JPH11253970A - Removal of organic chlorine compound in drainage - Google Patents
Removal of organic chlorine compound in drainageInfo
- Publication number
- JPH11253970A JPH11253970A JP6512298A JP6512298A JPH11253970A JP H11253970 A JPH11253970 A JP H11253970A JP 6512298 A JP6512298 A JP 6512298A JP 6512298 A JP6512298 A JP 6512298A JP H11253970 A JPH11253970 A JP H11253970A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- organic chlorine
- oxidizing agent
- drainage
- treated
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一般産業廃棄物や
産業廃棄物の処理敷設からの排水及び廃棄物最終処分場
侵出水に含まれるダイオキシン，ＰＣＢ，塩素系農薬等
の有機塩素化合物の除去方法に関する。The present invention relates to the removal of organic chlorine compounds such as dioxins, PCBs, and chlorinated pesticides contained in wastewater from the treatment and laying of general industrial waste and industrial waste, and in the effluent from the final waste disposal site. About the method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、廃棄物処理施設からの排水は、ＣＯＤ，ＢＯＤ成分
除去のための生物処理や凝集沈殿処理によるＳＳ分，重
金属の除去が行われ、ｐＨ調整をして放流されている。2. Description of the Related Art Conventionally, wastewater from a waste treatment facility is subjected to biological treatment for removing COD and BOD components and SS content and heavy metal by coagulation sedimentation treatment. It is released after adjusting the pH.
【０００３】近年廃棄物処理敷設からのダイオキシン類
の排出が問題となっており、各方面で生成の抑制、ガス
中ダイオキシン類の除去方法について検討がなされてい
る。[0003] In recent years, emission of dioxins from waste treatment laying has become a problem, and various aspects have been studied on methods of suppressing generation and removing dioxins in gas.
【０００４】しかしながら、排水中に含まれるダイオキ
シン類の除去については、まだ効果的な除去方法が確立
されておらず、有効な除去方法の確立が望まれている。
本発明は、上記問題に鑑み、排水中のダイオキシン類を
はじめとする有機塩素化合物の効果的な除去方法を提供
することを課題とする。[0004] However, for the removal of dioxins contained in wastewater, no effective removal method has yet been established, and it is desired to establish an effective removal method.
In view of the above problems, an object of the present invention is to provide a method for effectively removing dioxins and other organic chlorine compounds in wastewater.
【０００５】[0005]
【課題を解決するための手段】前記課題を解決する本発
明の［請求項１］の発明は、排水中に含まれる有機塩素
化合物の除去方法であって、被処理水中に酸化剤を添加
し触媒の存在下に処理することを特徴とする。Means for Solving the Problems The invention of claim 1 of the present invention for solving the above-mentioned problems is a method for removing an organic chlorine compound contained in waste water, wherein an oxidizing agent is added to the water to be treated. The treatment is performed in the presence of a catalyst.
【０００６】［請求項２］の発明は、請求項１におい
て、上記酸化物が、過酸化物，オゾン，酸素，空気のう
ちの少なくとも一種以上であり、上記触媒がＰｔ，Ｐ
ｄ，Ｒｈ，Ｉｒ，Ａｕ，Ａｇ，Ｆｅ，Ｃｏ，Ｎｉ，Ｖ，
Ｃｒ，Ｍｎ，Ｔｉ，Ａｌ，Ｓｉ，Ｚｒ，Ｍｏ，Ｗの少な
くとも一種以上の元素からなることを特徴とする。According to a second aspect of the present invention, in the first aspect, the oxide is at least one of peroxide, ozone, oxygen and air, and the catalyst is Pt, P
d, Rh, Ir, Au, Ag, Fe, Co, Ni, V,
It is characterized by comprising at least one element of Cr, Mn, Ti, Al, Si, Zr, Mo and W.
【０００７】[0007]
【発明の実施の形態】以下、本発明の排水中の有機塩素
化合物除去方法の実施形態を説明するが、本発明はこれ
に限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the method for removing organic chlorine compounds in waste water according to the present invention will be described, but the present invention is not limited thereto.
【０００８】本発明の排水中の有機塩素化合物除去方法
は、一般産業廃棄物や産業廃棄物の処理敷設等からの排
水中に含まれる有機塩素化合物の除去方法であって、被
処理水中に酸化剤を添加し触媒の存在下に処理するもの
である。The method for removing organic chlorine compounds in wastewater of the present invention is a method for removing organic chlorine compounds contained in wastewater from the treatment laying of general industrial wastes or industrial wastes. An agent is added and the treatment is performed in the presence of a catalyst.
【０００９】ここで、本発明で上記酸化物とは、過酸化
物，オゾン，酸素，空気のうちの少なくとも一種以上か
ら選ばれてなるものである。また、本発明で触媒とは、
Ｐｔ，Ｐｄ，Ｒｈ，Ｉｒ，Ａｕ，Ａｇ，Ｆｅ，Ｃｏ，Ｎ
ｉ，Ｖ，Ｃｒ，Ｍｎ，Ｔｉ，Ａｌ，Ｓｉ，Ｚｒ，Ｍｏ，
Ｗの少なくとも一種以上の元素から選ばれてなるもので
ある。Here, in the present invention, the oxide is selected from at least one of peroxide, ozone, oxygen and air. In the present invention, the catalyst is
Pt, Pd, Rh, Ir, Au, Ag, Fe, Co, N
i, V, Cr, Mn, Ti, Al, Si, Zr, Mo,
It is selected from at least one element of W.
【００１０】上記除去装置は、担体に触媒を担持させた
ものを処理管に充填し、該処理管内に被処理水を導入す
るものであるが、処理に際しては被処理水に酸化剤を溶
解等により添加している。ここで、触媒を担持させる担
体は公知のものを用いることができ、本発明は何等限定
されるものではないが、例えばＴｉＯ2 ，Ａｌ2 Ｏ3 ，
ＳｉＯ2 ，ＺｒＯ 2 ，ＴｉＯ2 −ＳｉＯ2 等を挙げるこ
とができる。また、担持量は触媒の種類に応じて変動す
るが担体に対して触媒を0.１〜５重量％程度担持するよ
うにしている。In the above-mentioned removing device, the catalyst is supported on a carrier.
What is to be treated is filled into a treatment tube and water to be treated is introduced into the treatment tube.
However, during treatment, an oxidizing agent is dissolved in the water to be treated.
It is added by solution. Here, the charge for supporting the catalyst is
Known bodies can be used, and the present invention is not limited
Although not required, for example, TiOTwo, AlTwoOThree,
SiOTwo, ZrO Two, TiOTwo-SiOTwoEtc.
Can be. In addition, the amount supported varies depending on the type of catalyst.
However, about 0.1 to 5% by weight of the catalyst is supported on the carrier.
I'm trying.
【００１１】処理する場合の温度は３０℃以上が好まし
く、また酸化剤にオゾン，酸素，空気等の気体を用いる
場合は、排水中への酸化剤の溶解を促進するため大気圧
以上の加圧下で処理するのが望ましい。この場合単独の
場合や併用する場合において、排水が沸騰しない程度の
条件とするのが望ましい。The temperature for the treatment is preferably 30 ° C. or higher, and when a gas such as ozone, oxygen, or air is used as the oxidizing agent, the pressure under atmospheric pressure or higher is used to promote the dissolution of the oxidizing agent in the wastewater. It is desirable to process with. In this case, when used alone or in combination, it is desirable that the condition is such that the wastewater does not boil.
【００１２】本発明によれば、被処理水に添加した酸化
剤中の酸素が触媒粒子の表面に活性な状態で吸着し、そ
の酸素によってダイオキシン類等の有機塩素系化合物が
効果的に酸化除去される。なお、触媒が存在しない場合
には、後述する実施例に示すように、酸化剤とダイオキ
シン類の有機塩素系化合物との反応が極めて遅くなり、
処理効果が発現されないものとなる。According to the present invention, oxygen in the oxidizing agent added to the water to be treated is adsorbed on the surface of the catalyst particles in an active state, and the oxygen effectively removes organic chlorine-based compounds such as dioxins by oxidation. Is done. When no catalyst is present, the reaction between the oxidizing agent and the dioxin-based organic chlorine-based compound becomes extremely slow, as shown in Examples described later,
No treatment effect is exhibited.
【００１３】[0013]
【実施例】以下、本発明の効果を示す実施例について説
明するが、本発明はこれに限定されるものではない。The present invention will now be described by way of examples which show the effects of the present invention, but the present invention is not limited to these examples.
【００１４】＜実施例１＞担体ＴｉＯ2 にＰｔを0.１重
量％（as Pt)を担持した直径1.５ｍｍのペレット３０ｍ
ｌを触媒として用意し、直径２０ｍｍのガラス管状容器
に充填した。一方、ダイオキシン類が１０ｎｇ／ｌ含ま
れる排水を被処理水とし、該被処理水中に、Ｈ2 Ｏ
2 （過酸化水素）を２００ｐｐｍ添加し、５０℃の条件
で３０ｍｌ／ｈｒの供給量で上記触媒を充填したガラス
状管容器中に通過させ、排水中の有機塩素化合物を除去
した。除去後の被処理水中のダイオキシン類を測定した
ところ0.１ｎｇ／ｌに減少していた。<Example 1> A 30 m pellet having a diameter of 1.5 mm and having Pt supported on a carrier TiO 2 by 0.1% by weight (as Pt) was used.
1 was prepared as a catalyst and filled in a glass tubular container having a diameter of 20 mm. On the other hand, wastewater containing 10 ng / l of dioxins is treated water, and H 2 O is contained in the treated water.
2 (hydrogen peroxide) was added in an amount of 200 ppm, and the mixture was passed through a glass tube vessel filled with the catalyst at a supply rate of 30 ml / hr at 50 ° C. to remove organic chlorine compounds in the wastewater. When dioxins in the water to be treated after removal were measured, they were reduced to 0.1 ng / l.
【００１５】＜実施例２〜６＞担体ＴｉＯ2 にＰｔの代
わりにＰｄ，Ｒｈ，Ｉｒ，Ａｕ，Ａｇを各々0.１重量％
（as Pt)を担持した直径1.５ｍｍのペレット３０ｍｌを
触媒として用意し、直径２０ｍｍのガラス管状容器に充
填した以外は実施例１と同様に操作した。Examples 2 to 6 Each of Pd, Rh, Ir, Au and Ag instead of Pt was added to the carrier TiO 2 in an amount of 0.1% by weight.
The procedure of Example 1 was repeated, except that 30 ml of 1.5 mm diameter pellets supporting (as Pt) were prepared as a catalyst and filled in a glass tubular container having a diameter of 20 mm.
【００１６】＜実施例７〜１４＞担体ＴｉＯ2 にＰｔの
代わりにＦｅ５重量％（as Fe2O3 )，Ｃｏ５重量％（as
CoO )，Ｎｉ５重量％（as NiO) ，Ｖ５重量％（as V2O
5 ) ，Ｃｒ５重量％（asCr2O3) ，Ｍｎ５重量％（as Mn
O2)，Ｍｏ５重量％（as MoO3 ) ，Ｗ重量％（asWO3 )を
各々担持した直径1.５ｍｍのペレット３０ｍｌを触媒と
して用意し、直径２０ｍｍのガラス管状容器に充填した
以外は実施例１と同様に操作した。[0016] <Example 7-14> instead of Pt on a support TiO 2 Fe5 wt% (as Fe 2 O 3) , Co5 wt% (the as
CoO), Ni 5% by weight (as NiO), V5% by weight (as V 2 O
5 ), 5 % by weight of Cr (asCr 2 O 3 ), 5% by weight of Mn (as Mn
Example 2 Except that 30 ml of 1.5 mm diameter pellets each supporting O 2 ), Mo 5 wt% (as MoO 3 ), and W wt% (asWO 3 ) were prepared as a catalyst and filled in a glass tubular container having a diameter of 20 mm. The same operation was performed as in 1.
【００１７】＜実施例１５〜１８＞担体ＴｉＯ2 の代わ
りに、Ａｌ2 Ｏ3 ，ＳｉＯ2 ，ＺｒＯ2 ，ＴｉＯ2 −Ｓ
ｉＯ2 を用意し、Ｐｔ0.１重量％（as Pt)を各々担持し
た直径1.５ｍｍのペレット３０ｍｌを触媒として用意
し、直径２０ｍｍのガラス管状容器に充填した以外は実
施例１と同様に操作した。<Examples 15 to 18> Instead of the carrier TiO 2 , Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 —S
The same operation as in Example 1 was carried out except that iO 2 was prepared, 30 ml of 1.5 mm diameter pellets each carrying Pt 0.1% by weight (as Pt) were prepared as a catalyst, and filled in a glass tubular container having a diameter of 20 mm. did.
【００１８】＜実施例１９〜２１＞酸化剤としてＨ2 Ｏ
2 の代わりに、２５atm の圧力下において、Ｏ2 、１０
ｇ／Ｎｍ3 の濃度のＯ3 ／Ｏ2 、空気を各々被処理水に
溶解させ、該圧力下で触媒を通過させた。<Examples 19 to 21> H 2 O as an oxidizing agent
2 instead, under a pressure of 25 atm, O 2, 10
O 3 / O 2 at a concentration of g / Nm 3 and air were each dissolved in the water to be treated, and the catalyst was passed under the pressure.
【００１９】＜比較例１＞実施例１において、触媒を用
いない以外は実施例１と同様に操作した。Comparative Example 1 The procedure of Example 1 was repeated except that no catalyst was used.
【００２０】＜実施例２２〜３９＞実施例１〜１８で用
いた触媒を用い、ダイオキシンの代わりにＰＣＢを２０
ｎｇ／ｌ溶解させた被処理水の処理を行った。<Examples 22 to 39> Using the catalysts used in Examples 1 to 18, PCB was replaced with 20 instead of dioxin.
ng / l of the water to be treated was dissolved.
【００２１】＜比較例２＞実施例２２において、触媒を
用いない以外は実施例２２と同様に操作した。Comparative Example 2 The procedure of Example 22 was repeated, except that no catalyst was used.
【００２２】以上の その結果を「表１」に示す。The results are shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】「表１」に示すように、触媒が存在しない
場合には、ダイオキシン類及びＰＣＢの除去効果が全く
発現されないが、触媒の存在する場合には、ダイオキシ
ン類及びＰＣＢが除去され、本発明の有効性を確認し
た。As shown in Table 1, when no catalyst is present, no effect of removing dioxins and PCB is exhibited, but when a catalyst is present, dioxins and PCB are removed. The effectiveness of the invention was confirmed.
【００２５】[0025]
【発明の効果】以上説明したように、本発明では、排水
中に含まれる有機塩素化合物の除去方法であって、被処
理水中に酸化剤を添加し触媒の存在下に処理するので、
ダイオキシン類及びＰＣＢの効果的な除去が可能とな
る。また、上記酸化物が、過酸化物，オゾン，酸素，空
気のうちの少なくとも一種以上であり、上記触媒がＰ
ｔ，Ｐｄ，Ｒｈ，Ｉｒ，Ａｕ，Ａｇ，Ｆｅ，Ｃｏ，Ｎ
ｉ，Ｖ，Ｃｒ，Ｍｎ，Ｔｉ，Ａｌ，Ｓｉ，Ｚｒ，Ｍｏ，
Ｗの少なくとも一種以上の元素からなるものは、除去効
率が高いものとなる。As described above, according to the present invention, there is provided a method for removing an organochlorine compound contained in wastewater, wherein an oxidizing agent is added to the water to be treated and treated in the presence of a catalyst.
Effective removal of dioxins and PCBs becomes possible. Further, the oxide is at least one of peroxide, ozone, oxygen and air, and the catalyst is P
t, Pd, Rh, Ir, Au, Ag, Fe, Co, N
i, V, Cr, Mn, Ti, Al, Si, Zr, Mo,
An element composed of at least one element of W has a high removal efficiency.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 23/34 Ｂ０１Ｊ 23/34 Ｍ 23/42 23/42 Ｍ 23/44 23/44 Ｍ 23/46 23/46 Ｍ ３１１ ３１１Ｍ 23/50 23/50 Ｍ 23/52 23/52 Ｍ 23/745 Ｃ０２Ｆ 1/58 ＺＡＢＡ 23/75 1/74 Ｚ 23/755 1/78 Ｃ０２Ｆ 1/58 ＺＡＢ Ｂ０１Ｊ 23/74 ３０１Ｍ 1/74 ３１１Ｍ 1/78 ３２１Ｍ (72)発明者 岩下 浩一郎 東京都千代田区丸の内二丁目５番１号 三 菱重工業株式会社内────────────────────────────────────────────────── ─── Continued on front page (51) Int.Cl. 6 Identification code FI B01J 23/34 B01J 23/34 M 23/42 23/42 M 23/44 23/44 M 23/46 23/46 M 311 311M 23/50 23/50 M 23/52 23/52 M 23/745 C02F 1/58 ZABA 23/75 1/74 Z 23/755 1/78 C02F 1/58 ZAB B01J 23/74 301M 1/74 311M 1 / 78 321M (72) Inventor Koichiro Iwashita 2-5-1 Marunouchi, Chiyoda-ku, Tokyo Sanishi Heavy Industries, Ltd.
Claims (2)
方法であって、 被処理水中に酸化剤を添加し触媒の存在下に処理するこ
とを特徴とする排水中の有機塩素化合物除去方法。1. A method for removing an organic chlorine compound contained in waste water, the method comprising adding an oxidizing agent to the water to be treated and treating it in the presence of a catalyst.
少なくとも一種以上であり、上記触媒がＰｔ，Ｐｄ，Ｒ
ｈ，Ｉｒ，Ａｕ，Ａｇ，Ｆｅ，Ｃｏ，Ｎｉ，Ｖ，Ｃｒ，
Ｍｎ，Ｔｉ，Ａｌ，Ｓｉ，Ｚｒ，Ｍｏ，Ｗの少なくとも
一種以上の元素からなることを特徴とする排水中の有機
塩素化合物除去方法。2. The method according to claim 1, wherein the oxide is at least one of peroxide, ozone, oxygen, and air, and the catalyst is Pt, Pd, R
h, Ir, Au, Ag, Fe, Co, Ni, V, Cr,
A method for removing organic chlorine compounds in wastewater, comprising at least one element of Mn, Ti, Al, Si, Zr, Mo, and W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6512298A JP3392749B2 (en) | 1998-03-16 | 1998-03-16 | Method for removing dioxin and PCB from wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6512298A JP3392749B2 (en) | 1998-03-16 | 1998-03-16 | Method for removing dioxin and PCB from wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11253970A true JPH11253970A (en) | 1999-09-21 |
| JP3392749B2 JP3392749B2 (en) | 2003-03-31 |
Family
ID=13277767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6512298A Expired - Fee Related JP3392749B2 (en) | 1998-03-16 | 1998-03-16 | Method for removing dioxin and PCB from wastewater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3392749B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1076041A2 (en) * | 1999-08-09 | 2001-02-14 | Nippon Shokubai Co., Ltd. | Method for decomposing or oxidizing dioxins and/or poly chlorinated biphenyls contained in liquid |
| WO2001030706A1 (en) * | 1999-10-28 | 2001-05-03 | Kazuto Hashizume | Improved method and apparatus for water treatment |
| WO2012133006A1 (en) * | 2011-03-29 | 2012-10-04 | 公立大学法人大阪市立大学 | Method for treating organic halogen compound |
-
1998
- 1998-03-16 JP JP6512298A patent/JP3392749B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1076041A2 (en) * | 1999-08-09 | 2001-02-14 | Nippon Shokubai Co., Ltd. | Method for decomposing or oxidizing dioxins and/or poly chlorinated biphenyls contained in liquid |
| EP1076041A3 (en) * | 1999-08-09 | 2001-12-12 | Nippon Shokubai Co., Ltd. | Method for decomposing or oxidizing dioxins and/or poly chlorinated biphenyls contained in liquid |
| WO2001030706A1 (en) * | 1999-10-28 | 2001-05-03 | Kazuto Hashizume | Improved method and apparatus for water treatment |
| US6773609B1 (en) | 1999-10-28 | 2004-08-10 | Kazuto Hashizume | Advanced water treatment system and advanced water treatment method |
| WO2012133006A1 (en) * | 2011-03-29 | 2012-10-04 | 公立大学法人大阪市立大学 | Method for treating organic halogen compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3392749B2 (en) | 2003-03-31 |
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