CN101678285A - 复合半透膜 - Google Patents
复合半透膜 Download PDFInfo
- Publication number
- CN101678285A CN101678285A CN200880020970A CN200880020970A CN101678285A CN 101678285 A CN101678285 A CN 101678285A CN 200880020970 A CN200880020970 A CN 200880020970A CN 200880020970 A CN200880020970 A CN 200880020970A CN 101678285 A CN101678285 A CN 101678285A
- Authority
- CN
- China
- Prior art keywords
- silver
- semipermeable membrane
- composite semipermeable
- antibacterial agent
- series antibacterial
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 230000003115 biocidal effect Effects 0.000 claims description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- -1 carboxylic acid halides Chemical class 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims 1
- 230000000813 microbial effect Effects 0.000 abstract description 10
- 238000011109 contamination Methods 0.000 abstract description 8
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- 239000007864 aqueous solution Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 239000010408 film Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000149 penetrating effect Effects 0.000 description 9
- 238000001223 reverse osmosis Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920001744 Polyaldehyde Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- CVTKPHKRKFDAAO-UHFFFAOYSA-N 1,1,2,2-tetrachlorocyclohexane Chemical compound ClC1(Cl)CCCCC1(Cl)Cl CVTKPHKRKFDAAO-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- UQBNGMRDYGPUOO-UHFFFAOYSA-N 1-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(NC)=C1 UQBNGMRDYGPUOO-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 description 1
- JZFFFBJQJAXQQH-UHFFFAOYSA-N ClC1=C(C(=C(C(=C1)C(=O)Cl)C(=O)Cl)S(=O)(=O)Cl)Cl Chemical compound ClC1=C(C(=C(C(=C1)C(=O)Cl)C(=O)Cl)S(=O)(=O)Cl)Cl JZFFFBJQJAXQQH-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00791—Different components in separate layers
-
- 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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
-
- 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
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Abstract
本发明的目的在于提供耐污染特性、特别是耐微生物污染特性优异的复合半透膜以及使用该复合半透膜的水处理方法。本发明涉及一种复合半透膜,其为在多孔性支撑体的表面形成含有使多官能胺成分与多官能酰卤成分反应而得的聚酰胺系树脂的皮层的复合半透膜,其特征在于,在皮层上直接或隔着其他层形成含有银系抗菌剂和聚合物成分的抗菌层,抗菌层中的银系抗菌剂与聚合物成分的重量比为55∶45~95∶5(银系抗菌剂∶聚合物成分)。
Description
技术领域
本发明涉及包括含聚酰胺系树脂的皮层与支撑其的多孔性支撑体的复合半透膜及使用了该复合半透膜的水处理方法。所述复合半透膜适于超纯水的制造、咸水或海水的脱盐,另外,可以从作为染色废水、电沉积涂料废水等公害发生原因的污染物等中除去·回收其中含有的污染源或有效物质,有助于废水的封闭(close)化。另外,可以用于食品用途等中将有效成分浓缩、将净水、污水用途等中的有害成分除去等高度处理中。
背景技术
目前,在使用了复合半透膜的水处理工序中,会发生随时间经过水通透量或盐截留率等水通透特性降低的现象,即发生污垢,在水处理设施的运营中,污垢所导致的损失处理及防止污垢所用成本最多。因此,需要应对这种污垢的根本防止方法。
因此引起污垢的原因物质根据其性状分为无机结晶质污垢、有机物污垢、粒子及溶胶污垢、微生物污垢。为聚酰胺系复合半透膜时,由存在于水中的微生物吸附于分离膜的表面形成薄的生物膜所产生的微生物污垢是主要原因物质。
为了减少污垢,广泛使用原水的前处理、分离膜表面的电性质改性、模件(モジュ一ル)工程条件改性、周期性清洁等方法。特别是在为复合半透膜中最频繁发生的微生物所导致的污垢时,已知通过氯等杀菌剂的处理,微生物所导致的污垢显著减少。但是,氯由于会产生致癌物质等副产物,因此直接用于生产饮料水的工序中具有很多问题。
最近的抗污垢分离膜的研究基本将焦点聚集在改变表面的电荷特性。例如提出在反渗透复合膜上形成含有具有非离子系亲水性基团的、交联的有机聚合物的表层的方法(专利文献1)。另外,还提出了在聚酰胺薄膜上使用交联有环氧化合物的非水溶性高分子进行亲水性涂布的方法(专利文献2)。另外,还提出了具有在分离膜表面以纳米大小的粒状含有TiO2的构造的纳米构造形反渗透分离膜(专利文献3)。另外,还提出了在分离活性层中配合纳米粒子的方法或者在分离活性层上设置含有纳米粒子的亲水性层的方法(专利文献4)。
但是,专利文献1的方法仅将表面改性成电中性,一旦细菌等附着时,由于没有杀灭该菌、抑制其繁殖的功能,因此抑制由于生物来源的污染或者由其引起的次级污染等所导致的膜特性降低的效果差。
专利文献2的方法由于也没有杀灭所附着的菌、抑制其繁殖的功能,因此对于生物来源的污染而言,效果很差。
专利文献3的方法使用纳米大小的光催化剂,但光催化剂不被光照射则不表现分解有机物的作用。因此,在按照反渗透分离膜能够在实际的水处理工序中使用而加工的螺旋元件以及将该螺旋元件装于水处理装置中的耐压容器中,由于光线无法到达,因此不会发挥催化剂活性,无法分解膜面的附着物,因此对于污染性的效果差。
专利文献4的方法中,虽然分离活性层要求分子水平的极高致密性,但可预料当以纳米粒子混存的状态进行制膜时会损害分离活性层的致密性,膜性能显著降低。另外,为了抑制纳米粒子的凝集添加分散剂等,但当为了保持抗菌持续性提高纳米粒子浓度时,易于发生凝集,难以均匀地形成分离活性层或亲水性层。
【专利文献1】日本专利特开平11-226367号公报
【专利文献2】日本专利特开2004-25102号公报
【专利文献3】日本专利特开2003-53163号公报
【专利文献4】国际公开第06/098872号小册子
发明内容
本发明的目的在于,提供耐污染特性、特别是耐微生物污染特性优异的复合半透膜以及使用该复合半透膜的水处理方法。
本发明人等为了完成上述课题进行了认真地研究,结果发现,通过以下所示复合半透明可以达成上述目的,进而完成了本发明。
也就是说,本发明涉及一种复合半透膜,其为在多孔性支撑体的表面形成有含有使多官能胺成分与多官能酰卤成分反应而得的聚酰胺系树脂的皮层的复合半透膜,其特征在于,在皮层上直接或隔着其他层形成含有银系抗菌剂和聚合物成分的抗菌层,抗菌层中的银系抗菌剂与聚合物成分的重量比为55∶45~95∶5(银系抗菌剂∶聚合物成分)。
本发明的复合半透膜具有含有银系抗菌剂和聚合物成分的抗菌层,利用该抗菌层可以长期间持续耐微生物污染特性。特别是通过将抗菌层中的银系抗菌剂与聚合物成分的重量比调整为55∶45~95∶5(银系抗菌剂∶聚合物成分)、相比较于聚合物成分过量地添加银系抗菌剂,可以使银系抗菌剂的一部分露出至抗菌层表面,由此表现优异的耐微生物污染特性。当银系抗菌剂的重量比小于55时,由于银系抗菌剂难以露出至抗菌层表面,因此无法充分地表现耐微生物污染特性。另一方面,当银系抗菌剂的重量比超过95时,露出至抗菌层表面的银系抗菌剂易于在水处理工序中脱落·流出,无法长期间持续耐微生物污染特性。另外,本发明中在皮层上直接或隔着其它层形成抗菌层,由于未将抗菌剂分散于皮层中,因此维持了皮层的致密性。由此,可以抑制皮层的性能降低,不仅可以高度维持耐污染性,还可以高度维持水通透性能和盐截留率。
本发明中,银系抗菌剂优选为含有银离子的载体。含有银离子的载体由于以致密地分散的状态负载有银离子,因此使用该载体形成抗菌层时,可以增大抗菌层每单位面积的银的总表面积。由此,银与处理水的接触面积增大,表现优异的耐微生物污染特性。
银系抗菌剂优选平均粒径为1.5μm以下。银系抗菌剂的平均粒径超过1.5μm时,当将复合半透膜作为螺旋元件卷绕时,由于摩擦等物理损伤,有复合半透膜的性能降低的倾向。
银系抗菌剂优选在700℃以上进行加热处理。通过使用在700℃以上进行了加热处理的银系抗菌剂,在通水时可以提高银系抗菌剂所含银成分的保持性。
抗菌层中的银含量优选为30mg/m2以上。由此,可以维持长期间优异的抗菌特性。
聚合物成分优选为不溶解皮层和多孔性支撑体、另外在水处理操作中不会溶出的聚乙烯醇。
上述聚乙烯醇的皂化度优选为99%以上。皂化度为99%以上的聚乙烯醇由于分子链间氢键的影响,可溶于热水(80℃左右),但在常温附近(25℃左右)为水不溶性,即便交联度低,相对于水溶液的溶解性也降低,因此优选。另外,由于可以在抗菌层表面大量赋予羟基,因此不仅相对于污染物质的耐性增高,而且从提高复合半透膜的亲水性(水通透性能的提高)的观点出发也优选。
另外,也可通过使用皂化度90%以上的聚乙烯醇、使该聚乙烯醇交联于上述皮层的聚酰胺系树脂,实现水处理操作时的抗菌层的水不溶性。
另外,本发明涉及使用上述复合半透膜的水处理方法。使用本发明的复合半透膜时,由于可以长期间抑制微生物污垢的发生,因此可以削减水处理设施的运营成本、提高生产性。
具体实施方式
以下,说明本发明的具体实施方式。本发明的复合半透膜为在多孔性支撑体的表面形成了含有使多官能胺成分与多官能酰卤成分反应而得的聚酰胺系树脂的皮层,进而在该皮层上直接或隔着其他层形成抗菌层。
多官能胺成分是具有2个以上的反应性氨基的多官能胺,可列举如芳香族、脂肪族及脂环式多官能胺。
芳香族多官能胺可列举如间苯二胺、对苯二胺、邻苯二胺、1,3,5-三氨基苯、1,2,4-三氨基苯、3,5-二氨基苯甲酸、2,4-二氨基甲苯、2,6-二氨基甲苯、N,N’-二甲基-间苯二胺、2,4-二氨基苯甲醚、阿米酚、苯二甲基二胺等。
脂肪族多官能胺可列举如乙二胺、丙二胺、三(2-氨基乙基)胺、n-苯基-乙二胺等。
脂环式多官能胺可列举如1,3-二氨基环己烷、1,2-二氨基环己烷、1,4-二氨基环己烷、哌嗪、2,5-二甲基哌嗪、4-氨基甲基哌嗪等。
这些多官能胺可以使用1种,也可以将2种以上并用。为了得到高盐截留性能的皮层,优选使用芳香族多官能胺。
多官能酰卤成分为具有2个以上的反应性羰基的多官能酰卤。
多官能酰卤可列举如芳香族、脂肪族及脂环式的多官能酰卤。
芳香族多官能酰卤可列举如均苯三甲酰三氯、对苯二甲酰二氯、间苯二甲酰二氯、联苯基二甲酰二氯、萘二甲酰二氯、苯三磺酰三氯、苯二磺酰二氯、氯磺酰基苯二甲酰二氯等。
脂肪族多官能酰卤可列举如丙烷二甲酰二氯、丁烷二甲酰二氯、戊烷二甲酰二氯、丙烷三甲酰三氯、丁烷三甲酰三氯、戊烷三甲酰三氯、戊二酰卤、己二酰卤等。
脂环式多官能酰卤可列举如环丙烷三甲酰三氯、环丁烷四甲酰四氯、环戊烷三甲酰三氯、环戊烷四甲酰四氯、环己烷三甲酰三氯、四氢呋喃四甲酰四氯、环戊烷二甲酰二氯、环丁烷二甲酰二氯、环己烷二甲酰二氯、四氢呋喃二甲酰二氯等。
这些多官能酰卤可以使用1种,也可以使用2种以上。为了得到高盐截留性能的皮层,优选使用芳香族多官能酰卤。另外,多官能酰卤成分的至少一部分使用3价以上的多官能酰卤,优选形成交联结构的。
另外,为了提高含有聚酰胺系树脂的皮层的性能,也可以使用聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酸等聚合物,山梨糖醇、甘油等多元醇等与其进行共聚。
支撑皮层的多孔性支撑体只要是可以支撑皮层的即可,没有特别的限定,通常优选使用具有平均孔径10~500左右的微孔的超滤膜。作为多孔性支撑体的形成材料,可列举如聚砜、聚醚砜之类的聚芳醚砜、聚酰亚胺、聚偏氟乙烯等各种材料,从化学的、机械的、热的稳定的角度考虑,特别优选使用聚砜、聚芳醚砜。所述多孔性支撑体的厚度通常为约25~125μm、优选约40~75μm,但不一定受该限制。另外,多孔性支撑体也可以用织布、无纺布等衬里被补强。
在多孔性支撑体的表面形成含有聚酰胺系树脂的皮层的方法没有特别限制,可以使用所有公知的手法。例如可以举出界面缩合法、相分离法、薄膜涂布法等。作为界面缩合法,具体来说有如下所述的方法,即,使含有多官能胺成分的胺水溶液与含有多官能酰卤成分的有机溶液接触而使其发生界面聚合,由此形成皮层,在该多孔性支撑体上载置该皮层的方法;或利用在多孔性支撑体上的所述界面聚合,在多孔性支撑体上直接形成聚酰胺系树脂的皮层的方法。该界面缩合法的条件等的具体情况在日本专利特开昭58-24303号公报、日本专利特开平1-180208号公报等中有记载,可以适当采用这些公知技术。
对多孔性支撑体上形成的皮层的厚度没有特别限制,通常为0.05~2μm左右,优选0.1~1μm。
在多孔性支撑体的表面上形成皮层后,在该皮层上直接或隔着其他层形成含有银系抗菌剂和聚合物成分的抗菌层。抗菌层中的银系抗菌剂与聚合物成分的重量比有必要为55∶45~95∶5(银系抗菌剂∶聚合物成分)、优选为60∶40~90∶10。
本发明使用的银系抗菌剂只要是含有银成分的化合物则无特别限定,例如可举出金属银、氧化银、卤化银、含银离子的载体等。其中特别优选使用含有银离子的载体。作为载体例如可以举出沸石、二氧化硅凝胶、磷酸钙、磷酸锆等。其中优选使用磷酸锆。磷酸锆与其他载体相比疏水性强,在水处理时可以长期间持续银离子的抗菌效果。优选载体为多孔质构造。多孔质构造的载体由于可以将银离子保持于其内部,因此不仅可以增多银成分的含量,还可提高银成分的持续性能(保持性能)。
银系抗菌剂的平均粒径优选为1.5μm以下、更优选为1μm以下。予以说明,平均粒径的测定方法记载于实施例。
银系抗菌剂优选在700℃以上经加热处理。通过使用在700℃以上进行了加热处理的银系抗菌剂,在通水时可以提高银系抗菌剂所含银成分的保持性。具体地说,通过使用上述银系抗菌剂,可以使通过累积通透水量13m3/m2左右原水后的抗菌层中的银含量相对于通水前含量为50%以上,通过加热处理温度还可使其为90%以上。加热处理温度更优选为900℃以上、特别优选为1000℃以上。加热处理温度的上限只要银系抗菌剂可以保持抗菌特性、为了均匀地分散银系抗菌剂粒子不会热分解的温度则无特别限定,通常为1300℃左右。
聚合物成分只要是不溶解皮层和多孔性支撑体、另外在水处理操作时不会溶出的聚合物则无特别限定,例如可以举出聚乙烯醇、聚乙烯吡咯、聚乙烯吡咯烷酮、羟丙基纤维素、聚乙二醇和皂化聚乙烯-醋酸乙烯酯共聚物等。其中,优选使用聚乙烯醇,特别优选使用皂化度99%以上的聚乙烯醇。
另外,通过使用皂化度90%以上的聚乙烯醇、将该聚乙烯醇交联于上述皮层的聚酰胺系树脂,还可防止水处理操作时的聚乙烯醇的溶出。作为使聚乙烯醇交联的方法,例如可以举出在皮层上形成抗菌层后浸渍于盐酸酸性的多元醛溶液中的方法。作为多元醛例如可举出戊二醛和对酞叉醛等二醛。另外,作为交联剂还可使用环氧化合物、多元酸等有机交联剂、硼化合物等无机交联剂。
抗菌层通过下述方法形成,即,在皮层上直接或隔着其它层(例如含有亲水性树脂的保护层等)涂布含有上述银系抗菌剂和上述聚合物成分的水溶液,之后进行干燥而形成。涂布方法例如可以举出喷雾、涂布、淋浴等。溶剂除了水之外,还可并用不会降低皮层等的性能的有机溶剂。这种有机溶剂例如可举出甲醇、乙醇、丙醇和丁醇等脂肪族醇;甲氧基甲醇和甲氧基乙醇等低级醇。
水溶液中的银系抗菌剂的浓度优选为0.1~10重量%、更优选为0.5~5重量%。水溶液中的聚合物成分的浓度优选为0.01~1重量%、更优选为0.1~0.7重量%。
水溶液的温度只要是该水溶液作为液体存在的温度范围则无特别限定,从防止皮层恶化的观点及处理容易等出发,优选为10~90℃、更优选为10~60℃、特别优选为10~45℃。
进行干燥处理时的温度并无特别限定,优选为20~150℃、更优选为40~130℃。小于20℃时,干燥处理所花费的时间过长、干燥变得不足,超过150℃时,由于热所导致的膜结构变化,有膜性能降低的倾向。
抗菌层的厚度并无特别限定,通常为0.05~5μm、优选为0.1~3μm、进一步优选为0.1~2μm。抗菌层的厚度过薄,则抗菌性无法充分地发挥,另外卷绕成螺旋元件时由于划擦易对膜造成损伤、有盐截留率降低的危险。另一方面,如抗菌层的厚度过厚,则水通过通量有降低至实用范围以下的危险。
抗菌层中的银含量优选为30mg/m2以上、更优选为35mg/m2以上。银含量小于30mg/m2时,难以维持长期间优异的抗菌特性。另外,抗菌层中的银含量从成本及防膜损伤的观点出发优选为1000mg/m2以下、更优选为500mg/m2以下。予以说明,抗菌层中的银含量测定方法记载于实施例。
另外,为了提高复合半透膜的盐截留性、透水性、耐氧化剂性等,还可实施以往公知的各种处理。
本发明的复合半透膜适用于超纯水的制造、咸水或海水的脱盐、废水处理等公知的水处理方法。
实施例
以下,例举实施例来说明本发明,但本发明不限于这些实施例。
〔评价及测定方法〕
(平均粒径的测定)
银系抗菌剂的平均粒径使用激光衍射式粒度分布计通过激光衍射法以体积标准进行测定。
(抗菌层中的银含量的测定)
将所制作的复合半透膜剪切成6mm大小、获得样品。将该样品放入容器,在其中加入浓硝酸4ml和氢氟酸1ml进行密封。之后,向该容器照射微波,然后在容器表面达到最高230℃的条件下进行加热,进行加压氧分解。分解后,向容器内加入超纯水,获得50ml的水溶液。之后,使用诱导结合等离子体质量分析装置(ICP-MS)测定该水溶液中的银含量,求得抗菌层1m2中的银含量(mg)。
(通过通量及盐截留率的测定)
将制得的平膜状复合半透膜切割成规定的形状、大小,放置于平膜评价用的盒子(cell)中。在25℃下,向膜的供给侧与通透侧施加1.5MPa的差压,使含有NaCl约1500mg/L并用NaOH调整至pH6.5~7.5的水溶液与膜接触。测定利用该操作得到的通透水的通透速度和电导率,算出通透通量(m3/m2·d)及盐截留率(%)。就盐截留率而言,事先制作NaCl浓度与水溶液电导率的相关(标准曲线),使用它们利用下式算出。另外,将所制得的平膜状复合半透膜加工成螺旋状,制作螺旋元件,利用与上述同样的方法计算其通透通量(m3/m2·d)及盐截留率(%)。
盐截留率(%)={1-(通透液中的NaCl浓度[mg/L])/(供给液中的NaCl浓度[mg/L])}×100
(抗菌性的评价)
根据JIS Z2801:2000进行评价。以下示出试验概要。用普通肉汤培养基(NB)在35℃下振动培养,之后使用1/500NB稀释增殖了的大肠菌,制备2.5~10×105cfu/ml的大肠菌溶液。将该大肠菌溶液滴加于超低压反渗透复合膜(日东电工制、型号:ES20、没有抗菌层)和所制得的复合半透膜上,盖上膜后,在35℃下培养24小时。之后,从超低压反渗透复合膜和复合半透膜回收大肠菌溶液,分别测定存活的菌数。菌数使用大肠菌测定用培替氏膜(3M社制)进行计数。
当(超低压反渗透复合膜的活菌数)/(复合半透膜的活菌数)为1×104以上时评价为○(抗菌性优异)、为1×102以下时评价为×(没有抗菌性)。
实施例1
将含有平均粒径0.9μm的银系抗菌剂(东亚合成制、ノバロンAG1100)0.7重量%和聚乙烯醇(皂化度:99%)0.5重量%的水溶液涂布于超低压反渗透复合膜(日东电工制、型号:ES20、皮层:聚酰胺系树脂、性能:以上述测定方法为通过通量1.2(m3/m2·d)、盐截留率99.6(%))的皮层,之后使用烘箱在130℃下干燥3分钟形成抗菌层,制作复合半透膜。
实施例2
除了将银系抗菌剂从0.7重量%改变为2重量%之外,利用与实施例1同样的方法制作复合半透膜。
实施例3
除了将银系抗菌剂从0.7重量%改变为5重量%之外,利用与实施例1同样的方法制作复合半透膜。
实施例4
将含有平均粒径0.9μm的银系抗菌剂(东亚合成制、ノバロンAG1100)2重量%和聚乙烯醇(皂化度:90%)0.5重量%的水溶液(异丙醇∶水=3∶7)涂布于超低压反渗透复合膜(日东电工制、型号:ES20)的皮层上,之后使用烘箱在130℃下干燥3分钟形成抗菌层。之后将所制得的复合膜浸渍于含有0.24N盐酸酸性的戊二醛0.001重量%的水溶液中10秒钟,再次在130℃下干燥5分钟制作复合半透膜。
实施例5
除了将银系抗菌剂从0.7重量%改变为2重量%、将聚乙烯醇从0.5重量%改变为0.2重量%之外,利用与实施例1同样的方法制作复合半透膜。
实施例6
除了使用在800℃下加热处理过银系抗菌剂(东亚合成制、ノバロンAG1100)的产物之外,利用与实施例5同样的方法制作复合半透膜。之后,将所制得的复合半透膜放于金属制的盒内,作为原水使用30℃的RO水,以膜通过通量1.22(m3/m2·d)和线速0.33(m3/m2·秒)运行11天。之后,取出复合半透膜,利用与上述相同的方法测定抗菌层中的银含量。将其结果示于表2。
实施例7
除了使用在1000℃下加热处理过银系抗菌剂(东亚合成制、ノバロンAG1100)的产物之外,利用与实施例5同样的方法制作复合半透膜。之后,利用与实施例6相同的方法测定抗菌层中的银含量。将其结果示于表2。
实施例8
除了使用在1200℃下加热处理过银系抗菌剂(东亚合成制、ノバロンAG1100)的产物之外,利用与实施例5同样的方法制作复合半透膜。之后,利用与实施例6相同的方法测定抗菌层中的银含量。将其结果示于表2。
比较例1
将含有聚乙烯醇(皂化度:99%)0.25重量%的水溶液涂布于超低压反渗透复合膜(日东电工制、型号:ES20)的皮层上,之后使用烘箱在130℃下干燥3分钟形成聚合物层,制作复合半透膜。
比较例2
除了将银系抗菌剂从0.7重量%改变为0.04重量%,利用与实施例1同样的方法制作复合半透膜。
Claims (9)
1.一种复合半透膜,其为在多孔性支撑体的表面形成有含有使多官能胺成分与多官能酰卤成分反应而得的聚酰胺系树脂的皮层的复合半透膜,其特征在于,
在皮层上直接或隔着其他层形成有含有银系抗菌剂和聚合物成分的抗菌层,抗菌层中的银系抗菌剂与聚合物成分的重量比即银系抗菌剂:聚合物成分为55∶45~95∶5。
2.根据权利要求1所述的复合半透膜,其中,银系抗菌剂为含有银离子的载体。
3.根据权利要求1或2所述的复合半透膜,其中,银系抗菌剂的平均粒径为1.5μm以下。
4.根据权利要求1或2所述的复合半透膜,其中,银系抗菌剂在700℃上经过了加热处理。
5.根据权利要求1所述的复合半透膜,其中,抗菌层中的银含量为30mg/m2以上。
6.根据权利要求1所述的复合半透膜,其中,聚合物成分为聚乙烯醇。
7.根据权利要求6所述的复合半透膜,其中,聚乙烯醇的皂化度为99%以上。
8.根据权利要求6所述的复合半透膜,其中,聚乙烯醇的皂化度为90%以上、且交联于所述皮层的聚酰胺系树脂。
9.使用权利要求1所述的复合半透膜的水处理方法。
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WO2006098872A2 (en) * | 2005-03-09 | 2006-09-21 | The Regents Of The University Of California | Nanocomposite membranes and methods of making and using same |
Cited By (3)
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CN106474945A (zh) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | 一种抗菌聚酰胺高分子膜及其制备方法和应用 |
CN111871223A (zh) * | 2020-07-23 | 2020-11-03 | 华中科技大学 | 一种高通量抗菌纳滤膜及其制备方法 |
CN111871223B (zh) * | 2020-07-23 | 2021-10-08 | 华中科技大学 | 一种高通量抗菌纳滤膜及其制备方法 |
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EP2168667A4 (en) | 2012-07-25 |
JP2009034673A (ja) | 2009-02-19 |
WO2009008500A1 (ja) | 2009-01-15 |
KR20100033426A (ko) | 2010-03-29 |
CN101678285B (zh) | 2014-12-10 |
EP2168667A1 (en) | 2010-03-31 |
US8672142B2 (en) | 2014-03-18 |
JP5701475B2 (ja) | 2015-04-15 |
KR101185701B1 (ko) | 2012-09-24 |
US20100178489A1 (en) | 2010-07-15 |
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