CN113908696A - Method for preparing reverse osmosis membrane and reverse osmosis membrane prepared thereby - Google Patents
Method for preparing reverse osmosis membrane and reverse osmosis membrane prepared thereby Download PDFInfo
- Publication number
- CN113908696A CN113908696A CN202010645266.7A CN202010645266A CN113908696A CN 113908696 A CN113908696 A CN 113908696A CN 202010645266 A CN202010645266 A CN 202010645266A CN 113908696 A CN113908696 A CN 113908696A
- Authority
- CN
- China
- Prior art keywords
- chloride
- phase solution
- reverse osmosis
- osmosis membrane
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 97
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 239000008346 aqueous phase Substances 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 44
- 239000012074 organic phase Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 92
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- 235000006708 antioxidants Nutrition 0.000 claims description 27
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 24
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 24
- 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 23
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 16
- 239000004745 nonwoven fabric Substances 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkyl phosphate Chemical compound 0.000 claims description 15
- 229920002492 poly(sulfone) Polymers 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 9
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 8
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- KVZJLSYJROEPSQ-UHFFFAOYSA-N 1,2-dimethylcyclohexane Chemical compound CC1CCCCC1C KVZJLSYJROEPSQ-UHFFFAOYSA-N 0.000 claims description 6
- SGVUHPSBDNVHKL-UHFFFAOYSA-N 1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 claims description 6
- QRMPKOFEUHIBNM-UHFFFAOYSA-N 1,4-dimethylcyclohexane Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 6
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 6
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical group N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 4
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims description 4
- 229960003180 glutathione Drugs 0.000 claims description 4
- 235000003969 glutathione Nutrition 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 4
- 229940116269 uric acid Drugs 0.000 claims description 4
- GQDRGBVPGCYTNU-UHFFFAOYSA-N 1,2-diethylcyclohexane Chemical compound CCC1CCCCC1CC GQDRGBVPGCYTNU-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
- WJUNKQFLRQGJAR-UHFFFAOYSA-N 1,3-diethylcyclohexane Chemical compound CCC1CCCC(CC)C1 WJUNKQFLRQGJAR-UHFFFAOYSA-N 0.000 claims description 3
- SMAKEJNOUFLEEJ-UHFFFAOYSA-N 1,4-diethylcyclohexane Chemical compound CCC1CCC(CC)CC1 SMAKEJNOUFLEEJ-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
- AMBFNDRKYCJLNH-UHFFFAOYSA-N 1-(3-piperidin-1-ylpropyl)piperidine Chemical compound C1CCCCN1CCCN1CCCCC1 AMBFNDRKYCJLNH-UHFFFAOYSA-N 0.000 claims description 3
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 3
- FFROMNOQCNVNIH-UHFFFAOYSA-N 2-methylpropylcyclohexane Chemical compound CC(C)CC1CCCCC1 FFROMNOQCNVNIH-UHFFFAOYSA-N 0.000 claims description 3
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 3
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910004878 Na2S2O4 Inorganic materials 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-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
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 claims description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical class C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 2
- QAQJMLQRFWZOBN-LAUBAEHRSA-N L-ascorbyl-6-palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-LAUBAEHRSA-N 0.000 claims description 2
- 239000011786 L-ascorbyl-6-palmitate Substances 0.000 claims description 2
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- 235000010385 ascorbyl palmitate Nutrition 0.000 claims description 2
- 235000010350 erythorbic acid Nutrition 0.000 claims description 2
- 229940026239 isoascorbic acid Drugs 0.000 claims description 2
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims description 2
- 235000019136 lipoic acid Nutrition 0.000 claims description 2
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013616 tea Nutrition 0.000 claims description 2
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- 239000010410 layer Substances 0.000 abstract description 73
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000012695 Interfacial polymerization Methods 0.000 description 31
- 238000003756 stirring Methods 0.000 description 27
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 230000004907 flux Effects 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000008569 process Effects 0.000 description 5
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- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 230000002829 reductive effect Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 102000010637 Aquaporins Human genes 0.000 description 1
- 108010063290 Aquaporins Proteins 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Abstract
The present application relates to a method of preparing a reverse osmosis membrane and a reverse osmosis membrane prepared thereby. The preparation method comprises the following steps: (1) contacting a porous polymer supporting layer with an amine monomer aqueous phase solution containing an antioxidant, and then contacting the porous polymer supporting layer contacted with the aqueous phase solution with an organic phase solution containing an acyl chloride monomer, or contacting the porous polymer supporting layer with the organic phase solution containing the acyl chloride monomer, and then contacting the porous polymer supporting layer contacted with the organic phase solution with the amine monomer aqueous phase solution containing the antioxidant; (2) and carrying out post-treatment and drying to obtain the reverse osmosis membrane. The functional layer of the reverse osmosis membrane prepared by the method has high crosslinking degree, so that the repeated cleaning resistance of the reverse osmosis membrane is improved, and the service life of the reverse osmosis membrane is greatly prolonged.
Description
Technical Field
The application relates to the technical field of water treatment membranes, in particular to the technical field of reverse osmosis membranes, and particularly relates to a preparation method of a reverse osmosis membrane and the reverse osmosis membrane prepared by the preparation method. The method improves the crosslinking degree of the functional layer in the reverse osmosis membrane under the condition of basically not influencing the water flux and the salt rejection rate of the reverse osmosis membrane.
Background
The reverse osmosis membrane is widely applied to the fields of reclaimed water reuse, brackish water desalination, seawater desalination, garbage penetrating fluid treatment and the like. However, in the application process, the cleaning resistance and the service life of the current reverse osmosis membrane are seriously tested. The strength of the polyamide functional layer determines the performance of the polyamide reverse osmosis membrane during application. In the interfacial polymerization process, amine water phase monomers are easy to generate oxidation reaction to form quinone, so that the crosslinking degree of a polyamide layer is reduced, and the polyamide layer with low crosslinking degree is most easily damaged in the repeated washing process, so that the flux and the desalination rate of the reverse osmosis membrane are reduced, and an application system fails. Therefore, the preparation of the polyamide reverse osmosis membrane with high crosslinking degree is an effective means for improving the service cycle of the membrane.
So far, no technology exists for controlling the interfacial polymerization reaction by inhibiting the oxidation of amine aqueous phase monomers and improving the crosslinking degree of a polyamide layer.
Patent document CN201810378598.6 "method for producing high flux reverse osmosis membrane, and reverse osmosis membrane production system" discloses a method for producing high flux reverse osmosis membrane, which comprises obtaining polyamide reverse osmosis membrane by interfacial polymerization, and then subjecting the polyamide reverse osmosis membrane to oxidation post-treatment to produce high flux reverse osmosis membrane. The polyamide layer is oxidized by post-treatment to produce a high flux reverse osmosis membrane without controlling the formation of polyamide at the interfacial polymerization level.
Patent document cn201710981617.x "reverse osmosis membrane and preparation method and application thereof" adds ammonium salt into an aqueous solution of interfacial polymerization to make the surface of a polyamide layer carry positive charges, so that the anti-pollution performance of the reverse osmosis membrane is improved, the interfacial polymerization reaction is not regulated, the oxidation of amine in the aqueous phase cannot be inhibited, and the degree of crosslinking of the polyamide layer cannot be improved.
In patent document CN201710615106.6, "reverse osmosis membrane and its preparation method and application", phenolic compounds are added during interfacial polymerization to perform a crosslinking reaction with acyl chloride, thereby increasing the degree of crosslinking of polyamide layer and thus increasing the salt rejection of membrane. The interfacial polymerization reaction is not essentially regulated and inhibited from oxidation of the amine in the aqueous phase.
Patent document CN201911159558.3 "preparation method of porous nano antibacterial particles and composite reverse osmosis membrane", and composite reverse osmosis membrane "adds porous nano particles in polyamide layer to improve membrane performance and antibacterial property, and does not regulate and control interfacial polymerization reaction.
Patent document CN201610096515.5 "a composite reverse osmosis membrane and its preparation method" adds aquaporin in the water phase by interfacial polymerization to increase the flux of the reverse osmosis membrane, and does not regulate and control the polyamide layer, nor inhibit the oxidation of amine in the water phase.
In patent document CN201711400593.0, "a method for preparing an anti-pollution reverse osmosis composite membrane and a reverse osmosis composite membrane", an anti-pollution coating is coated on a polyamide layer to improve the anti-pollution performance of the reverse osmosis membrane. The oxidation of amine in the aqueous phase cannot be inhibited, and the interfacial polymerization reaction is not regulated.
Patent document CN201811566147.1 "a method for producing a reverse osmosis membrane and a reverse osmosis membrane produced thereby" increases the thickness of a polyamide layer by increasing the monomer reaction concentration during interfacial polymerization by adding a cosolvent during interfacial polymerization, but cannot suppress oxidation of an amine in an aqueous phase.
The above prior art generally adopts the following preparation method:
(1) surface modification: the surface of the polyamide layer of the reverse osmosis membrane is modified, and the performance of the reverse osmosis membrane is improved by changing the surface charge, the terminal group and the like of the surface of the polyamide layer. The surface modification process is only a post-treatment process of the polyamide layer, and can not regulate and control interfacial polymerization reaction, inhibit amine oxidation and improve the crosslinking degree of the polyamide layer.
(2) Polyamide layer blending inorganic, organic nanoparticles: the blended polyamide layer structure is obtained by adding inorganic and organic nano particles into the water phase or the oil phase. The addition of the particles easily causes cracks to appear on the polyamide layer structure, has no influence on interface polymerization, can not inhibit the oxidation of amine and can not improve the crosslinking degree of the polyamide layer.
(3) Surface coating: the performance of the reverse osmosis membrane is improved by coating a functional layer on the surface of the polyamide layer, and the interfacial polymerization reaction is not regulated.
(4) Introducing a cosolvent: introducing a cosolvent into the water phase and the oil phase of the interfacial polymerization, increasing the space of the interfacial polymerization reaction and reducing the steric hindrance. The thickness of the polyamide layer can be effectively increased, but the oxidation of amine in the water phase cannot be inhibited, and the degree of crosslinking of the polyamide cannot be increased.
Disclosure of Invention
Problems to be solved by the invention
Aiming at the problems in the prior art, namely, in the process of preparing the reverse osmosis membrane, amine aqueous phase monomers are easily oxidized to form quinine, so that the degree of crosslinking of a polyamide functional layer is low, and the polyamide layer with the low degree of crosslinking is most easily damaged in the repeated washing process, so that the flux and the salt rejection rate of the reverse osmosis membrane are reduced.
Means for solving the problems
The inventors of the present application have made extensive studies to achieve the above object and have found that addition of an antioxidant to a water phase can effectively inhibit oxidation of an amine monomer in the water phase, promote interfacial polymerization, increase the degree of crosslinking of a polyamide functional layer, improve the repeated washing resistance of a reverse osmosis membrane, greatly increase the service life of the reverse osmosis membrane, and hardly affect the water flux and salt rejection rate of the reverse osmosis membrane.
The application provides a preparation method of a reverse osmosis membrane, which comprises the following steps:
(1) contacting a porous polymer supporting layer with an amine monomer aqueous phase solution containing an antioxidant, and then contacting the porous polymer supporting layer contacted with the aqueous phase solution with an organic phase solution containing an acyl chloride monomer, or contacting the porous polymer supporting layer with the organic phase solution containing the acyl chloride monomer, and then contacting the porous polymer supporting layer contacted with the organic phase solution with the amine monomer aqueous phase solution containing the antioxidant;
(2) and carrying out post-treatment and drying to obtain the reverse osmosis membrane.
The preparation method comprises the steps of preparing a mixture of a sodium hydroxide, a zinc hydroxide2S2O3、Na2S、Na2SO3、Na2S2O4One or more of zinc chloride, zinc sulfate, boric acid, alkyl boric acid and organic boron compounds, wherein the addition amount of the antioxidant is 0.01-10 wt% based on the total weight of the amine monomer aqueous phase solution.
According to the preparation method, the amine monomer is aniline, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amicrol, xylylenediamine, 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, piperazine, ethylene glycol amine, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, ethanolamine, polyethyleneimine, triethylamine, tris (2-aminoethyl) amine, diethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, 1, 3-cyclohexanediamine, 1, 3-bispiperidylpropane, 4-aminomethyl piperazine, ethanolamine, diethanolamine, hexamethylene diamine, One or more of diglycolamine, wherein the concentration of the amine monomer in the amine monomer aqueous phase solution is 0.01-10 wt%.
According to the preparation method, the acyl chloride monomer is one or more of biphenyl diformyl chloride, trimesoyl chloride, benzoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, benzene disulfonyl chloride, cyclopentane diacid chloride, cyclopentane triacyl chloride, cyclohexane triacyl chloride, butane diacid chloride, pentane triacyl chloride, glutaryl chloride, hexane triacyl chloride, hexane diacid chloride, cyclopentane tetracoyl chloride, cyclohexane diacid chloride, decane triacyl chloride, tetrahydrofuran diacid chloride, tetrahydrofuran tetracoyl chloride, cyclopropane triacyl chloride, cyclobutane diacid chloride, cyclobutane tetracoyl chloride and cyclohexane tetracoyl chloride; the concentration of the acyl chloride monomer is 0.01 wt% -1 wt% based on the total weight of the organic phase solution.
The preparation method comprises the step of dissolving the organic phase solution in a solvent selected from the group consisting of n-hexane, cyclohexane, n-heptane, Isopar G, methane, ethane, propane, butane, pentane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, isopropylcyclohexane, 1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, 1, 4-dimethylcyclohexane, 1, 2-diethylcyclohexane, 1, 3-diethylcyclohexane and 1, 4-diethylcyclohexane in an organic solvent.
According to the preparation method provided by the invention, the porous polymer supporting layer is one or more of a porous polysulfone supporting layer, a porous polyether sulfone supporting layer, a porous sulfonated polyether sulfone supporting layer, a porous polypropylene supporting layer and a porous polyacrylonitrile supporting layer.
The production method according to the present invention, wherein the porous polymer support layer is formed on the reinforcing material.
According to the preparation method, the reinforcing material is non-woven fabric.
The present application also provides a reverse osmosis membrane prepared by the preparation method according to the present application.
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation method of the reverse osmosis membrane provided by the application inhibits the oxidation of amine aqueous phase monomers, so that the crosslinking degree of a polyamide functional layer prepared by interfacial polymerization is greatly improved, the repeated cleaning resistance of the reverse osmosis membrane is improved, the service life of the reverse osmosis membrane is greatly prolonged, and the water flux and the salt rejection rate of the reverse osmosis membrane are basically not influenced.
Detailed Description
The application relates to a preparation method of a reverse osmosis membrane, which comprises the following steps:
(1) contacting a porous polymer supporting layer with an amine monomer aqueous phase solution containing an antioxidant, and then contacting the porous polymer supporting layer contacted with the aqueous phase solution with an organic phase solution containing an acyl chloride monomer, or contacting the porous polymer supporting layer with the organic phase solution containing the acyl chloride monomer, and then contacting the porous polymer supporting layer contacted with the organic phase solution with the amine monomer aqueous phase solution containing the antioxidant; preferably, the porous polymer support layer is contacted with an amine monomer aqueous phase solution containing an antioxidant or an organic phase solution containing an acyl chloride monomer at room temperature, the contact time is preferably 3 s-300 s, and the amine monomer aqueous phase solution containing the antioxidant or the organic phase solution containing the acyl chloride monomer, which is remained on the surface, is removed after the contact;
(2) and carrying out post-treatment and drying to obtain the reverse osmosis membrane.
The technical idea of the preparation method is that the oxidation of amine aqueous phase monomers is inhibited, and the interfacial polymerization reaction efficiency is improved, so that the crosslinking degree of the polyamide functional layer is improved, and the performance of the reverse osmosis membrane is optimized.
In the step (1), the formula of the aqueous phase solution is optimized, and the antioxidant is added into the aqueous phase solution to inhibit the oxidation of the amine aqueous phase monomer and ensure the high efficiency of the interfacial polymerization reaction.
In the preparation method of the present application, preferably, the excess amine-based monomer aqueous phase solution on the surface of the porous polymer support layer is removed after the porous polymer support layer is contacted with the amine-based monomer aqueous phase solution containing the antioxidant, and then the porous polymer support layer contacted with the aqueous phase solution is contacted with the organic phase solution containing the acyl chloride-based monomer.
In the preparation method of the present application, the antioxidantIs selected from the group consisting of uric acid, lipoic acid, glutathione, ascorbic acid, isoascorbic acid, ascorbyl palmitate, tea polyphenol, xylylbiguanide, tolylbiguanide, phenylhexamethylenebiguanide, tricresylphbiguanide, arylamine acetoacetate, alkyl phosphate, dialkyl phosphate, alkyl monophenol, alkylated polyphenol, thiobisphenol, polyalkylphenol, ethylene diamine tetraacetate, hypochlorotrimethylene phosphonate, stannous chloride, sodium bisulfite, Na2S2O3、Na2S、Na2SO3、Na2S2O4One or more of zinc chloride, zinc sulfate, boric acid, alkyl boric acid and organic boron compounds, wherein the addition amount of the antioxidant is 0.01-10 wt% based on the total weight of the amine monomer aqueous phase solution, and further, the preferred addition amount of the antioxidant is 0.1-5 wt%. If the amount of the antioxidant added is less than 0.01 wt%, the effect of inhibiting the oxidation of the amine-based monomer is not achieved; if the addition amount of the antioxidant is more than 10 wt%, the flux of the reverse osmosis membrane is remarkably increased and the salt rejection rate is remarkably decreased.
In the production method of the present application, preferably, the amine monomer is aniline, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amicrol, xylylenediamine, 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, piperazine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, polyethyleneimine, triethylamine, tris (2-aminoethyl) amine, diethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, 1, 3-cyclohexanediamine, 1, 3-dipiperidinopropane, 4-aminomethylpiperazine, ethanolamine, diethanolamine, hexamethylenediamine, or the like, One or more of diglycolamine, wherein the concentration of the amine monomer in the amine monomer aqueous phase solution is 0.01-10 wt%. Further, the preferable amine monomer concentration is 0.1 wt% to 5 wt%. If the concentration of the amine monomer is less than 0.01 wt%, the polyamide layer is not easily formed into a film; if the concentration of the amine monomer is higher than 10 wt%, the crosslinking degree of the polyamide layer is low, and the performance of the membrane is poor.
In the preparation method of the present application, preferably, the acyl chloride monomer is one or more of biphenyl diformyl chloride, trimesoyl chloride, benzoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, benzene disulfonyl chloride, cyclopentane diacid chloride, cyclopentane triacyl chloride, cyclohexane triacyl chloride, butane diacid chloride, pentane tetraacyl chloride, cyclohexane diacid chloride, decane triacyl chloride, tetrahydrofuran diacid chloride, tetrahydrofuran tetraacyl chloride, cyclopropane triacyl chloride, cyclobutane diacid chloride, cyclobutane tetraacyl chloride and cyclohexane tetraacyl chloride, and the concentration of the acyl chloride monomer in the organic phase solution is 0.01 wt% to 1 wt%. Further, the concentration of the acyl chloride monomer is preferably 0.05 wt% to 0.5 wt%. If the concentration of the acyl chloride monomer is less than 0.01 wt%, the polyamide layer is not easy to form a film; if the concentration of the acyl chloride monomer is higher than 1 wt%, the crosslinking degree of the polyamide layer is too high, and the performance of the membrane is poor.
In the preparation method of the present application, preferably, the solvent in the organic phase solution is one or any several of n-hexane, cyclohexane, n-heptane, isoparaffin solvent Isopar G, methane, ethane, propane, butane, pentane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, isopropylcyclohexane, 1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, 1, 4-dimethylcyclohexane, 1, 2-diethylcyclohexane, 1, 3-diethylcyclohexane, 1, 4-diethylcyclohexane.
In the preparation method of the present application, preferably, the porous polymer support layer is one or more of a porous polysulfone support layer, a porous polyethersulfone support layer, a porous sulfonated polyethersulfone support layer, a porous polypropylene support layer, and a porous polyacrylonitrile support layer.
In the production method of the present application, preferably, the porous polymer support layer is formed on a reinforcing material. Preferably, the reinforcing material is a nonwoven fabric. The material of the nonwoven fabric is not particularly limited, and may be, for example, polypropylene (PP), Polyester (PET), Polyamide (PA), viscose, acrylic, polyethylene (HDPE), polyvinyl chloride (PVC), cellulose, or a derivative thereof, and is preferably a polypropylene (PP) nonwoven fabric or a Polyester (PET) nonwoven fabric.
In the preparation method of the present application, the post-treatment is preferably to remove excess solution from the surface of the porous polymer support layer, followed by washing, for example with deionized water. The drying temperature is not particularly limited, and is usually 30 to 100 ℃; the drying time is also not particularly limited, and is usually 1 to 20 minutes.
The present application also relates to a reverse osmosis membrane prepared by the preparation method according to the present application, preferably, the reverse osmosis membrane may include: a nonwoven layer, a porous polymeric support layer, and a functional layer formed on the porous polymeric support layer according to the method of manufacture of the present application.
Examples
The present invention is further illustrated in detail below with reference to specific comparative examples and examples, but the technical solution of 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 comparative examples and examples are conventional products commercially available unless otherwise specified.
Comparative example
Preparing an aqueous solution: 200g of m-phenylenediamine is dissolved in 5kg of water and stirred until the m-phenylenediamine is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 1
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of uric acid as an antioxidant, and stirring until the uric acid is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 2
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of glutathione as an antioxidant, and stirring until the glutathione is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 3
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of tea polyphenol as an antioxidant, and stirring until the tea polyphenol is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 4
Preparing an aqueous solution: 200g of m-phenylenediamine is dissolved in 5kg of water, stirred until the m-phenylenediamine is completely dissolved, and 10g of Na is taken2S2O3As an antioxidant, stirring until completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 5
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of zinc chloride as an antioxidant, and stirring until the zinc chloride is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 6
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of ethylenediamine tetraacetate as an antioxidant, and stirring until the m-phenylenediamine is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 7
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of stannous chloride as an antioxidant, and stirring until the stannous chloride is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 8
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of sodium bisulfite as an antioxidant, and stirring until the sodium bisulfite is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
Example 9
Preparing an aqueous solution: dissolving 200g of m-phenylenediamine in 5kg of water, stirring until the m-phenylenediamine is completely dissolved, and then taking 10g of zinc sulfate as an antioxidant, and stirring until the zinc sulfate is completely dissolved;
preparing an organic phase solution: dissolving 7.5g of trimesoyl chloride in 10kg of normal hexane, and stirring until the trimesoyl chloride is completely dissolved;
interfacial polymerization experiment: immersing a porous base membrane comprising a porous polysulfone support layer formed on PET non-woven fabric in the aqueous phase solution for 10s, taking out, draining the surface residual solution, then immersing in the organic phase solution, reacting for 10s, taking out, and draining the surface residual solution. And rinsing with deionized water, putting into a 60 ℃ oven, drying for 3min, and taking out to obtain the reverse osmosis membrane.
The reverse osmosis membranes prepared in comparative example and examples 1-9 were tested on a membrane test bench using 2000ppm aqueous NaCl at 25 deg.C at an operating pressure of 225psi to test the rejection (i.e., salt rejection) and water flux of NaCl (as the solute) and the results are summarized in Table 1.
The N/O ratios of the polyamide layers obtained in comparative examples and examples 1 to 9 were calculated by elemental analysis using an EDX spectrometer, and the results are summarized in Table 1.
TABLE 1
| Water flux (GFD) | Desalting Rate (% NaCl) | N/O ratio | |
| Comparative example | 24.83 | 99.65 | 0.62 |
| Example 1 | 25.44 | 99.67 | 0.65 |
| Example 2 | 26.83 | 99.68 | 0.68 |
| Example 3 | 28.64 | 99.70 | 0.67 |
| Example 4 | 27.96 | 99.71 | 0.70 |
| Example 5 | 28.64 | 99.74 | 0.68 |
| Example 6 | 26.34 | 99.73 | 0.72 |
| Example 7 | 29.34 | 99.68 | 0.74 |
| Example 8 | 28.61 | 99.69 | 0.72 |
| Example 9 | 28.74 | 99.73 | 0.74 |
From the above results, it can be seen that the N/O ratio of the polyamide functional layer of the reverse osmosis membrane obtained by the preparation method of the present application is significantly increased, and the larger the N/O ratio, the higher the degree of crosslinking of the polyamide layer. The polyamide layer has high crosslinking degree, improves the repeated cleaning resistance and the service life of the reverse osmosis membrane, and improves the membrane flux and the salt rejection rate to a certain extent from the test result.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like within the spirit and scope of the present invention should be included.
Industrial applicability
The preparation method of the reverse osmosis membrane can inhibit the oxidation of the amine aqueous phase monomer, thereby improving the crosslinking degree of the polyamide functional layer, improving the repeated cleaning resistance and prolonging the service life of the reverse osmosis membrane, and improving the membrane flux and the salt rejection rate to a certain extent.
Claims (9)
1. A preparation method of a reverse osmosis membrane is characterized by comprising the following steps:
(1) contacting a porous polymer supporting layer with an amine monomer aqueous phase solution containing an antioxidant, and then contacting the porous polymer supporting layer contacted with the aqueous phase solution with an organic phase solution containing an acyl chloride monomer, or contacting the porous polymer supporting layer with the organic phase solution containing the acyl chloride monomer, and then contacting the porous polymer supporting layer contacted with the organic phase solution with the amine monomer aqueous phase solution containing the antioxidant;
(2) and carrying out post-treatment and drying to obtain the reverse osmosis membrane.
2. The method of claim 1, wherein the antioxidant is uric acid, lipoic acid, glutathione, ascorbic acid, isoascorbic acid, ascorbyl palmitate, tea polyphenol, xylylbiguanide, tolylbiguanide, phenylhexamethylenebiguanide, tricresylguanide, acetoacetarylamine, alkyl phosphate, dialkyl phosphate, alkyl monophenol, alkylated polyphenol, thiobisphenol, polyalkylphenol, edetate, hypochlorotrimethylene phosphonate, stannous chloride, sodium bisulfite, Na2S2O3、Na2S、Na2SO3、Na2S2O4One or more of zinc chloride, zinc sulfate, boric acid, alkyl boric acid and organic boron compounds, wherein the addition amount of the antioxidant is 0.01-10 wt% based on the total weight of the amine monomer aqueous phase solution.
3. The production method according to claim 1 or 2, wherein the amine monomer is aniline, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amisole, xylylenediamine, 1, 4-cyclohexanediamine, 1, 2-cyclohexanediamine, piperazine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, polyethyleneimine, triethylamine, tris (2-aminoethyl) amine, diethylenetriamine, N- (2-hydroxyethyl) ethylenediamine, 1, 3-cyclohexanediamine, 1, 3-bispiperidylpropane, 4-aminomethylpiperazine, ethanolamine, tris (2-aminoethyl) amine, One or more of diethanolamine, hexanediol amine and diglycolamine, wherein the concentration of the amine monomer in the amine monomer aqueous phase solution is 0.01-10 wt%.
4. The preparation method according to claim 1 or 2, wherein the acyl chloride monomer is one or more of biphenyl diformyl chloride, trimesoyl chloride, benzoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, benzene disulfonyl chloride, cyclopentane diacyl chloride, cyclopentane triacyl chloride, cyclohexane triacyl chloride, butane diacid chloride, pentane triacyl chloride, glutaryl chloride, hexane triacyl chloride, hexane diacid chloride, cyclopentane tetracoyl chloride, cyclohexane diacid chloride, decane triacyl chloride, tetrahydrofuran diacid chloride, tetrahydrofuran tetracoyl chloride, cyclopropane triacyl chloride, cyclobutane diacid chloride, cyclobutane tetracoyl chloride, and cyclohexane tetracoyl chloride; the concentration of the acyl chloride monomer is 0.01 wt% -1 wt% based on the total weight of the organic phase solution.
5. The method according to claim 1 or 2, wherein the solvent in the organic phase solution is one or more selected from n-hexane, cyclohexane, n-heptane, isoparaffin solvent Isopar G, methane, ethane, propane, butane, pentane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, isopropylcyclohexane, 1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane, 1, 4-dimethylcyclohexane, 1, 2-diethylcyclohexane, 1, 3-diethylcyclohexane, and 1, 4-diethylcyclohexane.
6. The preparation method according to claim 1 or 2, wherein the porous polymer support layer is one or more of a porous polysulfone support layer, a porous polyethersulfone support layer, a porous sulfonated polyethersulfone support layer, a porous polypropylene support layer and a porous polyacrylonitrile support layer.
7. The method of claim 6, wherein the porous polymer support layer is formed on the reinforcing material.
8. The method of claim 7, wherein the reinforcing material is a nonwoven fabric.
9. A reverse osmosis membrane produced by the production method according to any one of claims 1 to 8.
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