JP5918644B2 - Method for purifying contaminated water containing persistent volatile organic compounds - Google Patents
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Description
本発明は、ハロメタン類やハロエタン類などの揮発性有機化合物を含有する汚染水を浄化する技術に関する。 The present invention relates to a technique for purifying contaminated water containing volatile organic compounds such as halomethanes and haloethanes.
工場跡地における地下水汚染など、水の汚染が発見される事例は未だ多く、汚染水を浄化するためのより良い技術が求められている。水の汚染の一形態として、揮発性有機化合物（ＶＯＣ）による汚染がある。ＶＯＣは揮発性、低粘性であり、かつ水よりも比重が大きいものが多く、土壌や水中では分解されにくいため、ＶＯＣにより汚染された水の浄化は容易ではない。 There are still many cases where water contamination, such as groundwater contamination in factory sites, has been discovered, and there is a need for better technology to purify contaminated water. One form of water contamination is volatile organic compound (VOC) contamination. VOCs are volatile, low viscosity, and have a greater specific gravity than water, and are not easily decomposed in soil or water, so it is not easy to purify water contaminated by VOCs.
例えば特許文献１には、土中のＶＯＣを酸化させる方法であって、まず過硫酸塩などの過酸化化合物を土に導入して土のオキシダント要求量の大半を満たし、次いで過マンガン酸塩を前記土に導入し該過マンガン酸塩によってＶＯＣを酸化する方法が開示されている。しかし、特許文献１のような方法では、四塩化炭素およびジクロロメタンなどのハロメタン類、ならびに１，１，１−トリクロロエタンおよび１，２−ジクロロエタンなどのハロエタン類のような難分解性のＶＯＣは分解することが難しい。 For example, Patent Document 1 discloses a method for oxidizing VOCs in soil, in which a peroxy compound such as persulfate is first introduced into the soil to satisfy most of the soil oxidant requirements, and then the permanganate is added. A method of introducing VOC into the soil and oxidizing VOCs with the permanganate is disclosed. However, in a method such as Patent Document 1, refractory VOCs such as halomethanes such as carbon tetrachloride and dichloromethane and haloethanes such as 1,1,1-trichloroethane and 1,2-dichloroethane are decomposed. It is difficult.
本発明は、ハロメタン類およびハロエタン類のような難分解性のＶＯＣに汚染された水であっても容易に浄化する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 easily purifying water contaminated with persistent VOCs such as halomethanes and haloethanes.
検討の結果、本発明者らはフェントン反応を応用した新規な汚染水の浄化方法を見出した。本発明の要旨は以下のとおりである。
（１）揮発性有機化合物を含有する汚染水に過酸化水素と鉄(II)イオン源または銅(I)イオン源とを含むフェントン反応剤を加える工程、フェントン反応の反応熱により前記汚染水を昇温させる工程、および前記汚染水に過硫酸塩を加える工程を含む、汚染水の浄化方法。
（２）揮発性有機化合物がハロゲン化炭化水素から選択される少なくとも１種の化合物を含む、（１）に記載の方法。
（３）汚染水を５０℃以上に昇温させた後に過硫酸塩を加える、（１）または（２）に記載の方法。
（４）過硫酸塩と共に鉄(II)イオン源または銅(I)イオン源を加える、（１）〜（３）のいずれかに記載の方法。
As a result of the study, the present inventors have found a novel method for purifying contaminated water using the Fenton reaction. The gist of the present invention is as follows.
(1) A step of adding a Fenton reagent containing hydrogen peroxide and an iron (II) ion source or a copper (I) ion source to contaminated water containing a volatile organic compound, and the contaminated water by reaction heat of Fenton reaction. A method for purifying contaminated water, comprising a step of raising the temperature and a step of adding persulfate to the contaminated water.
(2) The method according to (1), wherein the volatile organic compound comprises at least one compound selected from halogenated hydrocarbons.
(3) The method according to (1) or (2), wherein the persulfate is added after raising the temperature of the contaminated water to 50 ° C. or higher.
(4) The method according to any one of (1) to (3), wherein an iron (II) ion source or a copper (I) ion source is added together with a persulfate.
本発明によれば、従来技術では分解が困難であったハロメタン類およびハロエタン類のような難分解性のＶＯＣに汚染された水を浄化することができる。 According to the present invention, it is possible to purify water contaminated with persistent VOCs such as halomethanes and haloethanes, which are difficult to decompose by the prior art.
本発明の方法は、揮発性有機化合物（ＶＯＣ：Volatile Organic Compounds）に汚染された水を対象とする。ＶＯＣとは、揮発性を有し、大気中に気体状で存在しうる有機化合物（２０℃で０．０１ｋＰａ以上の蒸気圧を有する化合物）を広く意味する。水の汚染において着目すべきＶＯＣの具体例としては、ハロゲン化炭化水素および芳香族炭化水素が挙げられる。 The method of the present invention is directed to water contaminated with volatile organic compounds (VOCs). VOC broadly means organic compounds (compounds having a vapor pressure of 0.01 kPa or more at 20 ° C.) that are volatile and can exist in a gaseous state in the atmosphere. Specific examples of VOCs to which attention should be paid in water contamination include halogenated hydrocarbons and aromatic hydrocarbons.
ハロゲン化炭化水素の具体例としては、ハロメタン類、ハロエタン類、ハロプロパン類、ハロブタン類、ハロエチレン類、ハロプロピレン類などが挙げられる。 Specific examples of the halogenated hydrocarbon include halomethanes, haloethanes, halopropanes, halobutanes, haloethylenes, halopropylenes and the like.
ハロメタン類としては、クロロメタン、ジクロロメタン、クロロホルム、四塩化炭素、ブロモメタン、ジブロモメタン、ブロモホルム、四臭化炭素、ヨードメタン、ジヨードメタン、ヨードホルム、ブロモクロロメタン、ブロモジクロロメタン、クロロジブロモメタン、トリクロロブロモメタン、トリクロロフルオロメタン、ジクロロジフルオロメタン、ブロモクロロジフルオロメタン、ブロモトリフルオロメタンなどが挙げられる。 Halomethanes include chloromethane, dichloromethane, chloroform, carbon tetrachloride, bromomethane, dibromomethane, bromoform, carbon tetrabromide, iodomethane, diiodomethane, iodoform, bromochloromethane, bromodichloromethane, chlorodibromomethane, trichlorobromomethane, trichloro Examples include fluoromethane, dichlorodifluoromethane, bromochlorodifluoromethane, and bromotrifluoromethane.
ハロエタン類としては、クロロエタン、１，１−ジクロロエタン、１，２−ジクロロエタン、１，１，１−トリクロロエタン、１，１，２−トリクロロエタン、１，１，１，２−テトラクロロエタン、ペンタクロロエタン、ヘキサクロロエタン、ブロモエタン、１，２−ジブロモエタン、１，１，２−トリブロモエタン、１，１，２，２−テトラブロモエタン、ヨードエタン、トリクロロトリフルオロエタン、ジクロロテトラフルオロエタン、クロロペンタフルオロエタン、ジブロモテトラフルオロエタンなどが挙げられる。 The haloethanes include chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, pentachloroethane, hexa Chloroethane, bromoethane, 1,2-dibromoethane, 1,1,2-tribromoethane, 1,1,2,2-tetrabromoethane, iodoethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, chloropentafluoroethane, And dibromotetrafluoroethane.
ハロプロパン類としては、１−クロロプロパン、２−クロロプロパン、１−ブロモプロパン、２−ブロモプロパン、１，２−ジクロロプロパン、１，３−ジクロロプロパン、１，２−ジブロモプロパン、１，３−ジブロモプロパン、１−ブロモ−３−クロロプロパン、１，２，３−トリクロロプロパン、１，２−ジブロモ−３−クロロプロパン、ヘプタクロロプロパンなどが挙げられる。 Examples of halopropanes include 1-chloropropane, 2-chloropropane, 1-bromopropane, 2-bromopropane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2-dibromopropane, 1,3-dibromo. Examples include propane, 1-bromo-3-chloropropane, 1,2,3-trichloropropane, 1,2-dibromo-3-chloropropane, and heptachloropropane.
ハロブタン類としては、１−クロロブタン、２−クロロブタン、１−ブロモブタン、２−ブロモブタン、１，３−ジクロロブタン、１，４−ジクロロブタン、２，３−ジクロロブタン、１，２−ジブロモブタン、１，３−ジブロモブタン、１，４−ジブロモブタン、２，３−ジブロモブタンなどが挙げられる。 Examples of halobutanes include 1-chlorobutane, 2-chlorobutane, 1-bromobutane, 2-bromobutane, 1,3-dichlorobutane, 1,4-dichlorobutane, 2,3-dichlorobutane, 1,2-dibromobutane, 1 , 3-dibromobutane, 1,4-dibromobutane, 2,3-dibromobutane and the like.
ハロエチレン類としては、クロロエチレン、トリクロロエチレン、テトラクロロエチレン、塩化ビニリデン、１，２−ジクロロエチレン、１，２−ジブロモエチレンなどが挙げられる。 Examples of haloethylenes include chloroethylene, trichloroethylene, tetrachloroethylene, vinylidene chloride, 1,2-dichloroethylene, 1,2-dibromoethylene, and the like.
ハロプロピレン類としては、塩化アリル、臭化アリル、ヨウ化アリル、２−ブロモ−１−プロペン、１，３−ジクロロプロペン、２，３−ジクロロ−１−プロペンなどが挙げられる。 Examples of halopropylenes include allyl chloride, allyl bromide, allyl iodide, 2-bromo-1-propene, 1,3-dichloropropene, and 2,3-dichloro-1-propene.
芳香族炭化水素の具体例としては、ベンゼン、トルエン、スチレン、エチルベンゼン、キシレン、パラジクロロベンゼンなどが挙げられる。 Specific examples of the aromatic hydrocarbon include benzene, toluene, styrene, ethylbenzene, xylene, paradichlorobenzene and the like.
ＶＯＣのなかでも、ハロゲン化炭化水素、特にハロメタン類およびハロエタン類は、その分解が難しいことが知られている。本発明の方法によれば、そのような難分解性のＶＯＣであるハロメタン類やハロエタン類を酸化分解することが可能である。 Among VOCs, halogenated hydrocarbons, particularly halomethanes and haloethanes, are known to be difficult to decompose. According to the method of the present invention, it is possible to oxidatively decompose such halomethanes and haloethanes, which are such persistent VOCs.
本発明の汚染水の浄化方法は、汚染水に過酸化水素と鉄(II)イオン源または銅(I)イオン源とを含むフェントン反応剤を加える工程、フェントン反応の反応熱により汚染水を昇温させる工程、および過硫酸塩を加える工程を含むことを特徴とする。 The method for purifying contaminated water according to the present invention includes a step of adding a Fenton reactant containing hydrogen peroxide and an iron (II) ion source or a copper (I) ion source to the contaminated water, and increasing the contaminated water by reaction heat of Fenton reaction. It is characterized by including a step of heating and a step of adding persulfate.
フェントン反応は、過酸化水素が鉄(II)イオン（Ｆｅ２＋、第一鉄イオン）または銅(I)イオン（Ｃｕ＋、第一銅イオン）と触媒的に反応して非常に強い酸化力を有するヒドロキシラジカルを生じさせる反応である。フェントン反応は強い発熱を伴う反応であることが知られている。 In the Fenton reaction, hydrogen peroxide catalytically reacts with iron (II) ions (Fe 2+ , ferrous ions) or copper (I) ions (Cu + , cuprous ions), resulting in a very strong oxidizing power. It is a reaction that produces a hydroxy radical. It is known that the Fenton reaction is a reaction with a strong exotherm.
フェントン反応剤に用いる鉄(II)イオン源または銅(I)イオン源としては、硫酸鉄(II)、塩化鉄(II)、硝酸鉄(II)、水酸化鉄(II)、硫酸銅(I)、塩化銅(I)、硝酸銅(I)、水酸化銅(I)などを用いることができる。また、フェントン反応剤に用いる過酸化水素は約３０〜３５％の水溶液を用いることが好ましい。なお、本明細書において、過酸化水素水の濃度はいずれも重量％を表す。 The iron (II) ion source or copper (I) ion source used for the Fenton reactant includes iron (II) sulfate, iron (II) chloride, iron (II) nitrate, iron (II) hydroxide, copper sulfate (I ), Copper chloride (I), copper nitrate (I), copper hydroxide (I), and the like. Moreover, it is preferable to use about 30-35% aqueous solution for hydrogen peroxide used for the Fenton reactant. In addition, in this specification, all the density | concentrations of hydrogen peroxide water represent weight%.
フェントン反応剤は、フェントン反応の反応熱により汚染水を十分加熱することができるような量で用いることが好ましい。過酸化水素水は６５ｍＬの汚染水に対して３５〜４５ｍＬ用いることが好ましい。また、鉄(II)イオン源または銅(I)イオン源は汚染水と過酸化水素水の混合液１００ｍＬに対して０．０２〜０．０７モル、特に０．０３〜０．０４モル用いることが好ましい。 The Fenton reactant is preferably used in such an amount that the contaminated water can be sufficiently heated by the reaction heat of the Fenton reaction. It is preferable to use 35 to 45 mL of hydrogen peroxide water with respect to 65 mL of contaminated water. The iron (II) ion source or copper (I) ion source should be used in an amount of 0.02 to 0.07 mol, particularly 0.03 to 0.04 mol, based on 100 mL of the mixed solution of contaminated water and hydrogen peroxide water. Is preferred.
本発明の方法では、汚染水をフェントン反応の反応熱により通常５０℃以上、好ましくは５５℃以上、より好ましくは６０℃以上に昇温させる。昇温することにより過硫酸塩の酸化分解作用を強力化することができる。本発明の方法は、汚染水の昇温をフェントン反応の反応熱で行うため、特に熱源を用意する必要がなくコスト面からも有利であるといえる。 In the method of the present invention, the contaminated water is heated to usually 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher by the reaction heat of the Fenton reaction. By raising the temperature, the oxidative decomposition action of persulfate can be strengthened. In the method of the present invention, since the temperature of the contaminated water is raised by the reaction heat of the Fenton reaction, it is not particularly necessary to prepare a heat source and it can be said that it is advantageous from the viewpoint of cost.
本発明の方法で用いることができる過硫酸塩としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸マグネシウム、過硫酸カルシウム、過硫酸アンモニウム、過硫酸リチウム、などが挙げられる。なかでもコスト等の面から過硫酸ナトリウムが好ましい。過硫酸塩は、汚染水と過酸化水素水の混合液１００ｍＬに対して０．００４〜０．０１モル、特に０．００７〜０．００９モル、とりわけ０．００８モル用いることが好ましい。 Examples of the persulfate that can be used in the method of the present invention include sodium persulfate, potassium persulfate, magnesium persulfate, calcium persulfate, ammonium persulfate, and lithium persulfate. Of these, sodium persulfate is preferable in terms of cost and the like. The persulfate is preferably used in an amount of 0.004 to 0.01 mol, particularly 0.007 to 0.009 mol, especially 0.008 mol, per 100 mL of the mixed solution of contaminated water and hydrogen peroxide solution.
過硫酸塩と共に、触媒として鉄(II)イオン源または銅(I)イオン源を加えることが、酸化作用の向上の面から好ましい。鉄(II)イオン源および銅(I)イオン源としては、フェントン反応剤におけるものと同様に、硫酸鉄(II)、塩化鉄(II)、硝酸鉄(II)、水酸化鉄(II)、硫酸銅(I)、塩化銅(I)、硝酸銅(I)、水酸化銅(I)などを用いることができる。触媒としての鉄(II)イオン源または銅(I)イオン源は汚染水と過酸化水素水の混合液１００ｍＬに対して０．００４〜０．０１モル、特に０．００８〜０．０１モル用いることが好ましい。 It is preferable to add an iron (II) ion source or a copper (I) ion source as a catalyst together with the persulfate from the viewpoint of improving the oxidation action. As the iron (II) ion source and the copper (I) ion source, as in the Fenton reactant, iron (II) sulfate, iron (II) chloride, iron (II) nitrate, iron (II) hydroxide, Copper (I) sulfate, copper (I) chloride, copper nitrate (I), copper hydroxide (I) and the like can be used. An iron (II) ion source or a copper (I) ion source as a catalyst is used in an amount of 0.004 to 0.01 mol, particularly 0.008 to 0.01 mol, per 100 mL of a mixed solution of contaminated water and hydrogen peroxide water. It is preferable.
本発明の方法では、フェントン反応による酸化と、昇温状態での過硫酸塩での酸化とを組み合わせることにより、従来技術では得られなかった強力な酸化分解作用が得られる。本発明の方法によれば、汚染水に含まれるハロメタン類やハロエタン類などの従来技術では分解することが難しかった難分解性のＶＯＣの酸化分解が可能になる。また、従来技術でも分解可能であったＶＯＣについても、その酸化分解効率を向上させることが可能になる。さらに、本発明の方法によれば、ＰＣＢやダイオキシンについても分解できる可能性がある。 In the method of the present invention, a powerful oxidative decomposition action that cannot be obtained by the prior art can be obtained by combining the oxidation by the Fenton reaction and the oxidation with the persulfate in the elevated temperature state. According to the method of the present invention, it is possible to oxidatively decompose hardly decomposable VOCs that were difficult to be decomposed by conventional techniques such as halomethanes and haloethanes contained in contaminated water. In addition, it is possible to improve the oxidative decomposition efficiency of VOCs that can be decomposed even by the conventional technique. Furthermore, according to the method of the present invention, PCBs and dioxins may be decomposed.
本発明の汚染水浄化方法によれば、従来は揚水処理で対応していたハロメタン類やハロエタン類による地下水汚染についても、原位置（in situ）での浄化を行うことが可能となる。 According to the contaminated water purification method of the present invention, it is possible to perform in situ purification of groundwater contamination by halomethanes and haloethanes, which have been conventionally handled by pumping treatment.
以下、実施例を用いて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.
１．フェントン反応による昇温試験
過酸化水素の濃度が所定の値となり、かつ溶液量が５０ｍＬとなるよう、３５％過酸化水素水と蒸留水とを混合した。そこに硫酸第一鉄を１００ｍｇ添加し、デジタル温度計を用いて３０秒間隔で溶液の温度を測定した。過酸化水素濃度と溶液の最高温度、温度上昇量、および過酸化水素１モルあたりの発熱量の関係を表１に示す。過酸化水素濃度を３５％とした場合では突沸が発生したため考慮から除外すると、過酸化水素１モルあたりおよそ５０ｋＪ／ｍｏｌの発熱量が得られることがわかった。この発熱量は、概ね数十リットルの３５％過酸化水素水で地盤１ｍ３の間隙水を６０℃まで加熱できるレベルに相当する。
1. Temperature rise test by Fenton reaction 35% hydrogen peroxide solution and distilled water were mixed so that the concentration of hydrogen peroxide became a predetermined value and the amount of the solution became 50 mL. 100 mg of ferrous sulfate was added thereto, and the temperature of the solution was measured at intervals of 30 seconds using a digital thermometer. Table 1 shows the relationship between the hydrogen peroxide concentration, the maximum temperature of the solution, the amount of temperature rise, and the calorific value per mole of hydrogen peroxide. It was found that when the hydrogen peroxide concentration was 35%, bumping occurred, and when excluding from consideration, a calorific value of approximately 50 kJ / mol per mole of hydrogen peroxide was obtained. This calorific value corresponds to a level at which the pore water of 1 m 3 of ground can be heated to 60 ° C. with approximately several tens of liters of 35% hydrogen peroxide solution.
２．汚染水浄化試験
汚染水のモデルとして１，２−ジクロロエタンを約１０ｍｇ／Ｌの濃度で含む水を用いた。１２５ｍＬの茶褐色バイアル瓶に汚染水５０ｍＬ、過硫酸ナトリウム１ｇ、硫酸第一鉄１ｇを入れ、さらに３５％過酸化水素水１．５ｍＬを添加し密栓した試料を４本作製した。
2. Contaminated Water Purification Test Water containing 1,2-dichloroethane at a concentration of about 10 mg / L was used as a contaminated water model. In a 125 mL brown-brown vial, 50 mL of contaminated water, 1 g of sodium persulfate and 1 g of ferrous sulfate were added, and 1.5 mL of 35% hydrogen peroxide solution was further added to prepare four sealed samples.
（実施例）
作成した試料を６０℃の恒温槽で湯浴し、所定の時間ごとに、ヘッドスペースサンプラ（Ｇ１８８８、Agilent社製）とＧＣ／ＭＳ（ＧＣ６８９０／ＭＳ５９７３Ｎ、長さ６０ｍ、内径０．３２ｍｍ、膜厚０．５２μｍのキャピラリカラムＨＰ−１を使用、いずれもAgilent社製）を組み合わせた装置を用いて１，２−ジクロロエタンの濃度を測定した。経過時間と１，２−ジクロロエタン濃度の関係を表２に示す。２時間が経過した段階で、１，２−ジクロロエタン濃度は検出限界である０．００１ｍｇ／ｍＬ未満であった。
(Example)
The prepared sample was bathed in a constant temperature bath at 60 ° C., and a headspace sampler (G1888, manufactured by Agilent) and GC / MS (GC6890 / MS5973N, length 60 m, inner diameter 0.32 mm, film thickness at predetermined time intervals. The concentration of 1,2-dichloroethane was measured using an apparatus combining a 0.52 μm capillary column HP-1 (all manufactured by Agilent). Table 2 shows the relationship between elapsed time and 1,2-dichloroethane concentration. At the stage where 2 hours had elapsed, the concentration of 1,2-dichloroethane was less than the detection limit of 0.001 mg / mL.
１，２−ジクロロエタンに代えてジクロロメタンを用いて同様の試験を行ったところ、６時間が経過した段階で検出限界である０．００１ｍｇ／ｍＬ未満の濃度となった。また、１，１，１−トリクロロエタンを用いたところ、４８時間後に約７５％の分解率が確認された。 When a similar test was performed using dichloromethane instead of 1,2-dichloroethane, the concentration reached a detection limit of less than 0.001 mg / mL after 6 hours. When 1,1,1-trichloroethane was used, a decomposition rate of about 75% was confirmed after 48 hours.
（比較例）
作成した試料を２０℃の恒温槽に静置し、所定の時間が経過した後に取り出して１，２−ジクロロエタンの濃度を測定した。経過時間と１，２−ジクロロエタン濃度の関係を表３に示す。４８時間を経過しても１，２−ジクロロエタンの濃度はあまり低下しなかった。
(Comparative example)
The prepared sample was left in a constant temperature bath at 20 ° C., taken out after a predetermined time, and the concentration of 1,2-dichloroethane was measured. Table 3 shows the relationship between the elapsed time and the 1,2-dichloroethane concentration. Even after 48 hours, the concentration of 1,2-dichloroethane did not decrease much.
３．地下水浄化への適用例−１
図１は、本発明を用いた地下水浄化法の一例の概略を示した図である。注入井戸への処理剤注入の影響半径を２ｍ、帯水層厚さ２ｍ、間隙率３０％とすると、影響範囲に存在する地下水の量は７．５ｍ３となる。２０℃、７．５ｍ３の地下水を６０℃まで加熱するには、約２５００Ｌの３５％過酸化水素水が必要となる。鉄触媒の必要量を地下水の量の２％とすると１５０ｋｇの鉄触媒が必要となる。鉄触媒はできるだけ高濃度で注入したほうが過酸化水素との接触がよくなるため、７５０Ｌの水に１５０ｋｇの硫酸第一鉄を溶解させ（２０％溶液）、最初にポンプ等を使用して流速２０Ｌ／分程度で注入する。過硫酸ナトリウムの必要量も同様に地下水の量の２％とすると１５０ｋｇの過硫酸ナトリウムが必要となる。これを２５００Ｌの３５％過酸化水素溶液に溶解させ、ポンプ等を使用して流速２０Ｌ／分程度で注入する。あらかじめ注入井戸から２ｍ離れた地点に観測井戸を設置しておき、水温を監視する。水温が６０℃に達しないようであれば硫酸第一鉄溶液と過酸化水素溶液を追加で注入する。
3. Application example-1 for groundwater purification
FIG. 1 is a diagram showing an outline of an example of a groundwater purification method using the present invention. If the influence radius of the treatment agent injection into the injection well is 2 m, the aquifer thickness is 2 m, and the porosity is 30%, the amount of groundwater existing in the influence range is 7.5 m 3 . In order to heat 20 ° C. and 7.5 m 3 groundwater to 60 ° C., about 2500 L of 35% hydrogen peroxide solution is required. If the required amount of iron catalyst is 2% of the amount of groundwater, 150 kg of iron catalyst is required. When the iron catalyst is injected at a concentration as high as possible, contact with hydrogen peroxide is improved. Therefore, 150 kg of ferrous sulfate is dissolved in 750 L of water (20% solution), and a flow rate of 20 L / liter is first used using a pump or the like. Inject in about a minute. Similarly, if the required amount of sodium persulfate is 2% of the amount of groundwater, 150 kg of sodium persulfate is required. This is dissolved in 2500 L of 35% hydrogen peroxide solution and injected at a flow rate of about 20 L / min using a pump or the like. An observation well is installed in advance at a
４．地下水浄化への適用例−２
図２は、本発明を用いた地下水浄化法の他の一例の概略を示した図である。処理剤注入の前提条件は、上記３で説明したものと同様である。注入井戸を一辺が２ｍの正三角形の頂点上に３本設置し（井戸Ａ〜Ｃ）、最初に井戸Ａで７５０Ｌの水に溶かした硫酸第一鉄溶液を、ポンプ等を使用して流速２０Ｌ／分程度で注入する。次に井戸Ｂで過酸化水素溶液をポンプ等を使用して流速２０Ｌ／分程度で注入する。最後に井戸Ｃで７５０Ｌの水に１５０ｋｇの過硫酸ナトリウムを溶かした溶液を、ポンプ等を使用して流速２０Ｌ／分程度で注入する。あらかじめ注入井戸の正三角形の中心に観測井戸を設置しておき水温を監視する。水温が６０℃に達しないようであれば硫酸第一鉄溶液と過酸化水素溶液を追加で注入する。
4). Application example-2 for groundwater purification
FIG. 2 is a diagram showing an outline of another example of the groundwater purification method using the present invention. The preconditions for the treatment agent injection are the same as those described in 3 above. Three injection wells are installed on the apex of an equilateral triangle with a side of 2 m (wells A to C), and a ferrous sulfate solution first dissolved in 750 L of water in well A is flowed to a flow rate of 20 L using a pump or the like. Inject at about / min. Next, the hydrogen peroxide solution is injected into the well B at a flow rate of about 20 L / min using a pump or the like. Finally, in well C, a solution of 150 kg of sodium persulfate dissolved in 750 L of water is injected at a flow rate of about 20 L / min using a pump or the like. An observation well is installed in advance at the center of the equilateral triangle of the injection well and the water temperature is monitored. If the water temperature does not reach 60 ° C., ferrous sulfate solution and hydrogen peroxide solution are additionally injected.
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