JP2925352B2 - Method and apparatus for treating surface treatment waste liquid - Google Patents
Method and apparatus for treating surface treatment waste liquidInfo
- Publication number
- JP2925352B2 JP2925352B2 JP3109463A JP10946391A JP2925352B2 JP 2925352 B2 JP2925352 B2 JP 2925352B2 JP 3109463 A JP3109463 A JP 3109463A JP 10946391 A JP10946391 A JP 10946391A JP 2925352 B2 JP2925352 B2 JP 2925352B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- ozone
- surface treatment
- liquid
- treating
- 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 - Lifetime
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- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、めっき工場などから生
じる表面処理廃液の処理方法および装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for treating a surface treatment waste liquid generated from a plating factory or the like.
【０００２】[0002]
【従来の技術】めっき処理に使用するめっき浴には、め
っき金属を金属錯塩として溶解させて使用する場合があ
る。一方、工場廃液に対しては水質基準法，水質汚染の
公害防止法などで公共用水域に放流する排水の水質基準
が規定されており、めっき工場などで生じるニッケル，
銅, 亜鉛などの重金属を含む表面処理廃液を前記の水質
基準で定められた水質をクリアするように処理して放流
することが必要である。2. Description of the Related Art In a plating bath used for a plating treatment, a plating metal may be used after being dissolved as a metal complex salt. On the other hand, water quality standards for wastewater discharged into public waters are stipulated by the Water Quality Standard Law and the Water Pollution Prevention Law for industrial wastewater.
It is necessary to treat and discharge the surface treatment waste liquid containing heavy metals such as copper and zinc so as to clear the water quality defined by the above water quality standards.
【０００３】そこで、前記しためっき浴などの表面処理
廃液の処理方法として、従来よりイオン交換樹脂により
廃液中にイオンの形で溶存している金属類を吸着させる
方法、電気分解により金属類を電極面上に析出させて分
離，回収する方法、あるいは廃液中に過酸化水素を吹き
込んで金属錯塩を酸化させ、水酸化物に変えて沈澱処理
する方法などが実施されている。[0003] Therefore, as a method of treating the surface treatment waste liquid such as the plating bath described above, a method of adsorbing metals dissolved in the form of ions in the waste liquid with an ion exchange resin, and a method of electrolyzing metals to an electrode. A method of depositing on a surface for separation and recovery, or a method of blowing hydrogen peroxide into a waste liquid to oxidize a metal complex and converting it to a hydroxide to perform a precipitation treatment is carried out.
【０００４】[0004]
【発明が解決しようとする課題】ところで、前記した従
来の廃液処理方式を実施するには設備，運転管理面で次
記のような問題点がある。すなわち、イオン交換樹脂，
電気分解法による処理方式は、設備費，および運転など
の保守管理にかかる経費が高く、また、過酸化水素を使
用する処理方式は設備上で厳しい法的規制がある他、そ
の運転管理には高度な化学専門知識を必要とするなど、
比較的小規模な中，小企業のめっき工場では経費，運用
面からこれらの処理方式を採用することか中々困難であ
る。However, implementing the above-mentioned conventional waste liquid treatment system has the following problems in terms of equipment and operation management. That is, ion exchange resin,
The treatment method using the electrolysis method is expensive in terms of equipment costs and maintenance costs such as operation, and the treatment method using hydrogen peroxide has strict legal regulations on the equipment. Require advanced chemistry expertise,
It is quite difficult to adopt these treatment methods for plating plants of small and medium-sized enterprises and small enterprises in terms of cost and operation.
【０００５】本発明は、上記の点にかんがみなされたも
のであり、設備，並びに運転維持にかかる経費が比較的
安価で済み、かつ過酸化水素などのように法的規制を受
ける薬剤を使用せずに処理できるようにした表面処理廃
液の処理方法および装置を提供することを目的とする。The present invention has been made in view of the above points, and has relatively low costs for equipment and operation and maintenance, and uses a drug which is subject to legal restrictions such as hydrogen peroxide. It is an object of the present invention to provide a method and an apparatus for treating a surface treatment waste liquid which can be treated without using the same.
【０００６】[0006]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明の処理方法によれば、めっき浴などを対象
とした表面処理廃液の処理方法であって、廃液をアルカ
リ側に調整する第１のｐＨ調整工程と、オゾンとの接触
反応により廃液中の金属錯塩を水酸化物に変えて析出さ
せるオゾン処理工程と、前工程で析出した水酸化物を凝
集濃縮して上澄水と分離する固液分離工程と、固液分離
工程で分離した上澄液を中和させる第２のｐＨ調整工程
を経て放流する表面処理廃液の処理方法において、オゾ
ン処理工程では、オゾン処理槽を経由する閉ル−プで廃
液を循環送流させながら、その循環送流過程で廃液中に
オゾンを注入することとする。According to the present invention, there is provided a method for treating a surface treatment waste liquid for a plating bath or the like, wherein the waste liquid is adjusted to an alkali side. A first pH adjustment step, an ozone treatment step of converting a metal complex salt in a waste liquid into a hydroxide by a contact reaction with ozone to precipitate, and an agglomeration / concentration of the hydroxide precipitated in the previous step to obtain supernatant water. In the method for treating a surface treatment waste liquid discharged through a solid-liquid separation step of separating and a second pH adjustment step of neutralizing the supernatant separated in the solid-liquid separation step, the ozone treatment step is performed through an ozone treatment tank. While the waste liquid is circulated and sent through the closed loop, ozone is injected into the waste liquid during the circulation and sending process.
【０００７】ここで、オゾンを注入した廃液に紫外線を
照射させると良い。特に廃液に照射する紫外線の波長帯
域が２１０〜３７４ｎｍであると好ましい。また、オゾ
ン処理槽内で廃液に超音波を照射すると良い。Here, it is preferable that the waste liquid into which ozone is injected is irradiated with ultraviolet rays. In particular, it is preferable that the wavelength band of the ultraviolet light applied to the waste liquid is 210 to 374 nm. Further, it is preferable to irradiate the waste liquid with ultrasonic waves in the ozone treatment tank.
【０００８】また、本発明の処理方法の基礎となる参考
例によれば、めっき浴などを対象とした表面処理廃液の
処理方法であって、廃液をアルカリ側に調整する第１の
ｐＨ調整工程と、オゾンとの接触反応により廃液中の金
属錯塩を水酸化物に変えて析出させるオゾン処理工程
と、前工程で析出した水酸化物を凝集濃縮して上澄水と
分離する固液分離工程と、固液分離工程で分離した上澄
液を中和させる第２のｐＨ調整工程を経て放流する表面
処理廃液の処理方法において、固液分離工程で廃液に凝
集剤を加えて水酸化物を濃縮するとともに、さらに濃縮
した水酸化物のスラリを脱水処理し、この脱水処理で回
収した濾水を上澄液に合流させることとする。According to a reference example serving as a basis of the treatment method of the present invention, there is provided a method of treating a surface treatment waste liquid for a plating bath or the like, wherein a first pH adjusting step of adjusting the waste liquid to an alkali side is performed. And an ozone treatment step in which the metal complex salt in the waste liquid is converted into hydroxide by a contact reaction with ozone to precipitate, and a solid-liquid separation step in which the hydroxide precipitated in the previous step is coagulated and concentrated to be separated from the supernatant water. In a method for treating a surface treatment waste liquid discharged through a second pH adjustment step of neutralizing the supernatant separated in the solid-liquid separation step, a flocculant is added to the waste liquid in the solid-liquid separation step to concentrate the hydroxide. At the same time, the concentrated slurry of the hydroxide is dehydrated, and the filtrate collected by the dehydration is combined with the supernatant.
【０００９】更に、本発明の処理方法の別の態様によれ
ば、めっき浴などを対象とした表面処理廃液の処理方法
であって、廃液をアルカリ側に調整する第１のｐＨ調整
工程と、オゾンとの接触反応により廃液中の金属錯塩を
水酸化物に変えて析出させるオゾン処理工程と、前工程
で析出した水酸化物を凝集濃縮して上澄水と分離する固
液分離工程と、固液分離工程で分離した上澄液を中和さ
せる第２のｐＨ調整工程を経て放流する表面処理廃液の
処理方法において、アンモニア錯体を含む表面処理液に
対して、第１のｐＨ調整工程で廃液中にＮａｃｌを添加
することとする。ここで、Ｎａｃｌの添加量が廃液量の
約０．１％であると好適である。Further, according to another aspect of the treatment method of the present invention, there is provided a method for treating a surface treatment waste liquid for a plating bath or the like, comprising: a first pH adjusting step of adjusting the waste liquid to an alkali side; An ozone treatment step of converting metal complex salts in the waste liquid into hydroxides by a contact reaction with ozone to precipitate them, a solid-liquid separation step of coagulating and concentrating the hydroxides precipitated in the previous step and separating them from the supernatant water, In the method for treating a surface treatment waste liquid discharged through a second pH adjustment step of neutralizing the supernatant separated in the liquid separation step, the waste liquid in the first pH adjustment step is compared with a surface treatment liquid containing an ammonia complex. NaCl will be added inside. Here, it is preferable that the addition amount of NaCl is about 0.1% of the waste liquid amount.
【００１０】一方、本発明の処理装置によれば、めっき
浴などを対象とした表面処理廃液の処理方法であって、
廃液をアルカリ側に調整する第１のｐＨ調整工程と、オ
ゾンとの接触反応により廃液中の金属錯塩を水酸化物に
変えて析出させるオゾン処理工程と、前工程で析出した
水酸化物を凝集濃縮して上澄水と分離する固液分離工程
と、固液分離工程で分離した上澄液を中和させる第２の
ｐＨ調整工程を経て放流する表面処理廃液の処理方法の
実施に使用する表面処理廃液の処理装置であって、廃液
のｐＨをアルカリ側に調整する第1のｐＨ調整槽と、オ
ゾンとの接触反応／脱気を行うオゾン処理槽，オゾナイ
ザに接続したオゾン注入用エゼクタ，送液ポンプ，およ
びこれらの間を経由する閉ル−プの廃液循環ラインで構
成したオゾン処理部と、該オゾン処理部の後段側に接続
した固液分離槽と、第２のｐＨ調整槽とからなることと
する。ここで、オゾン注入用エゼクタからオゾン処理槽
に至る廃液循環ラインの途中に紫外線照射装置を設置す
ること、オゾン処理槽内の液中に超音波発振器を設置す
ること、固液分離槽が凝集剤を添加して水酸化物を凝
集，沈降させる凝集沈殿槽であるものとすること、固液
分離槽にスラリ脱水機を接続したものとすること、がで
きる。On the other hand, according to the treatment apparatus of the present invention, there is provided a method for treating a surface treatment waste liquid for a plating bath or the like,
A first pH adjusting step of adjusting the waste liquid to an alkaline side, an ozone treatment step of converting a metal complex salt in the waste liquid into a hydroxide by contact reaction with ozone to precipitate, and agglomerating the hydroxide precipitated in the previous step. A surface used for carrying out a method for treating a surface treatment waste liquid discharged through a solid-liquid separation step of concentrating and separating from supernatant water and a second pH adjusting step of neutralizing the supernatant separated in the solid-liquid separation step An apparatus for treating a processing waste liquid, comprising: a first pH adjusting tank for adjusting the pH of the waste liquid to an alkaline side; an ozone processing tank for performing a contact reaction / deaeration with ozone; an ozone injection ejector connected to an ozonizer; An ozone treatment section comprising a liquid pump and a closed loop waste liquid circulation line passing between them, a solid-liquid separation tank connected to the downstream side of the ozone treatment section, and a second pH adjustment tank. It will be. Here, an ultraviolet irradiation device should be installed in the waste liquid circulation line from the ozone injection ejector to the ozone treatment tank, an ultrasonic oscillator should be installed in the liquid in the ozone treatment tank, and the solid-liquid separation tank should be a flocculant. Can be used as a coagulation and sedimentation tank for coagulating and settling the hydroxide, and a solid-liquid separation tank connected to a slurry dehydrator.
【００１１】[0011]
【作用】上記の処理方法，装置において、第１のｐＨ調
整工程でアルカリ側に調整された廃液は、次のオゾン処
理工程でオゾンとの接触反応により廃液中の錯体が破壊
され、さらに金属イオンは水中のＯＨ基との反応により
不溶性の金属水酸化物に変化して液中に析出する。ま
た、液中に析出した金属水酸化物は続く固液分離工程で
廃液中から分離，回収される。したがって、金属錯塩を
殆ど含まない上澄水のみが次の第２のｐＨ調整工程で中
和された後に公共用水域に放流されることになる。一
方、廃液中から分離回収された金属水酸化物のスラッジ
は産業廃棄物として別途処理される。In the treatment method and apparatus described above, the waste liquid adjusted to the alkali side in the first pH adjustment step destroys the complex in the waste liquid by a contact reaction with ozone in the next ozone treatment step. Changes into an insoluble metal hydroxide by reaction with OH groups in water and precipitates in the liquid. Further, the metal hydroxide precipitated in the liquid is separated and recovered from the waste liquid in the subsequent solid-liquid separation step. Therefore, only the supernatant water containing almost no metal complex is discharged into the public water area after being neutralized in the next second pH adjustment step. On the other hand, sludge of metal hydroxide separated and recovered from waste liquid is separately treated as industrial waste.
【００１２】一方、前記のオゾン処理工程では、廃液を
オゾン処理槽を経由して循環送流しつつ、エゼクタを通
じてオゾナイザで生成したオゾンを液中に強制注入する
ことにより、廃液とオゾンとが効果的に接触してオゾン
反応効率が高まる。また、この場合に廃液に紫外線，超
音波を照射することにより、オゾンがＯＨ* ラジカルに
分解してオゾンの酸化作用を強めるので、金属イオンは
このＯＨ基と反応して効率よく水酸化物に変わって液中
に析出される。また、特にニッケルめっき浴のようにア
ンモニア・ニッケル錯体を含む廃液に対しては、第１の
ｐＨ調整工程で廃液中にNaclを少量 (約０.1％）添加す
ることにより、錯化しているアンモニア成分の一部がガ
ス化して廃液から分離する反応を促進する効果がある。
これにより続くオゾン処理工程でニッケル成分を効率よ
く水酸化物に変えることができる。さらに、固液分離工
程で廃液に凝集剤を加えて水酸化物を凝集，分離すると
ともに、水酸化物のスラリを脱水処理することにより、
廃棄物となるスラッジを減容できる。On the other hand, in the above-mentioned ozone treatment step, the waste liquid and the ozone are effectively injected by forcibly injecting the ozone generated by the ozonizer into the liquid through the ejector while circulating the waste liquid through the ozone treatment tank. To increase ozone reaction efficiency. In this case, by irradiating the waste liquid with ultraviolet rays or ultrasonic waves, ozone is decomposed into OH * radicals and the oxidizing action of ozone is enhanced, so that metal ions react with the OH groups to efficiently form hydroxides. Instead, it is deposited in the liquid. In addition, in the case of a waste solution containing an ammonia / nickel complex, such as a nickel plating bath, complexing is performed by adding a small amount (about 0.1%) of Nacl to the waste solution in the first pH adjustment step. This has the effect of promoting a reaction in which a part of the ammonia component is gasified and separated from the waste liquid.
This allows the nickel component to be efficiently converted to hydroxide in the subsequent ozone treatment step. In addition, a flocculant is added to the waste liquid in the solid-liquid separation step to flocculate and separate the hydroxide, and by dehydrating the hydroxide slurry,
Sludge that becomes waste can be reduced in volume.
【００１３】[0013]
【実施例】以下、本発明の実施例を図面に基づいて説明
する。まず、図１は廃液処理方法の工程図であり、めっ
き工程などで生じた表面処理廃水の原水は、まず、第１
のｐＨ処理工程でｐＨ１０〜１３．５に調整した後、オ
ゾン処理工程に移して廃液中にイオンの形で溶存してい
る金属錯塩をオゾンとの接触反応により水酸化物に変え
て液中に析出させる。続く固液分離工程では廃液を金属
水酸化物と上澄水とに分離し、さらに水酸化物のスラリ
を脱水工程で脱水する。一方、上澄水は必要により濾過
工程を経て第２のｐＨ調整工程で中和した後に公共用水
域に放流される。なお、ニッケルめっき浴のようにアン
モニア・ニッケル錯体を含む廃液を処理する場合には、
前記した第１のｐＨ調整工程で廃液にNaclを少量（廃液
量の約０.1％程度） を添加する。また、廃液中に含ま
れている金属イオンを水酸化物に効率よく変えるため
に、続くオゾン処理工程では廃液に紫外線, 超音波を照
射し、さらに、固液分離工程では液中に析出した金属水
酸化物を凝集濃縮させるために凝集剤を添加するように
している。Embodiments of the present invention will be described below with reference to the drawings. First, FIG. 1 is a process diagram of a waste liquid treatment method, and raw water of surface treatment waste water generated in a plating step and the like is firstly treated in the first step.
After the pH is adjusted to 10 to 13.5 in the pH treatment step, the mixture is transferred to the ozone treatment step, and the metal complex salt dissolved in the form of ions in the waste liquid is changed to hydroxide by a contact reaction with ozone, and the solution is dissolved in the liquid. Precipitate. In the subsequent solid-liquid separation step, the waste liquid is separated into metal hydroxide and supernatant water, and the hydroxide slurry is dehydrated in the dehydration step. On the other hand, the supernatant water is discharged into a public water area after being neutralized in a second pH adjustment step through a filtration step as necessary. When treating a waste solution containing an ammonia / nickel complex as in a nickel plating bath,
In the above-mentioned first pH adjustment step, a small amount of Nacl (about 0.1% of the waste liquid amount) is added to the waste liquid. In addition, in order to efficiently convert metal ions contained in the waste liquid into hydroxides, the waste liquid is irradiated with ultraviolet rays and ultrasonic waves in the subsequent ozone treatment step, and the metal precipitates in the liquid in the solid-liquid separation step. A coagulant is added to coagulate and concentrate the hydroxide.
【００１４】次に、前記の廃液処理方法を実施するため
に使用する処理装置のシステム・フローを図２に示す。
図２において、１は第１のｐＨ調整槽、２はオゾン処理
部、３は固液分離槽、４は濾過槽、５は第２のｐＨ調整
槽であり、これらで処理装置を構成している。ここで、
オゾン処理部２は、オゾンとの反応／脱気を行うオゾン
処理槽６（気液の接触効果を高めるように槽内にラシリ
ング，有孔板が装填されている）と、液溜槽７と、オゾ
ナイザ８に接続したオゾン注入用エゼクタ９と、送液ポ
ンプ１０と、これらの間を経由する閉ループの廃液循環
ライン１１とで構成されており、さらにエゼクタ９とオ
ゾン処理槽６との間の配管路には紫外線照射装置１２
が、またオゾン処理槽６の槽内底部には超音波発振器１
３が設置してある。なお、１４は濾過槽４の前段に接続
した送液ポンプ、１５〜２１は系内の要所に接続した開
閉弁、２２は固液分離槽３に接続した脱水機、２３は固
液分離槽３に凝集剤を供給する凝集剤添加装置である。Next, FIG. 2 shows a system flow of a processing apparatus used for carrying out the above-mentioned waste liquid processing method.
In FIG. 2, 1 is a first pH adjustment tank, 2 is an ozone treatment unit, 3 is a solid-liquid separation tank, 4 is a filtration tank, and 5 is a second pH adjustment tank, and these constitute a processing apparatus. I have. here,
The ozone treatment section 2 includes an ozone treatment tank 6 (reactor and perforated plate are loaded in the tank so as to enhance a gas-liquid contact effect) for performing reaction / deaeration with ozone, a liquid storage tank 7, An ozone injection ejector 9 connected to the ozonizer 8, a liquid feed pump 10, and a closed loop waste liquid circulation line 11 passing therebetween are provided, and a pipe between the ejector 9 and the ozone treatment tank 6 is further provided. UV irradiation device 12 on the road
However, an ultrasonic oscillator 1 is provided at the bottom of the ozone treatment tank 6.
3 are installed. In addition, 14 is a liquid feed pump connected to the previous stage of the filtration tank 4, 15 to 21 are on-off valves connected to important points in the system, 22 is a dehydrator connected to the solid-liquid separation tank 3, and 23 is a solid-liquid separation tank. 3 is a flocculant addition device for supplying a flocculant to the apparatus.
【００１５】次に上記処理装置による廃液の処理手順を
説明する。まず弁２０を閉とした状態で送液ポンプ１０
を始動し、めっき工程で生じた廃液の所定量を第１のｐ
Ｈ調整槽１に送り込み、ここで苛性ソーダを加えて、廃
液のｐＨを１０〜１３．５程度のアルカリ性に調整した
上で、弁１５を通じてオゾン処理部２に送り込む。な
お、この段階では弁１６を閉, 弁１７を開としておく。
オゾン処理部２に所定量の廃液が送りこまれた段階で、
次に弁１５を閉、弁１６を開, 弁１７を閉とした上で送
液ポンプ１０により廃液を閉ループの循環ライン１１で
循環送流しつつ、オゾナイザ８で生成したオゾンをエゼ
クタ９を通じて液中に連続的に送り込むと同時に、紫外
線照射装置１２，超音波発振器１３を動作させる。これ
により、エゼクタ９を介してオゾンが廃液中に注入さ
れ、さらに廃液は送液配管路の途中で紫外線照射を浴
び、続くオゾン処理槽６で超音波照射を受けつつ槽内で
の上昇過程でオゾンとの接触反応が進行する。したがっ
て、オゾンが廃液中の錯体を破壊し、さらに金属イオン
は水中のＯＨ基と反応して不溶性の水酸化物に変わる。Next, the processing procedure of the waste liquid by the above processing apparatus will be described. First, with the valve 20 closed,
Is started, and a predetermined amount of waste liquid generated in the plating step is set to the first p.
The wastewater is sent to the H adjusting tank 1 where caustic soda is added to adjust the pH of the waste liquid to about 10 to 13.5 alkalinity. At this stage, the valve 16 is closed and the valve 17 is opened.
At the stage when a predetermined amount of waste liquid is sent to the ozone treatment unit 2,
Next, the valve 15 is closed, the valve 16 is opened, and the valve 17 is closed. Then, while the waste liquid is circulated and sent by the liquid sending pump 10 through the closed loop circulation line 11, the ozone generated by the ozonizer 8 is discharged through the ejector 9. And the ultraviolet irradiation device 12 and the ultrasonic oscillator 13 are operated at the same time. As a result, ozone is injected into the waste liquid through the ejector 9, and the waste liquid is irradiated with ultraviolet rays in the middle of the liquid feed pipe line, and is subsequently irradiated with ultrasonic waves in the ozone treatment tank 6 during the rising process in the tank. The contact reaction with ozone proceeds. Therefore, ozone destroys the complex in the waste liquid, and further, the metal ion reacts with the OH group in the water to change to an insoluble hydroxide.
【００１６】この場合に第１のｐＨ調整槽１で廃水のｐ
Ｈが１０〜１３．５程度となるようにアルカリ側に調整
することで水酸化物の生成効率が高まり、さらにオゾン
処理工程でオゾン注入後に紫外線，超音波を照射するこ
とでオゾンの酸化作用が促進される。また、廃液はオゾ
ン処理槽６の上部でオーバーフローして液留槽７に流下
した後にここから再び系内を循環し、その送流過程でエ
ゼクタ９から繰り返しオゾンが注入される。なお、オゾ
ン処理槽６に生じた余剰オゾンはオゾンキラー２４で無
害化処理した上で排ガスとして大気中に放出される。ま
た、特に表面処理廃液がニッケルめっき浴のようにアン
モニア・ニッケル錯体を含む場合には、第１のｐＨ調整
槽１で廃液に少量のNaclを添加することにより水酸化ニ
ッケルの生成がより一層促進される。In this case, the pH of the wastewater is
By adjusting the alkali side so that H is about 10 to 13.5, the generation efficiency of hydroxide is increased, and the ozone oxidizing action is increased by irradiating ultraviolet rays and ultrasonic waves after injecting ozone in the ozone treatment step. Promoted. Further, the waste liquid overflows in the upper part of the ozone treatment tank 6, flows down to the liquid storage tank 7, and then circulates through the system again, and the ozone is repeatedly injected from the ejector 9 in the flow process. The surplus ozone generated in the ozone treatment tank 6 is detoxified by the ozone killer 24 and then released into the atmosphere as exhaust gas. In particular, when the surface treatment waste liquid contains an ammonia / nickel complex such as a nickel plating bath, the generation of nickel hydroxide is further promoted by adding a small amount of Nacl to the waste liquid in the first pH adjustment tank 1. Is done.
【００１７】上記のオゾン処理の進行により廃液中の錯
塩濃度が十分に低下した状態になると、オゾナイザ８か
らのオゾン注入を停止する。次に弁１７を開、弁２０を
開とした上で送液ポンプ１０によりオゾン処理部２の液
溜槽７から廃液を後段の固液分離槽３送り込む。ここ
で、固液分離槽３は凝集剤添加装置２３から凝集剤を加
えて金属水酸化物を濃縮，沈降させる凝集沈澱槽であ
り、廃液を前段のオゾン処理で析出させた金属水酸化物
と上澄水とに固液分離する。また、固液分離槽３の槽内
底部に溜まった金属水酸化物のスラリは脱水機２２に排
出して脱水処理し低含水率のスラッジに変えるととも
に、脱水機２２から排出した濾水を処理ラインに戻して
上澄水に合流させる。なお、金属水酸化物のスラッジは
脱水機２２から回収し、産業廃棄物として別途処理して
処分する。一方、固液分離槽３からの上澄水は送液ポン
プ１４により濾過槽４へ送り込んで液中に浮遊している
細かな粒子を濾過した後に第２のｐＨ調整槽５に送り込
み、ここで中和剤を添加してｐＨ調整した後に公共用水
域に放流される。なお、固液分離槽３で分離した上澄水
の清澄度が十分であれば濾過槽４を省略することも可能
である。When the concentration of the complex salt in the waste liquid becomes sufficiently low due to the progress of the ozone treatment, the injection of ozone from the ozonizer 8 is stopped. Next, after the valve 17 is opened and the valve 20 is opened, the waste liquid is fed from the liquid storage tank 7 of the ozone treatment unit 2 to the solid-liquid separation tank 3 at the subsequent stage by the liquid sending pump 10. Here, the solid-liquid separation tank 3 is a coagulation sedimentation tank for concentrating and precipitating the metal hydroxide by adding the coagulant from the coagulant addition device 23, and includes a metal hydroxide obtained by precipitating the waste liquid by the ozone treatment in the preceding stage. Solid-liquid separation with supernatant water. The metal hydroxide slurry collected at the bottom of the solid-liquid separation tank 3 is discharged to the dehydrator 22 to be dehydrated to be converted into sludge having a low water content, and the drainage discharged from the dehydrator 22 is treated. Return to the line and join the supernatant. The sludge of the metal hydroxide is collected from the dehydrator 22 and separately treated and disposed of as industrial waste. On the other hand, the supernatant water from the solid-liquid separation tank 3 is sent to the filtration tank 4 by the liquid sending pump 14 to filter fine particles floating in the liquid, and then sent to the second pH adjustment tank 5, where After adjusting the pH by adding a wetting agent, the water is discharged into public water bodies. If the clarity of the supernatant water separated in the solid-liquid separation tank 3 is sufficient, the filtration tank 4 can be omitted.
【００１８】次に、各種のめっき廃液を試料として、前
記処理方法を評価するために本発明者等が行った実験結
果について述べる。まず、図４はアンモニア・ニッケル
錯塩を含む廃液を試料として、第１のｐＨ調整工程で廃
液をｐＨ１２〜１３.5の範囲で適正値に調整し、さらに
Naclを０.1％添加して紫外線, 超音波の照射条件の下で
行ったオゾン処理時間と処理済廃液のニッケル濃度 (pp
m)，ＣＯＤ（化学的酸素要求量）との関係を表したもの
である。この実験により、処理前にはニッケル濃度３３
ppm であった廃液が約１時間のオゾン処理で０.5ppm ま
でに低下した。また、当初は約２８０ppm であったＣＯ
Ｄも処理時間の経過とともに減少し、約３時間の処理で
７０ppm まで低減することが確認された。Next, the results of experiments conducted by the present inventors to evaluate the above-mentioned treatment method using various kinds of plating waste liquid as samples will be described. First, FIG. 4 shows that the waste liquid containing ammonia / nickel complex salt is used as a sample, and the waste liquid is adjusted to an appropriate value in a pH range of 12 to 13.5 in a first pH adjustment step.
Ozone treatment time under 0.1% Nacl added under ultraviolet and ultrasonic irradiation conditions and nickel concentration of treated waste liquid (pp
m) and COD (chemical oxygen demand). According to this experiment, the nickel concentration was 33 before the treatment.
The waste liquid which was ppm decreased to 0.5 ppm by ozone treatment for about 1 hour. In addition, CO was initially about 280 ppm.
It was confirmed that D also decreased with the lapse of the treatment time, and was reduced to 70 ppm in the treatment for about 3 hours.
【００１９】図８はエチレンジアミン四酢酸ナトリウム
とＣｕとの錯塩を含む廃液を試料として、第１のｐＨ調
整工程において廃液をｐＨ１０〜１２.5の範囲で適正値
に調整した後に、オゾン処理を行った場合のオゾン処理
時間と処理済廃液のＣｕ濃度との関係を示したものであ
り、処理前には廃液のＣｕ濃度が１４.2ppm であったも
のが約１時間のオゾン処理で２.5ppmまで低下し、さら
にオゾン処理を続けると３時間後には０.7ppm まで減少
することが確認された。FIG. 8 shows a waste liquid containing a complex salt of sodium ethylenediaminetetraacetate and Cu as a sample, and in the first pH adjustment step, the waste liquid is adjusted to an appropriate value within the range of pH 10 to 12.5, and then subjected to ozone treatment. Shows the relationship between the ozone treatment time and the Cu concentration of the treated waste liquid in the case where the waste liquid had a Cu concentration of 14.2 ppm before the treatment. It was confirmed that when the ozone treatment was continued, the concentration decreased to 0.7 ppm after 3 hours.
【００２０】図９はエチレンジアミン四酢酸ナトリウム
とＺｎとの錯塩を含む廃液を試料として、第１のｐＨ調
整工程において廃液をｐＨ１０〜１２.5の範囲で適正値
に調整した後に、オゾン処理を行った場合のオゾン処理
時間と処理済廃液のＺｎ濃度との関係を示したものであ
り、処理前には廃液のＺｎ濃度が８.5ppm であったもの
が約1.５時間のオゾン処理で1.０ppm まで低減すること
が確認された。FIG. 9 shows that a waste liquid containing a complex salt of sodium ethylenediaminetetraacetate and Zn is used as a sample, and the waste liquid is adjusted to an appropriate value within the range of pH 10 to 12.5 in the first pH adjustment step, and then subjected to ozone treatment. Shows the relationship between the ozone treatment time and the Zn concentration of the treated waste liquid when the Zn concentration of the waste liquid was 8.5 ppm before the treatment. It was confirmed that the amount was reduced to 0.0 ppm.
【００２１】一方、前記した各種めっき廃液を試料とし
て第１のｐＨ調整工程で廃液のｐＨを様々な値に調整し
て実験したところ、廃液のめっき金属濃度を放流可能な
レベルまで低下させるに必要なオゾン処理時間が図３で
表すように変化することが明らかになった。このことか
ら、第１のｐＨ調整工程において廃液のｐＨを１０〜１
３.5の範囲に調整するのが好ましいことが判った。ま
た、オゾン処理と並行して行うNaclの添加、紫外線照
射、超音波照射の効果を確かめるために、アンモニア・
ニッケル錯塩を含む廃液を試料として、前述の実験（図
４で述べた実験）とは別にNaclの添加無し、紫外線照射
無し、超音波照射無しの条件でオゾン処理を行ったとこ
ろ、図５，図６，図７のような実験結果を得た。このこ
とから、Naclの添加、紫外線，超音波の照射が処理時間
の短縮化に極めて有効であることが確認された。なお、
エチレンジアミン四酢酸ナトリウムとＣｕとの錯塩を含
む廃液、エチレンジアミン四酢酸ナトリウムとＺｎとの
錯塩を含む廃液についても、前記と同様にNaclの添加無
し、紫外線照射無し、超音波照射無しの条件でオゾン処
理を行って図８，図９と比較したところ、いずれの場合
でもNaclの添加、紫外線，超音波の照射が処理時間の短
縮化に有効であることが確認されている。On the other hand, when the pH of the waste liquid was adjusted to various values in the first pH adjustment step using the above-mentioned various plating waste liquid as a sample and the experiment was carried out, it was necessary to reduce the plating metal concentration of the waste liquid to a level at which it can be discharged. It became clear that the ozone treatment time varied as shown in FIG. From this, in the first pH adjustment step, the pH of the waste liquid was adjusted to 10 to 1
It has been found that it is preferable to adjust the value to the range of 3.5. In order to confirm the effects of adding Nacl, ultraviolet irradiation, and ultrasonic irradiation in parallel with the ozone treatment, ammonia
The waste liquid containing nickel complex salt was used as a sample and subjected to ozone treatment under the conditions of no addition of NaCl, no irradiation of ultraviolet rays, and no irradiation of ultrasonic waves, separately from the above-described experiment (the experiment described in FIG. 4). 6, experimental results as shown in FIG. 7 were obtained. From this, it was confirmed that the addition of Nacl and the irradiation of ultraviolet rays and ultrasonic waves were extremely effective in shortening the processing time. In addition,
Wastewater containing a complex salt of sodium ethylenediaminetetraacetate and Cu and wastewater containing a complex salt of sodium ethylenediaminetetraacetate and Zn are also treated with ozone under the same conditions as above without addition of Nacl, no ultraviolet irradiation, and no ultrasonic irradiation. 8 and FIG. 9, it was confirmed that in each case, the addition of NaCl and the irradiation of ultraviolet rays and ultrasonic waves were effective for shortening the processing time.
【００２２】[0022]
【発明の効果】以上述べたように、本発明による表面処
理廃液の処理方法によれば、めっき浴などの廃液中に溶
存している金属錯塩を、オゾン処理により不溶性の水酸
化物に変えた上で液中から除去するようにしたので、従
来実施されているイオン交換法，電解法，過酸化ガスに
よる酸化法と比べて遜色なしに廃液を所定の水質基準に
まで浄化して公共用水域に放水することができる。As described above, according to the method for treating a surface treatment waste liquid according to the present invention, a metal complex salt dissolved in a waste liquid such as a plating bath is converted into an insoluble hydroxide by ozone treatment. Since it is removed from the liquid above, the waste liquid is purified to a predetermined water quality standard without inferior to the conventional ion exchange method, electrolytic method, and oxidation method using peroxide gas, and is used for public water areas. Can be discharged.
【００２３】また、本発明の廃液処理装置によれば、設
備費，運転維持費がともに従来方式と比べて安価で、か
つ過酸化水素を扱う設備のように法的な規制を受けず、
しかも高度な専門知識がなくても運転管理することがで
きるなど、比較的小規模な中，小企業のめっき工場向け
として好適な廃液処理装置が提供できる。Further, according to the waste liquid treatment apparatus of the present invention, the equipment cost and the operation and maintenance cost are both lower than those of the conventional system, and are not subject to legal restrictions as in the case of equipment that handles hydrogen peroxide.
In addition, it is possible to provide a waste liquid treatment apparatus suitable for plating plants of relatively small and medium-sized enterprises, for example, because the operation can be managed without a high level of specialized knowledge.
【図１】本発明の実施例による処理方法の工程図FIG. 1 is a process diagram of a processing method according to an embodiment of the present invention.
【図２】本発明の実施例による処理装置のシステム・フ
ロー図FIG. 2 is a system flow diagram of a processing apparatus according to an embodiment of the present invention.
【図３】第１のｐＨ調整工程での廃液のｐＨ値とオゾン
処理時間との関係を表す図FIG. 3 is a diagram showing a relationship between a pH value of a waste liquid and an ozone treatment time in a first pH adjustment step.
【図４】アンモニア・ニッケル錯体を含む廃液を試料と
して行った本発明の処理方法によるオゾン処理時間とニ
ッケル濃度，ＣＯＤとの関係を表す図FIG. 4 is a diagram showing the relationship between ozone treatment time, nickel concentration, and COD by the treatment method of the present invention using a waste liquid containing ammonia / nickel complex as a sample.
【図５】オゾン処理時間と廃液中のニッケル濃度との関
係について、Nacl添加無しの条件で行った実験結果を図
４の処理特性と比較して表した図FIG. 5 is a diagram showing the relationship between the ozone treatment time and the nickel concentration in the waste liquid in comparison with the treatment characteristics in FIG.
【図６】オゾン処理時間とニッケル濃度との関係につい
て、紫外線照射無しの条件で行った実験結果を図４の処
理特性と比較して表した図FIG. 6 is a diagram showing the relationship between the ozone treatment time and the nickel concentration in comparison with the treatment characteristics in FIG.
【図７】オゾン処理時間とニッケル濃度との関係につい
て、超音波照射無しの条件で行った実験結果を図４の処
理特性と比較して表した図FIG. 7 is a diagram showing the relationship between the ozone treatment time and the nickel concentration in comparison with the treatment characteristics of FIG.
【図８】エチレンジアミン四酢酸ナトリウムとＣｕとの
錯塩を含む廃液を試料として行った本発明の処理方法に
よるオゾン処理時間とＣｕ濃度との関係を表す図FIG. 8 is a diagram showing the relationship between the ozone treatment time and the Cu concentration according to the treatment method of the present invention using a waste liquid containing a complex salt of sodium ethylenediaminetetraacetate and Cu as a sample.
【図９】エチレンジアミン四酢酸ナトリウムとＺｎとの
錯塩を含む廃液を試料として行った本発明の処理方法に
よるオゾン処理時間とＺｎ濃度との関係を表す図FIG. 9 is a diagram showing the relationship between the ozone treatment time and the Zn concentration according to the treatment method of the present invention using a waste liquid containing a complex salt of sodium ethylenediaminetetraacetate and Zn as a sample.
１ 第１のｐＨ調整槽 ２ オゾン処理部 ３ 固液分離槽 ５ 第２のｐＨ調整槽 ６ オゾン処理槽 ８ オゾナイザ ９ エゼクタ １０ 送液ポンプ １１ 廃液循環ライン １２ 紫外線照射装置 １３ 超音波発振器 ２２ 脱水機 ２３ 凝集剤添加装置 DESCRIPTION OF SYMBOLS 1 1st pH adjustment tank 2 Ozone treatment part 3 Solid-liquid separation tank 5 2nd pH adjustment tank 6 Ozone treatment tank 8 Ozonizer 9 Ejector 10 Liquid sending pump 11 Waste liquid circulation line 12 Ultraviolet irradiation device 13 Ultrasonic oscillator 22 Dehydrator 23 Coagulant addition device
フロントページの続き (72)発明者 横幕 博行 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 河原 裕二 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (56)参考文献 特開 昭52−56070（ＪＰ，Ａ) 特開 昭52−56752（ＪＰ，Ａ) 特開 昭55−18229（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C02F 1/78 C02F 1/32 C02F 1/36 Continued on the front page (72) Inventor Hiroyuki Yokomaku 1-1, Tanabe-Nitta, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fuji Electric Co., Ltd. (72) Inventor Yuji Kawahara 1-1-1, Tanabe-Nitta, Kawasaki-ku, Kawasaki-ku, Kanagawa (56) References JP-A-52-56070 (JP, A) JP-A-52-56752 (JP, A) JP-A-55-18229 (JP, A) (58) Fields investigated Int.Cl. 6 , DB name) C02F 1/78 C02F 1/32 C02F 1/36
Claims (11)
処理方法であって、廃液をアルカリ側に調整する第１の
ｐＨ調整工程と、オゾンとの接触反応により廃液中の金
属錯塩を水酸化物に変えて析出させるオゾン処理工程
と、前工程で析出した水酸化物を凝集濃縮して上澄水と
分離する固液分離工程と、固液分離工程で分離した上澄
液を中和させる第２のｐＨ調整工程を経て放流する表面
処理廃液の処理方法において、 オゾン処理工程では、オゾン処理槽を経由する閉ル−プ
で廃液を循環送流させながら、その循環送流過程で廃液
中にオゾンを注入することを特徴とする表面処理廃液の
処理方法。1. A method for treating a surface treatment waste liquid for a plating bath or the like, comprising: a first pH adjustment step of adjusting the waste liquid to an alkali side; and a metal complex salt in the waste liquid by a contact reaction with ozone. An ozone treatment step of precipitating instead of oxides, a solid-liquid separation step of coagulating and concentrating the hydroxide precipitated in the previous step and separating it from the supernatant water, and neutralizing the supernatant separated in the solid-liquid separation step In the method for treating a surface treatment waste liquid discharged through a second pH adjustment step, in the ozone treatment step, while the waste liquid is circulated through a closed loop passing through an ozone treatment tank, the waste liquid is circulated during the circulation flow step. A method for treating a surface treatment waste liquid, comprising injecting ozone into the surface.
ンを注入した廃液に紫外線を照射させることを特徴とす
る表面処理廃液の処理方法。2. A method according to claim 1, wherein the ozone-injected waste liquid is irradiated with ultraviolet rays.
に照射する紫外線の波長帯域が２１０〜３７４ｎｍであ
ることを特徴とする表面処理廃液の処理方法。3. The method for treating surface treatment waste liquid according to claim 2, wherein the wavelength band of the ultraviolet light applied to the waste liquid is 210 to 374 nm.
ン処理槽内で廃液に超音波を照射することを特徴とする
表面処理廃液の処理方法。4. A method for treating surface treatment waste liquid according to claim 1, wherein the waste liquid is irradiated with ultrasonic waves in an ozone treatment tank.
処理方法であって、廃液をアルカリ側に調整する第１の
ｐＨ調整工程と、オゾンとの接触反応により廃液中の金
属錯塩を水酸化物に変えて析出させるオゾン処理工程
と、前工程で析出した水酸化物を凝集濃縮して上澄水と
分離する固液分離工程と、固液分離工程で分離した上澄
液を中和させる第２のｐＨ調整工程を経て放流する表面
処理廃液の処理方法において、 アンモニア錯体を含む表面処理液に対して、第１のｐＨ
調整工程で廃液中にＮａｃｌを添加することを特徴とす
る表面処理廃液の処理方法。5. A method for treating a surface treatment waste liquid for a plating bath or the like, comprising: a first pH adjustment step of adjusting the waste liquid to an alkali side; and a metal complex salt in the waste liquid by a contact reaction with ozone. An ozone treatment step of precipitating instead of oxides, a solid-liquid separation step of coagulating and concentrating the hydroxide precipitated in the previous step and separating it from the supernatant water, and neutralizing the supernatant separated in the solid-liquid separation step In the method for treating a surface treatment waste liquid discharged through a second pH adjustment step, the first pH is adjusted with respect to the surface treatment liquid containing an ammonia complex.
A method for treating a surface treatment waste liquid, comprising adding NaCl to the waste liquid in the adjusting step.
ｃｌの添加量が廃液量の約０．１％であることを特徴と
する表面処理廃液の処理方法。6. The method according to claim 5, wherein Na
A method for treating surface treatment waste liquid, wherein the amount of cl added is about 0.1% of the waste liquid amount.
処理方法であって、廃液をアルカリ側に調整する第１の
ｐＨ調整工程と、オゾンとの接触反応により廃液中の金
属錯塩を水酸化物に変えて析出させるオゾン処理工程
と、前工程で析出した水酸化物を凝集濃縮して上澄水と
分離する固液分離工程と、固液分離工程で分離した上澄
液を中和させる第２のｐＨ調整工程を経て放流する表面
処理廃液の処理方法の実施に使用する表面処理廃液の処
理装置であって、 廃液のｐＨをアルカリ側に調整する第1のｐＨ調整槽
と、オゾンとの接触反応／脱気を行うオゾン処理槽，オ
ゾナイザに接続したオゾン注入用エゼクタ，送液ポン
プ，およびこれらの間を経由する閉ル−プの廃液循環ラ
インで構成したオゾン処理部と、該オゾン処理部の後段
側に接続した固液分離槽と、第２のｐＨ調整槽とからな
ることを特徴とする表面処理廃液の処理装置。7. A method for treating a surface treatment waste liquid for a plating bath or the like, comprising: a first pH adjustment step of adjusting the waste liquid to an alkali side; and a metal complex salt in the waste liquid by a contact reaction with ozone. An ozone treatment step of precipitating instead of oxides, a solid-liquid separation step of coagulating and concentrating the hydroxide precipitated in the previous step and separating it from the supernatant water, and neutralizing the supernatant separated in the solid-liquid separation step An apparatus for treating a surface treatment waste liquid used for carrying out a method for treating a surface treatment waste liquid discharged through a second pH adjustment step, comprising: a first pH adjustment tank for adjusting the pH of the waste liquid to an alkali side; An ozone treatment tank comprising an ozone treatment tank for performing a contact reaction / deaeration of an ozone, an ejector for injecting ozone connected to an ozonizer, a liquid feed pump, and a closed loop waste liquid circulation line passing between them; Connects to the downstream side of the processing section A solid-liquid separation tank that, the processor of the surface treatment liquid waste, characterized in that comprising a second pH adjustment tank.
ン注入用エゼクタからオゾン処理槽に至る廃液循環ライ
ンの途中に紫外線照射装置を設置したことを特徴とする
表面処理廃液の処理装置。8. An apparatus for treating surface treatment waste liquid according to claim 7, wherein an ultraviolet irradiation device is provided in the waste liquid circulation line from the ejector for ozone injection to the ozone treatment tank.
ン処理槽内の液中に超音波発振器を設置したことを特徴
とする表面処理廃液の処理装置。9. An apparatus for treating surface treatment waste liquid according to claim 7, wherein an ultrasonic oscillator is installed in the liquid in the ozone treatment tank.
液分離槽が凝集剤を添加して水酸化物を凝集，沈降させ
る凝集沈殿槽であることを特徴とする表面処理廃液の処
理装置。10. The treatment apparatus according to claim 7, wherein the solid-liquid separation tank is a coagulation settling tank for coagulating and sedimenting a hydroxide by adding a coagulant. .
液分離槽にスラリ脱水機を接続したことを特徴とする表
面処理廃液の処理装置。11. The apparatus for treating surface treatment waste liquid according to claim 7, wherein a slurry dehydrator is connected to the solid-liquid separation tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3109463A JP2925352B2 (en) | 1990-10-04 | 1991-05-15 | Method and apparatus for treating surface treatment waste liquid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26685490 | 1990-10-04 | ||
| JP2-266854 | 1990-10-04 | ||
| JP3109463A JP2925352B2 (en) | 1990-10-04 | 1991-05-15 | Method and apparatus for treating surface treatment waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04250889A JPH04250889A (en) | 1992-09-07 |
| JP2925352B2 true JP2925352B2 (en) | 1999-07-28 |
Family
ID=26449212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3109463A Expired - Lifetime JP2925352B2 (en) | 1990-10-04 | 1991-05-15 | Method and apparatus for treating surface treatment waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2925352B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101493962B1 (en) * | 2012-12-27 | 2015-02-17 | 아름다운 환경건설(주) | Apparatus for treating water using ozone and ultrasonic wave |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010000952A (en) * | 2000-10-31 | 2001-01-05 | 지영호 | Removal of Nitrogen in Waste Water using Plasma Device |
| JP5954687B2 (en) * | 2012-05-11 | 2016-07-20 | 三菱レイヨン株式会社 | Waste water treatment apparatus and waste water treatment method |
| CN103848490B (en) * | 2012-12-05 | 2015-09-23 | 宁波金和锂电材料有限公司 | Remove the method for cobalt in cobalt-containing wastewater |
| CN104058521A (en) * | 2014-07-12 | 2014-09-24 | 长春黄金研究院 | Non-ferrous mine waste water treatment technology |
| CN111689628A (en) * | 2020-06-19 | 2020-09-22 | 安徽国星生物化学有限公司 | Treatment device and method for 2, 3-dichloropyridine production wastewater |
| JP7621889B2 (en) * | 2021-06-04 | 2025-01-27 | 上村工業株式会社 | Method and system for treating electroless plating wastewater |
-
1991
- 1991-05-15 JP JP3109463A patent/JP2925352B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101493962B1 (en) * | 2012-12-27 | 2015-02-17 | 아름다운 환경건설(주) | Apparatus for treating water using ozone and ultrasonic wave |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04250889A (en) | 1992-09-07 |
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