CN115337800B - High-desalination antioxidant polyamide reverse osmosis membrane, preparation method and application thereof - Google Patents
High-desalination antioxidant polyamide reverse osmosis membrane, preparation method and application thereof Download PDFInfo
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- CN115337800B CN115337800B CN202211149074.2A CN202211149074A CN115337800B CN 115337800 B CN115337800 B CN 115337800B CN 202211149074 A CN202211149074 A CN 202211149074A CN 115337800 B CN115337800 B CN 115337800B
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- reverse osmosis
- osmosis membrane
- membrane
- polyamide
- phase solution
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- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 95
- 239000004952 Polyamide Substances 0.000 title claims abstract description 76
- 229920002647 polyamide Polymers 0.000 title claims abstract description 76
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003078 antioxidant effect Effects 0.000 title abstract description 9
- 239000003963 antioxidant agent Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000001263 acyl chlorides Chemical group 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 71
- 229920002492 poly(sulfone) Polymers 0.000 claims description 36
- 239000008346 aqueous phase Substances 0.000 claims description 33
- 230000003064 anti-oxidating effect Effects 0.000 claims description 28
- 238000000108 ultra-filtration Methods 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 20
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 16
- 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 16
- 239000012071 phase Substances 0.000 claims description 16
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000012695 Interfacial polymerization Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- -1 isophthaloyl Chemical group 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000004982 aromatic amines Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 claims description 3
- MDJZGXRFYKPSIM-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanedihydrazide Chemical compound NNC(=O)[C@H](O)[C@@H](O)C(=O)NN MDJZGXRFYKPSIM-JCYAYHJZSA-N 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- IKWQWOFXRCUIFT-UHFFFAOYSA-N benzene-1,2-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C(=O)NN IKWQWOFXRCUIFT-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
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- CRMQURWQJQPUMY-UHFFFAOYSA-N cyclopropane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CC1(C(Cl)=O)C(Cl)=O CRMQURWQJQPUMY-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
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003141 primary amines Chemical group 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- DDOVHJODVHQLCS-UHFFFAOYSA-N pyridine-2,6-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=N1 DDOVHJODVHQLCS-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
- 150000007519 polyprotic acids Polymers 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract 1
- 239000008399 tap water Substances 0.000 abstract 1
- 235000020679 tap water Nutrition 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 32
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005266 casting Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UIMAOHVEKLXJDO-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triethylazanium Chemical compound CCN(CC)CC.C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C UIMAOHVEKLXJDO-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 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 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a high-desalination antioxidant polyamide reverse osmosis membrane, a preparation method and application thereof. According to the invention, the dihydrazide compound and the acyl chloride form the second polyamide layer, so that the density of the reverse osmosis membrane desalination layer is effectively improved, the reverse osmosis membrane desalination rate can be remarkably improved, and meanwhile, the second polyamide layer can be used as an oxidation sacrificial layer to improve the oxidation resistance of the reverse osmosis membrane, so that the method has a good application prospect in the water treatment fields of tap water purification and higher active chlorine content in water inlet sources.
Description
Technical Field
The invention relates to the technical field of reverse osmosis, in particular to a high-desalination antioxidative polyamide reverse osmosis membrane, a preparation method and application thereof.
Background
At present, the application of the reverse osmosis membrane element in the field of water treatment is more and more extensive, and as a core component of the reverse osmosis membrane element, the performance of the reverse osmosis membrane is more and more concerned by users. Most of reverse osmosis membranes widely used in the market at present are aromatic polyamide reverse osmosis membranes. The reverse osmosis membrane is formed by utilizing m-phenylenediamine and trimesoyl chloride to perform interfacial polycondensation reaction on the surface of a polysulfone porous support layer. Because the aromatic polyamide reverse osmosis membrane has better desalination rate, permeation flux and acid and alkali resistance, the aromatic polyamide reverse osmosis membrane is widely applied to the fields of pure water manufacture, wastewater treatment/recycling, sea water desalination and the like.
According to the application scene and the difference of water source of intaking, can put forward different demands to reverse osmosis membrane. If the quality of the inflow water is poor, the reverse osmosis membrane is often required to have good interception performance so as to ensure that indexes such as total dissolved salt, total hardness, chemical oxygen consumption, special ion content and the like in the produced water reach standards. In general, a method for enhancing rejection of a reverse osmosis membrane is realized by enhancing the density of a desalting layer of the reverse osmosis membrane or enhancing the electric charge of the surface of the membrane. For example, chinese patent No. 1211151C discloses that after a certain period of time of coating an acyl chloride solution, before the organic phase is not dried, the acyl chloride solution with high concentration is coated again, the secondary reaction is performed to increase the density of the reverse osmosis membrane, and meanwhile, the excessive acyl chloride hydrolysis generates more carboxyl groups to increase the hydrophilicity of the membrane, so that the rejection rate of the membrane to sodium chloride is increased from 93% to 97%, and the rejection performance of the reverse osmosis membrane is remarkably improved. Chinese patent No. CN104781001a discloses that a second organic solvent having a lower volatility than the first organic solvent is coated on the polyamide active layer to promote an additional interfacial polymerization reaction between the remaining acid chloride on the polyamide active layer and the unreacted portion of the amine compound, so as to improve the density of reverse osmosis, and the desalination rate of the reverse osmosis membrane is significantly improved compared with the comparative example.
In addition, in the scene of higher active chlorine content in the water inlet source, the reverse osmosis membrane used is required to have better oxidation resistance. Sodium hypochlorite is widely used as a sterilizing disinfectant for industrial water and domestic drinking water, is the most widely occurring oxidizing substance in reverse osmosis membrane inflow water, and in order to control the content of active chlorine in reverse osmosis membrane inflow water to a level that does not damage a polyamide desalination layer, excessive sodium hypochlorite needs to be consumed by using reducing substances such as sodium bisulphite and the like. However, when the pretreatment fluctuates, excessive sodium hypochlorite enters the reverse osmosis membrane device to cause irreversible degradation of the polyamide desalting layer, thereby reducing the performance and the service life of the membrane. Therefore, it is necessary and valuable to improve the oxidation resistance of reverse osmosis membranes. The reactive chlorine destroying polyamide reverse osmosis membranes are generally due to the fact that the active hydrogens of the amide groups and primary amino groups contained in the desalination layer are easily replaced by reactive chlorine and subsequent polymer degradation occurs. As a method for improving the oxidation resistance of a reverse osmosis membrane, it is common to introduce an oxidation-resistant compound inside a polyamide layer or to graft a sacrificial protective layer on the surface. As a practice of these methods, there has been a great deal of work. For example, the Chinese patent No. CN104379243A has improved oxidation resistance by adding a solvent index of no 9 (J/cm 3)1/2 is 22 (J/cm 3)1/2 is an antioxidant, thereby remarkably improving the oxidation resistance of the reverse osmosis membrane) to an organic acid chloride solution, the Chinese patent No. CN109173742A, CN109794174A has improved oxidation resistance by coating aliphatic aldehyde, glycidyl ether substances and polyvinyl alcohol on the surface of the membrane as a crosslinking protective layer on the surface of the reverse osmosis membrane, however, the introduction of the protective layer inevitably reduces the permeation flux of the membrane, and the Chinese patent No. CN110975644A and CN111282458A introduce sulfur-containing substances such as polypeptide substances and glutathione on the surface of the reverse osmosis membrane as attack sites of active chlorine by a chemical grafting method, thereby remarkably improving the oxidation resistance of the membrane.
The method for improving the desalination rate and the oxidation resistance of the reverse osmosis membrane has difficulty in improving the oxidation resistance of the membrane at the same time under the condition of improving the desalination rate.
Disclosure of Invention
The invention aims to provide a high-desalination and oxidation-resistance polyamide reverse osmosis membrane, which aims to solve the problem that the desalination rate and the oxidation resistance cannot be simultaneously achieved in the prior art.
The invention also aims to provide a preparation method of the high-desalination antioxidant polyamide reverse osmosis membrane.
The invention also aims to provide application of the high-desalination antioxidant polyamide reverse osmosis membrane in a water treatment assembly, a device and a water treatment method.
In order to achieve the purpose, the invention adopts the following technical scheme:
A high desalination antioxidation polyamide reverse osmosis membrane comprises a polysulfone ultrafiltration support membrane, a first polyamide layer formed on the polysulfone ultrafiltration support membrane, and a second polyamide layer containing dihydrazide compounds formed on the first polyamide layer.
Wherein the dihydrazide compound is selected from any one or more of oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, tartaric acid dihydrazide, isophthaloyl hydrazine, terephthaloyl hydrazine, phthalic acid dihydrazide and pyridine-2, 6-dicarboxylic acid dihydrazide.
The first polyamide layer is prepared by reacting a polyfunctional amine-containing monomer with a polybasic acyl chloride-containing monomer;
The second polyamide layer is obtained by coating a second aqueous phase solution containing dihydrazide compound on the surface of the nascent reverse osmosis membrane provided with the first polyamide layer for heat treatment.
In another aspect of the present invention, there is provided a method for preparing a high desalination and antioxidation polyamide reverse osmosis membrane, the method comprising the steps of: (1) Firstly, contacting a polysulfone ultrafiltration support membrane with a first aqueous phase solution containing a polyfunctional amine monomer; (2) Then contacting the solution with an organic phase solution containing polybasic acyl chloride to form a nascent reverse osmosis membrane with a first polyamide layer; (3) And then coating a second aqueous phase solution containing dihydrazide compound on the surface of the nascent reverse osmosis membrane with the first polyamide layer, and performing heat treatment at a certain temperature to obtain the high-desalination and antioxidation polyamide reverse osmosis membrane.
In a specific embodiment, the preparation method of the high desalination and antioxidation polyamide reverse osmosis membrane is characterized by comprising the following steps:
(1) Immersing a polysulfone ultrafiltration support membrane in a first aqueous solution containing a polyfunctional amine monomer; removing the residual first aqueous phase solution on the surface of the polysulfone ultrafiltration support membrane after taking out;
(2) Pouring the prepared organic phase solution containing the polybasic acyl chloride on the surface of the polysulfone ultrafiltration support membrane obtained in the step (1) for interfacial polymerization reaction, then pouring the organic phase solution out, and uniformly sweeping the surface of the membrane by adopting an air knife or an air knife to form a nascent reverse osmosis membrane with a first polyamide layer;
(3) Pouring the prepared second aqueous phase solution containing dihydrazide compound on the surface of the nascent reverse osmosis membrane formed in the step (2) for secondary polymerization reaction, pouring out the redundant second aqueous phase solution, then placing the solution into an oven for heat treatment, and finally taking out the membrane and washing the membrane to obtain the high-desalination antioxidation polyamide reverse osmosis membrane.
In the present invention, the preparation of the polysulfone ultrafiltration support membrane in the step (1) may be performed by using known techniques in the art, and is not limited in any way. In a preferred embodiment, the polymer solution for preparing the polysulfone ultrafiltration support membrane can contain 15.0-20.0 wt% of polysulfone resin, and the components are dissolved in a polar solvent to obtain polysulfone casting membrane solution; then the filtering defoamed polysulfone casting film liquid is coated and scraped on non-woven fabrics (such as polyester non-woven fabrics and the like); then the solution enters a gel bath to be subjected to phase inversion to form a membrane, and the polysulfone ultrafiltration support membrane is obtained after cleaning; the polar solvent preferably comprises one or more of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
In the present invention, the immersion contact time between the polysulfone ultrafiltration support membrane and the first aqueous solution of the polyfunctional amine monomer in the step (1) is preferably 10 to 300 seconds, more preferably 30 to 180 seconds; the contact temperature is preferably 10 to 50 ℃, more preferably 15 to 35 ℃.
In the invention, the polyfunctional amine monomer in the first aqueous solution in the step (1) is an aromatic amine or an aliphatic amine containing at least two primary amine groups; preferably, the aromatic amine comprises m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, xylylenediamine, 1,3, 5-triaminobenzene which are bonded to benzene rings in the ortho-, meta-, and para-positions, and the aliphatic amine comprises ethylenediamine, propylenediamine, piperazine; more preferably, the polyfunctional amine is m-phenylenediamine; the mass percentage of the polyfunctional amine in the first aqueous solution is 0.5 to 10.0wt%, preferably 1.0 to 5.0wt%.
Wherein, the first aqueous phase solution in the step (1) preferably further contains an acid receiving agent, and the acid receiving agent is selected from weak base, buffer pair formed by weak base and acid, hydroxide, carbonate and bicarbonate of alkali metal, or organic compound; wherein the weak base comprises triethylamine and sodium phosphate; the buffer pair comprises triethylamine hydrochloride and triethylamine camphorsulfonate; the hydroxide, carbonate and bicarbonate of alkali metal include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the organic compound comprises tetramethylammonium hydroxide and tetraethylammonium hydroxide; preferably, the acid acceptor is triethylamine camphorsulfonate; preferably, the first aqueous phase solution contains 1.1 to 3.5 weight percent of triethylamine and 2.3 to 6.5 weight percent of camphorsulfonic acid; more preferably, the pH of the first aqueous phase is 9-12.
In the invention, the solvent in the organic phase solution in the step (2) is selected from isoparaffins with a boiling point higher than 160 ℃, and is preferably one or a mixture of more than one of n-hexane, n-decane, isopar G and Isopar L.
In the present invention, the polybasic acyl chloride in the step (2) is selected from aromatic and/or aliphatic polybasic acyl chloride, the aromatic polybasic acyl chloride is selected from any one of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and naphthalene dicarboxylic acid chloride, and the aliphatic polybasic acyl chloride is selected from any one of adipoyl chloride and cyclopropane tricarboxylic acid chloride; preferably, the polybasic acyl chloride is trimesoyl chloride; in the organic phase solution of the polybasic acyl chloride, the mass concentration of the polybasic acyl chloride is 0.01-1 wt%, preferably 0.05-0.5 wt%.
In the present invention, the interfacial polymerization time between the polysulfone ultrafiltration support membrane and the polybasic acyl chloride in the step (2) is preferably 5 to 120 seconds, more preferably 10 to 60 seconds; the reaction temperature is preferably 10 to 50℃and more preferably 15 to 35 ℃.
In the invention, the concentration of the dihydrazide compound in the second aqueous phase solution in the step (3) is 0.01 to 5.0 weight percent, preferably 0.1 to 3.0 weight percent; the temperature of the second aqueous phase solution is 10 to 50 ℃, preferably 15 to 35 ℃.
In the invention, the time of the secondary polymerization reaction of the nascent reverse osmosis membrane and the second water phase in the step (3) is preferably 5-300 seconds, more preferably 10-120 seconds; the temperature of the secondary polymerization reaction is preferably 10 to 50 ℃, more preferably 15 to 35 ℃.
Wherein the heat treatment temperature in the step (3) is 50-120 ℃, preferably 60-100 ℃; the heat treatment time is 3 to 10 minutes, preferably 5 to 8 minutes.
In a preferred embodiment, the first polyamide layer is a crosslinked aromatic polyamide having a three-dimensional network structure formed by interfacial polycondensation of metaphenylene diamine and trimesoyl chloride. And then coating a second aqueous phase on the surface of the first polyamide layer, and performing heat treatment to obtain a second polyamide layer containing dihydrazide compounds, and washing with water to obtain the high-desalination and antioxidation polyamide reverse osmosis membrane.
Finally, the present invention provides the use of a highly desalinated, antioxidative polyamide reverse osmosis membrane in a water treatment module, apparatus and/or water treatment process.
The "water treatment component or device" can be any component or device which can be applied to the water treatment process and is provided with the high desalination and antioxidation polyamide reverse osmosis membrane. The "application in a water treatment module or device" includes application to a module or device product in which the high desalination, antioxidation polyamide reverse osmosis membrane of the present invention is installed, and also includes application to the preparation of such a module or device product. The modules may be, for example, spiral wound modules, disc tube flat sheet modules, and the like. The device can be, for example, a household/commercial reverse osmosis water purifier, an industrial boiler water supply reverse osmosis pure water device, an industrial water reuse reverse osmosis device, a sea water desalination device and the like. The water treatment method may be, for example: drinking water production, waste water reuse, sea water desalination, beverage concentration, etc. Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The invention obtains the reverse osmosis membrane with high desalination and oxidation resistance improvement on the basis of the non-woven fabric, the polysulfone ultrafiltration membrane and the first polyamide layer and the second polyamide layer containing dihydrazide compounds.
(2) According to the invention, the dihydrazide compound is grafted to the surface layer of the polyamide layer through secondary polymerization reaction, and the dihydrazide compound reacts with the multi-component acyl chloride which is not completely reacted with the first polyamide layer and the residual acyl chloride groups to further crosslink the low-density area in the first polyamide layer, so that the density of the polyamide layer is obviously improved, and the desalination rate of the reverse osmosis membrane is further improved.
(3) The dihydrazide compound has an amide bond structure, and reacts with polybasic acyl chloride and residual acyl chloride groups to form a second polyamide layer with amide bonds, so that the second polyamide layer with rich amide bonds on the surface layer can serve as an attack site of active chlorine, the damage of the active chlorine to the first polyamide layer mainly playing a role in separation is reduced, and the integral oxidation resistance of the reverse osmosis membrane is further improved.
(4) The preparation method of the high-desalination antioxidation polyamide reverse osmosis membrane is simple, convenient and feasible, is easy to amplify, can keep high desalination and antioxidation performance permanently and efficiently, and can be applied to the water treatment fields of industrial water supply, wastewater reuse and the like.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The raw materials used in the following examples and comparative examples are commercially available conventional raw materials, and the main raw material information is shown in table 1 below, unless otherwise specified.
Table 1: information of main raw material
The methods used or possible to be used in the examples or comparative examples of the present invention are described below:
1. evaluation of desalination Rate and permeation flux
Desalination rate and permeate flux are two important parameters for evaluating reverse osmosis membrane separation performance. The invention evaluates the separation performance of the reverse osmosis membrane according to GB/T32373-2015 reverse osmosis membrane test method.
The desalination rate (R) is defined as: under certain operating conditions, the difference between the salt concentration of the feed solution (C f) and the salt concentration of the permeate solution (C p) is divided by the salt concentration of the feed solution (C f), as shown in formula (1).
The permeate flux is defined as: under certain operating conditions, the volume of water which is transmitted per unit area of membrane in unit time is L.m -2·h-1.
The operating conditions adopted for measuring the performance of the reverse osmosis membrane in the invention are as follows: the feed solution was 250ppm aqueous sodium chloride solution at a pH of 7.5.+ -. 0.5, an operating pressure of 60psi and an operating temperature of 25.+ -. 1 ℃.
2. Evaluation of antioxidant Properties
And (3) performing initial performance test on the prepared high-desalination and antioxidation polyamide reverse osmosis membrane, immersing the membrane after the test in NaClO solution with the available chlorine of 500ppm at 25 ℃ and ph=7.0 for 24 hours, taking out the membrane, washing the membrane with deionized water, immersing the membrane in 1% sodium sulfite solution for reduction for 10 minutes, washing the membrane with deionized water again, and evaluating the test.
Example 1
Preparing polysulfone membrane casting solution containing 16.5wt% of polysulfone resin in N, N-dimethylformamide; uniformly coating the polysulfone membrane casting solution after filtration and deaeration on a polyester non-woven fabric; immediately soaking in coagulating bath deionized water, performing phase inversion to form a membrane, and cleaning to obtain a polysulfone ultrafiltration membrane;
Cutting the prepared polysulfone-based membrane into a proper size, sticking the proper size on a plate frame, immersing the plate frame in a first aqueous phase solution containing 2.5% by mass of m-phenylenediamine, 3.2% by mass of camphorsulfonic acid and 1.6% by mass of triethylamine, keeping the plate frame for 30s, taking out the plate frame, placing the plate frame on a paper towel at the top of a plastic plate, slightly squeezing the plate frame by using a compression roller to remove superfluous aqueous phase solution left on the surface, then carrying out contact reaction on the plate frame and an n-decane solution containing 0.1% by mass of trimesoyl chloride for 30s, pouring the superfluous n-decane solution, then uniformly sweeping the plate frame by adopting an air knife until no residual solvent exists on the surface of the plate frame, immediately coating a second aqueous phase solution containing 0.1% by mass of oxalic acid dihydrazide, 3.2% by mass of camphorsulfonic acid and 1.6% by mass of triethylamine, removing the superfluous second aqueous phase solution, putting the plate frame into an oven at 80 ℃ for heat treatment for 6min, finally taking out and washing the plate frame, and obtaining the high-oxidation-resistant reverse osmosis membrane containing oxalic acid dihydrazide.
Example 2
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the first water phase uses 1.5% of m-phenylenediamine to replace 2.5% of m-phenylenediamine, the organic phase uses 0.08% of trimesoyl chloride to replace 0.1% of trimesoyl chloride, and the second water phase solution contains 0.5% of oxalic dihydrazide.
Example 3
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the first water phase uses 4.0% of m-phenylenediamine to replace 2.5% of m-phenylenediamine, the organic phase uses 0.20% of trimesoyl chloride to replace 0.1% of trimesoyl chloride, and the second water phase solution contains 1.0% of oxalic dihydrazide.
Example 4
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the first water phase uses m-phenylenediamine with the mass fraction of 6.0 percent to replace 2.5 percent of m-phenylenediamine, camphorsulfonic acid with the mass fraction of 6.5 percent to replace 3.2 percent of camphorsulfonic acid, triethylamine with the mass fraction of 3.2 percent to replace 1.6 percent of triethylamine, the organic phase solvent uses Isopar L to replace n-decane, trimesic acid chloride with the mass fraction of 0.30 percent to replace 0.1 percent of trimesic acid chloride, and the second water phase solution contains oxalic acid dihydrazide with the mass fraction of 3.0 percent.
Example 5
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the first water phase uses 4.0% camphorsulfonic acid to replace 3.2% camphorsulfonic acid, 2.0% triethylamine to replace 1.6% triethylamine, the organic phase solvent uses Isopar L to replace n-decane, and the second water phase solution contains malonic acid dihydrazide with the mass percentage of 1.0%.
Example 6
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the first water phase uses 2.3% camphorsulfonic acid to replace 3.2% camphorsulfonic acid, 1.1% triethylamine to replace 1.6% triethylamine, 0.16% trimesoyl chloride to replace 0.1% trimesoyl chloride, and the second water phase solution contains 1.0% succinic dihydrazide.
Example 7
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. Except that the mass percentage of adipic acid dihydrazide in the second aqueous phase solution is 1.0%.
Example 8
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the mass percentage of the intermediate phthalhydrazide in the second aqueous phase solution is 1.0%.
Example 9
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that the mass percentage of the tartaric acid dihydrazide in the second aqueous phase solution is 1.0 percent.
Example 10
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that Isopar G is used for replacing n-decane as an organic phase solvent, the mass percentage of oxalic acid dihydrazide in the second aqueous phase solution is 0.5%, and the mass percentage of adipic acid dihydrazide is 0.5%.
Example 11
A high desalination, antioxidation polyamide reverse osmosis membrane was prepared using the preparation process in example 1. The difference is that n-heptane is used as the organic phase solvent to replace n-decane, the mass percentage of oxalic acid dihydrazide in the second aqueous phase solution is 0.5 percent, the mass percentage of adipic acid dihydrazide is 0.25 percent, and the mass percentage of isophthaloyl dihydrazide is 0.25 percent.
Comparative example 1
Preparing polysulfone membrane casting solution containing 16.5wt% of polysulfone resin in N, N-dimethylformamide; uniformly coating the polysulfone membrane casting solution after filtration and deaeration on a polyester non-woven fabric; immediately soaking in coagulating bath deionized water, performing phase inversion to form a membrane, and cleaning to obtain a polysulfone ultrafiltration membrane;
And sticking the prepared polysulfone-based membrane on a plate frame, immersing the plate frame in a first aqueous phase solution containing 2.5 mass percent of m-phenylenediamine, 3.2 mass percent of camphorsulfonic acid and 1.6 mass percent of triethylamine for 30s, taking out the plate frame, placing the plate frame on a paper towel at the top of a plastic plate, slightly extruding by a compression roller to remove superfluous aqueous phase solution left on the surface, carrying out contact reaction on the plate frame and an n-decane solution containing 0.1 mass percent of trimesoyl chloride for 30s, pouring the superfluous organic phase solution, uniformly blowing by an air knife until no solvent remains on the surface of the membrane, placing the plate frame in an oven at 80 ℃ for heat treatment for 6min, and finally taking out and washing the membrane to obtain the reverse osmosis membrane without the second polyamide layer.
Comparative example 2
The preparation process in comparative example 1 was used to prepare a high desalination and antioxidation polyamide reverse osmosis membrane. The difference is that after the air knife is adopted to uniformly sweep the surface of the membrane and no residual solvent is left, a second aqueous phase solution containing 0.1 percent by mass of m-phenylenediamine, 3.2 percent by mass of camphorsulfonic acid and 1.6 percent by mass of triethylamine is immediately coated, the reaction time is 1min, and then the redundant second aqueous phase solution is removed, so that the reverse osmosis membrane with the second polyamide layer and no dihydrazide is obtained.
The amounts of the respective raw materials and the reaction conditions of the examples of the present invention or comparative examples are shown in tables 2 and 3 below, and the performance index data of the prepared reverse osmosis membranes are shown in table 4.
TABLE 2 reaction ingredients TABLE 1
TABLE 3 reaction recipe II
TABLE 4 Performance of reverse osmosis membranes
As can be seen from the experimental results in table 4, compared with the reverse osmosis membranes of comparative examples 1 and 2 having the dihydrazide compound-containing second polyamide layer, the desalination rate loss is less after the oxidation treatment, the better oxidation resistance is exhibited, and the application prospect is better.
The above examples are given for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (12)
1. The high-desalination antioxidation polyamide reverse osmosis membrane comprises a polysulfone ultrafiltration support membrane, a first polyamide layer formed on the polysulfone ultrafiltration support membrane, and a second polyamide layer containing dihydrazide compounds formed on the first polyamide layer, wherein the first polyamide layer is prepared by reacting a polyfunctional amine-containing monomer with a polybasic acyl chloride-containing monomer; the second polyamide layer is obtained by coating a second aqueous phase solution containing dihydrazide compounds on the surface of a nascent reverse osmosis membrane provided with the first polyamide layer for heat treatment; the polyfunctional amine monomer is an aromatic amine or aliphatic amine containing at least two primary amine groups; the aromatic amine comprises m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, xylylenediamine and 1,3, 5-triaminobenzene which are bonded on a benzene ring in an ortho-position, a meta-position and a para-position, and the aliphatic amine comprises ethylenediamine, propylenediamine and piperazine; the polybasic acyl chloride is selected from aromatic and/or aliphatic polybasic acyl chloride, the aromatic polybasic acyl chloride is selected from any one of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and naphthalene dicarboxylic acid chloride, and the aliphatic polybasic acyl chloride is selected from any one of adipoyl chloride and cyclopropane tricarboxylic acid chloride.
2. The high desalination, antioxidation polyamide reverse osmosis membrane of claim 1, wherein the dihydrazide compound is selected from any one or more of oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, tartaric acid dihydrazide, isophthaloyl dihydrazide, terephthaloyl dihydrazide, phthalic acid dihydrazide, pyridine-2, 6-dicarboxylic acid dihydrazide.
3. The process for preparing a high desalination, antioxidation polyamide reverse osmosis membrane as claimed in any one of claims 1-2, said process comprising the steps of: (1) Firstly, contacting a polysulfone ultrafiltration support membrane with a first aqueous phase solution containing a polyfunctional amine monomer; (2) Then contacting the solution with an organic phase solution containing polybasic acyl chloride to form a nascent reverse osmosis membrane with a first polyamide layer; (3) And then coating a second aqueous phase solution containing dihydrazide compound on the surface of the nascent reverse osmosis membrane with the first polyamide layer, and performing heat treatment at a certain temperature to obtain the high-desalination and antioxidation polyamide reverse osmosis membrane.
4. A method of preparation according to claim 3, wherein the method of preparation comprises the steps of:
(1) Immersing a polysulfone ultrafiltration support membrane in a first aqueous solution containing a polyfunctional amine monomer; removing the residual first aqueous phase solution on the surface of the polysulfone ultrafiltration support membrane after taking out;
(2) Pouring the prepared organic phase solution containing the polybasic acyl chloride on the surface of the polysulfone ultrafiltration support membrane obtained in the step (1) for interfacial polymerization reaction, then pouring the organic phase solution out, and uniformly sweeping the surface of the membrane by adopting an air knife or an air knife to form a nascent reverse osmosis membrane with a first polyamide layer;
(3) Pouring the prepared second aqueous phase solution containing dihydrazide compound on the surface of the nascent reverse osmosis membrane formed in the step (2) for secondary polymerization reaction, pouring out the redundant second aqueous phase solution, then placing the solution into an oven for heat treatment, and finally taking out the membrane and washing the membrane to obtain the high-desalination antioxidation polyamide reverse osmosis membrane.
5. The method of claim 4, wherein the immersion contact time of the polysulfone ultrafiltration support membrane in step (1) with the first aqueous solution of the polyfunctional amine monomer is 10 to 300 seconds; the contact temperature is 10-50 ℃; and/or, the polyfunctional amine is m-phenylenediamine; in the first aqueous phase solution, the mass percentage of the polyfunctional amine is 0.5-10.0 wt%.
6. The method of claim 5, wherein the immersion contact time of the polysulfone ultrafiltration support membrane in step (1) with the first aqueous solution of the polyfunctional amine monomer is 30 to 180 seconds; the contact temperature is 15-35 ℃; in the first aqueous phase solution, the mass percentage of the polyfunctional amine is 1.0-5.0 wt%.
7. The process according to any one of claims 3 to 6, wherein the first aqueous solution in step (1) further comprises an acid acceptor selected from the group consisting of weak bases, buffer pairs of weak bases and acids, hydroxides, carbonates and bicarbonates of alkali metals, and organic compounds.
8. The process according to any one of claims 3 to 6, wherein the solvent in the organic phase solution in step (2) is selected from isoparaffins having a boiling point higher than 160 ℃; and/or, the polybasic acyl chloride is trimesoyl chloride; in the organic phase solution of the polybasic acyl chloride, the mass concentration of the polybasic acyl chloride is 0.01-1 wt%.
9. The preparation method according to claim 8, wherein the solvent in the organic phase solution in the step (2) is one or more mixed solvents selected from n-hexane, n-decane, isopar G and Isopar L; and/or, the mass concentration of the polybasic acyl chloride in the organic phase solution of the polybasic acyl chloride is 0.05-0.5 wt%.
10. The method according to any one of claims 3 to 6, wherein the interfacial polymerization reaction time of the polysulfone ultrafiltration support membrane and the polybasic acid chloride in the step (2) is 5 to 120 seconds; the reaction temperature is 10-50 ℃; and/or, the time of the secondary polymerization reaction of the nascent reverse osmosis membrane and the second water phase in the step (3) is 5-300 seconds; the temperature of the secondary polymerization reaction is 10-50 ℃; and/or, the heat treatment temperature in the step (3) is 50-120 ℃; the heat treatment time is 3-10 minutes.
11. The method according to claim 10, wherein the interfacial polymerization reaction time of the polysulfone ultrafiltration support membrane and the polybasic acid chloride in the step (2) is 10 to 60 seconds; the reaction temperature is 15-35 ℃; and/or, the time of the secondary polymerization reaction of the nascent reverse osmosis membrane and the second water phase in the step (3) is 10-120 seconds; the temperature of the secondary polymerization reaction is 15-35 ℃; and/or, the heat treatment temperature in the step (3) is 60-100 ℃; the heat treatment time is 5-8 minutes.
12. Use of a high desalination, antioxidation polyamide reverse osmosis membrane as defined in any one of claims 1-2 or prepared by the preparation method as defined in any one of claims 3-11 in a water treatment module, apparatus and/or water treatment process.
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