JP2015117216A - Sterilization method of water system - Google Patents
Sterilization method of water system Download PDFInfo
- Publication number
- JP2015117216A JP2015117216A JP2013262680A JP2013262680A JP2015117216A JP 2015117216 A JP2015117216 A JP 2015117216A JP 2013262680 A JP2013262680 A JP 2013262680A JP 2013262680 A JP2013262680 A JP 2013262680A JP 2015117216 A JP2015117216 A JP 2015117216A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- concentration
- residual chlorine
- inorganic
- potential
- 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 36
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 30
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 71
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 71
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000007800 oxidant agent Substances 0.000 claims abstract description 53
- 230000001590 oxidative effect Effects 0.000 claims abstract description 35
- VGYXEINYMUQYBF-UHFFFAOYSA-N 1,2-dibromo-1-nitroethanol Chemical compound BrCC(Br)(O)[N+]([O-])=O VGYXEINYMUQYBF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000417 fungicide Substances 0.000 claims description 23
- 230000000855 fungicidal effect Effects 0.000 claims description 17
- 239000000645 desinfectant Substances 0.000 claims description 13
- -1 isothiazoline compound Chemical class 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 30
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 abstract description 27
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical group CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 abstract description 27
- 238000007792 addition Methods 0.000 abstract description 25
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 20
- KTQVJAPIQPIIPF-IOBHVTPZSA-N (1Z,2Z)-N,N'-dihydroxyethanediimidoyl dichloride Chemical compound O\N=C(/Cl)\C(\Cl)=N\O KTQVJAPIQPIIPF-IOBHVTPZSA-N 0.000 abstract description 5
- 239000003899 bactericide agent Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 38
- 230000000694 effects Effects 0.000 description 33
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 31
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- 239000003814 drug Substances 0.000 description 28
- 229940079593 drug Drugs 0.000 description 28
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000004471 Glycine Substances 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 12
- 230000000813 microbial effect Effects 0.000 description 12
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 239000000498 cooling water Substances 0.000 description 10
- 230000005764 inhibitory process Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 8
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 7
- 101710088194 Dehydrogenase Proteins 0.000 description 7
- 241000589248 Legionella Species 0.000 description 7
- 208000007764 Legionnaires' Disease Diseases 0.000 description 7
- 239000003966 growth inhibitor Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- FMNZAHDAULEOSO-UHFFFAOYSA-N 2,2-dibromo-2-nitroethanol Chemical compound OCC(Br)(Br)[N+]([O-])=O FMNZAHDAULEOSO-UHFFFAOYSA-N 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- 206010036790 Productive cough Diseases 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 3
- 210000003802 sputum Anatomy 0.000 description 3
- 208000024794 sputum Diseases 0.000 description 3
- 239000003206 sterilizing agent Substances 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000011575 calcium Substances 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000003640 drug residue Substances 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- VUSLYGKUDDJMMC-UHFFFAOYSA-N 2-bromo-[1,3]thiazolo[5,4-b]pyridine Chemical compound C1=CN=C2SC(Br)=NC2=C1 VUSLYGKUDDJMMC-UHFFFAOYSA-N 0.000 description 1
- ASKFWACWQQZSSS-UHFFFAOYSA-N 2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC=CC1=O ASKFWACWQQZSSS-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OMJKWVKPIOIQDM-UHFFFAOYSA-N 3-bromo-1-chloroimidazolidine-2,4-dione Chemical compound ClN1CC(=O)N(Br)C1=O OMJKWVKPIOIQDM-UHFFFAOYSA-N 0.000 description 1
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 1
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
- MENYRYNFSIBDQN-UHFFFAOYSA-N 5,5-dibromoimidazolidine-2,4-dione Chemical compound BrC1(Br)NC(=O)NC1=O MENYRYNFSIBDQN-UHFFFAOYSA-N 0.000 description 1
- NKEKPBPHPFSSIT-UHFFFAOYSA-N 5-chloro-2-(2,4,4-trimethylpentan-2-yl)-1,2-thiazol-3-one Chemical compound CC(C)(C)CC(C)(C)N1SC(Cl)=CC1=O NKEKPBPHPFSSIT-UHFFFAOYSA-N 0.000 description 1
- MMONDPHQMXRZDG-UHFFFAOYSA-N 5-chloro-2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC(Cl)=CC1=O MMONDPHQMXRZDG-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 208000035859 Drug effect increased Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 241000589242 Legionella pneumophila Species 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- BWJJSYVJOLHQFF-AMLDTQNSSA-N N'-(4-iodoanilino)-N-(4-nitrophenyl)iminobenzenecarboximidamide Chemical compound C1=CC=C(C=C1)/C(=N/NC2=CC=C(C=C2)I)/N=NC3=CC=C(C=C3)[N+](=O)[O-] BWJJSYVJOLHQFF-AMLDTQNSSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229940115932 legionella pneumophila Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Images
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、循環冷却水系などの水系の殺菌方法に係り、特に有機系殺菌剤と無機系酸化剤とを併用した水系の殺菌方法に関する。 The present invention relates to an aqueous sterilization method such as a circulating cooling water system, and more particularly to an aqueous sterilization method using an organic sterilizing agent and an inorganic oxidizing agent in combination.
冷却水は、種々の産業分野、例えば、石油化学産業や鉄鋼産業などにおいて、間接的又は直接的に被処理物を冷却する目的で、あるいは、ビルの空調や冷暖房及びその関連装置などに多量に利用されている。さらに、水資源の不足や有効利用の観点から、冷却水の使用量を削減するために、例えば、開放循環冷却水系の高濃縮運転における強制ブロー量の削減など、冷却水の高度利用が行われている。このように冷却水を高度に利用した場合には、溶存塩類や栄養源の濃縮などにより、循環冷却水の水質が悪化し、細菌、黴、藻類などの微生物群に、土砂、塵埃などが混ざり合って形成されるスライムが発生し、熱交換器における熱効率の低下や通水の悪化を引き起こし、またスライム付着下部において、機器や配管の局部腐食を誘発する。 A large amount of cooling water is used in various industrial fields, for example, in the petrochemical industry and the steel industry, for the purpose of indirectly or directly cooling the object to be treated, or for air conditioning, cooling and heating and related equipment of buildings. It's being used. Furthermore, in order to reduce the amount of cooling water used from the viewpoint of lack of water resources and effective use, advanced use of cooling water is performed, for example, reducing the amount of forced blow in the high concentration operation of an open circulating cooling water system. ing. In this way, when cooling water is used at a high level, the quality of circulating cooling water deteriorates due to the concentration of dissolved salts and nutrients, etc., and soil, sand, dust, etc. are mixed with microorganisms such as bacteria, sputum and algae. The slime formed is generated, which causes a decrease in thermal efficiency and deterioration of water flow in the heat exchanger, and also induces local corrosion of equipment and piping at the lower part of the slime adhesion.
そこで、このようなスライムによる障害を防止するために、種々の抗菌剤、例えば、次亜塩素酸などの酸化性抗菌剤などが用いられている。冷却水の高度利用がさらに進んだ場合には、スライムによる障害が激しくなり、抗菌剤の必要添加濃度が上昇する。しかし、酸化性抗菌剤の場合は、金属腐食を生ずる危険性が増すので、添加濃度を増加させることはできない。また、酸化性抗菌剤は、酸化力が強くスライムに対する浸透力に乏しいために、いったんスライム障害が発生すると、その進行を阻止することは極めて困難である。 Therefore, various antibacterial agents, for example, oxidizing antibacterial agents such as hypochlorous acid, and the like are used in order to prevent such damage caused by slime. When advanced use of cooling water further progresses, the slime damage becomes severe and the required concentration of antibacterial agent increases. However, in the case of an oxidizing antibacterial agent, the added concentration cannot be increased because the risk of causing metal corrosion increases. In addition, since the oxidizing antibacterial agent has a strong oxidizing power and a poor ability to penetrate slime, it is extremely difficult to prevent the progression of slime once it occurs.
有機系抗菌剤の場合は、酸化力がないか又は極めて低く、スライムに対する浸透力が強いために、いったんスライム障害が発生した場合でもその進行を阻止することは比較的容易である。しかし、選定する薬剤によって、細菌、黴、藻類などのスライムの構成要素に対して有効なスペクトルが異なる。また、素材コストが酸化性抗菌剤と比較して遥かに高価である。 In the case of an organic antibacterial agent, since it has no or very low oxidizing power and has a strong penetrating ability to slime, it is relatively easy to prevent the progression of slime once it has occurred. However, the effective spectrum for the constituents of slime such as bacteria, sputum, and algae varies depending on the selected drug. In addition, the material cost is much higher than that of the oxidizing antibacterial agent.
このために、スライム障害の激しい条件においても、細菌、黴、藻類などのあらゆるスライムの構成要素に対して有効であり、低コストでスライムを防除することができるスライム防除方法及び防除剤が求められている。 Therefore, there is a need for a slime control method and a control agent that are effective against all slime constituents such as bacteria, sputum, and algae even under severe slime damage conditions and that can control slime at low cost. ing.
特許文献１，２には、冷却水系に酸化性抗菌剤とイソチアゾロン化合物を添加することにより、各薬剤の相乗効果を発揮させ、冷却水系のスライムの付着を抑制する方法が記載されている。
有機系殺菌剤と無機系酸化剤とを併用すると、殺菌速度が大きく、殺菌効果に優れるが、無機系酸化剤を多くすると金属材に腐食が生じるので、なるべく添加量が少ないことが望まれる。 When an organic disinfectant and an inorganic oxidant are used in combination, the sterilization rate is large and the bactericidal effect is excellent. However, if the inorganic oxidant is increased, the metal material is corroded, so it is desirable that the addition amount be as small as possible.
本発明は、有機系殺菌剤と無機系酸化剤とを併用する水系の殺菌方法において、金属材の腐食を抑制することができると共に、有機系殺菌剤の使用量を少なくしても優れた殺菌効果を得るようにすることを目的とする。 The present invention is an aqueous sterilization method using an organic sterilant and an inorganic oxidant in combination, which can suppress corrosion of a metal material and is excellent in sterilization even if the amount of the organic sterilizer is reduced. The purpose is to obtain an effect.
本発明の水系の殺菌方法は、水系に有機系殺菌剤と無機系酸化剤とを添加する水系の殺菌方法において、該有機系殺菌剤と無機系酸化剤とを間欠的に添加することを特徴とするものである。 The aqueous sterilization method of the present invention is characterized in that, in the aqueous sterilization method in which an organic sterilizer and an inorganic oxidizer are added to an aqueous system, the organic sterilizer and the inorganic oxidizer are intermittently added. It is what.
本発明では、有機系殺菌剤と無機系酸化剤とを添加する時期と時期の間に、水系の残留塩素が実質的に検出されない非残留期間を設けることが好ましい。 In the present invention, it is preferable to provide a non-residual period in which water-based residual chlorine is not substantially detected between the time when the organic disinfectant and the inorganic oxidant are added.
また、本発明では、無機系酸化剤及び有機系殺菌剤の添加間隔を２４〜１００ｈとすることが好ましい。 Moreover, in this invention, it is preferable that the addition space | interval of an inorganic type oxidizing agent and an organic type fungicide shall be 24-100h.
本発明者が微生物燃料電池を用いて種々研究を重ねた結果、有機系殺菌剤と無機系酸化剤とを併用する水系の殺菌方法にあっては、両剤を間欠添加すると、添加量を少なくしても十分な殺菌効果が得られることが認められた。即ち、本発明で用いる有機系殺菌剤と無機系酸化剤とを併用して水系に添加した場合、添加を中断して水系に薬剤濃度がなくなった後も菌の代謝を阻害し続け、殺菌効果が持続することが見出された。 As a result of the inventor's extensive research using a microbial fuel cell, in an aqueous sterilization method using both an organic sterilizer and an inorganic oxidizer, the amount added can be reduced by intermittent addition of both agents. However, it was confirmed that a sufficient bactericidal effect was obtained. That is, when combined with an organic sterilizing agent and an inorganic oxidizing agent used in the present invention and added to an aqueous system, even after the addition is interrupted and the concentration of the drug in the aqueous system disappears, the metabolism of bacteria continues to be inhibited, and the sterilizing effect Was found to persist.
この理由については、微生物燃料電池を用いた評価結果より、次のように推察される。 About this reason, it estimates as follows from the evaluation result using a microbial fuel cell.
無機系酸化剤と有機系殺菌剤は作用点、作用機構が異なり、微生物燃料電池の電位阻害パターンが異なる。結合型塩素は薬剤接触とほぼ同時に急激な電位上昇がおこり、生物のエネルギー生産系の阻害に即効性があることを示す。しかし、残留しなくなると急激に効果が低下する。これは、エネルギー生産系にかかわる物質が破壊されていないためと推定される。 Inorganic oxidizers and organic fungicides have different points of action and mechanisms of action, and have different potential inhibition patterns for microbial fuel cells. Combined chlorine has a rapid potential increase almost simultaneously with drug contact, indicating that it has an immediate effect on the inhibition of the biological energy production system. However, when it does not remain, the effect decreases rapidly. This is presumed to be because the substances involved in the energy production system have not been destroyed.
一方、有機系殺菌剤は有効成分が微生物と接触すると、ゆっくりと電位上昇が起こる。これは、エネルギー生産系の阻害がゆっくりとおこっていることを示す。そして微生物燃料電池内の薬剤残留がなくなると、ゆっくりと電位回復が起こる。これは、エネルギー生産にかかわる物質の回復に時間がかかることを示している。無機系酸化剤と有機系殺菌剤とを併用すると、急激な電位上昇がおこり、上昇レベルも大きい。薬剤の残留がなくなると回復はゆっくりと起こる。 On the other hand, when an active ingredient comes into contact with microorganisms, an organic fungicide slowly increases in potential. This indicates that the energy production system is slowly inhibiting. When the drug residue in the microbial fuel cell is exhausted, the potential recovers slowly. This indicates that it takes time to recover materials involved in energy production. When an inorganic oxidizing agent and an organic disinfectant are used in combination, a rapid increase in potential occurs and the level of increase is large. Recovery occurs slowly when there is no drug residue.
これらの無機系酸化剤と有機系殺菌剤との化学的な性質の観点での違いは、無機系酸化剤（以下、酸化系増殖抑制剤又は単に酸化剤ということがある。）は酸化還元電位を変化させ、有機系殺菌剤はこの変化を引き起こさない点がある。 The difference in the chemical properties between these inorganic oxidizers and organic fungicides is that the inorganic oxidizer (hereinafter sometimes referred to as oxidative growth inhibitor or simply oxidizer) is a redox potential. There is a point that organic germicide does not cause this change.
これらの結果から推察されるのは、無機系酸化剤は細胞内の酸化還元電位勾配に影響を与え、電子伝達系のエネルギー生産部分を阻害しているが、このときエネルギー生産系の物質は不可逆的な科学的・物理的変化を受けないということである。そのため、酸化還元電位に影響する物質がなくなれば微生物は急速に機能を回復する。一方、有機系殺菌剤はエネルギー生産系にかかわる物質を、不可逆的に阻害するため、回復には物質生産を必要とするので時間がかかる。 From these results, it can be inferred that inorganic oxidants affect the redox potential gradient in the cell and inhibit the energy production part of the electron transfer system, but at this time the substances in the energy production system are irreversible. It is not subject to natural scientific and physical changes. For this reason, if there is no substance that affects the oxidation-reduction potential, the microorganism rapidly recovers its function. On the other hand, since organic germicides irreversibly inhibit substances involved in energy production systems, recovery requires substance production and thus takes time.
無機系酸化剤と有機系殺菌剤とを併用すると、酸化剤が代謝を停止させ、有機系殺菌剤の作用点への到達、及び化学反応が効率よく行われる。微生物機能の回復には物質の生産が必要なので、代謝機能の低下が大きい分回復に時間を要する。このようなメカニズムで、即効性のある殺菌がなされ、残留しない期間も効果持続期間が続く。さらに、細胞内で分解される殺菌成分も抑制されるので必要とされる薬剤濃度も低濃度となる。 When an inorganic oxidant and an organic fungicide are used in combination, the oxidant stops metabolism, reaching the action point of the organic fungicide, and a chemical reaction is performed efficiently. Since the production of substances is necessary for the recovery of microbial function, it takes time to recover due to the large decrease in metabolic function. By such a mechanism, immediate sterilization is performed, and the duration of the effect continues even when it does not remain. Furthermore, since the bactericidal component decomposed in the cells is also suppressed, the required drug concentration becomes low.
本発明では、無機系酸化剤が残留しない期間を設けるように添加することにより、腐食性も抑制される。 In the present invention, the corrosivity is also suppressed by adding so as to provide a period in which the inorganic oxidant does not remain.
本発明によると、有機系殺菌剤及び無機系酸化剤の添加量を少なくしても優れた殺菌効果が期待できるところから、経済性の向上を図ることができる。また、金属表面水系（例えば冷却塔）にレジオネラが検出された場合でも、本法によれば、その殺菌の速攻性と低腐食性によって迅速に対処することができる。 According to the present invention, even if the addition amount of the organic sterilizing agent and the inorganic oxidant is reduced, an excellent sterilizing effect can be expected, so that economic efficiency can be improved. Further, even when Legionella is detected in a metal surface water system (for example, a cooling tower), according to the present method, it is possible to quickly cope with the sterilization quickness and low corrosiveness.
本発明では、無機系酸化剤を添加するので即効性があり、また有機系殺菌剤を添加するので、水系に無機系酸化剤がなくなっても効果が持続し、安定した処理を行うことができる。また、目的とする系以外の系の殺菌を回避でき、排水系の活性汚泥や、環境への負荷低減を図ることができる。 In the present invention, since an inorganic oxidizer is added, there is an immediate effect, and since an organic sterilizer is added, even if the inorganic oxidizer is removed from the aqueous system, the effect is maintained and stable treatment can be performed. . In addition, sterilization of systems other than the target system can be avoided, and activated sludge in the drainage system and reduction of the load on the environment can be achieved.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明が処理対象とする水系としては、冷却水系、紙パルプ製造水系、スクラバー水系などが例示される。 Examples of water systems to be treated by the present invention include cooling water systems, paper pulp manufacturing water systems, scrubber water systems, and the like.
本発明で用いる無機系酸化剤としては、例えば、塩素ガス、次亜塩素酸ナトリウム、塩素化イソシアヌル酸などの塩素系酸化剤、ジブロモヒダントイン、ブロモクロロヒダントインなどの臭素剤、過ヨウ素酸カリウム、メタ過ヨウ素酸ナトリウム、パラ過ヨウ素酸ナトリウム、ヨウ素、ヨウ素酸カリウムなどのヨウ素剤、過酸化水素、オゾンなどを挙げることができるが、次亜塩素酸ナトリウムが好適である。 Examples of the inorganic oxidizing agent used in the present invention include chlorine oxidizing agents such as chlorine gas, sodium hypochlorite and chlorinated isocyanuric acid, bromine agents such as dibromohydantoin and bromochlorohydantoin, potassium periodate, Examples thereof include iodine agents such as sodium periodate, sodium paraperiodate, iodine, and potassium iodate, hydrogen peroxide, ozone, and the like, but sodium hypochlorite is preferred.
有機系殺菌剤としては、イソチアゾリン化合物、ジクロログリオキシム、ジブロモニトロエタノールのいずれか、またはこれらの組合わせを用いるのが好ましい。 As the organic fungicide, it is preferable to use any one of isothiazoline compounds, dichloroglyoxime, dibromonitroethanol, or a combination thereof.
イソチアゾリン化合物としては、例えば、２−メチル−４−イソチアゾリン−３−オン、２−エチル−４−イソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、５−クロロ−２−エチル−４−イソチアゾリン−３−オン、５−クロロ−２−ｔ−オクチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−シクロヘキシル−４−イソチアゾリン−３−オンなどを挙げることができる。これらのイソチアゾロン化合物は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。また、イソチアゾリン化合物としては、上述のイソチアゾリン化合物と塩化マグネシウム、硝酸マグネシウム、塩化銅、硝酸銅、塩化カルシウムなどとの錯化合物を用いてもよい。 Examples of the isothiazoline compound include 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2. -Methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4-isothiazolin-3-one, 4,5-dichloro 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, and the like. These isothiazolone compounds can be used individually by 1 type, or can also be used in combination of 2 or more type. As the isothiazoline compound, a complex compound of the above-mentioned isothiazoline compound and magnesium chloride, magnesium nitrate, copper chloride, copper nitrate, calcium chloride, or the like may be used.
本発明では、対象水系に対して、有機系殺菌剤（好ましくはイソチアゾリン化合物、ジクロログリオキシド、及びジブロモニトロエタノールのいずれか１種または２種以上）、無機酸化剤（好ましくは次亜塩素酸ナトリウム）を別々に、あるいは、事前に混合したのち添加する。酸化剤の安定化剤として窒素化合物（好ましくはグリシン、ポリペプトン、及びスルファミン酸のいずれか１種または２種以上）を別々にあるいは事前に混合して添加してもよい。 In the present invention, an organic disinfectant (preferably any one or more of isothiazoline compound, dichloroglycoxide and dibromonitroethanol), an inorganic oxidant (preferably sodium hypochlorite) with respect to the target aqueous system. ) Separately or in advance after mixing. Nitrogen compounds (preferably one or more of glycine, polypeptone, and sulfamic acid) may be added separately or in advance as a stabilizer for the oxidizing agent.
このとき、好ましくは、殺菌成分である有機系殺菌剤と増殖抑制成分である無機系酸化剤とが同時に残留する期間（残留期間）と両者とも残留しない非残留期間ができるように間欠的に添加する。この非残留期間においては、残留塩素が実質的に検出されないようにするのが好ましい。通常、残留塩素の各測定法には、測定下限値があり、残留していないことの確認には、測定下限値以下であることを確認すれば良い。例えば、ＤＰＤ法における残留塩素の測定下限値は０．１ｍｇ/Ｌである。 At this time, it is preferable to add intermittently so that an organic disinfectant that is a disinfecting component and an inorganic oxidant that is a growth inhibitory component remain simultaneously (residual period) and a non-residual period in which neither remains To do. It is preferable that substantially no residual chlorine is detected during this non-residual period. Usually, each measurement method of residual chlorine has a measurement lower limit value, and it can be confirmed that it is not more than the measurement lower limit value in order to confirm that there is no residue. For example, the lower limit of measurement of residual chlorine in the DPD method is 0.1 mg / L.
スライムコントロール効果は期待できないが、腐食に影響がない残留塩素濃度としては０．１ｍｇ/Ｌ未満が目安であり、実用上は０．１ｍｇ/Ｌ未満となる様に管理すれば良い。無機系酸化剤の添加により検出される残留塩素はスライムコントロールに有用であるが、本発明によれば、連続的に残留塩素が検出されなくても、スライムコントロール効果が維持される。 Although the slime control effect cannot be expected, the residual chlorine concentration that does not affect the corrosion is a guideline of less than 0.1 mg / L, and may be managed to be less than 0.1 mg / L in practical use. Residual chlorine detected by adding an inorganic oxidizing agent is useful for slime control. However, according to the present invention, the slime control effect is maintained even if residual chlorine is not detected continuously.
残留塩素濃度は遊離残留塩素濃度を超えることはなく、残留塩素濃度を一定値以下に保てば、遊離残留塩素濃度はそれ以下の値となる。遊離残留塩素は残留塩素よりも腐食性が高く、遊離塩素濃度を一定値以下にしない場合、残留塩素濃度で管理すれば目標が達成できる。 The residual chlorine concentration does not exceed the free residual chlorine concentration, and if the residual chlorine concentration is kept below a certain value, the free residual chlorine concentration becomes a value below that. Free residual chlorine is more corrosive than residual chlorine. If the free chlorine concentration is not below a certain level, the target can be achieved by managing the residual chlorine concentration.
無機系酸化剤と有機系殺菌剤との添加頻度は２４時間に１時間未満、例えば２４時間に０．１〜０．９時間特に０．２５〜０．５時間程度とするのが好ましい。添加時における有機系殺菌剤の添加量は１〜３０ｍｇ／Ｌ特に３〜１０ｍｇ／Ｌ程度が好ましく、無機系酸化剤の場合は１〜５０ｍｇ／ＬａｓＣｌ２特に３〜１０ｍｇ／ＬａｓＣｌ２程度が好ましい。１回の添加とその後の添加との間隔（非添加時間）は２４〜１００ｈ特に２５〜７２ｈ程度が好ましい。
無機系酸化剤と有機系殺菌剤とは同じタイミングで同時に添加するだけでなく、それらを別のタイミングで添加しても良い。
The addition frequency of the inorganic oxidizer and the organic fungicide is preferably less than 1 hour in 24 hours, for example, 0.1 to 0.9 hours in 24 hours, particularly about 0.25 to 0.5 hours. The addition amount of the organic fungicides is preferably about 1 to 30 mg / L, especially 3-10 mg / L at the time of the addition, 2 about 1~50mg / LasCl 2 particularly 3~10mg / LasCl For inorganic oxidizing agent is preferred. The interval (non-addition time) between one addition and the subsequent addition is preferably about 24 to 100 h, particularly about 25 to 72 h.
The inorganic oxidizer and the organic sterilizer may be added not only at the same time but also at different times.
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。なお、以下の実施例及び比較例において、濃度を示す「％」は「重量％」を表わす。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following examples and comparative examples, “%” indicating concentration represents “% by weight”.
［実施例１］
＜有機系殺菌剤（イソチアゾリン化合物）、窒素化合物（グリシン）及び無機系酸化剤（次亜塩素酸ナトリウム）の併用による殺菌効果の実験＞
＜方法＞
３００ｍＬ容三角フラスコに１００ｍＬの滅菌水を作成した。この滅菌水に目的濃度の下記スライムコントロール剤を添加し、培養した下記レジオネラ標準菌株懸濁液１０ｍＬを添加した。一定温度、所定時間振とうしたのち、増殖能力がある菌数を計測した。操作はすべてＰ２クリーンベンチ内で行い、培養はＰ２インキュベーターで行った。
[Example 1]
<Experiment of bactericidal effect by combined use of organic fungicide (isothiazoline compound), nitrogen compound (glycine) and inorganic oxidant (sodium hypochlorite)>
<Method>
100 mL of sterilized water was prepared in a 300 mL Erlenmeyer flask. The following slime control agent of the target concentration was added to this sterilized water, and 10 mL of the following Legionella standard strain suspension cultured was added. After shaking at a constant temperature for a predetermined time, the number of bacteria having growth ability was counted. All operations were performed in a P2 clean bench, and culture was performed in a P2 incubator.
スライムコントロール剤：食品添加用ＮａＣｌＯ溶液、
５−クロロ−２−メチル−４−イソチアゾリン−３−オン（
Ｃｌ−ＭＩＴ）１％とグリシン１％溶液
Slime control agent: NaClO solution for food addition,
5-chloro-2-methyl-4-isothiazolin-3-one (
Cl-MIT) 1% and
濃度測定はハックポケット残留塩素計を用い、ＤＰＤ試薬測定した。
遊離残留塩素濃度値はＤＰＤｆｒｅｅ測定試薬で行い、撹拌後、６０秒静置して測定した。
残留塩素濃度はＤＰＤｔｏｔａｌ測定試薬で行い、撹拌後、３ｍｉｎ静置して測定した。
５−クロロ−２−メチル−４−イソチアゾリン−３−オンの定量は液体クロマトグラフィーにより実施した。実測しなかった場合は設定値で示した。
滅菌水中の遊離残留塩素濃度、残留塩素濃度はレジオネラ添加後変化したので、レジオネラサンプリング時の残留濃度を採用した。
Concentration measurement was performed using a hack pocket residual chlorine meter and DPD reagent measurement.
The free residual chlorine concentration value was measured with a DPDfree measuring reagent, and was allowed to stand for 60 seconds after stirring.
Residual chlorine concentration was measured with a DPDtotal measurement reagent, and after stirring, allowed to stand for 3 min.
Quantification of 5-chloro-2-methyl-4-isothiazolin-3-one was performed by liquid chromatography. When it was not actually measured, it was shown as a set value.
Since free residual chlorine concentration and residual chlorine concentration in sterilized water changed after Legionella addition, the residual concentration at the time of Legionella sampling was adopted.
レジオネラ標準菌株はＬｅｇｉｏｎｅｌｌａ ｐｎｅｕｍｏｐｈｉｌａ ＧＩＦＵ９１３４（血清型ｓｅｒｏ１）である。あらかじめ、ＢＣＹＥα培地で培養し、滅菌水に懸濁して、試験管用吸光度計で６６０ｎｍの吸光度０．１に合わせた液を菌液として使用した。
スライムコントロール剤との接触条件は３０℃、１００ｒｐｍ、０分、６分、２７分、６０分とした。
Legionella standard strain is Legionella pneumophila GIFU 9134 (serotype sero1). A liquid which was previously cultured in a BCYEα medium, suspended in sterilized water, and adjusted to an absorbance of 660 nm of 0.1 with a test tube absorbance meter was used as a bacterial solution.
The contact conditions with the slime control agent were 30 ° C., 100 rpm, 0 minutes, 6 minutes, 27 minutes, and 60 minutes.
レジオネラの計測のために、三角フラスコから１０ｍｌをサンプリングし、チオ硫酸ナトリウム添加撹拌後、１００μＬをＢＣＹＥα培地の表面に塗抹した。３７℃で培養し、７日〜１０日後のコロニーを計測した。０分の値はあらかじめスライムコントロール剤を添加した液に、菌添加後、撹拌し、即座にサンプリングしたときの値を用いた。ブランクはスライムコントロール剤を添加しないで同様の操作を行った。 In order to measure Legionella, 10 ml was sampled from the Erlenmeyer flask, and after adding sodium thiosulfate and stirring, 100 μL was smeared on the surface of the BCYEα medium. After culturing at 37 ° C., colonies after 7 to 10 days were counted. The value of 0 minutes was the value obtained by immediately stirring after adding the bacteria to the solution to which the slime control agent had been added in advance. The blank was subjected to the same operation without adding a slime control agent.
その結果、表１の通り、Ｃｌ−ＭＩＴ（１９ｍｇ／Ｌ）と残留塩素（５〜１０ｍｇ／ＬａｓＣｌ２）の併用で、遊離残留塩素が０．１ｍｇ／Ｌ未満の条件で、６０分で９９．９％の殺菌に至った。このときの遊離残留塩素濃度は０．１ｍｇ/Ｌ未満であったので、遊離残留塩素による殺菌ではないと考えられる。 As a result, as shown in Table 1, the combined use of Cl-MIT (19 mg / L) and residual chlorine (5 to 10 mg / LasCl 2 ) under the condition that the free residual chlorine was less than 0.1 mg / L, 99. It resulted in 9% sterilization. Since the free residual chlorine concentration at this time was less than 0.1 mg / L, it is considered that it is not sterilization by free residual chlorine.
Ｃｌ−ＭＩＴ（１９ｍｇ／Ｌ）と残留塩素（５〜１０ｍｇ／ＬａｓＣｌ２）の併用で、遊離残留塩素が０．１ｍｇ／Ｌ未満の条件で、２７分で９５％以上の殺菌を示した。 The combined use of Cl-MIT (19 mg / L) and residual chlorine (5 to 10 mg / LasCl 2 ) showed sterilization of 95% or more in 27 minutes under the condition that the free residual chlorine was less than 0.1 mg / L.
［比較例１−１］
スライムコントロール剤として５−クロロ−２−メチル−４−イソチアゾリン−３−オン（Ｃｌ−ＭＩＴ）１％とグリシン１％溶液を用い、スライムコントロール剤との接触を３０℃、１００ｒｐｍ、２７分としたこと以外は実施例１と同一の試験を行った。
[Comparative Example 1-1]
As a slime control agent, 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) 1% and
その結果、表２の通り、Ｃｌ−ＭＩＴ（１９ｍｇ／Ｌ）で、２７分で約８０％の殺菌性しか示さず、殺菌性が劣った。 As a result, as shown in Table 2, Cl-MIT (19 mg / L) showed only about 80% bactericidal properties in 27 minutes and was inferior in bactericidal properties.
［比較例１−２］
スライムコントロール剤として食添用ＮａＣｌＯ溶液とグリシン１％溶液を用い、スライムコントロール剤との接触を３０℃、１００ｒｐｍ、０分、６分、２７分としたこと以外は実施例１と同様の試験を行った。
[Comparative Example 1-2]
The same test as in Example 1 was conducted except that an NaClO solution for food addition and a 1% glycine solution were used as slime control agents, and contact with the slime control agent was 30 ° C., 100 rpm, 0 minutes, 6 minutes, and 27 minutes. went.
その結果、表３の通り、残留塩素（１０ｍｇ／ＬａｓＣｌ２）の条件で、２７分で７５％の殺菌性しか示さず、殺菌効果は低かった。 As a result, as shown in Table 3, under the condition of residual chlorine (10 mg / LasCl 2 ), it showed only 75% bactericidal properties in 27 minutes, and the bactericidal effect was low.
［比較例１−３Ａ〜３Ｅ］
スライムコントロール剤として５−クロロ−２−メチル−４−イソチアゾリン−３−オン（Ｃｌ−ＭＩＴ）１％を用い、スライムコントロール剤との接触を３０℃、１００ｒｐｍ、１時間としたこと以外は実施例１と同一の試験を行った。
[Comparative Examples 1-3A to 3E]
Example except that 1% of 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) was used as the slime control agent, and the contact with the slime control agent was 30 ° C., 100 rpm, 1 hour. The same test as 1 was conducted.
その結果、表４の通り、Ｃｌ−ＭＩＴ（１０ｍｇ／Ｌ）、１時間接触で、殺菌された割合は３０〜８７％の範囲であり、殺菌性は低かった。 As a result, as shown in Table 4, the rate of sterilization after contact with Cl-MIT (10 mg / L) for 1 hour was in the range of 30 to 87%, and the bactericidal property was low.
９９％以上の殺菌性に至るには２４時間を要し、即効性に欠けた。 It took 24 hours to reach 99% or more of bactericidal properties and lacked immediate effect.
［実施例２］
一過性試験装置を用いて、カラム部分で滞留時間を設定し、ＣＦＵ測定により殺菌性を評価した。
[Example 2]
Using a transient test apparatus, the residence time was set at the column portion, and the bactericidal property was evaluated by CFU measurement.
一過性試験装置として、図１に示すフローのものを用いた。図１においてＰはポンプを表わす。 As a transient test apparatus, the one shown in FIG. 1 was used. In FIG. 1, P represents a pump.
フェルトを固定床とした培養装置（微生物燃料電池）に、脱塩素水に培地を追加したものを２０ｍｌ／ｍｉｎで流した。培地はポリペプトン、イーストエキストラクト、酢酸ナトリウムにより構成されるＰＹＡ培地を用いた。 A culture apparatus (microbial fuel cell) using felt as a fixed bed was passed at 20 ml / min with a medium added to dechlorinated water. As the medium, a PYA medium composed of polypeptone, yeast extract, and sodium acetate was used.
培養装置（微生物燃料電池）から流出した菌液を一過性で流した。この液を対象に、ＣＦＵを測定した。表５に示すスライムコントロール剤を菌液の流れの途中から添加した。 表５のＭＩＴはＣｌ−ＭＩＴである。この菌液をカラムで滞留させ、スライムコントロール剤の接触時間とした。 The bacterial solution that flowed out of the culture device (microbial fuel cell) was allowed to flow temporarily. CFU was measured for this solution. The slime control agent shown in Table 5 was added from the middle of the flow of the bacterial solution. The MIT in Table 5 is Cl-MIT. This bacterial solution was allowed to stay in the column and used as the contact time of the slime control agent.
スライムコントロール剤濃度は薬注直後とカラム出口（一定時間接触後）の濃度を測定した。 The slime control agent concentration was measured immediately after drug injection and at the column outlet (after contact for a certain period of time).
ＣＦＵ測定は１／１０ＰＹ培地を用いて、段階希釈法により実施した。今回試験対象になった菌は環境中で生育した一般細菌と考えられる。菌の顕微鏡観察や菌種の同定は行っていない。 CFU measurement was performed by serial dilution method using 1/10 PY medium. The bacteria that were tested this time are considered to be general bacteria that grew in the environment. Microscopic observation of bacteria and identification of bacterial species are not performed.
その結果、表５の通り、Ｃｌ−ＭＩＴと結合型塩素を併用すると、９９．９９％以上の殺菌性を示した。接触時間０分で殺菌効果を発揮し、約３０分の接触でさらに効果が増した。このとき、残留塩素濃度は約７ｍｇ／ＬａｓＣｌ２であった。遊離残留塩素濃度は０．１５ｍｇ／ＬａｓＣｌ２であった。 As a result, as shown in Table 5, when Cl-MIT and combined chlorine were used in combination, bactericidal properties of 99.99% or more were exhibited. The bactericidal effect was exhibited with a contact time of 0 minutes, and the effect was further increased with a contact time of about 30 minutes. At this time, the residual chlorine concentration was about 7 mg / LasCl 2 . Free residual chlorine concentration was 0.15mg / LasCl 2.
［比較例２−１］
スライムコントロール剤として、表５の通り、次亜塩素酸ナトリウムを用いなかったこと以外は実施例２と同様の試験を行った。
[Comparative Example 2-1]
As a slime control agent, as shown in Table 5, the same test as in Example 2 was performed except that sodium hypochlorite was not used.
［比較例２−２］
スライムコントロール剤として表５の通り、Ｃｌ−ＭＩＴを用いなかったこと以外は実施例２と同様の試験を行った。
[Comparative Example 2-2]
As the slime control agent, the same test as in Example 2 was conducted except that Cl-MIT was not used as shown in Table 5.
その結果、表５の通り結合型残留塩素単独では、約８ｍｇ／ＬａｓＣｌ２で約９０％の殺菌性を示した。このとき、遊離残留塩素濃度は約０．１ｍｇ／ＬａｓＣｌ２であった。また、Ｃｌ−ＭＩＴ単独の場合は、１０ｍｇ／Ｌ、３０ｍｉｎで明確な殺菌性は示さなかった。 As a result, as shown in Table 5, combined residual chlorine alone showed about 90% bactericidal property at about 8 mg / LasCl 2 . At this time, the free residual chlorine concentration was about 0.1 mg / LasCl 2 . In addition, Cl-MIT alone did not show clear bactericidal properties at 10 mg / L for 30 min.
［実施例３］
回転腐食試験装置を用い、下記条件にて腐食試験を行った。
＜スライムコントロール剤＞
実施例３−１：Ｃｌ−ＭＩＴ１％、グリシン１％、スルファミン酸３％含有４００ｍｇ／Ｌ＋ＮａＣｌＯ溶液を遊離残留塩素濃度０．１ｍｇ／ＬａｓＣｌ２になるよう添加
実施例３−２：Ｃｌ−ＭＩＴ１％、グリシン１％４００ｍｇ／Ｌ
＜防食剤＞
ベンゾトリアゾール（銅用防食剤、ＢＴ）：１ｍｇ／Ｌ（添加濃度）
マレイン酸系ポリマー：１．５ｍｇ／Ｌ（添加濃度）
ホスホン酸：２．４ｇｍ／Ｌ（添加濃度）
＜試験水水質（純水給水想定）＞
Ｍアルカリ度：７９ｍｇ／ｌ
Ｃａ硬度：２ｍｇ／Ｌ
Ｍｇ硬度：１ｍｇ／Ｌ
[Example 3]
A corrosion test was performed under the following conditions using a rotary corrosion tester.
<Slime control agent>
Example 3-1: 400 mg / L + NaClO solution containing 1% Cl-MIT, 1% glycine and 3% sulfamic acid was added to a free residual chlorine concentration of 0.1 mg / LasCl 2 Example 3-2: Cl-
<Anticorrosive>
Benzotriazole (corrosion inhibitor for copper, BT): 1 mg / L (addition concentration)
Maleic acid polymer: 1.5 mg / L (addition concentration)
Phosphonic acid: 2.4 gm / L (addition concentration)
<Test water quality (assuming pure water supply)>
M alkalinity: 79 mg / l
Ca hardness: 2 mg / L
Mg hardness: 1mg / L
試験水に上記防食剤、スライムコントロール剤が所定濃度になるように添加した。試験水、防食剤、スライムコントロール剤混合液を１Ｌ／ｄａｙの速度で注入し滞留時間を与えた。測定時、遊離残留塩素濃度が所定濃度を下回っていた場合は、ＮａＣｌＯ溶液をバッチで追加し、所定濃度にするようにした。
＜試験片＞
銅テストピース３１ｃｍ２（３０ｍｍ×５０ｍｍ×１ｍｍ）
回転腐食試験装置条件を１４０ｒｐｍ、水温３０℃、７日間とし、試験片の試験前の重量と後重量を測定し、一日当たり、ｄｍ２当たりの減量（ｍｇ）で比較した。
The anticorrosive and the slime control agent were added to the test water so as to have predetermined concentrations. Test water, anticorrosive, and slime control agent mixed solution were injected at a rate of 1 L / day to give a residence time. At the time of measurement, if the free residual chlorine concentration was lower than the predetermined concentration, a NaClO solution was added in batches so that the predetermined concentration was reached.
<Specimen>
Copper test piece 31cm 2 (30mm × 50mm × 1mm)
The conditions of the rotary corrosion test apparatus were 140 rpm, the water temperature was 30 ° C., 7 days, the weights of the test pieces before and after the test were measured, and the weight loss per day and dm 2 (mg) were compared.
その結果、表６の実施例３−１に示す通り、遊離残留塩素濃度平均が０．１ｍｇ／ＬａｓＣｌ２未満で、腐食速度は問題のないレベルであった。また、表７の通り、ＮａＣｌＯ追加時は遊離残留塩素濃度が一時０．１ｍｇ／ＬａｓＣｌ２を超えることがあったが、腐食速度に悪影響はなかった。遊離残留塩素濃度を０．１ｍｇ／ＬａｓＣｌ２以上に維持しなければ腐食速度が上がらないことが示された。 As a result, as shown in Example 3-1 of Table 6, the average free residual chlorine concentration was less than 0.1 mg / LasCl 2 , and the corrosion rate was at a level with no problem. Further, as shown in Table 7, although the time of NaClO added had the free residual chlorine concentration exceeds a temporary 0.1mg / LasCl 2, there was no adverse effect on corrosion rate. It was shown that the corrosion rate would not increase unless the free residual chlorine concentration was maintained at 0.1 mg / LasCl 2 or higher.
［比較例３］
スライムコントロール剤を次の通りとしたこと以外は実施例３と同一の試験を行った。
[Comparative Example 3]
The same test as in Example 3 was performed except that the slime control agent was as follows.
比較例３−１：スルファミン酸とＮａＣｌＯとの混合液をＮａＣｌＯ残留塩素濃度として１５ｍｇ／ＬａｓＣｌ２、遊離残留塩素濃度として０．３ｍｇ／ＬａｓＣｌ２になるよう添加
比較例３−２：スルファミン酸とＮａＣｌＯとの混合液をＮａＣｌＯ残留塩素濃度として５ｍｇ／ＬａｓＣｌ２、遊離残留塩素濃度として０．３ｍｇ／ＬａｓＣｌ２になるよう添加
Comparative Example 3-1: A mixture of sulfamic acid and NaClO was added to a NaClO residual chlorine concentration of 15 mg / LasCl 2 and a free residual chlorine concentration of 0.3 mg / LasCl 2 Comparative Example 3-2: Sulfamic acid and NaClO The mixture was added to a NaClO residual chlorine concentration of 5 mg / LasCl 2 and a free residual chlorine concentration of 0.3 mg / LasCl 2.
その結果、表６の通り、平均遊離残留塩素濃度０．１７ｍｇ／ＬａｓＣｌ２以上を維持すると、腐食速度は１ｍｄｄをこえ、腐食が心配される。 As a result, as shown in Table 6, when the average free residual chlorine concentration is maintained at 0.17 mg / LasCl 2 or more, the corrosion rate exceeds 1 mdd, and corrosion is a concern.
比較例３−２（遊離残留塩素濃度０．１７ｍｇ／ＬａｓＣｌ２）と同等の遊離残留塩素濃度及び残留塩素濃度で行った前述の表３の比較例１−２からわかるようにＮａＣｌＯ＋グリシンだけではレジオネラ属菌の殺菌効果は不十分であり、腐食の問題がない濃度での殺菌効果は期待できないことがわかった。 As can be seen from Comparative Example 1-2 in Table 3 which was carried out at a free residual chlorine concentration and a residual chlorine concentration equivalent to Comparative Example 3-2 (Free Residual Chlorine Concentration 0.17 mg / LasCl 2 ), Legionella alone was obtained with NaClO + glycine alone. It was found that the sterilization effect of the genus fungus is insufficient, and the bactericidal effect at a concentration without the problem of corrosion cannot be expected.
［実施例４］
間欠注入における薬剤の即効性と薬注停止後の効果を比較するために、図２のフローの微生物燃料電池のアノードに殺菌剤を間欠注入した。図２の通り、脱塩素水を窒素曝気により脱酸素して、培地を途中注入し微生物燃料電池のアノード側に流入させた。
[Example 4]
In order to compare the immediate effect of the drug in intermittent injection and the effect after stopping the injection, a disinfectant was intermittently injected into the anode of the microbial fuel cell in the flow of FIG. As shown in FIG. 2, the dechlorinated water was deoxygenated by nitrogen aeration, and the medium was injected halfway to flow into the anode side of the microbial fuel cell.
微生物燃料電池のカソード側には空気を吹き込み酸素供給を行った。微生物の生育によりアノード側からカソード側に電子が供給され、抵抗（５００Ω）をアノード・カソード間に接続し、電圧を測定した。カソードを基準としたマイナス電位の絶対値が大きければ大きいほど、微生物の生育が活発であることを示す。 Air was blown into the cathode side of the microbial fuel cell to supply oxygen. Electrons were supplied from the anode side to the cathode side due to the growth of microorganisms, a resistance (500Ω) was connected between the anode and cathode, and the voltage was measured. The greater the absolute value of the negative potential with respect to the cathode, the more active the microorganism is growing.
本試験において、薬剤注入により上昇した最高電位を到達電位、薬剤注入停止後薬剤注入前の電位に戻るまでの期間をエネルギー生産阻害持続期間として測定した。これらの値に基づいて有機系殺菌剤及び無機系酸化剤の効果を比較した。 In this test, the maximum potential increased by drug injection was measured as the ultimate potential, and the period until the potential returned to the potential before drug injection after stopping the drug injection was measured as the energy production inhibition duration. Based on these values, the effects of organic fungicides and inorganic oxidizers were compared.
図２の微生物燃料電池の条件は次の通りである。 The conditions of the microbial fuel cell in FIG. 2 are as follows.
アノード：５ｍｍ厚グラファイトフェルト５ｃｍ＊１５ｃｍ（アノード容量８０〜９０ｍＬ）
カソード：カーボンコーティングニッケル触媒
非導電性膜：ミリポア社製ニトロセルロース膜
抵抗：５００Ω
カソードには野木町水と空気を２Ｌ／ｍｉｎの送風量で供給した。アノード液には野木町水を曝気槽に取り、窒素ガスで曝気して溶存酸素を除いた水を８ｍＬ／ｍｉｎで送液し、アノード入口の前に培地をポンプにて所定濃度になるようにライン注入した。必要に応じてアノード入り口手前で、下記酸化系増殖抑制剤及び有機系殺菌剤をポンプで所定濃度になるように所定時間ライン注入した。アノードとカソードを抵抗を介した銅電線で接続し、生じた電位を連続測定した。なお、薬注停止後、アノード室の滞留時間の経過後、有機系殺菌剤と酸化系増殖抑制剤が検出されないことを確認した。
Anode: 5 mm thick graphite felt 5 cm * 15 cm (anode capacity 80-90 mL)
Cathode: Carbon coating nickel catalyst Non-conductive film: Nitrocellulose film manufactured by Millipore Corporation Resistance: 500Ω
Nogicho water and air were supplied to the cathode at a flow rate of 2 L / min. As the anolyte, take Nogi-cho water in an aeration tank, feed water with nitrogen gas removed from the dissolved oxygen at a rate of 8 mL / min, and adjust the culture medium to a predetermined concentration with a pump before the anode inlet. Line was injected. If necessary, before the anode entrance, the following oxidative growth inhibitor and organic fungicide were line-injected for a predetermined time with a pump so as to reach a predetermined concentration. The anode and the cathode were connected by a copper wire through a resistor, and the generated potential was continuously measured. In addition, it was confirmed that the organic disinfectant and the oxidative growth inhibitor were not detected after elapse of the residence time in the anode chamber after stopping the chemical injection.
試験条件は次の通りとした。
有機系殺菌剤：Ｃｌ−ＭＩＴ設定濃度５ｍｇ／Ｌ＋グリシン１０ｍｇ／Ｌ
酸化系増殖抑制剤：ＮａＣｌＯ設定濃度１０ｍｇ／Ｌ、培地有機物・グリシンと反応してほとんど結合型になっている。
注入時間：３ｈ
アノード滞留時間：１０〜２０ｍｉｎ（アノードセル内にはフェルトがあるため、正確な滞留時間を測定することは困難）
The test conditions were as follows.
Organic fungicide: Cl-
Oxidation system growth inhibitor: NaClO set concentration of 10 mg / L, reacts with medium organic substance / glycine to become almost bound type.
Injection time: 3h
Anode residence time: 10-20 min (Because there is felt in the anode cell, it is difficult to accurately measure the residence time)
評価方法は次の通りとした。
到達電位：薬品注入により電位上昇が起こり、到達した最高電位
エネルギー生産阻害持続期間：薬注停止後薬注前の電位に戻るまでの期間及び電位の経時変化の形状
The evaluation method was as follows.
Achieving potential: Maximum potential caused by drug injection and reaching the highest potential Energy production inhibition duration: Period until the potential returns to the potential before drug injection after stopping drug injection and shape of time-dependent change in potential
その結果、表８及び図３の通り、有機系殺菌剤と無機系酸化剤との併用により電位は急激な上昇を示し、単品使用よりも高い電位となった。到達電位は単品注入で上昇した電位を加算した値と同等となった。 As a result, as shown in Table 8 and FIG. 3, the combined use of the organic disinfectant and the inorganic oxidant showed a rapid increase in potential, which was higher than the single product. The ultimate potential was equivalent to the value obtained by adding the potentials increased by single injection.
無機系酸化剤と有機系殺菌剤とを併用した場合、電位回復は薬注停止後約１００ｍＶ低下し、急激な回復を示すが、その後は緩やかな回復を示した。エネルギー生産阻害持続時間は単品による阻害時間の加算とほぼ同等であった。 When the inorganic oxidizer and the organic fungicide were used in combination, the potential recovery decreased about 100 mV after stopping the drug injection and showed a rapid recovery, but thereafter showed a gradual recovery. The energy production inhibition duration was almost equal to the addition of inhibition time by single item.
この結果から、無機系酸化剤と有機系殺菌剤とを併用すると即効性が増し、阻害の程度が強くなり、薬注後の回復が遅れることが分かった。 From these results, it was found that when an inorganic oxidizing agent and an organic fungicide were used in combination, the immediate effect increased, the degree of inhibition increased, and recovery after drug injection was delayed.
［比較例４−１］
酸化系増殖抑制剤を用いなかったこと以外は実施例４と同一条件にて試験を行った。
[Comparative Example 4-1]
The test was performed under the same conditions as in Example 4 except that the oxidative growth inhibitor was not used.
その結果、表８及び図３の通り、電位の低下は実施例４、比較例４−２と比較すると緩やかで、３時間後も−４００ｍＶの電位を保っていた。薬注停止後の電位低下は緩やかであったが、上昇した電位幅が小さいので、４時間程度で元の電位に戻った。 As a result, as shown in Table 8 and FIG. 3, the decrease in the potential was more gradual as compared with Example 4 and Comparative Example 4-2, and the potential was maintained at −400 mV even after 3 hours. Although the potential drop after stopping the drug injection was gradual, the increased potential width was small, so it returned to the original potential in about 4 hours.
このことから、有機系殺菌剤の即効性が低いことが分かる。 From this, it can be seen that the immediate effect of the organic fungicide is low.
［比較例４−２］
有機系殺菌剤を用いなかったこと以外は実施例４と同一条件にて試験を行った。
[Comparative Example 4-2]
The test was performed under the same conditions as in Example 4 except that no organic fungicide was used.
この結果、表８及び図３の通り、電位は急激な上昇を示し−１５０ｍＶに達する。薬注停止直後、約２００ｍＶの急激な電位の低下（回復）が起こり、電位は−３００ｍＶに至る。このように、酸化系薬剤は即効性はあるが、薬注を停止すると急激にエネルギー生産阻害をする能力が消失するので、効果を維持するためには濃度を維持しなければならないと推定される。 As a result, as shown in Table 8 and FIG. 3, the potential increases rapidly and reaches −150 mV. Immediately after stopping the drug injection, a rapid potential drop (recovery) of about 200 mV occurs, and the potential reaches -300 mV. In this way, although the oxidative drugs are immediately effective, the ability to rapidly inhibit energy production disappears when drug injection is stopped, so it is estimated that the concentration must be maintained to maintain the effect .
［実施例５］
実施例４と同一の試験装置を用い、間欠注入時間を長くしたときの即効性と薬注停止後の効果に与える影響を、微生物燃料電池で下記条件にて比較した。
＜試験条件＞
有機系殺菌剤：Ｃｌ−ＭＩＴ設定濃度５ｍｇ／Ｌ
酸化系増殖抑制剤：結合型塩素（スルファミン酸＋ＮａＣｌＯ）残留塩素設定濃度１５ｍｇ／ＬａｓＣｌ２
注入時間：６ｈ
アノード滞留時間：１０〜２０ｍｉｎ
[Example 5]
Using the same test apparatus as in Example 4, the immediate effect when the intermittent injection time was increased and the effect on the effect after stopping the drug injection were compared using a microbial fuel cell under the following conditions.
<Test conditions>
Organic fungicide: Cl-MIT set concentration 5mg / L
Oxidative growth inhibitor: Combined chlorine (sulfamic acid + NaClO) residual
Injection time: 6h
Anode residence time: 10-20 min
その結果、図４、表９の通り、電位は薬注後即座に上昇し−１００ｍＶ以上となった。注入中はその電位が徐々に低下し続けた。到達した電位は−６７ｍＶであった。有機系殺菌剤と無機系酸化剤との併用により到達した電位は単独使用の上昇電位を加算した値には達せず、殺菌・増殖抑制の到達電位は上限があるようである。 As a result, as shown in FIG. 4 and Table 9, the potential immediately increased after the drug injection and became −100 mV or more. The potential continued to decline gradually during the injection. The potential reached was -67 mV. The potential reached by the combined use of the organic disinfectant and the inorganic oxidizer does not reach the value obtained by adding the increased potential of the single use, and the ultimate potential for disinfection / growth suppression seems to have an upper limit.
薬注停止後、無機系酸化剤と有機系殺菌剤とを併用した場合は、電位が即座に約１００ｍＶ低下したが、その後は緩やかな電位低下（回復）を示し、ものと電位に戻るまでに３９ｈを要した。単独使用の回復時間の和よりも、併用の方が９ｈ程度余分に時間を要した。このように、併用接触時間を延ばすと回復にかかる時間が延びた。 When the combination of an inorganic oxidizer and an organic fungicide was used after stopping drug injection, the potential immediately decreased by about 100 mV, but after that, it showed a gradual decrease in potential (recovery) until it returned to the potential. It took 39h. The combined use took about 9 hours more time than the sum of the recovery time for the single use. Thus, when the combined contact time is extended, the time required for recovery is extended.
この実施例５では、結合型塩素の結合相手をスルファミン酸としたが、実施例４と同様な阻害と回復のパターンを示すことが分かった。 In this Example 5, the binding partner of bound chlorine was sulfamic acid, but it was found that the same inhibition and recovery pattern as in Example 4 was exhibited.
無機系酸化剤と有機系殺菌剤との併用時間の延長により、十分に阻害された時間が延び、薬注停止後の回復も遅れる。このことから併用時間を長くすると、殺菌性の強さと薬注停止後の効果維持時間がより効率的になると考えられる。 By extending the combined use time of the inorganic oxidizer and the organic fungicide, the time that has been sufficiently inhibited is prolonged, and the recovery after stopping the drug injection is also delayed. From this fact, it is considered that when the combined use time is increased, the bactericidal strength and the effect maintaining time after stopping the drug injection become more efficient.
［比較例５−１］
有機系殺菌剤をＣｌ−ＭＩＴ設定濃度５ｍｇ／Ｌとしたこと以外は実施例５と同一条件にて試験を行った。
[Comparative Example 5-1]
The test was performed under the same conditions as in Example 5 except that the organic disinfectant was set to a Cl-MIT set concentration of 5 mg / L.
その結果、図４及び表９の通り、Ｃｌ−ＭＩＴ添加による阻害パータンは比較例４と同様であり、比較的緩やかであった。時間を延ばすとその電位上昇は３ｈの延長線上にあった。薬注停止後電位は無機系酸化剤に比較して緩やかに回復するパターンを示した。Ｃｌ−ＭＩＴ薬注後、電位回復に要する時間はＣｌ−ＭＩＴが１３ｈであった。 As a result, as shown in FIG. 4 and Table 9, the inhibition pattern due to the addition of Cl-MIT was the same as that in Comparative Example 4, and was relatively slow. When the time was extended, the potential increase was on the 3 h extension line. The potential after cessation of drug injection showed a pattern of moderate recovery compared to inorganic oxidants. The time required for the potential recovery after Cl-MIT injection was Cl-MIT was 13 h.
［比較例５−２］
酸化系増殖抑制剤を結合型塩素（スルファミン酸＋ＮａＣｌＯ）残留塩素設定濃度１５ｍｇ／ＬａｓＣｌ２としたこと以外は実施例５と同一条件にて試験を行った。
[Comparative Example 5-2]
The test was conducted under the same conditions as in Example 5 except that the oxidative growth inhibitor was a combined chlorine (sulfamic acid + NaClO) residual chlorine set concentration of 15 mg / LasCl 2 .
その結果、図４及び表９の通り、結合型塩素により、電位は直線的に３００ｍＶ上昇し、その後緩やかに上昇した。薬注を停止すると電位は約２００ｍＶ即座に回復（低下）した。その後緩やかに回復し、元の電位まで回復するためにかかる時間は約１６ｈであった。 As a result, as shown in FIG. 4 and Table 9, the potential increased linearly by 300 mV due to combined chlorine, and then gradually increased. When the drug injection was stopped, the potential immediately recovered (decreased) to about 200 mV. After that, it took about 16 hours to recover slowly and recover to the original potential.
［実施例６］
遊離残留塩素濃度が次亜塩素酸ナトリウム添加の直後に０．１ｍｇ／Ｌを超えても、０．１ｍｇ／Ｌ未満に下がる期間があれば腐食は抑制されることを示すための試験を行った。
[Example 6]
A test was conducted to show that even if the free residual chlorine concentration exceeds 0.1 mg / L immediately after the addition of sodium hypochlorite, the corrosion is suppressed if there is a period when it falls below 0.1 mg / L. .
この試験では、実施例３と同一の回転腐食試験装置を用いた。
＜スライムコントロール条件＞
実施例６−１：Ｃｌ−ＭＩＴ２％、グリシン２％、スルファミン酸３％含有液２００ｍｇ／ＬとＮａＣｌＯを遊離残留塩素濃度０．３ｍｇ／ＬａｓＣｌ２になるよう添加。一日一回。
実施例６−２：Ｃｌ−ＭＩＴ２％、グリシン２％、スルファミン酸３％含有液２００ｍｇ／ＬとＮａＣｌＯを遊離残留塩素濃度０．１ｍｇ／ＬａｓＣｌ２になるよう添加。一日一回。
実施例６−３：Ｃｌ−ＭＩＴ２％、グリシン２％、スルファミン酸３％含有液を２００ｍｇ／Ｌ
＜防食剤＞
ベンゾトリアゾール（銅用防食剤、ＢＴ）：１ｍｇ／Ｌ（最終濃度）
マレイン酸系ポリマー：１．５ｍｇ／Ｌ（最終濃度）
ホスホン酸：２．４ｇｍ／Ｌ（最終濃度）
＜試験水水質（純水給水想定）＞
Ｍアルカリ度：７９ｍｇ／Ｌ
Ｃａ硬度：２ｍｇ／Ｌ
Ｍｇ硬度：１ｍｇ／Ｌ
＜試験手順＞
試験水に防食剤、スライムコントロール剤が所定濃度になるように添加した。試験水、防食剤、スライムコントロール剤混合液を１Ｌ／ｄａｙの速度で注入し滞留時間を与えた。ＮａＣｌＯ溶液をバッチで一日一回追加し、所定濃度にするようにした。回転腐食試験装置条件は１４０ｒｐｍ、水温３０℃、７日間とした。
＜試験片＞
軟鋼テストピース３１ｃｍ２（３０ｍｍ×５０ｍｍ×１ｍｍ）
試験前の重量と後重量を測定し、一日当たり、ｄｍ２当たりの減量（ｍｇ）で比較した。
In this test, the same rotary corrosion test apparatus as in Example 3 was used.
<Slime control conditions>
Example 6-1: 200 mg / L of a solution containing 2% Cl-MIT, 2% glycine and 3% sulfamic acid and NaClO were added so that the free residual chlorine concentration was 0.3 mg / LasCl 2 . once a day.
Example 6-2: 200 mg / L of a solution containing 2% Cl-MIT, 2% glycine and 3% sulfamic acid and NaClO were added to a free residual chlorine concentration of 0.1 mg / LasCl 2 . once a day.
Example 6-3: A solution containing 2% Cl-MIT, 2% glycine and 3% sulfamic acid was 200 mg / L.
<Anticorrosive>
Benzotriazole (corrosion inhibitor for copper, BT): 1 mg / L (final concentration)
Maleic acid polymer: 1.5 mg / L (final concentration)
Phosphonic acid: 2.4 gm / L (final concentration)
<Test water quality (assuming pure water supply)>
M alkalinity: 79 mg / L
Ca hardness: 2 mg / L
Mg hardness: 1mg / L
<Test procedure>
An anticorrosive and a slime control agent were added to the test water so as to have predetermined concentrations. Test water, anticorrosive, and slime control agent mixed solution were injected at a rate of 1 L / day to give a residence time. The NaClO solution was added once a day in a batch to obtain a predetermined concentration. The conditions of the rotary corrosion test apparatus were 140 rpm, water temperature 30 ° C., and 7 days.
<Specimen>
Mild steel test piece 31cm 2 (30mm × 50mm × 1mm)
The weight before the test and the weight after the test were measured and compared with the weight loss (mg) per dm 2 per day.
その結果、表１０〜１２の通り、実施例６−１はＮａＣｌＯの間欠注入で遊離残留塩素濃度が１ｍｇ／ＬａｓＣｌ２以上に至っても翌日０．１未満に戻れば、腐食はＮａＣｌＯ無添加と同等である。 As a result, as shown in Tables 10 to 12, in Example 6-1, in the case of intermittent injection of NaClO, the free residual chlorine concentration reached 1 mg / LasCl 2 or more, and if it returned to less than 0.1 the next day, the corrosion was equivalent to no addition of NaClO. It is.
実施例６−２に示すようにＮａＣｌＯの間欠注入で遊離残留塩素濃度が０．１ｍｇ／ＬａｓＣｌ２未満を維持した場合も、腐食速度はＮａＣｌＯ無添加と同等である（表１１）。この結果から遊離残留塩素濃度が一時的に０．１ｍｇ／ＬａｓＣｌ２を超えても、確実に０．１ｍｇ／ＬａｓＣｌ２を下回る期間があれば、残留塩素無添加と比較して腐食は促進されない。 As shown in Example 6-2, when the free residual chlorine concentration is maintained below 0.1 mg / LasCl 2 by intermittent injection of NaClO, the corrosion rate is equivalent to that without addition of NaClO (Table 11). Even beyond this results from free residual chlorine concentration is temporarily 0.1mg / LasCl 2, if there is certainly a period of less than 0.1mg / LasCl 2, corrosion compared with residual chlorine no addition is not promoted.
［比較例６］
スライムコントロール条件を次の通りとしたこと以外は実施例６と同一条件にて試験を行った。
[Comparative Example 6]
The test was conducted under the same conditions as in Example 6 except that the slime control conditions were as follows.
比較例６−１：スルファミン酸、ＮａＣｌＯ混合液 ２００ｍｇ／Ｌ。残留塩素濃度として１５ｍｇ／ＬａｓＣｌ２、遊離残留塩素濃度として０．３ｍｇ／ＬａｓＣｌ２以上を維持。
比較例６−２：スルファミン酸、ＮａＣｌＯ混合液 ５０ｍｇ／Ｌ。残留塩素濃度５ｍｇ／ＬａｓＣｌ２、遊離残留塩素濃度として０．１−０．２ｍｇ／ＬａｓＣｌ２を維持。
Comparative Example 6-1: Sulfamic acid and NaClO
Comparative Example 6-2: Sulfamic acid, NaClO
その結果を表１０〜１２に示す。比較例６−２は実施例６−１よりも遊離残留塩素濃度の平均値が低くても、腐食速度は増大する。低濃度であっても遊離残留塩素濃度が維持されると腐食速度は増大する（表１０）。
比較例６−２よりも比較例６−１の方が腐食速度は大きく、腐食速度は遊離残留塩素維持濃度が上がると増加する（表１０）。
The results are shown in Tables 10-12. In Comparative Example 6-2, even if the average value of the free residual chlorine concentration is lower than that in Example 6-1, the corrosion rate increases. The corrosion rate increases when the free residual chlorine concentration is maintained even at low concentrations (Table 10).
Comparative Example 6-1 has a higher corrosion rate than Comparative Example 6-2, and the corrosion rate increases as the free residual chlorine maintenance concentration increases (Table 10).
遊離最大塩素濃度は比較例６−１よりも実施例６−１のほうが大きい。このことから、最大値よりも、最低値の方が腐食速度に影響すると考えられ、濃度を維持すると腐食速度の増大につながる（表１１，１２）。 The free maximum chlorine concentration is larger in Example 6-1 than in Comparative Example 6-1. From this, it is considered that the minimum value affects the corrosion rate rather than the maximum value, and maintaining the concentration leads to an increase in the corrosion rate (Tables 11 and 12).
［実施例７］
イソチアゾリン以外の有機系殺菌剤と酸化剤の併用による呼吸活性阻害の即効性増進について下記条件にて試験を行った。
＜有機系殺菌剤の種類＞
ジクロログリオキシム（ＤＣＧ）
２，２−ジブロモ−２−ニトロエタノール（ＤＢＮＥ）
＜無機系酸化剤＞
次亜塩素酸ナトリウムとスルファミン酸ナトリウム混合品
＜試験方法＞
Ｐｓｅｕｄｏｍｏｎａｓ.ｐｕｔｉｄを用いて評価した。
対象菌を滅菌水に懸濁し、６６０ｎｍ吸光度、０．１に調整し、１０ｍｌずつ試験管に分注した。有機系殺菌剤単独、無機系酸化剤単独、有機系殺菌剤と無機系酸化剤併用、各濃度を添加。
３０℃、１ｈ、１００ｒ．ｐ．ｍで振盪した。
その後、ポアサイズ０．４５μｍのニトロセルロースフィルターで濾過し、１０ｍＬの滅菌水を添加して、濾過し、薬品を取り除いた。
２−ｐ−ヨードフェニル−３−ｐ−ニトロフェニル−５−テトラゾリウムクロライド溶液(以下ＩＮＴ溶液、最終濃度０．０２％)と培地（ポリペプトン 最終濃度０．１ｇ／Ｌ、イーストエキストラクト 最終濃度０．１ｇ／Ｌ、ＮａＣｌ 最終濃度０．０５ｇ／Ｌ）を菌を濾過したフィルターに載せる。
３７℃、１ｈ静置する。
所定時間後濾過し、フィルターをクロロフォルム１ｍＬで抽出し、４９０ｎｍの吸光度を測定する。この値から菌のデハイドロゲナーゼにより生じたフォルマザン濃度を算出する。
対象菌のタンパク濃度を測定する。タンパク質濃度の定量はＦｏｌｉｎ−Ｃｉｏｃａｌｔｅｎのフェノール試薬による測定により実施した。
下式を用いて、抽出液量から抽出されたＩＮＴフォルマザンモル数を算出し、反応時間で除算するとデハイドロゲナーゼ活性を算出することができる。
デハイドロゲナーゼ活性［Ｕ］＝ミリモル濃度［ｍｍｏｌ／Ｌ］×μモル換算［１０００μｍｏｌ／ｍｍｏｌ］×抽出液量［Ｌ］／反応時間［ｍｉｎ］＝(０．０４４×４９０ｎｍ吸光度−０．０００４)×１０００×（１／１０００）／６０
（注） ミリモル濃度［ｍｍｏｌ／Ｌ]＝０．０４４×４９０ｎｍ吸光度−０．０００４
抽出液量 １ｍＬ
反応時間 ６０ｍｉｎ
[Example 7]
Tests were conducted under the following conditions for immediate improvement of respiratory activity inhibition by the combined use of an organic bactericide other than isothiazoline and an oxidizing agent.
<Types of organic fungicides>
Dichloroglyoxime (DCG)
2,2-dibromo-2-nitroethanol (DBNE)
<Inorganic oxidant>
Sodium hypochlorite and sodium sulfamate mixture <Test method>
Evaluation was performed using Pseudomonas.putid.
The target bacteria were suspended in sterilized water, adjusted to 660 nm absorbance, 0.1, and dispensed into test tubes in 10 ml aliquots. Organic disinfectant alone, inorganic oxidizer alone, combined use of organic disinfectant and inorganic oxidizer, each concentration added.
30 ° C., 1 h, 100 r. p. Shake at m.
Thereafter, the mixture was filtered through a nitrocellulose filter having a pore size of 0.45 μm, 10 mL of sterilized water was added, and the mixture was filtered to remove chemicals.
2-p-iodophenyl-3-p-nitrophenyl-5-tetrazolium chloride solution (hereinafter INT solution, final concentration 0.02%) and medium (polypeptone final concentration 0.1 g / L, yeast extract
Let stand at 37 ° C. for 1 h.
After a predetermined time, it is filtered, the filter is extracted with 1 mL of chloroform, and the absorbance at 490 nm is measured. From this value, the concentration of formazan produced by the fungal dehydrogenase is calculated.
Measure protein concentration of target bacteria. The protein concentration was quantified by measurement with Folin-Ciocalten's phenol reagent.
The dehydrogenase activity can be calculated by calculating the number of moles of INT formazan extracted from the amount of the extract using the following formula and dividing by the reaction time.
Dehydrogenase activity [U] = mmol concentration [mmol / L] × μmole conversion [1000 μmol / mmol] × extracted solution amount [L] / reaction time [min] = (0.044 × 490 nm absorbance−0.0004 ) × 1000 × (1/1000) / 60
(Note) millimolar concentration [mmol / L] = 0.044 × 490 nm absorbance−0.0004
Extraction volume 1mL
Reaction time 60min
デハイドロゲナーゼ活性をタンパク質の質量で除算し、菌体当たりの活性を求める。桁数が小さいので、さらに１０００００倍して結果とした。このデハイドロゲナーゼ活性が消失した単独及び併用の薬剤濃度を図５に示す。なお、図５のグラフ中の直線は相加効果直線を表しており、この直線より下にあると相乗効果ありと判断される。 Divide the dehydrogenase activity by the protein mass to determine the activity per cell. Since the number of digits is small, the result was further multiplied by 100,000. FIG. 5 shows single and combined drug concentrations at which this dehydrogenase activity disappeared. In addition, the straight line in the graph of FIG. 5 represents the additive effect straight line, and if it is below this straight line, it is judged that there exists a synergistic effect.
＜結果＞
（１） 薬剤を添加しないＰｓｅｕｄｏｍｏｎａｓ.ｐｕｔｉｄの菌体当たりの活性は４８４で、十分な活性を示した。
（２） 次亜塩素酸ナトリウムとスルファミン酸ナトリウム混合品で、デハイドロゲナーゼ活性を消失させるためには７０ｍｇ／ＬａｓＣｌ２以上の濃度を必要とし、また、ＤＣＧでは１０ｍｇ／Ｌを必要とした。併用すると、活性消失に必要とされる各剤は両者を足した場合よりも低濃度で達成され、併用されたことによる活性抑制の相乗効果が示された。
（３） 次亜塩素酸ナトリウムとスルファミン酸ナトリウム混合品で、デハイドロゲナーゼ活性を消失させるためには７０ｍｇ／ＬａｓＣｌ２以上の濃度を必要とし、また、ＤＢＮＥでは１０ｍｇ／Ｌを必要とした。併用すると、活性消失に必要とされる各剤は両者を足した場合よりも低濃度で達成され、併用されたことによる活性抑制の相乗効果が示された。
これらの結果から明らかなように、イソチアゾリン化合物以外の有機系殺菌剤と無機系酸化剤の併用においても、同様の機構が働き、相乗効果、速効性、効果の持続が達される。また、酸化剤の大幅な低減により、腐食のリスクも低減される。
<Result>
(1) The activity per cell of Pseudomonas.putid to which no drug was added was 484, indicating a sufficient activity.
(2) In order to eliminate dehydrogenase activity in a mixture of sodium hypochlorite and sodium sulfamate, a concentration of 70 mg / LasCl 2 or more was required, and DCG required 10 mg / L. When used in combination, each agent required for loss of activity was achieved at a lower concentration than when both were added, and a synergistic effect of activity suppression due to the combined use was shown.
(3) In order to eliminate dehydrogenase activity in a mixture of sodium hypochlorite and sodium sulfamate, a concentration of 70 mg / LasCl 2 or more was required, and DBNE required 10 mg / L. When used in combination, each agent required for loss of activity was achieved at a lower concentration than when both were added, and a synergistic effect of activity suppression due to the combined use was shown.
As is clear from these results, the same mechanism works also in the combined use of organic bactericides other than isothiazoline compounds and inorganic oxidizers, and a synergistic effect, rapid efficacy, and sustained effect are achieved. The risk of corrosion is also reduced due to the significant reduction in oxidant.
Claims (6)
該有機系殺菌剤と無機系酸化剤とを間欠的に添加することを特徴とする水系の殺菌方法。 In an aqueous sterilization method of adding an organic sterilant and an inorganic oxidizer to an aqueous system,
An aqueous sterilization method, wherein the organic sterilant and an inorganic oxidant are intermittently added.
ジクロログリオキシド、及びジブロモニトロエタノールよりなる群から選ばれる１種又は２種以上であることを特徴とする水系の殺菌方法。 In any 1 item | term of Claim 1 thru | or 3, an organic type fungicide is an isothiazoline compound,
A water-based sterilization method, which is one or more selected from the group consisting of dichloroglycoxide and dibromonitroethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013262680A JP6478455B2 (en) | 2013-12-19 | 2013-12-19 | Water sterilization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013262680A JP6478455B2 (en) | 2013-12-19 | 2013-12-19 | Water sterilization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015117216A true JP2015117216A (en) | 2015-06-25 |
| JP6478455B2 JP6478455B2 (en) | 2019-03-06 |
Family
ID=53530279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013262680A Expired - Fee Related JP6478455B2 (en) | 2013-12-19 | 2013-12-19 | Water sterilization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6478455B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6020697B1 (en) * | 2015-11-09 | 2016-11-02 | 栗田工業株式会社 | Method for inhibiting concentration reduction of isothiazoline compounds |
| JP2018122267A (en) * | 2017-02-02 | 2018-08-09 | オルガノ株式会社 | Method for modifying reverse osmosis membrane, reverse osmosis membrane, and method of treating uncharged material-containing water |
| WO2018142904A1 (en) * | 2017-02-02 | 2018-08-09 | オルガノ株式会社 | Method for modifying reverse osmosis membrane, reverse osmosis membrane, method for treating water containing non-charged substance, operation method for reverse osmosis membrane, and reverse osmosis membrane device |
| JP2018187572A (en) * | 2017-05-09 | 2018-11-29 | オルガノ株式会社 | Operation method for reverse osmosis membrane and reverse osmosis membrane device |
| JP6447687B1 (en) * | 2017-09-01 | 2019-01-09 | 栗田工業株式会社 | One-component water treatment agent and method for producing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001047059A (en) * | 1999-08-11 | 2001-02-20 | Kurita Water Ind Ltd | Slime control method and slime control agent |
| JP2008012424A (en) * | 2006-07-05 | 2008-01-24 | Somar Corp | Method of adding slime control agent |
| JP2009024895A (en) * | 2007-07-17 | 2009-02-05 | Miura Co Ltd | Water treatment system and treatment method of cooling system circulation water |
| JP2012036108A (en) * | 2010-08-04 | 2012-02-23 | Aquas Corp | Treatment method for open circulating cooling water system |
| JP2013158670A (en) * | 2012-02-02 | 2013-08-19 | Aquas Corp | Treatment method for open-circulating cooling water system |
| WO2013146786A1 (en) * | 2012-03-26 | 2013-10-03 | 栗田工業株式会社 | Method for controlling microorganisms in aqueous system |
-
2013
- 2013-12-19 JP JP2013262680A patent/JP6478455B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001047059A (en) * | 1999-08-11 | 2001-02-20 | Kurita Water Ind Ltd | Slime control method and slime control agent |
| JP2008012424A (en) * | 2006-07-05 | 2008-01-24 | Somar Corp | Method of adding slime control agent |
| JP2009024895A (en) * | 2007-07-17 | 2009-02-05 | Miura Co Ltd | Water treatment system and treatment method of cooling system circulation water |
| JP2012036108A (en) * | 2010-08-04 | 2012-02-23 | Aquas Corp | Treatment method for open circulating cooling water system |
| JP2013158670A (en) * | 2012-02-02 | 2013-08-19 | Aquas Corp | Treatment method for open-circulating cooling water system |
| WO2013146786A1 (en) * | 2012-03-26 | 2013-10-03 | 栗田工業株式会社 | Method for controlling microorganisms in aqueous system |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6020697B1 (en) * | 2015-11-09 | 2016-11-02 | 栗田工業株式会社 | Method for inhibiting concentration reduction of isothiazoline compounds |
| WO2017081875A1 (en) * | 2015-11-09 | 2017-05-18 | 栗田工業株式会社 | Method for suppressing reduction of isothiazoline compound concentration |
| CN108347934A (en) * | 2015-11-09 | 2018-07-31 | 栗田工业株式会社 | The concentration of iso thiazolinium compound reduces suppressing method |
| US10765115B2 (en) | 2015-11-09 | 2020-09-08 | Kurita Water Industries Ltd. | Method for suppressing reduction of isothiazoline compound concentration |
| CN108347934B (en) * | 2015-11-09 | 2021-06-04 | 栗田工业株式会社 | Method for inhibiting decrease in concentration of isothiazoline compound |
| JP2018122267A (en) * | 2017-02-02 | 2018-08-09 | オルガノ株式会社 | Method for modifying reverse osmosis membrane, reverse osmosis membrane, and method of treating uncharged material-containing water |
| WO2018142904A1 (en) * | 2017-02-02 | 2018-08-09 | オルガノ株式会社 | Method for modifying reverse osmosis membrane, reverse osmosis membrane, method for treating water containing non-charged substance, operation method for reverse osmosis membrane, and reverse osmosis membrane device |
| JP2018187572A (en) * | 2017-05-09 | 2018-11-29 | オルガノ株式会社 | Operation method for reverse osmosis membrane and reverse osmosis membrane device |
| JP6447687B1 (en) * | 2017-09-01 | 2019-01-09 | 栗田工業株式会社 | One-component water treatment agent and method for producing the same |
| WO2019044043A1 (en) * | 2017-09-01 | 2019-03-07 | 栗田工業株式会社 | Single-liquid-type water treatment agent and method for manufacturing same |
| JP2019043891A (en) * | 2017-09-01 | 2019-03-22 | 栗田工業株式会社 | One-pack type water treatment agent and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6478455B2 (en) | 2019-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110078194B (en) | Method for producing hypobromous acid stabilizing composition, and method for inhibiting fouling of separation membrane | |
| Jiang et al. | Synergistic inactivation of anaerobic wastewater biofilm by free nitrous acid and hydrogen peroxide | |
| JP4317762B2 (en) | Method for the preparation of biocides containing stabilized hypochlorite and bromide ion sources, and methods for controlling microbial fouling using the same | |
| JP6478455B2 (en) | Water sterilization method | |
| JP6533056B2 (en) | Filtration treatment system and filtration treatment method | |
| JP3015508B2 (en) | Disinfectant / bacteriostatic agent | |
| EP2729419B1 (en) | Multiple uses of amine salts for industrial water treatment | |
| WO2016104356A1 (en) | Method for controlling slime on separation membrane | |
| JP2016120457A (en) | Filtration treatment system and filtration treatment method | |
| JP4959062B2 (en) | Water treatment method | |
| JP2015063475A (en) | Antibacterial/algicidal method of cooling water system and antibacterial/algicidal agent | |
| JP6649697B2 (en) | Water sterilization method | |
| JP5635596B2 (en) | Halogenated amide biocidal compounds and methods of treating aqueous systems from near neutral to high pH | |
| JP3915560B2 (en) | Slime remover, slime remover composition and slime peel method | |
| US20100183738A1 (en) | Method and composition for inhibiting growth of microorganisms in industrial process waters in the presence of anionic anti-fouling additives | |
| JP5928938B2 (en) | Treatment method for open circulating cooling water system | |
| US6811747B2 (en) | Corrosion inhibitor | |
| US20180177191A1 (en) | Process for reducing the corrosiveness of a biocidal composition containing in situ generated sodium hypochlorite | |
| JP2016120486A (en) | Method for inhibiting slime in separation membrane | |
| JP5281465B2 (en) | Bactericidal algicide composition, water-based bactericidal algicide method, and method for producing bactericidal algicide composition | |
| JP2013158669A (en) | Treatment method for open-circulating cooling water system | |
| JP6548870B2 (en) | Method for controlling slime in papermaking process water | |
| JP6630563B2 (en) | Water sterilization method | |
| KR20140088207A (en) | Treating agent for ship ballast water and method for treating ship ballast water using same | |
| JP6331364B2 (en) | Corrosion reducing method and corrosion reducing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161007 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170314 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170411 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170607 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20171205 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180302 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20180312 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20180511 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181126 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190205 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6478455 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |