US20080083670A1 - Composite semipermeable membrane and process for producing the same - Google Patents
Composite semipermeable membrane and process for producing the same Download PDFInfo
- Publication number
- US20080083670A1 US20080083670A1 US11/869,678 US86967807A US2008083670A1 US 20080083670 A1 US20080083670 A1 US 20080083670A1 US 86967807 A US86967807 A US 86967807A US 2008083670 A1 US2008083670 A1 US 2008083670A1
- Authority
- US
- United States
- Prior art keywords
- semipermeable membrane
- composite semipermeable
- porous support
- alkali metal
- metal salt
- 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.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 153
- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 54
- 150000001412 amines Chemical class 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 25
- 150000004820 halides Chemical class 0.000 claims abstract description 25
- 239000004909 Moisturizer Substances 0.000 claims abstract description 14
- 230000001333 moisturizer Effects 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 11
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 10
- 239000003429 antifungal agent Substances 0.000 claims abstract description 9
- 229940121375 antifungal agent Drugs 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 55
- 238000011282 treatment Methods 0.000 claims description 42
- -1 organic acid alkali metal salt Chemical class 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 235000006708 antioxidants Nutrition 0.000 claims description 9
- 150000007524 organic acids Chemical group 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000005487 catechin Nutrition 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 229930195712 glutamate Natural products 0.000 claims description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002310 Isopropyl citrate Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229940072107 ascorbate Drugs 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229950001002 cianidanol Drugs 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- SKHXHUZZFVMERR-UHFFFAOYSA-L isopropyl citrate Chemical compound CC(C)OC(=O)CC(O)(C([O-])=O)CC([O-])=O SKHXHUZZFVMERR-UHFFFAOYSA-L 0.000 claims description 2
- 235000019300 isopropyl citrate Nutrition 0.000 claims description 2
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- 230000035699 permeability Effects 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 22
- 230000006866 deterioration Effects 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 230000004907 flux Effects 0.000 description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000001632 sodium acetate Substances 0.000 description 11
- 235000017281 sodium acetate Nutrition 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XMOCLSLCDHWDHP-UHFFFAOYSA-N L-Epigallocatechin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C1=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit 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
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- LVJJFMLUMNSUFN-UHFFFAOYSA-N gallocatechin gallate Natural products C1=C(O)C=C2OC(C=3C=C(O)C(O)=CC=3)C(O)CC2=C1OC(=O)C1=CC(O)=C(O)C(O)=C1 LVJJFMLUMNSUFN-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940001447 lactate Drugs 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000001540 sodium lactate Substances 0.000 description 2
- 235000011088 sodium lactate Nutrition 0.000 description 2
- 229940005581 sodium lactate Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- XMOCLSLCDHWDHP-SWLSCSKDSA-N (+)-Epigallocatechin Natural products C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-SWLSCSKDSA-N 0.000 description 1
- LSHVYAFMTMFKBA-PZJWPPBQSA-N (+)-catechin-3-O-gallate Chemical compound O([C@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-PZJWPPBQSA-N 0.000 description 1
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Natural products C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 description 1
- WMBWREPUVVBILR-GHTZIAJQSA-N (+)-gallocatechin gallate Chemical compound O([C@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-GHTZIAJQSA-N 0.000 description 1
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 description 1
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 description 1
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- ZKVMMSGRDBQIOQ-UHFFFAOYSA-N 1,1,2-trichloro-1-fluoroethane Chemical compound FC(Cl)(Cl)CCl ZKVMMSGRDBQIOQ-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
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
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- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 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
- 239000010409 thin film Substances 0.000 description 1
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical group [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- 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
- B01D67/0081—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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/28—Degradation or stability over time
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Definitions
- the present invention relates to a composite semipermeable membrane having a skin layer which includes a polyamide resin and a porous support that supports the skin layer, and to a process for producing the composite semipermeable membrane.
- the composite semipermeable membranes are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage.
- the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc.
- Patent Document 1 A composite semipermeable membrane, in which a skin layer includes polyamides obtained by interfacial polymerization of polyfunctional aromatic amines and polyfunctional aromatic acid halides and is formed on a porous support, has been proposed.
- Patent Document 2 A composite semipermeable membrane, in which a skin layer includes a polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional alicyclic acid halide and is formed on a porous support, has been also proposed (Patent Document 2).
- the composite semipermeable membrane produced is preferably a dried composite semipermeable membrane.
- a composite semipermeable membrane having a skin layer formed on the surface of the porous support is dried, there has occurred a problem of deterioration of salt-blocking performance and permeation flux, compared with characteristics before drying.
- a technique in which a reverse osmosis membrane is dried after hydrophilization treatment for the purpose of solving the problem has been disclosed (Patent Document 3).
- a method of drying a composite membrane after immersion treatment in a solution of saccharides having a molecular weight of 1000 or less has been disclosed (Patent Document 4).
- Patent Document 5 In order to obtain a dried composite reverse osmosis membrane having outstanding water permeability, organic matter blocking performance, and salt-blocking performance, a method of performing heat drying treatment of a compound reverse osmosis membrane after contact to an aqueous solution at a temperature of 40 to 100° C. has been disclosed (Patent Document 5).
- Patent Document 1 Japanese Patent Application Laid-Open No. 02-187135
- Patent Document 2 Japanese Patent Application Laid-Open No. 62-121603
- Patent Document 3 Japanese Patent Application Laid-Open No. 2003-320224
- Patent Document 4 Patent No. 3015853 specification
- Patent Document 5 Japanese Patent Application Laid-Open No. 10-165789
- the present invention aims at providing a composite semipermeable membrane in which water permeability and salt-blocking rate cannot deteriorate by long-term storage, and at providing a process for producing the same.
- the present invention relates to a composite semipermeable membrane having a skin layer formed on the surface of a porous support, the skin layer including a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component, wherein the porous support contains at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers, in an amount of 95% by weight or more with respect to the whole composite semipermeable membrane.
- Reasons for deterioration with time of performances, such as water permeability and solute blocking property, of a composite semipermeable membrane include possible degradation of the composite semipermeable membrane by increase of bacillus, appearance of mold, structural change by drying at the time of storage, and chemical change by oxidation, etc.
- the composite semipermeable membrane of the present invention is characterized by including the above-described additives mainly in the porous support. For this reason, the composite semipermeable membrane of the present invention can minimize secondary adverse effect to the skin layer, and can exhibit characteristics of giving no deterioration in water permeability and salt-blocking rate by long-term storage without deterioration of performance of the skin layer.
- the composite semipermeable membrane of the present invention is preferred to be a dried composite semipermeable membrane from viewpoints of workability, preservability, stability of quality and performance.
- moisturizers are preferably of organic acid metal salts and/or inorganic acid metal salts.
- the organic acid metal salt preferably include at least one kind of organic acid alkali metal salt selected from the group consisting of alkali metal acetate, alkali metal lactate, and alkali metal glutamate.
- the alkali metal is preferably selected from sodium or potassium.
- the inorganic acid metal salt preferably includes at least one kind of inorganic acid alkali metal salt selected from the group consisting of alkali metal hydrogencarbonate, dialkali metal monohydrogen phosphate, monoalkali metal dihydrogen phosphate,
- the alkali metal is preferably selected from sodium or potassium.
- the present invention also relates to a process for producing a composite semipermeable membrane comprising the steps of: forming a skin layer including a polyamide resin obtained by reaction between a polyfunctional amine component and a polyfunctional acid halide component on the surface of a porous support; and performing a treatment with additives onto the porous support by contact of an aqueous solution including at least one kind of additives selected from the group consisting of an antioxidant, an antibacterial agent, an antifungal agent, and a moisturizer, to a face without the skin layer of the porous support.
- a skin layer containing a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component is formed on the surface of a porous support, and the porous support contains at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers in an amount of 95% by weight or more with respect to the total weight of the composite semipermeable membrane.
- the polyfunctional amine component is defined as a polyfunctional amine having two or more reactive amino groups, and includes aromatic, aliphatic, and alicyclic polyfunctional amines.
- the aromatic polyfunctional amines include, for example, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triamino benzene, 1,2,4-triamino benzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, xylylene diamine etc.
- the aliphatic polyfunctional amines include, for example, ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, n-phenylethylenediamine, etc.
- the alicyclic polyfunctional amines include, for example, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethyl piperazine, etc.
- polyfunctional amines may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having a higher salt-blocking property, it is preferred to use the aromatic polyfunctional amines.
- the polyfunctional acid halide component represents polyfunctional acid halides having two or more reactive carbonyl groups.
- the polyfunctional acid halides include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
- the aromatic polyfunctional acid halides include, for example trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonyl benzenedicarboxylic acid dichloride etc.
- the aliphatic polyfunctional acid halides include, for example, propanedicarboxylic acid dichloride, butane dicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propane tricarboxylic acid trichloride, butane tricarboxylic acid trichloride, pentane tricarboxylic acid trichloride, glutaryl halide, adipoyl halide etc.
- the alicyclic polyfunctional acid halides include, for example, cyclopropane tricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, tetrahydrofuran dicarboxylic acid dichloride, etc.
- polyfunctional acid halides may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having higher salt-blocking property, it is preferred to use aromatic polyfunctional acid halides. In addition, it is preferred to form a cross linked structure using polyfunctional acid halides having trivalency or more as at least a part of the polyfunctional acid halide components.
- polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acids etc., and polyhydric alcohols, such as sorbitol and glycerin, may be copolymerized.
- the porous support for supporting the skin layer is not especially limited as long as it has a function for supporting the skin layer, and usually ultrafiltration membrane having micro pores with an average pore size approximately 10 to 500 angstroms may preferably be used.
- Materials for formation of the porous support include various materials, for example, polyarylether sulfones, such as polysulfones and polyether sulfones; polyimides; polyvinylidene fluorides; etc., and polysulfones and polyarylether sulfones are especially preferably used from a viewpoint of chemical, mechanical, and thermal stability.
- the thickness of this porous support is usually approximately 25 to 125 ⁇ m, and preferably approximately 40 to 75 ⁇ m, but the thickness is not necessarily limited to them.
- the porous support may be reinforced with backing by cloths, nonwoven fabric, etc.
- Processes for forming the skin layer including the polyamide resin on the surface of the porous support is not in particular limited, and any publicly known methods may be used.
- the publicly known methods include an interfacial condensation method, a phase separation method, a thin film application method, etc.
- the interfacial condensation method is a method, wherein an amine aqueous solution containing a polyfunctional amine component, an organic solution containing a polyfunctional acid halide component are forced to contact together to form a skin layer by an interfacial polymerization, and then the obtained skin layer is laid on a porous support, and a method wherein a skin layer of a polyamide resin is directly formed on a porous support by the above-described interfacial polymerization on a porous support. Details, such as conditions of the interfacial condensation method, are described in Japanese Patent Application Laid-Open No. 58-24303, Japanese Patent Application Laid-Open No. 01-180208, and these known methods are suitably employable.
- a covering layer of aqueous solution made from the amine aqueous solution containing a polyfunctional amine components is formed on the porous support, then an interfacial polymerization is performed by contact with an organic solution containing a polyfunctional acid halide component, and the covering layer of aqueous solution, and then a skin layer is formed.
- the concentration of the polyfunctional amine component in the amine aqueous solution is not in particular limited, the concentration is preferably 0.1 to 5% by weight, and more preferably 0.5 to 2% by weight. Less than 0.1% by weight of the concentration of the polyfunctional amine component may easily cause defect such as pinhole. in the skin layer, leading to tendency of deterioration of salt-blocking property. On the other hand, the concentration of the polyfunctional amine component exceeding 5% by weight allows easy permeation of the polyfunctional amine component into the porous support to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- the concentration of the polyfunctional acid halide component in the organic solution is not in particular limited, it is preferably 0.01 to 5% by weight, and more preferably 0.05 to 3% by weight. Less than 0.01% by weight of the concentration of the polyfunctional acid halide component is apt to make the unreacted polyfunctional amine component remain, to cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-blocking property. On the other hand, the concentration exceeding 5% by weight of the polyfunctional acid halide component is apt to make the unreacted polyfunctional acid halide component remain, to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- the organic solvents used for the organic solution is not especially limited as long as they have small solubility to water, and do not cause degradation of the porous support, and dissolve the polyfunctional acid halide component.
- the organic solvents include saturated hydrocarbons, such as cyclohexane, heptane, octane, and nonane, halogenated hydrocarbons, such as 1,1,2-trichlorofluoroethane, etc. They are preferably saturated hydrocarbons having a boiling point of 300° C. or less, and more preferably 200° C. or less, or naphthene solvents.
- additives may be added to the amine aqueous solution or the organic solution in order to provide easy film production and to improve performance of the composite semipermeable membrane to be obtained.
- the additives include, for example, surfactants, such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate; basic compounds, such as sodium hydroxide, trisodium phosphate, triethylamine, etc. for removing hydrogen halides formed by polymerization; acylation catalysts; compounds having a solubility parameter of 8 to 14 (cal/cm 3 ) 1/2 described in Japanese Patent Application Laid-Open No. 08-224452.
- the period of time after application of the amine aqueous solution until application of the organic solution on the porous support depends on the composition and viscosity of the amine aqueous solution, and on the pore size of the surface layer of the porous support, and it is preferably 15 seconds or less, and more preferably 5 seconds or less.
- Application interval of the solution exceeding 15 seconds may allow permeation and diffusion of the amine aqueous solution to a deeper portion in the porous support, and possibly cause a large amount of the residual unreacted polyfunctional amine components in the porous support. In this case, removal of the unreacted polyfunctional amine component that has permeated to the deeper portion in the porous support is probably difficult even with a subsequent membrane washing treatment. Excessive amine aqueous solution may be removed after covering by the amine aqueous solution on the porous support.
- the heating temperature is more preferably 70 to 200° C., and especially preferably 100 to 150° C.
- the heating period of time is preferably approximately 30 seconds to 10 minutes, and more preferably approximately 40 seconds to 7 minutes.
- the thickness of the skin layer formed on the porous support is not in particular limited, and it is usually approximately 0.05 to 2 ⁇ m, and preferably 0.1 to 1 ⁇ m.
- a washed composite semipermeable membrane may be obtained by subsequently applying membrane washing treatment to the produced composite semipermeable membrane.
- the method of the membrane washing treatment is not in particular limited, and conventionally publicly known methods are employable.
- the following membrane washing treatment is especially preferably adopted.
- the acidic substance concerned is not in particular limited as long as it is water-soluble, and for example, inorganic acids, such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids, such as formic acid, acetic acid, and citric acid, may be mentioned.
- inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid
- organic acids such as formic acid, acetic acid, and citric acid
- the inorganic salt is not in particular limited as long as it is a inorganic salt that can form a complex with an amido group and, for example, lithium chloride (LiCl), calcium chloride (CaCl 2 ), rhodan calcium [Ca(SCN) 2 ], and rhodan potassium (KSCN) may be mentioned.
- LiCl lithium chloride
- CaCl 2 calcium chloride
- KSCN rhodan potassium
- the concentration of the acidic substance and/or the mineral salt in the aqueous solution is preferably 10 ppm to 50% by weight, more preferably 50 ppm to 20% by weight, and especially preferably 1 to 10% by weight.
- the concentration of the acidic substance and/or the mineral salt less than 10 ppm shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane.
- the concentration exceeding 50% by weight has a great influence on performance of the semipermeable membrane, and shows a tendency for permeation flux to deteriorate.
- the water-soluble organic substance is not in particular limited, as long as it does not give adverse effect on membrane performance, and the substance include, for example, monohydric alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; polyhydric alcohols, such as ethylene glycol, triethylene glycol, and glycerin; ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; polar solvents, such as dimethylformamide, dimethylacetamide, and n-methylpyrrolidone.
- monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol
- polyhydric alcohols such as ethylene glycol, triethylene glycol, and glycerin
- ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol
- the concentration of the water-soluble organic substance in the aqueous solution can be suitably adjusted for every material to be used, and it is approximately 1 to 90% by weight, more preferably 10 to 80% by weight, and especially preferably 20 to 50% by weight. Less than 1% by weight of the concentration of the water soluble organic substance shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane. On the other hand, the concentration exceeding 90% by weight has a great influence on performance of the semipermeable membrane, and shows a tendency for permeation flux to deteriorate.
- a reversed order of contact with solutions cannot fully remove the unreacted polyfunctional amine component.
- Firstly conducted contact of the composite semipermeable membrane with the solution containing the water soluble organic substance can accelerate hydrophilization and swelling of the membrane. Therefore, this process allows quick permeation of the aqueous solution including the acidic substance to an inner portion of the membrane in the subsequent contact treatment, and can increase washing effect.
- the concentration of the water soluble organic substance in the solution can be suitably adjusted for every materials to be used, and usually, it is 1 to 100% by weight, preferably 10 to 80% by weight, and more preferably 20 to 50% by weight. It is especially preferred to use the aqueous solution having the above described concentration.
- the concentration of the water soluble organic substance less than 1% by weight shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane.
- the concentration of the acidic substance in the aqueous solution is preferably 10 ppm to 50% by weight, more preferably 50 ppm to 20% by weight, and especially preferably 1 to 10% by weight.
- the concentration of the acidic substance less than 10 ppm shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane.
- the concentration exceeding 50% by weight has a great influence on the performance of the semipermeable membrane.
- examples of the method of contacting the solution to the composite semipermeable membrane include all methods, such as a dipping, a pressurized water flow, a spray, an application, and a showering, and the dipping and the pressurized water flow methods are preferably used in order to obtain sufficient effect of contacting.
- the contact period of time is not limited at all within a range acceptable by an allowable content of the unreacted polyfunctional amine component in the composite semipermeable membrane after the membrane washing treatment, and manufacturing restrictions, and any period of time may be adopted.
- the contact period of time cannot necessarily be specified, it is usually several seconds to tens of minutes, and preferably 10 seconds to 3 minutes. Since the amount of removal of the unreacted polyfunctional amine component reaches an equilibrium, removing effect does not necessarily improve even with longer contact period of time. When the contact period of time is excessively lengthened, there is conversely shown a tendency for the membrane performance and manufacturing efficiency to deteriorate.
- the contact temperature in particular will not be limited as long as the solution is in a temperature range allowing existence as a liquid, from a view point of removing effect of the unreacted polyfunctional amine component, of prevention of the membrane from deterioration, and of easiness of treatment etc.
- the contact temperature is preferably 10 to 90° C., more preferably 10 to 60° C., and especially preferably 10 to 45° C.
- the pressure is not in particular limited, as long as the pressure in use of this solution with respect to the semipermeable membrane is in a range acceptable by the semipermeable membrane and the physical strength of the members and the equipment for pressure application.
- the pressurized water flow is preferably performed at 0.1 to 10 MPa, and more preferably at 1.5 to 7.5 Mpa.
- the pressurized water flow at a pressure less than 0.1 Mpa shows a tendency of extending the contact period of time, in order to obtain necessary effect. And when exceeding 10 Mpa, compaction caused by the pressure is apt to decrease the permeation flux.
- the present invention needs application of treatment to the porous support with additives by inclusion of at least one kind of the additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers.
- Methods for inclusion of the additives in the porous support is not in particular limited, and preferred is a method for contact of an aqueous solution including at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers to a face that does not have the skin layer of the porous support of the unwashed or washed composite semipermeable membrane produced by the method described above.
- the antioxidant include, for example, sulfites, such as sodium sulfite, sodium hyposulfite, sodium bisulfite, potassium sulfite, potassium hydrogen hyposulfite; sulfur dioxide; citrates, such as isopropyl citrate; and Vitamins C, such as ascorbic acid, alkyl ascorbate, and sodium ascorbate.
- sulfites such as sodium sulfite, sodium hyposulfite, sodium bisulfite, potassium sulfite, potassium hydrogen hyposulfite
- sulfur dioxide such as isopropyl citrate
- citrates such as isopropyl citrate
- Vitamins C such as ascorbic acid, alkyl ascorbate, and sodium ascorbate.
- the antibacterial agents and antifungal agents include, for example, silver based compounds; copper based compounds; photocatalytic compounds; chitosans; and catechins, such as catechin, epicatechin, gallocatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, and epigallocatechin gallate.
- the moisturizer includes, for example, organic acid alkali metal salts, such as sodium acetate, potassium acetate, sodium lactate, potassium lactate, sodium glutamate, and potassium glutamate; organic acid alkaline earth metal salts, such as magnesium acetate, calcium acetate, magnesium lactate, calcium lactate, magnesium glutamate, and calcium glutamate; inorganic acid alkaline metal salts, such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, disodium monohydrogen phosphate, dipotassium monohydrogen phosphate, monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, sodium phosphate, potassium phosphate; inorganic acid alkaline earth metal salts, such as magnesium hydrogencarbonate, calcium hydrogencarbonate, magnesium carbonate, calcium carbonate, magnesium primary phosphate, calcium primary phosphate, magnesium secondary phosphate, calcium secondary phosphate, magnesium tertiary phosphate, calcium tertiary phosphate: alkali metal
- the concentration of the additives in the aqueous solution is not in particular limited, and it is preferably 100 ppm to 30% by weight, and more preferably 500 ppm to 10% by weight.
- the concentration of the additives less than 100 ppm does not sufficiently exhibit effect for controlling deterioration in water permeability and salt-blocking rate after long-term storage, showing a tendency of requiring a longer processing time.
- the concentration of additives exceeding 30% by weight causes increase in costs, showing a tendency of giving an adverse effect to film performance.
- Methods for contacting the aqueous solution containing the additives in the porous support includes, for example, application method, spraying method of the aqueous solution containing the additives, or contact method with a vapor of the additives, etc., and is not limited to them, and publicly known method are employable.
- immersion of the composite semipermeable membrane in the aqueous solution containing the additives immersion of the composite semipermeable membrane is performed in a state where the skin layer is closely contacted to a roll, in order to realize inclusion of most of the additives in the porous support.
- the aqueous solution is preferably applied to only the surface of the porous support in order to prevent deterioration of performance of the skin layer.
- the temperature of the aqueous solution is not in particular limited as long as the solution is in a temperature range that allows existence of the aqueous solution as a liquid, from viewpoints of exhibition of target effect, prevention of the membrane from deterioration, easiness of treatment, etc., it is preferably 10 to 90° C., more preferably 10 to 60° C., especially preferably 10 to 45° C.
- Excessive aqueous solution may be removed after contact of the aqueous solution containing the additives in the composite semipermeable membrane by the above-described method.
- Removal methods include, for example, a contact type removal method with blades, made of plastics or rubbers, a non-contact type removal method with air knife, etc.
- the content of the additives in the porous support may be suitably adjusted based on the kinds of additives, the grade of targeted effect etc., and, it is preferably 1 mg/m 2 to 100 g/m 2 , and more preferably 10 mg/m 2 to 10 g/m 2 for sufficient expression of the targeted effect.
- the content of the additives less than 1 mg/m 2 shows a tendency of failing to exhibit sufficient deterioration inhibitory effect of the water permeability and the salt-blocking rate after long-term storage.
- the content exceeding 100 g/m 2 does not vary deterioration inhibitory effect of water permeability and salt-blocking rate after long-term storage for the increase of content, leading to possible lack of stability of water quality of the target compound caused by elution of the additives.
- porous support It is necessary for the porous support to have 95% by weight or more of content of the additives with respect to the whole composite semipermeable membrane, and preferably 96% by weight or more.
- the amount and content of the additives included in the whole composite semipermeable membrane and porous support may be measured by the following method.
- a composite semipermeable membrane is cut into a predetermined size and is separated into a skin layer and a porous support.
- a method of separation for example, a method wherein a pressure sensitive adhesive tape attached on the surface of the skin layer of the composite semipermeable membrane having a size of 50 mm ⁇ 50 mm is separated after slight friction may be mentioned.
- the skin layer and a microporous layer on an uppermost surface of the porous support is separated together with the pressure sensitive adhesive tape. The remaining portion that does not attach to the tape is defined as a porous support.
- the separated porous support is boiled in a specified amount of pure water, the obtained extracted liquid is analyzed using publicly known methods of analysis, such as ion chromatograph analysis, GC analysis, absorption spectrometry, and refractive index analysis to determine the amount of the additives in the porous support. Furthermore, the composite semipermeable membrane cut into a predetermined size is also measured for the amount of additives in a similar way. The two obtained values are substituted for the following expression, and the content of additives in the porous support is calculated.
- Contain rate (%) [(contain in porous support)/(contain in composite semipermeable membrane)] ⁇ 100
- the composite semipermeable membrane, to which the treatment with additives is applied with the method described above may be dried to obtain a dried composite semipermeable membrane.
- the temperature of drying treatment is not in particular limited, and it is preferably 20 to 150° C., and more preferably 40 to 130° C.
- the temperature less than 20° C. needs an excessively long drying treatment period, and likely gives insufficient drying.
- the temperature exceeding 150° C. shows a tendency to cause decrease of membrane performance due to structural change of the membrane caused by heat.
- the period of the drying treatment is not in particular limited, and it is preferred that drying is performed until the amount of solvents in the dried composite semipermeable membrane is 5% by weight or less.
- the membrane in the case of production of a dry spiral element, may be processed into a spiral shape in any stage from production of the above-described skin layer to drying treatment.
- the composite semipermeable membrane may be processed into a spiral shape before the washing treatment of the membrane to produce a membrane unit.
- the composite semipermeable membrane may be processed into a spiral shape after treatment with additives to produce the membrane unit, and the composite semipermeable membrane may be processed into a spiral shape before the drying treatment to produce the membrane unit.
- the membrane unit may be produced by simultaneous application of the washing treatment and the treatment with additives to the produced membrane unit.
- the same method as the one described above may be mentioned as the treatment method.
- the dried composite semipermeable membrane and dry spiral element produced by such a method have extremely small content of unreacted components.
- a permeated liquid separated and refined or a target compounds condensed by using the composite semipermeable membrane, etc. includes extremely small amount of impurities, and has a high purity.
- the dried composite semipermeable membrane and the dry spiral element of the present invention have outstanding workability and preservability because it is a dry type.
- the dried composite semipermeable membrane and the dry spiral element of the present invention are a dry type, they exhibit water permeability and salt-blocking rate equivalent to that of the wet type composite semipermeable membrane and spiral element, causing no deterioration of performance after long term storage.
- a dried composite semipermeable membrane produced with a shape of a flat film is cut into a predetermined shape and size, and is set to a cell for flat film evaluation.
- An aqueous solution containing NaCl of about 1500 mg/L and adjusted to a pH of 6.5 to 7.5 with NaOH was forced to contact to a supply side, and a permeation side of the membrane at a differential pressure of 1.5 MPa at 25° C.
- a permeation velocity and an electric conductivity of the permeated water obtained by this operation were measured for, and a permeation flux (m 3 /m 2 ⁇ d) and a salt-blocking rate (%) were calculated.
- the correlation (calibration curve) of the NaCl concentration and the electric conductivity of the aqueous solution was beforehand made, and the salt-blocking rate was calculated by a following equation.
- Salt-blocking rate (%) ⁇ 1 ⁇ (NaCl concentration [mg/L] in permeated liquid)/(NaCl concentration [mg/L] in supply solution) ⁇ 100
- a prepared dried composite semipermeable membrane was cut into a size of 1 cm ⁇ 3 cm to obtain samples A and B.
- a pressure sensitive adhesive tape (made by NITTO DENKO CORPORATION, No. 31-B) was attached on the surface of the skin layer of sample A, and the pressure sensitive adhesive tape was separated after light friction. The skin layer and the microporous layer on the uppermost surface of the porous support were removed together with the pressure sensitive adhesive tape. Subsequently, the separated porous support was immersed into 50 cc of pure water, and was boiled at 120° C. for 1 hour in a sealed state. The obtained extracted liquid was subjected to analysis with ion chromatography to obtain an amount of additives in the extracted liquid. Determination of the additives was performed by comparison to a calibration curve prepared using standard solutions beforehand prepared to several kinds of prescribed concentrations. Measurement conditions are shown as follows.
- Isolation column Ion Pac AS15 (4 mm ⁇ 250 mm)
- sample B was immersed into 50 cc of pure water, and was boiled for 1 hour at 120° C. in a sealed state. Subsequently, the extracted liquid was subjected to analysis under the same conditions as described above to obtain an amount of additives in the extracted liquid. The two obtained value were substituted for the following expression, and the content rate of the additives in the porous support was calculated.
- Content rate(%) [(content in porous support)/(content in composite semipermeable membrane)] ⁇ 100
- a dope for manufacturing a membrane containing 18% by weight of a polysulfone (produced by Solvay, P-3500) dissolved in N,N-dimethylformamide (DMF) was uniformly applied so that it might give 200 ⁇ m in thickness in wet condition on a nonwoven fabric base material. Subsequently, it was immediately solidified by immersion in water at 40 to 50° C., and DMF as a solvent was completely extracted by washing. Thus a porous support having a polysulfone microporous layer was produced on the nonwoven fabric base material.
- aqueous solution of amines containing 3% by weight of m-phenylenediamine, 3% by weight of triethylamine, and 6% by weight of camphorsulfonic acid was applied to the porous support, and then an excessive amount of the amine aqueous solution was removed to form a covering layer of the aqueous solution.
- an isooctane solution containing 0.2% by weight of trimesic acid chlorides was applied to the surface of the covering layer of the aqueous solution. Then, the excessive solution was removed, and the material was kept standing for 3 minutes in a hot air dryer at 120° C.
- an unwashed composite semipermeable membrane was obtained.
- the unwashed composite semipermeable membrane was immersed for 10 minutes at 50° C. in pure water for membrane washing treatment to produce a washed composite semipermeable membrane.
- a sodium acetate aqueous solution (concentration: 5% by weight) was applied to the surface (a face which does not have a formed skin layer) of the porous support of the washed composite semipermeable membrane under a condition of 30 cc/m 2 for treatment with additives.
- treated composite semipermeable membrane stood to remove the excessive sodium acetate aqueous solution, and then was kept standing for 5 minutes in a hot air dryer at 80° C., finally producing a dried composite semipermeable membrane.
- a dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium lactate aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- a dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium hydrogen carbonate aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- a composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium bisulfite aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution, and not drying after treatment with additives in example 1.
- a dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium bisulfite aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- a washed composite semipermeable membrane was produced in the same manner as in example 1. Subsequently, the washed composite semipermeable membrane was immersed in a sodium acetate aqueous solution (concentration: 5% by weight) for 1 minute at 25° C., and treatment with additives was applied. Then, the treated composite semipermeable membrane stood and thus the excessive sodium acetate aqueous solution was removed, and then was kept standing for 5 minutes in a hot air dryer at 80° C. to produce a dried composite semipermeable membrane.
- a sodium acetate aqueous solution concentration: 5% by weight
- a washed composite semipermeable membrane was produced in the same manner as in example 1. Subsequently, a sodium acetate aqueous solution (concentration: 5% by weight) 25° C. was applied on the surface of the skin layer of the washed composite semipermeable membrane under a condition of 30 cc/m 2 , the surface was uniformly smoothed using a PET film and then treatment with additives was applied. Then, the treated composite semipermeable membrane stood and thus the excessive sodium acetate aqueous solution was removed, and next was kept standing for 5 minutes in a hot air dryer at 80° C. to produce a dried composite semipermeable membrane.
- a dried composite semipermeable membrane was produced in the same manner as in example 1, except for not performing treatment with additives in example 1.
- a washed composite semipermeable membrane was produced in the same manner as in example 1. Appearance of mold in the skin layer was observed after storage for one week of the washed composite semipermeable membrane.
- An unwashed composite semipermeable membrane was produced in the same manner as in example 1.
- a composite semipermeable membrane having water permeability and salt-blocking rate without deterioration after long-term storage may be obtained by mainly including specific additives mainly in a porous support.
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Abstract
The present invention aims at providing a composite semipermeable membrane in which water permeability and salt-blocking rate cannot deteriorate by long-term storage, and at providing a process for producing the same. The present invention relates to a composite semipermeable membrane having a skin layer formed on the surface of a porous support, the skin layer including a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component, wherein the porous support contains at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers, in an amount of 95% by weight or more with respect to the whole composite semipermeable membrane.
Description
- The present invention relates to a composite semipermeable membrane having a skin layer which includes a polyamide resin and a porous support that supports the skin layer, and to a process for producing the composite semipermeable membrane. The composite semipermeable membranes are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage. Furthermore, the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc.
- Recently, a composite semipermeable membrane, in which a skin layer includes polyamides obtained by interfacial polymerization of polyfunctional aromatic amines and polyfunctional aromatic acid halides and is formed on a porous support, has been proposed (Patent Document 1). A composite semipermeable membrane, in which a skin layer includes a polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional alicyclic acid halide and is formed on a porous support, has been also proposed (Patent Document 2).
- However, when it is needed to obtain a target compounds condensed or refined as permeated liquid or non-permeated liquids using conventional composite semipermeable membranes in actual cases, there has occurred a problem of unstable water quality of target compounds due to deterioration with time of performances, such as water permeability and solute blocking property, of the composite semipermeable membranes.
- On the other hand, from viewpoints of subsequent workability, preservability, etc., the composite semipermeable membrane produced is preferably a dried composite semipermeable membrane. However, when a composite semipermeable membrane having a skin layer formed on the surface of the porous support is dried, there has occurred a problem of deterioration of salt-blocking performance and permeation flux, compared with characteristics before drying. A technique in which a reverse osmosis membrane is dried after hydrophilization treatment for the purpose of solving the problem has been disclosed (Patent Document 3). Furthermore, a method of drying a composite membrane after immersion treatment in a solution of saccharides having a molecular weight of 1000 or less has been disclosed (Patent Document 4).
- In order to obtain a dried composite reverse osmosis membrane having outstanding water permeability, organic matter blocking performance, and salt-blocking performance, a method of performing heat drying treatment of a compound reverse osmosis membrane after contact to an aqueous solution at a temperature of 40 to 100° C. has been disclosed (Patent Document 5).
- However, various kinds of above-described treatments, for the purpose of control of deterioration of the performance and quality, applied to a composite semipermeable membrane having a skin layer formed on the surface of a porous support conversely promotes deterioration of salt-blocking performance and permeation flux depending on kinds of chemicals used, treatment method, etc., in some case.
- [Patent Document 1] Japanese Patent Application Laid-Open No. 02-187135
- [Patent Document 2] Japanese Patent Application Laid-Open No. 62-121603
- [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-320224
- [Patent Document 4] Patent No. 3015853 specification
- [Patent Document 5] Japanese Patent Application Laid-Open No. 10-165789
- The present invention aims at providing a composite semipermeable membrane in which water permeability and salt-blocking rate cannot deteriorate by long-term storage, and at providing a process for producing the same.
- As a result of wholehearted investigation conducted by the present inventors for attaining the above-described objectives, it has been found out that inclusion of specific additives in a porous support after formation of a skin layer can provide a composite semipermeable membrane in which water permeability and salt-blocking rate cannot deteriorate after long-term storage, leading to completion of the present invention.
- That is, the present invention relates to a composite semipermeable membrane having a skin layer formed on the surface of a porous support, the skin layer including a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component, wherein the porous support contains at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers, in an amount of 95% by weight or more with respect to the whole composite semipermeable membrane.
- Reasons for deterioration with time of performances, such as water permeability and solute blocking property, of a composite semipermeable membrane include possible degradation of the composite semipermeable membrane by increase of bacillus, appearance of mold, structural change by drying at the time of storage, and chemical change by oxidation, etc.
- Furthermore, various treatments, as applied in various treatments for conventional composite semipermeable membranes, by entire immersion, etc., of the composite semipermeable membranes with a flat film form or with a processed spiral element form allow expression of objective function by the treatment agent, but at the same time the treatment possibly gives unpreferable modification, such as swelling, hydrolysis, denaturation, etc., to the skin layer, and some treatment measure may give physical damage to the skin layer. Such possibilities are considered to be one of the causes of degradation of the composite semipermeable membrane.
- The composite semipermeable membrane of the present invention is characterized by including the above-described additives mainly in the porous support. For this reason, the composite semipermeable membrane of the present invention can minimize secondary adverse effect to the skin layer, and can exhibit characteristics of giving no deterioration in water permeability and salt-blocking rate by long-term storage without deterioration of performance of the skin layer.
- The composite semipermeable membrane of the present invention is preferred to be a dried composite semipermeable membrane from viewpoints of workability, preservability, stability of quality and performance.
- In the present invention, moisturizers are preferably of organic acid metal salts and/or inorganic acid metal salts.
- The organic acid metal salt preferably include at least one kind of organic acid alkali metal salt selected from the group consisting of alkali metal acetate, alkali metal lactate, and alkali metal glutamate. The alkali metal is preferably selected from sodium or potassium.
- In addition, the inorganic acid metal salt preferably includes at least one kind of inorganic acid alkali metal salt selected from the group consisting of alkali metal hydrogencarbonate, dialkali metal monohydrogen phosphate, monoalkali metal dihydrogen phosphate, The alkali metal is preferably selected from sodium or potassium.
- Although a prolonged moisturing treatment is needed in order to obtain necessary effect when using as surfactants and saccharides as a moisturizer, use of the organic acid metal salts and/or inorganic acid metal salts can give sufficient effect by extremely short-time moisturing treatment, leading to great advantage on the productive process. In addition, although use of the surfactants or saccharides as a moisturizer may give poor effect depending on drying conditions (temperature, period of time, etc.), use of the organic acid metal salts and/or inorganic acid metal salts can provide sufficient effect independently of dry conditions, resulting in great advantage on the productive processes.
- The present invention also relates to a process for producing a composite semipermeable membrane comprising the steps of: forming a skin layer including a polyamide resin obtained by reaction between a polyfunctional amine component and a polyfunctional acid halide component on the surface of a porous support; and performing a treatment with additives onto the porous support by contact of an aqueous solution including at least one kind of additives selected from the group consisting of an antioxidant, an antibacterial agent, an antifungal agent, and a moisturizer, to a face without the skin layer of the porous support.
- The embodiments of the invention will, hereinafter, be described. In the composite semipermeable membrane of the present invention, a skin layer containing a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component is formed on the surface of a porous support, and the porous support contains at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers in an amount of 95% by weight or more with respect to the total weight of the composite semipermeable membrane.
- The polyfunctional amine component is defined as a polyfunctional amine having two or more reactive amino groups, and includes aromatic, aliphatic, and alicyclic polyfunctional amines.
- The aromatic polyfunctional amines include, for example, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triamino benzene, 1,2,4-triamino benzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, xylylene diamine etc.
- The aliphatic polyfunctional amines include, for example, ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, n-phenylethylenediamine, etc.
- The alicyclic polyfunctional amines include, for example, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethyl piperazine, etc.
- These polyfunctional amines may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having a higher salt-blocking property, it is preferred to use the aromatic polyfunctional amines.
- The polyfunctional acid halide component represents polyfunctional acid halides having two or more reactive carbonyl groups.
- The polyfunctional acid halides include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
- The aromatic polyfunctional acid halides include, for example trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonyl benzenedicarboxylic acid dichloride etc.
- The aliphatic polyfunctional acid halides include, for example, propanedicarboxylic acid dichloride, butane dicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propane tricarboxylic acid trichloride, butane tricarboxylic acid trichloride, pentane tricarboxylic acid trichloride, glutaryl halide, adipoyl halide etc.
- The alicyclic polyfunctional acid halides include, for example, cyclopropane tricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, tetrahydrofuran dicarboxylic acid dichloride, etc.
- These polyfunctional acid halides may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having higher salt-blocking property, it is preferred to use aromatic polyfunctional acid halides. In addition, it is preferred to form a cross linked structure using polyfunctional acid halides having trivalency or more as at least a part of the polyfunctional acid halide components.
- Furthermore, in order to improve performance of the skin layer including the polyamide resin, polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acids etc., and polyhydric alcohols, such as sorbitol and glycerin, may be copolymerized.
- The porous support for supporting the skin layer is not especially limited as long as it has a function for supporting the skin layer, and usually ultrafiltration membrane having micro pores with an average pore size approximately 10 to 500 angstroms may preferably be used. Materials for formation of the porous support include various materials, for example, polyarylether sulfones, such as polysulfones and polyether sulfones; polyimides; polyvinylidene fluorides; etc., and polysulfones and polyarylether sulfones are especially preferably used from a viewpoint of chemical, mechanical, and thermal stability. The thickness of this porous support is usually approximately 25 to 125 μm, and preferably approximately 40 to 75 μm, but the thickness is not necessarily limited to them. The porous support may be reinforced with backing by cloths, nonwoven fabric, etc.
- Processes for forming the skin layer including the polyamide resin on the surface of the porous support is not in particular limited, and any publicly known methods may be used. For example, the publicly known methods include an interfacial condensation method, a phase separation method, a thin film application method, etc. The interfacial condensation method is a method, wherein an amine aqueous solution containing a polyfunctional amine component, an organic solution containing a polyfunctional acid halide component are forced to contact together to form a skin layer by an interfacial polymerization, and then the obtained skin layer is laid on a porous support, and a method wherein a skin layer of a polyamide resin is directly formed on a porous support by the above-described interfacial polymerization on a porous support. Details, such as conditions of the interfacial condensation method, are described in Japanese Patent Application Laid-Open No. 58-24303, Japanese Patent Application Laid-Open No. 01-180208, and these known methods are suitably employable.
- In the present invention, it is especially preferred that a covering layer of aqueous solution made from the amine aqueous solution containing a polyfunctional amine components is formed on the porous support, then an interfacial polymerization is performed by contact with an organic solution containing a polyfunctional acid halide component, and the covering layer of aqueous solution, and then a skin layer is formed.
- In the interfacial-polymerization method, although the concentration of the polyfunctional amine component in the amine aqueous solution is not in particular limited, the concentration is preferably 0.1 to 5% by weight, and more preferably 0.5 to 2% by weight. Less than 0.1% by weight of the concentration of the polyfunctional amine component may easily cause defect such as pinhole. in the skin layer, leading to tendency of deterioration of salt-blocking property. On the other hand, the concentration of the polyfunctional amine component exceeding 5% by weight allows easy permeation of the polyfunctional amine component into the porous support to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- Although the concentration of the polyfunctional acid halide component in the organic solution is not in particular limited, it is preferably 0.01 to 5% by weight, and more preferably 0.05 to 3% by weight. Less than 0.01% by weight of the concentration of the polyfunctional acid halide component is apt to make the unreacted polyfunctional amine component remain, to cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-blocking property. On the other hand, the concentration exceeding 5% by weight of the polyfunctional acid halide component is apt to make the unreacted polyfunctional acid halide component remain, to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- The organic solvents used for the organic solution is not especially limited as long as they have small solubility to water, and do not cause degradation of the porous support, and dissolve the polyfunctional acid halide component. For example, the organic solvents include saturated hydrocarbons, such as cyclohexane, heptane, octane, and nonane, halogenated hydrocarbons, such as 1,1,2-trichlorofluoroethane, etc. They are preferably saturated hydrocarbons having a boiling point of 300° C. or less, and more preferably 200° C. or less, or naphthene solvents.
- Various kinds of additives may be added to the amine aqueous solution or the organic solution in order to provide easy film production and to improve performance of the composite semipermeable membrane to be obtained. The additives include, for example, surfactants, such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate; basic compounds, such as sodium hydroxide, trisodium phosphate, triethylamine, etc. for removing hydrogen halides formed by polymerization; acylation catalysts; compounds having a solubility parameter of 8 to 14 (cal/cm3)1/2 described in Japanese Patent Application Laid-Open No. 08-224452.
- The period of time after application of the amine aqueous solution until application of the organic solution on the porous support depends on the composition and viscosity of the amine aqueous solution, and on the pore size of the surface layer of the porous support, and it is preferably 15 seconds or less, and more preferably 5 seconds or less. Application interval of the solution exceeding 15 seconds may allow permeation and diffusion of the amine aqueous solution to a deeper portion in the porous support, and possibly cause a large amount of the residual unreacted polyfunctional amine components in the porous support. In this case, removal of the unreacted polyfunctional amine component that has permeated to the deeper portion in the porous support is probably difficult even with a subsequent membrane washing treatment. Excessive amine aqueous solution may be removed after covering by the amine aqueous solution on the porous support.
- In the present invention, after the contact with the covering layer of aqueous solution and the organic solution including the amine aqueous solution, it is preferred to remove the excessive organic solution on the porous support, and to dry the formed membrane on the porous support by heating at a temperature of 70° C. or more, forming the skin layer. Heat-treatment of the formed membrane can improve the mechanical strength, heat-resisting property, etc. The heating temperature is more preferably 70 to 200° C., and especially preferably 100 to 150° C. The heating period of time is preferably approximately 30 seconds to 10 minutes, and more preferably approximately 40 seconds to 7 minutes.
- The thickness of the skin layer formed on the porous support is not in particular limited, and it is usually approximately 0.05 to 2 μm, and preferably 0.1 to 1 μm.
- In the present invention, a washed composite semipermeable membrane may be obtained by subsequently applying membrane washing treatment to the produced composite semipermeable membrane. The method of the membrane washing treatment is not in particular limited, and conventionally publicly known methods are employable. The following membrane washing treatment is especially preferably adopted.
- 1) Method of washing the membrane by contact of the composite semipermeable membrane with pure water or ion exchange water.
- 2) Method of washing the membrane by contact of the composite semipermeable membrane with an aqueous solution containing an acidic substance and/or an inorganic salt, and an water-soluble organic substance.
- The acidic substance concerned is not in particular limited as long as it is water-soluble, and for example, inorganic acids, such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids, such as formic acid, acetic acid, and citric acid, may be mentioned.
- The inorganic salt is not in particular limited as long as it is a inorganic salt that can form a complex with an amido group and, for example, lithium chloride (LiCl), calcium chloride (CaCl2), rhodan calcium [Ca(SCN)2], and rhodan potassium (KSCN) may be mentioned.
- The concentration of the acidic substance and/or the mineral salt in the aqueous solution is preferably 10 ppm to 50% by weight, more preferably 50 ppm to 20% by weight, and especially preferably 1 to 10% by weight. The concentration of the acidic substance and/or the mineral salt less than 10 ppm shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane. On the other hand, the concentration exceeding 50% by weight has a great influence on performance of the semipermeable membrane, and shows a tendency for permeation flux to deteriorate.
- The water-soluble organic substance is not in particular limited, as long as it does not give adverse effect on membrane performance, and the substance include, for example, monohydric alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; polyhydric alcohols, such as ethylene glycol, triethylene glycol, and glycerin; ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; polar solvents, such as dimethylformamide, dimethylacetamide, and n-methylpyrrolidone.
- In view of the suppression effect of deterioration of removal performance and membrane performance of the unreacted polyfunctional amine component, the concentration of the water-soluble organic substance in the aqueous solution can be suitably adjusted for every material to be used, and it is approximately 1 to 90% by weight, more preferably 10 to 80% by weight, and especially preferably 20 to 50% by weight. Less than 1% by weight of the concentration of the water soluble organic substance shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane. On the other hand, the concentration exceeding 90% by weight has a great influence on performance of the semipermeable membrane, and shows a tendency for permeation flux to deteriorate.
- 3) A method of, first of all, making the composite semipermeable membrane contact with a solution including the water soluble organic substance, then making the semipermeable membrane contact with an aqueous solution containing the acidic substance to wash the membrane.
- A reversed order of contact with solutions cannot fully remove the unreacted polyfunctional amine component. Firstly conducted contact of the composite semipermeable membrane with the solution containing the water soluble organic substance can accelerate hydrophilization and swelling of the membrane. Therefore, this process allows quick permeation of the aqueous solution including the acidic substance to an inner portion of the membrane in the subsequent contact treatment, and can increase washing effect.
- In consideration of the suppression effect of deterioration of removal performance and membrane performance of the unreacted polyfunctional amine component, the concentration of the water soluble organic substance in the solution can be suitably adjusted for every materials to be used, and usually, it is 1 to 100% by weight, preferably 10 to 80% by weight, and more preferably 20 to 50% by weight. It is especially preferred to use the aqueous solution having the above described concentration. The concentration of the water soluble organic substance less than 1% by weight shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane.
- The concentration of the acidic substance in the aqueous solution is preferably 10 ppm to 50% by weight, more preferably 50 ppm to 20% by weight, and especially preferably 1 to 10% by weight. The concentration of the acidic substance less than 10 ppm shows a tendency of making difficult efficient removal of the unreacted polyfunctional amine component from the semipermeable membrane. On the other hand, the concentration exceeding 50% by weight has a great influence on the performance of the semipermeable membrane.
- In the membrane washing methods 1) to 3) described above, examples of the method of contacting the solution to the composite semipermeable membrane include all methods, such as a dipping, a pressurized water flow, a spray, an application, and a showering, and the dipping and the pressurized water flow methods are preferably used in order to obtain sufficient effect of contacting.
- The contact period of time is not limited at all within a range acceptable by an allowable content of the unreacted polyfunctional amine component in the composite semipermeable membrane after the membrane washing treatment, and manufacturing restrictions, and any period of time may be adopted. Although the contact period of time cannot necessarily be specified, it is usually several seconds to tens of minutes, and preferably 10 seconds to 3 minutes. Since the amount of removal of the unreacted polyfunctional amine component reaches an equilibrium, removing effect does not necessarily improve even with longer contact period of time. When the contact period of time is excessively lengthened, there is conversely shown a tendency for the membrane performance and manufacturing efficiency to deteriorate. Although the contact temperature in particular will not be limited as long as the solution is in a temperature range allowing existence as a liquid, from a view point of removing effect of the unreacted polyfunctional amine component, of prevention of the membrane from deterioration, and of easiness of treatment etc. the contact temperature is preferably 10 to 90° C., more preferably 10 to 60° C., and especially preferably 10 to 45° C.
- In the contact of the solution by the pressurized water flow method, the pressure is not in particular limited, as long as the pressure in use of this solution with respect to the semipermeable membrane is in a range acceptable by the semipermeable membrane and the physical strength of the members and the equipment for pressure application. The pressurized water flow is preferably performed at 0.1 to 10 MPa, and more preferably at 1.5 to 7.5 Mpa. The pressurized water flow at a pressure less than 0.1 Mpa shows a tendency of extending the contact period of time, in order to obtain necessary effect. And when exceeding 10 Mpa, compaction caused by the pressure is apt to decrease the permeation flux.
- The present invention needs application of treatment to the porous support with additives by inclusion of at least one kind of the additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers. Methods for inclusion of the additives in the porous support is not in particular limited, and preferred is a method for contact of an aqueous solution including at least one kind of additives selected from the group consisting of antioxidants, antibacterial agents, antifungal agents, and moisturizers to a face that does not have the skin layer of the porous support of the unwashed or washed composite semipermeable membrane produced by the method described above.
- The antioxidant include, for example, sulfites, such as sodium sulfite, sodium hyposulfite, sodium bisulfite, potassium sulfite, potassium hydrogen hyposulfite; sulfur dioxide; citrates, such as isopropyl citrate; and Vitamins C, such as ascorbic acid, alkyl ascorbate, and sodium ascorbate.
- The antibacterial agents and antifungal agents include, for example, silver based compounds; copper based compounds; photocatalytic compounds; chitosans; and catechins, such as catechin, epicatechin, gallocatechin, epigallocatechin, catechin gallate, epicatechin gallate, gallocatechin gallate, and epigallocatechin gallate.
- The moisturizer includes, for example, organic acid alkali metal salts, such as sodium acetate, potassium acetate, sodium lactate, potassium lactate, sodium glutamate, and potassium glutamate; organic acid alkaline earth metal salts, such as magnesium acetate, calcium acetate, magnesium lactate, calcium lactate, magnesium glutamate, and calcium glutamate; inorganic acid alkaline metal salts, such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, disodium monohydrogen phosphate, dipotassium monohydrogen phosphate, monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, sodium phosphate, potassium phosphate; inorganic acid alkaline earth metal salts, such as magnesium hydrogencarbonate, calcium hydrogencarbonate, magnesium carbonate, calcium carbonate, magnesium primary phosphate, calcium primary phosphate, magnesium secondary phosphate, calcium secondary phosphate, magnesium tertiary phosphate, calcium tertiary phosphate: alkali metal halides, such as sodium chloride; alkali earth metal halides, such as magnesium chloride; surfactants, such as sodium lauryl sulfate, lauryl potassium sulfate, sodium alkyl benzene sulfonate, and potassium alkylbenzene sulfonate; saccharides, such as glucose and saccharose; amino acids, such as glycine and leucine etc.
- The concentration of the additives in the aqueous solution is not in particular limited, and it is preferably 100 ppm to 30% by weight, and more preferably 500 ppm to 10% by weight. The concentration of the additives less than 100 ppm does not sufficiently exhibit effect for controlling deterioration in water permeability and salt-blocking rate after long-term storage, showing a tendency of requiring a longer processing time. On the other hand, the concentration of additives exceeding 30% by weight causes increase in costs, showing a tendency of giving an adverse effect to film performance.
- Methods for contacting the aqueous solution containing the additives in the porous support includes, for example, application method, spraying method of the aqueous solution containing the additives, or contact method with a vapor of the additives, etc., and is not limited to them, and publicly known method are employable. Alternatively, in the case of immersion of the composite semipermeable membrane in the aqueous solution containing the additives, immersion of the composite semipermeable membrane is performed in a state where the skin layer is closely contacted to a roll, in order to realize inclusion of most of the additives in the porous support.
- In the case of application of an aqueous solution containing additives to the composite semipermeable membrane, the aqueous solution is preferably applied to only the surface of the porous support in order to prevent deterioration of performance of the skin layer.
- Although the temperature of the aqueous solution is not in particular limited as long as the solution is in a temperature range that allows existence of the aqueous solution as a liquid, from viewpoints of exhibition of target effect, prevention of the membrane from deterioration, easiness of treatment, etc., it is preferably 10 to 90° C., more preferably 10 to 60° C., especially preferably 10 to 45° C.
- Excessive aqueous solution may be removed after contact of the aqueous solution containing the additives in the composite semipermeable membrane by the above-described method. Removal methods include, for example, a contact type removal method with blades, made of plastics or rubbers, a non-contact type removal method with air knife, etc.
- The content of the additives in the porous support may be suitably adjusted based on the kinds of additives, the grade of targeted effect etc., and, it is preferably 1 mg/m2 to 100 g/m2, and more preferably 10 mg/m2 to 10 g/m2 for sufficient expression of the targeted effect. The content of the additives less than 1 mg/m2 shows a tendency of failing to exhibit sufficient deterioration inhibitory effect of the water permeability and the salt-blocking rate after long-term storage. On the other hand, the content exceeding 100 g/m2 does not vary deterioration inhibitory effect of water permeability and salt-blocking rate after long-term storage for the increase of content, leading to possible lack of stability of water quality of the target compound caused by elution of the additives.
- It is necessary for the porous support to have 95% by weight or more of content of the additives with respect to the whole composite semipermeable membrane, and preferably 96% by weight or more.
- The amount and content of the additives included in the whole composite semipermeable membrane and porous support may be measured by the following method.
- A composite semipermeable membrane is cut into a predetermined size and is separated into a skin layer and a porous support. As a method of separation, for example, a method wherein a pressure sensitive adhesive tape attached on the surface of the skin layer of the composite semipermeable membrane having a size of 50 mm×50 mm is separated after slight friction may be mentioned. By this method, the skin layer and a microporous layer on an uppermost surface of the porous support is separated together with the pressure sensitive adhesive tape. The remaining portion that does not attach to the tape is defined as a porous support. Subsequently, the separated porous support is boiled in a specified amount of pure water, the obtained extracted liquid is analyzed using publicly known methods of analysis, such as ion chromatograph analysis, GC analysis, absorption spectrometry, and refractive index analysis to determine the amount of the additives in the porous support. Furthermore, the composite semipermeable membrane cut into a predetermined size is also measured for the amount of additives in a similar way. The two obtained values are substituted for the following expression, and the content of additives in the porous support is calculated.
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Contain rate (%)=[(contain in porous support)/(contain in composite semipermeable membrane)]×100 - In the present invention, subsequently, the composite semipermeable membrane, to which the treatment with additives is applied with the method described above, may be dried to obtain a dried composite semipermeable membrane.
- The temperature of drying treatment is not in particular limited, and it is preferably 20 to 150° C., and more preferably 40 to 130° C. The temperature less than 20° C. needs an excessively long drying treatment period, and likely gives insufficient drying. The temperature exceeding 150° C. shows a tendency to cause decrease of membrane performance due to structural change of the membrane caused by heat.
- The period of the drying treatment is not in particular limited, and it is preferred that drying is performed until the amount of solvents in the dried composite semipermeable membrane is 5% by weight or less.
- In addition, in the case of production of a dry spiral element, the membrane may be processed into a spiral shape in any stage from production of the above-described skin layer to drying treatment. In detail, the composite semipermeable membrane may be processed into a spiral shape before the washing treatment of the membrane to produce a membrane unit. Alternatively, the composite semipermeable membrane may be processed into a spiral shape after treatment with additives to produce the membrane unit, and the composite semipermeable membrane may be processed into a spiral shape before the drying treatment to produce the membrane unit.
- Furthermore, the membrane unit may be produced by simultaneous application of the washing treatment and the treatment with additives to the produced membrane unit. The same method as the one described above may be mentioned as the treatment method.
- The dried composite semipermeable membrane and dry spiral element produced by such a method have extremely small content of unreacted components. A permeated liquid separated and refined or a target compounds condensed by using the composite semipermeable membrane, etc., includes extremely small amount of impurities, and has a high purity. The dried composite semipermeable membrane and the dry spiral element of the present invention have outstanding workability and preservability because it is a dry type. Furthermore, although the dried composite semipermeable membrane and the dry spiral element of the present invention are a dry type, they exhibit water permeability and salt-blocking rate equivalent to that of the wet type composite semipermeable membrane and spiral element, causing no deterioration of performance after long term storage.
- For improvement in salt-blocking property, water permeability, anti-oxidation agent property, etc., of the dried composite semipermeable membrane or dry spiral element, various conventionally publicly known treatments may be applied.
- The present invention will, hereinafter, be described with reference to Examples, but the present invention is not limited at all by these Examples.
- A dried composite semipermeable membrane produced with a shape of a flat film is cut into a predetermined shape and size, and is set to a cell for flat film evaluation. An aqueous solution containing NaCl of about 1500 mg/L and adjusted to a pH of 6.5 to 7.5 with NaOH was forced to contact to a supply side, and a permeation side of the membrane at a differential pressure of 1.5 MPa at 25° C. A permeation velocity and an electric conductivity of the permeated water obtained by this operation were measured for, and a permeation flux (m3/m2·d) and a salt-blocking rate (%) were calculated. The correlation (calibration curve) of the NaCl concentration and the electric conductivity of the aqueous solution was beforehand made, and the salt-blocking rate was calculated by a following equation.
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Salt-blocking rate (%)={1−(NaCl concentration [mg/L] in permeated liquid)/(NaCl concentration [mg/L] in supply solution)}×100 - A prepared dried composite semipermeable membrane was cut into a size of 1 cm×3 cm to obtain samples A and B. A pressure sensitive adhesive tape (made by NITTO DENKO CORPORATION, No. 31-B) was attached on the surface of the skin layer of sample A, and the pressure sensitive adhesive tape was separated after light friction. The skin layer and the microporous layer on the uppermost surface of the porous support were removed together with the pressure sensitive adhesive tape. Subsequently, the separated porous support was immersed into 50 cc of pure water, and was boiled at 120° C. for 1 hour in a sealed state. The obtained extracted liquid was subjected to analysis with ion chromatography to obtain an amount of additives in the extracted liquid. Determination of the additives was performed by comparison to a calibration curve prepared using standard solutions beforehand prepared to several kinds of prescribed concentrations. Measurement conditions are shown as follows.
- Analyzer: Ion chromatograph, manufactured by DIONEX CORPORATION, DX-320
- Isolation column: Ion Pac AS15 (4 mm×250 mm)
- Guard column: Ion Pac AG15 (4 mm×50 mm)
- Detector: Conductometrical detector
- Eluate: KOH 2 mM→10 mM
- Eluate flow rate: 1.2 mL/min
- Specimen injection: 50 μL
- Furthermore, sample B was immersed into 50 cc of pure water, and was boiled for 1 hour at 120° C. in a sealed state. Subsequently, the extracted liquid was subjected to analysis under the same conditions as described above to obtain an amount of additives in the extracted liquid. The two obtained value were substituted for the following expression, and the content rate of the additives in the porous support was calculated.
-
Content rate(%)=[(content in porous support)/(content in composite semipermeable membrane)]×100 - A dope for manufacturing a membrane containing 18% by weight of a polysulfone (produced by Solvay, P-3500) dissolved in N,N-dimethylformamide (DMF) was uniformly applied so that it might give 200 μm in thickness in wet condition on a nonwoven fabric base material. Subsequently, it was immediately solidified by immersion in water at 40 to 50° C., and DMF as a solvent was completely extracted by washing. Thus a porous support having a polysulfone microporous layer was produced on the nonwoven fabric base material.
- An aqueous solution of amines containing 3% by weight of m-phenylenediamine, 3% by weight of triethylamine, and 6% by weight of camphorsulfonic acid was applied to the porous support, and then an excessive amount of the amine aqueous solution was removed to form a covering layer of the aqueous solution. Subsequently, an isooctane solution containing 0.2% by weight of trimesic acid chlorides was applied to the surface of the covering layer of the aqueous solution. Then, the excessive solution was removed, and the material was kept standing for 3 minutes in a hot air dryer at 120° C. to form a skin layer containing a polyamide resin on the porous support, an unwashed composite semipermeable membrane was obtained. After that time, the unwashed composite semipermeable membrane was immersed for 10 minutes at 50° C. in pure water for membrane washing treatment to produce a washed composite semipermeable membrane. Subsequently, a sodium acetate aqueous solution (concentration: 5% by weight) was applied to the surface (a face which does not have a formed skin layer) of the porous support of the washed composite semipermeable membrane under a condition of 30 cc/m2 for treatment with additives. And treated composite semipermeable membrane stood to remove the excessive sodium acetate aqueous solution, and then was kept standing for 5 minutes in a hot air dryer at 80° C., finally producing a dried composite semipermeable membrane.
- A dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium lactate aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- A dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium hydrogen carbonate aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- A composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium bisulfite aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution, and not drying after treatment with additives in example 1.
- A dried composite semipermeable membrane was produced in the same manner as in example 1, except for using a sodium bisulfite aqueous solution (concentration: 5% by weight) instead of the sodium acetate aqueous solution in example 1.
- A washed composite semipermeable membrane was produced in the same manner as in example 1. Subsequently, the washed composite semipermeable membrane was immersed in a sodium acetate aqueous solution (concentration: 5% by weight) for 1 minute at 25° C., and treatment with additives was applied. Then, the treated composite semipermeable membrane stood and thus the excessive sodium acetate aqueous solution was removed, and then was kept standing for 5 minutes in a hot air dryer at 80° C. to produce a dried composite semipermeable membrane.
- A washed composite semipermeable membrane was produced in the same manner as in example 1. Subsequently, a sodium acetate aqueous solution (concentration: 5% by weight) 25° C. was applied on the surface of the skin layer of the washed composite semipermeable membrane under a condition of 30 cc/m2, the surface was uniformly smoothed using a PET film and then treatment with additives was applied. Then, the treated composite semipermeable membrane stood and thus the excessive sodium acetate aqueous solution was removed, and next was kept standing for 5 minutes in a hot air dryer at 80° C. to produce a dried composite semipermeable membrane.
- A dried composite semipermeable membrane was produced in the same manner as in example 1, except for not performing treatment with additives in example 1.
- A washed composite semipermeable membrane was produced in the same manner as in example 1. Appearance of mold in the skin layer was observed after storage for one week of the washed composite semipermeable membrane.
- An unwashed composite semipermeable membrane was produced in the same manner as in example 1.
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TABLE 1 Content of additives (mg/m2) Initial Performance Whole Content of performance one week after Condition composite additives to Permeation Permeation of semipermeable Porous porous Salt-blocking Flux Salt-blocking Flux membrane Additive membrane support support (%) rate (%) (m3/m2 · d) rate (%) (m3/m2 · d) Example 1 Washed, Sodium 790 780 98.7 99.3 0.8 99.3 0.8 dry acetate Example 2 Washed, Sodium 1050 1020 97.1 99.5 0.9 99.6 0.8 dry lactate Example 3 Washed, Sodium 570 550 96.5 99.3 0.6 99.2 0.6 dry hydrogen carbonate Example 4 Washed, Sodium 580 570 98.3 99.4 0.6 99.3 0.6 wet bisulfite Example 5 Washed, Sodium 600 580 96.7 99.5 1.0 99.5 1.0 dry bisulfite Comparative Washed, Sodium 820 740 90.2 98.9 0.9 98.7 0.8 Example 1 dry acetate Comparative Washed, Sodium 660 590 89.4 97.9 1.1 97.1 1.2 Example 2 dry acetate Comparative Washed, — — — — Measurement impossible (permeation flux <0.1) Example 3 dry Comparative Washed, — — — — 99.5 0.9 99.1 0.7 Example 4 wet Comparative Unwashed, — — — — 99.5 0.9 99.0 1.4 Example 5 dry - As is clearly shown in table 1, a composite semipermeable membrane having water permeability and salt-blocking rate without deterioration after long-term storage may be obtained by mainly including specific additives mainly in a porous support.
Claims (14)
1. A composite semipermeable membrane having a skin layer formed on the surface of a porous support, the skin layer comprising a polyamide resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halide component, wherein the porous support contains at least one kind of additive selected from the group consisting of an antioxidant, an antibacterial agent, an antifungal agent, and a moisturizer in an amount of 95% by weight or more with respect to the whole composite semipermeable membrane.
2. The composite semipermeable membrane according to claim 1 , wherein the composite semipermeable membrane is a dried composite semipermeable membrane.
3. The composite semipermeable membrane according to claim 1 , wherein the moisturizer is an organic acid metal salt and/or an inorganic acid metal salt.
4. The composite semipermeable membrane according to claim 3 , wherein the organic acid metal salt is at least one kind of organic acid alkali metal salt selected from the group consisting of an alkali metal acetate, alkali metal lactate, and alkali metal glutamate.
5. The composite semipermeable membrane according to claim 3 , wherein the inorganic acid metal salt is at least one kind of inorganic acid alkali metal salt selected from the group consisting of an alkali metal hydrogencarbonate, dialkali metal monohydrogen phosphate, and monoalkali metal dihydrogen phosphate.
6. A process for producing a composite semipermeable membrane comprising:
forming a skin layer including a polyamide resin obtained by reaction between a polyfunctional amine component and a polyfunctional acid halide component on the surface of a porous support; and
performing a treatment with additives onto the porous support by contact of an aqueous solution including at least one kind of additives selected from the group consisting of an antioxidant, an antibacterial agent, an antifungal agent, and a moisturizer, to a face without the skin layer of the porous support.
7. The composite semipermeable membrane according to claim 2 , wherein the moisturizer is an organic acid metal salt and/or an inorganic acid metal salt.
8. The composite semipermeable membrane according to claim 7 , wherein the organic acid metal salt is at least one kind of organic acid alkali metal salt selected from the group consisting of an alkali metal acetate, alkali metal lactate, and alkali metal glutamate.
9. The composite semipermeable membrane according to claim 7 , wherein the inorganic acid metal salt is at least one kind of inorganic acid alkali metal salt selected from the group consisting of an alkali metal hydrogencarbonate, dialkali metal monohydrogen phosphate, and monoalkali metal dihydrogen phosphate.
10. The composite semipermeable membrane according to claim 1 , wherein the porous support contains an antioxidant selected from the group consisting of sodium sulfite, sodium hyposulfite, sodium bisulfite, potassium sulfite, potassium hydrogen hyposulfite, sulfur dioxide, isopropyl citrate, ascorbic acid, alkyl ascorbate, and sodium ascorbate.
11. The composite semipermeable membrane according to claim 1 , wherein the porous support contains an antibacterial agent selected from the group consisting of a silver based compound, a copper based compound, a photocatalytic compound, a chitosan, and a catechin.
12. The composite semipermeable membrane according to claim 1 , wherein the content of the additive(s) in the porous support is 1 mg/m2 to 100 g/m2.
13. The process of claim 6 , further comprising drying the treated composite semipermeable membrane.
14. The process of claim 6 , wherein concentration of the additives in the aqueous solution is 100 ppm to 30% by weight.
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Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1234567A (en) * | 1915-09-14 | 1917-07-24 | Edward J Quigley | Soft collar. |
US4005012A (en) * | 1975-09-22 | 1977-01-25 | The United States Of America As Represented By The Secretary Of The Interior | Semipermeable membranes and the method for the preparation thereof |
US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
US4520044A (en) * | 1984-07-30 | 1985-05-28 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
US4529646A (en) * | 1984-07-30 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
US4761234A (en) * | 1985-08-05 | 1988-08-02 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
US4830885A (en) * | 1987-06-08 | 1989-05-16 | Allied-Signal Inc. | Chlorine-resistant semipermeable membranes |
US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4938872A (en) * | 1989-06-07 | 1990-07-03 | E. I. Du Pont De Nemours And Company | Treatment for reverse osmosis membranes |
US4948507A (en) * | 1988-09-28 | 1990-08-14 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4950404A (en) * | 1989-08-30 | 1990-08-21 | Allied-Signal Inc. | High flux semipermeable membranes |
US4983291A (en) * | 1989-12-14 | 1991-01-08 | Allied-Signal Inc. | Dry high flux semipermeable membranes |
US5152901A (en) * | 1990-09-14 | 1992-10-06 | Ionics, Incorporated | Polyamine-polyamide composite nanofiltration membrane for water softening |
US5259950A (en) * | 1990-03-27 | 1993-11-09 | Toray Industries, Inc. | Composite membrane |
US5746916A (en) * | 1994-01-26 | 1998-05-05 | Mitsubishi Rayon Co., Ltd. | Microporous membrane made of non-crystalline polymers and method of producing the same |
US5783079A (en) * | 1994-08-29 | 1998-07-21 | Toyo Boseki Kabushiki Kaisha | Composite hollow fiber membrane and process for its production |
US6177011B1 (en) * | 1996-03-18 | 2001-01-23 | Nitto Denko Corporation | Composite reverse osmosis membrane having a separation layer with polyvinyl alcohol coating and method of reverse osmotic treatment of water using the same |
US20020063093A1 (en) * | 1997-06-06 | 2002-05-30 | Koch Membrane Systems, Inc. | High performance composite membrane |
US6551536B1 (en) * | 2001-07-30 | 2003-04-22 | Saehan Industries Incorporation | Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same |
US20040222146A1 (en) * | 2003-05-06 | 2004-11-11 | Nitto Denko Corporation | Composite semipermeable membrane and process for producing the same |
US7156997B2 (en) * | 2001-10-05 | 2007-01-02 | Dow Global Technologies Inc. | Package assembly for piperazine-based membranes |
US7220358B2 (en) * | 2004-02-23 | 2007-05-22 | Ecolab Inc. | Methods for treating membranes and separation facilities and membrane treatment composition |
US20080053893A1 (en) * | 2004-10-01 | 2008-03-06 | Tomomi Ohara | Semipermeable Composite Membrane and Process for Producing the Same |
US20080251447A1 (en) * | 2006-10-10 | 2008-10-16 | Atsuhito Koumoto | Process for producing a dried composite semipermeable membrane |
US20080257818A1 (en) * | 2004-10-01 | 2008-10-23 | Nitto Denko Corporation | Semipermeable Composite Membrane and Process for Producing the Same |
US20080277334A1 (en) * | 2004-10-01 | 2008-11-13 | Nitto Denko Corporation | Process for Producing Semipermeable Composite Membrane |
US20090050558A1 (en) * | 2004-10-04 | 2009-02-26 | Hirotoshi Ishizuka | Process for producing composite reverse osmosis membrane |
Family Cites Families (60)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2727087A (en) * | 1952-04-18 | 1955-12-13 | Gen Electric | Armored oil well cable |
US3023300A (en) * | 1959-08-10 | 1962-02-27 | Hackethal Draht & Kabelwerk Ag | Method and apparatus for forming cable sheath |
NL271831A (en) * | 1960-11-29 | |||
US3133137A (en) * | 1960-11-29 | 1964-05-12 | Univ California | High flow porous membranes for separating water from saline solutions |
US3567632A (en) * | 1968-09-04 | 1971-03-02 | Du Pont | Permselective,aromatic,nitrogen-containing polymeric membranes |
US3744642A (en) * | 1970-12-30 | 1973-07-10 | Westinghouse Electric Corp | Interface condensation desalination membranes |
JPS6038166B2 (en) | 1976-07-30 | 1985-08-30 | 東ソー株式会社 | Composite membrane manufacturing method |
JPS58180206A (en) | 1982-04-15 | 1983-10-21 | Toray Ind Inc | Production of selective permeable membrane |
JPS6146207A (en) | 1984-08-09 | 1986-03-06 | Nitto Electric Ind Co Ltd | Manufacture of composite semipermeable membrane |
JPS62121603A (en) | 1985-08-05 | 1987-06-02 | Toray Ind Inc | Composite semipermeable membrane and preparation thereof |
JPH0790152B2 (en) | 1986-02-26 | 1995-10-04 | 東レ株式会社 | Composite reverse osmosis membrane |
JP2510530B2 (en) | 1986-09-26 | 1996-06-26 | 東レ株式会社 | Manufacturing method of composite membrane |
JPS63218208A (en) | 1987-03-05 | 1988-09-12 | Toray Ind Inc | Composite semipermeable membrane and its production |
US4769148A (en) * | 1987-11-18 | 1988-09-06 | The Dow Chemical Company | Novel polyamide reverse osmosis membranes |
JPH0278428A (en) | 1988-06-07 | 1990-03-19 | Toray Ind Inc | Laminated semipermeable membrane and production thereof |
US5015380A (en) | 1989-04-20 | 1991-05-14 | E. I. Du Pont De Nemours And Company | Microporous support layer with interfacially polymerized copolyamide membrane thereon |
JPH0315853A (en) | 1989-06-14 | 1991-01-24 | Kao Corp | Electrophotographic sensitive body |
US4964998A (en) * | 1989-12-13 | 1990-10-23 | Filmtec Corporation | Use of treated composite polyamide membranes to separate concentrated solute |
JPH0523558A (en) | 1989-12-19 | 1993-02-02 | Exxon Res & Eng Co | Production of thin supporting layer film |
US5045354A (en) | 1989-12-19 | 1991-09-03 | Exxon Research & Engineering Company | Production of supported thin film membranes |
NL9001274A (en) * | 1990-06-06 | 1992-01-02 | X Flow Bv | SEMI-PERMEABLE COMPOSITE MEMBRANE, AND METHOD FOR MANUFACTURING IT. |
US5173335A (en) * | 1990-07-31 | 1992-12-22 | E. I. Du Pont De Nemours And Company | Method of producing multilayer reverse osmosis membrane of polyamide-urea |
CA2045109A1 (en) | 1991-06-20 | 1992-12-21 | Joseph Louis Feimer | Production of supported thin film membranes |
US5254261A (en) * | 1991-08-12 | 1993-10-19 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
US5234598A (en) * | 1992-05-13 | 1993-08-10 | Allied-Signal Inc. | Thin-film composite membrane |
US5368889A (en) | 1993-04-16 | 1994-11-29 | The Dow Chemical Company | Method of making thin film composite membranes |
US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
US5582725A (en) * | 1995-05-19 | 1996-12-10 | Bend Research, Inc. | Chlorine-resistant composite membranes with high organic rejection |
US5547701A (en) * | 1995-06-07 | 1996-08-20 | Kimberly-Clark Corporation | Method of forming a paper applicator containing a water insoluble coating |
JP3681214B2 (en) * | 1996-03-21 | 2005-08-10 | 日東電工株式会社 | High permeability composite reverse osmosis membrane |
JP3665692B2 (en) | 1996-12-05 | 2005-06-29 | 日東電工株式会社 | Method for producing dry composite reverse osmosis membrane |
US6413425B1 (en) * | 1997-04-10 | 2002-07-02 | Nitto Denko Corporation | Reverse osmosis composite membrane and reverse osmosis treatment method for water using the same |
US6132804A (en) * | 1997-06-06 | 2000-10-17 | Koch Membrane Systems, Inc. | High performance composite membrane |
JP3577917B2 (en) * | 1997-10-31 | 2004-10-20 | 株式会社日立製作所 | Automatic analyzer |
US6015495A (en) * | 1998-02-18 | 2000-01-18 | Saehan Industries Incorporation | Composite polyamide reverse osmosis membrane and method of producing the same |
JPH11319517A (en) | 1998-05-08 | 1999-11-24 | Sumitomo Heavy Ind Ltd | Membrane separation apparatus, membrane separation method, and method for washing membrane separation apparatus |
US6162358A (en) * | 1998-06-05 | 2000-12-19 | Nl Chemicals Technologies, Inc. | High flux reverse osmosis membrane |
JP4213789B2 (en) | 1998-07-10 | 2009-01-21 | 日東電工株式会社 | Method for producing liquid separation membrane |
JP2000153137A (en) | 1998-11-20 | 2000-06-06 | Nitto Denko Corp | Composite reverse osmosis membrane |
JP2000300974A (en) | 1999-04-21 | 2000-10-31 | Petroleum Energy Center | Semipermeable membrane, its manufacture and helium separating semipermeable membrane |
JP2000325759A (en) | 1999-05-17 | 2000-11-28 | Toray Ind Inc | Manufacture of membrane |
JP2001038175A (en) | 1999-05-27 | 2001-02-13 | Toyobo Co Ltd | Composite semipermeable membrane |
JP2000350928A (en) | 1999-06-10 | 2000-12-19 | Toyobo Co Ltd | Composite diaphragm, composite diaphragm module and its manufacture |
JP2001179061A (en) | 1999-12-22 | 2001-07-03 | Toray Ind Inc | Composite semipermeable membrane and manufacturing method thereof |
JP2001286741A (en) | 2000-04-04 | 2001-10-16 | Toray Ind Inc | Reverse osmosis composite membrane and manufacturing method therefor |
US6337018B1 (en) * | 2000-04-17 | 2002-01-08 | The Dow Chemical Company | Composite membrane and method for making the same |
JP2002095939A (en) | 2000-09-21 | 2002-04-02 | Toyobo Co Ltd | Composite semipermeable membrane, composite semipermeable membrane separation element, and their manufacturing method and rewetting method |
JP2002136849A (en) | 2000-10-31 | 2002-05-14 | Toray Ind Inc | Method for manufacturing composite membrane |
AUPR143400A0 (en) * | 2000-11-13 | 2000-12-07 | Usf Filtration And Separations Group Inc. | Modified membranes |
JP5030192B2 (en) | 2000-12-14 | 2012-09-19 | 東レ株式会社 | Manufacturing method of composite semipermeable membrane |
JP2002355938A (en) | 2001-05-30 | 2002-12-10 | Tonen Chem Corp | Composite film, its manufacturing method, and separator for battery using the same or filter |
JP3899485B2 (en) | 2002-03-22 | 2007-03-28 | 富士フイルム株式会社 | Application method and apparatus |
JP2003320224A (en) | 2002-04-26 | 2003-11-11 | Toray Ind Inc | Manufacturing method for dry reverse osmosis membrane |
JP2005066464A (en) | 2003-08-25 | 2005-03-17 | Nitto Denko Corp | Liquid separation membrane and manufacturing method therefor |
JP4177231B2 (en) | 2003-11-04 | 2008-11-05 | 日東電工株式会社 | Liquid separation membrane and method for producing the same |
PT1848473E (en) * | 2005-02-07 | 2013-08-28 | Hanuman Llc | Plasma concentrator device |
JP4793978B2 (en) | 2005-03-29 | 2011-10-12 | 日東電工株式会社 | Method for producing dry composite semipermeable membrane |
US7727434B2 (en) * | 2005-08-16 | 2010-06-01 | General Electric Company | Membranes and methods of treating membranes |
JP2008093544A (en) * | 2006-10-10 | 2008-04-24 | Nitto Denko Corp | Composite semipermeable membrane and manufacturing method thereof |
JP2008246419A (en) * | 2007-03-30 | 2008-10-16 | Nitto Denko Corp | Production method for composite semi-permeable membrane |
-
2006
- 2006-10-10 JP JP2006276661A patent/JP2008093544A/en active Pending
-
2007
- 2007-10-09 CN CN2007101809013A patent/CN101219345B/en not_active Expired - Fee Related
- 2007-10-09 KR KR1020070101304A patent/KR20080032609A/en not_active Application Discontinuation
- 2007-10-09 US US11/869,678 patent/US20080083670A1/en not_active Abandoned
-
2009
- 2009-10-27 US US12/606,518 patent/US8851297B2/en active Active
Patent Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1234567A (en) * | 1915-09-14 | 1917-07-24 | Edward J Quigley | Soft collar. |
US4005012A (en) * | 1975-09-22 | 1977-01-25 | The United States Of America As Represented By The Secretary Of The Interior | Semipermeable membranes and the method for the preparation thereof |
US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
US4520044A (en) * | 1984-07-30 | 1985-05-28 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
US4529646A (en) * | 1984-07-30 | 1985-07-16 | E. I. Du Pont De Nemours And Company | Production of composite membranes |
US4761234A (en) * | 1985-08-05 | 1988-08-02 | Toray Industries, Inc. | Interfacially synthesized reverse osmosis membrane |
US4830885A (en) * | 1987-06-08 | 1989-05-16 | Allied-Signal Inc. | Chlorine-resistant semipermeable membranes |
US4872984A (en) * | 1988-09-28 | 1989-10-10 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4948507A (en) * | 1988-09-28 | 1990-08-14 | Hydranautics Corporation | Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same |
US4938872A (en) * | 1989-06-07 | 1990-07-03 | E. I. Du Pont De Nemours And Company | Treatment for reverse osmosis membranes |
US4950404A (en) * | 1989-08-30 | 1990-08-21 | Allied-Signal Inc. | High flux semipermeable membranes |
US4950404B1 (en) * | 1989-08-30 | 1991-10-01 | Allied Signal Inc | |
US4983291A (en) * | 1989-12-14 | 1991-01-08 | Allied-Signal Inc. | Dry high flux semipermeable membranes |
US5259950A (en) * | 1990-03-27 | 1993-11-09 | Toray Industries, Inc. | Composite membrane |
US5152901A (en) * | 1990-09-14 | 1992-10-06 | Ionics, Incorporated | Polyamine-polyamide composite nanofiltration membrane for water softening |
US5746916A (en) * | 1994-01-26 | 1998-05-05 | Mitsubishi Rayon Co., Ltd. | Microporous membrane made of non-crystalline polymers and method of producing the same |
US5783079A (en) * | 1994-08-29 | 1998-07-21 | Toyo Boseki Kabushiki Kaisha | Composite hollow fiber membrane and process for its production |
US6177011B1 (en) * | 1996-03-18 | 2001-01-23 | Nitto Denko Corporation | Composite reverse osmosis membrane having a separation layer with polyvinyl alcohol coating and method of reverse osmotic treatment of water using the same |
US20020063093A1 (en) * | 1997-06-06 | 2002-05-30 | Koch Membrane Systems, Inc. | High performance composite membrane |
US6536605B2 (en) * | 1997-06-06 | 2003-03-25 | Koch Membrane Systems, Inc. | High performance composite membrane |
US6551536B1 (en) * | 2001-07-30 | 2003-04-22 | Saehan Industries Incorporation | Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same |
US7156997B2 (en) * | 2001-10-05 | 2007-01-02 | Dow Global Technologies Inc. | Package assembly for piperazine-based membranes |
US20040222146A1 (en) * | 2003-05-06 | 2004-11-11 | Nitto Denko Corporation | Composite semipermeable membrane and process for producing the same |
US7220358B2 (en) * | 2004-02-23 | 2007-05-22 | Ecolab Inc. | Methods for treating membranes and separation facilities and membrane treatment composition |
US20080053893A1 (en) * | 2004-10-01 | 2008-03-06 | Tomomi Ohara | Semipermeable Composite Membrane and Process for Producing the Same |
US20080257818A1 (en) * | 2004-10-01 | 2008-10-23 | Nitto Denko Corporation | Semipermeable Composite Membrane and Process for Producing the Same |
US20080277334A1 (en) * | 2004-10-01 | 2008-11-13 | Nitto Denko Corporation | Process for Producing Semipermeable Composite Membrane |
US20090050558A1 (en) * | 2004-10-04 | 2009-02-26 | Hirotoshi Ishizuka | Process for producing composite reverse osmosis membrane |
US20080251447A1 (en) * | 2006-10-10 | 2008-10-16 | Atsuhito Koumoto | Process for producing a dried composite semipermeable membrane |
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US20090050558A1 (en) * | 2004-10-04 | 2009-02-26 | Hirotoshi Ishizuka | Process for producing composite reverse osmosis membrane |
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Also Published As
Publication number | Publication date |
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CN101219345B (en) | 2012-03-21 |
KR20080032609A (en) | 2008-04-15 |
JP2008093544A (en) | 2008-04-24 |
CN101219345A (en) | 2008-07-16 |
US20100044902A1 (en) | 2010-02-25 |
US8851297B2 (en) | 2014-10-07 |
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