CN112996756A - Water treatment agent - Google Patents
Water treatment agent Download PDFInfo
- Publication number
- CN112996756A CN112996756A CN202080006059.5A CN202080006059A CN112996756A CN 112996756 A CN112996756 A CN 112996756A CN 202080006059 A CN202080006059 A CN 202080006059A CN 112996756 A CN112996756 A CN 112996756A
- Authority
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 502
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 461
- 229920000642 polymer Polymers 0.000 claims abstract description 231
- 239000000460 chlorine Substances 0.000 claims abstract description 218
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 216
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 159
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 151
- -1 chloramine compound Chemical class 0.000 claims abstract description 132
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 123
- 238000004519 manufacturing process Methods 0.000 claims abstract description 108
- 238000001514 detection method Methods 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims description 85
- 239000003381 stabilizer Substances 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 59
- 239000011259 mixed solution Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 26
- 230000002265 prevention Effects 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 238000005536 corrosion prevention Methods 0.000 claims description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 abstract description 99
- 230000000694 effects Effects 0.000 abstract description 77
- 238000005516 engineering process Methods 0.000 description 241
- 238000000034 method Methods 0.000 description 109
- 239000000126 substance Substances 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 37
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 29
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 26
- 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
- 238000005260 corrosion Methods 0.000 description 23
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 21
- 239000000498 cooling water Substances 0.000 description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 19
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 19
- 239000011976 maleic acid Substances 0.000 description 19
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 18
- 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
- 239000013043 chemical agent Substances 0.000 description 17
- 239000003814 drug Substances 0.000 description 17
- 229940079593 drug Drugs 0.000 description 17
- 239000004480 active ingredient Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 239000003513 alkali Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 230000001954 sterilising effect Effects 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 12
- 239000002455 scale inhibitor Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- 239000005708 Sodium hypochlorite Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000002925 chemical effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 6
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- 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
- 235000001014 amino acid Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 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
- 238000005259 measurement Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 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
- 238000005481 NMR spectroscopy Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005338 heat storage Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 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
- 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
- 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
- 230000009471 action Effects 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940006460 bromide ion Drugs 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
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 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
- 230000007721 medicinal effect Effects 0.000 description 2
- 150000002739 metals Chemical class 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
- 230000002688 persistence Effects 0.000 description 2
- 230000000144 pharmacologic effect Effects 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
- 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
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 229950000244 sulfanilic acid Drugs 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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-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
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- 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
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- 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
- 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
- 150000003862 amino acid derivatives 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
- 239000002519 antifouling agent Substances 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
- 238000010923 batch production Methods 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
- 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
- OCUAVNNESZWUEY-UHFFFAOYSA-N bromo(chloro)sulfamic acid Chemical compound BrN(S(O)(=O)=O)Cl OCUAVNNESZWUEY-UHFFFAOYSA-N 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
- 239000007795 chemical reaction product Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000007973 cyanuric acids 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
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond 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
- 230000000857 drug effect Effects 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
- 230000003631 expected effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002505 iron 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
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002609 medium Substances 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000004526 pharmaceutical 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- 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
- 230000009257 reactivity Effects 0.000 description 1
- 239000010802 sludge Substances 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
- 230000003068 static 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
- 230000002459 sustained effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 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
- 150000003751 zinc Chemical class 0.000 description 1
Images
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 invention provides a water treatment agent which exerts a good hypobromous acid effect when added to a water system. The present invention is a water treatment agent containing components (a) to (c) and having a pH of 10 or more, and/or containing an alkaline agent, a chloramine compound and a bromide salt, wherein the content of carboxyl groups in the (a) chloramine compound, (b) bromide salt, and (c) polymer is 0.8 g-COOH/g-polymer or less1 to 18% by mass of a polymer, and a water treatment agent having a total chlorine detection rate of 95% or more after production and a free chlorine content of 0.05% (as Cl) in the total chlorine concentration2Meter) below. The molar ratio of the chloramine compound to bromide salt is preferably 1: 0.1 to 1.0.
Description
Technical Field
The present technology relates to a technology for treating water such as a water treatment agent.
Background
In various water systems such as a hot water system, a pulp process water system, a dust collecting water system, and a washing tower water system, hypohalous acid (e.g., hypochlorous acid, hypobromous acid, etc.) is used for the purpose of obtaining effects such as prevention of adhesion of organisms, prevention of slime, and prevention of microorganisms (e.g., bacteria, fungi, algae) to pipes, filtration membranes, etc. of the water systems. As an example, the above-described effects can be obtained by circulating 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 an aqueous system 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 reaction product of a bromine compound and a chlorine-based oxidizing agent, and an aminosulfonic 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, which comprises: (a) a step for 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 for preparing sodium bromide as a bromide ion source; and (c) a step of adding the bromide ion source produced in the step (b) to the stabilized alkali metal or alkaline earth metal hypochlorite produced in the step (a) (for example, see claim 1 and paragraph [0047], etc.).
In addition, for example, in patent document 3, as a method for producing a stabilized bromine solution for controlling attachment of living organisms, a method for producing a stabilized bromine solution is proposed, which comprises: 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. a step of slowly adding a sodium hypochlorite solution as an oxidizing agent to the mixture; and c, a step of slowly adding a sodium hydroxide solution as an alkali source to the mixture to adjust the pH of the mixture to at least 13 (for example, see claim 1 and paragraph [0022], etc.).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 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 No. 2014-140056
Disclosure of Invention
Problems to be solved by the invention
A main object of the present technology is to provide a technology for water treatment in which hypobromous acid exhibits a good effect when added to an aqueous system.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a technique for water treatment which exhibits a favorable effect of hypobromous acid when added to an aqueous system can be provided, and have completed the present technique.
That is, the present technology is as follows.
[1] A water treatment agent which contains the following components (a) to (c) and has a pH of 10 or more:
(a) a chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content in the polymer is 1 to 18% by mass of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
[2] The water treatment agent according to the foregoing [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 any one of for slime control, for corrosion prevention, or for scale prevention.
[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, and an oxidizing agent.
[5]According to the above [1]]～[4]The water treatment agent according to any one of the above items, 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 Cl2The content is 0.05% or less.
[6] A method for producing a water treatment agent, wherein a mixed solution obtained by mixing an alkaline agent, a stabilizer and a bromide salt is mixed with an oxidizing agent.
[7] The method for producing a water treatment agent according to the above [6], wherein the stabilizer is an aminosulfonic 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 powdered 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 a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less is further mixed in an amount of 1 to 18% by mass.
[12] A water treatment agent comprises an alkaline agent, a chloramine compound and a bromide salt,
the total chlorine detection rate after the production of the water treatment agent is 95% or more, and the free chlorine content in the total chlorine concentration is Cl2The content is 0.05% or less.
[13] The water treatment agent according to item [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 this technique, a technique for water treatment can be provided in which the effect of hypobromous acid is exhibited well when added to an aqueous system. The effects described herein are not necessarily limited, and may be any of the effects described in the present specification.
Drawings
FIG. 1 shows the change with time of the total oxidant concentration in the water system (pH 8-9) when each of samples 1-4 was added. Sample 1: chloramine compound (x), sample 2: chloramine compound + bromide (. DELTA.), sample 3: chloramine compound + carboxyl polymer (□), sample 4: chloramine compound + carboxyl polymer + bromide (). The carboxyl group amount of the carboxyl polymer was 0.77 g-COOH/g-polymer. The concentration of the chloramine compound alone was set to 100%.
FIG. 2 shows the relationship between the hypobromous acid concentration (%) and the total oxidizing agent concentration (%) in a water system (pH 8-9) when each water treatment agent was added to the water system while changing the carboxyl group content (g-COOH/g-polymer) of the carboxyl group polymer in the water treatment agent. The concentration of the carboxyl polymer in the aqueous system was 5 mg-polymer/L, and the measurement was performed 48 hours after the addition. The hypobromous acid concentration in the case where no carboxyl polymer was added was set to 100%.
FIG. 3 shows the relationship between the hypobromous acid concentration (%) and the total oxidizing agent concentration (%) in a water system (pH 8-9) when each water treatment agent was added to the water system while changing the carboxyl group content (g-COOH/g-polymer) of the carboxyl group polymer in the water treatment agent. The concentration of the carboxyl polymer in the aqueous system was 30 mg-polymer/L, and the measurement was performed 48 hours after the addition. The hypobromous acid concentration in the case where no carboxyl polymer was added was set to 100%.
FIG. 4 shows the relationship between the concentration (mg/L) of a carboxyl polymer in a water system and the concentration (%) of hypobromous acid when each water treatment agent was added to the water system (pH 8-9) while changing the content of the carboxyl polymer in the water treatment agent. The hypobromous acid concentration in the case where no carboxyl polymer was added was set to 100%.
FIG. 5 shows the hypobromous acid concentration (mg/L in Cl) in a water system (pH 8-9) when the water treatment agent of the present technology is added to the water system2Meter) over time.
Fig. 6 shows changes in the total chlorine detection rate (%) of each water treatment agent in test example 29 (example 1), test example 30, and test example 31 (comparative example 1 and comparative example 2) when a fixed time has elapsed after the production of each water treatment agent.
Detailed Description
Hereinafter, a mode for carrying out the present technology will be described. The embodiments described below are merely examples of representative embodiments of the present technology, and the scope of the present technology is not to be interpreted in a limiting manner.
In the present specification, percentages are expressed by mass unless otherwise specified. The upper limit and the lower limit of each numerical range may be arbitrarily combined as required.
< 1. summary of the present technology
A main object of the present technology is to provide a technology for water treatment in which hypobromous acid exhibits a good effect when added to an aqueous system.
The present technology can provide the technology of water treatment according to the first embodiment of the present technology and the technology of water treatment according to the second embodiment of the present technology. Thus, a technique for water treatment can be provided in which the effect of hypobromous acid is exhibited well when added to an aqueous system.
The first embodiment of the present technology can provide a water treatment agent or the like containing the following components (a) to (c) and having a pH of 10 or more, wherein the content of carboxyl groups in the (a) chloramine compound, (b) bromide salt, and (c) polymer is 1 to 18% by mass, based on the mass of the carboxyl group polymer, at most 0.8 g-COOH/g-polymer.
The first embodiment can provide a water treatment technique such as a one-pack type water treatment agent in which the effect of hypobromous acid is exhibited well when added to an aqueous system and the chemical effect of other compounds is also exhibited well.
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 obtained by the production method, and 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 in the total chlorine concentration of 0.05% (in terms of Cl)2Calculated) the following water treatment agent, and the like.
The second embodiment can provide a water treatment technique such as a water treatment agent in which the effect of hypobromous acid is exhibited well when added to an aqueous system and the quality stability of the chemical agent is excellent.
Further, the present technology can combine the technologies of the first embodiment and the second embodiment. This provides a technique for water treatment which can exhibit the effect of hypobromous acid satisfactorily when added to an aqueous system, and further has the advantage of forming a single-liquid type which can exhibit the effect of a chemical agent of another compound satisfactorily and/or the advantage of excellent quality stability of the chemical agent.
The present technology can also be applied to a water treatment apparatus or a water treatment system in which the effect of hypobromous acid is expected. The present technology may 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 the hydrobromic acid is expected. The water treatment apparatus or water treatment system of the present technology preferably includes: storage devices for the components used in the present technology; means for adding the ingredients or mixing the ingredients; mixing devices and piping for mixing the components (e.g., mixing by stirring or convection). The water treatment apparatus or the water treatment system according to the present technology may further include a control unit or a control device described later. Further, an addition device or the like to which the water treatment agent or each component of the present technology is added can also be provided.
The water treatment method that exhibits the effects of hypobromous acid according to the present technology can also be realized by a control Unit (e.g., a computer or the like) including a Central Processing Unit (CPU) or the like for controlling the timing, amount, ratio, and the like of addition of each component or water treatment agent used in the present technology. The method of the present technology may be implemented by the control unit as a program stored in a hardware resource including a recording medium (such as a nonvolatile memory (USB) memory), a Hard Disk Drive (HDD), and an optical Disk (CD). The control unit may be configured to control the addition of the chemical to the water to be treated. Further, the present technology may provide a water treatment system or a water treatment apparatus including the control device or the addition device.
The water treatment technology of the first embodiment of the present technology, and the water treatment technology of the second embodiment of the present technology will be described in detail below. In the description of the present technology, overlapping configurations, components, and the like are appropriately omitted in the first and second embodiments.
< 2 > Water treatment agent according to first embodiment of the present technology
Hereinafter, a first embodiment of the present technology will be described. The embodiments described below are exemplary representative embodiments of the first embodiment of the present technology, and the scope of the first embodiment of the present technology is not to be interpreted in a limiting manner.
A main object of the first embodiment of the present technology is to provide a water treatment technology such as a one-pack type water treatment agent in which the effect of hypobromous acid is exhibited well when added to a water system and the chemical effect of other compounds is also exhibited well.
In general, since a polymer having a carboxyl group (hereinafter also referred to as "carboxyl polymer") is used as a chemical for slime control, corrosion prevention, scale prevention, or the like, the present inventors expect that when a carboxyl polymer (for example, a maleic acid-based or acrylic acid-based polymer) is added to a chloramine compound and a bromide salt to prepare a one-liquid type water treatment agent and the water treatment agent is added to a water system, the chemical effect of the carboxyl polymer can be exhibited in addition to the effect exhibited well by hypobromous acid.
However, the present inventors have found that when a water treatment agent containing a carboxyl polymer in a chloramine compound and a bromide salt is added to an aqueous system, the decomposition of hypobromous acid in the aqueous system proceeds rapidly due to the carboxyl polymer, the stability of hypobromous acid in the aqueous system with time is lowered, and the effect of hypobromous acid is not sustained (see fig. 1). However, the present inventors have diligently studied a one-pack type water treatment agent which can exert the chemical effect of the carboxyl polymer in addition to the effect exerted by hypobromous acid in a water system.
As a result, the present inventors have found that a one-pack type water treatment agent capable of obtaining good stability with time can be obtained when added to an aqueous system by adjusting the characteristics and content of a carboxyl polymer in a water treatment agent containing a chloramine compound and a bromide salt. The present inventors have also found that the effect of hypobromous acid can be exhibited well and that the medicinal effect of the carboxyl polymer can be exhibited well, and have completed the present technology.
That is, the present technology can adopt the following.
The first embodiment of the present technology can provide a water treatment agent containing 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 in the polymer is 1 to 18% by mass of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
In addition, the molar ratio of the aforementioned chloramine compound to bromide salt is preferably 1: 0.1 to 1.0.
The water treatment agent is preferably at least one of a slime control agent, an anticorrosive agent, and an antifouling agent.
The water treatment agent according to the first embodiment of the present technology contains a hypobromous acid-generating chloramine compound and a bromide salt, further contains a specific amount of a specific carboxyl polymer, and is adjusted to a basic region, whereby a single-liquid type water treatment agent is obtained, and hypobromous acid is not easily generated in the water treatment agent over time. Accordingly, the water treatment agent according to the first embodiment of the present technology is excellent in stability with time of chemical quality, and therefore can maintain stable quality even when distributed on the market as a single-liquid type, and a good effect can be expected even when the single-liquid type water treatment agent according to the first embodiment of the present technology is used in a water system after a fixed period of storage.
Further, the water treatment agent according to the first embodiment of the present technology contains a specific amount of the specific carboxyl polymer, and thus, when the water treatment agent according to the first embodiment of the present technology is added to an aqueous system, generation of hypobromous acid in the aqueous system can be controlled. 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 a short period of time in the water system. 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 of the first embodiment of the present technology is a one-pack type agent, and is also useful as a water treatment agent having a slow-release property. When hypobromous acid is rapidly released in the water system, corrosion or deterioration in the water system is likely to occur, but since the water treatment agent according to the first embodiment of the present technology is controlled so that the generation rate of hypobromous acid is slow, corrosion or deterioration in the water system can be reduced, and the effect (for example, a sterilizing effect or the like) due to 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-cycle system or the like having a cooling water system, a heat storage water system, a dust collection water system, a washing tower water system, or the like.
The carboxyl polymer used in the first embodiment of the present technology is a component that can be used for applications such as a slime control agent, an anticorrosive agent, and an antiscaling agent. Therefore, the water treatment agent according to the first embodiment of the present technology can exhibit the effect of hypobromous acid favorably when added to an aqueous system, and can also exhibit the drug effect of a carboxyl polymer as another compound favorably.
The present inventors have made the following assumptions about the mechanism of generating hypobromous acid in a water system when using the water treatment agent of the first embodiment of the present technology, 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 type agent, and is preferably designed to be present in the form of a chloramine compound (hereinafter, a chloramine compound) in which an aminosulfonic acid compound and hypochlorous acid are bonded, and bromide ions, 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 polymer having a carboxyl group whose characteristics are adjusted, and therefore the content of the carboxyl group in the carboxyl group polymer is adjusted to a predetermined range. It is also important that a single-component preparation contains a specific amount of the specific carboxyl polymer and is used in an aqueous system. In the first embodiment of the present technology, it is preferable that the water treatment agent is adjusted to a state where the pH is increased and an excessive amount of sulfamic acid is allowed to coexist, whereby the reaction of generating hypobromous acid from the chloramine compound can be 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 generate sulfamic acid, hypobromous acid, and the like. This can exert the bactericidal effect and the like due to hypobromous acid and the like produced in the water system, and can exert the pharmacological effect of the carboxyl polymer, which has been difficult to be achieved by the conventional one-liquid type water treatment agent, and can further exert the effect of hypobromous acid continuously.
< 2- (a) 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 formulas (1) and (2)2) A compound (XNHCl) obtained by the reaction wherein a hydrogen atom of an amino group is substituted with a chlorine atom. The compound has a weak oxidizing effect on metals, films, etc. in the water system, and thus can suppress the progress of corrosion or film deterioration, and can be used continuously and/or continuously in the water system.
The chloramine compound used in the first embodiment of the present technology is not particularly limited, but is preferably obtained by using any of a compound having a primary amino group, ammonia, and an ammonium salt (hereinafter, these are also referred to as "NH2A compound of the series ") is mixed with hypochlorous acid and/or hypochlorite to produce and obtain the product.
The compound having a primary amino group is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, sulfamic acid, Sulfanilic acid (sulfuranic 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 also be used in combination.
These NH groups2Of these compounds, sulfamic acid (more preferably NH) is preferred2SO2OH). If the monochloroamino sulfonic acid is formed using sulfamic acid, it becomes a stable chloroamine compound.
Examples of the sulfamic acid compound include compounds represented by the following general formula [1] and salts thereof.
(wherein, the general formula [1]]In, R1And R2Each independently hydrogen or a hydrocarbon having 1 to 8 carbon atoms. )
As such a sulfamate compound, for example, except for R1And R2Examples of the sulfamic acid which is hydrogen include N-methylaminosulfonic acid, N-dimethylaminesulfonic acid, and N-phenylaminosulfonic acid. One selected from the group consisting of these may be used alone, or two or more may also 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 salt and potassium salt; alkaline earth metal salts such as calcium salts, strontium salts, barium salts, etc.; manganese salt, copper salt, zinc salt, iron salt, cobalt salt, nickel salt and other metal salts; amine salts such as ammonium salts and guanidine salts, and amino acid salts, and one or a combination of two or more selected from these can be suitably used. Among them, an alkali metal salt (preferably sodium) is 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 also be used in combination.
In the first embodiment of the present technology, sulfamic acid and sulfamates thereof may be used alone or in combination of two or more selected from the group consisting of these.
On the other hand, as with NH2As the hypochlorite to be reacted with the compound, alkali metal salts of hypochlorous acid such as sodium hypochlorite; 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 also be used in combination.
In mixing of NH2When the chloramine compound is produced from the compound of the series and hypochlorous acid and/or hypochlorite, NH is used from the viewpoint of the efficiency and stability of chloramine production2The compound of the series and hypochlorous acid and/or hypochlorite are preferably generated from available chlorine (Cl) derived from hypochlorous acid and/or hypochlorite2) And is derived from NH2Molar ratio of nitrogen atom to N in the series of compounds, i.e. Cl2The molar ratio of N/0.1 to 1. If Cl2The molar ratio of N/NH is not more than the upper limit, the formation of free chlorine can be suppressed, and not less than the lower limit, the molar ratio is relative to NH used2The compound can inhibit the reduction of chloramine production efficiency.
The content of the chloramine compound is preferably 4 mass% or more, more preferably 6 mass% or more, and still more preferably 8 mass% or more as the lower limit value, and is preferably 24 mass% or less, more preferably 22 mass% or less, and still more preferably 20 mass% or less as the upper limit value in the water treatment agent according to the first embodiment. The numerical range is preferably 4 to 24% by mass, more preferably 6 to 22% by mass, and still more preferably 8 to 20% by 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 salts can be used.
Examples of the alkali metal bromide include, but are not limited to, sodium bromide, potassium bromide, and lithium bromide.
Examples of the amine bromide salt (a linear, branched, or cyclic alkyl or alkenyl group having 1 to 6 carbon atoms) 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 aforementioned bromide salt may use one or two or more selected from the group consisting of these.
The content of the bromide salt is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more as the lower limit value thereof, and is preferably 10 mass% or less, more preferably 9 mass% or less, and further preferably 8 mass% or less as the upper limit value thereof, in terms of bromide in the water treatment agent according to the first embodiment. The numerical range is preferably 0.1 to 10% by mass, more preferably 0.5 to 9% by mass, and still more preferably 1.0 to 8% by mass.
< bromide (Br)-) Measurement method
Bromide (Br) in the present technology-) Can be based on Japanese Industrial Standards (JIS) -K0101(1998)28.4 analysis and concentration determination.
< method of measuring pH >
The pH in the present technology can be measured at a normal temperature of 25 ℃ by using a general pH meter (for example, "Portable pH meter D-54 (pH/mV) (ORP)/COND/resistivity/salt/TDS)" manufactured by horiba, Ltd., or a subsequent model).
< 2- (c) carboxyl 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 group polymer used in the first embodiment of the present technology preferably has a specific ratio of carboxyl groups in the carboxyl group 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 an aqueous system, the action specific to the carboxyl polymer can be exhibited, and the action of hypobromous acid can be effectively exhibited without significantly decomposing hypobromous acid generated in the aqueous system.
The present inventors have found that by controlling the carboxyl group content in the carboxyl polymer and the carboxyl group concentration in the aqueous system, hypobromous acid in the aqueous system can be controlled so as not to decompose. Further, the present inventors have also found that the content of the carboxyl polymer contained in the water treatment agent can be specified by examining the correlation between the content of the carboxyl group in the carboxyl polymer and the concentration of the carboxyl group in the water system.
Thus, the present inventors have devised a one-pack type water treatment agent containing a chloramine compound as a component (a) and a bromide salt as a component (b) and containing a specific amount of a carboxyl polymer as a component (c). The water treatment agent is in the form of a single liquid, and can inhibit decomposition of other components due to mixed components. The water treatment agent can maintain the quality stably, and can exert the respective effects of hypobromous acid and carboxyl polymer well when added to a water system. Further, the effect of hypobromous acid can be exhibited continuously and for a longer period of time by using a specific amount of the specific carboxyl polymer in an aqueous system. Therefore, the water treatment agent according to the first embodiment of the present technology is excellent in terms of reduction in the number of times of addition to a water system due to slow release, simplification of work steps due to use of a single liquid type, sustainable expression of effects due to reduction in decomposition of hypobromous acid, cost reduction, and the like.
Therefore, the carboxyl group polymer according to the first embodiment of the present technology preferably has a carboxyl group content of 0.8 g-COOH/g-polymer or less, and the carboxyl group polymer is 1 to 18 mass% in the water treatment agent according to 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, as the upper limit value, and is preferably 0.1 g-COOH/g-polymer or more, more preferably 0.2 g-COOH/g-polymer or more, as the lower limit value. This numerical range is more preferably from 0.8 g-COOH/g-polymer to 0.1 g-COOH/g-polymer, and 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) >
Carbon derived from the carboxyl group (180ppm to 182ppm) can be quantified using 13C-Nuclear Magnetic Resonance (NMR) spectrometry (carbon 13 NMR) (measurement temperature 30 ℃ C.). The carbon derived from the carboxyl group can be quantified in terms of the concentration of sodium 3- (trimethylsilyl) propionate using sodium 3- (trimethylsilyl) propionate as a standard. In addition, the effect of the Nuclear Overhauser Effect (NOE) can be removed by gated decoupling (1J (C, H)).
The content of the carboxyl polymer in the water treatment agent of the first embodiment is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, further preferably 1.0% by mass or more, further preferably 1.5% by mass or more as the lower limit value thereof, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 18% by mass or less, further more preferably 15% by mass or less as the upper limit value thereof. The numerical range is preferably 0.5 to 25 mass%, more preferably 0.75 to 20 mass%, and still more preferably 1 to 18 mass%, from the viewpoints of cost, work efficiency, and effect.
< 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 technology can be measured by Gel Permeation Chromatography (GPC) analysis using standard polystyrene as a standard substance (for example, see patent document 4 (reference 1): japanese patent laid-open No. 2014-140056).
The kind 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-based polymers and (meth) acrylic acid-based polymers. The term "polymer" refers to a polymer or copolymer containing monomers.
More specifically, the carboxyl polymer includes, for example, 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 selected from the group consisting of these can 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 acid-based polymer. The content ratio (content) of the maleic acid-based polymer and/or the (meth) acrylic acid-based polymer in the carboxyl group polymer is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, particularly preferably 99% by mass or more, and most preferably substantially 100% by mass, and the effect expected in the present technology can be easily obtained when the content ratio in the carboxyl group polymer is high.
Examples of the unsaturated monomer copolymerizable with the maleic acid or (meth) acrylic acid monomer include 2-acrylamido-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, vinyl methyl ether, vinyl ethyl ether, and salts thereof.
Examples thereof include one or more polymers obtained by using one or more monomers selected from these monomers, and selected from the group consisting of homopolymers, copolymers, and copolymers of the above monomers and isobutylene.
When a chemical effect such as an anti-corrosion effect is expected, the weight average molecular weight of the carboxyl polymer is preferably from the 3 rd power to the 4 th power of 10, more specifically, preferably in the range of 200 to 50000, more preferably in the range of 500 to 30000, still more preferably in the range of 800 to 30000, and yet more preferably in the range of 1000 to 20000. The weight average molecular weight is preferably 500 or more for obtaining a chemical effect such as an anticorrosive effect, and is preferably 20000 or less, more preferably 16000 or less, from the viewpoint of workability, for reducing the viscosity of an aqueous solution.
The weight average molecular weight of the carboxyl polymer can be determined by the above-mentioned < method for determining weight average molecular weight of water-soluble polymer >.
From the viewpoint of obtaining a chemical effect such as an anticorrosive effect, the amount of the carboxyl polymer to be added to the aqueous system is preferably an amount such that the concentration in the aqueous system becomes 1 mg-polymer/L to 100 mg-polymer/L, more preferably 2 mg-polymer/L to 50 mg-polymer/L, and still more preferably 5 mg-polymer/L to 30 mg-polymer/L.
< pH of Water treatment agent in first embodiment of the present technology >
From the viewpoint of the stability of the chemical over time, the pH of the water treatment agent according to the first embodiment of the present technology is in the alkaline range, more preferably 10 or more, further preferably 11 or more, further preferably 12 or more, and particularly preferably 13 or more. By adjusting the chemical 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 over time can be maintained or improved.
< content and mass content ratio of each component in the water treatment agent of the first embodiment of the present technology >
[ molar ratio of the above-mentioned chloramine Compound to bromide salt ]
In the water treatment agent according to the first embodiment of the present technology, it is preferable that the molar ratio of the chloramine compound to the bromide salt is adjusted so that 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, and more preferably 1: 0.1 to 1.0, and 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 described above [ the carboxyl group content in the polymer ], and more preferably 0.3 to 0.72 (g-COOH/g-polymer).
In a preferred range of the carboxyl group content in the polymer, the concentration (%) of hypobromous acid in the aqueous system is not particularly limited, and it is preferable to prepare the water treatment agent of the first embodiment of the present technology so as to be preferably 75% or more, more preferably 80% or more, further preferably 85% or more, and further more preferably 90% or more, or to add the water treatment agent of the first embodiment of the present technology or each component used in the water treatment agent.
In a preferred range of the carboxyl group content in the polymer, the total oxidizing agent concentration (%) in the aqueous system is not particularly limited, and the water treatment agent according to the first embodiment of the present technology or the water treatment agent to which the water treatment agent according to the first embodiment of the present technology is added is preferably prepared so as to be 80% or more, more preferably 85% or more, and still more preferably 90% or more.
As described above, the water treatment agent according to the first embodiment of the present technology has excellent stability over time by using a specific amount of a specific carboxyl polymer. The total oxidizing agent concentration of the water treatment agent according to the first embodiment of the present technology after a fixed period of time has elapsed may be preferably 98% or more, more preferably 99% or more, when stored in a constant temperature bath for 20 days at 20 ℃, and may be preferably 85% or more, more preferably 90% or more, when stored for 20 days at 50 ℃.
The water treatment agent according to the first embodiment of the present technology is prepared by adjusting carboxyl group polymerization as described aboveExcellent slow release properties can be obtained by the characteristics of the product, the specific amount of the product used, and the like. The water treatment agent according to the first embodiment of the present technology can be adjusted so that the hypobromous acid concentration after 48 hours from the addition of the water system is preferably 0.25mg/L (as Cl)2In (v) 1.5mg/L (in Cl)2Calculated as Cl), more preferably 0.5mg/L (calculated as Cl)2In (calculated as Cl) 1mg/L2Meter).
Further, the technique of the second embodiment of the present technique described later may be adopted in the first embodiment of the present technique.
By combining the technique of the first embodiment and the technique of the second embodiment, a technique of single-liquid water treatment is provided in which the effect of hypobromous acid is exhibited well when added to an aqueous system and the chemical effect of another compound is also exhibited well, and this technique of single-liquid water treatment has an advantage of excellent quality stability of the chemical.
As an example of a technique using a second embodiment of the present technology described later, for example, the (a) chloramine compound and the (b) bromide salt in the first embodiment of the present technology may be a mixture containing the (a) and (b) compounds 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 terms of Cl)2Meter) below.
< 2- (d) optional component of the first embodiment of the present technology >
The water treatment agent according to the first embodiment of the present technology can be used in combination with any chemical agent within a range that does not impair the effects of the present technology. Examples of the optional chemical include an anticorrosive agent (corrosion inhibitor), a scale inhibitor, a slime control agent, a solvent or dispersion medium such as water, a dispersant enzyme, a bactericide, and an antifoaming agent, but the chemical is not limited thereto, and various chemicals generally used for water treatment may be used. One or two or more of these constituent groups can be appropriately selected.
The water treatment agent according to the first embodiment of the present technology can be obtained by appropriately mixing the essential components or optional components or agents, and can be produced by a general production method of a water treatment agent or a production method of the second embodiment of the present technology described later.
< corrosion inhibitor >
The corrosion inhibitor (corrosion inhibitor) other than the above carboxyl polymer is not particularly limited, and is preferably a corrosion inhibitor for a cooling water system. Azoles such as benzotriazole and tolyltriazole are preferable.
< 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 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, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid (also referred to as 1-hydroxyethane-1, 1-diphosphonic 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 agent and/or scale inhibitor 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.
< 2-2 > method of using water treatment agent of first embodiment of the present technology and method of water treatment using the same
The water treatment agent according to the first embodiment of the present technology is expected to have not only the effect of hypobromous acid (for example, a sterilizing effect, a slime controlling effect, and the like) but also the medicinal effect of the specific carboxyl polymer, and can be used for at least any one of slime controlling, corrosion preventing, scale preventing, and the like.
The first embodiment of the present technology can provide a use or a 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 an aqueous system, a sterilization method in an aqueous system, a slime control method in an aqueous system, an anticorrosion method in an aqueous system, a film scale prevention method in an aqueous system, and the like.
The first embodiment of the present technology may also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scale method in which the water treatment agent according to the first embodiment of the present technology is added to a water system. It is preferable to omit the configuration overlapping with the configuration described in the water treatment agent of the present technology.
From the viewpoint of stability over time, the pH of the aqueous system in the method according to the first embodiment of the present technology is in the alkaline range, more preferably 7 to 10, and still more preferably 8 to 9.
In addition, another aspect of the first embodiment of the present technology can provide a water treatment method, a sterilization method, a slime control method, an anticorrosion method, or an antiscaling 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. (a) A chloramine compound; (b) a bromide salt; (c) the carboxyl group content in the polymer is 1 to 18% by mass of a carboxyl group 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 drugs or the components in the aqueous system is not particularly limited, and they may be added at the same time or separately. And/or the site of addition of the drug or each component in the aqueous system is not particularly limited, and may be added to the same site or a different site. The components (a) to (c) can exhibit the effects expected in the first embodiment of the present technology by being added to and mixed with a water system, and the components can be added to the water system in such a manner that the components are mixed to form a water treatment agent.
For example, if sludge control or scale control is to be performed on the membrane, it is preferable to add a chemical agent before the membrane treatment. Further, the effects of the present technology can be obtained at any time or place in the water system in order to control slime, sterilize, and prevent corrosion of pipes and the like 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 including a metal or a metal pipe such as a cooling tank, a cooling tower, and a heat exchanger.
In the method according to the first embodiment of the present technology, the molar ratio of the chloramine compound as the component (a) to the bromide salt as the component (b) is preferably 1: 0.1 to 1.0. The molar ratio may be the same as that in the water treatment agent.
In the method according to the first embodiment of the present technology, the component (c), the carboxyl polymer, is preferably added so as to have a predetermined concentration in an aqueous system. The predetermined concentration in the aqueous system is not particularly limited, but the lower limit thereof is preferably 0.5mg/L or more, more preferably 1mg/L or more, and further preferably 2mg/L or more, and the upper limit thereof 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, and still more preferably 2mg/L to 50 mg/L.
In the first embodiment of the present technology, the water treatment agent kit may be used. In the case of the water treatment agent kit, the respective components (a) to (c) may be contained in different containers, or two kinds of components and one kind of component may be contained in different containers. In addition, any component may be appropriately blended in each container. The use or method of the water treatment agent kit can be performed in the same manner as the use or method of the water treatment agent.
< 3 > method for producing water treatment agent and water treatment agent according to second embodiment of the present technology
Hereinafter, a mode for implementing a second embodiment of the present technology will be described. The embodiments described below are merely examples of representative embodiments of the second embodiment of the present technology, and thus the scope of the second embodiment of the present technology is not to be construed in a limiting manner.
A main object of the second embodiment of the present technology is to provide a water treatment agent which exhibits a good hypobromous acid effect when added to an aqueous system and has excellent quality stability of a chemical agent.
As a result of intensive studies, the present inventors have found that a water treatment agent obtained by mixing an oxidizing agent into a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed maintains a high total chlorine detection rate and a low free chlorine content in the total chlorine concentration even after a fixed time has elapsed after the production. That is, the present inventors have completed the present technology by obtaining a water treatment agent which exhibits a good hypobromous acid effect when added to a water system and has excellent quality stability of a chemical agent.
That is, the present technology can adopt the following.
In the second embodiment of the present technology, a method for producing a water treatment agent can be provided 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 an aminosulfonic 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 powdered 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 in the total chlorine concentration of 0.05% (as Cl)2Calculated) 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 > A water treatment agent according to a second embodiment of the present technology and a method for producing the same
A second embodiment of the present technology can provide 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. When a mixed solution in which the alkaline agent, the stabilizer and the bromide salt are mixed is obtained, the order of mixing the alkaline agent, the stabilizer and the bromide salt may be any order, and is not particularly limited.
In addition, a second embodiment of the present technology can provide a water treatment agent obtained by mixing an oxidizing agent into 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 can provide a water treatment agent in which the total chlorine detection rate after production is higher than or equal to a certain level and/or the free chlorine content in the total chlorine concentration is lower than or equal to a certain level.
Thus, the second embodiment of the present technology can provide a water treatment agent that exhibits a favorable effect of hypobromous acid when added to an aqueous system and has excellent quality stability of a chemical agent.
< 3-2 > method for producing water treatment agent according to second embodiment of the present technology
The present inventors have studied a method for producing a biocide in patent document 2 (Japanese patent laid-open publication No. 2005-519089). Specifically, in patent document 2, hypochlorite and sulfamic acid are mixed in a sodium hydroxide solution to prepare a hypochlorite solution having at least pH11 or more, 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 powder is mixed by the method for producing a biocide of patent document 2, hypobromous acid having a high oxidizing power and being unstable is generated. The present inventors found that, by thus decreasing the stability of hypobromous acid, a tendency was observed that the effect of the active ingredient contained in the biocide also decreased. The present inventors have verified the reason, and as a result, when sodium bromide powder is added to a hypochlorous acid solution, a thick bromide solution is generated in a part of the solution when the powder is dissolved. The present inventors considered that unstable hypobromous acid is produced by the reaction with hypochlorous acid which coexists when the thick portion of the bromide solution is produced.
On the other hand, the present inventors have also studied a 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 the present inventors have found that since water must be added to sodium bromide at the same time as an aqueous solution, there is a problem that the concentration of sodium bromide which can be compounded decreases.
The present inventors have also studied a method for producing a stabilized bromine solution for controlling the adhesion of a living organism 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 present inventors have considered that, in the method of patent document 3, formation of hypobromous acid can be suppressed because a concentrated bromide solution is not formed in a part of the solution during preparation of the solution. However, in the method of patent document 3, since the oxidizing agent is mixed in the aqueous solution containing sodium bromide and sulfamic acid, the pH of the oxidizing agent is lowered. The present inventors have found that when the pH of the oxidizing agent is lowered, an unstable component having a high oxidizing power (for example, dichlorosulfamic acid, bromochloroaminosulfonic acid, or the like) is generated, and the unstable component has a problem that the effect of stabilizing the active ingredient contained in the bromine solution is lowered.
Further, the present inventors have conducted intensive studies and as a result, as shown in the following [ example ], among water treatment agents obtained by using an alkaline agent, a stabilizer, a bromide salt and an oxidizing agent, 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 is superior to the water treatment agents of patent documents 2 and 3 in terms of the overall of the total chlorine detection rate, the total chlorine concentration and the free chlorine content in the total chlorine concentration. That is, the water treatment agent according to the second embodiment of the present technology obtained in this way exhibits a good hypobromous acid effect when added to an aqueous system and is excellent in the quality stability of the chemical 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 set to the first or last. The reason for this is considered to be that the stabilized chloramine compound is obtained from the alkali agent-stabilizer-oxidizing agent, and therefore, the mixing of these agents is considered as an integrated process. The present inventors have been able to break through the conventional persistence and have thus obtained an excellent water treatment agent according to the second embodiment of the present technology, and have found that the mixing order is not predictable from the prior art.
That is, the method for producing a water treatment agent according to the second embodiment of the present technology is characterized in that a mixed solution in which an alkaline agent, a stabilizer, and a bromide salt are mixed is mixed with an oxidizing agent. The method for producing a water treatment agent according to the second embodiment of the present technology has an advantage that a single-liquid type water treatment agent that can stably maintain the quality of a chemical for a long period of time can be obtained.
< method for measuring free chlorine concentration, bound chlorine concentration and total chlorine concentration >
In this technique, the free chlorine concentration, the bound chlorine concentration and the total chlorine concentration can be measured by the DPD method using N, N-diethyl-1, 4-phenylenediamine as described in JIS K0400-33-10:1999, and Cl2Is measured by the method of (1). The following definitions are proposed in JIS K0400-33-10: 1999.
That is, the free chlorine is chlorine existing as hypochlorous acid, hypochlorite ions, or dissolved chlorine. The bound chlorine is chlorine present as chloramine, organic chloramine, or the like, and is not included in the free chlorine, but is total chlorine measured by the DPD method. Total chlorine is chlorine present as free chlorine, bound chlorine, or both.
< detection ratio of total chlorine (%) > and free chlorine content (%) >
In the present technology, the "total chlorine detection rate (%)" is a residual rate (%) of total chlorine concentration as an active ingredient in the water treatment agent, and can be determined by "an actual measurement value (%) of total chlorine concentration in the water treatment agent as Cl%2Theoretical value of total chlorine concentration in water treatment agent (% in Cl)2Meter) "× 100 (%). The theoretical value of the total chlorine concentration is calculated to calculate the total chlorine concentration formed in the water treatment agent when the oxidizing agent and the stabilizer are mixed at the time of productionThe value of (c).
In the present technique, the "content ratio of free chlorine (% (in terms of Cl) in the total chlorine concentration" is2Calculated) of the water treatment agent) can be passed [ free chlorine concentration in the water treatment agent (% in Cl)2Calculated)/total chlorine concentration in water treatment agent (% in Cl)2Meter)]X 100% calculated.
In the second embodiment, < bromide (Br)-) Measurement method > and pH measurement method > with the bromide (Br) described in the first embodiment-) Measurement methods > and < pH measurement method > were 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 according to the second embodiment of the present technology are as follows.
< 3-2-1(a) alkaline agent >
The alkaline agent used in the second embodiment of the present technology is not particularly limited, and examples thereof include basic inorganic salts, basic organic salts, and the like.
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 the like, and one or two or more selected from the group consisting of these can be used.
The oxide, salt hydroxide, carbonate are preferably alkali metal or alkaline earth metal. One or two or more selected from the group consisting of these may be used in combination.
Among the above alkaline agents, basic inorganic salts are preferred, and among them, salt hydroxides are more preferred from the viewpoint of workability and cost. Among the salt hydroxides, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is further preferable from the viewpoint of cost.
The acidic agent for adjusting 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 acids can 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 a reaction with an oxidizing agent (preferably, an inorganic chlorine agent).
Examples of the chlorine stabilizer include a compound having a primary amino group, ammonia, and an ammonium salt (hereinafter, these are also referred to as "NH2A series of compounds "), one or two or more selected from these compounds 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, and amino acids, and one or two or more selected from the group consisting of these can 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 can be used.
More specific examples of the chlorine stabilizer include sulfamic acid compounds; isocyanuric acid; hydantoins such as 5, 5' -dimethylhydantoin, and amide compounds such as 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 and histamine; ammonia; ammonium salts such as ammonium sulfate, and one or two or more selected from the group consisting of these can be used.
Among the chlorine-based stabilizers, an aminosulfonic acid compound is preferable from the viewpoint of environmental load, and examples of the aminosulfonic acid compound include aminosulfonic acid, an aminosulfonic acid derivative, and salts thereof, and one or more selected from the group consisting of these can be used.
The aforementioned chlorine stabilizer (preferably NH)2Of the series of compounds), sulfamic acid (more preferably NH) is preferred2SO2OH). It is preferable to use sulfamic acid to form monochloroamino sulfonic acid because it is a stable chloroamine compound.
The sulfamate compound may be a compound represented by the general formula [1] or a salt thereof, which is described in the first embodiment of the present technology.
The salt of the compound used in the stabilizer is not particularly limited, and the above-mentioned "salt of the compound used in the first embodiment of the present technology" can be used. Among them, an alkali metal salt (preferably sodium) is 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 above-described "sulfamic acid compound used in the first embodiment of the present technology" may be used.
Among the above stabilizers, sulfamates are more preferred.
< 3-2-1(c) Bromide salt >
The bromide salt used in the second embodiment of the present technology is not particularly limited, and the above-mentioned "bromide salt used in the first embodiment of the present technology" may be used.
The alkali metal bromide and amine bromide salt used in the second embodiment of the present technology are not particularly limited, and the "alkali metal bromide" and "amine bromide salt" used in the first embodiment of the present technology can be used.
The form of the bromide salt when mixed in the solution may be either a chloride solution or a powder chloride salt, but from the viewpoint of increasing the concentration of the active ingredient, it is preferable to use a powder bromide.
< 3-2-1(d) oxidant >
The oxidizing agent used in the second embodiment of the present technology is not particularly limited, and a halogen-based oxidizing agent is preferred, and a chlorine-based oxidizing agent is preferred from the viewpoint that a chloramine compound can be obtained from the chlorine-based oxidizing agent and a 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 chlorinated isocyanuric acid or a salt thereof, and one or more selected from the group consisting of these can be used.
Specific examples of the salt-forming substance are not particularly limited, and include: alkali metal hypochlorite such as sodium hypochlorite and potassium hypochlorite; alkali earth hypochlorite metal salts such as calcium hypochlorite and barium hypochlorite; alkali metal chlorite salts such as sodium chlorite and potassium chlorite; alkaline earth metal chlorite salts such as barium chlorite; other metal salts of chlorous acid such as nickel chlorous acid; alkali metal chlorate such as ammonium chlorate, sodium chlorate, potassium chlorate, etc.; alkali earth metal chlorate such as calcium chlorate and barium chlorate, and one or more selected from the group consisting of these salts can 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 second embodiment of the present technology
In the method for producing a 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 three-chemical mixture solution and mix them. The mixing of the oxidizing agent can be carried out in accordance with the following < 3-2-2-2. oxidizing agent mixing step >.
Example 1 of the embodiment of the production method according to the second embodiment 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 the below-described step of mixing the oxidizing agent < 3-2-2-2 >.
The three-agent mixed solution may be prepared in advance, or may be prepared in the same manufacturing line or different manufacturing lines. For example, a solution prepared in the step of preparing a mixed solution of an alkaline agent, a stabilizer and a bromide salt, which is described below as < 3-2-2-1, can be used as the three-chemical mixed solution.
From the viewpoint of quality stability of the water treatment agent, it is more preferable that after mixing the three chemicals, the oxidizing agent is quickly mixed into the three-chemical mixture solution to obtain the water treatment agent.
In addition, from the viewpoint of work efficiency and from the viewpoint of easy adjustment of active ingredients in the water treatment agent, example 2 of the embodiment in the production method of the second embodiment of the present technology more preferably includes a step of preparing a mixed solution in which the alkaline agent, the stabilizer, and the bromide salt are mixed, and a step of mixing the oxidizing agent in the three-agent mixed solution.
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 alkali agent, the stabilizer, the bromide salt and the oxidizing agent, and water is preferred from the viewpoint of safety, operability and cost. The water may contain other solvents within a range not impairing the effect of the present technology, and it is preferable that 99% or more of the solvents be water. Examples of the other solvent include hydrophilic organic solvents, such as glycols (e.g., ethylene glycol, diethylene glycol), glycol ethers (e.g., diethylene glycol monomethyl ether), glycol dimethyl ethers (glyme), ketones, esters (e.g., methyl acetate), alcohols (e.g., ethanol, aminoethanol), and amides (e.g., N-dimethylacetamide), and among them, glycols, glycol ethers, esters, and 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 is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, in the water treatment agent according to the second embodiment.
The production conditions of the production method according to the second embodiment of the present technology can be performed by referring to known production conditions, and can be performed, for example, by a batch or continuous process, or can be performed at a temperature of about 4 to 40 ℃.
Hereinafter, an example of the method for producing a water treatment agent according to the second embodiment of the present technology will be described using the production method of example 2 of the embodiment of the present technology, but the production method of the second embodiment of the present technology is not limited to this description. In the manufacturing method according to the second embodiment of the present technology, the step of preparing the three-drug mixed solution can be omitted.
The manufacturing method of example 2 of the second embodiment of the present technology includes a step of preparing a three-chemical agent mixed solution and a step of mixing an oxidizing agent in the mixed solution.
< 3-2-2-1. Process for preparing a mixed solution containing an alkaline agent, a stabilizer and a bromide salt
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-chemical mixed solution preparation step") in the production of the second embodiment of the present technology, the order of mixing the respective components of the alkaline agent, the stabilizer and the bromide salt is not particularly limited.
The three-chemical mixture solution according to the second embodiment of the present technology can be obtained by adding and mixing the three chemicals, i.e., the alkaline agent, the stabilizer, and the bromide salt, at the same time or separately. More specifically, the three drugs may be added sequentially, or two drugs may be mixed and the remaining drugs may be mixed, or the three drugs may be mixed at the same time.
When the three agents 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-drug mixing preparation step of the second embodiment of the present technology, it is preferable that an alkaline agent is first mixed in a solution. As described later, the pH of the solution can be adjusted to a basic 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 alkaline, the quality stability of each drug mixed in the solution is also good.
By sequentially or appropriately mixing the chemicals in the solution adjusted to the alkaline region, a water treatment agent having excellent quality stability can be obtained.
In the step of mixing and preparing the three chemical agents according to the second embodiment of the present technology, it is more preferable to mix the alkaline agent, the stabilizer and the bromide salt in this order, or to mix the alkaline agent, the bromide salt and the stabilizer in this order.
The treatment temperature in the step of preparing the three-chemical mixed solution according to the second embodiment of the present technology is not particularly limited, and the step may be performed under a temperature condition of about 4 to 40 ℃. In addition, as the mixing means in the three-chemical mixed solution preparation step, a known means (for example, a stirring means) capable of mixing the respective chemicals and the solution can be used.
From the viewpoint of maintaining the quality stability of the chemicals of the water treatment agent according to the second embodiment of the present technology, it is desirable that the pH of the three-chemical mixed solution prepared as described above is adjusted by the alkaline agent. The pH of the three-agent mixed solution is more preferably 10 or more, further preferably 11 or more, further preferably 12 or more, and particularly preferably 13 or more. By adjusting the pH of the three-chemical mixed solution in this manner, 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 thereby the effect of the active ingredient of the water treatment agent according to the second embodiment of the present technology can be exhibited well. In addition, an alkaline agent may be appropriately 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, in view of maintaining the quality stability of the chemical in the water treatment agent according to the second embodiment of the present technology, the concentrations of the stabilizer and the bromide salt contained in the three chemical mixed solutions prepared as described above can be adjusted by the following blending amounts.
The amount of the stabilizer (preferably, chlorine-based stabilizer) used for the preparation of the three-chemical mixture 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 three-chemical mixture solution.
The amount of the stabilizer (preferably, chlorine-based stabilizer) used for the preparation of the three-agent mixed solution is not particularly limited. When the oxidizing agent is an inorganic chlorine agent, from the viewpoint of sufficient reactivity of these, the amount of the oxidizing agent is preferably 1 to 5 moles, more preferably 1 to 4 moles, and still more preferably 1.2 to 3 moles, based on 1 mole of the oxidizing component contained in the inorganic chlorine agent. Thus, even a single-liquid type water treatment agent can maintain the effective component satisfactorily.
The amount of bromide salt to be used for preparing the three-chemical mixture solution is not particularly limited, and is preferably 3% to 50%, more preferably 6% to 40%, and still more preferably 12% to 30% of the three-chemical mixture solution.
< 3-2-2-2. procedure for mixing oxidizing agent
In the "step of mixing an oxidizing agent in the three-chemical mixture solution" (hereinafter also referred to as "oxidizing agent mixing step") in the production of the second embodiment of the present technology, the oxidizing agent is mixed in the solution prepared in the above step and mixed with the alkaline agent, the stabilizer, and the bromide salt. Thus, a mixed solution of four agents can be obtained.
In addition, 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, the chloramine compound) and a bromide salt can be prepared in an alkaline region.
The amount of the oxidizing agent to be mixed in the three-chemical mixture solution is not particularly limited, but is preferably 20% to 55%, more preferably 30% to 55%, and still more preferably 40% to 50% of the four-chemical mixture solution.
The mixing mass ratio of the three-chemical mixed solution and the oxidizing agent is not particularly limited, but the oxidizing agent is preferably 0.5 to 1.5, and more preferably 0.7 to 1.3, relative to the three-chemical mixed solution 1.
The water treatment agent obtained by the production method according to the second embodiment of the present technology exhibits a good hypobromous acid effect when added to a water system and has excellent quality stability of the chemical agent. Further, the single-component drug obtained by the production method can exhibit the desired effect even when stored in the single-component state for a long period of time, and can maintain constant quality.
The water treatment agent obtained by the production method according to the second embodiment of the present technology contains an alkaline agent, a halamine 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% (as Cl) of the total chlorine concentration after production2In terms of) the following is preferable because the concentration of the active ingredient after production can be suppressed from decreasing.
The content of the stabilizer in the water treatment agent according to the second embodiment of the present technology is adjusted to: the lower limit value is preferably 3% or more, more preferably 5% or more, further preferably 8% or more, and the upper limit value is preferably 40% or less, more preferably 35% or less, further preferably 30% or less, more preferably a numerical range of 5% to 35%, further 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 value is preferably 1% or more, more preferably 3% or more, further preferably 6% or more, and the upper limit value is preferably 25% or less, more preferably 20% or less, further preferably 15% or less, more preferably a numerical range of 3% to 20%, further preferably 6% to 15%.
The content of the oxidizing agent in the water treatment agent according to the second embodiment of the present technology is adjusted to: the lower limit value is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and the upper limit value is preferably 60% or less, more preferably 55% or less, further preferably 50% or less, more preferably a numerical range of 30% to 55%, further preferably 40% to 50%.
The "total chlorine detection rate (%)" in the water treatment agent of 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 ratio of free chlorine in total chlorine concentration (% (in terms of Cl) in the water treatment agent of the second embodiment2In terms of the content of the amino acid derivative) is 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 used2"is more preferably 4.1% or more, still more preferably 4.2% or more, and still more preferably 4.3% or more. In the method of the second embodiment of the present technology, the total chlorine concentration (% in Cl) in the water treatment agent of the second embodiment is considered2In terms of percentage) can be increased to 4.4% to 4.7%, and therefore, 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, in the water treatment agent according to the second embodiment of the present technology, the total chlorine detection rate (%) and the total chlorine concentration (% in Cl) are determined from the viewpoint of reducing the decomposition of the active ingredient and efficiently adding the active ingredient to the water system2In terms of the total chlorine concentration), and the content of free chlorine in the total chlorine concentration is preferably a concentration from 4 hours after production to 1 hour after production. The water treatment agent according to the second embodiment of the present technology is not used immediately 0 hour after production, and has a high and stable total chlorine detection rate and total chlorine concentration up to about 4 hours after production. Therefore, even if a manufacturing apparatus for a water treatment agent is not installed near the site of addition of the water system, handling such as transportation can be performed. In addition, in 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 from about 3 months after the production2Meter), and a sharp increase in the concentration of free chlorine in the total chlorine concentration can be suppressed.
The storage conditions for storing the water treatment agent according to the second embodiment of the present technology after production are not particularly limited, but the storage at room temperature or at room temperature in the dark is preferable, and the temperature control of about 4 to 40 ℃ is more preferable.
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 an ordinary temperature of about 4 to 40 ℃, and can suppress a decrease in the concentration of the active ingredient even when stored at an ordinary temperature for a long period of time (for example, about 3 months after production). Further, the water treatment agent according to the second embodiment of the present technology can provide a product having stable quality by suppressing the generation of hypochlorous acid in the obtained water treatment agent according to the second embodiment and reducing the decrease in the concentration of the active ingredient by preventing the generation of a thick bromide solution during the mixing process 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 after production to the same or less degree as the water treatment agent of patent document 2 or patent document 3, and the target effect can be exhibited well and the quality stability of the chemical agent is also excellent.
In the present technology, the term "quality stability of a drug" means that an active ingredient in the drug is hardly decomposed during storage of the drug for a fixed period of time, and the concentration of the active ingredient is maintained within a certain range. More specifically, it is desirable that hypochlorous acid is hardly generated in the drug 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, it is preferable that the molar ratio of the chloramine compound to the bromide salt is adjusted so that the molar ratio of the chloramine compound to the bromide salt is 1: 0.05 to 3.0, more preferably 1: 0.1 to 1.5, and more preferably 1: 0.1 to 1.0, and more preferably 1: 0.2 to 1.0. In the method for producing a water treatment agent according to the second embodiment of the present technology, the molar ratio may be appropriately adjusted.
The water treatment agent according to the second embodiment of the present technology has excellent quality stability of the chemical, and when added to an aqueous system, the effect of hypochlorous acid can be exhibited well based on the alkaline agent, the halamine compound (preferably, chloramine compound), and the bromide salt in the chemical. Further, the water treatment agent according to the second embodiment of the present technology can slowly generate hypobromous acid in an aqueous system over time, and thus can maintain the effect of hypobromous acid in the aqueous system for a longer period of time.
Another aspect of the water treatment agent of the second embodiment of the present technology is a one-pack type agent, and is also useful as a water treatment agent having a slow-release property. When hypobromous acid is rapidly released in the water system, corrosion or deterioration in the water system is likely to occur, but since the water treatment agent according to the second embodiment of the present technology is controlled so that the generation rate of hypobromous acid is slow, corrosion or deterioration in the water system can be reduced, and the effect (for example, a sterilizing effect or the like) due to 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-cycle system or the like having a cooling water system, a heat storage water system, a dust collection water system, a washing tower water system, or the like.
< 3-2-3 > an optional component of the second embodiment of the present technology
In any of the production steps of the water treatment agent according to the second embodiment of the present technology, an arbitrary chemical agent can be mixed as an arbitrary component within a range not to impair the effects of the present technology.
Examples of the optional chemical include an anticorrosive agent (corrosion inhibitor), a scale inhibitor, 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 selected from the group consisting of these may be used. The drug described in the first embodiment can be suitably used as any drug.
< corrosion inhibitor >
The corrosion inhibitor (corrosion inhibitor) is not particularly limited, and is preferably an anticorrosive for a cooling water system. For example, polymers such as carboxyl polymers are preferable; 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, maleic acid-based polymers and (meth) acrylic acid-based polymers. The term "polymer" refers to a polymer or copolymer containing monomers.
More specifically, the carboxyl polymer includes, for example, 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 one or two or more selected from the group consisting of these can 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 acid-based polymer. The content ratio (content) of the maleic acid-based polymer and/or the (meth) acrylic acid-based polymer in the carboxyl group polymer is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass or more, and the expected effect of the present technology can be easily obtained when the content ratio in the carboxyl group polymer is high.
Examples of the unsaturated monomer copolymerizable with the maleic acid or (meth) acrylic acid monomer include 2-acrylamido-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, vinyl methyl ether, vinyl ethyl ether, and salts thereof.
Examples thereof include one or more polymers obtained by using one or more monomers selected from the group consisting of these monomers, and selected from the group consisting of homopolymers, copolymers, and copolymers of the above monomers and isobutylene.
When a chemical effect such as an anti-corrosion effect is expected, the weight average molecular weight of the carboxyl polymer is preferably from the 3 rd power to the 4 th power of 10, more specifically, preferably in the range of 200 to 50000, more preferably in the range of 500 to 30000, still more preferably in the range of 800 to 30000, and yet more preferably in the range of 1000 to 20000.
The carboxyl polymer may be the one used in the first embodiment of the present technology, and the amount thereof used. Further, in the second embodiment, a mixture obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an 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 a water treatment agent or a water treatment agent kit using the components (a) to (c) of the first embodiment. As a result, in addition to the effects of the second embodiment of the present technology, as in the first embodiment of the present technology, a one-liquid type water treatment technology in which the pharmaceutical effects of other compounds can be exhibited well can be provided more well.
The method of measuring the weight average molecular weight of the < water-soluble polymer > in the second embodiment can be performed in the same manner as the method of 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 < scale inhibitor > < used in the first embodiment of the present technology described above can be used.
The content of the anticorrosive agent and/or scale inhibitor 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 water treatment agent and method for water treatment using the same
The water treatment agent according to the second embodiment of the present technology is expected to have the effects of hypobromous acid (for example, a bactericidal effect, a slime control effect, and the like) as described above, and can be used as at least one of a slime control agent, an anticorrosive agent, a scale control agent, and the like.
The second embodiment of the present technology can provide a use or a 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 an aqueous system, a sterilization method in an aqueous system, a slime control method in an aqueous system, an anticorrosion method in an aqueous system, a film scale prevention method in an aqueous system, and the like.
The second embodiment of the present technology may also provide a water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scale method in which the water treatment agent according to the second embodiment of the present technology is added to a water system. It is preferable to omit the configuration overlapping with the configuration described in the water treatment agent of the present technology.
From the viewpoint 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 range, more preferably 7 to 10, and still more preferably 8 to 9. The water temperature of the water system is not particularly limited, and may be 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 depending on the respective water systems to be treated, but it is generally preferable to add the water treatment agent continuously or intermittently at a concentration of 1mg/L to 1000mg/L to each water system to be treated.
In the second embodiment of the present technology, the timing of adding the chemical or each component in the aqueous system is not particularly limited, and the chemical or each component may be added at the same timing or separately. And/or the site of addition of the drug or each component in the aqueous system is not particularly limited, and may be added to the same site or a different site.
For example, in the case of use purpose of slime control or scale prevention of the film, it is preferable to add a chemical agent before the film treatment. Further, the effects of the present technology can be obtained at any time or place in the water system in order to control slime, sterilize, and prevent corrosion of pipes and the like in the water system.
In the second embodiment of the present technology, a cooling water system is preferred, and more preferably, the cooling water system is a cooling water system including a metal or a metal pipe such as a cooling tank, a cooling tower, and a heat exchanger.
In the second embodiment of the present technology, the water treatment agent may be used as a water treatment agent kit including the water treatment agent of the second embodiment of the present technology and an arbitrary component.
For example, a water treatment agent kit or the like is provided, which comprises: 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 group content of 0.8 g-COOH/g-polymer or less in the polymer (c) contained in one container (B), wherein the carboxyl polymer is contained in an amount of 1 to 18% by mass and has a pH of 10 or more.
In the case of the water treatment agent kit, the kit may be stored in different containers for each component, or may be stored in different containers for two kinds of mixed components and one component. In addition, any component may be appropriately blended in each container. The use or method of the water treatment agent kit can be performed in the same manner as the use or method of the water treatment agent.
The present technology may employ the following configuration.
[1] A water treatment agent containing the following components (a) to (c) and having a pH of 10 or more:
(a) a chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content in the polymer is 1 to 18% by mass of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
[2] the water treatment agent according to the foregoing [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 any one of for slime control, for corrosion prevention, or for scale prevention.
[4] 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 items, 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 0.05% (as Cl)2Meter) below.
[6] 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 contains 50% by mass or more of the carboxyl polymer.
[7] 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.
[8] the water treatment agent according to any one of the above [1] to [7], wherein the bromide salt is one or more selected from 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 anticorrosion method or an antiscaling method, wherein the water treatment agent according to any one of the above [1] to [8] is added to a water system.
[10] the method according to the above [9], wherein the water treatment agent is added to the water system so that the carboxyl group concentration in the water system becomes 1mg/L to 100 mg/L.
[11] A water treatment method, a sterilization method, a slime control method, an anticorrosion method or an antiscaling method, wherein 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:
(a) a chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content in the polymer is 1 to 18% by mass of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
[12] the method according to any one of the above [10] to [12], wherein the ratio of the molar ratio of the chloramine compound as the component (a) to the bromide salt as the component (b) is 1: 0.1 to 1.0, and/or the component (c) is added so that the carboxyl group concentration in the aqueous system is 5mg/L to 50 mg/L.
[13] the method according to any one of the above [9] to [12], wherein the water system is a cooling water system, and preferably the cooling water system is a cooling water system including a metal or metal pipe such as a cooling tank, a cooling tower, a heat exchanger, or the like.
In addition, the present technology may employ the following configuration.
[14] A process for producing a water treatment agent, which comprises mixing a mixed solution containing an alkaline agent, a stabilizer and a bromide salt with an oxidizing agent. Preferably, an oxidizing agent is added to the mixed solution and mixed.
[15] the method for producing a water treatment agent according to [14], 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.
[16] the method for producing a water treatment agent according to the above [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.
[17] 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). In mixing the oxidizing agent, the pH of the mixed solution is preferably adjusted.
[18] 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.
[19] the method for producing a water treatment agent according to any one of [14] to [18], wherein the mixture is further mixed with 1 to 18 mass% of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less. Preferably, the mixed solution and the carboxyl polymer are further mixed.
[20] the method for producing a water treatment agent according to any one of [14] to [19], wherein the solution containing the alkali agent, the stabilizer and the bromide salt is 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.
[21] the method for producing a water treatment agent according to any one of [14] to [20], wherein 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 the method for producing a water treatment agent according to any one of the above [14] to [21 ]. Preferably, the water treatment agent contains an alkaline agent, a halamine 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% (as Cl)2Meter) below. Further, it is preferable that the total chlorine concentration after production is 4.1% (as Cl)2Meter) above.
[24] the water treatment agent according to the above [22] or [23], which is obtained by mixing a mixed solution in which an alkaline agent, a stabilizer and a bromide salt are mixed with an oxidizing agent.
[25] the water treatment agent according to any one of [22] to [24], wherein the water treatment agent is further mixed to a carboxyl polymer in an amount of 1 to 18% by mass, and the carboxyl content in the carboxyl polymer is 0.8 g-COOH/g-polymer or less.
The carboxyl polymer preferably contains a maleic acid-based polymer and/or a (meth) acrylic polymer, and more preferably contains 50 mass% or more of the carboxyl polymer.
[26] 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.
[27] the water treatment agent according to any one of the aforementioned [21] to [26], wherein the water treatment agent is a slow-release preparation of hypobromous acid.
[28] the water treatment agent according to any one of the above [21] to [27], which further contains an anticorrosive and/or scale inhibitor. Preferably, the corrosion inhibitor and/or scale inhibitor is contained in an amount of 0.5 to 30% by mass.
[29] A water treatment method, a sterilization method, a slime control method, an anti-corrosion method, or an anti-scale method, wherein a water treatment agent obtained by the method for producing a water treatment agent according to any one of the above [14] to [21] or the water treatment agent according to any one of the above [22] to [28] is added to a water system.
Preferably applied to a water treatment apparatus. The method is applied to an open circulation type device with a cooling water system, a heat storage water system, a dust collecting 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 a water treatment system comprising an apparatus or a system for adding a water treatment agent or components used in the water treatment agent,
the water treatment agent is the water treatment agent according to any one of the above [1] to [14] or the water treatment agent according to any one of the above [23] to [28 ].
The water treatment device or water treatment system may further also include a device or system for storage, and/or may also include 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 provided.
Further, each component used in the water treatment agent according to any one of the above [1] to [14] and each component used in the water treatment agent according to any one of the above [22] to [28] may be appropriately blended and used. The hypobromous acid effect can also be exhibited by adding the water treatment agent in a state in which the respective components are mixed. Further, the hypobromous acid effect can also be exhibited by adding the respective components to the aqueous system at the same time or sequentially and mixing the respective components in the aqueous system.
Examples
The following test examples, comparative examples, and the like will be given to describe embodiments of the present technology. The scope of the present technology is not limited to the test examples and examples.
< test example 1 to test example 28 (first embodiment) >
[ test examples 1 to 4: the combination of the components: sample 1 to sample 4
In FIG. 1, samples 1 to 4 were added to open-circulation cooling water (pH8 to 9) so that the concentration of the sample (water treatment agent) became 0.8 g/L, and the change with time of the total oxidizing agent concentration in the water system was shown.
The water treatment agent (x) of sample 1 in test example 1 contained the chloramine compound at a concentration of 9%.
The water treatment agent (. DELTA.) of sample 2 in test example 2 contained the chloramine compound concentration of 9% and the bromide concentration of 3.9%.
The water treatment agent (□) of sample 3 in test example 3 contained 9% of the chloramine compound and 1.6% of the carboxyl polymer.
The water treatment agent (. diamond.) of sample 4 in test example 4 contained the chloramine compound concentration of 9%, the carboxyl polymer concentration of 1.6%, the bromide concentration of 3.9%, and the pH of 13.
The chloramine compounds used in test examples 1 to 28 were hypochlorous acid and sulfamic acid (HN)2SO2OH) by reaction with Cl2The molar ratio of N/0.1 to 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% by mass or more), the carboxyl group content in 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 measurement method of the content of carboxyl groups (g-COOH/g-polymer) & gt.
The weight average molecular weight of the carboxyl polymer was determined by the above-mentioned < method of determining the weight average molecular weight of the water-soluble polymer >.
The measurement methods used in the respective test examples are as follows.
< total oxidant concentration >: the total of chloramine, hypochlorous acid, and hypobromous acid was measured using DPD total (total) reagent. The total oxidant concentration is in mg/L in terms of chlorine, in terms of Cl2And (4) metering and representing.
< hypobromous acid >: after reacting free chlorine with glycine, the residue was measured with DPD free (free) reagentHypobromous acid. Hypobromous acid concentration in mg/L in terms of chlorine, in terms of Cl2And (4) metering and representing.
The DPD method used in the present technology is carried out according to JIS K0400-33-10:1999 using a DPD method using N, N-diethyl-1, 4-phenylenediamine.
Fig. 1 shows the change with time of the total oxidant concentration when the carboxyl polymer and the bromide are made to coexist, assuming that the concentration when only the chloramine compound is added is 100%.
When the carboxyl polymer and the bromide were added to the chloramine compound separately, no difference was observed in the residual ratio, but when both the carboxyl polymer and the bromide were added to the chloramine compound, the residual ratio decreased by 10% or more.
Since the residual rate is significantly reduced when only the chloramine compound is present together with the brominating agent and the carboxyl polymer, it is considered that the hypobromous acid generated in the aqueous system reacts with the carboxyl polymer to be decomposed.
Thus, the water treatment agent of sample 4 is expected to have a pharmacological effect of the carboxyl polymer. However, although sample 4 is designed to use hypobromous acid which is stronger than hypochlorous acid, sample 4 is not so good in the stability with time of hypobromous acid in an aqueous system, and thus the effect of hypobromous acid (for example, the sterilization effect and the like) is considered to be insufficient in the persistence. Therefore, in sample 4, it is considered difficult to provide a one-pack type water treatment agent in which the effect of hypobromous acid is exhibited well when added to an aqueous system and the chemical effect of other compounds can also be exhibited well.
[ test example 5 to test example 16: carboxyl group content of carboxyl group Polymer ]
Each of the water treatment agents used in test examples 5 to 16 contained 9% of the chloramine compound, 1.6% of the carboxyl polymer, and 3.9% of the bromide compound, and the water treatment agent prepared using the one having a pH of 13 as a raw material was used.
The carboxyl polymer used in each of the water treatment agents used in test examples 5 to 16 was a maleic acid polymer, and a polymer having a weight average molecular weight in the range of 1000 to 16000 was used.
In this case, as the carboxyl polymer of each water treatment agent, those having a carboxyl group content (g-COOH/g-polymer) in the carboxyl polymers shown in tables 1 and 2 were used.
Specifically, the content of carboxyl groups in the carboxyl group polymer in each of the water treatment agents of test examples 5 to 16 was measured, and the results were test examples 5 and 11: 0.63 g-COOH/g-polymer, test examples 6 and 12: 0.43 g-COOH/g-polymer, test examples 7 and 13: 0.49 g-COOH/g-polymer, test examples 8 and 14: 0.52 g-COOH/g-polymer, test examples 9 and 15: 0.71 g-COOH/g-polymer, test examples 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.
Each water treatment agent was prepared so that the carboxyl polymer concentration in the water treatment agent became 30 mg-polymer/L when added to 1L of water, and was used in each of test examples 11 to 16.
Assuming that the chloramine compound is 1, the molar ratio of the chloramine compound to the bromide salt of each of the water treatment agents used in test examples 5 to 16 was 1: 0.2 to 1.0.
In test examples 5 to 10, each water treatment agent was added to open-circulation cooling water (pH8 to 9) so that the carboxyl polymer concentration became 5 mg-polymer/L, and the hypobromous acid concentration (mg/L, as Cl) in the water system after 48 hours was measured2Meter). The results are shown in fig. 2 and table 1.
In test examples 11 to 16, each water treatment agent was added to open-circulation cooling water (pH8 to 9) so that the carboxyl polymer concentration became 30 mg-polymer/L, and the hypobromous acid concentration (mg/L, as Cl) in the water system after 48 hours was measured2Meter). The results are shown in fig. 3 and table 2.
[ Table 1]
TABLE 1
[ Table 2]
TABLE 2
[ test examples 17 to 27: concentration of carboxyl Polymer in Water System ]
The water treatment agents used in test examples 17 to 29 were obtained by changing the concentration of the carboxyl polymer in the water system shown in table 3 using the water treatment agent used in test example 5 as a raw material.
In test examples 17 to 27, each water treatment agent was added to the open circulation type cooling water (pH8 to 9) so that the carboxyl polymer concentration (mg-polymer/L) in the water system shown in table 3 below was obtained. After each water treatment agent was added, the hypobromous acid concentration (mg/L in terms of Cl) in the water system after 48 hours was measured2Meter). The results are shown in FIG. 4 and Table 3.
[ Table 3]
TABLE 3
< nodules >
The results of test examples 5 to 16 are shown in fig. 2 and 3, and table 1 and table 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 polymer used in the water treatment agent is 0.77%, the concentration of the hypobromous acid in the added water system can be maintained at about 80%. Further, from the viewpoint that the concentration of the added aqueous hypobromous acid can be adjusted to 90% or more, the carboxyl group content in the polymer is more preferably 0.35 to 0.75.
When the concentration of the carboxyl polymer in the aqueous system is 5 mg-polymer/L to 30 mg-polymer/L when the water treatment agent is added to the aqueous system, the total concentration (%) of the oxidizing agent and the concentration (%) of the hypobromous acid in the aqueous system are high and good.
Further, the amount of the water treatment agent added to the water system is preferably 40mg/L to 200mg/L from the viewpoint of the effect and cost. Further, as described above, when the concentration of the carboxyl polymer in the aqueous system when the water treatment agent is added to the aqueous system is preferably 5 mg-polymer/L to 30 mg-polymer/L, the concentration of the carboxyl polymer contained in the water treatment agent is preferably 18 mass% or less (more preferably 15 mass% or less), and is preferably 1 mass% or more (more preferably 1.5 mass% or more) from the viewpoint of cost, work efficiency, effect, and the like. For example, the polymer content in the water treatment agent is 0.15 mg-polymer/mg (i.e., 15 mass%) when [ polymer concentration in the water system is 30 mg-polymer/L ]/[ amount of water treatment agent added 200mg/L to the water system ].
The same effects as those of the water treatment agent of test example 7 were obtained even when the maleic acid polymer used in the water treatment agent of test example 7 was converted to an acrylic acid polymer (the carboxyl group content in the polymer was 0.5 g-COOH/g-polymer; weight average molecular weight was 1000 to 16000).
The total oxidizing agent concentration of 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, respectively, in the static storage in the thermostatic bath.
[ 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 open-circulation cooling water (pH 8-9) so that the concentration of the carboxyl polymer became 0.2g/L, and the concentration of hypobromous acid (mg/L, in terms of Cl) in the water system was measured over time2Meter).
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 if the weight average molecular weight of the carboxyl polymer is 10 to the power of 3 to the power of 4, the hypochlorous acid concentration is approximately the same as that of the carboxyl polymer with the weight average molecular weight of 3900. When a carboxyl polymer having a weight average molecular weight of about 1000 to 20000 is used, a further excellent hypobromous acid concentration (about 40% to 60%) can be obtained.
The content of carboxyl groups in the polymer was measured by the above-mentioned measuring method of the content of carboxyl groups (g-COOH/g-polymer) & gt.
The weight average molecular weight of the carboxyl polymer was determined by the above-mentioned < method of determining the weight average molecular weight of the water-soluble polymer >.
The water treatment agent of the first embodiment can be adjusted so that the concentration of hypobromous acid after 48 hours from the addition of water is preferably 0.25mg/L (as Cl)2In (v) 1.5mg/L (in Cl)2Calculated as Cl), more preferably 0.5mg/L (calculated as Cl)2In (calculated as Cl) 1mg/L2Meter).
[ Table 4]
TABLE 4
< test example 29 to test example 31 (second embodiment) >
The measurement methods used in the respective test examples are as follows.
< total oxidant concentration >: the total of chloramine, hypochlorous acid, hypobromous acid was measured using the DPD total reagent. The total oxidant concentration is in mg/L in terms of chlorine, in terms of Cl2And (4) metering and representing.
< hypobromous acid >: after reacting free chlorine with glycine, residual hypobromous acid was measured using DPD free reagent. Hypobromous acid concentration in mg/L in terms of chlorine, in terms of Cl2And (4) metering and representing.
The DPD method used in the present technology is carried out according to JIS K0400-33-10:1999 using a DPD method using N, N-diethyl-1, 4-phenylenediamine.
[ test examples: test example 29 (example 1), test example 30 (comparative example 1), and test example 31 (comparative example 2) ]
In this test, the components shown in Table 5 were mixed with water (about 10 ℃ C. to 20 ℃ C.) in the mixing order shown in Table 5 to prepare each one-pack type water treatment agent.
In this case, the components shown in table 5 were blended so that 20 mass% (remainder) of water, 10 mass% of sodium sulfamate, 5 mass% of sodium bromide and pH14 were obtained in the water treatment agent immediately after the production (0 hour). Sodium hydroxide was used as the alkaline agent and powdered sodium bromide was used as the sodium bromide. Sodium hypochlorite was used so that hypochlorous acid (free type) was 1 mole with respect to 1.5 moles of sulfamic acid (free type).
In addition, in test example 29 (example 1), test example 30, and test example 31 (comparative example 1 and comparative example 2), when sodium sulfamate and sodium hypochlorite were mixed, the total chlorine concentration (%) in the water treatment agent generated was calculated (as Cl)2Calculated) was 4.4%. Each "total chlorine detection rate (%)" 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 passed through the measured value (% in Cl) of the total chlorine concentration in the water treatment agent2Theoretical value of total chlorine concentration in water treatment agent (% in Cl)2Meter) "× 100 (%).
The method for producing the water treatment agent of test example 29 (example 1) was:
500g of sodium hydroxide was added to 1.0L of water and mixed to adjust the pH to 14 or more, thereby obtaining an aqueous alkali agent mixture solution.
To this alkali agent mixed aqueous solution, 400g of sodium sulfamate was added, followed by addition and mixing of 250g of powdered sodium bromide to obtain three agent mixed aqueous solutions.
To the three-agent mixed aqueous solution, 2000g of sodium hypochlorite was added and mixed to obtain a water treatment agent. Sodium hypochlorite was added to 1 mole of hypochlorous acid (free type) so that sulfamic acid (free type) was 1.5 moles.
Sodium sulfamate, sodium bromide powder and sodium hypochlorite were used, respectively, from tokyo chemical industries, and japan light metals.
The concentrations of the respective components in the one-pack type water treatment agent are as described above.
Further, "the content (%) of free chlorine in the total chlorine concentration" is defined by [ the concentration (%) of free chlorine in the water treatment agent as Cl%2Calculated)/total chlorine concentration in water treatment agent (% in Cl)2Meter)]X 100 (%) was calculated.
In addition, the water spot as test example 32 (example 2)And the physical agent changes the adding sequence of the sodium sulfamate and the powder sodium bromide when preparing the mixed aqueous solution of the three agents. That is, three-agent mixed aqueous solutions were prepared by adding powdered sodium bromide to an alkaline agent mixed aqueous solution, then adding sodium sulfamate to the solution, and mixing the solution. 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)2Calculated as Cl), and the content of free chlorine in the total chlorine concentration was 0.04 (% by Cl)2Meter). Therefore, the water treatment agent of test example 32 (example 2) has a quality stability substantially the same as that of the water treatment agent of test example 29 (example 1).
Each of the water treatment agents (test example 29 (example 1), test example 30, and test example 31 (comparative example 1 and comparative example 2)) was stored at a temperature of about 15 to 25 ℃ for a fixed period of time after production of the aqueous solution. The total chlorine concentration and free chlorine in each water treatment agent were measured for each elapsed time (1 hour, 2 hours, 3 hours, 4 hours) after production, and the results are shown in table 6.
[ Table 5]
Table 5: production steps of respective water treatment agents
[ Table 6]
Table 6: the total chlorine concentration in each water treatment agent and the free chlorine content in the 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 terms of Cl)2Meter).
As shown in test example 29 (example 1) in tables 5 to 7, a mixed solution in which a chemical other than a bromide salt is mixed is prepared, and a bromide salt is added to and mixed with the mixed solution, whereby a one-liquid type water treatment agent containing a chloramine compound + bromide ions can be 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 the production2Calculated) was 4.3% and became stable, and the free chlorine content in the total chlorine concentration was also 0.04% and became stable. It is considered that the effective components in the water treatment agent become stable by the stationary state, and therefore the stable state lasts for several weeks or more.
On the other hand, it is considered that the water treatment agent of test example 31 (comparative example 2) continued the decrease in the total chlorine concentration even after 4 hours from the production, and thereafter was much lower than the total chlorine detection rate of 60% and the total chlorine concentration (% in Cl)2Calculated) 2.8 percent. In addition, the water treatment agent of test example 30 (comparative example 1) showed a total chlorine detection rate of about 93% and a total chlorine concentration (% in Cl) after 4 hours from the production2Calculated) was 4.1% and became steady, and the free chlorine content in the total chlorine concentration was also 0.05% and became steady.
The loss of the total chlorine detection rate of the water treatment agent of test example 29 (example 1) was about 3% between 1 hour after the production and 4 hours after the production, 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) and the loss rate of the total chlorine concentration in the water treatment agent of test example 30 (comparative example 1) are compared, the water treatment agent of test example 29 (example 1) can keep the loss rate at half or less and substantially close to 100%, and thus can be said to be extremely excellent in quality stability.
As described above, the water treatment agent according to the second embodiment of the present technology can maintain a high level of the active ingredient, and therefore, it can be said that the effect of hypobromous acid is exhibited well when added to an aqueous 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 elapsed2Calculated) is 4.1% or less, but the total chlorine concentration (% in Cl) of the water treatment agent of the second embodiment of the present technology2In terms of) at least 4.2% or more even after 2 hours, 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.
The water treatment agent according to the second embodiment of the present technology, which is produced in the above-described order, has excellent quality stability of the chemical agent and can greatly suppress the decrease of the active ingredient, and thus hypobromous acid can be generated at a high concentration when added to an aqueous 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 exhibit the effect of hypobromous acid well. Therefore, the water treatment agent according to the second embodiment of the present technology can further exhibit effects of hypobromous acid such as a high bactericidal effect and a high slime prevention effect.
The water treatment agent according to the second embodiment of the present technology does not include a special device or other chemical agent to exhibit such an effect, but can exhibit such an excellent effect by devising the order of mixing the components. That is, from the viewpoint that the production method of the second embodiment of the present technology thus drawn and the water treatment agent obtained by the production method can achieve cost reduction, work efficiency, and improvement in quality stability, the second embodiment of the present technology can also be said to find an unpredictable configuration and an unpredictable effect resulting therefrom.
Claims (14)
1. A water treatment agent which contains the following components (a) to (c) and has a pH of 10 or more:
(a) a chloramine compound,
(b) Bromide salt,
(c) The carboxyl group content in the polymer is 1 to 18% by mass of a carboxyl group polymer having a carboxyl group content of 0.8 g-COOH/g-polymer or less.
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 for slime control, for corrosion prevention, or for scale prevention.
4. The water treatment agent according to any one of claims 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, and an oxidizing agent.
5. The water treatment agent according to any one of claims 1 to 4, 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 Cl2The content is 0.05% or less.
6. A method for producing a water treatment agent, wherein a mixed solution obtained by mixing an alkaline agent, a stabilizer and a bromide salt is mixed with an oxidizing agent.
7. The method for producing a water treatment agent according to claim 6, wherein the stabilizer is an aminosulfonic acid compound.
8. The method for producing a water treatment agent according to claim 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 claims 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 claims 6 to 9, wherein the mixed solution is a solution in which a powdered bromide salt is mixed as the bromide salt.
11. The method for producing a water treatment agent according to any one of claims 6 to 10, wherein the mixture is further mixed so that the carboxyl group content in the carboxyl group polymer is 0.8 g-COOH/g-polymer or less in an amount of 1 to 18% by mass.
12. A water treatment agent comprises an alkaline agent, a chloramine compound and a bromide salt,
the total chlorine detection rate after the production of the water treatment agent is 95% or more, and the free chlorine content in the total chlorine concentration is Cl2The content is 0.05% or less.
13. The water treatment agent according to claim 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 claim 13, wherein the pH of the water treatment agent is 13 or more.
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| JP2019065290A JP6787429B2 (en) | 2019-03-29 | 2019-03-29 | Water treatment agent |
| JP2019-065290 | 2019-03-29 | ||
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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 |
| US8883031B2 (en) | 2009-08-19 | 2014-11-11 | Hitachi Chemical Company, Ltd. | CMP polishing liquid 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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