WO2006038426A1 - 複合半透膜及びその製造方法 - Google Patents
複合半透膜及びその製造方法 Download PDFInfo
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- WO2006038426A1 WO2006038426A1 PCT/JP2005/016618 JP2005016618W WO2006038426A1 WO 2006038426 A1 WO2006038426 A1 WO 2006038426A1 JP 2005016618 W JP2005016618 W JP 2005016618W WO 2006038426 A1 WO2006038426 A1 WO 2006038426A1
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- Prior art keywords
- semipermeable membrane
- porous support
- membrane
- composite semipermeable
- treatment
- Prior art date
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- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YARQLHBOIGUVQM-UHFFFAOYSA-N benzene-1,2,3-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1S(Cl)(=O)=O YARQLHBOIGUVQM-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- BZFATHSFIGBGOT-UHFFFAOYSA-N butane-1,1,1-tricarbonyl chloride Chemical compound CCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O BZFATHSFIGBGOT-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000013921 calcium diglutamate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- UMVAYAXXQSFULN-QHTZZOMLSA-L calcium;(2s)-2-aminopentanedioate;hydron Chemical compound [Ca+2].[O-]C(=O)[C@@H](N)CCC(O)=O.[O-]C(=O)[C@@H](N)CCC(O)=O UMVAYAXXQSFULN-QHTZZOMLSA-L 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XWALRFDLDRDCJG-UHFFFAOYSA-N cyclobutane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1(C(Cl)=O)C(Cl)=O XWALRFDLDRDCJG-UHFFFAOYSA-N 0.000 description 1
- LXLCHRQXLFIZNP-UHFFFAOYSA-N cyclobutane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1 LXLCHRQXLFIZNP-UHFFFAOYSA-N 0.000 description 1
- PBWUKDMYLKXAIP-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCCC1(C(Cl)=O)C(Cl)=O PBWUKDMYLKXAIP-UHFFFAOYSA-N 0.000 description 1
- MLCGVCXKDYTMRG-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1 MLCGVCXKDYTMRG-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- DCXMNNZFVFSGJX-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1(C(Cl)=O)C(Cl)=O DCXMNNZFVFSGJX-UHFFFAOYSA-N 0.000 description 1
- JREFGECMMPJUHM-UHFFFAOYSA-N cyclopentane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCC1(C(Cl)=O)C(Cl)=O JREFGECMMPJUHM-UHFFFAOYSA-N 0.000 description 1
- YYLFLXVROAGUFH-UHFFFAOYSA-N cyclopentane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1 YYLFLXVROAGUFH-UHFFFAOYSA-N 0.000 description 1
- CRMQURWQJQPUMY-UHFFFAOYSA-N cyclopropane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CC1(C(Cl)=O)C(Cl)=O CRMQURWQJQPUMY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 229940075110 dibasic magnesium phosphate Drugs 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- WDRWZVWLVBXVOI-QTNFYWBSSA-L dipotassium;(2s)-2-aminopentanedioate Chemical compound [K+].[K+].[O-]C(=O)[C@@H](N)CCC([O-])=O WDRWZVWLVBXVOI-QTNFYWBSSA-L 0.000 description 1
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- CSVGEMRSDNSWRF-UHFFFAOYSA-L disodium;dihydrogen phosphate Chemical compound [Na+].[Na+].OP(O)([O-])=O.OP(O)([O-])=O CSVGEMRSDNSWRF-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000013918 magnesium diglutamate Nutrition 0.000 description 1
- 229940063886 magnesium glutamate Drugs 0.000 description 1
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 1
- 239000000626 magnesium lactate Substances 0.000 description 1
- 235000015229 magnesium lactate Nutrition 0.000 description 1
- 229960004658 magnesium lactate Drugs 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- MYUGVHJLXONYNC-QHTZZOMLSA-J magnesium;(2s)-2-aminopentanedioate Chemical compound [Mg+2].[O-]C(=O)[C@@H](N)CCC([O-])=O.[O-]C(=O)[C@@H](N)CCC([O-])=O MYUGVHJLXONYNC-QHTZZOMLSA-J 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000013919 monopotassium glutamate Nutrition 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- MTAAPVANJNSBGV-UHFFFAOYSA-N pentane-1,1,1-tricarbonyl chloride Chemical compound CCCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O MTAAPVANJNSBGV-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940116985 potassium lauryl sulfate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- GCAKFSUPQDLXIL-UHFFFAOYSA-N potassium rhodium Chemical compound [K].[Rh] GCAKFSUPQDLXIL-UHFFFAOYSA-N 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- VLRIRAGKJXODNO-UHFFFAOYSA-N propane-1,1,1-tricarbonyl chloride Chemical compound CCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O VLRIRAGKJXODNO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940073490 sodium glutamate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960004793 sucrose Drugs 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
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 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
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- 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
- 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
- B01D67/0095—Drying
-
- 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
- B01D67/0097—Storing or preservation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D69/1213—Laminated layers
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
Definitions
- the present invention relates to a composite semipermeable membrane comprising a skin layer containing a polyamide-based resin and a porous support for supporting the skin layer, and a method for producing the same.
- a powerful composite semipermeable membrane is suitable for the production of ultrapure water, desalination of brine or seawater, and stains that cause pollution such as dyeing drainage and electrodeposition paint drainage. Removes and recovers contaminated sources or effective substances, and contributes to the closure of wastewater. It can also be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications.
- a skin layer having a polyamide strength obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional aromatic acid halide is formed on a porous support.
- Patent Documents 1 to 4 a skin layer made of a polyamide obtained by interfacial polymerization between a polyfunctional aromatic amine and a polyfunctional alicyclic acid halide is formed on a porous support. Five).
- Patent Document 9 A membrane separation method for filtering water to be treated while washing is disclosed.
- Patent Document 10 a method for producing a fluid separation membrane in which unreacted aromatic monomers are removed by washing with a washing solution having a temperature of 50 ° C or higher is disclosed.
- Patent Document 9 is a method of removing dirt adhering to the membrane surface of the membrane element during the membrane separation operation, and is not a method of removing unreacted residues in the membrane element.
- Patent Document 1 Japanese Patent Application Laid-Open No. 55-147106
- Patent Document 2 Japanese Patent Laid-Open No. 62-121603
- Patent Document 3 JP-A 63-218208
- Patent Document 4 Japanese Patent Laid-Open No. 2-187135
- Patent Document 5 Japanese Patent Laid-Open No. 61-42308
- Patent Document 6 Patent No. 2947291 Specification
- Patent Document 7 Japanese Unexamined Patent Publication No. 2000-24470
- Patent Document 8 Special Table 2002-516743
- Patent Document 9 Japanese Patent Laid-Open No. 11 319517
- Patent Document 10 Patent No. 3525759
- An object of the present invention is to provide a composite semipermeable membrane excellent in water permeation performance and salt rejection, and having a very small amount of unreacted polyfunctional amine component in a porous support, and a method for producing the same. .
- the present invention provides a composite semipermeable membrane in which a skin layer containing a polyamide-based resin formed by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halogen component is formed on the surface of a porous support.
- the porous support has a microporous layer on the substrate, and the content of the unreacted polyfunctional amine component in the substrate after the membrane cleaning treatment is 0.5 mg / m 2 or less.
- the present invention relates to a composite semipermeable membrane characterized by being.
- the content of the unreacted multifunctional amine component in the substrate after the membrane cleaning treatment is preferably 0.3 mgZm 2 or less, more preferably 0.1 mgzm or less.
- the total content of unreacted polyfunctional amine components in the skin layer and the microporous layer after the membrane cleaning treatment is preferably 20 mgZm 2 or less, more preferably lOmgZm. 2 or less.
- the present invention also provides a composite semipermeable membrane obtained by forming a skin layer containing a polyamide-based resin obtained by interfacial polymerization of a polyfunctional amine component and a polyfunctional acid halogen component on the surface of a porous support.
- the porous support has a microporous layer on a substrate, and before forming an aqueous solution coating layer comprising an aqueous amine solution containing a polyfunctional amine component on the porous support.
- a method for producing a composite semipermeable membrane wherein the porous support is subjected to an amine impermeability treatment, and the content of the unreacted polyfunctional amine component in the base material after the membrane cleaning treatment is 0.5 mgZm 2 or less. , Regarding.
- the total content of unreacted polyfunctional amine components in the skin layer and the microporous layer after the membrane cleaning treatment is preferably 20 mgZm 2 or less. Preferably, it is lOmgZm 2 or less.
- the polyfunctional amine component in the porous support (especially in the base material) can be obtained by subjecting the porous support to an amine impermeability treatment in advance. Can be effectively prevented. Thereby, the content of the unreacted polyfunctional amine component in the porous support after the skin layer is formed can be reduced. Then, the subsequent simple and short-time membrane cleaning treatment can greatly reduce the content of the unreacted polyfunctional amine component in the porous support with almost no deterioration in membrane performance.
- the amine impermeability treatment is preferably a treatment for reducing the water content in the porous support to 20 gZ m 2 or less.
- Water content in the porous support is particularly preferably more preferably tool that is LOgZm 2 or less is LgZm 2 or less. Since the polyfunctional amine component is dissolved in water and coated on the porous support, the polyfunctional amine component in the porous support is reduced by reducing the water content in the porous support to 20 gZm 2 or less. Permeation and diffusion of amine components can be effectively suppressed.
- the moving speed is of 0. 3mgZm 2 'sec
- the following polyfunctional amine Ingredient of the porous support in when contacted at atmospheric pressure to the porous support Preferably, it is not more than 0.1 mgZm 2 ′ sec.
- the method for producing the composite semipermeable membrane of the present invention good comprise a step of amount of polyfunctional amine component supplied on the porous support is coated Amin solution so as to 200 ⁇ 600MgZm 2 Better!/,. More preferably, the amount of polyfunctional amine component is 400-600 mg / m 2 ! /. When the amount of the polyfunctional amine component is less than 200 mgZm 2 , defects such as pinholes are likely to occur in the skin layer, and it tends to be difficult to form a high-performance skin layer uniformly.
- the method for producing a composite semipermeable membrane of the present invention includes a moisturizing step of moisturizing the washed membrane after the membrane cleaning treatment, and a drying step of drying the membrane subjected to the moisturizing treatment.
- the composite semipermeable membrane is preferably a dry type from the standpoint of subsequent processability and storage stability.
- the method for producing a composite semipermeable membrane of the present invention includes a drying step of performing a moisturizing process simultaneously with the film cleaning process and further drying the film subjected to the cleaning moisturizing process.
- the production efficiency can be improved by performing the cleaning process and the moisturizing process at the same time.
- the moisturizing agent used for the moisturizing treatment is an organic acid metal salt and Z or an inorganic acid metal salt.
- the organic acid metal salt is preferably at least one organic acid alkali metal salt selected from the group consisting of alkali metal acetates, alkali metal lactates, and alkali metal glutamates.
- the alkali metal is preferably sodium or potassium.
- the inorganic acid metal salt is at least one inorganic acid alkali selected from the group consisting of an alkali metal hydrogen carbonate salt, a dihydrogen alkali metal phosphate salt, and a dihydrogen alkali metal salt salt.
- a metal salt is preferred.
- the alkali metal is preferably sodium or potassium.
- a surfactant or saccharide When a surfactant or saccharide is used as a moisturizing agent, a long-time moisturizing treatment must be performed to obtain the desired effect.
- the organic acid metal salt and Z or inorganic acid metal The use of salt provides a significant advantage in the production process because a sufficient effect can be obtained with a very short moisturizing treatment.
- the effect when a surfactant or saccharide is used as a moisturizing agent, the effect may be impaired depending on drying conditions (temperature, time, etc.), but the organic acid metal salt and Z or inorganic acid metal salt were used. In this case, a sufficient effect can be obtained regardless of the drying conditions, and there is a great merit in the production process.
- the present invention also relates to a composite semipermeable membrane obtained by the production method.
- the composite semipermeable membrane of the present invention has very few unreacted polyfunctional amine components in the porous support, and water permeation performance and salt inhibition that do not cause excessive membrane cleaning and thus do not deteriorate membrane performance. It is excellent in rate.
- the composite semipermeable membrane of the present invention has a multifunctional A skin layer containing a polyamide-based resin formed by interfacial polymerization of a amine component and a polyfunctional acid halogen component is formed on the surface of the porous support, and the porous support is formed on the base material. And the content of the unreacted multifunctional amine component in the substrate after the membrane cleaning treatment is 0.5 mg / m 2 or less.
- the composite semipermeable membrane is obtained by subjecting the porous support to an amine impermeability treatment before forming an aqueous solution coating layer containing a polyfunctional amine component on the porous support. It can be manufactured by performing a film cleaning treatment after the formation of the layer.
- the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines.
- aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1, 3, 5-triaminobenzene, 1, 2, 4-triamino. Benzene, 3,5-Diamino shoulder, Perfume acid, 2,4-Diaminotonolene, 2,6-Diaminotonolene, N, N '—Dimethyl-1-m-phenol-diamine, 2,4-Diaminoamine Nord, amido, xylylenediamine and the like.
- Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (
- Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylbiperazine, 4-aminomethylbiperazine and the like can be mentioned.
- polyfunctional amines may be used alone or in combination of two or more. In order to obtain a skin layer with high salt inhibition performance, it is preferable to use an aromatic polyfunctional amine.
- the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
- polyfunctional acid halide examples include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
- aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzene trisulfonic acid trichloride, and benzene disulfone. And acid dichloride and chlorosulfobenzenebenzene dicarboxylic acid dichloride.
- Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, and glutaryl halide. Ride, adiboyl halide and the like.
- Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, and cyclohexanetricarboxylic acid trichloride.
- Examples thereof include chloride, tetrano, iodofuran tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrate furan carboxylic acid dichloride.
- polyfunctional acid halides may be used alone or in combination of two or more.
- an aromatic polyfunctional acid halide it is preferable to use an aromatic polyfunctional acid halide.
- a polymer such as polyvinyl alcohol, polybutylpyrrolidone or polyacrylic acid or a polyhydric alcohol such as sorbitol or glycerin is copolymerized.
- a polymer such as polyvinyl alcohol, polybutylpyrrolidone or polyacrylic acid or a polyhydric alcohol such as sorbitol or glycerin is copolymerized.
- the porous support is one in which a microporous layer having a substantially separating function is formed on the surface of a substrate.
- the microporous layer usually has micropores with an average pore diameter of about 10 to 500A.
- Examples of the substrate include woven fabrics, nonwoven fabrics, mesh nets, and foamed sintered sheets made of polyester, polypropylene, polyethylene, polyamide, and the like. Of these, non-woven fabrics are preferably used in terms of film forming properties and cost.
- the nonwoven fabric preferably has a thickness of 0.08 to 0.15 mm and a density of 0.5 to 0.8 gZcm 3 . When the thickness is less than 0.08 mm or the density is less than 0.5 g / cm 3 , the strength as a reinforcing sheet cannot be obtained, and it tends to be difficult to maintain a back pressure strength of 2 g / cm 2 or more. It is in.
- the filtration resistance increases or the anchoring effect of the microporous layer on the nonwoven fabric decreases. Stripped at the interface with the porous layer There is a tendency for separation to occur.
- Examples of the material for forming the microporous layer include various materials such as polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyvinylidene fluoride, and the like. Polysulfone and polyarylethersulfone are also preferably used because of their mechanical and thermal stability. The thickness of such a microporous layer is usually about
- It is 25 to 125 ⁇ m, preferably about 40 to 75 ⁇ m, but is not necessarily limited thereto.
- the method for forming the microporous layer on the surface of the substrate is not particularly limited, and a conventionally known method can be appropriately employed.
- the method for forming the skin layer containing the polyamide-based resin on the surface of the porous support is not particularly limited, and any known method can be used.
- an interfacial condensation method, a phase separation method, a thin film coating method and the like can be mentioned.
- the interfacial condensation method is a method in which a skin layer is formed by interfacial polymerization by bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component.
- the porous support is subjected to an amine impermeability treatment before application of the aqueous amine solution, and then the aqueous solution coating layer composed of the aqueous amine solution containing a polyfunctional amine component is porously supported.
- a method of forming a skin layer by forming an organic polymer containing a polyfunctional acid halide component and an aqueous solution coating layer in contact with each other and interfacial polymerization is preferable.
- Examples of the amine impermeability treatment include: 1) treatment to reduce the water content in the porous support to 20 gZm 2 or less by drying; 2) the polyfunctional amine component is not substantially dissolved; A process in which a porous support is coated or impregnated in a porous support with a solvent such as a hydrocarbon solvent or a naphthenic solvent that is substantially immiscible with an aqueous solution. 3) An aqueous solution of inorganic acid or organic acid.
- the porous support (preferably pH 4 or less) is used to coat the porous support, Treatment to impregnate the porous support; 4) coating the porous support with an aqueous solution containing glycerin, ethylene glycol, polyethylene glycol, polybulal alcohol, etc. and having a viscosity of lOmPa's or more;
- the treatment include impregnation. Among these, it is particularly preferable to perform a treatment for reducing the water content in the porous support to 20 gZm 2 or less.
- the moving speed of the polyfunctional amine component in the porous support is By adjusting the amine aqueous solution so as to be 3 mgZm 2 ′ sec or less, the penetration and diffusion of the polyfunctional amine component into the porous support can be further suppressed.
- the method for adjusting the viscosity of the amine aqueous solution to 7 mPa's or more include a method of adding polyhydric alcohols such as glycerin, ethylene glycol and propylene glycol to the aqueous solution.
- a method of reducing the surface tension of the aqueous amine solution examples include, but are not limited to, not adding a component such as a surfactant and adjusting the pH to near neutrality by forming the aqueous solution of the amine solution.
- the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight. is there.
- the concentration of the polyfunctional amine component is less than 0.1% by weight, defects such as pinholes are likely to occur in the skin layer, and the salt blocking performance tends to be lowered.
- the concentration of the polyfunctional amine component exceeds 5% by weight, the polyfunctional amine component is likely to penetrate into the porous support, or the film becomes too thick to increase the permeation resistance. The flux tends to decrease.
- the concentration of the polyfunctional acid or ride component in the organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component will remain and the skin layer will be prone to defects such as pinholes, resulting in salt inhibition performance. It tends to decrease. On the other hand, when the concentration of the polyfunctional acid halide component exceeds 5% by weight However, the unreacted polyfunctional acid halide component tends to remain, the film thickness becomes too thick, the permeation resistance increases, and the permeation flux tends to decrease.
- the organic solvent used in the organic solution is not particularly limited as long as it does not degrade the porous support having low solubility in water and dissolves the polyfunctional acid halide component.
- Saturated hydrocarbons such as xane, heptane, octane, and nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorophlotriethane. Saturated hydrocarbons having a boiling point of 300 ° C or lower, more preferably 200 ° C or lower are preferred.
- additives can be added to the amine aqueous solution and the organic solution for the purpose of facilitating film formation and improving the performance of the resulting composite semipermeable membrane.
- the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate, sodium hydroxide that removes halogenated hydrogen generated by polymerization, trisodium phosphate, and Examples thereof include basic compounds such as triethylamine, assimilium catalysts, and compounds having a solubility parameter of 8 to 14 (calZcm 3 ) 1/2 described in JP-A-8-224452.
- the time from applying the aqueous amine solution on the porous support and applying the organic solution depends on the composition and viscosity of the aqueous amine solution and the pore size of the surface layer of the porous support. It is preferred that it is less than 2 seconds, and more preferred is less than 5 seconds.
- the application interval of the solution exceeds 15 seconds, the aqueous amine solution may penetrate and diffuse deep inside the porous support, and a large amount of unreacted polyfunctional amine component may remain in the porous support. .
- the unreacted polyfunctional amine component that has penetrated deep into the porous support tends to be difficult to remove by subsequent membrane cleaning treatment.
- an excess aqueous amine solution may be removed.
- the excess organic solution on the porous support is removed to form a formed film on the porous support. It is preferable to heat and dry at 70 ° C or higher to form a skin layer. By heat-treating the formed film, its mechanical strength, heat resistance, etc. can be increased.
- the heating temperature is more preferably 70 to 200 ° C, particularly preferably 100 to 150 ° C. Heating time is about 30 seconds to 10 minutes Is more preferable, and more preferably about 40 seconds to 7 minutes.
- the thickness of the skin layer formed on the porous support is not particularly limited.
- the produced unwashed composite semipermeable membrane is subjected to membrane cleaning treatment.
- the membrane cleaning treatment method is not particularly limited, and a conventionally known method can be adopted. In particular, the following membrane cleaning method is preferred.
- [0058] 2 A method of cleaning a membrane by bringing an aqueous solution containing an acidic substance and Z or inorganic salt, and an aqueous organic substance into contact with an unwashed composite semipermeable membrane.
- the acidic substance is not particularly limited as long as it is water-soluble, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as formic acid, acetic acid and citrate.
- the inorganic salt is not particularly limited as long as it forms a complex with an amide group.
- lithium chloride LiCl
- calcium chloride CaCl
- rhodancalcium Ca (SCN)
- the concentration of the acidic substance and Z or inorganic salt in the aqueous solution is preferably 10 ppm to 50% by weight, more preferably 50 ppm to 20% by weight, and particularly preferably 1 to 10% by weight.
- concentration of the acidic substance and Z or inorganic salt is less than 10 ppm, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- concentration of the acidic substance and Z or inorganic salt is less than 10 ppm, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- it exceeds 50% by weight the effect on the performance of the semipermeable membrane increases, and the permeation flux tends to decrease.
- the water-soluble organic substance is not particularly limited as long as it does not adversely affect the membrane performance.
- monohydric alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol
- Polyhydric alcohols such as triethylene glycol and glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethanolino etherenole, ether glycol such as ethylene glycol monomer monobutinoree etherenole, dimethylformamide, dimethylacetamide, n—
- Examples include polar solvents such as methyl pyrrolidone.
- the concentration of the water-soluble organic substance in the aqueous solution depends on the removal performance of unreacted polyfunctional amine components and the membrane. It can be adjusted as appropriate for each material to be used, taking into account the effect of suppressing performance degradation.
- It is about 1 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 20 to 50% by weight.
- concentration of the water-soluble organic substance is less than 1% by weight, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- concentration of the water-soluble organic substance is less than 1% by weight, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- it exceeds 90% by weight the effect on the performance of the separation membrane increases, and the permeation flux tends to decrease.
- the surface tension of the water-soluble organic substance is preferably 0.04 N / m or less, and more preferably 0.02-0.035 NZm, from the viewpoint of permeability in the membrane.
- the surface tension exceeds 0.04 NZm, the permeability into the membrane is lowered, and the removal effect of the unreacted polyfunctional amine component tends to be insufficient.
- it is a water-soluble organic substance with a surface tension of more than 0.04 N / m, if it is used in a small amount against a water-soluble organic substance with a surface tension of 0.04 NZm or less, it will promote swelling of the membrane. May increase the cleaning effect.
- an aqueous solution containing 50% by weight of ethanol (surface tension: 0.022NZm) and an aqueous solution containing 40% by weight of ethanol and 10% by weight of diethylene glycol (surface tension: 0.045NZm) use the latter.
- the unreacted polyfunctional amine component can be efficiently removed.
- glycerin surface tension: 0.063 NZm
- the amount of water-soluble organic material with a surface tension exceeding 0.04NZm depends on the surface tension of the water-soluble organic material used.
- the concentration of the water-soluble organic substance in the solution can be appropriately adjusted for each material to be used in consideration of the removal performance of the unreacted polyfunctional amine component and the effect of suppressing the deterioration of the membrane performance. It is 100% by weight, preferably 10 to 80% by weight, and more preferably 20 to 50% by weight. It is particularly preferable to use an aqueous solution having the above concentration. When the concentration of the water-soluble organic substance is less than 1% by weight, it tends to be difficult to efficiently remove 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 wt%, more preferably 50 ppm to 20 wt%, particularly preferably 1 to: LO wt%.
- concentration of the acidic substance is less than 10 ppm, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- concentration of the acidic substance is less than 10 ppm, it tends to be difficult to efficiently remove the unreacted polyfunctional amine component from the semipermeable membrane.
- it exceeds 50% by weight the effect on the performance of the semipermeable membrane becomes large.
- the contact time is not limited as long as the content of the unreacted polyfunctional amine component in the base material after the membrane cleaning treatment is 0.5 mgZm 2 or less and the manufacturing constraints allow. You can set an arbitrary time. In the present invention, since the content of the unreacted polyfunctional amine component in the porous support before the membrane washing treatment is small, the contact time in the membrane washing treatment may be short. Although it is not possible to generally define the contact time, it is usually several seconds to several tens of minutes, more preferably 10 seconds to 3 minutes. Even if the contact time is increased, the removal amount of the unreacted polyfunctional amine component reaches equilibrium, so the removal effect does not improve further. If the contact time is too long, the membrane performance and production efficiency tend to be lowered.
- the contact temperature is not particularly limited as long as the solution exists as a liquid, but it is 10 to 90 in view of the removal effect of the unreacted polyfunctional amine component, the viewpoint of preventing the deterioration of the film, and the ease of handling.
- the temperature is preferably 10 ° C, more preferably 10 to 60 ° C, and particularly preferably 10 to 45 ° C.
- the pressure at which the solution is applied to the semipermeable membrane is within the allowable range of the physical strength of the semipermeable membrane and the member for applying pressure.
- the allowable range of the physical strength of the semipermeable membrane and the member for applying pressure There is no limitation in the case of 0.1, but it is preferable to do with LOMPa, and more preferable is 1.5 to 7.5 MPa. 0. If it is less than IMPa, the contact time tends to be longer when trying to obtain the desired effect, and if it exceeds lOMPa, the permeate flow rate tends to decrease due to consolidation.
- the liquid in which the semipermeable membrane is immersed is not particularly limited as long as it does not deteriorate the performance of the semipermeable membrane, and examples thereof include organic solvents, distilled water, ion-exchanged water, and aqueous solutions containing organic and inorganic substances. Can be mentioned. It is particularly preferable to use an aqueous solution containing alcohol, acid, or alkali.
- Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, n -propyl alcohol, and isopropyl alcohol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and glycerin. These may be used alone or in combination of two or more.
- the alcohol concentration in the aqueous solution can be appropriately adjusted for each material to be used in consideration of the removal performance of the unreacted polyfunctional amine component and the effect of suppressing the deterioration of the membrane performance, but is usually about 1 to 90% by weight. More preferably, it is 10 to 80% by weight, particularly preferably 20 to 50% by weight.
- the alcohol concentration is less than 1% by weight, the semipermeable membrane does not swell sufficiently, and thus there is a tendency that a synergistic effect with ultrasonic cleaning cannot be obtained sufficiently.
- it exceeds 90% by weight the effect on the performance of the semipermeable membrane becomes large, and the salt rejection and the permeation flux tend to decrease.
- the acid is not particularly limited as long as it is water-soluble, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, and citrate.
- inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid
- organic acids such as formic acid, acetic acid, and citrate.
- the alkali is not particularly limited as long as it is water-soluble, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali earth metal hydroxides such as calcium hydroxide, and ammonia. And amines.
- the concentration of the acid or alkali in the aqueous solution can be appropriately adjusted for each material to be used in consideration of the removal performance of the unreacted polyfunctional amine component and the effect of suppressing the deterioration of the membrane performance.
- % By weight is preferred, more preferably 50 ppm to 20% by weight, especially preferred 1 ⁇ : LO weight%.
- the acid or alkali concentration is less than lOppm, the semipermeable membrane does not swell sufficiently, and thus there is a tendency that a synergistic effect with ultrasonic cleaning cannot be obtained sufficiently.
- it exceeds 50% by weight the effect on the performance of the semipermeable membrane increases, and the salt rejection and permeation flux tend to decrease.
- the temperature of the liquid in which the semipermeable membrane is immersed is not particularly limited, but may be 10 to 90 ° C in view of the removal performance of the unreacted polyfunctional amine component, the effect of suppressing the deterioration of the membrane performance, the ease of handling, and the like. It is more preferably 10 to 60 ° C, particularly preferably 10 to 45 ° C.
- the ultrasonic cleaning time can be appropriately adjusted for each material used in consideration of the removal performance of the unreacted polyfunctional amine component and the effect of suppressing the deterioration of the membrane performance, but it is usually several seconds to several minutes. Yes, preferably 10 seconds to 3 minutes. Even if the cleaning time is too long, the removal amount of the unreacted polyfunctional amine component reaches equilibrium, and the removal effect does not improve further. If the cleaning time is too long, the membrane performance and production efficiency tend to be lowered.
- the shape of the semipermeable membrane is not limited at all when the membrane cleaning treatment is performed. In other words, it is possible to treat all possible membrane shapes such as flat membrane shapes or spiral element shapes.
- the composite semipermeable membrane produced by such a production method is separated and purified using the composite semipermeable membrane having a very low content of unreacted polyfunctional amine component in the porous support.
- the target substance in excess or concentrated has very little impurities and high purity.
- the semipermeable membrane washed by the above method may be dried to form a dry type composite semipermeable membrane. In that case, before the washed semipermeable membrane is dried, the semipermeable membrane needs to be moisturized.
- the moisturizing treatment is performed by supplying a moisturizing agent to the washed semipermeable membrane.
- a moisturizing agent for example, immersion in a solution containing a humectant, application of a solution containing a humectant, spraying or pressurized water passage, and contact with a humectant vapor.
- a known method can be employed.
- the humectant can be any compound that can impart moisture retention to the washed semipermeable membrane.
- organic acid alkali metal salts such as sodium acetate, potassium acetate, sodium lactate, lactate, sodium glutamate, and potassium glutamate
- organic acid alkaline earth metal salts such as calcium glutamate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, disodium monohydrogen phosphate, dipotassium monohydrogen phosphate, disodium dihydrogen phosphate, phosphorus Inorganic acid alkali metal salts such as dibasic acid hydrogen, sodium phosphate, and potassium phosphate
- Cal Inorganic acid alkaline earth metal salts such as sodium, dibasic magnesium phosphate, dicalcium phosphate,
- the concentration of the humectant in the solution is not particularly limited, but it is preferably 100 ppm to 30% by weight, more preferably 500 ppm to 10% by weight.
- concentration of the humectant is less than lOOppm, there is a tendency that the water permeation performance and the salt inhibition rate are not sufficiently reduced after the drying treatment, and the moisturizing treatment time is long.
- concentration of the humectant exceeds 30% by weight, the cost tends to increase or the membrane performance tends to be adversely affected.
- the immersion time is not particularly limited, but is preferably 0.1 seconds to 30 minutes, more preferably 1 second. ⁇ 10 minutes.
- the immersion time is less than 0.1 second, the water permeation performance after the drying treatment and the effect of suppressing the decrease of the salt rejection rate tend not to be sufficiently obtained.
- the soaking time exceeds 30 minutes, the water permeation performance and the salt inhibition rate after the drying treatment are not changed so much and the production efficiency is lowered.
- the application surface should be one side. Although it may be present on both sides, it is preferably applied on both sides in order to exhibit the effect efficiently.
- the temperature of the solution is not particularly limited as long as the solution exists as a liquid.
- ⁇ Strength From 10 to 90 ° C from the viewpoint of moisturizing effect, prevention of film deterioration, ease of handling, and the like. More preferably, it is 10 to 60 ° C, particularly preferably 10 to 45 ° C.
- the pressure applied to the semipermeable membrane that has been subjected to the washing treatment of the powerful solution is the physical strength of the semipermeable membrane and the member for applying pressure.
- the cleaning process and the moisturizing process may be performed simultaneously on the manufactured uncleaned semipermeable membrane.
- the treatment method include a method in which the moisturizing agent is added to the washing liquid used in the washing treatment to prepare a washing moisturizing liquid, and the treatment is performed using the washing moisturizing liquid.
- the shape of the semipermeable membrane is not limited at all. In other words, it is possible to perform the drying treatment in all conceivable film shapes such as a flat film shape or a spiral shape.
- a semipermeable membrane may be processed into a spiral shape to produce a membrane unit, and the membrane unit may be dried to produce a dry spiral element.
- the temperature at which the drying treatment is performed is not particularly limited, but is preferably 20 to 150 ° C, more preferably 40 to 130 ° C. If the temperature is below 20 ° C, the drying process takes too much time or the drying becomes insufficient. If the temperature exceeds 150 ° C, the film performance tends to deteriorate due to the structural change of the film due to heat. .
- the time for performing the drying treatment is not particularly limited, but it is preferable to dry until the amount of the solvent in the semipermeable membrane is 5% by weight or less.
- the dried composite semipermeable membrane of the present invention is of a dry type, it is excellent in processability and storage stability.
- the dried composite semipermeable membrane of the present invention is a wet type while being a dry type. Water permeation performance and salt inhibition performance equivalent to the composite semipermeable membrane of.
- the composite semipermeable membrane ( ⁇ 25mm) before membrane cleaning treatment prepared in Examples and Comparative Examples is immersed in an aqueous solution (25 ° C) containing 50% by weight of ethanol, and left for about 8 hours to composite. Unreacted polyfunctional amine components in the semipermeable membrane were extracted. The UV absorbance at 210 nm of the obtained extract was measured. On the other hand, a correlation (calibration curve) between the concentration of the polyfunctional amine component in the 50% by weight ethanol aqueous solution and the 210 nm absorbance of the aqueous solution was prepared in advance, and used in the composite semipermeable membrane before membrane cleaning treatment. The amount of unreacted polyfunctional amine component contained was measured.
- the composite semipermeable membrane ( ⁇ 25 mm) is cut into a predetermined area and divided into 1) a substrate, 2) a skin layer and a microporous layer, and then the same method as described above. The amount of unreacted multifunctional amine component contained in each layer was measured. The results are shown in Tables 1-3.
- the produced flat membrane-shaped composite semipermeable membrane is cut into a predetermined shape and size and set in a cell for flat membrane evaluation.
- Aqueous solution containing about 1500 mg / L NaCl and adjusted to pH 6.5 to 7.5 with NaOH is applied to the membrane by applying a differential pressure of 1.5 MPa on the supply side and permeation side of the membrane at 25 ° C.
- the permeation rate and conductivity of the permeated water obtained by this operation were measured, and the permeation flux (m 3 Zm 2 'd) and the salt rejection (%) were calculated.
- the salt rejection was calculated in advance using a correlation (calibration curve) between NaCl concentration and aqueous solution conductivity in advance.
- Salt rejection (%) ⁇ 1— (NaCl concentration in permeate [mgZL]) Z (NaCl concentration in feed)
- aqueous amine solution was brought into contact with one side of the porous support to be used at normal pressure, and pure water was brought into contact with the other side at normal pressure.
- the amine is detected after a lapse of a certain time from the contact with the pure water side.
- the concentration begins to increase and then increases over time.
- the gradient was defined as the migration rate of the ammine component (mgZm 2 'sec).
- the concentration of the amine component on the pure water side was measured using an ultraviolet-visible spectrophotometer “UV-2450” (manufactured by Shimadzu Corporation).
- a support sample having a predetermined area was dried at a predetermined temperature, and the weight change force before and after the drying was calculated.
- Polysulfones (Solvay Co., P- 3500) 18 wt 0/0 N, was uniformly applied by wet thickness 200 m of the film dope dissolved in onto the nonwoven substrate N- dimethylformamide (D MF). Thereafter, the porous substrate having a polysulfone microporous layer on the nonwoven fabric substrate is immediately solidified by being immersed in water at 40 to 50 ° C., and DMF as a solvent is completely extracted and washed. Produced.
- DMF dimethylformamide
- the produced porous support was heated and dried at 40 ° C.
- the water content in the porous support after heat drying was lg / m 2 .
- a composite semipermeable membrane was prepared by immersing the unwashed composite semipermeable membrane in pure water at 50 ° C for 1 minute to perform a membrane cleaning treatment.
- Examples 2-15 As shown in Table 1, a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the drying temperature of the porous support and the composition of the aqueous amine solution were changed, and a permeation test was performed. Table 1 shows the results of the transmission test.
- a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the porous support was not dried and the composition of the aqueous amine solution was changed, and a permeation test was performed. The results of the penetration test are shown in Table 1. Since there are many unreacted polyfunctional amine components in the porous support, practicality is not satisfied.
- a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the porous support was not dried and the composition of the aqueous amine solution was changed, and a permeation test was performed. The results of the penetration test are shown in Table 1. Since there are too many unreacted polyfunctional amine components in the porous support, practicality is not satisfied.
- the produced porous support was air-dried at room temperature.
- the water content in the porous support after drying is 7 lgZ m.
- a composite semipermeable membrane was prepared by immersing the unwashed composite semipermeable membrane in pure water at 50 ° C for 1 minute to perform a membrane cleaning treatment.
- the produced porous support was heated and dried at 60 ° C.
- the water content in the porous support after heat drying was lg / m 2 .
- m- Hue - Renjiamin 1 wt 0/0, Toryechiruamin 3 weight 0/0, and 60GZm 2 to Amin aqueous solution containing 6 wt% camphorsulfonic acid on the porous support (m- Hue - Renjiamin: 600mgZm 2)
- an aqueous solution coating layer was formed by wiping and removing the excess aqueous amine solution.
- an isooctane solution containing 0.25% by weight of trimesic acid chloride was applied to the surface of the aqueous solution coating layer.
- the membrane can be washed by immersing the unwashed composite semipermeable membrane in pure water at 50 ° C for 1 minute. Processed. A permeation test was performed using the prepared composite semipermeable membrane. Table 2 shows the results of the transmission test.
- a composite semipermeable membrane was prepared in the same manner as in Example 18 except that the composition and supply amount of the aqueous amine solution were changed, and a permeation test was performed.
- Table 2 shows the results of the transmission test.
- Polysulfones (Solvay Co., P- 3500) 20 weight 0/0 N, was uniformly applied by wet thickness 200 m of the film dope dissolved in onto the nonwoven substrate N- dimethylformamide (D MF). Thereafter, the porous substrate having a polysulfone microporous layer on the nonwoven fabric substrate is immediately solidified by being immersed in water at 40 to 50 ° C., and DMF as a solvent is completely extracted and washed. Produced.
- DMF dimethylformamide
- the produced porous support was heated and dried at 40 ° C. Containing water of the porous support during after drying was lgZm 2.
- a composite semipermeable membrane was prepared by immersing the unwashed composite semipermeable membrane in pure water at 50 ° C for 1 minute to perform a membrane cleaning treatment.
- a composite semipermeable membrane was prepared in the same manner as in Example 23 except that the composition of the membrane dope, the drying temperature of the porous support, and the composition of the aqueous amine solution were changed. went.
- Table 3 shows the results of the transmission test.
- Example 33 A moisturizing composite semipermeable membrane was produced by immersing the washed composite semipermeable membrane produced in Example 1 in a 25 ° C. aqueous sodium acetate solution (concentration: 1 wt%) for 10 minutes. Thereafter, the moisture-retaining composite semipermeable membrane was dried at 120 ° C. for 10 minutes to produce a dry composite semipermeable membrane. Table 4 shows the results of the penetration test.
- a dry composite semipermeable membrane was produced in the same manner as in Example 33 under the conditions described in Table 4.
- Table 4 shows the results of the transmission test.
- Example 2 An unwashed composite semipermeable membrane produced by the same method as in Example 1 was immersed for 10 minutes in an aqueous sodium acetate solution (concentration: 1% by weight) in which sodium acetate was added to pure water at 50 ° C. Thus, washing and moisturizing treatment were simultaneously performed to produce a moisturizing composite semipermeable membrane. Thereafter, the moisture-retaining composite semipermeable membrane was dried at 120 ° C. for 10 minutes to produce a dry composite semipermeable membrane. Table 4 shows the results of the penetration test.
- a dry composite semipermeable membrane was produced in the same manner as in Example 52 under the conditions described in Table 4.
- Table 4 shows the results of the transmission test.
- a washed composite semipermeable membrane was produced in the same manner as in Example 1. Thereafter, the dried composite semipermeable membrane was dried at 120 ° C. for 2 minutes without applying a moisturizing treatment to produce a dry composite semipermeable membrane.
- Table 4 shows the results of the transmission test.
- Porous support Ammine aqueous solution Permeation test Amount of unreacted polyfunctional amine component
- Example 1 40 1 1 3 6 ⁇ 0.02 98.0 1.2 67 3.4 3.4 ⁇ 0.1
- Example 2 40 1 1.25 3 6 ⁇ 0.02 99.1 1.5 119 4.8 4.8 0.1 0.1
- Example 3 40 1 1.5 3 6 ⁇ 0.02 99.4 1.6 164 13 13 ⁇ 0.1
- Example 4 50 1 1 3 6 ⁇ 0,02 95.2 1.0 75 ⁇ 0.1 0.1 ⁇ 0.1
- Example 5 50 1 1.25 3 6 ⁇ 0.02 99.0 1.4 117 6.8 6.8 ⁇ 0.1
- Example 6 50 1 1.5 3 6 ⁇ 0.02 99.4 1.4 172 18.3 18.3 1 0.1
- Example 7 60 1 1.5 3 6 ⁇ 0.02 98.9 1.0 145 14.8 14.8 0 0.1
- Example 8 80 1 1.5 1.5 3 6 ⁇ 0.02 98.9 1.0 145 14.8 14.8 0 0.1
- Example 8 80 1 1.5 1.5 3 6 ⁇ 0.02 98.9 1.0 145 14.8 14.8 0 0.1
- Example 8 80 1 1.5
- Luamine sulfonic acid component (m 3 m 2 -d)
- Example 19 60 1 1 3 6 40 400 98.2 97.6 1.1 1.1 19 ⁇ 0.1.0.1 0.1 Example 20 60 1 1.5 2 4 40 600 95.8 95.0 0,7 0.6 3 ⁇ 0.1.0.1 0.1 0.1 Example 21 60 1 1.5 3 6 40 600 98.4 98.0 1.3 1.4 38 11.2 11.2 ⁇ 0.1 Example 22 60 1 1.5 4 8 40 600 98.7 98.8 1.0 1.2 110 11.3 11.3 ⁇ 0.1
- Example 23 20 ⁇ 40 1 1.5 3 6 40 98.3 0.6 26 less than 0.1 0.1 less 0.1
- Example 24 20-40 1 1.5 3 6 50 97.6 0.7 26 less than 0.1 less than 0.1
- Example 25 20 ⁇ 60 1 1.5 3 6 50 99.2 1.3 68 less than 0.1 less than 0.1
- Example 26 20-80 1 1.5 3 6 50 99.2 1.4 75 less than 0.1 less than 0.1 0.1
- Example 27 20-120 1 1.5 3 6 50 98.9 1.6 29 less than 0.1 0.1 0.1
- Example 28 16 10 40 1 1.5 3 6 40 98.9 1.0 123 15.0 15.0 less 0.1
- Example 29 16 10 60 1 1 3 6 50 96J
- the porous support is effectively prevented from penetrating the polyfunctional amine component into the porous support by subjecting it to an amine impermeability treatment. Can do. Thereby, the content of the unreacted polyfunctional amine component in the porous support after the skin layer is formed can be reduced. And for simple and short-time membrane cleaning Thus, the content of the unreacted polyfunctional amine component in the porous support can be greatly reduced with almost no decrease in membrane performance. Further, as is apparent from Table 4, a dry composite semipermeable membrane having excellent water permeation performance and salt rejection even after the drying treatment is obtained by applying moisture retention to the washed composite semipermeable membrane. be able to.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05782337A EP1820566B1 (en) | 2004-10-01 | 2005-09-09 | Prosses for producing a semipermeable composite membrane |
KR1020087031402A KR100888183B1 (ko) | 2004-10-01 | 2005-09-09 | 복합 반투막 및 그의 제조 방법 |
US11/664,371 US20080257818A1 (en) | 2004-10-01 | 2005-09-09 | Semipermeable Composite Membrane and Process for Producing the Same |
CNB2005800327012A CN100558452C (zh) | 2004-10-01 | 2005-09-09 | 复合半透膜及其制造方法 |
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JP2004290404 | 2004-10-01 | ||
JP2004-290404 | 2004-10-01 | ||
JP2005-094573 | 2005-03-29 | ||
JP2005094573A JP4656502B2 (ja) | 2004-10-01 | 2005-03-29 | 複合半透膜及びその製造方法 |
Publications (1)
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WO2006038426A1 true WO2006038426A1 (ja) | 2006-04-13 |
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PCT/JP2005/016618 WO2006038426A1 (ja) | 2004-10-01 | 2005-09-09 | 複合半透膜及びその製造方法 |
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US (1) | US20080257818A1 (ja) |
EP (1) | EP1820566B1 (ja) |
JP (1) | JP4656502B2 (ja) |
KR (2) | KR100884154B1 (ja) |
CN (1) | CN100558452C (ja) |
WO (1) | WO2006038426A1 (ja) |
Cited By (1)
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WO2013047398A1 (ja) * | 2011-09-29 | 2013-04-04 | 東レ株式会社 | 複合半透膜 |
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- 2005-09-09 KR KR1020077009861A patent/KR100884154B1/ko not_active IP Right Cessation
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Cited By (3)
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WO2013047398A1 (ja) * | 2011-09-29 | 2013-04-04 | 東レ株式会社 | 複合半透膜 |
CN103842062A (zh) * | 2011-09-29 | 2014-06-04 | 东丽株式会社 | 复合半透膜 |
JPWO2013047398A1 (ja) * | 2011-09-29 | 2015-03-26 | 東レ株式会社 | 複合半透膜 |
Also Published As
Publication number | Publication date |
---|---|
KR100888183B1 (ko) | 2009-03-10 |
EP1820566A4 (en) | 2008-05-07 |
KR20070057267A (ko) | 2007-06-04 |
EP1820566A1 (en) | 2007-08-22 |
JP2006122886A (ja) | 2006-05-18 |
CN101027116A (zh) | 2007-08-29 |
US20080257818A1 (en) | 2008-10-23 |
JP4656502B2 (ja) | 2011-03-23 |
EP1820566B1 (en) | 2012-06-06 |
KR100884154B1 (ko) | 2009-02-17 |
CN100558452C (zh) | 2009-11-11 |
KR20090007499A (ko) | 2009-01-16 |
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