CN114146566A - Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application - Google Patents
Preparation method of high-performance polyolefin substrate reverse osmosis membrane, reverse osmosis membrane and application Download PDFInfo
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- CN114146566A CN114146566A CN202111457011.9A CN202111457011A CN114146566A CN 114146566 A CN114146566 A CN 114146566A CN 202111457011 A CN202111457011 A CN 202111457011A CN 114146566 A CN114146566 A CN 114146566A
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- reverse osmosis
- chloride
- osmosis membrane
- polyolefin
- epoxy resin
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- 239000012528 membrane Substances 0.000 title claims abstract description 138
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 94
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 title claims abstract description 13
- 210000004379 membrane Anatomy 0.000 claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- -1 aromatic acyl chloride Chemical class 0.000 claims abstract description 39
- 229920000768 polyamine Polymers 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 23
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 5
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 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 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- TYJLAVGMVTXZQD-UHFFFAOYSA-N 3-chlorosulfonylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(S(Cl)(=O)=O)=C1C(Cl)=O TYJLAVGMVTXZQD-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- YARQLHBOIGUVQM-UHFFFAOYSA-N benzene-1,2,3-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1S(Cl)(=O)=O YARQLHBOIGUVQM-UHFFFAOYSA-N 0.000 claims description 2
- YBGQXNZTVFEKEN-UHFFFAOYSA-N benzene-1,2-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1S(Cl)(=O)=O YBGQXNZTVFEKEN-UHFFFAOYSA-N 0.000 claims description 2
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XWALRFDLDRDCJG-UHFFFAOYSA-N cyclobutane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1(C(Cl)=O)C(Cl)=O XWALRFDLDRDCJG-UHFFFAOYSA-N 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- DCXMNNZFVFSGJX-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1(C(Cl)=O)C(Cl)=O DCXMNNZFVFSGJX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 2
- 229940091173 hydantoin Drugs 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 claims description 2
- MEQCXWDKLOGGRO-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C1OC(C(Cl)=O)C(C(Cl)=O)C1C(Cl)=O MEQCXWDKLOGGRO-UHFFFAOYSA-N 0.000 claims description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 34
- 230000004907 flux Effects 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000011033 desalting Methods 0.000 description 11
- 238000010612 desalination reaction Methods 0.000 description 9
- 229940018564 m-phenylenediamine Drugs 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000003570 air Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a preparation method of a high-performance polyolefin substrate reverse osmosis membrane, the reverse osmosis membrane and application, wherein the method comprises the following steps: 1) carrying out surface hydrophilic modification on the polyolefin porous supporting layer; 2) coating the surface of the polyolefin porous supporting layer obtained in the step 1) with epoxy resin to obtain a polyolefin substrate film; 3) contacting a polyolefin basement membrane with an aqueous phase solution containing polyfunctional aromatic polyamine and micromolecular aliphatic polyamine, and then contacting with an oil phase solution of polyfunctional aromatic acyl chloride to carry out interfacial polymerization reaction to form a composite membrane containing polyamide; 4) exposing the composite membrane in a nitrous acid solution for post-treatment; rinsing and drying to obtain the epoxy modified reverse osmosis membrane. The invention can provide a polyolefin-based reverse osmosis membrane with low energy consumption and high performance.
Description
Technical Field
The invention relates to a polyolefin substrate reverse osmosis membrane, in particular to a preparation method of a high-performance polyolefin substrate reverse osmosis membrane, a reverse osmosis membrane and application.
Background
Reverse osmosis membrane application technology is also called reverse osmosis, is one of the most advanced water treatment technologies in the present day, and is widely applied, such as seawater desalination, pure water production, concentration and separation of aqueous solution and the like. Currently, the mainstream reverse osmosis membrane in the market is an aromatic polyamide reverse osmosis composite membrane, which has a membrane structure comprising a non-woven fabric support layer, a porous carrier intermediate layer and a polyamide desalination layer. In recent years, researchers have conducted researches on forming a polyamide desalination layer by an interfacial polycondensation reaction on a polyolefin (e.g., polyethylene) microporous membrane as a substrate, and have prepared a composite reverse osmosis membrane with a simple structure at low cost and a certain permeability. However, the polyolefin material has low surface energy and poor hydrophilicity, which limits the improvement of water flux, the polarity of the polyolefin material is greatly different from that of a polyamide functional layer, and the bonding force between the two basal planes is low, so that the polyolefin material is directly used as a substrate of the reverse osmosis membrane and limited by the material, the improvement of membrane performance is difficult, and the prepared reverse osmosis membrane is difficult to be used commercially.
In order to solve the above problems, the conventional treatment methods mostly focus on surface hydrophilization modification of polyolefin base films to solve the problem that the water phase is difficult to uniformly disperse on the surfaces during interfacial polymerization and to improve the water flux, for example, as disclosed in patents CN108970416A and CN 111760464A. The methods for modifying the surface of the polymer are many, and they are roughly classified into chemical methods and physical methods, among which the former methods mainly include solution treatment, ultraviolet irradiation, ion implantation, low-temperature plasma treatment, corona method, and the latter methods mainly include ultraviolet ozone or physical ray irradiation.
However, the inventors of the present invention have surprisingly found that after a polyolefin-based membrane is hydrophilically modified, the membrane surface of the polyolefin-based membrane has many defects while carrying hydrophilic active groups such as carboxyl groups or hydroxyl groups, and it is difficult to obtain a high salt rejection rate if the polyolefin-based membrane is directly used for preparing a reverse osmosis membrane. In addition, when reverse osmosis unit stopped the operation, the water that exists in the product water pipe will certainly produce certain pressure to reverse osmosis membrane product water side, and the product water pipe climbs higher, and pressure just is big more, therefore, reverse osmosis membrane's resistant backpressure nature is also the decisive factor that influences whether it can carry out industrial application.
In conclusion, the development of a high-performance polyolefin-based reverse osmosis membrane with high flux, high salt rejection and back pressure resistance plays an important role in promoting the development of reverse osmosis membrane technology.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a polyolefin-based reverse osmosis membrane with low energy consumption and high performance, a reverse osmosis membrane and application.
One of the purposes of the invention is to provide a preparation method of a polyolefin-based reverse osmosis membrane with low energy consumption and high performance. According to the method, firstly, the epoxy resin containing more than two epoxy groups is coated on the polyolefin porous supporting layer, and the epoxy resin can respectively react with polyolefin and water-phase main body polyfunctional aromatic polyamine (such as m-phenylenediamine), so that the prepared polyamide desalting layer is more tightly combined with the polyolefin porous supporting layer, the membrane surface defect of the polyolefin is repaired, and the desalting rate of the reverse osmosis membrane is improved. In addition, micromolecular aliphatic polyamine is added in the water phase main body to serve as a promoting agent, the components can competitively participate in interfacial polymerization reaction to change the crosslinking degree of the polyamide desalting layer, the water permeability of the reverse osmosis membrane is greatly improved, the reverse osmosis membrane with higher water flux is obtained, the components can preferentially react with epoxy resin, the consumption of the epoxy resin on polyfunctional aromatic polyamine is reduced, and the crosslinking density of the polyamide desalting layer is ensured on the basis of improving the bonding force between the polyamide desalting layer and the polyolefin porous supporting layer. And finally, performing nitrous acid post-treatment on the generated reverse osmosis membrane, further improving the salt rejection of the reverse osmosis membrane, and reducing the sacrificial influence of the introduction of the small-molecule aliphatic polyamine on the salt rejection. In addition, in the research process, the addition of the micromolecule aliphatic polyamine and the nitrous acid post-treatment have an obvious synergistic effect on the improvement of the water flux of the reverse osmosis membrane and the improvement of the back pressure resistance. Therefore, the high-performance polyolefin substrate reverse osmosis membrane with high flux, high salt rejection rate and back pressure resistance is prepared by the method.
The invention also aims to provide the high-performance polyolefin substrate reverse osmosis membrane with high flux, high desalination rate and back pressure resistance, which is prepared by the method.
It is a further object of the present invention to provide a high flux, high salt rejection and back pressure resistant high performance polyolefin based reverse osmosis membrane for use in water treatment assemblies or methods.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-performance polyolefin-based reverse osmosis membrane comprises the following steps:
1) carrying out surface hydrophilic modification on the polyolefin porous supporting layer; the polyolefin porous support layer can be a polyolefin film prepared by a known technology such as a dry method or a wet method, and can also be a polyolefin film product directly obtained by commercial purchase;
preferably, the thickness of the polyolefin porous support layer selected by the invention is 10-40 μm, the porosity is 30-50%, the pore diameter is 10-100nm, and the tensile strength is more than or equal to 1500Kgf/cm2The gram weight is 5-20g/m2。
In some examples, the material of the polyolefin porous support layer is polyethylene, polypropylene or a composite thereof, and preferably polyethylene.
In some examples, the method of hydrophilic modification of the surface is a corona method or a plasma method.
The preferable treatment voltage of the corona method is 2-4kv, and the preferable treatment time is 3-5 min; the corona method may employ any known corona modification film apparatus and method, such as those disclosed in the documents [ Menggis, Zhao Huaren, Chenchang, Corona treatment of polypropylene film ], foreign plastics, 1992(01):15+21-24], [ Liuchuan, Polypropylene film corona treatment and study of surface polarity decay mechanism, plastics packaging, 2019,29(5): 7], and patents CN108189381A, CN211587327U, which will not be described herein.
The processing atmosphere of the plasma method comprises one or more of nitrogen, oxygen and air. The plasma method can adopt any known device and method for modifying the membrane by plasma, such as those disclosed in the patent literature [ chendanmin, wuguanying, hujia, research on modified polyvinyl chloride ultrafiltration membrane (i) ], research on structure and performance of plasma modified membrane, membrane science and technology, 1996(01):51-57], [ gold prefecture, gem wearing, land inspection, and the like.
In the present invention, after corona or plasma treatment of the membrane surface, the polyolefin porous support layer is preferably immersed in a small molecule alcohol solution (such as isopropanol, ethanol, methanol) for 2 to 5min, and then replaced with pure water. The small molecule alcohol solution is preferably 40-80% ethanol water solution.
2) Coating the surface of the polyolefin porous supporting layer obtained in the step 1) with epoxy resin to obtain a polyolefin substrate film; the surface coating mode is single-side coating.
In some examples, the epoxy resin is a compound containing two or more epoxy groups, preferably one or more of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a polyphenol type glycidyl ether epoxy resin, an aliphatic glycidyl ether epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, an alicyclic epoxy resin, a heterocyclic type epoxy resin; preferably, the heterocyclic epoxy resin is one or more of cyanuric acid epoxy resin and hydantoin epoxy resin;
the epoxy resin selected by the invention is a compound containing more than two epoxy groups, one end of the epoxy resin can be subjected to graft reaction with polyolefin, and the other end of the epoxy resin can be subjected to reaction with aqueous-phase main-body polyfunctional aromatic polyamine (such as m-phenylenediamine), so that the prepared polyamide desalting layer is more tightly combined with the polyolefin porous supporting layer, the membrane surface defect of the polyolefin is repaired, and the desalting rate of the reverse osmosis membrane is improved.
Preferably, the concentration of epoxy resin applied in step 2) is 0.01 to 0.5%, preferably 0.05 to 0.2%. The epoxy resin may be dissolved and diluted by a common organic solvent such as water, acetone, cyclohexanone, ethanol, isopropanol, toluene, xylene, etc., preferably water or acetone.
Preferably, after the polyolefin porous support layer is coated with the epoxy resin, the residual solution is replaced by rinsing with pure water.
3) Contacting a polyolefin basement membrane with an aqueous phase solution taking polyfunctional aromatic polyamine as a main body, and then contacting with an oil phase solution of polyfunctional aromatic acyl chloride to carry out interfacial polymerization reaction to form a composite membrane containing polyamide;
the aqueous phase solution also contains micromolecular aliphatic polyamine, and the addition amount of the micromolecular aliphatic polyamine is 0.02-0.5 times of the mass of the multifunctional aromatic polyamine;
in some examples, the polyfunctional aromatic polyamine is one or more of m-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 2, 4-diaminoanisoyl, amicrol, xylylenediamine, ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine, 2, 5-dimethylpiperazine, 4-aminomethylpiperazine, preferably m-phenylenediamine;
the polyfunctional aromatic acyl chloride is one or more of trimesoyl chloride, terephthaloyl chloride, isophtalicyl chloride, biphenyldicarboxyl chloride, naphthalenedicarboxylic acid dichloride, benzenetrisulfonyl chloride, benzenedisulfonyl chloride, monochlorosulfonylbenzenedicarboxylic acid dichloride, propanetricarboxyloyl chloride, butanetricarboxyloyl chloride, pentanetricarboxyloyl chloride, glutaroyl halide, adipoyl halide, cyclopropanetricarboxyloyl chloride, cyclobutanetetracarboxylic acid chloride, cyclopentane tricarboxyloyl chloride, cyclopentane tetracarboxylic acid chloride, cyclohexane tricarboxyloyl chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentane dicarboxyl chloride, cyclobutane dicarboxyl chloride, cyclohexane dicarboxyl chloride, tetrahydrofuran dicarboxyl chloride, and the like, preferably trimesoyl chloride;
the micromolecule aliphatic polyamine is an aliphatic compound containing two or more amino groups and having the carbon number less than 10, and preferably one or more of ethylenediamine, propylenediamine, propylenetriamine, butylenediamine and pentylenediamine;
preferably, the mass concentration of the polyfunctional aromatic polyamine in the aqueous phase solution is 1-5%, and the mass concentration of the polyfunctional aromatic acyl chloride in the oil phase solution is 0.05-0.3%. The solvent of the oil phase solution is selected from one or more of aliphatic alkane, aromatic alkane and halogenated alkane, preferably aliphatic alkane, and further preferably at least one of isopar G, isopar L and isopar H isoparaffin of Exxon Mobil.
In some examples, in step 3), the polyolefin-based film is contacted with the aqueous phase solution for 15 to 30 seconds, and after removing the excess aqueous phase solution, the polyolefin-based film is contacted with the oil phase solution for 10 to 300 seconds to perform interfacial polymerization. The contact mode is dip coating or single-side coating, and the dip coating is preferred.
4) Exposing the composite membrane in a nitrous acid solution for post-treatment; rinsing and drying to obtain the epoxy modified reverse osmosis membrane.
In some examples, in step 4), the mass concentration of the nitrous acid solution is 0.1-0.5%; the nitrous acid solution can be prepared by mixing sodium nitrite and strong acid, wherein the strong acid is sulfuric acid or hydrochloric acid.
Preferably, the composite membrane is exposed to the nitrous acid solution for a time of 0.5-5 min.
In some examples, after the composite membrane is treated by the nitrous acid solution in the step 4), the residual nitrous acid solution on the composite membrane is rinsed by a reducing agent, and then is rinsed and dried by hot water at the temperature of 60-100 ℃;
preferably, the reducing agent is a 0.5-2% sodium sulfite solution.
According to the invention, diazo salt groups can be generated by treating the membrane subjected to interfacial polymerization with nitrous acid and further hydrolyzed to form azo groups, so that the polyamide structure is further crosslinked, the desalination rate of the reverse osmosis membrane is further improved, and the loss of the desalination rate caused by the introduction of micromolecule aliphatic polyamine can be compensated; in addition, surprisingly, on the basis of the scheme, the nitrous acid post-treatment further improves the water flux of the reverse osmosis membrane, and further research finds that the water flux of the reverse osmosis membrane can be further improved only by performing post-treatment on the reverse osmosis membrane through nitrous acid under the condition that the water phase contains the small-molecule aliphatic polyamine, and the technical scheme of the small-molecule aliphatic polyamine and nitrous acid treatment has an obvious synergistic effect on improving the membrane flux.
The invention also provides a high performance polyolefin based reverse osmosis membrane prepared according to the method described above. The modified reverse osmosis membrane has the characteristics of high flux, high desalination rate and back pressure resistance, and can widely meet application requirements.
The present invention also provides the use of a high performance polyolefin based reverse osmosis membrane prepared by the process as hereinbefore described in a water treatment module or in a water treatment process. The water treatment module may be any module or device to which the reverse osmosis membrane of the present invention is attached, which can be applied to a water treatment process. The water treatment module or the water treatment method includes application to a module or an apparatus in which the reverse osmosis membrane of the present invention is installed, and also includes application to the preparation of such a module or apparatus; the components can be spiral wound membrane components, disc tube type flat membrane components and the like, and also can be household/commercial reverse osmosis water purifiers, industrial boiler feed water reverse osmosis pure water devices, industrial reclaimed water recycling reverse osmosis devices and the like; the water treatment method may be, for example: bitter waste water reuse, drinking water production and the like.
The polyolefin substrate reverse osmosis membrane prepared by the invention has the characteristics of high flux, high desalination rate and back pressure resistance, has high performance, is beneficial to reducing the working energy consumption, and can be widely applied to the water treatment fields of industrial water supply, wastewater reuse and the like. In addition, the preparation method disclosed by the invention has the characteristics of greenness, safety, simplicity in operation, low production cost, easiness in industrial production and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a reverse osmosis membrane prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the reverse osmosis membrane prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
TABLE 1 information on the main raw materials
The performance test method comprises the following steps:
(1) evaluation of salt rejection and permeation flux
Salt rejection and permeate flux are two important parameters for evaluating the separation performance of reverse osmosis membranes. The invention evaluates the separation performance of the reverse osmosis membrane according to GB/T32373 and 2015 reverse osmosis membrane test method.
The salt rejection (R) is defined as: under certain operating conditions, the difference between the salt concentration (Cf) of the feed solution and the salt concentration (Cp) of the permeate is divided by the salt concentration (Cf) of the feed solution, as shown in equation (1).
Permeate flux is defined as: the volume of water per membrane area per unit time that permeates under certain operating conditions is expressed in L/(m)2·h)。
The reverse osmosis membrane performance measurement adopts the following operating conditions: the feed solution was 250ppm aqueous sodium chloride, the pH of the solution was 7.0. + -. 0.5, the operating pressure was 0.41MPa, and the operating temperature was 25 ℃.
(2) Evaluation of reverse osmosis Membrane for Back pressure resistance
First, the initial separation performance of the reverse osmosis membrane was tested, and the salt rejection and permeate flux were recorded. And then, reversely placing the reverse osmosis membrane on a test bench, adjusting the test pressure to be 0.41MPa, and after reversely pressing for 1h, forwardly placing the reverse osmosis membrane, and testing the change of the salt rejection rate. The lower the decline of the desalination rate is, the higher the bonding force between reverse osmosis membrane layers is, and the better the back pressure resistance is.
(3) Reverse osmosis membrane surface topography observation
The surface morphology of the obtained reverse osmosis membrane was observed by using a COXEM EM-30Plus high resolution desktop scanning electron microscope (Beijing Ohd optical technology Co., Ltd.).
[ PREPARATION EXAMPLE 1 ]
Carrying out corona treatment on the polyethylene film for 4min under the voltage condition of 2.5 kv; soaking the treated polyethylene film in 50% ethanol solution for 2 min. Subsequently, pure water was replaced for 2min to obtain a porous support layer A of polyethylene whose surface was modified by hydrophilization.
[ PREPARATION EXAMPLE 2 ]
Carrying out corona treatment on the polypropylene film for 4min under the voltage condition of 2.5 kv; soaking the treated polyethylene film in 50% ethanol solution for 2 min. Subsequently, pure water was replaced for 2min to obtain a surface-hydrophilized-modified polypropylene porous support layer B.
[ example 1 ]
Referring to the raw material information in table 2 and preparing an epoxy modified reverse osmosis membrane according to the following method:
(1) preparing acetone solution of epoxy resin, coating one side of the acetone solution on a polyolefin porous supporting layer, standing for 2min, removing redundant solution, and cleaning and replacing with pure water;
(2) soaking the coated polyolefin porous support layer in an aqueous solution mainly containing m-phenylenediamine, wherein the aqueous solution also contains part of ethylenediamine, and the addition amount of the ethylenediamine is 0.04 times of the mass of the m-phenylenediamine, so that the polyolefin porous support layer and the aqueous solution are in contact reaction for 30 seconds; removing redundant water phase, immersing the polyolefin porous supporting layer into an organic phase solution of trimesoyl chloride (the solvent is isopar G isoalkane), contacting for 30s, and reacting to generate a composite membrane containing a polyamide desalting layer; taking out the composite membrane, vertically draining in air for 1min, and treating in hot air at 100 deg.C for 6 min;
(3) and (3) immersing the composite membrane into a nitrous acid solution, contacting for 1min, then washing with pure water, immersing into a 0.5% sodium sulfite solution for treatment for 1min, finally rinsing with pure water, and drying at 70 ℃ to obtain the high-performance reverse osmosis membrane.
When the reverse osmosis membrane prepared in this example is observed by scanning electron microscopy, as shown in fig. 1, it can be seen that the membrane surface defects after hydrophilization treatment are substantially repaired, which is the key to improve the salt rejection of the reverse osmosis membrane of the present invention.
[ examples 2 to 10 ]
The high performance reverse osmosis membranes of examples 2 to 10 were prepared in substantially the same manner as in example 1, respectively, except that the respective raw materials and amounts shown in Table 2 were different.
[ COMPARATIVE EXAMPLES 1 to 7]
Reverse osmosis membranes in comparative examples 1 to 7 were prepared by respectively using the hydrophilic modified polyethylene porous support layer prepared in preparation example 1 as a base membrane and referring to substantially the same method as in example 1 except that the corresponding raw materials and the amounts used were different in table 2.
Meanwhile, as shown in fig. 2, when the reverse osmosis membrane prepared in comparative example 2 is observed by using a scanning electron microscope, it can be seen that the reverse osmosis membrane without epoxy resin modification still has many membrane surface defects, which directly affects the salt rejection effect of the reverse osmosis membrane.
Comparative example 8 coating modification with monohydroxy Polymer instead of epoxy resin
A reverse osmosis membrane was prepared in substantially the same manner as in example 1, except that: replacing the epoxy resin glycerol triglycidyl ether in the step (1) with 0.1% of polyvinyl alcohol.
Comparative example 9 preparation of reverse osmosis Membrane and coating with epoxy resin
This comparative example is substantially the same as example 1 except that the coating timing of the epoxy resin is different, and the reverse osmosis membrane is specifically prepared by the following steps:
(1) directly soaking the hydrophilic modified polyethylene porous support layer prepared in preparation example 1 in an aqueous solution containing 2.5% of m-phenylenediamine and 0.1% of ethylenediamine, and contacting for 30 s; taking out to remove redundant water phase, immersing the membrane into organic phase solution (solvent is isopar G isoalkane) of 0.15% trimesoyl chloride, and contacting for 30s to react to generate a composite membrane containing a polyamide desalting layer; taking out the composite membrane, vertically draining in air for 1min, and treating in hot air at 100 deg.C for 6 min.
(2) And (3) immersing the composite membrane into a 0.3% nitrous acid solution, contacting for 1min, then washing with pure water, immersing into a 0.5% sodium sulfite solution for treatment for 1min, finally rinsing with pure water, and drying at 70 ℃ to obtain the hydrophilic modified reverse osmosis membrane.
(3) Preparing an acetone solution of glycerol triglycidyl ether with the mass concentration of 0.1%, coating one side of the acetone solution on the surface of an active membrane layer of a hydrophilic modified reverse osmosis membrane, standing for 2min, removing redundant solution, and cleaning and replacing with pure water; and drying at 70 ℃ to obtain the reverse osmosis membrane.
The reverse osmosis membranes prepared in the respective examples and comparative examples were evaluated for salt rejection, permeate flux properties, and back pressure resistance, and the results are reported in table 3.
As can be seen from the test results in table 3, the polyolefin base reverse osmosis membrane prepared by the method of the present invention has both high permeation flux and salt rejection, and good back pressure resistance, compared to the existing scheme of comparative example 1, in which only hydrophilization treatment is performed without any modification. Example 1 has significantly improved salt rejection relative to the scheme of comparative example 2 in which no epoxy modification is performed, and significantly improved permeate flux and back pressure resistance relative to the scheme of comparative example 3 in which no small molecule aliphatic polyamine modification is performed. Comparative example 4 has not been subjected to nitrous acid modification as compared with example 1, and the salt rejection rate is significantly reduced. The comparison between the example 1 and the comparative examples 3, 4 and 6 shows that when the reverse osmosis membrane is modified by the micromolecular aliphatic polyamine and the nitrite, the membrane flux is greatly improved, which indicates that the membrane flux can be synergistically improved by the modification of the micromolecular aliphatic polyamine and the nitrite. Compared with the scheme of coating the epoxy resin in the example 1, the polyethylene base film in the comparative example 8 is coated with the polyvinyl alcohol after hydrophilic modification, and the permeation flux, the salt rejection rate and the back pressure resistance of the polyethylene base film cannot achieve the excellent technical effect of the invention; comparative example 9 after the epoxy resin coating process was placed in interfacial polymerization, although the salt rejection and back pressure resistance were good, the permeation flux decreased significantly.
Combining the above experimental results, it is shown that: according to the invention, the membrane surface defect can be well repaired by coating the epoxy resin compound on the surface of the hydrophilized polyethylene base membrane, the binding force of the polyamide desalting layer and the polyethylene porous supporting layer is increased, and the desalting rate of the prepared reverse osmosis membrane is greatly improved; meanwhile, after small molecular aliphatic polyamine is added into the water phase, the generated reverse osmosis membrane is subjected to nitrous acid treatment, the membrane flux is greatly improved, the salt rejection rate is kept at a high level, and the back pressure resistance is enhanced to a certain extent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Raw materials and amounts used in Table 2, examples 2-10 and comparative examples 1-7
TABLE 3 evaluation results of reverse osmosis membrane performance
Claims (10)
1. A preparation method of a high-performance polyolefin-based reverse osmosis membrane is characterized by comprising the following steps:
1) carrying out surface hydrophilic modification on the polyolefin porous supporting layer;
2) coating the surface of the polyolefin porous supporting layer obtained in the step 1) with epoxy resin to obtain a polyolefin substrate film;
3) contacting a polyolefin basement membrane with an aqueous phase solution taking polyfunctional aromatic polyamine as a main body, and then contacting with an oil phase solution of polyfunctional aromatic acyl chloride to carry out interfacial polymerization reaction to form a composite membrane containing polyamide;
the aqueous phase solution also contains micromolecular aliphatic polyamine, and the addition amount of the micromolecular aliphatic polyamine is 0.02-0.5 times of the mass of the multifunctional aromatic polyamine;
4) exposing the composite membrane in a nitrous acid solution for post-treatment; rinsing and drying to obtain the epoxy modified reverse osmosis membrane.
2. The method of claim 1 wherein the porous support layer of polyolefin is polyethylene, polypropylene or a composite thereof, preferably polyethylene.
3. The method of claim 2 wherein said surface hydrophilic modification is by corona or plasma.
4. The method of any one of claims 1-3, wherein the epoxy resin is a compound having two or more epoxy groups, preferably one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin; preferably, the heterocyclic epoxy resin is one or more of cyanuric acid epoxy resin and hydantoin epoxy resin;
preferably, the concentration of epoxy resin applied in step 2) is 0.01 to 0.5%, preferably 0.05 to 0.2%.
5. The method of claim 4 wherein the polyfunctional aromatic polyamine is one or more of meta-phenylenediamine, para-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 2, 4-diaminoanisoyl, amicrol, xylylenediamine, ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine, 2, 5-dimethylpiperazine, 4-aminomethylpiperazine, preferably meta-phenylenediamine;
the polyfunctional aromatic acyl chloride is one or more of trimesoyl chloride, terephthaloyl chloride, isophtalicyl chloride, biphenyldicarboxyl chloride, naphthalenedicarboxylic acid dichloride, benzenetrisulfonyl chloride, benzenedisulfonyl chloride, monochlorosulfonylbenzenedicarboxylic acid dichloride, propanetricarboxyloyl chloride, butanetricarboxyloyl chloride, pentanetricarboxyloyl chloride, glutaroyl halide, adipoyl halide, cyclopropanetricarboxyloyl chloride, cyclobutanetetracarboxylic acid chloride, cyclopentane tricarboxyloyl chloride, cyclopentane tetracarboxylic acid chloride, cyclohexane tricarboxyloyl chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentane dicarboxyl chloride, cyclobutane dicarboxyl chloride, cyclohexane dicarboxyl chloride, tetrahydrofuran dicarboxyl chloride, and the like, preferably trimesoyl chloride;
the micromolecule aliphatic polyamine is an aliphatic compound containing two or more amino groups and having the carbon number less than 10, and preferably one or more of ethylenediamine, propylenediamine, propylenetriamine, butylenediamine and pentylenediamine;
preferably, the mass concentration of the polyfunctional aromatic polyamine in the aqueous phase solution is 1-5%, and the mass concentration of the polyfunctional aromatic acyl chloride in the oil phase solution is 0.05-0.3%.
6. The method for preparing a high-performance polyolefin base reverse osmosis membrane according to any one of claims 1 to 3, wherein the polyolefin base membrane is contacted with the aqueous phase solution for 15 to 30 seconds in step 3), and after removing the excess aqueous phase solution, the polyolefin base membrane is contacted with the oil phase solution for 10 to 300 seconds to perform interfacial polymerization.
7. The method for preparing a high-performance polyolefin-based reverse osmosis membrane according to any one of claims 1-3, wherein in the step 4), the mass concentration of the nitrous acid solution is 0.1-0.5%;
preferably, the composite membrane is exposed to the nitrous acid solution for a time of 0.5-5 min.
8. The preparation method of the high-performance polyolefin-based reverse osmosis membrane according to claim 7, characterized in that after the composite membrane is treated by the nitrous acid solution in the step 4), the residual nitrous acid solution on the composite membrane is removed by rinsing with a reducing agent, and then the composite membrane is rinsed and dried with hot water at 60-100 ℃;
preferably, the reducing agent is a 0.5-2% sodium sulfite solution.
9. A high performance polyolefin based reverse osmosis membrane made according to the process of any one of claims 1-8.
10. Use of a high performance polyolefin based reverse osmosis membrane prepared according to the process of any one of claims 1 to 8 or a high performance polyolefin based reverse osmosis membrane according to claim 9 in a water treatment module or a water treatment process.
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