CN112996756B - Water treatment agent - Google Patents
Water treatment agent Download PDFInfo
- Publication number
- CN112996756B CN112996756B CN202080006059.5A CN202080006059A CN112996756B CN 112996756 B CN112996756 B CN 112996756B CN 202080006059 A CN202080006059 A CN 202080006059A CN 112996756 B CN112996756 B CN 112996756B
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- CN
- China
- Prior art keywords
- water treatment
- treatment agent
- polymer
- present technology
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 554
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 480
- 229920000642 polymer Polymers 0.000 claims abstract description 234
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 222
- 239000000460 chlorine Substances 0.000 claims abstract description 209
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 155
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 148
- -1 chloramine compound Chemical class 0.000 claims abstract description 127
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 claims abstract description 98
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims description 84
- 239000011259 mixed solution Substances 0.000 claims description 68
- 239000003381 stabilizer Substances 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 44
- 238000005260 corrosion Methods 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 26
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 20
- 239000011976 maleic acid Substances 0.000 claims description 20
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 abstract description 102
- 230000000694 effects Effects 0.000 abstract description 95
- 238000005516 engineering process Methods 0.000 description 247
- 238000000034 method Methods 0.000 description 107
- 238000012360 testing method Methods 0.000 description 79
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 24
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 22
- 239000000498 cooling water Substances 0.000 description 21
- 239000003814 drug Substances 0.000 description 20
- 239000013043 chemical agent Substances 0.000 description 19
- 229940079593 drug Drugs 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 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 18
- 239000004480 active ingredient Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 238000007792 addition Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 230000001954 sterilising effect Effects 0.000 description 14
- 238000004659 sterilization and disinfection Methods 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000005708 Sodium hypochlorite Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002455 scale inhibitor Substances 0.000 description 7
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 7
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 7
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
- 230000002925 chemical effect Effects 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000003405 preventing effect Effects 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000004155 Chlorine dioxide Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 229940006460 bromide ion Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000004526 pharmaceutical effect Effects 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- KDNIOKSLVIGAAN-UHFFFAOYSA-N 2-sulfamoylbenzoic acid Chemical compound NS(=O)(=O)C1=CC=CC=C1C(O)=O KDNIOKSLVIGAAN-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000001139 pH measurement Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OIIWPAYIXDCDNL-UHFFFAOYSA-M sodium 3-(trimethylsilyl)propionate Chemical compound [Na+].C[Si](C)(C)CCC([O-])=O OIIWPAYIXDCDNL-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- RTQPZPWCYWVQCL-UHFFFAOYSA-N 1-[3-(2-methoxyethoxy)phenyl]piperazine Chemical compound COCCOC1=CC=CC(N2CCNCC2)=C1 RTQPZPWCYWVQCL-UHFFFAOYSA-N 0.000 description 1
- ISAOUZVKYLHALD-UHFFFAOYSA-N 1-chloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)NC(=O)NC1=O ISAOUZVKYLHALD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- JJKVMNNUINFIRK-UHFFFAOYSA-N 4-amino-n-(4-methoxyphenyl)benzamide Chemical compound C1=CC(OC)=CC=C1NC(=O)C1=CC=C(N)C=C1 JJKVMNNUINFIRK-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 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
- 235000010338 boric acid Nutrition 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- RSIPQRDGPVEGLE-UHFFFAOYSA-L calcium;disulfamate Chemical compound [Ca+2].NS([O-])(=O)=O.NS([O-])(=O)=O RSIPQRDGPVEGLE-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- LMUXZMAPKWCYMI-UHFFFAOYSA-N chlorous acid nickel Chemical compound [Ni].Cl(=O)O LMUXZMAPKWCYMI-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- QOHWJRRXQPGIQW-UHFFFAOYSA-N cyclohexanamine;hydron;bromide Chemical compound Br.NC1CCCCC1 QOHWJRRXQPGIQW-UHFFFAOYSA-N 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- SDUXGMLGPOQMKO-UHFFFAOYSA-N dichlorosulfamic acid Chemical compound OS(=O)(=O)N(Cl)Cl SDUXGMLGPOQMKO-UHFFFAOYSA-N 0.000 description 1
- AATGHKSFEUVOPF-UHFFFAOYSA-N diethylazanium;bromide Chemical compound [Br-].CC[NH2+]CC AATGHKSFEUVOPF-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229960001340 histamine Drugs 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- FFJMLWSZNCJCSZ-UHFFFAOYSA-N n-methylmethanamine;hydrobromide Chemical compound Br.CNC FFJMLWSZNCJCSZ-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001818 nuclear effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- PHUJCVAICLQULC-UHFFFAOYSA-L strontium;disulfamate Chemical compound [Sr+2].NS([O-])(=O)=O.NS([O-])(=O)=O PHUJCVAICLQULC-UHFFFAOYSA-L 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- QOUAERHIFDVLAF-UHFFFAOYSA-N sulfuryl bromide chloride Chemical compound ClS(Br)(=O)=O QOUAERHIFDVLAF-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a water treatment agent which exhibits excellent hypobromous acid effect when added to a water system. The present invention provides a water treatment agent comprising components (a) to (c) and having a pH of 10 or more, and/or a water treatment agent comprising an alkaline agent, a chloramine compound and a bromide salt, wherein the (a) chloramine compound, (b) bromide salt, (c) carboxyl group-containing polymer having a carboxyl group content of 0.8 g-COOH/g-or less in the polymer is 1 to 18% by mass, and a water treatment agent having a total chlorine detection rate of 95% or more and a free chlorine content of 0.05% in total chlorine concentration after production (in Cl 2 Meter) is as follows. The molar ratio of chloramine compound to bromide salt is preferably 1:0.1 to 1.0.
Description
Technical Field
The present technology relates to water treatment technology such as water treatment agent.
Background
In various water systems such as a heat storage water system, a pulp process water system, a dust collection water system, and a scrubber water system, hypohalous acids (e.g., hypochlorous acid, hypobromous acid, etc.) are used for the purpose of obtaining the effects of preventing adhesion of organisms, preventing slime, and killing microorganisms (e.g., bacteria, fungi, algae, etc.) in pipes, filtration membranes, etc. of the water systems. As an example, the above-mentioned effect is obtained by flowing hypohalous acid through open-circulation cooling water or the like of cooling water. Among the hypohalous acids, hypobromous acid has a higher bactericidal activity than hypochlorous acid, and thus, use of hypobromous acid in water systems is attracting attention.
For example, patent document 1 describes a method for sterilizing water, in which a chlorine-based oxidizing agent and a stabilized hypobromous acid composition are added to water, respectively, and the stabilized hypobromous acid composition contains a bromine-based oxidizing agent, or a reactant of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound.
For example, in patent document 2, in order to control contamination by microorganisms in an aqueous system, a method for producing a biocide is proposed, the method comprising: (a) A step of preparing a stabilized alkali metal or alkaline earth metal hypochlorite having a pH of at least 11 by mixing unstabilized sodium hypochlorite with sulfamic acid as a stabilizer in an alkaline solution; (b) A step of preparing sodium bromide as a bromide ion source; and (c) a step of adding the bromide ion source prepared in the step (b) to the stabilized alkali metal or alkaline earth metal hypochlorite prepared in the step (a) (for example, refer to claim 1, paragraph [0047], and the like).
Further, for example, patent document 3 proposes a method for producing a stabilized bromine solution for controlling adhesion of organisms, the method comprising: a. a step of combining a sodium bromide solution as a bromine source with a solid sulfamate as a stabilizer to produce a mixture; b. slowly adding sodium hypochlorite solution as an oxidizing agent to the mixture; then, slowly adding a sodium hydroxide solution as an alkali source to the mixture, and adjusting the pH of the mixture to at least 13 (for example, refer to claim 1 and paragraph [0022 ]).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-209837
Patent document 2: japanese patent laid-open publication No. 2005-519089
Patent document 3: japanese patent laid-open publication No. 2002-540297
Patent document 4: japanese patent laid-open publication No. 2014-140056
Disclosure of Invention
Problems to be solved by the invention
The main object of the present technology is to provide a technology for water treatment which exhibits excellent hypobromous acid effects when added to water systems.
Solution for solving the problem
The present inventors have made intensive studies to solve the above problems, and as a result, have found that a technique for water treatment which can exert the effect of hypobromous acid well when added to a water system can be provided, and completed the present technique.
That is, the present technology is as follows.
[1] A water treatment agent comprising the following components (a) to (c) and having a pH of 10 or more:
(a) Chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content of the polymer is from 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
[2] The water treatment agent according to the above [1], wherein the molar ratio of the chloramine compound to the bromide salt is 1:0.1 to 1.0.
[3] The water treatment agent according to the above [1] or [2], wherein the water treatment agent is at least one of slime control, corrosion protection and scale control.
[4] The water treatment agent according to any one of the above [1] to [3], wherein the (a) chloramine compound and the (b) bromide salt in the water treatment agent are obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
[5]According to the above [1]]～[4]The water treatment agent according to any one of the above, wherein the total chlorine detection rate after production of the water treatment agent is 95% or more and the free chlorine content in the total chlorine concentration is expressed by Cl 2 Is 0.05% or less.
[6] A method for producing a water treatment agent, which comprises mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
[7] The method for producing a water treatment agent according to the above [6], wherein the stabilizer is a sulfamic acid compound.
[8] The method for producing a water treatment agent according to the above [6] or [7], wherein the oxidizing agent is a chlorine-based oxidizing agent.
[9] The method for producing a water treatment agent according to any one of the above [6] to [8], wherein the pH of the mixed solution is 13 or more.
[10] The method for producing a water treatment agent according to any one of the above [6] to [9], wherein the mixed solution is a solution in which a powdery bromide salt is mixed as the bromide salt.
[11] The method for producing a water treatment agent according to any one of the above [6] to [10], wherein the water treatment agent is further blended to form 1 to 18% by mass of a carboxyl polymer, and the carboxyl content in the carboxyl polymer is 0.8 g-COOH/g-polymer or less.
[12] A water treatment agent contains alkaline agent, chloramine compound and bromide salt,
the water treatment agent has a total chlorine detection rate of 95% or more and a free chlorine content in total chlorine concentration of Cl 2 Is 0.05% or less.
[13] The water treatment agent according to the above [12], wherein the water treatment agent is obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
[14] The water treatment agent according to the above [13], wherein the pH of the water treatment agent is 13 or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present technology, a technique of water treatment can be provided in which the effect of hypobromous acid is well exerted when added to a water system. The effects described herein are not necessarily limited, and may be any effects described in the present specification.
Drawings
FIG. 1 shows the change with time of the total oxidant concentration in the aqueous system (pH 8 to 9) when each sample 1 to 4 was added. Sample 1: chloramine compound (x), sample 2: chloramine compound + bromide (Δ), sample 3: chloramine compound+carboxyl polymer (≡), sample 4: chloramine compound + carboxyl polymer + bromide (). The carboxyl polymer had a carboxyl content of 0.77 g-COOH/g-polymer. The concentration when only chloramine compound was added was set to 100%.
FIG. 2 shows the relationship between the concentration (%) of hypobromous acid in the water system and the concentration (%) of the total oxidizing agent when the carboxyl group content (g-COOH/g-polymer) of the carboxyl group polymer in the water treatment agent is changed and each water treatment agent is added to the water system (pH 8 to 9). The concentration of the carboxyl polymer in the water system was 5 mg-polymer/L, and measurement was carried out 48 hours after the addition. The concentration of hypobromous acid without the addition of the carboxyl polymer was set to 100%.
FIG. 3 shows the relationship between the concentration (%) of hypobromous acid in the water system and the concentration (%) of the total oxidizing agent when the carboxyl group content (g-COOH/g-polymer) of the carboxyl group polymer in the water treatment agent is changed and each water treatment agent is added to the water system (pH 8 to 9). The concentration of the carboxyl polymer in the water system was 30 mg-polymer/L, and measurement was carried out 48 hours after the addition. The concentration of hypobromous acid without the addition of the carboxyl polymer was set to 100%.
Fig. 4 shows the relationship between the concentration (mg/L) of the carboxyl polymer and the concentration (%) of the hypobromous acid in the water system when the content of the carboxyl polymer in the water treatment agent is changed and each water treatment agent is added to the water system (pH 8 to 9). The concentration of hypobromous acid without the addition of the carboxyl polymer was set to 100%.
FIG. 5 shows the concentration of hypobromous acid (mg/L in Cl) in a water system when the water treatment agent of the present technology is added to the water system (pH 8 to 9) 2 Meter) over time.
Fig. 6 shows the change in the total chlorine detection rate (%) of each water treatment agent at the time of a fixed time after the production of each water treatment agent with respect to each water treatment agent of test example 29 (example 1), test example 30, and test example 31 (comparative examples 1 and 2).
Detailed Description
Hereinafter, a mode for carrying out the present technology will be described. The embodiments described below are examples of representative embodiments of the present technology, and the scope of the present technology is not limited to these.
In the present specification, the percentages are expressed by mass unless otherwise specified. The upper limit and the lower limit of each numerical range may be arbitrarily combined as necessary.
< 1. Summary of the present technology >
The main object of the present technology is to provide a technology for water treatment which exhibits excellent hypobromous acid effects when added to water systems.
The present technology can also provide the water treatment technology according to the first embodiment of the present technology and the water treatment technology according to the second embodiment of the present technology. Thus, a technique for water treatment can be provided which exhibits excellent hypobromous acid effects when added to a water system.
The first embodiment of the present technology provides a water treatment agent or the like containing the following components (a) to (c) and having a pH of 10 or more, wherein the component (a) is a chloramine compound, the component (b) is a bromide salt, and the carboxyl group content in the polymer is 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
The first embodiment provides a water treatment technique such as a single-liquid water treatment agent in which the effect of hypobromous acid is well exerted when added to a water system and the effect of other compounds is also well exerted.
The second embodiment of the present technology is a method for producing a water treatment agent by mixing a mixed solution containing an alkaline agent, a stabilizer and a bromide salt with an oxidizing agent, a water treatment agent produced by the production method, and a water treatment agent containing an alkaline agent, a chloramine compound and a bromide salt, wherein a total chlorine detection rate after production is 95% or more and a free chlorine content in a total chlorine concentration is 0.05% (in Cl 2 Meter) the following water treatment agent.
The second embodiment provides a water treatment technique such as a water treatment agent which exhibits excellent hypobromous acid effect when added to a water system and is excellent in the quality stability of the agent.
Furthermore, the present technology can be combined with the technologies of the first and second embodiments. Thus, a technique for water treatment which can exert a good effect of hypobromous acid when added to a water system can be provided, and further, the technique for water treatment has the advantage that the effect of a chemical agent which can form other compounds can be exerted well and/or the advantage that the quality stability of the chemical agent is excellent.
The present technology is also applicable to a water treatment apparatus or a water treatment system for which the effect of hypobromous acid is expected. The present invention can also provide a water treatment apparatus or a water treatment system configured to be implemented by combining the first embodiment and/or the second embodiment of the present technology with a conventional water treatment apparatus or a conventional water treatment system in which the effect of hydrobromic acid is expected. The water treatment apparatus or water treatment system of the present technology preferably includes: a storage device for each component used in the present technology; means for adding the ingredients or mixing the ingredients; mixing devices and pipes for mixing the components (e.g., mixing by stirring or convection), and the like. The water treatment apparatus or the water treatment system of the present technology may further include a control unit or a control device described later. Further, a water treatment agent of the present technology, an adding device for adding each component, and the like may be provided.
The water treatment method for exerting the effect of the hypobromous acid of the present technology can also be implemented by a control unit (for example, a computer) including a central processing unit (Central Processing Unit, CPU) and the like for controlling the timing of addition, the amount of addition, the mixing ratio and the like of each component or the water treatment agent used in the present technology. The method of the present technology may be realized by the control unit as a program stored in a hardware resource including a recording medium (a non-volatile memory (a universal serial bus (Universal Serial Bus, USB) memory, etc.), a Hard Disk Drive (HDD), a Compact Disc (CD), etc.), or the like. A control device or an adding device may be provided which controls the adding of the chemical to the water to be treated by the control unit. Further, the present technology may provide a water treatment system or a water treatment apparatus including the control device or the adding device.
The water treatment technology according to the first embodiment of the present technology and the water treatment technology according to the second embodiment of the present technology will be described in detail below. In the description of the present technology, the first and second embodiments are preferably omitted from their overlapping structures, components, and the like.
< 2 > Water treatment agent of the first embodiment of the present technology >
Hereinafter, a first embodiment for implementing the present technology will be described. The following embodiments are examples of representative embodiments showing the first embodiment of the present technology, and the scope of the first embodiment of the present technology is not limited to this.
The main object of the first embodiment of the present technology is to provide a water treatment technology such as a single-liquid water treatment agent that exhibits excellent hypobromous acid effect when added to a water system and also exhibits excellent chemical effect of other compounds.
In general, a polymer having a carboxyl group (hereinafter also referred to as "carboxyl polymer") is used as a chemical agent for slime control, corrosion protection, scale control, etc., and therefore, the present inventors have expected that when a carboxyl polymer (for example, a maleic acid-based or acrylic acid-based polymer) is mixed with a chloramine compound and a bromide salt to prepare a single-liquid water treatment agent, the water treatment agent can exert the chemical effect of the carboxyl polymer in addition to the effect exerted by hypobromous acid satisfactorily when the water treatment agent is added to a water system.
However, the present inventors have found that when a water treatment agent in which a carboxyl polymer is mixed with a chloramine compound and a bromide salt is added to a water system, the decomposition of hypobromous acid in the water system proceeds rapidly due to the carboxyl polymer, and the stability of hypobromous acid in the water system decreases with time, and the effect of hypobromous acid is not sustained (see fig. 1). However, the present inventors have eagerly studied on a single-liquid water treatment agent which can exert not only the effect of hypobromous acid but also the pharmaceutical effect of a carboxyl polymer in an aqueous system.
As a result, the present inventors have found that by adjusting the properties and content of a carboxyl polymer in a water treatment agent containing a chloramine compound and a bromide salt, a single-liquid water treatment agent which can obtain good stability with time can be obtained when the water treatment agent is added to a water system. The present inventors have found that the effect of the hypobromous acid can be satisfactorily exhibited, and that the effect of the carboxylic polymer can be satisfactorily exhibited, thereby completing the present technology.
That is, the present technology can employ the following.
The first embodiment of the present technology provides a water treatment agent containing the following components (a) to (c) and having a pH of 10 or more.
(a) Chloramine compounds
(b) Bromide salt
(c) The carboxyl group content of the polymer is from 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
In addition, the molar ratio of chloramine compound to bromide salt is preferably 1:0.1 to 1.0.
The water treatment agent is preferably at least one of slime control, corrosion protection and scale control.
The water treatment agent according to the first embodiment of the present technology contains a chloramine compound and a bromide salt that generate hypobromous acid, and further contains a specific amount of a specific carboxyl polymer, and the water treatment agent is adjusted to an alkaline region, thereby being a single-liquid water treatment agent, and hypobromous acid is not easily generated in the water treatment agent over time. Thus, the water treatment agent according to the first embodiment of the present technology is excellent in the stability with time of the quality of the agent, and therefore, even if the agent is circulated in the market as a single-liquid type, the stable quality can be maintained, and even when the water treatment agent according to the first embodiment of the present technology is used in a water system after a fixed period of storage, a favorable effect can be expected.
Further, the water treatment agent according to the first embodiment of the present technology can control the formation of hypobromous acid in a water system when the water treatment agent according to the first embodiment of the present technology is added to the water system by containing a specific amount of a specific carboxyl polymer. Therefore, the water treatment agent according to the first embodiment of the present technology can be controlled so that hypobromous acid is not rapidly generated in the water system in a short period of time. Further, the water treatment agent according to the first embodiment of the present technology can gradually generate hypobromous acid in the water system over time, and thus can maintain the effect of hypobromous acid in the water system for a longer period of time.
Another aspect of the water treatment agent according to the first embodiment of the present technology is a one-pack agent, and can also be used as a slow release water treatment agent. If hypobromous acid is rapidly released in the water system, corrosion or degradation in the water system is likely to occur, but the water treatment agent according to the first embodiment of the present technology can be controlled so as to slow down the rate of generation of hypobromous acid, and thus corrosion or degradation in the water system can be reduced, and the effect (for example, sterilization effect or the like) caused by hypobromous acid can be obtained continuously over a long period of time. Therefore, the water treatment agent according to the first embodiment of the present technology is more advantageously applied to an open circulation type device or the like having a cooling water system, a heat storage water system, a dust collection water system, a scrubber water system, or the like.
Further, the carboxyl polymer used in the first embodiment of the present technology is a component that can be used for purposes such as a slime control agent, an anticorrosive agent, and an antifouling agent. Therefore, the water treatment agent according to the first embodiment of the present technology can exert the effect of hypobromous acid satisfactorily when added to a water system, and can exert the effect of a medicament of a carboxyl polymer as another compound satisfactorily.
The present inventors have made the following assumptions about the mechanism for generating hypobromous acid in a water system when the water treatment agent according to the first embodiment of the present technology is used, and have further studied the mechanism of action of the first embodiment of the present technology.
The water treatment agent according to the first embodiment of the present technology is preferably a one-pack agent, and is preferably designed to exist in the form of a chloramine compound (hereinafter, chloramine compound) and bromide ion, in which a sulfamic acid compound is combined with hypochlorous acid, and to contain a specific amount of the specific carboxyl polymer. In the first embodiment of the present technology, it is important to use a carboxyl polymer having a characteristic that is adjusted, and therefore the carboxyl content in the carboxyl polymer is adjusted to a predetermined range. It is also important that a specific amount of the specific carboxyl polymer is contained in a single-unit agent and used in an aqueous system. In the first embodiment of the present technology, the water treatment agent is preferably adjusted to a state in which the pH is raised and an excessive amount of sulfamic acid is allowed to coexist, and thus the reaction of the chloramine compound to hypobromous acid is controlled to hardly occur.
When the water treatment agent according to the first embodiment of the present technology is added to an aqueous system, a chloramine compound and a bromide salt react with each other to produce sulfamic acid, hypobromous acid, and the like. Thus, the antibacterial effect and the like due to the hypobromous acid generated in the water system can be exerted, and the effect of the carboxyl polymer which is difficult to be achieved by the conventional single-liquid water treatment agent can be exerted, and the effect of the hypobromous acid can be continuously exerted.
< 2- (a) chloramine Compound >
The chloramine compound used in the first embodiment of the present technology is not particularly limited, and for example, hypochlorous acid (HOCl) and a compound having a primary amino group (XNH) are preferably reacted by the reactions shown in the following reaction formulae (1) and (2) 2 ) And a compound (xngcl) obtained by the reaction in which the hydrogen atom of the amino group is replaced with a chlorine atom. The compound has a weak oxidation effect on metals, films, and the like in a water system, and therefore can inhibit corrosion or film degradation, and can be continuously and/or continuously used in a water system.
The chloramine compound used in the first embodiment of the present technology is not particularly limited, and is preferably a compound having a primary amino group, ammonia, or any one of ammonium salts (hereinafter, these are also referred to as "NH" 2 A compound) and hypochlorous acid and/or hypochlorite.
The compound having a primary amino group is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, sulfamic acid, sulfanilic acid (Sulfanilic acid), sulfamoylbenzoic acid, and amino acids. Examples of the ammonium salt include ammonium chloride and ammonium sulfate. One selected from the group consisting of these may be used alone, or two or more may be used in combination.
These NH' s 2 Among the series compounds, sulfamic acid is preferable (more preferableSelecting NH 2 SO 2 OH). If sulfamic acid is used to form monochlorosulfamic acid, it becomes a stable chloramine compound.
The sulfamic acid compound may be a compound represented by the following general formula [1] or a salt thereof.
(wherein, the general formula [1]]Wherein R is 1 R is R 2 Each independently represents hydrogen or a hydrocarbon having 1 to 8 carbon atoms. )
As such sulfamic acid compounds, for example, other than R 1 And R is R 2 Examples of sulfamic acid that are each hydrogen include N-methyl sulfamic acid, N-dimethyl sulfamic acid, N-phenyl sulfamic acid, and the like. One selected from the group consisting of these may be used alone, or two or more may be used in combination.
The salt of the compound used in the first embodiment of the present technology is not particularly limited, and examples thereof include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts, strontium salts, barium salts, and the like; manganese salts, copper salts, zinc salts, iron salts, cobalt salts, nickel salts and other metal salts; amine salts such as ammonium salts and guanidine salts, amino acid salts, and the like may be suitably used, and one or a combination of two or more selected from the group consisting of these may be suitably used. Among them, alkali metal salts (preferably sodium) are preferable from the viewpoint of cost and ease of handling.
These salts can be used as salts of sulfamic acid compounds.
Examples of the sulfamic acid compound used in the first embodiment of the present technology include sodium sulfamate, potassium sulfamate, calcium sulfamate, strontium sulfamate, barium sulfamate, iron sulfamate, and zinc sulfamate. One selected from the group consisting of these may be used alone, or two or more may be used in combination.
In the first embodiment of the present technology, sulfamic acid and sulfamate of these may be used alone or in combination of two or more.
On the other hand, as NH 2 As hypochlorite for the reaction of the compound, alkali metal salts of hypochlorous acid such as sodium hypochlorite can be used; alkaline earth metal salts of hypochlorous acid such as calcium hypochlorite. One selected from the group consisting of these may be used alone, or two or more may be used in combination.
In mixing NH 2 When a chloramine compound is produced by reacting a chlorine-containing compound with hypochlorous acid and/or hypochlorite, NH is produced from the viewpoint of chloramine production efficiency and stability 2 The compound and hypochlorous acid and/or hypochlorite are preferably prepared from available chlorine (Cl) derived from hypochlorous acid and/or hypochlorite 2 ) And derived from NH 2 The molar ratio of N to Cl of the nitrogen atom of the compound 2 The molar ratio of N to N is 0.1 to 1. If Cl 2 When the molar ratio of N to N is not more than the upper limit, the formation of free chlorine can be suppressed, and when it is not less than the lower limit, NH is used 2 The compound can inhibit the decrease of chloramine production efficiency.
In the water treatment agent according to the first embodiment, the content of the chloramine compound is preferably at least 4 mass%, more preferably at least 6 mass%, even more preferably at least 8 mass%, and the upper limit thereof is preferably at most 24 mass%, more preferably at most 22 mass%, even more preferably at most 20 mass%. The numerical range is preferably 4 to 24 mass%, more preferably 6 to 22 mass%, and even more preferably 8 to 20 mass%.
< 2- (b) bromide salt >
The bromide salt used in the first embodiment of the present technology is not particularly limited, and examples thereof include alkali metal bromide salts, ammonium bromide salts, hydrobromic acid, and amine bromide salts, and one or two or more selected from the group consisting of these may be used.
Examples of the alkali metal bromide include sodium bromide, potassium bromide, and lithium bromide, but are not limited thereto.
Examples of the amine bromide salt (a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms or alkenyl group) include diethylamine hydrogen bromide, allylamine hydrogen bromide, cyclohexylamine hydrogen bromide, monomethylamine hydrogen bromide, dimethylamine hydrogen bromide, trimethylamine hydrogen bromide, n-butylamine hydrogen bromide, and ethylamine hydrogen bromide, but are not limited thereto.
The bromide salt may be used one or two or more selected from the group consisting of these.
In the water treatment agent according to the first embodiment, the content of the bromide salt is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1.0 mass% or more, as the lower limit value, and is preferably 10 mass% or less, more preferably 9 mass% or less, further preferably 8 mass% or less, as the upper limit value, as calculated by bromide conversion. The numerical range is preferably 0.1 to 10% by mass, more preferably 0.5 to 9% by mass, and even more preferably 1.0 to 8% by mass.
< bromide (Br) - ) Measurement method >
Bromide (Br) in the present technique - ) The concentration can be analyzed and measured based on the method of Japanese Industrial Standard (Japanese Industrial Standards, JIS) -K0101 (1998) 28.4.
< method for measuring pH >)
The pH in the present technology can be measured at room temperature of 25℃using a general pH meter (e.g., a "portable pH meter D-54 (pH/mV (ORP)/COND/resistivity/salt/TDS)" manufactured by horiba, inc.) or a subsequent model).
< 2- (c) carboxy Polymer >
The carboxyl polymer used in the first embodiment of the present technology is not particularly limited as long as it is a polymer compound having a specific amount of carboxyl groups.
The carboxyl polymer used in the first embodiment of the present technology preferably has a carboxyl content of a specific ratio in the carboxyl polymer (hereinafter also referred to as "polymer"). Thus, when the water treatment agent according to the first embodiment of the present technology is added to a water system, the effect peculiar to the carboxyl polymer can be exhibited, and the effect of hypobromous acid can be exhibited effectively without decomposing hypobromous acid generated in the water system so much.
The present inventors found that the content of carboxyl groups in the carboxyl group polymer and the concentration of carboxyl groups in the aqueous system can be controlled so that hypobromous acid in the aqueous system is not decomposed. Further, the present inventors have found that the content of the carboxyl polymer contained in the water treatment agent can be specified by examining the correlation between the carboxyl content of the carboxyl polymer and the carboxyl concentration in the water system.
Thus, the present inventors have devised a one-pack water treatment agent containing a chloramine compound (a) and a bromide salt (b) as components (a) and a specific carboxyl polymer (c) in a specific amount. The water treatment agent is in a single liquid form, and can inhibit other components from decomposing due to mixed components. The water treatment agent can stably maintain the quality and can well exert the respective effects of hypobromous acid and carboxyl polymer when added into water system. Further, by using a specific amount of the specific carboxyl polymer in the aqueous system, the effect of hypobromous acid can be continuously exhibited for a longer period of time. Therefore, the water treatment agent according to the first embodiment of the present technology is also excellent in terms of the reduction in the number of additions to the water system due to the slow release property, the simplification of the working process due to the single-liquid use, the sustainable expression of the effect by the reduction in the decomposition of hypobromous acid, the reduction in the cost, and the like.
Therefore, the carboxyl group content of the carboxyl group polymer in the first embodiment of the present technology is preferably 0.8 g-COOH/g-polymer or less, and the carboxyl group polymer is preferably 1 to 18% by mass in the water treatment agent of the first embodiment.
[ carboxyl group content in Polymer ]
In the water treatment agent according to the first embodiment of the present technology, the content of carboxyl groups in the polymer is preferably 0.8 g-COOH/g-polymer or less, more preferably 0.77 g-COOH/g-polymer or less, still more preferably 0.72 g-COOH/g-polymer or less, and the lower limit is preferably 0.1 g-COOH/g-polymer or more, more preferably 0.2 g-COOH/g-polymer or more. The numerical range is more preferably from 0.8 g-COOH/g-polymer to 0.1 g-COOH/g-polymer, still more preferably from 0.77 g-COOH/g-polymer to 0.2 g-COOH/g-polymer.
Method for measuring carboxyl group content (g-COOH/g-Polymer)
The carbon (180 ppm to 182 ppm) originating in the carboxyl group can be quantified using 13C-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrometry (carbon 13 nuclear magnetic resonance) (measurement temperature 30 ℃ C.). The carbon originating from the carboxyl group can be quantified according to the concentration of sodium 3- (trimethylsilyl) propionate using sodium 3- (trimethylsilyl) propionate as a standard substance. In addition, the effect of the ovnikose nuclear effect (nuclear Overhauser effect, NOE) can be removed by gating decoupling (1J (C, H)).
The content of the carboxyl polymer in the water treatment agent according to the first embodiment is preferably 0.5 mass% or more, more preferably 0.75 mass% or more, still more preferably 1.0 mass% or more, and still more preferably 1.5 mass% or more, and the upper limit thereof is preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 18 mass% or less, and still more preferably 15 mass% or less. The numerical range is preferably 0.5 to 25% by mass, more preferably 0.75 to 20% by mass, and even more preferably 1 to 18% by mass, from the viewpoints of cost, working efficiency, effect, and the like.
Method for measuring weight average molecular weight of Water-soluble Polymer
The weight average molecular weight of the water-soluble polymer used in the present technique can be measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) analysis using standard polystyrene as a standard substance (see, for example, patent document 4 (reference 1): japanese patent application laid-open No. 2014-140056, etc.).
The type of the carboxyl polymer used in the first embodiment of the present technology is not particularly limited, and examples thereof include water-soluble homopolymers and/or copolymers having a carboxyl group, and more specifically, examples thereof include maleic acid polymers and (meth) acrylic acid polymers. The term "polymer" means a polymer or copolymer containing monomers.
More specifically, examples of the carboxyl polymer include a maleic acid homopolymer, a (meth) acrylic acid homopolymer, and a copolymer of an unsaturated monomer copolymerizable with maleic acid or (meth) acrylic acid, and two or more kinds selected from the group consisting of these may be used.
The carboxyl polymer in the first embodiment of the present technology preferably contains a maleic acid-based polymer and/or a (meth) acrylic polymer. The content (content) of the maleic acid-based polymer and/or the (meth) acrylic acid-based polymer in the carboxyl polymer is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 99% by mass or more, and most preferably substantially 100% by mass, and the desirable effect of the present technology can be easily obtained when the content of the carboxyl polymer is high.
Examples of the unsaturated monomer copolymerizable with the monomer of maleic acid or (meth) acrylic acid include 2-acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-aryloxy-1-propanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, acrylamide, ethylene, propylene, isopropene, butene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene, isooctene, vinyl alcohol, vinylmethyl ether, and vinylethyl ether, and salts thereof.
One or more polymers selected from the group consisting of homopolymers, copolymers, and copolymers of the foregoing monomers and isobutylene, obtained by using one or more monomers selected from these monomers, are exemplified.
In order to expect a pharmaceutical effect such as an anticorrosive effect, the weight average molecular weight of the carboxyl polymer is preferably in the range of from 3 to 4 power of 10, more specifically, in the range of from 200 to 50000, more preferably in the range of from 500 to 30000, still more preferably in the range of from 800 to 30000, and still more preferably in the range of from 1000 to 20000. In order to obtain a chemical effect such as an anticorrosive effect, the weight average molecular weight is preferably 500 or more, and from the viewpoint of handleability, the weight average molecular weight is preferably 20000 or less, more preferably 16000 or less, in order to reduce the viscosity of the aqueous solution.
The weight average molecular weight of the above-mentioned carboxyl polymer can be measured by the above-mentioned < method for measuring weight average molecular weight of water-soluble polymer >.
The concentration of the carboxyl polymer in the aqueous system is preferably 1 mg-polymer/L to 100 mg-polymer/L, more preferably 2 mg-polymer/L to 50 mg-polymer/L, still more preferably 5 mg-polymer/L to 30 mg-polymer/L, from the viewpoint of obtaining the chemical effects such as corrosion preventing effect.
< pH of water treatment agent of first embodiment of the present technology >
The pH of the water treatment agent according to the first embodiment of the present technology is in the alkaline region, more preferably 10 or more, still more preferably 11 or more, still more preferably 12 or more, and particularly preferably 13 or more, from the viewpoint of the stability of the agent with time. By adjusting the chemical agent to the alkaline region with a pH adjuster (particularly, an alkaline agent), the generation of hypobromous acid in the water treatment agent can be suppressed, and the stability with time can be maintained or improved.
Content and mass content ratio of the respective components in the water treatment agent according to the first embodiment of the present technology
[ molar ratio of chloramine Compound to bromide salt ] described above
In the water treatment agent according to the first embodiment of the present technology, the molar ratio of the chloramine compound to the bromide salt is preferably adjusted, and when the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt is preferably 1:0.05 to 3.0, more preferably 1:0.1 to 1.5, more preferably 1:0.1 to 1.0, more preferably 1:0.2 to 1.0.
In the water treatment agent according to the first embodiment of the present technology, the preferable range of the carboxyl group content in the polymer is as shown in [ the carboxyl group content in the polymer ], and more preferably 0.3 to 0.72 (g-COOH/g-polymer).
The concentration (%) of hypobromous acid in the water system is not particularly limited within a preferable range of the carboxyl group content in the polymer, and the water treatment agent according to the first embodiment of the present technology is preferably prepared so as to be preferably 75% or more, more preferably 80% or more, still more preferably 85% or more, and still more preferably 90% or more, or the water treatment agent according to the first embodiment of the present technology or each component used in the water treatment agent is preferably added.
The total concentration (%) of the oxidizing agent in the water system is not particularly limited within the preferable range of the carboxyl group content in the polymer, and the water treatment agent according to the first embodiment of the present technology is preferably prepared so as to be preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more, or the water treatment agent according to the first embodiment of the present technology is added.
The water treatment agent according to the first embodiment of the present technology is excellent in stability with time by finding that a specific carboxyl polymer is used in a specific amount as described above. The total concentration of the oxidizing agent after the water treatment agent according to the first embodiment of the present technology is fixed, and in the storage at a constant temperature bath, the total concentration may be preferably 98% or more, more preferably 99% or more when stored at 20 ℃ for 20 days, and may be preferably 85% or more, more preferably 90% or more when stored at 50 ℃ for 20 days.
In addition, the water treatment agent according to the first embodiment of the present technology can obtain excellent slow release properties by adjusting the characteristics of the carboxyl polymer, the specific amount used, and the like as described above. The water treatment agent according to the first embodiment of the present technology is adjusted so that the concentration of hypobromous acid is preferably 0.25mg/L (Cl 2 Calculated as Cl) to 1.5mg/L 2 Calculated as Cl), more preferably 0.5mg/L (calculated as Cl) 2 Calculated by Cl) to 1mg/L 2 Meter).
Furthermore, the first embodiment of the present technology may employ the technology of the second embodiment of the present technology described later.
By combining the technique of the first embodiment and the technique of the second embodiment, it is possible to provide a technique of single-liquid water treatment that can exert the effect of hypobromous acid well and the effect of other compounds in the chemical agent well when added to a water system, and that has the advantage of excellent quality stability of the chemical agent.
As an example of the technology of the second embodiment using the present technology described later, for example, the (a) chloramine compound and the (b) bromide salt in the first embodiment of the present technologyThe mixture may be a mixture containing the above (a) and (b) obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent. By using the obtained mixture containing the above (a) and (b), the water treatment agent according to the first embodiment of the present technology may be such that the total chlorine detection rate after production is 95% or more and the free chlorine content in the total chlorine concentration is 0.05% (in Cl) 2 Meter) is as follows.
< 2- (d) >, any component of the first embodiment of the present technology
The water treatment agent according to the first embodiment of the present technology may be used in combination with any agent within a range that does not impair the effects of the present technology. Examples of the optional chemical include a corrosion inhibitor (corrosion inhibitor), an antiscalant, a slime control agent, a solvent or dispersion medium such as water, a dispersant enzyme, a bactericide, and an antifoaming agent, but the present invention is not limited thereto, and various chemicals generally used for water treatment may be used. One or two or more of these groups may be appropriately selected.
The water treatment agent according to the first embodiment of the present technology can be suitably obtained by mixing the above-described essential components, optional components, or each agent, etc., and can be produced according to a general method for producing a water treatment agent or a method for producing a second embodiment of the present technology described later.
Corrosion inhibitor
The corrosion inhibitor (corrosion inhibitor) other than the above-mentioned carboxyl polymer is not particularly limited, but a corrosion inhibitor for cooling water system is preferable. Preferably, the azole is benzotriazole or tolyltriazole.
< antiscaling agent >)
The scale inhibitor other than the above-mentioned carboxyl polymer is not particularly limited, and for example, a phosphoric acid-based scale inhibitor and/or a phosphonic acid-based scale inhibitor and the like are known.
Examples of the scale inhibitor include orthophosphoric acid, sodium tripolyphosphate, sodium hexametaphosphate, 2-phosphono-1, 2, 4-tricarboxybutane, 1-hydroxyethylidene-1, 1-diphosphonic acid, and aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid (1-hydroxyethane-1, 1-diyl-bisphosphonic acid, HEDP), and 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC). One or two or more selected from the group consisting of these may be used.
The content of the anticorrosive and/or antiscalant in the water treatment agent according to the first embodiment of the present technology is not particularly limited, but is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass.
2-2A method of Using the Water treatment agent of the first embodiment of the present technology and a Water treatment method Using the Water treatment agent
The water treatment agent according to the first embodiment of the present technology is expected to have the efficacy effect of the specific carboxyl polymer, in addition to the effect of hypobromous acid (for example, a sterilization effect, a slime control effect, etc.), and is useful as at least one of a slime control effect, an anticorrosive effect, an antiscaling effect, etc.
The first embodiment of the present technology can provide the use or the use method of the water treatment agent of the first embodiment of the present technology, and examples of the purpose of the use include water treatment in a water system, a sterilization method in a water system, a slime control method in a water system, an anti-corrosion method in a water system, and a film scale prevention method in a water system.
The first embodiment of the present technology can also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scaling method in which the water treatment agent of the first embodiment of the present technology is added to a water system. The configuration repeated with the configuration described in the water treatment agent of the present technology is preferably omitted.
From the viewpoint of stability over time, the pH of the aqueous system in the method of the first embodiment of the present technology is in the alkaline region, more preferably 7 to 10, and still more preferably 8 to 9.
In addition, according to another aspect of the first embodiment of the present technology, a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scaling method, in which the following components (a) to (c) are added to a water system at the same time or at different times and/or at the same place or at different places, can be provided. (a) chloramine compound; (b) a bromide salt; (c) The carboxyl group content of the polymer is from 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
In the first embodiment of the present technology, the timing of adding the chemical agent or each component in the water system is not particularly limited, and the chemical agent or each component may be added at the same timing or separately. And/or the site of adding the chemical or each component in the water system is not particularly limited, and may be added to the same site or different sites. The components (a) to (c) may be added to the water system and mixed to exhibit the effects expected in the first embodiment of the present technology, or may be added to the water system to form a water treatment agent.
For example, in order to control or prevent the scale of the slime of the membrane, it is preferable to add a chemical before the membrane treatment. In addition, the present technology can be used to control, sterilize, and prevent corrosion of slime such as piping in a water system, and the effect of the present technology can be obtained at any time and any place in the water system.
The object of the first embodiment of the present technology is preferably a cooling water system, and more preferably the cooling water system is a cooling water system provided with a metal or metal pipe such as a cooling tank, a cooling tower, a heat exchanger, or the like.
In the method according to the first embodiment of the present technology, it is preferable that the molar ratio of the chloramine compound of the component (a) to the bromide salt of the component (b) is 1:0.1 to 1.0. The molar ratio may be the same as that of the water treatment agent.
In the method according to the first embodiment of the present technology, the carboxyl polymer as the component (c) is preferably added so as to have a predetermined concentration in an aqueous system. The predetermined concentration in the water system is not particularly limited, but is preferably 0.5mg/L or more, more preferably 1mg/L or more, further preferably 2mg/L or more, and is preferably 500mg/L or less, more preferably 80mg/L or less, further preferably 60mg/L or less, further more preferably 50mg/L or less, and particularly preferably 40mg/L or less.
In the method according to the first embodiment of the present technology, the concentration of the carboxyl polymer as the component (c) in the aqueous system is preferably 1mg/L to 80mg/L, more preferably 2mg/L to 60mg/L, still more preferably 2mg/L to 50 mg/L.
In the first embodiment of the present technology, the present invention can be used as a water treatment agent kit. In the case of the water treatment agent kit, the components (a) to (c) may be contained in separate containers, or the two components may be mixed with one component and contained in separate containers. In addition, any component may be appropriately mixed in each container. The use or method of the water treatment agent kit may be performed in the same manner as the use or method of the water treatment agent described above.
< 3. Method for producing Water treatment agent according to the second embodiment of the present technology and Water treatment agent >)
A second embodiment for implementing the present technology will be described below. The following embodiments illustrate an example of a representative embodiment of the second embodiment of the present technology, and thus the scope of the second embodiment of the present technology is not to be interpreted in a limiting manner.
The main object of the second embodiment of the present technology is to provide a water treatment agent which exhibits excellent hypobromous acid effect when added to a water system and has excellent quality stability of the agent.
As a result of intensive studies, the present inventors have found that, regarding a water treatment agent obtained by mixing an oxidizing agent in a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed, even after a fixed time has elapsed after production, the total chlorine detection rate is maintained high and the content of free chlorine in the total chlorine concentration is also maintained low. That is, the present inventors have completed the present technology by obtaining a water treatment agent which exhibits excellent hypobromous acid effect when added to a water system and has excellent quality stability of the agent.
That is, the present technology can employ the following.
The second embodiment of the present technology can provide a method for producing a water treatment agent, in which a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed is mixed with an oxidizing agent.
The stabilizer is preferably a sulfamic acid compound.
The oxidizing agent is preferably a chlorine-based oxidizing agent.
The pH of the mixed solution is preferably 13 or more.
The mixed solution is preferably mixed with a powdery bromide salt as the bromide salt.
In addition, the second embodiment of the present technology is a water treatment agent containing an alkaline agent, a chloramine compound, and a bromide salt, and can provide a total chlorine detection rate after production of 95% or more and a free chlorine content of 0.05% in total chlorine concentration (in Cl 2 Meter) the following water treatment agent.
The water treatment agent according to the second embodiment of the present technology is preferably obtained by mixing a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed with an oxidizing agent.
The pH of the water treatment agent according to the second embodiment of the present technology is preferably 13 or more.
< 3-1. Water treatment agent according to the second embodiment of the present technology and method for producing the same
A second embodiment of the present technology provides a method for producing a water treatment agent, wherein a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed is mixed with an oxidizing agent. When a mixed solution in which the alkali agent, the stabilizer and the bromide salt are mixed is obtained, the mixing order of the alkali agent, the stabilizer and the bromide salt may be any order, and is not particularly limited.
Further, the second embodiment of the present technology can provide a water treatment agent obtained by mixing an oxidizing agent in a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed.
In the second embodiment of the present technology, a water treatment agent containing an alkaline agent, a chloramine compound, and a bromide salt is provided, and the water treatment agent can be produced such that the total chlorine detection rate after production is not less than a predetermined level and/or the free chlorine content in the total chlorine concentration is not more than a predetermined level.
Thus, the second embodiment of the present technology can provide a water treatment agent which exhibits excellent hypobromous acid effect when added to a water system and has excellent quality stability of the agent.
< 3-2. Method for producing Water treatment agent according to the second embodiment of the present technology >
The present inventors have studied a method for producing a biocide in patent document 2 (japanese patent application laid-open No. 2005-519089). Specifically, in patent document 2, hypochlorite solution having at least pH11 or more is prepared by mixing hypochlorite and sulfamic acid in sodium hydroxide solution, and sodium bromide is finally mixed in the solution to obtain a stable hypobromite solution as a biocide.
However, it is known that when sodium bromide in powder form is mixed by the method for producing a biocide in patent document 2, hypobromous acid having high oxidizing power and being unstable is produced. The present inventors found that the effect of the active ingredient contained in the biocide tends to be reduced by the decrease in stability of hypobromous acid in this manner. As a result of verifying the cause, the inventors of the present invention have found that when sodium bromide in powder form is added to hypochlorous acid solution, a concentrated bromide solution is formed in a part of the solution when the powder is dissolved. The present inventors thought that unstable hypobromous acid was generated by the reaction with hypochlorous acid coexisting when the concentrated portion of the bromide solution was generated.
On the other hand, the present inventors have studied the method of adding sodium bromide not as a powder but as a liquid in the method of producing a biocide of patent document 2, but have found that the concentration at which the sodium bromide can be compounded decreases because water must be added to sodium bromide as an aqueous solution.
The present inventors have studied a method for producing a stabilized bromine solution for controlling adhesion of organisms in patent document 3 (Japanese patent application laid-open No. 2002-540297). Specifically, in patent document 3, a stabilized bromine solution is obtained by mixing a sodium bromide solution with a solid sulfamate and then adding a sodium hypochlorite solution and a sodium hydroxide solution.
The inventors of the present invention considered that the method of patent document 3 can suppress the formation of hypobromous acid because a concentrated bromide solution is not formed in a part of the solution during the preparation of the solution. However, in the method of patent document 3, since the oxidizing agent is mixed with an aqueous solution containing sodium bromide and sulfamic acid, the pH of the oxidizing agent is lowered. The inventors of the present invention have found that when the pH of the oxidizing agent is lowered, an unstable component (for example, dichlorosulfamic acid, bromochlorosulfuric acid, or the like) having a high oxidizing power is generated, and that the effect of stabilizing the active ingredient contained in the bromine solution is lowered due to the unstable component.
Further, the present inventors have made intensive studies, and as a result, as shown in the following [ example ], the water treatment agent obtained by mixing an oxidizing agent in a mixed solution in which an alkaline agent, a stabilizer, a bromide salt and an oxidizing agent are mixed is excellent in the comprehensive point of view of the total chlorine detection rate, the total chlorine concentration and the free chlorine content in the total chlorine concentration, as compared with the water treatment agents of patent documents 2 and 3. That is, the water treatment agent according to the second embodiment of the present technology obtained in this way exhibits excellent hypobromous acid effect when added to a water system and is excellent in quality stability of the agent.
Conventionally, as shown in patent documents 2 and 3, when a water treatment agent containing a chloramine compound and a bromide salt is produced, the order of mixing the bromide salt into a solution is first or last. The reason for this is considered that a stable chloramine compound is obtained from an alkaline agent-stabilizer-oxidizing agent, and thus, the mixing of these agents is regarded as an overall process. The present inventors have made a breakthrough in the conventional state of the art, and thus have found that the water treatment agent according to the second embodiment of the present technology is excellent, and the mixing order is unpredictable from the prior art.
That is, the method for producing the water treatment agent according to the second embodiment of the present technology is characterized by mixing a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed with an oxidizing agent. The method for producing the water treatment agent according to the second embodiment of the present technology has an advantage that a single-liquid water treatment agent that can stably maintain the quality of the agent for a long period of time can be obtained.
Method for measuring free chlorine concentration, combined chlorine concentration and total chlorine concentration
In the present technique, the free chlorine concentration, the combined chlorine concentration and the total chlorine concentration can be determined by JIS K0400DPD method using N, N-diethyl-1, 4-phenylenediamine as shown in-33-10:1999 in Cl 2 Is measured by means of the concentration of (a). In JIS K0400-33-10:1999, the following definitions are proposed.
That is, the free chlorine is chlorine in the form of hypochlorous acid, hypochlorite ion or dissolved chlorine. The bound chlorine is chlorine in the form of chloramine, organochloramine, or the like, and is not included in the free chlorine, but is total chlorine measured by the DPD method. The total chlorine is defined as chlorine in the form of free chlorine, bound chlorine, or both.
< Total chlorine detection Rate (%) and free chlorine content Rate (%) >
In the present technology, the "total chlorine detection rate (%)" is the residual rate (%) of the total chlorine concentration as an active ingredient in the water treatment agent, and can be obtained by "the actual measurement value (% in Cl) of the total chlorine concentration in the water treatment agent" 2 Theoretical value of total chlorine concentration (% in Cl) in the treated water 2 Gauge) "×100 (%). The theoretical value of the total chlorine concentration is a value calculated as the total chlorine concentration formed in the water treatment agent when the oxidizing agent is mixed with the stabilizing agent at the time of production.
In the present technology, the "content of free chlorine in total chlorine concentration (% (in Cl) 2 "by weight percent (% in Cl) in the water treatment agent) 2 Total chlorine concentration (% in Cl) in the water treatment agent 2 Meter (C)]X 100% by weight.
In the second embodiment, < bromide (Br) - ) Measurement methods > and < pH measurement methods > can be the same as those described in the first embodiment < bromide (Br) - ) The measurement method > and the pH measurement method > are performed in the same manner.
< 2-2-1. Raw materials (alkaline agent, stabilizer, bromide salt and oxidizing agent) >)
The alkaline agent, the stabilizer, the bromide salt and the oxidizing agent used as the raw materials in the production method of the second embodiment of the present technology are as follows.
< 3-2-1 (a) alkaline Agents >)
The alkaline agent used in the second embodiment of the present technology is not particularly limited, and examples thereof include basic inorganic salts and basic organic salts.
Examples thereof include alkali metals (e.g., lithium, sodium, potassium, etc.), alkaline earth metals (e.g., calcium, magnesium, barium, etc.), salt oxides (e.g., sodium oxide, calcium oxide, etc.), salt hydroxides (e.g., sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc.), carbonates (e.g., sodium carbonate, potassium carbonate, calcium carbonate, etc.), and one or more selected from the group consisting of these may be used.
The oxide, salt hydroxide, carbonate is preferably an alkali metal or alkaline earth metal. One selected from the group consisting of these may be used or two or more may be used in combination.
Among the above alkaline agents, alkaline inorganic salts are preferable, and among them, salt hydroxides are more preferable from the viewpoints of workability and cost. Among these salt hydroxides, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is further preferable from the viewpoint of cost.
The acidic agent used to adjust the pH of the water treatment agent according to the second embodiment of the present technology is not particularly limited, and examples thereof include acidic inorganic salts and acidic organic salts. Examples thereof include citric acid, phosphoric acid, tartaric acid, acetic acid, boric acid, phthalic acid, maleic acid, succinic acid, and the like, and one or two or more selected from the group consisting of these may be used.
< 3-2-1 (b) stabilizer >
The stabilizer used in the second embodiment of the present technology is not particularly limited, and is preferably a chlorine stabilizer that generates a combined chlorine agent by reaction with an oxidizing agent (preferably an inorganic chlorine agent).
Examples of the chlorine stabilizer include any of a compound having a primary amino group, ammonia, and an ammonium salt (hereinafter, these are also referred to as "NH" 2 A compound) and the like, and one or two or more selected from these can be used.
The compound having a primary amino group is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, sulfamic acid, sulfanilic acid, sulfamoylbenzoic acid, amino acids, and the like, and one or two or more selected from the group consisting of these may be used.
Examples of the ammonium salt include ammonium chloride and ammonium sulfate, and one or two or more selected from the group consisting of these salts can be used.
More specifically, examples of the chlorine stabilizer include sulfamic acid compounds; isocyanuric acid; hydantoin compounds such as 5,5' -dimethylhydantoin, urea, biuret, methyl carbamate, ethyl carbamate, acetamide, nicotinamide, methanesulfonamide, and toluenesulfonamide; imide compounds such as maleimide, succinimide, and phthalimide; amino acids such as glycine, alanine, histidine, and lysine; amine compounds such as methylamine, hydroxylamine, morpholine, piperazine, imidazole, histamine, and the like; ammonia; ammonium salts such as ammonium sulfate, and one or two or more selected from the group consisting of these may be used.
Among the chlorine stabilizers, sulfamic acid compounds are preferable from the viewpoint of environmental load and the like, and examples of the sulfamic acid compounds include sulfamic acid, sulfamic acid derivatives, and salts thereof, and one or two or more selected from the group consisting of these can be used.
The chlorine stabilizer (preferably NH) 2 A compound of the series), sulfamic acid (more preferably NH) 2 SO 2 OH). The use of sulfamic acid to form monochlorosulfamic acid is preferred because it results in a stable chloramine compound.
The sulfamic acid compound may be a compound represented by the general formula [1] or a salt thereof according to the first embodiment of the present technology.
The salt of the compound used in the stabilizer is not particularly limited, and the "salt of the compound used in the first embodiment of the present technology" described above may be used. Among them, alkali metal salts (preferably sodium) are preferable from the viewpoint of cost and ease of handling.
The sulfamic acid compound used in the second embodiment of the present technology is not particularly limited, and the "sulfamic acid compound used in the first embodiment of the present technology" described above may be used.
Among the above stabilizers, sulfamates are more preferable.
< 3-2-1 (c) bromide salt >)
The bromide salt used in the second embodiment of the present technology is not particularly limited, and the "bromide salt used in the first embodiment of the present technology" described above may be employed.
The alkali metal bromide and the amine bromide salt used in the second embodiment of the present technology are not particularly limited, and the "alkali metal bromide salt" and the "amine bromide salt" used in the first embodiment of the present technology may be used.
The mode of the bromide salt when mixed into the solution may be either a chloride solution state or a powder chloride salt state, but from the viewpoint of increasing the concentration of the active ingredient, it is preferable to use powder bromide.
< 3-2-1 (d) oxidizer >
The oxidizing agent used in the second embodiment of the present technology is not particularly limited, but a halogen-based oxidizing agent is preferable, and the halogen-based oxidizing agent is not particularly limited, and a chlorine-based oxidizing agent is preferable from the viewpoint that a chloramine compound can be obtained from the chlorine-based oxidizing agent and the chlorine-based stabilizer.
The chlorine-based oxidizing agent used in the second embodiment of the present technology is not particularly limited, and examples thereof include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, and chloroisocyanuric acid or a salt thereof, and one or two or more selected from the group consisting of these can be used.
Specific examples of the salt-form substance include, but are not particularly limited to: alkali metal hypochlorite such as sodium hypochlorite and potassium hypochlorite; alkaline earth metal hypochlorous acid salts such as calcium hypochlorite and barium hypochlorite; alkali metal chlorites such as sodium chlorite and potassium chlorite; alkaline earth metal chlorites such as barium chlorite; other chlorous acid metal salts such as nickel chlorous acid; alkali metal chlorate salts such as ammonium chlorate, sodium chlorate and potassium chlorate; alkali earth metal chlorate such as calcium chlorate and barium chlorate, and one or two or more selected from the group consisting of these may be used.
Among the chlorine-based oxidizing agents, one or more selected from the group consisting of hypochlorite, chlorine dioxide, and chlorine gas are preferable, and among them, hypochlorite is more preferable from the viewpoint of easy handling.
< 3-2-2. Method for producing Water treatment agent according to the second embodiment of the present technology >
In the method for producing the water treatment agent according to the second embodiment of the present technology, it is preferable that at least a mixed solution (hereinafter also referred to as "three-agent mixed solution") in which an alkaline agent, a stabilizer, and a bromide salt are mixed is mixed with an oxidizing agent. Further, it is more preferable to add an oxidizing agent to the mixed solution of the three drugs and mix them. The mixing of the oxidizing agent can be performed by referring to < 3-2-2-2. The oxidizing agent mixing step > described later.
Example 1 of the second embodiment of the production method of the present technology preferably includes at least a step of mixing an oxidizing agent in a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed. The step of mixing the oxidizing agent can be performed in the same manner as < 3-2-2-2. The oxidizing agent mixing step > described later.
The above three drug mixed solutions may be prepared in advance, or may be prepared in the same manufacturing line or in different manufacturing lines. The three-agent mixed solution can be prepared by using, for example, < 3-2-2-1 described below, as the solution prepared in the step > of mixing the mixed solution of the alkali agent, the stabilizer and the bromide salt.
In view of the quality stability of the water treatment agent, it is more preferable that the water treatment agent is obtained by mixing three agents and then rapidly mixing an oxidizing agent into the mixed solution of the three agents.
In addition, from the viewpoint of work efficiency and easy adjustment of the effective components in the water treatment agent, example 2 of the second embodiment of the production method of the present technology more preferably includes a step of preparing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed, and a step of mixing an oxidizing agent in the mixed solution of the three agents.
The solvent of the solution used in the second embodiment of the present technology is not particularly limited as long as it can dissolve the alkaline agent, the stabilizer, the bromide salt and the oxidizing agent, and water is preferable from the viewpoints of safety, operability and cost. Other solvents may be contained in the water within a range that does not impair the effects of the present technology, and it is preferable that 99% or more of the solvents be water. Examples of the other solvents include hydrophilic organic solvents such as glycols (e.g., ethylene glycol, diethylene glycol, etc.), glycol ethers (e.g., diethylene glycol monomethyl ether, etc.), ethylene glycol dimethyl ethers (glyme), ketones, esters (e.g., methyl acetate, etc.), alcohols (e.g., ethanol, aminoethanol, etc.), amides (e.g., N-dimethylacetamide, etc.), etc., and among them, glycols, glycol ethers, esters, alcohols are preferable. One or two or more selected from the group consisting of these may be used.
In the production method according to the second embodiment of the present technology, the amount of the solvent (preferably water) to be mixed is not particularly limited, but in the water treatment agent according to the second embodiment, the solvent is preferably mixed so as to be 5 to 50% by mass, more preferably 10 to 40% by mass.
The production conditions of the production method according to the second embodiment of the present technology may be carried out with reference to known production conditions, and may be carried out in batch or continuous steps, or may be carried out at a temperature of about 4 to 40 ℃.
An example of the method for producing the water treatment agent according to the second embodiment of the present technology will be described below using the method for producing example 2 of the embodiment of the present technology, but the method for producing the water treatment agent according to the second embodiment of the present technology is not limited to this description. In addition, the manufacturing method according to the second embodiment of the present technology can omit the step of preparing a mixed solution of three kinds of drugs.
The method for producing example 2 according to the second embodiment of the present technology includes a step of preparing a mixed solution of three chemicals, and a step of mixing an oxidizing agent into the mixed solution.
< 3-2-2-1. Process for preparing a Mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed >
In the "step of preparing a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed" (hereinafter, also referred to as "three-agent mixed solution preparation step") in the production of the second embodiment of the present technology, the order of mixing the components of the alkaline agent, the stabilizer, and the bromide salt is not particularly limited.
The three-agent mixed solution according to the second embodiment of the present technology can be obtained by adding and mixing three agents, i.e., an alkali agent, a stabilizer, and a bromide salt, at the same time or separately. More specifically, the three medicines may be added sequentially, or the two medicines may be mixed and then the remaining medicines may be mixed, or the three medicines may be mixed at the same time.
When the above three drugs are added in this order, examples thereof include (1) the order of the alkali agent, the stabilizer, and the bromide salt, (2) the order of the alkali agent, the bromide salt, and the stabilizer, (3) the order of the stabilizer, the bromide salt, and the alkali agent, (4) the order of the stabilizer, the alkali agent, and the bromide salt, (5) the order of the bromide salt, the stabilizer, and the alkali agent, and (6) the order of the bromide salt, the alkali agent, and the stabilizer.
In the three-agent mixing preparation step according to the second embodiment of the present technology, it is preferable that an alkaline agent is initially mixed in a solution. As described later, the pH of the solution can be adjusted to an alkaline region by an alkaline agent, specifically, preferably 11 or more, more preferably 12 or more, and still more preferably 13 or more. By making the solution an alkaline region, the quality stability of each drug mixed in the solution is also good.
By sequentially or suitably compounding chemicals in a solution adjusted to an alkaline region, a water treatment agent having excellent quality stability can be obtained.
In the three-agent mixing preparation step according to the second embodiment of the present technology, it is more preferable to mix the alkali agent, the stabilizer and the bromide salt in this order, or to mix the alkali agent, the bromide salt and the stabilizer in this order.
The treatment temperature in the step of preparing the three-drug mixed solution according to the second embodiment of the present technology is not particularly limited, and the step may be performed at a temperature of about 4 to 40 ℃. In the mixing mechanism in the three-drug mixed solution preparation step, a known mechanism (for example, a stirring mechanism) that can mix each drug with a solution can be used.
In view of maintaining the quality stability of the chemical agent of the water treatment agent according to the second embodiment of the present technology, it is desirable that the pH of the three chemical agent mixed solution prepared above is adjusted by the alkali agent. The pH of the three-agent mixed solution is more preferably 10 or more, still more preferably 11 or more, still more preferably 12 or more, and particularly preferably 13 or more. By adjusting the pH of the mixed solution of the three agents in this way, the pH of the finally obtained water treatment agent according to the second embodiment of the present technology can be brought into the alkaline region, and the effect of the active ingredient of the water treatment agent according to the second embodiment of the present technology can be exhibited satisfactorily. In addition, an alkali agent may be suitably added to adjust the pH of the water treatment agent of the second embodiment within a range that does not impair the effects of the present technology.
In addition, from the viewpoint of maintaining the quality stability of the chemical agent of the water treatment agent according to the second embodiment of the present technology, the concentrations of the stabilizer and bromide salt contained in the three chemical agent mixed solution prepared above can be adjusted by the following compounding amounts.
The compounding amount of the stabilizer (preferably, chlorine-based stabilizer) used in the preparation of the above-mentioned three-drug mixed solution is not particularly limited, but is preferably 5% to 80%, more preferably 10% to 70%, and still more preferably 16% to 60% of the above-mentioned three-drug mixed solution.
The compounding amount of the stabilizer (preferably, chlorine-based stabilizer) used in the preparation of the above-described three-agent mixed solution is not particularly limited. In the case where the oxidizing agent is an inorganic chlorine agent, from the viewpoint of sufficient reactivity of these, 1 mol to 5 mol, more preferably 1 mol to 4 mol, and still more preferably 1.2 mol to 3 mol, relative to 1 mol of the oxidizing component contained in the inorganic chlorine agent. Thus, the active ingredient can be maintained well even in the case of the single-liquid water treatment agent.
The mixing amount of the bromide salt used for the preparation of the three-agent mixed solution is not particularly limited, but is preferably 3% to 50%, more preferably 6% to 40%, and still more preferably 12% to 30% of the three-agent mixed solution.
< 3-2-2-2. Oxidant mixing procedure >)
In the "step of mixing an oxidizing agent with the three-agent mixed solution" (hereinafter also referred to as "oxidizing agent mixing step") in the production of the second embodiment of the present technology, an oxidizing agent is mixed with the solution prepared in the aforementioned step and mixed with an alkaline agent, a stabilizer and a bromide salt. Thus, a mixed solution of four kinds of agents can be obtained.
When the four agents are mixed, the stabilizer and the oxidizing agent react to form a halamine compound (preferably a chloramine compound), and a water treatment agent containing the halamine compound (preferably a chloramine compound) and a bromide salt can be prepared in a basic region.
The amount of the oxidizing agent to be mixed in the three-agent mixed solution is not particularly limited, but is preferably 20% to 55%, more preferably 30% to 55%, and even more preferably 40% to 50% of the four-agent mixed solution.
The mixing mass ratio of the three-agent mixed solution and the oxidizing agent is not particularly limited, but the oxidizing agent is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, relative to the three-agent mixed solution 1.
The water treatment agent obtained by the method according to the second embodiment of the present technology exhibits excellent hypobromous acid effect when added to a water system, and has excellent quality stability. Further, the single-liquid type drug obtained by the production method can exhibit the target effect and maintain the constant quality even when stored for a long period of time in the single-liquid type state.
The water treatment agent obtained by the production method according to the second embodiment of the present technology contains an alkaline agent, a haloamine compound (preferably a chloramine compound), and a bromide salt, and has a total chlorine detection rate (%) of 95% or more and/or a free chlorine concentration of 0.05% of the total chlorine concentration (in Cl 2 Meter) below, can be maintained for a long period of time, and can suppress the decrease in the concentration of the active ingredient after production.
The content of the stabilizer in the water treatment agent of the second embodiment of the present technology is adjusted to: the lower limit is preferably 3% or more, more preferably 5% or more, still more preferably 8% or more, and the upper limit is preferably 40% or less, more preferably 35% or less, still more preferably 30% or less, still more preferably 5% to 35%, still more preferably 8% to 30%.
The content of bromide salt in the water treatment agent of the second embodiment of the present technology is adjusted to: the lower limit is preferably 1% or more, more preferably 3% or more, further preferably 6% or more, and the upper limit is preferably 25% or less, more preferably 20% or less, further preferably 15% or less, further preferably 3% to 20%, further preferably 6% to 15%.
The content of the oxidizing agent in the water treatment agent of the second embodiment of the present technology is adjusted to: the lower limit is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and the upper limit is preferably 60% or less, more preferably 55% or less, further preferably 50% or less, further preferably 30% to 55%, further preferably 40% to 50%.
The "total chlorine detection rate (%)" in the water treatment agent according to the second embodiment is more preferably 96% or more, still more preferably 97% or more, and still more preferably 97.5% or more.
The "content of free chlorine in total chlorine concentration (% (in Cl) in the water treatment agent of the second embodiment" is described above 2 More preferably 0.05% or less, still more preferably 0.04% or less).
"Total chlorine concentration (% in Cl)" when the water treatment agent of the second embodiment is used 2 "by weight)" is more preferably 4.1% or more, still more preferably 4.2% or more, and still more preferably 4.3% or more. In the case of the production method according to the second embodiment of the present technology, the total chlorine concentration (% in Cl) in the water treatment agent according to the second embodiment is considered 2 To 4.4% to 4.7%, and thus, as the upper limit value thereof, 4.7% or less, 4.6% or less, 4.5% or less, or 4.4% or less can be obtained.
In addition, from the viewpoint of reducing the decomposition of the active ingredient and adding it to the water system with good efficiency, the water treatment agent according to the second embodiment of the present technology has a total chlorine detection rate (%) and a total chlorine concentration (% is Cl) 2 Meter), and the content of free chlorine in the total chlorine concentration is preferably a concentration from after production to 4 hours of storage, more preferably from after production to 1 hour of storage. The water treatment agent according to the second embodiment of the present technology is not used immediately after 0 hours after production, and has a high and stable total chlorine detection rate and total chlorine concentration from about 4 hours after production. Therefore, even if the water treatment agent production apparatus is not provided near the site of water addition, handling such as transportation is possible. In addition, in the case of the water treatment agent obtained by the production method according to the second embodiment of the present technology, the total chlorine detection rate (%) and the total chlorine concentration (% in Cl) in the water treatment agent can be suppressed about 3 months after production 2 Meter), and can suppress a sharp increase in the free chlorine concentration in the total chlorine concentration.
The storage conditions in storing the water treatment agent according to the second embodiment of the present technology after production are not particularly limited, but it is preferably normal temperature storage or normal temperature dark storage, and more preferably temperature management at about 4 to 40 ℃.
The water treatment agent according to the second embodiment obtained by the production method according to the second embodiment of the present technology can be distributed on the market at a normal temperature of about 4 to 40 ℃, and can suppress a decrease in the concentration of the active ingredient even when stored at a normal temperature for a long period of time (for example, about 3 months after production). In addition, the water treatment agent according to the second embodiment of the present technology can provide a product with stable quality by suppressing hypochlorous acid formation in the water treatment agent according to the second embodiment, and reducing the decrease in the concentration of the active ingredient, since a concentrated bromide solution is not formed during the mixing in the production process.
The water treatment agent obtained by the production method according to the second embodiment of the present technology has a high total chlorine concentration and a low free chlorine concentration equal to or less than those of the water treatment agent of patent document 2 or the water treatment agent of patent document 3 after production, and can exhibit a good target effect and is excellent in quality stability of the agent.
In the present technology, the quality stability of a drug means that an active ingredient in the drug is hardly decomposed during a period in which the drug is stored and fixed, and the concentration of the active ingredient is maintained within a certain range. More specifically, it is desirable that hypochlorous acid is difficult to be generated in the pharmaceutical preparation and the decrease in the concentration of the active ingredient is small.
In the water treatment agent according to the second embodiment of the present technology, the molar ratio of the chloramine compound to the bromide salt is preferably adjusted, and when the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt is preferably 1:0.05 to 3.0, more preferably 1:0.1 to 1.5, more preferably 1:0.1 to 1.0, more preferably 1:0.2 to 1.0. In the method for producing the water treatment agent according to the second embodiment of the present technology, the molar ratio may be suitably adjusted.
With the water treatment agent according to the second embodiment of the present technology, the quality stability of the agent is excellent, and when the agent is added to a water system, the effect of hypochlorous acid can be favorably exhibited based on the alkali agent, the haloamine compound (preferably, chloramine compound), and the bromide salt in the agent. Further, the water treatment agent according to the second embodiment of the present technology can gradually generate hypobromous acid in the water system over time, and thus can maintain the effect of hypobromous acid in the water system for a longer period of time.
Another aspect of the water treatment agent according to the second embodiment of the present technology is a one-pack agent, and can also be used as a slow release water treatment agent. If hypobromous acid is rapidly released in the water system, corrosion or degradation in the water system is likely to occur, but the water treatment agent according to the second embodiment of the present technology can be controlled so as to slow down the rate of generation of hypobromous acid, and thus corrosion or degradation in the water system can be reduced, and the effect (e.g., sterilization effect, etc.) caused by hypobromous acid can be obtained continuously over a long period of time. Therefore, the water treatment agent according to the second embodiment of the present technology is more advantageously applied to an open circulation type device or the like having a cooling water system, a heat storage water system, a dust collection water system, a scrubber water system, or the like.
< 3-2-3. Any component of the second embodiment of the present technology >
In any of the steps of producing the water treatment agent according to the second embodiment of the present technology, any chemical agent as any component may be mixed within a range that does not impair the effects of the present technology.
Examples of the optional chemical include, but are not limited to, corrosion inhibitors (corrosion inhibitors), scale inhibitors, slime control agents, solvents or dispersion media such as water, dispersant enzymes, bactericides, and defoamers, and various chemical agents generally used for water treatment may be used. One or two or more selected from the group consisting of these may be used. Any of the agents described in the first embodiment can be suitably used.
Corrosion inhibitor
The corrosion inhibitor (corrosion inhibitor) is not particularly limited, but is preferably a corrosion inhibitor for cooling water systems. For example, a polymer such as a carboxyl polymer is preferable; and azoles such as benzotriazole and tolyltriazole.
The type of the carboxyl polymer is not particularly limited, and examples thereof include water-soluble homopolymers and/or copolymers having a carboxyl group, and more specifically, examples thereof include maleic acid polymers and (meth) acrylic acid polymers. The term "polymer" means a polymer or copolymer containing monomers.
More specifically, examples of the carboxyl polymer include a maleic acid homopolymer, a (meth) acrylic acid homopolymer, and a copolymer of an unsaturated monomer copolymerizable with maleic acid or (meth) acrylic acid, and two or more kinds selected from the group consisting of these may be used.
The carboxyl polymer in the second embodiment of the present technology preferably contains a maleic acid-based polymer and/or a (meth) acrylic polymer. The content (content) of the maleic acid-based polymer and/or the (meth) acrylic acid-based polymer in the carboxyl polymer is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more, and the desired effect of the present technology can be easily obtained when the content of the carboxyl polymer is high.
Examples of the unsaturated monomer copolymerizable with the monomer of maleic acid or (meth) acrylic acid include 2-acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-aryloxy-1-propanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, acrylamide, ethylene, propylene, isopropene, butene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene, isooctene, vinyl alcohol, vinylmethyl ether, and vinylethyl ether, and salts thereof.
One or more polymers selected from the group consisting of homopolymers, copolymers of the foregoing monomers with isobutylene, and the like, obtained by using one or more monomers selected from the group consisting of these monomers, are exemplified.
In order to expect a pharmaceutical effect such as an anticorrosive effect, the weight average molecular weight of the carboxyl polymer is preferably in the range of from 3 to 4 power of 10, more specifically, in the range of from 200 to 50000, more preferably in the range of from 500 to 30000, still more preferably in the range of from 800 to 30000, and still more preferably in the range of from 1000 to 20000.
The carboxyl polymer may be the carboxyl polymer used in the first embodiment of the present technology and the amount used. Further, in the second embodiment, the mixture solution in which the alkali agent, the stabilizer and the bromide salt are mixed with the oxidizing agent is preferably a mixture containing a chloramine compound and a bromide salt, and more preferably the mixture is mixed with the carboxyl polymer to provide the water treatment agent or the water treatment agent kit using the components (a) to (c) of the first embodiment. In addition to the effects of the second embodiment of the present technology, as shown in the first embodiment of the present technology, a single-liquid water treatment technology in which the chemical effects of other compounds can be more favorably exerted can be provided.
The method for measuring the weight average molecular weight of the water-soluble polymer in the second embodiment can be carried out in the same manner as the method for measuring the weight average molecular weight of the water-soluble polymer described in the first embodiment.
< antiscaling agent >)
The scale inhibitor used in the second embodiment of the present technology is not particularly limited, and the scale inhibitor used in the first embodiment of the present technology described above may be used.
The content of the anticorrosive and/or antiscalant in the water treatment agent according to the second embodiment of the present technology is not particularly limited, but is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass.
< 3-3. Method for Using the Water treatment agent according to the second embodiment of the present technology and method for Water treatment Using the Water treatment agent >)
The water treatment agent according to the second embodiment of the present technology is expected to have the effect of hypobromous acid (for example, a sterilization effect, a slime control effect, etc.) as described above, and is used as at least one of slime control, corrosion protection, scale control, etc.
The second embodiment of the present technology can provide the use or the use method of the water treatment agent of the second embodiment of the present technology, and examples of the purpose of the use include water treatment in a water system, a sterilization method in a water system, a slime control method in a water system, an anti-corrosion method in a water system, and a film scale prevention method in a water system.
The second embodiment of the present technology can also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scaling method in which the water treatment agent of the second embodiment of the present technology is added to a water system. The configuration repeated with the configuration described in the water treatment agent of the present technology is preferably omitted.
In terms of stability over time, the pH of the aqueous system in the method according to the second embodiment of the present technology is in the alkaline region, more preferably 7 to 10, and still more preferably 8 to 9. The water temperature of the water system is not particularly limited, and generally about 4 to 40 ℃.
The amount of the water treatment agent according to the second embodiment of the present technology to be added to the water system is not particularly limited, and may be appropriately adjusted according to the respective water systems to be treated, but is usually preferably added continuously or intermittently at a concentration of 1mg/L to 1000mg/L to the respective water systems to be treated.
In the second embodiment of the present technology, the timing of adding the chemical agent or each component in the water system is not particularly limited, and the chemical agent or each component may be added at the same timing or separately. And/or the site of adding the chemical or each component in the water system is not particularly limited, and may be added to the same site or different sites.
For example, in the case of the purpose of use for controlling the slime of the membrane or preventing scale, it is preferable to add a chemical before the membrane treatment. In addition, the present technology can be used to control, sterilize, and prevent corrosion of slime such as piping in a water system, and the effect of the present technology can be obtained at any time and any place in the water system.
The object of the second embodiment of the present technology is preferably a cooling water system, and more preferably the cooling water system is a cooling water system provided with a metal or metal pipe such as a cooling tank, a cooling tower, a heat exchanger, or the like.
In the second embodiment of the present technology, the present invention can be used as a water treatment agent kit including the water treatment agent of the second embodiment of the present technology and any component.
For example, a water treatment agent kit or the like may be provided having: a mixture containing (a) a chloramine compound and (b) a bromide salt, which is contained in one container a and obtained by the method for producing a water treatment agent according to the second embodiment; and a carboxyl polymer having a carboxyl content of 0.8 g-COOH/g-polymer or less in the polymer (c) contained in one container B, wherein the carboxyl polymer is 1 to 18% by mass and has a pH of 10 or more when these are mixed.
In the case of the water treatment agent kit, the components may be contained in different containers, or the two components may be mixed with one component and contained in different containers. In addition, any component may be appropriately mixed in each container. The use or method of the water treatment agent kit may be performed in the same manner as the use or method of the water treatment agent described above.
The present technology may also employ the following configuration.
[1] A water treatment agent comprising the following components (a) to (c) and having a pH of 10 or more:
(a) Chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content of the polymer is from 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
[2] the water treatment agent according to the aforementioned [1], wherein the molar ratio of the chloramine compound to the bromide salt is 1:0.1 to 1.0.
The water treatment agent according to [3] or [2], wherein the water treatment agent is at least one of slime control, corrosion protection and scale control.
The water treatment agent according to any one of the above [1] to [3], wherein the water treatment agent is obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
·[5]According to the above [1]]～[4]The water treatment agent according to any one of the above, wherein the water treatment agent has a total chlorine detection rate of 95% or more and a free chlorine content of 0.05% in total chlorine concentration (in Cl) 2 Meter) is as follows.
The water treatment agent according to any one of the above [1] to [5], wherein the carboxyl polymer contains a maleic acid-based polymer and/or a (meth) acrylic acid-based polymer, and preferably 50 mass% or more of the carboxyl polymer.
The water treatment agent according to any one of the above [1] to [6], wherein the pH of the water treatment agent is 13 or more.
The water treatment agent according to any one of the above [1] to [7], wherein the bromide salt is one or more selected from the group consisting of alkali metal bromide salts, ammonium bromide salts, hydrobromic acid and amine bromide salts.
[9] A water treatment method, a sterilization method, a slime control method, an anti-corrosion method or an anti-scale method, wherein the water treatment agent according to any one of the above [1] to [8] is added to a water system.
The method according to [9] above, wherein the water treatment agent is added to the water system so that the concentration of carboxyl groups in the water system is 1mg/L to 100 mg/L.
[11] A water treatment method, a sterilization method, a slime control method, an anti-corrosion method or an anti-scale method, wherein the following components (a) to (c) are added to a water system at the same or different times and/or at the same or different places:
(a) Chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content of the polymer is from 1 to 18% by mass of the carboxyl polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
The method according to any one of the preceding [10] to [12], wherein the molar ratio of the chloramine compound of the component (a) to the bromide salt of the component (b) is 1:0.1 to 1.0, and/or adding the component (c) so that the concentration of carboxyl groups in the water system becomes 5mg/L to 50 mg/L.
The method according to any one of [9] to [12], wherein the water system is a cooling water system, and preferably the cooling water system is a cooling water system comprising a metal or metal pipe such as a cooling tank, a cooling tower, a heat exchanger, or the like.
The present technology may also employ the following configuration.
[14] A method for producing a water treatment agent, characterized by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent. Preferably, an oxidizing agent is added to the mixed solution and mixed.
The method for producing a water treatment agent according to [15] above, wherein the stabilizer is a sulfamic acid compound. Preferably, the sulfamic acid compound is a compound represented by the general formula (1) or a salt thereof. Among them, sulfamic acid or a salt thereof is more preferable.
The method for producing a water treatment agent according to [14] or [15], wherein the oxidizing agent is a chlorine-based oxidizing agent. The chlorine-based oxidizing agent is preferably one or more selected from hypochlorite, chlorine dioxide and chlorine gas.
The method for producing a water treatment agent according to any one of [14] to [16], wherein the pH of the mixed solution is 12 or more (preferably 13 or more). When the oxidizing agent is mixed, the pH of the mixed solution is preferably adjusted.
The method for producing a water treatment agent according to any one of [14] to [17], wherein the mixed solution is a solution in which a powdery bromide salt is mixed as the bromide salt.
The method for producing a water treatment agent according to any one of [14] to [18], wherein 1 to 18% by mass of a carboxyl polymer having a carboxyl content of 0.8 g-COOH/g-polymer or less is further mixed. Preferably, the mixture is further mixed with the carboxyl polymer.
The method for producing a water treatment agent according to any one of [14] to [19], wherein the solution in which the alkali agent, the stabilizer and the bromide salt are mixed is a solution obtained by mixing the alkali agent into the solution and then mixing the stabilizer and/or the bromide salt at the same time or separately.
The method for producing a water treatment agent according to any one of [14] to [20], wherein when the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt in the water treatment agent is adjusted to 1:0.05 to 3.0.
[22] A water treatment agent obtained by a method for producing the water treatment agent according to any one of [14] to [21 ]. Preferably, the water treatment agent contains an alkaline agent, a haloamine compound (preferably a chloramine compound), and a bromide salt.
·[23]A water treatment agent comprising an alkaline agent, a chloramine compound and a bromide salt, wherein the total chlorine detection rate after production is 95% or more and the free chlorine content in the total chlorine concentration is 0.05% (in Cl) 2 Meter) is as follows. Further, the total chlorine concentration after production is preferably 4.1% (in Cl) 2 Meter) above.
The water treatment agent according to [24] above, wherein the water treatment agent is obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
The water treatment agent according to any one of [22] to [24], wherein the water treatment agent is further blended to form 1 to 18% by mass of a carboxyl polymer, and the carboxyl content of the carboxyl polymer is 0.8 g-COOH/g-polymer or less.
The carboxyl polymer preferably contains a maleic acid polymer and/or a (meth) acrylic polymer, and more preferably contains 50 mass% or more of the carboxyl polymer.
The water treatment agent according to any one of the above [21] to [24], wherein the pH of the water treatment agent is 13 or more.
The water treatment agent according to any one of the above [21] to [26], wherein the water treatment agent is a sustained release preparation of hypobromous acid.
A water treatment agent according to any one of the above [21] to [27], which further contains an anticorrosive agent and/or an antiscaling agent. Preferably, the anticorrosive and/or antiscalant is contained in an amount of 0.5 to 30 mass%.
[29] A water treatment method, a sterilization method, a slime control method, an anti-corrosion method or an anti-scale method, wherein the water treatment agent obtained by the method for producing a water treatment agent according to any one of [14] to [21] or the water treatment agent according to any one of [22] to [28] is added to a water system.
Preferably applied to a water treatment device. The present invention is applicable to an open circulation type device having a cooling water system, a heat storage water system, a dust collection water system, a washing tower water system, and the like.
The water treatment agent is preferably added continuously or intermittently to each water system to be treated at a concentration of 1mg/L to 1000 mg/L.
[30] A water treatment apparatus or water treatment system comprising an apparatus or system for adding a water treatment agent or components used in the water treatment agent,
the water treatment agent according to any one of the above [1] to [14], and the water treatment agent according to any one of the above [23] to [28 ].
The water treatment device or water treatment system may in turn also comprise a device or system for storage and/or may also comprise a device or piping or system for mixing. Further, a control device or a control system for controlling the method according to any one of the above [9] to [13] and/or the method according to the above [29] may be included.
The components used in the water treatment agent according to any one of [1] to [14] and the components used in the water treatment agent according to any one of [22] to [28] may be suitably mixed and used. The hypobromous acid effect can also be exerted by adding the water treatment agent in a state in which the components are mixed to form the water treatment agent to the water system. The hypobromous acid effect can be also exerted by adding the components to the water system at the same time or sequentially and mixing the components in the water system.
Examples
The following test examples, comparative examples, and the like are given to illustrate embodiments of the present technology. The scope of the present technology is not limited to the test examples, and the like.
Test example 1 to test example 28 (first embodiment)
Test example 1 to test example 4: combination of the components: sample 1 to sample 4
In FIG. 1, samples 1 to 4 were added to open-loop cooling water (pH 8 to 9) so that the sample (water treatment agent) became 0.8 g/L, and the change with time of the total oxidant concentration in the water system was shown.
The water treatment agent (x) of sample 1 in test example 1 contained chloramine compound concentration 9%.
The water treatment agent (. DELTA.) of sample 2 in test example 2 contained chloramine compound concentration 9% and bromide concentration 3.9%.
The water treatment agent (≡) of sample 3 in test example 3 contained chloramine compound at 9% and carboxyl polymer at 1.6%.
The water treatment agent (o) of sample 4 in test example 4 contained chloramine compound at 9%, carboxyl polymer at 1.6%, bromide at 3.9% and had a pH of 13.
The chloramine compounds used in test examples 1 to 28 were prepared by reacting hypochlorous acid and sulfamic acid (HN 2 SO 2 OH) reaction with Cl 2 The molar ratio of N is 0.1-1.
The bromide salt used in test examples 1 to 28 was potassium bromide.
The carboxyl polymer used in test examples 1 to 4 was a maleic acid polymer (99 mass% or more), the carboxyl content of the polymer was 0.77 g-COOH/g-polymer, and the weight average molecular weight of the carboxyl polymer was 3900.
The content of carboxyl groups in the carboxyl group polymer was measured by the above-mentioned < method for measuring the content of carboxyl groups (g-COOH/g-polymer) > as described above.
The weight average molecular weight of the carboxyl polymer was determined by the above-mentioned method for determining weight average molecular weight of the < water-soluble polymer >.
The measurement methods used in each test example are as follows.
< total oxidant concentration >: the total of chloramine, hypochlorous acid, and hypobromous acid was measured using the DPD total (total) reagent. Total oxidant concentration in mg/L in Cl in terms of chlorine conversion 2 And (3) meter representation.
< hypobromous acid >: after reacting free chlorine with glycine, residual hypobromous acid was measured using DPD free (free) reagent. The concentration of hypobromous acid is calculated in terms of chlorine, in mg/L and in Cl 2 And (3) meter representation.
The DPD method used in the present technology is performed according to the DPD method using N, N-diethyl-1, 4-phenylenediamine in JIS K0400-33-10:1999.
Fig. 1 shows the change with time of the total oxidant concentration when the concentration of the chloramine compound alone was 100% and the carboxyl polymer and bromide were allowed to coexist.
When the carboxyl polymer and the bromide are added to the chloramine compound, no difference in the residual ratio is observed, but when both the carboxyl polymer and the bromide are added to the chloramine compound, the residual ratio is reduced by 10% or more.
When only chloramine compound is present together with brominating agent and carboxyl polymer, the residual rate is significantly reduced, and thus it is considered that hypobromous acid generated in the aqueous system reacts with carboxyl polymer and is decomposed.
Thus, the pharmacological effect of the carboxyl polymer can be expected in the water treatment agent of sample 4. However, sample 4 is designed to use hypobromous acid stronger than hypochlorous acid, but sample 4 is not so good in temporal stability of hypobromous acid in a water system, and thus it is considered that the effect (for example, a sterilization effect or the like) of hypobromous acid is also lacking in persistence. Therefore, in sample 4, it is considered that it is difficult to provide a single-liquid water treatment agent that exhibits excellent hypobromous acid effect when added to water and also exhibits excellent chemical effect of other compounds.
Test example 5 to test example 16: carboxyl group content of carboxyl Polymer
The water treatment agents used in test examples 5 to 16 each contained 9% of chloramine compound, 1.6% of carboxyl polymer and 3.9% of bromide, and were prepared using a pH13 water treatment agent as a raw material.
The carboxyl polymer used in each of the water treatment agents used in test examples 5 to 16 was maleic acid polymer, and a polymer having a weight average molecular weight in the range of 1000 to 16000 was used.
In this case, the carboxyl polymers of the respective water treatment agents were used as the carboxyl polymers shown in tables 1 and 2, and the carboxyl content (g-COOH/g-polymer) was as shown in the following.
Specifically, the carboxyl group content of the carboxyl polymer in each of the water treatment agents of test examples 5 to 16 was measured, and as a result, test examples 5 and 11:0.63 g-COOH/g-polymer, test example 6 and 12:0.43 g-COOH/g-polymer, test example 7 and 13:0.49 g-COOH/g-polymer, test example 8 and 14:0.52 g-COOH/g-polymer, test example 9 and 15:0.71 g-COOH/g-polymer, test example 10 and 16:0.77 g-COOH/g-polymer.
Further, each water treatment agent was prepared so that the concentration of the carboxyl polymer in the water treatment agent became 5 mg-polymer/L when added to 1L of water, and was used in each of test examples 5 to 10.
The water treatment agents were prepared so that the concentration of the carboxyl polymer in the water treatment agent became 30 mg-polymer/L when added to 1L of water, and were used in test examples 11 to 16, respectively.
Assuming that the chloramine compound is 1, the mole ratio of the chloramine compound to the bromide salt of each of the water treatment agents used in test examples 5 to 16 is 1:0.2 to 1.0.
In test examples 5 to 10, each water treatment agent was added to open-loop cooling water (pH 8 to 9) so that the concentration of the carboxyl polymer became 5 mg-polymer/L, and the concentration of hypobromous acid (mg/L, cl) in the water system after 48 hours was measured 2 Meter). The results are shown in FIG. 2 and Table 1.
In test examples 11 to 16, each water treatment agent was added to open-loop cooling water (pH 8 to 9) so that the concentration of the carboxyl polymer became 30 mg-polymer/L, and the concentration of hypobromous acid (mg/L, cl) in the water system after 48 hours was measured 2 Meter). The results are shown in FIG. 3 and Table 2.
TABLE 1
TABLE 1
TABLE 2
TABLE 2
Test example 17 to test example 27: concentration of carboxyl Polymer in aqueous System
The water treatment agent used in test example 5 was changed to the concentration of the carboxyl polymer in the water system shown in table 3, and each of the water treatment agents used in test examples 17 to 29 was obtained.
In test examples 17 to 27, water treatment agents were added to the open-loop cooling water (pH 8 to 9) so as to obtain the concentration of the carboxyl polymer (mg-polymer/L) in the aqueous system of Table 3. After the addition of each water treatment agent, the concentration of hypobromous acid (mg/L, cl) in the water system after 48 hours was measured 2 Meter). The results are shown in FIG. 4 and Table 3.
TABLE 3
TABLE 3 Table 3
< nodule >
The results of test examples 5 to 16 are shown in fig. 2 and 3, and tables 1 and 2. The results of test examples 17 to 27 are shown in fig. 4 and table 3.
When the carboxyl group content of the carboxyl group polymer used in the water treatment agent is 0.77, the hypobromous acid concentration of the added water system can be maintained at about 80%. Further, the carboxyl group content in the polymer is more preferably 0.35 to 0.75, from the viewpoint that the concentration of hypobromous acid in the water system to be added can be 90% or more.
When the concentration of the carboxyl polymer in the water system is 5 mg-polymer/L to 30 mg-polymer/L, the total oxidizing agent concentration (%) and the hypobromous acid concentration (%) in the water system are high and good.
Further, the amount of the water treatment agent to be added to the water system is preferably 40mg/L to 200mg/L in terms of the effect and cost. Further, as described above, when considering that the concentration of the carboxyl polymer in the water system is preferably 5 mg-polymer/L to 30 mg-polymer/L when the water treatment agent is added to the water system, the concentration of the carboxyl polymer contained in the water treatment agent is preferably set to 18 mass% or less (more preferably 15 mass% or less), and is preferably set to 1 mass% or more (more preferably 1.5 mass% or more) from the viewpoints of cost, working efficiency, effect exertion, and the like. For example, the polymer concentration in the water system of 30 mg-polymer/L ]/[ water treatment agent addition amount to the water system of 200mg/L ] = polymer content in the water treatment agent of 0.15 mg-polymer/mg (i.e., 15 mass%) can be obtained.
In addition, even in the water treatment agent in which the maleic acid polymer used in the water treatment agent in test example 7 was converted into an acrylic acid polymer (carboxyl group content in the polymer: 0.5 g-COOH/g-polymer; weight average molecular weight: 1000 to 16000), the same effects as those of the water treatment agent in test example 7 were obtained.
In addition, the total concentration of the oxidizing agent in each of the water treatment agents of test examples 5 to 16 was 98% or more when stored at 20℃for 20 days and 90% or more when stored at 50℃for 20 days in the storage at a constant temperature of the tank.
Test example 28: slow release property and weight average molecular weight of carboxyl Polymer
As shown in Table 4, the water treatment agent used in test example 5 was added to the open-loop cooling water (pH 8 to 9) so that the concentration of the carboxyl polymer became 0.2g/L, and the concentration of hypobromous acid (mg/L, cl) in the water was measured with time 2 Meter).
The same test was carried out by replacing the carboxyl polymer having a weight average molecular weight of 3900 used in the water treatment agent of test example 5 with those having weight average molecular weights of 800, 14000 and 20000, respectively. Even in the case of these carboxyl polymers having a weight average molecular weight in the range of from the 3 rd power to the 4 th power of 10 th power, hypochlorous acid concentration of approximately the same level as that in the case of the carboxyl polymer having a weight average molecular weight of 3900 can be obtained. When a carboxyl polymer having a weight average molecular weight of about 1000 to 20000 is used, a more excellent hypobromous acid concentration (about 40% to 60%) can be formed.
The content of carboxyl groups in the polymer was measured by the above-mentioned < method of measuring carboxyl group content (g-COOH/g-polymer) > described above.
The weight average molecular weight of the carboxyl polymer was determined by the above-mentioned method for determining weight average molecular weight of the < water-soluble polymer >.
The water treatment agent according to the first embodiment is adjusted so that the concentration of hypobromous acid is preferably 0.25mg/L (in Cl) at 48 hours after the addition of the aqueous system 2 Calculated as Cl) to 1.5mg/L 2 Calculated as Cl), more preferably 0.5mg/L (calculated as Cl) 2 Calculated by Cl) to 1mg/L 2 Meter).
TABLE 4
TABLE 4 Table 4
Test example 29 to test example 31 (second embodiment)
The measurement methods used in each test example are as follows.
< total oxidant concentration >: using DPD totalThe reagent measures the sum of chloramine, hypochlorous acid, and hypobromous acid. Total oxidant concentration in mg/L in Cl in terms of chlorine conversion 2 And (3) meter representation.
< hypobromous acid >: after reacting the free chlorine with glycine, residual hypobromous acid was measured using DPD free reagent. The concentration of hypobromous acid is calculated in terms of chlorine, in mg/L and in Cl 2 And (3) meter representation.
The DPD method used in the present technology is performed according to the DPD method using N, N-diethyl-1, 4-phenylenediamine in JIS K0400-33-10:1999.
Test example: test example 29 (example 1), test example 30 (comparative example 1) and test example 31 (comparative example 2)
In this test, each component of Table 5 was mixed with water (about 10 to 20 ℃) in the mixing order shown in Table 5 to prepare each one-pack type water treatment agent.
At this time, the components shown in table 5 were mixed with water treatment agent immediately after production (0 hour) so as to be 20 mass% of water (remainder), 10 mass% of sodium sulfamate, 5 mass% of sodium bromide, and pH 14. Sodium hydroxide was used as the alkaline agent and powdered sodium bromide was used as the sodium bromide. Sodium hypochlorite was used in such a manner that hypochlorous acid (free form) was 1 mol per 1.5 mol of sulfamic acid (free form).
In addition, in test example 29 (example 1), test example 30 and test example 31 (comparative examples 1 and 2), when sodium sulfamate and sodium hypochlorite were mixed, the total chlorine concentration (%) (in Cl) in the water treatment agent was calculated 2 Calculated) was 4.4%. The measured values (% in Cl) of the total chlorine concentration in the "passing" water treatment agent for each of the "total chlorine detection rates (%)" of test example 29 (example 1), test example 30, and test example 31 (comparative example 1 and comparative example 2) shown in table 2 and fig. 5 2 Theoretical value of total chlorine concentration (% in Cl) in the treated water 2 Gauge) "×100 (%).
Method for producing water treatment agent of test example 29 (example 1):
500g of sodium hydroxide was added to 1.0L of water and mixed so that the pH was 14 or higher, to obtain an aqueous alkaline agent mixed solution.
400g of sodium sulfamate was added to the aqueous alkaline agent mixture solution, followed by addition of 250g of powdered sodium bromide and mixing to obtain an aqueous three-agent mixture solution.
2000g of sodium hypochlorite was added to the mixed aqueous solution of the three agents and mixed to obtain a water treatment agent. Sodium hypochlorite was added to 1.5 mol of sulfamic acid (free form) per 1 mol of hypochlorous acid (free form).
Sodium sulfamate was manufactured by tokyo chemical industry, sodium bromide powder was manufactured by tokyo chemical industry, and sodium hypochlorite was manufactured by japan light metal company.
The concentration of each component in the one-pack water treatment agent is as described above.
The "content (%) of free chlorine in the total chlorine concentration" is represented by [ the concentration (% of free chlorine in Cl) in the water treatment agent ] 2 Total chlorine concentration (% in Cl) in the water treatment agent 2 Meter (C)]Calculated as x 100 (%).
In addition, as the water treatment agent of test example 32 (example 2), the order of addition of sodium sulfamate and powdered sodium bromide was changed when three kinds of agent mixed aqueous solutions were prepared. That is, three kinds of aqueous drug mixed solutions were prepared by adding powdered sodium bromide to an aqueous alkaline agent mixed solution, adding sodium sulfamate to the aqueous alkaline agent mixed solution, and mixing the mixture. After 4 hours from the production, the total chlorine concentration in the water treatment agent of test example 32 (example 2) was 4.3% (in% Cl) 2 Calculated by Cl), and the content of free chlorine in the total chlorine concentration was 0.04% (in% by Cl) 2 Meter). Therefore, the water treatment agent of test example 32 (example 2) had substantially the same degree of mass stability as that of the water treatment agent of test example 29 (example 1).
The water treatment agents (test example 29 (example 1), test example 30 and test example 31 (comparative example 1 and comparative example 2)) were stored for a fixed period of time at a temperature of about 15 to 25 ℃ in the aqueous solution after production. The total chlorine concentration and the free chlorine in each water treatment agent were measured for each elapsed time (1 hour, 2 hours, 3 hours, and 4 hours) after production, and the results are shown in table 6.
TABLE 5
Table 5: the preparation steps of each water treatment agent
TABLE 6
Table 6: total chlorine concentration in each water treatment agent and free chlorine content in total chlorine concentration
TABLE 7
TABLE 7 Total chlorine detection Rate in Water treatment Agents
The theoretical value of the total chlorine concentration was set to 4.4 (%) (in Cl 2 Meter).
As shown in test example 29 (example 1) in tables 5 to 7, a mixed solution in which a chemical agent other than a bromide salt was mixed was prepared, and a single-liquid water treatment agent containing a chloramine compound and bromide ions was obtained by adding a bromide salt to the mixed solution and mixing, and in this production procedure, a water treatment agent excellent in the quality stability of the chemical agent and exhibiting a good effect of hypobromous acid when added to a water system was obtained.
Specifically, the water treatment agent of test example 29 (example 1) showed a total chlorine detection rate (%) of about 98% and a total chlorine concentration (% in Cl) at 4 hours after production 2 Calculated as) was 4.3% and was smoothed, and the free chlorine content in the total chlorine concentration was also 0.04% and was smoothed. It is considered that the stable state is continued for several weeks or more because the active ingredient in the water treatment agent becomes a stable state by the stable state.
On the other hand, the water treatment agent of test example 31 (comparative example 2) was continued to decrease in total chlorine concentration even after 4 hours had elapsed from productionSubsequently, it is believed that the total chlorine detection rate is significantly lower than 60% and the total chlorine concentration (% in Cl) 2 Calculated) 2.8%. In addition, the water treatment agent of test example 30 (comparative example 1) had a total chlorine detection rate of about 93% and a total chlorine concentration (% in Cl) after 4 hours from production 2 Calculated as) was 4.1% and became stationary, and the free chlorine content in the total chlorine concentration was also 0.05% and became stationary.
The loss of the total chlorine detection rate of the water treatment agent of test example 29 (example 1) after 1 hour and 4 hours after the production was about 3%, but the loss of the total chlorine detection rate of the water treatment agent of test example 30 (comparative example 1) was about 7%. When the loss rate of the total chlorine concentration in the water treatment agent of test example 29 (example 1) was compared with the loss rate of the total chlorine concentration in the water treatment agent of test example 30 (comparative example 1), the water treatment agent of test example 29 (example 1) can be said to be extremely excellent in quality stability because the loss rate was suppressed to half or less and a state substantially close to 100% could be maintained.
As described above, the water treatment agent according to the second embodiment of the present technology can maintain the active ingredient at a high level, and therefore, it can be said that the effect of hypobromous acid is exhibited well when added to the water system, and the quality stability of the agent is excellent.
In addition, the total chlorine concentration (% in Cl) of the water treatment agent of test example 30 (comparative example 1) after 2 hours had passed 2 Calculated as Cl) is 4.1% or less, but the total chlorine concentration (% in Cl) of the water treatment agent according to the second embodiment of the present technology 2 And the water treatment agent obtained by the production method according to the second embodiment of the present technology can be said to be a novel water treatment agent, maintaining at least 4.2% or more even after 2 hours have elapsed.
With the water treatment agent according to the second embodiment of the present technology manufactured in the above-described order, the quality stability of the agent is excellent, and the decrease in the active ingredient can be very suppressed, so that hypobromous acid can be produced at a high concentration when added to the water system. Therefore, the water treatment agent according to the second embodiment of the present technology can generate hypobromous acid at a higher concentration when added to a water system than other water treatment agents, that is, can exert the effect of hypobromous acid satisfactorily. Therefore, the water treatment agent according to the second embodiment of the present technology can further exhibit the effect of hypobromous acid such as a high bactericidal effect and a high slime preventing effect.
In addition, the water treatment agent according to the second embodiment of the present technology does not have to be mixed with a special device or other chemical agent to exhibit such an effect, but can exhibit such an excellent effect by designing the mixing order of the components. That is, the production method of the second embodiment of the present technology and the water treatment agent obtained by the production method thus drawn out can achieve low cost, high work efficiency, and stable improvement in quality, and from this viewpoint, the second embodiment of the present technology can also be said to find unpredictable constitution and unpredictable effects resulting therefrom.
Claims (8)
1. A water treatment agent comprising the following components (a) to (c) and having a pH of 10 or more:
(a) 6 to 24 mass% of chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content of the polymer is 1 to 18% by mass of the carboxyl polymer having a content of 0.1 g-COOH/g-polymer or more and 0.71 g-COOH/g-polymer or less,
wherein the (c) carboxyl polymer is a maleic acid polymer and/or a (meth) acrylic acid polymer.
2. The water treatment agent according to claim 1, wherein the molar ratio of the chloramine compound to the bromide salt is 1:0.1 to 1.0.
3. The water treatment agent according to claim 1 or 2, wherein the water treatment agent is at least any one of slime control, corrosion protection, and scale control.
4. The water treatment agent according to claim 1 or 2, wherein the (a) chloramine compound and the (b) bromide salt in the water treatment agent are obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
5. The water treatment agent according to claim 1 or 2, wherein a total chlorine detection rate after production of the water treatment agent is 95% or more and a free chlorine content in a total chlorine concentration is expressed as Cl 2 Is 0.05% or less.
6. A process for preparing water treating agent features that the mixed solution of alkali agent, stabilizer and bromide salt is mixed with oxidizing agent,
wherein the stabilizer and the bromide salt are mixed in an aqueous solution adjusted to a pH of 13 or more with the alkaline agent to prepare the mixed solution;
1.2 to 3 moles of the stabilizer are compounded with respect to 1 mole of the oxidizing agent;
the stabilizer is sulfamic acid compound;
the oxidant is hypochlorous acid or salt thereof,
the pH of the water treatment agent is more than 13.
7. The method for producing a water treatment agent according to claim 6, wherein the mixed solution is a solution in which a powdery bromide salt is mixed as the bromide salt.
8. The method for producing a water treatment agent according to claim 6 or 7, wherein the water treatment agent is further mixed to form 1 to 18 mass% of a carboxyl polymer, and the carboxyl content in the carboxyl polymer is 0.1 g-COOH/g-polymer or more and 0.8 g-COOH/g-polymer or less.
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| JP2019065290A JP6787429B2 (en) | 2019-03-29 | 2019-03-29 | Water treatment agent |
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| CN1312776A (en) * | 1998-08-17 | 2001-09-12 | 拜尔公司 | Composition for water treatment |
| JP2012130852A (en) * | 2010-12-21 | 2012-07-12 | Hakuto Co Ltd | Water system treating method suppressing microbial damage in water system |
| JP2017186294A (en) * | 2016-04-08 | 2017-10-12 | アクアス株式会社 | Microorganism inhibitor composition and microorganism inhibition method |
| JP2017214406A (en) * | 2017-07-10 | 2017-12-07 | オルガノ株式会社 | Water treatment agent composition, method for producing water treatment agent composition and water treatment method |
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| US6270722B1 (en) | 1999-03-31 | 2001-08-07 | Nalco Chemical Company | Stabilized bromine solutions, method of manufacture and uses thereof for biofouling control |
| KR100486381B1 (en) | 2002-03-05 | 2005-04-29 | 애큐랩주식회사 | A method for preparing biocide comprising stabilized hypochlorous acid and bromide ion source and a method of controlling microbial fouling using the same |
| KR101330956B1 (en) | 2009-08-19 | 2013-11-18 | 히타치가세이가부시끼가이샤 | Polishing solution for cmp and polishing method |
| JP6649697B2 (en) | 2015-05-12 | 2020-02-19 | オルガノ株式会社 | Water sterilization method |
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| CN1312776A (en) * | 1998-08-17 | 2001-09-12 | 拜尔公司 | Composition for water treatment |
| JP2012130852A (en) * | 2010-12-21 | 2012-07-12 | Hakuto Co Ltd | Water system treating method suppressing microbial damage in water system |
| JP2017186294A (en) * | 2016-04-08 | 2017-10-12 | アクアス株式会社 | Microorganism inhibitor composition and microorganism inhibition method |
| JP2017214406A (en) * | 2017-07-10 | 2017-12-07 | オルガノ株式会社 | Water treatment agent composition, method for producing water treatment agent composition and water treatment method |
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