JPS6338435B2

JPS6338435B2 -

Info

Publication number: JPS6338435B2
Application number: JP59226986A
Authority: JP
Inventors: Yorio Nakaji; Junsuke Ooishi
Original assignee: Toppan Printing Co Ltd
Current assignee: Toppan Inc
Priority date: 1984-10-29
Filing date: 1984-10-29
Publication date: 1988-07-29
Also published as: JPS61106788A

Description

【発明の詳細な説明】〔産業上の利用分野〕本発明は、廃液中に含まれる金属イオンを金属
粉体として回収する金属回収方法およびその装置
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a metal recovery method and apparatus for recovering metal ions contained in waste liquid as metal powder.

[Prior art and its problems]

従来、工場等から排出される廃液又は廃水は、
その内に含まれる金属イオンを中和し、沈澱さ
せ、濾過後、スラツジを形成し、この金属を含む
スラツジは、埋立又は海洋投棄されるだけで、再
利用等の有効利用されていない。 Conventionally, waste liquid or wastewater discharged from factories, etc.
The metal ions contained therein are neutralized, precipitated, and filtered to form sludge, and this metal-containing sludge is simply landfilled or dumped in the ocean, and is not used effectively by reuse.

また、上記方法による処理は、処理場として大
きな設置場所が必要なうえ、多額の薬品代を必要
とする欠点がある。 Moreover, the treatment according to the above method requires a large installation space as a treatment plant, and has the drawback of requiring a large amount of chemical costs.

この欠点を改良した回収装置として本発明者等
は、特願昭58―184864号で出願しており、この回
収装置は廃液中の金属イオンをキレート剤によつ
て濃縮し、この濃縮された金属イオンを脱離液で
脱離させて金属イオンの高濃度液を生成する濃縮
手段と、電極および絶縁ビーズを収納し、前記高
濃度液を電解して、前記電極面に金属を析出させ
る電解槽とからなり、前記絶縁ビーズを撹拌しな
がら金属を回収する装置である。 The present inventors have filed an application in Japanese Patent Application No. 184864/1983 as a recovery device that improves this drawback.This recovery device concentrates metal ions in waste liquid using a chelating agent, a concentrating means for desorbing ions with a desorption liquid to generate a highly concentrated metal ion liquid; and an electrolytic tank that houses electrodes and insulating beads and electrolyzes the highly concentrated liquid to deposit metals on the electrode surface. This device collects metal while stirring the insulating beads.

この装置は、金属イオンをスラツジとして回収
する装置と比較して、はるかに小さい装置で効率
よく高純度の金属を安価に回収できる利点があつ
た。 This device had the advantage of being able to efficiently recover high-purity metals at low cost with a much smaller device compared to devices that recover metal ions in the form of sludge.

しかしながら、上記装置により回収される金属
は高純度ではあるが、回収される状態が、電極に
密着したままで、しかも板状等の固体で回収され
るため、再利用の際、手間や費用がかかる欠点が
あつた。 However, although the metal recovered by the above device has high purity, it remains in close contact with the electrode and is recovered in a solid form such as a plate, so it takes time and money to reuse it. There were such shortcomings.

また、前記の状態で回収されるため回収毎に新
しい電極を用意しなければならなかつた。さら
に、金属を回収する時、絶縁ビーズを撹拌しなが
ら行なうので、電極に絶縁ビーズが付着するおそ
れがあつた。 Furthermore, since the electrodes are collected in the above-mentioned state, new electrodes had to be prepared each time they are collected. Furthermore, since the metal is recovered while stirring the insulating beads, there is a risk that the insulating beads may adhere to the electrodes.

〔解決しようとする問題点〕特願昭58―184864号に示した金属回収装置にお
いて高濃度液から電解により回収する金属を電極
上に付着することなく、しかも粉体の状態で回収
する金属回収方法およびその装置を得ることであ
る。[Problem to be solved] Metal recovery in which the metal recovered from a highly concentrated liquid by electrolysis in the metal recovery device shown in Japanese Patent Application No. 184864/1986 does not adhere to the electrode and is recovered in the form of powder. The object of the present invention is to obtain a method and an apparatus thereof.

[Means for solving problems]

すなわち本発明は、溶存状態の金属イオンを電
解析出法により粉体または粒体状に回収する金属
回収方法であつて、電解槽内の金属が析出する電
極の表面に超音波を照射するとともに、該電極の
表面に接触または近接した状態で該電極の表面と
相対運動する回収板により析出金属を掻き取るこ
とを特徴とする粉体または粒体状の金属を回収す
る方法であり、具体的には電解槽内に陰極または
陽極のいずれかで、円筒状の内電極と該内電極の
周囲に逆の極からなる外電極を設け、金属が析出
する電極の表面に接触または近接した状態に回収
板を設け、かつ金属の析出する電極表面に超音波
照射できる位置に超音波発振器を配置し、前記金
属が析出する電極と該電極表面に接する回収板の
うち少なくとも一方が回転する金属回収装置が提
供されるものである。 That is, the present invention is a metal recovery method in which dissolved metal ions are recovered in powder or granule form by electrolytic deposition, in which ultrasonic waves are irradiated onto the surface of an electrode in which metal is deposited in an electrolytic cell. , a method for recovering powder or granular metal, characterized in that the deposited metal is scraped off by a recovery plate that moves relative to the surface of the electrode while in contact with or in close proximity to the surface of the electrode. In this method, a cylindrical inner electrode is provided as either a cathode or an anode in the electrolytic cell, and an outer electrode with an opposite pole is provided around the inner electrode, and the outer electrode is placed in contact with or close to the surface of the electrode where metal is deposited. A metal recovery device in which a recovery plate is provided, an ultrasonic oscillator is arranged at a position where ultrasonic waves can be irradiated to the electrode surface on which metal is deposited, and at least one of the electrode on which the metal is deposited and the recovery plate in contact with the electrode surface rotates. is provided.

[Effect]

金属が析出する電極の析出面に超音波発振器か
ら発せられた超音波が照射されるので、金属は電
極に付着せず、粉体または粒体の状態で回収でき
る。 Since the deposition surface of the electrode on which the metal is deposited is irradiated with ultrasonic waves emitted from an ultrasonic oscillator, the metal does not adhere to the electrode and can be recovered in the form of powder or granules.

また、金属が析出する電極と該電極の金属析出
面に接するように設けた回収板の少なくとも一方
が回転可能に設けたので、電極付近に析出する金
属を電極に付着させることなく回収できる。 Furthermore, since at least one of the electrode on which the metal is deposited and the collection plate provided in contact with the metal deposition surface of the electrode is rotatably provided, the metal deposited near the electrode can be collected without adhering to the electrode.

〔Example〕

以下、本発明の装置の一実施例を図面に基づい
て説明する。 Hereinafter, one embodiment of the apparatus of the present invention will be described based on the drawings.

第１図は、本発明の金属回収装置を利用して工
場廃水を処理する工程を示すフローチヤートであ
る。 FIG. 1 is a flowchart showing the process of treating factory wastewater using the metal recovery device of the present invention.

図中１は廃水貯槽を示し、ここから金属イオン
を含有する廃水はPH調整槽２へ送られ、ここで金
属イオンを後述するキレート剤に選択吸着させる
のに好ましいPH値に硫酸又は水酸化ナトリウム等
を用いて調整する。PH調整された廃水は濾過塔３
へ送られ、ここで浮遊物質が除去された後、キレ
ート塔４へ送られる。キレート塔４において、廃
水中の金属イオンは、キレートに吸着、濃縮され
る。 1 in the figure indicates a wastewater storage tank, from which wastewater containing metal ions is sent to PH adjustment tank 2, where it is adjusted to a pH value suitable for selectively adsorbing metal ions to the chelating agent described below using sulfuric acid or sodium hydroxide. etc. to adjust. PH-adjusted wastewater is sent to filtration tower 3
After the suspended solids are removed there, it is sent to the chelate tower 4. In the chelate tower 4, metal ions in the wastewater are adsorbed to the chelate and concentrated.

金属イオンを除去された廃水は、PH調整槽５へ
送られ、ここで排水基準のPH値（PH＝７前後）に
調整された後、放流される。キレート塔４内のキ
レート剤に吸着された金属イオンは、脱離液槽８
から供給された脱離液に接触して脱離し、金属液
イオン含有液を生成する。例えば回収すべき金属
がCu、Niの場合には、H₂SO₄等が脱離液として
利用され、したがつてCuSO₄、NiSO₄が生成す
る。 The wastewater from which metal ions have been removed is sent to the pH adjustment tank 5, where it is adjusted to the wastewater standard pH value (PH = around 7) and then discharged. The metal ions adsorbed by the chelating agent in the chelate tower 4 are transferred to a desorption liquid tank 8.
The metal liquid is desorbed by contacting the desorption liquid supplied from the metal liquid ion, and a metal liquid ion-containing liquid is generated. For example, when the metal to be recovered is Cu or Ni, H ₂ SO ₄ or the like is used as a desorbing liquid, thus producing CuSO ₄ and NiSO ₄ .

キレート塔４において、脱離開始時と終了時に
金属イオン濃度の薄い液が生成するが、この薄い
液は脱離廃液槽７へ送られて貯蔵され、さらにこ
こから再濃縮のために廃水貯槽１へ送られる。脱
離開始時と脱離終了時の間の一定時間内において
金属イオン濃度の濃い液が生成するが、この高濃
度液は回収液槽６へ送られて貯蔵される。 In the chelate tower 4, a liquid with a low concentration of metal ions is produced at the start and end of desorption. sent to. A liquid with a high metal ion concentration is generated within a certain period of time between the start of desorption and the end of desorption, and this high concentration liquid is sent to the recovery liquid tank 6 and stored.

なお、キレート塔４は、処理すべき廃水の量が
多い場合や安全性を考慮して、通常２塔設置さ
れ、一方のキレート塔で脱離が実施されている間
に、他方のキレート塔で吸着が続行される。 Note that two chelate towers 4 are usually installed when the amount of wastewater to be treated is large or in consideration of safety, and while desorption is being performed in one chelate tower, desorption is being performed in the other chelate tower. Adsorption continues.

回収液槽６に貯蔵された高濃度液の一定量は、
循環槽９を介して送られ、ここで電解されて金属
粉体または粒体が回収される。電解槽１０の詳細
は第２図に示される。 A certain amount of high concentration liquid stored in the recovery liquid tank 6 is
It is sent through a circulation tank 9, where it is electrolyzed and metal powder or granules are recovered. Details of the electrolytic cell 10 are shown in FIG.

第２図および第３図に示すように電解槽１０
は、下方が先細り形状で、下部に回収部１２を有
する槽１１の中央にモーターにより回転可能な円
筒状でステンレス製の陰極１３を垂下させ、該陰
極１３の表面に接するように取付けたプラスチツ
ク製の回収板１４を設け、かつ回収板１４の外側
に前記陰極１３を囲むように円筒状でフエライト
製の３本の陽極１５を垂下させてなり、さらに陽
極１５の間に前記陰極１３の表面にムラなく超音
波が当るように３個の超音波発振器１６を設けて
なる。 As shown in FIGS. 2 and 3, the electrolytic cell 10
In this case, a cylindrical stainless steel cathode 13 that can be rotated by a motor is suspended from the center of a tank 11 which has a tapered shape at the bottom and a collection section 12 at the bottom, and a plastic cathode 13 is attached so as to be in contact with the surface of the cathode 13. A collection plate 14 is provided, and three cylindrical anodes 15 made of ferrite are suspended from the outside of the collection plate 14 so as to surround the cathode 13, and between the anodes 15, a Three ultrasonic oscillators 16 are provided so that ultrasonic waves are applied evenly.

一方、槽１１は、上部に高濃度液取入部１７、
該取入部１７の反対側中間部に電解処理液を循環
槽に戻す取出部１８を有する。この取出部１８か
ら循環槽９へ導く導管１９は、オーバーフロー可
能に取付けてあり、槽１１内の水位が一定に保つ
ことができる。 On the other hand, the tank 11 has a high concentration liquid intake section 17 at the top,
A take-out part 18 for returning the electrolytically treated liquid to the circulation tank is provided at the middle part on the opposite side of the take-in part 17. A conduit 19 leading from the extraction part 18 to the circulation tank 9 is installed to allow overflow, so that the water level in the tank 11 can be kept constant.

ここで、陰極１３が回転可能な構造であるが、
陰極に接触する回収板１４を回転させてもよい
し、また陰極１３と回収板１４とが互いに逆方向
に回転させてもよい。 Here, although the cathode 13 has a rotatable structure,
The collection plate 14 in contact with the cathode may be rotated, or the cathode 13 and the collection plate 14 may be rotated in opposite directions.

また、陰極１３は、円筒状とは、図示した円柱
状、ばかりでなく、円錐台状のものを含むもので
ある。 Further, the cylindrical shape of the cathode 13 includes not only the cylindrical shape shown in the figure but also a truncated conical shape.

第３図においては、陰極１３の外側に陽極１５
を配した構造を示したが、第４図に示したよう
に、陽極１５の外側に陰極１３を配した構造でも
よい。この場合陰極１３は陽極１５の外周と同じ
曲面を有する形状であることが好ましく、また回
収板１４は陰極１３の内面に接し、かつ回転可能
に取付けてなる。さらに、超音波発振器１６は、
陰極１３と陽極１５間に介在しない位置で、陰極
１３と陽極１５の中間の距離だけ離して配置させ
る。 In FIG. 3, an anode 15 is placed outside the cathode 13.
Although a structure in which a cathode 13 is arranged outside an anode 15 is shown, a structure in which a cathode 13 is arranged outside an anode 15 may be used as shown in FIG. In this case, the cathode 13 preferably has a shape having the same curved surface as the outer periphery of the anode 15, and the recovery plate 14 is in contact with the inner surface of the cathode 13 and is rotatably attached. Furthermore, the ultrasonic oscillator 16
The cathode 13 and the anode 15 are arranged at a position that is not interposed between the cathode 13 and the anode 15, and spaced apart from each other by an intermediate distance between the cathode 13 and the anode 15.

次に本発明の第２図に示した電解槽を有する装
置を用いた銅の回収例を説明する。 Next, an example of copper recovery using the apparatus having the electrolytic cell shown in FIG. 2 of the present invention will be described.

約300ppmの濃度の廃液をPH処理、濾過後、キレ
ート塔にてキレート剤ユニセツクUR―30（ユニ
チカ(株)製）からなるキレート剤に吸着し、上部か
ら硫酸により銅イオンを脱離し、約9000ppmの銅イ
オン濃度の高濃度液を貯液槽を介して電解槽へ送
る。電極槽は、70収納した槽に５〜60rpmの速
度で回転するステンレス製の直径が32mmで長さが
28cmの円柱状の陰極の表面に接触するポリ塩化ビ
ニル製の回収板、さらに３本の直径が14mmで長さ
が25cmのフエライト製陽極、該陽極間に３個の
28000Hzの超音波を発振可能な超音波発振器を配
してなり、前記濃度の高濃度液を9V、45Aの電
流条件で電解した。この条件で槽の底部から回収
した銅の回収量は、第４図に示した結果のとおり
である。 After the waste liquid with a concentration of approximately 300 ppm is subjected to PH treatment and filtered, it is adsorbed to a chelating agent consisting of the chelating agent Unisek UR-30 (manufactured by Unitika Co., Ltd.) in a chelating tower, and copper ions are desorbed from the upper part using sulfuric acid, resulting in a concentration of approximately 9000 ppm. A high-concentration solution with a copper ion concentration of The electrode tank is made of stainless steel with a diameter of 32 mm and a length that rotates at a speed of 5 to 60 rpm.
A collection plate made of polyvinyl chloride that contacts the surface of a 28 cm cylindrical cathode, and three ferrite anodes with a diameter of 14 mm and a length of 25 cm, and three ferrite anodes between the anodes.
It was equipped with an ultrasonic oscillator capable of oscillating ultrasonic waves at 28,000 Hz, and electrolyzed the highly concentrated liquid as described above under current conditions of 9 V and 45 A. The amount of copper recovered from the bottom of the tank under these conditions is as shown in FIG.

得られた銅粉の粒度は０〜30μの範囲で平均粒
度は5μであり、純度は99.86％と高純度のものが
得られた。 The particle size of the obtained copper powder was in the range of 0 to 30μ, the average particle size was 5μ, and the purity was 99.86%.

前記実施例の超音波の周波数を高くすればより
細かい粒径の金属粉、また低くすればより大きい
粒径の金属粉が得られることはいうまでもない。 It goes without saying that if the ultrasonic frequency of the above embodiment is increased, metal powder with finer particle size can be obtained, and if it is lowered, metal powder with larger particle size can be obtained.

前記説明は、銅について説明したが、キレート
剤、脱離液を変えることにより、ニツケル、銀、
クロムの回収も同様に行なうことができる。 The above explanation deals with copper, but by changing the chelating agent and desorbing liquid, nickel, silver,
Chromium recovery can be carried out in a similar manner.

〔Effect of the invention〕

本発明は、以上の構成からなるので、従来のス
ラツジとして回収処理装置に比べて、本発明は、
はるかに小さい装置で、かつ低電圧低電流で効率
よく高純度（99.5％以上）の金属粉を安価に回収
できる。 Since the present invention has the above configuration, compared to the conventional sludge recovery processing apparatus, the present invention has the following features:
Metal powder of high purity (over 99.5%) can be recovered efficiently and inexpensively using much smaller equipment and low voltage and low current.

また、回収される金属が、粉体または粒体で回
収できるので、再利用のとき、そのまま使用で
き、従来のように再使用における分離等の煩雑な
作業を必要としない。 Furthermore, since the recovered metal can be recovered in the form of powder or granules, it can be used as is when reusing it, and there is no need for complicated operations such as separation during reuse as in the past.

さらに、超音波の周波数を変えることにより、
回収する金属粉の粒径を変えることができ、所望
の金属粉を廃液から容易に得ることができる。 Furthermore, by changing the ultrasonic frequency,
The particle size of the recovered metal powder can be changed, and desired metal powder can be easily obtained from waste liquid.

[Brief explanation of the drawing]

第１図は、本発明の金属回収装置の一実施例を
廃水処理工程の中で説明するフローチヤート、第
２図は、本発明の装置の電解槽を示す説明図、第
３図は第２図の電極の配置例を示す説明図、第４
図は、他の電解槽の配置例を示す説明図、第５図
は、本発明の装置による銅の回収状態を示すグラ
フである。１０……電解槽、１１……槽、１２……回収
部、１３……陰極、１４……回収板、１５……陽
極、１６……超音波発振器。 FIG. 1 is a flowchart explaining one embodiment of the metal recovery device of the present invention in a wastewater treatment process, FIG. 2 is an explanatory diagram showing an electrolytic cell of the device of the present invention, and FIG. Explanatory diagram showing an example of the arrangement of the electrodes in Figure 4.
The figure is an explanatory diagram showing another example of the arrangement of electrolytic cells, and FIG. 5 is a graph showing the state of copper recovery by the apparatus of the present invention. 10... Electrolytic cell, 11... Tank, 12... Recovery section, 13... Cathode, 14... Recovery plate, 15... Anode, 16... Ultrasonic oscillator.

Claims

[Claims] 1. A metal recovery method in which dissolved metal ions are recovered in powder or granule form by electrolytic deposition, the method comprising irradiating ultrasonic waves onto the surface of an electrode on which metal is deposited in an electrolytic cell. A method for recovering powder or granular metal, characterized in that the deposited metal is scraped off by a recovery plate that moves relative to the surface of the electrode while in contact with or in close proximity to the surface of the electrode. 2 A cylindrical inner electrode is provided as either a cathode or an anode in the electrolytic cell, and an outer electrode with an opposite pole is provided around the inner electrode, and the metal is collected in contact with or close to the surface of the electrode where the metal is deposited. A metal recovery device in which a plate is provided, an ultrasonic oscillator is arranged at a position where ultrasonic waves can be irradiated to the electrode surface where metal is deposited, and at least one of the electrode where the metal is deposited and a recovery plate in contact with the electrode surface rotates. .