JPH07206714A - Decomposition of aromatic chloride - Google Patents
Decomposition of aromatic chlorideInfo
- Publication number
- JPH07206714A JPH07206714A JP2211094A JP2211094A JPH07206714A JP H07206714 A JPH07206714 A JP H07206714A JP 2211094 A JP2211094 A JP 2211094A JP 2211094 A JP2211094 A JP 2211094A JP H07206714 A JPH07206714 A JP H07206714A
- Authority
- JP
- Japan
- Prior art keywords
- decomposition
- aromatic chlorinated
- aromatic
- oxidizing agent
- aqueous solution
- 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.)
- Granted
Links
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- Fire-Extinguishing Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は芳香族塩素化物の新規な
分解方法に関するものである。さらに詳しくいえば、本
発明は、特に難分解性の芳香族塩素化物を、ダイオキシ
ンなどの発生による二次環境汚染をもたらすことがな
く、簡便な操作で、効率よく経済的有利に完全分解して
無害化する方法に関するものである。FIELD OF THE INVENTION The present invention relates to a novel method for decomposing aromatic chlorinated compounds. More specifically, the present invention is capable of completely decomposing aromatic chlorinated compounds, which are particularly difficult to decompose, in a simple operation, efficiently and economically, without causing secondary environmental pollution due to the generation of dioxins and the like. It is about how to make it harmless.
【０００２】[0002]
【従来の技術】従来、ポリ塩化ビフェニルのような難分
解性芳香族塩素化物は、微生物などにより分解されにく
いことから、自然界に蓄積され、環境汚染をもたらすこ
とが知られている。したがって、このような難分解性芳
香族塩素化物は、これまで焼却や化学手法による処理で
対応しているが、通常の焼却法ではダイオキシンなどの
有害物質を発生し、二次環境汚染をもたらすことから、
約２０００℃以上という非常に高い温度で処理しなけれ
ばならず、特殊な設備を必要とするため、処理コストが
高くなるのを免れない。2. Description of the Related Art Heretofore, it has been known that refractory aromatic chlorinated compounds such as polychlorinated biphenyls are hard to be decomposed by microorganisms and so are accumulated in nature and cause environmental pollution. Therefore, such refractory aromatic chlorinated compounds have been treated by incineration or treatment by chemical methods until now, but in the normal incineration method, harmful substances such as dioxin are generated and secondary environmental pollution is caused. From
Since it has to be processed at a very high temperature of about 2000 ° C. or higher and requires special equipment, the processing cost is inevitably high.
【０００３】ところで、近年、有害で難分解性の芳香族
塩素化物は、化学産業や一般家庭などから排出され、そ
の量も多くなってきており、しかも存在形態も水溶中あ
るいは土壌中と多様化しており、この難分解性の芳香族
塩素化物を低コストで完全に分解して無害化する方法の
開発が急務となっている。By the way, in recent years, harmful and hardly decomposable aromatic chlorinated substances have been discharged from the chemical industry and ordinary households, and the amount thereof has been increasing, and the existence form has been diversified into water or soil. Therefore, there is an urgent need to develop a method for completely decomposing and detoxifying this hardly decomposable aromatic chlorinated compound at a low cost.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、特に難分解性の芳香族塩素化物を、ダイ
オキシンなどの発生による二次環境汚染をもたらすこと
がなく、簡便な操作で、効率よく経済的有利に完全分解
して無害化する方法を提供することを目的としてなされ
たものである。Under the above circumstances, the present invention provides a simple and easy-to-use aromatic chlorinated compound that does not cause secondary environmental pollution due to the generation of dioxins and the like. The purpose of the present invention is to provide a method of completely detoxifying by performing efficient and economically advantageous complete decomposition.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、高温高圧下に
おいて、芳香族塩素化物を酸化剤含有水溶液と接触させ
ることにより、その目的を達成しうることを見出し、こ
の知見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that by contacting an aromatic chlorinated compound with an oxidizing agent-containing aqueous solution under high temperature and high pressure, It has been found that the object can be achieved, and the present invention has been completed based on this finding.
【０００６】すなわち、本発明は、温度３５０〜５５０
℃、圧力２００〜６００気圧の条件下で、芳香族塩素化
物を酸化剤含有水溶液と接触させることを特徴とする芳
香族塩素化物の分解方法を提供するものである。That is, according to the present invention, the temperature is 350 to 550.
Provided is a method for decomposing an aromatic chlorinated product, which comprises contacting the aromatic chlorinated product with an oxidizing agent-containing aqueous solution under conditions of a temperature of 200 ° C. and a pressure of 200 to 600 atm.
【０００７】本発明方法が適用される芳香族塩素化物と
は、芳香環に直接塩素原子が結合している化合物であっ
て、例えばポリ塩化ビフェニル、モノ塩化ビフェニル、
ジクロロジフェニルトリクロロエタン、ペンタクロロフ
ェノールなどを挙げることができる。The aromatic chlorinated compound to which the method of the present invention is applied is a compound in which a chlorine atom is directly bonded to an aromatic ring, and examples thereof include polychlorinated biphenyls and monochlorinated biphenyls.
Examples thereof include dichlorodiphenyltrichloroethane and pentachlorophenol.
【０００８】本発明方法においては、前記の芳香族塩素
化物は、高温高圧条件下で酸化剤含有水溶液と接触する
ことにより、分解される。この際の温度は３５０〜５５
０℃、好ましくは３８０〜５００℃の範囲にあることが
必要である。この温度が３５０℃未満では芳香族塩素化
物の分解が不十分であるし、５５０℃を超えると分解効
率の向上が認められないので、むしろ経済的に不利とな
る。また、圧力は２００〜６００気圧、好ましくは３０
０〜５００気圧の範囲にあることが必要である。この圧
力が２００気圧未満では、芳香族塩素化物の分解が十分
に起こらないし、また６００気圧を超えると分解効率の
向上が認められず、不必要な耐圧容器を必要とするの
で、経済的に不利となる。In the method of the present invention, the aromatic chlorinated product is decomposed by contacting it with an oxidizing agent-containing aqueous solution under high temperature and high pressure conditions. The temperature at this time is 350-55
It is necessary to be in the range of 0 ° C, preferably 380 to 500 ° C. If the temperature is lower than 350 ° C, the decomposition of the aromatic chlorinated product is insufficient, and if it exceeds 550 ° C, the decomposition efficiency is not improved, which is rather economically disadvantageous. The pressure is 200 to 600 atm, preferably 30 atm.
It must be in the range of 0 to 500 atmospheres. If the pressure is less than 200 atm, the aromatic chlorinated compound is not sufficiently decomposed, and if it exceeds 600 atm, the decomposition efficiency is not improved and an unnecessary pressure resistant container is required, which is economically disadvantageous. Becomes
【０００９】本発明方法において用いられる酸化剤とし
ては、無機過酸化物や有機過酸化物などを挙げることが
でき、これらは単独で用いてもよいし、２種以上を組み
合わせて用いてもよいが、水溶液として取り扱いやす
く、投入も容易である点で過酸化水素が特に好適であ
る。水溶液中における酸化剤の濃度は、１．０〜１０．
０重量％、好ましくは２〜５重量％の範囲で選ばれる。
この含有量が１．０重量％未満では芳香族塩素化物の分
解が十分に起こらないし、１０重量％を超えると処理条
件の制御が困難になる。Examples of the oxidizing agent used in the method of the present invention include inorganic peroxides and organic peroxides, which may be used alone or in combination of two or more kinds. However, hydrogen peroxide is particularly preferable because it is easy to handle as an aqueous solution and is easy to add. The concentration of the oxidizing agent in the aqueous solution is 1.0 to 10.
It is selected in the range of 0% by weight, preferably 2 to 5% by weight.
If the content is less than 1.0% by weight, the decomposition of the aromatic chlorinated product does not occur sufficiently, and if it exceeds 10% by weight, it becomes difficult to control the treatment conditions.
【００１０】本発明方法は回分式でも行うことができる
が、流通式高温高圧装置を用いる連続方式で行うのが好
ましい。この場合、酸化剤含有水溶液中に、液体状の芳
香族塩素化物を投入して接触させるが、この芳香族塩素
化物は、必要に応じて適当な有機溶媒で希釈して投入し
てもよい。この芳香族塩素化物の希釈に用いる有機溶媒
としては、炭素数が少ないもの、例えばｎ‐ヘキサン、
酢酸エチル、クロロホルム、メタノール、二硫化炭素な
どが好ましい。これらは単独で用いてもよいし、又は２
種以上を混合して用いてもよい。このように希釈溶媒を
用いる場合は、その量に応じて酸化剤の使用量を増加さ
せる必要があるので、希釈溶媒を用いない方が、望まし
い。The method of the present invention can be carried out batchwise, but it is preferably carried out in a continuous system using a flow type high temperature and high pressure apparatus. In this case, a liquid aromatic chlorinated product is put into contact with the oxidizing agent-containing aqueous solution, but this aromatic chlorinated product may be diluted with a suitable organic solvent and put in if necessary. The organic solvent used for diluting the aromatic chlorinated compound has a small carbon number, for example, n-hexane,
Ethyl acetate, chloroform, methanol, carbon disulfide and the like are preferable. These may be used alone or 2
You may mix and use 1 or more types. When using a diluting solvent as described above, it is necessary to increase the amount of the oxidizing agent to be used according to the amount of the diluting solvent. Therefore, it is preferable not to use the diluting solvent.
【００１１】このような連続流通方式の場合、芳香族塩
素化物と酸化剤含有水溶液との接触時間は、通常１／１
０００秒ないし１分程度である。In the case of such a continuous flow system, the contact time between the aromatic chlorinated product and the oxidizing agent-containing aqueous solution is usually 1/1.
It is about 000 seconds to 1 minute.
【００１２】本発明方法においては芳香族塩素化物は分
解処理の際に塩化水素が発生する。そして、通常、この
塩化水素は塩酸として系外に排出され、炭酸カルシウム
などの適当な中和剤を用いて中和処理が施される。In the method of the present invention, hydrogen chloride is generated during the decomposition treatment of the aromatic chlorinated product. Then, usually, this hydrogen chloride is discharged out of the system as hydrochloric acid, and subjected to neutralization treatment using an appropriate neutralizing agent such as calcium carbonate.
【００１３】[0013]
【発明の効果】本発明によると、特に難分解性の芳香族
塩素化物を、ダイオキシンなどの発生による二次環境汚
染をもたらすことがなく、簡便な操作により、連続的に
効率よく経済的有利に完全分解して無害化することがで
きる。したがって、本発明方法は、難分解性の芳香族塩
素化物の完全無害化連続処理法として好適である。According to the present invention, particularly difficult-to-decompose aromatic chlorinated compounds can be continuously and efficiently and economically advantageous by a simple operation without causing secondary environmental pollution due to generation of dioxins and the like. It can be completely decomposed and made harmless. Therefore, the method of the present invention is suitable as a complete detoxifying continuous treatment method for hardly decomposable aromatic chlorinated compounds.
【００１４】[0014]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
【００１５】実施例１ 温度計及び圧力計を備えた反応装置、高圧ポンプ、加熱
装置、圧力調整器で構成された連続流通式装置を用い、
これに酸化剤含有水溶液として濃度３．４重量％の過酸
化水素水を１．２ｍｌ／分の速度で送液し、同時に３‐
クロロビフェニルを０．２ミリモル／分の速度で供給
し、両者を温度３９０℃、圧力４９０気圧の条件で接触
させて分解処理を行った。Example 1 A continuous flow system comprising a reactor equipped with a thermometer and a pressure gauge, a high pressure pump, a heating device and a pressure regulator was used.
Hydrogen peroxide solution having a concentration of 3.4% by weight as an oxidant-containing aqueous solution was sent to this at a rate of 1.2 ml / min, and simultaneously with 3-
Chlorobiphenyl was supplied at a rate of 0.2 mmol / min, and both were brought into contact with each other under the conditions of a temperature of 390 ° C. and a pressure of 490 atm for decomposition treatment.
【００１６】反応帯式の管長は１０ｃｍで、滞留時間は
約１２秒であった。分解液を１０ｍｌずつ分割し、ガス
クロマトグラフィーで分析した結果、芳香族塩素化物は
全く検出されなかった。各フラクションの水素イオン濃
度測定結果を表１に示す。The reaction zone type tube length was 10 cm, and the residence time was about 12 seconds. The decomposition solution was divided into 10 ml portions and analyzed by gas chromatography. As a result, no aromatic chlorinated product was detected. Table 1 shows the measurement results of the hydrogen ion concentration of each fraction.
【００１７】実施例２ 実施例１において、圧力を４５０気圧に変えた以外は、
実施例１と同様にして実施した。その結果、芳香族塩素
化物は全く検出されなかった。また、各フラクションの
水素イオン濃度測定結果を表１に示す。Example 2 Example 2 was repeated except that the pressure was changed to 450 atm.
It carried out like Example 1. As a result, no aromatic chlorinated product was detected. Table 1 shows the measurement results of the hydrogen ion concentration of each fraction.
【００１８】比較例１ 実施例１において、温度を３２０℃に変えた以外は、実
施例１と同様にして実施した。ガスクロマトグラフィー
で分析した結果、分解率は２０〜３０％であった。各フ
ラクションの水素イオン濃度測定結果を表１に示す。Comparative Example 1 Example 1 was repeated except that the temperature was changed to 320 ° C. As a result of analysis by gas chromatography, the decomposition rate was 20 to 30%. Table 1 shows the measurement results of the hydrogen ion concentration of each fraction.
【００１９】比較例２ 実施例１において、圧力を１８０気圧に変えた以外は、
実施例１と同様にして実施した。ガスクロマトグラフィ
ーで分析した結果、分解率は７〜８％であった。各フラ
クションの水素イオン濃度測定結果を表１に示す。Comparative Example 2 Except that the pressure was changed to 180 atm in Example 1,
It carried out like Example 1. As a result of analysis by gas chromatography, the decomposition rate was 7 to 8%. Table 1 shows the measurement results of the hydrogen ion concentration of each fraction.
【００２０】[0020]
【表１】 [Table 1]
【００２１】上記の表において、塩化物の分解が進行す
ると塩酸が生じ、水素イオン濃度（ｐＨ）が低下するの
で、その数値の小さいものほど分解が行われているとい
うことが分る。In the above table, as the decomposition of chloride progresses, hydrochloric acid is generated and the hydrogen ion concentration (pH) decreases, so it can be seen that the smaller the value, the more the decomposition.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊東 祥太 宮城県仙台市青葉区木町16−10−105 (72)発明者 佐藤 修 宮城県仙台市宮城野区福室字境６番86−69 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shota Ito 16-10-105 Kimachi, Aoba-ku, Sendai-shi, Miyagi Prefecture (72) Inventor Osamu Sato 86-69, Fukumuro, Miyagino-ku, Sendai-shi, Miyagi Prefecture
Claims (3)
００気圧の条件下で、芳香族塩素化物を酸化剤含有水溶
液と接触させることを特徴とする芳香族塩素化物の分解
方法。1. A temperature of 350 to 550 ° C. and a pressure of 200 to 6
A method for decomposing an aromatic chlorinated product, which comprises bringing the aromatic chlorinated product into contact with an oxidizing agent-containing aqueous solution under a condition of 00 atm.
物１０〜３５モルの割合で接触させる請求項１記載の分
解方法。2. The decomposition method according to claim 1, wherein 10 to 35 mol of oxide is contacted with 1 equivalent of chlorine in the aromatic chlorinated product.
水溶液と接触させる請求項１又は２記載の分解方法。3. The decomposition method according to claim 1, which is brought into contact with an oxidizing agent-containing aqueous solution having an oxidizing agent concentration of 1 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6022110A JP2590421B2 (en) | 1994-01-20 | 1994-01-20 | Decomposition method of aromatic chlorinated products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6022110A JP2590421B2 (en) | 1994-01-20 | 1994-01-20 | Decomposition method of aromatic chlorinated products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07206714A true JPH07206714A (en) | 1995-08-08 |
| JP2590421B2 JP2590421B2 (en) | 1997-03-12 |
Family
ID=12073752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6022110A Expired - Lifetime JP2590421B2 (en) | 1994-01-20 | 1994-01-20 | Decomposition method of aromatic chlorinated products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2590421B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11513913A (en) * | 1996-03-22 | 1999-11-30 | エスアールアイ インターナショナル | A method for high temperature and supercritical water oxidation of materials using special reactants. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4543190A (en) * | 1980-05-08 | 1985-09-24 | Modar, Inc. | Processing methods for the oxidation of organics in supercritical water |
| JPS6438532A (en) * | 1987-08-04 | 1989-02-08 | Sanyo Electric Co | Air conditioner |
| JPH03503858A (en) * | 1988-03-18 | 1991-08-29 | ウェルチ，ジェームズ・フランシス | How to treat organic compounds |
-
1994
- 1994-01-20 JP JP6022110A patent/JP2590421B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4543190A (en) * | 1980-05-08 | 1985-09-24 | Modar, Inc. | Processing methods for the oxidation of organics in supercritical water |
| JPS6438532A (en) * | 1987-08-04 | 1989-02-08 | Sanyo Electric Co | Air conditioner |
| JPH03503858A (en) * | 1988-03-18 | 1991-08-29 | ウェルチ，ジェームズ・フランシス | How to treat organic compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11513913A (en) * | 1996-03-22 | 1999-11-30 | エスアールアイ インターナショナル | A method for high temperature and supercritical water oxidation of materials using special reactants. |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2590421B2 (en) | 1997-03-12 |
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