WO2024116641A1 - Water-treating agent and water treatment method - Google Patents
Water-treating agent and water treatment method Download PDFInfo
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- WO2024116641A1 WO2024116641A1 PCT/JP2023/037910 JP2023037910W WO2024116641A1 WO 2024116641 A1 WO2024116641 A1 WO 2024116641A1 JP 2023037910 W JP2023037910 W JP 2023037910W WO 2024116641 A1 WO2024116641 A1 WO 2024116641A1
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- WIPO (PCT)
- Prior art keywords
- water
- water treatment
- salt
- treatment agent
- ion
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 242
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 51
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 91
- 150000003839 salts Chemical class 0.000 claims abstract description 87
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 11
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 235000021317 phosphate Nutrition 0.000 claims abstract description 9
- 150000004760 silicates Chemical class 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 33
- 150000001450 anions Chemical class 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 239000007848 Bronsted acid Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000701 coagulant Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 46
- -1 quaternary ammonium ions Chemical class 0.000 description 91
- 239000007787 solid Substances 0.000 description 51
- 238000003756 stirring Methods 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 35
- 239000000706 filtrate Substances 0.000 description 33
- 239000006228 supernatant Substances 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 239000000126 substance Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002351 wastewater Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 239000010802 sludge Substances 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229920006317 cationic polymer Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- 150000003840 hydrochlorides Chemical class 0.000 description 7
- 239000010842 industrial wastewater Substances 0.000 description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical compound [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- QPDSALLMZSDJIM-UHFFFAOYSA-M 1-dodecyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=C(C)C=C1 QPDSALLMZSDJIM-UHFFFAOYSA-M 0.000 description 2
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 2
- YCMFMSOTJOUSLI-UHFFFAOYSA-M 1-hexadecyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=C(C)C=C1 YCMFMSOTJOUSLI-UHFFFAOYSA-M 0.000 description 2
- VLCPYIOIXOFLOK-UHFFFAOYSA-M 1-hexyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1=CC=C(C)C=C1 VLCPYIOIXOFLOK-UHFFFAOYSA-M 0.000 description 2
- JEOSMYVMLZTQOH-UHFFFAOYSA-M 1-hexylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1=CC=CC=C1 JEOSMYVMLZTQOH-UHFFFAOYSA-M 0.000 description 2
- WJDJWDHXZBNQNE-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 WJDJWDHXZBNQNE-UHFFFAOYSA-M 0.000 description 2
- SIHFYNZIBKOFFK-UHFFFAOYSA-N 1-tetradecylpyridin-1-ium Chemical compound CCCCCCCCCCCCCC[N+]1=CC=CC=C1 SIHFYNZIBKOFFK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- BNDXNEVHWSOJGV-UHFFFAOYSA-M benzyl-hexyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)CC1=CC=CC=C1 BNDXNEVHWSOJGV-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- FZCCKDYTOZQJJR-UHFFFAOYSA-M hexyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)C FZCCKDYTOZQJJR-UHFFFAOYSA-M 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- QAIGYXWRIHZZAA-UHFFFAOYSA-M 1-methylpyridin-1-ium;chloride Chemical compound [Cl-].C[N+]1=CC=CC=C1 QAIGYXWRIHZZAA-UHFFFAOYSA-M 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MOFMDILXKVAFKY-UHFFFAOYSA-M 4-methyl-1-octadecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+]1=CC=C(C)C=C1 MOFMDILXKVAFKY-UHFFFAOYSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- XEQSHFOMHJZUNS-UHFFFAOYSA-N azane;2-(chloromethyl)oxirane;n-methylmethanamine Chemical compound N.CNC.ClCC1CO1 XEQSHFOMHJZUNS-UHFFFAOYSA-N 0.000 description 1
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 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 1
- HTKPDYSCAPSXIR-UHFFFAOYSA-N octyltrimethylammonium ion Chemical compound CCCCCCCC[N+](C)(C)C HTKPDYSCAPSXIR-UHFFFAOYSA-N 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Definitions
- the present invention relates to a water treatment agent and a water treatment method. More specifically, the present invention relates to a water treatment agent and a water treatment method for removing water-soluble COD components from water containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge).
- water-soluble COD components such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge).
- Patent Document 2 proposes a water treatment method that can stably reduce water-soluble COD components even if an excessive amount of water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater.
- the water treatment method includes a step of adding to the water to be treated a water treatment agent containing a copolymer having a weight average molecular weight of 10,000 to 600,000, which is obtained by polymerizing a monomer having a cationic functional group and a monomer having no cationic functional group in a specific molar ratio, and a water treatment agent containing at least one salt selected from the group consisting of silicates, phosphates, and borates.
- a water treatment agent containing a copolymer having a weight average molecular weight of 10,000 to 600,000 which is obtained by polymerizing a monomer having a cationic functional group and a monomer having no cationic functional group in a specific molar ratio
- the present invention has been made in consideration of the problems of the prior art, and the object of the present invention is to provide a water treatment agent and a water treatment method that can stably reduce water-soluble COD components even when an excessive amount of the water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater, and that is remarkably effective in reducing water-soluble COD components.
- the present invention is a water treatment agent containing a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
- A quaternary ammonium salt
- S salt
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group
- X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- the present invention also provides a water treatment method comprising a step (I) of adding a quaternary ammonium salt (A) represented by any one of the general formulae (1) to (3) to the water to be treated, and a step (II) of adding at least one salt (S) selected from the group consisting of silicates, phosphates, and borates to the water to be treated.
- a quaternary ammonium salt A
- S at least one salt
- water-soluble COD component reduction effect means the effect of reducing the content of water-soluble COD components in water by forming water-insoluble complexes with the water-soluble COD components contained in the water to be treated, precipitating them, and separating and removing them.
- 1 is a graph showing the relationship between the amount (mg/L) of solids of a quaternary ammonium salt (A) added in a water treatment agent and COD (mg/L).
- the water treatment agent of the present embodiment contains a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
- A quaternary ammonium salt
- S salt
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group
- X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- X ⁇ represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- n is an integer of 5 to 17 representing the number of repeating methylene groups
- X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.
- the water treatment agent of this embodiment may be a one-component water treatment agent that is a composition containing the quaternary ammonium salt (A) and the salt (S), or may be a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S).
- the water treatment agent of this embodiment is preferably a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S).
- the quaternary ammonium salt (A) is a compound having a structure represented by any one of the general formulas (1) to (3).
- a compound having a structure represented by the general formula (1) will be referred to as compound (A1)
- a compound having a structure represented by the general formula (2) will be referred to as compound (A2)
- a compound having a structure represented by the general formula (3) will be referred to as compound (A3).
- n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
- linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A1) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
- R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group.
- X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
- Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids (sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)).
- X ⁇ is preferred.
- the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
- X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
- the cation (ammonium ion) in the compound (A1) include hexyltrimethylammonium ion, heptyltrimethylammonium ion, octyltrimethylammonium ion, nonyltrimethylammonium ion, decyltrimethylammonium ion, undecyltrimethylammonium ion, dodecyltrimethylammonium (lauryltrimethylammonium) ion, tridecyltrimethylammonium ion, tetradecyltrimethylammonium (myristyltrimethylammonium) ion, pentadecyltrimethylammonium ion, hexadecyltrimethylammonium ion, heptadecyltrimethylammonium ion, octadecyltrimethylammonium (trimethylstearylammonium) ion, and mixtures thereof.
- the hexadecyltrimethylammonium ion or octadecyltrimethylammonium (trimethylstearylammonium) ion is preferred.
- n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
- linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A2) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
- X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
- Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like.
- X ⁇ is preferred.
- the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
- X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
- cation (ammonium ion) in the compound (A2) include benzylhexyldimethylammonium ion, benzylheptyldimethylammonium ion, benzyloctyldimethylammonium ion, benzylnonyldimethylammonium ion, benzyldecyldimethylammonium ion, benzylundecyldimethylammonium ion, benzyldodecyldimethylammonium (benzyllauryldimethylammonium) ion, benzyltridecyldimethylammonium ion, benzyltetradecyldimethylammonium (benzylmyristyldimethylammonium) ion, benzylpentadecyldimethylammonium ion, benzylhexadecyldimethylammonium i
- n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
- linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A3) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
- X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Br ⁇ nsted acid or a quaternizing agent.
- Br ⁇ nsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like.
- X ⁇ is preferred.
- the quaternizing agent include methyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ), methyl bromide (i.e., X ⁇ ⁇ Br ⁇ ), dimethyl sulfate (i.e., X ⁇ ⁇ CH 3 SO 4 ⁇ ), and benzyl chloride (i.e., X ⁇ ⁇ Cl ⁇ ).
- X ⁇ is preferably Cl ⁇ , Br ⁇ or HSO 4 ⁇ .
- Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and from the viewpoint of the effect of reducing water-soluble COD components, a hydrogen atom or a methyl group is preferred.
- cation (ammonium ion) in the compound (A3) include 1-hexylpyridinium ion, 1-hexyl-4-methylpyridinium ion, 1-heptylpyridinium ion, 1-heptyl-4-methylpyridinium ion, 1-octylpyridinium ion, 1-octyl-4-methylpyridinium ion, 1-nonylpyridinium ion, 1-nonyl-4-methylpyridinium ion, 1-decylpyridinium ion, 1-decyl-4-methyl ...
- the salt (S) is at least one selected from the group consisting of silicates, phosphates, and borates.
- the salt (S) may be used alone or in combination of two or more.
- the silicate may be an alkali metal salt or an alkaline earth metal salt of silicic acid, or an alkali metal salt or an alkaline earth metal salt of condensed silicic acid.
- the silicate is preferably at least one selected from the group consisting of lithium silicate, sodium silicate, potassium silicate, and calcium silicate, and more preferably sodium silicate.
- the silicate may be in the form of a solid or an aqueous solution, and aqueous solutions of sodium silicate (No. 1, No. 2, No. 3, No. 4, No. 5), so-called water glass, may be used.
- the phosphate salt may be an alkali metal salt or an alkaline earth metal salt of phosphoric acid, or an alkali metal salt or an alkaline earth metal salt of condensed phosphoric acid (polyphosphoric acid, metaphosphoric acid, etc.).
- the phosphate salt is preferably at least one selected from the group consisting of monosodium phosphate, disodium phosphate, trisodium phosphate, potassium hydrogen phosphate, and sodium polyphosphate, and more preferably trisodium phosphate.
- the borate salt may be an alkali metal salt or an alkaline earth metal salt of boric acid, an alkali metal salt or an alkaline earth metal salt of polyboric acid, or a hydrate thereof.
- the borate salt is preferably at least one selected from the group consisting of trisodium borate, sodium metaborate, and sodium tetraborate, and more preferably sodium tetraborate decahydrate.
- the salt (S) preferably contains the silicate, and more preferably contains sodium silicate.
- the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) in the water treatment agent of this embodiment is preferably 0.01 to 30, more preferably 0.1 to 20, and even more preferably 1 to 10, from the viewpoints of the effect of reducing water-soluble COD components, the amount of sludge generated, and treatment costs.
- the water treatment agent of this embodiment may further contain water in addition to the quaternary ammonium salt (A) and the salt (S) from the viewpoint of operability (handling ability) and the like.
- the total content of the quaternary ammonium salt (A) and the salt (S) in the water treatment agent of this embodiment is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water.
- the content of the quaternary ammonium salt (A) in the water treatment agent of this embodiment is preferably 0.1 to 30% by weight, more preferably 1 to 15% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water.
- the total content of the quaternary ammonium salt (A), the salt (S), and water is preferably 90 to 100% by weight based on the weight of the water treatment agent.
- the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P1) may contain water in addition to the quaternary ammonium salt (A).
- the content of the quaternary ammonium salt (A) in the water treatment agent (P1) is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the water treatment agent (P1) from the viewpoint of operability and the effect of reducing water-soluble COD components.
- the total content of the quaternary ammonium salt (A) and water in the water treatment agent (P1) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P1).
- the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P2) may contain water in addition to the salt (S).
- the content of the salt (S) in the water treatment agent (P2) is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the weight of the water treatment agent (P2) from the viewpoint of operability and the effect of reducing water-soluble COD components.
- the content of the salt (S) in the water treatment agent (P2) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P2).
- the water treatment agent of this embodiment may contain an organic coagulant to the extent that the effect of the present invention is not impaired in order to further improve the removal performance of water-soluble COD components.
- the organic coagulant include polycondensates of epihalohydrin and amine and their hydrochlorides, polycondensates of epihalohydrin and alkylenediamine and their hydrochlorides, polyethyleneimine and its hydrochlorides, alkylenedihalide-alkylenepolyamine polycondensates and their hydrochlorides, aniline-formaldehyde polycondensates and their hydrochlorides, polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine and its hydrochlorides, (di)methyldi(meth)allylammonium chloride, and polyvinylimidazoline and its hydrochlorides.
- the organic coagulant may be used alone or in combination of two or more types.
- the organic coagulant may be contained in both or either of the
- the method for producing the water treatment agent of this embodiment is not particularly limited, but it can be produced, for example, as follows.
- the water treatment agent When the water treatment agent is a one-component type, it can be produced by mixing the quaternary ammonium salt (A) diluted with water as necessary, the salt (S) diluted with water as necessary, and additives as necessary.
- the mixing method is not particularly limited, and for example, mixing may be performed using a stirrer in a container such as a bucket.
- the quaternary ammonium salt (A) and the salt (S) may form a complex and become cloudy, but it can be used without problems by stirring and mixing again immediately before use.
- the water treatment agent (P1) can be produced by mixing the quaternary ammonium salt (A), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced by mixing the salt (B), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced.
- the method of diluting the quaternary ammonium salt (A) and/or the salt (S) with water is not particularly limited, but for example, a method can be used in which a predetermined amount of the quaternary ammonium salt (A) and/or the salt (S) is added to a previously measured amount of water while stirring it using a known stirring device (such as a jar tester), and the water is stirred for several hours (approximately 1 to 4 hours).
- the quaternary ammonium salt (A) forms a water-insoluble complex with the water-soluble COD components contained in the water to be treated, causing them to become insoluble and precipitate, and the precipitate is separated and removed, thereby reducing the water-soluble COD components.
- the water treatment agent further contains the salt (S)
- the complex between the quaternary ammonium salt (A) and the water-soluble COD components is coarsened, facilitating the separation and removal of the precipitate, and a further reduction effect in the water-soluble COD components can be expected.
- the salt (S) precipitates the excessively added quaternary ammonium salt (A), and the quaternary ammonium salt (A) itself becomes a water-soluble COD component and can suppress the increase in the water-soluble COD components, so it is presumed that a stable water-soluble COD reduction effect can be expressed.
- the salt (S) can precipitate a complex of the water-soluble COD components dissolved in water and the quaternary ammonium salt (A), and is presumed to have an effect of reducing water-soluble COD components.
- the water treatment agent of the present invention is very useful because, when added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steel, food, gravel, semiconductor-related and cleaning industries, etc.), sewage, purified water, sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress the increase in water-soluble COD components, even under conditions where the amount of water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and has a significantly excellent effect in reducing water-soluble COD components.
- the water treatment method of this embodiment includes a step (I) of adding the quaternary ammonium salt (A) to water to be treated (hereinafter, in this specification, may be referred to as water to be treated) containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge), and a step (II) of adding the salt (S) to the water to be treated.
- a step (I) of adding the quaternary ammonium salt (A) to water to be treated hereinafter, in this specification, may be referred to as water to be treated
- water-soluble COD components such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge)
- S salt
- Step (I) The step (I) is a step of adding the quaternary ammonium salt (A) to the water to be treated.
- the amount of the quaternary ammonium salt (A) added to the water to be treated can be adjusted depending on the type of water to be treated, the content of particles suspended in the water to be treated, the amount of water-soluble COD components, etc., and is not particularly limited. From the viewpoint of water-soluble COD component reduction performance, however, 1 mg to 10 g per 1 L of the water to be treated is preferable, 3 mg to 8 g is more preferable, 5 mg to 5 g is even more preferable, and 5 mg to 3 g is even more preferable.
- step (I) the method for adding the quaternary ammonium salt (A) to the water to be treated is not particularly limited, and the quaternary ammonium salt (A) can be added to the water to be treated and mixed by a known method.
- Step (II) is a step of adding the salt (S) to the water to be treated.
- the amount of the salt (S) added to the water to be treated is preferably an amount such that the weight ratio of the salt (S) to the weight of the quaternary ammonium salt (A) [(S)/(A)] is 0.01 to 30, more preferably an amount such that the weight ratio is 0.1 to 20, and even more preferably an amount such that the weight ratio is 1 to 10.
- step (II) the method for adding the salt (S) to the water to be treated is not particularly limited, and the salt (S) can be added to the water to be treated and mixed using a known method.
- the steps (I) and (II) may be carried out separately or simultaneously.
- the water treatment agent (P1) containing the quaternary ammonium salt (A) and the water treatment agent (P2) containing the salt (S) are added separately.
- the steps (I) and (II) are carried out simultaneously, the quaternary ammonium salt (A) and the salt (S) are mixed in advance and added as a one-agent type water treatment agent. From the viewpoint of the effect of reducing water-soluble COD components, it is preferable to carry out the steps (I) and (II) separately, and it is more preferable to carry out the step (II) after carrying out the step (I).
- the water treatment method of the present embodiment may further include, in addition to the step (I) and the step (II), a step (III) of adding an inorganic flocculant to the water to be treated.
- the inorganic flocculants include aluminum sulfate, polyaluminum chloride, ferric chloride, polyferric sulfate, and hydrated lime. Each of the inorganic flocculants may be used alone or in combination of two or more.
- the amount of inorganic flocculant added when the water treatment method of this embodiment includes step (III) varies depending on the type of sludge or wastewater, the size and content of suspended particles, the total sludge and the amount of water-soluble COD components in the wastewater, etc., but is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.8% by weight, and even more preferably 0.01 to 0.5% by weight based on the weight of the sludge or wastewater. If it is 0.001% by weight or more, the effect of reducing water-soluble COD components will be more pronounced, and if it is 1% by weight or less, the amount of sludge generated can be reduced.
- the steps (I) to (III) may be performed separately or simultaneously.
- the steps (I) to (III) are preferably performed in any one of the following procedures (i) to (iv).
- Step (i) After step (I), step (III) is carried out, and then step (II) is carried out.
- step (ii) After step (III), step (I) is carried out, and then step (II) is carried out.
- Step (iii) and step (III) are carried out simultaneously ⁇ i.e., the quaternary ammonium salt (A) and the inorganic flocculant are mixed in advance and then added to the water to be treated ⁇ , and then step (II) is carried out.
- Step (iv) After step (I), step (II) is carried out, and then step (III) is carried out.
- the water treatment method of this embodiment includes the step (III), from the viewpoint of treatment costs, it is preferable to carry out the step (II) after carrying out the steps (I) and (III). In other words, it is preferable to carry out the steps (I) to (III) in any of the above procedures (i) to (iii).
- pH adjustment step The pH of the water to be treated after the steps (I) and (II) have been performed, or after the steps (I) to (III) have been performed if the water treatment method of the present embodiment has the step (III), is preferably 1 to 12, more preferably 3 to 10, and even more preferably 5 to 8. In this range, the effects of the present invention, such as reduction of water-soluble COD components, can be more effectively achieved.
- the water treatment method of the present embodiment may have a pH adjustment step of adding an inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an inorganic solid acidic substance (acidic sodium phosphate, acidic sulfuric acid, ammonium chloride, ammonium sulfate, ammonium bicarbonate, sulfamic acid, etc.), an organic acid (oxalic acid, succinic acid, malic acid, etc.), an inorganic alkaline substance (e.g., sodium hydroxide, potassium hydroxide, ammonia, etc.), and an organic alkaline substance (e.g., guanidine, etc.) or an aqueous solution thereof, in order to adjust the pH of the water to be treated after the steps (I) and (II), etc. have been performed.
- an inorganic acid hydroochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
- an inorganic solid acidic substance
- the water treatment method of the present embodiment preferably further comprises a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after carrying out the steps (I) and (II) or, in the case where the water treatment method of the present embodiment comprises the step (III), after carrying out the steps (I) to (III) to form coarse flocs.
- the polymer flocculant is not particularly limited, and any commonly used known polymer flocculant can be suitably used.
- the polymer flocculant may be any of cationic, nonionic, anionic, and amphoteric polymer flocculants, and these may also be used in combination.
- the cationic polymer flocculant may be a homopolymer of polyethyleneimine, a Mannich modified poly(meth)acrylamide, a quaternized dialkylaminoethyl (meth)acrylate, or a copolymer with other monomers such as (meth)acrylamide, or a copolymer containing the cationic monomer as a constituent unit.
- the nonionic polymer flocculant may be polyacrylamide or the like with a Mw of more than 1,000,000.
- the anionic polymer flocculant may, for example, be sodium poly(meth)acrylate, hydrolyzed poly(meth)acrylamide, (meth)acrylamide-sodium (meth)acrylate copolymer, (meth)acrylamide-sodium (meth)acrylate-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, (meth)acrylamide-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, and other (co)polymers containing the anionic monomers described above.
- the amphoteric polymer flocculant may be a copolymer of a cationic monomer (such as dialkylaminoethyl (meth)acrylate quaternized products and other cationic monomers as described above) with an anionic monomer (such as (meth)acrylic acid (salt), 2-acrylamido-2-methylpropane-1-sulfonic acid (salt)), and, if necessary, a nonionic monomer (such as acrylamide).
- a cationic monomer such as dialkylaminoethyl (meth)acrylate quaternized products and other cationic monomers as described above
- anionic monomer such as (meth)acrylic acid (salt), 2-acrylamido-2-methylpropane-1-sulfonic acid (salt)
- a nonionic monomer such as acrylamide
- the polymer flocculant addition step there is no particular limitation on the method of adding the polymer flocculant.
- the polymer flocculant may be added as is, but from the viewpoint of uniform mixing, it is preferable to add the polymer flocculant to the water to be treated after making it into an aqueous solution.
- the concentration of the polymer flocculant is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight.
- the amount of polymer flocculant added varies depending on the type of water to be treated, the size and content of suspended particles, and the molecular weight of the polymer flocculant, but from the viewpoint of general flocculation performance, it is preferably 0.0001 to 0.5% by weight, more preferably 0.0002 to 0.3% by weight, even more preferably 0.0003 to 0.2% by weight, and even more preferably 0.0004 to 0.1% by weight based on the weight of the water to be treated.
- the water treatment method of this embodiment may include a solid-liquid separation step of removing precipitates precipitated in the water to be treated that has been treated in the step (I), the step (II), and the like, from the water to be treated.
- methods for separating the solid and liquid can be used, such as gravity settling, membrane filtration, column filtration, pressure flotation, concentrators (e.g., thickeners, etc.), and dehydrators (e.g., centrifuges, belt press dehydrators, filter press dehydrators, etc.).
- Example (1) After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, a solid-liquid separation step is carried out.
- Example (2) After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is carried out, and further, the solid-liquid separation step is carried out.
- Example (3) The steps (I), (II) and (III) are carried out, and the pH adjustment step is carried out as necessary, and then the solid-liquid separation step is carried out.
- Example (4) After carrying out the steps (I), (II) and (III) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is further carried out, and then the solid-liquid separation step is further carried out.
- examples (2) and (4) are preferred from the viewpoint of forming coarser flocs and facilitating solid-liquid separation.
- the water treatment method of this embodiment may also include an activated carbon treatment step in which the water to be treated after the solid-liquid separation step is treated with activated carbon.
- the COD of the treated wastewater may be measured directly, but the effect of reducing COD can also be evaluated using TOC (total organic carbon), which is commonly used in the field of wastewater treatment as an alternative means of monitoring COD and can be measured more easily than COD.
- TOC total organic carbon
- the raw materials represented by each symbol in Tables 1 to 5 are as follows.
- the amount of each raw material ⁇ quaternary ammonium salt (A), comparative quaternary ammonium salt (comparative A), cationic polymer (M) and salt (S) ⁇ added in Tables 1 to 5 is the amount (mg) of solids (components excluding water and volatile solvents) of each raw material added per 1 L of water to be treated (wastewater from chemical plant B described below).
- A1-1 Hexyl trimethyl ammonium chloride (A1-2): Lauryl trimethyl ammonium chloride (A1-3): Hexadecyl trimethyl ammonium chloride (A1-4): Trimethylstearyl ammonium chloride (A1-5): Tetradecyl trimethyl ammonium chloride (A1-6): Tetradecyl trimethyl ammonium bromide (A1-7): Hexadecyl trimethyl ammonium bromide (A1-8): Hexadecyl trimethyl ammonium hydroxide (A2-1): Benzyl hexyl dimethyl ammonium chloride (A2-2): Benzyl lauryl dimethyl ammonium chloride (A2-3): Benzyl Benzylhexadecyldimethylammonium chloride (A2-4): Benzyldimethylstearylammonium chloride (A3-1): 1-hexyl
- Comparative Production Example 1 Production of cationic polymer (M-1) and comparative water treatment agent (Comparative PM-1) A four-neck flask equipped with a stirrer, a temperature sensor, a cooling tube, a dropping funnel and a mantle heater was charged with 190 parts of isopropyl alcohol (hereinafter abbreviated as "IPA”) and 69 parts of ion-exchanged water, and heated to reflux under stirring.
- IPA isopropyl alcohol
- a mixed solution of 80 parts of IPA, 20 parts of ion-exchanged water, and 0.7 parts of azobisisobutyronitrile (hereinafter abbreviated as "AIBN”) was added as an initiator solution from the dropping port, and a homogeneous mixture of 80% by weight of trimethyl-2-methacryloyloxyethylammonium chloride aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 352 parts, styrene (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 48 parts, IPA 180 parts, and ion-exchanged water 60 parts was added dropwise to the flask simultaneously over 4 hours while stirring the flask at 80 to 85 ° C.
- AIBN azobisisobutyronitrile
- the aqueous solution was diluted with ion-exchanged water to a solid content of 10.0 wt %, to obtain a comparative water treatment agent (PM-1) containing a cationic polymer (M-1).
- the comparative water treatment agent (PM-1) had a solid content of 40.0 wt %, a pH of 4.5, and the Mw (weight average molecular weight measured by GPC) of the cationic polymer (M-1) was 180,000, and the colloid equivalent value (colloid equivalent value measured by colloid titration using potassium polyvinyl sulfate) was 4.1.
- Example 1 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-1) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
- P1-1 250 mg of quaternary ammonium salt (A) solid content equivalent
- Examples 2 to 30, 35 to 36, 38 to 43, and 59 to 62> The supernatant was filtered in the same manner as in Example 1, except that the types and amounts of the quaternary ammonium salt (A) and the water treatment agent (P1) and the salt (S) and the water treatment agent (P2) were changed to those shown in Table 1, Table 2, Table 3, or Table 4.
- the COD and TOC of the filtrate were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 4.
- Example 31 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
- P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
- Example 32 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 31, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) ⁇ the water treatment agent (P1-3) was replaced with (P1-4) ⁇ , were measured.
- the COD was 6 mg/L and the TOC was 9 mg/L.
- Example 33 1 L of wastewater from B chemical plant containing an anionic surfactant was collected in a beaker, and under stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] as an inorganic flocculant was added in an amount to a solid content concentration of 50 mg/L.
- Example 34 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 33, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) ⁇ the water treatment agent (P1-3) was replaced with (P1-4) ⁇ , were measured.
- the COD was 7 mg/L and the TOC was 10 mg/L.
- Example 37 50 parts of an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added to a 100 ml beaker. 50 parts of an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added and mixed under stirring to obtain a one-form water treatment agent (P-37) containing (A1-3) and (S-1).
- A1-3 quaternary ammonium salt
- Example 44 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-4) ⁇ the water treatment agent (P2-1) was replaced with (P2-4) ⁇ , were measured.
- the COD was 7 mg/L and the TOC was 10 mg/L.
- Example 45 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-5) ⁇ the water treatment agent (P2-1) was replaced with (P2-5) ⁇ , were measured.
- the COD was 6 mg/L and the TOC was 9 mg/L.
- Example 46 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-6) ⁇ the water treatment agent (P2-1) was replaced with (P2-6) ⁇ , were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- Example 47 The same procedure as in Example 3 was repeated except that the salt (S-1) was replaced with the salt (S-7) ⁇ the water treatment agent (P2-1) was replaced with the water treatment agent (P2-7) ⁇ , and the COD and TOC of the filtrate of the supernatant were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- Example 48 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with aluminum sulfate (manufactured by Taimei Chemical Industry Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- Example 49 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with polyferric sulfate (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
- the COD was 6 mg/L and the TOC was 9 mg/L.
- Example 50 The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with ferric chloride (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- Example 51 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-5) ⁇ the water treatment agent (P1-3) was replaced with (P1-5) ⁇ , were measured.
- the COD was 7 mg/L and the TOC was 10 mg/L.
- Example 52 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-6) ⁇ the water treatment agent (P1-3) was replaced with (P1-6) ⁇ , were measured.
- the COD was 9 mg/L and the TOC was 13 mg/L.
- Example 53 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-7) ⁇ the water treatment agent (P1-3) was replaced with (P1-7) ⁇ , were measured.
- the COD was 8 mg/L and the TOC was 12 mg/L.
- Example 54 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-8) ⁇ the water treatment agent (P1-3) was replaced with (P1-8) ⁇ , were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- ⁇ Example 55 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
- P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
- Example 56 1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight.
- P1-3 250 mg of quaternary ammonium salt (A) solid content equivalent
- Example 57 The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the anionic polymer flocculant "Sunfloc AH-400P (manufactured by Sanyo Chemical Industries, Ltd.),” and the COD and TOC of the filtrate of the supernatant were measured. The COD was 4 mg/L and the TOC was 6 mg/L.
- Example 58 The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the nonionic polymer flocculant "Sunfloc NOP (manufactured by Sanyo Chemical Industries, Ltd.),” and the COD and TOC of the filtrate of the supernatant were measured.
- the COD was 5 mg/L and the TOC was 7 mg/L.
- Example 63 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of an acrylamide-diallyldimethylammonium chloride copolymer, "Unisense FCA1000L (manufactured by Senka Corporation)," which is an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
- the COD was 4 mg/L and the TOC was 6 mg/L.
- Example 64 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of poly(diallyldimethylammonium chloride), an organic coagulant, "Unisense FPA100L (manufactured by Senka Corporation)" was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
- the COD was 4 mg/L and the TOC was 6 mg/L.
- Example 65 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dimethylamine-ammonia-epichlorohydrin condensate "Unisense KHE100L (manufactured by Senka Corporation)" as an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
- the COD was 7 mg/L and the TOC was 10 mg/L.
- Example 66 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-formalin condensate, "Unisense KHF11L (manufactured by Senka Corporation),” an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010,” manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
- the COD was 8 mg/L and the TOC was 11 mg/L.
- Example 67 The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-diethylenetriamine condensate "Unisense KHP10P (manufactured by Senka Corporation)" which is an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L).
- the COD was 7 mg/L and the TOC was 10 mg/L.
- ⁇ Comparative Example 7 1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and 1,000 mg (100 mg of quaternary ammonium salt (A) solid content equivalent) of a water treatment agent (P1-7) was added under stirring, which was an aqueous solution in which a quaternary ammonium salt (A2-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 50 mg/L, and the TOC was 76 mg/L.
- FIG. 1 shows a graph plotting the COD (mg/L) values against the amount (mg/L) of the solids of the quaternary ammonium salt (A) in the water treatment agent or comparative water treatment agent for combination (1) [combination of Examples 3, 38, 39] containing the same quaternary ammonium salt (A) (water treatment agent (A2-3)) and salt (S) (salt (S-1)), combination (2) [combination of Examples 7, 40, 41] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), combination (3) [combination of Examples 11, 42, 43] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), and combination (4) [combination of Comparative Examples 7, 8, 9] containing the same quaternary ammonium salt (A) (comparative treatment agent (ratio P)) but not
- the COD decreased up to an addition amount of 250 mg of quaternary ammonium salt (A), and the COD increased when the addition amount was further increased, and it can be seen that there is an optimum point for the addition amount of quaternary ammonium salt (A).
- the water treatment agent of the example containing salt (S) no increase in COD was observed even when an amount of quaternary ammonium salt (A) exceeding 250 mg, which was the optimum point for the comparative water treatment agent, was used.
- the COD value and TOC value before treatment in the above formula are 80 mg/L and 122 mg/L, respectively, as described in Comparative Example 1.
- the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) is shown in Tables 1 to 5.
- Tables 1 to 5 show that the water treatment agents according to Examples 1 to 67 have higher COD removal rates and TOC removal rates than the water treatment agents according to the comparative examples, and are significantly more effective at reducing water-soluble COD components. Furthermore, the results of (1) Examples 3, 38, and 39, (2) Examples 7, 40, and 41, and (3) Examples 11, 42, and 43 in Figure 1 show that the water treatment agent of the present invention can achieve a stable water-soluble COD reduction effect over a wide range of added amounts of the water treatment agent (addition amount of quaternary ammonium salt (A) in the water treatment agent).
- the water treatment agent of the present invention is very useful because, by being added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steelmaking, food, gravel extraction, semiconductor-related, and cleaning industries, etc.), sewage, purified water, and sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress an increase in water-soluble COD components, even under conditions where the amount of the water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and can exhibit a significantly excellent effect of reducing water-soluble COD components.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The present invention relates to: a water-treating agent that contains a quaternary ammonium salt (A) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates; and a water treatment method in which the water-treating agent is used. According to the present invention, it is possible to provide a water-treating agent and a water treatment method that have a remarkably exceptional effect for reducing the amount of water-soluble COD components, the agent and method stably reducing the amount of water-soluble COD components even if an excessive amount of water-treating agent is used in response to the type or amount of water-soluble COD components contained in water being treated or to the amount of water being discharged.
Description
本発明は、水処理剤及び水処理方法に関する。更に詳しくは、各種工場廃水、下水、浄水、及び汚泥（有機性汚泥及び無機性汚泥）等の水溶解性ＣＯＤ成分を含有した水から水溶解性ＣＯＤ成分を除去するための水処理剤及び水処理方法に関する。
The present invention relates to a water treatment agent and a water treatment method. More specifically, the present invention relates to a water treatment agent and a water treatment method for removing water-soluble COD components from water containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge).
従来、工場廃水等に含まれる水溶解性ＣＯＤ成分を除去する方法としては、活性炭処理、紫外線照射、オゾン処理、硫酸第一鉄と過酸化水素とを組み合わせたフェントン処理等が提案されている。しかし、いずれも処理コストが高く広く普及しているとは言い難い。
Traditionally, methods proposed for removing water-soluble COD components contained in industrial wastewater, etc., include activated carbon treatment, ultraviolet irradiation, ozone treatment, and Fenton treatment, which combines ferrous sulfate and hydrogen peroxide. However, all of these methods are expensive to treat, and are not widely used.
これに対して、いわゆる高分子凝集剤を用いて水溶解性ＣＯＤ成分を除去（低減）する方法が提案されている（例えば特許文献１）。しかしながら、従来の処理方法では高分子凝集剤等の水溶解性ＣＯＤ成分低減剤として排水中の水溶解性ＣＯＤ成分の種類の違いに対して広く対応できるものを使用しているものの、排水中の水溶解性ＣＯＤの種類及び量の変動や排水流量の変動に対して高分子凝集剤を過剰に添加することで対応していたために、高分子凝集剤を実際の最適添加量より過剰に添加すると高分子凝集剤自身が水溶解性ＣＯＤ成分となり、水溶解性ＣＯＤ成分量が増加してしまうという問題があった。
In response to this, a method has been proposed for removing (reducing) water-soluble COD components using so-called polymer flocculants (for example, Patent Document 1). However, while conventional treatment methods use water-soluble COD component reducers such as polymer flocculants that can widely accommodate different types of water-soluble COD components in wastewater, they deal with fluctuations in the type and amount of water-soluble COD in the wastewater and fluctuations in the wastewater flow rate by adding an excess of polymer flocculant, which creates the problem that adding more polymer flocculant than the actual optimal amount makes the polymer flocculant itself a water-soluble COD component, increasing the amount of water-soluble COD components.
また、処理対象の水に含まれる水溶解性ＣＯＤ成分の種類及び量や排水量の変動に対して水処理剤の量を過剰に使用して対応しても安定して水溶解性ＣＯＤ成分を低減できる水処理方法として、特許文献２では、特定の構造を有するカチオン性官能基を有するモノマー及びカチオン性官能基を有しないモノマーを特定のモル比で重合させてなる重量平均分子量が１０，０００～６００，０００の共重合体を含む水処理剤と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群から選ばれる少なくとも１種の塩を含む水処理剤とを処理対象の水に添加する工程を含む水処理剤が提案されているが、水溶解性ＣＯＤ除去率には改善の余地があり、水溶解性ＣＯＤ成分低減効果のさらなる向上が求められていた。
In addition, Patent Document 2 proposes a water treatment method that can stably reduce water-soluble COD components even if an excessive amount of water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater. The water treatment method includes a step of adding to the water to be treated a water treatment agent containing a copolymer having a weight average molecular weight of 10,000 to 600,000, which is obtained by polymerizing a monomer having a cationic functional group and a monomer having no cationic functional group in a specific molar ratio, and a water treatment agent containing at least one salt selected from the group consisting of silicates, phosphates, and borates. However, there is room for improvement in the water-soluble COD removal rate, and further improvement in the effect of reducing water-soluble COD components is desired.
本発明は前記従来技術の問題点に鑑みてなされたものであり、本発明の目的は、処理対象の水に含まれる水溶解性ＣＯＤ成分の種類及び量や排水量の変動に対して水処理剤の量を過剰に使用して対応しても安定して水溶解性ＣＯＤ成分を低減でき、かつ水溶解性ＣＯＤ成分低減効果が顕著に優れる水処理剤及び水処理方法を提供することにある。
The present invention has been made in consideration of the problems of the prior art, and the object of the present invention is to provide a water treatment agent and a water treatment method that can stably reduce water-soluble COD components even when an excessive amount of the water treatment agent is used in response to the type and amount of water-soluble COD components contained in the water to be treated or fluctuations in the amount of wastewater, and that is remarkably effective in reducing water-soluble COD components.
本発明者らは前記課題を解決すべく鋭意検討した結果、本発明に到達した。即ち本発明は、下記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）とを含有する水処理剤である。
［式（１）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｒ１～Ｒ３はそれぞれ独立にメチル基、エチル基、プロピル基、又はブチル基、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。］
［式（２）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。］
［式（３）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基であり、Ｙは水素原子又は炭素数１～６のアルキル基である。］
The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention is a water treatment agent containing a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
[In formula (1), n is an integer of 5 to 17 representing the number of repeating methylene groups, R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group, and X − represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.]
[In formula (2), n is an integer of 5 to 17 representing the number of repeating methylene groups, and X − represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.]
[In formula (3), n is an integer of 5 to 17 representing the number of repeating methylene groups, X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent, and Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]
また、本発明は、前記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）を処理対象の水に添加する工程（Ｉ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）を処理対象の水に添加する工程（ＩＩ）とを有する水処理方法である。
The present invention also provides a water treatment method comprising a step (I) of adding a quaternary ammonium salt (A) represented by any one of the general formulae (1) to (3) to the water to be treated, and a step (II) of adding at least one salt (S) selected from the group consisting of silicates, phosphates, and borates to the water to be treated.
本発明は、水処理剤の添加量が過剰となる条件下でも水溶解性ＣＯＤ成分の上昇を抑制し、優れた水溶解性ＣＯＤ成分低減効果を安定して得ることができる。なお、本明細書において、「水溶解性ＣＯＤ成分低減効果」とは、処理対象の水に含まれる水溶解性ＣＯＤ成分と水不溶性のコンプレックスを形成して析出させ、分離除去することにより、水中の水溶解性ＣＯＤ成分含有量を低減させる効果を意味する。
The present invention can suppress the increase of water-soluble COD components even under conditions where the amount of water treatment agent added is excessive, and can stably obtain an excellent water-soluble COD component reduction effect. In this specification, "water-soluble COD component reduction effect" means the effect of reducing the content of water-soluble COD components in water by forming water-insoluble complexes with the water-soluble COD components contained in the water to be treated, precipitating them, and separating and removing them.
＜水処理剤＞
本実施形態の水処理剤は、下記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）とを含有する。
［式（１）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｒ１～Ｒ３はそれぞれ独立にメチル基、エチル基、プロピル基、又はブチル基、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。］
［式（２）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。］
［式（３）中、ｎはメチレン基の繰り返し数を表す５～１７の整数であり、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基であり、Ｙは水素原子又は炭素数１～６のアルキル基である。］
<Water treatment agent>
The water treatment agent of the present embodiment contains a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
[In formula (1), n is an integer of 5 to 17 representing the number of repeating methylene groups, R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group, and X − represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.]
[In formula (2), n is an integer of 5 to 17 representing the number of repeating methylene groups, and X − represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent.]
[In formula (3), n is an integer of 5 to 17 representing the number of repeating methylene groups, X- represents a counter anion of an ammonium ion and is an anion group derived from a conjugate base of a Bronsted acid or a quaternizing agent, and Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]
本実施形態の水処理剤は、下記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）とを含有する。
The water treatment agent of the present embodiment contains a quaternary ammonium salt (A) represented by any one of the following general formulas (1) to (3) and at least one salt (S) selected from the group consisting of silicates, phosphates, and borates.
本実施形態の水処理剤は、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）とを含む組成物である一剤型の水処理剤であってもよく、前記４級アンモニウム塩（Ａ）を含有する水処理剤（Ｐ１）と前記塩（Ｓ）を含有する水処理剤（Ｐ２）とからなる二剤型の水処理剤であってもよい。本実施形態の水処理剤は、水溶解性ＣＯＤ成分低減効果の観点から、前記４級アンモニウム塩（Ａ）を含有する水処理剤（Ｐ１）と前記塩（Ｓ）を含有する水処理剤（Ｐ２）とからなる二剤型の水処理剤であることが好ましい。
The water treatment agent of this embodiment may be a one-component water treatment agent that is a composition containing the quaternary ammonium salt (A) and the salt (S), or may be a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S). From the viewpoint of the effect of reducing water-soluble COD components, the water treatment agent of this embodiment is preferably a two-component water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S).
〔４級アンモニウム塩（Ａ）〕
前記４級アンモニウム塩（Ａ）は、前記一般式（１）～（３）のいずれかで表される構造を有する化合物である。以下、前記一般式（１）で表される構造を有する化合物を化合物（Ａ１）、前記一般式（２）で表される構造を有する化合物を化合物（Ａ２）、前記一般式（３）で表される構造を有する化合物を化合物（Ａ３）と称する。 [Quaternary ammonium salt (A)]
The quaternary ammonium salt (A) is a compound having a structure represented by any one of the general formulas (1) to (3). Hereinafter, a compound having a structure represented by the general formula (1) will be referred to as compound (A1), a compound having a structure represented by the general formula (2) will be referred to as compound (A2), and a compound having a structure represented by the general formula (3) will be referred to as compound (A3).
前記４級アンモニウム塩（Ａ）は、前記一般式（１）～（３）のいずれかで表される構造を有する化合物である。以下、前記一般式（１）で表される構造を有する化合物を化合物（Ａ１）、前記一般式（２）で表される構造を有する化合物を化合物（Ａ２）、前記一般式（３）で表される構造を有する化合物を化合物（Ａ３）と称する。 [Quaternary ammonium salt (A)]
The quaternary ammonium salt (A) is a compound having a structure represented by any one of the general formulas (1) to (3). Hereinafter, a compound having a structure represented by the general formula (1) will be referred to as compound (A1), a compound having a structure represented by the general formula (2) will be referred to as compound (A2), and a compound having a structure represented by the general formula (3) will be referred to as compound (A3).
［化合物（Ａ１）］
化合物（Ａ１）は、前記一般式（１）で表される構造を有する。 [Compound (A1)]
The compound (A1) has a structure represented by the general formula (1).
化合物（Ａ１）は、前記一般式（１）で表される構造を有する。 [Compound (A1)]
The compound (A1) has a structure represented by the general formula (1).
前記一般式（１）において、ｎはメチレン基の繰り返し数を表す５～１７の整数である。ｎが４以下であると疎水性不足により水溶解性ＣＯＤ成分低減効果が低下する（水溶解性ＣＯＤ成分と４級アンモニウムイオンがコンプレックスを形成したとしても、該コンプレックスの水溶性が高いため析出しにくく、析出物として分離しにくい）傾向があり、１８以上であると水への溶解性不足により水溶解性ＣＯＤ成分低減効果が低下する（４級アンモニウムイオンの水溶性が低いため、水溶解性ＣＯＤ成分とコンプレックスを形成しにくく、水溶解性ＣＯＤ成分を析出物として分離するのが困難）傾向がある。ｎは水溶解性ＣＯＤ成分低減効果の観点から、１１～１７が好ましい。
In the general formula (1), n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
なお、直鎖アルキル基は同じ炭素数の分岐アルキル基と比較して分子間力が高いため会合しやすく、水溶解性ＣＯＤ成分と４級アンモニウムイオンのコンプレックスの粒子径が大きくなり、該コンプレックスが析出物として分離しやすい傾向があると推測される。よって、炭素数６～１８の直鎖アルキル基を有する化合物（Ａ１）は、同じ炭素数の分岐アルキル基を有する４級アンモニウム塩と比較して水溶解性ＣＯＤ成分低減効果に優れるものと推測される。
In addition, it is presumed that linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A1) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
前記一般式（１）において、Ｒ１～Ｒ３はそれぞれ独立にメチル基、エチル基、プロピル基、又はブチル基である。
In the general formula (1), R 1 to R 3 each independently represent a methyl group, an ethyl group, a propyl group, or a butyl group.
前記一般式（１）において、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。当該ブレンステッド酸としては無機酸（塩酸、臭化水素酸、硫酸、リン酸及び硝酸等）及び有機酸［スルホン酸（メチルスルホン酸、ドデシルベンゼンスルホン酸及びナフタレンスルホン酸等）、カルボン酸（シュウ酸及び酢酸及びマレイン酸等）及びホスホン酸（メチルホスホン酸及びフェニルホスホン酸等）等］等が挙げられ、水溶解性ＣＯＤ成分低減効果の観点から、塩酸（すなわち、Ｘ－＝Ｃｌ－）、臭化水素酸（すなわち、Ｘ－＝Ｂｒ－）、又は硫酸（すなわち、Ｘ－＝ＨＳＯ４
－）が好ましい。当該四級化剤としては、メチルクロライド（すなわち、Ｘ－＝Ｃｌ－）、メチルブロマイド（すなわち、Ｘ－＝Ｂｒ－）、ジメチル硫酸（すなわち、Ｘ－＝ＣＨ３ＳＯ４
－）及びベンジルクロライド（すなわち、Ｘ－＝Ｃｌ－）等が挙げられる。Ｘ－は水溶解性ＣＯＤ成分の低減効果の観点から、Ｃｌ－、Ｂｒ－又はＨＳＯ４
－が好ましい。
In the general formula (1), X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Brønsted acid or a quaternizing agent. Examples of the Brønsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids (sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)). From the viewpoint of the effect of reducing water-soluble COD components, hydrochloric acid (i.e., X - =Cl - ), hydrobromic acid (i.e., X - =Br - ), or sulfuric acid (i.e., X - =HSO 4 - ) is preferred. Examples of the quaternizing agent include methyl chloride (i.e., X − ═Cl − ), methyl bromide (i.e., X − ═Br − ), dimethyl sulfate (i.e., X − ═CH 3 SO 4 − ), and benzyl chloride (i.e., X − ═Cl − ). From the viewpoint of the effect of reducing water-soluble COD components, X − is preferably Cl − , Br − or HSO 4 − .
前記化合物（Ａ１）におけるカチオン（アンモニウムイオン）の具体例としては、ヘキシルトリメチルアンモニウムイオン、ヘプチルトリメチルアンモニウムイオン、オクチルトリメチルアンモニウムイオン、ノニルトリメチルアンモニウムイオン、デシルトリメチルアンモニウムイオン、ウンデシルトリメチルアンモニウムイオン、ドデシルトリメチルアンモニウム（ラウリルトリメチルアンモニウム）イオン、トリデシルトリメチルアンモニウムイオン、テトラデシルトリメチルアンモニウム（ミリスチルトリメチルアンモニウム）イオン、ペンタデシルトリメチルアンモニウムイオン、ヘキサデシルトリメチルアンモニウムイオン、ヘプタデシルトリメチルアンモニウムイオン、オクタデシルトリメチルアンモニウム（トリメチルステアリルアンモニウム）イオン及びこれらの混合物等が挙げられ、水溶解性ＣＯＤ成分低減効果の観点から、ヘキサデシルトリメチルアンモニウムイオン、又はオクタデシルトリメチルアンモニウム（トリメチルステアリルアンモニウム）イオンが好ましい。
Specific examples of the cation (ammonium ion) in the compound (A1) include hexyltrimethylammonium ion, heptyltrimethylammonium ion, octyltrimethylammonium ion, nonyltrimethylammonium ion, decyltrimethylammonium ion, undecyltrimethylammonium ion, dodecyltrimethylammonium (lauryltrimethylammonium) ion, tridecyltrimethylammonium ion, tetradecyltrimethylammonium (myristyltrimethylammonium) ion, pentadecyltrimethylammonium ion, hexadecyltrimethylammonium ion, heptadecyltrimethylammonium ion, octadecyltrimethylammonium (trimethylstearylammonium) ion, and mixtures thereof. From the viewpoint of the effect of reducing water-soluble COD components, the hexadecyltrimethylammonium ion or octadecyltrimethylammonium (trimethylstearylammonium) ion is preferred.
［化合物（Ａ２）］
化合物（Ａ２）は、前記一般式（２）で表される構造を有する。 [Compound (A2)]
The compound (A2) has a structure represented by the general formula (2).
化合物（Ａ２）は、前記一般式（２）で表される構造を有する。 [Compound (A2)]
The compound (A2) has a structure represented by the general formula (2).
前記一般式（２）において、ｎはメチレン基の繰り返し数を表す５～１７の整数である。ｎが４以下であると疎水性不足により水溶解性ＣＯＤ成分低減効果が低下する（水溶解性ＣＯＤ成分と４級アンモニウムイオンがコンプレックスを形成したとしても、該コンプレックスの水溶性が高いため析出しにくく、析出物として分離しにくい）傾向があり、１８以上であると水への溶解性不足により水溶解性ＣＯＤ成分低減効果が低下する（４級アンモニウムイオンの水溶性が低いため、水溶解性ＣＯＤ成分とコンプレックスを形成しにくく、水溶解性ＣＯＤ成分を析出物として分離するのが困難）傾向がある。ｎは水溶解性ＣＯＤ成分低減効果の観点から、１１～１７が好ましい。
In the general formula (2), n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
なお、直鎖アルキル基は同じ炭素数の分岐アルキル基と比較して分子間力が高いため会合しやすく、水溶解性ＣＯＤ成分と４級アンモニウムイオンのコンプレックスの粒子径が大きくなり、該コンプレックスが析出物として分離しやすい傾向があると推測される。よって、炭素数６～１８の直鎖アルキル基を有する化合物（Ａ２）は、同じ炭素数の分岐アルキル基を有する４級アンモニウム塩と比較して水溶解性ＣＯＤ成分低減効果に優れるものと推測される。
In addition, it is presumed that linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A2) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
前記一般式（２）において、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。当該ブレンステッド酸としては無機酸（塩酸、臭化水素酸、硫酸、リン酸及び硝酸等）及び有機酸［スルホン酸（メチルスルホン酸、ドデシルベンゼンスルホン酸及びナフタレンスルホン酸等）、カルボン酸（シュウ酸及び酢酸及びマレイン酸等）及びホスホン酸（メチルホスホン酸及びフェニルホスホン酸等）等］等が挙げられ、水溶解性ＣＯＤ成分低減効果の観点から、塩酸（すなわち、Ｘ－＝Ｃｌ－）、臭化水素酸（すなわち、Ｘ－＝Ｂｒ－）、又は硫酸（すなわち、Ｘ－＝ＨＳＯ４
－）が好ましい。当該四級化剤としては、メチルクロライド（すなわち、Ｘ－＝Ｃｌ－）、メチルブロマイド（すなわち、Ｘ－＝Ｂｒ－）、ジメチル硫酸（すなわち、Ｘ－＝ＣＨ３ＳＯ４
－）及びベンジルクロライド（すなわち、Ｘ－＝Ｃｌ－）等が挙げられる。Ｘ－は水溶解性ＣＯＤ成分の低減効果の観点から、Ｃｌ－、Ｂｒ－又はＨＳＯ４
－が好ましい。
In the general formula (2), X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Brønsted acid or a quaternizing agent. Examples of the Brønsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like. From the viewpoint of the effect of reducing water-soluble COD components, hydrochloric acid (i.e., X - =Cl - ), hydrobromic acid (i.e., X - =Br - ), or sulfuric acid (i.e., X - =HSO 4 - ) is preferred. Examples of the quaternizing agent include methyl chloride (i.e., X − ═Cl − ), methyl bromide (i.e., X − ═Br − ), dimethyl sulfate (i.e., X − ═CH 3 SO 4 − ), and benzyl chloride (i.e., X − ═Cl − ). From the viewpoint of the effect of reducing water-soluble COD components, X − is preferably Cl − , Br − or HSO 4 − .
前記化合物（Ａ２）におけるカチオン（アンモニウムイオン）の具体例としては、ベンジルヘキシルジメチルアンモニウムイオン、ベンジルヘプチルジメチルアンモニウムイオン、ベンジルオクチルジメチルアンモニウムイオン、ベンジルノニルジメチルアンモニウムイオン、ベンジルデシルジメチルアンモニウムイオン、ベンジルウンデシルジメチルアンモニウムイオン、ベンジルドデシルジメチルアンモニウム（ベンジルラウリルジメチルアンモニウム）イオン、ベンジルトリデシルジメチルアンモニウムイオン、ベンジルテトラデシルジメチルアンモニウム（ベンジルミリスチルジメチルアンモニウム）イオン、ベンジルペンタデシルジメチルアンモニウムイオン、ベンジルヘキサデシルジメチルアンモニウムイオン、ベンジルヘプタデシルジメチルアンモニウムイオン、ベンジルオクタデシルジメチルアンモニウム（ベンジルジメチルステアリルアンモニウム）イオン及びこれらの混合物等が挙げられ、水溶解性ＣＯＤ成分低減効果の観点から、ベンジルヘキサデシルジメチルアンモニウムイオン又はベンジルオクタデシルジメチルアンモニウムイオンが好ましい。
Specific examples of the cation (ammonium ion) in the compound (A2) include benzylhexyldimethylammonium ion, benzylheptyldimethylammonium ion, benzyloctyldimethylammonium ion, benzylnonyldimethylammonium ion, benzyldecyldimethylammonium ion, benzylundecyldimethylammonium ion, benzyldodecyldimethylammonium (benzyllauryldimethylammonium) ion, benzyltridecyldimethylammonium ion, benzyltetradecyldimethylammonium (benzylmyristyldimethylammonium) ion, benzylpentadecyldimethylammonium ion, benzylhexadecyldimethylammonium ion, benzylheptadecyldimethylammonium ion, benzyloctadecyldimethylammonium (benzyldimethylstearylammonium) ion, and mixtures thereof. From the viewpoint of the effect of reducing water-soluble COD components, benzylhexadecyldimethylammonium ion or benzyloctadecyldimethylammonium ion is preferred.
［化合物（Ａ３）］
化合物（Ａ３）は、前記一般式（３）で表される構造を有する。 [Compound (A3)]
The compound (A3) has a structure represented by the general formula (3).
化合物（Ａ３）は、前記一般式（３）で表される構造を有する。 [Compound (A3)]
The compound (A3) has a structure represented by the general formula (3).
前記一般式（３）において、ｎはメチレン基の繰り返し数を表す５～１７の整数である。ｎが４以下であると疎水性不足により水溶解性ＣＯＤ成分低減効果が低下する（水溶解性ＣＯＤ成分と４級アンモニウムイオンがコンプレックスを形成したとしても、該コンプレックスの水溶性が高いため析出しにくく、析出物として分離しにくい）傾向があり、１８以上であると水への溶解性不足により水溶解性ＣＯＤ成分低減効果が低下する（４級アンモニウムイオンの水溶性が低いため、水溶解性ＣＯＤ成分とコンプレックスを形成しにくく、水溶解性ＣＯＤ成分を析出物として分離するのが困難）傾向がある。ｎは水溶解性ＣＯＤ成分低減効果の観点から、１１～１７が好ましい。
In the general formula (3), n is an integer of 5 to 17, representing the number of repeating methylene groups. If n is 4 or less, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient hydrophobicity (even if the water-soluble COD components and the quaternary ammonium ion form a complex, the complex is highly water-soluble and therefore difficult to precipitate and to separate as a precipitate), whereas if n is 18 or more, there is a tendency for the effect of reducing water-soluble COD components to decrease due to insufficient solubility in water (as the water solubility of the quaternary ammonium ion is low, it is difficult to form a complex with the water-soluble COD components and it is difficult to separate the water-soluble COD components as a precipitate). From the viewpoint of the effect of reducing water-soluble COD components, n is preferably 11 to 17.
なお、直鎖アルキル基は同じ炭素数の分岐アルキル基と比較して分子間力が高いため会合しやすく、水溶解性ＣＯＤ成分と４級アンモニウムイオンのコンプレックスの粒子径が大きくなり、該コンプレックスが析出物として分離しやすい傾向があると推測される。よって、炭素数６～１８の直鎖アルキル基を有する化合物（Ａ３）は、同じ炭素数の分岐アルキル基を有する４級アンモニウム塩と比較して水溶解性ＣＯＤ成分低減効果に優れるものと推測される。
In addition, it is presumed that linear alkyl groups have stronger intermolecular forces than branched alkyl groups with the same number of carbon atoms, and therefore tend to associate more easily, resulting in a larger particle size for the complex of water-soluble COD components and quaternary ammonium ions, and that the complex tends to separate more easily as a precipitate. Therefore, it is presumed that compound (A3) having a linear alkyl group with 6 to 18 carbon atoms is more effective at reducing water-soluble COD components than quaternary ammonium salts having branched alkyl groups with the same number of carbon atoms.
前記一般式（３）において、Ｘ－はアンモニウムイオンの対アニオンを表し、ブレンステッド酸の共役塩基又は四級化剤に由来するアニオン基である。当該ブレンステッド酸としては無機酸（塩酸、臭化水素酸、硫酸、リン酸及び硝酸等）及び有機酸［スルホン酸（メチルスルホン酸、ドデシルベンゼンスルホン酸及びナフタレンスルホン酸等）、カルボン酸（シュウ酸及び酢酸及びマレイン酸等）及びホスホン酸（メチルホスホン酸及びフェニルホスホン酸等）等］等が挙げられ、水溶解性ＣＯＤ成分低減効果の観点から、塩酸（すなわち、Ｘ－＝Ｃｌ－）、臭化水素酸（すなわち、Ｘ－＝Ｂｒ－）、又は硫酸（すなわち、Ｘ－＝ＨＳＯ４
－）が好ましい。当該四級化剤としては、メチルクロライド（すなわち、Ｘ－＝Ｃｌ－）、メチルブロマイド（すなわち、Ｘ－＝Ｂｒ－）、ジメチル硫酸（すなわち、Ｘ－＝ＣＨ３ＳＯ４
－）及びベンジルクロライド（すなわち、Ｘ－＝Ｃｌ－）等が挙げられる。Ｘ－は水溶解性ＣＯＤ成分の低減効果の観点から、Ｃｌ－、Ｂｒ－又はＨＳＯ４
－が好ましい。
In the general formula (3), X - represents a counter anion of an ammonium ion, and is an anion group derived from a conjugate base of a Brønsted acid or a quaternizing agent. Examples of the Brønsted acid include inorganic acids (hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, etc.) and organic acids [sulfonic acids (methylsulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, maleic acid, etc.), and phosphonic acids (methylphosphonic acid, phenylphosphonic acid, etc.)], and the like. From the viewpoint of the effect of reducing water-soluble COD components, hydrochloric acid (i.e., X - =Cl - ), hydrobromic acid (i.e., X - =Br - ), or sulfuric acid (i.e., X - =HSO 4 - ) is preferred. Examples of the quaternizing agent include methyl chloride (i.e., X − ═Cl − ), methyl bromide (i.e., X − ═Br − ), dimethyl sulfate (i.e., X − ═CH 3 SO 4 − ), and benzyl chloride (i.e., X − ═Cl − ). From the viewpoint of the effect of reducing water-soluble COD components, X − is preferably Cl − , Br − or HSO 4 − .
前記一般式（３）において、Ｙは水素原子及び炭素数１～６のアルキル基であり、水溶解性ＣＯＤ成分低減効果の観点から水素原子又はメチル基が好ましい。
In the general formula (3), Y is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and from the viewpoint of the effect of reducing water-soluble COD components, a hydrogen atom or a methyl group is preferred.
前記化合物（Ａ３）におけるカチオン（アンモニウムイオン）の具体例としては、１－へキシルピリジニウムイオン、１－へキシル－４－メチルピリジニウムイオン、１－へプチルピリジニウムイオン、１－へプチル－４－メチルピリジニウムイオン、１－オクチルピリジニウムイオン、１－オクチル－４－メチルピリジニウムイオン、１－ノニルピリジニウムイオン、１－ノニル－４－メチルピリジニウムイオン、１－デシルピリジニウムイオン、１－デシル－４－メチルピリジニウムイオン、１－ウンデシルピリジニウムイオン、１－ウンデシル－４－メチルピリジニウムイオン、１－ドデシルピリジニウムイオン（１－ラウリルピリジニウムイオン）、１－ドデシル－４－メチルピリジニウムイオン（１－ラウリル－４－メチルピリジニウムイオン）、１－トリデシルピリジニウムイオン、１－トリデシル－４－メチルピリジニウムイオン、１－テトラデシルピリジニウムイオン（１－ミリスチルピリジニウムイオン）、１－テトラデシル－４－メチルピリジニウムイオン（１－ミリスチル－４－メチルピリジニウムイオン）、１－ペンタデシルピリジニウムイオン、１－ペンタデシル－４－メチルピリジニウムイオン、１－ヘキサデシルピリジニウムイオン、１－ヘキサデシル－４－メチルピリジニウムイオン、１－ヘプタデシルピリジニウムイオン、１－ヘプタデシル－４－メチルピリジニウムイオン、１－オクタデシルピリジニウムイオン（１－ステアリルピリジニウムイオン）、１－オクタデシル－４－メチルピリジニウムイオン（１－ステアリル－４－メチルピリジニウムイオン）及びこれらの混合物等が挙げられ、水溶解性ＣＯＤ成分の低減効果の観点から、１－ヘキサデシルピリジニウムイオン、１－ヘキサデシル－４－メチルピリジニウムイオン、１－オクタデシルピリジニウムイオン（１－ステアリル－４－メチルピリジニウムイオン）、又は１－オクタデシル－４－メチルピリジニウムイオン（１－ステアリル－４－メチルピリジニウムイオン）が好ましい。
Specific examples of the cation (ammonium ion) in the compound (A3) include 1-hexylpyridinium ion, 1-hexyl-4-methylpyridinium ion, 1-heptylpyridinium ion, 1-heptyl-4-methylpyridinium ion, 1-octylpyridinium ion, 1-octyl-4-methylpyridinium ion, 1-nonylpyridinium ion, 1-nonyl-4-methylpyridinium ion, 1-decylpyridinium ion, 1-decyl-4-methyl ... 1-ethylpyridinium ion, 1-undecylpyridinium ion, 1-undecyl-4-methylpyridinium ion, 1-dodecylpyridinium ion (1-laurylpyridinium ion), 1-dodecyl-4-methylpyridinium ion (1-lauryl-4-methylpyridinium ion), 1-tridecylpyridinium ion, 1-tridecyl-4-methylpyridinium ion, 1-tetradecylpyridinium ion (1-myristylpyridinium ion), 1-tetradecylpyridinium ion (1-myristylpyridinium ion), 1-pentadecylpyridinium ion, 1-pentadecyl-4-methylpyridinium ion, 1-hexadecylpyridinium ion, 1-hexadecyl-4-methylpyridinium ion, 1-heptadecylpyridinium ion, 1-heptadecyl-4-methylpyridinium ion, 1-octadecylpyridinium ion (1-stearylpyridinium ion), 1-octadecyl-4 -methylpyridinium ion (1-stearyl-4-methylpyridinium ion) and mixtures thereof, and from the viewpoint of the effect of reducing water-soluble COD components, 1-hexadecylpyridinium ion, 1-hexadecyl-4-methylpyridinium ion, 1-octadecylpyridinium ion (1-stearyl-4-methylpyridinium ion), or 1-octadecyl-4-methylpyridinium ion (1-stearyl-4-methylpyridinium ion) are preferred.
〔ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）〕
前記塩（Ｓ）は、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種である。当該塩（Ｓ）は、１種を単独で用いても２種以上を併用してもよい。 [At least one salt (S) selected from the group consisting of silicates, phosphates and borates]
The salt (S) is at least one selected from the group consisting of silicates, phosphates, and borates. The salt (S) may be used alone or in combination of two or more.
前記塩（Ｓ）は、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種である。当該塩（Ｓ）は、１種を単独で用いても２種以上を併用してもよい。 [At least one salt (S) selected from the group consisting of silicates, phosphates and borates]
The salt (S) is at least one selected from the group consisting of silicates, phosphates, and borates. The salt (S) may be used alone or in combination of two or more.
前記ケイ酸塩としては、ケイ酸のアルカリ金属塩又はアルカリ土類金属塩及び縮合ケイ酸のアルカリ金属塩又はアルカリ土類金属塩等が挙げられる。前記ケイ酸塩は、ケイ酸リチウム、ケイ酸ナトリウム、ケイ酸カリウム及びケイ酸カルシウムからなる群より選ばれる少なくとも１種が好ましく、ケイ酸ナトリウムより好ましい。当該ケイ酸塩の性状は固体でも水溶液でもよく、いわゆる水ガラスといわれるケイ酸ナトリウムの水溶液（１号、２号、３号、４号、５号）等を使用してもよい。
The silicate may be an alkali metal salt or an alkaline earth metal salt of silicic acid, or an alkali metal salt or an alkaline earth metal salt of condensed silicic acid. The silicate is preferably at least one selected from the group consisting of lithium silicate, sodium silicate, potassium silicate, and calcium silicate, and more preferably sodium silicate. The silicate may be in the form of a solid or an aqueous solution, and aqueous solutions of sodium silicate (No. 1, No. 2, No. 3, No. 4, No. 5), so-called water glass, may be used.
前記リン酸塩としては、リン酸のアルカリ金属塩又はアルカリ土類金属塩及び縮合リン酸（ポリリン酸及びメタリン酸等）のアルカリ金属塩又はアルカリ土類金属塩等が挙げられる。前記リン酸塩は、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、リン酸水素カリウム及びポリリン酸ナトリウムからなる群より選ばれる少なくとも１種が好ましく、リン酸三ナトリウムがより好ましい。
The phosphate salt may be an alkali metal salt or an alkaline earth metal salt of phosphoric acid, or an alkali metal salt or an alkaline earth metal salt of condensed phosphoric acid (polyphosphoric acid, metaphosphoric acid, etc.). The phosphate salt is preferably at least one selected from the group consisting of monosodium phosphate, disodium phosphate, trisodium phosphate, potassium hydrogen phosphate, and sodium polyphosphate, and more preferably trisodium phosphate.
前記ホウ酸塩としては、ホウ酸のアルカリ金属塩又はアルカリ土類金属塩、ポリホウ酸のアルカリ金属塩又はアルカリ土類金属塩及びこれらの水和物等が挙げられる。前記ホウ酸塩は、ホウ酸三ナトリウム、メタホウ酸ナトリウム及び四ホウ酸ナトリウムからなる群より選ばれる少なくとも１種が好ましく、四ホウ酸ナトリウム十水和物がより好ましい。
The borate salt may be an alkali metal salt or an alkaline earth metal salt of boric acid, an alkali metal salt or an alkaline earth metal salt of polyboric acid, or a hydrate thereof. The borate salt is preferably at least one selected from the group consisting of trisodium borate, sodium metaborate, and sodium tetraborate, and more preferably sodium tetraborate decahydrate.
前記塩（Ｓ）は、水溶解性ＣＯＤ成分の低減効果の観点から、前記ケイ酸塩を含有することが好ましく、ケイ酸ナトリウムを含有することがより好ましい。
From the viewpoint of the effect of reducing water-soluble COD components, the salt (S) preferably contains the silicate, and more preferably contains sodium silicate.
本実施形態の水処理剤中の前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）の重量比［（Ｓ）／（Ａ）］は、水溶解性ＣＯＤ成分の低減効果とスラッジ発生量及び処理コストの観点から、０．０１～３０が好ましく、０．１～２０がより好ましく、１～１０が更に好ましい。
The weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) in the water treatment agent of this embodiment is preferably 0.01 to 30, more preferably 0.1 to 20, and even more preferably 1 to 10, from the viewpoints of the effect of reducing water-soluble COD components, the amount of sludge generated, and treatment costs.
本実施形態の水処理剤は、操作性（ハンドリング性）等の観点から、前記４級アンモニア塩（Ａ）及び前記塩（Ｓ）の他に、更に水を含有してもよい。前記水処理剤が水を含有する場合、本実施形態の水処理剤における前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）の合計含有量は、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）と水との合計重量に基づいて０．１～８０重量％が好ましく、１～５０重量％がより好ましい。また、本実施形態の水処理剤における前記４級アンモニウム塩（Ａ）の含有量は、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）と水との合計重量に基づいて０．１～３０重量％が好ましく、１～１５重量％がより好ましい。
The water treatment agent of this embodiment may further contain water in addition to the quaternary ammonium salt (A) and the salt (S) from the viewpoint of operability (handling ability) and the like. When the water treatment agent contains water, the total content of the quaternary ammonium salt (A) and the salt (S) in the water treatment agent of this embodiment is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water. The content of the quaternary ammonium salt (A) in the water treatment agent of this embodiment is preferably 0.1 to 30% by weight, more preferably 1 to 15% by weight, based on the total weight of the quaternary ammonium salt (A), the salt (S), and the water.
なお、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）と水との合計含有量は、水処理剤の重量に基づいて９０～１００重量％が好ましい。
The total content of the quaternary ammonium salt (A), the salt (S), and water is preferably 90 to 100% by weight based on the weight of the water treatment agent.
本実施形態の水処理剤が上述の「前記４級アンモニウム塩（Ａ）を含有する水処理剤（Ｐ１）と前記塩（Ｓ）を含有する水処理剤（Ｐ２）とからなる二剤型の水処理剤」である場合、当該水処理剤（Ｐ１）は前記４級アンモニウム塩（Ａ）の他に水を含有してもよい。当該水処理剤（Ｐ１）が水を含有する場合、前記水処理剤（Ｐ１）中の前記４級アンモニウム塩（Ａ）の含有量は、操作性及び水溶解性ＣОＤ成分の低減効果の観点から、前記水処理剤（Ｐ１）の重量に基づいて０．１～５０重量％が好ましく、１～３０重量％がより好ましい。前記水処理剤（Ｐ１）中の前記４級アンモニウム塩（Ａ）と水の合計含有量は、前記水処理剤（Ｐ１）の重量に基づいて９０～１００重量％が好ましい。
When the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P1) may contain water in addition to the quaternary ammonium salt (A). When the water treatment agent (P1) contains water, the content of the quaternary ammonium salt (A) in the water treatment agent (P1) is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the water treatment agent (P1) from the viewpoint of operability and the effect of reducing water-soluble COD components. The total content of the quaternary ammonium salt (A) and water in the water treatment agent (P1) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P1).
本実施形態の水処理剤が上述の「前記４級アンモニウム塩（Ａ）を含有する水処理剤（Ｐ１）と前記塩（Ｓ）を含有する水処理剤（Ｐ２）とからなる二剤型の水処理剤」である場合、前記水処理剤（Ｐ２）は前記塩（Ｓ）の他に水を含有してもよい。当該水処理剤（Ｐ２）が水を含有する場合、前記水処理剤（Ｐ２）中の前記塩（Ｓ）の含有量は、操作性及び水溶解性ＣОＤ成分の低減効果の観点から、前記水処理剤（Ｐ２）の重量に基づいて０．１～８０重量％が好ましく、１～５０重量％がより好ましい。前記水処理剤（Ｐ２）中の前記塩（Ｓ）の含有量は、前記水処理剤（Ｐ２）の重量に基づいて９０～１００重量％が好ましい。
When the water treatment agent of this embodiment is the above-mentioned "two-agent type water treatment agent consisting of a water treatment agent (P1) containing the quaternary ammonium salt (A) and a water treatment agent (P2) containing the salt (S)," the water treatment agent (P2) may contain water in addition to the salt (S). When the water treatment agent (P2) contains water, the content of the salt (S) in the water treatment agent (P2) is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, based on the weight of the water treatment agent (P2) from the viewpoint of operability and the effect of reducing water-soluble COD components. The content of the salt (S) in the water treatment agent (P2) is preferably 90 to 100% by weight based on the weight of the water treatment agent (P2).
本実施形態の水処理剤は、水溶解性ＣＯＤ成分の除去性能を更に向上させるために、本発明の効果を阻害しない範囲で有機凝結剤を含有することができる。当該有機凝結剤としては、エピハロヒドリンとアミンとの重縮合体及びその塩酸塩、エピハロヒドリンとアルキレンジアミンとの重縮合体及びその塩酸塩、ポリエチレンイミン及びその塩酸塩、アルキレンジハライド－アルキレンポリアミン重縮合体及びその塩酸塩、アニリン－ホルムアルデヒド重縮合体及びその塩酸塩、ポリビニルベンジルトリメチルアンモニウムクロライド、ポリビニルピリジン及びその塩酸塩、（ジ）メチルジ（メタ）アリルアンモニウムクロライド並びにポリビニルイミダゾリン及びその塩酸塩等が挙げられる。当該有機凝結剤は１種を単独で用いても２種以上を併用してもよい。前記有機凝結剤は、前記水処理剤（Ｐ１）及び前記水処理剤（Ｐ２）の両方、又は何れかに含有されていてもよい。
The water treatment agent of this embodiment may contain an organic coagulant to the extent that the effect of the present invention is not impaired in order to further improve the removal performance of water-soluble COD components. Examples of the organic coagulant include polycondensates of epihalohydrin and amine and their hydrochlorides, polycondensates of epihalohydrin and alkylenediamine and their hydrochlorides, polyethyleneimine and its hydrochlorides, alkylenedihalide-alkylenepolyamine polycondensates and their hydrochlorides, aniline-formaldehyde polycondensates and their hydrochlorides, polyvinylbenzyltrimethylammonium chloride, polyvinylpyridine and its hydrochlorides, (di)methyldi(meth)allylammonium chloride, and polyvinylimidazoline and its hydrochlorides. The organic coagulant may be used alone or in combination of two or more types. The organic coagulant may be contained in both or either of the water treatment agent (P1) and the water treatment agent (P2).
本実施形態の水処理剤の製造方法は特に限定されないが、例えば下記のように製造することができる。
The method for producing the water treatment agent of this embodiment is not particularly limited, but it can be produced, for example, as follows.
前記水処理剤を一剤型とする場合、必要により水で希釈した前記４級アンモニア塩（Ａ）と必要により水で希釈した前記塩（Ｓ）と、及び必要により添加剤とを混合することで製造することができる。混合方法は特に限定されず、例えば、バケツ等の容器中で撹拌機を使用して混合してもよい。前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）とがコンプレックスを形成し白濁することがあるが、使用直前に再度撹拌混合することで問題なく使用できる。
When the water treatment agent is a one-component type, it can be produced by mixing the quaternary ammonium salt (A) diluted with water as necessary, the salt (S) diluted with water as necessary, and additives as necessary. The mixing method is not particularly limited, and for example, mixing may be performed using a stirrer in a container such as a bucket. The quaternary ammonium salt (A) and the salt (S) may form a complex and become cloudy, but it can be used without problems by stirring and mixing again immediately before use.
前記水処理剤を二剤型とする場合、必要により水で希釈した前記４級アンモニア塩（Ａ）と必要により添加剤とを混合することで前記水処理剤（Ｐ１）を製造し、必要により水で希釈した前記塩（Ｂ）と必要により添加剤とを混合することで前記水処理剤（Ｐ２）を製造することができる。
When the water treatment agent is a two-component type, the water treatment agent (P1) can be produced by mixing the quaternary ammonium salt (A), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced by mixing the salt (B), optionally diluted with water, with additives, and the water treatment agent (P2) can be produced.
前記水処理剤の製造において、前記４級アンモニウム塩（Ａ）及び／又は前記塩（Ｓ）を水で希釈する場合の希釈方法は特に限定はされないが、例えば予め計量した水を公知の撹拌装置（ジャーテスター等）を用いて撹拌しながら所定量の前記４級アンモニウム塩（Ａ）及び／又は前記塩（Ｓ）を加え、数時間（約１～４時間程度）撹拌する方法等が採用できる。
In the production of the water treatment agent, the method of diluting the quaternary ammonium salt (A) and/or the salt (S) with water is not particularly limited, but for example, a method can be used in which a predetermined amount of the quaternary ammonium salt (A) and/or the salt (S) is added to a previously measured amount of water while stirring it using a known stirring device (such as a jar tester), and the water is stirred for several hours (approximately 1 to 4 hours).
本実施形態の水処理剤は、前記４級アンモニウム塩（Ａ）が処理対象の水に含まれる水溶解性ＣＯＤ成分と水不溶性のコンプレックスを形成して不溶化・析出させ、析出物を分離除去することにより、水溶解性ＣОＤ成分を低減させる。前記水処理剤は更に前記塩（Ｓ）を含有するため、前記４級アンモニウム塩（Ａ）と水溶解性ＣＯＤ成分とのコンプレックスを粗大化させることで析出物の分離除去を促進し、さらなる水溶解性ＣОＤ成分の低減効果が期待できる。更に前記塩（Ｓ）は、処理対象の水に前記４級アンモニウム塩（Ａ）が過剰に添加された場合においても、過剰に添加された前記４級アンモニウム塩（Ａ）を析出させ、前記４級アンモニウム塩（Ａ）自体が水溶解性ＣＯＤ成分となって水溶解性ＣＯＤ成分を上昇させることを抑制することができるため、安定した水溶解性ＣＯＤ低減効果を発現できるものと推察される。また、前記塩（Ｓ）は、前記４級アンモニウム塩（Ａ）の添加量が少ない場合においても、水中に溶解している水溶解性ＣＯＤ成分と前記４級アンモニウム塩（Ａ）のコンプレックスを析出させることができ、水溶解性ＣＯＤ成分低減効果を示すものと推定される。
In the water treatment agent of this embodiment, the quaternary ammonium salt (A) forms a water-insoluble complex with the water-soluble COD components contained in the water to be treated, causing them to become insoluble and precipitate, and the precipitate is separated and removed, thereby reducing the water-soluble COD components. Since the water treatment agent further contains the salt (S), the complex between the quaternary ammonium salt (A) and the water-soluble COD components is coarsened, facilitating the separation and removal of the precipitate, and a further reduction effect in the water-soluble COD components can be expected. Furthermore, even if the quaternary ammonium salt (A) is added in excess to the water to be treated, the salt (S) precipitates the excessively added quaternary ammonium salt (A), and the quaternary ammonium salt (A) itself becomes a water-soluble COD component and can suppress the increase in the water-soluble COD components, so it is presumed that a stable water-soluble COD reduction effect can be expressed. In addition, even when the amount of the quaternary ammonium salt (A) added is small, the salt (S) can precipitate a complex of the water-soluble COD components dissolved in water and the quaternary ammonium salt (A), and is presumed to have an effect of reducing water-soluble COD components.
本発明の水処理剤は、各種工場廃水（紙パルプ、染色、自動車、金属加工、製鉄、食品、砂利採取、半導体関連及びクリーニング工業等の工場からの廃水）や下水、浄水、及び工場廃水等の処理で生じた汚泥（有機性汚泥及び無機性汚泥）等に添加することで、水処理剤の添加量が過剰となる条件下でも、水溶解性ＣＯＤ成分の上昇を抑制し、安定した水溶解性ＣＯＤ成分低減効果を発現でき、かつ水溶解性ＣＯＤ成分の低減効果が顕著に優れるという効果を奏するため非常に有用である。
The water treatment agent of the present invention is very useful because, when added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steel, food, gravel, semiconductor-related and cleaning industries, etc.), sewage, purified water, sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress the increase in water-soluble COD components, even under conditions where the amount of water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and has a significantly excellent effect in reducing water-soluble COD components.
＜水処理方法＞
本実施形態の水処理方法は、前記４級アンモニウム塩（Ａ）を、各種工場廃水、下水、浄水、及び汚泥（有機性汚泥及び無機性汚泥）等の水溶解性ＣＯＤ成分を含有した処理対象の水（以下、本明細書において、処理対象水と称することもある）に添加する工程（Ｉ）と、前記塩（Ｓ）を前記処理対象水に添加する工程（ＩＩ）とを有する。 <Water treatment method>
The water treatment method of this embodiment includes a step (I) of adding the quaternary ammonium salt (A) to water to be treated (hereinafter, in this specification, may be referred to as water to be treated) containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge), and a step (II) of adding the salt (S) to the water to be treated.
本実施形態の水処理方法は、前記４級アンモニウム塩（Ａ）を、各種工場廃水、下水、浄水、及び汚泥（有機性汚泥及び無機性汚泥）等の水溶解性ＣＯＤ成分を含有した処理対象の水（以下、本明細書において、処理対象水と称することもある）に添加する工程（Ｉ）と、前記塩（Ｓ）を前記処理対象水に添加する工程（ＩＩ）とを有する。 <Water treatment method>
The water treatment method of this embodiment includes a step (I) of adding the quaternary ammonium salt (A) to water to be treated (hereinafter, in this specification, may be referred to as water to be treated) containing water-soluble COD components, such as various industrial wastewater, sewage, purified water, and sludge (organic sludge and inorganic sludge), and a step (II) of adding the salt (S) to the water to be treated.
〔工程（Ｉ）〕
前記工程（Ｉ）は、前記４級アンモニウム塩（Ａ）を前記処理対象水に添加する工程である。 [Step (I)]
The step (I) is a step of adding the quaternary ammonium salt (A) to the water to be treated.
前記工程（Ｉ）は、前記４級アンモニウム塩（Ａ）を前記処理対象水に添加する工程である。 [Step (I)]
The step (I) is a step of adding the quaternary ammonium salt (A) to the water to be treated.
前記工程（Ｉ）において、前記４級アンモニウム塩（Ａ）の前記処理対象水への添加量は、当該処理対象水の種類、処理対象水に懸濁している粒子の含有量及び水溶解性ＣＯＤ成分量等によって調整することができ、特に限定はされないが、水溶解性ＣＯＤ成分低減性能の観点から、前記処理対象水１Ｌに対して、１ｍｇ～１０ｇが好ましく、３ｍｇ～８ｇがより好ましく、５ｍｇ～５ｇが更に好ましく、５ｍｇ～３ｇがより更に好ましい。
In step (I), the amount of the quaternary ammonium salt (A) added to the water to be treated can be adjusted depending on the type of water to be treated, the content of particles suspended in the water to be treated, the amount of water-soluble COD components, etc., and is not particularly limited. From the viewpoint of water-soluble COD component reduction performance, however, 1 mg to 10 g per 1 L of the water to be treated is preferable, 3 mg to 8 g is more preferable, 5 mg to 5 g is even more preferable, and 5 mg to 3 g is even more preferable.
前記工程（Ｉ）において、前記４級アンモニウム塩（Ａ）を前記処理対象水に添加する方法は特に限定されず、前記４級アンモニウム塩（Ａ）を公知の方法で前記処理対象水に添加し、混合することができる。
In step (I), the method for adding the quaternary ammonium salt (A) to the water to be treated is not particularly limited, and the quaternary ammonium salt (A) can be added to the water to be treated and mixed by a known method.
〔工程（ＩＩ）〕
前記工程（ＩＩ）は、前記塩（Ｓ）を前記処理対象水に添加する工程である。 [Step (II)]
The step (II) is a step of adding the salt (S) to the water to be treated.
前記工程（ＩＩ）は、前記塩（Ｓ）を前記処理対象水に添加する工程である。 [Step (II)]
The step (II) is a step of adding the salt (S) to the water to be treated.
前記工程（ＩＩ）において、前記塩（Ｓ）の前記処理対象水への添加量は、前記４級アンモニウム塩（Ａ）の重量に対する前記塩（Ｓ）の重量比率［（Ｓ）／（Ａ）］が０．０１～３０となる量が好ましく、０．１～２０となる量がより好ましく、１～１０となる量が更に好ましい。
In step (II), the amount of the salt (S) added to the water to be treated is preferably an amount such that the weight ratio of the salt (S) to the weight of the quaternary ammonium salt (A) [(S)/(A)] is 0.01 to 30, more preferably an amount such that the weight ratio is 0.1 to 20, and even more preferably an amount such that the weight ratio is 1 to 10.
前記工程（ＩＩ）において、前記塩（Ｓ）を前記処理対象水に添加する方法は特に限定されず、前記塩（Ｓ）を公知の方法で前記処理対象水に添加し、混合することができる。
In step (II), the method for adding the salt (S) to the water to be treated is not particularly limited, and the salt (S) can be added to the water to be treated and mixed using a known method.
前記工程（Ｉ）と前記工程（ＩＩ）は別々に行ってもよいし、同時に行ってもよい。前記工程（Ｉ）と前記工程（ＩＩ）を別々に行う場合、前記４級アンモニウム塩（Ａ）を含有する前記水処理剤（Ｐ１）と前記塩（Ｓ）を含有する前記水処理剤（Ｐ２）をそれぞれ別々に添加する。前記工程（Ｉ）と前記工程（ＩＩ）を同時に行う場合、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）をあらかじめ混合して一剤型の水処理剤として添加する。水溶解性ＣＯＤ成分の低減効果の観点からは、前記工程（Ｉ）及び前記工程（ＩＩ）は別々に行うことが好ましく、前記工程（Ｉ）を行った後に前記工程（ＩＩ）を行うことがより好ましい。
The steps (I) and (II) may be carried out separately or simultaneously. When the steps (I) and (II) are carried out separately, the water treatment agent (P1) containing the quaternary ammonium salt (A) and the water treatment agent (P2) containing the salt (S) are added separately. When the steps (I) and (II) are carried out simultaneously, the quaternary ammonium salt (A) and the salt (S) are mixed in advance and added as a one-agent type water treatment agent. From the viewpoint of the effect of reducing water-soluble COD components, it is preferable to carry out the steps (I) and (II) separately, and it is more preferable to carry out the step (II) after carrying out the step (I).
〔その他の工程〕
［工程（ＩＩＩ）］
本実施形態の水処理方法は、前記工程（Ｉ）及び前記工程（ＩＩ）に加え、更に無機凝集剤を処理対象の水に添加する工程（ＩＩＩ）を有してもよい。 [Other steps]
[Step (III)]
The water treatment method of the present embodiment may further include, in addition to the step (I) and the step (II), a step (III) of adding an inorganic flocculant to the water to be treated.
［工程（ＩＩＩ）］
本実施形態の水処理方法は、前記工程（Ｉ）及び前記工程（ＩＩ）に加え、更に無機凝集剤を処理対象の水に添加する工程（ＩＩＩ）を有してもよい。 [Other steps]
[Step (III)]
The water treatment method of the present embodiment may further include, in addition to the step (I) and the step (II), a step (III) of adding an inorganic flocculant to the water to be treated.
前記無機凝集剤としては、硫酸アルミニウム、ポリ塩化アルミニウム、塩化第２鉄、ポリ硫酸第２鉄及び消石灰等が挙げられる。前記無機凝集剤はそれぞれ１種を単独で用いても２種以上を併用してもよい。
The inorganic flocculants include aluminum sulfate, polyaluminum chloride, ferric chloride, polyferric sulfate, and hydrated lime. Each of the inorganic flocculants may be used alone or in combination of two or more.
本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合の前記無機凝集剤の添加量は、汚泥又は廃水の種類、懸濁している粒子の大きさ・含有量、廃水中のトータルスラッジ及び水溶解性ＣＯＤ成分量等によって異なるが、汚泥又は廃水の重量に基づいて好ましくは０．００１～１重量％、より好ましくは０．００５～０．８重量％、更に好ましくは０．０１～０．５重量％である。０．００１重量％以上であれば水溶解性ＣＯＤ成分低減効果が更に顕著となり、１重量％以下であればスラッジ発生量が低減できる。
The amount of inorganic flocculant added when the water treatment method of this embodiment includes step (III) varies depending on the type of sludge or wastewater, the size and content of suspended particles, the total sludge and the amount of water-soluble COD components in the wastewater, etc., but is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.8% by weight, and even more preferably 0.01 to 0.5% by weight based on the weight of the sludge or wastewater. If it is 0.001% by weight or more, the effect of reducing water-soluble COD components will be more pronounced, and if it is 1% by weight or less, the amount of sludge generated can be reduced.
本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合、前記工程（Ｉ）～（ＩＩＩ）は別々に行ってもよいし、同時に行ってもよい。前記工程（Ｉ）～（ＩＩＩ）は、下記手順（ｉ）～（ｉｖ）のいずれかの手順で行うことが好ましい。
・手順（ｉ）
工程（Ｉ）を行った後、工程（ＩＩＩ）を行い、次いで工程（ＩＩ）を行う。
・手順（ｉｉ）
工程（ＩＩＩ）を行った後、工程（Ｉ）を行い、次いで工程（ＩＩ）を行う。
・手順（ｉｉｉ）
工程（Ｉ）及び工程（ＩＩＩ）を同時に行った｛すなわち、４級アンモニウム塩（Ａ）と無機凝集剤をあらかじめ混合してから処理対象の水に添加した｝後、工程（ＩＩ）を行う。
・手順（ｉｖ）
工程（Ｉ）を行った後、工程（ＩＩ）を行い、次いで工程（ＩＩＩ）を行う。 When the water treatment method of the present embodiment includes the step (III), the steps (I) to (III) may be performed separately or simultaneously. The steps (I) to (III) are preferably performed in any one of the following procedures (i) to (iv).
Step (i)
After step (I), step (III) is carried out, and then step (II) is carried out.
Step (ii)
After step (III), step (I) is carried out, and then step (II) is carried out.
Step (iii)
Step (I) and step (III) are carried out simultaneously {i.e., the quaternary ammonium salt (A) and the inorganic flocculant are mixed in advance and then added to the water to be treated}, and then step (II) is carried out.
Step (iv)
After step (I), step (II) is carried out, and then step (III) is carried out.
・手順（ｉ）
工程（Ｉ）を行った後、工程（ＩＩＩ）を行い、次いで工程（ＩＩ）を行う。
・手順（ｉｉ）
工程（ＩＩＩ）を行った後、工程（Ｉ）を行い、次いで工程（ＩＩ）を行う。
・手順（ｉｉｉ）
工程（Ｉ）及び工程（ＩＩＩ）を同時に行った｛すなわち、４級アンモニウム塩（Ａ）と無機凝集剤をあらかじめ混合してから処理対象の水に添加した｝後、工程（ＩＩ）を行う。
・手順（ｉｖ）
工程（Ｉ）を行った後、工程（ＩＩ）を行い、次いで工程（ＩＩＩ）を行う。 When the water treatment method of the present embodiment includes the step (III), the steps (I) to (III) may be performed separately or simultaneously. The steps (I) to (III) are preferably performed in any one of the following procedures (i) to (iv).
Step (i)
After step (I), step (III) is carried out, and then step (II) is carried out.
Step (ii)
After step (III), step (I) is carried out, and then step (II) is carried out.
Step (iii)
Step (I) and step (III) are carried out simultaneously {i.e., the quaternary ammonium salt (A) and the inorganic flocculant are mixed in advance and then added to the water to be treated}, and then step (II) is carried out.
Step (iv)
After step (I), step (II) is carried out, and then step (III) is carried out.
本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合、処理コストの観点からは、工程（Ｉ）及び工程（ＩＩＩ）を行った後に前記工程（ＩＩ）を行うことが好ましい。すなわち、工程（Ｉ）～（ＩＩＩ）を上記手順（ｉ）～（ｉｉｉ）のいずれかの手順で行うことが好ましい。
When the water treatment method of this embodiment includes the step (III), from the viewpoint of treatment costs, it is preferable to carry out the step (II) after carrying out the steps (I) and (III). In other words, it is preferable to carry out the steps (I) to (III) in any of the above procedures (i) to (iii).
［ｐＨ調整工程］
前記工程（Ｉ）及び前記工程（ＩＩ）を行った後、また、本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合は前記工程（Ｉ）～（ＩＩＩ）を行った後の処理対象水のｐＨは、好ましくは１～１２、より好ましくは３～１０、更に好ましくは５～８である。この範囲であると水溶解性ＣＯＤ成分低減等の本発明の効果をより発揮させることができる。そのため、本実施形態の水処理方法は、前記工程（Ｉ）及び前記工程（ＩＩ）等を行った後の処理対象水のｐＨを調整するために、無機酸（塩酸、硫酸、硝酸及びリン酸等）、無機固体酸性物質（酸性リン酸ソーダ、酸性ぼう硝、塩化アンモン、硫安、重硫安及びスルファミン酸等）、有機酸（シュウ酸、コハク酸及びリンゴ酸等）、無機アルカリ性物質（例えば水酸化ナトリウム、水酸化カリウム及びアンモニア等）及び有機アルカリ性物質（例えばグアニジン等）又はそれらの水溶液を添加するｐＨ調整工程を有してもよい。 [pH adjustment step]
The pH of the water to be treated after the steps (I) and (II) have been performed, or after the steps (I) to (III) have been performed if the water treatment method of the present embodiment has the step (III), is preferably 1 to 12, more preferably 3 to 10, and even more preferably 5 to 8. In this range, the effects of the present invention, such as reduction of water-soluble COD components, can be more effectively achieved. Therefore, the water treatment method of the present embodiment may have a pH adjustment step of adding an inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an inorganic solid acidic substance (acidic sodium phosphate, acidic sulfuric acid, ammonium chloride, ammonium sulfate, ammonium bicarbonate, sulfamic acid, etc.), an organic acid (oxalic acid, succinic acid, malic acid, etc.), an inorganic alkaline substance (e.g., sodium hydroxide, potassium hydroxide, ammonia, etc.), and an organic alkaline substance (e.g., guanidine, etc.) or an aqueous solution thereof, in order to adjust the pH of the water to be treated after the steps (I) and (II), etc. have been performed.
前記工程（Ｉ）及び前記工程（ＩＩ）を行った後、また、本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合は前記工程（Ｉ）～（ＩＩＩ）を行った後の処理対象水のｐＨは、好ましくは１～１２、より好ましくは３～１０、更に好ましくは５～８である。この範囲であると水溶解性ＣＯＤ成分低減等の本発明の効果をより発揮させることができる。そのため、本実施形態の水処理方法は、前記工程（Ｉ）及び前記工程（ＩＩ）等を行った後の処理対象水のｐＨを調整するために、無機酸（塩酸、硫酸、硝酸及びリン酸等）、無機固体酸性物質（酸性リン酸ソーダ、酸性ぼう硝、塩化アンモン、硫安、重硫安及びスルファミン酸等）、有機酸（シュウ酸、コハク酸及びリンゴ酸等）、無機アルカリ性物質（例えば水酸化ナトリウム、水酸化カリウム及びアンモニア等）及び有機アルカリ性物質（例えばグアニジン等）又はそれらの水溶液を添加するｐＨ調整工程を有してもよい。 [pH adjustment step]
The pH of the water to be treated after the steps (I) and (II) have been performed, or after the steps (I) to (III) have been performed if the water treatment method of the present embodiment has the step (III), is preferably 1 to 12, more preferably 3 to 10, and even more preferably 5 to 8. In this range, the effects of the present invention, such as reduction of water-soluble COD components, can be more effectively achieved. Therefore, the water treatment method of the present embodiment may have a pH adjustment step of adding an inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an inorganic solid acidic substance (acidic sodium phosphate, acidic sulfuric acid, ammonium chloride, ammonium sulfate, ammonium bicarbonate, sulfamic acid, etc.), an organic acid (oxalic acid, succinic acid, malic acid, etc.), an inorganic alkaline substance (e.g., sodium hydroxide, potassium hydroxide, ammonia, etc.), and an organic alkaline substance (e.g., guanidine, etc.) or an aqueous solution thereof, in order to adjust the pH of the water to be treated after the steps (I) and (II), etc. have been performed.
［高分子凝集剤添加工程］
本実施形態の水処理方法は、固液分離を容易にする観点から、前記工程（Ｉ）及び前記工程（ＩＩ）を行った後、また、本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合は前記工程（Ｉ）～（ＩＩＩ）を行った後の処理対象水に、更に高分子凝集剤を添加・混合して粗大フロックを形成させる高分子凝集剤添加工程を有するのが好ましい。 [Polymer flocculant addition process]
From the viewpoint of facilitating solid-liquid separation, the water treatment method of the present embodiment preferably further comprises a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after carrying out the steps (I) and (II) or, in the case where the water treatment method of the present embodiment comprises the step (III), after carrying out the steps (I) to (III) to form coarse flocs.
本実施形態の水処理方法は、固液分離を容易にする観点から、前記工程（Ｉ）及び前記工程（ＩＩ）を行った後、また、本実施形態の水処理方法が前記工程（ＩＩＩ）を有する場合は前記工程（Ｉ）～（ＩＩＩ）を行った後の処理対象水に、更に高分子凝集剤を添加・混合して粗大フロックを形成させる高分子凝集剤添加工程を有するのが好ましい。 [Polymer flocculant addition process]
From the viewpoint of facilitating solid-liquid separation, the water treatment method of the present embodiment preferably further comprises a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after carrying out the steps (I) and (II) or, in the case where the water treatment method of the present embodiment comprises the step (III), after carrying out the steps (I) to (III) to form coarse flocs.
前記高分子凝集剤としては特に限定はなく、公知の高分子凝集剤として常用されているものを好適に使用でき、カチオン性、ノニオン性、アニオン性、両性のいずれの高分子凝集剤でもよく、またこれらを組み合わせて使用することもできる。
The polymer flocculant is not particularly limited, and any commonly used known polymer flocculant can be suitably used. The polymer flocculant may be any of cationic, nonionic, anionic, and amphoteric polymer flocculants, and these may also be used in combination.
前記カチオン性高分子凝集剤としては、ポリエチレンイミン、ポリ（メタ）アクリルアミドのマンニッヒ変性物、ジアルキルアミノエチル（メタ）アクリレート四級化物の単独重合体又は（メタ）アクリルアミド等の他の単量体との共重合体及びその他前記のカチオン性モノマーを構成単位として含む共重合体等が挙げられる。
The cationic polymer flocculant may be a homopolymer of polyethyleneimine, a Mannich modified poly(meth)acrylamide, a quaternized dialkylaminoethyl (meth)acrylate, or a copolymer with other monomers such as (meth)acrylamide, or a copolymer containing the cationic monomer as a constituent unit.
前記ノニオン性高分子凝集剤としては、ポリアクリルアミド等でＭｗが１，０００，０００を超えるものが挙げられる。
The nonionic polymer flocculant may be polyacrylamide or the like with a Mw of more than 1,000,000.
前記アニオン性高分子凝集剤としては、ポリ（メタ）アクリル酸ナトリウム、ポリ（メタ）アクリルアミドの加水分解物、（メタ）アクリルアミド・（メタ）アクリル酸ナトリウム共重合体、（メタ）アクリルアミド・（メタ）アクリル酸ナトリウム・２－アクリルアミド－２－メチルプロパン－１－スルホン酸ナトリウム共重合体、（メタ）アクリルアミド・２－アクリルアミド－２－メチルプロパン－１－スルホン酸ナトリウム共重合体及びその他前記のアニオン性モノマーを含む（共）重合体等が挙げられる。
The anionic polymer flocculant may, for example, be sodium poly(meth)acrylate, hydrolyzed poly(meth)acrylamide, (meth)acrylamide-sodium (meth)acrylate copolymer, (meth)acrylamide-sodium (meth)acrylate-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, (meth)acrylamide-sodium 2-acrylamido-2-methylpropane-1-sodium sulfonate copolymer, and other (co)polymers containing the anionic monomers described above.
前記両性高分子凝集剤としては、カチオン性モノマー［ジアルキルアミノエチル（メタ）アクリレート四級化物及びその他前記のカチオン性モノマー等］とアニオン性モノマー［（メタ）アクリル酸（塩）、２－アクリルアミド－２－メチルプロパン－１－スルホン酸（塩）等］及び必要によりノニオン性モノマー（アクリルアミド等）との共重合体等が挙げられる。
The amphoteric polymer flocculant may be a copolymer of a cationic monomer (such as dialkylaminoethyl (meth)acrylate quaternized products and other cationic monomers as described above) with an anionic monomer (such as (meth)acrylic acid (salt), 2-acrylamido-2-methylpropane-1-sulfonic acid (salt)), and, if necessary, a nonionic monomer (such as acrylamide).
前記高分子凝集剤添加工程において、前記高分子凝集剤を添加する方法としては特に限定はなく、前記高分子凝集剤をそのまま添加してもよいが、均一混合の観点から好ましいのは前記高分子凝集剤を水溶液にした後に処理対象水に添加する方法である。前記高分子凝集剤を水溶液として用いる場合、前記高分子凝集剤の濃度は、好ましくは０．０５～１重量％、より好ましくは０．１～０．５重量％である。溶解方法、溶解後の希釈方法は特に限定はないが、粉末状の高分子凝集剤を水に溶解する際は、一度に高分子凝集剤を加えるとままこを生じて水に溶解しにくくなるため、徐々に加えることが好ましい。
In the polymer flocculant addition step, there is no particular limitation on the method of adding the polymer flocculant. The polymer flocculant may be added as is, but from the viewpoint of uniform mixing, it is preferable to add the polymer flocculant to the water to be treated after making it into an aqueous solution. When using the polymer flocculant as an aqueous solution, the concentration of the polymer flocculant is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight. There is no particular limitation on the dissolution method and the dilution method after dissolution, but when dissolving a powdered polymer flocculant in water, it is preferable to add it gradually, since adding the polymer flocculant all at once will cause lumps and make it difficult to dissolve in water.
前記高分子凝集剤添加工程において、前記高分子凝集剤の添加量は、処理対象水の種類、懸濁している粒子の大きさ・含有量及び高分子凝集剤の分子量等によって異なるが、一般的な凝集性能の観点から、処理対象水の重量に基づいて、好ましくは０．０００１～０．５重量％、より好ましくは０．０００２～０．３重量％、更に好ましくは０．０００３～０．２重量％、より更に好ましくは０．０００４～０．１重量％である。
In the polymer flocculant addition step, the amount of polymer flocculant added varies depending on the type of water to be treated, the size and content of suspended particles, and the molecular weight of the polymer flocculant, but from the viewpoint of general flocculation performance, it is preferably 0.0001 to 0.5% by weight, more preferably 0.0002 to 0.3% by weight, even more preferably 0.0003 to 0.2% by weight, and even more preferably 0.0004 to 0.1% by weight based on the weight of the water to be treated.
［固液分離工程］
本実施形態の水処理方法は、前記工程（Ｉ）、及び前記工程（ＩＩ）等によって処理した前記処理対象水中に析出した析出物を前記処理対象水から除去する固液分離工程を有してもよい。 [Solid-liquid separation process]
The water treatment method of this embodiment may include a solid-liquid separation step of removing precipitates precipitated in the water to be treated that has been treated in the step (I), the step (II), and the like, from the water to be treated.
本実施形態の水処理方法は、前記工程（Ｉ）、及び前記工程（ＩＩ）等によって処理した前記処理対象水中に析出した析出物を前記処理対象水から除去する固液分離工程を有してもよい。 [Solid-liquid separation process]
The water treatment method of this embodiment may include a solid-liquid separation step of removing precipitates precipitated in the water to be treated that has been treated in the step (I), the step (II), and the like, from the water to be treated.
前記固液分離工程において、固液の分離を行う方法としては、例えば、重力沈降、膜ろ過、カラムろ過、加圧浮上、濃縮装置（例えばシックナー等）及び脱水装置（例えば、遠心分離器、ベルトプレス脱水機及びフィルタープレス脱水機等）等が利用できる。
In the solid-liquid separation step, methods for separating the solid and liquid can be used, such as gravity settling, membrane filtration, column filtration, pressure flotation, concentrators (e.g., thickeners, etc.), and dehydrators (e.g., centrifuges, belt press dehydrators, filter press dehydrators, etc.).
前記水処理方法の具体例として下記例（１）～（４）が挙げられる。
・例（１）
前記工程（Ｉ）及び前記工程（ＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、固液分離工程を行う。
・例（２）
前記工程（Ｉ）及び前記工程（ＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、前記高分子凝集剤添加工程を行い、更に前記固液分離工程を行う。
・例（３）
前記工程（Ｉ）、前記工程（ＩＩ）及び、前記工程（ＩＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、前記固液分離工程を行う。
・例（４）
前記工程（Ｉ）、前記工程（ＩＩ）及び、前記工程（ＩＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、更に前記高分子凝集剤添加工程を行い、その後更に固液分離工程を行う。 Specific examples of the water treatment method include the following examples (1) to (4).
・Example (1)
After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, a solid-liquid separation step is carried out.
・Example (2)
After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is carried out, and further, the solid-liquid separation step is carried out.
・Example (3)
The steps (I), (II) and (III) are carried out, and the pH adjustment step is carried out as necessary, and then the solid-liquid separation step is carried out.
・Example (4)
After carrying out the steps (I), (II) and (III) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is further carried out, and then the solid-liquid separation step is further carried out.
・例（１）
前記工程（Ｉ）及び前記工程（ＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、固液分離工程を行う。
・例（２）
前記工程（Ｉ）及び前記工程（ＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、前記高分子凝集剤添加工程を行い、更に前記固液分離工程を行う。
・例（３）
前記工程（Ｉ）、前記工程（ＩＩ）及び、前記工程（ＩＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、前記固液分離工程を行う。
・例（４）
前記工程（Ｉ）、前記工程（ＩＩ）及び、前記工程（ＩＩＩ）を行い、必要により前記ｐＨ調整工程を行った後、更に前記高分子凝集剤添加工程を行い、その後更に固液分離工程を行う。 Specific examples of the water treatment method include the following examples (1) to (4).
・Example (1)
After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, a solid-liquid separation step is carried out.
・Example (2)
After carrying out the step (I) and the step (II) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is carried out, and further, the solid-liquid separation step is carried out.
・Example (3)
The steps (I), (II) and (III) are carried out, and the pH adjustment step is carried out as necessary, and then the solid-liquid separation step is carried out.
・Example (4)
After carrying out the steps (I), (II) and (III) and, if necessary, carrying out the pH adjustment step, the polymer flocculant addition step is further carried out, and then the solid-liquid separation step is further carried out.
上記例（１）～（４）の内で、より粗大なフロックが形成され固液分離が容易になる観点から好ましいのは例（２）及び例（４）である。
Among the above examples (1) to (4), examples (2) and (4) are preferred from the viewpoint of forming coarser flocs and facilitating solid-liquid separation.
本実施形態の水処理方法は、前記固液分離工程後の処理対象水を活性炭で処理する活性炭処理工程を有してもよい。
The water treatment method of this embodiment may also include an activated carbon treatment step in which the water to be treated after the solid-liquid separation step is treated with activated carbon.
本発明における水溶解性ＣＯＤ成分低減効果を確認するために、処理後の排水のＣＯＤ（下記のＣＯＤＭｎ）を直接測定してもよいが、排水処理の分野でＣＯＤのモニタリングの代替手段として常用されており、ＣＯＤの測定より簡便に測定可能なＴＯＣ（全有機炭素）によってもＣＯＤの低減効果を評価可能である。以下の実施例においてはＣＯＤとＴＯＣを併記した。
To confirm the effect of reducing water-soluble COD components in this invention, the COD of the treated wastewater (CODMn below) may be measured directly, but the effect of reducing COD can also be evaluated using TOC (total organic carbon), which is commonly used in the field of wastewater treatment as an alternative means of monitoring COD and can be measured more easily than COD. In the following examples, both COD and TOC are shown.
以下、実施例及び比較例により本発明を更に説明するが、本発明はこれらに限定されるものではない。なお、特記しないかぎり、実施例中の部は重量部を表す。
The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited to these. Note that unless otherwise specified, parts in the examples refer to parts by weight.
表１～５中の各記号で表した原料は下記のとおりである。なお、表１～５中の各原料｛４級アンモニウム塩（Ａ）、比較の４級アンモニウム塩（比Ａ）、カチオン性重合体（Ｍ）及び塩（Ｓ）｝の添加量は、処理対象の水（後述のＢ化学工場排水）１Ｌに対する各原料の固形分（水及び揮発性溶剤を除いた成分）の添加量（ｍｇ）である。
＜４級アンモニウム塩（Ａ）＞
（Ａ１－１）：へキシルトリメチルアンモニウムクロライド
（Ａ１－２）：ラウリルトリメチルアンモニウムクロライド
（Ａ１－３）：ヘキサデシルトリメチルアンモニウムクロライド
（Ａ１－４）：トリメチルステアリルアンモニウムクロライド
（Ａ１－５）：テトラデシルトリメチルアンモニウムクロライド
（Ａ１－６）：テトラデシルトリメチルアンモニウムブロミド
（Ａ１－７）：ヘキサデシルトリメチルアンモニウムブロミド
（Ａ１－８）：ヘキサデシルトリメチルアンモニウムヒドロキシド
（Ａ２－１）：ベンジルヘキシルジメチルアンモニウムクロライド
（Ａ２－２）：ベンジルラウリルジメチルアンモニウムクロライド
（Ａ２－３）：ベンジルヘキサデシルジメチルアンモニウムクロライド
（Ａ２－４）：ベンジルジメチルステアリルアンモニウムクロライド
（Ａ３－１）：１－ヘキシルピリジニウムクロライド
（Ａ３－２）：１－ラウリルピリジニウムクロライド
（Ａ３－３）：１－ヘキサデシルピリジニウムクロライド
（Ａ３－４）：１－ステアリルピリジニウムクロライド
（Ａ３－５）：１－ヘキシル－４－メチルピリジニウムクロライド
（Ａ３－６）：１－ラウリル－４－メチルピリジニウムクロライド
（Ａ３－７）：１－ヘキサデシル－４－メチルピリジニウムクロライド
（Ａ３－８）：１－ステアリル－４－メチルピリジニウムクロライド
＜比較の４級アンモニウム塩（比Ａ）＞
（比Ａ１－１）：テトラメチルアンモニウムクロライド
（比Ａ２－１）：ベンジルトリメチルアンモニウムクロライド
（比Ａ３－１）：１－メチルピリジニウムクロライド
＜カチオン性重合体（Ｍ）＞
（Ｍ－１）：下記比較製造例１で製造したもの
＜塩（Ｓ）＞
（Ｓ－１）：ケイ酸ナトリウム溶液（３号）［富士化学社製］
（Ｓ－２）：リン酸３ナトリウム・十二水和物［富士フイルム和光純薬社製］
（Ｓ－３）：四ホウ酸ナトリウム・十水和物［富士フイルム和光純薬社製］
（Ｓ－４）：ケイ酸ナトリウム溶液（１号）［富士化学社製］
（Ｓ－５）：ケイ酸ナトリウム溶液（２号）［富士化学社製］
（Ｓ－６）：ケイ酸ナトリウム溶液（４号）［富士化学社製］
（Ｓ－７）：ケイ酸ナトリウム溶液（５号）［富士化学社製］ The raw materials represented by each symbol in Tables 1 to 5 are as follows. The amount of each raw material {quaternary ammonium salt (A), comparative quaternary ammonium salt (comparative A), cationic polymer (M) and salt (S)} added in Tables 1 to 5 is the amount (mg) of solids (components excluding water and volatile solvents) of each raw material added per 1 L of water to be treated (wastewater from chemical plant B described below).
<Quaternary ammonium salt (A)>
(A1-1): Hexyl trimethyl ammonium chloride (A1-2): Lauryl trimethyl ammonium chloride (A1-3): Hexadecyl trimethyl ammonium chloride (A1-4): Trimethylstearyl ammonium chloride (A1-5): Tetradecyl trimethyl ammonium chloride (A1-6): Tetradecyl trimethyl ammonium bromide (A1-7): Hexadecyl trimethyl ammonium bromide (A1-8): Hexadecyl trimethyl ammonium hydroxide (A2-1): Benzyl hexyl dimethyl ammonium chloride (A2-2): Benzyl lauryl dimethyl ammonium chloride (A2-3): Benzyl Benzylhexadecyldimethylammonium chloride (A2-4): Benzyldimethylstearylammonium chloride (A3-1): 1-hexylpyridinium chloride (A3-2): 1-laurylpyridinium chloride (A3-3): 1-hexadecylpyridinium chloride (A3-4): 1-stearylpyridinium chloride (A3-5): 1-hexyl-4-methylpyridinium chloride (A3-6): 1-lauryl-4-methylpyridinium chloride (A3-7): 1-hexadecyl-4-methylpyridinium chloride (A3-8): 1-stearyl-4-methylpyridinium chloride <Comparative quaternary ammonium salts (comparison A)>
(Ratio A1-1): Tetramethylammonium chloride (Ratio A2-1): Benzyltrimethylammonium chloride (Ratio A3-1): 1-methylpyridinium chloride <Cationic polymer (M)>
(M-1): Salt (S) produced in Comparative Production Example 1 below
(S-1): Sodium silicate solution (No. 3) [manufactured by Fuji Chemical Co., Ltd.]
(S-2): Trisodium phosphate dodecahydrate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(S-3): Sodium tetraborate decahydrate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(S-4): Sodium silicate solution (No. 1) [manufactured by Fuji Chemical Co., Ltd.]
(S-5): Sodium silicate solution (No. 2) [manufactured by Fuji Chemical Co., Ltd.]
(S-6): Sodium silicate solution (No. 4) [manufactured by Fuji Chemical Co., Ltd.]
(S-7): Sodium silicate solution (No. 5) [manufactured by Fuji Chemical Co., Ltd.]
＜４級アンモニウム塩（Ａ）＞
（Ａ１－１）：へキシルトリメチルアンモニウムクロライド
（Ａ１－２）：ラウリルトリメチルアンモニウムクロライド
（Ａ１－３）：ヘキサデシルトリメチルアンモニウムクロライド
（Ａ１－４）：トリメチルステアリルアンモニウムクロライド
（Ａ１－５）：テトラデシルトリメチルアンモニウムクロライド
（Ａ１－６）：テトラデシルトリメチルアンモニウムブロミド
（Ａ１－７）：ヘキサデシルトリメチルアンモニウムブロミド
（Ａ１－８）：ヘキサデシルトリメチルアンモニウムヒドロキシド
（Ａ２－１）：ベンジルヘキシルジメチルアンモニウムクロライド
（Ａ２－２）：ベンジルラウリルジメチルアンモニウムクロライド
（Ａ２－３）：ベンジルヘキサデシルジメチルアンモニウムクロライド
（Ａ２－４）：ベンジルジメチルステアリルアンモニウムクロライド
（Ａ３－１）：１－ヘキシルピリジニウムクロライド
（Ａ３－２）：１－ラウリルピリジニウムクロライド
（Ａ３－３）：１－ヘキサデシルピリジニウムクロライド
（Ａ３－４）：１－ステアリルピリジニウムクロライド
（Ａ３－５）：１－ヘキシル－４－メチルピリジニウムクロライド
（Ａ３－６）：１－ラウリル－４－メチルピリジニウムクロライド
（Ａ３－７）：１－ヘキサデシル－４－メチルピリジニウムクロライド
（Ａ３－８）：１－ステアリル－４－メチルピリジニウムクロライド
＜比較の４級アンモニウム塩（比Ａ）＞
（比Ａ１－１）：テトラメチルアンモニウムクロライド
（比Ａ２－１）：ベンジルトリメチルアンモニウムクロライド
（比Ａ３－１）：１－メチルピリジニウムクロライド
＜カチオン性重合体（Ｍ）＞
（Ｍ－１）：下記比較製造例１で製造したもの
＜塩（Ｓ）＞
（Ｓ－１）：ケイ酸ナトリウム溶液（３号）［富士化学社製］
（Ｓ－２）：リン酸３ナトリウム・十二水和物［富士フイルム和光純薬社製］
（Ｓ－３）：四ホウ酸ナトリウム・十水和物［富士フイルム和光純薬社製］
（Ｓ－４）：ケイ酸ナトリウム溶液（１号）［富士化学社製］
（Ｓ－５）：ケイ酸ナトリウム溶液（２号）［富士化学社製］
（Ｓ－６）：ケイ酸ナトリウム溶液（４号）［富士化学社製］
（Ｓ－７）：ケイ酸ナトリウム溶液（５号）［富士化学社製］ The raw materials represented by each symbol in Tables 1 to 5 are as follows. The amount of each raw material {quaternary ammonium salt (A), comparative quaternary ammonium salt (comparative A), cationic polymer (M) and salt (S)} added in Tables 1 to 5 is the amount (mg) of solids (components excluding water and volatile solvents) of each raw material added per 1 L of water to be treated (wastewater from chemical plant B described below).
<Quaternary ammonium salt (A)>
(A1-1): Hexyl trimethyl ammonium chloride (A1-2): Lauryl trimethyl ammonium chloride (A1-3): Hexadecyl trimethyl ammonium chloride (A1-4): Trimethylstearyl ammonium chloride (A1-5): Tetradecyl trimethyl ammonium chloride (A1-6): Tetradecyl trimethyl ammonium bromide (A1-7): Hexadecyl trimethyl ammonium bromide (A1-8): Hexadecyl trimethyl ammonium hydroxide (A2-1): Benzyl hexyl dimethyl ammonium chloride (A2-2): Benzyl lauryl dimethyl ammonium chloride (A2-3): Benzyl Benzylhexadecyldimethylammonium chloride (A2-4): Benzyldimethylstearylammonium chloride (A3-1): 1-hexylpyridinium chloride (A3-2): 1-laurylpyridinium chloride (A3-3): 1-hexadecylpyridinium chloride (A3-4): 1-stearylpyridinium chloride (A3-5): 1-hexyl-4-methylpyridinium chloride (A3-6): 1-lauryl-4-methylpyridinium chloride (A3-7): 1-hexadecyl-4-methylpyridinium chloride (A3-8): 1-stearyl-4-methylpyridinium chloride <Comparative quaternary ammonium salts (comparison A)>
(Ratio A1-1): Tetramethylammonium chloride (Ratio A2-1): Benzyltrimethylammonium chloride (Ratio A3-1): 1-methylpyridinium chloride <Cationic polymer (M)>
(M-1): Salt (S) produced in Comparative Production Example 1 below
(S-1): Sodium silicate solution (No. 3) [manufactured by Fuji Chemical Co., Ltd.]
(S-2): Trisodium phosphate dodecahydrate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(S-3): Sodium tetraborate decahydrate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(S-4): Sodium silicate solution (No. 1) [manufactured by Fuji Chemical Co., Ltd.]
(S-5): Sodium silicate solution (No. 2) [manufactured by Fuji Chemical Co., Ltd.]
(S-6): Sodium silicate solution (No. 4) [manufactured by Fuji Chemical Co., Ltd.]
(S-7): Sodium silicate solution (No. 5) [manufactured by Fuji Chemical Co., Ltd.]
＜比較製造例１：カチオン性重合体（Ｍ－１）及び比較の水処理剤（比ＰＭ－１）の製造＞
撹拌機、温度センサー、冷却管、滴下ロート及びマントルヒーターを備えた４つ口フラスコにイソプロピルアルコール（以下「ＩＰＡ」と略記）１９０部、イオン交換水６９部を投入し、撹拌下、加熱し還流させた。滴下口から開始剤溶液としてＩＰＡ８０部、イオン交換水２０部、アゾビスイソブチロニトリル（以下「ＡＩＢＮ」と略記）０．７部の混合溶液を、もう一方の滴下口からモノマー溶液として８０重量％のトリメチル－２－メタクロイルオキシエチルアンモニウムクロリド水溶液（東京化成工業株式会社製、試薬）３５２部、スチレン（東京化成工業株式会社製、試薬）４８部、ＩＰＡ１８０部、イオン交換水６０部の均一混合液を、フラスコ内を８０～８５℃で撹拌下、それぞれ４時間でフラスコ内に同時に滴下した。滴下後、同温度で２時間熟成し、ＩＰＡ８０部、イオン交換水２０部、ＡＩＢＮ２．０部の均一混合液を、８０～８５℃のフラスコ内に１時間で滴下し１８０分同温度で熟成した。その後、イオン交換水４６５部をフラスコ内に投入し、１００℃まで昇温してＩＰＡを除去し、カチオン性重合体（Ｍ－１）を含有する固形分含量４０．０重量％の水溶液１，０００部を得た。該水溶液を固形分含量１０．０重量％となるようイオン交換水で希釈することにより、カチオン性重合体（Ｍ－１）を含有する比較の水処理剤（ＰＭ－１）を得た。比較の水処理剤（ＰＭ－１）の固形分含量は４０．０重量％、ｐＨは４．５で、カチオン性重合体（Ｍ－１）のＭｗ（ＧＰＣ測定による重量平均分子量）は１８０，０００、コロイド当量値（ポリビニル硫酸カリウムを用いたコロイド滴定によるコロイド当量値）は４．１であった。 Comparative Production Example 1: Production of cationic polymer (M-1) and comparative water treatment agent (Comparative PM-1)
A four-neck flask equipped with a stirrer, a temperature sensor, a cooling tube, a dropping funnel and a mantle heater was charged with 190 parts of isopropyl alcohol (hereinafter abbreviated as "IPA") and 69 parts of ion-exchanged water, and heated to reflux under stirring. A mixed solution of 80 parts of IPA, 20 parts of ion-exchanged water, and 0.7 parts of azobisisobutyronitrile (hereinafter abbreviated as "AIBN") was added as an initiator solution from the dropping port, and a homogeneous mixture of 80% by weight of trimethyl-2-methacryloyloxyethylammonium chloride aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 352 parts, styrene (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 48 parts, IPA 180 parts, and ion-exchangedwater 60 parts was added dropwise to the flask simultaneously over 4 hours while stirring the flask at 80 to 85 ° C. After dropping, the mixture was aged for 2 hours at the same temperature, and a homogeneous mixture of 80 parts IPA, 20 parts ion-exchanged water, and 2.0 parts AIBN was dropped into a flask at 80 to 85 ° C. over 1 hour and aged at the same temperature for 180 minutes. Thereafter, 465 parts of ion-exchanged water was added to the flask, and the temperature was raised to 100 ° C. to remove the IPA, and 1,000 parts of an aqueous solution containing a cationic polymer (M-1) and a solid content of 40.0 wt % was obtained. The aqueous solution was diluted with ion-exchanged water to a solid content of 10.0 wt %, to obtain a comparative water treatment agent (PM-1) containing a cationic polymer (M-1). The comparative water treatment agent (PM-1) had a solid content of 40.0 wt %, a pH of 4.5, and the Mw (weight average molecular weight measured by GPC) of the cationic polymer (M-1) was 180,000, and the colloid equivalent value (colloid equivalent value measured by colloid titration using potassium polyvinyl sulfate) was 4.1.
撹拌機、温度センサー、冷却管、滴下ロート及びマントルヒーターを備えた４つ口フラスコにイソプロピルアルコール（以下「ＩＰＡ」と略記）１９０部、イオン交換水６９部を投入し、撹拌下、加熱し還流させた。滴下口から開始剤溶液としてＩＰＡ８０部、イオン交換水２０部、アゾビスイソブチロニトリル（以下「ＡＩＢＮ」と略記）０．７部の混合溶液を、もう一方の滴下口からモノマー溶液として８０重量％のトリメチル－２－メタクロイルオキシエチルアンモニウムクロリド水溶液（東京化成工業株式会社製、試薬）３５２部、スチレン（東京化成工業株式会社製、試薬）４８部、ＩＰＡ１８０部、イオン交換水６０部の均一混合液を、フラスコ内を８０～８５℃で撹拌下、それぞれ４時間でフラスコ内に同時に滴下した。滴下後、同温度で２時間熟成し、ＩＰＡ８０部、イオン交換水２０部、ＡＩＢＮ２．０部の均一混合液を、８０～８５℃のフラスコ内に１時間で滴下し１８０分同温度で熟成した。その後、イオン交換水４６５部をフラスコ内に投入し、１００℃まで昇温してＩＰＡを除去し、カチオン性重合体（Ｍ－１）を含有する固形分含量４０．０重量％の水溶液１，０００部を得た。該水溶液を固形分含量１０．０重量％となるようイオン交換水で希釈することにより、カチオン性重合体（Ｍ－１）を含有する比較の水処理剤（ＰＭ－１）を得た。比較の水処理剤（ＰＭ－１）の固形分含量は４０．０重量％、ｐＨは４．５で、カチオン性重合体（Ｍ－１）のＭｗ（ＧＰＣ測定による重量平均分子量）は１８０，０００、コロイド当量値（ポリビニル硫酸カリウムを用いたコロイド滴定によるコロイド当量値）は４．１であった。 Comparative Production Example 1: Production of cationic polymer (M-1) and comparative water treatment agent (Comparative PM-1)
A four-neck flask equipped with a stirrer, a temperature sensor, a cooling tube, a dropping funnel and a mantle heater was charged with 190 parts of isopropyl alcohol (hereinafter abbreviated as "IPA") and 69 parts of ion-exchanged water, and heated to reflux under stirring. A mixed solution of 80 parts of IPA, 20 parts of ion-exchanged water, and 0.7 parts of azobisisobutyronitrile (hereinafter abbreviated as "AIBN") was added as an initiator solution from the dropping port, and a homogeneous mixture of 80% by weight of trimethyl-2-methacryloyloxyethylammonium chloride aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 352 parts, styrene (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) 48 parts, IPA 180 parts, and ion-exchanged
＜実施例１＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ１－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－１）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤをＪＩＳ Ｋ０１０２：２０１６に記載のＣＯＤＭｎ分析方法に準じて測定した。またＴＯＣを全有機炭素分析装置［（株）アナリティクイエナジャパン製「ｍｕｌｔｉ Ｎ／Ｃ ３１００」］を用いて測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１２ｍｇ／Ｌであった。 Example 1
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-1) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1 wt% aqueous sulfuric acid solution was added dropwise while continuing to stir, and the pH was adjusted to 7.0. After stirring for 3 minutes, the mixture was left to stand for 5 minutes. The left-standing supernatant was filtered through a filter paper (No. 5C), and the COD of the filtrate was measured in accordance with the CODMn analysis method described in JIS K0102:2016. The TOC was measured using a total organic carbon analyzer [multi N/C 3100, manufactured by Analytik Jena Japan Co., Ltd.]. The COD was 8 mg/L and the TOC was 12 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ１－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－１）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤをＪＩＳ Ｋ０１０２：２０１６に記載のＣＯＤＭｎ分析方法に準じて測定した。またＴＯＣを全有機炭素分析装置［（株）アナリティクイエナジャパン製「ｍｕｌｔｉ Ｎ／Ｃ ３１００」］を用いて測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１２ｍｇ／Ｌであった。 Example 1
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-1) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1 wt% aqueous sulfuric acid solution was added dropwise while continuing to stir, and the pH was adjusted to 7.0. After stirring for 3 minutes, the mixture was left to stand for 5 minutes. The left-standing supernatant was filtered through a filter paper (No. 5C), and the COD of the filtrate was measured in accordance with the CODMn analysis method described in JIS K0102:2016. The TOC was measured using a total organic carbon analyzer [multi N/C 3100, manufactured by Analytik Jena Japan Co., Ltd.]. The COD was 8 mg/L and the TOC was 12 mg/L.
＜実施例２～３０、３５～３６及び３８～４３、５９～６２＞
４級アンモニウム塩（Ａ）及び水処理剤（Ｐ１）と塩（Ｓ）及び水処理剤（Ｐ２）の種類・添加量を表１、表２、表３、又は表４に記載のものに代える以外は実施例１と同様に処理して上澄み液をろ過したろ液を得た。ろ液のＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表１～４に示す。 <Examples 2 to 30, 35 to 36, 38 to 43, and 59 to 62>
The supernatant was filtered in the same manner as in Example 1, except that the types and amounts of the quaternary ammonium salt (A) and the water treatment agent (P1) and the salt (S) and the water treatment agent (P2) were changed to those shown in Table 1, Table 2, Table 3, or Table 4. The COD and TOC of the filtrate were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 4.
４級アンモニウム塩（Ａ）及び水処理剤（Ｐ１）と塩（Ｓ）及び水処理剤（Ｐ２）の種類・添加量を表１、表２、表３、又は表４に記載のものに代える以外は実施例１と同様に処理して上澄み液をろ過したろ液を得た。ろ液のＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表１～４に示す。 <Examples 2 to 30, 35 to 36, 38 to 43, and 59 to 62>
The supernatant was filtered in the same manner as in Example 1, except that the types and amounts of the quaternary ammonium salt (A) and the water treatment agent (P1) and the salt (S) and the water treatment agent (P2) were changed to those shown in Table 1, Table 2, Table 3, or Table 4. The COD and TOC of the filtrate were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 4.
＜実施例３１＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、カチオン系高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１０ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 31>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1 wt% aqueous sulfuric acid solution was added dropwise while continuing to stir, and the pH was adjusted to 7.0. Subsequently, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries, Ltd.) as a cationic polymer flocculant was added in an amount to a solid content concentration of 10 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C) and the filtrate was measured for COD and TOC in the same manner as in Example 1. The COD was 4 mg/L and the TOC was 6 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、カチオン系高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１０ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 31>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1 wt% aqueous sulfuric acid solution was added dropwise while continuing to stir, and the pH was adjusted to 7.0. Subsequently, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries, Ltd.) as a cationic polymer flocculant was added in an amount to a solid content concentration of 10 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C) and the filtrate was measured for COD and TOC in the same manner as in Example 1. The COD was 4 mg/L and the TOC was 6 mg/L.
＜実施例３２＞
実施例３１において、４級アンモニウム塩（Ａ１－３）を（Ａ１－４）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－４）に代える｝以外は実施例３１と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 32>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 31, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) {the water treatment agent (P1-3) was replaced with (P1-4)}, were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
実施例３１において、４級アンモニウム塩（Ａ１－３）を（Ａ１－４）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－４）に代える｝以外は実施例３１と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 32>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 31, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) {the water treatment agent (P1-3) was replaced with (P1-4)}, were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
＜実施例３３＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が５０ｍｇ／Ｌになる量を添加した。さらに、攪拌下、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 33>
1 L of wastewater from B chemical plant containing an anionic surfactant was collected in a beaker, and under stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] as an inorganic flocculant was added in an amount to a solid content concentration of 50 mg/L. Further, under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight, and after stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, 1 wt% sulfuric acid aqueous solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was left to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C) and the filtrate was measured for COD and TOC in the same manner as in Example 1. The COD was 4 mg/L and the TOC was 6 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が５０ｍｇ／Ｌになる量を添加した。さらに、攪拌下、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 33>
1 L of wastewater from B chemical plant containing an anionic surfactant was collected in a beaker, and under stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] as an inorganic flocculant was added in an amount to a solid content concentration of 50 mg/L. Further, under stirring, 2,500 mg of water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which is an aqueous solution in which quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight, and after stirring for 1 minute, 7,500 mg of water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which is an aqueous solution in which salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, 1 wt% sulfuric acid aqueous solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was left to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C) and the filtrate was measured for COD and TOC in the same manner as in Example 1. The COD was 4 mg/L and the TOC was 6 mg/L.
＜実施例３４＞
実施例３３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－４）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－４）に代える｝以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 34>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 33, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) {the water treatment agent (P1-3) was replaced with (P1-4)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
実施例３３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－４）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－４）に代える｝以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 34>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 33, except that the quaternary ammonium salt (A1-3) was replaced with (A1-4) {the water treatment agent (P1-3) was replaced with (P1-4)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
＜実施例３７＞
１００ｍｌビーカーに、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液５０部を添加した。攪拌下、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液５０部を添加し混合することにより、（Ａ１－３）及び（Ｓ－１）を含有してなる一剤型の水処理剤（Ｐ－３７）を得た。
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、上記水処理剤（Ｐ－３７）を５，０００ｍｇ（うち４級アンモニウム塩（Ａ）固形分２５０ｍｇ、塩（Ｓ）の固形分２５０ｍｇ）添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは２１ｍｇ／Ｌ、ＴＯＣは３２ｍｇ／Ｌであった。 <Example 37>
50 parts of an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added to a 100 ml beaker. 50 parts of an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added and mixed under stirring to obtain a one-form water treatment agent (P-37) containing (A1-3) and (S-1).
1 L of wastewater from chemical factory B containing an anionic surfactant was collected in a beaker, and 5,000 mg of the above water treatment agent (P-37) (including 250 mg of solids of quaternary ammonium salt (A) and 250 mg of solids of salt (S)) was added under stirring. After 3 minutes, 1 wt % aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After 3 minutes of stirring, the solution was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 21 mg/L, and the TOC was 32 mg/L.
１００ｍｌビーカーに、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液５０部を添加した。攪拌下、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液５０部を添加し混合することにより、（Ａ１－３）及び（Ｓ－１）を含有してなる一剤型の水処理剤（Ｐ－３７）を得た。
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、上記水処理剤（Ｐ－３７）を５，０００ｍｇ（うち４級アンモニウム塩（Ａ）固形分２５０ｍｇ、塩（Ｓ）の固形分２５０ｍｇ）添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは２１ｍｇ／Ｌ、ＴＯＣは３２ｍｇ／Ｌであった。 <Example 37>
50 parts of an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added to a 100 ml beaker. 50 parts of an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solids concentration of 10% by weight was added and mixed under stirring to obtain a one-form water treatment agent (P-37) containing (A1-3) and (S-1).
1 L of wastewater from chemical factory B containing an anionic surfactant was collected in a beaker, and 5,000 mg of the above water treatment agent (P-37) (including 250 mg of solids of quaternary ammonium salt (A) and 250 mg of solids of salt (S)) was added under stirring. After 3 minutes, 1 wt % aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After 3 minutes of stirring, the solution was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 21 mg/L, and the TOC was 32 mg/L.
＜実施例４４＞
実施例３において、塩（Ｓ－１）を（Ｓ－４）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－４）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 44>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-4) {the water treatment agent (P2-1) was replaced with (P2-4)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
実施例３において、塩（Ｓ－１）を（Ｓ－４）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－４）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 44>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-4) {the water treatment agent (P2-1) was replaced with (P2-4)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
＜実施例４５＞
実施例３において、塩（Ｓ－１）を（Ｓ－５）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－５）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 45>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-5) {the water treatment agent (P2-1) was replaced with (P2-5)}, were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
実施例３において、塩（Ｓ－１）を（Ｓ－５）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－５）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 45>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-5) {the water treatment agent (P2-1) was replaced with (P2-5)}, were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
＜実施例４６＞
実施例３において、塩（Ｓ－１）を（Ｓ－６）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－６）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 46>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-6) {the water treatment agent (P2-1) was replaced with (P2-6)}, were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例３において、塩（Ｓ－１）を（Ｓ－６）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－６）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 46>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the salt (S-1) was replaced with (S-6) {the water treatment agent (P2-1) was replaced with (P2-6)}, were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例４７＞
実施例３において、塩（Ｓ－１）を（Ｓ－７）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－７）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 47>
The same procedure as in Example 3 was repeated except that the salt (S-1) was replaced with the salt (S-7) {the water treatment agent (P2-1) was replaced with the water treatment agent (P2-7)}, and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例３において、塩（Ｓ－１）を（Ｓ－７）に代える｛水処理剤（Ｐ２－１）を（Ｐ２－７）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 47>
The same procedure as in Example 3 was repeated except that the salt (S-1) was replaced with the salt (S-7) {the water treatment agent (P2-1) was replaced with the water treatment agent (P2-7)}, and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例４８＞
実施例３３において、ポリ塩化アルミニウムを硫酸アルミニウム［大明化学工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 48>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with aluminum sulfate (manufactured by Taimei Chemical Industry Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例３３において、ポリ塩化アルミニウムを硫酸アルミニウム［大明化学工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 48>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with aluminum sulfate (manufactured by Taimei Chemical Industry Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例４９＞
実施例３３において、ポリ塩化アルミニウムをポリ硫酸第二鉄［タイキ薬品工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 49>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with polyferric sulfate (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
実施例３３において、ポリ塩化アルミニウムをポリ硫酸第二鉄［タイキ薬品工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 49>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with polyferric sulfate (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 6 mg/L and the TOC was 9 mg/L.
＜実施例５０＞
実施例３３において、ポリ塩化アルミニウムを塩化第二鉄［タイキ薬品工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 50>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with ferric chloride (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例３３において、ポリ塩化アルミニウムを塩化第二鉄［タイキ薬品工業株式会社製］に代える以外は実施例３３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 50>
The same procedure as in Example 33 was repeated except that polyaluminum chloride was replaced with ferric chloride (manufactured by Taiki Pharmaceutical Co., Ltd.), and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例５１＞
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－５）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－５）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 51>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-5) {the water treatment agent (P1-3) was replaced with (P1-5)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－５）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－５）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 51>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-5) {the water treatment agent (P1-3) was replaced with (P1-5)}, were measured. The COD was 7 mg/L and the TOC was 10 mg/L.
＜実施例５２＞
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－６）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－６）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは９ｍｇ／Ｌ、ＴＯＣは１３ｍｇ／Ｌであった。 <Example 52>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-6) {the water treatment agent (P1-3) was replaced with (P1-6)}, were measured. The COD was 9 mg/L and the TOC was 13 mg/L.
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－６）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－６）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは９ｍｇ／Ｌ、ＴＯＣは１３ｍｇ／Ｌであった。 <Example 52>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-6) {the water treatment agent (P1-3) was replaced with (P1-6)}, were measured. The COD was 9 mg/L and the TOC was 13 mg/L.
＜実施例５３＞
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－７）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－７）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１２ｍｇ／Ｌであった。 <Example 53>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-7) {the water treatment agent (P1-3) was replaced with (P1-7)}, were measured. The COD was 8 mg/L and the TOC was 12 mg/L.
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－７）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－７）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１２ｍｇ／Ｌであった。 <Example 53>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-7) {the water treatment agent (P1-3) was replaced with (P1-7)}, were measured. The COD was 8 mg/L and the TOC was 12 mg/L.
＜実施例５４＞
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－８）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－８）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 54>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-8) {the water treatment agent (P1-3) was replaced with (P1-8)}, were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例３において、４級アンモニウム塩（Ａ１－３）を（Ａ１－８）に代える｛水処理剤（Ｐ１－３）を（Ｐ１－８）に代える｝以外は実施例３と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 54>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 3, except that the quaternary ammonium salt (A1-3) was replaced with (A1-8) {the water treatment agent (P1-3) was replaced with (P1-8)}, were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例５５＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３０分間後、攪拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。３分後、撹拌を継続しながら、１重量％水酸ナトリウム水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 55>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After 30 minutes, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant under stirring in an amount such that the solid content concentration was 100 mg/L. After 3 minutes, a 1% by weight aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 4 mg/L, and the TOC was 6 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３０分間後、攪拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。３分後、撹拌を継続しながら、１重量％水酸ナトリウム水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 55>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After 30 minutes, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant under stirring in an amount such that the solid content concentration was 100 mg/L. After 3 minutes, a 1% by weight aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 4 mg/L, and the TOC was 6 mg/L.
＜実施例５６＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３０分間後、攪拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。３分後、撹拌を継続しながら、１重量％水酸ナトリウム水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、カチオン系高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 56>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After 30 minutes, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant under stirring in an amount such that the solid content concentration was 100 mg/L. After 3 minutes, a 1% by weight aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0. Next, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries, Ltd.) as a cationic polymer flocculant was added in an amount to give a solids concentration of 1 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 6 mg/L and the TOC was 9 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、４級アンモニウム塩（Ａ１－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－３）２，５００ｍｇ（４級アンモニウム塩（Ａ）固形分換算２５０ｍｇ）を添加し、１分間撹拌した後、塩（Ｓ－１）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ２－１）７，５００ｍｇ（塩（Ｓ）固形分換算７５０ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３０分間後、攪拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。３分後、撹拌を継続しながら、１重量％水酸ナトリウム水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、カチオン系高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは６ｍｇ／Ｌ、ＴＯＣは９ｍｇ／Ｌであった。 <Example 56>
1 L of wastewater from a chemical plant B containing an anionic surfactant was collected in a beaker, and 2,500 mg of a water treatment agent (P1-3) (250 mg of quaternary ammonium salt (A) solid content equivalent) was added, which was an aqueous solution in which a quaternary ammonium salt (A1-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After stirring for 1 minute, 7,500 mg of a water treatment agent (P2-1) (750 mg of salt (S) solid content equivalent) was added, which was an aqueous solution in which a salt (S-1) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing the stirring to adjust the pH to 7.0. After 30 minutes, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant under stirring in an amount such that the solid content concentration was 100 mg/L. After 3 minutes, a 1% by weight aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0. Next, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries, Ltd.) as a cationic polymer flocculant was added in an amount to give a solids concentration of 1 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 6 mg/L and the TOC was 9 mg/L.
＜実施例５７＞
実施例５６において、カチオン系高分子凝集剤「サンフロックＣＥ－７０６Ｐ」の０．２重量％水溶液をアニオン系高分子凝集剤「サンフロックＡＨ－４００Ｐ（三洋化成工業株式会社製）」の０．２重量％水溶液に代える以外は実施例５６と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 57>
The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the anionic polymer flocculant "Sunfloc AH-400P (manufactured by Sanyo Chemical Industries, Ltd.)," and the COD and TOC of the filtrate of the supernatant were measured. The COD was 4 mg/L and the TOC was 6 mg/L.
実施例５６において、カチオン系高分子凝集剤「サンフロックＣＥ－７０６Ｐ」の０．２重量％水溶液をアニオン系高分子凝集剤「サンフロックＡＨ－４００Ｐ（三洋化成工業株式会社製）」の０．２重量％水溶液に代える以外は実施例５６と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 57>
The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the anionic polymer flocculant "Sunfloc AH-400P (manufactured by Sanyo Chemical Industries, Ltd.)," and the COD and TOC of the filtrate of the supernatant were measured. The COD was 4 mg/L and the TOC was 6 mg/L.
＜実施例５８＞
実施例５６において、カチオン系高分子凝集剤「サンフロックＣＥ－７０６Ｐ」の０．２重量％水溶液をノニオン系高分子凝集剤「サンフロックＮＯＰ（三洋化成工業株式会社製）」の０．２重量％水溶液に代える以外は実施例５６と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 58>
The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the nonionic polymer flocculant "Sunfloc NOP (manufactured by Sanyo Chemical Industries, Ltd.)," and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
実施例５６において、カチオン系高分子凝集剤「サンフロックＣＥ－７０６Ｐ」の０．２重量％水溶液をノニオン系高分子凝集剤「サンフロックＮＯＰ（三洋化成工業株式会社製）」の０．２重量％水溶液に代える以外は実施例５６と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは５ｍｇ／Ｌ、ＴＯＣは７ｍｇ／Ｌであった。 <Example 58>
The same procedure as in Example 56 was repeated except that the 0.2% by weight aqueous solution of the cationic polymer flocculant "Sunfloc CE-706P" was replaced with a 0.2% by weight aqueous solution of the nonionic polymer flocculant "Sunfloc NOP (manufactured by Sanyo Chemical Industries, Ltd.)," and the COD and TOC of the filtrate of the supernatant were measured. The COD was 5 mg/L and the TOC was 7 mg/L.
＜実施例６３＞
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるアクリルアミド－ジアリルジメチルアンモニウムクロライド共重合物の水溶液「ユニセンスＦＣＡ１０００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 63>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of an acrylamide-diallyldimethylammonium chloride copolymer, "Unisense FCA1000L (manufactured by Senka Corporation)," which is an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L). The COD was 4 mg/L and the TOC was 6 mg/L.
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるアクリルアミド－ジアリルジメチルアンモニウムクロライド共重合物の水溶液「ユニセンスＦＣＡ１０００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 63>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of an acrylamide-diallyldimethylammonium chloride copolymer, "Unisense FCA1000L (manufactured by Senka Corporation)," which is an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (
＜実施例６４＞
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるポリ（ジアリルジメチルアンモニウムクロライド）の水溶液「ユニセンスＦＰＡ１００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 64>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of poly(diallyldimethylammonium chloride), an organic coagulant, "Unisense FPA100L (manufactured by Senka Corporation)" was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L). The COD was 4 mg/L and the TOC was 6 mg/L.
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるポリ（ジアリルジメチルアンモニウムクロライド）の水溶液「ユニセンスＦＰＡ１００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは４ｍｇ／Ｌ、ＴＯＣは６ｍｇ／Ｌであった。 <Example 64>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of poly(diallyldimethylammonium chloride), an organic coagulant, "Unisense FPA100L (manufactured by Senka Corporation)" was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (
＜実施例６５＞
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジメチルアミン－アンモニア－エピクロルヒドリン縮合物の水溶液「ユニセンスＫＨＥ１００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 65>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dimethylamine-ammonia-epichlorohydrin condensate "Unisense KHE100L (manufactured by Senka Corporation)" as an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L). The COD was 7 mg/L and the TOC was 10 mg/L.
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジメチルアミン－アンモニア－エピクロルヒドリン縮合物の水溶液「ユニセンスＫＨＥ１００Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 65>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dimethylamine-ammonia-epichlorohydrin condensate "Unisense KHE100L (manufactured by Senka Corporation)" as an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (
＜実施例６６＞
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジシアンジアミド－ホルマリン縮合物の水溶液「ユニセンスＫＨＦ１１Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１１ｍｇ／Ｌであった。 <Example 66>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-formalin condensate, "Unisense KHF11L (manufactured by Senka Corporation)," an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010," manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L). The COD was 8 mg/L and the TOC was 11 mg/L.
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジシアンジアミド－ホルマリン縮合物の水溶液「ユニセンスＫＨＦ１１Ｌ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは８ｍｇ／Ｌ、ＴＯＣは１１ｍｇ／Ｌであった。 <Example 66>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-formalin condensate, "Unisense KHF11L (manufactured by Senka Corporation)," an organic coagulant, was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010," manufactured by Taimei Chemical Industry Co., Ltd.] (
＜実施例６７＞
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジシアンジアミド－ジエチレントリアミン縮合物の水溶液「ユニセンスＫＨＰ１０Ｐ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 67>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-diethylenetriamine condensate "Unisense KHP10P (manufactured by Senka Corporation)" which is an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (solids concentration 100 mg/L). The COD was 7 mg/L and the TOC was 10 mg/L.
実施例５７において、ポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］（固形分濃度１００ｍｇ／Ｌ）の代わりに、有機凝結剤であるジシアンジアミド－ジエチレントリアミン縮合物の水溶液「ユニセンスＫＨＰ１０Ｐ（センカ株式会社製）」を固形分濃度が５０ｍｇ／Ｌとなるように添加した以外は実施例５７と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは７ｍｇ／Ｌ、ＴＯＣは１０ｍｇ／Ｌであった。 <Example 67>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 57 were measured, except that an aqueous solution of dicyandiamide-diethylenetriamine condensate "Unisense KHP10P (manufactured by Senka Corporation)" which is an organic coagulant was added to a solids concentration of 50 mg/L instead of polyaluminum chloride ["Taipac 6010" manufactured by Taimei Chemical Industry Co., Ltd.] (
＜比較例１＞
Ｂ化学工場排水そのもののＣＯＤ及びＴＯＣを測定した。ＣＯＤは８０ｍｇ／Ｌ、ＴＯＣは１２２ｍｇ／Ｌであった。 <Comparative Example 1>
The COD and TOC of the wastewater from Chemical Factory B were measured. The COD was 80 mg/L and the TOC was 122 mg/L.
Ｂ化学工場排水そのもののＣＯＤ及びＴＯＣを測定した。ＣＯＤは８０ｍｇ／Ｌ、ＴＯＣは１２２ｍｇ／Ｌであった。 <Comparative Example 1>
The COD and TOC of the wastewater from Chemical Factory B were measured. The COD was 80 mg/L and the TOC was 122 mg/L.
＜比較例２～４＞
４級アンモニウム塩（Ａ）の種類を表５に記載の比較の４級アンモニウム塩（比Ａ－１）に代え｛水処理剤（Ｐ１－１）を表５記載の（比Ｐ１）に代え｝、塩（Ｓ－１）｛及び水処理剤（Ｐ２－１）｝の添加量を表５に記載の量に代えた以外は実施例１と同様に処理して得られた上澄み液のろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表５に示す。 <Comparative Examples 2 to 4>
The type of quaternary ammonium salt (A) was changed to a comparative quaternary ammonium salt (comparison A-1) shown in Table 5 {the water treatment agent (P1-1) was changed to (comparison P1) shown in Table 5}, and the amount of salt (S-1) {and water treatment agent (P2-1)} added was changed to the amount shown in Table 5. The supernatant filtrate was treated in the same manner as in Example 1, except that the amount of salt added was changed to the amount shown in Table 5. The COD and TOC of the supernatant filtrate were measured in the same manner as in Example 1. The results are shown in Table 5.
４級アンモニウム塩（Ａ）の種類を表５に記載の比較の４級アンモニウム塩（比Ａ－１）に代え｛水処理剤（Ｐ１－１）を表５記載の（比Ｐ１）に代え｝、塩（Ｓ－１）｛及び水処理剤（Ｐ２－１）｝の添加量を表５に記載の量に代えた以外は実施例１と同様に処理して得られた上澄み液のろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表５に示す。 <Comparative Examples 2 to 4>
The type of quaternary ammonium salt (A) was changed to a comparative quaternary ammonium salt (comparison A-1) shown in Table 5 {the water treatment agent (P1-1) was changed to (comparison P1) shown in Table 5}, and the amount of salt (S-1) {and water treatment agent (P2-1)} added was changed to the amount shown in Table 5. The supernatant filtrate was treated in the same manner as in Example 1, except that the amount of salt added was changed to the amount shown in Table 5. The COD and TOC of the supernatant filtrate were measured in the same manner as in Example 1. The results are shown in Table 5.
＜比較例５＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。１分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１０ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４２ｍｇ／Ｌ、ＴＯＣ６４ｍｇ／Ｌであった。 <Comparative Example 5>
1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and while stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant in an amount to give a solids concentration of 100 mg/L. After 1 minute, a 1 wt% aqueous solution of sulfuric acid was added dropwise while continuing the stirring to adjust the pH to 7.0. Then, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries Co., Ltd.) as a polymer flocculant was added in an amount to give a solids concentration of 10 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The left-standing supernatant was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 42 mg/L, and the TOC was 64 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、無機凝集剤としてのポリ塩化アルミニウム［「タイパック６０１０」、大明化学工業株式会社製］を固形分濃度が１００ｍｇ／Ｌになる量を添加した。１分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。続いて、撹拌しながら、高分子凝集剤としてのサンフロックＣＥ－７０６Ｐ（三洋化成工業株式会社製）の０．２重量％水溶液を固形分濃度が１０ｍｇ／Ｌになる量を添加し、３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは４２ｍｇ／Ｌ、ＴＯＣ６４ｍｇ／Ｌであった。 <Comparative Example 5>
1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and while stirring, polyaluminum chloride ["Taipac 6010", manufactured by Taimei Chemical Industry Co., Ltd.] was added as an inorganic flocculant in an amount to give a solids concentration of 100 mg/L. After 1 minute, a 1 wt% aqueous solution of sulfuric acid was added dropwise while continuing the stirring to adjust the pH to 7.0. Then, while stirring, a 0.2 wt% aqueous solution of Sanfloc CE-706P (manufactured by Sanyo Chemical Industries Co., Ltd.) as a polymer flocculant was added in an amount to give a solids concentration of 10 mg/L, and the mixture was stirred for 3 minutes and then allowed to stand for 5 minutes. The left-standing supernatant was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 42 mg/L, and the TOC was 64 mg/L.
＜比較例６＞
実施例１において、４級アンモニウム塩（Ａ１－１）をカチオン性重合体（Ｍ－１）に代える｛水処理剤（Ｐ１－１）を比較の水処理剤（比ＰＭ－１）に代える｝以外は実施例１と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは３３ｍｇ／Ｌ、ＴＯＣ５０ｍｇ／Ｌであった。 <Comparative Example 6>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 1, except that the quaternary ammonium salt (A1-1) was replaced with the cationic polymer (M-1) (the water treatment agent (P1-1) was replaced with a comparative water treatment agent (Comparative PM-1)) in Example 1, were measured. The COD was 33 mg/L and the TOC was 50 mg/L.
実施例１において、４級アンモニウム塩（Ａ１－１）をカチオン性重合体（Ｍ－１）に代える｛水処理剤（Ｐ１－１）を比較の水処理剤（比ＰＭ－１）に代える｝以外は実施例１と同様に処理して得られた上澄み液のろ液のＣＯＤ及びＴＯＣを測定した。ＣＯＤは３３ｍｇ／Ｌ、ＴＯＣ５０ｍｇ／Ｌであった。 <Comparative Example 6>
The COD and TOC of the filtrate of the supernatant obtained by treating in the same manner as in Example 1, except that the quaternary ammonium salt (A1-1) was replaced with the cationic polymer (M-1) (the water treatment agent (P1-1) was replaced with a comparative water treatment agent (Comparative PM-1)) in Example 1, were measured. The COD was 33 mg/L and the TOC was 50 mg/L.
＜比較例７＞
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ２－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－７）１，０００ｍｇ（４級アンモニウム塩（Ａ）固形分換算１００ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは５０ｍｇ／Ｌ、ＴＯＣは７６ｍｇ／Ｌであった。 <Comparative Example 7>
1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and 1,000 mg (100 mg of quaternary ammonium salt (A) solid content equivalent) of a water treatment agent (P1-7) was added under stirring, which was an aqueous solution in which a quaternary ammonium salt (A2-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 50 mg/L, and the TOC was 76 mg/L.
アニオン性界面活性剤を含有するＢ化学工場排水１Ｌをビーカーに採取し、撹拌下、４級アンモニウム塩（Ａ２－３）を固形分濃度１０重量％となるようイオン交換水に溶解させた水溶液である水処理剤（Ｐ１－７）１，０００ｍｇ（４級アンモニウム塩（Ａ）固形分換算１００ｍｇ）を添加した。３分後、撹拌を継続しながら、１重量％硫酸水溶液を滴下してｐＨを７．０に調整した。３分間撹拌後、５分間静置した。静置した上澄み液をろ紙（Ｎｏ．５Ｃ）でろ過したろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した。ＣＯＤは５０ｍｇ／Ｌ、ＴＯＣは７６ｍｇ／Ｌであった。 <Comparative Example 7>
1 L of wastewater from a chemical factory B containing an anionic surfactant was collected in a beaker, and 1,000 mg (100 mg of quaternary ammonium salt (A) solid content equivalent) of a water treatment agent (P1-7) was added under stirring, which was an aqueous solution in which a quaternary ammonium salt (A2-3) was dissolved in ion-exchanged water to a solid content concentration of 10% by weight. After 3 minutes, a 1% by weight aqueous sulfuric acid solution was added dropwise while continuing stirring to adjust the pH to 7.0. After stirring for 3 minutes, the mixture was allowed to stand for 5 minutes. The supernatant liquid that had been allowed to stand was filtered through a filter paper (No. 5C), and the COD and TOC of the filtrate were measured in the same manner as in Example 1. The COD was 50 mg/L, and the TOC was 76 mg/L.
＜比較例８～９＞
比較例７において、４級アンモニウム塩（Ａ２－３）｛水処理剤（Ｐ１－７）｝の添加量を表５に記載の量に代えた以外は比較例７と同様にして得られた上澄み液のろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表５に示す。 <Comparative Examples 8 to 9>
In Comparative Example 7, the amount of the quaternary ammonium salt (A2-3) {water treatment agent (P1-7)} added was changed to the amount shown in Table 5. The supernatant filtrate was obtained in the same manner as in Comparative Example 7, but the amount was changed to the amount shown in Table 5. The COD and TOC were measured in the same manner as in Example 1. The results are shown in Table 5.
比較例７において、４級アンモニウム塩（Ａ２－３）｛水処理剤（Ｐ１－７）｝の添加量を表５に記載の量に代えた以外は比較例７と同様にして得られた上澄み液のろ液について、ＣＯＤ及びＴＯＣを実施例１と同様にして測定した結果を表５に示す。 <Comparative Examples 8 to 9>
In Comparative Example 7, the amount of the quaternary ammonium salt (A2-3) {water treatment agent (P1-7)} added was changed to the amount shown in Table 5. The supernatant filtrate was obtained in the same manner as in Comparative Example 7, but the amount was changed to the amount shown in Table 5. The COD and TOC were measured in the same manner as in Example 1. The results are shown in Table 5.
同一の４級アンモニウム塩（Ａ）（水処理剤（Ａ１－３））と塩（Ｓ）（塩（Ｓ－１））とを含有する実施例の組み合わせ（１）［実施例３、３８、３９の組み合わせ］、同一の４級アンモニウム塩（Ａ）（水処理剤（Ａ２－３））と塩（Ｓ）（塩（Ｓ－１））とを含有する実施例の組み合わせ（２）［実施例７、４０、４１の組み合わせ］、同一の４級アンモニウム塩（Ａ）（水処理剤（Ａ３－３））と塩（Ｓ）（塩（Ｓ－１））とを含有する実施例の組み合わせ（３）［実施例１１、４２、４３の組み合わせ］、及び同一の４級アンモニウム塩（Ａ）（比較の処理剤（比Ｐ））を含有し塩（Ｓ）を含有しない比較例の組み合わせ（４）［比較例７、８、９の組み合わせ］について、水処理剤又は比較の水処理剤中の４級アンモニウム塩（Ａ）の固形分の添加量（ｍｇ／Ｌ）に対してＣＯＤ（ｍｇ／Ｌ）の値をプロットしたグラフを図１に示す。塩（Ｓ）を含有しない比較例の水処理剤の場合、４級アンモニウム塩（Ａ）の添加量が２５０ｍｇまではＣＯＤが減少し、更に添加量を増やすとＣＯＤが上昇しており、４級アンモニウム塩（Ａ）の添加量に最適点があることが分かる。これに対して、塩（Ｓ）を含有する実施例の水処理剤の場合、比較の水処理剤で最適点であった２５０ｍｇを超える量の４級アンモニウム塩（Ａ）を使用してもＣＯＤの上昇は認められなかった。すなわち、水処理剤の添加量が過剰となる条件下でも、水溶解性ＣＯＤ成分の上昇を抑制し、安定した水溶解性ＣＯＤ成分低減効果を発現していることが分かる。さらに、実施例の水処理剤の場合、比較の水処理剤で最適点であった２５０ｍｇより４級アンモニウム塩（Ａ）の添加量が少ない場合でも、水溶解性ＣＯＤ成分低減効果に優れることが分かる。
FIG. 1 shows a graph plotting the COD (mg/L) values against the amount (mg/L) of the solids of the quaternary ammonium salt (A) in the water treatment agent or comparative water treatment agent for combination (1) [combination of Examples 3, 38, 39] containing the same quaternary ammonium salt (A) (water treatment agent (A2-3)) and salt (S) (salt (S-1)), combination (2) [combination of Examples 7, 40, 41] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), combination (3) [combination of Examples 11, 42, 43] containing the same quaternary ammonium salt (A) (water treatment agent (A3-3)) and salt (S) (salt (S-1)), and combination (4) [combination of Comparative Examples 7, 8, 9] containing the same quaternary ammonium salt (A) (comparative treatment agent (ratio P)) but not salt (S). In the case of the comparative water treatment agent not containing salt (S), the COD decreased up to an addition amount of 250 mg of quaternary ammonium salt (A), and the COD increased when the addition amount was further increased, and it can be seen that there is an optimum point for the addition amount of quaternary ammonium salt (A). In contrast, in the case of the water treatment agent of the example containing salt (S), no increase in COD was observed even when an amount of quaternary ammonium salt (A) exceeding 250 mg, which was the optimum point for the comparative water treatment agent, was used. In other words, it can be seen that even under conditions where the addition amount of the water treatment agent is excessive, the increase in water-soluble COD components is suppressed, and a stable water-soluble COD component reduction effect is expressed. Furthermore, in the case of the water treatment agent of the example, it can be seen that the water-soluble COD component reduction effect is excellent even when the addition amount of quaternary ammonium salt (A) is less than 250 mg, which was the optimum point for the comparative water treatment agent.
実施例１～５８及び比較例２～９について、得られたＣＯＤ及びＴＯＣの値から、ＣＯＤ除去率及びＴＯＣ除去率を下記の式に基づいて算出し、各水処理剤の水溶解性ＣＯＤ成分の低減効果を評価した。得られた結果を表１～５に示す。
ＣＯＤ除去率（％）＝（処理前のＣＯＤの値－処理後のＣＯＤの値）／処理前のＣＯＤの値×１００
ＴＯＣ除去率（％）＝（処理前のＴＯＣの値－処理後のＴＯＣの値）／処理前のＴＯＣの値×１００
ただし、上記式における処理前のＣＯＤの値及びＴＯＣの値は、比較例１に記載の通り、それぞれ８０ｍｇ／Ｌ及び１２２ｍｇ／Ｌである。
また、各実施例及び比較例について、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）の重量比［（Ｓ）／（Ａ）］を表１～５に記載した。 For Examples 1 to 58 and Comparative Examples 2 to 9, the COD removal rate and TOC removal rate were calculated from the obtained COD and TOC values according to the following formula, and the effect of reducing water-soluble COD components of each water treatment agent was evaluated. The obtained results are shown in Tables 1 to 5.
COD removal rate (%) = (COD value before treatment - COD value after treatment) / COD value before treatment x 100
TOC removal rate (%)=(TOC value before treatment−TOC value after treatment)/TOC value before treatment×100
However, the COD value and TOC value before treatment in the above formula are 80 mg/L and 122 mg/L, respectively, as described in Comparative Example 1.
For each of the Examples and Comparative Examples, the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) is shown in Tables 1 to 5.
ＣＯＤ除去率（％）＝（処理前のＣＯＤの値－処理後のＣＯＤの値）／処理前のＣＯＤの値×１００
ＴＯＣ除去率（％）＝（処理前のＴＯＣの値－処理後のＴＯＣの値）／処理前のＴＯＣの値×１００
ただし、上記式における処理前のＣＯＤの値及びＴＯＣの値は、比較例１に記載の通り、それぞれ８０ｍｇ／Ｌ及び１２２ｍｇ／Ｌである。
また、各実施例及び比較例について、前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）の重量比［（Ｓ）／（Ａ）］を表１～５に記載した。 For Examples 1 to 58 and Comparative Examples 2 to 9, the COD removal rate and TOC removal rate were calculated from the obtained COD and TOC values according to the following formula, and the effect of reducing water-soluble COD components of each water treatment agent was evaluated. The obtained results are shown in Tables 1 to 5.
COD removal rate (%) = (COD value before treatment - COD value after treatment) / COD value before treatment x 100
TOC removal rate (%)=(TOC value before treatment−TOC value after treatment)/TOC value before treatment×100
However, the COD value and TOC value before treatment in the above formula are 80 mg/L and 122 mg/L, respectively, as described in Comparative Example 1.
For each of the Examples and Comparative Examples, the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) is shown in Tables 1 to 5.
表１～５の結果から、実施例１～６７に係る水処理剤は、比較例に係る水処理剤と比較してＣＯＤ除去率及びＴＯＣ除去率が高く、水溶解性ＣＯＤ成分の低減効果が顕著に優れることが分かる。また、図１の（１）実施例３、３８、３９、（２）実施例７、４０、４１、（３）実施例１１、４２、４３の結果から、本発明の水処理剤は、幅広い水処理剤の添加量（水処理剤中の４級アンモニウム塩（Ａ）の添加量）の範囲で安定した水溶解性ＣＯＤ低減効果を発現できることが分かる。
The results in Tables 1 to 5 show that the water treatment agents according to Examples 1 to 67 have higher COD removal rates and TOC removal rates than the water treatment agents according to the comparative examples, and are significantly more effective at reducing water-soluble COD components. Furthermore, the results of (1) Examples 3, 38, and 39, (2) Examples 7, 40, and 41, and (3) Examples 11, 42, and 43 in Figure 1 show that the water treatment agent of the present invention can achieve a stable water-soluble COD reduction effect over a wide range of added amounts of the water treatment agent (addition amount of quaternary ammonium salt (A) in the water treatment agent).
本発明の水処理剤は、各種工場廃水（紙パルプ、染色、自動車、金属加工、製鉄、食品、砂利採取、半導体関連及びクリーニング工業等の工場からの廃水）や下水、浄水、及び工場廃水等の処理で生じた汚泥（有機性汚泥及び無機性汚泥）等に添加することで、水処理剤の添加量が過剰となる条件下でも、水溶解性ＣＯＤ成分の上昇を抑制し、安定した水溶解性ＣＯＤ成分低減効果を発現でき、かつ水溶解性ＣＯＤ成分の低減効果が顕著に優れるという効果を奏するため非常に有用である。
The water treatment agent of the present invention is very useful because, by being added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steelmaking, food, gravel extraction, semiconductor-related, and cleaning industries, etc.), sewage, purified water, and sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress an increase in water-soluble COD components, even under conditions where the amount of the water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and can exhibit a significantly excellent effect of reducing water-soluble COD components.
The water treatment agent of the present invention is very useful because, by being added to various industrial wastewater (wastewater from factories in the paper pulp, dyeing, automobile, metal processing, steelmaking, food, gravel extraction, semiconductor-related, and cleaning industries, etc.), sewage, purified water, and sludge (organic sludge and inorganic sludge) generated in the treatment of industrial wastewater, etc., it can suppress an increase in water-soluble COD components, even under conditions where the amount of the water treatment agent added is excessive, and can exhibit a stable water-soluble COD component reduction effect, and can exhibit a significantly excellent effect of reducing water-soluble COD components.
Claims (9)
- 下記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）とを含有する水処理剤。
- 前記塩（Ｓ）がケイ酸塩を含有する請求項１に記載の水処理剤。 The water treatment agent according to claim 1, wherein the salt (S) contains a silicate.
- 水処理剤中の前記４級アンモニウム塩（Ａ）と前記塩（Ｓ）との重量比［（Ｓ）／（Ａ）］が０．１～２０である請求項１又は２に記載の水処理剤。 The water treatment agent according to claim 1 or 2, wherein the weight ratio [(S)/(A)] of the quaternary ammonium salt (A) to the salt (S) in the water treatment agent is 0.1 to 20.
- 下記一般式（１）～（３）のいずれかで表される４級アンモニウム塩（Ａ）を処理対象の水に添加する工程（Ｉ）と、ケイ酸塩、リン酸塩及びホウ酸塩からなる群より選ばれる少なくとも１種の塩（Ｓ）を処理対象の水に添加する工程（ＩＩ）とを有する水処理方法。
- 前記工程（Ｉ）を行った後に前記工程（ＩＩ）を行うことを特徴とする請求項４に記載の水処理方法。 The water treatment method according to claim 4, characterized in that the step (II) is carried out after the step (I).
- 無機凝集剤を処理対象の水に添加する工程（ＩＩＩ）を有する請求項４に記載の水処理方法。 The water treatment method according to claim 4, comprising a step (III) of adding an inorganic coagulant to the water to be treated.
- 前記工程（Ｉ）及び前記工程（ＩＩＩ）を行った後に前記工程（ＩＩ）を行うことを特徴とする請求項６に記載の水処理方法。 The water treatment method according to claim 6, characterized in that the step (II) is carried out after the steps (I) and (III).
- 前記工程（Ｉ）及び前記工程（ＩＩ）を行った後の処理対象の水に、高分子凝集剤を添加・混合して粗大フロックを形成させる高分子凝集剤添加工程を有する請求項４に記載の水処理方法。 The water treatment method according to claim 4, further comprising a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after steps (I) and (II) to form coarse flocs.
- 前記工程（Ｉ）、前記工程（ＩＩ）、及び前記工程（ＩＩＩ）を行った後の処理対象の水に、高分子凝集剤を添加・混合して粗大フロックを形成させる高分子凝集剤添加工程を有する請求項６又は７に記載の水処理方法。
8. The water treatment method according to claim 6 or 7, further comprising a polymer flocculant addition step of adding and mixing a polymer flocculant to the water to be treated after the steps (I), (II), and (III) have been performed, thereby forming coarse flocs.
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| JP2004344829A (en) * | 2003-05-26 | 2004-12-09 | Sanyo Chem Ind Ltd | Organic coagulant and polymer coagulant |
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| JP2004344829A (en) * | 2003-05-26 | 2004-12-09 | Sanyo Chem Ind Ltd | Organic coagulant and polymer coagulant |
| WO2014001078A1 (en) * | 2012-06-26 | 2014-01-03 | Unilever N.V. | Water clarification composition and process |
| JP2019214037A (en) * | 2018-06-07 | 2019-12-19 | 三洋化成工業株式会社 | Water treatment method and water treatment agent |
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