JPH06158359A - Closed electrolytic cell for treating waste etchant - Google Patents
Closed electrolytic cell for treating waste etchantInfo
- Publication number
- JPH06158359A JPH06158359A JP31724592A JP31724592A JPH06158359A JP H06158359 A JPH06158359 A JP H06158359A JP 31724592 A JP31724592 A JP 31724592A JP 31724592 A JP31724592 A JP 31724592A JP H06158359 A JPH06158359 A JP H06158359A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- cathode
- electrolytic cell
- chamber
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- ing And Chemical Polishing (AREA)
- Electrolytic Production Of Metals (AREA)
- Weting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エッチング廃液を処理
するための電解槽に関するもので、特にクローズドシス
テムでエッチング廃液を処理することに適する電解槽に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic bath for treating etching waste liquid, and more particularly to an electrolytic bath suitable for treating etching waste liquid in a closed system.
【０００２】[0002]
【従来の技術】例えば、集積回路基板のパターンを形成
する際には、塩化第二銅や塩化第二鉄の溶液を用いて、
必要な配線部分以外を溶解させるようにしている。2. Description of the Related Art For example, when forming a pattern of an integrated circuit board, a solution of cupric chloride or ferric chloride is used.
The parts other than the necessary wiring parts are melted.
【０００３】塩化銅エッチング工程中において、During the copper chloride etching process,
【０００４】[0004]
【化１】 [Chemical 1]
【０００５】の反応式で生成される塩化第一銅ＣｕＣｌ
を含むエッチング廃液や、塩化第二鉄溶液を使用するエ
ッチング工程から流出するエッチング廃液は、環境汚染
防止上および経済的要請から再生して、エッチング操作
に再利用することが望ましく、これら廃液から銅を回収
し、かつエッチング液を再生する手段として、従来から
種々の方法が提案され、実用化されている。Cuprous chloride CuCl produced by the reaction formula
It is desirable to recycle the etching waste liquid containing slag and the etching waste liquid flowing out from the etching process using the ferric chloride solution for the purpose of preventing environmental pollution and economical requirements, and reusing them in the etching operation. Various methods have been proposed and put to practical use in the past as means for recovering and recovering the etching solution.
【０００６】塩化第一銅を含むエッチング廃液に対する
処理方法としては、例えば、当該エッチング廃液を給送
する陽極側で発生する塩素によって塩化第一銅ＣｕＣｌ
を塩化第二銅ＣｕＣｌ2に塩素化してエッチング液を再
生するとともに、同様に廃液を給送する陰極側で銅イオ
ンを還元して金属銅として析出回収する電解処理法が特
公昭５６−１７４２９号公報等において提案され、実用
化されている。As a treatment method for the etching waste liquid containing cuprous chloride, for example, cuprous chloride CuCl is generated by chlorine generated on the anode side which feeds the etching waste liquid.
Is a chlorinated cupric chloride CuCl 2 to regenerate the etching solution, and similarly, an electrolytic treatment method in which copper ions are reduced on the cathode side which feeds the waste solution and deposited and recovered as metallic copper is disclosed in JP-B-56-17429. It has been proposed and put into practical use in publications and the like.
【０００７】特に、同公報においては、電解槽の陰極室
の液組成を調整することが、推奨されている。In particular, in this publication, it is recommended to adjust the liquid composition of the cathode chamber of the electrolytic cell.
【０００８】しかしながら、当該電解処理法は、エッチ
ング廃液を電解槽の陰極室及び陽極室に夫々給送し、特
に陰極室の液組成を第一銅および第二銅イオンの銅換算
濃度６５ｇ／ｌ以下に保持する等、液組成の管理、陰極
液・陽極液の供給量調整、圧力バランスの管理等、操作
に手間がかかる他、発生する塩素ガスを有効利用するこ
とが考慮されておらず、単に放出するのみであるため、
その処理無くしては放出塩素ガスにより作業環境が悪化
する恐れがある。However, in this electrolytic treatment method, the etching waste liquid is fed to the cathode chamber and the anode chamber of the electrolytic cell, respectively, and the liquid composition of the cathode chamber is set to 65 g / l in terms of copper equivalent concentration of cuprous and cupric ions. In addition to the following, it takes time and effort to operate such as liquid composition management, catholyte / anolyte supply amount adjustment, pressure balance management, etc., and effective use of chlorine gas generated is not considered, It just releases it,
Without such treatment, the work environment may be deteriorated by the chlorine gas released.
【０００９】また塩化第二鉄溶液を用いたエッチング工
程からのエッチング廃液に対しても、隔膜によって陽極
室と陰極室とに区分された電解槽を用いてエッチング廃
液を電解処理することが、知られている。It is also known that the etching waste liquid from the etching process using the ferric chloride solution is electrolytically treated using an electrolytic cell divided into an anode chamber and a cathode chamber by a diaphragm. Has been.
【００１０】このエッチング廃液中には、塩化鉄及び銅
基板からのイオンとしての３価の鉄イオン、２価の鉄イ
オン、２価の銅イオン及び１価の銅イオンが含まれてい
るが、その回収装置をクローズド化して連続的に電解を
行う場合には、一旦陰極で析出した金属銅が再び溶液中
に溶解することのないようにしなければならない。そこ
でその電解還元工程を、塩化第二鉄イオン・塩化第二銅
イオンから塩化第一鉄イオン・塩化第一銅イオンへ還元
する第一工程と、金属銅を析出する第二工程とに区分す
ることが、特開昭５５−１８５５８号公報に提案されて
いる。This etching waste liquid contains trivalent iron ions, divalent iron ions, divalent copper ions and monovalent copper ions as ions from the iron chloride and copper substrates. When the recovery device is closed and electrolysis is continuously performed, it is necessary to prevent the metallic copper once deposited at the cathode from being dissolved again in the solution. Therefore, the electrolytic reduction step is divided into a first step of reducing ferric chloride ion / cupric chloride ion to ferrous chloride ion / cuprous chloride ion and a second step of depositing metallic copper. Is proposed in Japanese Patent Laid-Open No. 55-18558.
【００１１】しかしながら、当該公報に開示された電解
法に基づく銅回収方法は、電解還元工程を２段階に分
け、１段目で、銅電析を起こす直前までエッチング液を
還元する方法であり、設備が複雑な上、液組成の管理が
難しい等の欠点がある。また、特公昭５６−１７４２９
号公報と同様に、発生する塩素ガスを有効利用すること
が考慮されておらず、単に放出するのみであるため、そ
の処理無くしては放出塩素ガスにより作業環境が悪化す
る恐れがある。However, the copper recovery method based on the electrolytic method disclosed in this publication is a method in which the electrolytic reduction step is divided into two steps, and the etching solution is reduced in the first step until just before copper electrodeposition occurs, There are drawbacks such as complicated equipment and difficult management of liquid composition. In addition, Japanese Examined Japanese Patent Publication Sho 56-17429
As in the publication, the effective use of the generated chlorine gas is not taken into consideration, and it is simply released. Therefore, without the treatment, the released chlorine gas may deteriorate the working environment.
【００１２】[0012]
【発明が解決しようとする課題】そこで本発明者らは、
上記した従来方法での問題に鑑み、電解処理を１段のみ
で行いながら、エッチング液再生方法全体をクローズド
化した場合に生じるとされている種々の不具合を回避し
て、簡単な操作で、しかも低い運転コストで、エッチン
グ廃液を処理するとともに、発生する塩素ガスを系外に
放出することなく、安全に有効利用することを目的に、
塩化第一銅または銅を含む塩化第二鉄のエッチング液を
隔膜電解法で処理し、陰極室で銅を電析回収するととも
に、陽極室で発生する塩素ガスをエッチング工程で使用
している別のエッチング液に導き、当該液を再生するこ
とを、特願平３−２８１３７０号及び特願平３−２９３
１２７号においてそれぞれ提案した。Therefore, the present inventors have found that
In view of the above-mentioned problems in the conventional method, various problems that are said to occur when the entire etching liquid regenerating method is closed while performing the electrolytic treatment in only one stage are performed, and simple operation is possible. With the aim of treating the etching waste liquid at a low operating cost and releasing the generated chlorine gas to the outside of the system safely and effectively,
An etching solution of cupric chloride or ferric chloride containing copper is treated by a diaphragm electrolysis method to deposit and recover copper in the cathode chamber, and chlorine gas generated in the anode chamber is used in the etching process. Of Japanese Patent Application No. 3-281370 and Japanese Patent Application No. 3-293 that lead to the etching solution of No. 3 and regenerate the solution.
No. 127, respectively.
【００１３】この新たなエッチング液再生方法は、陽極
で発生する塩素ガスを全て利用するものであり、従来の
電解法がガス発生を考慮せず、従って開放型の電解槽を
用いているのに対して、発生ガスを放出しない閉鎖型の
電解槽において実施する必要がある。This new etching solution regeneration method utilizes all chlorine gas generated at the anode, and the conventional electrolysis method does not consider gas generation, and therefore, an open type electrolytic cell is used. On the other hand, it is necessary to carry out in a closed type electrolytic cell that does not release the generated gas.
【００１４】したがって、上記クローズド化したエッチ
ング液再生方法を実施するに適した電解槽を提供するこ
とが、本発明の課題である。Therefore, it is an object of the present invention to provide an electrolytic cell suitable for carrying out the above-mentioned closed etching solution regenerating method.
【００１５】[0015]
【課題を解決するための手段】上記課題を解決するため
に、本発明により、エッチング廃液をクローズド化して
処理するための電解槽は、ガス流出口を有する陽極室
と、原液流入口、循環陰極液流入口・流出口および析出
金属引出口を有する陰極室と、当該陰極室と陽極室とを
分離する隔膜と、陰極室に配置された陰極板に析出する
金属を掻き取るための掻き取り手段とを備えることが提
案される。In order to solve the above problems, according to the present invention, an electrolytic cell for closing and treating an etching waste liquid includes an anode chamber having a gas outlet, a raw liquid inlet, and a circulating cathode. A cathode chamber having a liquid inlet / outlet and a metal deposit outlet, a diaphragm separating the cathode chamber and the anode chamber, and a scraping means for scraping the metal deposited on the cathode plate arranged in the cathode chamber. It is proposed to provide.
【００１６】[0016]
【作用】エッチング槽で生じたエッチング廃液を原液流
入口から陰極室に供給し、隔膜電解することによって、
陰極液から銅を析出させ、析出銅の付着した陰極板から
掻き取り手段を用いて析出銅を掻き取って、引出口から
当該銅を回収する。一方、この隔膜電解の際、陽極室で
は、塩素ガスが発生するが、当該ガスを放出せずにガス
流出口を介して吸収塔に導き、そこで、本電解槽に導か
れるものとは別のエッチング廃液あるいは銅回収後の陰
極液と合流する当該別のエッチング液中に存在する塩化
第一銅や塩化第一鉄を塩化第二銅や塩化第二鉄に酸化す
る。エッチング廃液をクローズド化して処理するための
電解槽であるから、各室は密閉空間を形成する。[Function] By supplying the etching waste liquid generated in the etching tank to the cathode chamber from the raw liquid inlet, and electrolyzing the diaphragm,
Copper is deposited from the catholyte, and the deposited copper is scraped off from the cathode plate to which the deposited copper is attached using a scraping means, and the copper is recovered from the outlet. On the other hand, during this diaphragm electrolysis, chlorine gas is generated in the anode chamber, but the chlorine gas is led to the absorption tower through the gas outlet without releasing the gas, and is different from that introduced to the electrolytic cell. The cuprous chloride and ferrous chloride present in the etching waste liquid or the other etching liquid that joins with the catholyte after copper recovery are oxidized to cupric chloride and ferric chloride. Each chamber forms a closed space because it is an electrolytic cell for processing the etching waste liquid by closing it.
【００１７】また銅回収後の陰極液を陽極室に給送して
１価の銅イオンや２価の鉄を２価の銅イオンや３価の鉄
に酸化する工程を含むエッチング廃液処理方法のために
は、陽極室に陽極液流出口および陰極液流入口を備える
ことが必要である。In addition, a method for treating an etching waste liquid including a step of feeding a catholyte solution after recovering copper into an anode chamber to oxidize monovalent copper ions or divalent iron into divalent copper ions or trivalent iron. In order to do so, it is necessary to provide the anode chamber with an anolyte outlet and a catholyte inlet.
【００１８】銅の回収効率を高めるために、陰極板の表
面積を多くする場合には、複数枚の陰極板を備えること
になるが、これに対応する陽極板を備える陽極室を複数
個設けるにあたり、陰極室が当該複数個の陽極室を収容
するのが好適である。In order to increase the surface area of the cathode plate in order to improve the recovery efficiency of copper, a plurality of cathode plates will be provided. When providing a plurality of anode chambers with corresponding anode plates, Suitably, the cathode chamber contains the plurality of anode chambers.
【００１９】金属銅を陰極室で析出回収する際に、陽極
室では塩素ガスが発生する。これをガス流出口から集め
て、エッチング廃液中に存在する塩化第一銅や塩化第一
鉄を塩化第二銅や塩化第二鉄に酸化する工程に利用する
にあたり、陽極液から塩素ガスがセパレートする分離効
率を高めるために、陽極室のガス流出口に接続する気液
分離手段を更に設けるようにすれば、好都合である。When the metallic copper is deposited and recovered in the cathode chamber, chlorine gas is generated in the anode chamber. When this is collected from the gas outlet and used in the process of oxidizing cuprous chloride or ferrous chloride present in the etching waste liquid to cupric chloride or ferric chloride, chlorine gas is separated from the anolyte. It is advantageous to further provide a gas-liquid separation means connected to the gas outlet of the anode chamber in order to increase the separation efficiency.
【００２０】本発明で使用される隔膜としては、陰極
中に存在する銅乃至鉄の塩素錯体が陽極側に移動するこ
とを制限し、多少の液面の揺れ等では、陰極液と陽極液
の混合が起こらない程度の気密性を有し、できるかぎ
り電極間の電圧を上昇させないものであり、耐薬品
性、とりわけ耐塩素化性に優れるものであって、膜自
体が複極を形成しない、電気的に中性、即ち、極性を持
たないものである等の特性を有することが要求され、例
えば、モドアクリル、酢酸ビニル、ポリエステル、サラ
ン等を挙げることができる。The diaphragm used in the present invention restricts the migration of the copper or iron chlorine complex present in the cathode to the anode side, and when the liquid level slightly fluctuates, the catholyte and the anolyte are separated. It has airtightness to the extent that mixing does not occur, does not increase the voltage between the electrodes as much as possible, is excellent in chemical resistance, especially chlorination resistance, and the film itself does not form a bipolar electrode, It is required to have characteristics such as being electrically neutral, that is, having no polarity, and examples thereof include modacrylic, vinyl acetate, polyester, and saran.
【００２１】また陽極には、塩素ガス発生の際の過電圧
を低下させる機能を有するものが求められ、白金や、寸
方安定アノード(dimentionaly stable anode、ＤＳＡと
略称される)と称される(Ru-Sn)O2/Ti、(Ir-Pt)O2/Tiを
用いるのが好ましい。陰極には、チタンを用いるのが好
ましい。これらの電極仕様により、液に全く不純物を溶
出させることなく、また電極板から剥離しやすい銅の結
晶を得ることが可能となる。The anode is required to have a function of lowering the overvoltage when chlorine gas is generated, and is called platinum or a dimentionaly stable anode (abbreviated as DSA) (Ru). It is preferable to use -Sn) O 2 / Ti and (Ir-Pt) O 2 / Ti. Titanium is preferably used for the cathode. With these electrode specifications, it is possible to obtain copper crystals that are easy to peel off from the electrode plate without elution of impurities into the liquid.
【００２２】[0022]
【実施例】以下に本発明の実施例をあげてさらに具体的
に説明する。EXAMPLES The present invention will be more specifically described below with reference to examples.
【００２３】図１に示されるように、本発明の電解槽
は、複数の陽極室10と、当該陽極室10を収容する陰極室
11と、当該陰極室11と陽極室10とを隔てるために陽極室
10を覆った隔膜12と、陰極室11内に配置された陰極板13
に析出する銅を掻き取るためのスクレーパ14とを有して
いる。更に、気液セパレータ15が陰極室11の外部に配置
されている。As shown in FIG. 1, the electrolytic cell of the present invention comprises a plurality of anode chambers 10 and a cathode chamber containing the anode chambers 10.
11 and the anode chamber 11 for separating the cathode chamber 11 and the anode chamber 10 from each other.
Diaphragm 12 covering 10 and cathode plate 13 placed in cathode chamber 11
And a scraper 14 for scraping off the copper deposited on the surface. Further, the gas-liquid separator 15 is arranged outside the cathode chamber 11.
【００２４】箱状に形成された陽極室10には、下部領域
に液流入管16が、上部領域には液流出管17がそれぞれ取
り付けられていて、陽極液を循環できるようになってい
る。陽極室10の液流入管16には、開閉弁(図示せず)を介
して、循環陰極液用配管(図示せず)が接続しており、銅
回収後の陰極液を陽極液に給送して酸化反応させる工程
を含むエッチング廃液処理方法を実施する際には、開閉
弁を開いて陰極液を陽極室に給送する。またガス流出口
と陽極液流出口を兼ねる液流出管17は、気液セパレータ
15に接続している。陽極室10の側方には、内部に収容さ
れる陽極板に繋がる陽極ターミナル18が突き出ている。
液流入管16、液流出管17および陽極ターミナル18に繋が
る導線は、陰極室11を貫通している。A liquid inflow pipe 16 is attached to the lower region of the box-shaped anode chamber 10 and a liquid outflow pipe 17 is attached to the upper region thereof, so that the anolyte can be circulated. A circulating catholyte pipe (not shown) is connected to the liquid inflow pipe 16 of the anode chamber 10 through an on-off valve (not shown), and the catholyte after copper recovery is fed to the anolyte. When the etching waste liquid treatment method including the step of causing the oxidation reaction is performed, the on-off valve is opened and the catholyte is fed to the anode chamber. Further, the liquid outflow pipe 17, which also serves as the gas outlet and the anode liquid outlet, is a gas-liquid separator.
Connected to 15. At the side of the anode chamber 10, an anode terminal 18 connected to an anode plate housed inside projects.
Conductive wires connected to the liquid inflow pipe 16, the liquid outflow pipe 17, and the anode terminal 18 penetrate the cathode chamber 11.
【００２５】複数の陽極室10を収容する陰極室11は、下
部が下方に向かい窄んだ円錐形状を形成し、上部は密閉
型箱形となっている。下部形状は、析出銅を一時的に堆
積し排出するのに適する形状であればよく、円錐形状に
限らず、例えば、角錐形状でもよい。この陰極室11に
は、下方の円錐部の上端付近に原液流入管19が、その下
方に循環陰極液流入管20が、上部両側面に循環陰極液流
出管21が、最下部に析出銅引出口22がそれぞれ配置され
ている。原液流入管19は、エッチング槽(図示せず)に繋
がっている。流入管20と流出管21とに接続された不図示
の循環陰極液用配管が配置される結果、陰極液は循環
し、その濃度の均一化が図られる。陰極液の循環は、流
出管21からのオーバーフロー形式で行われ、陰極側に発
生するガスの圧力変動を抑えるとともに、陰極側・陽極
側の圧バランスを調整する。引出口22には排出弁23が備
えられ、適宜開いて、析出銅を回収する。このような構
成にすることにより、従来の電解槽のように、極板を取
り外すことなく析出銅を回収することが可能となる。陰
極室11の上面には陰極側ガス抜きのための開口部24が設
けられ、操作中に圧力変動の生じることを回避する。The cathode chamber 11 for accommodating the plurality of anode chambers 10 has a conical shape in which the lower part is narrowed downward and the upper part is a closed box shape. The lower shape may be any shape that is suitable for temporarily depositing and discharging deposited copper, and is not limited to a conical shape, and may be, for example, a pyramidal shape. In this cathode chamber 11, a stock solution inflow pipe 19 is located near the upper end of the lower conical portion, a circulating catholyte inflow pipe 20 is located therebelow, a circulating catholyte outflow pipe 21 is located on both sides of the upper part, and a copper deposit is deposited at the bottom. Each outlet 22 is arranged. The stock solution inflow pipe 19 is connected to an etching tank (not shown). As a result of arranging a circulating catholyte pipe (not shown) connected to the inflow pipe 20 and the outflow pipe 21, the catholyte circulates and its concentration is made uniform. The circulation of the catholyte is performed in the form of overflow from the outflow pipe 21, suppresses the pressure fluctuation of the gas generated on the cathode side and adjusts the pressure balance between the cathode side and the anode side. The outlet 22 is provided with a discharge valve 23, which is appropriately opened to collect the deposited copper. With such a configuration, it becomes possible to recover the deposited copper without removing the electrode plate as in the conventional electrolytic cell. An opening 24 for venting gas on the cathode side is provided on the upper surface of the cathode chamber 11 to prevent pressure fluctuation during operation.
【００２６】陰極室11内部に収容された複数の陽極室10
のそれぞれの間に配置された陰極板13は、図２に示され
るように、側方下部に陰極ターミナル25を備え、当該陰
極ターミナル25は、陰極室11を貫通して突き出ており
（図１）、貫通個所はＯリング等でシールされている。
図３で理解されるように、各陰極板13の両面のそれぞれ
に接するようにスクレーパ14が配置され、電解槽上方に
配置されたエアシリンダ26（図１）の駆動によって、自
動車ワイパーのように動き、陰極板13に析出する銅を掻
き取る。スクレーパの駆動は、公知の駆動手段であれば
基本的にどのようなものでもよく、エアシリンダに限定
されないのは当然である。A plurality of anode chambers 10 housed inside the cathode chamber 11
As shown in FIG. 2, the cathode plate 13 disposed between each of the cathode plates 13 is provided with a cathode terminal 25 at a lower side portion thereof, and the cathode terminal 25 projects through the cathode chamber 11 (see FIG. 1). ), The penetration point is sealed with an O-ring or the like.
As can be seen in FIG. 3, scrapers 14 are arranged so as to contact both sides of each cathode plate 13, and by driving an air cylinder 26 (FIG. 1) arranged above the electrolytic cell, a scraper 14 is formed like an automobile wiper. It moves and scrapes the copper deposited on the cathode plate 13. The scraper can be driven by basically any known drive means, and it goes without saying that it is not limited to the air cylinder.
【００２７】隔膜12は、陽極室の両面にガスケット等押
え部材を介して圧着させてもよいが、構造を簡単にしつ
つシール性を高めるために、袋状に形成させて、その中
に陽極室を収容するのがよい。The diaphragm 12 may be pressure-bonded to both surfaces of the anode chamber via a pressing member such as a gasket, but in order to improve the sealing property while simplifying the structure, the diaphragm 12 is formed in a bag, and the anode chamber is formed therein. Should be accommodated.
【００２８】液流出管17に接続する気液セパレータ15
は、図４に示されるように、内部に邪魔板27を備えてお
り、当該邪魔板27に、陽極室10から液流出管17を介して
給送される陽極液とガスの混合流体がぶつかり、気液分
離が効率よく行われる。分離されたガスは上方から流出
し、吸収塔(図示せず)に導かれる。また分離された陽極
液は下方から流出し、配管を通って液流入管16へ戻され
る。配管の途中に、陽極液に残ったガスを分離するため
の分岐管28が配置され、当該分岐管28を通るガスは、気
液セパレータ15の上方から流出するガスと合流する。休
転時など、気液セパレータ15内の液を抜き出す場合
は、、適宜、排出弁29を開いて、陽極液をドレンとして
引き抜く。A gas-liquid separator 15 connected to the liquid outflow pipe 17.
As shown in FIG. 4, the baffle plate 27 is provided inside, and the baffle plate 27 collides with the mixed fluid of the anolyte and gas fed from the anode chamber 10 through the liquid outflow pipe 17. , Gas-liquid separation is efficiently performed. The separated gas flows out from above and is guided to an absorption tower (not shown). The separated anolyte flows out from below and is returned to the liquid inflow pipe 16 through the pipe. A branch pipe 28 for separating the gas remaining in the anolyte is arranged in the middle of the pipe, and the gas passing through the branch pipe 28 joins the gas flowing out from above the gas-liquid separator 15. When the liquid in the gas-liquid separator 15 is to be drained at the time of rest, the discharge valve 29 is opened appropriately and the anolyte is drained as a drain.
【００２９】上記のような構成の電解槽において、例示
として塩化第一銅を含むエッチング廃液の電解処理を以
下に説明する。The electrolytic treatment of the etching waste liquid containing cuprous chloride as an example in the electrolytic cell having the above structure will be described below.
【００３０】塩化銅エッチング工程において生成した塩
化第一銅を含むエッチング廃液を、原液として不図示の
エッチング槽から流入管19を介して、所定の電解電圧が
かかった陰極室11へ供給する。循環陰極液の流入・流出
する当該陰極室11内で、過剰の１価の銅イオンおよび２
価の銅イオンを還元電析し、陰極板13の表面に針状又は
粒状の金属銅として析出する。エアシリンダ26を駆動す
ることにより、スクレーパ14を所定時間動かし、陰極板
13から金属銅を払い落とす。エアシリンダ26をオフして
スクレーパ14を止め、金属銅が自然沈降して陰極室11の
下部、引出口22近傍に堆積する程度の時間が経過後に、
排出弁23を開いて、当該析出銅を回収して、再び当該排
出弁23を閉じる。このスクレーパのオンオフ、排出弁の
開閉の動作は、一定間隔をおいて繰り返される。The etching waste liquid containing cuprous chloride produced in the copper chloride etching step is supplied as a stock solution from an etching tank (not shown) to a cathode chamber 11 to which a predetermined electrolytic voltage is applied, through an inflow pipe 19. In the cathode chamber 11 where the circulating catholyte flows in and out, excess monovalent copper ions and 2
Valuable copper ions are reduced and electrodeposited to deposit as acicular or granular metallic copper on the surface of the cathode plate 13. By driving the air cylinder 26, the scraper 14 is moved for a predetermined time, and the cathode plate
Brush off metallic copper from 13. After turning off the air cylinder 26 and stopping the scraper 14, after a lapse of time such that metallic copper naturally precipitates and accumulates in the lower part of the cathode chamber 11 and in the vicinity of the outlet 22,
The discharge valve 23 is opened to collect the deposited copper, and the discharge valve 23 is closed again. The operations of turning the scraper on and off and opening and closing the discharge valve are repeated at regular intervals.
【００３１】銅濃度を減じ、流出管21からオーバーフロ
ーで陰極室11を出た液を、不図示の循環液用配管から流
入管16を介して陽極室10へ導く。当該陽極室10では、塩
素イオンが電子を失い、塩素ガスが発生する。塩素ガス
と陽極液の混合流体を、流出管17を介して気液セパレー
タ15へ供給する。混合流体は、気液セパレータ15内で塩
素ガスと陽極液に分離される。分離された塩素ガスを、
不図示の吸収塔に導き、別のエッチング廃液に通じて、
当該廃液中の塩化第一銅を塩化第二銅に酸化する。酸化
された当該液は再生エッチャントとしてエッチング槽に
戻される。The liquid that has flown out of the cathode chamber 11 due to overflow from the outflow pipe 21 while reducing the copper concentration is introduced into the anode chamber 10 through the inflow pipe 16 from a circulating liquid pipe (not shown). In the anode chamber 10, chlorine ions lose electrons and chlorine gas is generated. A mixed fluid of chlorine gas and anolyte is supplied to the gas-liquid separator 15 via the outflow pipe 17. The mixed fluid is separated into chlorine gas and anolyte in the gas-liquid separator 15. The separated chlorine gas,
Lead to an absorption tower (not shown) and lead to another etching waste liquid,
Cuprous chloride in the waste liquid is oxidized to cupric chloride. The oxidized liquid is returned to the etching tank as a regeneration etchant.
【００３２】塩素ガスの発生により塩素濃度を減じ１価
の銅イオンを２価の銅イオンに電解酸化された分離陽極
液は、陽極室10に戻されるのではなく、再生エッチャン
トとしてエッチング槽に戻される。The separated anolyte obtained by electrolytically oxidizing monovalent copper ions into divalent copper ions by reducing the chlorine concentration due to the generation of chlorine gas is not returned to the anode chamber 10 but returned to the etching tank as a regenerating etchant. Be done.
【００３３】なお、銅濃度を減じて陰極室11を出る液を
陽極室10へ導かずに、別のエッチング廃液に合流させて
処理する方法においては、陽極液全量が流入管16及び流
出管17を介して陽極室10を循環する。In the method of treating the solution by reducing the copper concentration and leaving the liquid leaving the cathode chamber 11 to the anode chamber 10 and joining it with another etching waste liquid, the total amount of the anolyte liquid is the inflow pipe 16 and the outflow pipe 17. Through the anode chamber 10.
【００３４】[0034]
【発明の効果】請求項１の電解槽によれば、ガス流出口
を有する陽極室と、原液流入口、循環陰極液流入口・流
出口および析出金属引出口を有する陰極室と、当該陰極
室と陽極室とを分離する隔膜と、陰極室に配置された陰
極板に析出する金属を掻き取るための掻き取り手段とを
備えるので、隔膜電解法と塩素ガス法を併用して簡単な
操作でしかも低い運転コストでエッチング廃液を処理す
る方法に優れて適応される。According to the electrolytic cell of the present invention, an anode chamber having a gas outlet, a cathode chamber having a raw solution inlet, a circulating catholyte inlet / outlet, and a deposited metal outlet, and the cathode chamber are provided. Since it is equipped with a diaphragm that separates the anode chamber and the anode chamber, and a scraping means for scraping the metal deposited on the cathode plate placed in the cathode chamber, a simple operation is possible by using the diaphragm electrolysis method and the chlorine gas method together. Moreover, it is excellently applied to a method of treating an etching waste liquid at a low operating cost.
【００３５】請求項３の電解槽によれば、陰極室が陽極
室を収容するので、槽全体の組み立てが容易で、確実な
ものとなる。According to the electrolytic cell of the third aspect, since the cathode chamber accommodates the anode chamber, the assembly of the entire chamber is easy and reliable.
【００３６】請求項４の電解槽によれば、陽極室のガス
流出口に接続する気液分離手段を更に設けるので、請求
項１の効果を奏し、特に陽極室で発生するガスが放出さ
れることなく分離回収され、その有効利用が可能とな
る。According to the electrolytic cell of the fourth aspect, since the gas-liquid separating means connected to the gas outlet of the anode chamber is further provided, the effect of the first aspect can be obtained, and particularly the gas generated in the anode chamber is released. It can be separated and collected without any use, and its effective use becomes possible.
【図１】本発明の電解槽の例示的斜視図である。FIG. 1 is an exemplary perspective view of an electrolytic cell of the present invention.
【図２】陰極板とスクレーパの位置関係を示す概略部分
正面図である。FIG. 2 is a schematic partial front view showing a positional relationship between a cathode plate and a scraper.
【図３】図２に対応する概略部分側面図である。FIG. 3 is a schematic partial side view corresponding to FIG.
【図４】陽極室から気液セパレータでの混合流体の流れ
の概略部分側面図である。FIG. 4 is a schematic partial side view of the flow of the mixed fluid from the anode chamber to the gas-liquid separator.
１０ 陽極室 １１ 陰極室 １２ 隔膜 １４ スクレーパ １５ 気液セパレータ 10 Anode chamber 11 Cathode chamber 12 Diaphragm 14 Scraper 15 Gas-liquid separator
Claims (4)
口、循環陰極液流入口・流出口および析出金属引出口を
有する陰極室と、当該陰極室と陽極室とを分離する隔膜
と、陰極室に配置された陰極板に析出する金属を掻き取
るための掻き取り手段とを備えることを特徴とするエッ
チング廃液クローズド系処理のための電解槽。1. An anode chamber having a gas outlet, a cathode chamber having a raw liquid inlet, a circulating catholyte inlet / outlet and a metal deposit outlet, and a diaphragm separating the cathode chamber and the anode chamber. An electrolytic cell for etching waste liquid closed system treatment, comprising: scraping means for scraping metal deposited on a cathode plate arranged in a cathode chamber.
流入口を備えることを特徴とする請求項１に記載の電解
槽。2. The electrolytic cell according to claim 1, wherein the anode chamber is provided with an anolyte outlet and a catholyte inlet.
を特徴とする請求項１又は２に記載の電解槽。3. The electrolytic cell according to claim 1, wherein the cathode chamber accommodates the anode chamber.
分離手段を設けることを特徴とする請求項１〜３のいず
れか一項に記載の電解槽。4. The electrolytic cell according to claim 1, further comprising a gas-liquid separating unit connected to a gas outlet of the anode chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31724592A JP2912511B2 (en) | 1992-11-26 | 1992-11-26 | Electrolysis tank for closed processing of waste etching liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31724592A JP2912511B2 (en) | 1992-11-26 | 1992-11-26 | Electrolysis tank for closed processing of waste etching liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06158359A true JPH06158359A (en) | 1994-06-07 |
| JP2912511B2 JP2912511B2 (en) | 1999-06-28 |
Family
ID=18086103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31724592A Expired - Fee Related JP2912511B2 (en) | 1992-11-26 | 1992-11-26 | Electrolysis tank for closed processing of waste etching liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2912511B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10300597A1 (en) * | 2003-01-10 | 2004-07-22 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Process for regeneration of acid chloride etching solutions containing copper and/or iron chloride as oxidizing agents involves cathodic separation of dissolved copper from catholyte solution with pumping of anolyte through two-part cell |
| WO2008080118A1 (en) * | 2006-12-23 | 2008-07-03 | Miox Corporation | Internal flow control in electrolytic cells |
| ES2310971A1 (en) * | 2007-07-04 | 2009-01-16 | Novoltec Automatizacion, S.A. | System of electrode cleaning of a reactor electrolyte (Machine-translation by Google Translate, not legally binding) |
| WO2011032212A1 (en) * | 2009-09-16 | 2011-03-24 | Davey Water Products Pty Ltd | A salt water chlorinator |
| CN111394729A (en) * | 2020-04-26 | 2020-07-10 | 江苏地一环保科技有限公司 | Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof |
| CN113493915A (en) * | 2020-04-01 | 2021-10-12 | 健鼎（湖北）电子有限公司 | Regeneration method and system of acidic etching waste liquid |
-
1992
- 1992-11-26 JP JP31724592A patent/JP2912511B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10300597A1 (en) * | 2003-01-10 | 2004-07-22 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Process for regeneration of acid chloride etching solutions containing copper and/or iron chloride as oxidizing agents involves cathodic separation of dissolved copper from catholyte solution with pumping of anolyte through two-part cell |
| WO2008080118A1 (en) * | 2006-12-23 | 2008-07-03 | Miox Corporation | Internal flow control in electrolytic cells |
| ES2310971A1 (en) * | 2007-07-04 | 2009-01-16 | Novoltec Automatizacion, S.A. | System of electrode cleaning of a reactor electrolyte (Machine-translation by Google Translate, not legally binding) |
| WO2011032212A1 (en) * | 2009-09-16 | 2011-03-24 | Davey Water Products Pty Ltd | A salt water chlorinator |
| US8920615B2 (en) | 2009-09-16 | 2014-12-30 | Davey Water Products Pty Ltd | Salt water chlorinator |
| CN113493915A (en) * | 2020-04-01 | 2021-10-12 | 健鼎（湖北）电子有限公司 | Regeneration method and system of acidic etching waste liquid |
| CN111394729A (en) * | 2020-04-26 | 2020-07-10 | 江苏地一环保科技有限公司 | Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2912511B2 (en) | 1999-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0071443B1 (en) | Device for waste water treatment | |
| KR100256895B1 (en) | Method for regenerating etchant | |
| JPH0780466A (en) | Method and device for regenerating aqueous solution containing metal ion and sulfuric acid | |
| CA1140495A (en) | Apparatus for the electrolytic recovery of metal | |
| DE2650912C2 (en) | ||
| CN100413999C (en) | Method for regenerating etching solutions containing iron for the use in etching or pickling copper or copper alloys and an apparatus for carrying out said method | |
| JP3427879B2 (en) | Method for removing copper from copper-containing nickel chloride solution | |
| JP2912511B2 (en) | Electrolysis tank for closed processing of waste etching liquid | |
| GB1572756A (en) | Electrolytic method and device for the treatment of effluent | |
| US4064022A (en) | Method of recovering metals from sludges | |
| US5225054A (en) | Method for the recovery of cyanide from solutions | |
| KR101545245B1 (en) | Device for regeneration of etchant and copper recovery using rgb color sensor and orp sensor | |
| JP3243929B2 (en) | Adjustment method of copper ion concentration of copper removal electrolytic solution | |
| JP4121223B2 (en) | Electrolytic cell | |
| JP2698253B2 (en) | Treatment method of ferric chloride etching solution containing copper | |
| US1365032A (en) | Electrolytic apparatus | |
| JPH08276187A (en) | Method for electrochemical processing of sulfite-containing solution | |
| JPH0770784A (en) | Method for regenerating copper chloride etching solution | |
| JPH06240475A (en) | Treatment of iron chloride based etchant containing nickel | |
| EP0172847A1 (en) | Metal recovery process. | |
| US1345846A (en) | Process of extracting metals from their ores | |
| US1344030A (en) | Metallurgical process | |
| JPH09263983A (en) | Treatment of iron chloride solution containing nickel and device for executing this method | |
| JPH05117879A (en) | Treatment of etching liquid | |
| US1365034A (en) | Electrolytic apparatus |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090409 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090409 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100409 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110409 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |