JPH10225632A - Method for detoxicate polychlorinated biphenyl by supercritical water - Google Patents
Method for detoxicate polychlorinated biphenyl by supercritical waterInfo
- Publication number
- JPH10225632A JPH10225632A JP9115966A JP11596697A JPH10225632A JP H10225632 A JPH10225632 A JP H10225632A JP 9115966 A JP9115966 A JP 9115966A JP 11596697 A JP11596697 A JP 11596697A JP H10225632 A JPH10225632 A JP H10225632A
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- JP
- Japan
- Prior art keywords
- pcb
- alkali
- water
- supercritical water
- weight units
- 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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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Fire-Extinguishing Compositions (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は臨界温度（６４７．
３Ｋ）及び臨界圧力（２２．１２ＭＰａ）を超えた超臨
界水によってポリ塩化ビフェニル（ＰＣＢ）を分解処理
することにより、無害化する方法に関するものである。[0001] The present invention relates to a critical temperature (647.
The present invention relates to a method for detoxifying polychlorinated biphenyl (PCB) by decomposing it with supercritical water exceeding 3K) and a critical pressure (22.12 MPa).
【０００２】[0002]
【従来の技術】分解処理の対象となるＰＣＢは、化学的
に極めて安定な難分解性の有害物質である。その製造が
禁止されるまでは優れた絶縁性、脂溶性、低揮発性のた
め、絶縁油、機械油、可塑剤、塗料など様々な用途で広
く利用されていた。しかし１９６６年にＰＣＢによる環
境汚染が初めて報告され、食物連鎖を通じて高濃度のＰ
ＣＢが生物に蓄積される危険性が明らかになり、１９７
０年代前半に製造が禁止された結果、全世界で約１００
万トン、日本でも約６万トンの保管が２０年以上続いて
いる。そのため一刻も早い分解・無害化技術の確立が望
まれている。ＰＣＢを分解・無害化する幾つかの方法が
既に提案されている。その代表的なものとして、（１）
燃焼室内を１３７３Ｋ以上の温度に保ってＰＣＢを完全
分解する高温焼却法、（２）ＰＣＢにアルカリと水素供
与体を加え、触媒存在下で加熱するアルカリ触媒分解法
（ＢＣＤ法）、（３）アルコール中にＰＣＢと水酸化ナ
トリウムを数％の濃度で溶解して、紫外線を照射する紫
外線脱塩素化法、（４）微生物によりＰＣＢを分解する
微生物分解法、（５）酸化剤を加えた超臨界水でＰＣＢ
を分解する方法等がある。しかしながら、（１）の高温
焼却法では、完全分解するのに燃焼室を１３７３Ｋ以上
の高温に保つ必要があるので工業的に不利である。また
燃焼温度が下がると猛毒のダイオキシンが副生する恐れ
があるので燃焼室の温度調節を精密に行わねばならない
という問題点がある。（２）のＢＣＤ法では、ＰＣＢか
ら塩素原子がとれてビフェニルが生成するので、条件に
よっては塩素原子が再結合してＰＣＢを再合成する恐れ
があるという問題点がある。（３）の紫外線脱塩素化法
では、完全分解するのに長い時間がかかり、更にエネル
ギー効率が極めて低いためにコストが大きくなり工業的
に不利である。また反応後、ビフェニルが生成するので
ＰＣＢを再合成する恐れがあるという問題点もある。
（４）の微生物分解法では、（３）の方法以上に長い反
応時間を必要とし、分解工程が主に開放系であるという
問題点のほかに、微生物の代謝活性を高めるために温
度、ｐＨ等を調節しなければならないという問題点があ
る。（５）の酸化剤を加えた超臨界水を用いる分解法で
は、強い腐食雰囲気が形成されるため、装置劣化が著し
いという問題を生じる上、媒体油中のＰＣＢを分解する
場合には、ＰＣＢのみならず、媒体油まで酸化分解され
てしまうので、良質の媒体油の回収が困難であるという
問題を含む。2. Description of the Related Art PCBs to be decomposed are chemically very stable and hardly decomposable harmful substances. Before its production was banned, it was widely used in various applications such as insulating oils, machine oils, plasticizers and paints because of its excellent insulating properties, fat solubility and low volatility. However, in 1966, environmental pollution by PCBs was first reported, and high levels of P
The danger of CB accumulating in living organisms has been revealed.
Production was banned in the early 0's, resulting in about 100
10,000 tons and about 60,000 tons in Japan have been stored for more than 20 years. Therefore, it is desired to establish a decomposing and detoxifying technology as soon as possible. Several methods for disassembling and detoxifying PCBs have already been proposed. Typical examples are (1)
A high-temperature incineration method that completely decomposes PCB while maintaining the temperature of the combustion chamber at 1373K or more, (2) an alkali catalyst decomposition method (BCD method) in which an alkali and a hydrogen donor are added to PCB and heated in the presence of a catalyst, (3) An ultraviolet dechlorination method in which PCB and sodium hydroxide are dissolved at a concentration of several percent in alcohol and irradiated with ultraviolet light, (4) a microbial decomposition method in which PCB is decomposed by microorganisms, and PCB in critical water
And the like. However, the high-temperature incineration method (1) is industrially disadvantageous because the combustion chamber needs to be maintained at a high temperature of 1373 K or more for complete decomposition. Further, when the combustion temperature is lowered, highly toxic dioxin may be produced as a by-product, so that the temperature of the combustion chamber must be precisely controlled. In the BCD method (2), since a chlorine atom is removed from the PCB to generate biphenyl, there is a problem that the chlorine atom may recombine and resynthesize the PCB depending on conditions. In the ultraviolet dechlorination method (3), it takes a long time to completely decompose and furthermore, the energy efficiency is extremely low, so that the cost increases and the method is industrially disadvantageous. There is also a problem that PCB is resynthesized because biphenyl is formed after the reaction.
The microbial decomposition method (4) requires a longer reaction time than the method (3), and has the problem that the decomposition process is mainly an open system. Etc. must be adjusted. In the decomposition method (5) using supercritical water to which an oxidizing agent is added, a strong corrosive atmosphere is formed, which causes a problem that the device is significantly deteriorated. In addition, since the medium oil is oxidatively decomposed, it is difficult to recover high-quality medium oil.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、超臨界水に
よりＰＣＢを分解し、無害化するための工業的に有利な
方法を提供することを課題とする。An object of the present invention is to provide an industrially advantageous method for decomposing and detoxifying PCB with supercritical water.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、ポリ塩
化ビフェニルを、（i）超臨界水単独、（ii）アルカリ
を加えた超臨界水又は（iii）アルカリと酸化剤を加え
た超臨界水で分解処理することを特徴とするポリ塩化ビ
フェニルの無害化方法が提供される。また、本発明によ
れば、ポリ塩化ビフェニルを含む媒体油を、（i）超臨
界水単独、（ii）アルカリを加えた超臨界水又は（ii
i）アルカリと酸化剤を加えた超臨界水で該ポリ塩化ビ
フェニル分解して無害化する工程と、該工程で得られた
ポリ塩化ビフェニルが無害化された後の媒体油を回収す
る工程からなるポリ塩化ビフェニルを含む媒体油の無害
化処理方法が提供される。According to the present invention, polychlorinated biphenyls are prepared by adding (i) supercritical water alone, (ii) supercritical water to which an alkali is added, or (iii) supercritical water to which an alkali and an oxidizing agent are added. There is provided a method for detoxifying polychlorinated biphenyls, which comprises decomposing the same with supercritical water. Further, according to the present invention, a medium oil containing polychlorinated biphenyl is used as (i) supercritical water alone, (ii) supercritical water to which alkali is added, or (ii)
i) a step of detoxifying the polychlorinated biphenyl by supercritical water to which an alkali and an oxidizing agent are added, and a step of collecting a medium oil after the detoxified polychlorinated biphenyl obtained in the step. A method for detoxifying a medium oil containing polychlorinated biphenyl is provided.
【０００５】[0005]
【発明の実施の形態】本発明の方法を好ましく実施する
ためには、（i）ＰＣＢの１重量単位に対して５０〜１
５０重量単位の水、（ii）ＰＣＢの１重量単位に対して
５０〜１５０重量単位の水と１〜５重量単位の水酸化ナ
トリウム等のアルカリ、又は（iii）ＰＣＢの１重量単
位に対して５０〜１５０重量単位の水、２〜２０重量単
位の過酸化水素等の酸化剤及び１〜５重量単位の水酸化
ナトリウム等のアルカリを反応器に充填し、加熱炉にて
水の臨界温度以上の６５３Ｋ〜８７３Ｋ、好ましくは６
５３Ｋ〜７７３Ｋに加熱する。この時、反応圧力は反応
器に充填した水の重量により調整する。通常、圧力範囲
は２２〜４０ＭＰａ、好ましくは２５〜３５ＭＰａであ
る。また反応時問は５〜６０分、好ましくは５〜３０分
である。前記酸化剤としては、過酸化水素の他、酸素や
空気等を好ましく用いることができる。また、アルカリ
としては、水酸化ナトリウムの他、水酸化カルシウム、
炭酸ナトリウム等を好ましく用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION In order to carry out the method of the present invention preferably, (i) 50 to 1 to 1 unit by weight of PCB.
50 weight units of water, (ii) 50 to 150 weight units of water and 1 to 5 weight units of alkali such as sodium hydroxide per 1 weight unit of PCB, or (iii) 1 weight unit of PCB A reactor is charged with 50 to 150 weight units of water, 2 to 20 weight units of an oxidizing agent such as hydrogen peroxide and 1 to 5 weight units of an alkali such as sodium hydroxide, and heated to a temperature not lower than the critical temperature of water in a heating furnace. 653K to 873K, preferably 6
Heat to 53K-773K. At this time, the reaction pressure is adjusted by the weight of the water charged in the reactor. Usually, the pressure range is between 22 and 40 MPa, preferably between 25 and 35 MPa. The reaction time is 5 to 60 minutes, preferably 5 to 30 minutes. As the oxidizing agent, oxygen, air, and the like can be preferably used in addition to hydrogen peroxide. In addition, as the alkali, in addition to sodium hydroxide, calcium hydroxide,
Sodium carbonate or the like can be preferably used.
【０００６】本発明の被処理対象となるＰＣＢは、純粋
なＰＣＢ又は媒体油中に含まれているＰＣＢである。純
粋なＰＣＢの場合、その純度は、通常、６０重量％以
上、好ましくは８０重量％以上である。一方、媒体油中
に含まれているＰＣＢの場合、そのＰＣＢの濃度は０．
００１〜５重量％である。媒体油中に含まれているＰＣ
Ｂの処理は、そのＰＣＢを含む媒体油を超臨界水で処理
し、そのＰＣＢを分解して無害化し、そのＰＣＢの無害
化後、媒体油を反応器から回収する。前記媒体油の代表
的なものの１例としては、ＪＩＳ Ｃ ２３２０に定めら
れた鉱油やアルキルベンゼンからなる電気絶縁油が挙げ
られる。The PCB to be treated in the present invention is a pure PCB or a PCB contained in a medium oil. In the case of pure PCB, its purity is usually at least 60% by weight, preferably at least 80% by weight. On the other hand, in the case of the PCB contained in the medium oil, the concentration of the PCB is 0.1.
001 to 5% by weight. PC contained in medium oil
In the treatment of B, the medium oil containing the PCB is treated with supercritical water, the PCB is decomposed and made harmless, and after the PCB is made harmless, the medium oil is recovered from the reactor. Typical examples of the medium oil include a mineral oil specified in JIS C 2320 and an electrical insulating oil composed of alkylbenzene.
【０００７】[0007]
【発明の効果】本発明ではＰＣＢ分解に対して超臨界水
を用いているので、従来技術の（１）で示した高温焼却
法のように、高い反応温度を必要としない。更に本発明
で用いるＰＣＢ分解条件はダイオキシンの分解条件でも
あるので、たとえダイオキシンが一時的に副生したとし
ても直ちに分解されてしまうという利点もある。また本
発明の方法においては、ＰＣＢの骨格構造を破壊してフ
ェノールや二酸化炭素まで分解してしまうので、従来技
術の（２）と（３）で示したＢＣＤ法や紫外線脱塩素化
法のようにＰＣＢの再合成の恐れもない。また、本発明
法は閉鎖系内で高い反応活性を持つ超臨界水を反応溶媒
に用いているので、従来技術の（３）と（４）で示した
紫外線脱塩素化法や微生物分解法のように、長い反応時
問を必要とするといった問題や環境への悪影響もない。
さらに、本発明において、アルカリを添加した超臨界水
を用いた場合には、ＰＣＢの分解により生じた腐食性の
強い塩化水素を中和しながら分解処理を行うので、前記
（５）で示した酸化剤を含む超臨界水を用いる分解法の
場合のように著しい装置腐食が起らない。また、アルカ
リのみを添加した超臨界水では、媒体油の酸化分解の恐
れがないので、良質の媒体油を回収することができる。According to the present invention, since supercritical water is used for PCB decomposition, a high reaction temperature is not required unlike the high temperature incineration method shown in the prior art (1). Furthermore, since the PCB decomposition conditions used in the present invention are also the conditions for decomposing dioxin, there is an advantage that even if dioxin is temporarily produced as a by-product, it is immediately decomposed. In the method of the present invention, the skeleton structure of the PCB is destroyed and phenol and carbon dioxide are decomposed, so that the BCD method and the ultraviolet dechlorination method shown in the prior art (2) and (3) are used. In addition, there is no fear of resynthesis of PCB. Further, since the method of the present invention uses supercritical water having a high reaction activity in a closed system as a reaction solvent, the method of the ultraviolet dechlorination method or the microbial decomposition method shown in the prior art (3) and (4) is used. As described above, there is no problem that a long reaction time is required and there is no adverse effect on the environment.
Furthermore, in the present invention, when supercritical water to which an alkali is added is used, the decomposition treatment is performed while neutralizing strongly corrosive hydrogen chloride generated by the decomposition of PCB. Significant equipment corrosion does not occur as in the case of the decomposition method using supercritical water containing an oxidizing agent. In addition, supercritical water to which only an alkali is added has no fear of oxidative decomposition of the medium oil, so that a high-quality medium oil can be recovered.
【０００８】[0008]
【実施例】次に本発明を実施例により更に詳細に説明す
る。 実施例１ 反応器に所定量の水と純ＰＣＢを充填し、反応温度７２
３Ｋ、反応圧力３０ＭＰａ、反応時問２０分で超臨界水
単独でＰＣＢの分解を行った。その実験結果を表１のＲ
−ｌに示す。この条件ではＰＣＢの９７．４６％を分解
できた。Next, the present invention will be described in more detail by way of examples. Example 1 A reactor was charged with a predetermined amount of water and pure PCB, and a reaction temperature of 72.
Decomposition of PCB was performed using supercritical water alone at 3K, reaction pressure of 30 MPa, and reaction time of 20 minutes. The experimental results are shown in Table 1
-L. Under these conditions, 97.46% of the PCB could be decomposed.
【０００９】実施例２ 反応器に所定量の水、純ＰＣＢ、水酸化ナトリウム（Ｐ
ＣＢ中の塩素原子のモル数に対して３〜１０倍当量）を
添加し、反応温度７２３Ｋ、反応圧力３０ＭＰａ、反応
時間２０分の条件下でＰＣＢの分解を行った。その実験
結果を表１のＲ−２、３、４に示す。アルカリとして水
酸化ナトリウムを加えると、９９．９％以上のＰＣＢを
分解することができた。Example 2 A predetermined amount of water, pure PCB, sodium hydroxide (P
3 to 10 times the equivalent of the number of moles of chlorine atoms in CB), and the PCB was decomposed at a reaction temperature of 723 K, a reaction pressure of 30 MPa, and a reaction time of 20 minutes. The experimental results are shown in R-2, 3, and 4 in Table 1. When sodium hydroxide was added as an alkali, 99.9% or more of PCB could be decomposed.
【００１０】実施例３ 反応器に所定量の水、純ＰＣＢ、過酸化水素（ＰＣＢ中
の塩素原子のモル数に対して３〜５倍当量）、水酸化ナ
トリウム（ＰＣＢ中の塩素原子のモル数に対して２倍当
量）を添加し、反応温度７２３Ｋ、反応圧力３０ＭＰ
ａ、反応時問２０分の条件下でＰＣＢの分解を行った。
その実験結果を表１のＲ−５、６に示す。酸化剤とアル
カリの両者を加えた場合、９９．９％以上のＰＣＢを分
解することができた。Example 3 In a reactor, a predetermined amount of water, pure PCB, hydrogen peroxide (equivalent to 3 to 5 times the number of moles of chlorine atoms in the PCB), sodium hydroxide (moles of chlorine atoms in the PCB) The reaction temperature was 723K and the reaction pressure was 30MP.
a, The PCB was decomposed under the conditions of a reaction time of 20 minutes.
The experimental results are shown in Tables R-5 and R-6. When both the oxidizing agent and the alkali were added, 99.9% or more of the PCB could be decomposed.
【００１１】実施例４ 反応器に所定量の水と絶縁油に溶解している２ｗｔ％Ｐ
ＣＢを充填し、反応温度７２３Ｋ、反応圧力３０ＭＰ
ａ、反応時間２０分で超臨界水単独でＰＣＢの分解を行
った。その実験結果を表１のＲ−７に示す。この条件で
はＰＣＢの９２．０９％を分解できた。Example 4 2 wt% P dissolved in a predetermined amount of water and insulating oil in a reactor
Filled with CB, reaction temperature 723K, reaction pressure 30MP
a, PCB was decomposed with supercritical water alone in a reaction time of 20 minutes. The result of the experiment is shown in R-7 of Table 1. Under these conditions, 92.09% of the PCB could be decomposed.
【００１２】実施例５ 反応器に所定量の水、絶縁油に溶解している２ｗｔ％Ｐ
ＣＢ、水酸化ナトリウム（ＰＣＢ中の塩素原子のモル数
に対して５〜１０倍当量）を充填し、反応温度７２３
Ｋ、反応圧力３０ＭＰａ、反応時間２０分の条件下でＰ
ＣＢの分解を行った。その実験結果を表１のＲ−８、９
に示す。アルカリとして水酸化ナトリウムを加えると、
９９．５％以上のＰＣＢを分解できた。Example 5 2 wt% P dissolved in a predetermined amount of water and insulating oil in a reactor
CB and sodium hydroxide (equivalent to 5 to 10 times the number of moles of chlorine atoms in the PCB) were charged, and the reaction temperature was 723.
K, P at a reaction pressure of 30 MPa and a reaction time of 20 minutes.
Decomposition of CB was performed. The experimental results are shown in Table 1 for R-8, 9
Shown in When sodium hydroxide is added as an alkali,
99.5% or more of PCB could be decomposed.
【００１３】実施例６ 反応器に所定量の水、絶縁油に溶解している２ｗｔ％Ｐ
ＣＢ、水酸化ナトリウム（ＰＣＢ中の塩素原子のモル数
に対して１０倍当量）を充填し、反応温度６５３Ｋ、反
応圧力３０ＭＰａ、反応時間２０分の条件下でＰＣＢの
分解を行った。その実験結果を表１のＲ−１０に示す。
アルカリとして水酸化ナトリウムを加えると、９９．６
％以上のＰＣＢを分解することができた。更にこの温度
条件下では、加熱による絶縁油の性能劣化がないことが
確かめられた。Example 6 2 wt% P dissolved in a predetermined amount of water and insulating oil in a reactor
CB and sodium hydroxide (equivalent to 10 times the number of moles of chlorine atoms in the PCB) were charged, and the PCB was decomposed at a reaction temperature of 653 K, a reaction pressure of 30 MPa, and a reaction time of 20 minutes. The experimental result is shown in R-10 of Table 1.
Addition of sodium hydroxide as alkali gives 99.6
% Or more of PCB could be decomposed. Further, it was confirmed that under these temperature conditions, the performance of the insulating oil did not deteriorate due to heating.
【００１４】[0014]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大竹 勝人 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 岡野 誠 東京都港区芝浦３丁目９番14号 芝浦工業 大学工学部内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Katsuhito Otake 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Makoto Okano 3-9-114 Shibaura, Minato-ku, Tokyo Shibaura Institute of Technology
Claims (2)
単独、（ii）アルカリを加えた超臨界水又は（iii）ア
ルカリと酸化剤を加えた超臨界水で分解処理することを
特徴とするポリ塩化ビフェニルの無害化方法。1. A polychlorinated biphenyl is decomposed with (i) supercritical water alone, (ii) supercritical water to which an alkali is added, or (iii) supercritical water to which an alkali and an oxidizing agent are added. To detoxify polychlorinated biphenyls.
（i）超臨界水単独、（ii）アルカリを加えた超臨界水
又は（iii）アルカリと酸化剤を加えた超臨界水で該ポ
リ塩化ビフェニル分解して無害化する工程と、該工程で
得られたポリ塩化ビフェニルが無害化された後の媒体油
を回収する工程からなるポリ塩化ビフェニルを含む媒体
油の無害化処理方法。2. A medium oil containing polychlorinated biphenyl,
(I) supercritical water alone, (ii) supercritical water to which an alkali is added, or (iii) supercritical water to which an alkali and an oxidizing agent are added to decompose the polychlorinated biphenyl to make it harmless; A method for detoxifying a medium oil containing polychlorinated biphenyl, comprising a step of recovering the medium oil after the polychlorinated biphenyl has been rendered harmless.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09115966A JP3106180B2 (en) | 1996-12-13 | 1997-05-07 | Detoxification method of polychlorinated biphenyl with supercritical water |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33320596 | 1996-12-13 | ||
| JP8-333205 | 1996-12-13 | ||
| JP09115966A JP3106180B2 (en) | 1996-12-13 | 1997-05-07 | Detoxification method of polychlorinated biphenyl with supercritical water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10225632A true JPH10225632A (en) | 1998-08-25 |
| JP3106180B2 JP3106180B2 (en) | 2000-11-06 |
Family
ID=26454380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09115966A Expired - Lifetime JP3106180B2 (en) | 1996-12-13 | 1997-05-07 | Detoxification method of polychlorinated biphenyl with supercritical water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3106180B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138057A (en) * | 2000-10-27 | 2002-05-14 | Ishikawajima Harima Heavy Ind Co Ltd | Method and equipment for treating halogen based organic waste |
| KR20050115809A (en) * | 2004-06-04 | 2005-12-08 | 이상환 | Supercritical water or subcritical water, and oxidation method of organic material using thereof |
| KR100675106B1 (en) * | 2006-05-18 | 2007-01-29 | 김경심 | Treatment system of polychlorinated biphenyls |
| KR101006279B1 (en) * | 2008-01-04 | 2011-01-06 | 송길섭 | Method for Separating and Treating the Polychlorinated Biphenyl Emulsion |
| JP2013208510A (en) * | 2012-03-30 | 2013-10-10 | Tokyo Electric Power Co Inc:The | Method for treating large-sized instrument contaminated with pcb and treatment device to be used for the same |
-
1997
- 1997-05-07 JP JP09115966A patent/JP3106180B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138057A (en) * | 2000-10-27 | 2002-05-14 | Ishikawajima Harima Heavy Ind Co Ltd | Method and equipment for treating halogen based organic waste |
| KR20050115809A (en) * | 2004-06-04 | 2005-12-08 | 이상환 | Supercritical water or subcritical water, and oxidation method of organic material using thereof |
| KR100675106B1 (en) * | 2006-05-18 | 2007-01-29 | 김경심 | Treatment system of polychlorinated biphenyls |
| KR101006279B1 (en) * | 2008-01-04 | 2011-01-06 | 송길섭 | Method for Separating and Treating the Polychlorinated Biphenyl Emulsion |
| JP2013208510A (en) * | 2012-03-30 | 2013-10-10 | Tokyo Electric Power Co Inc:The | Method for treating large-sized instrument contaminated with pcb and treatment device to be used for the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3106180B2 (en) | 2000-11-06 |
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