JP2006296608A

JP2006296608A - Method and apparatus for removing halogenated organic compound by ionic liquid

Info

Publication number: JP2006296608A
Application number: JP2005120422A
Authority: JP
Inventors: Mitsumasa Taguchi; 光正田口; Machiko Takigami; 眞知子瀧上; Takuji Kojima; 拓治小嶋; Atsushi Kimura; 敦木村
Original assignee: Japan Atomic Energy Agency
Current assignee: Japan Atomic Energy Agency
Priority date: 2005-04-18
Filing date: 2005-04-18
Publication date: 2006-11-02
Anticipated expiration: 2025-04-18
Also published as: JP4646685B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide a a method for decomposing treatment of an organic compound in liquid and gas which is inexpensively performed, highly effective, and has a reduced environmental load. <P>SOLUTION: A method for removing the organic compound includes the following steps (1) and (2). In the step (1), an ionic liquid is brought into contact with the gas or liquid containing the organic compound to extract the organic compound to the ionic liquid to purify the gas. In the step (2), the organic compound extracted to the ionic liquid is decomposed by irradiation or electric field application to make the ionic liquid harmless. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

この出願の発明は、有機化合物に汚染された気体と液体の浄化方法、および、これらの方法を用いた処理装置に関するものである。より詳しくは、有機化合物を含有する気体または液体から、イオン性液体を利用して有機化合物を抽出・除去し、これを無害化処理する浄化方法に関するものである。 The invention of this application relates to a method for purifying gas and liquid contaminated with an organic compound, and a treatment apparatus using these methods. More specifically, the present invention relates to a purification method for extracting and removing an organic compound from a gas or liquid containing the organic compound using an ionic liquid and detoxifying it.

ダイオキシンや内分泌かく乱物質をはじめとするハロゲン化有機化合物やその他有害な有機化合物の処理方法として、溶液中の有機化合物をイオン性液体で抽出し処理する方法（特許文献１）がある。この方法においては、イオン性液体を使用して溶液中の有機化合物を液―液二相分配で抽出を行い、減圧下でイオン性液体中に取り込んだ有機化合物を揮発させ、発生した気体を放射線で分解処理する。イオン性液体より抽出した有機化合物は一旦揮発させて処理することから、揮発性の低い有機化合物の処理には適していなかった。さらに、有機化合物を揮発させずにそのままイオン性液体を放射線で直接処理することは技術的には可能であるものの、有機化合物の十分な分解を得るためには大量の放射線を照射する必要があり、この照射に伴ってイオン性液体の著しく分解劣化し、新たな有害物質が発生するため、非効率で処理コストが高いという欠点があった。 As a method for treating halogenated organic compounds such as dioxins and endocrine disrupting substances and other harmful organic compounds, there is a method of extracting an organic compound in a solution with an ionic liquid (Patent Document 1). In this method, an ionic liquid is used to extract an organic compound in solution by liquid-liquid two-phase partitioning, the organic compound taken into the ionic liquid is volatilized under reduced pressure, and the generated gas is radiated. Disassemble with. Since the organic compound extracted from the ionic liquid is once volatilized and processed, it was not suitable for processing an organic compound having low volatility. Furthermore, although it is technically possible to directly treat an ionic liquid with radiation without volatilizing the organic compound, it is necessary to irradiate a large amount of radiation to obtain sufficient decomposition of the organic compound. The ionic liquid is significantly decomposed and deteriorated with this irradiation, and new harmful substances are generated. Therefore, there is a disadvantage that the treatment cost is inefficient.

いっぽう、気体中の有害有機化合物の処理には、活性炭吸着による除去方法や、熱処理による分解方法などがある。前者は吸着した有害有機化合物を無害化するための後処理が必要であることから処理コストが高く、活性炭の定期的な交換が必要なためメンテナンス性にも問題があった。また、後者は高温処理を必要とするため装置および稼動コストが高いという問題があった。いっぽうで、気体中の有害有機化合物の直接的な処理方法として、放射線を汚染気体に直接照射にする方法（特許文献２）がある。この方法では、電子線を照射した空気を排ガスに混入することで処理効率は増加するものの、同時に環境負荷の高いＮＯ_Ｘが発生・増加し、排ガスの後処理が必要であるという欠点があった。
特開２００４−３１３９３２号公報特開２００４−０９８０３５号公報 On the other hand, the treatment of harmful organic compounds in gas includes a removal method by activated carbon adsorption and a decomposition method by heat treatment. Since the former requires post-treatment for detoxifying the adsorbed harmful organic compounds, the treatment cost is high, and there is a problem in maintainability because the activated carbon needs to be replaced periodically. Moreover, since the latter requires a high temperature process, there existed a problem that an apparatus and operation cost were high. On the other hand, as a direct processing method for harmful organic compounds in a gas, there is a method (Patent Document 2) in which radiation is directly irradiated onto a contaminated gas. Although this method increases the processing efficiency by mixing the air irradiated with the electron beam into the exhaust gas, there is a drawback in that NO _X with high environmental load is generated and increased at the same time, and exhaust gas post-treatment is required. .
JP 2004-313932 A JP 2004-098035 A

この出願の発明は、液体および気体中の有機化合物の分解処理方法であって、安価で実施可能な高効率で環境負荷の低い処理方法を提供することを課題とする。 An object of the invention of this application is to provide a method for decomposing an organic compound in a liquid and a gas, which can be carried out at a low cost and has a high efficiency and a low environmental load.

この出願の発明者らは、上記の問題を解決するため鋭意研究を行った結果、イオン性液体が有する性質を利用した分離技術と、放射線照射や電場印加による有機化合物の分解技術とを組み合わせて使用する、液体および気体中の有機化合物の分解処理方法を完成させた。 The inventors of this application, as a result of earnest research to solve the above problems, combined a separation technique using the properties of an ionic liquid with a technique for decomposing organic compounds by radiation irradiation or electric field application. The method for decomposing organic compounds in liquids and gases was completed.

すなわち、この出願の発明は、第１には、以下のステップ（１）（２）
（１）有機化合物を含有する気体にイオン性液体を接触させ、有機化合物をイオン性液体へ抽出し気体を浄化するステップ、
（２）イオン性液体に抽出された有機化合物を分解し、イオン性液体を無害化するステップ。
からなることを特徴とする気体中の有機化合物の除去方法を提供する。第２には、ステップ（２）における有機化合物の分解操作が、イオン性液体に放射線照射することにより行われることを特徴とする前記の気体中の有機化合物の除去を提供する。第３には、ステップ（２）における有機化合物の分解操作が、イオン性液体に電場を印加することにより行われることを特徴とする前記の気体中の有機化合物の除去方法を提供する。第４には、ステップ（２）において無害化されたイオン性液体を、ステップ（１）におけるイオン性液体として再利用することを特徴とする前記の気体中の有機化合物の除去方法を提供する。 That is, the invention of this application is firstly based on the following steps (1) and (2):
(1) contacting an ionic liquid with a gas containing an organic compound, extracting the organic compound into the ionic liquid, and purifying the gas;
(2) The step of decomposing the organic compound extracted into the ionic liquid to render the ionic liquid harmless.
A method for removing an organic compound from a gas is provided. Second, the organic compound decomposition operation in the step (2) is performed by irradiating the ionic liquid with radiation, and the removal of the organic compound in the gas is provided. Thirdly, the organic compound decomposing operation in the step (2) is performed by applying an electric field to the ionic liquid. The method for removing an organic compound in the gas is provided. Fourth, there is provided the method for removing an organic compound in the gas, wherein the ionic liquid detoxified in step (2) is reused as the ionic liquid in step (1).

さらに、この出願の発明は、第５には、有機化合物として、少なくともハロゲン化有機化合物が含まれていることを特徴とする前記の気体中の有機化合物の除去方法を、第６には、有機化合物として、少なくとも内分泌撹乱化学物質が含まれていることを特徴とする前記の気体中の有機化合物の除去方法を、第７には、有機化合物として、少なくともダイオキシン類が含まれていることを特徴とする前記の気体中の有機化合物の除去方法を提供する。また、この出願の発明は、第８には、有機化合物を含有する気体とイオン性液体との接触が、少なくとも該気体中に該イオン性液体を噴霧および／または噴射する操作を含み、気相中で連続的に気−液抽出することを特徴とする前記の気体中の有機化合物の除去方法を提供する。第９には、有機化合物を含有する気体とイオン性液体の流れが互いに向流となるように、重力方向に該イオン性液体を噴霧および／または噴射させ、重力と逆方向に該気体を連続通気し、気相中で連続的に気−液抽出することを特徴とする、前記の気体中の有機化合物の除去方法を提供する。第１０には、有機化合物を含有する気体とイオン性液体との接触が、イオン性液体中に該気体を曝気する操作を含み、液相中で連続的に気−液抽出することを特徴とする、前記の気体中の有機化合物の除去方法を提供する。そして、この出願の発明は、第１１には、前記の気体中の有機化合物の除去方法を用いた、気体中の有機化合物の除去装置を提供する。 Furthermore, the invention of this application is characterized in that, in the fifth aspect, the organic compound in the gas is removed by containing at least a halogenated organic compound as the organic compound. The method for removing an organic compound from the gas, characterized in that the compound contains at least an endocrine disrupting chemical substance, and seventh, the organic compound contains at least dioxins. A method for removing an organic compound in the gas is provided. Further, in the invention of this application, eighthly, the contact between the gas containing the organic compound and the ionic liquid includes at least an operation of spraying and / or jetting the ionic liquid into the gas, A method for removing an organic compound from a gas is provided, wherein gas-liquid extraction is continuously performed in the gas. Ninth, the ionic liquid is sprayed and / or sprayed in the direction of gravity so that the flow of the gas containing the organic compound and the ionic liquid are counter-current to each other, and the gas is continued in the direction opposite to the direction of gravity. The present invention provides a method for removing an organic compound in a gas, characterized by performing gas-liquid extraction in a gas phase by aeration. Tenth, the contact between the gas containing the organic compound and the ionic liquid includes an operation of aeration of the gas into the ionic liquid, and gas-liquid extraction is continuously performed in the liquid phase. The method for removing an organic compound in the gas is provided. An eleventh aspect of the present invention provides an apparatus for removing an organic compound in a gas, using the method for removing an organic compound in the gas.

この出願の発明は、第１２には、以下のステップ（１）（２）
（１）有機化合物を含有する液体にイオン性液体を接触させ、有機化合物をイオン性液体へ抽出し液体を浄化するステップ、
（２）イオン性液体に抽出された有機化合物を分解し、イオン性液体を無害化するステップ。
からなることを特徴とする液体中の有機化合物の除去方法を提供する。第１３には、ステップ（２）における有機化合物の分解操作が、イオン性液体に放射線照射することにより行われることを特徴とする前記の液体中の有機化合物の除去方法を提供する。第１４には、ステップ（２）における有機化合物の分解操作が、イオン性液体に電場を印加することにより行われることを特徴とする前記の有機化合物の除去方法を提供する。第１５には、ステップ（２）において無害化されたイオン性液体を、ステップ（１）におけるイオン性液体として再利用することを特徴とする前記の液体中の有機化合物の除去方法を提供する。
また、この出願の発明は、第１６には、有機化合物として、少なくともハロゲン化有機化合物が含まれていることを特徴とする前記の液体中の有機化合物の除去方法を、第１７には、有機化合物として、少なくとも内分泌撹乱化学物質が含まれていることを特徴とする前記の液体中の有機化合物の除去方法を、第１８には、有機化合物として、少なくともダイオキシン類が含まれていることを特徴とする前記の液体中の有機化合物の除去方法を提供する。さらに、この出願の発明は、第１９には、有機化合物を含有する液体とイオン性液体との接触が、イオン性液体に有機化合物を含有する液体を導入し、液相中で連続的に液−液抽出することを特徴とする、前記の液体中の有機化合物の除去方法を提供する。第２０には、有機化合物を含有する液体とイオン性液体の流れが互いに向流となるように、重力方向に該イオン性液体を流通させ、重力と逆方向に該液体を連続通液し、液相中で連続的に液−液抽出することを特徴とする、前記の液体中の有機化合物の除去方法を提供する。そしてこの出願の発明は、第２１には、前記の液体中の有機化合物の除去方法を用いた、液体中の有機化合物の除去装置を提供する。 In the twelfth aspect of the present invention, the following steps (1) and (2)
(1) contacting an ionic liquid with a liquid containing an organic compound, extracting the organic compound into the ionic liquid, and purifying the liquid;
(2) The step of decomposing the organic compound extracted into the ionic liquid to render the ionic liquid harmless.
A method for removing an organic compound in a liquid is provided. 13thly, the organic compound decomposition | disassembly operation in step (2) is performed by irradiating an ionic liquid with radiation, The removal method of the organic compound in the said liquid characterized by the above-mentioned is provided. 14thly, the organic compound decomposition | disassembly operation in step (2) is performed by applying an electric field to an ionic liquid, The said removal method of the organic compound characterized by the above-mentioned is provided. 15thly provides the removal method of the organic compound in the said liquid characterized by reusing the ionic liquid detoxified in step (2) as an ionic liquid in step (1).
In addition, the invention of the present application provides, in a sixteenth aspect, the method for removing an organic compound from a liquid, wherein the organic compound includes at least a halogenated organic compound. The method for removing an organic compound from a liquid as described above, characterized in that at least an endocrine disrupting chemical substance is contained as the compound. Eighteenth, at least dioxins are contained as the organic compound. A method for removing an organic compound in the liquid is provided. Further, in the nineteenth aspect of the invention of this application, the contact between the liquid containing the organic compound and the ionic liquid introduces the liquid containing the organic compound into the ionic liquid, and the liquid is continuously liquid in the liquid phase. -A method of removing an organic compound in the liquid, characterized by performing liquid extraction. In a twentieth aspect, the ionic liquid is circulated in the direction of gravity so that the liquid containing the organic compound and the ionic liquid flow countercurrently, and the liquid is continuously passed in the direction opposite to the gravity, There is provided a method for removing an organic compound in a liquid, which comprises performing liquid-liquid extraction continuously in a liquid phase. According to a twenty-first aspect of the present invention, there is provided an apparatus for removing an organic compound in a liquid using the method for removing an organic compound in a liquid.

この出願の発明の液体および気体中の有機化合物の浄化方法ならびに浄化装置により、ダイオキシン類および内分泌かく乱物質を含むハロゲン化有機化合物を高効率で除去し、放射線照射や電場印加によって分解・無害化することが可能となる。これより、それらの有機化合物で汚染された気体および液体を、安価な処理コストで効率よく分解・処理することが可能となる。 The method and apparatus for purifying organic compounds in liquids and gases according to the invention of this application removes halogenated organic compounds containing dioxins and endocrine disrupting substances with high efficiency, and decomposes and renders them harmless by radiation irradiation or electric field application. It becomes possible. As a result, it becomes possible to efficiently decompose and treat gases and liquids contaminated with these organic compounds at a low processing cost.

この出願の発明においては次のプロセス（１）（２）によって気体または液体中の有機化合物を除去・分解することができる。
（１）気体または液体中の有機化合物を、イオン性液体に抽出するプロセス。
（２）イオン性液体に抽出された有機化合物を分解・無害化するプロセス。 In the invention of this application, organic compounds in gas or liquid can be removed and decomposed by the following processes (1) and (2).
(1) A process of extracting an organic compound in a gas or liquid into an ionic liquid.
(2) A process for decomposing and detoxifying organic compounds extracted into ionic liquids.

このプロセス（１）においては、通常の気−液２相分配、あるいは液−液２相分配により、イオン性液体中に被処理気体あるいは被処理液体中の有機化合物を効率よく抽出する。抽出操作においては、非処理気体あるいは被処理液体が互いに向流となるように接触させたり、気体の場合には気体中にイオン性液体を拡散噴霧させ、液体の場合には超音波振動を加えることにより接触面積を増大させ、抽出効率を上昇させることができる。また、この抽出プロセスを多段にすることによっても抽出効率を上昇させることが可能である。 In this process (1), the gas to be treated or the organic compound in the liquid to be treated is efficiently extracted into the ionic liquid by normal gas-liquid two-phase distribution or liquid-liquid two-phase distribution. In the extraction operation, the non-processed gas or the liquid to be processed is brought into contact with each other so as to be counter-current to each other, or in the case of gas, an ionic liquid is diffused and sprayed in the gas, and in the case of liquid, ultrasonic vibration is applied As a result, the contact area can be increased and the extraction efficiency can be increased. It is also possible to increase the extraction efficiency by making this extraction process multistage.

このプロセス（２）においては、イオン性液体を分解することなく、プロセス（１）で抽出した有機化合物を分解処理する。好ましくは、イオン性液体に放射線を照射または電場を印加して、イオン性液体中の有機化合物を分解処理する。分解処理に必要な放射線照射強度は１ｋＧｙ以上であって、好ましくは５ｋＧｙである。また、分解処理に必要な電場強度は１Ｖ／ｃｍ以上であって、好ましくは２V／ｃｍである。この分解プロセスによって、イオン性液体そのものはほとんど劣化しないために、イオン性液体を再利用することが可能であり、この再利用はメンテナンス性およびコストの観点からは特に好ましい。また、有機化合物は多くは二酸化炭素などの無害な物質に分解される。ハロゲン化有機化合物を抽出した場合は、ハロゲン化物を環境に放出することなく、ハロゲン化イオンとしてイオン性液体中にハロゲンを蓄積することができるため、イオン性液体中のハロゲン化イオンがある程度の濃度になった時点で、水を用いてイオン性液体からハロゲン化イオンを液−液抽出することが望ましい。 In this process (2), the organic compound extracted in the process (1) is decomposed without decomposing the ionic liquid. Preferably, the organic compound in the ionic liquid is decomposed by irradiating the ionic liquid with radiation or applying an electric field. The irradiation intensity required for the decomposition treatment is 1 kGy or more, preferably 5 kGy. Further, the electric field strength required for the decomposition treatment is 1 V / cm or more, and preferably 2 V / cm. Since the ionic liquid itself is hardly deteriorated by this decomposition process, the ionic liquid can be reused, and this reuse is particularly preferable from the viewpoint of maintainability and cost. In addition, many organic compounds are decomposed into harmless substances such as carbon dioxide. When a halogenated organic compound is extracted, halogen can be accumulated in the ionic liquid as halide ions without releasing the halide into the environment, so that the halide ions in the ionic liquid have a certain concentration. At this point, it is desirable to liquid-liquid extract halide ions from the ionic liquid using water.

以下、模式図を用いて発明の実施の態様を説明する。 Hereinafter, embodiments of the invention will be described with reference to schematic diagrams.

図１はイオン性液体Yを循環使用しない気体の浄化装置構成である。イオン性液体はイオン性液体貯留槽３に蓄えられており、重力を利用して被処理気体Gと互いに向流となるように抽出塔１の内に噴射または散布される。貯留槽３から抽出塔１へのイオン性液体の供給は、重力を利用した供給でもよいし、送液ポンプ３１を使用してもよい。抽出塔１の内部は、散布されたイオン性液体が被処理気体中に拡散している噴霧状イオン性液体滞留部３Ｓ、および、液体としてイオン性液体が貯留されその中に被処理気体がバブル２Ｂとして流通している液状イオン性液体滞留部３Ｌから構成されている。イオン性液体Yの流通は、強制流通であり、好ましくは抽出塔１上部の噴射ノズル３２から抽出塔１へ供給され重力方向へ流通させる。イオン性液体Yは、被処理気体Gから有機化合物などを抽出した後に、抽出塔１下部の液状イオン性液体滞留部３Ｌに滞留し、イオン性液体排出口３３から放射線照射による浄化処理ユニット４へ送られる。 FIG. 1 shows the configuration of a gas purification device that does not circulate and use the ionic liquid Y. The ionic liquid is stored in the ionic liquid storage tank 3, and is sprayed or sprayed into the extraction tower 1 so as to counter-flow with the gas G to be processed using gravity. The supply of the ionic liquid from the storage tank 3 to the extraction tower 1 may be a supply using gravity, or a liquid feed pump 31 may be used. Inside the extraction tower 1, the sprayed ionic liquid retention part 3S in which the dispersed ionic liquid is diffused in the gas to be treated, and the ionic liquid as a liquid are stored, and the gas to be treated is bubbled therein. It is comprised from the liquid ionic liquid retention part 3L currently distribute | circulating as 2B. The circulation of the ionic liquid Y is forced circulation, and is preferably supplied to the extraction tower 1 from the injection nozzle 32 at the upper part of the extraction tower 1 and is circulated in the direction of gravity. The ionic liquid Y is extracted from the gas G to be treated, and then stays in the liquid ionic liquid retention part 3L at the lower part of the extraction tower 1, and is transferred from the ionic liquid discharge port 33 to the purification unit 4 by radiation irradiation. Sent.

いっぽう、汚染気体の流通も、強制流通とするが、被処理気体流通ポンプ２１によって抽出搭１下部より供給され、好ましくは液状イオン性液体滞留部３Ｌ中に供給される。さらに、被処理気体とイオン性液体との接触面積を増大させるために、液状イオン性液体滞留部３Ｌへの被処理気体Gの供給は多孔質フィルタ２２を用い微小バブルとして導入するのが特に好ましい。被処理気体Gは排気口２３を通じ抽出塔上部から排気される。処理された被処理気体Gに含まれる分解生成物は二酸化炭素など低分子化合物であり、汚染を生じず、ガスを大気環境中に放出できる。 On the other hand, although the circulation of the pollutant gas is also forced circulation, it is supplied from the lower part of the extraction tower 1 by the gas flow pump 21 to be treated, and is preferably supplied into the liquid ionic liquid retention part 3L. Furthermore, in order to increase the contact area between the gas to be processed and the ionic liquid, the supply of the gas to be processed G to the liquid ionic liquid retention part 3L is particularly preferably introduced as a microbubble using the porous filter 22. . The gas to be treated G is exhausted from the upper part of the extraction tower through the exhaust port 23. The decomposition product contained in the treated gas G is a low-molecular compound such as carbon dioxide, which does not cause contamination and can release the gas into the atmospheric environment.

浄化処理ユニットは、放射線照射式もしくは電場印加式とすることができる。例えば、放射線照射式では、照射窓４２から放射線Ｘを照射処理室４１内に照射して、イオン性液体に抽出した有機化合物を分解する。また、電場印加式では、浄化処理ユニット４内に電極４４を配置し、電場印加室４３で電場を印加することによって分解処理を行ってもよい。いずれの場合も、放射線照射または電場印加によって発生した電子の還元作用によって、直接イオン性液体中の有機化合物を無害な程度に分解することができる。なお、放射線発生装置５や電場印加のための電源装置６は公知のものが使用できる。この出願の発明の処理方法はコンパクトな処理装置で実現できるため、既存のプロセスヘの付設が容易である。 The purification processing unit can be a radiation irradiation type or an electric field application type. For example, in the radiation irradiation type, the radiation X is irradiated into the irradiation processing chamber 41 from the irradiation window 42 to decompose the organic compound extracted into the ionic liquid. Further, in the electric field application type, the decomposition process may be performed by arranging the electrode 44 in the purification processing unit 4 and applying an electric field in the electric field application chamber 43. In either case, the organic compound in the ionic liquid can be directly decomposed to a harmless degree by the reducing action of electrons generated by irradiation with radiation or application of an electric field. In addition, a well-known thing can be used for the radiation generator 5 and the power supply device 6 for electric field application. Since the processing method of the invention of this application can be realized by a compact processing apparatus, it can be easily attached to an existing process.

図１はイオン性液体Yを循環使用しない例であるが、もちろん、イオン性液体中の有害有機化合物は浄化処理ユニット４を導通することで分解されており、また、イオン性液体そのものは、放射線照射や電場印加によってほとんど劣化しないため、排出された使用済みイオン性液体を貯留しておき、再利用してもよい。さらに、図２に示すとおりにイオン性液体に貯留槽を設けず、イオン性液体の浄化処理ユニット４から直接抽出塔１内へイオン性液体を循環することもできる。 FIG. 1 shows an example in which the ionic liquid Y is not circulated. Of course, harmful organic compounds in the ionic liquid are decomposed by conducting the purification treatment unit 4, and the ionic liquid itself is radiation. Since it hardly deteriorates due to irradiation or electric field application, the discharged used ionic liquid may be stored and reused. Further, as shown in FIG. 2, the ionic liquid can be circulated directly from the ionic liquid purification unit 4 into the extraction tower 1 without providing a storage tank in the ionic liquid.

さらに、抽出塔から排気された被処理気体を再度同様の抽出塔へ導入して、残存する有機化合物をさらにイオン性液体中に抽出・除去する、２段階の処理も可能である（図３・図４）。この場合、１次抽出ユニット１ＰＵと２次抽出ユニット１ＳＵ、それぞれのイオン性液体を別々に浄化処理しても構わないが、特に放射線照射による浄化処理を行う場合は、装置の複雑さやコストの観点から、単一の浄化処理ユニットを採用し、１次抽出ユニット１ＰＵと２次抽出ユニット１ＳＵからのイオン性液体の有機化合物分解処理を共通の浄化処理ユニット４で行うことが望ましい。 Furthermore, a two-stage process is also possible in which the gas to be treated exhausted from the extraction tower is introduced again into the same extraction tower, and the remaining organic compound is further extracted and removed from the ionic liquid (FIG. 3). FIG. 4). In this case, the ionic liquids of the primary extraction unit 1PU and the secondary extraction unit 1SU may be separately purified. In particular, when the purification process by radiation irradiation is performed, in view of the complexity and cost of the apparatus. Therefore, it is desirable to adopt a single purification treatment unit 4 and to perform the organic compound decomposition treatment of the ionic liquid from the primary extraction unit 1PU and the secondary extraction unit 1SU in the common purification treatment unit 4.

さらにまた、抽出搭をタンデムに連結し多段で処理することも可能である（図５、ｎ≧１）。図５において多段抽出塔は、初期搭ユニット１ＩＵと最終抽出ユニット１ＦＵの間に、任意段数の中間抽出搭ユニットを配置して構成することができる。イオン性液体の処理は図５に示すように全段からのイオン性液体を単一の浄化処理ユニット４で集中処理してもよいが、数段ごとを一つの単位として分散処理してもよいし、各段ごとの個別処理としてもよく、処理の態様は特に限定されない。 Furthermore, the extraction tower can be connected in tandem and processed in multiple stages (FIG. 5, n ≧ 1). In FIG. 5, the multistage extraction tower can be configured by arranging an arbitrary number of intermediate extraction tower units between the initial tower unit 1IU and the final extraction unit 1FU. As shown in FIG. 5, the ionic liquid from all stages may be intensively processed by a single purification processing unit 4 as shown in FIG. 5, but may be dispersedly processed every several stages as one unit. However, individual processing may be performed for each stage, and the mode of processing is not particularly limited.

いっぽう、有機化合物に汚染された液体の浄化処理装置は、基本的に気体の場合と同様の構成とすることができる。すなわち、気体の浄化処理装置と相違するのは抽出塔１内での被処理気体とイオン性液体との接触の態様であり、イオン性液体の浄化処理や再利用に関しては気体の浄化処理装置と同様に考えることができる。図６に示す液体の浄化装置においては、被処理液体Lとイオン性液体Ｙとの密度の違いから、抽出塔の下部から被処理液体Ｌを導入し、上部からイオン性液体Ｙを通じて、互いが向流になるように接触させ、被処理液体Ｌからイオン性液体Yへ有機化合物の液−液抽出を行う。この構成では、イオン性液体中に被処理液体を通じて抽出処理を行うが、好ましくは超音波発生装置８を使用し、抽出にかかる接触面積を増大させ抽出効率の向上をはかる。また、気体の場合と同様に抽出塔をタンデムに連結し、多段式の構成としてもよい。 On the other hand, the liquid purification apparatus contaminated with an organic compound can be basically configured in the same manner as in the case of gas. That is, what is different from the gas purification treatment apparatus is the mode of contact between the gas to be treated and the ionic liquid in the extraction tower 1, and with respect to the purification treatment and reuse of the ionic liquid, The same can be considered. In the liquid purification apparatus shown in FIG. 6, due to the difference in density between the liquid to be processed L and the ionic liquid Y, the liquid to be processed L is introduced from the lower part of the extraction tower, and the ionic liquid Y is passed through the ionic liquid Y from the upper part. Liquid-liquid extraction of the organic compound is performed from the liquid L to be treated to the ionic liquid Y by making contact so as to be countercurrent. In this configuration, the extraction process is performed through the liquid to be processed in the ionic liquid. Preferably, the ultrasonic generator 8 is used to increase the contact area for extraction and improve the extraction efficiency. Further, as in the case of gas, the extraction tower may be connected in tandem to have a multistage configuration.

なお、この出願の発明において、「ハロゲン化有機化合物」としては原子組成や化学構造によらないが、四塩化炭素、塩化メチル、ジクロロメタン、1,2-ジクロロエタン、1,1-ジクロロエチレン、シス-1,2-ジクロロエチレン、1,1,1-トリクロロエチレン、1,1,2-トリクロロエチレン、トリクロロエチレン、テトラクロエチレン、CFC-12(CCl₂F₂)、 CFC-113(CCl₂F-CCl₂)、HCFC-22(HCClF₂)、HCFC-123(CF₃-CHCl₂)、 HCFC-141b(CH₃-CFCl₂)、 HCFC-142b(CH₃-CF₂Cl)、PCB、ダイオキシンおよびそれらの異性体などが例示されるが、これらに限定されない。 In the invention of this application, the “halogenated organic compound” does not depend on the atomic composition or chemical structure, but carbon tetrachloride, methyl chloride, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethylene, cis-1 , 2-dichloroethylene, 1,1,1-trichloroethylene, 1,1,2-trichloroethylene, trichlorethylene, tetrachlorethylene, CFC-12 (CCl ₂ F ₂ ), CFC-113 (CCl ₂ F-CCl ₂ ), HCFC -22 (HCClF ₂ ), HCFC-123 (CF ₃ -CHCl ₂ ), HCFC-141b (CH ₃ -CFCl ₂ ), HCFC-142b (CH ₃ -CF ₂ Cl), PCB, dioxin and their isomers, etc. However, the present invention is not limited to these examples.

また、この出願の発明において、「ダイオキシン」とは、酸素原子を二つ含む六員環不飽和含酸素複素化合物の総称であり、例えば、ポリ塩化ジベンゾパラジオキシン(PCDD) 、ポリ塩化ジベンゾフラン(PCDF) 、コプラナーポリ塩化ビフェニール(コプラナPCB)およびそれらの異性体を示す。また、「内分泌かく乱物質」とは、生体内でホルモン類似した挙動を示す物質であり、例えばジクロロトリフェニルトリクロロエタン（DDT）が示される。 Further, in the invention of this application, `` dioxin '' is a general term for a six-membered unsaturated oxygen-containing hetero compound containing two oxygen atoms. ), Coplanar polychlorinated biphenyls (coplana PCB) and their isomers. The “endocrine disrupting substance” is a substance that exhibits a hormone-like behavior in a living body, and for example, dichlorotriphenyltrichloroethane (DDT) is shown.

この出願の発明における「イオン性液体」は、エチルメチルイミダゾリウムPF₆、ブチルメチルイミダゾリウムPF₆(II)、1-ブチル 4-メチルピリジニウムAlC1₃、1-メチル 4-エチルイミダゾリウムAlCl₃、1,3-ジエチルイミダゾリウムトリフレートなどの、カチオンとアニオンのみを構成成分とする室温から高温で液体状の溶融塩全般を指す。イオン性液体は、対象となる有害有機物により、適したものを選択することができる。 The `` ionic liquid '' in the invention of this application is ethylmethylimidazolium PF ₆ , butylmethylimidazolium PF ₆ (II), 1-butyl 4-methylpyridinium AlC1 ₃ , 1-methyl 4-ethylimidazolium AlCl ₃ , It refers to all molten salts that are liquid from room temperature to high temperature, such as 1,3-diethylimidazolium triflate, which contain only cations and anions. As the ionic liquid, a suitable one can be selected depending on the target harmful organic substance.

この出願の発明における「放射線」とは、加速器を含む照射装置により発生させたX線（または制動放射線）や電子線、γ線が挙げられる。ここで、X線とは電気的に発生させた非常に短い波長の光を指し、電子線とは、加速器により発生させた電子の流れであり、さらには、γ線とはコバルトなどの放射性同位元素から放出される高エネルギーの光を指す。
この出願の発明にいうにおける「電場印加」とはこのような直流電圧を電極間に印加し、電場を形成することをいう。直流電圧とは、一般的には直流電圧発生装置による電圧を指す。電場印加の態様は、定常的に正または負の電圧を印加することができるが、一定の時間間隔で正と負を逆転させながら直流電圧を印加する方法も利用できる。
The “radiation” in the invention of this application includes X-rays (or bremsstrahlung) generated by an irradiation device including an accelerator, electron beams, and γ rays. Here, X-rays refer to light of a very short wavelength generated electrically, electron beams are the flow of electrons generated by an accelerator, and γ rays are radioisotopes such as cobalt. High energy light emitted from elements.
“Electric field application” in the invention of this application means that such a DC voltage is applied between electrodes to form an electric field. The DC voltage generally refers to a voltage generated by a DC voltage generator. As an aspect of applying an electric field, a positive or negative voltage can be constantly applied, but a method of applying a DC voltage while reversing positive and negative at a constant time interval can also be used.

〔実施例１〕
図３に示す構成の装置を用いて、オンラインによる連続方式でこの出願の発明の排ガス浄化を行った。200ppmの1,2-ジクロロエタンを含む室温の排ガスを毎分１0Lで抽出塔に導入し、イオン性液体を毎分0.5Lで噴霧した。抽出塔からの排ガス中の1,2-ジクロロエタン濃度は4ppm以下であり、抽出率は98%以上であった。次いで、抽出塔下部から導出したイオン性液体に電子線を5kGy照射することにより、1,2-ジクロロエタンをほぼ100%分解することができた。この結果、もとの排ガス中の1,2-ジクロロエタンを98%以上除去することができた。
〔実施例２〕
図４に示す構成の装置を用いて、1,1-ジクロロエチレンを400ppm程度含む室温の排ガスを毎分10Lで抽出塔に導入し、イオン性液体を毎分0.5Lで噴霧した。抽出塔からの排ガス中の1,1-ジクロロエチレン濃度は12ppm以下であった。次いで、抽出塔下部から導出したイオン性液体に直流電圧を３V印加することにより、1,1-ジクロロエチレンをほぼ100%分解することができた。この結果、もとの排ガス中の1,1-ジクロロエチレンをほぼ97%以上除去できた。 [Example 1]
Exhaust gas purification of the invention of this application was performed in an online continuous system using the apparatus having the configuration shown in FIG. Room temperature exhaust gas containing 200 ppm 1,2-dichloroethane was introduced into the extraction tower at 10 L / min and the ionic liquid was sprayed at 0.5 L / min. The 1,2-dichloroethane concentration in the exhaust gas from the extraction tower was 4 ppm or less, and the extraction rate was 98% or more. Next, by irradiating the ionic liquid derived from the lower part of the extraction tower with 5 kGy of electron beam, 1,2-dichloroethane could be decomposed almost 100%. As a result, 98% or more of 1,2-dichloroethane in the original exhaust gas could be removed.
[Example 2]
Using the apparatus having the configuration shown in FIG. 4, room temperature exhaust gas containing about 400 ppm of 1,1-dichloroethylene was introduced into the extraction tower at 10 L / min, and the ionic liquid was sprayed at 0.5 L / min. The 1,1-dichloroethylene concentration in the exhaust gas from the extraction tower was 12 ppm or less. Next, by applying a DC voltage of 3 V to the ionic liquid derived from the lower part of the extraction tower, 1,1-dichloroethylene could be decomposed almost 100%. As a result, 97% or more of 1,1-dichloroethylene in the original exhaust gas could be removed.

イオン性液体の処理を放射線照射で行う気体浄化装置の模式図。The schematic diagram of the gas purification apparatus which processes an ionic liquid by radiation irradiation. イオン性液体の処理を放射線照射で行う循環式気体浄化装置の模式図。The schematic diagram of the circulation type gas purification apparatus which processes an ionic liquid by radiation irradiation. イオン性液体の処理を放射線照射で行う２段循環式気体浄化装置の模式図。The schematic diagram of the two-stage circulation type gas purification apparatus which processes an ionic liquid by radiation irradiation. イオン性液体の処理を電場印加で行う２段循環式気体浄化装置の模式図。The schematic diagram of the two-stage circulation type gas purification apparatus which processes an ionic liquid by electric field application. イオン性液体循環式の多段循環式気体浄化装置の模式図。The schematic diagram of an ionic liquid circulation type multistage circulation type gas purification apparatus. イオン性液体循環式の液体浄化装置の模式図。The schematic diagram of the liquid purification apparatus of an ionic liquid circulation type.

Explanation of symbols

１抽出塔
１ＰＵ一次抽出塔ユニット
１ＳＵ二次抽出塔ユニット
１ＩＵ初期抽出塔ユニット
１ＲＵ中間抽出塔ユニット
１ＦＵ最終抽出塔ユニット
２被処理気体採取口
２１被処理気体輸送ポンプ
２２抽出塔内の吸気口（多孔質フィルタ）
２３抽出塔内の排気口
２４被処理気体排気口
２５被処理気体輸送ポンプ
２Ｂ被処理気体バブル
３イオン性液体貯留槽
３１送液ポンプ
３２噴射ノズル
３３抽出塔内のイオン性液体排出口
３４送液ポンプ
３５イオン性液体廃液口
３Ｓ噴霧状イオン性液体滞留部
３Ｌ液状イオン性液体滞留部
４浄化処理ユニット
４１照射処理室
４２照射窓
４３電場印加室
４４電極
５放射線もしくは電子線の発生装置
６直流電流の発生装置
７被処理気体採取口
７１被処理液体輸送ポンプ
７２抽出塔内の吸液口
７３抽出塔内の排液口
７４被処理液体排液口
８超音波発生装置
Ｇ被処理気体
Ｌ被処理液体
Ｘ放射線もしくは電子線
Ｙイオン性液体 DESCRIPTION OF SYMBOLS 1 Extraction tower 1PU Primary extraction tower unit 1SU Secondary extraction tower unit 1IU Initial extraction tower unit 1RU Intermediate extraction tower unit 1FU Final extraction tower unit 2 Processed gas sampling port 21 Processed gas transport pump 22 Intake port in extraction tower (porous Quality filter)
23 Exhaust port in extraction tower 24 Processed gas exhaust port 25 Processed gas transport pump 2B Processed gas bubble 3 Ionic liquid storage tank 31 Liquid feed pump 32 Injection nozzle 33 Ionic liquid discharge port 34 in the extraction tower Pump 35 Ionic liquid waste outlet 3S Spray ionic liquid retention part 3L Liquid ionic liquid retention part 4 Purification treatment unit 41 Irradiation treatment chamber 42 Irradiation window 43 Electric field application chamber 44 Electrode 5 Radiation or electron beam generator 6 DC current Generator 7 to-be-processed gas sampling port 71 to-be-processed liquid transport pump 72 liquid suction port 73 in the extraction tower drainage port in the extraction tower 74 to-be-processed liquid drainage port 8 ultrasonic generator G to-be-processed gas L to be processed Liquid X Radiation or electron beam Y Ionic liquid

Claims

A method for removing an organic compound in a gas, comprising the following steps (1) and (2).
(1) contacting an ionic liquid with a gas containing an organic compound, extracting the organic compound into the ionic liquid, and purifying the gas;
(2) The step of decomposing the organic compound extracted into the ionic liquid to render the ionic liquid harmless.

The method for removing an organic compound from a gas according to claim 1, wherein the decomposition operation of the organic compound in step (2) is performed by irradiating the ionic liquid with radiation.

The method for removing an organic compound from a gas according to claim 1, wherein the decomposition operation of the organic compound in step (2) is performed by applying an electric field to the ionic liquid.

The ionic liquid detoxified in step (2) is reused as the ionic liquid in step (1), wherein the organic compound in the gas according to any one of claims 1 to 3 is used. Removal method.

The method for removing an organic compound in a gas according to any one of claims 1 to 4, wherein the organic compound contains at least a halogenated organic compound.

The method for removing an organic compound in a gas according to any one of claims 1 to 5, wherein the organic compound contains at least an endocrine disrupting chemical substance.

The method for removing an organic compound in a gas according to any one of claims 1 to 6, wherein at least dioxins are contained as the organic compound.

Contact between the gas containing the organic compound and the ionic liquid includes at least an operation of spraying and / or spraying the ionic liquid into the gas, and continuously gas-liquid extraction in the gas phase A method for removing an organic compound in a gas according to any one of claims 1 to 7.

The ionic liquid is sprayed and / or sprayed in the direction of gravity so that the flow of the gas containing the organic compound and the ionic liquid is countercurrent to each other, and the gas is continuously vented in the direction opposite to the direction of gravity. 9. The method for removing an organic compound from a gas according to claim 8, wherein gas-liquid extraction is continuously performed in the gas.

The contact between the gas containing an organic compound and the ionic liquid includes an operation of aeration of the gas into the ionic liquid, and gas-liquid extraction is continuously performed in the liquid phase. The removal method of the organic compound in the gas in any one of thru | or 9.

The removal apparatus of the organic compound in gas using the removal method of the organic compound in gas in any one of Claim 1 thru | or 10.

A method for removing an organic compound in a liquid, comprising the following steps (1) and (2).
(1) contacting an ionic liquid with a liquid containing an organic compound, extracting the organic compound into the ionic liquid, and purifying the liquid;
(2) The step of decomposing the organic compound extracted into the ionic liquid to render the ionic liquid harmless.

The method for removing an organic compound from a liquid according to claim 12, wherein the decomposition operation of the organic compound in step (2) is performed by irradiating the ionic liquid with radiation.

The method for removing an organic compound in a liquid according to claim 12, wherein the decomposition operation of the organic compound in step (2) is performed by applying an electric field to the ionic liquid.

The ionic liquid detoxified in step (2) is reused as the ionic liquid in step (1). 15. The organic compound in the liquid according to any one of claims 12 to 14, Removal method.

The method for removing an organic compound from a liquid according to any one of claims 12 to 15, wherein the organic compound contains at least a halogenated organic compound.

The method for removing an organic compound in a liquid according to any one of claims 12 to 16, wherein at least an endocrine disrupting chemical substance is contained as the organic compound.

The method for removing an organic compound from a liquid according to any one of claims 12 to 17, wherein the organic compound contains at least dioxins.

13. The contact between a liquid containing an organic compound and an ionic liquid introduces a liquid containing an organic compound into the ionic liquid and performs continuous liquid-liquid extraction in the liquid phase. A method for removing an organic compound in a liquid according to any one of items 18 to 18.

The ionic liquid is circulated in the direction of gravity so that the flow of the organic compound-containing liquid and the ionic liquid is countercurrent to each other, and the liquid is continuously passed in the direction opposite to the direction of gravity. 20. The method for removing an organic compound in a liquid according to claim 19, wherein liquid-liquid extraction is performed.

An apparatus for removing an organic compound in a liquid, using the method for removing an organic compound in a liquid according to any one of claims 12 to 19.