JP2010203930A - Method and system for treating tetrachloroethylene waste liquid containing radioactive material - Google Patents

Method and system for treating tetrachloroethylene waste liquid containing radioactive material Download PDF

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JP2010203930A
JP2010203930A JP2009050025A JP2009050025A JP2010203930A JP 2010203930 A JP2010203930 A JP 2010203930A JP 2009050025 A JP2009050025 A JP 2009050025A JP 2009050025 A JP2009050025 A JP 2009050025A JP 2010203930 A JP2010203930 A JP 2010203930A
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tetrachloroethylene
waste liquid
tetrachlorethylene
iron composite
composite particles
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JP4834871B2 (en
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Hisaaki Takagi
久承 高城
Yuji Sato
有司 佐藤
Nobuyuki Hamada
宣幸 濱田
Masayuki Takeda
正幸 竹田
Takashi Akiyama
隆司 秋山
Tomokazu Sekine
智一 関根
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Japan Atomic Energy Agency
Ebara Industrial Cleaning Co Ltd
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Japan Atomic Energy Agency
Ebara Industrial Cleaning Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive method for treating a tetrachloroethylene waste liquid containing impurities such as radioactive materials generated in nuclear facilities. <P>SOLUTION: The method for treating the tetrachloroethylene waste liquid containing radioactive materials implements the process (a) for distilling the tetrachloroethylene waste liquid containing radioactive materials and the process (b) for mixing the tetrachloroethylene obtained through the distillation, pure water and iron composite particles and decomposing the tetrachloroethylene. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、原子力施設内で発生する、放射性物質等の不純物を含有するテトラクロロエチレン廃液の処理方法と処理装置に関する。   The present invention relates to a treatment method and a treatment apparatus for a tetrachlorethylene waste liquid containing impurities such as radioactive substances generated in a nuclear facility.

テトラクロロエチレンが原子力施設内のアスファルト固化装置点検時の洗浄剤として使用されている。発生するテトラクロロエチレン廃液は、アスファルト中に取り込まれている放射性物質を含む不溶性固形物、水分、低沸点溶剤等の不純物を含有しているので、当該テトラクロロエチレン廃液は通常の産業廃棄物処理に付されない。当該テトラクロロエチレン廃液を８００℃以上の燃焼ガス中に２秒間以上滞留させ、放射性物質を含む煤煙を濾過する高温焼却法が、ダイオキシンの発生を防止する当該テトラクロロエチレン廃液の処理方法として可能である。しかしながら、当該テトラクロロエチレン廃液の発生量を考慮すると、当該高温焼却法のコストはかなり高価である。   Tetrachlorethylene is used as a cleaning agent when checking asphalt solidification equipment in nuclear facilities. Since the generated tetrachlorethylene waste liquid contains impurities such as insoluble solids containing radioactive substances incorporated in asphalt, moisture, and low boiling point solvents, the tetrachloroethylene waste liquid is not subjected to normal industrial waste treatment. A high-temperature incineration method in which the tetrachloroethylene waste liquid is retained in a combustion gas at 800 ° C. or higher for 2 seconds or longer and the soot containing radioactive material is filtered is possible as a method for treating the tetrachloroethylene waste liquid to prevent generation of dioxins. However, considering the amount of tetrachloroethylene waste liquid generated, the cost of the high temperature incineration method is quite expensive.

一方、有機ハロゲン化合物で汚染された土壌及び／又は地下水を鉄複合粒子と接触させ、有機ハロゲン化合物を分解する土壌及び／又は地下水の浄化処理方法が検討された（例えば、特許文献１参照）。   On the other hand, soil and / or groundwater contaminated with organic halogen compounds is brought into contact with iron composite particles, and a soil and / or groundwater purification method for decomposing organic halogen compounds has been studied (for example, see Patent Document 1).

特開２００４−８２１０２号公報JP 2004-82102 A

本発明が解決しようとする課題は、原子力施設内で発生する、放射性物質等の不純物を含有するテトラクロロエチレン廃液の安価な処理方法の提供である。本発明が解決しようとする別の課題は、上記処理方法を実施する装置の提供である。   The problem to be solved by the present invention is to provide an inexpensive method for treating tetrachlorethylene waste liquid containing impurities such as radioactive substances generated in nuclear facilities. Another problem to be solved by the present invention is to provide an apparatus for carrying out the above processing method.

本発明の発明者らは、上記課題を解決するために鋭意検討した結果、放射性物質を含有するテトラクロロエチレン廃液を蒸留して放射性物質とテトラクロロエチレンを分離し、蒸留によって得たテトラクロロエチレンを鉄複合粒子を使用して可燃性ガスに分解できることを見出し、本発明を完成させるに至った。   As a result of diligent investigations to solve the above-mentioned problems, the inventors of the present invention distills a tetrachloroethylene waste liquid containing a radioactive substance to separate the radioactive substance and tetrachloroethylene, and use tetrachloroethylene obtained by distillation using iron composite particles. As a result, it was found that it can be decomposed into a combustible gas, and the present invention has been completed.

本発明の放射性物質を含有するテトラクロロエチレン廃液の処理方法は、放射性物質を含有するテトラクロロエチレン廃液が蒸留される工程（ａ）、蒸留により得られたテトラクロロエチレン、純水及び鉄複合粒子が混合され、テトラクロロエチレンが分解される工程（ｂ）を実施する。   The method for treating a tetrachloroethylene waste liquid containing a radioactive substance according to the present invention includes a step (a) in which a tetrachloroethylene waste liquid containing a radioactive substance is distilled, tetrachloroethylene obtained by distillation, pure water and iron composite particles are mixed, and tetrachloroethylene is mixed. Step (b) to be decomposed is carried out.

上記工程（ｂ）における鉄複合粒子の好ましい使用量は、テトラクロロエチレン及び純水に対して０．０１〜５質量％である。上記工程（ｂ）におけるテトラクロロエチレン、純水及び鉄複合粒子を含む処理水に溶解している好ましいテトラクロロエチレン濃度は１５０〜５０００ｍｇ／ｌである。好ましくは、上記工程（ｂ）におけるテトラクロロエチレン、純水及び鉄複合粒子を含む処理水のｐＨはイオン交換樹脂で７〜９に調整される。   The preferable usage-amount of the iron composite particle in the said process (b) is 0.01-5 mass% with respect to tetrachloroethylene and a pure water. A preferable concentration of tetrachlorethylene dissolved in the treated water containing tetrachloroethylene, pure water and iron composite particles in the step (b) is 150 to 5000 mg / l. Preferably, the pH of the treated water containing tetrachloroethylene, pure water and iron composite particles in the step (b) is adjusted to 7 to 9 with an ion exchange resin.

本発明の放射性物質を含有するテトラクロロエチレン廃液の処理装置は、放射性物質を含有するテトラクロロエチレン廃液を蒸留する蒸留器、蒸留により得られたテトラクロロエチレン、純水及び鉄複合粒子を混合し、テトラクロロエチレンを分解する分解槽ユニットを含む。好ましくは、分解槽にテトラクロロエチレンを注入するポンプ、攪拌機、イオン交換樹脂塔及び排気ダクトが上記分解槽ユニットに付加される。   The apparatus for treating a tetrachloroethylene waste liquid containing a radioactive substance according to the present invention is a distillation apparatus for distilling a tetrachloroethylene waste liquid containing a radioactive substance, mixing tetrachloroethylene obtained by distillation, pure water and iron composite particles, and decomposing to decompose tetrachloroethylene Includes tank unit. Preferably, a pump for injecting tetrachlorethylene into the decomposition tank, a stirrer, an ion exchange resin tower, and an exhaust duct are added to the decomposition tank unit.

本発明の放射性物質を含有するテトラクロロエチレン廃液の処理方法は、放射性物質を含有するテトラクロロエチレン廃液からテトラクロロエチレンを分離し、可燃性ガスに分解する一連の工程を安価に実施できる。本発明の放射性物質を含有するテトラクロロエチレン廃液の処理装置は簡素で小型であり、上記一連の工程を安価に実施できる。   The method for treating a tetrachloroethylene waste liquid containing a radioactive substance according to the present invention can perform a series of steps for separating tetrachloroethylene from a tetrachloroethylene waste liquid containing a radioactive substance and decomposing it into a combustible gas at a low cost. The tetrachloroethylene waste liquid treatment apparatus containing the radioactive substance of the present invention is simple and small in size, and can perform the above-described series of processes at low cost.

放射性物質を含有するテトラクロロエチレン廃液処理システムを示す図Diagram showing a tetrachlorethylene waste liquid treatment system containing radioactive substances

以下、本発明の好ましい実施態様を表す図面を示し、本発明を詳細に説明する。
図１は、放射性物質を含有するテトラクロロエチレン廃液処理システムを示す図である。図中、１はテトラクロロエチレン廃液貯蔵タンク、２はテトラクロロエチレン廃液移送ポンプ、３は蒸留器を備える蒸留塔、４は不純物回収容器、５はテトラクロロエチレン回収タンク、６はテトラクロロエチレン注入ポンプ、７は攪拌機、８は攪拌機モーター、９は処理水移送ポンプ、１０は鉄複合粒子、１１は処理水、１２は鉄複合粒子移送ポンプ、１３は排気ダクト、１４はイオン交換樹脂塔、１５は分解槽、１６は分解槽ユニット、１７は可燃性ガスセンサー、１８は排気装置を示す。 Hereinafter, the present invention will be described in detail with reference to the drawings showing preferred embodiments of the present invention.
FIG. 1 is a diagram showing a tetrachlorethylene waste liquid treatment system containing a radioactive substance. In the figure, 1 is a tetrachlorethylene waste liquid storage tank, 2 is a tetrachloroethylene waste liquid transfer pump, 3 is a distillation tower equipped with a distiller, 4 is an impurity recovery container, 5 is a tetrachloroethylene recovery tank, 6 is a tetrachloroethylene injection pump, 7 is a stirrer, 8 is Stirrer motor, 9 treated water transfer pump, 10 iron composite particles, 11 treated water, 12 iron composite particle transfer pump, 13 exhaust duct, 14 ion exchange resin tower, 15 decomposition tank, 16 decomposition tank A unit, 17 is a combustible gas sensor, and 18 is an exhaust device.

テトラクロロエチレン廃液貯蔵タンク１に貯蔵されている放射性物質等の不純物を含有するテトラクロロエチレン廃液が、テトラクロロエチレン廃液移送ポンプ２により蒸留器を備える蒸留塔３に移送され、蒸留によりテトラクロロエチレンと放射性物質等の不純物が分離される。蒸留温度は、テトラクロロエチレンの沸点である１２１℃前後であり、好ましくは１２５℃近傍である。蒸留器は特定の型に限定されない。温度制御のし易さの観点から、好ましい蒸留器は電気加熱型蒸留器である。蒸留は複数回繰り返し行われ得る。蒸留により得られるテトラクロロエチレンの純度は蒸留の繰り返しにより向上する。なお、上記テトラクロロエチレン廃液中の不純物は、蒸留の前に濾過等により除去され得る。   Tetrachloroethylene waste liquid containing impurities such as radioactive substances stored in the tetrachloroethylene waste liquid storage tank 1 is transferred to a distillation tower 3 equipped with a distiller by a tetrachloroethylene waste liquid transfer pump 2, and the impurities such as tetrachloroethylene and radioactive substances are separated by distillation. Is done. The distillation temperature is around 121 ° C., which is the boiling point of tetrachlorethylene, and preferably around 125 ° C. The distiller is not limited to a particular type. From the viewpoint of ease of temperature control, a preferred distiller is an electric heating distiller. The distillation can be repeated multiple times. The purity of tetrachloroethylene obtained by distillation is improved by repeated distillation. The impurities in the tetrachlorethylene waste liquid can be removed by filtration or the like before distillation.

上記テトラクロロエチレン廃液から分離された不純物は、不純物回収容器４に回収される。上記テトラクロロエチレン廃液から分離されたテトラクロロエチレンは、テトラクロロエチレン回収タンク５に回収される。   Impurities separated from the tetrachlorethylene waste liquid are collected in the impurity collection container 4. Tetrachloroethylene separated from the tetrachlorethylene waste liquid is recovered in the tetrachlorethylene recovery tank 5.

放射性物質を含有するテトラクロロエチレン廃液が蒸留される上記工程は、連続式であってもバッチ式であってもよい。   The above-mentioned process in which the tetrachlorethylene waste liquid containing the radioactive substance is distilled may be a continuous type or a batch type.

テトラクロロエチレン回収タンク５に回収されたテトラクロロエチレンは、純水及び鉄複合粒子と混合される。これらの混合方法は限定されない。これらの混合方法の具体例は以下のとおりである。鉄複合粒子１０が分解槽１５に張り込まれた純水に投入され、攪拌機モーター８により運転される攪拌機７により攪拌される。次に、テトラクロロエチレン回収タンク５に回収されたテトラクロロエチレンが、分解槽１５にテトラクロロエチレンを注入するポンプであるテトラクロロエチレン注入ポンプ６により、分解槽１５に注入される。   Tetrachloroethylene recovered in the tetrachlorethylene recovery tank 5 is mixed with pure water and iron composite particles. These mixing methods are not limited. Specific examples of these mixing methods are as follows. The iron composite particles 10 are put into pure water stuck in the decomposition tank 15 and stirred by the stirrer 7 operated by the stirrer motor 8. Next, the tetrachlorethylene collected in the tetrachlorethylene recovery tank 5 is injected into the decomposition tank 15 by a tetrachlorethylene injection pump 6 which is a pump for injecting tetrachloroethylene into the decomposition tank 15.

本明細書の鉄複合粒子は、α−ＦｅからなるコアがＦｅ3Ｏ4からなるシェルで被覆される構造を有する粒子である。鉄複合粒子は市販されており、還元性に富む粒子である。鉄複合粒子の具体例は、戸田工業（株）製ＲＮＩＰ（平均粒子径７０ｎｍ、比表面積３０ｍ2／ｇの鉄複合粒子のスラリー）である。 The iron composite particles of the present specification are particles having a structure in which a core made of α-Fe is covered with a shell made of Fe 3 O 4 . Iron composite particles are commercially available and are highly reducible particles. A specific example of the iron composite particles is RNIP (a slurry of iron composite particles having an average particle diameter of 70 nm and a specific surface area of 30 m 2 / g) manufactured by Toda Kogyo Co., Ltd.

鉄複合粒子の使用量は特定の範囲に限定されない。好ましい当該使用量は、テトラクロロエチレン及び純水に対して０．０１〜５質量％である。   The amount of iron composite particles used is not limited to a specific range. The said preferable usage-amount is 0.01-5 mass% with respect to tetrachloroethylene and pure water.

テトラクロロエチレンが分解槽１５中の純水に注入される際、純水に溶解するテトラクロロエチレン濃度は特定の範囲に限定されない。好ましい当該濃度はテトラクロロエチレン飽和濃度（１５０ｍｇ／ｌ）〜５０００ｍｇ／ｌである。   When tetrachlorethylene is injected into the pure water in the decomposition tank 15, the concentration of tetrachlorethylene dissolved in the pure water is not limited to a specific range. The preferred concentration is tetrachloroethylene saturated concentration (150 mg / l) to 5000 mg / l.

水相中のテトラクロロエチレンが鉄複合粒子に接触すると、テトラクロロエチレンが分解される。本明細書のテトラクロロエチレンの分解は、テトラクロロエチレンが化学反応により可燃性ガスに変換されることである。可燃性ガスの主成分はエチレンガスであると考えられる。純水に溶解しているテトラクロロエチレン濃度はテトラクロロエチレンの分解により低下していくが、当該濃度が所定濃度以上に保たれるように、テトラクロロエチレン回収タンク５に回収されたテトラクロロエチレンが分解槽１５に注入され、テトラクロロエチレンの分解速度は所定の速度以上に保たれる。なお、鉄複合粒子が利用されるテトラクロロエチレンの分解は水相で可能であるが、テトラクロロエチレンに鉄複合粒子を投入してもテトラクロロエチレンは分解されない。   When tetrachlorethylene in the aqueous phase comes into contact with the iron composite particles, tetrachloroethylene is decomposed. The decomposition of tetrachlorethylene in this specification is that tetrachlorethylene is converted into a combustible gas by a chemical reaction. The main component of the combustible gas is considered to be ethylene gas. The concentration of tetrachlorethylene dissolved in the pure water decreases due to the decomposition of tetrachlorethylene, but the tetrachlorethylene recovered in the tetrachlorethylene recovery tank 5 is injected into the decomposition tank 15 so that the concentration is maintained at a predetermined concentration or higher. The decomposition rate of tetrachlorethylene is kept above a predetermined rate. In addition, although the decomposition | disassembly of the tetrachloroethylene using an iron composite particle is possible in an aqueous phase, even if an iron composite particle is thrown into tetrachloroethylene, tetrachloroethylene is not decomposed | disassembled.

テトラクロロエチレンの分解により発生する可燃性ガスは排気ダクト１３により排気装置１８に排気される。可燃性ガスセンサー１７が排気装置１８の入口に設置されており、可燃性ガス濃度が基準値を超えた場合、テトラクロロエチレン注入ポンプ６及び攪拌機モーター８は停止され、テトラクロロエチレンの分解によるエチレン等のガスの発生が抑制される。   The combustible gas generated by the decomposition of tetrachloroethylene is exhausted to the exhaust device 18 by the exhaust duct 13. When the combustible gas sensor 17 is installed at the inlet of the exhaust device 18 and the combustible gas concentration exceeds the reference value, the tetrachloroethylene injection pump 6 and the agitator motor 8 are stopped, and the gas such as ethylene due to the decomposition of the tetrachloroethylene is stopped. Occurrence is suppressed.

塩酸がテトラクロロエチレンの分解により生成すると考えられ、分解槽１５中の処理水１１のｐＨが低下し、鉄複合粒子が溶解されてくる。そこで、処理水１１のｐＨの低下を抑制するため、処理水１１が処理水移送ポンプ９によりイオン交換樹脂塔１４に移送され、処理水１１のｐＨが７〜９に調整される。   It is considered that hydrochloric acid is generated by the decomposition of tetrachloroethylene, the pH of the treated water 11 in the decomposition tank 15 is lowered, and the iron composite particles are dissolved. Then, in order to suppress the fall of pH of the treated water 11, the treated water 11 is transferred to the ion exchange resin tower 14 by the treated water transfer pump 9, and the pH of the treated water 11 is adjusted to 7-9.

テトラクロロエチレンの分解により発生する可燃性ガスの濃度が、初期濃度に比べて著しく低下している場合、鉄複合粒子１０が劣化していると考えられる。そこで、鉄複合粒子１０が鉄複合粒子移送ポンプ１２により分解槽１５から排出される。その際、処理水１１の排出は極力抑えられる。その後、新しい鉄複合粒子が分解槽１５に投入される。   When the concentration of the combustible gas generated by the decomposition of tetrachloroethylene is significantly lower than the initial concentration, it is considered that the iron composite particles 10 are deteriorated. Therefore, the iron composite particles 10 are discharged from the decomposition tank 15 by the iron composite particle transfer pump 12. At that time, discharge of the treated water 11 is suppressed as much as possible. Thereafter, new iron composite particles are introduced into the decomposition tank 15.

蒸留により得られたテトラクロロエチレン、純水及び鉄複合粒子が混合され、テトラクロロエチレンが分解される工程は、連続式であってもバッチ式であってもよい。   The process in which tetrachloroethylene, pure water, and iron composite particles obtained by distillation are mixed and tetrachloroethylene is decomposed may be a continuous process or a batch process.

以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されない。（１）テトラクロロエチレン廃液中のテトラクロロエチレン濃度及び（２）ガスクロマトグラフィーによるテトラクロロエチレン濃度の測定方法は、それぞれ以下のとおりである。   EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. (1) Tetrachlorethylene concentration in the tetrachlorethylene waste liquid and (2) Tetrachloroethylene concentration measurement methods by gas chromatography are as follows.

（１）テトラクロロエチレン廃液中のテトラクロロエチレン濃度の測定方法
テトラクロロエチレン廃液が、（株）スギヤマゲン製の有機塩素系化合物用蒸留器に注入され、次いで、留分が回収できなくなるか又は１５０℃に達するまで蒸留された。テトラクロロエチレン濃度は以下の式（ａ）により計算された。
テトラクロロエチレン濃度＝留分量／テトラクロロエチレン廃液注入量×１００（％）
・・・（ａ） (1) Method for measuring tetrachlorethylene concentration in tetrachlorethylene waste liquor Tetrachloroethylene waste liquor is poured into a distiller for organochlorine compounds manufactured by Sgiamagen and then distilled until the fraction cannot be recovered or reaches 150 ° C. It was. The tetrachlorethylene concentration was calculated by the following formula (a).
Tetrachloroethylene concentration = fraction amount / tetrachloroethylene waste liquid injection amount x 100 (%)
... (a)

（２）ガスクロマトグラフィーによるテトラクロロエチレン濃度の測定方法
ジーエルサイエンス（株）製ＧＣ−４０００型がガスクロマトグラフ装置として使用され、使用カラムがＩｎｅｒｔＣａｐ１、注入口温度及び検出器温度が２４０℃、オーブン昇温が１００〜２２０℃、昇温速度が４０℃／分という条件で、テトラクロロエチレン濃度が測定された。 (2) Method for measuring tetrachloroethylene concentration by gas chromatography GC-4000 type manufactured by GL Sciences Inc. is used as a gas chromatograph device, the column used is InertCap1, the inlet temperature and detector temperature are 240 ° C, and the oven temperature rises Tetrachloroethylene concentration was measured under the conditions of 100 to 220 ° C. and a temperature increase rate of 40 ° C./min.

実施例１
原子力施設内のアスファルト固化装置点検時の洗浄で発生した１０種類のテトラクロロエチレン廃液が蒸留され、これらの廃液中のテトラクロロエチレン濃度がそれぞれ測定された。その結果を表１に示す。なお、テトラクロロエチレンは表１〜５においてＣ2Ｃｌ4と表記されている。 Example 1
Ten types of tetrachlorethylene waste liquids generated by washing during inspection of asphalt solidification equipment in nuclear facilities were distilled, and the concentrations of tetrachlorethylene in these waste liquids were measured. The results are shown in Table 1. Tetrachloroethylene is represented as C 2 Cl 4 in Tables 1-5.

Figure 2010203930
Figure 2010203930

Ｎｏ．６〜１０のテトラクロロエチレン廃液が蒸留されて得られる残渣の量は、Ｎｏ．１〜５のテトラクロロエチレン廃液が蒸留されて得られる残渣の量より多かった。従って、Ｎｏ．６〜１０のテトラクロロエチレン廃液中のアスファルト等の不純物の含有量は、Ｎｏ．１〜５のテトラクロロエチレン廃液中の不純物の含有量より多いと考えられる。
１０種類のテトラクロロエチレン廃液が蒸留されて得られた留分中のテトラクロロエチレンの濃度が、ガスクロマトグラフィーにより測定された。その結果を表２に示す。 No. The amount of residue obtained by distilling 6 to 10 tetrachlorethylene waste liquor is 1-5 tetrachlorethylene waste liquor was more than the amount of residue obtained by distillation. Therefore, no. The content of impurities such as asphalt in the 6 to 10 tetrachlorethylene waste liquid is No. 1. It is thought that there is more content of the impurity in 1-5 tetrachlorethylene waste liquid.
The concentration of tetrachlorethylene in the fraction obtained by distilling 10 types of tetrachlorethylene waste liquid was measured by gas chromatography. The results are shown in Table 2.

Figure 2010203930
Figure 2010203930

１０種類のテトラクロロエチレン廃液がそれぞれ蒸留されて得られた留分中のテトラクロロエチレンの濃度は、ほぼ１００％であった。更に、これらの留分中の不純物はトリクロロエチレンであると判明した。トリクロロエチレンは、原子力施設のアスファルト固化装置点検時の洗浄に使用されたテトラクロロエチレンに含まれていたと考えられる。   The concentration of tetrachlorethylene in the fractions obtained by distilling each of the 10 types of tetrachlorethylene waste liquid was almost 100%. Furthermore, the impurity in these fractions was found to be trichlorethylene. Trichlorethylene is considered to have been contained in the tetrachlorethylene used for cleaning during the inspection of the asphalt solidification equipment at the nuclear facility.

実施例２
テトラクロロエチレンが純水に注入されて攪拌され、更に、得られた混合物に鉄複合粒子を含むスラリーである戸田工業（株）製ＲＮＩＰが投入され、攪拌された。鉄複合粒子が投入された直後の処理水中のテトラクロロエチレン濃度が３００ｍｇ／ｌ、テトラクロロエチレン及び純水に対する鉄複合粒子の使用量が１又は５質量％に調整された。鉄複合粒子が投入されてから４８時間後の処理水中のテトラクロロエチレン濃度がガスクロマトグラフィーにより測定された。その結果を表３に示す。 Example 2
Tetrachloroethylene was poured into pure water and stirred, and RNIP manufactured by Toda Kogyo Co., Ltd., which is a slurry containing iron composite particles, was added to the resulting mixture and stirred. The tetrachloroethylene concentration in the treated water immediately after the iron composite particles were charged was 300 mg / l, and the amount of the iron composite particles used relative to tetrachloroethylene and pure water was adjusted to 1 or 5% by mass. The concentration of tetrachlorethylene in the treated water 48 hours after the introduction of the iron composite particles was measured by gas chromatography. The results are shown in Table 3.

Figure 2010203930
Figure 2010203930

テトラクロロエチレン及び純水に対する鉄複合粒子の使用量が１質量％に調整された処理水中のテトラクロロエチレン濃度、同じく５質量％に調整された処理水中のテトラクロロエチレン濃度は、共に検出限界である１０ｐｐｍ未満となった。   The tetrachlorethylene concentration in the treated water in which the amount of the iron composite particles used relative to tetrachlorethylene and pure water was adjusted to 1% by mass, and the tetrachlorethylene concentration in the treated water also adjusted to 5% by mass were both below the detection limit of 10 ppm. .

実施例３
テトラクロロエチレンが純水に注入されて攪拌され、更に、得られた混合物に鉄複合粒子を含むスラリーである戸田工業（株）製ＲＮＩＰが投入され、攪拌された。鉄複合粒子が投入された直後の処理水中のテトラクロロエチレン濃度が１６００ｍｇ／ｌ、テトラクロロエチレン及び純水に対する鉄複合粒子の使用量が０．０１質量％、０．０５質量％又は０．１質量％に調整された。鉄複合粒子が投入されてから８９．５時間後及び９５時間後の処理水中のテトラクロロエチレン濃度がガスクロマトグラフィーにより測定された。その結果を表４に示す。 Example 3
Tetrachloroethylene was poured into pure water and stirred, and RNIP manufactured by Toda Kogyo Co., Ltd., which is a slurry containing iron composite particles, was added to the resulting mixture and stirred. The tetrachloroethylene concentration in the treated water immediately after the iron composite particles are charged is 1600 mg / l, and the amount of the iron composite particles used for tetrachloroethylene and pure water is adjusted to 0.01 mass%, 0.05 mass%, or 0.1 mass%. It was done. The tetrachlorethylene concentration in the treated water 89.5 hours and 95 hours after the introduction of the iron composite particles was measured by gas chromatography. The results are shown in Table 4.

Figure 2010203930
Figure 2010203930

テトラクロロエチレン及び純水に対する鉄複合粒子の使用量が０．０１質量％に調整された処理水中のテトラクロロエチレン濃度、同じく０．０５質量％に調整された処理水中のテトラクロロエチレン濃度、同じく０．１質量％に調整された処理水中のテトラクロロエチレン濃度は、いずれも９５時間後には検出限界である１０ｐｐｍ未満となった。   Tetrachloroethylene concentration in the treated water adjusted to 0.01% by mass, the tetrachlorethylene concentration in the treated water adjusted to 0.05% by mass, and also 0.1% by mass with respect to tetrachloroethylene and pure water The tetrachlorethylene concentration in the adjusted treated water was less than the detection limit of 10 ppm after 95 hours.

実施例４
テトラクロロエチレンが純水に注入されて攪拌され、更に、得られた混合物に鉄複合粒子を含むスラリーである戸田工業（株）製ＲＮＩＰが投入され、攪拌された。鉄複合粒子が投入された直後の処理水中のテトラクロロエチレン濃度が２０００ｍｇ／ｌ又は５０００ｍｇ／ｌ、テトラクロロエチレン及び純水に対する鉄複合粒子の使用量が０．１質量％に調整された。鉄複合粒子が投入された直後の処理水のｐＨ、鉄複合粒子がテトラクロロエチレン濃度２０００ｍｇ／ｌの処理水、テトラクロロエチレン濃度５０００ｍｇ／ｌの処理水に投入されてからそれぞれ１２０時間後、１７０時間後の処理水のｐＨが（株）堀場製作所製ｐＨメーターＴ−５４で測定された。その結果を表５に示す。 Example 4
Tetrachloroethylene was poured into pure water and stirred, and RNIP manufactured by Toda Kogyo Co., Ltd., which is a slurry containing iron composite particles, was added to the resulting mixture and stirred. The tetrachloroethylene concentration in the treated water immediately after the iron composite particles were charged was 2000 mg / l or 5000 mg / l, and the amount of the iron composite particles used relative to tetrachloroethylene and pure water was adjusted to 0.1% by mass. Treatment pH immediately after the iron composite particles were added, treatment after 120 hours and 170 hours after the iron composite particles were added to the treated water having a tetrachlorethylene concentration of 2000 mg / l and the treated water having a tetrachlorethylene concentration of 5000 mg / l, respectively. The pH of water was measured with a pH meter T-54 manufactured by Horiba, Ltd. The results are shown in Table 5.

Figure 2010203930
Figure 2010203930

鉄複合粒子が投入された直後の処理水中のテトラクロロエチレン濃度が２０００ｍｇ／ｌの処理水のｐＨ、同じく５０００ｍｇ／ｌの処理水のｐＨは共に低下した。上記処理水のｐＨの低下の原因は、テトラクロロエチレンの分解により発生した塩素イオンによる塩酸の生成であると考えられる。従って、鉄複合粒子の劣化防止の観点から、テトラクロロエチレン、純水及び鉄複合粒子を含む処理水のｐＨを７〜９に保つため、好ましくは、当該処理水がイオン交換樹脂で処理される。   The pH of the treated water having a tetrachlorethylene concentration of 2000 mg / l in the treated water immediately after the iron composite particles were charged and the pH of the treated water having the same 5000 mg / l decreased. The cause of the decrease in the pH of the treated water is considered to be the production of hydrochloric acid by chlorine ions generated by the decomposition of tetrachloroethylene. Therefore, from the viewpoint of preventing deterioration of the iron composite particles, the treated water is preferably treated with an ion exchange resin in order to maintain the pH of the treated water containing tetrachloroethylene, pure water, and iron composite particles at 7-9.

本発明の放射性物質を含有するテトラクロロエチレン廃液の処理方法及び処理装置は、放射性物質等の不純物を含有するテトラクロロエチレン廃液の安価の処理に好適である。   The method and apparatus for treating tetrachlorethylene waste liquid containing a radioactive substance of the present invention is suitable for inexpensive treatment of tetrachloroethylene waste liquid containing impurities such as radioactive substances.

１…テトラクロロエチレン廃液貯蔵タンク、２…テトラクロロエチレン廃液移送ポンプ、３…蒸留塔、４…不純物回収容器、５…テトラクロロエチレン回収タンク、６…テトラクロロエチレン注入ポンプ、７…攪拌機、８…攪拌機モーター、９…処理水移送ポンプ、１０…鉄複合粒子、１１…処理水、１２…鉄複合粒子移送ポンプ、１３…排気ダクト、１４…イオン交換樹脂塔、１５…分解槽、１６…分解槽ユニット、１７…可燃性ガスセンサー、１８…排気装置 DESCRIPTION OF SYMBOLS 1 ... Tetrachloroethylene waste liquid storage tank, 2 ... Tetrachloroethylene waste liquid transfer pump, 3 ... Distillation tower, 4 ... Impurity collection container, 5 ... Tetrachloroethylene collection tank, 6 ... Tetrachloroethylene injection pump, 7 ... Stirrer, 8 ... Stirrer motor, 9 ... Treated water Transfer pump, 10 ... iron composite particles, 11 ... treated water, 12 ... iron composite particle transfer pump, 13 ... exhaust duct, 14 ... ion exchange resin tower, 15 ... decomposition tank, 16 ... decomposition tank unit, 17 ... combustible gas Sensor, 18 ... exhaust system

Claims (6)

放射性物質を含有するテトラクロロエチレン廃液が蒸留される工程（ａ）、
蒸留により得られたテトラクロロエチレン、純水及び鉄複合粒子が混合され、テトラクロロエチレンが分解される工程（ｂ）が実施される、放射性物質を含有するテトラクロロエチレン廃液の処理方法。 A step (a) in which a tetrachlorethylene waste liquid containing a radioactive substance is distilled;
A method for treating a tetrachlorethylene waste liquid containing a radioactive substance, wherein step (b) in which tetrachloroethylene obtained by distillation, pure water, and iron composite particles are mixed and tetrachloroethylene is decomposed is performed. 上記工程（ｂ）における鉄複合粒子の使用量が、テトラクロロエチレン及び純水に対して０．０１〜５質量％である、請求項１に記載された放射性物質を含有するテトラクロロエチレン廃液の処理方法。 The processing method of the tetrachloroethylene waste liquid containing the radioactive substance of Claim 1 whose usage-amount of the iron composite particle in the said process (b) is 0.01-5 mass% with respect to tetrachloroethylene and a pure water. 上記工程（ｂ）におけるテトラクロロエチレン、純水及び鉄複合粒子を含む処理水に溶解しているテトラクロロエチレン濃度が１５０〜５０００ｍｇ／ｌである、請求項１又は２に記載された放射性物質を含有するテトラクロロエチレン廃液の処理方法。 Tetrachloroethylene waste solution containing a radioactive substance according to claim 1 or 2, wherein the concentration of tetrachloroethylene dissolved in the treated water containing tetrachloroethylene, pure water and iron composite particles in the step (b) is 150 to 5000 mg / l. Processing method. 上記工程（ｂ）におけるテトラクロロエチレン、純水及び鉄複合粒子を含む処理水のｐＨをイオン交換樹脂で７〜９に調整する、請求項１〜３のいずれか１項に記載された放射性物質を含有するテトラクロロエチレン廃液の処理方法。 The radioactive substance according to any one of claims 1 to 3, wherein the pH of the treated water containing tetrachloroethylene, pure water and iron composite particles in the step (b) is adjusted to 7 to 9 with an ion exchange resin. To treat tetrachlorethylene waste liquid. 放射性物質を含有するテトラクロロエチレン廃液を蒸留する蒸留器、蒸留により得られたテトラクロロエチレン、純水及び鉄複合粒子を混合し、テトラクロロエチレンを分解する分解槽ユニットを含む、放射性物質を含有するテトラクロロエチレン廃液の処理装置。 Distiller for distilling tetrachloroethylene waste liquid containing radioactive material, treatment equipment for tetrachlorethylene waste liquid containing radioactive material, including a decomposition tank unit for decomposing tetrachloroethylene by mixing tetrachloroethylene obtained by distillation, pure water and iron composite particles . 分解槽にテトラクロロエチレンを注入するポンプ、攪拌機、イオン交換樹脂塔及び排気ダクトが上記分解槽ユニットに付加されている、請求項５に記載された放射性物質を含有するテトラクロロエチレン廃液の処理装置。 6. The apparatus for treating a tetrachlorethylene waste liquid containing a radioactive substance according to claim 5, wherein a pump for injecting tetrachlorethylene into the decomposition tank, a stirrer, an ion exchange resin tower and an exhaust duct are added to the decomposition tank unit.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013039270A (en) * 2011-08-18 2013-02-28 Japan Atomic Energy Agency Method for dechlorinating chlorinated aliphatic hydrocarbon compound and device for dechlorination
JP2014001957A (en) * 2012-06-15 2014-01-09 Swing Corp Method and device for decontamination of radioactive waste liquid
JP2016040036A (en) * 2015-10-06 2016-03-24 国立研究開発法人日本原子力研究開発機構 Dechlorination method and dechlorination device for chlorinated ethylene

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JP2004082102A (en) * 2002-07-03 2004-03-18 Toda Kogyo Corp Purification agent and its production method for soil and groundwater polluted with organic halide, and purification method of soil and groundwater polluted with organic halide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013039270A (en) * 2011-08-18 2013-02-28 Japan Atomic Energy Agency Method for dechlorinating chlorinated aliphatic hydrocarbon compound and device for dechlorination
JP2014001957A (en) * 2012-06-15 2014-01-09 Swing Corp Method and device for decontamination of radioactive waste liquid
JP2016040036A (en) * 2015-10-06 2016-03-24 国立研究開発法人日本原子力研究開発機構 Dechlorination method and dechlorination device for chlorinated ethylene

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