JPH051078B2 - - Google Patents

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Publication number
JPH051078B2
JPH051078B2 JP60045542A JP4554285A JPH051078B2 JP H051078 B2 JPH051078 B2 JP H051078B2 JP 60045542 A JP60045542 A JP 60045542A JP 4554285 A JP4554285 A JP 4554285A JP H051078 B2 JPH051078 B2 JP H051078B2
Authority
JP
Japan
Prior art keywords
organic halogen
water
halogen compounds
compounds
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP60045542A
Other languages
Japanese (ja)
Other versions
JPS61204082A (en
Inventor
Tsutomu Kagitani
Seiichi Nishimoto
Takashi Hagita
Hiroshi Hatsuta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to JP4554285A priority Critical patent/JPS61204082A/en
Publication of JPS61204082A publication Critical patent/JPS61204082A/en
Publication of JPH051078B2 publication Critical patent/JPH051078B2/ja
Granted legal-status Critical Current

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Description

【発明の詳細な説明】[Detailed description of the invention]

[産業上の利用分野] 本発明は有機ハロゲン化合物で汚染された水の
浄化法に関する。 [従来の技術] 現在、水は上水、下水のいかんにかかわらず多
かれ少なかれ有機ハロゲン化合物で汚染されてい
る。たとえば、上水道においては、塩素や次亜塩
素酸塩などの活性塩素化合物を用いて水が殺菌さ
れている。しかし、その過程で、それらの活性塩
素化合物により水中の有機物が塩素化され、トリ
ハロメタンなどの有機塩素化合物が生じている。
また、下水道においても、たとえばドライクリー
ニングなどに用いられているトリクレンやパーク
レンが流入したり、都市ゴミなどの焼却により生
じた有害なハロゲン化合物が流入したりしてい
る。最近の研究によつて、これら有機ハロゲン化
合物の中には発ガン性の強いものが含まれている
ことが明らかになり、重大な社会問題となつてい
る。 そうした水中の有機ハロゲン化合物は、現在、
活性炭などの吸着剤を用いて吸着除去されている
が、吸着量に制限があると共に、吸着剤の再生工
程が複雑であり、そのために除去率が低く、処理
コストが極めて高いことが欠点となつている。 本発明者らは、光化学の研究過程において、波
長200〜300nmの紫外線と過酸化水素を併用する
か、または波長200nm以下の遠紫外線を照射する
ことにより、水中のトリハロメタンを酸化分解し
うることを見出した。この方法は、トリハロメタ
ンを二酸化炭素と塩化水素などに分解できるとい
うすぐれた浄化法ではあるが、飲料水や焼却燃焼
排ガス洗浄水などの大量の水を処理する方法とし
ては、有効な浄化法とはいえない。 また、本発明者らは、各種有機化合物水溶液の
放射線化学反応を研究中に、水の放射線分解によ
つて生ずるOHラジカルと水和電子が種々の物質
に作用すると、とくにOHラジカルは有機化合物
から水素原子を引き抜いて有機化合物の酸化分解
を促進し、水和電子は有機ハロゲン化合物を還元
的に分解することを見出だした。この放射線化学
的方法も有機ハロゲン化合物含有水の浄化法とし
て応用でき、原子力時代に適した水の浄化法とな
りうる可能性があるが、この方法を実用化するた
めには大線量の放射線源が必要となるなどの問題
がある。 [発明が解決しようとする問題] 本発明は、きわめて簡単な処理で効率よく水中
の有機ハロゲン化合物を無機化分解する方法を提
供することを目的とする。 [問題点を解決するための手段] 本発明は、鉛、銅または銅を主成分とする合金
(以下、特定の金属材料という)により陰極を構
成し、電極間に電流を通して水中の有機ハロゲン
化合物を無機化分解することを特徴とする有機ハ
ロゲン化合物汚染水の浄化法に関する。 [作用] 本発明における作用原理については目下詳細に
研究中であるが、水中の有機ハロゲン化合物が陰
極表面において還元的に分解されて無機化し、し
かも有機ハロゲン化合物の分解率や生成物の種類
が陰極材料の材質によつて異なることからみて、
前記特定の金属材料が触媒作用を果たしているも
のと推定される。また前記特定の金属材料がすぐ
れた有機ハロゲン化合物の分解効率を示す理由も
未だ明らかではないが、それらの金属材料は有機
ハロゲン化合物の吸着量が多く、かつ有機ハロゲ
ン化合物に対する電荷の移動を容易にするという
性質を有しており、そうした性質が重要な役割を
果たしいるものと考えられる。 [実施例] 本発明においては、陰極は前記特定の金属材料
で構成されるが、それらの金属材料は少なくとも
陰極表面に存在していればよく、必ずしも陰極全
体を前記特定の金属材料で作成する必要はない。
したがつて、たとえばプラスチツク板上に前記金
属材料をメツキしたり、金属箔を貼り付けたりす
る方法などによつて被覆したものでもよく、また
金属酸化物などと前記特定の金属材料粉とを混合
成形したものでもよい。 陽極としては、酸化することによつて水中に金
属イオンとして溶出することが不都合であるばあ
いには、溶出量の少ない材料、たとえば白金、ス
テンレス銅、炭素などにより構成するのが好まし
い。 本発明で用いる電極は、物質的方法や化学的方
法によるエツチングなどの表面処理をして電力効
率を向上させることもできる。 電極間に印加する電圧や通電量はとくに限定さ
れないが、通常0.5〜1000V、好ましくは3〜30V
の電圧で0.1〜1000A/m2、好ましくは1〜
100A/m2の電流密度で行なうことが好ましい。
また処理時間は電流密度や有機ハロゲン化合物の
濃度などによつて異なるが、通常数秒〜数十時間
でよい。 本発明の浄化法は、電極を備えたセルなどの容
器中に有機ハロゲン化合物汚染水を通して処理す
る連続法でもよいし、廃水溜などに滞留している
被処理水中に電極を浸漬して処理するバツチ法で
もよい。また、従来用いられている活性炭処理と
併用してもよい。 本発明の方法によるとときは種々の有機ハロゲ
ン化合物の無機化分解処理が可能であるが、とく
に有害なクロロホルム、ブロモジクロルメタン、
トリクロルエタン、トリクレン、パークレン、ク
ロルベンゼン、四塩化炭素、ポリ塩化ビフエニ
ル、ペンタクロロフエノールなどの脂肪族または
芳香族ハロゲン化合物の分解に有効である。これ
らの有機ハロゲン化合物は本発明の方法によつて
は無害な化合物に無機化変換される。たとえば、
クロロホルムはメタンと塩化水素に還元的に変換
され、トリクレンはエタンと塩化水素に、四塩化
炭素はメタンと塩化水素に、1,1,1−トリク
ロルエタンはエタンと塩化水素に、モノクロルベ
ンゼンはベンゼンと塩化水素に、またプロモジク
ロルメタンはメタンと塩化水素および臭化水素に
変換される。 本発明の浄化法によるときは、陰極材料の種
類、有機ハロゲン化合物の種類、濃度、電流密
度、反応時間などによつて異なるが、約70%以
上、多くは90%台の分解率がえられる。 つぎに本発明の方法を実施例および比較例に基
づいて説明するが、本発明はかかる実施例のみに
限定されるものではない。 実施例 1 陽極(極板面積52cm2)材料としてSUS−304の
ステンレス鋼を用い、陰極(極板面積52cm2)材料
として第1表に示す金属材料を用い、陽イオン交
換膜で仕切つた電解セル中にクロロホルムを
6mM濃度で含有するクロロホルム水溶液を入れ、
これを閉鎖循環系で240分間通電(電流密度5.77
×10- 4A/m2)し、432クーロンあたりのクロロ
ホルムの分解率を調べた。結果を第1表に示す。
[Industrial Application Field] The present invention relates to a method for purifying water contaminated with organic halogen compounds. [Prior Art] Currently, water is contaminated to some extent with organic halogen compounds, regardless of whether it is tap water or sewage. For example, in water supplies, water is sterilized using active chlorine compounds such as chlorine and hypochlorite. However, in the process, organic substances in the water are chlorinated by these active chlorine compounds, producing organic chlorine compounds such as trihalomethane.
Furthermore, sewage systems are also subject to inflows of trichrene and percrene, which are used in dry cleaning, as well as harmful halogen compounds generated from the incineration of municipal waste. Recent research has revealed that some of these organic halogen compounds are highly carcinogenic, which has become a serious social problem. Such organic halogen compounds in water are currently
Adsorption and removal is done using adsorbents such as activated carbon, but the amount of adsorption is limited and the regeneration process of the adsorbent is complicated, resulting in low removal rates and extremely high processing costs. ing. In the process of researching photochemistry, the present inventors discovered that trihalomethanes in water can be oxidized and decomposed by using ultraviolet rays with a wavelength of 200 to 300 nm in combination with hydrogen peroxide, or by irradiating deep ultraviolet rays with a wavelength of 200 nm or less. I found it. Although this method is an excellent purification method that can decompose trihalomethane into carbon dioxide and hydrogen chloride, it is not an effective purification method for treating large amounts of water such as drinking water or incineration flue gas cleaning water. I can't say that. In addition, while researching the radiochemical reactions of aqueous solutions of various organic compounds, the present inventors found that when OH radicals and hydrated electrons generated by radiolysis of water act on various substances, OH radicals in particular are released from organic compounds. It was discovered that oxidative decomposition of organic compounds is promoted by abstracting hydrogen atoms, and hydrated electrons reductively decompose organic halogen compounds. This radiochemical method can also be applied to purify water containing organic halogen compounds, and has the potential to become a water purification method suitable for the nuclear age, but in order to put this method into practical use, a high-dose radiation source is required. There are issues such as the need for [Problems to be Solved by the Invention] An object of the present invention is to provide a method for efficiently decomposing organic halogen compounds in water into minerals with extremely simple processing. [Means for Solving the Problems] The present invention comprises a cathode made of lead, copper, or an alloy containing copper as a main component (hereinafter referred to as a specific metal material), and a current is passed between the electrodes to remove organic halogen compounds in water. This invention relates to a method for purifying water contaminated with organic halogen compounds, which is characterized by decomposing organic halogen compounds into minerals. [Operation] The principle of operation of the present invention is currently being studied in detail, but it is clear that the organic halogen compound in water is reductively decomposed and mineralized on the cathode surface, and that the decomposition rate of the organic halogen compound and the types of products are different. Considering that it differs depending on the material of the cathode material,
It is presumed that the specific metal material plays a catalytic role. Furthermore, it is not yet clear why the above-mentioned specific metal materials exhibit excellent decomposition efficiency of organic halogen compounds, but these metal materials have a large adsorption amount of organic halogen compounds and can easily transfer charge to organic halogen compounds. It is thought that this property plays an important role. [Example] In the present invention, the cathode is composed of the above-mentioned specific metal materials, but it is sufficient that these metal materials exist at least on the surface of the cathode, and the entire cathode is not necessarily made of the above-mentioned specific metal materials. There's no need.
Therefore, for example, a plastic plate may be coated with the metal material by plating or pasting metal foil, or a metal oxide or the like may be mixed with the specific metal material powder. It may also be molded. If it is inconvenient for the anode to be eluted into water as metal ions by oxidation, it is preferable to use a material that elutes in a small amount, such as platinum, stainless steel copper, carbon, or the like. The electrode used in the present invention can also be surface-treated by physical or chemical methods such as etching to improve power efficiency. The voltage and amount of current applied between the electrodes are not particularly limited, but are usually 0.5 to 1000 V, preferably 3 to 30 V.
0.1 to 1000 A/m 2 , preferably 1 to 1000 A/m 2 at a voltage of
Preferably it is carried out at a current density of 100 A/m 2 .
Further, the treatment time varies depending on the current density, the concentration of the organic halogen compound, etc., but is usually several seconds to several tens of hours. The purification method of the present invention may be a continuous method in which organic halogen compound-contaminated water is passed through a container such as a cell equipped with an electrode, or it may be a continuous method in which the electrode is immersed in the water to be treated accumulated in a wastewater reservoir or the like. The batch method may also be used. It may also be used in combination with conventionally used activated carbon treatment. According to the method of the present invention, various organic halogen compounds can be decomposed into minerals, but especially harmful chloroform, bromodichloromethane,
Effective for decomposing aliphatic or aromatic halogen compounds such as trichloroethane, trichrene, perchlorene, chlorobenzene, carbon tetrachloride, polychlorinated biphenyl, and pentachlorophenol. These organic halogen compounds are mineralized into harmless compounds by the method of the present invention. for example,
Chloroform is reductively converted to methane and hydrogen chloride, trichlene is converted to ethane and hydrogen chloride, carbon tetrachloride is converted to methane and hydrogen chloride, 1,1,1-trichloroethane is converted to ethane and hydrogen chloride, and monochlorobenzene is converted to benzene. and hydrogen chloride, and bromodichloromethane is converted to methane and hydrogen chloride and hydrogen bromide. When using the purification method of the present invention, a decomposition rate of about 70% or more, often in the 90% range, can be obtained, although it varies depending on the type of cathode material, type of organic halogen compound, concentration, current density, reaction time, etc. . Next, the method of the present invention will be explained based on Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 Electrolysis using SUS-304 stainless steel as the material for the anode (plate area 52cm 2 ) and the metal materials shown in Table 1 as the material for the cathode (plate area 52cm 2 ) separated by a cation exchange membrane. chloroform in the cell
Add a chloroform aqueous solution containing 6mM concentration,
This is energized for 240 minutes in a closed circulation system (current density 5.77
×10 - 4 A/m 2 ), and the decomposition rate of chloroform per 432 coulombs was investigated. The results are shown in Table 1.

【表】 第1表から明らかなごとく、本発明における特
定の金属材料で陰極を構成した実施例1〜8で
は、クロロホルムの分解率および生成物の電流効
率が比較例(SUS−304)に比して数倍以上も大
きい。 実施例9〜13 被処理化合物としてクロロホルムに代えて第2
表に示す有機ハロゲン化合物を用いたほかは実施
例5と同様にして処理し、各有機ハロゲン化合物
の分解率を実施例1と同様にして調べた。結果を
第2表に示す。
[Table] As is clear from Table 1, in Examples 1 to 8 in which the cathode was constructed of a specific metal material according to the present invention, the decomposition rate of chloroform and the current efficiency of the product were compared to the comparative example (SUS-304). It is several times larger. Examples 9 to 13 The second compound was used instead of chloroform as the compound to be treated.
The treatment was carried out in the same manner as in Example 5, except that the organic halogen compounds shown in the table were used, and the decomposition rate of each organic halogen compound was examined in the same manner as in Example 1. The results are shown in Table 2.

【表】 第2から明らかなごとく、本発明の方法による
ときは、脂肪族、芳香族を問わず種々の有機ハロ
ゲン化合物を高い効率で分解できる。
[Table] As is clear from the second table, the method of the present invention can decompose various organic halogen compounds regardless of whether they are aliphatic or aromatic with high efficiency.

Claims (1)

【特許請求の範囲】[Claims] 1 鉛、銅または銅を主成分とする合金により陰
極を構成し、電極間に電流を通して水中の有機ハ
ロゲン化合物を無機化分解することを特徴とする
有機ハロゲン化合物汚染水の浄化法。
1. A method for purifying water contaminated with organic halogen compounds, characterized in that the cathode is made of lead, copper, or an alloy containing copper as a main component, and an electric current is passed between the electrodes to decompose the organic halogen compounds in the water into inorganic form.
JP4554285A 1985-03-07 1985-03-07 Cleaning up method of water contaminated with organic halogen compound Granted JPS61204082A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4554285A JPS61204082A (en) 1985-03-07 1985-03-07 Cleaning up method of water contaminated with organic halogen compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4554285A JPS61204082A (en) 1985-03-07 1985-03-07 Cleaning up method of water contaminated with organic halogen compound

Publications (2)

Publication Number Publication Date
JPS61204082A JPS61204082A (en) 1986-09-10
JPH051078B2 true JPH051078B2 (en) 1993-01-07

Family

ID=12722255

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4554285A Granted JPS61204082A (en) 1985-03-07 1985-03-07 Cleaning up method of water contaminated with organic halogen compound

Country Status (1)

Country Link
JP (1) JPS61204082A (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004016911A (en) * 2002-06-14 2004-01-22 Ohbayashi Corp Method, apparatus and system for treatment of organic chlorine compound
JP2006088009A (en) * 2004-09-22 2006-04-06 Matsushita Electric Ind Co Ltd Purification method of contamination of soil and ground water
JP4519605B2 (en) * 2004-11-04 2010-08-04 大成建設株式会社 Contaminated soil treatment apparatus and contaminated soil treatment method
ITMI20081282A1 (en) * 2008-07-15 2010-01-16 Industrie De Nora Spa PROCESS OF INDUSTRIAL WASTE TREATMENT
JP2013039270A (en) * 2011-08-18 2013-02-28 Japan Atomic Energy Agency Method for dechlorinating chlorinated aliphatic hydrocarbon compound and device for dechlorination
JP6061315B2 (en) * 2015-10-06 2017-01-18 国立研究開発法人日本原子力研究開発機構 Method and apparatus for dechlorination of chlorinated ethylenes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027745A1 (en) * 1979-10-23 1981-04-29 Creconsult Limited A process for the electrochemical degradation of persistent organic compounds, with harmful or potentially harmful properties

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027745A1 (en) * 1979-10-23 1981-04-29 Creconsult Limited A process for the electrochemical degradation of persistent organic compounds, with harmful or potentially harmful properties

Also Published As

Publication number Publication date
JPS61204082A (en) 1986-09-10

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