JP2809367B2 - Exhaust gas treatment method - Google Patents
Exhaust gas treatment methodInfo
- Publication number
- JP2809367B2 JP2809367B2 JP4339936A JP33993692A JP2809367B2 JP 2809367 B2 JP2809367 B2 JP 2809367B2 JP 4339936 A JP4339936 A JP 4339936A JP 33993692 A JP33993692 A JP 33993692A JP 2809367 B2 JP2809367 B2 JP 2809367B2
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- methane
- chlorine
- chlorine derivative
- derivative
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 5
- 125000001309 chloro group Chemical class Cl* 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 18
- 150000001804 chlorine Chemical class 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- 150000004045 organic chlorine compounds Chemical class 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- -1 trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical class C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GZETWZZNDACBTQ-UHFFFAOYSA-N [Cl].C=C Chemical class [Cl].C=C GZETWZZNDACBTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はメタンの塩素誘導体を含
んだ排ガスの処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating an exhaust gas containing a chlorine derivative of methane.
【０００２】[0002]
【従来の技術】基板洗浄ライン等より排出されるトリク
ロロエチレン、テトラクロロエチレン、１，１，１−ト
リクロロエタン、四塩化炭素、クロロホルム、ジクロロ
メタン等の有害な揮発性有機塩素化合物を含有する排水
は、ばっ気して大気中に未処理のまま放出されているの
が現状であり、地球環境保全上問題があった。2. Description of the Related Art Wastewater containing harmful volatile organic chlorine compounds such as trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, carbon tetrachloride, chloroform and dichloromethane discharged from a substrate washing line or the like is aerated. At present, it is released untreated into the atmosphere, which poses a problem for global environmental protection.
【０００３】[0003]
【発明が解決しようとする課題】上記問題点を解決する
ための手段として、本発明者は既に「排ガス処理装置」
（実願平２〜１１０５００号）を初め、種々の技術を提
案している。これらの内容は波長１８４．９ｎｍの紫外
線（ＵＶ）と紫外線により生成された発生期のオゾン
（Ｏ3 ）、あるいは光触媒によって排ガス中に含まれる
揮発性有機塩素化合物を無機化合物に分解し、さらにオ
ゾン分解触媒により残留オゾンを酸素に分解して無害化
する方法である。しかしながら、四塩化炭素、クロロホ
ルム、ジクロロメタン等のメタンの塩素誘導体は紫外線
照射やオゾン並びに光触媒下では容易に分解しないとい
う問題があった。As a means for solving the above problems, the present inventor has already proposed an "exhaust gas treatment apparatus".
(Japanese Utility Model Application No. 2-110500). These contents include ultraviolet rays (UV) having a wavelength of 184.9 nm and nascent ozone (O 3 ) generated by the ultraviolet rays, or a volatile organic chlorine compound contained in exhaust gas decomposed into an inorganic compound by a photocatalyst, and furthermore, ozone In this method, residual ozone is decomposed into oxygen by a decomposition catalyst to render it harmless. However, there has been a problem that chlorine derivatives of methane such as carbon tetrachloride, chloroform and dichloromethane are not easily decomposed under ultraviolet irradiation, ozone and photocatalyst.
【０００４】本発明は上記技術水準に鑑み、容易に分解
しないメタンの塩素誘導体を含む排ガス無害化するため
の処理方法を提供しようとするものである。The present invention has been made in view of the above-mentioned state of the art, and has as its object to provide a treatment method for detoxifying an exhaust gas containing a chlorine derivative of methane which is not easily decomposed.
【０００５】[0005]
【課題を解決するための手段】本発明はメタンの塩素誘
導体を含む排ガス中にガス状のエチレンの塩素誘導体を
少量加えた後、該ガスに紫外線を照射することを特徴と
するメタンの塩素誘導体を含む排ガスの処理方法であ
る。The present invention is characterized in that a small amount of gaseous chlorine derivative of ethylene is added to an exhaust gas containing a chlorine derivative of methane, and the gas is irradiated with ultraviolet rays. It is a method for treating exhaust gas containing.
【０００６】本発明でいうメタンの塩素誘導体とは四塩
化炭素、クロロホルム、ジクロロメタン、クロロメタン
などであり、エチレンの塩素誘導体とはトリクロロエチ
レン、テトラクロロエチレンなどである。In the present invention, the chlorine derivative of methane is carbon tetrachloride, chloroform, dichloromethane, chloromethane and the like, and the chlorine derivative of ethylene is trichloroethylene, tetrachloroethylene and the like.
【０００７】[0007]
【作用】有機塩素化合物は紫外線を照射することにより
二酸化炭素（ＣＯ2 ）と塩化水素ガス（ＨＣｌ）に分解
されることが知られている。｛今川 隆，化学工業 4
1，(1) 24〜27 '90，久永輝明，原田賢二等 水処理技
術 29，(8)483〜487 '88｝また、一般にメタンの誘導
体はエチレンの誘導体より分解しにくく、かつ炭素数が
同じ場合には置換塩素の数が多いほど分解しにくいこと
もよく知られていることである。（久永輝明，原田賢二
等，工技院レポート '89）[Action] Organic chlorine compounds are exposed to ultraviolet light
Carbon dioxide (COTwo) And hydrogen chloride gas (HCl)
Is known to be. ｛Takashi Imagawa, Chemical IndustryFour
1, (1) 24-27 '90, Kusunaga Teruaki, Harada Kenji, etc. Water treatment techniques
Art29, (8) 483-487 '88｝ Also, generally methane induction
The body is more difficult to decompose than the ethylene derivative,
In the same case, the higher the number of substituted chlorines, the more difficult it is to decompose
Is also well known. (Terukiaki Hisaga, Kenji Harada
Etc., Technical Institute Report '89)
【０００８】例えば、トリクロロエチレン（Ｃ2 ＨＣｌ
3 ）の紫外線（ＵＶ）による分解反応は次のようであ
り、ラジカルを経て分解される。For example, trichlorethylene (C 2 HCl)
3 ) The decomposition reaction by ultraviolet rays (UV) is as follows, and is decomposed via radicals.
【０００９】[0009]
【化１】 Embedded image
【００１０】一方、メタンの塩素誘導体は紫外線の照射
のみでは同様なラジカルを生成しにくいため分解しにく
い。そこで、難分解性有機塩素化合物を含む排ガスの中
に紫外線照射により分解しやすい物質を少量加え、これ
を分解させることにより（１）式で生じたＨ・ラジカル
が下記（３）式に示すようにＯ3 の分解時に発生する発
生期の酸素（Ｏ* ）あるいは（４）式に示すようにＨ2
Ｏと反応して強い酸化力をもつ・ＯＨラジカルに変換す
る。この・ＯＨラジカルがメタンの塩素誘導体を酸化分
解することにより、下記（５）式，（６）式に示すよう
に紫外線照射のみでは分解されにくいジクロロメタンの
如きメタンの塩素誘導体も容易に分解される。すなわち
トリクロロエチレンはラジカル分解反応の開始剤として
作用する。一度・ＯＨラジカルが生成された後は（４）
式に示すように１個のＨ・ラジカルから２個のＨ・ラジ
カルが生成するので連鎖反応により瞬時に分解が進行
し、短時間で高い分解率が得られることになる。On the other hand, a chlorine derivative of methane is not easily decomposed because it is difficult to generate similar radicals only by irradiation with ultraviolet rays. Therefore, a small amount of a substance which is easily decomposed by ultraviolet irradiation is added to an exhaust gas containing a hardly decomposable organic chlorine compound, and the H. radical generated in the formula (1) is decomposed as shown in the following formula (3). The nascent oxygen (O * ) generated when O 3 is decomposed or H 2 as shown in equation (4).
It reacts with O and has strong oxidizing power. It is converted into OH radical. The OH radical oxidizes and decomposes the chlorine derivative of methane, thereby easily decomposing the chlorine derivative of methane, such as dichloromethane, which is difficult to decompose only by ultraviolet irradiation as shown in the following formulas (5) and (6). . That is, trichloroethylene acts as an initiator of the radical decomposition reaction. Once the OH radical is generated (4)
As shown in the formula, two H. radicals are generated from one H. radical, so that decomposition proceeds instantaneously by a chain reaction, and a high decomposition rate can be obtained in a short time.
【００１１】[0011]
【化２】 Embedded image
【００１２】[0012]
【実施例】本発明の一実施態様としての試験装置の構成
を図１に従って詳述する。図１において、テドラーバッ
グ１内で所定濃度に調整された排ガスをポンプ２で光分
解反応器４に所定流量で流す。３は光分解反応器４に所
定（一定）量で流すためのバッファタンクである。光分
解反応器４内に設置したＨｇランプ５から紫外線を発生
させ排ガス中の有機塩素化合物を分解する。分解率はサ
ンプリング点６及びサンプリング点７から排ガスを採取
しＦＩＤ検出器付きのガスクロマトグラフで濃度を分析
して算出する。紫外線発生時に副生するオゾンが排ガス
中に残存すると分析中（ガスクロマトグラフによる分
析）に有機塩素化合物と反応して有機塩素化合物濃度が
低くなり、排ガス中の濃度を正しく分析することができ
なくなるため、事前にハイポ溶液などでオゾンを吸収す
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of a test apparatus as one embodiment of the present invention will be described in detail with reference to FIG. In FIG. 1, an exhaust gas adjusted to a predetermined concentration in a Tedlar bag 1 is flown at a predetermined flow rate into a photolysis reactor 4 by a pump 2. Reference numeral 3 denotes a buffer tank for flowing a predetermined (constant) amount into the photolysis reactor 4. Ultraviolet rays are generated from the Hg lamp 5 installed in the photolysis reactor 4 to decompose the organic chlorine compounds in the exhaust gas. The decomposition rate is calculated by collecting exhaust gas from sampling points 6 and 7 and analyzing the concentration using a gas chromatograph equipped with an FID detector. If ozone produced as a by-product in the generation of ultraviolet rays remains in the exhaust gas, it reacts with the organic chlorine compound during analysis (analysis by gas chromatography) to lower the concentration of the organic chlorine compound, so that the concentration in the exhaust gas cannot be correctly analyzed. Absorb ozone with a hypo solution in advance.
【００１３】（実験例）１００ｐｐｍあるいは１０００
ｐｐｍに調整したメタンの塩素誘導体及び１ｐｐｍある
いは１０ｐｐｍに調整したエチレンの塩素誘導体を含む
排ガスに１８４．９ｎｍの紫外線を含む紫外線を発生さ
せるＨｇランプを照射した結果を表１に示す。メタンの
塩素誘導体のみでは分解しにくいのに比べてエチレンの
塩素誘導体を微量共存させることにより大巾な分解率の
向上が見られる。(Experimental example) 100 ppm or 1000 ppm
Table 1 shows the results of irradiating an exhaust gas containing a methane chlorine derivative adjusted to ppm and an ethylene chlorine derivative adjusted to 1 ppm or 10 ppm with an Hg lamp that generates ultraviolet rays including 184.9 nm ultraviolet rays. Compared with the case where the chlorine derivative of methane alone is not easily decomposed, a large improvement in the decomposition rate can be seen by coexisting a trace amount of the chlorine derivative of ethylene.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【発明の効果】紫外線の照射及び紫外線照射時に副生す
るオゾンの作用並びに光触媒によっても分解しにくいメ
タンの塩素誘導体を含む排ガスの中に、エチレンの塩素
誘導体を微量加えることでメタンの塩素誘導体を迅速
に、かつ高効率に無機化合物に分解し、外部へ排出され
るガスを無害化するので、地球環境保全に役立つ。According to the present invention, the chlorine derivative of methane can be reduced by adding a trace amount of the chlorine derivative of ethylene to the exhaust gas containing the chlorine derivative of methane, which is hardly decomposed by the irradiation of ultraviolet light and ultraviolet light and the action of photocatalyst. It quickly and efficiently decomposes into inorganic compounds and detoxifies the gas emitted to the outside, thus contributing to global environmental protection.
【図１】本発明の一実施態様としての試験装置の構成
図。FIG. 1 is a configuration diagram of a test apparatus as one embodiment of the present invention.
Claims (1)
ス状のエチレンの塩素誘導体を少量加えた後、該ガスに
紫外線を照射することを特徴とするメタンの塩素誘導体
を含む排ガスの処理方法。1. A method for treating exhaust gas containing a chlorine derivative of methane, comprising adding a small amount of a gaseous chlorine derivative of ethylene to an exhaust gas containing the chlorine derivative of methane, and irradiating the gas with ultraviolet rays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4339936A JP2809367B2 (en) | 1992-12-21 | 1992-12-21 | Exhaust gas treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4339936A JP2809367B2 (en) | 1992-12-21 | 1992-12-21 | Exhaust gas treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06182151A JPH06182151A (en) | 1994-07-05 |
| JP2809367B2 true JP2809367B2 (en) | 1998-10-08 |
Family
ID=18332165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4339936A Expired - Fee Related JP2809367B2 (en) | 1992-12-21 | 1992-12-21 | Exhaust gas treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2809367B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69942497D1 (en) | 1998-06-22 | 2010-07-29 | Canon Kk | Process for the decomposition of halogenated aliphatic and aromatic compounds |
| US6497795B1 (en) | 1998-12-16 | 2002-12-24 | Canon Kabushiki Kaisha | Method and apparatus for decomposing gaseous aliphatic hydrocarbon halide compound |
| JP3825959B2 (en) * | 2000-06-16 | 2006-09-27 | キヤノン株式会社 | Pollutant decomposition method and apparatus |
| JP2003205221A (en) | 2001-11-12 | 2003-07-22 | Canon Inc | Method for treating organochlorine compound and apparatus used therefor, method for repairing soil and apparatus used therefor |
| US7018514B2 (en) | 2001-11-12 | 2006-03-28 | Canon Kabushiki Kaisha | Method and apparatus for processing substances to be decomposed |
-
1992
- 1992-12-21 JP JP4339936A patent/JP2809367B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06182151A (en) | 1994-07-05 |
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