JP6057526B2 - Treatment method for open circulating cooling water system - Google Patents
Treatment method for open circulating cooling water system Download PDFInfo
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- JP6057526B2 JP6057526B2 JP2012073433A JP2012073433A JP6057526B2 JP 6057526 B2 JP6057526 B2 JP 6057526B2 JP 2012073433 A JP2012073433 A JP 2012073433A JP 2012073433 A JP2012073433 A JP 2012073433A JP 6057526 B2 JP6057526 B2 JP 6057526B2
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- 239000000498 cooling water Substances 0.000 title claims description 121
- 238000011282 treatment Methods 0.000 title claims description 92
- 238000000034 method Methods 0.000 title claims description 44
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 72
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 71
- 229910052801 chlorine Inorganic materials 0.000 claims description 71
- 239000000460 chlorine Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 241000589248 Legionella Species 0.000 claims description 53
- 208000007764 Legionnaires' Disease Diseases 0.000 claims description 51
- 229910052736 halogen Inorganic materials 0.000 claims description 42
- 150000002367 halogens Chemical class 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229920006317 cationic polymer Polymers 0.000 claims description 36
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 29
- 239000000417 fungicide Substances 0.000 claims description 28
- 230000001590 oxidative effect Effects 0.000 claims description 27
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 claims description 22
- 230000000855 fungicidal effect Effects 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 17
- 239000000645 desinfectant Substances 0.000 claims description 16
- 230000000717 retained effect Effects 0.000 claims description 16
- 238000003672 processing method Methods 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 9
- -1 isothiazoline compound Chemical class 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000003814 drug Substances 0.000 description 35
- 229940079593 drug Drugs 0.000 description 35
- 241000894006 Bacteria Species 0.000 description 27
- 230000000694 effects Effects 0.000 description 21
- 241000233866 Fungi Species 0.000 description 18
- 241000195493 Cryptophyta Species 0.000 description 17
- 241000224489 Amoeba Species 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000001954 sterilising effect Effects 0.000 description 14
- 239000005708 Sodium hypochlorite Substances 0.000 description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 13
- 238000004659 sterilization and disinfection Methods 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 7
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 5
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 4
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 4
- 241000589323 Methylobacterium Species 0.000 description 4
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
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- 239000007769 metal material Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Diphosphoinositol tetrakisphosphate Chemical compound OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- UEFCKYIRXORTFI-UHFFFAOYSA-N 1,2-thiazolidin-3-one Chemical compound O=C1CCSN1 UEFCKYIRXORTFI-UHFFFAOYSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- DLMGITXUPDHMKV-UHFFFAOYSA-N 1,3-dichloro-5,5-diethylimidazolidine-2,4-dione Chemical compound CCC1(CC)N(Cl)C(=O)N(Cl)C1=O DLMGITXUPDHMKV-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 150000000185 1,3-diols Chemical class 0.000 description 1
- PIEXCQIOSMOEOU-UHFFFAOYSA-N 1-bromo-3-chloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Br)C(=O)N(Cl)C1=O PIEXCQIOSMOEOU-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 230000008014 freezing Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
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- 150000001469 hydantoins Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、レジオネラ属菌を確実に殺菌し、その増殖を抑制して、冷却水中のレジオネラ属菌数を長期間不検出レベルに維持することができ、しかも、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等が繁殖しにくい開放循環冷却水系の処理方法に関する。 The present invention can reliably sterilize Legionella, suppress its growth, maintain the number of Legionella in cooling water at an undetectable level for a long time, and has drug-resistant bacteria and drug resistance. The present invention relates to a processing method for an open circulating cooling water system in which algae, fungi and the like are difficult to propagate.
冷却水系などの循環水系において、バイオフィルムは機器や水系周辺の汚染原因となるとともに、冷却水系においては熱交換効率低下の原因になり、その抑制のために様々な技術的提案が行われている。 In circulating water systems such as cooling water systems, biofilms cause contamination of equipment and surroundings of water systems, and in cooling water systems, it causes a decrease in heat exchange efficiency, and various technical proposals have been made to control them. .
このような技術のうち、ハロゲン系酸化物による処理は、特表２００３−５０３３２３号公報（特許文献１）や特表平１１−５０６１３９号公報（特許文献２）に開示されており、本出願人も特開２００９−１６０５０５号公報（特許文献３）で水系水におけるスライム抑制方法を提案している。この特許文献３により提案された方法は、低濃度のハロゲン系酸化物を含む薬剤を水系水に添加する技術であり、水系の金属材質に対する腐食を防止しながら極めて効果的にバイオフィルムの抑制が可能となる。このように、ハロゲン系酸化物は細菌類の殺菌、バイオフィルムの成長抑制には極めて有効である。 Among such techniques, the treatment with a halogen-based oxide is disclosed in Japanese Patent Application Publication No. 2003-503323 (Patent Document 1) and Japanese Patent Application Publication No. 11-506139 (Patent Document 2). JP 2009-160505 A (Patent Document 3) proposes a slime suppression method in aqueous water. The method proposed by Patent Document 3 is a technique of adding a chemical containing a low-concentration halogen-based oxide to aqueous water, and can effectively suppress biofilm while preventing corrosion of the aqueous metal material. It becomes possible. Thus, halogen-based oxides are extremely effective for sterilizing bacteria and suppressing biofilm growth.
ここで、開放循環冷却水系では、バイオフィルムの抑制の他に、レジオネラ属菌に対する除菌効果も求められる。 Here, in the open circulation cooling water system, in addition to the suppression of the biofilm, a disinfection effect against Legionella is also required.
上記のようなハロゲン系酸化物は、実験室での試験ではレジオネラ属菌に対して優れた殺菌作用を示すが、実際の開放循環冷却水系をハロゲン系酸化物で処理してみると、充分な殺菌、抑制効果が得られない場合が多く、驚くべきことに、遊離残留塩素濃度として２ｍｇ／Ｌを維持してもレジオネラ属菌を殺菌できない水系も存在する。 Although the halogen-based oxides described above show excellent bactericidal action against Legionella in laboratory tests, it is sufficient to treat an actual open circulating cooling water system with a halogen-based oxide. In many cases, the sterilization and inhibitory effects cannot be obtained. Surprisingly, there is an aqueous system in which Legionella spp. Cannot be sterilized even if the free residual chlorine concentration is maintained at 2 mg / L.
さらに、ハロゲン系酸化物の水系への添加を長期間継続すると、塩素剤に対して強い耐性を示すメチロバクテリウム等の細菌類や真菌類等が繁殖し、バイオフィルムを形成する恐れがある。 Furthermore, if the addition of halogenated oxides to the aqueous system is continued for a long period of time, there is a risk that bacteria such as methylobacterium and fungi that exhibit strong resistance to chlorinated agents will proliferate and form biofilms. .
一方、有機系の各種の殺菌剤は、レジオネラ属菌の殺菌処理に古くから使われており、高濃度で添加したり、連続的に水系に添加することにより、レジオネラ属菌を効果的に殺菌し、その増殖を抑制することができるとされている。このような技術は、例えば特開平７−８０４６８号公報（特許文献４）に開示されている。 On the other hand, various organic fungicides have long been used for sterilization of Legionella, and can be effectively sterilized by adding them at high concentrations or by continuously adding them to aqueous systems. And it is said that the proliferation can be suppressed. Such a technique is disclosed in, for example, Japanese Patent Laid-Open No. 7-80468 (Patent Document 4).
しかし、一般に有機系の殺菌剤は、バイオフィルムに対する殺菌効果や剥離効果が弱いので、間欠的な処理で一時的に水中に浮遊しているレジオネラ属菌が不検出になった場合でも、水系内にバイオフィルムが残存し、これがレジオネラ属菌繁殖の温床となって、比較的短期間でレジオネラ属菌が水中に検出されるようになる。また、ある種の有機系殺菌剤はアメーバの嚢子やカビの胞子に対する効果が弱く、特にアメーバを殺滅しきれない場合には生残したアメーバ内でレジオネラ属菌が増殖するため、レジオネラ属菌の除菌効果が充分に得られない。加えて、有機系殺菌剤はハロゲン系酸化物と比較して耐性菌や耐性を持った藻類が繁殖しやすいという欠点も有する。 However, organic disinfectants generally have weak disinfecting and peeling effects on biofilms, so even if Legionella spp. Temporarily suspended in water are not detected by intermittent treatment, The biofilm remains on the surface, and this becomes a hotbed for breeding Legionella, and Legionella is detected in water in a relatively short period of time. Also, certain organic fungicides have a weak effect on amoeba spore and mold spores, especially when the amoebae cannot be killed, Legionella spp. The bacteria disinfection effect cannot be obtained sufficiently. In addition, organic fungicides also have the disadvantage that resistant bacteria and resistant algae are easier to propagate than halogen-based oxides.
また、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体は、特開平２−１３８１０３号公報（特許文献５）や特開平５−３３１００２号公報（特許文献６）で微生物の増殖阻止用組成物や藻類防除剤として提案されているが、この化合物もバイオフィルムに対する殺菌効果や剥離効果が弱く、レジオネラ属菌に対する殺菌力も充分とは云えなかった。 Water-soluble cationic polymers obtained by the reaction of dimethylamine and epichlorohydrin are disclosed in Japanese Patent Application Laid-Open No. 2-138103 (Patent Document 5) and Japanese Patent Application Laid-Open No. 5-331002 (Patent Document 6). However, this compound also has a weak bactericidal effect and exfoliating effect on biofilms, and it cannot be said that the bactericidal power against Legionella spp. Is sufficient.
このような問題点の解決手段として、本出願人は特開２０１２−３６１０８号公報（特許文献７）でハロゲン系酸化物による処理と有機系殺菌剤による処理を併用する方法を提案している。この特許文献７によって提案された方法は、ハロゲン系酸化物の殺菌力、バイオフィルムの成長抑制力を保ちながら、欠点であるレジオネラ属菌の繁殖を防止する優れた方法だか、本発明者等の詳細な検討の結果、有機系殺菌剤としてイソチアゾリン系化合物やグルタルアルデヒドを使用した特許文献７の方法では、１ヶ月以上の長期間処理を継続した場合に、レジオネラ属菌の繁殖を充分に抑えることができない水系があることが判明した。 As a means for solving such a problem, the present applicant has proposed a method in which treatment with a halogen-based oxide and treatment with an organic disinfectant are used together in JP 2012-36108 A (Patent Document 7). The method proposed by Patent Document 7 is an excellent method for preventing the proliferation of Legionella spp., Which is a defect, while maintaining the bactericidal power of halogen-based oxides and the ability to suppress the growth of biofilms. As a result of detailed examination, the method of Patent Document 7 using isothiazoline-based compounds and glutaraldehyde as an organic fungicide sufficiently suppresses the growth of Legionella spp. It turned out that there was an aqueous system that could not.
従って、レジオネラ属菌を確実に殺菌し、その増殖を抑制して、冷却水中のレジオネラ属菌数を長期間不検出レベルに維持することができ、しかも、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等が繁殖しにくい開放循環冷却水系の処理方法が求められていた。 Therefore, it is possible to reliably sterilize Legionella, suppress its growth, maintain the number of Legionella in cooling water at a non-detectable level for a long time, and also drug resistant bacteria and drug-resistant algae Therefore, there has been a demand for a method for treating an open circulating cooling water system in which fungi and the like are difficult to propagate.
本発明は、上記課題を解決する、すなわち、レジオネラ属菌を確実に殺菌し、その増殖を抑制して、冷却水中のレジオネラ属菌数を長期間不検出レベルに維持することができ、しかも、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等が繁殖しにくい開放循環冷却水系の処理方法を提供することを目的とする。 The present invention solves the above-mentioned problem, that is, can reliably sterilize Legionella spp., Suppress its growth, and maintain the number of Legionella spp. In the cooling water at an undetectable level for a long time, It is an object of the present invention to provide a treatment method of an open circulating cooling water system in which drug-resistant bacteria, drug-resistant algae, fungi and the like are difficult to propagate.
本発明の開放循環冷却水系の処理方法は、上記課題を解決するために、請求項１に記載
の通り、開放循環冷却水系の冷却水に対して、ハロゲン系酸化物による処理を２４時間に１時間以上行い、かつ、有機系殺菌剤による処理を３０日間に１回以上行う、開放循環冷却水系の処理方法であって、前記ハロゲン系酸化物による処理が、水中で遊離塩素を生成する物質を前記冷却水に添加し、前記冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上５ｍｇ／Ｌ以下の範囲に維持する処理、あるいは、水中で結合塩素を生成する物質を前記冷却水に添加し、前記冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下の範囲に維持する処理であり、前記有機系殺菌剤による処理が、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を、前記冷却水に添加する処理であり、該ハロゲン系酸化物による処理と該有機系殺菌剤による処理を、１ヶ月を越えて継続して行い、レジオネラ属菌およびアメーバに対する殺菌、抑制効果を維持することを特徴とする開放循環冷却水系の処理方法である。
In order to solve the above-described problems, the open circulating cooling water system treatment method of the present invention, as described in claim 1, treats the cooling water of the open circulating cooling water system with a halogen-based oxide in 24 hours. An open circulating cooling water treatment method that is performed for at least an hour and is treated with an organic disinfectant at least once every 30 days, wherein the treatment with the halogen-based oxide generates a free chlorine in water. A treatment that is added to the cooling water and maintains the oxidizing power in the cooling water within a range of 0.01 mg / L or more and 5 mg / L or less as a free residual chlorine concentration, or a substance that generates bound chlorine in the water. It was added to the and oxidizing power of the cooling water to a process of maintaining a range of 0.5 mg / L or higher 100 mg / L as total residual chlorine concentration, treatment with the organic fungicide, dimethylamine and Epiku The water-soluble cationic polymer obtained by the reaction of Rohidorin, a process to be added to the cooling water, the processing by the processing and organic fungicides by the halogen-based oxide, continued beyond the 1 month It is a processing method of an open circulation cooling water system characterized in that the effect of sterilization and inhibition against Legionella and amoeba is maintained.
本発明の開放循環冷却水系の処理方法は、請求項２に記載の通り、請求項１に記載の開放循環冷却水系の処理方法において、前記有機系殺菌剤による処理が、前記ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を、前記冷却水系の保有水量に対する添加濃度が、有効成分濃度として１ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下となるように添加する処理であり、かつ、該有機系殺菌剤による処理を、２日間ないし３０日間に１回行うことを特徴とする。 The processing method of the open circulating cooling water system according to the present invention is the processing method of the open circulating cooling water system according to claim 1, wherein the treatment with the organic disinfectant is the dimethylamine and epichloro A process of adding a water-soluble cation polymer obtained by reaction with hydrin so that the additive concentration relative to the amount of water retained in the cooling water system is 1 mg / L or more and 200 mg / L or less as the active ingredient concentration, and The treatment with the organic fungicide is performed once every 2 to 30 days.
本発明の開放循環冷却水系の処理方法は、請求項３に記載の通り、請求項１または請求項２に記載の開放循環冷却水系の処理方法において、前記有機系殺菌剤による処理が、前記ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とともに、イソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールを前記冷却水に添加する処理であることを特徴とする。 The processing method of the open circulating cooling water system of the present invention is the processing method of the open circulating cooling water system according to claim 1 or 2, wherein the treatment with the organic disinfectant is the dimethyl as described in claim 3. This is a treatment of adding an isothiazoline-based compound and / or 2-bromo-2-nitropropane-1,3-diol to the cooling water together with a water-soluble cationic polymer obtained by a reaction between an amine and epichlorohydrin. It is characterized by that.
本発明の開放循環冷却水系の処理方法は、請求項４に記載の通り、請求項３に記載の開放循環冷却水系の処理方法において、前記有機系殺菌剤による処理が、前記ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を、前記冷却水系の保有水量に対する添加濃度が、有効成分濃度として１ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下となるように添加するとともに、前記イソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールを、前記冷却水系の保有水量に対する添加濃度が、有効成分濃度として０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下となるように添加する処理であり、かつ、該有機系殺菌剤による処理を、２日間ないし３０日間に１回行うことを特徴とする。 The processing method of the open circulating cooling water system according to the present invention is the processing method of the open circulating cooling water system according to claim 3, wherein the treatment with the organic disinfectant is the dimethylamine and epichloro A water-soluble cation polymer obtained by reaction with hydrin is added so that an addition concentration with respect to the amount of water retained in the cooling water system is 1 mg / L or more and 200 mg / L or less as an active ingredient concentration, and the isothiazoline system The compound and / or 2-bromo-2-nitropropane-1,3-diol is added so that the concentration of the cooling water system relative to the amount of retained water is 0.1 mg / L or more and 100 mg / L or less as the active ingredient concentration And the treatment with the organic disinfectant is performed once every 2 to 30 days.
本発明の開放循環冷却水系の処理方法は、請求項６に記載の通り、請求項５に記載の開放循環冷却水系の処理方法において、前記ハロゲン系酸化物による処理が、水中で遊離塩素を生成する物質を前記冷却水に添加し、該冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上１ｍｇ／Ｌ以下の範囲に維持する処理であり、かつ、該ハロゲン系酸化物による処理を常時行うことを特徴とする。 The open circulation cooling water system treatment method according to the present invention is the open circulation cooling water system treatment method according to claim 5, wherein the treatment with the halogen-based oxide generates free chlorine in water. A substance to be added to the cooling water, and maintaining the oxidizing power in the cooling water within a range of 0.01 mg / L or more and 1 mg / L or less as a free residual chlorine concentration, and the treatment with the halogen-based oxide Is always performed.
本発明の開放循環冷却水系の処理方法は、請求項８に記載の通り、請求項７に記載の開放循環冷却水系の処理方法において、前記ハロゲン系酸化物による処理が、水中で結合塩素を生成する物質を前記冷却水に添加し、該冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１０ｍｇ／Ｌ以下の範囲に維持する処理であり、かつ、該ハロゲン系酸化物による処理を常時行うことを特徴とする。 The open circulation cooling water system treatment method of the present invention is the open circulation cooling water system treatment method according to claim 7, wherein the treatment with the halogen-based oxide generates bound chlorine in water. A substance to be added to the cooling water, and maintaining the oxidizing power in the cooling water in the range of 0.5 mg / L or more and 10 mg / L or less as the total residual chlorine concentration, and the treatment with the halogen-based oxide Is always performed.
本発明の開放循環冷却水系の処理方法によれば、ハロゲン系酸化物による処理と有機系殺菌剤による処理を併用する際に、有機系殺菌剤として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を使用することで、これら薬剤単独使用時に得られる効果からは想到できない優れた効果が得られる。すなわち、レジオネラ属菌を確実に殺菌し、その増殖を抑制して、冷却水中のレジオネラ属菌数を長期間不検出レベルに維持することができ、しかも、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等が繁殖しにくい開放循環冷却水系とすることができる。 According to the treatment method of the open circulation cooling water system of the present invention, when the treatment with the halogen-based oxide and the treatment with the organic fungicide are used in combination, as an organic fungicide, by the reaction of dimethylamine and epichlorohydrin. By using the obtained water-soluble cationic polymer, an excellent effect that cannot be conceived from the effect obtained when these drugs are used alone can be obtained. In other words, it can sterilize Legionella genus, suppress its growth, maintain the number of Legionella genus in cooling water at a non-detectable level for a long time, and drug-resistant bacteria and drug-resistant algae Moreover, it can be set as the open circulation cooling water system which fungi etc. cannot propagate easily.
このとき、有機系殺菌剤による処理として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を、冷却水系の保有水量に対する添加濃度が、有効成分濃度として１ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下となるように添加する処理を、２日間ないし３０日間に１回行うことにより、少ない有機系殺菌剤の添加量で、レジオネラ属菌の殺菌、抑制効果を長期間持続することができ、さらに、メチロバクテリウム等の塩素耐性菌の繁殖を抑制することが可能となる。 At this time, as a treatment with an organic disinfectant, a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin is added at an active ingredient concentration of 1 mg / L or more as the active ingredient concentration. By performing the treatment to be added to 200 mg / L or less once every 2 to 30 days, the effect of sterilizing and suppressing Legionella can be maintained for a long time with a small amount of organic fungicide added. In addition, it is possible to suppress the propagation of chlorine-resistant bacteria such as methylobacterium.
さらに、有機系殺菌剤による処理として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体と、イソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールとを併用することで、長期間のレジオネラ属菌の殺菌、抑制効果に加えて、塩素耐性菌や有機系殺菌剤に耐性を持った細菌類、藻類、真菌類等の繁殖抑制効果も充分なものとなる。 Further, as a treatment with an organic fungicide, a water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin, an isothiazoline compound and / or 2-bromo-2-nitropropane-1,3- Combined with diol, in addition to the long-term sterilization and suppression effects of Legionella spp., Sufficient suppression of growth of bacteria, algae, fungi, etc. that are resistant to chlorine-resistant bacteria and organic fungicides It will be something.
特に、有機系殺菌剤による処理として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を冷却水系の保有水量に対する有効成分濃度として１ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下、イソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールを冷却水系の保有水量に対する有効成分濃度として０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下の濃度で添加する処理を、２日間ないし３０日間に１回行うことにより、少ない有機系殺菌剤の添加量で、レジオネラ属菌の殺菌、抑制効果を長期間、確実に得ることができ、また、各種耐性菌等の繁殖も充分に抑制できるので、開放循環冷却水系の各種微生物障害の防止方法として有用である。 In particular, as a treatment with an organic disinfectant, a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin is used as an active ingredient concentration with respect to the amount of water held in the cooling water system. A treatment in which a compound and / or 2-bromo-2-nitropropane-1,3-diol is added at a concentration of 0.1 mg / L or more and 100 mg / L or less as an active ingredient concentration with respect to the amount of water retained in the cooling water system for 2 days In addition, by performing once every 30 days, the effect of sterilizing and suppressing Legionella spp. Can be reliably obtained over a long period of time with a small amount of addition of an organic fungicide, and the propagation of various resistant bacteria is sufficient. Since it can be suppressed, it is useful as a method for preventing various microbial failures in an open circulating cooling water system.
本発明において、ハロゲン系酸化物として水中で遊離塩素を生成する物質を使用し、冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上５ｍｇ／Ｌ以下の範囲に２４時間に１時間以上維持する処理を行うことで、レジオネラ属菌繁殖の温床となるバイオフィルムの付着、成長を有効に抑制することができ、また、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖も有効に抑えることができる。 In the present invention, a substance that generates free chlorine in water is used as a halogen-based oxide, and the oxidizing power in cooling water is within a range of 0.01 mg / L or more and 5 mg / L or less as a free residual chlorine concentration for 1 hour in 24 hours. By performing the above-mentioned treatment, it is possible to effectively suppress the adhesion and growth of biofilms that serve as a hotbed for Legionella spp., And the propagation of drug-resistant bacteria, drug-resistant algae, fungi, etc. Can also be effectively suppressed.
さらに、冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上１ｍｇ／Ｌ以下の範囲に常時維持することで、水系で用いられる機器などの軟鋼や銅などの金属に対する腐食を抑制しつつ、バイオフィルムの付着、成長を極めて効果的に抑制できるので、レジオネラ属菌数を長期間不検出レベルに維持することが可能となる。また、耐性菌、耐性藻類、真菌類等の繁殖も充分に抑えることができる。 Furthermore, by constantly maintaining the oxidizing power in the cooling water within the range of 0.01 mg / L or more and 1 mg / L or less as the free residual chlorine concentration, corrosion against mild steel such as equipment used in water systems and metals such as copper is suppressed. On the other hand, since the adhesion and growth of the biofilm can be extremely effectively suppressed, the number of Legionella bacteria can be maintained at a non-detection level for a long time. In addition, the propagation of resistant bacteria, resistant algae, fungi and the like can be sufficiently suppressed.
また、ハロゲン系酸化物として水中で結合塩素を生成する物質を使用することで、冷却水中に酸化力を維持することが容易となり、このとき、冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下の範囲に２４時間に１時間以上維持することで、レジオネラ属菌繁殖の温床となるバイオフィルムの付着、成長を効果的に抑制することができる。また、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖も、より有効に抑えることができる。 Further, by using a substance that generates bound chlorine in water as the halogen-based oxide, it becomes easy to maintain the oxidizing power in the cooling water. At this time, the oxidizing power in the cooling water is set to 0. By maintaining in the range of 5 mg / L or more and 100 mg / L or less for 1 hour or more in 24 hours, it is possible to effectively suppress the adhesion and growth of a biofilm serving as a hotbed for Legionella spp. In addition, propagation of drug-resistant bacteria, drug-resistant algae, fungi, and the like can be suppressed more effectively.
加えて、冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１０ｍｇ／Ｌ以下の範囲に常時維持することで、水系で用いられる機器などの軟鋼や銅などの金属に対する腐食をより効果的に防ぎながら、レジオネラ属菌数を、より確実に不検出レベルに維持することが可能となり、また、耐性菌、耐性藻類、真菌類等の繁殖も、より確実に抑えることができる。 In addition, by constantly maintaining the oxidizing power in the cooling water within the range of 0.5 mg / L to 10 mg / L as the total residual chlorine concentration, the corrosion of mild steel such as equipment used in water systems and metals such as copper is further improved. While effectively preventing, the number of Legionella spp. Can be more reliably maintained at the non-detection level, and the propagation of resistant bacteria, resistant algae, fungi, etc. can be more reliably suppressed.
本発明の開放循環冷却水系の処理方法は、上述のように、開放循環冷却水系の冷却水に対して、ハロゲン系酸化物による処理を２４時間に１時間以上行い、かつ、特定の有機系殺菌剤による処理を３０日間に１回以上行うことを特徴とする開放循環冷却水系の処理方法である。 As described above, the method for treating an open circulating cooling water system according to the present invention is to treat the cooling water of an open circulating cooling water system with a halogen-based oxide for 1 hour or more in 24 hours, and to perform a specific organic sterilization. It is a processing method of the open circulation cooling water system characterized by performing the process by an agent once or more for 30 days.
本発明において、ハロゲン系酸化物としては、水中で酸化力を示すハロゲン系酸化物であれば良く、具体的には、水中で遊離塩素を生成する物質及び水中で結合塩素を生成する物質から選択される少なくとも１種の物質を用いる。 In the present invention, the halogen-based oxide may be any halogen-based oxide that exhibits oxidizing power in water. Specifically, it is selected from substances that generate free chlorine in water and substances that generate bound chlorine in water. At least one substance is used.
水中で遊離塩素を生成する物質とは、その物質を添加した水系水をＪＩＳ Ｋ０１０１ ２８に記載の残留塩素測定法により測定した際に、遊離残留塩素が検出される物質のことであり、例えば、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、次亜臭素酸ナトリウム等の次亜ハロゲン酸塩、ジクロロイソシアヌル酸ナトリウム、トリクロロイソシアヌル酸等のハロゲン化イソシアヌル酸、１−ブロモ−３−クロロ−５，５−ジメチルヒダントイン、１，３−ジブロモ−５，５−ジメチルヒダントイン、１，３−ジクロロ−５，５−ジメチルヒダントイン、１，３−ジクロロ−５，５−エチルメチルヒダントイン、及び、１，３−ジクロロ−５，５−ジエチルヒダントイン等のハロゲン化ヒダントイン等を挙げることができる。 The substance that generates free chlorine in water is a substance in which free residual chlorine is detected when the aqueous water to which the substance is added is measured by the residual chlorine measurement method described in JIS K0101 28. Hypohalites such as sodium hypochlorite, calcium hypochlorite and sodium hypobromite, halogenated isocyanuric acids such as sodium dichloroisocyanurate and trichloroisocyanuric acid, 1-bromo-3-chloro-5, 5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-ethylmethylhydantoin, and 1,3 -Halogenated hydantoins such as dichloro-5,5-diethylhydantoin.
また、水中で結合塩素を生成する物質とは、その物質を添加した水系水をＪＩＳ Ｋ０１０１ ２８に記載の残留塩素測定法により測定した際に、結合残留塩素が検出される物質のことであり、例えば、モノクロラミン、ジクロラミン、トリクロラミン、クロラミンＢ（ベンゼンスルホンクロラミドナトリウム塩）、及び、クロラミンＴ（Ｎ−クロロ−ｐ−トルエンスルホンアミドナトリウム塩）等のクロラミン類、及び、安定化次亜ハロゲン酸塩等を挙げることができる。 In addition, the substance that generates bound chlorine in water is a substance in which bound residual chlorine is detected when the aqueous water added with the substance is measured by the residual chlorine measuring method described in JIS K0101 28. For example, chloramines such as monochloramine, dichloramine, trichloramine, chloramine B (benzenesulfonchloramide sodium salt), and chloramine T (N-chloro-p-toluenesulfonamide sodium salt), and stabilized hypohalogen An acid salt etc. can be mentioned.
安定化次亜ハロゲン酸塩としては、特表２００３−５０３３２３号公報（特許文献１）や特表平１１−５０６１３９号公報（特許文献２）に開示されているように、次亜塩素酸塩とスルファミン酸塩とから得られる安定化次亜塩素酸塩、臭化ナトリウム、臭化カリウム、臭化リチウム等から１種以上選ばれる臭素イオン源、次亜塩素酸塩、及び、スルファミン酸塩から得られる安定化次亜臭素酸塩、または、これらの混合物を用いることができる。 As stabilized hypohalite, as disclosed in JP-T-2003-503323 (Patent Document 1) and JP-A-11-506139 (Patent Document 2), hypochlorite and Obtained from a bromine ion source selected from one or more of stabilized hypochlorite, sodium bromide, potassium bromide, lithium bromide and the like obtained from sulfamate, hypochlorite, and sulfamate Stabilized hypobromite or mixtures thereof can be used.
また、水中で結合塩素を生成する物質として、予めアンモニアが存在している水系に次亜ハロゲン酸塩を添加して、水系中でクロラミン類を生成させたり、予めスルファミン酸塩が存在している水系に次亜ハロゲン酸塩を添加して、水系中で安定化次亜ハロゲン酸塩を生成させても良く、この場合も本発明に含まれる。 In addition, as a substance that generates bound chlorine in water, hypohalite is added to an aqueous system in which ammonia is present in advance to generate chloramines in the aqueous system, or sulfamate is present in advance. Hypohalite may be added to the aqueous system to form a stabilized hypohalite in the aqueous system, and this case is also included in the present invention.
ここで、次亜ハロゲン酸塩などの水中で遊離塩素を生成する物質の場合、冷却水中の有機物などと反応して速やかに分解してしまうため、有効濃度を一定レベルに維持するのが難しく、その結果、濃度低下のために充分な微生物抑制効果が得られなかったり、あるいは、過剰添加により重要な機器に腐食が生じたりするおそれがある。一方、水中で結合塩素を生成する物質、特に、次亜ハロゲン酸塩とスルファミン酸塩とを反応させて得られる安定化次亜ハロゲン酸塩は、冷却水中での分解速度が遅く、その濃度変化が少ないので、有効濃度の維持が容易であり、結果として安定した効果が得られるので好ましい。 Here, in the case of substances that generate free chlorine in water such as hypohalite, it reacts with organic matter in cooling water and decomposes quickly, so it is difficult to maintain an effective concentration at a certain level, As a result, there is a risk that sufficient microbial control effect cannot be obtained due to the decrease in concentration, or that important equipment is corroded due to excessive addition. On the other hand, substances that produce bound chlorine in water, especially stabilized hypohalite obtained by reacting hypohalite and sulfamate, have a slow decomposition rate in cooling water, and its concentration changes. Therefore, the effective concentration can be easily maintained, and as a result, a stable effect can be obtained, which is preferable.
開放循環冷却水系の冷却水に、これらハロゲン系酸化物を添加するハロゲン系酸化物による処理は、レジオネラ属菌繁殖の温床となるバイオフィルムの付着、成長を効果的に抑制し、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖を有効に抑えるためには、２４時間に少なくとも１時間以上行う必要がある。充分な微生物抑制効果を得るためには、高濃度のハロゲン系酸化物による処理が好ましいが、高濃度のハロゲン系酸化物を冷却水に添加すると、冷却水系を構成する機器、配管等の金属材質が腐食するリスクが高まる。従って、比較的低濃度のハロゲン系酸化物で常時連続的に処理することが、レジオネラ属菌の殺菌と、耐性菌、耐性藻類、真菌類等の繁殖抑制を維持しながら、金属材質の腐食を低レベルに制御するためには好ましい。 Treatment with halogen-based oxides that add these halogen-based oxides to the cooling water of the open circulating cooling water system effectively suppresses the adhesion and growth of biofilms that serve as a hotbed for Legionella spp. In order to effectively suppress the propagation of drug-resistant algae, fungi, etc., it is necessary to carry out at least 1 hour in 24 hours. In order to obtain a sufficient microbial control effect, treatment with high-concentration halogen-based oxides is preferable. However, when high-concentration halogen-based oxides are added to cooling water, metal materials such as equipment and pipes constituting the cooling water system Increases the risk of corrosion. Therefore, continuous treatment with a relatively low concentration of halogen-based oxides prevents corrosion of metal materials while maintaining sterilization of Legionella spp. And suppressing the growth of resistant bacteria, resistant algae, fungi, etc. It is preferable for controlling to a low level.
そこで、水中で遊離塩素を生成する物質で処理するときのハロゲン系酸化物の濃度は、２４時間に１時間、あるいはそれよりも長く、間欠的に処理を行う場合には冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上５ｍｇ／Ｌ以下の範囲に維持するように、また、常時連続的に処理を行う場合には冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上１ｍｇ／Ｌ以下の範囲に維持するように、添加量を調整する。なお、遊離残留塩素の測定は、ＪＩＳ Ｋ０１０１ ２８に準拠した方法で実施する。また、ＪＩＳ Ｋ０１０１ ２８に記載の方法と同様の測定結果が得られる方法であれば、遊離残留塩素濃度測定電極や、その他の測定機器を用いて測定しても構わない。 Therefore, the concentration of the halogen-based oxide when treated with a substance that generates free chlorine in water is 1 hour per 24 hours or longer, and in the case of intermittent treatment, the oxidizing power in the cooling water is increased. The free residual chlorine concentration is maintained within the range of 0.01 mg / L or more and 5 mg / L or less. In the case of continuous continuous treatment, the oxidizing power in the cooling water is set to 0.01 mg / L as the free residual chlorine concentration. The addition amount is adjusted so as to maintain the range of L to 1 mg / L. In addition, the measurement of free residual chlorine is implemented by the method based on JISK010128. Moreover, as long as the measurement result similar to the method described in JIS K0101 28 is obtained, the measurement may be performed using a free residual chlorine concentration measuring electrode or other measuring equipment.
水中で遊離塩素を生成する物質を用いてハロゲン系酸化物による処理を行う場合の、より好ましい処理方法は、冷却水中の酸化力を遊離残留塩素濃度として０．０１ｍｇ／Ｌ以上０．１ｍｇ／Ｌ以下の範囲に常時維持する方法であり、この方法によると、レジオネラ属菌繁殖の温床となるバイオフィルムの付着、成長を効果的に抑制し、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖を有効に抑えるとともに、冷却水系を構成する機器、配管等の腐食リスクを極めて低レベルに抑えることができる。 A more preferable treatment method in the case of performing treatment with a halogen-based oxide using a substance that generates free chlorine in water is 0.01 mg / L or more and 0.1 mg / L as the free residual chlorine concentration in the cooling water. This method is always maintained within the following range. According to this method, the adhesion and growth of the biofilm that is a hotbed for Legionella spp. Breeding is effectively suppressed, and drug-resistant bacteria and drug-resistant algae and fungi It is possible to effectively reduce the risk of corrosion of equipment, piping, etc. constituting the cooling water system.
一方、水中で結合塩素を生成する物質で処理するときのハロゲン系酸化物の濃度は、２４時間に１時間、あるいはそれよりも長く、間欠的に処理を行う場合には冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下の範囲に維持するように、また、常時連続的に処理を行う場合には冷却水中の酸化力を全残留塩素濃度として０．５ｍｇ／Ｌ以上１０ｍｇ／Ｌ以下の範囲に維持するように、添加量を調整する。なお、全残留塩素の測定は、ＪＩＳ Ｋ０１０１ ２８に準拠した方法で実施する。また、ＪＩＳ Ｋ０１０１ ２８に記載の方法と同様の測定結果が得られる方法であれば、全残留塩素濃度測定電極や、その他の測定機器を用いて測定しても構わない。 On the other hand, the concentration of the halogen-based oxide when treated with a substance that generates bound chlorine in water is 1 hour per 24 hours or longer, and in the case of intermittent treatment, the oxidizing power in the cooling water is reduced. In order to maintain the total residual chlorine concentration in the range of 0.5 mg / L to 100 mg / L, and in the case of continuous continuous treatment, the oxidizing power in the cooling water is set to 0.5 mg / L as the total residual chlorine concentration. The addition amount is adjusted so as to maintain the range of L or more and 10 mg / L or less. In addition, the measurement of total residual chlorine is implemented by the method based on JISK010128. Moreover, as long as the measurement result similar to the method described in JIS K0101 28 is obtained, the measurement may be performed using a total residual chlorine concentration measurement electrode or other measurement equipment.
水中で結合塩素を生成する物質を用いてハロゲン系酸化物による処理を行う場合の、より好ましい処理方法は、水中で結合塩素を生成する物質として次亜ハロゲン酸塩とスルファミン酸塩とを反応させて得られる安定化次亜ハロゲン酸塩を用いる方法であり、このとき、冷却水中の酸化力を全残留塩素濃度として１ｍｇ/Ｌ以上２ｍｇ／Ｌ以下の範囲に常時維持することがさらに好ましい。安定化次亜ハロゲン酸塩は、他のハロゲン系酸化物と比較して冷却水中で安定であり、冷却水中の酸化力を低濃度レベルに維持するのに適している。従って、この方法によると、レジオネラ属菌繁殖の温床となるバイオフィルムの付着、成長を効果的に抑制し、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖を有効に抑えるとともに、冷却水系を構成する機器、配管等の腐食リスクを極めて低レベルに抑えるという効果を、より確実に発揮させることができる。 A more preferable treatment method in the case of performing treatment with a halogen-based oxide using a substance that generates bonded chlorine in water is to react hypohalite and sulfamate as a substance that generates bonded chlorine in water. In this case, it is more preferable to always maintain the oxidizing power in the cooling water within the range of 1 mg / L or more and 2 mg / L or less as the total residual chlorine concentration. Stabilized hypohalite is more stable in cooling water than other halogen-based oxides, and is suitable for maintaining the oxidizing power in cooling water at a low concentration level. Therefore, according to this method, the adhesion and growth of the biofilm that becomes the hotbed of Legionella spp. Propagation is effectively suppressed, and the propagation of drug-resistant bacteria, drug-resistant algae, fungi, etc. is effectively suppressed, The effect of suppressing the corrosion risk of equipment, piping, etc. constituting the cooling water system to an extremely low level can be exhibited more reliably.
本発明において行う有機系殺菌剤による処理は、レジオネラ属菌の殺菌、抑制効果を長期間維持するためには、３０日間に１回以上行う必要がある。このとき、２日間よりも短い期間に１回の割合での有機系殺菌剤による処理、あるいは、継続した有機系殺菌剤による処理を行うことは、薬剤を多量に消費するにもかかわらず、その消費量の増加に見合った効果の増大は得られにくい。 In order to maintain the bactericidal and inhibitory effects of Legionella spp. For a long period of time, the treatment with an organic fungicide performed in the present invention needs to be performed at least once every 30 days. At this time, the treatment with the organic fungicide at a rate of once in a period shorter than 2 days, or the continuous treatment with the organic fungicide, does not consume a large amount of the drug. It is difficult to increase the effect commensurate with the increase in consumption.
本発明で有機系殺菌剤として使用する、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とは、具体的には下記化学式（１）で表される構成単位を有する化合物である。 The water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin used as an organic fungicide in the present invention specifically has a structural unit represented by the following chemical formula (1). A compound.
本発明におけるジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体の添加濃度は、冷却水系の保有水量に対する有効成分濃度として１ｍｇ／Ｌ以上２００ｍｇ／Ｌ以下であり、有機系殺菌剤による処理１回につき当該濃度に相当する量の薬剤を冷却水に一括投入する。このような処理を２日間ないし３０日間に１回行うことで、確実かつ効果的に長期間にわたってレジオネラ属菌数を不検出レベルに維持することができる。より好ましいジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体の添加濃度は５ｍｇ／Ｌ以上５０ｍｇ／Ｌ以下である。 The addition concentration of the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin in the present invention is 1 mg / L or more and 200 mg / L or less as the active ingredient concentration with respect to the amount of water retained in the cooling water system. An amount of chemical corresponding to the concentration is batch-fed into the cooling water per treatment with the bactericide. By performing such treatment once every 2 to 30 days, it is possible to reliably and effectively maintain the Legionella genus count at an undetectable level over a long period of time. The addition concentration of the water-soluble cationic polymer obtained by a more preferable reaction between dimethylamine and epichlorohydrin is 5 mg / L or more and 50 mg / L or less.
また、本発明でジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体と併用するイソチアゾリン系化合物としては、たとえば５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−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、及び、１，２−ベンゾイソチアゾリン−３−オンが挙げられ、これらから少なくとも１種を選択し、冷却水系の保有水量に対するイソチアゾリン系化合物の合計濃度が０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下となるように冷却水に添加する。より好ましいイソチアゾリン系化合物の添加濃度は０．５ｍｇ／Ｌ以上２０ｍｇ／Ｌ以下である。 Examples of the isothiazoline compound used in combination with the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin in the present invention include, for example, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 1,2-benzisothiazolin-3-one, and at least one of them is selected. The isothiazoline-based compound is added to the cooling water so that the total concentration of the isothiazoline-based compound with respect to the amount of retained water in the cooling water system is 0.1 mg / L to 100 mg / L. A more preferable addition concentration of the isothiazoline-based compound is 0.5 mg / L or more and 20 mg / L or less.
また、本発明でジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体と併用する２−ブロモ−２−ニトロプロパン−１，３−ジオールの添加濃度は、冷却水系の保有水量に対する添加濃度として０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下、より好ましくは１ｍｇ／Ｌ以上５０ｍｇ／Ｌ以下である。 In addition, the addition concentration of 2-bromo-2-nitropropane-1,3-diol used in combination with the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin in the present invention is maintained in the cooling water system. The concentration added to the amount of water is from 0.1 mg / L to 100 mg / L, more preferably from 1 mg / L to 50 mg / L.
さらに、本発明では、イソチアゾリン系化合物と２−ブロモ−２−ニトロプロパン−１，３−ジオールの両方をジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体と併用しても良く、この場合は、イソチアゾリン系化合物と２−ブロモ−２−ニトロプロパン−１，３−ジオールの合計濃度が０．１ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下となるように冷却水に添加する。 Further, in the present invention, both an isothiazoline compound and 2-bromo-2-nitropropane-1,3-diol are used in combination with a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin. In this case, it is added to the cooling water so that the total concentration of the isothiazoline-based compound and 2-bromo-2-nitropropane-1,3-diol is 0.1 mg / L or more and 100 mg / L or less.
有機系殺菌剤としてジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とイソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールとを併用する場合、冷却水への各薬剤の添加は、各薬剤が同時に冷却水中に残存する状態を作り出せる限りにおいて、同時に行っても、別々の日時に行っても構わない。但し、各薬剤を併用することによる微生物に対する相乗効果を最大限に発揮させるためには、ほぼ同時刻に添加することが好ましい。この際、各薬剤を別々に添加しても、各薬剤を混合し一液化した薬剤を添加しても同様の効果を得ることができる。 When a water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin and an isothiazoline compound and / or 2-bromo-2-nitropropane-1,3-diol are used in combination as an organic fungicide The addition of each drug to the cooling water may be performed at the same time or at different dates and times as long as it can create a state in which each drug remains in the cooling water at the same time. However, in order to maximize the synergistic effect on microorganisms by using each drug together, it is preferable to add them almost at the same time. In this case, the same effect can be obtained even if each drug is added separately or a drug obtained by mixing each drug into a single solution is added.
このように、本発明における有機系殺菌剤による処理を、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とイソチアゾリン系化合物および／または２−ブロモ−２−ニトロプロパン−１，３−ジオールとの併用処理とし、その頻度を２日間ないし３０日間に１回とすることで、長期間のレジオネラ属菌の殺菌、抑制効果を一層確実にし、塩素耐性菌の繁殖を抑えるとともに、有機系殺菌剤に耐性を持った細菌類、藻類、真菌類等の繁殖抑制効果も充分なものとなる。 Thus, the treatment with the organic fungicide in the present invention is carried out by subjecting the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin to the isothiazoline-based compound and / or 2-bromo-2-nitropropane- By using the combination treatment with 1,3-diol and once every 2 to 30 days, the long-term sterilization and suppression effect of Legionella is further ensured, and the growth of chlorine-resistant bacteria is suppressed. At the same time, the effect of suppressing the growth of bacteria, algae, fungi and the like having resistance to organic fungicides is also sufficient.
上記したハロゲン系酸化物による処理と、特定の有機系殺菌剤による処理を併用することで、レジオネラ属菌を確実に不検出レベルに殺菌し、その増殖を抑制することができ、その効果を長期間持続させることができる。しかも、薬剤耐性菌や薬剤耐性を持った藻類、真菌類、あるいは、メチロバクテリウム等の強い塩素耐性を示す細菌類等の繁殖も効果的に抑えることができるので、開放循環冷却水系の微生物制御方法として非常に有用である。 By combining the treatment with the halogen-based oxide described above and the treatment with a specific organic fungicide, it is possible to reliably sterilize Legionella spp. Can last for a period. In addition, the growth of drug-resistant bacteria, drug-resistant algae, fungi, or bacteria with strong chlorine resistance, such as methylobacterium, can be effectively suppressed. It is very useful as a control method.
本発明の開放循環冷却水系の処理方法は、さらにその特性を改良するなどの目的で、本発明の効果が損なわれない限り、例えばアクリル酸系、マレイン酸系、メタクリル酸系、スルホン酸系、イタコン酸系、または、イソブチレン系の各重合体やこれらの共重合体、燐酸系重合体、有機ホスホン酸、有機ホスフィン酸、あるいはこれらの水溶性塩などのスケール防止剤、例えばベンゾトリアゾール、トリルトリアゾール等のアゾール類、例えばエチレンジアミン、ジエチレントリアミン等のアミン系化合物、例えばニトリロ三酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸等のアミノカルボン酸系化合物、例えばグルコン酸、クエン酸、シュウ酸、ギ酸、酒石酸、フィチン酸、琥珀酸、乳酸等の有機カルボン酸など、各種の水処理剤を併用することができ、その場合も本発明に含まれる。 The treatment method of the open circulating cooling water system of the present invention is not limited to the effects of the present invention for the purpose of further improving the characteristics, for example, acrylic acid-based, maleic acid-based, methacrylic acid-based, sulfonic acid-based, Itaconic acid-based or isobutylene-based polymers and copolymers thereof, phosphoric acid-based polymers, organic phosphonic acids, organic phosphinic acids, or water-soluble salts thereof such as benzotriazole and tolyltriazole Such as ethylenediamine, diethylenetriamine, and other amine compounds, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylic acid compounds such as gluconic acid, citric acid, oxalic acid, formic acid, tartaric acid, and phytin. Various waters such as acids, succinic acid, organic carboxylic acids such as lactic acid It can be used in combination with physical agents, in which case is also included in the present invention.
特に、アゾール類等の防食剤を併用することにより、ハロゲン系酸化物の使用による銅管の腐食を効果的に抑制することができるので、好ましい。 In particular, it is preferable to use an anticorrosive agent such as azoles in combination, since corrosion of the copper tube due to the use of a halogen-based oxide can be effectively suppressed.
以下に、本発明の開放循環冷却水系の処理方法の実施例について具体的に説明するが、本発明はこれらによって限定されるものではない。 Examples of the processing method of the open circulation cooling water system of the present invention will be specifically described below, but the present invention is not limited to these.
＜実施例１ 冷却塔模擬試験装置による評価＞
１ヶ月間の無処理運転により、レジオネラ属菌を定着させた冷却塔模擬試験装置（屋外に設置：保有水量は６０Ｌでポンプにより循環しており、電熱ヒーターで循環水温を３５℃に調節、試験期間は７月から９月）８台を使用して条件１から条件８の処理条件で薬剤を添加し、８週間にわたりレジオネラ属菌数およびアメーバ数の推移を調査した。また、８週間後に冷却塔内の充填材を目視観察するとともに充填材への付着物を採取し、顕微鏡観察を行った。条件１から条件５（比較例）の結果を表１に、条件６から条件８（実施例）の結果を表２に示す。
<Evaluation by Example 1 Cooling Tower Simulation Test Device>
Cooling tower simulation test device with Legionella genus colonized by one month of no-treatment operation (installed outdoors: the amount of water held is circulated by a pump at 60L, and the circulating water temperature is adjusted to 35 ° C with an electric heater and tested. The period was from July to September), 8 drugs were added under the treatment conditions from Condition 1 to Condition 8, and changes in the number of Legionella and amoeba were investigated over 8 weeks. Further, after 8 weeks, the filler in the cooling tower was visually observed, and deposits on the filler were collected and observed with a microscope. The results of Condition 1 to Condition 5 (Comparative Example) are shown in Table 1, and the results of Conditions 6 to 8 (Example) are shown in Table 2.
［条件１（遊離残留塩素による単独処理）］
次亜塩素酸ナトリウムの１２重量％溶液を、冷却水中の酸化力が遊離残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を１日に１時間維持するように添加した。１週間に１回、採水当日の次亜塩素酸ナトリウム添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 1 (single treatment with free residual chlorine)]
A 12% by weight solution of sodium hypochlorite was added so that the oxidizing power in the cooling water maintained a free residual chlorine concentration in the range of 1 mg / L to 2 mg / L for 1 hour per day. The cooling water was sampled once a week before the addition of sodium hypochlorite on the day of sampling, and the number of Legionella and amoeba were measured.
［条件２（結合残留塩素による単独処理）］
次亜塩素酸ナトリウム７重量％とスルファミン酸ナトリウム２０重量％とを含有する安定化次亜塩素酸ナトリウム製剤を、冷却水中の酸化力が全残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を常時維持するように添加した。１週間に１回、冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 2 (single treatment with bound residual chlorine)]
A stabilized sodium hypochlorite preparation containing 7% by weight of sodium hypochlorite and 20% by weight of sodium sulfamate, wherein the oxidizing power in the cooling water is in the range of 1 mg / L or more and 2 mg / L or less as the total residual chlorine concentration Was added so as to always maintain. Cooling water was sampled once a week, and the number of Legionella bacteria and the number of amoeba were measured.
［条件３（ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体、イソチアゾリン系化合物、２−ブロモ−２−ニトロプロパン−１，３−ジオールの３種混合有機系殺菌剤による単独処理）］
有機系殺菌剤として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を１０重量％、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを１重量％、２−メチル−４−イソチアゾリン−３−オンを０．３重量％、２−ブロモ−２−ニトロプロパン−１，３−ジオールを５重量％、それぞれ含有する混合製剤を、１週間に１回、１８ｇずつ添加した。このときの添加濃度は、保有水量に対する有効成分濃度として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体が３０ｍｇ／Ｌ、イソチアゾリン系化合物の合計濃度が３．９ｍｇ/Ｌ、２−ブロモ−２−ニトロプロパン−１，３−ジオールが１５ｍｇ／Ｌである。毎週、上記混合製剤を添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 3 (a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, an isothiazoline-based compound, 2-bromo-2-nitropropane-1,3-diol mixed organic fungicide) Single processing)]
10% by weight of a water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin, 1% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one as an organic fungicide, A mixed preparation containing 0.3% by weight of 2-methyl-4-isothiazolin-3-one and 5% by weight of 2-bromo-2-nitropropane-1,3-diol, once a week, 18 g each was added. The added concentration at this time is 30 mg / L for the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, and the total concentration of the isothiazoline-based compound is 3.9 mg / L as the active ingredient concentration relative to the amount of retained water. L, 2-bromo-2-nitropropane-1,3-diol is 15 mg / L. Every week, before adding the drug on the day of adding the above mixed preparation, cooling water was collected, and the number of Legionella and amoeba were measured.
［条件４（遊離残留塩素による処理とイソチアゾリン系化合物による処理とを併用）］
次亜塩素酸ナトリウムの１２重量％溶液を、冷却水中の酸化力が遊離残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を１日に１時間維持するように添加するとともに、有機系殺菌剤として、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを１０重量％、２−メチル−４−イソチアゾリン−３−オンを３重量％、それぞれ含有するイソチアゾリン製剤を、１週間に１回、３ｇずつ添加した。このときの添加濃度は、保有水量に対するイソチアゾリン系化合物の合計濃度として、６．５ｍｇ／Ｌである。毎週、イソチアゾリン製剤を添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 4 (Combination of treatment with free residual chlorine and treatment with isothiazoline compound)]
A 12% by weight solution of sodium hypochlorite was added so that the oxidizing power in the cooling water maintained a free residual chlorine concentration in the range of 1 mg / L to 2 mg / L for 1 hour per day, and organic sterilization. As an agent, an isothiazoline preparation containing 10% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one and 3% by weight of 2-methyl-4-isothiazolin-3-one, respectively, was added once a week. 3g each time. The added concentration at this time is 6.5 mg / L as the total concentration of the isothiazoline-based compound with respect to the amount of retained water. Every week, before adding the drug on the day of adding the isothiazoline preparation, cooling water was collected, and the number of Legionella and amoeba were measured.
［条件５（結合残留塩素による処理とグルタルアルデヒドによる処理とを併用）］
次亜塩素酸ナトリウム７重量％とスルファミン酸ナトリウム２０重量％とを含有する安定化次亜塩素酸ナトリウム製剤を、冷却水中の酸化力が全残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を常時維持するように添加するとともに、有機系殺菌剤として、グルタルアルデヒドの２０重量％溶液を、１週間に１回、６ｇずつ添加した。このときの添加濃度は、保有水量に対する有効成分濃度として、２０ｍｇ／Ｌである。毎週、グルタルアルデヒドを添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 5 (Combined treatment with bound residual chlorine and treatment with glutaraldehyde)]
A stabilized sodium hypochlorite preparation containing 7% by weight of sodium hypochlorite and 20% by weight of sodium sulfamate, wherein the oxidizing power in the cooling water is in the range of 1 mg / L or more and 2 mg / L or less as the total residual chlorine concentration Was constantly added, and 6 g of a 20% by weight solution of glutaraldehyde was added once a week as an organic disinfectant. The addition concentration at this time is 20 mg / L as an active ingredient concentration with respect to the amount of retained water. Every week, before adding the drug on the day of adding glutaraldehyde, cooling water was collected, and the number of Legionella and amoeba were measured.
［条件６（遊離残留塩素による処理とジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体による処理とを併用）］
次亜塩素酸ナトリウムの１２重量％溶液を、冷却水中の酸化力が遊離残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を１日に１時間維持するように添加するとともに、有機系殺菌剤として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体の１０重量％溶液を、１週間に１回、１２ｇずつ添加した。このときの添加濃度は、保有水量に対する有効成分濃度として、２０ｍｇ／Ｌである。毎週、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 6 (Combination of treatment with free residual chlorine and treatment with water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin)]
A 12% by weight solution of sodium hypochlorite was added so that the oxidizing power in the cooling water maintained a free residual chlorine concentration in the range of 1 mg / L to 2 mg / L for 1 hour per day, and organic sterilization. As an agent, 12 g of a 10% by weight solution of a water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin was added once a week. The addition concentration at this time is 20 mg / L as an active ingredient concentration with respect to the amount of retained water. Every week, the cooling water was collected before adding the drug on the day of adding the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, and the number of Legionella and amoeba were measured.
［条件７（結合残留塩素による処理とジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とイソチアゾリン系化合物との混合製剤による処理とを併用）］
次亜塩素酸ナトリウム７重量％とスルファミン酸ナトリウム２０重量％とを含有する安定化次亜塩素酸ナトリウム製剤を、冷却水中の酸化力が全残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を常時維持するように添加するとともに、有機系殺菌剤として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を１０重量％、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを１重量％、２−メチル−４−イソチアゾリン−３−オンを０．３重量％、それぞれ含有する混合製剤を、１週間に１回、６ｇずつ添加した。このときの添加濃度は、保有水量に対する有効成分濃度として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体が１０ｍｇ/Ｌ、イソチアゾリン系化合物の合計濃度が１．３ｍｇ/Ｌである。毎週、上記混合製剤を添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 7 (Combined treatment with bound residual chlorine and treatment with a mixed preparation of water-soluble cationic polymer and isothiazoline compound obtained by reaction of dimethylamine and epichlorohydrin)]
A stabilized sodium hypochlorite preparation containing 7% by weight of sodium hypochlorite and 20% by weight of sodium sulfamate, wherein the oxidizing power in the cooling water is in the range of 1 mg / L or more and 2 mg / L or less as the total residual chlorine concentration 10% by weight of a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin as an organic fungicide, 5-chloro-2-methyl-4- 6 g of a mixed preparation containing 1% by weight of isothiazolin-3-one and 0.3% by weight of 2-methyl-4-isothiazolin-3-one was added once a week. The addition concentration at this time is 10 mg / L for the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, and the total concentration of the isothiazoline-based compound is 1.3 mg / L as the active ingredient concentration relative to the amount of retained water. L. Every week, before adding the drug on the day of adding the above mixed preparation, cooling water was collected, and the number of Legionella and amoeba were measured.
［条件８（遊離残留塩素による処理とジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体と２−ブロモ−２−ニトロプロパン−１，３−ジオールとの混合製剤による処理とを併用）］
次亜塩素酸ナトリウムの１２重量％溶液を、冷却水中の酸化力が遊離残留塩素濃度として１ｍｇ／Ｌ以上２ｍｇ／Ｌ以下の範囲を１日に１時間維持するように添加するとともに、有機系殺菌剤として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を１０重量％、２−ブロモ−２−ニトロプロパン−１，３−ジオールを５重量％、それぞれ含有する混合製剤を、１週間に１回、６ｇずつ添加した。このときの添加濃度は、保有水量に対する有効成分濃度として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体が１０ｍｇ/Ｌ、２−ブロモ−２−ニトロプロパン−１，３−ジオールが５ｍｇ/Ｌである。毎週、上記混合製剤を添加する日の薬剤添加前に冷却水を採水し、レジオネラ属菌数およびアメーバ数を測定した。
[Condition 8 (treatment with free residual chlorine and mixed preparation of water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin and 2-bromo-2-nitropropane-1,3-diol) Together with)]
A 12% by weight solution of sodium hypochlorite was added so that the oxidizing power in the cooling water maintained a free residual chlorine concentration in the range of 1 mg / L to 2 mg / L for 1 hour per day, and organic sterilization. A mixture containing 10% by weight of a water-soluble cationic polymer obtained by reaction of dimethylamine and epichlorohydrin and 5% by weight of 2-bromo-2-nitropropane-1,3-diol, respectively. The formulation was added 6g once a week. The addition concentration at this time is 10 mg / L of a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin as an active ingredient concentration with respect to the amount of retained water, 2-bromo-2-nitropropane-1, 3-diol is 5 mg / L. Every week, before adding the drug on the day of adding the above mixed preparation, cooling water was collected, and the number of Legionella and amoeba were measured.
表１より、遊離塩素や結合塩素による単独処理では、レジオネラ属菌やアメーバを殺滅する効果は殆ど得られず、塩素剤に強い細菌類や真菌類の繁殖を抑えることができないことが、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体、イソチアゾリン系化合物、２−ブロモ−２−ニトロプロパン−１，３−ジオールの３種混合有機系殺菌剤を用いても、有機系殺菌剤だけの処理では、レジオネラ属菌やアメーバを長期間不検出とすることができず、バイオフィルムの付着抑制効果も充分ではないことが判る。また、ハロゲン系酸化物とイソチアゾリン系化合物やグルタルアルデヒドを併用した場合にも、レジオネラ属菌やアメーバの抑制効果は長期間持続せず、各有機系殺菌剤に耐性を持った藻類や真菌類の繁殖を抑制できなかった。 From Table 1, it can be seen that singular treatment with free chlorine or combined chlorine has little effect on killing Legionella and amoeba, and it is difficult to suppress the growth of bacteria and fungi that are resistant to chlorinating agents. Even when using a water-soluble cationic polymer obtained by the reaction of an amine and epichlorohydrin, an isothiazoline-based compound, and a mixed organic fungicide of three kinds of 2-bromo-2-nitropropane-1,3-diol, It can be seen that treatment with only an organic disinfectant cannot make Legionella spp. Or amoeba undetectable for a long period of time, and the biofilm adhesion-suppressing effect is not sufficient. In addition, when a halogen-based oxide is used in combination with an isothiazoline-based compound or glutaraldehyde, the inhibitory effect of Legionella spp. Or amoebae does not last for a long period of time. The breeding could not be suppressed.
一方、表２より、本発明の開放循環冷却水系の処理方法であるハロゲン系酸化物とジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体との併用処理を行うことで、レジオネラ属菌やアメーバに対する殺菌、抑制効果を長期間持続することができ、特に、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体とともに、イソチアゾリン系化合物や２−ブロモ−２−ニトロプロパン−１，３−ジオールを添加することで、試験期間中、レシオネラ属菌、アメーバともに不検出レベルを維持することができた。しかも、この処理条件では、他の微生物の充填材への付着も全く認められなかった。 On the other hand, from Table 2, by using the combined treatment of a halogen-based oxide, a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, which is a treatment method of the open circulation cooling water system of the present invention. The sterilizing and inhibiting effects against Legionella spp. And amoeba can be maintained for a long period of time. Particularly, together with a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, isothiazoline compounds and 2-bromo By adding -2-nitropropane-1,3-diol, it was possible to maintain a non-detectable level for both the ratioionella and amoeba during the test period. Moreover, no adhesion of other microorganisms to the filler was observed under these treatment conditions.
＜実施例２ 実機冷却水系での評価＞
城茨県内にある空調用冷却水系（冷凍能力５００ＲＴ、保有水量２０ｍ3）で、次亜塩素酸ナトリウムの１２重量％溶液を連続的に注入し、冷却水中の遊離残留塩素濃度を常時０．３ｍｇ／Ｌ以上０．６ｍｇ／Ｌ以下の範囲に維持するとともに、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを１０重量％、２−メチル−４−イソチアゾリン−３−オンを３重量％、それぞれ含有するイソチアゾリン製剤を、２週間に１回、２ｋｇ（保有水量に対するイソチアゾリン系化合物の合計濃度で１３ｍｇ／Ｌ）ずつ添加する処理を２ヶ月間継続した。この間、冷却水中のレジオネラ属菌数に減少は認められず、１０2個／１００ｍＬオーダーを維持したままであった。そこで、遊離塩素による処理は継続したまま、上記イソチアゾリン製剤を添加する処理に替えて、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体を１０重量％、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを２重量％、２−メチル−４−イソチアゾリン−３−オンを０．６重量％、２−ブロモ−２−ニトロプロパン−１，３−ジオールを５重量％、それぞれ含有する混合製剤を、２週間に１回、４ｋｇずつ添加する処理に変更した。このときの添加濃度は、保有水量に対する有効成分濃度として、ジメチルアミンとエピクロロヒドリンとの反応によって得られる水溶性陽イオン重合体が２０ｍｇ/Ｌ、イソチアゾリン系化合物の合計濃度が５．２ｍｇ/Ｌ、２−ブロモ−２−ニトロプロパン−１，３−ジオールが１０ｍｇ／Ｌである。処理変更１週間後には、レジオネラ属菌は不検出（１０個／１００ｍＬ未満）となり、その後３ヶ月間、不検出の状態を継続した。また、この間、冷却塔充填材に付着物は認められず、清浄な状態が保たれた。
<Example 2 Evaluation in actual cooling water system>
A 12% by weight solution of sodium hypochlorite is continuously injected into the cooling water system for air conditioning (freezing capacity: 500RT, water volume: 20m 3 ) located in Shiroi Prefecture, and the free residual chlorine concentration in the cooling water is always 0.3mg. / L to 0.6 mg / L, and 10% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one and 3% of 2-methyl-4-isothiazolin-3-one %, Each of the isothiazoline preparations contained therein was added every 2 weeks at a rate of 2 kg (13 mg / L in terms of the total concentration of isothiazoline compounds relative to the amount of water retained) for 2 months. During this time, the reduction in Legionella number of bacteria in the cooling water is not observed, it was still maintaining a 10 2 / 100mL order. Therefore, while continuing the treatment with free chlorine, instead of the treatment adding the isothiazoline preparation, 10% by weight of a water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, 5-chloro- 2% by weight of 2-methyl-4-isothiazolin-3-one, 0.6% by weight of 2-methyl-4-isothiazolin-3-one, and 5 of 2-bromo-2-nitropropane-1,3-diol The mixed preparation containing 4% by weight was changed to a process of adding 4 kg once every two weeks. The added concentration at this time is 20 mg / L for the water-soluble cationic polymer obtained by the reaction of dimethylamine and epichlorohydrin, and the total concentration of the isothiazoline-based compound is 5.2 mg / as the active ingredient concentration relative to the amount of water retained. L, 2-bromo-2-nitropropane-1,3-diol is 10 mg / L. One week after the treatment change, Legionella was not detected (less than 10 cells / 100 mL), and the non-detected state was continued for 3 months thereafter. During this time, no deposits were observed on the cooling tower packing material, and the clean state was maintained.
以上の結果から、本発明の開放循環冷却水系の処理方法によれば、レジオネラ属菌を確実に不検出レベルに殺菌し、その増殖を抑制することができ、しかもその効果を長期間持続させることができること、加えて、薬剤耐性菌や薬剤耐性を持った藻類、真菌類、あるいは、メチロバクテリウム等の強い塩素耐性を示す細菌類等の繁殖も効果的に抑えることができることが理解される。 From the above results, according to the processing method of the open circulation cooling water system of the present invention, it is possible to surely sterilize Legionella spp. To a non-detectable level, suppress its growth, and maintain its effect for a long period of time. In addition, it is understood that the propagation of drug-resistant bacteria, drug-resistant algae, fungi, or bacteria showing strong chlorine resistance such as methylobacterium can be effectively suppressed. .
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