JP2019072718A - Disinfection method of ammoniacal nitrogen-containing discharge water - Google Patents
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本発明は、アンモニア性窒素含有排水の消毒方法に関し、特に、下水処理場、ポンプ場、雨水吐き口から公共用水域に放流されるアンモニア性窒素を含む排水中の大腸菌又は大腸菌群を殺菌処理する消毒方法に関する。 The present invention relates to a method for disinfecting ammonia nitrogen containing wastewater, and in particular, sterilizes E. coli or coliforms in wastewater containing ammonia nitrogen discharged from sewage treatment plant, pumping station, rainwater outlet to public water area. It relates to the disinfection method.
下水処理場は、家庭や工場から排出される汚水等を無害化して公共用水域に放流するための施設であるが、設計値を上回る降雨があった場合には、中継基地であるポンプ場や雨水吐き口から、雨水の混ざった汚水（以下、雨天時下水という）が、数十秒から数分で、十分に処理されない状態で公共用水域に放流される。この場合、粗大浮遊物やＳＳ（suspended substance：浮遊物質）が公共用水域に放流されるために、美観上問題となる場合
があるばかりか、水質汚濁防止法に定める放流基準値（３０００ＣＦＵ／ｍＬ以下）を大幅に上回る大腸菌群や大腸菌が検出される場合がある。
The sewage treatment plant is a facility to harmonize the sewage discharged from homes and factories and release it to public water areas, but if there is rainfall exceeding the design value, the pumping station or relay station will Sewage mixed with rainwater (hereinafter referred to as rain-time sewage) is discharged from the rainwater outlet into public waters without being sufficiently treated in a few dozen seconds to a few minutes. In this case, large floats and SS (suspended substance) may be released to the public water area, which may cause cosmetic problems, and the standard value of discharge defined by the Water Pollution Control Law (3000 CFU / mL E. coli groups and E. coli that are significantly higher than the following may be detected.
下水処理場においても、流入下水が処理能力を大幅に上回る場合には、一部の雨天時下水を簡易処理し放流する場合がある。この場合、細菌の殺菌が十分に実施されないため、水質汚濁防止法に定める放流基準値（３０００ＣＦＵ／ｍＬ以下）を大幅に上回る大腸菌群や大腸菌が検出される場合がある。これらは、特に合流式下水道にみられる現象であるが、分流式下水道においても、土壌性大腸菌群や粗大浮遊物が流入するため、それらが越流して公共水域に放流された場合には、合流式下水道と同様の問題が生じていた。 In the case of sewage treatment plants, when inflowing sewage greatly exceeds the treatment capacity, some of the rainy weathered sewage may be simply treated and released. In this case, since sterilization of bacteria is not sufficiently carried out, coliforms and coliforms may be detected significantly exceeding the discharge standard value (less than 3000 CFU / mL) specified in the Water Pollution Control Law. These are phenomena that are particularly found in combined sewers, but also in diversion sewers, because soil-borne coliforms and coarse floats flow in, when they are overflowed and released into public waters, they are joined. The same problem as the type sewerage had occurred.
下水処理場での消毒は、「下水道施設計画・設計指針と解説」（日本下水道協会発行、２００９年版）によれば、次亜塩素酸ナトリウム、液化塩素、塩素化イソシアヌル酸、次亜塩素酸カルシウムなどの塩素剤を用い、それらを混和池で、１５分以上、下水と接触させることによって大腸菌群を消毒する方法が示されている。また、「下水道施設計画・設計指針と解説」には、オゾンや紫外線による消毒についても記載されている。更に、数万ｍ３の貯留池を設けて雨天時下水を一時貯留し、貯留量以上の降雨量によって越流が起こった場合には、上記の塩素系消毒剤を用いて消毒を行う方法も提案されている。 According to the “Sewerage Facility Planning and Design Guidelines and Comments” published by the Japan Sewerage Association (2009 edition), disinfection at sewage treatment plants is sodium hypochlorite, liquefied chlorine, chlorinated isocyanuric acid, calcium hypochlorite The method of disinfecting coliform bacteria by making them contact with sewage for more than 15 minutes in a mixing tank using a chlorination agent such as is shown. In addition, "Sewer facility plan, design guidelines and commentary" also describes disinfection with ozone and ultraviolet light. Furthermore, a method of storing several tens of thousands of m 3 reservoirs to temporarily store sewage during rainy weather and disinfecting using the above-mentioned chlorine-based disinfectant when overflow occurs due to rainfall more than the storage amount Proposed.
しかし、塩素系消毒剤は、雨天時下水のように降雨強度が大きく短時間で公共用水域に放流される場合には排水との接触時間が短いため殺菌作用が十分に発揮されないこと、及びアンモニア性窒素含有量が多い排水においては、塩素とアンモニア性窒素とが反応してクロラミンを形成しやすく、殺菌作用が低減することから、水質汚濁防止法で定める基準値以下に大腸菌群数を減少させることができないという問題、及び、クロラミンが公共用水域に結合性塩素として長時間残留して環境に悪影響を与えるという問題などがある。そのため、たとえば、次亜塩素酸ナトリウムに対して臭化ナトリウムを等モル以上添加して形成される次亜臭素酸若しくは次亜臭素酸塩の溶液を排水に添加する消毒方法（特許文献１）、（Ａ）次亜塩素酸ナトリウム又は１，３−ジクロロ−５，５−ジメチルヒダントイン、（Ｂ）臭化ナトリウム又は臭化カリウム、及び（Ｃ）Ｌ−アスコルビン酸、グリコール酸又はグリオキシル酸を（Ａ）次亜塩素酸：（Ｂ）臭化物イオン＝１：１〜１：５（モル比）及び（Ａ）次亜塩素酸：（Ｃ）＝１：０．０５〜１：１（モル比）となる量で含む消毒水を排水に添加する消毒方法（特許文献２）、次亜塩素酸、臭化物及び５，５−ジメチルヒダントインを１：（０．２〜３）：（０．２〜０．９）（モル比）で用い、次亜塩素酸類と５，５−ジメチルヒダントインとの反応により残存した次亜塩素酸類に対応して臭化物を混合して形成される次亜臭素酸及びＮ−モノクロロ−５，５−ジメチルヒダントインを含む水溶液である殺微生物剤（特許文献３）など次亜臭素酸を用いる方法が提案されている。 However, chlorine-based disinfectants, such as sewage when it rains, have a large rainfall intensity and are released to public water areas in a short time, and the contact time with the drainage is short, so the sterilization effect is not sufficiently exhibited, and ammonia Chlorinated water and ammoniacal nitrogen react easily to form chloramine in waste water with a large amount of reactive nitrogen content, and the bactericidal action is reduced, so the number of coliform bacteria is reduced below the standard value specified by the Water Pollution Control Law. In addition, there is a problem that chloramines remain in public water areas as binding chlorine for a long time and adversely affect the environment. Therefore, for example, a disinfecting method in which a solution of hypobromous acid or hypobromous acid salt formed by adding equal molar or more of sodium bromide to sodium hypochlorite is added to waste water (Patent Document 1), (A) sodium hypochlorite or 1,3-dichloro-5,5-dimethylhydantoin, (B) sodium bromide or potassium bromide, and (C) L-ascorbic acid, glycolic acid or glyoxylic acid (A) ) Hypochlorous acid: (B) bromide ion = 1: 1 to 1: 5 (molar ratio) and (A) hypochlorous acid: (C) = 1: 0.05 to 1: 1 (molar ratio) The disinfecting method which adds the disinfecting water containing the following amounts to drainage (patent document 2), hypochlorous acid, a bromide, and 5, 5- dimethyl hydantoin 1: (0.2-3): (0.2-0. 9) (molar ratio), hypochlorous acid and 5, 5-dimethyl A microbicide which is an aqueous solution containing hypobromous acid and N-monochloro-5,5-dimethylhydantoin which is formed by mixing a bromide corresponding to hypochlorous acid remaining by reaction with dantoin (Patent Document 3) The method of using hypobromous acid etc. is proposed.
従来提案されている次亜臭素酸を用いる方法であっても、アンモニア性窒素を含む排水の殺菌効果が不十分で、大腸菌群の放流基準値３０００ＣＦＵ／ｍＬ以下に処理できないことや、大腸菌を十分に殺菌できないことがあった。 Even with the method using hypobromous acid, which has been proposed conventionally, the bactericidal effect of the wastewater containing ammonia nitrogen is insufficient, and it can not be processed to the discharge standard value 3000 CFU / mL or less of coliform bacteria, Could not be sterilized.
本発明は、アンモニア性窒素を含む排水中の大腸菌及び大腸菌群の殺菌処理を確実、簡易、且つ経済的に行う方法を提供することを目的とする。 An object of the present invention is to provide a method for reliably, simply and economically carrying out the sterilizing treatment of E. coli and coliform bacteria in waste water containing ammonia nitrogen.
大腸菌とはEsherichia coliであり、大腸菌群とはEsherichia coli以外にCitrobacter
属、Enterobacter属、Klebsiella属などを含む。大腸菌群は糞便汚染の指標であり、腸管系病原菌（チフス菌、赤痢菌等）に対する安全性を確認するための検査項目である。本発明者らは、反応して次亜臭素酸塩を生成する２種以上の薬剤を組み合わせて各薬剤の添加量を排水中のアンモニア性窒素濃度に応じて調整することにより、従来の大腸菌群のみを指標とする殺菌作用ばかりでなく、大腸菌も指標とする殺菌作用が発揮されることを確認し、本発明を完成するに至った。
E. coli is Esherichia coli, and E. coli is Citrobacter besides Esherichia coli
The genus includes the genus Enterobacter, the genus Klebsiella, and the like. The coliform bacteria group is an index of fecal contamination, and is a test item for confirming the safety against intestinal pathogens (typhoid bacteria, Shigella etc.). The present inventors combine conventional two or more agents which react to form hypobromite, and adjust the addition amount of each agent according to the concentration of ammonia nitrogen in waste water, thereby to obtain the conventional coliform bacteria group. It was confirmed that not only the bactericidal action based on only the indicator but also E. coli also exhibited the bactericidal action as the indicator, the present invention was completed.
本発明によれば下記実施態様のアンモニア性窒素含有排水中の大腸菌及び大腸菌群を殺菌処理するアンモニア性窒素含有排水の消毒方法が提供される。具体的態様は以下のとおりである。
［１］アンモニア性窒素を含有する排水に、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）と、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）と、を添加して前記排水中の大腸菌及び大腸菌群を殺菌するアンモニア性窒素含有排水の消毒方法であって、前記排水中のアンモニア性窒素濃度に応じて、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比を調節して、前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加することを特徴とする方法。
［２］前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ＜１．０となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加し、前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ≧１．０となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加することを特徴とする［１］に記載の方法。
［３］前記薬剤（Ａ）は、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上を含み、前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含む、ことを特徴とする［１］又は［２］に記載の方法。
［４］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、前記排水に添加する前には反応させないことを特徴とする［１］〜［３］のいずれかに記載の方法。
［５］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、固体として前記排水に添加される、ことを特徴とする［１］〜［４］のいずれかに記載の方法。
［６］前記薬剤（Ａ）及び前記薬剤（Ｂ）は、それぞれ別個の溶液として前記排水に添加
される、ことを特徴とする［１］〜［４］のいずれかに記載の方法。
［７］前記薬剤（Ａ）及び前記薬剤（Ｂ）を含む混合溶液として前記排水に添加する、ことを特徴とする［１］〜［３］のいずれかに記載の方法。
According to the present invention, there is provided a method of disinfecting ammonia nitrogen-containing wastewater, which sterilizes E. coli and coliform bacteria in ammonia nitrogen-containing wastewater according to the following embodiment. The specific aspect is as follows.
[1] in wastewater containing ammonia nitrogen, hypochlorite ions in water - an agent (A) for generating, bromide ion in water (OCl) (Br -) and drug (B) that generates a A method for disinfecting ammonia nitrogen containing waste water, which is added to sterilize E. coli and coliform bacteria in the waste water, wherein Cl in the drug (A) and the drug (A) are added according to the concentration of ammonia nitrogen in the waste water B) A method characterized in that the agent (A) and the agent (B) are added to the waste water by adjusting the molar ratio to Br.
[2] When the ammoniacal nitrogen concentration in the waste water is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl <1.0 The drug (A) and the drug (B) are added to the waste water in an amount such that, if the ammoniacal nitrogen concentration in the waste water exceeds 30 mg / L, Cl in the drug (A) and the drug (B) The method according to [1], wherein the drug (A) and the drug (B) are added to the waste water in an amount such that the molar ratio to Br in the medium is Br / Cl ≧ 1.0. .
[3] The agent (A) contains one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder), The method according to [1] or [2], wherein the agent (B) contains one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide.
[4] The method according to any one of [1] to [3], wherein the drug (A) and the drug (B) are not reacted before being added to the waste water.
[5] The method according to any one of [1] to [4], wherein the drug (A) and the drug (B) are added to the waste water as a solid.
[6] The method according to any one of [1] to [4], wherein the drug (A) and the drug (B) are added to the waste water as separate solutions.
[7] The method according to any one of [1] to [3], which is added to the waste water as a mixed solution containing the drug (A) and the drug (B).
本発明によれば、排水中のアンモニア性窒素濃度に応じて最適な次亜臭素酸塩による大腸菌及び大腸菌群の殺菌作用を利用することにより、従来提案されている次亜塩素酸塩に対して等モル以上の臭化物を添加して形成する消毒剤及び殺菌方法や、有機酸又はヒダントインなどの第３成分を添加する殺菌剤及び殺菌方法と比較して短時間でより優れた大腸菌群や大腸菌に対する殺菌効果を発揮することができ、かつ経済的である、アンモニア性窒素含有排水中の大腸菌及び大腸菌群を殺菌処理する消毒方法が提供される。 According to the present invention, by utilizing the bactericidal action of E. coli and coliform bacteria by hypobromous acid optimum according to the concentration of ammoniacal nitrogen in waste water, the hypochlorite which has been conventionally proposed can be obtained. Compared to disinfectants and disinfectants formed by adding more than equimolar bromide, and disinfectants and disinfectants that add a third component such as organic acid or hydantoin, superior coliform bacteria and coliforms in a short time Provided is a disinfecting method for disinfecting E. coli and coliform bacteria in ammonia nitrogen-containing wastewater, which can exert a bactericidal effect and is economical.
以下、添付図面を参照しながら本発明を詳細に説明する。
本発明は、アンモニア性窒素を含有する排水に、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）と、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）と、を添加してアンモニア性窒素含有排水中の大腸菌又は大腸菌群を殺菌処理する消毒方法を提供する。
Hereinafter, the present invention will be described in detail with reference to the attached drawings.
The present invention relates to an agent (A) for generating hypochlorite ion (OCl − ) in water and an agent (B) for generating bromide ion (Br − ) in water, in waste water containing ammonia nitrogen. To provide a disinfecting method for sterilizing E. coli or coliforms in ammonia nitrogen-containing wastewater.
従来の方法は、次亜塩素酸塩１モルに対して金属臭化塩１モル以上を混合して形成される次亜臭素酸塩溶液を排水に添加するが、本発明は、排水中のアンモニア性窒素濃度に応じて、水中で次亜塩素酸イオン（ＯＣｌ−）を発生する薬剤（Ａ）中Ｃｌと、水中で臭化物イオン（Ｂｒ−）を発生する薬剤（Ｂ）中Ｂｒとのモル比を調製することを特徴とする。具体的には、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、薬剤（Ａ）中のＣｌに対して薬剤（Ｂ）中のＢｒのモル比Ｂｒ／Ｃｌが１．０未満、好ましくは０．５以下、０．２以上となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）をアンモニア性窒素含有排水に添加し、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中のＣｌに対して薬剤（Ｂ）中のＢｒのモル比Ｂｒ／Ｃｌが１．０以上、好ましくは１．５以上、２．０以下となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）をアンモニア性窒素含有排水に添加することを特徴とする。排水中のアンモニア性窒素濃度に応じて、薬剤（Ａ）及び薬剤（Ｂ）の添加比率を調整することにより、最適な殺菌作用を経済的に達成し得る。 Although the conventional method adds a hypobromous acid solution formed by mixing one or more moles of metal bromide to one mole of hypochlorite to the waste water, the present invention relates to ammonia in the waste water. depending on the sex of nitrogen concentration, in water hypochlorite ion molar ratio of the medium agent (B) Br for generating (OCl - -) and the medium agent (a) Cl for generating, bromide ion in water (Br) To prepare. Specifically, when the concentration of ammoniacal nitrogen in the waste water is 30 mg / L or less, the molar ratio Br / Cl of Br in the drug (B) to Cl in the drug (A) is less than 1.0, Preferably, the drug (A) and the drug (B) are added to the ammoniacal nitrogen-containing wastewater in an amount of 0.5 or less and 0.2 or more, and the ammoniacal nitrogen concentration in the wastewater exceeds 30 mg / L. The agent (A) is used in an amount such that the molar ratio Br / Cl of Br in the drug (B) to Cl in the drug (A) is 1.0 or more, preferably 1.5 or more and 2.0 or less. And the agent (B) is added to the ammoniacal nitrogen-containing waste water. By adjusting the addition ratio of the drug (A) and the drug (B) according to the concentration of ammoniacal nitrogen in the waste water, an optimal bactericidal action can be economically achieved.
前記薬剤（Ａ）は、次亜塩素酸塩、ジクロロイソシアヌル酸またはその塩、トリクロロイソシアヌル酸またはその塩、及び次亜塩素酸カルシウム（さらし粉）から選択される１種以上を含み、前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含むことが好ましく、任意の薬剤（Ａ）と薬剤（Ｂ）の組合せを用いることができる。薬剤（Ａ）の塩としては、次亜塩素酸ナトリウム、次亜塩素酸カリウム、ジクロロイソシアヌル酸ナトリウム、ジクロロイソシアヌル酸カリウム、トリ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カリウムな
どを好適に用いることができる。薬剤（Ａ）と薬剤（Ｂ）との組合せは、次亜塩素酸ナトリウムと臭化ナトリウム、次亜塩素酸カルシウム（さらし粉）と臭化ナトリウム、ジクロロイソシアヌル酸ナトリウムと臭化ナトリウム、ジクロロイソシアヌル酸ナトリウムと臭化カリウム、ジクロロイソシアヌル酸ナトリウムと臭化カルシウムなどを好適に用いることができる。
The agent (A) includes one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder), and the agent (B) Preferably,) includes one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide, and a combination of any drug (A) and drug (B) can be used. As a salt of the drug (A), sodium hypochlorite, potassium hypochlorite, sodium dichloroisocyanurate, potassium dichloroisocyanurate, sodium trichloroisocyanurate, potassium trichloroisocyanurate and the like can be suitably used. Combinations of drug (A) and drug (B) are sodium hypochlorite and sodium bromide, calcium hypochlorite (exfoliated powder) and sodium bromide, sodium dichloroisocyanurate and sodium bromide, sodium dichloroisocyanurate And potassium bromide, sodium dichloroisocyanurate, calcium bromide and the like can be suitably used.
前記薬剤（Ａ）及び前記薬剤（Ｂ）は、前記排水に添加する前には反応させないことが好ましい。薬剤（Ａ）及び薬剤（Ｂ）を個別に排水に添加することにより、排水の水質に応じたＢｒ／Ｃｌモル比の制御が容易である。このため、それほど大量ではない降雨が長期間にわたり続き、雨水量が多くなり下水が希釈された場合や、降雨量が少なくなり下水の滞留時間が長くなる場合など、経時的に変化する状況であっても、薬剤（Ａ）及び薬剤（Ｂ）の添加量を個別に制御し、好適なモル比で供給することができる。 It is preferable that the agent (A) and the agent (B) are not reacted before being added to the waste water. By separately adding the drug (A) and the drug (B) to the waste water, it is easy to control the Br / Cl molar ratio according to the water quality of the waste water. For this reason, it is a situation that changes with time, such as when the rainfall which is not so large continues for a long time and the amount of rainwater increases and the sewage is diluted or when the amount of rainfall decreases and the residence time of the sewage becomes long. However, the addition amounts of the drug (A) and the drug (B) can be separately controlled and supplied in a suitable molar ratio.
一方、被処理水の水質変動が小さく、アンモニア性窒素濃度が安定している場合、薬剤（Ａ）と薬剤（Ｂ）の混合比率を変化させる必要はなく、一定比率における運転制御が可能となる。この場合、薬剤（Ａ）と薬剤（Ｂ）の添加量を別個に制御する必要がないので混合してから添加することができる。薬剤（Ａ）と薬剤（Ｂ）を混合してから添加することにより、被処理水への添加ラインを1系統とすることができ、運転管理や注入量を制御
し易くなる。
On the other hand, when the water quality fluctuation of the water to be treated is small and the ammoniacal nitrogen concentration is stable, it is not necessary to change the mixing ratio of the drug (A) and the drug (B), and operation control at a constant ratio becomes possible. . In this case, the addition amounts of the drug (A) and the drug (B) do not need to be separately controlled, so they can be mixed and then added. By adding the drug (A) and the drug (B) after adding them, the addition line to the water to be treated can be made into one system, and it becomes easy to control the operation control and the injection amount.
前記薬剤（Ａ）及び前記薬剤（Ｂ）は別個の固体として、あるいは混合された固体として、前記排水に添加されることが好ましい。先行技術文献に開示されているような２種類の薬剤をあらかじめ混合して調製した溶液を排水に添加する場合には、溶解装置、溶液貯留槽、溶液注入装置など付属装置が多くなるため設備全体が大型化し、装置構成が複雑になり、管理コストが増大するが、薬剤（Ａ）及び薬剤（Ｂ）を固体のまま直接排水に添加することにより、溶液を添加する場合に必要となる設備やコストが不要となる。 Preferably, the drug (A) and the drug (B) are added to the waste water as separate solids or as mixed solids. When adding a solution prepared by mixing two types of drugs in advance as disclosed in the prior art to the drainage, there are many accessories such as a dissolving device, a solution reservoir, a solution injection device, etc. Increases the size of the equipment, complicates the equipment configuration, and increases the management cost, but the equipment required for adding the solution by adding the drug (A) and drug (B) directly to the waste water as a solid Cost is not required.
あるいは、前記薬剤（Ａ）及び前記薬剤（Ｂ）はそれぞれ別個に調製された溶液として排水に添加してもよい。この場合、薬剤（Ａ）及び薬剤（Ｂ）の別個の溶液として容易に定量供給することができる。 Alternatively, the agent (A) and the agent (B) may be added to the waste water as separately prepared solutions. In this case, it can be easily quantified as separate solutions of drug (A) and drug (B).
あるいは、薬剤（Ａ）及び薬剤（Ｂ）をあらかじめ混合して調製した混合溶液として添加してもよい。被処理水の流動性が著しく低く、薬剤添加位置における薬剤（Ａ）と薬剤（Ｂ）の接触効率が低い場合、または、薬剤（Ａ）と薬剤（Ｂ）の溶解性が低い場合には、あらかじめ混合して調整した混合液として添加することにより殺菌効果を高めることができる。 図１に、本発明の消毒方法を下水処理場に適用する場合の処理フローを示す。図中「○」はバルブを示す。通常の下水処理場では、排水は第一沈殿池、曝気槽、第二沈殿池により処理された後、河川に放流される。大量の雨水が流入する場合には、曝気槽及び第二沈殿池における処理能力を超えるため、第一沈殿池における処理の後、雨天時簡易放流水として河川に放流される。本発明の消毒方法は、この雨天時簡易放流水に、薬剤（Ａ）及び薬剤（Ｂ）を好ましくは固体のまま、個別に添加する。薬剤（Ａ）と薬剤（Ｂ）の添加量は、雨天時簡易放流水の放流ラインに設けられたアンモニア性窒素検出器（ＮＨ４−Ｎセンサー）により検出されるアンモニア性窒素濃度に応じて、演算子により決定される。具体的には、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０未満、好ましくはＢｒ／Ｃｌが０．５以下、０．２以上とし、アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０以上、好ましくは２．０以下とする。河川への放流の前に、雨天時簡易放流水の残留ハロゲン濃度を測定し、残留ハロゲン濃度が高い場合には薬剤（Ａ）及び（Ｂ）の全注入量を減らすことが好ましい。 Alternatively, the drug (A) and the drug (B) may be added as a mixed solution prepared in advance. When the fluidity of the water to be treated is extremely low and the contact efficiency between the drug (A) and the drug (B) at the drug addition position is low, or when the solubility of the drug (A) and the drug (B) is low, The bactericidal effect can be enhanced by adding it as a mixed solution prepared by mixing in advance. The process flow in the case of applying the disinfection method of this invention to a sewage treatment plant in FIG. 1 is shown. "(Circle)" shows a valve in the figure. In a normal sewage treatment plant, wastewater is treated by the first settling tank, aeration tank, and the second settling tank, and then discharged to the river. When a large amount of rainwater flows in, it exceeds the treatment capacity of the aeration tank and the second sedimentation tank, and therefore, after being treated in the first sedimentation tank, it is released to the river as a simple discharge during rainy weather. In the disinfection method of the present invention, the drug (A) and the drug (B) are added separately, preferably as a solid, to the simple discharge water in rainy weather. The addition amount of the drug (A) and the drug (B) depends on the ammonia nitrogen concentration detected by the ammonia nitrogen detector (NH 4 -N sensor) provided in the discharge line of the simple release water at rainy weather. Determined by the operator. Specifically, when the ammoniacal nitrogen concentration is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is less than 1.0, preferably Br / Cl. When the ammoniacal nitrogen concentration exceeds 30 mg / L, the molar ratio of Cl in drug (A) to Br in drug (B): Br / Cl is 1.0 The above, preferably 2.0 or less. Before release to rivers, it is preferable to measure the residual halogen concentration of the simple release water during rainy weather, and to reduce the total injection amount of drugs (A) and (B) when the residual halogen concentration is high.
図２に、本発明の消毒方法を雨水ポンプ所に適用する場合の処理フローを示す。図中「○」はバルブを示す。通常の雨水ポンプ所では、雨水は、沈砂池及びポンプ井にて処理された後、河川に放流される。本発明の消毒方法は、沈砂池に、薬剤（Ａ）及び薬剤（Ｂ）を好ましくは固体のまま、個別に添加する。薬剤（Ａ）と薬剤（Ｂ）の添加量は、雨水を沈砂池に供給するラインに設けられたアンモニア性窒素検出器（ＮＨ４−Ｎセンサー）により検出されるアンモニア性窒素濃度に応じて、演算子により決定される。具体的には、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０未満、好ましくはＢｒ／Ｃｌが０．５以下、０．２以上とし、アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、薬剤（Ａ）中Ｃｌと薬剤（Ｂ）中Ｂｒのモル比：Ｂｒ／Ｃｌが１．０以上、好ましくは２．０以下とする。河川への放流の前に、雨水処理放流水の残留ハロゲン濃度を測定し、残留ハロゲン濃度が高い場合には薬剤（Ａ）及び（Ｂ）の全注入量を減らすことが好ましい。 The process flow in the case of applying the disinfection method of this invention to FIG. 2 to a rainwater pump station is shown. "(Circle)" shows a valve in the figure. In normal rainwater pumping stations, rainwater is treated by settling basins and pump wells and then released to the river. In the disinfecting method of the present invention, the drug (A) and the drug (B) are added separately, preferably in solid form, to the sedimentation basin. The addition amount of the drug (A) and the drug (B) depends on the ammonia nitrogen concentration detected by the ammonia nitrogen detector (NH 4 -N sensor) provided in the line for supplying rainwater to the sedimentation basin, Determined by the operator. Specifically, when the ammoniacal nitrogen concentration is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B): Br / Cl is less than 1.0, preferably Br / Cl. When the ammoniacal nitrogen concentration exceeds 30 mg / L, the molar ratio of Cl in drug (A) to Br in drug (B): Br / Cl is 1.0 The above, preferably 2.0 or less. It is preferable to measure the residual halogen concentration of the storm water treatment effluent before discharging to the river, and reduce the total injection amount of the drugs (A) and (B) if the residual halogen concentration is high.
図１及び２において、Ｃｌ供給機からの薬剤（Ａ）及びＢｒ供給機からの（Ｂ）の注入量は、演算子によって制御する。演算子は、排水中のアンモニア性窒素濃度に加えて、降雨量、降雨時間、雨天時簡易放流開始時間又は雨水ポンプ運転開始時間などの外部因子からの信号を受けて、薬剤（Ａ）及び（Ｂ）のモル比に加えて全注入量を制御することが好ましい。薬剤（Ａ）及び（Ｂ）は固体のまま投入されることが好ましく、例えば特開２００４−１８０１３号公報に開示されている粉体供給設備などを用いて投入することができる。また、薬剤（Ａ）及び（Ｂ）は、別個の溶液として、あるいはあらかじめ混合して溶液として供給されてもよい。 In Figures 1 and 2, the dose of drug (A) from the Cl dispenser and (B) from the Br dispenser is controlled by the operator. In addition to ammonia nitrogen concentration in the drainage, the operator receives signals from external factors such as rainfall amount, rainfall time, rainy season simple discharge start time or rain water pump operation start time, In addition to the molar ratio of B), it is preferred to control the total injection volume. The agents (A) and (B) are preferably introduced in solid form, and can be introduced, for example, using a powder supply facility disclosed in JP-A-2004-18013. Also, the agents (A) and (B) may be supplied as a separate solution or as a premixed solution.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。
試験水として、降雨量７mm／時の降雨の際の雨天時簡易放流水を用いた。試験水の性状を表１に示す。
Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited thereto.
As test water, rainwater simple discharge water at the time of rainfall of 7 mm / h was used. The properties of the test water are shown in Table 1.
試験水１Lをビーカーに採取し、ジャーテスターにセットして１２０ｒｐｍで撹拌しな
がら、表２に示す種類及び比率で薬剤（Ａ）及び（Ｂ）を添加し、３分後に撹拌を停止して試験水を１００ｍｌ採取した。採取後速やかに、試験水の一部を遊離残留塩素濃度及び全残留塩素濃度の分析に供し、試験水の一部をチオ硫酸ナトリウム入り滅菌瓶に採取した。滅菌瓶に採取した試験水を用いて大腸菌数（クロモアガーＥＣＣ培地、平板培養法）及び大腸菌群数（デソキシコール酸塩培地、平板培養法）の測定を行った。
1 L of test water is collected in a beaker, set in a jar tester and added with drugs (A) and (B) in the type and ratio shown in Table 2 while stirring at 120 rpm. 100 ml of water was collected. Immediately after collection, part of the test water was subjected to analysis of free residual chlorine concentration and total residual chlorine concentration, and part of the test water was collected in a sodium thiosulfate-containing sterile bottle. Using the test water collected in a sterile bottle, the number of E. coli (chromager ECC medium, plate culture method) and the number of E. coli group (desoxycholate medium, plate culture method) were measured.
また、表１に示す試験水に対して所定量の塩化アンモニウムを添加して、表２に示すアンモニア性窒素濃度に調整し、同様の測定を行った。結果を表２に示す。
用いた薬剤は以下のとおりである。
薬剤（Ａ）
・ジクロロイソシアヌル酸ナトリウム
ネオクロール・60（四国化成製、有効塩素含有量64.48%、白色結晶性固体）
・さらし粉
高度さらし粉（日本ソーダ工業会規格JSIA07-1-1998 I種、有効塩素70%以上）
・次亜塩素酸ナトリウム
次亜塩素酸ソーダ試薬（和光純薬工業 試薬特級 有効塩素12%）
・トリクロロイソシアヌル酸
ネオクロール・90（四国化成製、有効塩素含有量90%、白色結晶性固体）
薬剤（Ｂ）
・臭化ナトリウム（和光純薬工業 試薬特級）
・臭化アンモニウム（和光純薬工業 試薬特級）
・臭化カルシウム（和光純薬工業 試薬特級）
・臭化カリウム（和光純薬工業 試薬特級）
Further, a predetermined amount of ammonium chloride was added to the test water shown in Table 1 to adjust to the ammoniacal nitrogen concentration shown in Table 2, and the same measurement was performed. The results are shown in Table 2.
The drugs used are as follows.
Drug (A)
-Sodium dichloroisocyanurate neochlor-60 (manufactured by Shikoku Kasei Co., effective chlorine content 64.48%, white crystalline solid)
Exfoliated powder Highly exfoliated powder (Japan Soda Industry Association Standard JSIA 07-1-1998 Class I, available chlorine 70% or more)
・ Hypochlorous acid sodium hypochlorite sodium reagent (Wako Pure Chemical Industries reagent special grade 12% effective chlorine)
Trichloroisocyanuric acid Neochlor 90 (manufactured by Shikoku Kasei Co., effective chlorine content 90%, white crystalline solid)
Drug (B)
・ Sodium bromide (Wako Pure Chemical Industries, reagent grade special grade)
-Ammonium bromide (Wako Pure Chemical Industries, reagent grade special grade)
· Calcium Bromide (Wako Pure Chemical Industries, Reagent grade)
-Potassium bromide (Wako Pure Chemical Industries, reagent grade special grade)
排水中アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満とすることにより、大腸菌数及び大腸菌群数ともに減少しており、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たすが、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上とすると、大腸菌群数が放流基準値を満た
していないことがわかる。
When the ammoniacal nitrogen concentration in the waste water is 30 mg / L or less, the number of E. coli and the number of E. coli groups are reduced by setting the molar ratio of Br in the drug (B) to less than 1.0 with respect to Cl in the drug (A). Although the discharge standard value (3,000 CFU / mL or less) is satisfied, when the molar ratio of Br in the drug (B) to Cl in the drug (A) is 1.0 or more, the coliform group number is the discharge standard value It is understood that the
一方、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上とすることにより、大腸菌数及び大腸菌群数ともに減少しており、放流基準値（３，０００ＣＦＵ／ｍＬ以下）を満たすが、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満とすると、大腸菌群数が放流基準値を満たしていないことがわかる。 On the other hand, when the concentration of ammoniacal nitrogen in the waste water exceeds 30 mg / L, the number of E. coli and the number of E. coli groups can be increased by setting the molar ratio of Br in the drug (B) to 1.0 in Cl in the drug (A). If the molar ratio of Br in drug (B) to Cl in drug (A) is less than 1.0, the number of coliforms is released. It can be seen that the standard value is not met.
また、従来法である５，５−ジメチルヒダントインを添加した比較例１８及び１９では、アンモニア性窒素濃度が３０ｍｇ／Ｌ以下の場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０未満としても、排水中アンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合、薬剤（Ａ）中Ｃｌに対して薬剤（Ｂ）中Ｂｒをモル比１．０以上としても、大腸菌群数が放流基準値を満たしていない。薬剤（Ａ）及び薬剤（Ｂ）から生成される次亜臭素酸塩及び次亜塩素酸塩が５，５−ジメチルヒダントインと反応し、５，５−ジメチルヒダントインの塩素化物及び臭素化物が生成され、酸化活性が弱まることに起因すると推察される。 Further, in Comparative Examples 18 and 19 in which 5,5-dimethylhydantoin, which is the conventional method, is added, when the ammoniacal nitrogen concentration is 30 mg / L or less, Br in the drug (B) is lower than Cl in the drug (A). Even if the molar ratio is less than 1.0, when the concentration of ammoniacal nitrogen in the waste water exceeds 30 mg / L, the coliform bacteria group is also obtained when the molar ratio of Br in the drug (B) is 1.0 or more to Cl in the drug (A). The number does not meet the discharge standard value. Hypobromite and hypochlorite produced from the drug (A) and the drug (B) react with 5,5-dimethylhydantoin to form 5,5-dimethylhydantoin chloride and bromide. It is presumed that this is due to the weakening of the oxidation activity.
次に、表１に示す試験水に対して、所定量の塩化アンモニウムを添加してアンモニア性窒素濃度を５ｍｇ／Ｌ、２５ｍｇ／Ｌ及び４０ｍｇ／Ｌとした試験水３種を調製し、次亜塩素酸ナトリウム及び臭化カリウムのモル比を表３に示すように変えてそれぞれ固体のまま別個に添加し、消毒効果を比較した。結果を表３及び図３〜４に示す。 Next, three types of test water were prepared by adding predetermined amounts of ammonium chloride to the test water shown in Table 1 to make the ammoniacal nitrogen concentration 5 mg / L, 25 mg / L and 40 mg / L, The molar ratio of sodium chlorate and potassium bromide was changed as shown in Table 3 and each solid was added separately to compare the disinfecting effect. The results are shown in Table 3 and Figs.
Claims (7)
前記排水中のアンモニア性窒素濃度が３０ｍｇ／Ｌを超える場合には、前記薬剤（Ａ）中Ｃｌと、前記薬剤（Ｂ）中Ｂｒとのモル比がＢｒ／Ｃｌ≧１．０となる量で前記薬剤（Ａ）及び前記薬剤（Ｂ）を前記排水に添加する
ことを特徴とする請求項１に記載の方法。 When the ammoniacal nitrogen concentration in the waste water is 30 mg / L or less, the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl <1.0 Adding the drug (A) and the drug (B) to the waste water,
When the ammoniacal nitrogen concentration in the waste water exceeds 30 mg / L, the molar ratio of Cl in the drug (A) to Br in the drug (B) is Br / Cl ≧ 1.0 The method according to claim 1, characterized in that the drug (A) and the drug (B) are added to the waste water.
前記薬剤（Ｂ）は、臭化ナトリウム、臭化カリウム、臭化アンモニウム、及び臭化カルシウムから選ばれる１種以上を含む、ことを特徴とする請求項１又は２に記載の方法。 The agent (A) contains one or more selected from hypochlorite, dichloroisocyanuric acid or a salt thereof, trichloroisocyanuric acid or a salt thereof, and calcium hypochlorite (exfoliated powder),
The method according to claim 1 or 2, wherein the agent (B) contains one or more selected from sodium bromide, potassium bromide, ammonium bromide and calcium bromide.
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