JPH0686990A - Method for treating volatile organic halogen compound - Google Patents
Method for treating volatile organic halogen compoundInfo
- Publication number
- JPH0686990A JPH0686990A JP24049292A JP24049292A JPH0686990A JP H0686990 A JPH0686990 A JP H0686990A JP 24049292 A JP24049292 A JP 24049292A JP 24049292 A JP24049292 A JP 24049292A JP H0686990 A JPH0686990 A JP H0686990A
- Authority
- JP
- Japan
- Prior art keywords
- volatile organic
- organic halogen
- halogen compound
- packed bed
- gas
- 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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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は揮発性有機ハロゲン化合
物の処理方法に係り、特に、揮発性有機ハロゲン化合物
含有水を接触還元処理するにあたり、還元性ガスを該揮
発性有機ハロゲン化合物含有水中に効率的に溶解させ
て、揮発性有機ハロゲン化合物の液相分解を可能とする
揮発性有機ハロゲン化合物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 a volatile organic halogen compound, and more particularly to a catalytic reduction treatment of water containing a volatile organic halogen compound, in which a reducing gas is added to the water containing the volatile organic halogen compound. The present invention relates to a method for treating a volatile organic halogen compound, which is capable of being efficiently dissolved to enable liquid phase decomposition of the volatile organic halogen compound.
【０００２】[0002]
【従来の技術】揮発性有機ハロゲン化合物は環境汚染物
質の一つであり、その処理が必要である。従来、トリク
ロロエチレン等の揮発性有機ハロゲン化合物を含む用水
や排水の処理方法としては、次のような方法が検討され
ている。2. Description of the Related Art Volatile organic halogen compounds are one of environmental pollutants, and their treatment is necessary. Conventionally, the following methods have been studied as a method for treating water or wastewater containing a volatile organic halogen compound such as trichlorethylene.
【０００３】曝気法 吸着法 触媒熱分解法 紫外線酸化法 生物処理法Aeration method Adsorption method Catalytic pyrolysis method UV oxidation method Biological treatment method
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、の曝
気法では、放散ガスによる大気汚染が問題となる。この
ため、との吸着法とを組み合せて処理される場合も
あるが、その場合でも、活性炭などの吸着剤の吸着性能
が湿度の影響を受けて低下するといった問題がある。However, in the aeration method (1), air pollution due to the emitted gas poses a problem. For this reason, there is a case where it is treated in combination with the adsorption method of and, but even in that case, there is a problem that the adsorption performance of the adsorbent such as activated carbon is affected by humidity and deteriorates.
【０００５】また、の触媒熱分解法、の紫外線酸化
法では、処理に過大なエネルギーを必要とする上、副反
応物生成の問題があり、の生物処理法は未だ実用段階
に至っていないのが実情である。Further, the catalytic thermal decomposition method and the ultraviolet oxidation method require a large amount of energy for the treatment and have a problem of side reaction product formation. Therefore, the biological treatment method has not yet reached a practical stage. It's a reality.
【０００６】このため、用水や排水中に含まれる揮発性
有機ハロゲン化合物等の汚染物質を揮散させることな
く、二次汚染を引き起こすことなく、液相系のまま処理
できる直接処理法が望まれている。Therefore, there is a demand for a direct treatment method capable of treating a liquid phase system without volatilizing a pollutant such as a volatile organic halogen compound contained in water or waste water without causing secondary pollution. There is.
【０００７】なお、揮発性有機ハロゲン化合物含有水
に、Ｈ2 ガス等の還元性ガスを直接接触させて溶解させ
ようとすると、該揮発性有機ハロゲン化合物含有水にＨ
2 ガスを吹き込んで曝気することになり、揮発性有機ハ
ロゲン化合物が大気中に揮散してしまう。従って、揮発
性有機ハロゲン化合物含有水のまま処理するために、揮
発性有機ハロゲン化合物を揮散させずに、還元性ガスを
揮発性有機ハロゲン化合物含有水に効率的に溶解させる
方法が望まれている。When a reducing gas such as H 2 gas is brought into direct contact with the volatile organic halogen compound-containing water to dissolve it, H 2 gas is added to the volatile organic halogen compound-containing water.
2 Gas is blown in for aeration, and the volatile organic halogen compound is volatilized into the atmosphere. Therefore, in order to treat the volatile organic halogen compound-containing water as it is, a method for efficiently dissolving the reducing gas in the volatile organic halogen compound-containing water without volatilizing the volatile organic halogen compound is desired. .
【０００８】本発明は上記従来の実情に鑑みてなされた
ものであって、揮発性有機ハロゲン化合物含有水を液相
還元分解により効率的に処理する揮発性有機ハロゲン化
合物の処理方法を提供することを目的とする。The present invention has been made in view of the above-mentioned conventional circumstances, and provides a method for treating a volatile organic halogen compound which efficiently treats water containing a volatile organic halogen compound by liquid phase reductive decomposition. With the goal.
【０００９】[0009]
【課題を解決するための手段】本発明の揮発性有機ハロ
ゲン化合物の処理方法は、揮発性有機ハロゲン化合物含
有水を還元性ガスと接触させ、該水中に溶解している揮
発性有機ハロゲン化合物を該水中において接触還元反応
させるようにした揮発性有機ハロゲン化合物の処理方法
において、充填材を充填してなる充填層内に該揮発性有
機ハロゲン化合物含有水を上方から供給し、揮発性有機
ハロゲン化合物含有水を該充填層内に連続した空間部が
残るように流下させると共に、該充填層内に前記還元性
ガスを供給し、このガスを該充填層内の前記空間部を通
過させて揮発性有機ハロゲン化合物含有水と接触させた
後、該充填層流出水を金属触媒充填層に通液することを
特徴とする。A method for treating a volatile organic halogen compound according to the present invention comprises contacting water containing a volatile organic halogen compound with a reducing gas to remove a volatile organic halogen compound dissolved in the water. In the method for treating a volatile organohalogen compound which is subjected to a catalytic reduction reaction in the water, the volatile organohalogen compound-containing water is supplied from above into a packed bed filled with a filler to obtain a volatile organohalogen compound. The contained water is caused to flow down so that a continuous space portion remains in the packed bed, and the reducing gas is supplied into the packed bed, and the gas is passed through the space portion in the packed bed to be volatile. After being brought into contact with the organic halogen compound-containing water, the packed bed outflow water is passed through the metal catalyst packed bed.
【００１０】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１１】本発明において、処理対象となる揮発性有
機ハロゲン化合物としては、例えば、トリクロロエチレ
ン、テトラクロロエチレン、１，１−ジクロロエチレ
ン、シス−ジクロロエチレン、トランス−ジクロロエチ
レン、１，１，１−トリクロロエタン、四塩化炭素、ク
ロロホルムなどが挙げられる。Examples of the volatile organic halogen compound to be treated in the present invention include trichloroethylene, tetrachloroethylene, 1,1-dichloroethylene, cis-dichloroethylene, trans-dichloroethylene, 1,1,1-trichloroethane and carbon tetrachloride. , Chloroform and the like.
【００１２】また、還元性ガスとしては水素（Ｈ2 ）ガ
ス等が用いられる。As the reducing gas, hydrogen (H 2 ) gas or the like is used.
【００１３】充填材としてはガラスビーズやラシヒリン
グ等の、表面積の大きい充填材が好ましい。As the filler, a filler having a large surface area such as glass beads or Raschig rings is preferable.
【００１４】金属触媒は、金属を担体に担持したもので
あって、金属としては白金、パラジウム、ルテニウム、
ロジウム、銅、イリジウム、ニッケル、鉄などが挙げら
れ、また、担体としては、アルミナ、チタニア、活性
炭、ジルコニア、ゼオライト、シリカ、ガラス、イオン
交換樹脂などが挙げられる。これら担体の形状には特に
制限はなく、球状、ペレット状、粉末状などとすること
ができる。なお、金属触媒の金属担持量は通常０．１〜
１０重量％とする。The metal catalyst is a metal supported on a carrier, and examples of the metal include platinum, palladium, ruthenium,
Examples include rhodium, copper, iridium, nickel, iron, and the like, and examples of the carrier include alumina, titania, activated carbon, zirconia, zeolite, silica, glass, ion exchange resins, and the like. The shape of these carriers is not particularly limited and may be spherical, pellet-like, powder-like or the like. The amount of metal supported on the metal catalyst is usually 0.1 to
It is set to 10% by weight.
【００１５】以下に本発明の実施に好適な装置の一例を
示す図１を参照して、本発明を詳細に説明する。The present invention will be described in detail below with reference to FIG. 1 showing an example of an apparatus suitable for carrying out the present invention.
【００１６】図１の装置は、下部に金属触媒を充填して
触媒層２を形成し、触媒層２の上部にガラスビース等の
充填材を充填して充填層３を形成した反応カラム１の上
部から、配管４より原水（揮発性有機ハロゲン化合物含
有水）を供給すると共に、同じく反応カラム１の上部に
設けた配管５よりＨ2 ガスを供給し、充填層３内で原水
とＨ2 ガスとを接触させて原水中にＨ2 ガスを溶解させ
た後、触媒層２にて接触還元処理し、処理水を配管６よ
り排出するものである。なお、７は圧力計、８はバル
ブ、Ｌは液面である。The apparatus shown in FIG. 1 is a reaction column 1 having a lower part filled with a metal catalyst to form a catalyst layer 2 and an upper part of the catalyst layer 2 filled with a filler such as glass beads to form a packed layer 3. Raw water (water containing a volatile organic halogen compound) is supplied from the upper part through a pipe 4, and H 2 gas is supplied from a pipe 5 also provided at the upper part of the reaction column 1, so that the raw water and the H 2 gas are supplied in the packed bed 3. And H 2 gas are dissolved in the raw water, and catalytic reduction treatment is carried out in the catalyst layer 2, and the treated water is discharged from the pipe 6. In addition, 7 is a pressure gauge, 8 is a valve, and L is a liquid level.
【００１７】この装置では、反応カラム１内の充填層３
において、上方から供給された原水である揮発性有機ハ
ロゲン化合物含有水は、充填材の表面に沿って且つ充填
材相互間に空間部が残るように流下される。そして、こ
の充填材同志の間の空間部に存在するＨ2 ガスと接触
し、これにより、Ｈ2 ガスは原水中に効率的に溶解す
る。In this apparatus, the packed bed 3 in the reaction column 1 is
In the above, the volatile organic halogen compound-containing water, which is the raw water supplied from above, flows down along the surface of the filler so that a space remains between the fillers. Then, it comes into contact with the H 2 gas existing in the space between the fillers, whereby the H 2 gas is efficiently dissolved in the raw water.
【００１８】しかして、溶存Ｈ2 を含む原水は、触媒層
２にて、含有される揮発性有機ハロゲン化合物が効率的
に還元分解される。In the raw water containing dissolved H 2 , the volatile organic halogen compound contained in the raw water is efficiently reductively decomposed in the catalyst layer 2.
【００１９】本発明において、充填層容量や触媒層容量
等には特に制限はなく、また、原水の通液速度、還元性
ガスの供給量等についても特に制限はなく、原水中の揮
発性有機ハロゲン化合物濃度や揮発性有機ハロゲン化合
物の種類等によって適宜決定される。In the present invention, there are no particular restrictions on the capacity of the packed bed, the capacity of the catalyst layer, etc., and there is also no particular restriction on the rate of passage of raw water, the supply amount of reducing gas, etc. It is appropriately determined depending on the halogen compound concentration, the type of volatile organic halogen compound, and the like.
【００２０】特に、本発明においては、還元性ガスの供
給圧を変えることにより、原水中の揮発性有機ハロゲン
化合物濃度の変化に好適に対処することができ、安定か
つ確実な処理を行なうことができる。In particular, in the present invention, by changing the supply pressure of the reducing gas, it is possible to suitably cope with the change in the concentration of the volatile organic halogen compound in the raw water, and to carry out a stable and reliable treatment. it can.
【００２１】なお、図１に示す装置は、本発明の実施に
好適な装置の一例であって、本発明は何ら図示の方法に
限定されるものではない。例えば、充填層と触媒層とは
同一反応カラム内に形成せずに、別々のカラム内に形成
し、充填層カラムと触媒層カラムとを直列に連結して処
理を行なうようにしても良い。The apparatus shown in FIG. 1 is an example of an apparatus suitable for carrying out the present invention, and the present invention is not limited to the illustrated method. For example, the packed bed and the catalyst layer may be formed not in the same reaction column but in separate columns, and the packed bed column and the catalyst layer column may be connected in series to perform the treatment.
【００２２】[0022]
【作用】揮発性有機ハロゲン化合物、例えばトリクロロ
エチレンは、還元性ガス、例えばＨ2 ガスにより、次の
ような反応式に従って分解される。A volatile organic halogen compound such as trichloroethylene is decomposed by a reducing gas such as H 2 gas according to the following reaction formula.
【００２３】 Ｃ2 ＨＣｌ3 ＋４Ｈ2 →Ｃ2 Ｈ6 ＋３ＨＣｌ このような分解反応を液相で行なうためには、溶存Ｈ2
が反応に関わることから、原水中にＨ2 ガスを効率的に
溶解させる必要がある。C 2 HCl 3 + 4H 2 → C 2 H 6 + 3HCl In order to carry out such a decomposition reaction in the liquid phase, dissolved H 2
Is involved in the reaction, it is necessary to efficiently dissolve H 2 gas in the raw water.
【００２４】本発明においては、充填層に供給された揮
発性有機ハロゲン化合物含有水と還元性ガスとが、充填
材表面での液境膜部分での気液接触により効率的に接触
し、還元性ガスは揮発性有機ハロゲン化合物含有水中に
速やかに溶解する。この溶存還元性ガスを含む揮発性有
機ハロゲン化合物含有水は、次いで、触媒層にて効率的
に接触還元処理される。In the present invention, the volatile organic halogen compound-containing water supplied to the packed bed and the reducing gas are efficiently contacted by the gas-liquid contact at the liquid boundary film portion on the surface of the packing material to reduce the gas. The volatile gas dissolves rapidly in water containing volatile organic halogen compounds. The volatile organic halogen compound-containing water containing the dissolved reducing gas is then efficiently catalytically reduced in the catalyst layer.
【００２５】特に、本発明においては、還元性ガスの供
給圧を変えることにより、還元性ガスの溶解効率を増減
することができ、これにより、原水中の揮発性有機ハロ
ゲン化合物濃度の変化に好適に対処することができるこ
とから、安定かつ確実な処理を行なうことができる。Particularly, in the present invention, by changing the supply pressure of the reducing gas, it is possible to increase or decrease the dissolving efficiency of the reducing gas, which is suitable for changing the concentration of the volatile organic halogen compound in the raw water. Therefore, stable and reliable processing can be performed.
【００２６】[0026]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００２７】実施例１〜３ 表１に示す濃度でトリクロロエチレンを含む原水を図１
に示す装置で処理し、トリクロロエチレンの除去率を測
定し、結果を表１に示した。Examples 1 to 3 FIG. 1 shows raw water containing trichlorethylene at the concentrations shown in Table 1.
Was treated with the apparatus shown in Table 1 and the removal rate of trichlorethylene was measured, and the results are shown in Table 1.
【００２８】なお、触媒としてはＰｔ（０．５重量％）
−γ−Ａｌ2 Ｏ3 （１／８インチペレット）を使用し、
これを内径２０ｍｍ，長さ３００ｍｍの反応カラム内に
高さ１００ｍｍに充填し、この触媒層上に粒径約２ｍｍ
のガラスビーズを充填した。As the catalyst, Pt (0.5% by weight)
-Γ-Al 2 O 3 (1/8 inch pellet) is used,
This was packed in a reaction column having an inner diameter of 20 mm and a length of 300 mm to a height of 100 mm, and a particle size of about 2 mm was formed on the catalyst layer.
Of glass beads.
【００２９】この反応カラムに原水を流量５ｍｌ／ｍｉ
ｎ，触媒層に対する流速ＳＶ＝１０ｈｒ-1で送液すると
共に、Ｈ2 ガスを供給圧１ｋｇ／ｃｍ2 Ｇで送給した。Raw water was flown into this reaction column at a flow rate of 5 ml / mi.
n, the flow rate to the catalyst layer was SV = 10 hr −1 , and the H 2 gas was fed at a supply pressure of 1 kg / cm 2 G.
【００３０】実施例４ テトラクロロエチレンを表１に示す濃度で含む原水を、
実施例１と同様に処理し、テトラクロロエチレンの除去
率を測定し、結果を表１に示した。Example 4 Raw water containing tetrachloroethylene at a concentration shown in Table 1 was added to
The treatment was carried out in the same manner as in Example 1, the removal rate of tetrachloroethylene was measured, and the results are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】表１より、本発明の揮発性有機ハロゲン化
合物の処理方法によれば、液相処理にて、揮発性有機ハ
ロゲン化合物を効率的に分解除去できることが明らかで
ある。It is clear from Table 1 that the volatile organic halogen compound treatment method of the present invention can efficiently decompose and remove the volatile organic halogen compound by the liquid phase treatment.
【００３３】[0033]
【発明の効果】以上詳述した通り、本発明の揮発性有機
ハロゲン化合物の処理方法によれば、原水中の揮発性有
機ハロゲン化合物を液相のまま、従って二次汚染を引き
起こすことなく効率的に分解処理することができる。し
かも、還元ガスの供給圧を調節することにより、原水の
揮発性有機ハロゲン化合物濃度変化にも良好に対応する
ことができ、安定かつ確実な処理を行なうことが可能と
される。As described above in detail, according to the method for treating a volatile organic halogen compound of the present invention, the volatile organic halogen compound in the raw water remains in the liquid phase and is therefore effective without causing secondary pollution. Can be decomposed into Moreover, by adjusting the supply pressure of the reducing gas, it is possible to favorably cope with the change in the concentration of the volatile organic halogen compound in the raw water, and it is possible to perform a stable and reliable treatment.
【図１】本発明の揮発性有機ハロゲン化合物の処理方法
の実施に好適な装置の一例を示す系統図である。FIG. 1 is a system diagram showing an example of an apparatus suitable for carrying out the method for treating a volatile organic halogen compound according to the present invention.
１ 反応カラム ２ 触媒層 ３ 充填層 1 Reaction column 2 Catalyst layer 3 Packed bed
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鶴丸 陽佳 東京都新宿区西新宿３丁目４番７号 栗田 工業株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Haruka Tsurumaru 3-4-7 Nishishinjuku, Shinjuku-ku, Tokyo Kurita Industry Co., Ltd.
Claims (1)
性ガスと接触させ、該水中に溶解している揮発性有機ハ
ロゲン化合物を該水中において接触還元反応させるよう
にした揮発性有機ハロゲン化合物の処理方法において、 充填材を充填してなる充填層内に該揮発性有機ハロゲン
化合物含有水を上方から供給し、揮発性有機ハロゲン化
合物含有水を該充填層内に連続した空間部が残るように
流下させると共に、該充填層内に前記還元性ガスを供給
し、このガスを該充填層内の前記空間部を通過させて揮
発性有機ハロゲン化合物含有水と接触させた後、該充填
層流出水を金属触媒充填層に通液することを特徴とする
揮発性有機ハロゲン化合物の処理方法。1. A treatment of a volatile organohalogen compound, which comprises contacting volatile organohalogen compound-containing water with a reducing gas to cause a catalytic reduction reaction of the volatile organohalogen compound dissolved in the water. In the method, the volatile organic halogen compound-containing water is supplied from above into a packed bed filled with a filler, and the volatile organic halogen compound-containing water is flowed down so that a continuous space remains in the packed bed. In addition, the reducing gas is supplied into the packed bed, and the gas is passed through the space in the packed bed to be brought into contact with the volatile organic halogen compound-containing water. A method for treating a volatile organic halogen compound, which comprises passing a liquid through a metal catalyst packed bed.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24049292A JPH0686990A (en) | 1992-09-09 | 1992-09-09 | Method for treating volatile organic halogen compound |
| US08/032,573 US5490941A (en) | 1992-03-25 | 1993-03-17 | Method of treatment of a fluid containing volatile organic halogenated compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24049292A JPH0686990A (en) | 1992-09-09 | 1992-09-09 | Method for treating volatile organic halogen compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0686990A true JPH0686990A (en) | 1994-03-29 |
Family
ID=17060324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24049292A Pending JPH0686990A (en) | 1992-03-25 | 1992-09-09 | Method for treating volatile organic halogen compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686990A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998047824A1 (en) * | 1997-04-22 | 1998-10-29 | Nippon Shokubai Co., Ltd. | Apparatus for treating waste water |
-
1992
- 1992-09-09 JP JP24049292A patent/JPH0686990A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998047824A1 (en) * | 1997-04-22 | 1998-10-29 | Nippon Shokubai Co., Ltd. | Apparatus for treating waste water |
| KR100349460B1 (en) * | 1997-04-22 | 2003-10-11 | 가부시키가이샤 닛폰 쇼쿠바이 | Drainage |
| US6730215B2 (en) * | 1997-04-22 | 2004-05-04 | Nippon Shokubai Co., Ltd. | Apparatus for treating waste water |
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