JP2003313595A - Method for decontaminating organic halogen contaminant and decontamination system for the same - Google Patents
Method for decontaminating organic halogen contaminant and decontamination system for the sameInfo
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- JP2003313595A JP2003313595A JP2002123735A JP2002123735A JP2003313595A JP 2003313595 A JP2003313595 A JP 2003313595A JP 2002123735 A JP2002123735 A JP 2002123735A JP 2002123735 A JP2002123735 A JP 2002123735A JP 2003313595 A JP2003313595 A JP 2003313595A
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- organic halogen
- cleaning
- water
- decontaminating
- organic solvent
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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
物に汚染された有機ハロゲン汚染物を、洗浄剤で洗浄す
る有機ハロゲン汚染物の除染方法及びその除染システム
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for decontaminating an organic halogen contaminant contaminated with an organic halogen compound with a cleaning agent, and a decontamination system therefor.
【０００２】[0002]
【従来の技術】ポリ塩化ビフェニル（以下、「ＰＣＢ」
という場合がある。）、ダイオキシン類等の有機ハロゲ
ン化合物は、環境汚染物質として知られており、近年、
これらの有機ハロゲン化合物に汚染された有機ハロゲン
汚染物を如何に除染するかが問題となっている。特に、
ＰＣＢは、非常に化学的に安定しており分解され難く、
しかも、絶縁性（電気抵抗）が高いことから、従前にお
いてはトランスやコンデンサー等の絶縁材料や熱媒体等
に頻繁に用いられていたため、トランスやコンデンサー
等のＰＣＢ汚染物を如何に除染するかが重大な問題とな
っている。2. Description of the Related Art Polychlorinated biphenyl (hereinafter referred to as "PCB")
There is a case. ), Organic halogen compounds such as dioxins are known as environmental pollutants, and in recent years,
The problem is how to decontaminate organic halogen contaminants contaminated with these organic halogen compounds. In particular,
PCB is very chemically stable and difficult to decompose,
Moreover, because of its high insulation (electrical resistance), it has been frequently used in the past as an insulating material for transformers, capacitors, etc., and as a heat medium. How to decontaminate PCB contaminants such as transformers, capacitors, etc. Has become a serious problem.
【０００３】従来、この種の有機ハロゲン汚染物の除染
方法としては、有機ハロゲン化合物を溶かしうる有機溶
媒を洗浄剤（洗浄液）として用い、有機ハロゲン汚染物
を洗浄することにより、汚染物に含まれる有機ハロゲン
化合物を除去する除染方法が採用されている。この方法
によれば、汚染物に含まれる有機ハロゲン化合物を溶か
しうる有機溶媒を洗浄剤として用いることから、効率的
に汚染物中の有機ハロゲン化合物を洗浄除去することが
できる。Conventionally, as a method for decontaminating organic halogen pollutants of this type, an organic solvent capable of dissolving an organic halogen compound is used as a cleaning agent (cleaning liquid), and the organic halogen pollutants are washed to contain them. The decontamination method of removing the organic halogen compound is adopted. According to this method, since the organic solvent capable of dissolving the organic halogen compound contained in the contaminant is used as the cleaning agent, the organic halogen compound in the contaminant can be efficiently washed and removed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記従
来の有機ハロゲン汚染物の除染方法に於いては、有機ハ
ロゲン化合物の殆ど含まれない除染物とするためには、
洗浄剤たる有機溶媒を何度も代えて多数回洗浄を行う必
要があり、その為、洗浄作業に時間がかかり、多量の洗
浄剤を使用しなければならないという問題を有してい
る。更に、上述の如き除染物とする為には、洗浄後、真
空加熱により、残存する有機ハロゲン化合物を蒸発除去
する必要があるという問題をも有している。しかも、洗
浄廃液には、多くの有機ハロゲン化合物が含まれている
ことから、これらの洗浄廃液中の有機ハロゲン化合物を
アルカリ金属を用いて分解し、無害化させるという洗浄
廃液の無害化処理が必要となるという問題も有してい
る。However, in the above conventional method for decontaminating organic halogen pollutants, in order to obtain a decontamination product containing almost no organic halogen compound,
Since it is necessary to change the organic solvent as a cleaning agent many times and perform cleaning many times, the cleaning operation takes time and a large amount of cleaning agent must be used. Further, in order to obtain the decontaminated product as described above, there is also a problem that it is necessary to evaporate and remove the remaining organic halogen compound by vacuum heating after washing. Moreover, since the cleaning waste liquid contains many organic halogen compounds, it is necessary to detoxify the cleaning waste liquid by decomposing the organic halogen compounds in these cleaning waste liquids with an alkali metal to render them harmless. It also has the problem that
【０００５】そこで、上記従来の問題点に鑑み、本発明
の課題は、多量の洗浄剤を使用する必要も無く、比較的
短時間の洗浄によって、有機ハロゲン化合物を殆ど含ま
ない除染物とすることができ、しかも、洗浄廃液に有機
ハロゲン化合物が殆ど含まれない有機ハロゲン汚染物の
除染方法及びその除染システムを提供することにある。Therefore, in view of the above-mentioned conventional problems, an object of the present invention is to provide a decontamination product containing almost no organic halogen compound by cleaning for a relatively short time without using a large amount of cleaning agent. And a decontamination method of an organic halogen contaminant in which the cleaning waste liquid contains almost no organic halogen compound.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記従来の
問題点に鑑み鋭意検討した結果、下記手段によって上記
課題を解決できることを見出し、本発明に至った。即
ち、本発明に係る有機ハロゲン汚染物の除染方法は、有
機ハロゲン化合物で汚染された有機ハロゲン化合物を洗
浄剤で洗浄する有機ハロゲン汚染物の除染方法であっ
て、前記洗浄剤として、アルカリ金属が存在した状態の
有機溶媒を用いることを特徴とする。As a result of intensive studies in view of the above-mentioned conventional problems, the present inventor has found that the above-mentioned problems can be solved by the following means, and has completed the present invention. That is, the method for decontaminating an organic halogen contaminant according to the present invention is a method for decontaminating an organic halogen contaminant contaminated with an organic halogen compound with a cleaning agent, wherein the cleaning agent is an alkali It is characterized by using an organic solvent in the presence of a metal.
【０００７】斯かる方法に於いては、洗浄剤で汚染物を
洗浄すると、汚染物に含まれる有機ハロゲン化合物は、
有機溶媒に溶解し、有機溶媒中に存在するアルカリ金属
により脱ハロゲン化される。このとき、アルカリ金属と
有機ハロゲン化合物は、ラジカル反応（機構）により脱
ハロゲン化され、多量の反応熱を放出することから、該
反応熱によって、有機溶媒が加熱され、有機ハロゲン化
合物の溶解性が向上する。そして、汚染物から更に有機
ハロゲン化合物が溶出し、溶出した有機ハロゲン化合物
は、有機溶媒中でアルカリ金属により脱ハロゲン化さ
れ、連鎖的に、有機ハロゲン化合物の溶出と脱ハロゲン
化が繰り返され、洗浄が一気に進行する。従って、洗浄
剤を何度も取り替えて多数回洗浄することを要せず、多
量の洗浄剤を使用することなく、比較的短時間で除染物
にすることができ、しかも、有機溶媒に溶出した有機ハ
ロゲン化合物がアルカリ金属により脱ハロゲン化される
ことから、洗浄廃液は、有機ハロゲン化合物が殆ど含ま
れないものとなる。In this method, when the contaminant is washed with the detergent, the organic halogen compound contained in the contaminant is
It is dissolved in an organic solvent and dehalogenated by an alkali metal present in the organic solvent. At this time, the alkali metal and the organohalogen compound are dehalogenated by a radical reaction (mechanism) and release a large amount of heat of reaction, so that the organic solvent is heated by the heat of reaction and the solubility of the organohalogen compound is increased. improves. Then, the organic halogen compound is further eluted from the contaminants, and the eluted organic halogen compound is dehalogenated by an alkali metal in an organic solvent, and the elution and dehalogenation of the organic halogen compound are repeated in a chain to wash. Progresses all at once. Therefore, it is not necessary to replace the cleaning agent many times and wash many times, and a decontamination product can be obtained in a relatively short time without using a large amount of cleaning agent, and moreover, it was eluted in an organic solvent. Since the organic halogen compound is dehalogenated by the alkali metal, the cleaning waste liquid contains almost no organic halogen compound.
【０００８】本発明に於いては、前記有機溶媒として
は、有機ハロゲン化合物を溶かし得るものであれば、特
に限定されるものでは無いが、２重結合を有しない炭化
水素が好ましい。斯かる有機溶媒であれば、有機溶媒と
アルカリ金属が反応してアルカリ金属を消費する虞が低
減され、更に、アルカリ金属がアルカリ金属イオンとな
り有機溶媒に溶解して反応性が無くなる虞も低減される
ことから、アルカリ金属の浪費を抑制することができ
る。In the present invention, the organic solvent is not particularly limited as long as it can dissolve an organic halogen compound, but a hydrocarbon having no double bond is preferable. With such an organic solvent, the risk that the organic solvent reacts with the alkali metal to consume the alkali metal is reduced, and further, the risk that the alkali metal becomes an alkali metal ion and dissolves in the organic solvent to reduce the reactivity is also reduced. Therefore, waste of the alkali metal can be suppressed.
【０００９】また、本発明に於いて、前記炭化水素とし
ては、パラフィンが好ましい。パラフィンは、非常に安
定で、アルカリ金属によって比較的脱プロトン化されに
くく、アルカリ金属を浪費する虞がより一層低減すると
共に、パラフィン同士が重合し難く、有機溶媒の粘度上
昇による洗浄性の低下を抑制することができる。特に、
パラフィンの中でも、ノルマルパラフィンが好ましい。
ノルマルパラフィンは、第３級炭素を有しない為、より
一層脱プロトン化されにくく、更に、アルカリ金属を浪
費する虞がより一層低減すると共に、上記洗浄性の低下
をより一層抑制することができる。また、パラフィン、
特に、ノルマルパラフィンは、不飽和結合を有さず酸化
安定性に優れており、有機ハロゲン化合物とアルカリ金
属との反応熱によっても酸化され難いことから、洗浄廃
液から回収して洗浄に再利用した場合でも、酸化物によ
りアルカリ金属が消費されるという虞も殆どない。In the present invention, the hydrocarbon is preferably paraffin. Paraffin is extremely stable and is relatively difficult to be deprotonated by an alkali metal, which further reduces the risk of wasting the alkali metal, and makes it difficult for paraffins to polymerize with each other, resulting in a decrease in detergency due to an increase in viscosity of the organic solvent. Can be suppressed. In particular,
Among paraffins, normal paraffin is preferable.
Since normal paraffin does not have a tertiary carbon, it is more difficult to deprotonate, the risk of wasting alkali metal is further reduced, and the deterioration of the above-mentioned detergency can be further suppressed. Also paraffin,
In particular, normal paraffin does not have an unsaturated bond and is excellent in oxidative stability, and is not easily oxidized by the heat of reaction between an organic halogen compound and an alkali metal. Therefore, normal paraffin is recovered from the cleaning waste liquid and reused for cleaning. Even in this case, there is almost no fear that the oxide will consume the alkali metal.
【００１０】更に、本発明に於いては、前記汚染物がコ
ンデンサー素子であるのが好ましい。斯かる方法によれ
ば、洗浄後に水洗することにより、コンデンサー素子の
アルミ箔を、水洗に用いた水、即ち、未反応のアルカリ
金属が溶解してアルカリ性となった水に溶かすことがで
きるので、従来困難であったアルミ箔と絶縁紙との分離
を容易に行うことができる。Further, in the present invention, the contaminant is preferably a capacitor element. According to such a method, by washing with water after washing, the aluminum foil of the capacitor element can be dissolved in water used for washing, that is, unreacted alkali metal is dissolved and becomes alkaline, It is possible to easily separate the aluminum foil and the insulating paper, which has been difficult in the past.
【００１１】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、ハロゲンを有す
るジベンゾフラン類、ポリ塩化ベンゼン、塩化メチレン
或いはこれらに含まれる塩素原子が臭素原子に置換され
た臭素化物等の有害な有機ハロゲン化合物を挙げること
ができる。また、アルカリ金属としては、ナトリウム、
リチウム、カリウム、ルビジウム等を挙げることがで
き、中でも反応速度、取扱いの容易さからナトリウムが
好ましい。Examples of the organic halogen compound in the present invention include harmful substances such as PCB, dioxins, halogen-containing dibenzofurans, polychlorobenzene, methylene chloride and bromides in which chlorine atoms contained in these are substituted by bromine atoms. Examples thereof include organic halogen compounds. Also, as the alkali metal, sodium,
Examples thereof include lithium, potassium and rubidium. Among them, sodium is preferable from the viewpoint of reaction rate and easy handling.
【００１２】本発明に係る有機ハロゲン汚染物の除染シ
ステムは、有機ハロゲン化合物で汚染された有機ハロゲ
ン汚染物を洗浄剤で洗浄する洗浄部を備えた有機ハロゲ
ン汚染物の除染システムであって、前記洗浄剤が、アル
カリ金属が存在した状態の有機溶媒であることを特徴と
する。斯かる構成からなる有機ハロゲン汚染物の無害化
処理システムによれば、請求項１記載の方法を好適に実
施することができる。The organic halogen contaminant decontamination system according to the present invention is an organic halogen contaminant decontamination system having a cleaning unit for cleaning an organic halogen contaminant contaminated with an organic halogen compound with a cleaning agent. The cleaning agent is an organic solvent in the presence of an alkali metal. According to the detoxification treatment system for organic halogen pollutants having such a constitution, the method according to claim 1 can be suitably implemented.
【００１３】[0013]
【発明の実施の形態】以下、本発明の好ましい実施の形
態として、有機ハロゲン汚染物として、コンデンサーを
例に取り、除染方法及びその除染システムについて図面
を参照しつつ説明する。BEST MODE FOR CARRYING OUT THE INVENTION As a preferred embodiment of the present invention, a decontamination method and its decontamination system will be described with reference to the drawings, taking a condenser as an example of an organic halogen contaminant.
【００１４】先ず、除染システムについて説明する。図
１は、本実施形態に於けるＰＣＢの無害化処理方法及び
そのシステムを示す概略フロー図である。図１に示すよ
うに、本実施形態のシステムは、コンデンサーに充填さ
れた油（ＰＣＢ）を抜く抜油部２と、抜油されたコンデ
ンサーを解体する解体部３と、解体部３にて解体された
解体物を洗浄槽内にて金属ナトリウムが存在した状態の
有機溶媒で洗浄する洗浄部１と、洗浄部１にて洗浄され
除染された解体物たる除染物を乾燥させる乾燥部５とを
備えている。尚、本実施形態に於いては、前記有機溶媒
として、炭素数９〜１３、好ましくは、炭素数１０〜１
２のパラフィン、特に、ノルマルパラフィンが使用され
る。前記除染システムは、更に、洗浄廃液中に存在する
ＰＣＢとナトリウムとの反応生成物たる塩化ナトリウム
を水に抽出させるべく、洗浄廃液に水を添加する水和部
６と、水和後、静置分離又は蒸留により、水と有機溶媒
とを分離する油水分離部７とを備え、油水分離部７にて
分離された有機溶媒は、洗浄剤用として、洗浄部１にて
再利用されるように構成されている。First, the decontamination system will be described. FIG. 1 is a schematic flow chart showing a detoxification processing method for a PCB and its system according to the present embodiment. As shown in FIG. 1, the system according to the present embodiment is disassembled by an oil removing section 2 for removing oil (PCB) filled in a condenser, a disassembling section 3 for disassembling the removed oil condenser, and a disassembling section 3. A cleaning unit 1 for cleaning the dismantled material with an organic solvent in a state where metallic sodium is present in the cleaning tank, and a drying unit 5 for drying the decontaminated material as the dismantled material cleaned and decontaminated by the cleaning unit 1 are provided. ing. In the present embodiment, the organic solvent has 9 to 13 carbon atoms, preferably 10 to 1 carbon atoms.
Two paraffins are used, especially normal paraffins. The decontamination system further comprises a hydration unit 6 for adding water to the cleaning waste liquid in order to extract sodium chloride, which is a reaction product of PCB and sodium present in the cleaning waste liquid, into water, and a hydration unit after hydration. An oil-water separation unit 7 that separates water and an organic solvent by standing separation or distillation is provided, and the organic solvent separated by the oil-water separation unit 7 is reused in the cleaning unit 1 as a cleaning agent. Is configured.
【００１５】図２によく示されているように、前記解体
部３は、コンデンサーを解体し、解体物とするように構
成されている。具体的には、コンデンサーを構成部材た
るコンデンサー容器、コンデンサー素子、付属物にそれ
ぞれ解体分離し、３種の解体物とするように構成されて
いる。本実施形態に於いては、前記洗浄部１として、解
体部３にて解体分離された各種解体物（コンデンサー容
器、コンデンサー素子、及び付属物）をそれぞれ別々に
洗浄しうるように、コンデンサー容器用、コンデンサー
素子用、付属物用の洗浄部１をそれぞれ備えており、更
に、洗浄後の各種解体物をそれぞれ水洗し、付着した未
反応のナトリウムを分解しつつ水に抽出させる水洗部４
と、水洗後の各種解体物をそれぞれ乾燥させる乾燥部５
とをそれぞれ備えている。As shown in FIG. 2, the dismantling section 3 is configured to dismantle a capacitor to form a dismantled object. Specifically, the capacitor is configured to be disassembled and separated into a condenser container, a condenser element, and an accessory, which are constituent members, to obtain three kinds of disassembled articles. In the present embodiment, the cleaning unit 1 is for a capacitor container so that various dismantled objects (capacitor container, capacitor element, and accessories) disassembled and separated by the dismantling unit 3 can be separately cleaned. A washing section 4 for washing the dismantled materials after washing and decomposing the unreacted sodium adhering to water while decomposing the unreacted sodium.
And a drying unit 5 for drying various dismantled materials after washing with water
And are provided respectively.
【００１６】更に、本実施形態に於いては、コンデンサ
ー素子を水洗する水洗部４から排出される廃水を、炭酸
ガスの注入等により中和する中和部９と、中和部９によ
り析出する固形分たる水酸化アルミニウムを乾燥させる
乾燥部５を備えている。Further, in the present embodiment, the waste water discharged from the washing section 4 for washing the condenser element is deposited by the neutralization section 9 for neutralizing by injection of carbon dioxide gas and the neutralization section 9. A drying unit 5 for drying solid aluminum hydroxide is provided.
【００１７】次に、本実施形態のシステムを用いて、コ
ンデンサーを除染する除染方法について説明する。先
ず、コンデンサーに穴を開け、抜油部２にてコンデンサ
ーに充填された油（ＰＣＢ）を抜油する。次いで、解体
部３にて、コンデンサーの蓋を切断し、汚染された３種
の構成部材、即ち、コンデンサーをコンデンサー容器
（蓋を含む）、コンデンサー素子、その他の付属物に解
体分離して、汚染された３種の解体物とする。Next, a decontamination method for decontaminating a capacitor using the system of this embodiment will be described. First, a hole is made in the condenser, and the oil (PCB) filled in the condenser is removed in the oil removing section 2. Next, in the disassembly unit 3, the lid of the condenser is cut, and the three kinds of contaminated constituent members, that is, the condenser, are disassembled and separated into a condenser container (including the lid), a condenser element, and other accessories to contaminate. The three types of dismantled objects are
【００１８】次いで、各種解体物を、それぞれ別々の洗
浄部１の洗浄槽に供給し、洗浄剤としてナトリウムが分
散した有機溶媒を用い、該有機溶媒を洗浄槽に満たして
洗浄する。即ち、コンデンサー容器をコンデンサー容器
用の洗浄部１に、コンデンサー素子をコンデンサー素子
用の洗浄部１に、付属品を付属品用の洗浄部１に供給
し、それぞれ各洗浄部１にて洗浄する。尚、有機溶媒と
しては、炭素数９〜１３のノルマルパラフィンを使用す
る。具体的には、洗浄槽内に解体物とナトリウムの分散
した有機溶媒とを供給し、反応熱を利用して加熱しつ
つ、攪拌により洗浄する。斯かる操作により、アルカリ
金属と解体物に付着したＰＣＢは、有機溶媒中に溶出
し、有機溶媒中に分散したアルカリ金属と反応して脱ハ
ロゲン化されると共に、周囲に反応熱を放出する。更
に、反応熱により加熱された有機溶媒は、ＰＣＢの溶解
性が向上することから、更に多くのＰＣＢが有機溶媒に
溶出し、更に多くのＰＣＢが連鎖的にアルカリ金属によ
って脱ハロゲン化される。尚、洗浄剤を用いた洗浄にお
いては、循環ポンプを用いて洗浄槽内の洗浄剤を循環さ
せたり、超音波発信器により洗浄剤を振動させることに
より（即ち、超音波洗浄を採用することにより）、洗浄
効率を向上させても良い。尚、反応を円滑に進行させる
ためには、ＰＣＢの塩素量よりも過剰のナトリウムが必
要であり、しかも、解体物には、ナトリウムを消費する
水分、硫黄、フェノール、及び水酸基含有成分等が含ま
れている虞もあることから、通常、ＰＣＢの分解に必要
な化学当量よりも３〜１０倍のナトリウムを洗浄槽に供
給する。Next, the various dismantled materials are supplied to the respective separate cleaning tanks of the cleaning unit 1, and an organic solvent in which sodium is dispersed is used as a cleaning agent, and the cleaning tank is filled with the organic solvent for cleaning. That is, the condenser container is supplied to the condenser container cleaning unit 1, the capacitor element is supplied to the capacitor element cleaning unit 1, and the accessory is supplied to the accessory cleaning unit 1, and each cleaning unit 1 cleans. As the organic solvent, normal paraffin having 9 to 13 carbon atoms is used. Specifically, the dismantled material and the organic solvent in which sodium is dispersed are supplied into the cleaning tank, and cleaning is performed by stirring while heating by using reaction heat. By such an operation, the PCB adhering to the alkali metal and the dismantled product is eluted in an organic solvent, reacts with the alkali metal dispersed in the organic solvent to be dehalogenated, and releases heat of reaction to the surroundings. Further, since the solubility of PCB in the organic solvent heated by the heat of reaction is improved, more PCB is eluted in the organic solvent, and more PCB is chain-dehalogenated by the alkali metal. In the case of cleaning with a cleaning agent, the cleaning agent in the cleaning tank is circulated using a circulation pump, or the cleaning agent is vibrated by an ultrasonic transmitter (that is, by using ultrasonic cleaning. ), And cleaning efficiency may be improved. In order for the reaction to proceed smoothly, sodium in excess of the chlorine content of PCB is required, and the dismantled product contains water that consumes sodium, sulfur, phenol, and hydroxyl group-containing components. Therefore, 3 to 10 times more sodium than the chemical equivalent required for the decomposition of PCB is usually supplied to the cleaning tank.
【００１９】更に、洗浄に際しては、更に、イソプロピ
ルアルコールや水等の水素供与体を洗浄槽に供給する。
斯かる操作により、脱ハロゲン化反応により生成したビ
フェニルラジカルは、水素の供与を受け、粘度の高いビ
フェニルの重合体が生成する虞が抑制され、反応を円滑
に進めることができる。Further, upon cleaning, a hydrogen donor such as isopropyl alcohol and water is further supplied to the cleaning tank.
By such an operation, the biphenyl radical generated by the dehalogenation reaction receives the donation of hydrogen and the possibility that a high-viscosity biphenyl polymer is generated is suppressed, and the reaction can proceed smoothly.
【００２０】洗浄後、洗浄槽から各種解体物を金網等を
用いて濾別し、水洗部４にて、各種解体物を水に浸漬し
て水洗する。斯かる操作により、各種解体物に付着した
未反応のナトリウムは、分解され水酸化ナトリウムとし
て水に抽出される。更に、コンデンサー素子のアルミニ
ウムは、水酸化ナトリウムと反応して水酸化アルミニウ
ムとして水に抽出される。従って、コンデンサー素子の
構成部材たる絶縁紙とアルミ箔とを分離する作業を別途
行うことなく、絶縁紙をアルミニウムと分離して回収す
ることができる。After washing, various dismantled materials are filtered out from the cleaning tank by using a wire net or the like, and in the water washing section 4, the various dismantled materials are immersed in water and washed with water. By such an operation, unreacted sodium adhering to various dismantled products is decomposed and extracted into water as sodium hydroxide. Furthermore, the aluminum of the capacitor element reacts with sodium hydroxide and is extracted into water as aluminum hydroxide. Therefore, the insulating paper can be separated and collected from the aluminum without separately performing the work of separating the insulating paper and the aluminum foil, which are the constituent members of the capacitor element.
【００２１】尚、この水酸化アルミニウムは、アルカリ
に可溶であるが、中性の水には不溶であるので、水酸化
アルミニウムを抽出した水を、中和部９にて炭酸ガスの
注入等によって中和することにより、水酸化アルミニウ
ムを固形分として析出させることができる。このとき、
水酸化ナトリウムが炭酸水素ナトリウムとなって炭酸水
素ナトリウムが析出することから、固形分を中性の水で
洗い炭酸水素ナトリウムを水に溶かすことにより、炭酸
水素ナトリウムを殆ど含まない水酸化アルミニウムの固
形分を回収できる。この水酸化アルミニウムの固形分
は、例えば、埋め立て等により廃棄しうる。Since this aluminum hydroxide is soluble in alkali but insoluble in neutral water, the water from which aluminum hydroxide has been extracted is fed with carbon dioxide gas at the neutralization section 9 or the like. By neutralizing with, aluminum hydroxide can be precipitated as a solid content. At this time,
Since sodium hydroxide turns into sodium hydrogen carbonate and sodium hydrogen carbonate precipitates, the solid content is washed with neutral water and the sodium hydrogen carbonate is dissolved in water. The minutes can be collected. The solid content of this aluminum hydroxide can be discarded by, for example, landfill.
【００２２】前記水洗部４にて各種解体物を水洗した
後、各種解体物をそれぞれ乾燥部５にて乾燥させ、乾燥
後、除染物として鉄、絶縁紙、水酸化アルミニウム等を
回収する。After the various demolition products are washed with water in the water washing unit 4, the various demolition products are respectively dried in the drying unit 5, and after drying, iron, insulating paper, aluminum hydroxide and the like are recovered as decontamination products.
【００２３】前記洗浄部１にて洗浄した後の洗浄廃液
は、水和部６に供給し、水和部６にて水を添加する。解
体物の洗浄により排出される洗浄廃液には、反応生成物
たる塩化ナトリウム、ナトリウムイソプロポキシド、未
反応のナトリウム等が含まれているが、斯かる操作によ
り、洗浄廃液中の塩化ナトリウムは、水に抽出され、未
反応のナトリウムは、水に分解されて抽出される。同時
に、未反応のイソプロピルアルコールやナトリウムイソ
プロポキシドも同様に水に抽出される。The cleaning waste liquid after cleaning in the cleaning unit 1 is supplied to the hydration unit 6, and water is added in the hydration unit 6. The cleaning waste liquid discharged by the cleaning of the dismantled product contains reaction products such as sodium chloride, sodium isopropoxide, and unreacted sodium, but by such an operation, sodium chloride in the cleaning waste liquid is Extracted into water, unreacted sodium is decomposed into water and extracted. At the same time, unreacted isopropyl alcohol and sodium isopropoxide are also extracted into water.
【００２４】次いで、水和部６にて水の添加された洗浄
廃液を、油水分離部７に供給する。油水分離部７に於い
ては、静置分離により、洗浄剤とビフェニルと水とを分
離する。具体的には、先ず、静置し５℃以下に冷却する
ことにより、水層と油層に層分離させる。この時、洗浄
剤に溶解したビフェニルは、水層と油層との中間部に析
出することになる。次いで、ビフェニルを濾過等により
回収し、層分離した油層たる洗浄剤と水層たる塩化ナト
リウムを抽出した水とを分離回収する。回収した有機溶
媒は、洗浄部１に於ける洗浄剤用として再利用する。斯
かる操作により、ビフェニルの殆ど混ざっていない有機
溶媒を回収し洗浄部１にて再利用することができる。
尚、回収したビフェニルは廃棄し、水は、廃アルカリと
して処分する。若しくは、適宜生物処理及び活性炭処理
等の処理を施して廃水として放流する。或いは、蒸留等
により、水やアルコールを分離回収し、水を水和部６に
て再利用したり、水やアルコールを水素供与体として再
利用する。Then, the washing waste liquid to which water has been added in the hydration unit 6 is supplied to the oil / water separation unit 7. In the oil / water separator 7, the cleaning agent, biphenyl and water are separated by static separation. Specifically, first, the mixture is allowed to stand and cooled to 5 ° C. or lower to separate the water layer and the oil layer. At this time, the biphenyl dissolved in the detergent deposits in the intermediate portion between the water layer and the oil layer. Next, the biphenyl is recovered by filtration or the like, and the cleaning agent as an oil layer and the water in which sodium chloride is extracted as an aqueous layer are separated and recovered. The recovered organic solvent is reused as a cleaning agent in the cleaning unit 1. By such an operation, the organic solvent in which biphenyl is hardly mixed can be recovered and reused in the cleaning unit 1.
The recovered biphenyl will be discarded and the water will be disposed of as waste alkali. Alternatively, biological treatment and activated carbon treatment are appropriately applied and discharged as wastewater. Alternatively, water or alcohol is separated and recovered by distillation or the like, and water is reused in the hydration unit 6, or water or alcohol is reused as a hydrogen donor.
【００２５】尚、本実施形態の有機ハロゲン汚染物の除
染方法及びその除染システムは、上記如き構成を採用し
たが、本発明の有機ハロゲン汚染物の除染方法及びその
除染システムは、上記構成に限定されず適宜設計変更可
能である。例えば、本実施形態に於いては、解体部３に
て、複数の構成部材に解体分離して複数種の解体物とし
たが、複数の構成部材に分離せずに破砕して解体物と
し、該解体物を１つの洗浄部１で洗浄する場合であって
も、本発明の意図する範囲内である。The decontamination method for organic halogen contaminants and the decontamination system thereof according to the present embodiment employ the above-described structure. However, the decontamination method for organic halogen contaminants and the decontamination system thereof according to the present invention are as follows. The design is not limited to the above configuration, and the design can be changed as appropriate. For example, in the present embodiment, in the dismantling section 3, a plurality of constituent members are disassembled and separated into a plurality of kinds of dismantled objects, but the plurality of constituent members are not separated and crushed into disassembled objects, Even when the dismantled material is cleaned by one cleaning unit 1, it is within the scope intended by the present invention.
【００２６】また、本実施形態に於いては、ナトリウム
の分散した有機溶媒を洗浄剤として洗浄槽に供給するこ
とにより、汚染物（汚染された解体物）の洗浄を行った
が、本発明に於いては、先ず、洗浄槽に有機溶媒を供給
し、次いで、アルカリ金属やその分散体を供給すること
により、洗浄槽内にて、アルカリ金属の存在した状態の
有機溶媒とし、該有機溶媒を洗浄剤として用いて汚染物
の洗浄を行う場合であっても本発明の意図する範囲内で
ある。また、本実施形態に於いては、汚染物として、コ
ンデンサーを対象としたが、汚染物として、トランス、
安定器、土壌、ウエス、感圧紙等を対象とする場合であ
っても本発明の意図する範囲内である。In the present embodiment, the contaminants (contaminated dismantled substances) are washed by supplying the organic solvent in which sodium is dispersed as a detergent to the washing tank. In that case, first, an organic solvent is supplied to a cleaning tank, and then an alkali metal or a dispersion thereof is supplied to form an organic solvent in a state in which an alkali metal is present in the cleaning tank. It is within the scope of the present invention even when the contaminants are used for cleaning as a cleaning agent. Further, in the present embodiment, the condenser is targeted as the contaminant, but the transformer is
It is within the scope of the present invention even when it is intended for a stabilizer, soil, waste cloth, pressure-sensitive paper and the like.
【００２７】[0027]
【実施例】以下、本発明の効果を確認すべく行った実施
例について説明する。実施例
先ず、コンデンサーを解体し、構成部材の中でＰＣＢの
除去が最も困難なコンデンサー素子（アルミと絶縁紙の
積層品）を取り出し、該素子を幅７〜１０ｍｍ、長さ３
０〜１００ｍｍの短冊状に切断して汚染された解体物
（ＰＣＢ含有量２７０００ｍｇ／ｋｇ）とした。この解
体物（６０ｇ）を有機溶媒たるｎ−パラフィン（商品名
「ＮＳクリーン」、日鉱石油化学（株）製）３０００ｇ
と共に洗浄槽に入れ、不活性雰囲気下で攪拌しながら、
熱源を用いて８０℃まで加熱した。次いで、この有機溶
媒にナトリウム分散体（Ｎａ濃度３１．５ｗｔ％）引き
続きイソプロピルアルコールを徐々に添加し、有機溶媒
中全体にナトリウムを拡散させて洗浄剤を調製しつつ且
つ攪拌しつつ洗浄を行った。尚、添加する分散体の分散
媒としては、絶縁油（出光トランスフォーマーオイル
Ｈ）を用いた。また、洗浄は、ナトリウム分散体の添加
による反応熱により、洗浄槽内の温度が上昇することか
ら、ナトリウムの添加速度を制御して、洗浄槽内を９０
℃に維持しつつ１８０分間行った。最終的なナトリウム
分散体の添加量は１８０ｇ、イソプロピルアルコールの
添加量は７．５ｇであった。洗浄後、素子を絶縁油から
濾別し、水に浸漬して素子に付着した金属ナトリウムを
水に抽出させた。この時、素子中のアルミ箔は、金属ナ
トリウムを抽出してアルカリ性となった水に溶解した。
残存した絶縁紙を用いて、水溶出試験を行ったところ、
検査液中のＰＣＢ濃度は、０．００２１ｍｇ／Ｌ−検液
であった。また、洗浄後の洗浄廃液のＰＣＢ濃度を測定
したところ、検出限界（０．０２ｍｇ／ｋｇ）以下であ
った。尚、水溶出試験としては、試料（絶縁紙）２０ｇ
と水（塩酸を加えてｐＨ５．８〜６．３に調整したも
の）２００ｍｌとを分液ロートに入れ、６時間振盪し、
次いで、静置後に濾過し、その濾液を検液とし、ＪＩＳ
Ｋ００９３（工場排水中のＰＣＢの試験方法）に準拠
して測定する方法を採用した。EXAMPLES Examples will be described below for confirming the effects of the present invention. Example First, a capacitor is disassembled, and a capacitor element (a laminated product of aluminum and insulating paper) in which the PCB is most difficult to remove among the constituent members is taken out, and the element is set to a width of 7 to 10 mm and a length of 3
A stripped product (PCB content 27,000 mg / kg) was obtained by cutting into strips of 0 to 100 mm. 3000 g of this dismantled product (60 g) was used as an organic solvent, n-paraffin (trade name "NS Clean", manufactured by Nikko Petrochemical Co., Ltd.).
Put it in a washing tank together with, while stirring under an inert atmosphere,
It heated up to 80 degreeC using the heat source. Next, a sodium dispersion (Na concentration: 31.5 wt%) and then isopropyl alcohol were gradually added to this organic solvent to diffuse sodium throughout the organic solvent to prepare a cleaning agent and perform cleaning while stirring. . Insulating oil (Idemitsu Transformer Oil H) was used as the dispersion medium of the dispersion to be added. Further, in the cleaning, the temperature in the cleaning tank rises due to the reaction heat due to the addition of the sodium dispersion, so that the sodium addition rate is controlled to control the inside of the cleaning tank to 90%.
It was performed for 180 minutes while maintaining the temperature at ℃. The final amount of sodium dispersion added was 180 g, and the amount of isopropyl alcohol added was 7.5 g. After washing, the element was filtered from the insulating oil and immersed in water to extract the metallic sodium adhering to the element into water. At this time, the aluminum foil in the element was dissolved in water that had become alkaline by extracting metallic sodium.
When the water elution test was performed using the remaining insulating paper,
The PCB concentration in the test solution was 0.0021 mg / L-test solution. Moreover, the PCB concentration of the cleaning waste liquid after cleaning was measured and found to be below the detection limit (0.02 mg / kg). In addition, as a water elution test, 20 g of sample (insulating paper)
And 200 ml of water (adjusted to pH 5.8 to 6.3 by adding hydrochloric acid) were placed in a separating funnel and shaken for 6 hours,
Then, after standing, it is filtered, and the filtrate is used as a test solution.
The method of measurement was adopted in accordance with K0093 (test method for PCB in factory wastewater).
【００２８】比較例
ナトリウム分散体及びイソプロピルアルコールを添加せ
ず、熱源を利用して９０℃まで加熱しその温度で維持し
た以外は、実施例と同じ条件の洗浄を、洗浄剤を替えて
４回（１８０分×４）行った。洗浄後、絶縁紙とアルミ
箔とを分離し、絶縁紙（２０ｇ）を用いて同条件で水溶
出試験を行ったところ、検査液中のＰＣＢ濃度は、０．
０５２ｍｇ／Ｌ−検液であった。また、洗浄後のアルミ
箔（１０ｇ）の残存ＰＣＢ濃度を特別管理廃棄物に係る
基準の検定方法別表第２の３（部材採取試験法）により
測定したところ残存ＰＣＢ濃度は３．３ｍｇ／ｋｇであ
った。尚、４回洗浄後の洗浄廃液（１ｇ）のＰＣＢ濃度
を特別管理廃棄物に係る基準の検定方法別表第２の第１
（洗浄液試験）により測定したところ、１ｍｇ／ｋｇで
あった。 Comparative Example Washing under the same conditions as in Example except that the sodium dispersion and isopropyl alcohol were not added and the temperature was raised to 90 ° C. using a heat source and maintained at that temperature, four times by changing the detergent. (180 minutes × 4) After washing, the insulating paper and the aluminum foil were separated, and a water elution test was performed using insulating paper (20 g) under the same conditions. The PCB concentration in the test solution was found to be 0.
It was 052 mg / L-test liquid. In addition, the residual PCB concentration of the aluminum foil (10 g) after cleaning was measured by the standard inspection method attached table 2-3 (member sampling test method) for specially controlled waste, and the residual PCB concentration was 3.3 mg / kg. there were. In addition, the PCB concentration of the cleaning waste liquid (1 g) after cleaning four times is the standard inspection method of the standard relating to specially controlled waste, Table 1 of the second table.
It was 1 mg / kg as measured by (washing liquid test).
【００２９】[0029]
【発明の効果】以上のように、本発明に係る有機ハロゲ
ン化合物の除染方法は、多量の洗浄剤を使用する必要も
無く、比較的短時間の洗浄によって、有機ハロゲン化合
物を殆ど含まない除染物とすることができ、しかも、洗
浄廃液に有機ハロゲン化合物が殆ど含まれないという効
果を奏する。As described above, the method for decontaminating an organohalogen compound according to the present invention does not require the use of a large amount of detergent, and the decontamination method containing almost no organohalogen compound can be performed by washing for a relatively short time. There is an effect that it can be a dyed product and that the cleaning waste liquid contains almost no organic halogen compound.
【図１】一実施形態の有機ハロゲン化合物の処理方法及
び処理システムを示す概略フロー図。FIG. 1 is a schematic flow chart showing a treatment method and a treatment system of an organic halogen compound according to an embodiment.
【図２】同実施形態のコンデンサーから除染物となるま
での詳細フロー図。FIG. 2 is a detailed flow chart from the condenser of the embodiment to a decontaminated product.
１・・・洗浄部 1 ... Cleaning section
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 3B201 AA46 AB01 BB02 BB82 BB92 BB95 CC01 CC11 4H003 BA12 DA14 DA15 DC03 EA22 EA25 EB02 ED28 FA01 FA03 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 3B201 AA46 AB01 BB02 BB82 BB92 BB95 CC01 CC11 4H003 BA12 DA14 DA15 DC03 EA22 EA25 EB02 ED28 FA01 FA03
Claims (6)
ロゲン汚染物を洗浄剤で洗浄する有機ハロゲン汚染物の
除染方法であって、 前記洗浄剤として、アルカリ金属が存在した状態の有機
溶媒を用いることを特徴とする有機ハロゲン汚染物の除
染方法。1. A method for decontaminating an organic halogen contaminant contaminated with an organic halogen compound with a cleaning agent, wherein an organic solvent in the presence of an alkali metal is used as the cleaning agent. A method for decontaminating organic halogen pollutants, which is characterized in that
化水素である請求項１記載の有機ハロゲン汚染物の除染
方法。2. The method for decontaminating an organic halogen contaminant according to claim 1, wherein the organic solvent is a hydrocarbon having no double bond.
２記載の有機ハロゲン汚染物の除染方法。3. The method for decontaminating organic halogen contaminants according to claim 2, wherein the hydrocarbon is paraffin.
ある請求項３記載の有機ハロゲン汚染物の除染方法。4. The method for decontaminating organic halogen contaminants according to claim 3, wherein the paraffin is normal paraffin.
求項１乃至４の何れかに記載の有機ハロゲン汚染物の除
染方法。5. The method for decontaminating an organic halogen contaminant according to claim 1, wherein the contaminant is a capacitor element.
ロゲン汚染物を洗浄剤で洗浄する洗浄部（１）を備えた
有機ハロゲン汚染物の除染システムであって、 前記洗浄剤が、アルカリ金属が存在した状態の有機溶媒
であることを特徴とする有機ハロゲン汚染物の除染シス
テム。6. A decontamination system for organic halogen contaminants, comprising a cleaning unit (1) for cleaning organic halogen contaminants contaminated with organic halogen compounds with a cleaning agent, wherein the cleaning agent is an alkali metal A decontamination system for organic halogen pollutants characterized by being an organic solvent in a state of being present.
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| CN108722981A (en) * | 2018-04-20 | 2018-11-02 | 朱清 | A kind of method of paraffin in quick removing dewatering box |
| CN108722981B (en) * | 2018-04-20 | 2021-02-05 | 朱清 | Method for quickly removing paraffin in dehydration box |
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