JP3535536B2 - Decomposition method of halogenated organic compounds - Google Patents
Decomposition method of halogenated organic compoundsInfo
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- JP3535536B2 JP3535536B2 JP07676093A JP7676093A JP3535536B2 JP 3535536 B2 JP3535536 B2 JP 3535536B2 JP 07676093 A JP07676093 A JP 07676093A JP 7676093 A JP7676093 A JP 7676093A JP 3535536 B2 JP3535536 B2 JP 3535536B2
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- halogen
- organic compound
- decomposing
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Description
【０００１】[0001]
【産業上の利用分野】本発明はハロゲン系有機化合物を
分解して無害化する方法に係り、さらに詳しくはハロゲ
ン系有機化合物を溶媒で溶解し液相状態で紫外線を照射
し、分解反応を行わせて無害化する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for decomposing a halogen-based organic compound to render it harmless. More specifically, it dissolves a halogen-based organic compound in a solvent and irradiates it with ultraviolet rays in a liquid phase to perform a decomposition reaction. It also relates to a method of making it harmless.
【０００２】[0002]
【従来の技術】従来、トリクレン，ポリクロロビフェニ
ル (PCB)，フロンなどのハロゲン系有機化合物は、化学
工業などの各種分野で広く使われてきているが、塩素化
合物であるトリクレンや PCBは人体に対する毒性が明ら
かになってきており、さらにフッ素を含むフロンは人体
に無害なもののオゾン層を破壊して地球環境を悪化させ
ることが近年明らかにされている。このような状況に対
応して、前記ハロゲン系有機化合物の分解・無害化方法
などがいろいろ検討されているが、まだ実用段階まで完
成した技術は知られていない。2. Description of the Related Art Conventionally, halogen-based organic compounds such as trichlene, polychlorobiphenyl (PCB) and freon have been widely used in various fields such as the chemical industry. Toxicity has been revealed, and it has been revealed in recent years that although CFCs containing fluorine are harmless to the human body, they destroy the ozone layer and deteriorate the global environment. In response to such a situation, various methods for decomposing / detoxifying the halogen-based organic compound have been studied, but a technique completed to a practical stage is not known yet.
【０００３】具体的には、水などの液相中のハロゲン系
有機化合物を対象とする無害化法として、触媒法，電子
線法あるいはナトリウム分解法など開発が進められてい
る。そして、触媒法は操作も簡単で、かつ必要エネルギ
ーも少なくて済むため、経済性が高い反面、液相の酸素
濃度が低いことに伴い分解能が低く、さらに分解時に発
生するハロゲン化合物により、触媒が急速に劣化する問
題点がある。また、紫外線などを利用する電子線分解法
は分解能が低くいので、電子線の照射だけで完全に分解
することは困難であるばかりでなく、処理装置も大型化
する欠点、あるいは発生するハロゲン化合物(HF)により
装置が腐食する危険性も他の方法より大きいという問題
もある。さらに、ナトリウム分解法の場合は、分解能は
高いがナトリウムを多量に消耗するので経済性に欠ける
とともに、取扱い上の安全対策も大型化する欠点があ
る。Specifically, as methods for detoxifying halogen-based organic compounds in a liquid phase such as water, the catalytic method, electron beam method, sodium decomposition method and the like are being developed. Since the catalytic method is easy to operate and requires less energy, it is highly economical, but on the other hand, the resolution is low due to the low oxygen concentration in the liquid phase, and the halogen compound generated during decomposition decomposes the catalyst. There is a problem of rapid deterioration. In addition, since the electron beam decomposition method using ultraviolet rays etc. has a low resolution, it is not only difficult to completely decompose it by irradiating it with an electron beam, but also a drawback that the processing apparatus becomes large, or a halogen compound generated There is also a problem that the risk of device corrosion due to (HF) is greater than other methods. Further, in the case of the sodium decomposition method, there is a drawback that the resolution is high, but a large amount of sodium is consumed, so that it is not economical and the safety measure in handling becomes large.
【０００４】前記液相中のハロゲン系有機化合物を無害
化する手段として知られている触媒法，電子線法，ナト
リウム分解法の中で、紫外線分解法は注目されており、
最も実用化の可能性が高く、従来、分解速度を上げるた
めに、アルカリを含むアルコール溶媒にフロンを溶解さ
せ紫外線を照射するなどの手段が試みられている。つま
り、アルコール溶媒の溶媒和効果によって分解率が向上
するとともに、分解時に生成したハロゲンをアルカリ添
加により塩の形で処理・反応系外に除去できるため、所
要の処理反応を持続させることができる。そしてこの方
法の試みでは、多くのハロゲン系有機化合物の分解が確
認され、その効果も認められていた。Among the catalytic method, electron beam method, and sodium decomposition method known as means for detoxifying the halogen-based organic compound in the liquid phase, the ultraviolet decomposition method is drawing attention.
It has the highest possibility of being put to practical use, and conventionally, in order to increase the decomposition rate, a means such as dissolving CFC in an alcohol solvent containing an alkali and irradiating it with ultraviolet rays has been tried. That is, the decomposition rate is improved by the solvation effect of the alcohol solvent, and the halogen generated during decomposition can be removed from the treatment / reaction system in the form of a salt by addition of an alkali, so that the required treatment reaction can be continued. In the attempt of this method, decomposition of many halogen-based organic compounds was confirmed, and its effect was also recognized.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記紫
外線照射によるハロゲン系有機化合物の分解方法では、
紫外線照射により生じた分解生成物、たとえばアルデヒ
ドなどがアルカリの共存下で、溶媒を成すアルコールと
の間でアルドール縮合型の重合反応を起こすなど、分解
反応の継続・進行にに悪影響を与えるため、分解可能な
操作条件が狭く実用性に乏しいという不都合な問題があ
る。このような問題に対して、本発明者らは、アルカリ
を含まない液相で紫外線を照射してハロゲン系有機化合
物を分解・処理する方法をいろいろ検討した。そして、
この方法での問題点として、液相にアルカリが存在し
ないため、溶媒和効果が低くなり近紫外領域波長の紫外
線では分解しにくいか、または全く分解しないこと、
また比較的単波長の紫外線を用いても従来に比べ分解速
度が非常に遅くなることなどを確認した。However, in the method for decomposing a halogen-based organic compound by the above-mentioned ultraviolet irradiation,
Decomposition products generated by UV irradiation, such as aldehydes, in the presence of alkali, cause an aldol condensation-type polymerization reaction with the alcohol forming the solvent, which adversely affects the continuation and progress of the decomposition reaction. There is an inconvenient problem that the operating conditions that can be disassembled are narrow and the practicality is poor. With respect to such a problem, the present inventors have studied various methods of irradiating ultraviolet rays in a liquid phase containing no alkali to decompose and treat the halogen-based organic compound. And
As a problem with this method, since there is no alkali in the liquid phase, the solvation effect becomes low and it is difficult to decompose with ultraviolet rays in the near ultraviolet region wavelength, or it does not decompose at all.
It was also confirmed that the decomposition rate was much slower than in the past even with the use of ultraviolet rays having a relatively single wavelength.
【０００６】本発明は上記検討などに基づき、液相での
紫外線分解法において、フロンなどの分解速度を速め、
大幅に分解性能を改善した有機ハロゲン化合物分解法の
提供を目的とする。Based on the above-mentioned studies, the present invention accelerates the decomposition rate of CFCs in the liquid phase ultraviolet decomposition method,
It is an object of the present invention to provide a method for decomposing an organohalogen compound with greatly improved decomposition performance.
【０００７】[0007]
【課題を解決するための手段】本発明に係るハロゲン系
有機化合物の分解法は、アルカリ成分を実質的に含まな
い溶媒にハロゲン系有機化合物が溶解され、かつ光増感
剤を含む液体に紫外線を照射する第１の工程と、前記液
体をアルカリ処理する第２の工程とを備えたことを骨子
とする。The method for decomposing a halogenated organic compound according to the present invention does not substantially contain an alkali component.
A halogen-based organic compound is dissolved in a solvent and is photosensitized
First step of irradiating a liquid containing an agent with ultraviolet rays, and the liquid
The main point is to have a second step of subjecting the body to alkali treatment .
【０００８】そして、このような本発明は、ハロゲン系
有機化合物の分解方法の中で最も効率向上が期待できる
紫外線分解方法について鋭意研究を重ねた結果に基づく
物である。すなわち、溶媒としてアルコールなどを用い
て液相で分解無害化するに当たり、液相（溶媒）に、た
とえばケトン構造，アルデヒド構造などの光増感剤を添
加しておくことにより、比較的長波長の紫外線でも分解
効率の低下など招来せずに、容易に所要のハロゲン系有
機化合物の分解・無害化を行い得るとの知見に基づいて
成されたものであり、さらに具体的には、光増感剤を含
むアルコール系液相状態にあるハロゲン系有機化合物に
紫外線を照射し、前記ハロゲン系有機化合物を分解によ
り無害化することを特徴とするハロゲン系有機化合物の
分解法、もしくは光増感剤を含むアルコール系液相状態
にあるハロゲン系有機化合物に紫外線を照射し、前記ハ
ロゲン系有機化合物を分解により無害化する工程と、前
記紫外線を照射したアルコール系液相にアルカリ処理を
施す工程とを具備して成ることを特徴とするハロゲン系
有機化合物の分解法として把握し得る。The present invention is based on the results of earnest studies on the ultraviolet decomposition method which can be expected to improve the efficiency most among the decomposition methods for halogen-containing organic compounds. That is, when decomposing and detoxifying in the liquid phase by using alcohol or the like as a solvent, by adding a photosensitizer having, for example, a ketone structure or an aldehyde structure to the liquid phase (solvent), It was made based on the knowledge that the required halogen-based organic compounds can be decomposed and harmless easily even with ultraviolet rays without degrading the decomposition efficiency. A method for decomposing a halogen-based organic compound, which comprises irradiating a halogen-based organic compound in an alcohol-based liquid phase state containing an agent with ultraviolet rays to detoxify the halogen-based organic compound, or a photosensitizer. A step of irradiating the halogen-containing organic compound in the alcohol-based liquid phase state with ultraviolet rays to detoxify the halogen-based organic compound by decomposing, and an alcohol irradiated with the ultraviolet rays. Be made by including a step of alkali treatment in the system liquid phase may grasp the decomposition method of halogenated organic compounds characterized by.
【０００９】本発明において、液相を形成するため用い
る溶媒としては、たとえばアルコール類などの極性溶
媒、アルコール類と他の極性溶媒との混合系、アルコー
ル類と非極性溶媒との混合系など挙げられるが、たとえ
ばイソプロピルアルコール，ノルマルプロピルアルコー
ル，エタノール，メタノールなどが挙げられ、特にイソ
プロピルアルコールが好ましい。一方、光増感剤として
は、ケトン構造もしくはアルデヒド構造を有するものが
望ましく、なかでもアセトン、エチルメチルケトン、ア
セトアルデヒドなど効率性の点で好ましい。そして、光
増感剤の添加量は、光増感剤の種類、溶媒の種類、分解
・無害化するハロゲン系有機化合物の種類、照射する紫
外線の波長などでも変わるが、前記分解・無害化するハ
ロゲン系有機化合物の等モル量以下で充分である。さら
に、前記紫外線照射によってハロゲン系有機化合物を分
解・無害化した後、処理済みの液相系にアルカリ処理を
施す場合は、前記分解・無害化に伴う生成物を塩とする
に足る量のアルカリ成分、たとえばナトリウムを添加す
る。In the present invention, examples of the solvent used for forming the liquid phase include polar solvents such as alcohols, mixed systems of alcohols and other polar solvents, mixed systems of alcohols and non-polar solvents, and the like. Examples thereof include isopropyl alcohol, normal propyl alcohol, ethanol and methanol, and isopropyl alcohol is particularly preferable. On the other hand, as the photosensitizer, those having a ketone structure or an aldehyde structure are preferable, and among them, acetone, ethylmethylketone, acetaldehyde and the like are preferable in terms of efficiency. The amount of the photosensitizer added varies depending on the type of the photosensitizer, the type of the solvent, the type of the halogen-based organic compound that is decomposed / detoxified, the wavelength of the ultraviolet light to be irradiated, and the like. An equimolar amount or less of the halogen-based organic compound is sufficient. Further, after decomposing / detoxifying the halogen-based organic compound by the ultraviolet irradiation, when the treated liquid phase system is subjected to alkali treatment, an amount of alkali sufficient to salt the product accompanying the decomposing / detoxification. Ingredients such as sodium are added.
【００１０】[0010]
【作用】前記のごとく、液相を成す被処理系に紫外線を
照射する段階では、液相系にアルカリ成分が存在しない
ので、紫外線照射により生じた分解生成物、たとえばア
ルデヒドなどがアルカリの共存下で、溶媒を成すアルコ
ールとの間でアルドール縮合型の重合反応を起こすな
ど、分解反応の継続・進行にに悪影響を与えるため、分
解可能な操作条件が狭く実用性に乏しいという問題が解
消される。また、液相系（溶媒系）に、光増感剤を添加
・共存させたので、紫外線（波長 365nm）の照射でも 1
00％の分解が可能となる。As described above, at the stage of irradiating the system to be treated in the liquid phase with ultraviolet rays, since no alkaline component is present in the liquid phase system, decomposition products such as a product generated by the irradiation with ultraviolet rays are generated.
Aldehyde, etc., forms a solvent in the presence of alkali.
Do not cause an aldol condensation type polymerization reaction with
However, since it adversely affects the continuation and progress of the decomposition reaction,
The problem is that the solvable operating conditions are narrow and the practicality is poor.
Be erased. In addition, since a photosensitizer was added to and coexisted in the liquid phase (solvent system), it can be irradiated with ultraviolet light (wavelength 365 nm).
100% of the decomposition is possible.
【００１１】[0011]
【実施例】以下本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【００１２】実施例１
図１は本発明に係るハロゲン系有機化合物の分解方法の
実施態様を模式的に示したもので、たとえば内容積1000
mlの分解槽１に、先ず、ハロゲン系有機化合物としてた
とえばフロン11を 3％含有するメタノール 500ml、光増
感剤としてのアセトンを 2mlを加えてなる溶液（液相）
２を収容した。次いで、主波長 254nmの紫外線ランプ３
を用いて、前記溶液２を 100分間紫外線を照射して、溶
液２中のフロン11を分解・無害化させた。なお、前記分
解・無害化の処理前後における溶液２中のフロン11濃度
を、ガスクロマトグラフグラフでそれぞれ測定し、次式
で分解率を求めたところ、分解率は 100％であった。Example 1 FIG. 1 schematically shows an embodiment of the method for decomposing a halogen-based organic compound according to the present invention.
A solution (liquid phase) prepared by adding 500 ml of methanol containing 3% of Freon 11 as a halogen-based organic compound and 2 ml of acetone as a photosensitizer to the decomposition tank 1 of ml.
Accommodated two. Next, an ultraviolet lamp with a main wavelength of 254 nm 3
The solution 2 was irradiated with ultraviolet rays for 100 minutes to decompose and detoxify the flon 11 in the solution 2. The CFC 11 concentration in the solution 2 before and after the decomposition / detoxification treatment was measured by a gas chromatograph, and the decomposition rate was calculated by the following equation. The decomposition rate was 100%.
【００１３】分解率＝ 100＊（処理前の濃度−処理後の
濃度）／（処理前の濃度）
図２は前記分解・無害化の処理過程における分解率の経
時変化を示したもので、曲線Ａは実施例の場合を示す。Decomposition rate = 100 * (concentration before treatment-concentration after treatment) / (concentration before treatment) FIG. 2 shows the change over time in the decomposition rate during the above-mentioned decomposition / detoxification treatment process. A shows the case of the example.
【００１４】比較例１
前記実施例１の場合と同様に、フロン11を 3％含むメタ
ノール 500mlを溶液に、アセトンを加えない状態で主波
長 254nmの紫外線ランプ３で 100分間紫外線を照射し
て、溶液中のフロン11を分解・無害化させた。なお、前
記分解・無害化の処理前後における溶液中のフロン11濃
度を、ガスクロマトグラフグラフでそれぞれ測定し、次
式で分解率を求めたところ、分解率は47％であった。Comparative Example 1 As in the case of Example 1, 500 ml of methanol containing 3% of CFC 11 was irradiated to a solution for 100 minutes by an ultraviolet lamp 3 having a main wavelength of 254 nm without adding acetone, Freon 11 in the solution was decomposed and made harmless. The concentration of Freon 11 in the solution before and after the decomposition / detoxification treatment was measured by a gas chromatograph, and the decomposition rate was calculated by the following formula. The decomposition rate was 47%.
【００１５】分解率＝ 100＊（処理前の濃度−処理後の
濃度）／（処理前の濃度）
前記分解・無害化の処理過程における分解率の経時変化
は、図２に曲線ａで示すごとくであった。Decomposition rate = 100 * (concentration before treatment-concentration after treatment) / (concentration before treatment) The change with time of the decomposition rate in the above-mentioned decomposition / detoxification treatment process is shown by a curve a in FIG. Met.
【００１６】実施例２
実施例１の場合において、フロン11を 3％含むイソプロ
ピルアルコール 500mlに光増感剤としてアセトンを 5ml
加えた溶液を被処理体２として、内容積1000mlの分解槽
１に収容した後、主波長 365nmの紫外線ランプ３で20分
間、紫外線を照射してフロン11の分解・無害化処理を行
った。前記分解・無害化処理後の液中のフロン濃度をガ
スクロマトグラフで測定し、実施例１の場合と同様に分
解率を求めたところ、分解率は 100％であった。また、
前記分解・無害化の処理過程における分解率の経時変化
は、図３に曲線Ｂで示すごとくであった。Example 2 In the case of Example 1, 5 ml of acetone as a photosensitizer was added to 500 ml of isopropyl alcohol containing 3% of Freon 11.
The solution thus added was treated as a substance to be treated 2 and housed in a decomposition tank 1 having an internal volume of 1000 ml, and then irradiated with ultraviolet rays from an ultraviolet lamp 3 having a main wavelength of 365 nm for 20 minutes to decompose and detoxify the CFC 11. The fluorocarbon concentration in the liquid after the decomposition / detoxification treatment was measured by a gas chromatograph, and the decomposition ratio was determined in the same manner as in Example 1. The decomposition ratio was 100%. Also,
The change over time in the decomposition rate during the decomposition / detoxification treatment process was as shown by the curve B in FIG.
【００１７】さらに、前記被処理体（溶液）に添加した
光増感剤をエチルメチルケトン、アセトアルデヒド、ア
セトフェノン、ベンゾフェノン、もしくはビアセチルに
換えて同様の条件でフロン11の分解・無害化処理を行っ
た。なお、このときの光増感剤の添加量はいずれもフロ
ン11の 1/2モル量とした。これらの分解・無害化処理過
程における分解率の経時変化それぞれを図３に併記し
た。図３において曲線Ｃは光増感剤がエチルメチルケト
ン、曲線Ｄは光増感剤がアセトアルデヒド、曲線Ｅは光
増感剤がアセトフェノン、曲線Ｆは光増感剤がベンゾフ
ェノン、曲線Ｇは光増感剤がビアセチルの場合をそれぞ
れ示す。Further, the photosensitizer added to the object to be treated (solution) was replaced with ethyl methyl ketone, acetaldehyde, acetophenone, benzophenone, or biacetyl to decompose and detoxify CFC 11 under the same conditions. . The amount of the photosensitizer added at this time was 1/2 mol of Freon 11. FIG. 3 also shows changes over time in the decomposition rate during these decomposition / detoxification treatment processes. In FIG. 3, the curve C is ethyl methyl ketone as the photosensitizer, the curve D is acetaldehyde as the photosensitizer, the curve E is acetophenone as the photosensitizer, the curve F is benzophenone as the photosensitizer, and the curve G is photosensitizer. The case where the sensitizer is biacetyl is shown respectively.
【００１８】比較例２
実施例２の場合において、フロン11を 3％含むイソプロ
ピルアルコール 500ml溶液（アセトンなど光増感剤不添
加）を被処理体２として、内容積1000mlの分解槽１に収
容した後、主波長 365nmの紫外線ランプ３で 3時間、紫
外線を照射してフロン11の分解・無害化処理を行った。
前記分解・無害化処理後の液中のフロン濃度をガスクロ
マトグラフで測定し、実施例１の場合と同様に分解率を
求めたところ、分解率は 0％であり、フロン11は全然分
解しなかった。Comparative Example 2 In the case of Example 2, 500 ml of an isopropyl alcohol solution containing 3% of CFC 11 (without addition of a photosensitizer such as acetone) was used as the object to be treated 2 and accommodated in the decomposition tank 1 having an internal volume of 1000 ml. After that, the fluorocarbon 3 having a main wavelength of 365 nm was irradiated with ultraviolet rays for 3 hours to decompose and detoxify CFC 11.
The CFC concentration in the liquid after the decomposition / detoxification treatment was measured by a gas chromatograph, and the decomposition rate was determined in the same manner as in Example 1. The decomposition rate was 0%, and CFC 11 did not decompose at all. It was
【００１９】実施例３
図４に概略構成を示すような、分解槽１およびアルカリ
処理槽４を分離して設けたハロゲン系有機化合物分解装
置を先ず用意した。図４において３は紫外線源、たとえ
ば紫外線ランプ、５は分解槽１およびアルカリ処理槽４
を接続する輸送管に設置された液送ポンプ、６はアルカ
リ溶液6aを収容するアルカリ貯液槽、７，８は開閉可能
なバルブである。この装置においては、分解槽１に被処
理液としての液相系を成すハロゲン系有機化合物溶液２
が収容され、ここで所要の分解処理が行われた後、液送
ポンプ５によってアルカリ処理槽４に送られ、アルカリ
貯液槽６から適量のアルカリ溶液、たとえば苛性ソーダ
水溶液6aが、処理済みのハロゲン系有機化合物溶液２′
に添加混合される。そして、前記アルカリ処理槽４内に
おいて、ハロゲン系有機化合物溶液２′中の分解正生物
と苛性ソーダ水溶液6a中のアルカリ成分とで塩を生成
し、沈殿物2a′としてアルカリ処理槽４の底部に沈積す
るので、バルブ８を開放して排出可能になっている。Example 3 First, an apparatus for decomposing a halogen-based organic compound, in which a decomposition tank 1 and an alkali treatment tank 4 were separately provided, as shown in FIG. 4, was prepared. In FIG. 4, 3 is an ultraviolet source, for example, an ultraviolet lamp, 5 is a decomposition tank 1 and an alkali treatment tank 4.
Is a liquid feed pump installed in the transport pipe connecting the above, 6 is an alkaline storage tank for storing the alkaline solution 6a, and 7 and 8 are valves that can be opened and closed. In this apparatus, a halogen-based organic compound solution 2 that forms a liquid phase system as a liquid to be treated is provided in a decomposition tank 1.
Is stored therein, and after the required decomposition treatment is carried out there, it is sent to the alkali treatment tank 4 by the liquid feed pump 5, and an appropriate amount of alkali solution, for example, caustic soda aqueous solution 6a, is treated from the alkali storage tank 6 and treated with halogen. Organic compound solution 2 '
Is added to and mixed with. Then, in the alkali treatment tank 4, a salt is formed by the decomposition product in the halogen-based organic compound solution 2'and the alkali component in the caustic soda solution 6a, and deposited as a precipitate 2a 'at the bottom of the alkali treatment tank 4. Therefore, the valve 8 can be opened and discharged.
【００２０】前記構成の装置を用い、ハロゲン系有機化
合物としてたとえばフロン11を 3％含有するメタノール
500ml、光増感剤としてのアセトンを 2mlを加えてなる
溶液（液相）２を分解槽１内に収容した。次いで、主波
長 254nmの紫外線ランプ３を用いて、前記溶液２を 100
分間紫外線を照射して、溶液２中のフロン11を分解・無
害化させた。なお、前記分解・無害化の処理前後におけ
る溶液２中のフロン11濃度を、ガスクロマトグラフグラ
フでそれぞれ測定し、実施例１の場合と同様に分解率を
求めたところ、分解率は 100％であった。Methanol containing 3% of CFC 11 as a halogen-based organic compound is prepared using the apparatus having the above-mentioned structure.
A solution (liquid phase) 2 obtained by adding 500 ml and 2 ml of acetone as a photosensitizer was placed in the decomposition tank 1. Then, using an ultraviolet lamp 3 with a main wavelength of 254 nm,
The Freon 11 in the solution 2 was decomposed and made harmless by irradiating with ultraviolet rays for a minute. The CFC 11 concentration in the solution 2 before and after the decomposition / detoxification treatment was measured by a gas chromatograph, and the decomposition rate was calculated in the same manner as in Example 1. The decomposition rate was 100%. It was
【００２１】その後、液送ポンプ５を駆動して分解槽１
内から、処理済みの溶液２′をアルカリ処理槽４に移送
し、バルブ７を開放してアルカリ貯液槽６に収容されて
いるアルカリ溶液6aの適量を添加・混合した。このアル
カリ溶液6aの適量の添加・混合により、処理済みの溶液
２′中には塩が析出して、アルカリ処理槽４の底部に沈
殿物2a′として沈積した。この沈殿物2a′をバルブ８の
開放により排出してから、処理済みの溶液２′を分析・
評価したところ、分解槽１内に戻して被処理液相を構成
する溶媒として再利用可能であった。Then, the liquid feed pump 5 is driven to drive the decomposition tank 1
From the inside, the treated solution 2'was transferred to the alkali treatment tank 4, the valve 7 was opened, and an appropriate amount of the alkali solution 6a contained in the alkali storage tank 6 was added and mixed. By adding and mixing an appropriate amount of this alkaline solution 6a, a salt was deposited in the treated solution 2'and deposited as a precipitate 2a 'on the bottom of the alkaline treatment tank 4. The precipitate 2a 'is discharged by opening the valve 8 and then the treated solution 2'is analyzed.
As a result of evaluation, it could be returned to the decomposition tank 1 and reused as a solvent constituting the liquid phase to be treated.
【００２２】なお、上記ではハロゲン系有機化合物とし
てフロン11の分解処理を例示したが、 トリクロロエチ
レン， PCBなどについても同様の分解・無害化が可能で
ある。In the above description, CFC 11 is decomposed as a halogen-based organic compound, but trichloroethylene, PCB and the like can be decomposed and made harmless in the same manner.
【００２３】[0023]
【発明の効果】以上の説明ないし具体的な例示から分か
るように、本発明に係るハロゲン系有機化合物の分解方
法によれば、煩雑な操作などを要せずに、また操作上厳
しい制約などもなく、効率よくかつ容易に所要の無害化
処理を達成し得る。つまり、本発明は、従来注目されな
がら、実用性に問題があった液相系に対する紫外線照射
によるハロゲン系有機化合物の分解・無害化に実用化の
途を開いたものといえる。As can be seen from the above description and specific examples, the method for decomposing a halogen-based organic compound according to the present invention does not require any complicated operation and has severe restrictions on operation. Therefore, the required detoxification treatment can be achieved efficiently and easily. In other words, it can be said that the present invention has been put into practical use for decomposing / detoxifying a halogen-based organic compound by irradiating a liquid-phase system with ultraviolet rays, which has been problematic in practical use, while receiving attention in the past.
【図１】本発明の実施態様例を示す模式図。FIG. 1 is a schematic diagram showing an example of an embodiment of the present invention.
【図２】本発明の一実施態様例における紫外線照射の経
過時間と分解率の関係例を従来の方法と比較して示す曲
線図。FIG. 2 is a curve diagram showing an example of the relationship between the elapsed time of ultraviolet irradiation and the decomposition rate in an embodiment of the present invention in comparison with a conventional method.
【図３】本発明の他の実施態様例における紫外線照射の
経過時間と分解率の関係例を比較して示す曲線図。FIG. 3 is a curve diagram showing a comparison example of the relationship between the elapsed time of ultraviolet irradiation and the decomposition rate in another embodiment of the present invention.
【図４】本発明の一実施態様例に使用する装置の概略構
成を示す断面図。FIG. 4 is a cross-sectional view showing a schematic configuration of an apparatus used in an embodiment of the present invention.
１…分解槽 ２…被処理溶液（反応液） ２′…処
理済みの被処理溶液
2a′…沈殿物 ３…紫外線ランプ ４…アルカリ処
理槽 ５…液送ポンプ ６…アルカリ貯液槽 6a
…アルカリ溶液 ７，８…開閉可能なバルブDESCRIPTION OF SYMBOLS 1 ... Decomposition tank 2 ... Treated solution (reaction solution) 2 '... Treated treated solution 2a' ... Precipitate 3 ... UV lamp 4 ... Alkaline treatment tank 5 ... Liquid feed pump 6 ... Alkaline storage tank 6a
… Alkaline solution 7,8… Valve that can be opened and closed
フロントページの続き (56)参考文献 特開 昭61−146387（ＪＰ，Ａ) 特開 昭56−67580（ＪＰ，Ａ) 特開 平４−266777（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/30 - 1/32 A62D 1/00 - 9/00 Continuation of front page (56) References JP-A-61-146387 (JP, A) JP-A-56-67580 (JP, A) JP-A-4-266777 (JP, A) (58) Fields investigated (Int .Cl. 7 , DB name) C02F 1/30-1/32 A62D 1/00-9/00
Claims (11)
ハロゲン系有機化合物が溶解され、かつ光増感剤を含む
液体に光増感剤を添加して紫外線を照射する第１の工程
と、 前記液体をアルカリ処理する第２の工程と を備える ことを特徴とするハロゲン系有機化合物の分解
方法。1. A solvent containing substantially no alkali component
Halogen organic compound is dissolved and contains photosensitizer
First step of adding photosensitizer to liquid and irradiating with ultraviolet light
When method for decomposing halogenated organic compounds, characterized in that it comprises a second step of alkali treatment the liquid.
徴とする請求項１記載のハロゲン系有機化合物の分解方
法。2. The solvent comprises alcohol.
The method for decomposing a halogen-based organic compound according to claim 1, which is a characteristic of the method.
ール、ｎ−プロパノールおよびイソプロパノールから選
択された少なくとも１種であることを特徴とする請求項
２記載のハロゲン系有機化合物の分解方法。3. The alcohol is methanol or ethano.
Alcohol, n-propanol and isopropanol.
At least one selected from claims
2. The method for decomposing a halogen-based organic compound according to 2 .
囲の波長を含むことを特徴とする請求項１乃至３のいず4. The wavelength range of any one of claims 1 to 3 is included.
れか１項記載のハロゲン系有機化合物の分解方法。2. A method for decomposing a halogen-based organic compound according to item 1.
分を前記液体に添加することにより、前記アルカリ成分By adding a component to the liquid,
を塩の形で前記液体から析出させる第３の工程と、A third step of precipitating from the liquid in the form of a salt, 析出された前記塩を前記液体から除去する第４の工程をA fourth step of removing the precipitated salt from the liquid
備えたことを特徴とする請求項１乃至４のいずれか１項5. The method according to claim 1, further comprising:
記載のハロゲン系有機化合物の分解方法。A method for decomposing a halogen-based organic compound as described.
化合物を含むことを特徴とする請求項１乃至５のいずれAny of claims 1 to 5 containing a compound.
か１項記載のハロゲン系有機化合物の分解方法。2. A method for decomposing a halogen-based organic compound according to item 1.
セトン、メチルエチルケトン、アセトアルデヒド、アセCetone, methyl ethyl ketone, acetaldehyde, acetone
トフェノン、ベンゾフェノンおよびビアセチルから選択Select from tophenone, benzophenone and biacetyl
された少なくとも１種であることを特徴とする請求項１At least one selected from the above.
乃至６のいずれか１項記載のハロゲン系有機化合物の分To the halogen-based organic compound according to any one of
解方法。Solution method.
を含むことを特徴とする請求項１乃至７のいずれか１項8. The method according to claim 1, further comprising:
記載のハロゲン系有機化合物の分解方法。A method for decomposing a halogen-based organic compound as described.
あることを特徴とする請求項１乃至８のいずれか１項記9. Any one of claims 1 to 8 characterized in that
載のハロゲン系有機化合物の分解方法。The decomposition method of the halogen-based organic compounds listed above.
にハロゲン系有機化合物が溶解され、かつ光増感剤を含Halogen-containing organic compound is dissolved in the
む液体に紫外線を照射する第１の工程と、A first step of irradiating the liquid with ultraviolet rays; 前記液体をアルカリ処理する第２の工程とを備えることA second step of treating the liquid with an alkali
を特徴とするハロゲン系有機化合物の分解方法。And a method for decomposing a halogen-based organic compound.
にハロゲン系有機化合物が溶解され、かつ光増感剤を含Halogen-containing organic compound is dissolved in the
む液体を用意する第１の工程と、A first step of preparing a liquid, アルカリ成分が実質的に存在しない状態で前記ハロゲンThe halogen described above in the substantial absence of alkali components
系有機化合物を分解するために有効な波長の光を前記液The liquid with a wavelength of light effective for decomposing organic compounds
体に照射する第２の工程と、The second step of irradiating the body, 前記液体をアルカリ処理する第３の工程とを備えることA third step of treating the liquid with an alkali
を特徴とするハロゲン系有機化合物の分解方法。And a method for decomposing a halogen-based organic compound.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07676093A JP3535536B2 (en) | 1993-04-02 | 1993-04-02 | Decomposition method of halogenated organic compounds |
| US08/105,625 US5393394A (en) | 1992-08-18 | 1993-08-13 | Method and apparatus for decomposing organic halogen-containing compound |
| DE4327804A DE4327804A1 (en) | 1992-08-18 | 1993-08-18 | Decomposition of organic halogen cpds. - by exposing soln. to UV light then adding alkali to ppte. salt, for economical destruction of e.g. tri:chloroethylene, poly:chloro-bi:phenyl and chloro-fluorocarbon cpds. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07676093A JP3535536B2 (en) | 1993-04-02 | 1993-04-02 | Decomposition method of halogenated organic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06285460A JPH06285460A (en) | 1994-10-11 |
| JP3535536B2 true JP3535536B2 (en) | 2004-06-07 |
Family
ID=13614553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07676093A Expired - Fee Related JP3535536B2 (en) | 1992-08-18 | 1993-04-02 | Decomposition method of halogenated organic compounds |
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| Country | Link |
|---|---|
| JP (1) | JP3535536B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160713A (en) * | 2004-12-10 | 2006-06-22 | Sanwa Yuka Kogyo Kk | Methods for synthesizing and recovering hydrofluorocarbons |
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1993
- 1993-04-02 JP JP07676093A patent/JP3535536B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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