CN105008031A - Composite semipermeable membrane - Google Patents
Composite semipermeable membrane Download PDFInfo
- Publication number
- CN105008031A CN105008031A CN201480010817.5A CN201480010817A CN105008031A CN 105008031 A CN105008031 A CN 105008031A CN 201480010817 A CN201480010817 A CN 201480010817A CN 105008031 A CN105008031 A CN 105008031A
- Authority
- CN
- China
- Prior art keywords
- composite semipermeable
- semipermeable membrane
- functional layer
- separating
- membrane
- 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 249
- 239000002131 composite material Substances 0.000 title claims abstract description 169
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 71
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- 239000002346 layers by function Substances 0.000 claims description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 106
- 239000007864 aqueous solution Substances 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 66
- 239000004952 Polyamide Substances 0.000 claims description 36
- 229920002647 polyamide Polymers 0.000 claims description 36
- 150000001412 amines Chemical class 0.000 claims description 22
- 229920006037 cross link polymer Polymers 0.000 claims description 22
- 150000002433 hydrophilic molecules Chemical class 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 13
- 230000003746 surface roughness Effects 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 claims description 4
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000012466 permeate Substances 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract 1
- 238000009285 membrane fouling Methods 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 51
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- 235000002639 sodium chloride Nutrition 0.000 description 46
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- 239000003153 chemical reaction reagent Substances 0.000 description 22
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- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 11
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- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 9
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- 125000003118 aryl group Chemical group 0.000 description 7
- 238000006149 azo coupling reaction Methods 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
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- 229920002521 macromolecule Polymers 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
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- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004647 alkyl sulfenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- QTCANKDTWWSCMR-UHFFFAOYSA-N costic aldehyde Natural products C1CCC(=C)C2CC(C(=C)C=O)CCC21C QTCANKDTWWSCMR-UHFFFAOYSA-N 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004997 halocarbonyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- ISTFUJWTQAMRGA-UHFFFAOYSA-N iso-beta-costal Natural products C1C(C(=C)C=O)CCC2(C)CCCC(C)=C21 ISTFUJWTQAMRGA-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical group COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 150000004986 phenylenediamines Chemical group 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229950004354 phosphorylcholine Drugs 0.000 description 1
- PYJNAPOPMIJKJZ-UHFFFAOYSA-N phosphorylcholine chloride Chemical compound [Cl-].C[N+](C)(C)CCOP(O)(O)=O PYJNAPOPMIJKJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000005320 surfactant adsorption Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 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
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 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
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Transplantation (AREA)
- Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a composite semipermeable membrane, which is capable of achieving a high permeate volume and has high desorption properties with respect to membrane-fouling substances. This composite semipermeable membrane is provided with a support membrane comprising a base material and a porous support layer, and a separation function layer provided on the porous support layer. The surface zeta potential (A) of the separation function layer under measurement conditions of pH 6 and 10 mM NaCl is in the range of +-15 mV, and the potential difference between the surface zeta potential (B) of the separation function layer under measurement conditions of pH 6 and 1 mM NaCl and the surface zeta potential (A) is +-10 mV or more.
Description
Technical field
The present invention relates to and realize the high transmission water yield and can the composite semipermeable membrane of long-term stable operation.The composite semipermeable membrane obtained by the present invention can be suitable for the desalination of such as salt water.
Background technology
About the separation of mixture, there is the multiple technology being dissolved in the material (such as salt) in solvent (such as water) for removing.In recent years, as the technique of saving energy consumption He economize on resources, the application of membrane separation process expands.As the film used in membrane separation process, there are microfiltration membranes, milipore filter, NF membrane, reverse osmosis membrane etc.These films are used to the situation being obtained drinking water by such as seawater, salt water, water etc. containing harmful substance, or for the recovery etc. of the manufacture of industrial ultra-pure water, wastewater treatment, valuables.
Most of reverse osmosis membrane commercially available at present and NF membrane are composite semipermeable membranes, and have following two kinds: the composite semipermeable membrane on support membrane with the active layer of gel layer and crosslinked polymer; And be there is the composite semipermeable membrane of the active layer formed by monomer polycondensation on support membrane.Wherein, the composite semipermeable membrane obtained by following separating. functional layer coating on support membrane as through the water yield, select the high diffusion barrier of separation property and be widely used, described separating. functional layer is formed by crosslinked polyamide, and this crosslinked polyamide is obtained by the polycondensation reaction of polyfunctional amine and multifunctional etheride.
For using the desalting plant (fresh water generator) of reverse osmosis membrane, in order to reduce operating cost further, need higher through the water yield.For this requirement, there will be a known and make the method (see patent document 1) that the composite semipermeable membrane containing crosslinked polyamide polymer in isolating active layer contacts with containing nitrous aqueous acid or the method (see patent document 2) etc. contacted with the aqueous solution containing chlorine.
In addition, the fouling that one of produced problem causes for the fouling membrane material such by inorganic matter, organic matter in the desalting plant using reverse osmosis membrane.Due to fouling, significantly reducing through the water yield of reverse osmosis membrane.As the method improved it, propose by separating. functional layer surface pva coating thus make electriferous state be the method (see patent document 3) etc. that neutrality suppresses fouling.
In addition, in order to eliminate fouling, normally after the work carrying out certain period, alkali, acid etc. is utilized to carry out liquid cleaning.Therefore in order to can be continual and steady for a long time work, need composite semipermeable membrane to the durability of alkali, acid, the film properties change namely contacted before and after chemicals is little.In order to improve the alkali resistance of composite semipermeable membrane, disclose the method (see patent document 4) making composite semipermeable membrane contact the hydrogen ion concentration aqueous solution of pH9 ~ 13.In addition, in order to improve the acid resistance of composite semipermeable membrane, disclose the method (see patent document 5) making composite semipermeable membrane contact cyclic sulfates.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-125856 publication
Patent document 2: Japanese Laid-Open Patent Publication 63-54905 publication
Patent document 3: No. 97/34686th, International Publication
Patent document 4: Japanese Unexamined Patent Publication 2006-102624 publication
Patent document 5: Japanese Unexamined Patent Publication 2010-234284 publication
Summary of the invention
Thus, for the performance required by reverse osmosis membrane, not only require desalination performance, through the water yield, also requirement can work steadily in the long term.Although film described in patent document 1, patent document 2 can improve through the water yield, there is the problem that resistance to fouling tendency is low.On the other hand, the film recorded in patent document 3 causes due to coating sometimes declining through the water yield.In addition, for the composite semipermeable membrane recorded in patent document 4, patent document 5, although the chemical proofing of composite semipermeable membrane can be obtained, sometimes needing high-frequency liquid to clean to eliminate fouling, in steady operation, there is the leeway of research.
The object of the present invention is to provide and can realize the high transmission water yield and can the composite semipermeable membrane of long-term stable operation.
To achieve these goals, the present invention has following formation.
(1) composite semipermeable membrane, it has the support membrane comprising base material and porous supporting course and the separating. functional layer be arranged on above-mentioned porous supporting course, wherein,
The surperficial Zeta potential A of above-mentioned separating. functional layer under pH6, NaCl 10mM condition determination within ± 15mV,
Further, the potential difference of the surperficial Zeta potential B of above-mentioned separating. functional layer under pH6, NaCl 1mM condition determination and above-mentioned surperficial Zeta potential A is ± more than 10mV.
(2) composite semipermeable membrane as described in above-mentioned (1), wherein, the rms surface roughness on the surface of above-mentioned separating. functional layer is more than 60nm.
(3) composite semipermeable membrane as described in above-mentioned (1) or (2), wherein, above-mentioned separating. functional layer is formed by polyamide, and described polyamide is obtained by the polymerisation of polyfunctional amine and multifunctional etheride.
(4) composite semipermeable membrane according to any one of above-mentioned (1) ~ (3), wherein, the potential difference of the surperficial Zeta potential C of above-mentioned separating. functional layer under pH3, NaCl 1mM condition determination and the surperficial Zeta potential D of above-mentioned separating. functional layer under pH10, NaCl 1mM condition determination is below 40mV.
(5) composite semipermeable membrane according to any one of above-mentioned (1) ~ (4), wherein, above-mentioned separating. functional layer contains amino and amide groups, and the ratio of the molar equivalent of the molar equivalent/amide groups of amino is more than 0.2.
(6) composite semipermeable membrane according to any one of above-mentioned (1) ~ (5), wherein, above-mentioned separating. functional layer has amide groups, azo group and phenolic hydroxyl, and the ratio of phenolic hydroxyl/amide groups is less than 0.1.
(7) composite semipermeable membrane according to any one of above-mentioned (1) ~ (6), wherein, the surface of above-mentioned separating. functional layer is crosslinked polymer and is coated to.
(8) composite semipermeable membrane as described in above-mentioned (7), wherein, above-mentioned cross-linked polymer is the cross-linking agent of hydrophilic compounds.
(9) composite semipermeable membrane as described in above-mentioned (7) or (8), wherein, the surface of above-mentioned cross-linked polymer and above-mentioned separating. functional layer forms covalent bond.
(10) composite semipermeable membrane according to any one of above-mentioned (7) ~ (9), wherein, composite semipermeable membrane before being coated to using the surface of above-mentioned separating. functional layer by above-mentioned cross-linked polymer, under the pressure condition of 1.55MPa to 25 DEG C, pH6.5, NaCl concentration is 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F1 through the water yield, after the surface of above-mentioned separating. functional layer is coated to by above-mentioned cross-linked polymer be set to F2 through the water yield time, the value of F2/F1 is more than 0.80.
(11) composite semipermeable membrane according to any one of above-mentioned (1) ~ (10), wherein, in 25 DEG C, by with the pressure of 1.55MPa to pH6.5, NaCl concentration for 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F3 through the water yield, then in the above-mentioned aqueous solution, add polyoxyethylene (10) octyl phenyl ether and make its concentration become 100mg/l, by after 1 hour is filtered to the solution of gained with NaCl concentration be the aqueous cleaning 1 of 500mg/l little constantly be set to F4 through the water yield time, the value of F4/F3 is more than 0.85.
The present invention can provide and can realize the high transmission water yield and can the composite semipermeable membrane of long-term stable operation.By using this composite semipermeable membrane, can obtain with low energy consumption and stably quality high through water.
Detailed description of the invention
1. composite semipermeable membrane
Composite semipermeable membrane of the present invention has the polyamide separating. functional layer on the support membrane comprising base material and porous supporting course and the porous supporting course being formed in this support membrane.The feature of composite semipermeable membrane of the present invention is, when measuring the surperficial Zeta potential of separating. functional layer under the condition of pH6, NaCl 10mM, the surperficial Zeta potential of separating. functional layer is controlled in ± 15mV within, and potential difference between itself and surperficial Zeta potential when measuring under the condition of pH6, NaCl 1mM is ± more than 10mV.
(1-1) separating. functional layer
Separating. functional layer is the layer being responsible for the function being separated solute in composite semipermeable membrane.The formation of the composition and thickness etc. of separating. functional layer can be set in conjunction with the application target of composite semipermeable membrane.
Specifically, separating. functional layer is formed by crosslinked polyamide, and described crosslinked polyamide is obtained by the interfacial polycondensation of polyfunctional amine and multifunctional etheride.Below, also the separating. functional layer in the present invention is designated as " polyamide separating. functional layer ".
Herein, polyfunctional amine preferably comprises at least one composition be selected from aromatic series polyfunctional amine and aliphatic polyfunctional amine.
So-called aromatic series polyfunctional amine is the aromatic amine in a part with more than 2 amino, although be not particularly limited, and can example m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,3,5-triaminobenzene etc.In addition, as its N-alkylates, can example N, N-dimethyl-m-phenylenediamine, N, N-diethyl m-phenylene diamine (MPD), N, N-dimethyl-p-phenylenediamine, N, N-diethyl p-phenylenediamine etc.From the viewpoint of the stability of performance, particularly preferably m-phenylene diamine (MPD) or 1,3,5-triaminobenzene.
In addition, so-called aliphatic polyfunctional amine is the aliphatic amine in a part with more than 2 amino, preferred piperazine system amine and derivative thereof.Such as, can example piperazine, 2,5-lupetazins, 2-methyl piperazine, 2,6-dimethyl-piperizine, 2,3,5-tri methyl piperazines, 2,5-diethyl piperazines, 2,3,5-triethyl group piperazines, 2-n-pro-pyl piperazine, 2,5-di-n-butyl piperazines, ethylenediamine etc.From the viewpoint of the stability of performance, particularly preferably piperazine or 2,5-lupetazin.
These polyfunctional amines can be used alone a kind, also can be mixed with two or more.
So-called multifunctional etheride, for having the etheride of halo carbonyl of more than 2 in a part, as long as be just not particularly limited by generating polyamide with the reaction of above-mentioned polyfunctional amine.As multifunctional etheride, such as can use oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, 1,3,5-cyclohexane tricarboxylic acid, 1,3-cyclohexane cyclohexanedimethanodibasic, 1,4-cyclohexane cyclohexanedimethanodibasic, 1,3,5-benzenetricarboxylic acid, 1,2, the halide of 4-benzenetricarboxylic acid, 1,3-phthalic acid, Isosorbide-5-Nitrae-phthalic acid etc.In etheride, preferred acyl chlorides compound, from the viewpoint of economy, the easy degree obtained, processing ease degree, reactive easy degree etc., particularly preferably as 1,3, the equal benzene front three etheride of the etheride of 5-benzenetricarboxylic acid.Above-mentioned multifunctional etheride can be used alone a kind, also can be mixed with two or more.
Present inventor conducts in-depth research, and found that, the solution absorption through the water yield and the fouling membrane material that is attached to film surface of the surperficial Zeta potential of separating. functional layer and composite semipermeable membrane is closely related.
So-called Zeta potential, be the standard of the clean fixed charge for evaluating ultra-thin film layers surface, the Zeta potential of thin-film surface of the present invention can be obtained by Hai Muhuozi-Si Muluqiaosiji (Helmholtz-Smoluchowski) formula shown in following mathematical expression (1) by electromobility.
(in formula (1), U is electromobility, and ε is the dielectric constant of solution, and η is the viscosity of solution.Herein, the dielectric constant of solution, viscosity use literature value when measuring temperature.)
The measuring principle of Zeta potential is described.With (water) solution of material, due to the impact of the electric charge of material surface, there is the quiescent layer that can not flow near surface.Zeta potential is the current potential relative to solution (it is present in the quiescent layer of material and the boundary face (sliding surface) of fluidized bed).
Herein, if the aqueous solution in research quartz glass groove, then because quartz surfaces is usually electronegative, so the ion of positively charged, particle are gathered near rooved face.On the other hand, the electronegative ion in groove center portion, particle become many, in groove, create ion distribution.If apply electric field in this condition, then reflection ion distribution in groove, the position of ion in groove is with different mobility speed swimmings (being called EOF).Due to the electric charge of mobility speed reflection rooved face, so by obtaining the distribution of this mobility speed, the electric charge (surface potential) of rooved face can be evaluated thus.
The mensuration of usual Zeta potential can be carried out as follows, namely, use is of a size of the film sample of 20mm × 30mm, the standard particle (it is the polystyrene particle (particle diameter 520nm) that surface is coated with hydroxypropyl cellulose) being used for carrying out electrophoresis is dispersed in the NaCl aqueous solution being adjusted to normal concentration and measures.Determinator such as can Shi Yong Otsuka Electronics Co., Ltd. electrophoretic light scattering photometer ELS-8000 etc.
For composite semipermeable membrane of the present invention, need the surperficial Zeta potential of separating. functional layer to be controlled when measuring under the condition of pH6, NaCl 10mM within ± 15mV (surperficial Zeta potential A), and when measuring under the condition of NaCl 1mM, the potential difference of (surperficial Zeta potential B) and surperficial Zeta potential A is ± more than 10mV.
Containing from the unreacted amino of polyfunctional amine and multifunctional etheride and carboxyl in polyamide separating. functional layer, according to the difference of the degree of dissociation of these functional groups, the value of Zeta potential changes.The Zeta potential during pH6 of separating. functional layer is relevant to the adsorptivity of fouling membrane material, if controlled by the Zeta potential under NaCl 10mM condition within ± 15mV, then can suppress the surperficial raw-material interaction of fouling membrane material and film.This is because, if Zeta potential be controlled in ± 15mV within, then represent that film surface is electroneutral, can suppress and the electric interactions with the fouling membrane material of charged group that exists in water.Zeta potential is ± more than 15mV time, film surface produces electrical bias, therefore becomes and the electric interactions with the fouling membrane material with charged group easily occurs.
On the other hand, if the degree of dissociation of functional group is high, then composite semipermeable membrane desalination performance and uprise through the water yield.This is considered because, because functional group's quantitative change of separating. functional layer is many, thus Coulomb repulsion becomes large, or hydrophily uprises.In the present invention, be ± more than 10mV by making Zeta potential A when measuring under NaCl10mM condition, with the potential difference of surperficial Zeta potential B when measuring under NaCl 1mM condition, the solution absorption of the fouling membrane material under high salt concentration can be met thus, but also high desalination performance, the high transmission water yield can be met simultaneously.When described potential difference be less than ± 10mV, significantly reduce through the water yield, or with the interaction grow of fouling membrane material.
The surperficial Zeta potential C of above-mentioned separating. functional layer under pH3, NaCl 1mM condition determination, relevant with the stability of composite semipermeable membrane to the potential difference of the surperficial Zeta potential D of above-mentioned separating. functional layer under pH 10, NaCl 1mM condition determination, when this potential difference is below 40mV, during cleaning composite semipermeable membrane, the fissility of polluter is high, therefore preferably, be more preferably below 25mV.
In order to meet the scope of above-mentioned Zeta potential, the functional group's ratio " (amino molar equivalent)/(molar equivalent of amide groups) " in separating. functional layer is preferably more than 0.2, is more preferably more than 0.6.If the ratio of " (amino molar equivalent)/(molar equivalent of amide groups) " is more than 0.2, amount of functional groups then in polyamide separating. functional layer is abundant, so the hydrophily of film can be maintained, improve through the water yield, in addition, significant effect can be obtained at coating layer described later in the immobilization of separating. functional layer.
Amount of functional groups in polyamide separating. functional layer such as can use
13c solid NMR method measures.Specifically, from composite semipermeable membrane peeling base, obtain polyamide separating. functional layer and porous supporting course, then dissolve, remove porous supporting course, obtain polyamide separating. functional layer.The polyamide separating. functional layer obtained is utilized DD/MAS-
13c solid NMR method measures, and can calculate each functional group ratio by the comparison of the integrated value at the carbon peak of institute of the Tan Fenghuoge functional group bonding of each functional group.
In addition, the elemental ratio of polyamide separating. functional layer such as can use X-ray photoelectron spectroscopy (XPS) to analyze.Specifically, can by using " Journal ofPolymer Science ", Vol.26,559-572 (1988) and " Japan is Hui Chi (Japanese bonding association magazine) then ", in Vol.27, No.4 (1991), illustrative X-ray photoelectron spectroscopy (XPS) is obtained.
As the method for Zeta potential controlling separating. functional layer, there is the method that the quantitative change of carrying out controlling the functional group that separating. functional layer is had when forming separating. functional layer is few; The functional group conversions had by separating. functional layer is the method for other structures; The method etc. of (being coated to) polymer is coated with on the surface of separating. functional layer.These methods can be used alone, and also plurality of methods can be combinationally used.But, with regard to the method for only coated polymeric, although the interaction of separating. functional layer and fouling membrane material can be reduced, reducing through the water yield of film, thus not preferred.
For the method for the surperficial coated polymeric at separating. functional layer, preferred polymers is hydrophilic compounds.By using hydrophilic compounds, the reduction through the water yield of the composite semipermeable membrane caused by coating treatment can be alleviated.In addition, above-mentioned polymer is also preferably cross-linked polymer.If coating polymer is cross-linked polymer, then when using composite semipermeable membrane continuously, when cleaning with liquid, the stripping of coating can be suppressed, performance steady in a long-term can be presented.
Hydrophilic compounds of the present invention preferably have at least 1 with the reactive group of the functional group reactions on film surface.As long as it can be then arbitrary reactive group that reactive group can form covalent bond with the functional group on film surface, such as, as the reactive group of the etheride bonding with film surface, hydroxyl, amino, epoxy radicals etc. can be enumerated.As the example of concrete hydrophilic compounds, the partly-hydrolysed thing etc. of polyvinyl alcohol, the partly-hydrolysed thing of polyvinyl acetate, polymine, PAH, poly-table ammonia alcohol (polyepiaminohydrin), amine modification Polyglycol 166-450, polyoxyethylene dipropylamine, the copolymer employing the monomer containing amino or hydroxyl, the partly-hydrolysed thing of vinyl acetate and methacrylate copolymer, vinyl acetate and 2-methacryloxyethyl phosphocholine copolymer can be enumerated.They can be used alone, also can be used in combination.Wherein, from the viewpoint of the performance of reactive, gained film, preferably use primary amino compound or secondary amino compound or there is the polymer of hydroxyl.When amino and etheride react, form amido link between crosslinked polyamide separating. functional layer and hydrophilic compounds, when hydroxyl and etheride react, between crosslinked polyamide separating. functional layer and hydrophilic compounds, form ester bond.
In addition, having at least 1, also to have with the hydrophilic compounds of the reactive group of the functional group reactions on film surface be not also preferred mode with the hydrophilic radical of the functional group reactions on film surface.As hydrophilic radical, such as, can enumerate ether, amide groups, ester group, uncle's amino, quaternary ammonium group, cyano group, nitro, alkoxyl, carboxyl, carbonyl, ketone group, alkoxy carbonyl, amide groups, cyano group, formoxyl, sulfydryl, imino group, alkyl sulfenyl, sulfinyl, sulfonyl, sulfonic group, nitroso, phosphate, phosphorylcholine etc.The particularly preferably electroneutral hydrophilic radical such as ether, amide groups, ester group.In addition, the both sexes electropolymer that equivalent contains positively charged group and electronegative group is also preferred from the viewpoint of control Zeta potential of the present invention.
Such there is at least 1 form covalent bond with the hydrophilic compounds of the reactive group of the functional group reactions on film surface and the functional group reactions on bridging property polyamide separating. functional layer surface and this hydrophilic compounds is fixed on film surface by making, thus compared with the situation of only adsorbing, performance steady in a long-term can be presented.
The functional group existed in above-mentioned separating. functional layer can be converted into different functional groups by the chemical reaction suitably selected.Such as, by using dinitrogen tetroxide, nitrous acid, nitric acid, sodium hydrogensulfite, clorox etc. as reagent, can there is the diazo coupling via aromatic diazonium salt in aromatic series amino.In addition, also amino can be converted into azo group by amino with the reaction etc. of nitroso compound.By change reaction reagent concentration, reaction time temperature and time, the Zeta potential of above-mentioned separating. functional layer can be controlled.In addition, when transforming functional group, because the amount of the functional group before reaction also impacts the Zeta potential of the separating. functional layer obtained, so also can be controlled the Zeta potential of separating. functional layer by following method, described method is: the method for the remaining quantity reduction of unreacting substance during by making the thinner thickness of porous supporting course thus making manufacture; Formed and to be cleaned by hot water after separating. functional layer thus to remove the method etc. of the compound with functional group.
When being contacted with reagent (it is with amino, carboxyl reaction) by separating. functional layer, the yellow colour index of separating. functional layer is preferably less than more than 15 50, is more preferably less than more than 20 45.Yellow colour index changes according to the amount of the azo-compound in separating. functional layer and azo group, if in above-mentioned scope, then can obtain the stability of Zeta potential of the present invention and hydrophilic compounds.If the yellow colour index of separating. functional layer is less than 15, then the amount of the azo-compound in separating. functional layer is few, so can not obtain Zeta potential of the present invention.If yellow colour index is more than 50, then the amount of azo-compound is many, so through water yield step-down.
So-called azo-compound is the organic compound with azo group (-N=N-), generates when making separating. functional layer contact with reagent (it is with amino, carboxyl reaction) and is kept in separating. functional layer.
So-called yellow colour index, as Japanese Industrial Standards' JIS K7373 (2006) defined, is the degree that the tone of polymer departs from from colourless or white to yellow direction, and with on the occasion of form represent.
The yellow colour index of separating. functional layer can utilize chromascope (color meter) to measure.Such as, support membrane is provided with when measuring yellow colour index in the composite semipermeable membrane of separating. functional layer, reflection measurement method is easy.In addition, also can measure in the following way: composite semipermeable membrane is positioned over after on glass plate in separating. functional layer mode down, by only dissolving the dissolution with solvents of support membrane and removing support membrane, by measuring residual separating. functional layer sample on a glass through assay method.It should be noted that, when composite semipermeable membrane is positioned on glass plate, preferably the base material of support membrane is peeled off in advance.Chromascope can use SugaTest Instruments Co., Ltd. SM Colour Computer SM-7 etc.
In the present invention, by making polyamide separating. functional layer, there is amide groups, azo group and phenolic hydroxyl and make the ratio of phenolic hydroxyl/amide groups be less than 0.10, the change composite semipermeable membrane that also little, chemical proofing is high through the water yield and low fouling tendency after contacting with acid, alkali can be obtained thus, therefore preferably.Protonated or deprotonation is there is in phenolic hydroxyl along with the change of pH value of solution, therefore the state-of-charge of polyamide chains owing to forming separating. functional layer changes, the higher order structure of polyamide chains changes, and causes desalination amount, desalination performance may change.Although there is not phenolic hydroxyl in the crosslinked aromatic polyamide formed by the interfacial polycondensation of multifunctional aromatic amine and multifunctional etheride, but in the post processing after interfacial polycondensation by with the reagent reacting such as dinitrogen tetroxide, nitrous acid, nitric acid, sodium hydrogensulfite, clorox, aromatic amine basal orientation aromatic diazonium salt transforms thus.Afterwards, by contacting with water, there is the reaction that aromatic diazonium salt transforms to phenolic hydroxyl.In addition, by the diazo coupling making aromatic diazonium salt and phenols react, non-existent phenolic hydroxyl in the crosslinked aromatic polyamide after interfacial polycondensation just completes also can be imported.
It should be noted that, the lower limit of the ratio of phenolic hydroxyl/amide groups is not particularly limited, but this ratio is as being more than 0.005, or also can be more than 0.01.
In composite semipermeable membrane of the present invention, reacted by the carbon acid with proton making aromatic diazonium salt (it is generated by the post processing of crosslinked aromatic polyamide) high with the aromatic compound or acidity with electron-donating group, it can be made preferentially diazo coupling to occur, suppress the generation of the phenolic hydroxyl generated by the reaction with water.As electron-donating group, such as, can enumerate hydroxyl, amino, alkoxyl, but preferably not use the phenoloid with hydroxyl as mentioned above, if consider water-soluble, then preferably use the compound with aromatic series amino.
The rms surface roughness (Rms) of separating. functional layer is preferably more than 60nm.By making rms surface roughness be more than 60nm, the surface area of separating. functional layer becomes large, uprises through the water yield.On the other hand, when coating thickness, rms surface roughness are less than 60nm, significantly reduce through the water yield.
The rms surface roughness of separating. functional layer can be controlled by the monomer concentration when being formed separating. functional layer by interfacial polycondensation, temperature.Such as, if temperature during interfacial polycondensation is low, then rms surface roughness diminishes, if temperature height, rms surface roughness becomes large.In addition, when the coating of polymer is carried out on separating. functional layer surface, if coating thickness, then rms surface roughness diminishes.
It should be noted that, rms surface roughness measures by AFM (AFM).Rms surface roughness is by from datum level to the square root of the value obtained that square to be averaged of the deviation of given side.Herein, mensuration face refers to the face showing whole determination data, and given side is the face of the object as roughness metering, refers in mensuration face with the specific part that fixture is specified, when datum level to refer to the mean value of the height of given side as Z0, with the plane represented by Z=Z0.AFM such as can use Digital Instruments Inc. NanoScope IIIa.
(1-2) support membrane
The polyamide separating. functional layer that support membrane is used for having separating property gives intensity, and himself does not have in fact the separating property to ion etc.Support membrane is formed by base material and porous supporting course.
The size in the hole of support membrane, the distribution in hole are not particularly limited, but preferred following support membrane: such as, there is even and small hole, or there is the micropore increased gradually to another side from the surface forming separating. functional layer side, further, the size forming the micropore on the surface of separating. functional layer side is the support membrane of more than 0.1nm below 100nm.
Support membrane can obtain as follows, that is, such as pass through curtain coating high molecular polymer on base material thus on base material, form porous supporting course.The material that support membrane uses, its shape are not particularly limited.
As base material, can the cloth and silk that formed by least one be selected from polyester and aromatic polyamide of example.Particularly preferably use mechanical stability and the high polyester of heat endurance.
As the cloth and silk for base material, can preferably use nonwoven fabric of long fibers, staple fiber nonwoven fabric.From the aspect of film forming requiring the excellence not producing following undesirable condition, more preferably nonwoven fabric of long fibers can be used, described undesirable condition is: on base material during the solution of curtain coating high molecular polymer because it crosses infiltration through the back side, base material and porous supporting course are peeled off, or produce the defect such as uneven homogenize or pin hole of film because of base material fluffing etc.As nonwoven fabric of long fibers, the nonwoven fabric of long fibers etc. be made up of thermoplastic continuous filament can be enumerated.By forming base material by nonwoven fabric of long fibers, uneven homogenize, the film defect during Polymer Solution curtain coating produced because of fluffing produced when using staple fiber nonwoven fabric can be suppressed.In addition, from carrying out composite semipermeable membrane the operation of continuous film forming, the film forming direction of base material apply tension force in consider, as base material, also preferably use the nonwoven fabric of long fibers of excellent in dimensional stability.Be the orientation of the fiber of opposition side with porous supporting course be particularly machine-direction oriented relative to film forming direction by what make to be configured in base material, can keep the intensity of base material, prevent film rupture etc., be therefore preferred.Herein, machine-direction orientedly refer to that the differently-oriented directivity of fiber is parallel with film forming direction or close to parallel.On the contrary, the differently-oriented directivity of fiber and film forming direction situation at a right angle or close to right angle is called horizontal orientation.
As the fiber-wall-element model degree of non-woven fabrics base material, be preferably that the degree of orientation of the fiber of opposition side is the scope of 0 ° ~ 25 ° with porous supporting course.Herein, so-called fiber-wall-element model degree is the index in the direction of the fiber representing the non-woven fabrics base material forming support membrane, refer to using film forming direction when carrying out continuous film forming as 0 °, the direction at a right angle with film forming direction, non-woven fabrics base material width as when 90 °, the average angle of the fiber that forms non-woven fabrics base material.Therefore, fiber-wall-element model degree, more close to 0 °, represents more for machine-direction oriented, and fiber-wall-element model degree, more close to 90 °, represents to be more horizontal orientation.
In the manufacturing process of composite semipermeable membrane or the manufacturing process of element, comprise heating process, but by heating, the phenomenon that support membrane or composite semipermeable membrane shrink can be caused.Particularly in continuous film forming, because do not give tension force in the direction of the width, therefore easily shrink in the direction of the width.Because support membrane or composite semipermeable membrane shrink, the problem of the aspects such as dimensional stability can be produced, so as base material, expect the base material that hot size changing rate is little.
In non-woven fabrics base material, be configured in porous supporting course when be the fiber of opposition side being 10 ° ~ 90 ° with the difference of the degree of orientation of the fiber being configured in porous supporting course side, can suppress the change of the width caused by thermal conductance, be preferred.
The air permeability of base material is preferably 2.0cc/cm
2/ more than sec.If air permeability is within the scope of this, then the improving through the water yield of composite semipermeable membrane.Think this is because: formed support membrane operation in, curtain coating high molecular polymer on base material when being immersed in coagulating bath, because the non-solvent replacing velocity from substrate side accelerates, so the internal structure change of porous supporting course, the monomer maintenance dose in the operation of formation separating. functional layer afterwards, diffusion velocity are impacted.
It should be noted that, can based on JIS L1096 (2010), measure air permeability by Fu Leize type testing machine (Frazier type tester).Such as, the base material of 200mm × 200mm size is cut, as sample.This sample is arranged on Fu Leize type testing machine, adjustment suction fan and airport are with the pressure making apsacline barometer become 125Pa, air capacity by base material, i.e. air permeability can be calculated from the kind of the pressure shown by vertical-type barometer now and the airport used.Fu Leize type testing machine can use KATO TECHCO., LTD. KES-F8-AP1 etc.
In addition, the thickness of base material preferably more than 10 μm in the scope of less than 200 μm, more preferably more than 30 μm in the scope of less than 120 μm.
Support membrane in the present invention has base material and porous supporting course, does not have in fact the separating property to ion etc., for giving intensity to the separating. functional layer in fact with separating property.
For the raw material of porous supporting course, following substances can be used alone or as a mixture: homopolymers or the copolymer such as polysulfones, polyether sulfone, polyamide, polyester, cellulose-based polymer, vinyl polymer (vinyl polymer), polyphenylene sulfide, PPSS, PPSU, polyphenylene oxide.Herein, as cellulose-based polymer, can cellulose acetate, celluloid etc. be used, as vinyl polymer, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile etc. can be used.Wherein, homopolymers or the copolymer such as preferred polysulfones, polyamide, polyester, cellulose acetate, celluloid, polyvinyl chloride, polyacrylonitrile, polyphenylene sulfide, PPSS.More preferably enumerate cellulose acetate, polysulfones, PPSS or PPSU, further, in these raw material, because the chemical stability of polysulfones, mechanical stability, heat endurance are high, easily shaping, so usually polysulfones can be used.
Specifically, if use the polysulfones formed by the repetitive shown in following chemical formula, be then easy to the aperture controlling support membrane, dimensional stability is high, therefore preferably.
Such as, by the N by above-mentioned polysulfones, dinethylformamide (DMF) solution with certain thickness curtain coating on the close mylar knitted or polyester non-woven fabric, then make its wet type in water solidify, the major part that can obtain surface thus has the support membrane that diameter is the micropore of several below 10nm.
The thickness of above-mentioned support membrane can the packed density to the intensity of obtained composite semipermeable membrane and when being made into element impact.In order to obtain sufficient mechanical strength and packed density, the thickness of support membrane preferably more than 30 μm in the scope of less than 300 μm, more preferably more than 100 μm in the scope of less than 220 μm.
The form of porous supporting course can be observed by SEM, transmission electron microscope or AFM.Such as, if use SEM to observe, then, after peeling off porous supporting course from base material, utilize freeze fracturing to be cut off thus make the sample for cross-section.Platinum, platinum-palladium or ruthenic chloride (preferred ruthenic chloride) are applied on this sample thinly, under the accelerating potential of 3 ~ 15kV, use high-resolution field emission scanning electron microscope (UHR-FE-SEM) to observe.High-resolution field emission scanning electron microscope can use Hitachi Co., Ltd S-900 type electron microscope etc.
The support membrane used in the present invention both can be selected from the such various commercially available material of Millipore Inc. " Milliporefilter VSWP " (trade name) or filter paper Inc. of Japan " Ultrafilter UK10 " (trade name), also can according to " Office of Saline WaterResearch and Development Progress Report ", the manufactures such as the method recorded in No.359 (1968).
The thickness of porous supporting course is preferably more than 20 μm in the scope of less than 100 μm.By making the thickness of porous supporting course be more than 20 μm, can obtain good resistance to pressure, can obtain simultaneously and not have defective uniform support membrane, therefore, the composite semipermeable membrane with such porous supporting course can demonstrate good desalination performance.If the thickness of porous supporting course is more than 100 μm, then the remaining quantity of unreacting substance when manufacturing increases, and reduces thus through the water yield, and chemical proofing reduces simultaneously.
It should be noted that, measure the thickness of base material and the thickness of composite semipermeable membrane by digital thickness meter (digital thickness gauge).In addition, because compared with support membrane, the thickness of separating. functional layer is very thin, so the thickness of composite semipermeable membrane can be considered as the thickness of support membrane.Therefore, measure the thickness of composite semipermeable membrane with digital thickness meter, and deduct the thickness of base material from the thickness of composite semipermeable membrane, thus the thickness of porous supporting course can be calculated easily.As digital thickness meter, the PEACOCK etc. of Co., Ltd. of tail rugged making institute can be used.When using digital thickness meter, measure the thickness of 20 positions, calculate mean value.
It should be noted that, when the thickness of base material or the thickness of composite semipermeable membrane are difficult to be measured by calibrator, SEM can be used to measure.For 1 sample, measure thickness from the electron micrograph of the cross-section of any 5 positions, calculate mean value, obtain thickness thus.
2. manufacture method
Next, the manufacture method of above-mentioned composite semipermeable membrane is described.Manufacture method comprises the formation process of support membrane and the formation process of separating. functional layer.
(2-1) formation process of support membrane
The formation process of support membrane is included in the operation that base material is coated with Polymer Solution and is immersed in by the described base material being coated with solution in coagulating bath thus the operation that macromolecule is solidified.
Base material is coated with in the operation of Polymer Solution, by the macromolecule dissolution of the composition as porous supporting course is prepared Polymer Solution in this high molecular good solvent.
About the temperature of Polymer Solution during coating Polymer Solution, at use polysulfones as in high molecular situation, be preferably the scope of 10 DEG C ~ 60 DEG C.If the temperature of Polymer Solution is within the scope of this, then macromolecule can not be separated out, Polymer Solution in abundant impregnation until Post RDBMS between the fiber of base material.Its result, makes porous supporting course engage securely with base material by anchor effect (anchor effect), can obtain good support membrane.It should be noted that, the preferred range of Polymer Solution suitably can adjust according to high molecular kind used, desired solution viscosity etc.
In the time after base material is coated with Polymer Solution, to being immersed in coagulating bath preferably in the scope of 0.1 ~ 5 second.If the time to being immersed in coagulating bath is within the scope of this, then containing the abundant impregnation of high molecular organic solvent solution until base material fiber between Post RDBMS.It should be noted that, the preferable range of the time to being immersed in coagulating bath suitably can adjust according to the kind of Polymer Solution used, desired solution viscosity etc.
As coagulating bath, usually use water, as long as but high molecular coagulating bath for not dissolving composition as porous supporting course.Different according to the composition of coagulating bath, the film form of the support membrane obtained can change, and thus obtained composite semipermeable membrane also can change.The temperature of coagulating bath is preferably-20 DEG C ~ 100 DEG C, more preferably 10 DEG C ~ 50 DEG C.If the temperature of coagulating bath is higher than above-mentioned scope, then the vibration on the coagulating bath surface caused by warm-up movement becomes fierce, and the flatness on the film surface after film is formed is easy to reduce.On the contrary, if temperature is too low, then setting rate is slack-off, and film forming reduces.
Next, in order to remove the solvent remained in film, the support membrane hot water obtained as mentioned above is cleaned.The temperature of hot water is now preferably 40 DEG C ~ 100 DEG C, more preferably 60 DEG C ~ 95 DEG C.If within the scope of this, then the degree of shrinkage of support membrane is greatly constant, good through the water yield.On the contrary, if temperature is too low, then cleaning performance is little.
(2-2) formation process of separating. functional layer
Next, the formation process of the separating. functional layer forming composite semipermeable membrane is described.In the formation process of polyamide separating. functional layer, use the aqueous solution containing above-mentioned polyfunctional amine and the organic solvent solution containing above-mentioned multifunctional etheride, carry out interfacial polycondensation on the surface of support membrane, form polyamide separating. functional layer thus.
As the organic solvent dissolving multifunctional etheride, as long as be nonmiscibility with water and do not destroy support membrane and do not hinder the solvent of the reaction of formation of crosslinked polyamide then all can use.As representative examples, the halogenated hydrocarbons such as liquid hydrocarbon, trichorotrifluoroethane can be enumerated.If be thought of as do not damage the ozone layer material, the easy degree of acquisition, the easy degree of operation, operational security, then preferably use one matter or their mixtures such as hexane, heptane, octane, nonane, decane, hendecane, dodecane, tridecane, the tetradecane, heptadecane, hexadecane, cyclooctane, ethyl cyclohexane, 1-octene, 1-decene.
At the polyfunctional amine aqueous solution or containing in the organic solvent solution of multifunctional etheride, as long as do not hinder the reaction between two-component, then also can contain the compound such as acylation catalyst, polar solvent, bundle acid agent, surfactant, antioxidant as required.
In order to carry out interfacial polycondensation on support membrane, first, support membrane surface is coated to the polyfunctional amine aqueous solution.Herein, the concentration of the aqueous solution containing polyfunctional amine is preferably less than more than 0.1 % by weight 20 % by weight, is more preferably less than more than 0.5 % by weight 15 % by weight.
As the method being coated to support membrane surface with the polyfunctional amine aqueous solution, as long as to carry out evenly the surface of support membrane by this aqueous solution and continuous print is coated to, by known coating process (such as, the aqueous solution is applied to the method on support membrane surface, by support membrane dipping method etc. in aqueous) carry out.Time of contact of support membrane and the polyfunctional amine aqueous solution preferably more than 5 seconds in the scope of less than 10 minutes, more preferably more than 10 seconds in the scope of less than 3 minutes.Then, preferably by discharge opeing operation, the aqueous solution of excessive coating is removed.As the method for discharge opeing, there is the method etc. such as face being remained on vertical direction and liquid is flowed down naturally.After discharge opeing, also can by dry for face to remove all or part of the water in the aqueous solution.
Thereafter, the organic solvent solution containing above-mentioned multifunctional etheride is coated on the support membrane after being coated to the polyfunctional amine aqueous solution, is formed the separating. functional layer of crosslinked polyamide by interfacial polycondensation.The time of carrying out interfacial polycondensation is preferably more than 0.1 second less than 3 minutes, is more preferably more than 0.1 second less than 1 minute.
The concentration of the multifunctional etheride in organic solvent solution is not particularly limited, if but it is too low, then likely there is the defect that the formation of active layer and separating. functional layer is insufficient, if too high, be disadvantageous from the viewpoint of cost, be therefore preferably the degree of less than more than 0.01 % by weight 1.0 % by weight.
Next, preferably by discharge opeing operation, reacted organic solvent solution is removed.About the removing of organic solvent, can use and such as film be held as vertical direction and make unnecessary organic solvent naturally flow down thus the method removed.In this situation, as the time held as vertical direction, be preferably the scope of more than 1 minute less than 5 minutes, be more preferably the scope of more than 1 minute less than 3 minutes.If the time of holding more than 1 minute, then easily obtains the separating. functional layer with objective function, if below 3 minutes, then can suppress the generation of the defect caused by the overdrying of organic solvent, therefore can reduce by rejection.
For the composite semipermeable membrane obtained by said method, further by implementing the operation of carrying out the cleaning treatment of 1 minute ~ 60 minutes in the scope of 25 DEG C ~ 90 DEG C with hot water, thus the solute that can improve composite semipermeable membrane further stops performance, through the water yield.But, when the temperature of hot water is too high, if after hot water cleaning treatment quick refrigeration, then chemical proofing reduce.Therefore, hot water cleaning is preferably carried out in the scope of 25 DEG C ~ 60 DEG C.In addition, when being greater than 60 DEG C and carrying out hot water cleaning treatment under being the high temperature of less than 90 DEG C, preferably after hot water cleaning treatment, Slow cooling is carried out.Such as, have and periodically make it contact with low-temperature water heating thus be cooled to the method etc. of room temperature.
In addition, carry out in the operation of hot water cleaning described, also can in the hot water containing acid or alcohol.By containing acid or alcohol, the formation of the hydrogen bond in separating. functional layer more easily can be controlled.As acid, the inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid or the organic acid such as citric acid, oxalic acid etc. can be enumerated.As the concentration of acid, be preferably adjusted to below pH2, be more preferably below pH1.As alcohol, the polyalcohols such as the monohydric alcohols such as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerine can be enumerated.The concentration of alcohol is preferably 10 ~ 100 % by weight, is more preferably 10 ~ 50 % by weight.
When the method that the functional group by being had by separating. functional layer carries out transforming controls the Zeta potential of separating. functional layer, next, above-mentioned separating. functional layer is made to contact with reagent (it is with the unreacted functional group reactions contained in separating. functional layer).Reaction reagent is not particularly limited, and can enumerate such as to react with the primary amino radical in separating. functional layer to generate the nitrous acid of diazol or derivatives thereof and the aqueous solution of salt, nitrosyl compounds etc. thereof.The aqueous solution due to nitrous acid, nitrosyl compounds is easy to produce gas and decompose, so preference is as progressively generated nitrous acid by the reaction of nitrite and acid solution.Usually, nitrite and hydrogen ion react and generate nitrous acid (HNO
2), the pH of the aqueous solution be less than 7, be preferably below pH5, more preferably below pH4 time can generate efficiently.Wherein, from the simplicity of operation, be particularly preferably in aqueous with the aqueous solution of the natrium nitrosum of hydrochloric acid or sulfuric acid reaction.
The concentration of reacting nitrous acid in the reagent generating diazol or derivatives thereof or nitrite with above-mentioned primary amino radical preferably 0.01 ~ 1 % by weight scope.If be the concentration of more than 0.01 % by weight, be then easy to obtain sufficient effect, when nitrous acid or nitrite concentration are below 1 % by weight, the operation of solution becomes easy.
The temperature of nitrous acid aqueous solution is preferably 15 DEG C ~ 45 DEG C.If the temperature of solution is less than 15 DEG C, then react spended time, if be greater than 45 DEG C, then the decomposition of nitrous acid is fast, operating difficulties.
Be the time that diazol and/or its derivative generate with the time of contact of nitrous acid aqueous solution, can process with the short time under high concentration, but when being low concentration, then need long-time.Therefore, for the solution of above-mentioned concentration, within being preferably time of contact 10 minutes, within being more preferably 3 minutes.In addition, the method for contact is not particularly limited, the solution of reagent can be coated with, also composite semipermeable membrane can be immersed in the solution of reagent.As long as the solvent solubilized reagent of solubilising reagent and composite semipermeable membrane are not etched, then can use any solvent.In addition, as long as do not hinder the reaction of primary amino radical and reagent, then surfactant, acid compound, alkali compounds etc. can be contained in solution.
A part and the water of the diazol or derivatives thereof generated by contacting react, thus are converted into phenolic hydroxyl.In addition, also react with the aromatic rings of compound that contains in the aromatic rings formed in the material of support membrane, separating. functional layer or separating. functional layer, formation azo group.
Next, the composite semipermeable membrane generating diazol or derivatives thereof can be made further to contact with reagent (it reacts with diazol or derivatives thereof).Reagent used herein can enumerate chloride ion, bromide ion, cyanide ion, iodide ion, fluoboric acid, hypophosphorous acid, sodium hydrogensulfite, sulfurous acid ion, aromatic amine, phenols, hydrogen sulfide, thiocyanic acid etc.
Such as, by with the reactions such as copper chloride (I), copper bromide (I), KI, can halogen be imported.In addition, by contacting with aromatic amine, phenols, there is diazo coupling thus, aromatic series can be imported at face.It should be noted that, these reagent can be used alone, and also can mix plural number kind and use, also can contact with different reagent through plural number.In these reagent, cause the reagent of diazo coupling effectively to play a role in the de-boron rate improving composite semipermeable membrane, therefore particularly preferably use.This is considered because, by diazo coupling, the substituting group volume imported for alternative amino is larger, can obtain blocking in separating. functional layer the effect in the hole existed.
As the reagent causing diazo coupling, can enumerate and there is the aromatic rings of electron rich or the compound of hetero-aromatic ring.As the compound of the aromatic rings or hetero-aromatic ring with electron rich, aromatic amine derivative, heteroaromatic amine derivative, amphyl, hydroxyl heteroaromatic ring derivative can be enumerated.As the object lesson of above-claimed cpd, such as aniline can be enumerated, with ortho position, between position, the optional position relation of contraposition is bonded to the aminoanisole of phenyl ring, 2 amino are with ortho position, between position, the optional position relation of contraposition is bonded to the phenylenediamine of phenyl ring, amino and hydroxyl are with ortho position, between position, the optional position relation of contraposition is bonded to the amino-phenol of phenyl ring, 1, 3, 5-triaminobenzene, 1, 2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 3-aminobenzyl amine, 4-aminobenzyl amine, sulfanilic acid, 3, 3 '-dihydroxybiphenyl amine, 1-amino naphthalenes, 2-amino naphthalenes, 1-amino-2-naphthol-4-sulfonic acid, 2-amido-8-naphthol-6-sulfonic acid, 2-amino-5-naphthols-7-sulfonic acid, or its N-alkylates and its esters, phenol, ortho position, between the cresols of position or contraposition, catechol, resorcinol, quinhydrones, phloroglucin, hydroxyquinol, 1,2,3,-thrihydroxy-benzene, tyrosine, 1-naphthols, beta naphthal and salt etc. thereof.
In order to obtain target effect, suitably can regulate the concentration of the reagent that these and diazol or derivatives thereof react and time.Contact Temperature is preferably 10 ~ 90 DEG C, is more preferably 20 ~ 60 DEG C.When Contact Temperature is less than 10 DEG C, reaction is difficult to carry out, and can not obtain the effect expected, sometimes be converted into phenolic hydroxyl by the reaction with water, when being greater than the high temperature of 90 DEG C, sometimes causing the contraction of polymer, reducing through the water yield.In addition, the concentration of reagent is preferably 0.01 ~ 10 % by weight, is more preferably 0.05 ~ 1 % by weight.When concentration is less than 0.01 % by weight, sometimes need the long period with the reaction of diazol or derivatives thereof, when concentration is greater than 10 % by weight, be sometimes difficult to control the reaction with diazol or derivatives thereof.
Next, the operation that above-mentioned separating. functional layer arranges hydrophilic compounds is described.Hydrophilic compounds is carried out heating after on separating. functional layer by overlaying on by the solution containing the compound with hydrophilic radical and is formed.
Hydrophilic compounds can be used alone and also can mix several and use.Hydrophilic compounds preferably uses with the form of the solution counting 10ppm ~ 1% according to weight concentration.If the concentration of hydrophilic compounds is less than 10ppm, then separating. functional layer is coating insufficient, and the attachment of fouling membrane material becomes remarkable, is therefore difficult to make the desorb of fouling membrane material when cleaning.If be greater than 1%, then coating layer is thickening, and can not realize surperficial Zeta potential A (current potential of its reflection film most surface) with the potential difference of surperficial Zeta potential B (thinking that it is subject to the impact of ion free in water less and reflects the current potential of separating. functional layer) is ± more than 10mV.
As the solvent used in the solution containing above-mentioned hydrophilic compounds, preferably use water, lower alcohol, halogenated hydrocarbons, acetone, acetonitrile etc.They can be used alone a kind, also can mix two or more and use.
Other compound can be mixed as required in the solution.Such as, in order to promote reaction, the alkaline metal cpds such as sodium carbonate, NaOH, sodium phosphate can be added, being the reaction product of the solvent of nonmiscibility, free multifunctional etheride and amines with water to remove remaining, also preferably adding the surfactant such as lauryl sodium sulfate, benzene sulfonic acid sodium salt.
The method that hydrophilic compounds is crosslinked is not particularly limited, but preferably carries out heat cross-linking.As heating means when carrying out heat cross-linking, such as, can use the method for blowing hot-air.Heating-up temperature now preferably in the scope of 30 ~ 150 DEG C, more preferably in the scope of 30 ~ 130 DEG C, more preferably in the scope of 60 ~ 100 DEG C.If heating-up temperature is lower than 30 DEG C, then can not heat fully, there is the tendency that cross-linking reaction speed reduces, if more than 150 DEG C, then side reaction becomes and is easy to carry out.In addition, if carry out heat cross-linking more than 150 DEG C, then the thermal contraction of composite semipermeable membrane becomes large sometimes, there is the tendency through water yield step-down.
Hydrophilic compounds crosslinked in preferably use crosslinking agent.As crosslinking agent, such as, can enumerate the aldehyde etc. in 1 molecule such as aforesaid acid or alkali, glyoxal or glutaraldehyde with at least 2 functional groups.Particularly preferably be, the raw material of cross-linked polymer is polyvinyl alcohol, and crosslinking agent is glutaraldehyde, and cross-linked polymer contains the reactant of polyvinyl alcohol and glutaraldehyde.
As the interpolation concentration of crosslinking agent, preferably in the scope of 0.01 ~ 5.0 % by weight, more preferably in the scope of 0.01 ~ 1.0 % by weight, preferred in the scope of 0.01 ~ 0.5 % by weight further.If concentration is lower than 0.01 % by weight, then crosslink density step-down, the water-insoluble of cross-linked polymer is easy to become insufficient, if be greater than 5.0 % by weight, then crosslink density uprises, and there is the tendency through water yield step-down, and cross-linking reaction speed accelerates, be easy to gelation occurs, there is the tendency being difficult to even spread.The reaction time of cross-linking reaction is preferably 10 seconds ~ 3 minutes.If be less than 10 seconds, then sometimes react insufficient carrying out, if more than 3 minutes, be then difficult to be adjusted to Zeta potential of the present invention.
Herein, preferably, be coated to even if composite semipermeable membrane of the present invention is crosslinked polymer, also not easily reduce through the water yield in coating front and back.Namely, by use the surface of separating. functional layer be crosslinked polymer be coated to before composite semipermeable membrane, under the pressure condition of 1.55MPa to 25 DEG C, pH6.5, NaCl concentration is 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F1 through the water yield, the surface of separating. functional layer is crosslinked polymer be coated to after be set to F2 through the water yield time, the value of F2/F1 is preferably more than 0.80.Be more preferably more than 0.90.By using such composite semipermeable membrane, can when not significantly reduce film through the water yield, give film surface with the high solution absorption to fouling membrane material.
3. the utilization of composite semipermeable membrane
Composite semipermeable membrane of the present invention and former current pipeline material, the tricots (tricot) etc. such as plastic wire through current pipeline material and as required for improve resistance to pressure film together be wound on be equipped with multiple hole tubular collector pipe around, the composite semipermeable membrane element of screw type can be suitable as.In addition, also this element serial or parallel connection can be accommodated in pressure vessel and make composite semipermeable membrane assembly.
In addition, above-mentioned composite semipermeable membrane or its element, assembly can with supply to them former water pump, the combinations such as the device of pre-treatment are carried out to this former water, thus form fluid separation device.By using this separator, former water can be separated into drinking water etc. through water with not through the condensed water of film, thus obtain the water meeting object.
The composite semipermeable membrane of the application of the invention, such as, in the scope that operating pressure is 0.1 ~ 3MPa, in such in the scope of more preferably 0.1 ~ 1.5MPa area of low pressure, use composite semipermeable membrane, flow separating element with can maintaining the high transmission water yield.In order to can operating pressure be reduced, the capacity of pump used etc. can be reduced, suppress power consumption, the low cost desalinated can be realized.If operating pressure is lower than 0.1MPa, then there is the tendency through discharge reduction, if be greater than 3MPa, then the power consumption of pump etc. increases, and easily causes the blocking of the film caused by fouling.
For composite semipermeable membrane of the present invention, preferably, use pH6.5, concentration be 2,000mg/l sodium-chloride water solution, 25 DEG C, filter under the condition of operating pressure 1.0MPa 1 little constantly be 0.5 ~ 3m through the water yield
3/ m
2/ d.Such composite semipermeable membrane such as can manufacture by suitably selecting aforesaid manufacture method.Be 0.5 ~ 3m by making the transit dose of water
3/ m
2the scope of/d, can the generation of moderate inhibition fouling, stably desalinates.
In sewage with composite semipermeable membrane process of the present invention, sometimes comprise the difficult Biodegradable organic matters such as the surfactant that utilizing carries out a biological disposal upon is not decomposed completely.If utilize existing composite semipermeable membrane to process, then SURFACTANT ADSORPTION is on film surface, reduces through the water yield.But, composite semipermeable membrane of the present invention owing to having the high transmission water yield and the high solution absorption to fouling membrane material, so stable performance can be presented.
Herein, the solution absorption of composite semipermeable membrane of the present invention to fouling membrane material is high.Namely, in 25 DEG C, by with the pressure of 1.55MPa to pH6.5, NaCl concentration for 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F3 through the water yield, then in the above-mentioned aqueous solution, add polyoxyethylene (10) octyl phenyl ether and make its concentration become 100mg/l, by after 1 hour is filtered to the solution of gained with NaCl concentration be the aqueous cleaning 1 of 500mg/l little constantly be set to F4 through the water yield time, the value of F4/F3 is preferably more than 0.85.Be more preferably more than 0.90.By using such composite semipermeable membrane, even if when the surface of film generation fouling etc., by being that the aqueous solution of more than 500mg/l cleans by NaCl concentration, the interactional effect of also can be inhibited film and polluter, therefore, it is possible to easily desorb.Therefore, be namely used in height process of sewage etc., also can work steadily in the long term.
It should be noted that, when the surface of the separating. functional layer of composite semipermeable membrane of the present invention be crosslinked polymer coating, above-mentioned identical through water yield F2 with aforesaid through water yield F3.
embodiment
The present invention will be described below to provide embodiment, but the present invention is not by any restriction of these embodiments.
(NaCl removal rate)
To be adjusted to temperature 25 DEG C, pH7, sodium chloride concentration 2,000ppm evaluation water under the condition of operating pressure 1.55MPa, be supplied to composite semipermeable membrane thus carry out membrane filtration process.Measure for feedwater and through electrical conductivity of water with East Asia electric wave Industrial Co., Ltd conductivity meter, thus obtain respective practical salinity and NaCl concentration.Based on thus obtained NaCl concentration and following formula, calculate NaCl removal rate.
NaCl removal rate (%)=100 × { 1-(the NaCl concentration through in the NaCl concentration in water/confession feedwater) }
(through the water yield)
In the test of preceding paragraph, measure and supply the film of feedwater (the NaCl aqueous solution) through the water yield, and will the value of the permeable amount (cubic meter) of 1 day of every 1 square metre of face be scaled as membrane permeate flux (m
3/ m
2/ d).
It should be noted that, when film forming through in assessment of water quantity, separating. functional layer surface be crosslinked polymer coating when, by use coating before composite semipermeable membrane, under the pressure condition of 1.55MPa to 25 DEG C, pH6.5, NaCl concentration is 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F1 through the water yield, by be crosslinked polymer be coated to after be set to F2 through the water yield, calculate the value of F2/F1.
After cleaning through in assessment of water quantity, in 25 DEG C, by with the pressure of 1.55MPa to pH6.5, NaCl concentration for 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F3 through the water yield, then add polyoxyethylene (10) octyl phenyl ether in aqueous and make its concentration become 100mg/l, by after 1 hour is filtered to the solution of gained with NaCl concentration be the aqueous cleaning 1 of 500mg/l little constantly be set to F4 through the water yield, calculate the value of F4/F3.
(porous supporting course thickness)
The thickness of base material before being formed by tail rugged making institute Co., Ltd. PEACOCK digital thickness meter mensuration porous supporting course and the thickness of the composite semipermeable membrane after completing, using the thickness of their difference as porous supporting course.About the thickness of base material and the thickness of composite semipermeable membrane, respective width measures 20 points, calculates mean value.
Porous supporting course thickness (μm)=film thickness (μm)-base material thickness (μm)
(Zeta potential)
Use ultra-pure water cleaning composite semipermeable membrane, its mode contacted with monitoring particle solution with the separation function aspect of composite semipermeable membrane is arranged in plane plate specimen groove, utilizes Otsuka Electronics Co., Ltd. electrophoretic light scattering photometer (ELS-8000) to measure.As monitoring particle solution, be used in the mensuration liquid of the monitoring particle gained of rnonodisperse polystyrene latex in the NaCl aqueous solution respectively concentration being adjusted to pH6, pH10 or pH3.
Use each mensuration liquid, measure the surperficial Zeta potential A (pH6, NaCl 10mM) of separating. functional layer, surperficial Zeta potential B (pH6, NaCl 1mM), surperficial Zeta potential C (pH3, NaCl 1mM), surperficial Zeta potential D (pH10, NaCl 1mM) respectively.
(amount of functional groups)
About the amount of functional groups in polyamide separating. functional layer, peeling base from composite semipermeable membrane, after obtaining polyamide separating. functional layer and porous supporting course, dissolves with carrene, removes porous supporting course, obtain polyamide separating. functional layer.Utilize DD/MAS-
13c solid NMR method measures the polyamide separating. functional layer obtained, and calculates each amount of functional groups by the comparison of the integrated value at the carbon peak of institute of the Tan Fenghuoge functional group bonding of each functional group.
(rms surface roughness)
Composite semipermeable membrane ultra-pure water is cleaned, composite semipermeable membrane after air-dry is cut out 1cm square and with sticking double faced adhesive tape on slide, use AFM (NanoscopeIIIa:Digital Instruments company), under percussion mode (tapping mode), measure the rms surface roughness (RMS) of separating. functional layer.Use Veeco InstrumentsNCHV-1 as cantilever (cantilever), measure at normal temperatures and pressures.Sweep speed is 1Hz, and number of sampling is the square of 512 pixels.Analysis software uses Gwyddion.For measurement result, all carry out one dimension baseline correction (slope correction) in X-axis and Y-axis.
(air permeability)
Based on JIS L1096 (2010), Fu Leize type testing machine is utilized to measure air permeability.Base material is cut out 200mm × 200mm size, and be arranged on Fu Leize type testing machine, adjustment suction fan and airport with the pressure making apsacline barometer become 125Pa, from the pressure shown by vertical-type barometer now and the kind of airport that uses to obtain air permeability.Fu Leize type testing machine uses KATO TECH CO., LTD. KES-F8-AP1.
(making of composite semipermeable membrane)
(comparative example 1)
Utilizing non-woven fabrics (the air permeability 1.0cc/cm formed by polyester fiber of copy paper method manufacture
2/ sec) in 15.0 % by weight dimethyl formamide (DMF) solution of room temperature (25 DEG C) casting polysulfones, then flood 5 minutes in pure water at once, thus preparation porous supporting course thickness is the support membrane of 40 μm.
Next, this support membrane is immersed in the aqueous solution containing 3.5 % by weight m-phenylene diamine (MPD)s, then the unnecessary aqueous solution is removed, further with the mode coating solution (it is dissolved with equal benzene front three etheride and is 0.14 % by weight and obtains in n-decane) that the surface of porous supporting course can be fully wet out.Next, in order to remove unnecessary solution from film, making costal fold straight thus carrying out discharge opeing, blow out the air of 20 DEG C with hair-dryer thus make it dry.Then, clean with the pure water of 40 DEG C thus obtain composite semipermeable membrane.Evaluate thus obtained composite semipermeable membrane, film properties is the value shown in table 1.
(embodiment 1)
The composite semipermeable membrane obtained in comparative example 1 is flooded 1 minute in the following aqueous solution, the described aqueous solution in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight, glutaraldehyde 0.2 % by weight, adds the hydrochloric acid as acid catalyst and makes concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 30 seconds, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 2)
The composite semipermeable membrane obtained in comparative example 1 is flooded 1 minute in the following aqueous solution, the described aqueous solution in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, adds the hydrochloric acid as acid catalyst and makes concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 1 minute, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 2)
The composite semipermeable membrane obtained in comparative example 1 to be immersed in the following aqueous solution 2 minutes, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 4 minutes, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 3)
The composite semipermeable membrane obtained in comparative example 1 to be immersed in the aqueous solution containing polyvinyl alcohol (saponification degree 99%, average degree of polymerization 500) 0.5 % by weight 2 minutes.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 4 minutes, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 4)
By the composite semipermeable membrane obtained in comparative example 1 in 30 DEG C with the sodium nitrite in aqueous solution process 1 minute utilizing sulfuric acid to be adjusted to 0.3 % by weight of pH3.Take out composite semipermeable membrane from nitrous acid aqueous solution after, with the pure water cleaning of 20 DEG C, obtain composite semipermeable membrane.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 3)
The composite semipermeable membrane obtained in comparative example 4 to be immersed in the following aqueous solution 1 minute, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 45 seconds, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 4)
The composite semipermeable membrane obtained in comparative example 4 is flooded 1 minute in the following aqueous solution, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 1 minute, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 5)
The composite semipermeable membrane obtained in comparative example 4 is flooded 2 minutes in the following aqueous solution, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 3 minutes, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 5)
The composite semipermeable membrane obtained in comparative example 4 is flooded 2 minutes in 80 DEG C of aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 1 % by weight.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 1 minute, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 6)
By the composite semipermeable membrane obtained in comparative example 1 in 30 DEG C with the sodium nitrite in aqueous solution process 1 minute utilizing sulfuric acid to be adjusted to 0.4 % by weight of pH3.Take out composite semipermeable membrane from nitrous acid aqueous solution after, it is made to flood 1 minute in aniline 0.1% aqueous solution in 30 DEG C.Then flood 2 minutes in the sodium sulfite aqueous solution of 0.1 % by weight.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 6)
The composite semipermeable membrane obtained in comparative example 6 is flooded 1 minute in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 30 seconds, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(embodiment 7)
The composite semipermeable membrane obtained in comparative example 6 is flooded 1 minute in the following aqueous solution, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 30 seconds, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
(comparative example 7)
The composite semipermeable membrane obtained in comparative example 6 is flooded 2 minutes in the following aqueous solution, the described aqueous solution is in the aqueous solution containing polyvinyl alcohol (saponification degree 88%, weight average molecular weight 2,000) 0.5 % by weight and glutaraldehyde 0.2 % by weight, add the hydrochloric acid as acid catalyst and make concentration of hydrochloric acid be the aqueous solution of 0.1 mol/L.Vertical maintenance 1 minute thus after removing unnecessary liquid, with air drier in 90 DEG C of dryings 3 minutes, obtain the composite semipermeable membrane that separating. functional layer has been coated to by polyvinyl alcohol.For composite semipermeable membrane, before evaluation, to be immersed in 10% isopropanol water solution 10 minutes thus to carry out hydrophilicity-imparting treatment.Evaluate thus obtained composite semipermeable membrane, result film properties is the value shown in table 1.
As above, composite semipermeable membrane of the present invention has the high transmission water yield and the high solution absorption to fouling membrane material, can the stable performance of long term maintenance.
[table 1]
In detail and describe the present invention with reference to specific embodiment, but to those skilled in the art, obviously can carry out various change or amendment without departing from the spirit and scope in the present invention.Japanese patent application (Japanese Patent Application 2013-39648) CLAIM OF PRIORITY that the application files an application based on the Japanese patent application (Japanese Patent Application 2013-39605) of filing an application on February 28th, 2013 and on February 28th, 2013, these contents are incorporated to herein as reference.
Utilizability in industry
Use composite semipermeable membrane of the present invention, former water can be separated into drinking water etc. through water with not through the condensed water of film, thus can target water be obtained.Composite semipermeable membrane of the present invention can be specially adapted to salt water or extra large water demineralizing.
Claims (11)
1. a composite semipermeable membrane, it has the support membrane comprising base material and porous supporting course and the separating. functional layer be arranged on described porous supporting course, wherein,
The surperficial Zeta potential A of described separating. functional layer under pH6, NaCl 10mM condition determination within ± 15mV,
Further, the potential difference of the surperficial Zeta potential B of described separating. functional layer under pH6, NaCl 1mM condition determination and described surperficial Zeta potential A is ± more than 10mV.
2. composite semipermeable membrane as claimed in claim 1, wherein, the rms surface roughness on the surface of described separating. functional layer is more than 60nm.
3. composite semipermeable membrane as claimed in claim 1 or 2, wherein, described separating. functional layer is formed by polyamide, and described polyamide is obtained by the polymerisation of polyfunctional amine and multifunctional etheride.
4. the composite semipermeable membrane according to any one of claims 1 to 3, wherein, the potential difference of the surperficial Zeta potential C of described separating. functional layer under pH3, NaCl 1mM condition determination and the surperficial Zeta potential D of described separating. functional layer under pH10, NaCl 1mM condition determination is below 40mV.
5. the composite semipermeable membrane according to any one of Claims 1 to 4, wherein, described separating. functional layer contains amino and amide groups, and the ratio of the molar equivalent of the molar equivalent/amide groups of amino is more than 0.2.
6. the composite semipermeable membrane according to any one of Claims 1 to 5, wherein, described separating. functional layer has amide groups, azo group and phenolic hydroxyl, and the ratio of phenolic hydroxyl/amide groups is less than 0.1.
7. the composite semipermeable membrane according to any one of claim 1 ~ 6, wherein, the surface of described separating. functional layer is crosslinked polymer and is coated to.
8. composite semipermeable membrane as claimed in claim 7, wherein, described cross-linked polymer is the cross-linking agent of hydrophilic compounds.
9. composite semipermeable membrane as claimed in claim 7 or 8, wherein, the surface of described cross-linked polymer and described separating. functional layer forms covalent bond.
10. the composite semipermeable membrane according to any one of claim 7 ~ 9, wherein, composite semipermeable membrane before being coated to using the surface of described separating. functional layer by described cross-linked polymer, under the pressure condition of 1.55MPa to 25 DEG C, pH6.5, NaCl concentration is 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F1 through the water yield, after the surface of described separating. functional layer is coated to by described cross-linked polymer be set to F2 through the water yield time, the value of F2/F1 is more than 0.80.
11. composite semipermeable membranes according to any one of claim 1 ~ 10, wherein, in 25 DEG C, by with the pressure of 1.55MPa to pH6.5, NaCl concentration for 2, the aqueous solution of 000mg/l filter 1 little constantly be set to F3 through the water yield, then in the described aqueous solution, add polyoxyethylene (10) octyl phenyl ether and make its concentration become 100mg/l, by after 1 hour is filtered to the solution of gained with NaCl concentration be the aqueous cleaning 1 of 500mg/l little constantly be set to F4 through the water yield time, the value of F4/F3 is more than 0.85.
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| CN202110032552.0A CN112870995A (en) | 2013-02-28 | 2014-02-28 | Composite semipermeable membrane |
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| PCT/JP2014/055061 WO2014133132A1 (en) | 2013-02-28 | 2014-02-28 | Composite semipermeable membrane |
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| JP (1) | JP6481366B2 (en) |
| KR (1) | KR102172598B1 (en) |
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| CN113463394A (en) * | 2021-06-10 | 2021-10-01 | 阜阳和益鞋业有限公司 | Indoor cotton shoe with deodorization and antibiosis functions and production process thereof |
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| WO2016052669A1 (en) * | 2014-09-30 | 2016-04-07 | 東レ株式会社 | Composite semipermeable membrane |
| JP6511808B2 (en) * | 2014-12-26 | 2019-05-15 | 東レ株式会社 | Composite semipermeable membrane |
| US11167249B2 (en) * | 2015-07-31 | 2021-11-09 | Toray Industries, Inc. | Separation membrane, separation membrane element, water purifier, and method for producing separation membrane |
| KR101975155B1 (en) * | 2015-10-27 | 2019-05-03 | 도레이 카부시키가이샤 | Composite semipermeable membrane and method for its production |
| WO2018198679A1 (en) | 2017-04-28 | 2018-11-01 | 東レ株式会社 | Semipermeable composite membrane and method for producing same |
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| KR102169136B1 (en) * | 2017-11-15 | 2020-10-23 | 한국화학연구원 | Membranes through crosslinking reaction and its preparation method |
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Also Published As
| Publication number | Publication date |
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| KR20150124952A (en) | 2015-11-06 |
| WO2014133132A1 (en) | 2014-09-04 |
| KR102172598B1 (en) | 2020-11-02 |
| CN112870995A (en) | 2021-06-01 |
| JPWO2014133132A1 (en) | 2017-02-02 |
| JP6481366B2 (en) | 2019-03-13 |
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