making a reverse osmosis membrane of the present application.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the preparation method, the mesoporous material is immobilized on the surface of the base film by using the silane coupling agent, and as the surface silicon hydroxyl of the silane coupling agent and the hydroxyl on the surface of the mesoporous material are subjected to dehydration condensation reaction, the defect caused by incompatibility of the inorganic nano material and the organic material is reduced, the high strength and high temperature resistance of the base film are provided, and meanwhile, the flux of the base film is improved by the mesoporous material. In the preparation process of the reverse osmosis membrane, the porous property of the mesoporous material can cause the adsorption quantity of the base membrane to the aqueous phase solution to be increased, so that the increase of the local monomer concentration promotes the diffusion of the aqueous phase monomer, the prepared reverse osmosis membrane has higher crosslinking degree and higher desalination rate, and meanwhile, the base membrane with the mesoporous material can reduce the permeation resistance of water so as to increase the permeation flux of the reverse osmosis membrane; the high-temperature resistant auxiliary agent is introduced into the desalting layer to increase the solubility of the water phase monomer in the organic phase, and the reaction activity of the organic phase monomer can be increased, so that the effects of optimizing the structure of the compact separating layer and increasing the mechanical strength and heat resistance of the reverse osmosis membrane are achieved.
The reverse osmosis membrane obtained by the preparation method disclosed by the application not only has high water flux, but also can resist high temperature, can stably operate at high temperature, and meanwhile, still maintains excellent retention rate when operating at high temperature, and can be favorably applied to the fields of separation and purification of high-temperature fluid, high-temperature disinfection and cleaning and the like.
Detailed Description
The application provides a preparation method of a reverse osmosis membrane, which comprises the following steps:
Preparing a casting solution, and solidifying the casting solution on a support material to form a base film, wherein the casting solution comprises a polymer, a solvent, a silane coupling agent and a mesoporous material;
Immersing the base film in an aqueous phase solution containing at least one selected from the group consisting of imidazole compounds and imidazolidinones and an amine compound as an aqueous phase monomer, and an organic phase solution containing an acyl chloride compound as an organic phase monomer in this order;
And (5) post-treating and drying to obtain the reverse osmosis membrane.
The technical conception of the application is as follows: the mesoporous material is introduced into the base film by utilizing the silane coupling agent, so that the mechanical strength and the temperature resistance of the base film are improved, the adsorption quantity of the water phase monomer is increased, and the crosslinking degree of a polyamide functional layer formed by subsequent interfacial polymerization reaction is improved; in addition, at least one selected from imidazole compounds and imidazolidone compounds is introduced as a high-temperature resistant auxiliary agent, so that the solubility of the aqueous phase monomer in the organic phase can be increased in the interfacial polymerization reaction stage, and the reactivity of the organic phase monomer can be increased, thereby achieving the purposes of optimizing the structure of the compact separation layer and increasing the mechanical strength and heat resistance of the reverse osmosis membrane.
In the preparation method of the application, the polymer is at least one of bisphenol A type PSF, polyarylsulfone, polyethersulfone, sulfonated polyethersulfone, polydiazanaphthalene ether sulfone ketone, polyarylethersulfone ketone, phthalazinone polyarylethernitrile ketone and polyacrylonitrile. The molecular weight of the polymer is not particularly limited, and it is preferable that the number average molecular weight is between 30000 and 50000.
In the production method of the present application, the solvent in the casting solution is not particularly limited as long as it can sufficiently dissolve the polymer, and preferably the solvent in the casting solution is at least one of N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
The support material is not particularly limited, and preferably the support material is a nonwoven fabric, and more preferably, may be a polypropylene (PP) nonwoven fabric, a Polyester (PET) nonwoven fabric, an acrylic (PAN) nonwoven fabric, and a polyvinyl chloride (PVC) nonwoven fabric.
Preferably, the polymer is used in an amount of 15 to 35wt%, preferably 15 to 30wt%, more preferably 16 to 25wt%, based on the weight of the casting solution. If the amount of the polymer is less than 15wt%, the pressure resistance of the film obtained may be lowered. If the amount of the polymer is more than 35wt%, the viscosity of the casting solution may be increased, which may increase the difficulty and defects of the preparation of the base film.
The mesoporous material is a porous material with the pore diameter of 2-50 nm, and has the characteristics of extremely high specific surface area, regular and ordered pore canal structure, narrow pore diameter distribution, continuously adjustable pore diameter and the like. In the application, the mesoporous material is fixed in the base film by utilizing the silane coupling agent, so that the mesoporous material can endow better water flux, mechanical strength and high temperature resistance. Meanwhile, the reverse osmosis membrane with better heat resistance is obtained by taking the reverse osmosis membrane as a base membrane and taking at least one selected from imidazole compounds and imidazolidone compounds as a high-temperature resistant auxiliary agent so as to improve the separation performance and the permeability of the membrane at high temperature.
Firstly, blending a silane coupling agent and a mesoporous material, and fixedly carrying the mesoporous material into a base film by utilizing dehydration condensation between silicon hydroxyl of the silane coupling agent and hydroxyl on the surface of the mesoporous material to prepare the base film with high flux and high temperature resistance; the silane coupling agent improves the dispersibility of the mesoporous material in the base film, reduces the defects caused by organic-inorganic blending, and improves the uniformity of the base film.
In the preparation process of the reverse osmosis membrane, the mesoporous material can influence the adsorption and diffusion of water phase monomers and influence the film forming dynamic process, and meanwhile, the crosslinking degree and the heat resistance of the polyamide separation layer are improved by taking at least one selected from imidazole compounds and imidazolidone compounds as high-temperature resistant auxiliary agents, so that the high-temperature stable reverse osmosis membrane (also known as a reverse osmosis membrane suitable for high-temperature disinfection) is prepared.
At least one selected from imidazole compounds and imidazolidone compounds is used as a high-temperature resistant auxiliary agent, so that the solubility of the aqueous phase monomer in the organic phase can be increased in the interfacial polymerization reaction stage, and the reactivity of the organic phase monomer can be increased, thereby achieving the purposes of optimizing the structure of the compact separation layer and increasing the mechanical strength and heat resistance of the reverse osmosis membrane.
In the preparation method of the application, the silane coupling agent is at least one of vinyl trimethoxy silane, 3-aminopropyl-triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and N-beta-aminoethyl-gamma-aminopropyl methyl dimethoxy silane.
Preferably, the content of the silane coupling agent is 0.1wt% to 5.0wt%, more preferably 0.1wt% to 2.0wt%, based on the total weight of the casting solution.
In the preparation method of the application, the mesoporous material is at least one of mesoporous SiO 2, mesoporous Al 2O3, mesoporous nano TiO 2, mesoporous SnO 2, mesoporous VO 2, mesoporous MnO 2 and mesoporous ZrO 2.
Preferably, the content of the mesoporous material is 0.01 to 0.5 weight percent based on the total weight of the casting solution.
The method of coating the nonwoven fabric with the casting solution is not particularly limited, and coating methods generally used in the art, such as casting, dip coating, blade coating, spin coating, and the like, may be used, and blade coating is more preferred. The coating on the nonwoven fabric is then immersed in a coagulation bath, so that the casting solution is coagulated into a film.
In the present application, the method for forming the base film is not particularly limited, and the base film is preferably formed by a liquid-solid phase conversion method. Preferably, the phase inversion time is controlled to be 0.5-1 min, the water bath temperature is 10-20 ℃, and the heat curing water bath temperature is 60-80 ℃.
As a non-limiting example, the base film preparation process includes:
16 to 25 weight percent of polysulfone (at least one of bisphenol A type PSF, polyarylsulfone and polyether sulfone), 0.1 to 2.0 weight percent of silane coupling agent and 0.01 to 0.5 weight percent of mesoporous material are dissolved in Dimethylformamide (DMF) or Dimethylacetamide (DMAC), and the mixture is stirred at 120 to 180 ℃ until the polymer is completely dissolved and is defoamed in vacuum.
And forming a base film on the non-woven fabric by a liquid-solid phase conversion method, controlling the phase conversion time to be 0.5-1 min, controlling the phase conversion water bath temperature to be 10-18 ℃, the cleaning water temperature to be 25 ℃, and the heat curing water bath temperature to be 60-80 ℃, and soaking the obtained base film in deionized water for storage to complete the preparation of the base film.
In the preparation method of the application, the imidazole compound is at least one of 1-methylimidazole, 2-methylimidazole, 1-propylimidazole, imidazole-2-formaldehyde, 1-acetylimidazole, imidazoline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, phenethylimidazole and benzimidazole.
Preferably, the imidazole compound is contained in an amount of 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
In the preparation method of the application, the imidazolidinone compound is at least one of 2-imidazolidinone, 1-chloroformyl-2-imidazolidinone, 1, 3-dimethyl-2-imidazolidinone, 1-acetyl-2-imidazolidinone and 1-chloroformyl-3-methanesulfonyl-2-imidazolidinone.
Preferably, the content of the imidazolidinone compound is 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
Preferably, the total content of the imidazole compound and the imidazolidone compound is 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
In the preparation method of the application, the amine compound is at least one of aniline, diphenylamine, 2-ethylaniline, 4-ethylaniline, p-propylaniline, p-chloroaniline, o-nitroaniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, N-dimethyl-m-phenylenediamine, 2-fluorobenzylamine, 3-fluorobenzylamine, ethylamine, ethylenediamine, propylamine, di-N-propylamine, N-butylamine, isobutylamine, diisobutylamine, piperazine, 3-aminopiperazine, diethanolamine, triethanolamine, cyclobutylamine, N-hexylamine and polyetheramine.
Preferably, the amine compound is present in an amount of 5.0wt% to 9.0wt% based on the total weight of the aqueous solution.
A pH adjuster may also be optionally included in the aqueous phase solution to adjust the pH of the solution to a range of 9 to 12, thereby further facilitating the interfacial polymerization reaction. The pH adjuster may be at least one selected from the group consisting of sodium hydroxide, potassium hydrogen phosphate, potassium hydroxide, sodium carbonate, triethylamine/camphorsulfonic acid. Wherein triethylamine and camphorsulfonic acid are used in combination for adjusting the pH, which can make the reaction relatively mild, and are common pH adjustment collocation in interfacial polymerization reaction.
Preferably, the pH regulator is present in an amount of 0.5wt% to 5.0wt% based on the total weight of the aqueous phase solution.
The contact time and the contact temperature of the base film and the aqueous solution are not particularly limited, and contact at a temperature range of 20 to 30℃for 5 to 60 seconds is preferable.
In the preparation method of the application, the acyl chloride compound is at least one of trimesoyl chloride, pyromellitic chloride, terephthaloyl chloride, o-chlorobenzoyl chloride and isophthaloyl chloride.
Preferably, the content of the acid chloride compound is 0.01wt% to 5wt% based on the total weight of the organic phase solution.
The contact time and the contact temperature of the base film and the organic phase solution are not particularly limited, and contact at a temperature range of 25 to 30℃for 5 to 60 seconds is preferable.
As a non-limiting example, the process for preparing the functional layer (also called separation layer or desalination layer) includes:
Immersing the base film in an aqueous phase solution containing 0.1-10wt% of at least one selected from imidazole compounds and imidazolidinone compounds, 5.0-9.0wt% of amine compounds and 0.5-5.0wt% of pH regulator for 5-60 seconds, taking out and blowing off superfluous solution on the surface by nitrogen;
Then immersing in an organic solvent (at least one of n-hexane, ethylcyclohexane, n-heptane, ISOPAR G, ISOPAR E) containing 0.01-5.0 wt% of an acyl chloride compound for 5-60 seconds, and then taking out and rinsing the surface of the film with pure water.
The resulting film may optionally be subjected to a moisture-retaining treatment with an aqueous solution comprising 10 to 20wt% glycerol and then dried at a temperature of 60 to 80 ℃.
The application also provides a reverse osmosis membrane prepared by the preparation method, which not only has high water flux, but also can resist high temperature, can stably operate at high temperature, still maintains excellent retention rate when operating at high temperature, and can be favorably applied to the fields of separation and purification of high-temperature fluid, high-temperature disinfection and cleaning and the like.
Examples
The present invention will be described in further detail with reference to the following specific examples, but the present invention is by no means limited to the following examples. It should be noted that the reagents and raw materials used in the examples of the present invention are commercially available conventional products unless otherwise specified.
Comparative example
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. Wherein the solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, and the non-woven fabric is: polypropylene (PP).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) into an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the solution, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 20s; finally taking out, washing with deionized water, and drying in an oven at 80 ℃. The aqueous phase monomer is: m-phenylenediamine with the content of 5 weight percent; the organic phase monomers are: trimesoyl chloride, 0.3 wt.% and ISOPAR G as solvent.
Example 1
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. The solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, the silane coupling agent is vinyltrimethoxysilane, the content is 0.5wt%, the mesoporous material is mesoporous MnO 2, the concentration is 0.3wt%, and the non-woven fabric is: polypropylene (PP).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) in an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the base film, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 30s; taking out, cleaning the membrane surface with pure water for 3min, and drying in an oven, wherein the temperature of the oven is set to 80 ℃ for 10min. The aqueous phase monomer is: m-phenylenediamine, the content of which is 5 weight percent, the high-temperature resistant auxiliary agent is 2-methylimidazole, and the content of which is 2 weight percent; the organic phase monomers used were: trimesoyl chloride with a content of 0.3% and ISOPAR G as solvent.
Example 2
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. The solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, the silane coupling agent is 3-aminopropyl-triethoxysilane, the content is 0.5wt%, the mesoporous material is mesoporous SiO 2, the content is 0.3wt%, and the non-woven fabric is: polypropylene (PP).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) in an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the base film, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 30s; taking out, cleaning the membrane surface with pure water for 3min, and drying in an oven, wherein the temperature of the oven is set to 80 ℃ for 10min. The aqueous phase monomer is: m-phenylenediamine with the viscosity of 5 weight percent, and the high-temperature resistant auxiliary agent of 2-phenylimidazole with the content of 2 weight percent; the organic phase monomers used were: trimesoyl chloride, 0.3 wt.% and ISOPAR G as solvent.
Example 3
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. The solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, the silane coupling agent is gamma-glycidol ether oxypropyl trimethoxy silane, the content is 0.5wt%, the mesoporous material is mesoporous SiO 2, the content is 0.3wt%, and the non-woven fabric is: polypropylene (PP).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) in an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the base film, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 30s; taking out, cleaning the membrane surface with pure water for 3min, and drying in an oven, wherein the temperature of the oven is set to 80 ℃ for 10min. The aqueous phase monomer is: m-phenylenediamine with the content of 6 weight percent, and the high-temperature resistant auxiliary agent is phenethyl imidazole with the content of 2 weight percent; the organic phase monomers used were: trimesic acid chloride with the content of 0.5 percent and normal hexane as the solvent.
Example 4
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. The solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, the silane coupling agent is vinyltrimethoxysilane, the content is 0.5wt%, the mesoporous material is mesoporous SiO 2, the content is 0.5wt%, and the non-woven fabric is: polypropylene (PP).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) in an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the base film, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 30s; taking out, cleaning the membrane surface with pure water for 3min, and drying in an oven, wherein the temperature of the oven is set to 80 ℃ for 10min. The aqueous phase monomer is: m-phenylenediamine with the content of 6 weight percent, and the high-temperature resistant auxiliary agent is phenethyl imidazole with the content of 2 weight percent; the organic phase monomers used were: trimesoyl chloride with a content of 0.5wt% and n-hexane as solvent.
Example 5
(1) Preparation of base film
Dissolving a polymer in a solvent, standing for defoaming treatment, then scraping the solution onto a non-woven fabric, and carrying out phase separation on the solvent and the polymer through a coagulating bath to prepare the base film with the porous structure. The solvent is N, N-Dimethylformamide (DMF); the polymer is: bisphenol A type PSF with a content of 20wt%; the coagulating bath is pure water, the temperature is 12 ℃, the silane coupling agent is N-beta-aminoethyl-gamma-aminopropyl methyl dimethoxy silane, the content is 0.5wt%, the mesoporous material is mesoporous Al 2O3, the content is 0.5wt%, and the non-woven fabric is: polyester (PET).
(2) Preparation of reverse osmosis membrane
Immersing the base film prepared in the step (1) in an aqueous phase solution containing an aqueous phase monomer for 10 seconds, taking out the base film, and blowing off the redundant solution by using nitrogen; then immersing the mixture into an organic phase solution containing organic phase monomers for 30s; taking out, cleaning the membrane surface with pure water for 3min, and drying in an oven, wherein the temperature of the oven is set to 80 ℃ for 10min. The aqueous phase monomer is: m-phenylenediamine with the content of 6 weight percent, and the high-temperature resistant auxiliary agent is phenethyl imidazole with the content of 2 weight percent; the organic phase monomers used were: trimesoyl chloride with a content of 0.5wt% and n-hexane as solvent.
Performance test and results
The reverse osmosis membranes prepared in comparative examples and examples 1 to 5 were tested for initial performance at 225psi pressure in 2000ppm NaCl solution, ph=6 to 7, water flux and rejection of the membrane at various solution temperatures, and run time was 30min. Taking produced water and raw water to test the salt concentration of the produced water and the raw water respectively, wherein the rejection rate of the membrane is as follows: [1- (concentration of salt of produced water/concentration of salt of fed water) ]. Times.100. The test results are shown in table 1 below.
TABLE 1
From the above results, it can be seen that the reverse osmosis membranes prepared in examples 1 to 5 not only maintained high water flux, but also were able to withstand high temperatures of 70 ℃ and 90 ℃ and were able to stably operate at high temperatures of 70 ℃ and 90 ℃ while still maintaining excellent rejection rate when operating at high temperatures, relative to the reverse osmosis membranes prepared in comparative examples.
Industrial applicability
The reverse osmosis membrane obtained by the preparation method disclosed by the application not only has high water flux, but also can resist high temperature, can stably operate at high temperature, and meanwhile, still maintains excellent retention rate when operating at high temperature, and can be favorably applied to the fields of separation and purification of high-temperature fluid, high-temperature disinfection and cleaning and the like.
Claims (10)
1. The preparation method of the reverse osmosis membrane is characterized by comprising the following steps of:
Preparing a casting solution, and solidifying the casting solution on a support material to form a base film, wherein the casting solution comprises a polymer, a solvent, a silane coupling agent and a mesoporous material;
Immersing the base film in an aqueous phase solution containing at least one selected from the group consisting of imidazole compounds and imidazolidinones and an amine compound as an aqueous phase monomer, and an organic phase solution containing an acyl chloride compound as an organic phase monomer in this order;
And (5) post-treating and drying to obtain the reverse osmosis membrane.
2. The method of claim 1, wherein the polymer is at least one of bisphenol a PSF, polyarylsulfone, polyethersulfone, sulfonated polyethersulfone, polydinaphthyridine ether sulfone ketone, polyarylethersulfone ketone, phthalazinone polyarylethernitrile ketone, and polyacrylonitrile.
3. The preparation method according to claim 1 or 2, wherein the solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone; preferably, the support material is a nonwoven fabric.
4. The production method according to claim 1 or 2, wherein the silane coupling agent is at least one of vinyltrimethoxysilane, 3-aminopropyl-triethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -methacryloxypropyl trimethoxysilane, and N- β -aminoethyl- γ -aminopropyl methyldimethoxysilane; preferably, the content of the silane coupling agent is 0.1 to 5.0wt% based on the total weight of the casting solution.
5. The preparation method according to claim 1 or 2, wherein the mesoporous material is at least one of mesoporous SiO 2, mesoporous Al 2O3, mesoporous nano TiO 2, mesoporous SnO 2, mesoporous VO 2, mesoporous MnO 2 and mesoporous ZrO 2; preferably, the content of the mesoporous material is 0.01 to 0.5 weight percent based on the total weight of the casting solution.
6. The production method according to claim 1 or 2, wherein the imidazole compound is at least one of 1-methylimidazole, 2-methylimidazole, 1-propylimidazole, imidazole-2-carbaldehyde, 1-acetylimidazole, imidazoline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, phenethylimidazole, and benzimidazole; preferably, the imidazole compound is contained in an amount of 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
7. The preparation method according to claim 1 or 2, wherein the imidazolidone compound is at least one of 2-imidazolidone, 1-chloroformyl-2-imidazolidone, 1, 3-dimethyl-2-imidazolidone, 1-acetyl-2-imidazolidone, 1-chloroformyl-3-methanesulfonyl-2-imidazolidone; preferably, the content of the imidazolidinone compound is 0.1wt% to 10wt% based on the total weight of the aqueous phase solution.
8. The production method according to claim 1 or 2, wherein the amine compound is at least one of aniline, diphenylamine, 2-ethylaniline, 4-ethylaniline, p-propylaniline, p-chloroaniline, o-nitroaniline, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, N-dimethyl-m-phenylenediamine, 2-fluorobenzylamine, 3-fluorobenzylamine, ethylamine, ethylenediamine, propylamine, di-N-propylamine, N-butylamine, isobutylamine, diisobutylamine, piperazine, 3-aminopiperazine, diethanolamine, triethanolamine, cyclobutylamine, N-hexylamine, and polyether amine; preferably, the amine compound is contained in an amount of 3.0wt% to 9.0wt% based on the total weight of the aqueous phase solution.
9. The production method according to claim 1 or 2, wherein the acid chloride compound is at least one of trimesoyl chloride, pyromellitic chloride, terephthaloyl chloride, o-chlorobenzoyl chloride and isophthaloyl chloride; preferably, the content of the acid chloride compound is 0.01wt% to 5.0wt% based on the total weight of the organic phase solution.
10. A reverse osmosis membrane produced according to the production process of any one of claims 1 to 9.
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