JP2001302553A - Method for treating organohalogen compound - Google Patents
Method for treating organohalogen compoundInfo
- Publication number
- JP2001302553A JP2001302553A JP2000129067A JP2000129067A JP2001302553A JP 2001302553 A JP2001302553 A JP 2001302553A JP 2000129067 A JP2000129067 A JP 2000129067A JP 2000129067 A JP2000129067 A JP 2000129067A JP 2001302553 A JP2001302553 A JP 2001302553A
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- JP
- Japan
- Prior art keywords
- alkali metal
- halogen compound
- organic halogen
- decomposing
- metal dispersion
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機ハロゲン化合
物、例えばポリ塩化ビフェニール（以下、ＰＣＢと略記
する）類等の有機ハロゲン化合物を、アルカリ金属によ
り脱ハロゲン分解させて処理する有機ハロゲン化合物の
分解方法に関するものである。The present invention relates to a method for decomposing an organic halogen compound, for example, an organic halogen compound such as polychlorinated biphenyl (hereinafter abbreviated as PCB), by dehalogenating with an alkali metal. It is about the method.
【０００２】[0002]
【従来の技術】従来、有機ハロゲン化合物とアルカリ金
属分散体とを反応させて有機ハロゲン化合物を分解処理
する方法は知られており、例えば、本出願人による特開
昭４９−８２５７０号公報には、環境汚染物質であるＰ
ＣＢ類又はＰＣＢ類を含む有機溶媒溶液を分散状態にあ
るアルカリ金属と共に加熱処理する環境汚染物質の処理
方法が記載され、同じく本出願人による特開平９−２１
６８３８号公報には、有機溶媒中でハロゲン化合物とア
ルカリ金属分散体とを、該有機溶媒と混じらない活性水
素化合物を加えて反応させるハロゲン化合物の分解方法
が記載されている。2. Description of the Related Art Conventionally, a method of decomposing an organic halogen compound by reacting an organic halogen compound with an alkali metal dispersion is known. For example, Japanese Patent Application Laid-Open No. 49-82570 by the present applicant discloses a method. , P which is an environmental pollutant
A method for treating environmental pollutants in which an organic solvent solution containing CBs or PCBs is heat-treated with an alkali metal in a dispersed state is described.
No. 6838 describes a method for decomposing a halogen compound by reacting a halogen compound with an alkali metal dispersion in an organic solvent by adding an active hydrogen compound which is not mixed with the organic solvent.
【０００３】また、特開昭５９−２０１７９号公報に
は、炭化水素ベースの油に溶解している有機ハロゲン化
物と溶融ナトリウム粒子群とを１００〜１６０℃の温度
範囲で反応させ、有機ハロゲン化物の脱ハロゲン化プロ
セスが記載され、カナダ特許第１１４２５５１号明細書
には、塩化ビフェニール組成物をアルカリ金属と加熱条
件下で反応させる塩化ビフェニール組成物の処理方法が
記載されている。JP-A-59-20179 discloses that an organic halide dissolved in a hydrocarbon-based oil is reacted with molten sodium particles in a temperature range of 100 to 160 ° C. to form an organic halide. And Canadian Patent No. 1142551 describes a method for treating a biphenyl chloride composition by reacting the biphenyl chloride composition with an alkali metal under heating conditions.
【０００４】[0004]
【発明が解決しようとする課題】上記従来の有機ハロゲ
ン化合物とアルカリ金属分散体とを反応させて有機ハロ
ゲン化合物を分解処理する方法においては、有機ハロゲ
ン化合物とアルカリ金属分散体を一度に混合し、加熱等
して反応させる方法のみが記載されている。現存するＰ
ＣＢ等の有機ハロゲン化合物は、長期保存された結果、
保存状態によっては、酸化物等の不純物を含んでいる可
能性があるものである。また、他の存在形態として、ト
ランスオイル中に低濃度で存在しており、同様に保存状
態によってはトランスオイルが空気酸化等により劣化し
ている可能性がある。保存状態によってその性状が異な
るＰＣＢ等を、上記従来技術によって分解方法する場
合、酸化物等の不純物のため、再現性が得られない場合
があるという問題があった。In the above-described conventional method for decomposing an organic halogen compound by reacting an organic halogen compound with an alkali metal dispersion, the organic halogen compound and the alkali metal dispersion are mixed at once. Only the method of reacting by heating or the like is described. Existing P
Organic halogen compounds such as CB are stored for a long time,
Depending on the state of storage, it may contain impurities such as oxides. Further, as another existence form, there is a low concentration in the transformer oil, and similarly, depending on the storage state, the transformer oil may be deteriorated by air oxidation or the like. When a PCB or the like having different properties depending on the storage state is decomposed by the above-described conventional technique, there is a problem that reproducibility may not be obtained due to impurities such as oxides.
【０００５】本発明の課題は、有機ハロゲン化合物をア
ルカリ金属分散体により脱塩素分解処理する方法におい
て、従来の方法よりも、再現性よく、安定的に無害化処
理することができる有機ハロゲン化合物の分解方法を提
供することにある。An object of the present invention is to provide a method for dechlorination-decomposition treatment of an organic halogen compound using an alkali metal dispersion, which is more reproducible and more stable than conventional methods. It is to provide a decomposition method.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討した結果、用いるアルカリ金属分
散体を複数回に分割して添加することで、上記課題を解
決することができることを見出し、本発明を完成するに
至った。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, it has been found that the above-mentioned problems can be solved by adding the alkali metal dispersion to be used in a plurality of divided portions. They have found that they can do this and have completed the present invention.
【０００７】即ち、本発明は、（１）有機溶媒中で、有
機ハロゲン化合物とアルカリ金属分散体を反応させる有
機ハロゲン化合物の分解方法において、アルカリ金属分
散体を複数回に分割して添加することを特徴とする有機
ハロゲン化合物の分解方法、（２）有機溶媒中で、有機
ハロゲン化合物とアルカリ金属分散体とを、該有機溶媒
と混合しない活性水素化合物を加えて反応させる有機ハ
ロゲン化合物の分解方法において、アルカリ金属分散体
を複数回に分割して添加することを特徴とする有機ハロ
ゲン化合物の分解方法、（３）有機溶媒中で、有機ハロ
ゲン化合物とアルカリ金属分散体とを、該有機溶媒と混
合しない活性水素化合物を加えて反応させる有機ハロゲ
ン化合物の分解方法において、アルカリ金属分散体を複
数回に分割して添加した後、該有機溶媒と混合しない活
性水素化合物を添加することを特徴とする有機ハロゲン
化合物の分解方法、That is, the present invention provides (1) a method for decomposing an organic halogen compound and an alkali metal dispersion in an organic solvent, wherein the alkali metal dispersion is added in a plurality of portions. (2) a method for decomposing an organic halogen compound by reacting an organic halogen compound and an alkali metal dispersion in an organic solvent by adding an active hydrogen compound which is not mixed with the organic solvent; In the method for decomposing an organic halogen compound, wherein the alkali metal dispersion is added in a plurality of times, (3) the organic halogen compound and the alkali metal dispersion are mixed with the organic solvent in the organic solvent. In a method for decomposing an organic halogen compound in which an active hydrogen compound that is not mixed is added and reacted, an alkali metal dispersion is added in a plurality of portions. After method the decomposition of organic halogen compounds, characterized by adding an active hydrogen compound that does not mix with the organic solvent,
【０００８】（４）活性水素化合物が水、メタノール、
及びエタノールからなる群より選ばれる少なくとも１種
以上であることを特徴とする（１）〜（３）のいずれか
に記載の有機ハロゲン化合物の分解方法、（５）有機溶
媒が、アルカリ金属に不活性な脂肪族及び／又は芳香族
炭化水素を溶媒であることを特徴とする（１）〜（４）
のいずれかに記載の有機ハロゲン化合物の分解方法、
（６）アルカリ金属に不活性な脂肪族又は芳香族炭化水
素として、ケロシン、デカリン、トランス油（ＪＩＳ
Ｃ ２３２０−１９９３に記載のトランス油）、重油
（ＪＩＳ Ｋ２２０５に記載）、洗浄油から選ばれた１
種又は２種以上を用いることを特徴とする（５）に記載
の有機ハロゲン化合物の分解方法、（７）アルカリ金属
分散体として、アルカリ金属の８０％以上が直径３０ミ
クロン以下のアルカリ金属粒子を含むアルカリ金属分散
体を用いることを特徴とする（１）〜（６）のいずれか
に記載の有機ハロゲン化合物の分解方法、（８）アルカ
リ金属が、ナトリウムであることを特徴とする（７）に
記載の有機ハロゲン化合物の分解方法、（９）有機ハロ
ゲン化合物がポリ塩化ビフェニル類を含む難分解性ハロ
ゲン化合物であることを特徴とする（１）〜（８）のい
ずれかに記載の有機ハロゲン化合物の分解方法に関す
る。(4) The active hydrogen compound is water, methanol,
And (3) the method for decomposing an organic halogen compound according to any one of (1) to (3), wherein (5) the organic solvent is incompatible with the alkali metal. (1) to (4), wherein active aliphatic and / or aromatic hydrocarbons are used as a solvent.
A method for decomposing an organic halogen compound according to any one of the above,
(6) As aliphatic or aromatic hydrocarbons inert to alkali metals, kerosene, decalin, trans oil (JIS
1 selected from C2320-1993 transformer oil), heavy oil (described in JIS K2205), and washing oil
(5) The method for decomposing an organic halogen compound according to (5), wherein at least 80% of the alkali metal particles have a diameter of 30 μm or less as an alkali metal dispersion. (1) A method for decomposing an organic halogen compound according to any one of (1) to (6), wherein the alkali metal is sodium. (9) The organic halogen compound according to any one of (1) to (8), wherein the organic halogen compound is a hardly decomposable halogen compound containing polychlorinated biphenyls. The present invention relates to a method for decomposing a compound.
【０００９】[0009]
【発明の実施の形態】本発明における有機ハロゲン化合
物としては、例えばＰＣＢ、ダイオキシン類、ポリ塩素
化ジベンゾフラン類、ポリ塩素化ベンゼン、ＤＤＴ、Ｂ
ＨＣ等を挙げることができ、これら有機ハロゲン化合物
は、そのまま用いてもよいが、溶媒に溶解して有機ハロ
ゲン化合物溶液として用いることができる。そして、有
機ハロゲン化物を溶解する溶媒としては、アルカリ金属
に不活性な脂肪族炭化水素又は芳香族炭化水素が好まし
く、例えば、ヘキサン、シクロヘキサン、ベンゼン、ケ
ロシン、デカリン、トランス油（ＪＩＳ Ｃ ２３２０
−１９９３に記載のトランス油）、重油（ＪＩＳ Ｋ２
２０５に記載）、又は洗浄油を挙げることができ、これ
らは単独でもしくは混合物として用いることができる。
かかる溶媒の沸点や引火点は高いほうが好ましく、更に
アルカリ金属分散体を安定化する点で、これら溶媒の中
でもトランス油は特に好適に用いることができる。尚、
洗浄油とは、フロン、トリクロロエタン、灯油等の代替
品として、自動車、電子部品、精密機器の洗浄用に用い
られる炭化水素系を主成分とした溶剤を意味する。これ
らの溶剤は、沸点、引火点が比較的高く、低毒性である
ことから、作業環境上、安全上優れた特性を有するもの
である。具体的には、ナフテゾール（日本石油（株）
製）、ＪＯＭＯ ＭＴＦ（（株）ジャパンエナジー製）
等を例示することができる。また、有機ハロゲン化合物
により汚染されたケロシン、デカリン、トランス油等を
溶媒として用いることも可能である。BEST MODE FOR CARRYING OUT THE INVENTION As the organic halogen compound in the present invention, for example, PCB, dioxins, polychlorinated dibenzofurans, polychlorinated benzene, DDT, B
HC can be used, and these organic halogen compounds may be used as they are, or they may be dissolved in a solvent and used as an organic halogen compound solution. As the solvent for dissolving the organic halide, an aliphatic hydrocarbon or an aromatic hydrocarbon which is inert to an alkali metal is preferable. For example, hexane, cyclohexane, benzene, kerosene, decalin, trans oil (JIS C 2320)
-Trans oil described in 1993), heavy oil (JIS K2)
205) or washing oils, which can be used alone or as a mixture.
It is preferable that the boiling point and the flash point of such a solvent be high, and among these solvents, trans oil can be particularly suitably used in terms of stabilizing the alkali metal dispersion. still,
The cleaning oil refers to a hydrocarbon-based solvent used for cleaning automobiles, electronic components, and precision equipment as a substitute for Freon, trichloroethane, kerosene, and the like. Since these solvents have a relatively high boiling point and a high flash point and are low in toxicity, they have excellent properties in terms of working environment and safety. Specifically, naphthesol (Nippon Oil Co., Ltd.)
JOMO MTF (manufactured by Japan Energy Co., Ltd.)
And the like. It is also possible to use kerosene, decalin, trans oil or the like contaminated with an organic halogen compound as a solvent.
【００１０】本発明におけるアルカリ金属としては、ナ
トリウム、カリウム、リチウム、セシウム、又はこれら
の合金を例示することができる。そして、本発明におい
てはアルカリ金属は溶媒に分散した分散体の形態で使用
され、アルカリ金属分散体の調製に用いられる溶媒とし
ては、沸点が１００℃以上でアルカリ金属に不活性な脂
肪族炭化水素又は芳香族炭化水素、例えば、トルエン、
キシレン、ケロシン、トランス油（ＪＩＳ Ｃ ２３２
０−１９９３に記載のトランス油）、デカリン、流動パ
ラフィン、重油（ＪＩＳ Ｋ２２０５に記載）、洗浄油
又はそれらの混合物を挙げることができる。溶媒として
は、前述の有機ハロゲン化合物の分解反応に用いるもの
と同一又は異なっていてもよい。また、事前にステアリ
ン酸アルミ等の分散剤や凝集防止剤を加えてもよく、溶
媒として高粘度のアルカリ分散体を安定化させる溶媒を
用いた場合、分散剤、凝集防止剤を用いなくてもよい。In the present invention, examples of the alkali metal include sodium, potassium, lithium, cesium, and alloys thereof. In the present invention, the alkali metal is used in the form of a dispersion dispersed in a solvent. As the solvent used for preparing the alkali metal dispersion, an aliphatic hydrocarbon having a boiling point of 100 ° C. or higher and inert to the alkali metal is used. Or aromatic hydrocarbons, for example, toluene,
Xylene, kerosene, trans oil (JIS C232
0-1993), decalin, liquid paraffin, heavy oil (described in JIS K2205), washing oil or mixtures thereof. The solvent may be the same as or different from the solvent used for the above-mentioned decomposition reaction of the organic halogen compound. Also, a dispersant or an anti-agglomeration agent such as aluminum stearate may be added in advance, and when a solvent that stabilizes a high-viscosity alkali dispersion is used as a solvent, the dispersant or the anti-agglomeration agent may be used. Good.
【００１１】アルカリ金属分散体中のアルカリ金属濃度
は、任意に選択することが可能であるが、特に５〜５０
％程度のものが好ましい。また、アルカリ金属分散体は
公知の方法により調製することができ、例えばホモジナ
イザーを用いた方法などを適用することができるが、ア
ルカリ金属分散体におけるアルカリ金属の８０％以上
が、３０ミクロン以下、好ましくは１５ミクロン以下の
直径のアルカリ金属粒子であることが好ましい。The concentration of the alkali metal in the alkali metal dispersion can be arbitrarily selected.
% Is preferable. Further, the alkali metal dispersion can be prepared by a known method, for example, a method using a homogenizer can be applied. However, 80% or more of the alkali metal in the alkali metal dispersion is preferably 30 μm or less. Is preferably alkali metal particles having a diameter of 15 microns or less.
【００１２】本発明に用いられる活性水素化合物は、反
応に用いられる有機溶媒と混合しない化合物であれば、
特に制限されず、具体的には水、低級アルコール類、２
級低級アミン類、酢酸等の低級カルボン酸等を例示する
ことができ、これらは、１種又は２種以上の混合物とし
て使用することができる。特に、水、メタノール、エタ
ノール、ｎ−プロパノール、及びイソプロパノールから
なる群より選ばれる１種以上の化合物が好ましい。活性
水素化合物の添加量は、用いるアルカリ分散体に対して
２倍モル以下が好ましく、０．１〜１．５倍モル用いる
のが更に好ましい。The active hydrogen compound used in the present invention is a compound which does not mix with the organic solvent used in the reaction.
There is no particular limitation, and specifically, water, lower alcohols, 2
Examples thereof include lower amines, lower carboxylic acids such as acetic acid, and the like, and these can be used alone or as a mixture of two or more. In particular, one or more compounds selected from the group consisting of water, methanol, ethanol, n-propanol, and isopropanol are preferred. The amount of the active hydrogen compound to be added is preferably 2 times or less, more preferably 0.1 to 1.5 times the mole of the alkali dispersion used.
【００１３】本発明の有機ハロゲン化合物の分解方法
は、有機ハロゲン化合物とアルカリ金属分散体とを０℃
〜２００℃の温度範囲において反応させることができる
が、室温から溶媒沸点の温度範囲で行うのが好ましい。
また、活性水素化合物を用いる場合、室温から活性水素
化合物の沸点の温度範囲で行うのが好ましい。The method for decomposing an organic halogen compound according to the present invention comprises the steps of:
The reaction can be carried out at a temperature in the range of from 200 ° C. to 200 ° C., but is preferably carried out in a temperature range from room temperature to the boiling point of the solvent.
When an active hydrogen compound is used, the reaction is preferably performed at a temperature ranging from room temperature to the boiling point of the active hydrogen compound.
【００１４】また、本発明の有機ハロゲン化合物の分解
方法は、有機ハロゲン化合物のハロゲン原子１モルに対
して、１〜５００倍モル、好ましくは１．０５〜２００
モルのアルカリ金属分散体を使用する。特に反応温度を
１５０〜２００℃の高温で行う際、有機ハロゲン化合物
のハロゲン原子に対して２倍モル未満、中でも１倍モル
から２倍モル未満、特に１．１倍モルから１．６倍モル
のアルカリ金属分散体を使用するのが好ましい。The method for decomposing an organic halogen compound according to the present invention may be carried out in an amount of 1 to 500 times, preferably 1.05 to 200 times, 1 mole of a halogen atom of the organic halogen compound.
A molar alkali metal dispersion is used. In particular, when the reaction is carried out at a high temperature of 150 to 200 ° C., less than 2 moles, more preferably 1 mole to less than 2 moles, especially 1.1 mole to 1.6 moles, of the halogen atoms of the organic halogen compound. It is preferable to use an alkali metal dispersion of
【００１５】有機ハロゲン化合物とアルカリ金属分散体
との反応を実施する場合、反応液中に占める有機ハロゲ
ン化合物の濃度が高くなりすぎると、有機ハロゲン化合
物からの脱ハロゲン化により生成する重合物によって均
一な分散状態を得られなくなり、また反対に、有機ハロ
ゲン化合物濃度が低くなりすぎると、有機ハロゲン化合
物の処理に必要なアルカリ金属量が多くなることから、
アルカリ金属分散体と有機ハロゲン化合物とを混合した
時点で、有機ハロゲン化合物の混合液全体に占める濃度
が０．３重量％以上、より好ましくは１重量％以上、２
０重量％以下、より好ましくは１５重量％以下とするこ
とが望ましいが、分解処理する対象が、０．３重量未満
の有機ハロゲン化合物により汚染された有機溶媒の場合
でも、適切なアルカリ金属を用いるなら特に限定されな
い。また、反応は、安全のためアルゴン、窒素等の不活
性ガスの雰囲気下で行うことが望ましい。When the reaction between the organic halogen compound and the alkali metal dispersion is carried out, if the concentration of the organic halogen compound in the reaction solution is too high, the concentration of the organic halogen compound in the reaction solution is increased by the polymer produced by dehalogenation from the organic halogen compound. Disperse state cannot be obtained, and conversely, if the concentration of the organic halogen compound is too low, the amount of alkali metal required for treatment of the organic halogen compound increases,
At the time when the alkali metal dispersion and the organic halogen compound are mixed, the concentration of the organic halogen compound in the whole mixed solution is 0.3% by weight or more, more preferably 1% by weight or more,
It is desirable that the content be 0% by weight or less, more preferably 15% by weight or less. Even when the decomposition target is an organic solvent contaminated with less than 0.3% by weight of an organic halogen compound, an appropriate alkali metal is used. Is not particularly limited. The reaction is desirably performed in an atmosphere of an inert gas such as argon or nitrogen for safety.
【００１６】アルカリ金属分散体と有機ハロゲン化合物
との混合操作、及び反応を進行させるための反応液の加
熱操作としては、加熱したアルカリ金属分散体に有機ハ
ロゲン化合物もしくは有機ハロゲン化合物の溶液を加え
る方法、アルカリ金属分散体と有機ハロゲン化合物もし
くは有機ハロゲン化合物の溶液を混合した後に加熱する
方法、加熱した有機ハロゲン化合物の溶液にアルカリ金
属分散体を添加する方法、アルカリ金属分散体と有機ハ
ロゲン化合物もしくは有機ハロゲン化合物の溶液の双方
を加熱した後に混合する方法などを挙げることができ
る。The mixing operation of the alkali metal dispersion and the organic halogen compound and the heating operation of the reaction solution for promoting the reaction include adding an organic halogen compound or a solution of the organic halogen compound to the heated alkali metal dispersion. A method in which an alkali metal dispersion and a solution of an organic halogen compound or an organic halogen compound are mixed and then heated; a method in which an alkali metal dispersion is added to the heated solution of the organic halogen compound; A method in which both of the halogen compound solutions are heated and then mixed and the like can be mentioned.
【００１７】また、更に活性水素化合物を用いた場合、
その添加順序は任意に選択することができるが、中で
も、有機ハロゲン化合物とアルカリ金属分散体を混合し
ておき、加熱攪拌下、活性水素化合物を添加する方法が
好ましい。本発明においては、アルカリ金属分散体を１
度にではなく、複数回に分割して添加することを特徴と
する。これにより、反応系に含まれる不純物がアルカリ
金属分散体と反応することにより、除去され、後の反応
活性を低下させない効果がある。Further, when an active hydrogen compound is further used,
The order of addition can be arbitrarily selected, and among them, a method in which an organic halogen compound and an alkali metal dispersion are mixed, and an active hydrogen compound is added under heating and stirring is preferable. In the present invention, the alkali metal dispersion is
It is characterized in that it is added not every time but in multiple portions. This has the effect that impurities contained in the reaction system are removed by reacting with the alkali metal dispersion, and the subsequent reaction activity is not reduced.
【００１８】回数は、２回以上であれば、特に限定され
ないが、反応操作上、２回に分割して行うのが好まし
い。分割して添加する量は、分解反応に供される試料の
性状によってことなるが、最低限アルカリ金属分散体の
活性を失活させる化合物を除去できるだけの量を分割し
て添加するのが好ましい。具体的には、２回に分割して
添加する場合、添加する合計量の２分の１ずつを、順次
添加する方法を例示することができる。The number of times is not particularly limited as long as it is at least two times, but it is preferable to carry out the reaction in two times in view of the reaction operation. The amount to be divided and added depends on the properties of the sample to be subjected to the decomposition reaction, but it is preferable that the amount be divided and added so as to at least remove the compound that deactivates the activity of the alkali metal dispersion. Specifically, in the case of adding twice, for example, a method of sequentially adding one half of the total amount to be added can be exemplified.
【００１９】有機ハロゲン化合物、活性水素化合物との
添加順序についても、アルカリ金属分散体を分割して添
加すれば、特に限定されない。例えば、アルカリ金属分
散体を均等に２分割して加える方法において、加熱した
所定量の半分のアルカリ金属分散体に有機ハロゲン化合
物もしくは有機ハロゲン化合物の溶液を加えた後、更に
所定量の半分のアルカリ金属分散体を加える方法、所定
量の半分のアルカリ金属分散体に有機ハロゲン化合物も
しくは有機ハロゲン化合物の溶液を混合した後に加熱
し、更に所定量の半分のアルカリ金属分散体を加える方
法、加熱した有機ハロゲン化合物の溶液に所定量の半分
のアルカリ金属分散体を添加し、更に所定量の半分のア
ルカリ金属分散体を添加する方法、有機ハロゲン化合物
と所定量の半分のアルカリ金属分散体を混合しておき、
加熱攪拌下、活性水素化合物を添加し、更に、所定量の
半分のアルカリ金属分散体を添加する方法、有機ハロゲ
ン化合物と所定量の半分のアルカリ金属分散体を混合し
ておき、加熱攪拌下、所定量の半分の活性水素化合物を
添加し、更に、所定量の半分のアルカリ金属分散体を添
加し、所定量の半分の活性水素化合物を添加する方法等
を例示することができる。The order of addition of the organic halogen compound and the active hydrogen compound is not particularly limited as long as the alkali metal dispersion is added separately. For example, in a method in which an alkali metal dispersion is added in two equal portions, an organic halogen compound or a solution of an organic halogen compound is added to half of a heated predetermined amount of an alkali metal dispersion, and then a half of a predetermined amount of an alkali metal dispersion is further added. A method of adding a metal dispersion, a method of mixing an organic halogen compound or a solution of an organic halogen compound with half a predetermined amount of an alkali metal dispersion, heating the mixture, and further adding a predetermined amount of a half of an alkali metal dispersion; A method of adding a predetermined amount of a half alkali metal dispersion to a solution of a halogen compound, and further adding a predetermined amount of a half alkali metal dispersion, mixing an organic halogen compound and a predetermined amount of a half alkali metal dispersion. Every
Under heating and stirring, the active hydrogen compound is added, and further, a method of adding a predetermined amount of half of the alkali metal dispersion, mixing an organic halogen compound and a predetermined amount of half of the alkali metal dispersion, and heating and stirring, For example, a method of adding a half of the predetermined amount of the active hydrogen compound, further adding a half of the predetermined amount of the alkali metal dispersion, and adding a half of the predetermined amount of the active hydrogen compound can be exemplified.
【００２０】アルカリ金属分散体と有機ハロゲン化合物
の混合に費やす時間は、反応熱による温度上昇が操作上
の障害にならない温度範囲に収まる限り短縮することが
できる。この分解反応に要する時間は反応温度やアルカ
リ金属分散体の使用量により決定されるが、時間が長く
かかりすぎると処理能力が低下することから好ましくな
い。また、かかる反応を行うために用いられる装置とし
ては、回分式（バッチ式）あるいは連続式の反応装置を
使用することができ、これら反応装置に撹拌羽根等の攪
拌手段を設けて反応中の反応液を撹拌することが望まし
い。The time spent mixing the alkali metal dispersion and the organohalogen compound can be reduced as long as the temperature rise due to the heat of reaction does not hinder the operation. The time required for the decomposition reaction is determined by the reaction temperature and the amount of the alkali metal dispersion used. However, if the time is too long, it is not preferable because the processing capacity is reduced. In addition, a batch-type (batch-type) or continuous-type reaction apparatus can be used as an apparatus used for performing such a reaction. The reaction apparatus provided with stirring means such as a stirring blade may be used. It is desirable to stir the liquid.
【００２１】有機ハロゲン化合物とアルカリ金属との反
応が終了した後の処理方法としては従来公知の方法を適
用することができ、例えば、有機ハロゲン化合物がＰＣ
Ｂ等の場合には、まず、残存したアルカリ金属を、残存
したアルカリ金属と等モル以上の活性水素化合物、例え
ば、メタノール、エタノール、プロパノール、ブタノー
ル等のアルコール類、水、有機酸、あるいはこれらの混
合物と反応させる。この活性水素化合物にはアルカリ金
属ハロゲン化物、及びアルカリ金属水酸化物を含んでい
てもよい。脱ハロゲン化により重合物などの固形物が生
成する場合、濾過や遠心分離などの方法により、該固形
物と用いた溶媒などの液体に分離する。該固形物が生成
せず、活性水素化合物と混合しない有機溶媒を用いた場
合は、分液操作により、溶媒と水等の活性水素化合物を
分離する。As a treatment method after the reaction between the organic halogen compound and the alkali metal is completed, a conventionally known method can be applied.
In the case of B or the like, first, the remaining alkali metal is converted into an active hydrogen compound in an equimolar amount or more with the remaining alkali metal, for example, alcohols such as methanol, ethanol, propanol and butanol, water, organic acids, or these. React with the mixture. The active hydrogen compound may contain an alkali metal halide and an alkali metal hydroxide. When a solid such as a polymer is generated by dehalogenation, the solid is separated into a liquid such as a solvent used by a method such as filtration or centrifugation. When an organic solvent that does not generate the solid and does not mix with the active hydrogen compound is used, the solvent and the active hydrogen compound such as water are separated by a liquid separation operation.
【００２２】次に、必要に応じて液体成分から活性水素
化合物を分離し、必要なら活性白土による処理を行う
と、液体成分は再度溶媒として使用可能である。トラン
スオイルを用いた場合は、再びトランスオイルとして再
利用することが可能である。Next, if necessary, the active hydrogen compound is separated from the liquid component, and if necessary, treated with activated clay, the liquid component can be used again as a solvent. When using trans oil, it can be reused again as trans oil.
【００２３】以下に実施例を挙げて本発明を更に具体的
に説明するが、本発明の範囲はこれらの例示に限定され
るものではない。Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited to these examples.
【００２４】[0024]
【実施例】実施例１ １Ｌの反応容器にＰＣＢを４０ｐｐｍ含有する長期保存
されたトランスオイル２７０ｇを仕込んだ。反応容器中
を窒素により置換した後、前記溶液を６０℃まで加熱
し、撹拌混合しながら、新しいトランスオイルを溶媒と
して製造した１０重量％の金属ナトリウム分散体（以下
ＳＤと略す）２．５ｇ（粒径１０μｍ）を少しずつ添加
した。その後、温度を６０〜６５℃に維持し第１表に示
す所定の時間反応させた。その後、ＳＤを更に３．０ｇ
を添加し、更に温度を６０〜６５℃に維持し、水０．３
ｇを１時間かけて添加した。混合液の一部を抜き取り、
シリカゲルカラムによる前処理を施した後、ＥＣＤ検出
器付ガスクロマトグラフにより分析した。再現性を見る
ため第１回目のＳＤ添加後の時間につき２ロット繰り返
し反応を行った結果を第１表に示す。Example 1 A 1 L reaction vessel was charged with 270 g of long-term stored trans oil containing 40 ppm of PCB. After the atmosphere in the reaction vessel was replaced with nitrogen, the solution was heated to 60 ° C., and while stirring and mixing, 2.5 g of a 10% by weight sodium metal dispersion (hereinafter abbreviated as SD) manufactured using fresh trans oil as a solvent (hereinafter abbreviated as SD) (Particle size 10 μm) was added little by little. Thereafter, the temperature was maintained at 60 to 65 ° C., and the reaction was carried out for a predetermined time shown in Table 1. Then, further 3.0 g of SD
And maintaining the temperature at 60-65 ° C.
g was added over 1 hour. Withdraw part of the mixture,
After pretreatment with a silica gel column, analysis was performed by gas chromatography with an ECD detector. Table 1 shows the results of two lots of the reaction repeated for the time after the first SD addition in order to check the reproducibility.
【００２５】比較例１ 実施例１において、ＳＤを２回に分割して添加している
のを、分割せずに１度で添加した以外同様に反応をおこ
なった、再現性を見るため、５ロット繰り返し反応を行
った結果を第１表に示す。COMPARATIVE EXAMPLE 1 In Example 1, the addition of SD in two portions was repeated, except that the reaction was carried out in the same manner except that SD was added only once without dividing. Table 1 shows the results of the lot repetition reaction.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】以上本発明の有機ハロゲン化合物をアル
カリ金属分散体により脱塩素分解する処理方法におい
て、従来の方法よりも、分解に供される試料の性状に左
右されることなく、効率のよい無害化処理が可能となっ
た。As described above, in the treatment method of the present invention for dechlorinating and decomposing an organic halogen compound with an alkali metal dispersion, it is more efficient than conventional methods without being affected by the properties of the sample subjected to decomposition. Detoxification processing is now possible.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2E191 BA12 BA13 BB00 BC01 BC05 BD11 4H006 AA05 AC13 BA02 BB11 BB14 BB15 BB61 BC10 BC34 BD21 BE60 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2E191 BA12 BA13 BB00 BC01 BC05 BD11 4H006 AA05 AC13 BA02 BB11 BB14 BB15 BB61 BC10 BC34 BD21 BE60
Claims (9)
カリ金属分散体を反応させる有機ハロゲン化合物の分解
方法において、アルカリ金属分散体を複数回に分割して
添加することを特徴とする有機ハロゲン化合物の分解方
法。1. A method for decomposing an organic halogen compound by reacting an organic halogen compound and an alkali metal dispersion in an organic solvent, wherein the alkali metal dispersion is added in a plurality of portions. Decomposition method.
カリ金属分散体とを、該有機溶媒と混合しない活性水素
化合物を加えて反応させる有機ハロゲン化合物の分解方
法において、アルカリ金属分散体を複数回に分割して添
加することを特徴とする有機ハロゲン化合物の分解方
法。2. A method for decomposing an organic halogen compound in an organic solvent, comprising adding an active hydrogen compound which is not mixed with the organic solvent to the organic halogen compound and the alkali metal dispersion. A method for decomposing an organic halogen compound, which is divided and added.
カリ金属分散体とを、該有機溶媒と混合しない活性水素
化合物を加えて反応させる有機ハロゲン化合物の分解方
法において、アルカリ金属分散体を複数回に分割して添
加した後、該有機溶媒と混合しない活性水素化合物を添
加することを特徴とする有機ハロゲン化合物の分解方
法。3. A method for decomposing an organic halogen compound, wherein an organic halogen compound and an alkali metal dispersion are reacted with an active hydrogen compound which is not mixed with the organic solvent in an organic solvent. A method for decomposing an organic halogen compound, which comprises adding an active hydrogen compound that is not mixed with the organic solvent after the addition.
タノールからなる群より選ばれる少なくとも１種以上で
あることを特徴とする請求項１〜３のいずれかに記載の
有機ハロゲン化合物の分解方法。4. The method for decomposing an organic halogen compound according to claim 1, wherein the active hydrogen compound is at least one selected from the group consisting of water, methanol and ethanol.
族及び／又は芳香族炭化水素を溶媒であることを特徴と
する請求項１〜４のいずれかに記載の有機ハロゲン化合
物の分解方法。5. A method for decomposing an organic halogen compound according to claim 1, wherein the organic solvent is an aliphatic and / or aromatic hydrocarbon inert to an alkali metal. .
炭化水素として、ケロシン、デカリン、トランス油（Ｊ
ＩＳ Ｃ ２３２０−１９９３に記載のトランス油）、
重油（ＪＩＳ Ｋ２２０５に記載）、洗浄油から選ばれ
た１種又は２種以上を用いることを特徴とする請求項５
に記載の有機ハロゲン化合物の分解方法。6. An aliphatic or aromatic hydrocarbon inert to an alkali metal, such as kerosene, decalin or trans oil (J).
Transformer oil described in IS C 2320-1993),
6. One or more kinds selected from heavy oil (described in JIS K2205) and cleaning oil are used.
The method for decomposing an organic halogen compound according to the above.
の８０％以上が直径３０ミクロン以下のアルカリ金属粒
子を含むアルカリ金属分散体を用いることを特徴とする
請求項１〜６のいずれかに記載の有機ハロゲン化合物の
分解方法。7. The alkali metal dispersion according to claim 1, wherein an alkali metal dispersion containing at least 80% of the alkali metal particles having a diameter of 30 μm or less is used as the alkali metal dispersion. A method for decomposing an organic halogen compound.
特徴とする請求項７に記載の有機ハロゲン化合物の分解
方法。8. The method for decomposing an organic halogen compound according to claim 7, wherein the alkali metal is sodium.
類を含む難分解性ハロゲン化合物であることを特徴とす
る請求項１〜８のいずれかに記載の有機ハロゲン化合物
の分解方法。9. The method for decomposing an organic halogen compound according to claim 1, wherein the organic halogen compound is a hardly decomposable halogen compound containing polychlorinated biphenyls.
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| JP2000129067A JP4514284B2 (en) | 2000-04-28 | 2000-04-28 | Method for treating organohalogen compounds |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193482A (en) * | 2005-01-14 | 2006-07-27 | Kobelco Eco-Solutions Co Ltd | Method and apparatus for treating organohalogen compound |
| JP2006273802A (en) * | 2005-03-30 | 2006-10-12 | Nippon Soda Co Ltd | Method for inactivating residual alkali metal |
| JP2011217982A (en) * | 2010-04-11 | 2011-11-04 | Chugoku Electric Power Co Inc:The | Method and device for detoxifying pcb-containing insulating oil |
| JP2011255010A (en) * | 2010-06-09 | 2011-12-22 | Chugoku Electric Power Co Inc:The | Method of de-toxifying pcb mixed-in insulating oil and storage method for the same |
| JP2011254867A (en) * | 2010-06-07 | 2011-12-22 | Chugoku Electric Power Co Inc:The | De-toxifying equipment for pcb mixed-in insulating oil |
| JP2011254868A (en) * | 2010-06-07 | 2011-12-22 | Chugoku Electric Power Co Inc:The | Method of de-toxifying for pcb mixed-in insulating oil and storage method for the same |
| JP2013056065A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056062A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056066A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056067A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013223737A (en) * | 2013-05-30 | 2013-10-31 | Chugoku Electric Power Co Inc:The | Detoxification device of pcb-mixed insulating oil |
| JP2013236733A (en) * | 2012-05-15 | 2013-11-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for making organic halogen compound harmless |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4982570A (en) * | 1972-12-15 | 1974-08-08 | ||
| JPS6214061A (en) * | 1985-07-09 | 1987-01-22 | ラボフイナ・ソシエテ・アノニム | Method of treating oil containing poly-chlorinated biphenyl |
| JPH09216838A (en) * | 1996-02-09 | 1997-08-19 | Nippon Soda Co Ltd | Decomposition of halogen compound |
| JP2000015088A (en) * | 1998-06-29 | 2000-01-18 | Nippon Soda Co Ltd | Method for treating organic halogen compound |
-
2000
- 2000-04-28 JP JP2000129067A patent/JP4514284B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4982570A (en) * | 1972-12-15 | 1974-08-08 | ||
| JPS6214061A (en) * | 1985-07-09 | 1987-01-22 | ラボフイナ・ソシエテ・アノニム | Method of treating oil containing poly-chlorinated biphenyl |
| JPH09216838A (en) * | 1996-02-09 | 1997-08-19 | Nippon Soda Co Ltd | Decomposition of halogen compound |
| JP2000015088A (en) * | 1998-06-29 | 2000-01-18 | Nippon Soda Co Ltd | Method for treating organic halogen compound |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193482A (en) * | 2005-01-14 | 2006-07-27 | Kobelco Eco-Solutions Co Ltd | Method and apparatus for treating organohalogen compound |
| JP2006273802A (en) * | 2005-03-30 | 2006-10-12 | Nippon Soda Co Ltd | Method for inactivating residual alkali metal |
| JP2011217982A (en) * | 2010-04-11 | 2011-11-04 | Chugoku Electric Power Co Inc:The | Method and device for detoxifying pcb-containing insulating oil |
| JP2011254867A (en) * | 2010-06-07 | 2011-12-22 | Chugoku Electric Power Co Inc:The | De-toxifying equipment for pcb mixed-in insulating oil |
| JP2011254868A (en) * | 2010-06-07 | 2011-12-22 | Chugoku Electric Power Co Inc:The | Method of de-toxifying for pcb mixed-in insulating oil and storage method for the same |
| JP2011255010A (en) * | 2010-06-09 | 2011-12-22 | Chugoku Electric Power Co Inc:The | Method of de-toxifying pcb mixed-in insulating oil and storage method for the same |
| JP2013056065A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056062A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056066A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013056067A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| JP2013236733A (en) * | 2012-05-15 | 2013-11-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for making organic halogen compound harmless |
| JP2013223737A (en) * | 2013-05-30 | 2013-10-31 | Chugoku Electric Power Co Inc:The | Detoxification device of pcb-mixed insulating oil |
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