WO2015068657A1 - 複合半透膜 - Google Patents
複合半透膜 Download PDFInfo
- Publication number
- WO2015068657A1 WO2015068657A1 PCT/JP2014/079087 JP2014079087W WO2015068657A1 WO 2015068657 A1 WO2015068657 A1 WO 2015068657A1 JP 2014079087 W JP2014079087 W JP 2014079087W WO 2015068657 A1 WO2015068657 A1 WO 2015068657A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite semipermeable
- semipermeable membrane
- layer
- thickness
- polymer porous
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 74
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- 238000000926 separation method Methods 0.000 claims abstract description 27
- 229920002647 polyamide Polymers 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 72
- 230000004907 flux Effects 0.000 claims description 36
- 239000004745 nonwoven fabric Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000002346 layers by function Substances 0.000 claims description 21
- 239000012466 permeate Substances 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
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- 239000002351 wastewater Substances 0.000 abstract description 5
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- 239000000243 solution Substances 0.000 description 21
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- 239000002253 acid Substances 0.000 description 18
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- 230000014759 maintenance of location Effects 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- -1 glutaryl halide Chemical class 0.000 description 7
- 238000012695 Interfacial polymerization Methods 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
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- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229960005141 piperazine Drugs 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000996 additive effect 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
- 238000009835 boiling Methods 0.000 description 2
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- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-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
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- 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
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
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- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
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- ITTFEPALADGOBD-UHFFFAOYSA-N 2-butylpropanedioyl dichloride Chemical compound CCCCC(C(Cl)=O)C(Cl)=O ITTFEPALADGOBD-UHFFFAOYSA-N 0.000 description 1
- IPOVOSHRRIJKBR-UHFFFAOYSA-N 2-ethylpropanedioyl dichloride Chemical compound CCC(C(Cl)=O)C(Cl)=O IPOVOSHRRIJKBR-UHFFFAOYSA-N 0.000 description 1
- MLNSYGKGQFHSNI-UHFFFAOYSA-N 2-propylpropanedioyl dichloride Chemical compound CCCC(C(Cl)=O)C(Cl)=O MLNSYGKGQFHSNI-UHFFFAOYSA-N 0.000 description 1
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 239000004642 Polyimide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 230000010933 acylation Effects 0.000 description 1
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- 239000003899 bactericide agent Substances 0.000 description 1
- 150000007514 bases Chemical class 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
- YBGQXNZTVFEKEN-UHFFFAOYSA-N benzene-1,2-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1S(Cl)(=O)=O YBGQXNZTVFEKEN-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
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 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
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- 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
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- 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
- 230000006866 deterioration Effects 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
- 239000010840 domestic wastewater Substances 0.000 description 1
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- QYDOSFKIGGBBQJ-UHFFFAOYSA-N furan-2,3,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C=1OC(C(Cl)=O)=C(C(Cl)=O)C=1C(Cl)=O QYDOSFKIGGBBQJ-UHFFFAOYSA-N 0.000 description 1
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- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 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
- 239000003960 organic solvent Substances 0.000 description 1
- LSHSZIMRIAJWRM-UHFFFAOYSA-N oxolane-2,3-dicarbonyl chloride Chemical compound ClC(=O)C1CCOC1C(Cl)=O LSHSZIMRIAJWRM-UHFFFAOYSA-N 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
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 238000002360 preparation method Methods 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
- 230000009467 reduction Effects 0.000 description 1
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- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
- B01D63/107—Specific properties of the central tube or the permeate channel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
- B01D63/12—Spiral-wound membrane modules comprising multiple spiral-wound assemblies
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
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- 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
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- 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
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- 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
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- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Definitions
- the present invention relates to a composite semipermeable membrane for separating and concentrating specific substances from various liquids.
- An object of the present invention is to provide a composite semipermeable membrane having high processing efficiency (particularly flux) even when such a method is used, and in which the processing efficiency is not easily lowered even during a pressure increase operation under high pressure.
- the present invention provides a composite semipermeable membrane having a polymer porous layer on one side of a nonwoven fabric layer and a polyamide-based separation functional layer on the polymer porous layer, the thickness of the polymer porous layer and the thickness of the nonwoven fabric layer. Relates to a composite semipermeable membrane having a ratio of 0.22 to 0.45.
- the composite semipermeable membrane has an initial permeation flux (F0) of 1.0 m 3 / m 2 / d or more when pure water is permeated at a pressure of 1.5 MPa, and is pure at a pressure of 5.5 MPa. After passing water under pressure for 4 hours, the permeation flux (F1) when pure water is permeated at a pressure of 1.5 MPa is 1.0 m 3 / m 2 / d or more, and the pressure water flow
- the composite semipermeable membrane has a front and rear permeation flux ratio (F1 / F0) of 0.8 or more, that is, a permeation flux retention (F1 / F0 ⁇ 100) of 80% or more.
- the thickness of the polymer porous layer in the composite semipermeable membrane is preferably 10 ⁇ m or more and 35 ⁇ m or less. Further, it is more preferably 32 ⁇ m or less, particularly preferably 29 ⁇ m or less, and most preferably 23 ⁇ m or less.
- the nonwoven fabric layer preferably has a thickness of 120 ⁇ m or less.
- the polyamide-based separation functional layer is preferably a separation functional layer using a polyfunctional amine component containing piperazine or m-phenylenediamine as a raw material component.
- the function of the present invention can be further enhanced by coating the surface of the polyamide-based separation functional layer with polyvinyl alcohol having a saponification degree of 99% or more.
- the composite semipermeable membrane of the present invention is not particularly limited to this, but is a perforated hollow having a plurality of holes on a wall surface, in which an envelope-like membrane folded in two and a channel material are laminated. It is preferably used as a spiral type composite semipermeable membrane element wound around a tube and integrated using an end member and an exterior material.
- 30 to 40 sets of the envelope-like membrane can be used, which further contributes to higher efficiency of the element.
- the thickness of the flow path material provided on the inner surface of the envelope membrane is 0.9 mm or more and 1.3 mm or less, so that the composite semipermeable membrane of the present invention is further used. It has been found that the permeation flux retention of a spiral type composite semipermeable membrane element using a membrane can be increased.
- a composite semipermeable membrane having a polymer porous layer on one side of a nonwoven fabric layer and further having a polyamide-based separation functional layer thereon, the thickness of the polymer porous layer and the thickness of the nonwoven fabric layer
- the ratio is 0.22 to 0.45.
- the present inventors have found a composite semipermeable membrane in which the permeation flux (Flux) is significantly less than that in the past.
- the composite semipermeable membrane is not particularly limited as long as it has a polyamide-based separation functional layer on the polymer porous layer of the composite semipermeable membrane support composed of a nonwoven fabric and a polymer porous layer.
- the thickness is about 40 to 200 ⁇ m. If this composite semipermeable membrane is too thin, high-pressure processing becomes difficult, for example, the film surface is missing due to pressure during processing. Therefore, 55 ⁇ m or more is preferable, and 75 ⁇ m or more is more preferable. On the other hand, as the composite semipermeable membrane is thinner, more membranes can be loaded in a certain element space, so that the performance can be improved.
- Such composite semipermeable membranes are called RO (reverse osmosis) membranes, NF (nanofiltration) membranes, and FO (forward osmosis) membranes depending on their filtration performance and treatment method, and they are used for ultrapure water production and seawater desalination. It can be used for desalination of brine, reuse of waste water, etc.
- the polyamide-based separation functional layer is generally a homogeneous membrane having no visible pores and has a desired ion separation ability.
- the separation functional layer is not particularly limited as long as it is a polyamide-based thin film that is difficult to peel off from the polymer porous layer.
- a polyfunctional amine component and a polyfunctional acid halide component are formed on the porous support membrane.
- a polyamide-based separation functional layer obtained by interfacial polymerization is well known.
- Such a polyamide-based separation functional layer is known to have a pleated microstructure, and the thickness of this layer is not particularly limited, but is about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m. It is known that if this layer is too thin, film surface defects are likely to occur, and if it is too thick, the transmission performance deteriorates.
- the method for forming the polyamide-based separation functional layer on the surface of the polymer porous layer is not particularly limited, and any known method can be used. Examples of the method include an interfacial polymerization method, a phase separation method, and a thin film coating method. In the present invention, the interfacial polymerization method is particularly preferably used. In the interfacial polymerization method, for example, the polymer porous layer is coated with a polyfunctional amine component-containing amine aqueous solution, and then an organic solution containing a polyfunctional acid halide component is brought into contact with the amine aqueous solution-coated surface to cause interfacial polymerization. This is a method for forming a skin layer.
- a removal method a method of inclining a target film, a method of blowing off a gas, a rubber, For example, a method of scraping off a blade by contacting the blade is preferably used.
- the time required for the aqueous amine solution and the organic solution to contact is approximately 1 to 120 seconds, although it depends on the composition of the aqueous amine solution, the viscosity, and the pore diameter of the surface of the porous support membrane. Is about 2 to 40 seconds. If the interval is too long, the aqueous amine solution may permeate and diffuse deep inside the porous support membrane, and a large amount of unreacted polyfunctional amine component may remain in the porous support membrane, resulting in problems. . When the application interval of the solution is too short, an excessive amine aqueous solution remains, so that the film performance tends to be lowered.
- the heating temperature is more preferably 70 to 200 ° C., particularly preferably 80 to 130 ° C.
- the heating time is preferably about 30 seconds to 10 minutes, more preferably about 40 seconds to 7 minutes.
- the polyfunctional amine component contained in the amine aqueous solution is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines.
- the aromatic polyfunctional amine include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5- Examples thereof include diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, xylylenediamine and the like.
- Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
- Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine and the like. It is done. These polyfunctional amines may be used alone or in combination of two or more.
- m-phenylenediamine when a high rejection is required for reverse osmosis membrane performance, it is preferable to use m-phenylenediamine as a main component, which can provide a highly dense separation function layer, and high flux retention in NF membrane performance.
- piperazine when determining the rate, it is preferable to use piperazine as the main component.
- the polyfunctional acid halide component contained in the organic solution is a polyfunctional acid halide having two or more reactive carbonyl groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
- aromatic polyfunctional acid halide include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, and chlorosulfonylbenzene.
- dicarboxylic acid dichloride 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, glutaryl halide, azide. Poil halide etc. are mentioned.
- Examples of the alicyclic polyfunctional acid halide include cyclopropane tricarboxylic acid trichloride, cyclobutane tetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentane tetracarboxylic acid tetrachloride, cyclohexane tricarboxylic acid trichloride, and tetrahydro Examples include furantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic 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.
- the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 7% by weight, more preferably 1 to 5% by weight. If the concentration of the polyfunctional amine component is too low, defects are likely to occur in the skin layer, and the salt blocking performance tends to be reduced. On the other hand, when the concentration of the polyfunctional amine component is too high, it becomes too thick and the permeation flux tends to decrease.
- the concentration of the polyfunctional acid halide 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 too low, the unreacted polyfunctional amine component is increased, and defects are likely to occur in the skin layer. On the other hand, if the concentration of the polyfunctional acid halide component is too high, the amount of unreacted polyfunctional acid halide component increases, so that the skin layer becomes too thick and the permeation flux tends to decrease.
- the organic solvent containing the polyfunctional acid halide is not particularly limited as long as it has low solubility in water and does not deteriorate the porous support membrane, and can dissolve the polyfunctional acid halide component.
- cyclohexane examples thereof include saturated hydrocarbons such as heptane, octane and nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorotrifluoroethane.
- Preferred is a saturated hydrocarbon having a boiling point of 300 ° C. or lower, more preferably a boiling point of 200 ° C. or lower.
- the additive may add the additive for the purpose of the improvement of various performance and a handleability to the said amine aqueous solution and organic solution.
- the additive include polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid, polyhydric alcohols such as sorbitol and glycerin, and surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate.
- Basic compounds such as sodium hydroxide, trisodium phosphate and triethylamine for removing hydrogen halide produced by polymerization, acylation catalysts, and solubility parameters described in JP-A-8-224452 are 8 to 14 (cal / Cm 3 ) 1/2 compound and the like.
- a coating layer composed of various polymer components may be provided on the exposed surface of the polyamide-based separation functional layer.
- the polymer component is not particularly limited as long as it does not dissolve the separation functional layer and the porous support membrane and does not elute during the water treatment operation.
- polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyethylene And glycols and saponified polyethylene-vinyl acetate copolymers for example, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyethylene And glycols and saponified polyethylene-vinyl acetate copolymers.
- polyvinyl alcohol in particular, by using polyvinyl alcohol having a saponification degree of 99% or more, or by crosslinking polyvinyl alcohol having a saponification degree of 90% or more with the polyamide-based resin of the skin layer, It is preferable to use a structure that does not easily dissolve during water treatment.
- the charge state of the film surface is adjusted and hydrophilicity is imparted, so that the adhesion of contaminants can be suppressed, and further, the flux retention effect is achieved by a synergistic effect with the present invention. Can be further enhanced.
- the nonwoven fabric layer is not particularly limited as long as it provides an appropriate mechanical strength while maintaining the separation performance and permeation performance of the composite semipermeable membrane, and a commercially available nonwoven fabric can be used.
- a material made of polyolefin, polyester, cellulose or the like is used, and a material in which a plurality of materials are mixed can also be used.
- polyester in terms of moldability.
- a long fiber nonwoven fabric or a short fiber nonwoven fabric can be used as appropriate, but a long fiber nonwoven fabric can be preferably used from the viewpoint of fine fuzz that causes pinhole defects and uniformity of the film surface.
- the air permeability of the nonwoven fabric layer at this time is not limited to this, but it can be about 0.5 to 10 cm 3 / cm 2 ⁇ s, and 1 to 5 cm 3 / s. Those having a size of about cm 2 ⁇ s are preferably used.
- the thickness of the nonwoven fabric layer is preferably 120 ⁇ m or less, more preferably 100 ⁇ m or less, and particularly preferably 78 ⁇ m or less. If this thickness is too thick, the permeation resistance becomes too high and the flux tends to decrease. On the other hand, if it is too thin, the mechanical strength as a composite semipermeable membrane support will decrease, making it difficult to obtain a stable composite semipermeable membrane. Therefore, it is preferably 30 ⁇ m or more, and more preferably 45 ⁇ m or more.
- the polymer porous layer is not particularly limited as long as it can form the polyamide-based separation functional layer, but is usually a microporous layer having a pore diameter of about 0.01 to 0.4 ⁇ m.
- the material for forming the microporous layer may include various materials such as polysulfone, polyarylethersulfone exemplified by polyethersulfone, polyimide, and polyvinylidene fluoride.
- the thickness of the polymer porous layer is preferably 35 ⁇ m or less, and more preferably 32 ⁇ m or less. It has been found that if it is too thick, the flux retention after pressurization tends to decrease. Furthermore, 29 ⁇ m or less is particularly preferable, and 23 ⁇ m or less is most preferable. By forming the thin film to this extent, the stability of the flux retention rate can be further increased. Moreover, since it will become easy to produce a defect when it is too thin, 10 micrometers or more are preferable and 15 micrometers or more are more preferable.
- the polymer porous layer can be produced by a method generally called a wet method or a dry wet method.
- a solution preparation step in which polysulfone, a solvent and various additives are dissolved
- a coating step in which the nonwoven fabric is coated with the solution
- a drying step in which the solvent in the solution is evaporated to cause microphase separation, a water bath, etc.
- the polymer porous layer can be formed on the non-woven fabric through an immobilization step of immobilizing by immersing in the coagulation bath.
- the thickness of the polymer porous layer can be set by adjusting the solution concentration and the coating amount after calculating the ratio of impregnation into the nonwoven fabric layer.
- the ratio of the thickness of the polymer porous layer and the thickness of the nonwoven fabric layer of the composite semipermeable membrane support thus obtained (the thickness of the polymer porous layer / the thickness of the nonwoven fabric layer) Is within a range of 0.22 to 0.45, and pure water is supplied at a pressure of 1.5 MPa using a composite semipermeable membrane before and after passing pure water at a pressure of 5.5 MPa for 4 hours.
- the permeation flux retention when permeated is 80% or more. This is presumed that the flux retention varies greatly depending on the thickness balance between the porous polymer layer and the nonwoven fabric layer, and the flow around the separation functional layer is influenced by the correlation of the compression degree of each layer. It is done. This range is more preferably 0.23 to 0.38.
- the non-woven fabric layer and the polymer porous layer have the above thickness ratio, and the polyamide-based separation functional layer is formed so that the initial permeate flow when pure water is permeated at a pressure of 1.5 MPa.
- a composite semipermeable membrane having a bundle of 1.0 m 3 / m 2 / d or more, preferably 1.3 m 3 / m 2 / d or more, more preferably 1.5 m 3 / m 2 / d or more can be obtained.
- the permeation flux preferably retains the permeation flux even in the composite semipermeable membrane after pressurized water flow.
- the initial permeation flux (F0) when pure water is permeated at a pressure of 1.5 MPa is 1.0 m 3 / m 2 / d or more, and the pure water is supplied at a pressure of 5.5 MPa.
- the permeation flux (F1) measured by allowing pure water to permeate at a pressure of 1.5 MPa was 1.0 m 3 / m 2 / d or more, and the ratio (F1) A composite semipermeable membrane having a / F0) of 0.8 or more, more preferably 0.85 or more can be obtained.
- the composite semipermeable membrane is usually processed into the form of a membrane element and loaded into a pressure vessel (vessel) for use.
- the form of the membrane element is not particularly limited, and examples include a flat membrane type such as a frame and plate type, a spiral type, and a pleat type.
- a spiral type composite semipermeable membrane element is used due to the relationship between pressure and flow efficiency. Can be preferably used.
- the spiral type composite semipermeable membrane element has a plurality of wall surface holes in a state in which a channel material on the inner surface side (concave surface) and a channel material on the outer surface side of the folded composite semipermeable membrane are laminated. It is wound around a central tube (a perforated hollow tube) and further fixed with an end member or an exterior material.
- the channel material generally has a role of ensuring a gap for uniformly supplying fluid to the membrane surface.
- a channel material for example, a net, a knitted fabric, a concavo-convex processed sheet or the like can be used, and a material having a maximum thickness of about 0.1 to 3 mm can be used as needed.
- the pressure loss is low, and further, a material that causes an appropriate turbulent flow effect is preferable.
- the channel material is installed on both sides of the separation membrane, but it is common to use different channel materials as the supply side channel material on the supply liquid side and the permeate side channel material on the permeate side. .
- the supply-side channel material uses a coarse and thick net-like channel material, while the permeate-side channel material uses a fine woven or knitted channel material.
- the supply side channel material is provided on the inner surface side of the bi-folded composite semipermeable membrane.
- a network structure in which linear objects are generally arranged in a lattice can be preferably used.
- a material to comprise Polyethylene, a polypropylene, etc. are used. These resins may contain bactericides and antibacterial agents.
- the thickness of the supply side channel material is generally 0.2 to 2.0 mm, preferably 0.5 to 1.0 mm. If the thickness is too thick, the amount of permeation decreases with the amount of film that can be accommodated in the element.
- the permeate side channel material is provided on the outer surface side of the bi-folded composite semipermeable membrane.
- This permeation side channel material is required to support the pressure applied to the membrane from the back side of the membrane and secure a permeate channel.
- a net or tricot knitted fabric made of polyethylene or polypropylene is used.
- a tricot knitted fabric made of polyethylene terephthalate is particularly preferably used.
- the center tube is not particularly limited as long as it is a perforated hollow tube having a plurality of small holes on the wall surface of the pipe (hollow tube).
- the permeated water that has passed through the composite semipermeable membrane enters the hollow tube from the hole in the wall surface to form a permeated water channel.
- the length of the central tube is generally longer than the length of the element in the axial direction, but a central tube having a connection structure such as a plurality of divisions may be used.
- tube A thermosetting resin or a thermoplastic resin is used.
- Example 1 A polymer porous layer having a thickness of 21.1 ⁇ m is formed by applying and coagulating a mixed solution of polysulfone and dimethylformamide on the surface of a commercially available polyester nonwoven fabric for water treatment membrane support having a thickness of 61.0 ⁇ m.
- a composite semipermeable membrane support was prepared. After contacting the surface of the porous polymer layer of the composite semipermeable membrane support with a solution A in which 3.6% by weight of piperazine hexahydrate and 0.15% by weight of sodium lauryl sulfate are mixed, an excess solution A is added. Removed to form a coating layer of solution A.
- a solution B containing 0.4% by weight of trimesic acid chloride in a hexane solvent was brought into contact with the surface of the solution A coating layer.
- the separation functional layer was formed by drying in an environment of 120 ° C. to obtain a composite semipermeable membrane.
- Example 2 A composite semipermeable membrane was produced in the same manner as in Example 1 except that a composite semipermeable membrane support having a 27.2 ⁇ m thick polymer porous layer formed on the surface of a polyester non-woven fabric having a thickness of 114.0 ⁇ m was used. did.
- Example 3 A composite semipermeable membrane was produced in the same manner as in Example 1 except that a composite semipermeable membrane support having a 31.2 ⁇ m thick polymer porous layer formed on the surface of a 109.8 ⁇ m thick polyester nonwoven fabric was used. did.
- Example 4 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that a composite semipermeable membrane support having a 31.8 ⁇ m thick polymer porous layer formed on the surface of a 107.6 ⁇ m thick polyester nonwoven fabric was used. did.
- Example 1 A composite semipermeable membrane was produced in the same manner as in Example 1 except that a composite semipermeable membrane support having a porous polymer layer having a thickness of 19.1 ⁇ m formed on the surface of a polyester nonwoven fabric having a thickness of 96.0 ⁇ m was used. did.
- Example 2 A composite semipermeable membrane was prepared in the same manner as in Example 1 except that a composite semipermeable membrane support having a 28.3 ⁇ m thick polymer porous layer formed on the surface of a 61.8 ⁇ m thick polyester nonwoven fabric was used. did.
- Example 3 A composite semipermeable membrane was produced in the same manner as in Example 1 except that a composite semipermeable membrane support having a 30.9 ⁇ m thick polymer porous layer formed on the surface of a polyester nonwoven fabric having a thickness of 65.9 ⁇ m was used. did.
- the obtained composite semipermeable membrane was set in a test unit (manufactured by Nitto Denko Corporation: C40-B), and the initial permeation flux at an operating pressure of 1.5 MPa was measured using pure water at a temperature of 25 ° C. .
- the permeation flux was measured at an operating pressure of 1.5 MPa using pure water at a temperature of 25 ° C., as in the initial stage, The flux ratio was calculated.
- the thickness was measured using a commercially available thickness measuring instrument (Ozaki Mfg. Co., Ltd .: Dial Thickness Gauge G-7C).
- the thickness of the nonwoven fabric layer is measured in advance, and the thickness of the entire composite semipermeable membrane support is formed with the polymer porous layer formed on the nonwoven fabric layer.
- the difference between the thickness of the composite semipermeable membrane support and the thickness of the non-woven fabric was determined to obtain the thickness of the polymer porous layer.
- an average value of arbitrary ten points measured values on the same film surface was used.
- Examples 1 to 4 according to the configuration of the present invention have a permeation flux (Flux) retention of 80% or more, and the effect is good.
- the permeation flux (Flux) retention rate is significantly lowered.
- the present invention since the present invention has a high flux performance, the energy efficiency can be remarkably increased, and a high flux can be maintained even before and after high-pressure processing. This can effectively contribute to wastewater treatment in oil fields and factories where the turbidity of the supply liquid is particularly high.
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Abstract
Description
厚さ61.0μmの市販の水処理膜支持体用ポリエステル製不織布の表面に、ポリスルホンとジメチルホルムアミドの混合溶液を塗布及び凝固処理することで厚さ21.1μmのポリマー多孔質層を形成し、複合半透膜支持体を準備した。この複合半透膜支持体のポリマー多孔質層表面に、ピペラジン6水和物3.6重量%、ラウリル硫酸ナトリウム0.15重量%を混合した溶液Aを接触させた後、余分の溶液Aを除去して、溶液Aの被覆層を形成した。次いで、溶液A被覆層の表面に、ヘキサン溶媒中にトリメシン酸クロライド0.4重量%を含有する溶液Bを接触させた。その後、120℃の環境下で乾燥することで分離機能層を形成し、複合半透膜とした。
厚さ114.0μmのポリエステル製不織布の表面に、厚さ27.2μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
厚さ109.8μmのポリエステル製不織布の表面に、厚さ31.2μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
厚さ107.6μmのポリエステル製不織布の表面に、厚さ31.8μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
厚さ96.0μmのポリエステル製不織布の表面に、厚さ19.1μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
厚さ61.8μmのポリエステル製不織布の表面に、厚さ28.3μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
厚さ65.9μmのポリエステル製不織布の表面に、厚さ30.9μmのポリマー多孔質層を形成した複合半透膜支持体を用いた以外は実施例1と同様にして複合半透膜を作製した。
得られた複合半透膜をテストユニット(日東電工(株)製:C40-B)にセットし、温度25℃の純水を用いて操作圧力1.5MPaでの初期の透過流束を測定した。次に、5.5MPaの操作圧力で4時間加圧通水した後、初期と同様に温度25℃の純水を用いて操作圧力1.5MPaで透過流束を測定し、加圧前後の透過流束比率を算出した。
厚さ測定は市販の厚さ測定器((株)尾崎製作所製:ダイヤルシックネスゲージ G-7C)を用いて測定を行った。不織布層とポリマー多孔質層の厚さ測定については、あらかじめ不織布層の厚さを測定しておき、その不織布層上にポリマー多孔質層を形成した状態で複合半透膜支持体全体の厚さを測定した。その後、複合半透膜支持体の厚さと不織布の厚さの差を求め、ポリマー多孔質層の厚さとした。各厚さ測定では同一膜面における任意十点測定値の平均値を用いた。
2:複合半透膜
3:透過側流路材
4:封筒状膜
5:中心管
6:供給側流路材
7:供給水
8:透過水
9:濃縮水
Claims (6)
- 不織布層の片面にポリマー多孔質層を有し、そのポリマー多孔質層上にポリアミド系分離機能層を有する複合半透膜において、前記ポリマー多孔質層の厚さと不織布層の厚さからなる比が0.22~0.45である複合半透膜。
- 圧力1.5MPaで純水を透過させたときの初期透過流束(F0)が1.0m3/m2/d以上であって、さらに5.5MPaの圧力で純水を4時間加圧通水させた後、圧力1.5MPaで純水を透過させたときの透過流束(F1)が1.0m3/m2/d以上であり、且つそれらの比(F1/F0)が0.8以上である請求項1記載の複合半透膜。
- 前記ポリマー多孔質層の厚さが10μm以上35μm以下である請求項1または2記載の複合半透膜。
- 前記不織布層の厚さが120μm以下であり、且つ前記ポリマー多孔質層の厚さが10μm以上29μm以下である請求項1または2記載の複合半透膜。
- 前記ポリアミド系分離機能層が、ピペラジンまたはm-フェニレンジアミンを含む多官能アミン成分を原料成分として用いた分離機能層である請求項1~4のいずれかに記載の複合半透膜。
- 前記ポリアミド系分離機能層の表面をケン化度99%以上のポリビニルアルコールでコーティングした請求項1~5のいずれかに記載の複合半透膜。
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