JP5839087B1 - Cellulose acetate reverse osmosis membrane cleaning solution and method for producing the same - Google Patents
Cellulose acetate reverse osmosis membrane cleaning solution and method for producing the same Download PDFInfo
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- JP5839087B1 JP5839087B1 JP2014137735A JP2014137735A JP5839087B1 JP 5839087 B1 JP5839087 B1 JP 5839087B1 JP 2014137735 A JP2014137735 A JP 2014137735A JP 2014137735 A JP2014137735 A JP 2014137735A JP 5839087 B1 JP5839087 B1 JP 5839087B1
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- cleaning
- cellulose acetate
- reverse osmosis
- osmosis membrane
- membrane
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- 238000004140 cleaning Methods 0.000 title claims abstract description 127
- 239000012528 membrane Substances 0.000 title claims abstract description 110
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 76
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 34
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 30
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 37
- 229910052801 chlorine Inorganic materials 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 35
- -1 chloramine compound Chemical class 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 9
- 239000013535 sea water Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 57
- 239000012459 cleaning agent Substances 0.000 abstract description 40
- 239000003513 alkali Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 238000010612 desalination reaction Methods 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000003599 detergent Substances 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000004907 flux Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- 238000011109 contamination Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008400 supply water Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 231100001240 inorganic pollutant Toxicity 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- KDNIOKSLVIGAAN-UHFFFAOYSA-N 2-sulfamoylbenzoic acid Chemical class NS(=O)(=O)C1=CC=CC=C1C(O)=O KDNIOKSLVIGAAN-UHFFFAOYSA-N 0.000 description 1
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VVSMKOFFCAJOSC-UHFFFAOYSA-L disodium;dodecylbenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1 VVSMKOFFCAJOSC-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000005485 electric heating Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
-
- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Detergent Compositions (AREA)
Abstract
【課題】水処理分野で使用された酢酸セルロース系ＲＯ膜が、有機物や無機物で汚染され、透過水量や脱塩率などの性能が低下した際に、従来の洗浄剤では十分に除去できない汚染物質を、膜劣化を防止して効果的に剥離除去し、その性能を回復させることができる洗浄液を提供する。【解決手段】１級アミノ基を有する化合物、アンモニア及びアンモニウム塩よりなる群から選ばれる１種又は２種以上と、次亜塩素酸及び／又は次亜塩素酸塩と、アルカリ剤とを混合することにより得られた、ｐＨ１１以上の水溶液よりなる酢酸セルロース系逆浸透膜の洗浄剤。この洗浄剤を、水で希釈し、酸を混合して、ｐＨ３以上８．５以下の水溶液に調整して酢酸セルロース系逆浸透膜の洗浄に用いる。【選択図】図２A pollutant that cannot be sufficiently removed by conventional cleaning agents when the cellulose acetate RO membrane used in the water treatment field is contaminated with organic or inorganic substances and the performance such as the amount of permeated water and the desalination rate is reduced. Thus, it is possible to effectively remove and remove the film while preventing film deterioration, and to provide a cleaning liquid capable of recovering its performance. One or more selected from the group consisting of a compound having a primary amino group, ammonia and an ammonium salt, hypochlorous acid and / or hypochlorite, and an alkali agent are mixed. A cellulose acetate reverse osmosis membrane cleaning agent comprising an aqueous solution having a pH of 11 or more. This detergent is diluted with water, mixed with an acid, adjusted to an aqueous solution having a pH of 3 or more and 8.5 or less, and used for washing a cellulose acetate reverse osmosis membrane. [Selection] Figure 2
Description
本発明は、水処理分野で使用される酢酸セルロース系逆浸透（ＲＯ）膜が、有機物や無機物で汚染され、透過水量や脱塩率などの性能が低下した際に、その性能を効果的に回復させる洗浄剤及び洗浄液に関する。 The present invention is effective when the cellulose acetate reverse osmosis (RO) membrane used in the water treatment field is contaminated with organic matter and inorganic matter, and the performance such as the amount of permeated water and the desalination rate is reduced. The present invention relates to a cleaning agent and a cleaning liquid to be recovered.
ＲＯ膜システムによる分離、精製は、蒸発や電気透析を用いたシステムに対して省エネルギープロセスであり、海水、かん水の淡水化や、工業用水及び超純水の製造、排水回収などに広く用いられている。一方、ＲＯ膜が汚染されることによる性能の低下を防ぐため、定期的な洗浄が必要となることが問題であり、より有効な洗浄剤、洗浄プロセスの開発が望まれている。 Separation and purification by RO membrane system is an energy-saving process for systems using evaporation and electrodialysis, and is widely used for desalination of seawater and brine, production of industrial water and ultrapure water, wastewater recovery, etc. Yes. On the other hand, in order to prevent the performance from being deteriorated due to the contamination of the RO membrane, it is a problem that regular cleaning is required, and development of more effective cleaning agents and cleaning processes is desired.
ＲＯ膜に対して使用される洗浄剤としては、膜汚染物質の性質に応じて、酸（シュウ酸、クエン酸など）、アルカリ（水酸化ナトリウムなど）、界面活性剤、キレート剤（ＥＤＴＡなど）、塩素剤、酵素含有洗剤などが挙げられる（非特許文献１）。 Cleaning agents used for RO membranes include acids (oxalic acid, citric acid, etc.), alkalis (sodium hydroxide, etc.), surfactants, chelating agents (EDTA, etc.) depending on the nature of the membrane contaminants. , Chlorinating agents, enzyme-containing detergents, etc. (Non-Patent Document 1).
現在用いられているＲＯ膜の材質は、芳香族ポリアミド系と酢酸セルロース系に大別することができる。芳香族ポリアミド系ＲＯ膜は、塩素に対する耐性が低いため、塩素剤による膜洗浄が行えない。一方、酢酸セルロース系ＲＯ膜は、芳香族ポリアミド系ＲＯ膜よりも塩素に対する耐性が高く、例えば、三酢酸セルロース製のＲＯ膜は、短時間であれば塩素濃度５ｍｇ／Ｌの条件でも耐性を有するとの報告がなされている（非特許文献２）。 Currently used RO membrane materials can be broadly divided into aromatic polyamides and cellulose acetates. Since the aromatic polyamide RO membrane has low resistance to chlorine, the membrane cannot be cleaned with a chlorine agent. On the other hand, cellulose acetate RO membranes have higher resistance to chlorine than aromatic polyamide RO membranes. For example, RO membranes made of cellulose triacetate have resistance even under conditions of a chlorine concentration of 5 mg / L for a short time. There is a report (Non-Patent Document 2).
しかし、酢酸セルロース系ＲＯ膜はアルカリに対する耐性が低いため、ｐＨ９以上のアルカリ条件での洗浄が行えないという問題点がある。このため、酢酸セルロース系ＲＯ膜の洗浄には、膜劣化を引き起こすアルカリ剤を使用することができないため、アルカリ性条件による洗浄でないと十分に除去できないシリカスケールなどによる膜汚染に対しては、有効な洗浄剤が見出されていないのが現状である。 However, since the cellulose acetate RO membrane has low resistance to alkali, there is a problem that it cannot be washed under alkaline conditions of pH 9 or higher. For this reason, since an alkali agent that causes membrane deterioration cannot be used for cleaning the cellulose acetate RO membrane, it is effective for membrane contamination due to silica scale or the like that cannot be sufficiently removed unless cleaning is performed under alkaline conditions. The current situation is that no cleaning agent has been found.
一方、特開２００６−２６３５１０号公報には、次亜塩素酸塩とスルファミン酸からなる膜分離用スライム防止剤及び膜分離方法が開示されており、該スライム防止剤はｐＨ１２以上で安定である旨、実施例では硫酸を用いてｐＨ調整し、ｐＨ５．５で適用する旨の記載がある。また、特開２０１０−２０１３１２号公報にも、次亜塩素酸塩とスルファミン酸を膜のスライムコントロール剤として添加することが記載されている。
しかし、いずれの場合も、主として対象とする逆浸透膜の素材はポリアミド膜であり、酢酸セルロース系ＲＯ膜に適用することについての記載はない。また、有機汚染物質であるスライムに対する剥離効果については記載があるものの、膜面に付着したシリカに対する洗浄効果については記載がない。
On the other hand, Japanese Patent Application Laid-Open No. 2006-263510 discloses a membrane separation slime inhibitor and a membrane separation method comprising hypochlorite and sulfamic acid, and that the slime inhibitor is stable at a pH of 12 or more. In the examples, there is a description that the pH is adjusted with sulfuric acid and applied at pH 5.5. Japanese Patent Application Laid-Open No. 2010-201312 also describes adding hypochlorite and sulfamic acid as a slime control agent for the film.
However, in any case, the material of the target reverse osmosis membrane is a polyamide membrane, and there is no description about application to a cellulose acetate RO membrane. Further, although there is a description about the peeling effect on slime, which is an organic contaminant, there is no description on the cleaning effect on silica adhering to the film surface.
本発明は、水処理分野で使用された酢酸セルロース系ＲＯ膜が、有機物や無機物で汚染され、透過水量や脱塩率などの性能が低下した際に、従来の洗浄剤では十分に除去できない汚染物質、特にシリカを、膜劣化を防止して効果的に剥離除去し、その性能を回復させることができる洗浄剤及び洗浄液を提供することを課題とする。 In the present invention, when the cellulose acetate RO membrane used in the water treatment field is contaminated with organic matter or inorganic matter and the performance such as the amount of permeated water or the desalination rate is deteriorated, the conventional cleaning agent cannot sufficiently remove the contamination. It is an object of the present invention to provide a cleaning agent and a cleaning liquid that can effectively peel and remove a substance, particularly silica, effectively preventing film deterioration and recovering its performance.
本発明者は上記課題を解決すべく鋭意検討を重ねた結果、スルファミン酸等のＮＨ２系化合物と次亜塩素酸塩とアルカリ剤を混合して得られた、結合塩素剤からなるアルカリ性の洗浄剤を、希釈してｐＨ８．５以下の水溶液とすることで、アルカリ剤による洗浄が行えない酢酸セルロース系ＲＯ膜であっても、有機物や無機物を効果的に除去することができ、洗浄液として良好な洗浄効果が得られること、こうした洗浄効果は、次亜塩素酸塩のみを用いた洗浄では得ることができず、また、本発明の洗浄液によれば、酢酸セルロース系ＲＯ膜の劣化を引き起こすことなくシリカを効果的に洗浄除去することができ、洗浄後も十分な脱塩率を維持することができることを見出した。 As a result of intensive studies to solve the above problems, the present inventor obtained an alkaline cleaning comprising a combined chlorine agent obtained by mixing an NH 2 compound such as sulfamic acid, a hypochlorite and an alkali agent. By diluting the agent to an aqueous solution with a pH of 8.5 or less, organic and inorganic substances can be effectively removed even with a cellulose acetate RO membrane that cannot be washed with an alkaline agent, and it is good as a washing solution Cleansing effect can not be obtained by cleaning with hypochlorite alone, and according to the cleaning liquid of the present invention, the cellulose acetate RO membrane is deteriorated. It was found that silica can be effectively removed by washing, and a sufficient desalting rate can be maintained even after washing.
本発明はこのような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
［１］ アルカリ剤水溶液中での、１級アミノ基を有する化合物、アンモニア及びアンモニウム塩よりなる群から選ばれる１種又は２種以上（以下「ＮＨ２系化合物」と称す。）と、次亜塩素酸及び／又は次亜塩素酸塩（以下「次亜塩素酸（塩）」と称す。）との反応生成物であるｐＨ１１以上のクロラミン化合物水溶液と、酸との混合物であって、ｐＨ３以上８．５以下の水溶液であることを特徴とする酢酸セルロース系逆浸透膜の洗浄液。 [1] One or more selected from the group consisting of a compound having a primary amino group, ammonia and an ammonium salt (hereinafter referred to as “NH 2 -based compound”) in an alkaline agent aqueous solution, and hypoxia. A mixture of an aqueous solution of a chloramine compound having a pH of 11 or more, which is a reaction product with chloric acid and / or hypochlorite (hereinafter referred to as “hypochlorous acid (salt)”), and an acid, and having a pH of 3 or more A cleaning solution for a cellulose acetate reverse osmosis membrane, which is an aqueous solution of 8.5 or less.
［２］ ［１］において、結合塩素濃度が０．０１〜０．１４Ｍであることを特徴とする酢酸セルロース系逆浸透膜の洗浄液。 [2] In [1], the washing liquid of cellulose acetate reverse osmosis membrane, characterized in that the binding chlorine concentration is 0.01～0.14M.
［３］ ［１］又は［２］において、更に界面活性剤を含むことを特徴とする酢酸セルロース系逆浸透膜の洗浄液。 [3] [1] or in [2], further the washing liquid of cellulose acetate reverse osmosis membrane which comprises a surfactant.
［４］ ［１］ないし［３］のいずれかにおいて、前記酢酸セルロース系逆浸透膜に付着したシリカを除去するための洗浄液であることを特徴とする酢酸セルロース系逆浸透膜の洗浄液。 [ 4 ] In any one of [ 1 ] to [ 3 ], the cellulose acetate reverse osmosis membrane cleaning solution is a cleaning solution for removing silica adhering to the cellulose acetate reverse osmosis membrane.
［５］ ［４］において、前記酢酸セルロース系逆浸透膜が、海水又はかん水を処理することによりシリカが付着した酢酸セルロース系逆浸透膜であることを特徴とする酢酸セルロース系逆浸透膜の洗浄液。
［６］ １級アミノ基を有する化合物、アンモニア及びアンモニウム塩よりなる群から選ばれる１種又は２種以上（以下「ＮＨ ２ 系化合物」と称す。）と、次亜塩素酸及び／又は次亜塩素酸塩（以下「次亜塩素酸（塩）」と称す。）と、アルカリ剤とを混合することにより、ｐＨ１１以上のクロラミン化合物の水溶液を得、該水溶液と酸を混合して、ｐＨ３以上８．５以下の水溶液に調整することを特徴とする酢酸セルロース系逆浸透膜の洗浄液の製造方法。
［７］ ［６］において、前記洗浄液の結合塩素濃度が０．０１〜０．１４Ｍであることを特徴とする酢酸セルロース系逆浸透膜の洗浄液の製造方法。
［８］ ［６］又は［７］において、前記クロラミン化合物水溶液に、更に界面活性剤を混合することを特徴とする酢酸セルロース系逆浸透膜の洗浄液の製造方法。
[ 5 ] The washing solution for cellulose acetate reverse osmosis membrane according to [ 4 ], wherein the cellulose acetate reverse osmosis membrane is a cellulose acetate reverse osmosis membrane to which silica is adhered by treating seawater or brine. .
[6] One or more selected from the group consisting of a compound having a primary amino group, ammonia and an ammonium salt (hereinafter referred to as “NH 2 -based compound”), hypochlorous acid and / or hypochlorous acid. By mixing a chlorate (hereinafter referred to as “hypochlorous acid (salt)”) and an alkaline agent, an aqueous solution of a chloramine compound having a pH of 11 or more is obtained, and the aqueous solution and the acid are mixed to obtain a pH of 3 or more. A method for producing a cleaning liquid for a cellulose acetate reverse osmosis membrane, characterized by adjusting the aqueous solution to 8.5 or less.
[7] A method for producing a cleaning liquid for a cellulose acetate reverse osmosis membrane according to [6], wherein the combined chlorine concentration of the cleaning liquid is 0.01 to 0.14M.
[8] The method for producing a washing liquid for a cellulose acetate reverse osmosis membrane according to [6] or [7], wherein a surfactant is further mixed with the chloramine compound aqueous solution.
本発明によれば、水処理分野で使用された酢酸セルロース系ＲＯ膜が、有機物や無機物で汚染され、透過水量や脱塩率などの性能が低下した際に、従来の洗浄剤では十分に除去できない汚染物質を、膜劣化を防止して効果的に剥離除去し、その性能を回復させることができる。本発明は特に、海水又はかん水を処理することによりシリカが付着した酢酸セルロース系ＲＯ膜からシリカを除去するための洗浄に好適に適用される。 According to the present invention, when a cellulose acetate RO membrane used in the field of water treatment is contaminated with organic matter or inorganic matter and performance such as the amount of permeated water or the desalination rate is reduced, it is sufficiently removed by conventional cleaning agents. It is possible to effectively remove the contaminants that cannot be removed while preventing the film from deteriorating and restore the performance. Especially this invention is applied suitably for the washing | cleaning for removing a silica from the cellulose acetate type RO membrane to which the silica adhered by processing seawater or brackish water.
以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の酢酸セルロース系ＲＯ膜の洗浄剤は、１級アミノ基を有する化合物、アンモニア及びアンモニウム塩よりなる群から選ばれる１種又は２種以上（以下「ＮＨ２系化合物」と称す。）と、次亜塩素酸及び／又は次亜塩素酸塩（以下「次亜塩素酸（塩）」と称す。）と、アルカリ剤とを混合することにより得られたｐＨ１１以上の水溶液よりなるものであり、本発明の酢酸セルロース系ＲＯ膜の洗浄液は、この洗浄剤を水で希釈し、酸を混合して、ｐＨ３以上８．５以下の水溶液に調整してなるものであり、「洗浄剤」と「洗浄液」とは区別される。 The cellulose acetate RO membrane cleaning agent of the present invention is one or more selected from the group consisting of a compound having a primary amino group, ammonia and an ammonium salt (hereinafter referred to as “NH 2 compound”). Hypochlorous acid and / or hypochlorite (hereinafter referred to as “hypochlorous acid (salt)”) and an alkaline agent, and an aqueous solution having a pH of 11 or more. The cellulose acetate RO membrane cleaning liquid of the present invention is prepared by diluting this cleaning agent with water, mixing the acid, and adjusting to an aqueous solution having a pH of 3 or more and 8.5 or less. Differentiated from “cleaning liquid”.
［酢酸セルロース系ＲＯ膜］
本発明で洗浄対象とするＲＯ膜は、アルカリ耐性が低いために、アルカリ洗浄でシリカを除去することができない酢酸セルロース系ＲＯ膜である。例えば、海水、河川水は、下記表１に示すような成分を含み、このような水の処理に使用された酢酸セルロース系ＲＯ膜は、有機汚染物質のみならず、シリカ等の無機汚染物質が付着してその性能が低下する。本発明はこのような有機汚染物質及び無機汚染物質、特にシリカ汚染の進行した酢酸セルロース系ＲＯ膜の洗浄に有効である。
[Cellulose acetate RO membrane]
The RO membrane to be cleaned in the present invention is a cellulose acetate RO membrane in which silica cannot be removed by alkali cleaning because alkali resistance is low. For example, seawater and river water contain components as shown in Table 1 below, and the cellulose acetate RO membrane used for the treatment of such water contains not only organic pollutants but also inorganic pollutants such as silica. It will adhere and reduce its performance. The present invention is effective for cleaning such organic pollutants and inorganic pollutants, in particular, cellulose acetate RO membranes with advanced silica contamination.
［酢酸セルロース系ＲＯ膜の洗浄剤］
本発明の洗浄剤では、ＮＨ２系化合物と次亜塩素酸（塩）との反応で生成するクロラミン化合物が有効成分として洗浄効果を発揮する。クロラミン化合物を生成させるためのＮＨ２系化合物のうち、１級アミノ基を有する化合物としては、脂肪族アミン、芳香族アミン、スルファミン酸、スルファニル酸、スルファモイル安息香酸、アミノ酸などを挙げることができる。また、アンモニウム塩としては、塩化アンモニウム、硫酸アンモニウム等が挙げられる。これらは、１種を単独で用いてもよく、２種以上を混合して用いてもよい。これらのＮＨ２系化合物の中でもスルファミン酸（ＮＨ２ＳＯ２ＯＨ）が好ましい。スルファミン酸を用いてモノクロロスルファミンを生成させると安定なクロラミン化合物となる。また、スルファミン酸は、炭素を含まないため洗浄剤のＴＯＣ値を増加させない。
[Cleaning agent for cellulose acetate RO membrane]
In the cleaning agent of the present invention, a chloramine compound produced by a reaction between an NH 2 -based compound and hypochlorous acid (salt) exhibits a cleaning effect as an active ingredient. Among the NH 2 -based compounds for producing a chloramine compound, examples of the compound having a primary amino group include aliphatic amines, aromatic amines, sulfamic acids, sulfanilic acids, sulfamoylbenzoic acids, and amino acids. Examples of ammonium salts include ammonium chloride and ammonium sulfate. These may be used alone or in combination of two or more. Of these NH 2 compounds, sulfamic acid (NH 2 SO 2 OH) is preferable. When monochlororosulfamine is produced using sulfamic acid, it becomes a stable chloramine compound. Moreover, since sulfamic acid does not contain carbon, it does not increase the TOC value of the cleaning agent.
一方、ＮＨ２系化合物と反応させる次亜塩素酸（塩）の次亜塩素酸塩としては、次亜塩素酸ナトリウム等の次亜塩素酸のアルカリ金属塩、次亜塩素酸カルシウム等の次亜塩素酸のアルカリ土類金属塩等を用いることができる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。 On the other hand, hypochlorite of hypochlorous acid (salt) to be reacted with NH 2 -based compounds includes alkali metal salts of hypochlorous acid such as sodium hypochlorite and hypochlorous acid such as calcium hypochlorite. An alkaline earth metal salt of chloric acid or the like can be used. These may be used alone or in combination of two or more.
ＮＨ２系化合物と次亜塩素酸（塩）を混合してクロラミン化合物を生成させる場合、ＮＨ２系化合物と次亜塩素酸（塩）とは、次亜塩素酸（塩）由来の有効塩素（Ｃｌ２）と、ＮＨ２系化合物由来の窒素原子Ｎとのモル比であるＣｌ２／Ｎモル比が、０．１〜０．９、特に０．２〜０．７、とりわけ０．３〜０．５となるように用いることが、クロラミン化合物の生成効率と安定性の点において好ましい。 When mixing a NH 2 -based compound and hypochlorous acid (salt) to produce a chloramine compound, the NH 2 -based compound and hypochlorous acid (salt) are effective chlorine derived from hypochlorous acid (salt) (salt). Cl 2 ) and the Cl 2 / N molar ratio, which is the molar ratio of the NH 2 -based compound-derived nitrogen atom N, is 0.1 to 0.9, particularly 0.2 to 0.7, especially 0.3 to It is preferable to use it so that it may become 0.5 from the point of the production | generation efficiency and stability of a chloramine compound.
Ｃｌ２／Ｎモル比が上記上限よりも大きいと遊離塩素が生成する可能性があり、上記下限よりも小さいと使用したＮＨ２系化合物に対してクロラミンの生成効率が低くなる。
なおこの場合は、洗浄剤中のクロラミン化合物量、即ち、結合塩素量は、次亜塩素酸（塩）の量が基準となる。
If the Cl 2 / N molar ratio is larger than the above upper limit, free chlorine may be generated. If the Cl 2 / N molar ratio is smaller than the above lower limit, the production efficiency of chloramine is lowered with respect to the NH 2 -based compound used.
In this case, the amount of chloramine compound in the cleaning agent, that is, the amount of bound chlorine is based on the amount of hypochlorous acid (salt).
本発明の洗浄剤に用いるアルカリ剤は、クロラミン化合物の水溶液中における可溶性を維持するためのものであり、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物を用いることができる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。
アルカリ剤は、クロラミン化合物の可溶性を維持するために、洗浄剤水溶液のｐＨが１１以上、好ましくは１２〜１３となるように、ＮＨ２系化合物に対しモル比で１〜２倍用いることが好ましい。
The alkaline agent used in the cleaning agent of the present invention is for maintaining the solubility of the chloramine compound in an aqueous solution, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. These may be used alone or in combination of two or more.
In order to maintain the solubility of the chloramine compound, the alkaline agent is preferably used in a molar ratio of 1 to 2 times with respect to the NH 2 -based compound so that the pH of the cleaning solution is 11 or more, preferably 12 to 13. .
本発明の洗浄剤は界面活性剤を含むものであってもよく、界面活性剤を含むことにより、有機物の洗浄除去効果を高めることができる。界面活性剤としては、洗浄効果の面から、分子量１０００以下のものが好ましい。分子量が過度に大きい界面活性剤では洗浄効果が得られないだけでなく、膜を汚染する場合がある。 The cleaning agent of the present invention may contain a surfactant, and the inclusion of the surfactant can enhance the effect of washing and removing organic matter. As the surfactant, those having a molecular weight of 1000 or less are preferable from the viewpoint of cleaning effect. A surfactant having an excessively high molecular weight may not only provide a cleaning effect, but may contaminate the membrane.
界面活性剤としては、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、ドデシル硫酸ナトリウム、ラウリル硫酸ナトリウム等のアルキル硫酸塩といったアニオン系界面活性剤、ジエチレングリコールモノメチルエーテルなどのポリアルキレングリコールモノアルキルエーテルのようなノニオン系界面活性剤などの１種又は２種以上を用いることができる。これらのうち、特に分散効果の面でアニオン系界面活性剤が好ましい。
なお、界面活性剤の中には、高濃度ＮＨ２系化合物と混合して一剤化しても問題のないものと、高濃度ＮＨ２系化合物の存在下では析出してしまうものとがある。ＮＨ２系化合物として、スルファミン酸を用いる場合、ドデシル硫酸ナトリウムは比較的高濃度のＮＨ２系化合物と混在できるため、本発明の洗浄剤に用いられる界面活性剤として特に好ましい。
Surfactants include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, anionic surfactants such as alkyl sulfates such as sodium dodecyl sulfate and sodium lauryl sulfate, and polyalkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether. 1 type, or 2 or more types, such as a nonionic surfactant, can be used. Among these, an anionic surfactant is particularly preferable in terms of dispersion effect.
Some surfactants may be mixed with a high-concentration NH 2 -based compound to form a single agent, and others may precipitate in the presence of a high-concentration NH 2 -based compound. When sulfamic acid is used as the NH 2 -based compound, sodium dodecyl sulfate can be mixed with a relatively high concentration of NH 2 -based compound, and thus is particularly preferable as a surfactant used in the cleaning agent of the present invention.
なお、洗浄剤中のＮＨ２系化合物及び次亜塩素酸（塩）の濃度については、洗浄剤を希釈して得られる後述の洗浄液の結合塩素濃度が後述の好適濃度となるような濃度であればよく、通常の場合、ＮＨ２系化合物と次亜塩素酸（塩）との反応で生成した結合塩素濃度として０．１〜０．９Ｍ、特に０．２〜０．７Ｍとなるように調製される。
また界面活性剤については、その種類や洗浄対象の酢酸セルロース系ＲＯ膜の汚染物質等により適宜決定され、特に制限はないが、油分などの有機汚染物質に対して０．０３〜０．３重量％、特に０．１〜０．２重量％程度用いられる。
The concentration of the NH 2 -based compound and hypochlorous acid (salt) in the cleaning agent should be such that the combined chlorine concentration of the cleaning solution described below obtained by diluting the cleaning agent becomes the preferable concentration described below. Usually, it is prepared so that the combined chlorine concentration generated by the reaction between the NH 2 -based compound and hypochlorous acid (salt) is 0.1 to 0.9 M, particularly 0.2 to 0.7 M. Is done.
The surfactant is appropriately determined depending on the type and contaminants of the cellulose acetate RO membrane to be cleaned, and is not particularly limited, but is 0.03 to 0.3% by weight with respect to organic contaminants such as oil. %, Particularly about 0.1 to 0.2% by weight.
［洗浄液］
本発明の酢酸セルロース系ＲＯ膜の洗浄液は、上記の洗浄剤を水で希釈すると共に、酸を添加してｐＨ３〜８．５に調整してなるものである。
ここで用いる酸としては、塩酸、硫酸、硝酸等の無機酸の１種又は２種以上を用いることができる。
[Cleaning liquid]
The cellulose acetate RO membrane cleaning solution of the present invention is prepared by diluting the above-mentioned cleaning agent with water and adding an acid to adjust the pH to 3 to 8.5.
As an acid used here, 1 type, or 2 or more types of inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, can be used.
本発明の洗浄液のｐＨが８．５より高いとアルカリ耐性の低い酢酸セルロース系ＲＯ膜を劣化させるおそれがある。洗浄液のｐＨが低過ぎると、結合塩素が分解されやすくなり、洗浄効果が低下するおそれがある。洗浄液の好ましいｐＨは４．０〜７．０である。 If the pH of the cleaning liquid of the present invention is higher than 8.5, the cellulose acetate RO membrane having low alkali resistance may be deteriorated. If the pH of the cleaning liquid is too low, bound chlorine is likely to be decomposed and the cleaning effect may be reduced. The preferred pH of the cleaning liquid is 4.0 to 7.0.
また、本発明の洗浄液は、上記の洗浄剤を希釈することにより、ＮＨ２系化合物と次亜塩素酸（塩）との反応で生成した結合塩素濃度が０．０１〜０．１４Ｍ、特に０．０２〜０．０７Ｍとなるように調整することが好ましい。この結合塩素濃度が０．０１Ｍ未満では、十分な洗浄効果、特にシリカの洗浄除去効果を得ることができず、０．１４Ｍを超えると酢酸セルロース系ＲＯ膜の劣化を引き起こす可能性がある。 Further, the cleaning liquid of the present invention has a concentration of bound chlorine generated by the reaction of NH 2 -based compound and hypochlorous acid (salt) by diluting the above-mentioned cleaning agent, and is 0.01 to 0.14M, particularly 0. It is preferable to adjust so that it may become 0.02-0.07M. If the combined chlorine concentration is less than 0.01M, it is not possible to obtain a sufficient cleaning effect, particularly a silica cleaning and removing effect, and if it exceeds 0.14M, the cellulose acetate RO membrane may be deteriorated.
＜洗浄剤及び洗浄液の製造方法＞
本発明の洗浄剤は、例えば、前述のアルカリ剤の水溶液にスルファミン酸等のＮＨ２系化合物を添加して溶解し、得られたＮＨ２系化合物水溶液に、次亜塩素酸（塩）を添加して混合することにより調製することができる。上記アルカリ剤の水溶液は、水の量を５０〜９０重量％とすることが好ましい。洗浄剤に界面活性剤を混合使用する場合、界面活性剤は、洗浄剤の調製工程のうち、いずれの工程で添加されてもよく、アルカリ剤の水溶液に予め含まれていてもよく、また、ＮＨ２系化合物水溶液に次亜塩素酸（塩）を添加する際に添加してもよく、次亜塩素酸（塩）の添加の前後で添加してもよい。好ましくは、界面活性剤は次亜塩素酸（塩）の添加の後に添加される。
<Manufacturing method of cleaning agent and cleaning liquid>
For example, the cleaning agent of the present invention is prepared by adding an NH 2 compound such as sulfamic acid to the aqueous solution of the alkali agent described above and dissolving it, and adding hypochlorous acid (salt) to the resulting NH 2 compound aqueous solution. And can be prepared by mixing. It is preferable that the amount of water in the aqueous solution of the alkali agent is 50 to 90% by weight. When a surfactant is mixed and used in the cleaning agent, the surfactant may be added in any step of the cleaning agent preparation step, and may be included in the aqueous solution of the alkaline agent in advance. It may be added when hypochlorous acid (salt) is added to the NH 2 -based compound aqueous solution, or may be added before or after the addition of hypochlorous acid (salt). Preferably, the surfactant is added after the addition of hypochlorous acid (salt).
スルファミン酸等の１級アミノ基を有する化合物は、塩の形で添加してもよい。この塩としては、アルカリ水溶液としたときに可溶性のものが挙げられ、スルファミン酸ナトリウム、スルファミン酸カリウム、スルファミン酸アンモニウム等を用いることができる。ＮＨ２系化合物は、粉末状態で、あるいは水溶液の状態で添加することができる。ＮＨ２系化合物としてスルファミン酸塩を用いる場合、スルファミン酸塩に含まれるアルカリ金属の量は、アルカリとして加算される。水溶液を用いる場合は、水溶液に含まれる水の量は、前記アルカリ水溶液の水の量として加算される。 A compound having a primary amino group such as sulfamic acid may be added in the form of a salt. Examples of the salt include those that are soluble in an alkaline aqueous solution, and sodium sulfamate, potassium sulfamate, ammonium sulfamate, and the like can be used. The NH 2 -based compound can be added in a powder state or in an aqueous solution state. When using a sulfamate as the NH 2 -based compound, the amount of alkali metal contained in the sulfamate is added as an alkali. When an aqueous solution is used, the amount of water contained in the aqueous solution is added as the amount of water in the alkaline aqueous solution.
一方、次亜塩素酸（塩）は、有効塩素（Ｃｌ２）濃度として５〜２０重量％、好ましくは１０〜１５重量％の水溶液として添加するのが好ましい。次亜塩素酸（塩）は、ＮＨ２系化合物と次亜塩素酸（塩）との割合が、前述のＣｌ２／Ｎモル比となるように添加される。これにより発泡や塩素臭の発生はなく、反応性、安定性、取扱性、無塩素臭等に優れた水溶液製剤からなる本発明の洗浄剤を効率よく製造することができる。この場合でも、次亜塩素酸（塩）は徐々に添加して混合するのが好ましい。 On the other hand, hypochlorous acid (salt) is preferably added as an aqueous solution having an effective chlorine (Cl 2 ) concentration of 5 to 20 wt%, preferably 10 to 15 wt%. Hypochlorous acid (salt) is added so that the ratio of the NH 2 -based compound and hypochlorous acid (salt) is the aforementioned Cl 2 / N molar ratio. Thereby, there is no generation | occurrence | production of foaming and a chlorine odor, and the cleaning agent of this invention which consists of aqueous solution formulation excellent in reactivity, stability, handleability, a chlorine-free odor, etc. can be manufactured efficiently. Even in this case, it is preferable to gradually add and mix hypochlorous acid (salt).
本発明の洗浄液は、このようにして製造された本発明の洗浄剤を水、好ましくは純水で希釈すると共に、酸を添加して所定のｐＨとなるように調整することで製造される。 The cleaning liquid of the present invention is manufactured by diluting the cleaning agent of the present invention thus manufactured with water, preferably pure water, and adding an acid to adjust to a predetermined pH.
＜その他の洗浄剤成分＞
本発明で用いる洗浄剤又は洗浄液には、その洗浄効果を損なわない範囲において、他の洗浄剤成分を添加してもよい。
例えば、膜汚染物質の剥離効果を高めるために、ＥＤＴＡ（エチレンジアミン四酢酸）、ＥＧＴＡ（エチレングリコールビス（アミノエチルエーテル）四酢酸）、ＩＤＡ（イミノ二酢酸）等のキレート剤などの他の洗浄剤成分の１種又は２種以上を添加してもよい。
<Other cleaning ingredients>
To the cleaning agent or cleaning liquid used in the present invention, other cleaning component may be added as long as the cleaning effect is not impaired.
For example, other cleaning agents such as chelating agents such as EDTA (ethylenediaminetetraacetic acid), EGTA (ethyleneglycolbis (aminoethylether) tetraacetic acid), IDA (iminodiacetic acid), etc. in order to enhance the peeling effect of membrane contaminants One or more components may be added.
また、分子量１０００以下、好ましくは分子量６０〜１０００のポリオール化合物を併用することにより、ＲＯ膜への浸透と汚染物質の溶解の作用で更に洗浄効果を高めることができる。ここで、ポリオール化合物の分子量が１０００を超えるとＲＯ膜等の透過膜汚染に寄与する可能性がある。分子量１０００以下のポリオール化合物としては、例えばエチレングリコール、プロピレングリコール、ポリエチレングリコール（重合度２〜２２）等を用いることができる。これらのポリオール化合物は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
このようなポリオール化合物は、本発明の洗浄剤又は洗浄液に添加してもよく、以下の酸水溶液に添加して用いてもよい。
In addition, when a polyol compound having a molecular weight of 1000 or less, preferably 60 to 1000 is used in combination, the cleaning effect can be further enhanced by the action of penetration into the RO membrane and dissolution of contaminants. Here, when the molecular weight of the polyol compound exceeds 1000, there is a possibility of contributing to permeable membrane contamination such as RO membrane. As the polyol compound having a molecular weight of 1000 or less, for example, ethylene glycol, propylene glycol, polyethylene glycol (degree of
Such a polyol compound may be added to the cleaning agent or cleaning liquid of the present invention, or may be added to the following acid aqueous solution.
また、本発明の洗浄液による酢酸セルロース系ＲＯ膜の洗浄に前後して、他の洗浄液による膜洗浄を行ってもよい。他の洗浄液による膜洗浄を組み合わせることにより洗浄効果をより一層高めることができる。 Further, before and after the cleaning of the cellulose acetate RO membrane with the cleaning solution of the present invention, the membrane may be cleaned with another cleaning solution. The cleaning effect can be further enhanced by combining film cleaning with other cleaning liquids.
特に、本発明の洗浄液による洗浄に先立ち、炭酸カルシウム等のスケールや鉄等の金属コロイド除去に有効な酸洗浄を行うことが好ましく、その酸洗浄には、塩酸、硝酸、クエン酸、シュウ酸などの酸の１種又は２種以上を含む水溶液を用いることができる。この酸水溶液のｐＨは、洗浄効果と取り扱い性の面から、ｐＨ４以下、特にｐＨ１〜３であることが好ましい。また、界面活性剤等で、予め有機汚染物質を洗浄除去してもよい。このような酸洗浄等でスケール成分や有機汚染物質等を除去した後に本発明の洗浄液により洗浄を行うと、膜劣化をより確実に防止して効果的な洗浄を行える。 In particular, prior to cleaning with the cleaning liquid of the present invention, it is preferable to perform acid cleaning effective for removing metal colloids such as scales such as calcium carbonate and iron, such as hydrochloric acid, nitric acid, citric acid, oxalic acid, etc. An aqueous solution containing one or more of these acids can be used. The pH of the acid aqueous solution is preferably pH 4 or less, particularly preferably pH 1 to 3, in terms of cleaning effect and handleability. In addition, the organic contaminants may be removed in advance with a surfactant or the like. When cleaning is performed with the cleaning liquid of the present invention after removing scale components, organic contaminants, and the like by such acid cleaning, film deterioration can be more reliably prevented and effective cleaning can be performed.
＜洗浄方法＞
本発明の洗浄液を用いて酢酸セルロース系ＲＯ膜を洗浄する方法としては、この洗浄液に酢酸セルロース系ＲＯ膜を接触させればよく、特に制限はない。通常、酢酸セルロース系ＲＯ膜モジュールの原水側に洗浄液を導入して静置する浸漬洗浄が行われる。
<Washing method>
The method for cleaning the cellulose acetate RO membrane using the cleaning liquid of the present invention is not particularly limited as long as the cellulose acetate RO membrane is brought into contact with the cleaning liquid. Usually, immersion cleaning is performed by introducing a cleaning liquid into the raw water side of the cellulose acetate RO membrane module and allowing it to stand.
本発明の洗浄液による洗浄の前後で、前述の酸水溶液等の他の洗浄液を用いて洗浄を行う場合も、通常の場合、上記と同様の浸漬洗浄が採用される。 When washing is performed using another cleaning solution such as the above-described acid aqueous solution before and after cleaning with the cleaning solution of the present invention, the same immersion cleaning as described above is usually employed.
本発明の洗浄液、その他の洗浄液による浸漬洗浄時間には特に制限はなく、目的とする膜性能の回復率が得られる程度であればよいが、通常２〜２４時間程度である。 The immersion cleaning time with the cleaning liquid of the present invention and other cleaning liquids is not particularly limited as long as the recovery rate of the target film performance can be obtained, but is usually about 2 to 24 hours.
上記の洗浄液による洗浄後は、通常、純水等の高純度水を通水して仕上げ洗浄を行う。その後、酢酸セルロース系ＲＯ膜システムの運転を再開する。 After washing with the above-described washing liquid, finishing washing is usually performed by passing high-purity water such as pure water. Thereafter, the operation of the cellulose acetate RO membrane system is resumed.
以下に、実験例、実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to experimental examples, examples and comparative examples.
なお、以下において、ＮＨ２系化合物としてはスルファミン酸（和光純薬製）を用い、次亜塩素酸塩としては次亜塩素酸ナトリウム（ＮａＣｌＯ、有効塩素濃度１０％、シグマアルドリッチ社製）を用いた。
In the following, sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd.) is used as the NH 2 compound, and sodium hypochlorite (NaClO,
［実験例１］
スルファミン酸、次亜塩素酸ナトリウム、４８％水酸化ナトリウム、水を重量比で１８：５０：２３：９の割合で混合して、洗浄剤を調製した。この洗浄剤のＣｌ２／Ｎモル比は０．４６で、水酸化ナトリウムはスルファミン酸に対して１．５モル倍であり、ｐＨは１３である。
また、この洗浄剤を水で１２．５倍に希釈し、塩酸でｐＨを６．５に調整して、結合塩素濃度０．０７Ｍの洗浄液を調製した。
上記の洗浄剤と洗浄液をそれぞれ６０℃に保管して、全残留塩素濃度をＤＰＤ法で測定し、全残留塩素の残存率の経時変化を調べ、加速条件下での安定性を比較した。
結果を図１に示す。
図１より明らかなように、洗浄剤原液と比較して、ｐＨ６．５の洗浄液は、最初の５日間はある程度安定であるが、以降急激に全残留塩素の残存率が低下していることが分かる。このことから、希釈後の洗浄液ではなく、洗浄剤（原液）の状態で保管を行うことが望ましいことが分かる。
[Experiment 1]
A cleaning agent was prepared by mixing sulfamic acid, sodium hypochlorite, 48% sodium hydroxide and water in a weight ratio of 18: 50: 23: 9. This cleaning agent has a Cl 2 / N molar ratio of 0.46, sodium hydroxide is 1.5 molar times that of sulfamic acid, and pH is 13.
Further, this cleaning agent was diluted 12.5 times with water, and the pH was adjusted to 6.5 with hydrochloric acid to prepare a cleaning solution having a combined chlorine concentration of 0.07M.
The above-mentioned cleaning agent and cleaning solution were each stored at 60 ° C., the total residual chlorine concentration was measured by the DPD method, the change over time in the residual rate of total residual chlorine was examined, and the stability under accelerated conditions was compared.
The results are shown in FIG.
As is clear from FIG. 1, the pH 6.5 cleaning solution is somewhat stable for the first 5 days as compared with the cleaning agent stock solution. I understand. This shows that it is desirable to store in the state of a cleaning agent (stock solution) rather than a diluted cleaning solution.
［洗浄実験Ｉ］
洗浄実験Ｉにおいて、汚染酢酸セルロース系ＲＯ膜としては、海水の淡水化処理に使用した東洋紡製海淡用三酢酸セルロース（ＣＴＡ）−ＲＯ中空糸膜（以下、「汚染ＣＴＡ−ＲＯ膜」と称す。）を用いた。
[Cleaning experiment I]
In the washing experiment I, as the contaminated cellulose acetate RO membrane, the cellulose triacetate (CTA) -RO hollow fiber membrane (hereinafter referred to as “contaminated CTA-RO membrane”) manufactured by Toyobo used for seawater desalination treatment. .) Was used.
＜実施例Ｉ−１＞
汚染ＣＴＡ−ＲＯ膜を細かく裁断したもの２５ｇを５００ｍＬの純水を満たしたビーカーに浸漬させ、スターラーで１６時間撹拌することで、純水による洗浄を行った。その後、ビーカーから取り出したＣＴＡ−ＲＯ膜を５００ｍＬの０．０１Ｍ塩酸水溶液（ｐＨ２）を満たしたビーカーに浸漬し、スターラーで１６時間撹拌することで、酸洗浄を行った。続いて、実験例１で調製した洗浄剤を結合塩素濃度が０．０１Ｍになるよう純水で希釈し、濃塩酸でｐＨが５．５〜６．５になるよう調製した洗浄液（以下「洗浄液Ｉ」と称す。）を５００ｍＬ満たしたビーカーに、酸洗浄後のＣＴＡ−ＲＯ膜を浸漬し、スターラーで１６時間撹拌することで、本発明の洗浄液による洗浄を行った。
<Example I-1>
25 g of finely cut contaminated CTA-RO membrane was immersed in a beaker filled with 500 mL of pure water and stirred with a stirrer for 16 hours to perform washing with pure water. Thereafter, the CTA-RO membrane taken out from the beaker was immersed in a beaker filled with 500 mL of 0.01 M hydrochloric acid aqueous solution (pH 2), and stirred for 16 hours with a stirrer to perform acid cleaning. Subsequently, the cleaning agent prepared in Experimental Example 1 was diluted with pure water so that the combined chlorine concentration was 0.01 M, and the cleaning solution prepared to have a pH of 5.5 to 6.5 with concentrated hydrochloric acid (hereinafter “cleaning solution”). The CTA-RO membrane after acid cleaning was immersed in a beaker filled with 500 mL of “I”.) And stirred with a stirrer for 16 hours to perform cleaning with the cleaning liquid of the present invention.
その後、洗浄液からＣＴＡ−ＲＯ膜を取り出し、ＤＰＤ法により、洗浄に使用した洗浄液に含まれる全残留塩素量を求め、必要量の３５％重亜流酸ナトリウム水溶液を加えることで、残留塩素を中和した。また、水酸化ナトリウム水溶液を加えて、洗浄液のｐＨを中性に合わせた。その後、この洗浄液をＮｏ．５Ａの濾紙、次いで、孔径０．４５μｍの親水性ＰＴＦＥ膜で濾過した。採取した濾液について、全有機炭素計（ＴＯＣ）計で、溶出ＴＯＣ濃度を測定し、その結果から洗浄効果を調べた。このＴＯＣ値が大きいほど、洗浄による溶出ＴＯＣ濃度が高く、有機汚染物質の洗浄効果に優れることを示す。
また、この濾液について、モリブデンブルー法（シリカ）、ペルオキソ二硫酸カリウム分解法（全リン、ＪＩＳ−Ｋ−０１０１．４３．３．１）、電気加熱原子吸光法（鉄、ＪＩＳ−Ｋ−０１０１．６０．３）、フレーム原子吸光法（カルシウム、ＪＩＳ−Ｋ−０１０１．４９．２）により無機成分の溶出濃度の分析を行った。
Thereafter, the CTA-RO membrane is taken out from the cleaning solution, and the total residual chlorine amount contained in the cleaning solution used for cleaning is obtained by the DPD method, and the required amount of 35% sodium bisulfite aqueous solution is added to neutralize the residual chlorine. did. Further, an aqueous sodium hydroxide solution was added to adjust the pH of the cleaning solution to neutral. Thereafter, this washing solution was designated as No. The mixture was filtered through 5A filter paper and then with a hydrophilic PTFE membrane having a pore diameter of 0.45 μm. About the extract | collected filtrate, the elution TOC density | concentration was measured with the total organic carbon meter (TOC) meter, and the washing | cleaning effect was investigated from the result. The larger this TOC value, the higher the TOC concentration eluted and the better the organic pollutant cleaning effect.
Moreover, about this filtrate, the molybdenum blue method (silica), the potassium peroxodisulfate decomposition method (all phosphorus, JIS-K-01014.33.1), the electric heating atomic absorption method (iron, JIS-K-0101. 60.3), and elution concentrations of inorganic components were analyzed by flame atomic absorption spectrometry (calcium, JIS-K0101.49.2).
＜実施例Ｉ−２＞
洗浄液として、実験例１で調製した洗浄剤を結合塩素濃度が０．０３Ｍとなるように希釈したものを使用した他は、実施例Ｉ−１と同様に洗浄実験を行い、同様に溶出ＴＯＣ濃度を調べた。なお、この洗浄液について、シリンガルダジン法試験紙（アクアチェック３、日産化学社製）で測定した遊離塩素濃度は５ｍｇ／Ｌであった。
<Example I-2>
A washing experiment was conducted in the same manner as in Example I-1, except that the washing agent prepared in Experimental Example 1 was diluted to have a combined chlorine concentration of 0.03 M. I investigated. In addition, about this washing | cleaning liquid, the free chlorine density | concentration measured with the syringaldazin method test paper (
＜実施例Ｉ−３＞
洗浄液として、実験例１で調製した洗浄剤を結合塩素濃度が０．０７Ｍとなるよう希釈したものを使用した他は、実施例Ｉ−１と同様に洗浄実験を行い、同様に溶出ＴＯＣ濃度と無機成分の溶出濃度の分析を行った。
<Example I-3>
A washing experiment was performed in the same manner as in Example I-1, except that the cleaning agent prepared in Experimental Example 1 was diluted to have a combined chlorine concentration of 0.07 M. The elution concentration of the inorganic component was analyzed.
＜比較例Ｉ−１＞
洗浄液Ｉの代わりに純水を用いて洗浄した他は、実施例Ｉ−１と同様に洗浄実験を行い、同様に溶出ＴＯＣ濃度と無機成分の分析を行った。
<Comparative Example I-1>
A washing experiment was conducted in the same manner as in Example I-1 except that pure water was used in place of the washing liquid I, and the elution TOC concentration and inorganic components were similarly analyzed.
＜比較例Ｉ−２＞
洗浄液Ｉの代わりに、遊離塩素濃度５ｍｇ／ＬのＮａＣｌＯ水溶液（ｐＨ７．０）を用いた他は、実施例Ｉ−１と同様に洗浄実験を行い、同様にＴＯＣ値と無機成分の分析を行った。なお、ＮａＣｌＯ水溶液のｐＨは濃塩酸で調整し、遊離塩素濃度はＤＰＤ法で測定した。
<Comparative Example I-2>
A washing experiment was conducted in the same manner as in Example I-1 except that a NaClO aqueous solution (pH 7.0) having a free chlorine concentration of 5 mg / L was used instead of the washing solution I, and the TOC value and the inorganic component were similarly analyzed. It was. The pH of the NaClO aqueous solution was adjusted with concentrated hydrochloric acid, and the free chlorine concentration was measured by the DPD method.
実施例Ｉ−１〜３及び比較例Ｉ−１，２の溶出ＴＯＣ濃度の測定結果を図２（ａ）に、また、実施例Ｉ−１，３、比較例Ｉ−１，２の無機成分溶出濃度の測定結果を図２（ｂ）に示す。
図２（ａ），（ｂ）より、洗浄液に含まれる結合塩素濃度が０．０１Ｍ以上、特に０．０３Ｍ以上であれば、ＣＴＡ−ＲＯ膜の有機汚染物質を効率良く分解除去できることが分かる。また、ＮａＣｌＯによる洗浄は、有機物に対しては有効であっても、シリカや無機成分に対しては純水による洗浄と殆ど変わらず、効果的でないことが分かる。ここで、結合塩素濃度が０．０１Ｍでは、有機汚染物質の除去効果は純水の場合と殆ど変わらないにも関わらず、シリカに対する洗浄効果には優れたものとなるという異質な効果が得られている。
また、図２（ｂ）より、本発明の洗浄液を用いれば、膜に付着したシリカを除去することができ、結合塩素の濃度をさらに増やせば、シリカの除去効果が高くなるだけでなく、リン、カルシウムといったその他の無機汚染物質も除去できることが分かる。一方、ＮａＣｌＯによる洗浄は、シリカをわずかに除去できたのみで、純水による洗浄とほぼ変わらず、効果的でないことが分かる。
The measurement results of the elution TOC concentrations of Examples I-1 to 3 and Comparative Examples I-1 and 2 are shown in FIG. 2 (a), and the inorganic components of Examples I-1 and 3 and Comparative Examples I-1 and 2 are shown in FIG. The measurement result of the elution concentration is shown in FIG.
2 (a) and 2 (b), it can be seen that organic contaminants in the CTA-RO membrane can be efficiently decomposed and removed if the concentration of bound chlorine contained in the cleaning liquid is 0.01M or more, particularly 0.03M or more. Further, it can be understood that the cleaning with NaClO is not effective because it is effective for organic substances but is almost the same as the cleaning with pure water for silica and inorganic components. Here, when the combined chlorine concentration is 0.01M, the effect of removing organic pollutants is almost the same as that of pure water, but the extraordinary effect that the cleaning effect on silica is excellent is obtained. ing.
Further, from FIG. 2 (b), if the cleaning liquid of the present invention is used, silica adhering to the film can be removed. If the concentration of bound chlorine is further increased, not only the silica removal effect is increased, but also It can be seen that other inorganic contaminants such as calcium can also be removed. On the other hand, it is understood that the cleaning with NaClO is not effective because it can remove silica slightly and is almost the same as the cleaning with pure water.
［洗浄実験II］
洗浄実験IIでは、ＲＯ膜として、東レ社製酢酸セルロース系ＲＯ膜「ＳＣ−３２００」を用い、図３に示す平膜試験装置を用いて洗浄効果を調べた。
この平膜試験装置において、ＲＯ膜供給水は、配管１１より高圧ポンプ４で、密閉容器１のＲＯ膜（膜面積８ｃｍ２）をセットした平膜セル２の下側の原水室１Ａに供給される。図３（ｂ）に示すように、密閉容器１は、原水室１Ａ側の下ケース１ａと、透過水室１Ｂ側の上ケース１ｂとで構成され、下ケース１ａと上ケース１ｂとの間に、平膜セル２がＯリング８を介して固定されている。平膜セル２はＲＯ膜２Ａの透過水側が多孔質支持板２Ｂで支持された構成とされている。平膜セル２の下側の原水室１Ａ内はスターラー３で攪拌子５を回転させることにより攪拌される。ＲＯ膜透過水は平膜セル２の上側の透過水室１Ｂを経て配管１２より取り出される。濃縮水は配管１３より取り出される。密閉容器１内の圧力は、給水配管１１に設けた圧力計６と、濃縮水取出配管１３に設けた圧力調整バルブ７により調整される。
[Cleaning Experiment II]
In cleaning experiment II, the cellulose acetate RO membrane “SC-3200” manufactured by Toray Industries, Inc. was used as the RO membrane, and the cleaning effect was examined using the flat membrane test apparatus shown in FIG.
In this flat membrane test apparatus, RO membrane supply water is supplied from the
また、界面活性剤として、ドデシル硫酸ナトリウム（ＳＤＳ、和光純薬社製）、又はドデシルベンゼン硫酸ナトリウム（ＳＤＢＳ、和光純薬社製）を用いた。 Further, sodium dodecyl sulfate (SDS, manufactured by Wako Pure Chemical Industries, Ltd.) or sodium dodecylbenzene sulfate (SDBS, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a surfactant.
純水フラックス測定条件は、供給水流量１ｍＬ／ｍｉｎ、圧力０．７５ＭＰａ、水温２５℃とし、回収率、フラックス、フラックス比は以下の式で求めた。
回収率［％］＝（透過水流量[ｍＬ／ｍｉｎ]／供給水流量[ｍＬ／ｍｉｎ]）×１００
フラックス[ｍ３／(ｍ２・ｄ)]＝透過水流量[ｍ３／ｄ]／膜面積[ｍ２]×温度換算係数[-]
フラックス比[-]＝汚染及び洗浄後の純水フラックス[ｍ３／(ｍ２・ｄ)]／初期純水フラックス[ｍ３／(ｍ２・ｄ)]
The pure water flux measurement conditions were a supply water flow rate of 1 mL / min, a pressure of 0.75 MPa, a water temperature of 25 ° C., and the recovery rate, flux, and flux ratio were determined by the following equations.
Recovery [%] = (permeate flow rate [mL / min] / feed water flow rate [mL / min]) × 100
Flux [m 3 / (m 2 · d)] = permeate flow rate [m 3 / d] / membrane area [m 2 ] × temperature conversion coefficient [−]
Flux ratio [-] = pure water flux after contamination and cleaning [m 3 / (m 2 · d)] / initial pure water flux [m 3 / (m 2 · d)]
＜比較例II−１＞
まず、ＲＯ膜の初期純水フラックスを測定し、その後、ＲＯ膜を有機物質と無機物質で汚染させるため、グアガム１ｍｇ／Ｌとフルボ酸１ｍｇ／Ｌをカルシウム１０ｍｇ／Ｌ、シリカ３０ｍｇ／Ｌ、アルミニウム０．０５ｍｇ／Ｌの無機物を含む水溶液に混合して調製した模擬汚染水を平膜試験装置に通水した。通水条件は、供給水流量０．７ｍＬ／ｍｉｎ、回収率８０％、水温２５℃、ｐＨ６．５、通水時間２５０時間とした。その後、圧力開放条件で純水を２．５ｍＬ／ｍｉｎで２時間通水することによりＲＯ膜をリンスし、汚染後の純水フラックスを測定した。
その後、以下の手順で洗浄を行った。
洗浄手順としては、まず、洗浄液として０．１５重量％ＳＤＢＳを含んだ界面活性剤水溶液を、圧力開放条件で２．５ｍＬ／ｍｉｎで１時間通水した。その後、通水ポンプを停止して、ＲＯ膜を洗浄液に１６時間浸漬させた。浸漬後、圧力開放条件で純水を２．５ｍＬ／ｍｉｎで２時間通水することによりＲＯ膜をリンスし、洗浄後の純水フラックスを測定した。
<Comparative Example II-1>
First, the initial pure water flux of the RO membrane is measured, and then the RO membrane is contaminated with organic and inorganic substances, so that guar gum 1 mg / L and fulvic acid 1 mg / L are
Thereafter, washing was performed according to the following procedure.
As a washing procedure, first, a surfactant aqueous solution containing 0.15 wt% SDBS as a washing solution was passed through at a pressure release condition of 2.5 mL / min for 1 hour. Thereafter, the water pump was stopped and the RO membrane was immersed in the cleaning solution for 16 hours. After immersion, the RO membrane was rinsed by passing pure water at 2.5 mL / min for 2 hours under pressure release conditions, and the pure water flux after washing was measured.
＜比較例II−２＞
洗浄液として、遊離塩素濃度１ｍｇ／ＬのＮａＣｌＯ水溶液（ｐＨ６．５）を使用したこと以外は比較例II−１と同様に洗浄を行い、洗浄後の純水フラックスを測定した。
<Comparative Example II-2>
Cleaning was performed in the same manner as in Comparative Example II-1 except that a NaClO aqueous solution (pH 6.5) having a free chlorine concentration of 1 mg / L was used as the cleaning liquid, and the pure water flux after the cleaning was measured.
＜比較例II−３＞
洗浄液として、０．１５重量％ＳＤＳを含んだ界面活性剤水溶液を使用したこと以外は比較例II−１と同様に洗浄を行い、洗浄後の純水フラックスを測定した。
<Comparative Example II-3>
Cleaning was performed in the same manner as in Comparative Example II-1 except that a surfactant aqueous solution containing 0.15 wt% SDS was used as the cleaning liquid, and the pure water flux after the cleaning was measured.
＜実施例II−１＞
洗浄液として、実施例Ｉ−３に記載の方法で調製した結合塩素濃度が０．０７Ｍの洗浄液を使用したこと以外は比較例II−１と同様に洗浄を行い、洗浄後の純水フラックスを測定した。
<Example II-1>
Cleaning was performed in the same manner as in Comparative Example II-1 except that a cleaning liquid having a combined chlorine concentration of 0.07M prepared by the method described in Example I-3 was used as the cleaning liquid, and the pure water flux after cleaning was measured. did.
＜実施例II−２＞
洗浄液として、実施例Ｉ−３に記載の方法で、洗浄剤を希釈した後、ＳＤＳを含んだ界面活性剤水溶液を加え、結合塩素濃度が０．０１Ｍ、ＳＤＳ濃度が０．１５重量％となるように調整した洗浄液を用いたこと以外は比較例II−１と同様に洗浄を行い、洗浄後の純水フラックスを測定した。
<Example II-2>
As a cleaning solution, after the cleaning agent is diluted by the method described in Example I-3, an aqueous surfactant solution containing SDS is added, so that the combined chlorine concentration is 0.01 M and the SDS concentration is 0.15 wt%. Cleaning was performed in the same manner as in Comparative Example II-1 except that the cleaning liquid adjusted as described above was used, and the pure water flux after cleaning was measured.
比較例II−１〜３及び実施例II−１，２の洗浄結果を表２に示す。 Table 2 shows the cleaning results of Comparative Examples II-1 to II and Examples II-1 and II.
表２より、界面活性剤水溶液やＮａＣｌＯ水溶液で洗浄した場合よりも、本発明の洗浄液を使用した場合、あるいは更に界面活性剤を含む本発明の洗浄液で洗浄した場合の方が、フラックス比の回復率が大きく、本発明によれば効果的に酢酸セルロースＲＯ膜を洗浄できることが分かる。 From Table 2, the flux ratio is recovered when the cleaning liquid of the present invention is used, or when the cleaning liquid of the present invention further containing a surfactant is used, rather than the case of cleaning with a surfactant aqueous solution or NaClO aqueous solution. It can be seen that the cellulose acetate RO membrane can be effectively cleaned according to the present invention.
１ 容器
２ 平膜セル
２Ａ ＲＯ膜
２Ｂ 多孔質支持板
３ スターラー
４ 高圧ポンプ
５ 攪拌子
６ 圧力計
７ 圧力調整バルブ
８ Ｏリング
DESCRIPTION OF SYMBOLS 1
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| JP2006263510A (en) * | 2005-03-22 | 2006-10-05 | Kurita Water Ind Ltd | Slime preventing agent for membrane separation and membrane separation method |
| JP2010063998A (en) * | 2008-09-10 | 2010-03-25 | Japan Organo Co Ltd | Slime preventive agent composition for separation membrane and membrane separation method |
| WO2011125762A1 (en) * | 2010-03-31 | 2011-10-13 | 栗田工業株式会社 | Combined chlorine agent, and manufacturing method and method of use for same |
| WO2012057188A1 (en) * | 2010-10-29 | 2012-05-03 | 東レ株式会社 | Fresh water generation method and fresh water generation device |
| WO2013179775A1 (en) * | 2012-05-30 | 2013-12-05 | 栗田工業株式会社 | Agent for cleaning permeation film, and cleaning method |
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| JP2006263510A (en) * | 2005-03-22 | 2006-10-05 | Kurita Water Ind Ltd | Slime preventing agent for membrane separation and membrane separation method |
| JP2010063998A (en) * | 2008-09-10 | 2010-03-25 | Japan Organo Co Ltd | Slime preventive agent composition for separation membrane and membrane separation method |
| WO2011125762A1 (en) * | 2010-03-31 | 2011-10-13 | 栗田工業株式会社 | Combined chlorine agent, and manufacturing method and method of use for same |
| WO2012057188A1 (en) * | 2010-10-29 | 2012-05-03 | 東レ株式会社 | Fresh water generation method and fresh water generation device |
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