JP3796822B2 - Method and apparatus for recovering valuable metal from waste liquid containing cyanide - Google Patents

Method and apparatus for recovering valuable metal from waste liquid containing cyanide Download PDF

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Publication number
JP3796822B2
JP3796822B2 JP18538096A JP18538096A JP3796822B2 JP 3796822 B2 JP3796822 B2 JP 3796822B2 JP 18538096 A JP18538096 A JP 18538096A JP 18538096 A JP18538096 A JP 18538096A JP 3796822 B2 JP3796822 B2 JP 3796822B2
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Prior art keywords
anode
waste liquid
cyan
recovering valuable
valuable metals
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JP18538096A
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JPH1018074A (en
Inventor
正栄 高田
慎一 中西
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Dowa Holdings Co Ltd
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Dowa Holdings Co Ltd
Dowa Mining Co Ltd
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  • Electrolytic Production Of Metals (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は有価金属を含有するメッキ廃液やメッキ剥離廃液から有価金属を回収する方法に関し、更に詳しくは新規な電解装置を用いることによって、これらの廃液から有価金属を回収する手段を提供することを目的とする。
【０００２】
【従来の技術】
従来、シアンが含まれるメッキ廃液、剥離廃液の処理方法としては、液中に含まれるシアンを分解させるために次亜塩素酸等の薬品を添加していた。これらの液中にＡｕ，Ａｇ，Ｃｕ等の有価金属が含有されている場合には、ＳＢＨやホルマリン等の還元剤を更に添加して上記有価金属を粉体状に析出させた後、固液分離して回収していた。
【０００３】
また、剥離剤を含有しないメッキ廃液の場合には、各種電解装置によってＡｕ，Ａｇ等の有価金属を電解採取していたが、この電解方法では薬品添加量の制御が難しくバッチ操業とならざるを得なく、このため過剰な薬品添加量となりコストアップとなり、また、有価金属の回収率もバラつき不安定であった。
【０００４】
一方、剥離剤が含まれるメッキ廃液の場合、上記の電解法では処理が難しいとされ、上述のシアン分解法によって処理されるのが一般的であった。この原因として電解法で処理しようとすると、陽極の電流密度を高める必要があるが、２００Ａ／ｍ2 以上になると陽極に用いられるＳＵＳ材が溶け出すことが上げられる。
【０００５】
【発明が解決しようとする課題】
上述のように剥離剤の含まれるシアン系廃液中の有価金属の回収法としては、現行法では一旦シアン分解する工程が必要で、このためコスト的に高くつく原因となっていたため、安価な電解採取法を改良することによって上記剥離剤含有シアン廃液から次亜塩素酸等の薬品を添加することなく有価金属を回収する手段の開発が望まれていた。
【０００６】
【課題を解決するための手段】
本発明者等は斯かる課題を解決するために鋭意研究したところ、陰極の電着効率には極板を回転させると効果があり、それには回転数が影響していることと、また陽極でのシアン分解作用においても、陽極材質と電流密度が影響することを見出し、本発明のシアン廃液からの有価金属回収方法と回収装置とを提供することができた。
【０００７】
【作用】
本発明に用いる電解装置は図１に示すように電解槽３中に、先ず循環槽１より循環ポンプ２にて処理原料液のメッキ廃液を供給し、オーバーフローして循環槽１に繰り返されるシステムとなっている。
【０００８】
電解槽３内には整流器４に連接する２本の陽極と１本の陰極６とが挿入されているが、この場合、陰極は回転モーター７により回る構造とし、これによって極板表面の濃度分極を小さくして液との接触を良くし、電流効率の向上を図っている。
【０００９】
また、陽極の材質として当初ＳＵＳ材を用いて実験したところ、電流密度を高める毎にＳＵＳ材表面が溶出して電解が不可能となったことから、各種不溶性陽極を検討し、Ｐｔ−Ｔｉ材やフェライト極板が長期間使用しても不溶化しないことを見出した。
【００１０】
なお、カーボン電極の場合は、長期使用により液中にカーボン粒子が溶出し、液の懸濁や極板厚みの減少が見られるが、短期の使用には可能であることが判った。
【００１１】
上記構造の陰極及び陽極を用いてシアン廃液を電気分解するが、本発明においては、陰極に用いる円板の回転数を５００〜１０００ｒｐｍ（周速５〜１０ｍ／秒）の範囲にしているが、この範囲が電着効率を良くし、これ以外では電着効率が低下することによる。
【００１２】
また、液中のシアンを分解するために陽極に用いたＰｔ−Ｔｉ板またはフェライト電極に対して電流密度（ＤＡ）を２００〜５００Ａ／ｍ2 の範囲で通電させると、短期間にシアンが分解することを見出した。
【００１３】
【発明の実施の形態】
以下図面を参照して本発明のシアン廃液中からの有価金属の回収方法とその回収装置について詳細に説明する。
【００１４】
（実施例１）
【００１５】
図１に示す装置を用いて処理液中の有価金属としてのＡｕを回収した。先ず、循環槽１中にＡｕ５４０ｐｐｍ、ＣＮ１７０ｐｐｍ含有のメッキ剥離回収液を貯留し、循環ポンプ２で電解槽３中に３７０リットル供給し、常温中、電解条件をＤＫ１０００Ａ／ｍ2 、ＤＡ３００Ａ／ｍ2 、陰極６の回転数７５０ｒｐｍとして電解を続け、図２の実線に示すように、１２日目にはＡｕ０．１ｐｐｍ、ＣＮ２．０ｐｐｍという濃度変化を得、陰極板上に析出したＡｕを実収率９９．９％で回収した。
【００１６】
この場合、陰極に用いたものは直径２０ｃｍ×厚み３ｍｍの円盤体のＳＵＳ板で、一方、陽極としてフェライト電極材を用いた。
【００１７】
（比較例１）
【００１８】
最適電解条件を求めるため、ＤＫ（電流密度）を実施例１に示す１０００Ａ／ｍ2 から５００Ａ／ｍ2 に変えた以外は全て同一の条件で電解処理したところ１２日目における電解槽中のＡｕ，ＣＮ濃度は図２に点線で示したようにＡｕ０．２ｐｐｍ、ＣＮ１０．５ｐｐｍとなり、実施例１に比べ特にＣＮの分解日数を更に必要とすることが判明した。
【００１９】
【発明の効果】
上述のように従来電解処理が困難とされたシアン剥離剤含有廃液から有価金属を回収すると共に、シアン自体を薬品の添加なしに分解できる新規な本発明装置の開発から、有価金属の回収率を向上させることができると共に、処理コストを従来法より低下させることができた。
【図面の簡単な説明】
【図１】本発明の装置を示す概略図である。
【図２】本発明における電解によって得られる液中のＡｕ，ＣＮ濃度変化を示す図である。
【符号の説明】
１ 循環槽
２ 循環ポンプ
３ 電解槽
４ 整流器
５ 陽極
６ 陰極
７ 回転用モーター[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for recovering valuable metals from plating waste liquids and plating stripping waste liquids containing valuable metals, and more specifically, by providing a means for recovering valuable metals from these waste liquids by using a novel electrolysis apparatus. Objective.
[0002]
[Prior art]
Conventionally, as a treatment method for plating waste liquid and stripping waste liquid containing cyanide, chemicals such as hypochlorous acid have been added in order to decompose cyan contained in the liquid. When valuable metals such as Au, Ag, and Cu are contained in these liquids, a reducing agent such as SBH or formalin is further added to precipitate the valuable metals in a powder form, and then a solid liquid. Separated and recovered.
[0003]
In the case of a plating waste solution that does not contain a release agent, valuable metals such as Au and Ag have been electrolyzed with various electrolysis devices. However, this electrolysis method makes it difficult to control the amount of chemicals added and is a batch operation. As a result, excessive amounts of chemicals were added, resulting in increased costs, and the recovery rate of valuable metals was unstable and unstable.
[0004]
On the other hand, in the case of a plating waste solution containing a release agent, it is considered that the treatment is difficult by the above electrolytic method, and the treatment is generally performed by the cyan decomposition method. If it is going to process by an electrolytic method as this cause, it will be necessary to raise the current density of an anode, but if it becomes 200 A / m < 2 > or more, it will raise that the SUS material used for an anode melt | dissolves.
[0005]
[Problems to be solved by the invention]
As described above, as a method for recovering valuable metals in cyanic waste liquid containing a release agent, the current method requires a step of decomposing cyan once, and this has been a cause of high cost. By improving the method, it has been desired to develop a means for recovering valuable metals without adding chemicals such as hypochlorous acid from the release agent-containing cyan waste liquid.
[0006]
[Means for Solving the Problems]
The inventors of the present invention have intensively studied to solve such a problem, and it is effective to rotate the electrode plate on the electrodeposition efficiency of the cathode. It was also found that the anode material and the current density also affect the cyanide decomposition action, and the valuable metal recovery method and recovery apparatus from the cyan waste liquid of the present invention could be provided.
[0007]
[Action]
As shown in FIG. 1, the electrolysis apparatus used in the present invention is a system in which a plating waste solution of a processing raw material liquid is first supplied from a circulation tank 1 by a circulation pump 2 into an electrolytic tank 3, overflowed and repeated in the circulation tank 1. It has become.
[0008]
In the electrolytic cell 3, two anodes connected to the rectifier 4 and one cathode 6 are inserted. In this case, the cathode is rotated by a rotary motor 7, whereby concentration polarization on the surface of the electrode plate is performed. To improve the current efficiency by improving the contact with the liquid.
[0009]
In addition, when an experiment was initially performed using a SUS material as a material for the anode, every time the current density was increased, the surface of the SUS material was eluted and electrolysis became impossible. And the ferrite electrode plate was found to be insoluble even after long-term use.
[0010]
In the case of a carbon electrode, carbon particles are eluted in the liquid after long-term use, and the suspension of the liquid and the decrease in the electrode plate thickness are observed.
[0011]
Although the cyan waste liquid is electrolyzed using the cathode and anode having the above structure, in the present invention, the number of rotations of the disk used for the cathode is in the range of 500 to 1000 rpm (circumferential speed 5 to 10 m / second). This range improves the electrodeposition efficiency, and otherwise the electrodeposition efficiency decreases.
[0012]
In addition, when a current density (D A ) is applied in the range of 200 to 500 A / m 2 to the Pt—Ti plate or ferrite electrode used for the anode in order to decompose cyan in the liquid, cyan can be generated in a short period of time. It was found to decompose.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a method for recovering valuable metals from a cyan waste liquid and a recovery apparatus thereof will be described in detail with reference to the drawings.
[0014]
Example 1
[0015]
Au as a valuable metal in the treatment liquid was recovered using the apparatus shown in FIG. First, Au540ppm in the circulation tank 1, storing the plating peeling recovering solution containing CN170ppm, the electrolytic bath 3 in the circulation pump 2 is supplied 370 liters, ambient temperature during, DK1000A / m 2 the electrolysis conditions, DA300A / m 2, Electrolysis was continued at a rotational speed of the cathode 6 of 750 rpm, and as shown by the solid line in FIG. 2, concentration changes of 0.1 ppm of Au and 2.0 ppm of CN were obtained on the 12th day, and Au deposited on the cathode plate had an actual yield of 99. Recovered at 9%.
[0016]
In this case, a disc-shaped SUS plate having a diameter of 20 cm and a thickness of 3 mm was used as the cathode, while a ferrite electrode material was used as the anode.
[0017]
(Comparative Example 1)
[0018]
In order to determine the optimum electrolysis conditions, the DK (current density) was changed from 1000 A / m 2 shown in Example 1 to 500 A / m 2, and all were subjected to electrolysis under the same conditions. , CN concentration was 0.2 ppm Au and 10.5 ppm CN as indicated by the dotted line in FIG. 2, and it was found that the number of days of CN decomposition was further required compared with Example 1.
[0019]
【The invention's effect】
As described above, valuable metals are recovered from waste liquid containing cyan remover, which has been difficult to perform by conventional electrolytic treatment, and the recovery rate of valuable metals has been improved by developing a new device according to the present invention that can decompose cyan itself without adding chemicals. As a result, the processing cost can be reduced as compared with the conventional method.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an apparatus of the present invention.
FIG. 2 is a graph showing changes in Au and CN concentrations in a liquid obtained by electrolysis according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Circulation tank 2 Circulation pump 3 Electrolysis tank 4 Rectifier 5 Anode 6 Cathode 7 Motor for rotation

Claims (5)

金を含有するシアン廃液を電解槽に供給し、陽極に不溶性材質を用いると共に、陰極円板を回転させながら電気分解を行ない、該陰極円板表面に金を析出させることを特徴とするシアン含有廃液からの有価金属の回収方法。Supplying a cyan liquid waste containing gold to the electrolytic cell, the use of insoluble material in the anode performs electrolysis while rotating the cathode disc, cyan-containing, characterized in that gold is to be deposited to the cathode disc surface A method for recovering valuable metals from waste liquids. 上記電気分解は、陽極に対して電流密度を２００〜５００Ａ／ｍ2 の範囲で通電させることを特徴とする請求項１記載のシアン含有廃液からの有価金属の回収方法。The electrolysis method of recovering valuable metals from claim 1 cyan-containing waste liquid of, wherein the energizing current density with respect to the anode in a range of 200~500A / m 2. 上記電気分解は、陰極に用いる円板の回転数を５００〜１０００ｒｐｍの範囲で行うことを特徴とする請求項１または２記載のシアン含有廃液からの有価金属の回収方法。The electrolysis method of recovering valuable metals from cyanide-containing waste liquid according to claim 1 or 2, wherein the performing the rotational speed of the disc used for the negative electrode in the range of 500-1000 rpm. 液槽内に陽極と陰極円板とを設けた電解槽において、陽極は不溶性材質であり、陰極円板は回転機構を有することを特徴とするシアン含有廃液からの有価金属の回収装置。An apparatus for recovering valuable metals from cyanide-containing waste liquid, wherein an anode is made of an insoluble material and the cathode disk has a rotating mechanism in an electrolytic cell in which an anode and a cathode disk are provided in the liquid tank. 上記陽極は、カーボン材、Ｐｔ−Ｔｉ材、フェライト材から選択される不溶性材質であることを特徴とする請求項４記載のシアン含有廃液からの有価金属の回収装置。  The said anode is an insoluble material selected from a carbon material, a Pt-Ti material, and a ferrite material, The collection | recovery apparatus of the valuable metal from the cyan containing waste liquid of Claim 4 characterized by the above-mentioned.
JP18538096A 1996-06-27 1996-06-27 Method and apparatus for recovering valuable metal from waste liquid containing cyanide Expired - Fee Related JP3796822B2 (en)

Priority Applications (1)

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JP18538096A JP3796822B2 (en) 1996-06-27 1996-06-27 Method and apparatus for recovering valuable metal from waste liquid containing cyanide

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Application Number Priority Date Filing Date Title
JP18538096A JP3796822B2 (en) 1996-06-27 1996-06-27 Method and apparatus for recovering valuable metal from waste liquid containing cyanide

Related Child Applications (1)

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JP2005301877A Division JP2006070364A (en) 2005-10-17 2005-10-17 Method for collecting valuable metal from cyanide-containing liquid, and collecting apparatus therefor

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JP3796822B2 true JP3796822B2 (en) 2006-07-12

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* Cited by examiner, † Cited by third party
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KR20040036977A (en) * 2002-10-25 2004-05-04 한국수력원자력 주식회사 electrochemical decontamination system for the removal of surface contamination in radioactive metal waste and method thereof
CN106006862A (en) * 2016-08-09 2016-10-12 成都虹华环保科技股份有限公司 Electroplating wastewater nickel recovery and treatment system
KR102025071B1 (en) * 2018-01-10 2019-09-25 (주)다남이엔이 Method for recovering metal and Process for recovering metal comprising the same
CN115057560B (en) * 2022-06-30 2024-09-17 重庆瀚渝再生资源有限公司 Inorganic cyanide waste liquid treatment process

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