JP6330399B2 - Nitrifying bacteria inhibitor and method for inhibiting nitrifying bacteria - Google Patents

Nitrifying bacteria inhibitor and method for inhibiting nitrifying bacteria Download PDF

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JP6330399B2
JP6330399B2 JP2014055083A JP2014055083A JP6330399B2 JP 6330399 B2 JP6330399 B2 JP 6330399B2 JP 2014055083 A JP2014055083 A JP 2014055083A JP 2014055083 A JP2014055083 A JP 2014055083A JP 6330399 B2 JP6330399 B2 JP 6330399B2
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nitrifying bacteria
thiabendazole
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靖 村野
靖 村野
直宏 永井
直宏 永井
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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Description

本発明は硝化細菌抑制剤及び硝化細菌抑制方法に係り、詳しくは、密閉冷却水系又は蓄熱水系等の、金属防食剤として亜硝酸塩が添加されている水系において、亜硝酸塩が水中に存在する硝化細菌により酸化されて防食効果が低下することを抑制する硝化細菌抑制剤と、この硝化細菌抑制剤を用いた硝化細菌抑制方法に関する。
本発明の硝化細菌抑制剤は、食品添加物として認可されているチアベンダゾールを有効成分とするため、安全性が高い。
The present invention relates to a nitrifying bacteria inhibitor and a method for inhibiting nitrifying bacteria, and more specifically, a nitrifying bacterium in which nitrite is present in water in an aqueous system to which nitrite is added as a metal anticorrosive, such as a sealed cooling water system or a heat storage water system. The present invention relates to a nitrifying bacteria inhibitor that suppresses the deterioration of the anticorrosive effect due to oxidation and a method for inhibiting nitrifying bacteria using this nitrifying bacteria inhibitor.
Since the nitrifying bacteria inhibitor of the present invention contains thiabendazole, which is approved as a food additive, as an active ingredient, it has high safety.

密閉冷却水系や蓄熱水系においては、金属防食剤として亜硝酸ナトリウム等の亜硝酸塩が添加されているが、亜硝酸塩は、水中の硝化細菌によって酸化されて硝酸となり、防食効果が低下するという問題がある。   In sealed cooling water systems and heat storage water systems, nitrites such as sodium nitrite are added as metal anticorrosives. However, nitrites are oxidized by nitric acid bacteria in water to become nitric acid, which reduces the anticorrosion effect. is there.

硝化細菌の繁殖を抑制する方法として、従来、ヒドラジン、イソチアゾリン化合物、アミン類などが用いられてきた。例えば、特許文献1には、ニトロソヒドロキシルアミン又はその塩を用いることが記載されている。しかしながら、これらはいずれも食品添加物として認可されていない物質であるため、人体や環境への影響が懸念される。   Conventionally, hydrazine, isothiazoline compounds, amines, and the like have been used as methods for suppressing the growth of nitrifying bacteria. For example, Patent Document 1 describes using nitrosohydroxylamine or a salt thereof. However, since these are substances that are not approved as food additives, there are concerns about the effects on the human body and the environment.

一方、食品添加物として認可されている薬剤としては、次亜塩素酸や過酸化水素などの無機酸化剤系の殺菌剤があるが、これらは銅や軟鋼などの金属材質に対する腐食性が高く適用が困難であった。   On the other hand, chemicals approved as food additives include inorganic oxidizers such as hypochlorous acid and hydrogen peroxide, which are highly corrosive to metal materials such as copper and mild steel. It was difficult.

なお、本発明において、硝化細菌抑制剤の有効成分として用いるチアベンダゾールは、銅用防食剤として知られているが(特許文献2)、硝化細菌抑制効果を示すことは知られていない。   In the present invention, thiabendazole used as an active ingredient of a nitrifying bacteria inhibitor is known as an anticorrosive for copper (Patent Document 2), but it is not known to exhibit a nitrifying bacteria inhibitory effect.

特公昭62−17561号公報Japanese Patent Publication No.62-17561 特公昭59−25034号公報Japanese Patent Publication No.59-25034

上記の通り、従来は、安全性が高く、かつ金属材質に対して腐食性が低い硝化細菌抑制剤が提供されていなかった。   As described above, conventionally, there has not been provided a nitrifying bacteria inhibitor that has high safety and low corrosiveness to metal materials.

本発明は、上記従来の問題点を解決し、食品添加物として認可されており、安全性が高く、かつ金属材質に対して腐食性が低い物質を有効成分とする硝化細菌抑制剤と、この硝化細菌抑制剤を用いた硝化細菌抑制方法を提供することを課題とする。   The present invention solves the above-mentioned conventional problems, is approved as a food additive, has a high safety and a nitrifying bacteria inhibitor comprising a substance that is highly corrosive to metal materials as an active ingredient, and this It is an object of the present invention to provide a method for inhibiting nitrifying bacteria using a nitrifying bacteria inhibitor.

本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、食品添加物として認可されているチアベンダゾールが硝化細菌の活動を抑制し、亜硝酸塩の酸化を有効に防止することができることができることを見出した。しかも、チアベンダゾールであれば、硝化細菌抑制作用と共に、銅材質の防食効果をも得ることができる。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that thiabendazole, which is approved as a food additive, can suppress the activity of nitrifying bacteria and effectively prevent nitrite oxidation. I found out that I can do it. Moreover, if it is thiabendazole, the anticorrosive effect of a copper material can be obtained with the nitrifying bacteria inhibitory action.

本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。   The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] チアベンダゾールを有効成分として含有し、増粘剤によりスラリー状となっている硝化細菌抑制剤。 [1] A nitrifying bacteria inhibitor containing thiabendazole as an active ingredient and in a slurry form with a thickener .

[2] 金属防食剤として亜硝酸塩が添加されている水系に使用されることを特徴とする[1]に記載の硝化細菌抑制剤。 [2] The nitrifying bacteria inhibitor according to [1], which is used in an aqueous system to which nitrite is added as a metal anticorrosive.

[3] 前記水系が、密閉冷却水系又は蓄熱水系であることを特徴とする[2]に記載の硝化細菌抑制剤。 [3] The nitrifying bacteria inhibitor according to [2], wherein the water system is a sealed cooling water system or a heat storage water system.

[4] 前記硝化細菌抑制剤が、食品添加物素材からなる前記増粘剤によりスラリー状となっていることを特徴とする[1]ないし[3]のいずれかに記載の硝化細菌抑制剤。 [4] The nitrifying bacteria inhibitors, nitrification bacteria inhibitor according to any one of [1], characterized in that has a slurry by the thickener consisting of food additives material [3].

[5] 前記増粘剤が、ポリアクリル酸ナトリウムであることを特徴とする[4]に記載の硝化細菌抑制剤。 [5] The nitrifying bacteria inhibitor as described in [4], wherein the thickener is sodium polyacrylate.

[6] [1]ないし[5]のいずれかに記載の硝化細菌抑制剤を、対象水系にチアベンダゾール濃度が3mg/L以上となるように添加することを特徴とする硝化細菌抑制方法。 [6] A method for inhibiting nitrifying bacteria, comprising adding the nitrifying bacteria inhibitor according to any one of [1] to [5] to a target aqueous system so that the thiabendazole concentration is 3 mg / L or more.

本発明によれば、密閉冷却水系、蓄熱水系等の水系において金属防食剤として添加されている亜硝酸塩が、水中の硝化細菌により硝酸に酸化され防食効果が低下することを有効に防止することができる。
しかも、チアベンダゾールは銅材質に対する防食効果も発揮するため、本発明の硝化細菌抑制剤により、銅材質の腐食抑制効果をも得ることができる。
According to the present invention, it is possible to effectively prevent nitrite added as a metal anticorrosive agent in an aqueous system such as a sealed cooling water system or a heat storage water system from being oxidized to nitric acid by nitrifying bacteria in water and reducing the anticorrosion effect. it can.
And since thiabendazole also exhibits the anti-corrosion effect with respect to a copper material, the corrosion inhibitory effect of a copper material can also be acquired with the nitrifying bacteria inhibitor of this invention.

本発明で有効成分とするチアベンダゾールは、食品添加物として認可されている物質であり、人体や環境への問題がなく、従って、本発明の硝化細菌抑制剤は、特に安全性を重視する食品工場、飲料、医薬関係などの工場等における密閉冷却水系や蓄熱水系においても好適に使用することができる。   Thiabendazole as an active ingredient in the present invention is a substance that has been approved as a food additive and has no problems with the human body and the environment. Therefore, the nitrifying bacteria inhibitor of the present invention is a food factory that places particular emphasis on safety. It can also be suitably used in a sealed cooling water system or a heat storage water system in factories such as beverages and medicines.

実施例1〜4及び比較例1,2の結果を示すグラフである。It is a graph which shows the result of Examples 1-4 and Comparative Examples 1 and 2. FIG.

以下に本発明の実施の形態を詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail.

本発明の硝化細菌抑制剤は、チアベンダゾールを有効成分として含有するものである。
チアベンダゾールは、下記構造式で表される、食品添加物として認可された物質である。
前述のように、チアベンダゾールは銅用防食剤として知られており、金属に対する腐食性も低いものであるが、硝化細菌を抑制する作用は知られておらず、本発明者らにより初めて見出されたものである。
The nitrifying bacteria inhibitor of the present invention contains thiabendazole as an active ingredient.
Thiabendazole is a substance approved as a food additive represented by the following structural formula.
As mentioned above, thiabendazole is known as an anticorrosive for copper and has a low corrosiveness to metals, but its action to suppress nitrifying bacteria is not known and was first discovered by the present inventors. It is a thing.

Figure 0006330399
Figure 0006330399

チアベンダゾールは、粉末または水溶液の状態で対象水系に添加することができるが、チアベンダゾールは水に溶けにくいため、増粘剤を用いてスラリーとして添加することが好ましい。   Thiabendazole can be added to the target aqueous system in the form of a powder or an aqueous solution. However, thiabendazole is difficult to dissolve in water, and thus it is preferably added as a slurry using a thickener.

この場合、チアベンダゾールをスラリーとするために添加する増粘剤についても、食品添加物素材を使用することが好ましい。このような増粘剤としては、カルボキシメチルセルロースナトリウム、アラビアガム、キサンタンガム、グアーガム、ローカストビーンガム、ポリアクリル酸ナトリウムなどが使用できるが、チアベンダゾールをスラリーにし易く、また多糖類ではないことから生分解性が低いポリアクリル酸ナトリウムを使用することが好ましい。なお、ポリアクリル酸ナトリウムの分子量としては200万〜600万程度が好ましい。   In this case, it is preferable to use a food additive material for the thickener added to make thiabendazole into a slurry. As such thickeners, sodium carboxymethylcellulose, gum arabic, xanthan gum, guar gum, locust bean gum, sodium polyacrylate, etc. can be used, but it is easy to make thiabendazole into a slurry and it is not a polysaccharide, so it is biodegradable. It is preferred to use low polysodium acrylate. The molecular weight of sodium polyacrylate is preferably about 2 million to 6 million.

チアベンダゾールをスラリー化するためのポリアクリル酸ナトリウム等の増粘剤の配合割合は、チアベンダゾールを0.01〜2.0重量%、好ましくは0.1〜1.0重量%程度含有するスラリー中に、0.05〜0.2重量%、特にチアベンダゾールに対して0.1〜1重量倍程度とするのが、スリラーの安定性の面から好ましい。スラリーの増粘剤濃度が上記下限未満では、増粘剤によるスラリーの安定化効果が不十分であり、チアベンダゾールが分離し易くなり、上記上限を超えて配合すると粘性が高くなり流動性がなくなるため使い勝手が悪くなる。
なお、チアベンダゾールスラリー中のチアベンダゾール濃度については、添加効果とスラリー安定性、取り扱い性等の面で、上記の濃度範囲とすることが好ましい。
The blending ratio of a thickener such as sodium polyacrylate for slurrying thiabendazole is 0.01 to 2.0% by weight of thiabendazole, preferably 0.1 to 1.0% by weight. 0.05 to 0.2% by weight, particularly about 0.1 to 1 times by weight with respect to thiabendazole is preferable from the viewpoint of the stability of the thriller. If the concentration of the thickener in the slurry is less than the above lower limit, the effect of stabilizing the slurry by the thickener is insufficient, and thiabendazole is likely to be separated. Usability is poor.
The thiabendazole concentration in the thiabendazole slurry is preferably in the above-mentioned concentration range in terms of the effect of addition, slurry stability, handleability, and the like.

チアベンダゾールスラリーを調製するには、チアベンダゾールと増粘剤とを所定の割合で水に添加して、ミキサーやホモジナイザー等を用いて混合、分散すればよい。   In order to prepare a thiabendazole slurry, thiabendazole and a thickener may be added to water at a predetermined ratio and mixed and dispersed using a mixer, a homogenizer, or the like.

本発明の硝化細菌抑制剤は、金属防食剤として亜硝酸ナトリウム、亜硝酸カリウム、亜硝酸アンモニウム等の亜硝酸塩が添加されている水系、特に密閉冷却水系又は蓄熱水系における硝化細菌による亜硝酸塩の酸化防止のために好ましく用いられるが、その際の硝化細菌抑制剤の添加量としては、水系のチアベンダゾール濃度が3mg/L以上、特に5〜20mg/L程度となるような量とすることが好ましい。水系のチアベンダゾール濃度が上記下限未満では、チアベンダゾールによる硝化細菌抑制効果を十分に得ることができない場合がある。水系のチアベンダゾール濃度は、過度に高くしても硝化細菌抑制効果に差異はないため、上記上限以下とすることが好ましい。   The nitrifying bacteria inhibitor of the present invention is used to prevent oxidation of nitrite by nitrifying bacteria in water systems, particularly sealed cooling water systems or heat storage water systems, in which nitrites such as sodium nitrite, potassium nitrite, and ammonium nitrite are added as metal anticorrosives. Therefore, the amount of the nitrifying bacteria inhibitor to be added is preferably such that the aqueous thiabendazole concentration is 3 mg / L or more, particularly about 5 to 20 mg / L. If the aqueous thiabendazole concentration is less than the above lower limit, the nitrifying bacteria inhibitory effect by thiabendazole may not be sufficiently obtained. Even if the aqueous thiabendazole concentration is excessively high, there is no difference in the nitrifying bacteria inhibitory effect.

なお、本発明の硝化細菌抑制剤は、チアベンダゾール、或いはチアベンダゾール及び増粘剤以外の他の薬剤を含むものであってもよい。例えば、本発明の硝化細菌抑制剤は、金属防食剤としての亜硝酸塩を含むものであってもよく、更に他の防食剤を含むものであってもよい。   In addition, the nitrifying bacteria inhibitor of the present invention may contain thiabendazole, or a drug other than thiabendazole and a thickener. For example, the nitrifying bacteria inhibitor of the present invention may contain nitrite as a metal anticorrosive, and may further contain another anticorrosive.

本発明の硝化細菌抑制剤は、密閉冷却水系又は蓄熱水系等の水系、特に、安全性が重視されている食品、飲料、医薬関係などの工場における密閉冷却水系又は蓄熱水系等に好適に使用される。   The nitrifying bacteria inhibitor of the present invention is suitably used in a water system such as a sealed cooling water system or a heat storage water system, in particular, in a sealed cooling water system or a heat storage water system in factories where food safety, food, beverages, and pharmaceuticals are important. The

以下に実施例及び比較例を挙げて本発明をより具体的に説明する。   Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

<実施例1〜4,比較例1,2>
以下の方法で硝化細菌抑制試験を行った。
1Lビーカーに水道水の脱塩素水を1L入れ、ここへ、10重量%亜硝酸ナトリウム水溶液と、濾過設備の逆洗排水汚泥と、硝化細菌水溶液を添加すると共に、0.1重量%チアベンダゾール水溶液を所定のチアベンダゾール濃度となるように添加した(ただし、比較例1ではチアベンダゾール水溶液添加せず)。
その後、散気球によるエアレーションと、マグネチックスターラーによる撹拌を開始し、撹拌開始時(試験開始時)と、撹拌開始7日後(試験7日後)と14日後(試験14日後)の亜硝酸イオン濃度を測定し、下記式で亜硝酸イオン残存率を算出した。
亜硝酸イオン残存率(%)=
(試験7日後又は14日後の亜硝酸イオン濃度)÷(試験開始時の亜硝酸イオン濃度)
100
上記の試験結果を下記表1及び図1に示す。
<Examples 1-4, Comparative Examples 1 and 2>
A nitrifying bacteria suppression test was conducted by the following method.
Add 1L of dechlorinated tap water to a 1L beaker, add 10% by weight sodium nitrite aqueous solution, backwash drainage sludge for filtration equipment, and nitrifying bacteria aqueous solution, and 0.1% by weight thiabendazole aqueous solution. It added so that it might become a predetermined | prescribed thiabendazole density | concentration (however, the thiabendazole aqueous solution was not added in the comparative example 1).
After that, aeration with an air balloon and stirring with a magnetic stirrer were started, and the nitrite ion concentrations at the start of stirring (at the start of the test), 7 days after the start of stirring (after 7 days of the test), and 14 days after (after 14 days of the test) Measured, and the nitrite ion residual ratio was calculated by the following formula.
Nitrite ion residual rate (%) =
(Nitrite ion concentration after 7 days or 14 days after test) ÷ (Nitrite ion concentration at start of test)
100
The test results are shown in Table 1 and FIG.

Figure 0006330399
Figure 0006330399

表1及び図1より明らかなように、チアベンダゾール3mg/L以上の添加で亜硝酸イオン濃度低下の防止効果が認められた。   As is clear from Table 1 and FIG. 1, the effect of preventing a decrease in nitrite ion concentration was observed when thiabendazole was added in an amount of 3 mg / L or more.

<参考例1>
チアベンダゾールとポリアクリル酸ナトリウム(分子量200万〜600万)とを表2に示す濃度となるように水に添加し、ミキサーで混合分散し、スラリーの安定状態を目視観察し、結果を表2に示した。
<Reference Example 1>
Thiabendazole and sodium polyacrylate (molecular weight: 2,000,000 to 6,000,000) were added to water so as to have the concentrations shown in Table 2, mixed and dispersed with a mixer, the stable state of the slurry was visually observed, and the results are shown in Table 2. Indicated.

Figure 0006330399
Figure 0006330399

表2より、チアベンダゾールに対して0.1〜1重量倍程度のポリアクリル酸ナトリウムを用いることにより、チアベンダゾールを安定なスラリーとして水系に添加することができることが分かる。   From Table 2, it is understood that thiabendazole can be added to the aqueous system as a stable slurry by using about 0.1 to 1 times by weight sodium polyacrylate with respect to thiabendazole.

Claims (6)

チアベンダゾールを有効成分として含有し、増粘剤によりスラリー状となっている硝化細菌抑制剤。 A nitrifying bacteria inhibitor containing thiabendazole as an active ingredient and in a slurry form with a thickener . 金属防食剤として亜硝酸塩が添加されている水系に使用されることを特徴とする請求項1に記載の硝化細菌抑制剤。 The nitrifying bacteria inhibitor according to claim 1, which is used in an aqueous system to which nitrite is added as a metal anticorrosive. 前記水系が、密閉冷却水系又は蓄熱水系であることを特徴とする請求項2に記載の硝化細菌抑制剤。   The nitrifying bacteria inhibitor according to claim 2, wherein the water system is a sealed cooling water system or a heat storage water system. 前記硝化細菌抑制剤が、食品添加物素材からなる前記増粘剤によりスラリー状となっていることを特徴とする請求項1ないし3のいずれか1項に記載の硝化細菌抑制剤。 The nitrifying bacteria inhibitors, nitrification bacteria inhibitor according to any one of claims 1 to 3, characterized in that a slurry by the thickener consisting of food additives material. 前記増粘剤が、ポリアクリル酸ナトリウムであることを特徴とする請求項4に記載の硝化細菌抑制剤。   The nitrifying bacteria inhibitor according to claim 4, wherein the thickener is sodium polyacrylate. 請求項1ないし5のいずれか1項に記載の硝化細菌抑制剤を、対象水系にチアベンダゾール濃度が3mg/L以上となるように添加することを特徴とする硝化細菌抑制方法。   A method for inhibiting nitrifying bacteria, comprising adding the nitrifying bacteria inhibitor according to any one of claims 1 to 5 to a target aqueous system so that the thiabendazole concentration is 3 mg / L or more.
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