JP2002035159A - Method for treating oil contaminated with organic halogen compound and apparatus for treating it - Google Patents
Method for treating oil contaminated with organic halogen compound and apparatus for treating itInfo
- Publication number
- JP2002035159A JP2002035159A JP2000228242A JP2000228242A JP2002035159A JP 2002035159 A JP2002035159 A JP 2002035159A JP 2000228242 A JP2000228242 A JP 2000228242A JP 2000228242 A JP2000228242 A JP 2000228242A JP 2002035159 A JP2002035159 A JP 2002035159A
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- Prior art keywords
- oil
- organic halogen
- contaminated
- halogen compound
- treatment
- Prior art date
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- Fire-Extinguishing Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (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
物に汚染された汚染油の処理方法およびその処理装置に
関し、特に高濃度の有機ハロゲン化合物で汚染された汚
染油の処理に好適な処理方法および処理装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating contaminated oil contaminated with an organic halogen compound and a treatment apparatus therefor, and more particularly to a method and a method suitable for treating contaminated oil contaminated with a high concentration of an organic halogen compound. It relates to a processing device.
【０００２】[0002]
【従来の技術】従来、例えばポリ塩化ビフェニル（以
下、ＰＣＢともいう）等の有機ハロゲン化合物、及びこ
れによって汚染された汚染油（以下、単に汚染油とい
う）の処理手段としては、汚染油にアルカリ金属を添加
して有機ハロゲン化合物を脱ハロゲン化し、反応終了後
に水を添加して残存したアルカリ金属を水和し、炭酸ガ
ス等を注入して中和し、さらに水と油とを分離すること
により、脱塩素化された油を分離回収していた。2. Description of the Related Art Conventionally, as a means for treating an organic halogen compound such as polychlorinated biphenyl (hereinafter, also referred to as PCB) and a contaminated oil contaminated by the same (hereinafter, simply referred to as a contaminated oil), the contaminated oil is treated with an alkali. Adding a metal to dehalogenate an organic halogen compound, adding water after the reaction, hydrating the remaining alkali metal, injecting carbon dioxide or the like to neutralize, and further separating water and oil. As a result, the dechlorinated oil was separated and collected.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、汚染油
中の有機ハロゲン化合物の濃度が高い場合には、該有機
ハロゲン化合物はアルカリ金属との反応に際して副生成
物を生成し易く、このような副生成物が生成すれば、後
工程の処理が煩雑なものとなるという問題があった。However, when the concentration of the organic halogen compound in the contaminated oil is high, the organic halogen compound is liable to form a by-product when reacting with an alkali metal. If a product is generated, there is a problem that the processing in the subsequent process becomes complicated.
【０００４】従って、従来、高濃度で有機ハロゲン化合
物を含有する汚染油を処理する方法としては、アルカリ
金属分散体を含む多量の溶媒中に、該有機ハロゲン化合
物を少量ずつ加えることによって、これを脱塩素化する
方法が採用されていた。しかしながら、かかる処理方法
では、有機ハロゲン化合物の汚染油に対して、アルカリ
金属分散体を含む溶媒をきわめて多量に要することとな
り、経済性の悪いものであった。[0004] Therefore, conventionally, as a method of treating a contaminated oil containing a high concentration of an organic halogen compound, the organic halogen compound is added little by little to a large amount of a solvent containing an alkali metal dispersion. The method of dechlorination was adopted. However, such a processing method requires an extremely large amount of a solvent containing an alkali metal dispersion with respect to contaminated oil of an organic halogen compound, which is economically inefficient.
【０００５】また、高濃度の有機ハロゲン化合物を希釈
すべく希釈用の油を使用することも可能であるが、多量
の汚染油を処理する為には、それに応じて多量の希釈油
が必要になるとともに多量の処理済みの油が発生するこ
とにもなり、極めて効率の悪いものとなっていた。It is also possible to use a diluting oil to dilute a high concentration of an organic halogen compound. However, in order to treat a large amount of contaminated oil, a correspondingly large amount of diluting oil is required. As a result, a large amount of treated oil is generated, which is extremely inefficient.
【０００６】そこで、本発明は、汚染油中に含有した有
機ハロゲン化合物を処理する際に、副生成物の生成を抑
制しつつ、且つ効率よく処理することを課題とする。Accordingly, an object of the present invention is to efficiently treat an organic halogen compound contained in contaminated oil while suppressing the generation of by-products.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の課
題に鑑みて鋭意研究を重ねた結果、以下の発明を完成す
るに至った。Means for Solving the Problems The present inventors have made intensive studies in view of the above problems, and as a result, have completed the following invention.
【０００８】即ち、本発明の手段は、有機ハロゲン化合
物に汚染された汚染油にアルカリ金属又はアルカリ土類
金属を反応させて有機ハロゲン化合物を脱ハロゲン化処
理し、水を加えて水和処理し、中和剤を加えて中和処理
し、脱ハロゲン化された油と生成した塩を含む塩含有水
とに分離する有機ハロゲン化合物汚染油の処理方法にお
いて、前記脱ハロゲン化処理時における有機ハロゲン化
合物濃度を下げるべく、前記脱ハロゲン化された油を添
加することを特徴とする有機ハロゲン化合物汚染油の処
理方法にある。脱ハロゲン化された油の添加に際して
は、脱ハロゲン化処理時における液中の有機ハロゲン化
合物の濃度が３０重量％以下となるように添加すること
が好ましい。That is, in the means of the present invention, the contaminated oil contaminated with an organic halogen compound is reacted with an alkali metal or an alkaline earth metal to dehalogenate the organic halogen compound, and then hydrated by adding water. A neutralizing treatment by adding a neutralizing agent to separate the dehalogenated oil and salt-containing water containing the generated salt from the organic halogenated compound-contaminated oil. A method for treating an oil contaminated with an organic halogen compound, comprising adding the dehalogenated oil to reduce the compound concentration. When adding the dehalogenated oil, it is preferable to add the oil so that the concentration of the organic halogen compound in the liquid at the time of the dehalogenation treatment is 30% by weight or less.
【０００９】かかる処理方法によれば、汚染油中に高濃
度の有機ハロゲン化合物が含有されている場合や、汚染
油が有機ハロゲン化合物のみである場合にも、分離され
た油を希釈用として再利用することによって該有機ハロ
ゲン化合物の濃度を好ましい濃度にまで低減させること
ができるため、アルカリ金属又はアルカリ土類金属（以
下、これらを合わせてアルカリ金属等という）との反応
において副生成物の生成を抑制しつつ、且つ系外より希
釈油を加える必要もなく、効率的に有機ハロゲン化合物
を処理することが可能となる。According to this treatment method, the separated oil is reused for dilution even when the contaminated oil contains a high concentration of an organic halogen compound or when the contaminated oil is only an organic halogen compound. Since the concentration of the organic halogen compound can be reduced to a preferable concentration by using the compound, the formation of a by-product in a reaction with an alkali metal or an alkaline earth metal (hereinafter, these are collectively referred to as an alkali metal or the like). , And it is not necessary to add a diluting oil from outside the system, and it is possible to efficiently treat the organic halogen compound.
【００１０】さらに、本発明の手段は、前記脱ハロゲン
化された油をさらに脱水処理した後に、前記汚染油に添
加する有機ハロゲン化合物汚染油の処理方法にある。油
中に含まれる微量の水をさらに脱水処理することによ
り、脱塩素化反応の為に加えるアルカリ金属又はアルカ
リ土類金属と水が反応して該アルカリ金属等が消費され
ることを防止できるため、汚染油を希釈するために使用
する油として、より好ましいものとなる。Further, the means of the present invention is a method for treating an organic halogen compound contaminated oil to be added to the contaminated oil after the dehalogenated oil is further dehydrated. By further dehydrating a trace amount of water contained in the oil, the alkali metal or alkaline earth metal added for the dechlorination reaction can be prevented from reacting with water to consume the alkali metal or the like. Thus, the oil used for diluting the contaminated oil is more preferable.
【００１１】さらに、前記脱水処理が、減圧蒸留法によ
ってなされる有機ハロゲン化合物汚染油の処理方法にあ
る。前記脱水処理が減圧蒸留法によってなされることに
より、遠心分離等の比重差を利用した分離手段では分離
困難な微量の水をも除去できるため、処理油の希釈用と
してより好適な高純度の油を得ることが可能となる。ま
た、減圧蒸留法によれば、通常の蒸留と比べて低い加熱
温度で処理することができるため、副生成物の生成が少
なく、油が劣化しにくいという利点がある。Further, there is provided a method for treating an organic halogen compound contaminated oil, wherein the dehydration treatment is performed by a vacuum distillation method. Since the dehydration treatment is performed by a reduced pressure distillation method, it is possible to remove even a trace amount of water that is difficult to separate by a separation means utilizing a specific gravity difference such as centrifugation, and thus a high-purity oil more suitable for diluting the treated oil. Can be obtained. In addition, according to the vacuum distillation method, since the treatment can be performed at a lower heating temperature than in the ordinary distillation, there is an advantage that the generation of by-products is small and the oil is hardly deteriorated.
【００１２】また、前記脱水処理においては、脱水剤を
使用することが好ましく、該脱水剤としては、前記塩含
有水を加熱して得られる塩の無水物を使用することがで
きる。該処理方法において副生成する塩の無水物を使用
することによって、別途脱水剤を必要とせず、且つ油を
不必要に加熱する必要がない。In the dehydration treatment, a dehydrating agent is preferably used. As the dehydrating agent, an anhydride of a salt obtained by heating the salt-containing water can be used. By using an anhydride of a salt by-produced in the treatment method, there is no need for a separate dehydrating agent and no need to unnecessarily heat the oil.
【００１３】さらに、本発明の手段は、前記塩含有水よ
り水を蒸発させて回収し、前記脱ハロゲン化処理又は前
記水和処理において使用する有機ハロゲン化合物汚染油
の処理方法にある。油と分離された塩含有水には、高濃
度の塩類や有機物等が含まれているため、従来は希釈水
を加えて塩濃度を下げた後、生物処理する必要があった
が、本発明によれば、このような排水処理が不要とな
る。Further, the means of the present invention is a method for treating an organic halogen compound contaminated oil used in the dehalogenation treatment or the hydration treatment by recovering the salt-containing water by evaporating water. Since salt-containing water separated from oil contains high-concentration salts and organic substances, conventionally, it was necessary to reduce the salt concentration by adding dilution water and then carry out biological treatment. According to this, such wastewater treatment becomes unnecessary.
【００１４】また、本発明の手段は、前記塩含有水より
水を蒸発させて残留物を固体状にする有機ハロゲン化合
物汚染油の処理方法にある。残留物を固体状にすること
により、生物処理で発生する汚泥を処理する場合に比べ
て取り扱いが容易になる。[0014] The means of the present invention is a method for treating an oil contaminated with an organic halogen compound by evaporating water from the salt-containing water to solidify the residue. By making the residue solid, handling becomes easier than when sludge generated in biological treatment is treated.
【００１５】また、本発明の手段は、有機ハロゲン化合
物に汚染された汚染油にアルカリ金属又はアルカリ土類
金属を反応させて該有機ハロゲン化合物を脱ハロゲン化
処理する脱ハロゲン化手段と、水を加えて水和処理する
水和手段と、中和剤を加えて中和処理する中和手段と、
脱ハロゲン化された油と生成した塩を含む塩含有水とに
分離する分離手段からなる有機ハロゲン化合物の処理装
置において、前記脱ハロゲン化された油を前記汚染油に
添加するような油循環手段が具備されたことを特徴とす
る有機ハロゲン化合物汚染油の処理装置にある。The present invention also provides a dehalogenating means for reacting a contaminated oil contaminated with an organic halogen compound with an alkali metal or an alkaline earth metal to dehalogenate the organic halogen compound; In addition, a hydration means for performing a hydration treatment, and a neutralization means for adding a neutralizer and performing a neutralization treatment
An apparatus for treating an organic halogen compound, comprising a separating means for separating a dehalogenated oil and a salt-containing water containing a generated salt, wherein an oil circulating means for adding the dehalogenated oil to the contaminated oil The treatment device for contaminated oil of an organic halogen compound is characterized by comprising:
【００１６】[0016]
【発明の実施の形態】以下、本発明に係る有機ハロゲン
化合物汚染油の処理方法および処理装置について、図面
を参照しつつ説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method and an apparatus for treating oil contaminated with an organic halogen compound according to the present invention will be described with reference to the drawings.
【００１７】本発明の処理装置の一実施形態は、図１に
概略フローを示したように、反応装置１、分離装置２、
脱水装置３を主たる構成要素として構成される。ここ
で、反応装置１は脱ハロゲン化手段と水和手段と中和手
段を兼ね備えたものであり、具体的には、処理対象であ
る有機ハロゲン化合物含有の汚染油Ａの供給装置１０、
アルカリ金属等Ｂの供給装置１１、水Ｃの供給装置１
２、中和剤Ｄの供給装置１３が具備され、さらに、反応
後の処理液が分離手段である分離装置２へ輸送されるべ
く構成されてなる。また、分離装置２には、反応装置１
の処理液が供給される処理液供給装置１４が具備される
とともに、該処理液を分離した後の塩含有水Ｅと油Ｆと
を排出する排出装置１５、１６がそれぞれ具備されてな
る。One embodiment of the processing apparatus of the present invention, as shown in a schematic flow chart in FIG.
The dehydrating device 3 is configured as a main component. Here, the reactor 1 has both dehalogenation means, hydration means, and neutralization means. Specifically, the supply apparatus 10 for the contaminated oil A containing the organic halogen compound to be treated,
Supply device 11 for B such as alkali metal, supply device 1 for water C
2. A supply device 13 for the neutralizing agent D is provided, and furthermore, the treatment liquid after the reaction is configured to be transported to the separation device 2 as a separation means. Further, the separation device 2 includes the reaction device 1
And a discharge device 15, 16 for discharging the salt-containing water E and the oil F after the separation of the processing liquid.
【００１８】さらに、前記処理装置には、油Ｆの排出装
置１６には、該油Ｆの一部を分岐させて脱水装置３へ供
給する油分岐装置１７と、該脱水装置３から油Ｆを再び
汚染油Ａに供給すべく構成された油循環装置１８とが具
備されてなる。Further, in the treatment device, an oil F discharging device 16 includes an oil branching device 17 that branches a part of the oil F and supplies the oil F to the dehydrating device 3, and the oil F from the dehydrating device 3. And an oil circulation device 18 configured to supply the contaminated oil A again.
【００１９】以下、上記処理装置の使用方法とともに、
本発明に係る有機ハロゲン化合物汚染油の処理方法の一
実施例について、図２に基づき説明する。Hereinafter, together with the method of using the above-described processing apparatus,
One embodiment of the method for treating an organic halogen compound contaminated oil according to the present invention will be described with reference to FIG.
【００２０】まず、前記反応装置１に汚染油Ａ、及び溶
媒中に分散させたアルカリ金属等Ｂを入れ、有機ハロゲ
ン化合物にアルカリ金属等を作用させることにより、該
有機ハロゲン化合物を脱ハロゲン化処理する。ここでの
反応温度は、副生成物の生成を抑えるために７０〜１０
０℃、好ましくは８０〜９０℃とする。脱ハロゲン化処
理した後に残存するアルカリ金属等は、水Ｃを添加する
ことによって水和処理し、さらに中和剤Ｄを加えること
によって中和処理する。以上の処理を行うことにより、
反応装置１内には、主として塩類を含有した塩含有水
と、脱ハロゲン化された有機物を含有する油（「脱ハロ
ゲン化された油」ともいう）との混合物が生成される。First, the contaminated oil A and the alkali metal B dispersed in a solvent are put into the reactor 1 and the organic halogen compound is allowed to act on the organic halogen compound, thereby dehalogenating the organic halogen compound. I do. The reaction temperature here is 70 to 10 to suppress the generation of by-products.
0 ° C., preferably 80 to 90 ° C. The alkali metal and the like remaining after the dehalogenation treatment are hydrated by adding water C, and further neutralized by adding a neutralizing agent D. By performing the above processing,
In the reaction device 1, a mixture of salt-containing water mainly containing salts and an oil containing a dehalogenated organic substance (also referred to as “dehalogenated oil”) is generated.
【００２１】次いで、該混合物を分離装置２へ輸送し、
該分離装置２において塩含有水Ｅと脱ハロゲン化された
油Ｆとに分離する。さらに、該脱ハロゲン化された油Ｆ
を脱水装置３によって脱水処理した後、油循環装置１８
を介して有機ハロゲン化合物の濃度を下げるべく汚染油
Ａに添加する。Next, the mixture is transported to the separation device 2,
In the separation device 2, the water E is separated into salt-containing water E and dehalogenated oil F. Further, the dehalogenated oil F
Is dehydrated by the dehydration device 3 and then the oil circulation device 18
To the contaminated oil A to reduce the concentration of the organic halogen compound.
【００２２】ここで、汚染油中の有機ハロゲン化合物を
効率的に脱ハロゲン化処理するためには、アルカリ金属
等との接触の際の反応液中の有機ハロゲン化合物濃度が
少なくとも３０重量％以下、好ましくは２０重量％以下
であることが好ましい。濃度が３０重量％より高くなれ
ば、反応液（汚染油Ａに脱ハロゲン化された油Ｆ、およ
び必要に応じてアルカリ金属等の分散媒や反応促進剤等
を加えたもの）の粘度が増大し、反応液の混合攪拌に多
大なエネルギーを要することとなり、あるいは攪拌が不
十分となって反応効率が低下するという点で好ましくな
い。Here, in order to efficiently dehalogenate the organic halogen compound in the contaminated oil, the concentration of the organic halogen compound in the reaction solution upon contact with an alkali metal or the like should be at least 30% by weight or less. It is preferably 20% by weight or less. When the concentration is higher than 30% by weight, the viscosity of the reaction solution (contaminated oil A to which dehalogenated oil F and, if necessary, a dispersing medium such as an alkali metal and a reaction accelerator) are increased. However, a large amount of energy is required for the mixing and stirring of the reaction solution, or the stirring is insufficient and the reaction efficiency is lowered, which is not preferable.
【００２３】従って、汚染油Ａの希釈に際しては、予め
測定した汚染油Ａ中の有機ハロゲン化合物の濃度、およ
びアルカリ金属等分散媒や反応促進剤の添加量に応じ
て、上記の好ましい濃度範囲となるような量を調整しつ
つ脱ハロゲン化された油Ｆを添加する。Accordingly, when diluting the contaminated oil A, the preferred concentration range described above depends on the concentration of the organic halogen compound in the contaminated oil A measured in advance and the amount of the dispersing medium such as an alkali metal and the reaction accelerator added. The dehalogenated oil F is added while adjusting the amount to be as small as possible.
【００２４】前記有機ハロゲン化合物汚染油の処理方法
によれば、汚染油Ａ中に高濃度の有機ハロゲン化合物が
含有されている場合にも、脱ハロゲン化された油Ｆを添
加することによって該濃度を低下させ、脱ハロゲン化反
応において好適な濃度とすることが可能となる。また、
前記処理装置によれば、油循環装置を具備しているた
め、上記方法による汚染油の処理を効率良く行うことが
可能となる。According to the above-mentioned method for treating an organic halogen compound-contaminated oil, even when a high concentration of an organic halogen compound is contained in the contaminated oil A, the concentration of the organic halogen compound can be reduced by adding the dehalogenated oil F. And a suitable concentration in the dehalogenation reaction can be obtained. Also,
According to the treatment device, since the oil circulation device is provided, the treatment of the contaminated oil by the above method can be performed efficiently.
【００２５】ここで、前記脱水処理の手段としては、副
生成物の生成を抑えつつ、脱ハロゲン化された油に含ま
れた微小量の水分を効率よく除去することを鑑みれば、
減圧蒸留法か、若しくは脱水剤を使用するものが好まし
い。Here, considering the means for the dehydration treatment, in view of efficiently removing a minute amount of water contained in the dehalogenated oil while suppressing the generation of by-products,
A vacuum distillation method or a method using a dehydrating agent is preferred.
【００２６】減圧蒸留法としては、前記油Ｆを圧力８０
〜１２０Ｔｏｒｒ、温度９０〜１００℃の条件下におい
て、０．５〜２．０時間の蒸留操作を行うことにより、
脱ハロゲン化された油を変質させることなく脱水処理す
ることができる。In the vacuum distillation method, the oil F is subjected to a pressure of 80
By performing a distillation operation for 0.5 to 2.0 hours under the conditions of to 120 Torr and a temperature of 90 to 100 ° C.,
The dehalogenated oil can be dehydrated without altering the quality.
【００２７】また、前記脱水剤としては、シリカゲル等
の公知の脱水剤を使用することも可能であるが、当該処
理工程において生成される塩類を脱水剤として利用する
こともでき、これによって別途脱水剤が不要となる。即
ち、脱ハロゲン化された油Ｆと分離された塩含有水Ｅよ
り水分を蒸発させ、残存する塩類をさらに加熱すること
によって、塩類が無水化された無水物を得ることがで
き、該無水物と前記脱ハロゲン化された油Ｆとを接触さ
せることによって、脱ハロゲン化された油Ｆ中に含まれ
る水分を好適に除去することができる。As the dehydrating agent, a known dehydrating agent such as silica gel can be used, but salts formed in the treatment step can be used as the dehydrating agent. No agent is required. That is, by evaporating the water from the dehalogenated oil F and the separated salt-containing water E and further heating the remaining salts, it is possible to obtain an anhydride in which the salts are dehydrated, By bringing the oil F into contact with the dehalogenated oil F, water contained in the dehalogenated oil F can be suitably removed.
【００２８】より具体的に説明すれば、例えば、アルカ
リ金属等Ａとして金属ナトリウムを使用し、中和剤Ｄと
して炭酸ガスを注入した場合には、塩類として炭酸ナト
リウムが生成されるが、これを加熱処理することによっ
て得られる炭酸ナトリウムの無水物を、前記脱水剤とし
て利用することができる。More specifically, for example, when sodium metal is used as the alkali metal A or the like and carbon dioxide gas is injected as the neutralizing agent D, sodium carbonate is generated as salts. Anhydrous sodium carbonate obtained by heat treatment can be used as the dehydrating agent.
【００２９】また、前記塩含有水Ｅについては、蒸発乾
固処理することが好ましい。より具体的に説明すると、
先ず、前記塩含有水を加熱して水分を蒸発させることに
より、含有されている塩を濃縮する。次いで、窒素ガス
雰囲気下、約３００〜４５０℃の条件において更に加熱
することにより、水分を完全に除去し、前記塩を固形物
として回収する。一方、加熱において蒸発した水蒸気
は、触媒を作用させて極微小量の有機ハロゲン化合物を
も分解した後、凝縮して回収する。The salt-containing water E is preferably subjected to an evaporation to dryness treatment. More specifically,
First, the salt is concentrated by heating the salt-containing water to evaporate the water. Next, by further heating under a nitrogen gas atmosphere at about 300 to 450 ° C., water is completely removed, and the salt is recovered as a solid. On the other hand, the water vapor evaporated during the heating is decomposed by a catalyst to decompose an extremely small amount of an organic halogen compound, and then condensed and recovered.
【００３０】このような蒸発乾固処理を行うことによっ
て、塩含有水Ｅについて、従来のような生物処理や活性
炭処理をすることが不要となり、また、含有成分である
塩類についても、固形物として取り扱うことができるた
め、従来のように汚泥として処理する場合に比べて処理
が極めて容易となる。加えて、蒸発乾固処理によって得
られた塩類の固形物は、上述のような脱水剤として利用
することができる。By performing the evaporation to dryness treatment, the salt-containing water E does not need to be subjected to the conventional biological treatment or activated carbon treatment, and the salts as the components are also converted into solids. Since it can be handled, the treatment becomes extremely easy as compared with the conventional case of treating as sludge. In addition, the solids of salts obtained by the evaporating and drying treatment can be used as a dehydrating agent as described above.
【００３１】さらに、塩含有水Ｅを蒸発乾固する際に蒸
発した水を回収することにより、前記水和処理において
使用する水Ｃとして再利用することが可能となり、水に
ついては系外への排出をなくすことが可能となる。Further, by recovering the water evaporated when the salt-containing water E is evaporated to dryness, the water can be reused as the water C used in the hydration treatment. Emissions can be eliminated.
【００３２】本発明の処理対象である有機ハロゲン化合
物としては、例えば、ポリ塩化ビフェニル類（ＰＣＢ）
やダイオキシン類等の塩素化有機化合物を挙げることが
でき、また、汚染油としては、例えば、電気絶縁油や、
熱媒体用の油、潤滑油、あるいは、固体中に含まれる有
機ハロゲン化合物を抽出した鉱油等を挙げることができ
る。The organic halogen compounds to be treated in the present invention include, for example, polychlorinated biphenyls (PCB)
And chlorinated organic compounds such as dioxins and the like, and as the contaminated oil, for example, electric insulating oil,
Examples include oils for heat medium, lubricating oils, and mineral oils from which organic halogen compounds contained in solids are extracted.
【００３３】また、前記アルカリ金属としては、リチウ
ム、ナトリウム、カリウム等を使用することができ、前
記アルカリ土類金属としては、カルシウム、ストロンチ
ウム等を使用することができる。また、これらアルカリ
金属等は、不活性な有機溶剤中に、５０μｍ以下、好ま
しくは１〜１０μｍの粒子として分散された状態で使用
されることが好ましい。As the alkali metal, lithium, sodium, potassium and the like can be used, and as the alkaline earth metal, calcium, strontium and the like can be used. These alkali metals and the like are preferably used in a state of being dispersed as particles of 50 μm or less, preferably 1 to 10 μm in an inert organic solvent.
【００３４】さらに、中和処理において使用する中和剤
としては、前記アルカリ金属等を中和するものであれば
よいが、中でも前記アルカリ金属等との中和反応および
その後の加熱処理によって脱水剤として使用可能な無水
塩を生成するものが好ましく、かかる点を考慮すれば、
炭酸ガス、硫酸、リン酸が好ましい。これら以外にも、
塩酸、硝酸等の無機酸、あるいは酢酸、ギ酸、シュウ酸
等の有機酸を中和剤として使用することができる。The neutralizing agent used in the neutralization treatment may be any as long as it neutralizes the above alkali metal and the like. Among them, a dehydrating agent is obtained by the neutralization reaction with the above alkali metal and the like and the subsequent heat treatment. It is preferable to produce an anhydrous salt that can be used as
Carbon dioxide, sulfuric acid and phosphoric acid are preferred. Besides these,
Inorganic acids such as hydrochloric acid and nitric acid, or organic acids such as acetic acid, formic acid and oxalic acid can be used as neutralizing agents.
【００３５】尚、分離された油Ｆは、必ずしも全量を希
釈用に使用するものに限定するものではなく、生成した
量及び汚染油中の有機ハロゲン化合物濃度に応じて適宜
系外へ出すものとする。Incidentally, the separated oil F is not necessarily limited to the whole used for dilution, but may be appropriately discharged to the outside according to the generated amount and the concentration of the organic halogen compound in the contaminated oil. I do.
【００３６】また、脱ハロゲン化された油を添加する際
には、汚染油に直接添加する場合に限られず、予め反応
装置へ入れておくことや、アルカリ金属等の分散媒に加
えておくことも可能である。即ち、脱ハロゲン化処理時
において、有機ハロゲン化合物の濃度が所定値以下とな
るように加えるものであればよく、その方法や時期につ
いては限定するものではない。The addition of the dehalogenated oil is not limited to the direct addition to the contaminated oil, but may be carried out beforehand in a reactor or in a dispersion medium such as an alkali metal. Is also possible. That is, it is only necessary to add the organic halogen compound at the time of the dehalogenation treatment so that the concentration of the organic halogen compound becomes a predetermined value or less, and the method and timing are not limited.
【００３７】以下、本発明の実施例について説明する。Hereinafter, embodiments of the present invention will be described.
【００３８】（実施例１）汚染油としてＰＣＢ（ＫＣ−
３００相当）７５ｇを準備し、これに事前の処理におい
て脱ハロゲン化された油３８０ｇと反応促進剤としてイ
ソプロピルアルコール６５ｇを１０００ｍｌの混合容器
に入れた後、攪拌混合して被処理液を調整した。次い
で、２０００ｍｌの反応容器に脱ハロゲン化された油５
０ｇ、及びトランス油に金属ナトリウムを分散させた金
属ナトリウム分散液（Ｎａ濃度４０重量％）２００ｇと
を仕込み、攪拌しながら前記被処理液を加えた。(Example 1) PCB (KC-
75 g of (equivalent to 300) were prepared, and 380 g of the oil dehalogenated in the previous treatment and 65 g of isopropyl alcohol as a reaction accelerator were put in a 1000 ml mixing vessel, followed by stirring and mixing to prepare a liquid to be treated. Then, the dehalogenated oil 5 was placed in a 2000 ml reaction vessel.
0 g and 200 g of a metallic sodium dispersion (Na concentration: 40% by weight) in which metallic sodium was dispersed in transformer oil were added, and the above-mentioned liquid to be treated was added with stirring.
【００３９】さらに、この状態のまま温度を９０℃に保
ちつつ３時間反応させた後、反応液のＰＣＢ濃度をガス
クロマトグラフ分析計で測定したところ、ＰＣＢ濃度が
０．０５ｍｇ／ｋｇ以下であることが確認できた。After reacting for 3 hours while maintaining the temperature at 90 ° C. in this state, when the PCB concentration of the reaction solution was measured by a gas chromatograph analyzer, it was found that the PCB concentration was 0.05 mg / kg or less. Was confirmed.
【００４０】続いて、反応液に水１０００ｍｌを加えて
残存金属ナトリウムを水和処理し、さらに、水和処理後
の液に炭酸ガスを１５ｌ／ｍｉｎで６０分間吹き込み、
中和処理した。中和処理後の液を１２時間静置し、油水
分離することにより、脱ハロゲン化された油を回収する
ことができた。Subsequently, 1000 ml of water was added to the reaction solution to hydrate the remaining metallic sodium, and carbon dioxide gas was blown into the solution after the hydration treatment at 15 l / min for 60 minutes.
Neutralized. The liquid after the neutralization treatment was allowed to stand for 12 hours, and oil-water separation was performed to recover the dehalogenated oil.
【００４１】[0041]
【発明の効果】以上のように、本発明に係る有機ハロゲ
ン化合物汚染油の処理方法によれば、汚染油中に高濃度
の有機ハロゲン化合物が含まれている場合にも、処理後
の油を再利用することによって副生成物の生成を抑制し
つつ且つ効率よく該有機ハロゲン化合物を脱ハロゲン化
処理することができる。As described above, according to the method for treating oil contaminated with an organic halogen compound according to the present invention, even if the contaminated oil contains a high concentration of an organic halogen compound, the oil after the treatment can be used. By reusing, the organic halogen compound can be efficiently dehalogenated while suppressing generation of by-products.
【図1】本発明に係る有機ハロゲン化合物の処理装置の
一実施形態を示す概略フロー図。FIG. 1 is a schematic flow chart showing one embodiment of an apparatus for treating an organic halogen compound according to the present invention.
【図２】本発明の処理工程の一実施形態を示した図。FIG. 2 is a view showing one embodiment of a processing step of the present invention.
Ａ…汚染油、Ｂ…アルカリ金属又はアルカリ土類金属、
Ｃ…水、Ｄ…中和剤、Ｅ…塩含有水、Ｆ…油、１…反応
装置、２…分離装置、３…脱水装置、１８…循環装置A: contaminated oil, B: alkali metal or alkaline earth metal,
C: water, D: neutralizing agent, E: salt-containing water, F: oil, 1: reaction device, 2 ... separation device, 3 ... dehydration device, 18 ... circulation device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 22/04 Ｃ０７Ｃ 22/04 Ｃ１０Ｇ 17/08 Ｃ１０Ｇ 17/08 29/04 29/04 29/06 29/06 31/08 31/08 53/10 53/10 (72)発明者 加藤 治 加古川市神野町石守467−１ Ｃ12−307 Ｆターム(参考） 2E191 BA13 BC01 BD11 4D017 AA04 BA01 CA05 CB01 DA01 EA03 4D076 AA02 AA12 AA14 AA22 BA01 BB13 CD22 HA03 HA06 JA01 4H006 AA05 AC24 BA02 BA06 BA85 4H029 DA04 DA06 DA14 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C07C 22/04 C07C 22/04 C10G 17/08 C10G 17/08 29/04 29/04 29/06 29 / 06 31/08 31/08 53/10 53/10 (72) Inventor Osamu Kato 467-1 Ishimori, Kaminocho, Kakogawa C12-307 F term (reference) 2E191 BA13 BC01 BD11 4D017 AA04 BA01 CA05 CB01 DA01 EA03 4D076 AA02 AA12 AA14 AA22 BA01 BB13 CD22 HA03 HA06 JA01 4H006 AA05 AC24 BA02 BA06 BA85 4H029 DA04 DA06 DA14
Claims (9)
にアルカリ金属又はアルカリ土類金属を反応させて有機
ハロゲン化合物を脱ハロゲン化処理し、水を加えて水和
処理し、中和剤を加えて中和処理し、脱ハロゲン化され
た油と生成した塩を含む塩含有水とに分離する有機ハロ
ゲン化合物汚染油の処理方法において、前記脱ハロゲン
化処理時における有機ハロゲン化合物濃度を下げるべ
く、前記脱ハロゲン化された油を添加することを特徴と
する有機ハロゲン化合物汚染油の処理方法。1. An organic metal compound is dehalogenated by reacting the contaminated oil contaminated with the organic halogen compound with an alkali metal or an alkaline earth metal, water is added thereto, hydrated, and a neutralizing agent is added. Neutralization treatment, in a method for treating an organic halogen compound-contaminated oil separated into dehalogenated oil and salt-containing water containing a generated salt, in order to reduce the concentration of the organic halogen compound during the dehalogenation treatment, A method for treating oil contaminated with an organic halogen compound, comprising adding the dehalogenated oil.
ロゲン化合物濃度が３０重量％以下となるように、前記
脱ハロゲン化された油を添加する請求項１記載の有機ハ
ロゲン化合物汚染油の処理方法。2. The method according to claim 1, wherein the dehalogenated oil is added so that the concentration of the organic halogen compound during the dehalogenation treatment is 30% by weight or less.
処理した後に、前記汚染油に添加する請求項１又は２記
載の有機ハロゲン化合物汚染油の処理方法。3. The method according to claim 1, wherein the dehalogenated oil is further dehydrated and then added to the contaminated oil.
される請求項３記載の有機ハロゲン化合物汚染油の処理
方法。4. The method according to claim 3, wherein the dehydration treatment is performed by a vacuum distillation method.
れる請求項３又は４記載の有機ハロゲン化合物汚染油の
処理方法。5. The method according to claim 3, wherein a dehydrating agent is used in the dehydration treatment.
水物を前記脱水剤とする請求項５記載の有機ハロゲン化
合物汚染油の処理方法。6. The method according to claim 5, wherein an anhydride of a salt obtained by heating the salt-containing water is used as the dehydrating agent.
し、前記脱ハロゲン化処理又は前記水和処理において使
用する請求項１〜６のいずれかに記載の有機ハロゲン化
合物汚染油の処理方法。7. The method for treating a contaminated oil of an organic halogen compound according to claim 1, wherein the salt-containing water is recovered by evaporating water and used in the dehalogenation treatment or the hydration treatment. .
を固体状にする請求項１〜７のいずれかに記載の有機ハ
ロゲン化合物汚染油の処理方法。8. The method for treating oil contaminated with an organic halogen compound according to claim 1, wherein water is evaporated from the salt-containing water to solidify the residue.
にアルカリ金属又はアルカリ土類金属を反応させて該有
機ハロゲン化合物を脱ハロゲン化処理する脱ハロゲン化
手段と、水を加えて水和処理する水和手段と、中和剤を
加えて中和処理する中和手段と、脱ハロゲン化された油
と生成した塩を含む塩含有水とに分離する分離手段から
なる有機ハロゲン化合物の処理装置において、前記脱ハ
ロゲン化された油を前記汚染油に添加するような油循環
手段が具備されたことを特徴とする有機ハロゲン化合物
汚染油の処理装置。9. A dehalogenating means for reacting a contaminated oil contaminated with an organic halogen compound with an alkali metal or an alkaline earth metal to dehalogenate the organic halogen compound, and hydrating by adding water. In an apparatus for treating an organic halogen compound, the apparatus comprises a hydration means, a neutralization means for adding a neutralizing agent and performing a neutralization treatment, and a separation means for separating the dehalogenated oil and salt-containing water containing a produced salt. And an oil circulating means for adding the dehalogenated oil to the contaminated oil.
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|---|---|---|---|
| JP2000228242A JP3771120B2 (en) | 2000-07-28 | 2000-07-28 | Method and apparatus for treating organic halogen compound contaminated oil |
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Cited By (5)
| 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 |
| JPWO2009087994A1 (en) * | 2008-01-07 | 2011-05-26 | 財団法人名古屋産業科学研究所 | Aromatic halide dehalogenation method |
| JP2013056063A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| WO2015146769A1 (en) * | 2014-03-26 | 2015-10-01 | 株式会社ネオス | Method for low-temperature selective fixing of halogenated aromatic compound contained in medium |
| WO2023095035A1 (en) * | 2021-11-23 | 2023-06-01 | Sabic Global Technologies B.V. | Systems and methods for removal of halogenated contaminants from pyrolysis oil by inert gas purging |
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|---|---|---|---|---|
| JPS62152479A (en) * | 1985-12-06 | 1987-07-07 | チバ−ガイギ アクチエンゲゼルシヤフト | Dehalogenation of halogenated aliphatic and aromatic compounds |
| JP2001231882A (en) * | 2000-02-23 | 2001-08-28 | Tosoh Corp | Method for dehalogenation of organic halogen compound |
| JP2001294539A (en) * | 2000-04-13 | 2001-10-23 | Tosoh Corp | Method for dehalogenating organic halogen compound |
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2000
- 2000-07-28 JP JP2000228242A patent/JP3771120B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62152479A (en) * | 1985-12-06 | 1987-07-07 | チバ−ガイギ アクチエンゲゼルシヤフト | Dehalogenation of halogenated aliphatic and aromatic compounds |
| JP2001231882A (en) * | 2000-02-23 | 2001-08-28 | Tosoh Corp | Method for dehalogenation of organic halogen compound |
| JP2001294539A (en) * | 2000-04-13 | 2001-10-23 | Tosoh Corp | Method for dehalogenating organic halogen compound |
Cited By (6)
| 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 |
| JPWO2009087994A1 (en) * | 2008-01-07 | 2011-05-26 | 財団法人名古屋産業科学研究所 | Aromatic halide dehalogenation method |
| JP2013056063A (en) * | 2011-09-08 | 2013-03-28 | Chugoku Electric Power Co Inc:The | Method and apparatus for detoxicating halogen compound-containing oil |
| WO2015146769A1 (en) * | 2014-03-26 | 2015-10-01 | 株式会社ネオス | Method for low-temperature selective fixing of halogenated aromatic compound contained in medium |
| JPWO2015146769A1 (en) * | 2014-03-26 | 2017-04-13 | 株式会社ネオス | Low temperature selective fixing method of halogenated aromatic compound contained in medium |
| WO2023095035A1 (en) * | 2021-11-23 | 2023-06-01 | Sabic Global Technologies B.V. | Systems and methods for removal of halogenated contaminants from pyrolysis oil by inert gas purging |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3771120B2 (en) | 2006-04-26 |
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