JP2019104685A - Nitrifying bacteria inhibitor and nitrifying bacteria inhibition method - Google Patents

Nitrifying bacteria inhibitor and nitrifying bacteria inhibition method Download PDF

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JP2019104685A
JP2019104685A JP2017236142A JP2017236142A JP2019104685A JP 2019104685 A JP2019104685 A JP 2019104685A JP 2017236142 A JP2017236142 A JP 2017236142A JP 2017236142 A JP2017236142 A JP 2017236142A JP 2019104685 A JP2019104685 A JP 2019104685A
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nitrifying bacteria
inhibitor
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匠 佐々木
Takumi Sasaki
匠 佐々木
隆志 居安
Takashi Iyasu
隆志 居安
晶 飯村
Akira Iimura
晶 飯村
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Kurita Water Industries Ltd
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Abstract

To provide a nitrifying bacteria inhibitor containing a material having both of excellent handleability and an anti-corrosive effect on a copper material, as an active ingredient, and a nitrifying bacteria inhibiting method using the nitrifying bacteria inhibitor.SOLUTION: A nitrifying bacteria inhibitor contains one or more selected from the group consisting of 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole, a salt thereof, and a derivative thereof as an active ingredient. A nitrifying bacteria inhibiting method includes adding the nitrifying bacteria inhibitor to a target water system having a copper member.SELECTED DRAWING: Figure 1

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、循環冷却水、密閉式冷・温水（密閉式冷水および密閉式温水）又は開放式冷・温水（開放式冷水および開放式温水）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効果と、銅の防食効果とを併せ持つ硝化細菌抑制剤と、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。   The present invention relates to a nitrifying bacteria inhibitor and a nitrifying bacteria control method, and more specifically, circulating cooling water, closed cold / hot water (closed cold water and closed hot water) or open cold / hot water (open cold water and open hot water) And the like, in an aqueous system to which nitrite is added as a metal corrosion inhibitor, the nitrification bacteria suppression effect to suppress the reduction of the corrosion protection effect by the oxidation of nitrite by nitrification bacteria present in water, and the corrosion resistance effect of copper And a method for suppressing nitrifying bacteria using this nitrifying bacteria inhibitor.

密閉式冷・温水や開放式冷・温水においては、金属防食剤として亜硝酸ナトリウム等の亜硝酸塩が広く用いられているが、亜硝酸塩は、水中に存在する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 closed cold / hot water and open cold / hot water, nitrites such as sodium nitrite are widely used as metal corrosion inhibitors, but nitrite is oxidized by nitrifying bacteria present in water to form nitric acid, There is a problem that the anticorrosion effect decreases.

従来、水中の硝化細菌を抑制するためにイソチアゾリン化合物、４級アンモニウム塩、次亜塩素酸や過酸化水素、ヒドラジンが使用されてきた。
しかし、イソチアゾリン化合物、４級アンモニウム塩、次亜塩素酸や過酸化水素等は銅への腐食性があるため、これらと共に銅用防食剤を併用する必要がある（特許文献１）。
また、ヒドラジンは発がん性物質である点で取り扱いに注意が必要である。 Heretofore, isothiazoline compounds, quaternary ammonium salts, hypochlorous acid, hydrogen peroxide and hydrazine have been used to control nitrifying bacteria in water.
However, since isothiazoline compounds, quaternary ammonium salts, hypochlorous acid, hydrogen peroxide and the like are corrosive to copper, it is necessary to use an anticorrosive for copper in combination (Patent Document 1).
In addition, care must be taken in handling, since hydrazine is a carcinogen.

金属腐食性の低いチアベンダゾールを用いて硝化抑制する方法も提案されているが（特許文献２）、チアベンダゾールは水に溶けにくく、水系に添加しにくいという課題がある。   Although a method of suppressing nitrification using thiabendazole having low metal corrosion properties has also been proposed (Patent Document 2), thiabendazole is difficult to dissolve in water and has a problem of being difficult to add to water systems.

アゾール系化合物は銅用防食剤として知られている。例えば特許文献３には、トリルトリアゾール、ベンゾトリアゾール、メルカプトベンゾチアゾール等が例示されているが、これらのアゾール系化合物が硝化細菌抑制効果を示すことは知られていない。   Azole compounds are known as copper corrosion inhibitors. For example, Patent Document 3 exemplifies tolyltriazole, benzotriazole, mercaptobenzothiazole and the like, but it is not known that these azole compounds show a nitrifying bacteria inhibitory effect.

特開２００２−１９３７１１号公報Japanese Patent Application Laid-Open No. 2002-193711 特開２０１５−１７４８６２号公報JP, 2015-174862, A 特開２０１３−２４５３８９号公報JP, 2013-245389, A

上記の通り、従来は、取り扱い性に優れ、かつ銅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 mentioned above, conventionally, the nitrifying bacteria inhibitor which is excellent in handleability and low in corrosion resistance to copper has not been provided.

本発明は、上記従来の問題点を解決し、取り扱い性に優れ、かつ銅材質に対する防食効果をも併せ持つ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, and is a nitrification bacteria inhibitor containing as an active ingredient a substance which is excellent in handleability and also has an anticorrosive effect on copper material, and nitrification bacteria suppression using this nitrification bacteria inhibitor The task is to provide a method.

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、２−メルカプトベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、これらの塩類、及びこれらの誘導体が、取り扱い性に優れ、発がん性も認められず、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上に、銅材質に対して優れた防食効果を発揮することを見出した。   As a result of intensive studies to solve the above problems, the present inventors found that 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole, salts thereof and derivatives thereof are easy to handle. It was found that the excellent carcinogenic activity was not observed, the activity of nitrifying bacteria could be suppressed, the oxidation of nitrite could be effectively prevented, and in addition, the copper material exhibited an excellent anticorrosive effect.

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 of the present invention is as follows.

［１］ ２−メルカプトベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、これらの塩類、及びこれらの誘導体よりなる群から選ばれる１種又は２種以上を有効成分として含有する硝化細菌抑制剤。 [1] Nitrifying bacteria control containing as an active ingredient one or more selected from the group consisting of 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole, salts thereof, and derivatives thereof Agent.

［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 corrosion inhibitor.

［３］ 前記水系が、循環冷却水、密閉式冷・温水又は開放式冷・温水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 circulating cooling water, closed cold / hot water or open cold / hot water.

［４］ ［１］ないし［３］のいずれかに記載の硝化細菌抑制剤を、銅部材を有する対象水系に添加することを特徴とする硝化細菌抑制方法。 [4] A method for suppressing nitrifying bacteria, which comprises adding the nitrifying bacteria inhibitor according to any one of [1] to [3] to a target aqueous system having a copper member.

［５］ ２−メルカプトベンゾチアゾール換算濃度が０．４５ｍｇ／Ｌ以上又は３−メルカプト−１，２，４−トリアゾール換算濃度が３ｍｇ／Ｌ以上となるように前記硝化細菌抑制剤を前記対象水系に添加することを特徴とする［４］に記載の硝化細菌抑制方法。 [5] The nitrification bacteria inhibitor is used as the target water system such that the concentration of 2-mercaptobenzothiazole conversion is 0.45 mg / L or more or the concentration of 3-mercapto-1,2,4-triazole conversion is 3 mg / L or more The nitrifying bacteria suppression method as described in [4] characterized by adding.

本発明によれば、循環冷却水、密閉式冷・温水又は開放式冷・温水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、２−メルカプトベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、これらの塩類、及びこれらの誘導体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、一剤で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, nitrite added as a metal corrosion inhibitor in a water system such as circulating cooling water, closed cold / hot water or open cold / hot water is oxidized to nitric acid by nitrifying bacteria in the water and the anticorrosive effect is reduced. Can be effectively prevented.
In addition, 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole, salts thereof and derivatives thereof also exhibit an anticorrosive effect on copper materials, and therefore, the agent for inhibiting nitrification bacteria according to the present invention is an agent It is also possible to obtain the corrosion inhibiting effect of copper material.

本発明で有効成分とする２−メルカプトベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、これらの塩類、及びこれらの誘導体は、発がん性物質ではなく、取り扱い性に優れ、水溶液として容易に対象水系に添加することもできる。   The 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole, salts thereof and derivatives thereof as active ingredients in the present invention are not carcinogens, and are excellent in handleability and easily as an aqueous solution. It can also be added to the target water system.

実験例１の結果を示すグラフである。7 is a graph showing the results of Experimental Example 1. 実験例２の結果を示すグラフである。It is a graph which shows the result of example 2 of an experiment.

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

本発明の硝化細菌抑制剤は、２−メルカプトベンゾチアゾール（以下「ＭＢＴ」と略記する場合がある。）、３−メルカプト−１，２，４−トリアゾール（以下「ＭＴ」と略記する場合がある。）、これらの塩類、及びこれらの誘導体の３−メルカプト−１，２，４−トリアゾールよりなる群から選ばれる１種又は２種以上を有効成分として含有するものである。   The nitrifying bacteria inhibitor of the present invention may be abbreviated as 2-mercaptobenzothiazole (hereinafter sometimes abbreviated as "MBT"), 3-mercapto-1,2,4-triazole (hereinafter abbreviated as "MT") And the like, and one or more selected from the group consisting of 3-mercapto-1,2,4-triazole of these salts, and derivatives thereof, as an active ingredient.

ＭＢＴは下記構造式（１）で表され、ＭＴは下記構造式（２）で表されるものである。   MBT is represented by the following structural formula (1), and MT is represented by the following structural formula (2).

Figure 2019104685
Figure 2019104685

ＭＢＴ、ＭＴの塩類としては、これらの化合物のナトリウム塩、カリウム塩等のアルカリ金属塩や、亜鉛塩、シクロヘキシルアミン塩等のアミン塩などが挙げられる。具体的には、２−メルカプトベンゾチアゾールのナトリウム塩、亜鉛塩、シクロヘキシルアミン塩、３−メルカプト−１，２，４−トリアゾールのナトリウム塩等が挙げられる。
また、ＭＢＴ、ＭＴの誘導体としては、ＭＢＴ、ＭＴの水素原子がメチル基等のアルキル基やアミノ基等で置換されたものや、分子内水素原子の移動で二重結合の位置が変化したものなどが挙げられ、具体的には、３−メルカプト−４−メチル−４Ｈ−１，２，４−トリアゾール、３−アミノ−５−メルカプト−１，２，４−トリアゾールなどが挙げられる。 Examples of salts of MBT and MT include alkali metal salts such as sodium salts and potassium salts of these compounds, and amine salts such as zinc salts and cyclohexylamine salts. Specifically, sodium salt of 2-mercaptobenzothiazole, zinc salt, cyclohexylamine salt, sodium salt of 3-mercapto-1,2,4-triazole and the like can be mentioned.
Further, as derivatives of MBT and MT, those in which the hydrogen atom of MBT and MT is substituted with an alkyl group such as a methyl group or the like, or those in which the position of the double bond is changed due to the movement of the hydrogen atom in the molecule Specifically, 3-mercapto-4-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole and the like can be mentioned.

前述の通り、アゾール化合物は、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、これらのアゾール化合物が硝化細菌を抑制する作用を奏することは知られておらず、本発明者らにより初めて見出されたものである。   As described above, the azole compounds are known as copper corrosion inhibitors and have low corrosiveness to metals, but these azole compounds are not known to have an effect of suppressing nitrifying bacteria, It is found for the first time by the present inventors.

ＭＢＴ、ＭＴ、これらの塩類、及びこれらの誘導体の多くは水溶性であり、水溶液として対象水系に容易に添加することができる。
ＭＢＴ、ＭＴ、これらの塩類、及びこれらの誘導体を水溶液として添加する場合、その水溶液中のＭＢＴ、ＭＴ及びこれらの塩類の濃度は、添加効果と取り扱い性等の面で、０．０１〜４０重量％程度とすることが好ましい。 MBT, MT, their salts, and many of their derivatives are water soluble and can easily be added to the target water system as an aqueous solution.
When MBT, MT, their salts, and their derivatives are added as an aqueous solution, the concentration of MBT, MT, and their salts in the aqueous solution is 0.01 to 40% by weight in terms of addition effect and handleability, etc. It is preferable to set it as%.

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、特に循環冷却水、密閉式冷・温水又は開放式冷・温水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、ＭＢＴ、その塩類及び／又はその誘導体を有効成分とする場合は、ＭＢＴ換算の濃度で０．４５ｍｇ／Ｌ以上、特に０．４５〜１０００ｍｇ／Ｌ程度となるような量で添加することが好ましい。また、ＭＴ、その塩類及び／又はその誘導体を有効成分とする場合は、ＭＴ換算の濃度で３ｍｇ／Ｌ以上、特に３〜１０００ｍｇ／Ｌ程度となるような量で添加することが好ましい。対象水系への有効成分の添加濃度が上記下限未満では、ＭＢＴ、ＭＴ、これらの塩類、及びこれらの誘導体による硝化細菌抑制効果も銅に対する防食効果も十分に得ることができない場合がある。水系の有効成分濃度は、過度に高くしても硝化細菌抑制効果及び防食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 an aqueous system to which nitrites such as sodium nitrite, potassium nitrite, ammonium nitrite and the like are added as a metal corrosion inhibitor, particularly in circulating cooling water, closed cold / hot water or open cold / hot water It is preferably used to prevent the oxidation of nitrite by nitrifying bacteria, and the addition amount of the nitrifying bacteria inhibitor at that time may be MBT, its salts and / or its derivative as the active ingredient, and the concentration in terms of MBT. It is preferable to add it in such an amount that it will be 0.45 mg / L or more, particularly about 0.45 to 1000 mg / L. When MT, its salts and / or its derivative is used as an active ingredient, it is preferable to add it in an amount of 3 mg / L or more, particularly about 3 to 1000 mg / L in terms of MT concentration. If the concentration of the active ingredient added to the target water system is less than the above lower limit, MBT, MT, salts thereof, and derivatives thereof may not be able to sufficiently obtain the nitrifying bacteria suppressing effect and the corrosion preventing effect on copper. Even if the concentration of the active ingredient in the water system is excessively high, there is no difference in the nitrifying bacteria suppressing effect and the anticorrosion effect, and therefore, it is preferable to set the concentration to the above upper limit or less.

なお、本発明の硝化細菌抑制剤は、ＭＢＴ、ＭＴ、これらの塩類、及びこれらの誘導体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 other agents other than MBT, MT, salts thereof, and derivatives thereof. For example, the nitrifying bacteria inhibitor of the present invention may contain nitrite as a metal corrosion inhibitor, and may further contain other corrosion inhibitors.

本発明の硝化細菌抑制剤は、循環冷却水、密閉式冷・温水又は開放式冷・温水等の水系、特に、銅部材を保有し、亜硝酸塩が添加されている密閉式冷・温水又は開放式冷・温水等に好適に使用される。   The nitrifying bacteria inhibitor of the present invention is an aqueous system such as circulating cooling water, closed cold / hot water or open cold / hot water, in particular, a closed cold / hot water or open water holding a copper member and to which nitrite is added. It is suitably used for cold / hot water etc.

以下に実施例及び比較例に代わる実験例を挙げて本発明をより具体的に説明する。   The present invention will be more specifically described below with reference to experimental examples instead of the examples and comparative examples.

＜実験例１＞
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、４０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％のＭＢＴ又はＭＴ水溶液を所定のＭＢＴ又はＭＴ濃度となるように添加した。
その後、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１４日後（試験１４日後）の亜硝酸イオン濃度（ｍｇ／Ｌ）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。 Experimental Example 1
The nitrifying bacteria suppression test was conducted by the following method.
Add 1 L of dechlorinated water of tap water into a 1 L beaker, add to it a 40 wt% aqueous solution of sodium nitrite, backwash wastewater sludge from a filtering facility, and an aqueous solution of nitrifying bacteria and add 0.1 wt% of MBT or An aqueous MT solution was added to a predetermined MBT or MT concentration.
After that, stirring with a magnetic stirrer is started, and the nitrite ion concentration (mg / L) at the start of stirring (at the start of the test) and 14 days after the start of the stirring (after the test 14 days) is measured. The residual rate was calculated.
Nitrite ion retention rate (%) =
(Nitrite ion concentration after 14 days of test) ÷ (nitrite ion concentration at the start of test) × 100
The above test results are shown in Table 1 below and FIG.

Figure 2019104685
Figure 2019104685

表１及び図１より明らかなように、ＭＢＴ０．４５ｍｇ／Ｌ以上、ＭＴ３ｍｇ／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 addition of MBT 0.45 mg / L or more and MT 3 mg / L or more showed the effect of preventing a decrease in nitrite ion concentration.

＜実験例２＞
以下の方法で腐食試験を行った。
比較薬剤としては、５−クロロ−２−メチル−４−イソチアゾリン−３−オン（Ｃｌ−ＭＩＴ）を用いた。
ＩＬビーカーに純水を１Ｌ入れ、ここへ塩化ナトリウム（Ｃｌ−として１０００ｍｇ／Ｌ）及び硫酸ナトリウム（ＳＯ４ ２−として１０００ｍｇ／Ｌ）と、０．１重量％のＣｌ−ＭＩＴ、ＭＢＴ又はＭＴ水溶液を所定のＣｌ−ＭＩＴ、ＭＢＴ又はＭＴ濃度となるように添加した。
このようにして調製した試験液に、銅（Ｃ１２２０）製試験片（３０×５０×１ｍｍ）を浸漬して回転速度１６０ｒｐｍ、温度４０℃の条件で回転させる回転腐食試験を用い、７日間での腐食速度を下記式で算出した。
腐食速度（ｍｄｄ：ｍｇ／ｄｍ２／ｄａｙ）＝｛試験前の試験片重量（ｍｇ）−試験後の試験片重量（ｍｇ）｝÷｛試験片の表面積（ｄｍ２）×試験期間（ｄａｙ）｝
上記の試験結果を下記表２及び図２に示す。 <Experimental Example 2>
The corrosion test was conducted by the following method.
As a comparative drug, 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) was used.
Add 1 L of pure water to an IL beaker, and add sodium chloride (1000 mg / L as Cl − ) and sodium sulfate (1000 mg / L as SO 4 2− ) to this and 0.1 wt% Cl-MIT, MBT or MT aqueous solution Was added to give a predetermined Cl-MIT, MBT or MT concentration.
A test piece (30 × 50 × 1 mm) made of copper (C1220) is immersed in the test solution prepared in this manner, and rotated at 160 rpm under the conditions of a temperature of 40 ° C. for 7 days using a rotational corrosion test. The corrosion rate was calculated by the following equation.
Corrosion rate (mdd: mg / dm 2 / day) = {Weight of test piece before test (mg)-Test piece weight after test (mg)} ÷ {surface area of test piece (dm 2 ) × test period (day) }
The above test results are shown in Table 2 below and FIG.

Figure 2019104685
Figure 2019104685

表２及び図２より明らかなように、ＭＢＴ０．４５ｍｇ／Ｌ以上、ＭＴ３ｍｇ／Ｌ以上の濃度で添加すれば十分な防食効果が得られることが分かる。
一方、比較薬剤として用いたＣｌ−ＭＩＴでは防食効果は得られなかった。 As is clear from Table 2 and FIG. 2, it can be seen that a sufficient anticorrosion effect can be obtained by adding MBT at a concentration of 0.45 mg / L or more and MT 3 mg / L or more.
On the other hand, no anticorrosive effect was obtained with Cl-MIT used as a comparative drug.

Claims (5)

２−メルカプトベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、これらの塩類、及びこれらの誘導体よりなる群から選ばれる１種又は２種以上を有効成分として含有する硝化細菌抑制剤。   The nitrifying bacteria inhibitor which contains 1 type (s) or 2 or more types selected from the group which consists of 2-mercaptobenzothiazole, 3-mercapto-1,2,4- triazole, these salts, and these derivatives as an active ingredient. 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 corrosion inhibitor. 前記水系が、循環式冷却水、密閉式冷・温水又は開放式冷・温水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 circulating cooling water, closed cold / hot water or open cold / hot water. 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を、銅部材を有する対象水系に添加することを特徴とする硝化細菌抑制方法。   A method for suppressing nitrifying bacteria, which comprises adding the nitrifying bacteria inhibitor according to any one of claims 1 to 3 to a target aqueous system having a copper member. ２−メルカプトベンゾチアゾール換算濃度が０．４５ｍｇ／Ｌ以上又は３−メルカプト−１，２，４−トリアゾール換算濃度が３ｍｇ／Ｌ以上となるように前記硝化細菌抑制剤を前記対象水系に添加することを特徴とする請求項４に記載の硝化細菌抑制方法。   The nitrifying bacteria inhibitor is added to the target water system such that the concentration of 2-mercaptobenzothiazole conversion is 0.45 mg / L or more or the concentration of 3-mercapto-1,2,4-triazole conversion is 3 mg / L or more. The method for suppressing nitrifying bacteria according to claim 4, characterized in that
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