JP2013158669A - Treatment method for open-circulating cooling water system - Google Patents
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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 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。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。 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. 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.
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。 In addition, organic fungicides also have the disadvantage that resistant bacteria and resistant algae are easier to propagate than halogen-based oxides.
そこで、有機系殺菌剤として下記一般式（１）で示される化合物が、特開２００５−３２５０３６号公報（特許文献４）、特開２００６−２１１０５号公報（特許文献５）、特開２００９−２１５２７１号公報（特許文献６）等により微生物防除剤として提案されてきた。本薬剤は、細菌類の殺菌効果に加えてアメーバの殺滅効果やバイオフィルムの剥離効果を有し、レジオネラ属菌の殺菌、増殖抑制にも有効な薬剤だが、単独で長期間使用を続けると耐性菌が発生することがあり、それが各種微生物障害の原因となるため、さらなる改良が望まれている。 Therefore, compounds represented by the following general formula (1) as organic fungicides are disclosed in JP-A-2005-325036 (Patent Document 4), JP-A-2006-21105 (Patent Document 5), and JP-A-2009-215271. Has been proposed as a microorganism control agent. In addition to the bactericidal effect of bacteria, this drug has an amoeba killing effect and biofilm peeling effect, and is also effective in killing Legionella spp. Since resistant bacteria may be generated, which causes various microbial disorders, further improvement is desired.
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、該有機系殺菌剤による処理が、下記一般式（１）で示される化合物を、前記冷却水に添加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. The treatment with the organic disinfectant is represented by the following general formula (1). A method for treating an open circulating cooling water system, wherein a compound is added to the cooling water.
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５ｍｇ／Ｌ以下の範囲に維持する処理であることを特徴とする。 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 1, wherein the treatment with the halogen-based oxide generates free chlorine in water. The substance to be added is added to the cooling water, and the oxidizing power in the cooling water is maintained in the range of 0.01 mg / L or more and 5 mg / L or less as the free residual chlorine concentration.
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２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 of the present invention is the open circulation cooling water system treatment method according to claim 2, 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４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１００ｍｇ／Ｌ以下の範囲に維持する処理であることを特徴とする。 The open circulating cooling water system treatment method according to the present invention is the open circulating cooling water system treatment method according to claim 1, wherein the treatment with the halogen-based oxide generates bound chlorine in water. The substance to be added is added to the cooling water, and the oxidizing power in the cooling water is maintained in the range of 0.5 mg / L to 100 mg / L as the total residual chlorine concentration.
本発明の開放循環冷却水系の処理方法は、請求項５に記載の通り、請求項４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 circulating cooling water system treatment method of the present invention is the open circulating cooling water system treatment method according to claim 4, 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は、請求項６に記載の通り、請求項１ないし請求項５のいずれか１項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、前記一般式（１）で示される化合物を、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０．５ｍｇ／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 circulation cooling water system of the present invention is the processing method of the open circulation cooling water system according to any one of claims 1 to 5 according to claim 6, wherein the organic fungicide is used. The treatment is a treatment in which the compound represented by the general formula (1) is added so that the addition concentration with respect to the amount of retained water in the cooling water system is 0.5 mg / L or more and 100 mg / L or less as the active ingredient concentration, In addition, 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７に記載の通り、請求項１ないし請求項６のいずれか１項に記載の開放循環冷却水系の処理方法において、前記一般式（１）で示される化合物が、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドであることを特徴とする。 The processing method of the open circulation cooling water system of this invention is the processing method of the open circulation cooling water system of any one of Claim 1 thru | or 6 as described in Claim 7, In the processing method of the open circulation cooling water system, the said General formula (1) A compound represented by the formula is 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide.
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前記一般式（１）で示される化合物による処理とを併用することで、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, by using the treatment with the halogen-based oxide and the treatment with the compound represented by the general formula (1) in combination, the Legionella spp. An open circulating cooling water system that suppresses growth and maintains the number of Legionella bacteria in cooling water at a non-detectable level for a long period of time, and that is resistant to the growth of drug-resistant bacteria, drug-resistant algae, and fungi It can be.
このとき、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、また、薬剤耐性菌や薬剤耐性を持った藻類、真菌類等の繁殖を有効に抑えることができる。 At this time, by attaching the oxidizing power in the cooling water as a free residual chlorine concentration within a range of 0.01 mg / L or more and 5 mg / L or more for 1 hour or more in 24 hours, the biofilm that serves as a hotbed for Legionella spp. The growth can be effectively suppressed, and the propagation of drug-resistant bacteria, drug-resistant algae, fungi and the like can 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効果的に防ぎながら、レジオネラ属菌を効果的に不検出レベルに抑制することが可能となり、また、耐性菌、耐性藻類、真菌類等の繁殖も充分に抑えることができる。 Furthermore, by maintaining the oxidizing power in 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 of mild steel such as equipment used in water systems and metals such as copper is effective. Therefore, Legionella spp. Can be effectively suppressed to a non-detection level, and 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、より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、真菌類等の繁殖を、より有効に抑えることができる。 In addition, 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 0 as the total residual chlorine concentration. By maintaining in the range of 0.5 mg / L or more and 100 mg / L or less for 1 hour or more in 24 hours, 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 more effectively suppressed.
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、レジオネラ属菌を、より確実に不検出レベルに抑制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, Legionella spp. Can be more reliably suppressed to a non-detection level, and the propagation of resistant bacteria, resistant algae, fungi and the like can be suppressed more reliably.
本発明では、有機系殺菌剤による処理として、前記一般式（１）で示される化合物を、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０．５ｍｇ／Ｌ以上１００ｍｇ／Ｌ以下の範囲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、抑制効果を長期間得ることができ、さらに、メチロバクテリウム等の塩素耐性菌の繁殖を効果的に抑えることが可能となる。 In the present invention, as the treatment with the organic fungicide, the concentration of the compound represented by the general formula (1) with respect to the amount of water retained in the cooling water system is 0.5 mg / L or more and 100 mg / L or less as the active ingredient concentration. By performing the treatment to be in a range once every 2 to 30 days, with a small amount of organic fungicide added, it is possible to obtain a long-term effect of sterilization and suppression of Legionella spp., Propagation of chlorine-resistant bacteria such as methylobacterium can be effectively suppressed.
特に、前記一般式（１）で示される化合物として、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドを使用することで、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、開放循環冷却水系の各種微生物障害を防止することが可能となる。 In particular, by using 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide as the compound represented by the general formula (1), sterilization and inhibition of Legionella spp. The effect can be obtained reliably for a long period of time, and various microbial failures in the open circulation cooling water system can be prevented.
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、前記一般式（１）で示される化合物による処理を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 treatment method of the open circulation cooling water system of the present invention is that the treatment with the halogen-based oxide is performed for 24 hours or more on the cooling water of the open circulation cooling water system, and the general formula (1 ) Is performed at least once every 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確実に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 with certainty.
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、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、前記一般式（１）で示される有機系殺菌剤による処理は、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 the present invention, in order to maintain the bactericidal and inhibitory effects of Legionella spp. For a long period of time, the treatment with the organic fungicide represented by the general formula (1) 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.
前記一般式（１）で示される有機系殺菌剤の添加濃度は、冷却水系の保有水量に対する有効成分濃度として０．５ｍｇ／Ｌ以上１００ｍｇ／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回行うことにより、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。より好ましい有機系殺菌剤の添加濃度は２．５ｍｇ／Ｌ以上２５ｍｇ／Ｌ以下である。 The addition concentration of the organic fungicide represented by the general formula (1) is 0.5 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, and per treatment with the organic fungicide. An amount of the drug corresponding to the concentration is put into the cooling water all at once. By performing such treatment once every 2 to 30 days, the number of Legionella spp. Can be maintained at a non-detection level reliably and effectively over a long period of time. A more preferable addition concentration of the organic fungicide is 2.5 mg / L or more and 25 mg / L or less.
本発明の一般式（１）で示される化合物は、例えば、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンの塩、１，４−ビス［３，３’−（１−オクチルピリジニウム）メチルオキシ］ブタンの塩、１，４−ビス［３，３’−（１−ドデシルピリジニウム）メチルオキシ］ブタンの塩、１，４−ビス［４，４’−（１−デシルピリジニウム）メチルオキシ］ブタンの塩、１，４−ビス［４，４’−（１−オクチルピリジニウム）メチルオキシ］ブタンの塩、１，４−ビス［４，４’−（１−ドデシルピリジニウム）メチルオキシ］ブタンの塩、等が挙げられ、これらから１種以上選択して用いることができる。特に１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド、１，４−ビス［３，３’−（１−オクチルピリジニウム）メチルオキシ］ブタンジブロマイド、１，４−ビス［３，３’−（１−ドデシルピリジニウム）メチルオキシ］ブタンジブロマイドが好ましく、さらに好ましくは１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドが選択される。 The compound represented by the general formula (1) of the present invention is, for example, a salt of 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butane, 1,4-bis [3,3 ′ -(1-octylpyridinium) methyloxy] butane salt, 1,4-bis [3,3 '-(1-dodecylpyridinium) methyloxy] butane salt, 1,4-bis [4,4'-( 1-decylpyridinium) methyloxy] butane salt, 1,4-bis [4,4 ′-(1-octylpyridinium) methyloxy] butane salt, 1,4-bis [4,4 ′-(1- And a salt of dodecylpyridinium) methyloxy] butane, and the like, and one or more thereof can be selected and used. In particular, 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide, 1,4-bis [3,3 ′-(1-octylpyridinium) methyloxy] butanedibromide, , 4-bis [3,3 ′-(1-dodecylpyridinium) methyloxy] butanedibromide, more preferably 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedi. Bromide is selected.
上記のハロゲン系酸化物による処理と、前記一般式（１）で示される有機系殺菌剤による処理とを併用することで、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 above halogen-based oxide and the treatment with the organic fungicide represented by the general formula (1), it is possible to reliably sterilize Legionella spp. To a non-detectable level and suppress its growth. And the effect can be maintained for a long time. 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、その特性をさらに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 circulation cooling water system of the present invention is, for example, acrylic acid-based, maleic acid-based, methacrylic acid-based, sulfonic acid-based, as long as the effects of the present invention are not impaired for the purpose of further improving the characteristics. 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, 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）７台を使用して条件１から条件７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、条件７（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. During the period from July to September, the drug was added under the treatment conditions from Condition 1 to Condition 7 using 7 units, 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. Table 1 shows the results of Condition 1 to Condition 5 (Comparative Example), and Table 2 shows the results of Conditions 6 and 7 (Examples).
［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（１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドによる単独処理）］
有機系殺菌剤として、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドの５重量％溶液を、１週間に１回、６ｇ（保有水量に対する有効成分濃度で５ｍｇ／Ｌ）ずつ添加した。毎週、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイ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 3 (single treatment with 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide)]
As an organic disinfectant, 6 g (active ingredient concentration with respect to the amount of retained water) once a week of a 5 wt% solution of 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide At 5 mg / L). Each week, 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide is added to the cooling water before the drug is added, and the number of Legionella and amoeba are measured. did.
［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（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６．５ｍｇ／Ｌ）ずつ添加した。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. 3 g (6.5 mg / L of the total concentration of isothiazoline compounds relative to the amount of retained water) was added. Every week, before adding the drug on the day of adding the isothiazoline preparation, cooling water was collected, and the number of Legionella and the number of 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（保有水量に対する有効成分濃度で２０ｍｇ／Ｌ）ずつ添加した。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 In addition, 6 g (20 mg / L of active ingredient concentration with respect to the amount of retained water) of a 20 wt% solution of glutaraldehyde was added once a week as an organic disinfectant. 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１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド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、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドの５重量％溶液を、１週間に１回、６ｇ（保有水量に対する有効成分濃度で５ｍｇ／Ｌ）ずつ添加した。毎週、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイ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 6 (Combined treatment with free residual chlorine and treatment with 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide)]
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, a 5 wt% solution of 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide was added once a week to 6 g (active ingredient concentration with respect to the amount of retained water 5 mg / L) was added in increments. Each week, 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide is added to the cooling water before the drug is added, and the number of Legionella and amoeba are measured. did.
［条件７（結合残留塩素による処理と１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイ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、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドの５重量％溶液を、１週間に１回、６ｇ（保有水量に対する有効成分濃度で５ｍｇ／Ｌ）ずつ添加した。毎週、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイ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 7 (Combined treatment with bound residual chlorine and treatment with 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide)]
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 Is constantly added, and a 5% by weight solution of 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide as an organic disinfectant is added 1 per week. Each time, 6 g (5 mg / L of active ingredient concentration with respect to the amount of retained water) was added. Each week, 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide is added to the cooling water before the drug is added, and the number of Legionella and amoeba are measured. did.
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、１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドによる単独処理では、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 said that the single treatment with free chlorine or combined chlorine hardly obtains the effect of killing Legionella sp. Or amoeba, and cannot suppress the growth of bacteria and fungi that are resistant to chlorinating agents. , 4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide cannot prevent Legionella spp. And amoeba for a long period of time, and suppresses biofilm adhesion. Is not enough. 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 time, and the algae and fungi that are resistant to each organic fungicide 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遊離塩素や結合塩素と１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドの併用処理では、レジオネラ属菌やアメーバを長期間不検出状態に保つことができ、しかも、試験期間中、他の微生物の繁殖も認められなかった。 On the other hand, from Table 2, the combined treatment of free chlorine and combined chlorine and 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide, which is the treatment method of the open circulating cooling water system of the present invention. Therefore, Legionella spp. And amoeba could be kept undetected for a long period of time, and the growth of other microorganisms was not observed during the test period.
＜実施例２ 実機冷却水系での評価＞
千葉県内にある空調用冷却水系（冷凍能力３００ＲＴ、保有水量１０ｍ3）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、１ｋｇ（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１，４−ビス［３，３’−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイドの５重量％溶液を、２週間に１回、２ｋｇ（保有水量に対する有効成分濃度で１０ｍｇ／Ｌ）ずつ添加する処理に変更した。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、冷却塔充填材には付着物は認められず、清浄な状態が常に保たれた。
<Example 2 Evaluation in actual cooling water system>
In a cooling water system for air conditioning in Chiba Prefecture (refrigeration capacity 300RT, retained water volume 10m 3 ), a 12% by weight solution of sodium hypochlorite is continuously injected, and the free residual chlorine concentration in the cooling water is always 0.3mg / L and maintained in the range of 0.6 mg / L or less, 10% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one, 3% by weight of 2-methyl-4-isothiazolin-3-one Each of the isothiazoline preparations contained therein was added once a week for 2 months at a rate of 1 kg (13 mg / L in terms of the total concentration of isothiazoline compounds relative to the amount of water retained). 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 of adding the isothiazoline preparation, a 5% by weight solution of 1,4-bis [3,3 ′-(1-decylpyridinium) methyloxy] butanedibromide was used. It changed to the process which adds 2 kg (10 mg / L in the active ingredient density | concentration with respect to the amount of water holding | maintenance) once every two weeks. 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 adhering matter was observed on the cooling tower packing material, and a clean state was always 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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