JPH07150384A - Electrolytic metal recovering method and device therefor - Google Patents
Electrolytic metal recovering method and device thereforInfo
- Publication number
- JPH07150384A JPH07150384A JP30005993A JP30005993A JPH07150384A JP H07150384 A JPH07150384 A JP H07150384A JP 30005993 A JP30005993 A JP 30005993A JP 30005993 A JP30005993 A JP 30005993A JP H07150384 A JPH07150384 A JP H07150384A
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- JP
- Japan
- Prior art keywords
- plate
- cathode
- metal
- solution
- silver
- 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.)
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- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は自動現像機の処理液、そ
の中でも写真廃液特に水洗水の銀回収装置に関する。特
に本発明は、該水洗水より銀を電解回収する技術におい
て、例えば銀の含有率が100ppm以下であるような低濃度
の銀含有水洗水の廃液からも有効に銀を回収することを
可能ならしめた銀回収装置に関するものであり、更に本
発明はこのような装置を使って、金，白金のような貴金
属や一般金属を含有する溶液から回収する方法にも関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for an automatic processor, and more particularly to a silver recovery apparatus for photographic waste solution, especially washing water. In particular, the present invention is a technique for electrolytically recovering silver from the wash water, if it is possible to effectively recover silver from a waste liquid of wash water containing silver at a low concentration such that the content of silver is 100 ppm or less. The present invention also relates to an apparatus for recovering silver, and the present invention also relates to a method for recovering from a solution containing a noble metal such as gold or platinum or a general metal using such an apparatus.
【０００２】[0002]
【従来の技術】写真廃液より銀を電解回収する技術は従
来より知られているが、従来の電解回収技術、例えば回
転型電解槽を用いた銀回収にあっては、電解する廃液中
の銀濃度が100mg／リットル以下（約100ppm以下）にな
るとそれ以上の銀回収は困難で、イオン交換樹脂を用い
た回収方法や銀よりイオン化傾向の大きい金属を用いた
金属置換法で更に銀回収を行わざるを得なかった。しか
しながら、これらの方法でも１ppm以下の銀回収は困難
であった。2. Description of the Related Art Although a technique for electrolytically recovering silver from a photographic waste liquid has been conventionally known, in the conventional electrolytic recovery technique, for example, silver recovery using a rotary electrolytic cell, silver in the waste liquid to be electrolyzed. When the concentration is 100 mg / liter or less (about 100 ppm or less), it is difficult to recover more silver, and further silver recovery is performed by a recovery method using an ion exchange resin or a metal replacement method using a metal having a greater ionization tendency than silver. I had no choice. However, even with these methods, it was difficult to recover silver of 1 ppm or less.
【０００３】写真廃液中に銀は、公害問題への対策上か
らもできるだけ低濃度にすることが望まれ、再利用可能
な形で回収しないとしても、例えば薬剤添加による沈殿
法を用いてでき得る限り完全に除去する必要がある。It is desired that the concentration of silver in the photographic waste liquid is as low as possible in view of the problem of pollution, and even if it is not recovered in a reusable form, it can be produced by, for example, a precipitation method by adding a chemical. It is necessary to completely remove it.
【０００４】[0004]
【発明が解決しようとする課題】上記のように、従来の
電解による銀回収技術では、銀回収に限度があり、それ
を越えると電解速度が著しくは低下して事実上銀濃度を
それより低くできず、銀濃度が100ppm以下であるような
廃液からの銀回収はできなかった。従って、電解により
銀回収を行う場合でも、電解で銀濃度を低下させた後
に、イオン交換樹脂法や金属置換法を用いて低濃度まで
銀回収を行う必要があった。あるいは沈殿法で銀を除去
する必要があった。As described above, in the conventional electrolytic silver recovery technology, there is a limit to the recovery of silver, and beyond that, the electrolysis rate is remarkably reduced and the silver concentration is effectively lowered. No silver could be recovered from the waste liquid with a silver concentration of 100 ppm or less. Therefore, even when silver is recovered by electrolysis, it is necessary to recover silver to a low concentration by using the ion exchange resin method or the metal substitution method after reducing the silver concentration by electrolysis. Alternatively, it was necessary to remove silver by the precipitation method.
【０００５】しかしイオン交換樹脂法は、イニシャルコ
スト，ランニングコストともに高く、実用上不利であ
る。However, the ion exchange resin method has a high initial cost and a high running cost and is disadvantageous in practical use.
【０００６】金属置換法では、充分濃度が低下しきれ
ず、かつ鉄イオンも溶出するという問題がある。The metal substitution method has a problem that the concentration cannot be lowered sufficiently and iron ions are also eluted.
【０００７】薬剤添加による銀の除去あるいは回収法
は、ランニングコストが高額であるとともに、操作が難
しい。The method for removing or recovering silver by adding chemicals has a high running cost and is difficult to operate.
【０００８】特開昭53-65218号には、流動床を用いた電
解法の開示があるが、これでは必ずしも充分な銀回収は
達成できず、また、特開昭61-270752号公報には、流動
床電解法を用いた技術が開示されており、これによれば
かなりの低濃度までの銀回収は可能と考えられている
が、環境規制の難しいところ（例えばアメリカなど）で
は、規制に充分見合うまで安定して銀回収をするには不
充分である。Japanese Unexamined Patent Publication (Kokai) No. 53-65218 discloses an electrolysis method using a fluidized bed, but this does not always achieve sufficient silver recovery, and Japanese Unexamined Patent Publication (Kokai) No. 61-270752 discloses the method. , A technology using the fluidized bed electrolysis method has been disclosed, and it is thought that silver recovery to a considerably low concentration is possible, but in places where environmental regulations are difficult (for example, in the United States), it is Insufficient for stable silver recovery until well worth it.
【０００９】また、本発明者等は電解銀回収装置の検討
により、電極間距離や電解電圧を調整する一般的な方法
で１ppmに近い濃度まで金属回収できる条件を見出した
が１ppm以下の銀回収は困難であった。Further, the present inventors have studied the electrolytic silver recovery apparatus and found a condition that metal can be recovered to a concentration close to 1 ppm by a general method of adjusting the distance between electrodes or the electrolysis voltage. Was difficult.
【００１０】本発明は上記問題点を解決せんとするもの
で、コストや操作の点で有利である電解による銀回収技
術を改良して、極めて低濃度まで金属を安定して回収す
ることができる水洗水からの金属回収装置を提供し、更
にそのような装置を用いて金や白金等の金属含有溶液か
ら該金属をも回収することを目的とする。The present invention is intended to solve the above problems, and improves the silver recovery technique by electrolysis, which is advantageous in terms of cost and operation, and can stably recover metals to an extremely low concentration. An object of the present invention is to provide a device for recovering metal from washing water, and further to recover the metal from a metal-containing solution such as gold or platinum using such a device.
【００１１】[0011]
【課題を解決するための手段】この目的は次の技術手段
(1)〜(11)の何れか１項によって達成される。[Means for Solving the Problems]
It is achieved by any one of (1) to (11).
【００１２】(1) 溶液中に含有される金属イオンを電解
により金属単体として回収する電解金属回収装置におい
て、１枚の陽極板に対して陰極板を対峙させ該陰極板の
該陽極板と逆方向に更に１枚以上の陰極板を積層するよ
うにした少なくとも１組のユニットを構成したことを特
徴とする電解金属回収装置。(1) In an electrolytic metal recovery apparatus for recovering metal ions contained in a solution as a simple metal by electrolysis, a cathode plate is opposed to one anode plate and the cathode plate is opposite to the anode plate. An electrolytic metal recovery apparatus comprising at least one set of units in which one or more cathode plates are further laminated in the direction.
【００１３】(2) 溶液中に含有される銀イオンを電解に
より金属単体として回収する電解金属回収装置におい
て、相隣る２枚の陽極板間に陰極板が３〜５枚積層され
て配設されていることを特徴とする電解金属回収装置。(2) In an electrolytic metal recovery apparatus for recovering silver ions contained in a solution as a simple metal by electrolysis, 3 to 5 cathode plates are stacked between two adjacent anode plates. An electrolytic metal recovery device characterized in that
【００１４】(3) 前記陰極板の少なくとも最外部に位置
する陰極板に対して内側に位置する陰極板は開孔部を有
することを特徴とする(1)項又は(2)項に記載の電解金属
回収装置。(3) The cathode plate located inside of at least the outermost cathode plate of the cathode plate has an opening, characterized in that (1) or (2) Electrolytic metal recovery device.
【００１５】(4) 前記陽極板，陰極板間で形成される通
路に沿って、溶液が蛇行して流れるようにしたことを特
徴とする(1)，(2)，(3)の何れか１項に記載の電解金属
回収装置。(4) Any one of (1), (2), and (3) is characterized in that the solution meanders along the passage formed between the anode plate and the cathode plate. Item 1. The electrolytic metal recovery device according to item 1.
【００１６】(5) 前記陰極板にはパンチングプレートを
使用し、相隣る該陰極板の開孔部の位置がずれているこ
とを特徴とする(1)〜(4)の何れか１項に記載の電解金属
回収装置。(5) A punching plate is used for the cathode plate, and the positions of the apertures of the adjacent cathode plates are deviated from each other, (1) to (4) The electrolytic metal recovery device described in 1.
【００１７】(6) 前記陽極板及び陰極板を含めた相隣る
電極板間の距離が１〜５mmであることを特徴とする(1)
〜(5)の何れか１項に記載の電解金属回収装置。(6) The distance between adjacent electrode plates including the anode plate and the cathode plate is 1 to 5 mm (1)
~ The electrolytic metal recovery device according to any one of (5).
【００１８】(7) 前記電極の電源としてパルス電源を用
いたことを特徴とする請求項１〜６の何れか１項に記載
の電解金属回収装置。(7) The electrolytic metal recovery apparatus according to any one of claims 1 to 6, wherein a pulse power source is used as a power source for the electrodes.
【００１９】(8) 前記溶液はハロゲン化銀感光材料の処
理液又は水洗水であり前記金属が銀であることを特徴と
する(1)〜(7)の何れか１項に記載の電解金属回収装置。(8) The electrolytic metal according to any one of (1) to (7), wherein the solution is a silver halide light-sensitive material processing solution or washing water and the metal is silver. Recovery device.
【００２０】(9) 前記溶液がチオ硫酸塩を含有して銀イ
オンを溶解しており電解電圧は0.7〜1.5Ｖであることを
特徴とする(8)項に記載の電解金属回収装置。(9) The electrolytic metal recovery apparatus according to item (8), wherein the solution contains thiosulfate to dissolve silver ions and the electrolysis voltage is 0.7 to 1.5V.
【００２１】(10) 前記金属は金，白金であることを特
徴とする(1)〜(7)項の何れか１項に記載の電解金属回収
装置。(10) The electrolytic metal recovery apparatus according to any one of items (1) to (7), wherein the metal is gold or platinum.
【００２２】(11) (1)〜(8)の何れか１項の電解金属回
収装置を使用して100ppm以下の低濃度金属含有溶液から
の金属回収を行う電解金属回収方法。(11) An electrolytic metal recovery method for recovering a metal from a low-concentration metal-containing solution of 100 ppm or less using the electrolytic metal recovery device according to any one of (1) to (8).
【００２３】[0023]
【作用】１枚の陽極板に対して陰極板を対峙させ、更に
該陰極板の該陽極板と逆方向に更に１枚以上の陰極板を
積層することで、理論的には外側の陰極板上に金属は析
出しないはずであるが、陽極板から離れた陰極板上にも
電解により金属が析出し、それによって微量金属の回収
速度を著しく高めることができ、条件によっては、0.1p
pmまで金属回収を可能ならしめることを発見した。The cathode plate is opposite to the anode plate, and one or more cathode plates are further laminated in the direction opposite to the anode plate of the cathode plate. Although no metal should be deposited on the top, the metal is also deposited on the cathode plate apart from the anode plate by electrolysis, which can significantly increase the recovery rate of trace metals, and depending on the conditions, 0.1 p
It was discovered that metal recovery would be possible up to pm.
【００２４】また、陰極板に例えばパンチングプレート
やメッシュ板等開孔部を有する電極を使用することで、
溶液の撹拌、陰極裏側への溶液の回り込み効果や開孔部
に起こるうず流効果により回収金属の量が開孔部のない
陰極板を積層したものよりも更に増大する。ちなみに開
孔率は特に規定しないが５〜40％のものが好ましい。ま
た、開孔径，開孔形状も特に規定されないが１〜20mmの
円形が好ましい。Further, by using an electrode having an opening portion such as a punching plate or a mesh plate for the cathode plate,
The amount of recovered metal is further increased as compared with the case where the cathode plates having no openings are stacked due to the stirring of the solution, the effect of the solution flowing to the back side of the cathode, and the eddy flow effect occurring in the openings. By the way, the porosity is not particularly specified, but it is preferably 5 to 40%. The diameter and shape of the aperture are not particularly limited, but a circle of 1 to 20 mm is preferable.
【００２５】本発明に使用する電極板のうち、陽極材質
としては、特に規定されないが、従来から使用されてい
る例えば寸法安定性電極（ＤＳＥ）や白金電極、白金メ
ッキ電極、チタンに白金，ルテニウム，パラジウム，イ
リジウムまたはその酸化物をコーティングした電極、炭
素材，炭素系複合材，炭素繊維布，グラファイトの電極
等が使用できる。陰極材質としては導電性材料であれば
いかなるものも用いることができるが、金属材質例えば
ステンレス，チタン，白金コートのチタン板，ニッケ
ル，銅，鉄及び前記金属の合金メッキあるいはグラファ
イト等も用いることができる。但し、腐食性，操作性の
観点からステンレスを用いることが好ましい。ステンレ
ス材としてはＳＵＳ−304，ＳＵＳ−316，ＳＵＳ−316
Ｌ，ＳＵＳ−317等がある。Of the electrode plates used in the present invention, the material of the anode is not particularly limited, but conventionally used, for example, dimensionally stable electrodes (DSE), platinum electrodes, platinum-plated electrodes, titanium with platinum and ruthenium. , Electrodes coated with palladium, iridium or its oxide, carbon materials, carbon-based composite materials, carbon fiber cloth, graphite electrodes, etc. can be used. Any material can be used as the cathode material as long as it is a conductive material, but a metal material such as stainless steel, titanium, a platinum-coated titanium plate, nickel, copper, iron, alloy plating of the above metal, or graphite can also be used. it can. However, it is preferable to use stainless steel from the viewpoint of corrosiveness and operability. Stainless steel material is SUS-304, SUS-316, SUS-316
L, SUS-317, etc.
【００２６】そして、複数の電極板で形成される流路に
溶液を蛇行式に流すことで、小型ポンプによって溶液が
電極表面を移動する速度ＬＶ値を上げることができ乱流
が生じて電極板表面に形成される拡散二重層が破壊され
るため低濃度溶液からの金属回収効果が向上され好まし
い。By flowing the solution in a meandering manner in a flow path formed by a plurality of electrode plates, the speed LV at which the solution moves on the electrode surface can be increased by a small pump, and a turbulent flow is generated to cause electrode plates. Since the diffusion double layer formed on the surface is destroyed, the metal recovery effect from the low concentration solution is improved, which is preferable.
【００２７】また、極間距離は短い方が電流効率がよ
く、金属回収効果も向上するが、１mm未満では析出金属
による導電頻度が高くなりメンテナンス上不利である。
また、５mm以上になると特に低濃度の金属回収効果が低
下するので１〜５mmの範囲が良好である。Further, the shorter the distance between the electrodes is, the better the current efficiency is and the more the metal recovery effect is improved, but if it is less than 1 mm, the frequency of conduction due to the deposited metal is high, which is disadvantageous for maintenance.
Further, if it is 5 mm or more, the effect of recovering particularly low-concentration metal is deteriorated, so that the range of 1 to 5 mm is preferable.
【００２８】更に、陰極板の開孔部位置を隣接する陰極
板同士でずらすことにより溶液の撹拌効果や電極との接
触性を高めることができ金属回収効果が更に向上する。Furthermore, by shifting the positions of the openings of the cathode plates between the adjacent cathode plates, the stirring effect of the solution and the contact property with the electrode can be enhanced, and the metal recovery effect is further improved.
【００２９】このとき相隣る陰極板の開孔位置は、少し
でもずれていればよいが、好ましくは該開孔間ピッチの
ほぼ２分の１ずらされている場合金属回収の効果が高
い。At this time, the positions of the apertures of the adjacent cathode plates may be displaced as much as possible, but preferably, the metal recovery effect is high when the aperture positions are shifted by approximately ½ of the pitch between the apertures.
【００３０】また、チオ硫酸塩を主成分とする銀イオン
含有溶液からの銀回収では電解電圧を0.7〜1.5Ｖで行う
ことにより硫化銀の生成が抑制され臭気の発生がなくな
り好ましい。即ち、0.7Ｖ未満では銀回収効率が低下
し、1.5Ｖ以上では硫酸銀が生成しＨ2Ｓの臭気が発生す
る。Further, in the silver recovery from the silver ion-containing solution containing thiosulfate as the main component, it is preferable to carry out the electrolysis at an electric voltage of 0.7 to 1.5 V so that the production of silver sulfide is suppressed and no odor is generated. That is, if it is less than 0.7 V, the silver recovery efficiency is lowered, and if it is 1.5 V or more, silver sulfate is produced and an odor of H 2 S is generated.
【００３１】更に、定常的な直流電源よりもパルス電源
の方が硫化銀の生成が抑制し易く、パルス電源を使用す
る場合、極性反転条件は、カソード基準のマイナス電気
量をプラス側の電気量より多くすることが好ましく、定
電流条件で極性反転比が(−)：(＋)＝５：１〜500：１
の電気量とすることが好ましい。極性反転時間は0.1ms
〜100msの範囲で極性反転比が(−)：(＋)＝100：１〜
５：１が好ましい。Further, the pulsed power supply suppresses the generation of silver sulfide more easily than the steady DC power supply, and when the pulsed power supply is used, the polarity reversal condition is that the negative reference electric quantity on the cathode side is the electric quantity on the positive side. It is preferable to increase the ratio, and the polarity reversal ratio is (−): (+) = 5: 1 to 500: 1 under constant current conditions.
The amount of electricity is preferably Polarity reversal time is 0.1ms
The polarity reversal ratio is (-): (+) = 100: 1-
5: 1 is preferred.
【００３２】本電解金属回収装置を用いて回収する金属
は例えば銀，金，白金，ルテニウム，パラジウム，イリ
ジウム，ニッケル，銅，鉄，クロム，鉛，コバルト，
錫，アルミニウム，亜鉛であるが、好ましくは銀及び
金，白金の貴金属であり、最も好ましくは銀である。Metals recovered by the electrolytic metal recovery system of the present invention are, for example, silver, gold, platinum, ruthenium, palladium, iridium, nickel, copper, iron, chromium, lead, cobalt,
Tin, aluminum and zinc are preferred, but silver, gold and noble metals such as platinum are preferred, and silver is most preferred.
【００３３】ところで、本発明の請求項１で述べた溶液
中に含有される金属イオンとはフリーイオンの状態又
は、錯形成物質と錯塩を形成し溶解している状態を示し
ている。By the way, the metal ion contained in the solution described in claim 1 of the present invention indicates a state of free ion or a state of forming a complex salt with a complex-forming substance and dissolving it.
【００３４】また、電解により金属単体として回収する
ことは、金属固体とすることであり、場合によっては溶
液中の物質を不純物として含有することがある。この金
属単体は、電解により陰極上に析出するものであり、そ
の分離方法としては、陰極を装置外に取り出し、スクレ
ーパーにより剥離するか又はハンマー等で叩くことによ
り衝撃で脱落させることが好ましく、また、溶解液によ
り直接溶解し、金属イオン濃縮液として分離し、金属純
度を上げる精製作業をする方法も好ましい。Further, to recover as a simple metal by electrolysis is to make a metal solid, and in some cases, the substance in the solution may be contained as an impurity. This metal simple substance is deposited on the cathode by electrolysis, and as a method for separating it, it is preferable to take the cathode out of the apparatus and peel it off with a scraper or drop it by impact by hitting with a hammer or the like. Also preferred is a method of directly dissolving with a dissolving solution, separating as a metal ion concentrated solution, and performing a refining operation for increasing the metal purity.
【００３５】また、請求項４に述べた電解槽の電極配列
構造は、形成される電極板間通路をＵターンさせながら
蛇行式に処理液を流す構成であり、これによって、小型
ポンプによって溶液が電極表面を移動して行く速度ＬＶ
値を上げることができ、乱流が生じて電極板表面に形成
される拡散二重層が破壊されるために、低濃度溶液から
の金属回収効率が向上するものと思われる。Further, the electrode arrangement structure of the electrolytic cell according to the fourth aspect is a structure in which the treatment liquid is caused to flow in a meandering manner while making a U-turn in the formed inter-electrode plate passage. Velocity LV moving on the electrode surface
The value can be increased, and turbulent flow is generated to destroy the diffusion double layer formed on the surface of the electrode plate, which is thought to improve the metal recovery efficiency from the low-concentration solution.
【００３６】この本発明の方式は、従来の陽極板，陰極
板にそれぞれ開孔部を設け処理液を電極板に垂直に流す
方式や、これとは反対にＵターンさせることなく電極板
に平行に一方向に流すだけの方式にくらべて、上述のよ
うに格段の金属回収効果の向上を見るに至った。The method of the present invention is such that the conventional anode plate and cathode plate are provided with openings respectively to allow the treatment liquid to flow vertically to the electrode plate, or conversely to this, parallel to the electrode plate without making a U-turn. As described above, we have seen a marked improvement in the metal recovery effect as compared with the method in which the flow is carried out in only one direction.
【００３７】尚、積層する電極形状は、平板型が簡単で
好ましいが、その他の形状として、例えば、回転ドラム
型電解槽で使用されるような円筒形であってもよいが、
製作にやや難しさがある。The electrode shape to be laminated is preferably a flat plate type, but other shapes may be used, such as a cylindrical shape used in a rotary drum type electrolytic cell.
It's a little difficult to make.
【００３８】請求項８で述べたハロゲン化銀感光材料の
処理液の種類としては特に規定はされないが、現像液，
漂白定着液，定着液，予備水洗水，水洗水，リンス液，
安定液等があげられ、好ましくは、定着液，定着液が混
入する予備水洗水，リンス液又は安定液である。The kind of the processing solution for the silver halide light-sensitive material described in claim 8 is not particularly specified, but a developing solution,
Bleach fixer, fixer, preliminary wash water, wash water, rinse solution,
Examples of the stabilizing solution include a fixing solution, a prewash water containing the fixing solution, a rinse solution, and a stabilizing solution.
【００３９】請求項９では前記ハロゲン化銀感光材料の
処理液がチオ硫酸塩を含有して銀イオンを溶解している
ものを電解液としているが、この電解液はハロゲン化銀
感光材料の銀定着剤としてチオ硫酸塩を含有した処理液
又は水洗水が処理により銀イオンを溶解し含有した溶液
となったものである。In the ninth aspect, the processing solution for the silver halide light-sensitive material uses an electrolytic solution containing thiosulfate and dissolving silver ions. This electrolytic solution is silver for the silver halide light-sensitive material. The treatment liquid containing thiosulfate as a fixing agent or the washing water was dissolved to form a solution containing silver ions.
【００４０】請求項11では前記金属回収装置は100ppm以
下の低濃度金属溶液からの金属回収に効果的であること
を述べたが、好ましくは、溶液中の金属イオン濃度が10
ppm以下であり、特に1.0ppm以下に低下させる目的に関
して効果が顕著である。In claim 11, it is stated that the metal recovery device is effective in recovering a metal from a low-concentration metal solution of 100 ppm or less, but preferably, the metal ion concentration in the solution is 10
The effect is remarkable for the purpose of lowering it to 1.0 ppm or less, especially to 1.0 ppm or less.
【００４１】[0041]
【実施例】以下に本発明を実施例に基づき説明するが、
本発明はこれらに限定されてしまうものではない。EXAMPLES The present invention will be described below based on examples.
The present invention is not limited to these.
【００４２】本発明の電解金属回収装置の実験装置を図
１に示し、後述する溶液を用いて銀回収を行った結果を
図２のグラフを用いて説明する。An experimental apparatus of the electrolytic metal recovery apparatus of the present invention is shown in FIG. 1, and the results of silver recovery using the solution described later will be described with reference to the graph of FIG.
【００４３】図１の電解槽21は正面の幅41mm、高さ210m
m、奥行500mmであり槽内には図４の（ａ）又は（ｂ）で
示されるような陽極板22Ａ又は22Ｂの間に図５の（ａ）
又は（ｂ）で示されるような陰極板23Ａ又は23Ｂが３枚
平行に入れられており、該陽極板の材質はグラファイト
であり、該陰極板の材質はＳＵＳ 316 パンチングプレ
ートであり、陽極板と陰極板の面間距離は、３mm、陰極
板同士の間の面間距離は２mmであり、陰極面積は１枚の
場合表裏両面で12dm2であり２枚は24dm2３枚で36dm2に
なっている。The electrolytic cell 21 in FIG. 1 has a front width of 41 mm and a height of 210 m.
m, depth 500 mm, and inside the tank, as shown in FIG. 4 (a) or (b), between the anode plates 22A or 22B shown in FIG. 5 (a).
Alternatively, three cathode plates 23A or 23B as shown in (b) are put in parallel, the material of the anode plate is graphite, the material of the cathode plate is SUS 316 punching plate, and The face-to-face distance of the cathode plates is 3 mm, the face-to-face distance between the cathode plates is 2 mm, and the cathode area is 12 dm 2 on both front and back sides with one sheet, and 24 dm 2 with 3 sheets is 36 dm 2 . ing.
【００４４】そして、電解電圧は1.0Ｖ，温度は室温，
流速は10リットル／分である。The electrolysis voltage is 1.0 V, the temperature is room temperature,
The flow rate is 10 l / min.
【００４５】実施例に用いた溶液は チオ硫酸アンモニウム 70％溶液 2.32ml／リットル 亜硫酸アンモニウム 95mg／リットル 銀イオン 60mg／リットル （ヨウ素消費料：1.6ｇ／リットル，pＨ：6.0） である。The solution used in the examples is ammonium thiosulfate 70% solution 2.32 ml / liter ammonium sulfite 95 mg / liter silver ion 60 mg / liter (iodine consumption: 1.6 g / liter, pH: 6.0).
【００４６】このような溶液５リットルを図１に示す処
理槽11に入れ、バルブ32，ポンプ31を介して電解槽21の
左方にある入口24に配管し、右方にある該電解槽21の出
口25から再び処理槽11に戻すようにして循環路を形成さ
せてある。5 liters of such a solution is placed in the treatment tank 11 shown in FIG. 1, and is piped through the valve 32 and the pump 31 to the inlet 24 on the left side of the electrolytic cell 21, and the electrolytic cell 21 on the right side. A circulation path is formed by returning from the outlet 25 to the processing tank 11 again.
【００４７】このような電解金属回収装置において陰極
板を１〜５枚に変化させて銀回収実験を行った。In such an electrolytic metal recovery apparatus, a silver recovery experiment was conducted by changing the number of cathode plates to 1 to 5.
【００４８】その結果は図２の銀回収がされて行く途中
における該溶液の銀濃度の時間に対する変化曲線のよう
になり、陰極板枚数を増やすと銀回収速度が上がり、特
に銀濃度が１ppm以下になっても銀濃度にほぼ比例して
銀濃度が減少して行くという特徴がみられた。The result is as shown in FIG. 2 which is a curve of the silver concentration of the solution with respect to time in the course of silver recovery. The silver recovery rate increases as the number of cathode plates increases, and especially the silver concentration is 1 ppm or less. However, the characteristic was that the silver concentration decreased almost in proportion to the silver concentration.
【００４９】特に３枚以上で効果が高かった。The effect was particularly high when the number of sheets was 3 or more.
【００５０】また、図１における陰極板を開孔部を有さ
ないものに替えて、同様な銀回収実験を行った結果、図
２の結果より若干銀回収速度は低下するが積層すること
により１枚のものよりも低濃度まで銀を回収することが
可能であった。Further, as a result of conducting a similar silver recovery experiment by replacing the cathode plate in FIG. 1 with one having no opening, the silver recovery rate is slightly lower than the result of FIG. It was possible to recover silver to a lower concentration than the one.
【００５１】以上の効果は電解槽を図３に示すように陽
極板１枚に対し陰極板を２枚〜３枚平行に並べてユニッ
トを構成した電解槽21においても同様の傾向が見られ
た。A similar tendency was observed in the electrolytic cell 21 in which a unit was constructed by arranging two to three cathode plates in parallel with one anode plate as shown in FIG.
【００５２】尚、図４（ａ）又は（ｂ）に示すように陽
極板22Ａ又は22Ｂは切欠き部又は開口部を片方に有して
いるが、どちらを使用しても良い。しかし、その切欠き
部又は開口部は相隣るもの同士互いに前後逆になるよう
に配置してある。これにより電解槽21内の水溶液の流れ
はＵターンして流れ電極板表面を移動する速度ＬＶ値が
増し、溶液の撹拌効果が上がり銀回収効率も上がってい
る。Although the anode plate 22A or 22B has a notch or an opening on one side as shown in FIG. 4 (a) or (b), either one may be used. However, the cutouts or openings are arranged so that adjacent ones are opposite to each other. As a result, the flow of the aqueous solution in the electrolytic bath 21 makes a U-turn to increase the velocity LV value of moving on the surface of the electrode plate, the stirring effect of the solution is increased, and the silver recovery efficiency is also increased.
【００５３】また、図５（ａ），（ｂ）に示すように陰
極板23Ａ，23Ｂはパンチングプレートが使用されている
が、その孔の配列は左右上下に0.5ピッチずつずれたも
のになっている。このような陰極板23Ａと23Ｂを互い違
いに配列しておくことにより流過する溶液の撹拌効果と
電極への接触性が高められ銀回収効果が更に向上する。As shown in FIGS. 5A and 5B, punching plates are used for the cathode plates 23A and 23B, but the holes are arranged in the left and right and up and down by 0.5 pitch. There is. By staggering the cathode plates 23A and 23B, the stirring effect of the flowing solution and the contact property with the electrode are enhanced, and the silver recovery effect is further improved.
【００５４】次に本実験装置に使用した陽極板22Ａ又は
22Ｂと陰極板23Ａ又は23Ｂを多連にして電解槽21の中に
配設したものが図６の平面断面図である。Next, the anode plate 22A used in the experimental apparatus or
A plan cross-sectional view of FIG. 6 shows a structure in which 22B and the cathode plate 23A or 23B are arranged in a line in the electrolytic cell 21.
【００５５】電解槽21にはグラファイト板よりなる厚さ
４mmの陽極板の10枚が等間隔に配置されその切欠部22Ｃ
又は開口部22Ｄの部分を隣同士前後逆になるように配列
してある。そしてその陽極板22Ａ又は22Ｂの間にはＳＵ
Ｓ 316のパンチングプレートで作られた厚さ１mmの陰極
板23Ａ又は23Ｂを交互に３枚ずつ配設されている。ま
た、両端の陽極板22Ａ又は22Ｂの外側に陰極板23Ａ又は
23Ｂが各１枚ずつ配置されている。In the electrolytic cell 21, ten 4 mm-thick anode plates made of graphite plates are arranged at equal intervals, and their cutouts 22C are formed.
Alternatively, the openings 22D are arranged so that the portions adjacent to each other are turned upside down. The SU is placed between the anode plates 22A or 22B.
Three 1 mm-thick cathode plates 23A or 23B made of S316 punching plates are alternately arranged. Further, the cathode plate 23A or 22B is provided outside the anode plate 22A or 22B at both ends.
One 23B each is arranged.
【００５６】[0056]
【発明の効果】本発明により低濃度の金属イオン溶液か
ら金属回収が効率よくできるようになった。そしてその
装置は小型で簡単に作られるもので低コストで確実な金
属回収ができ、特にチオ硫酸塩を主成分とする銀イオン
含有溶液からの銀回収では銀回収中及び回収後の溶液も
脱臭されており作業環境も良好にすることができる。According to the present invention, metal can be efficiently recovered from a low concentration metal ion solution. The equipment is small and easy to make, and can reliably collect metals at low cost. Especially, in the silver recovery from a silver ion-containing solution whose main component is thiosulfate, the solution during and after the silver recovery is deodorized. Therefore, the working environment can be improved.
【図１】本発明の一実施例のフロー図。FIG. 1 is a flowchart of an embodiment of the present invention.
【図２】本発明の実験結果を示す銀濃度変化曲線。FIG. 2 is a silver concentration change curve showing the experimental results of the present invention.
【図３】本発明の別の実施例を示す正面図。FIG. 3 is a front view showing another embodiment of the present invention.
【図４】陽極板の平面図。FIG. 4 is a plan view of an anode plate.
【図５】陰極板の平面図。FIG. 5 is a plan view of a cathode plate.
【図６】本発明の他の実施例の電解槽の平面図。FIG. 6 is a plan view of an electrolytic cell according to another embodiment of the present invention.
11 水洗水槽（処理槽） 21 電解槽 21Ａ 固定板 21Ｂ 蓋 21Ｃ パッキン 21Ｄ 外側のフレーム 21Ｅ 導電部材 22Ａ，22Ｂ 陽極板 23Ａ，23Ｂ 陰極板 24 入口 25 出口 26 接触端子 27，27Ａ 接触接片 11 Rinsing water tank (treatment tank) 21 Electrolytic tank 21A Fixed plate 21B Lid 21C Packing 21D Outer frame 21E Conductive member 22A, 22B Anode plate 23A, 23B Cathode plate 24 Inlet 25 Outlet 26 Contact terminal 27, 27A Contact piece
Claims (11)
より金属単体として回収する電解金属回収装置におい
て、１枚の陽極板に対して陰極板を対峙させ該陰極板の
該陽極板と逆方向に更に１枚以上の陰極板を積層するよ
うにした少なくとも１組のユニットを構成したことを特
徴とする電解金属回収装置。1. In an electrolytic metal recovery apparatus for recovering metal ions contained in a solution as a simple metal by electrolysis, a cathode plate is opposed to a single anode plate and the cathode plate is opposite to the anode plate. An electrolytic metal recovery apparatus, characterized in that at least one set of units is further formed by stacking one or more cathode plates.
り金属単体として回収する電解金属回収装置において、
相隣る２枚の陽極板間に陰極板が３〜５枚積層されて配
設されていることを特徴とする電解金属回収装置。2. An electrolytic metal recovery device for recovering silver ions contained in a solution as a simple metal by electrolysis,
An electrolytic metal recovery device, characterized in that 3 to 5 cathode plates are stacked and disposed between two adjacent anode plates.
る陰極板に対して内側に位置する陰極板は開孔部を有す
ることを特徴とする請求項１又は２に記載の電解金属回
収装置。3. The electrolytic metal recovery device according to claim 1, wherein at least the outermost cathode plate of the cathode plate is located inside the cathode plate and has an opening.
に沿って、溶液が蛇行して流れるようにしたことを特徴
とする請求項１〜３の何れか１項に記載の電解金属回収
装置。4. The electrolytic metal according to claim 1, wherein the solution meanders along a passage formed between the anode plate and the cathode plate. Recovery device.
用し、相隣る該陰極板の開孔部の位置がずれていること
を特徴とする請求項１〜４の何れか１項に記載の電解金
属回収装置。5. The punching plate is used as the cathode plate, and the positions of the apertures of the adjacent cathode plates are displaced from each other, according to any one of claims 1 to 4. Electrolytic metal recovery device.
極板間の距離が１〜５mmであることを特徴とする請求項
１〜５の何れか１項に記載の電解金属回収装置。6. The electrolytic metal recovery device according to claim 1, wherein a distance between adjacent electrode plates including the anode plate and the cathode plate is 1 to 5 mm. .
たことを特徴とする請求項１〜６の何れか１項に記載の
電解金属回収装置。7. The electrolytic metal recovery apparatus according to claim 1, wherein a pulse power source is used as a power source for the electrodes.
液又は水洗水であり前記金属が銀であることを特徴とす
る請求項１〜７の何れか１項に記載の電解金属回収装
置。8. The electrolytic metal recovery apparatus according to claim 1, wherein the solution is a processing solution of silver halide light-sensitive material or washing water, and the metal is silver.
ンを溶解しており電解電圧は0.7〜1.5Ｖであることを特
徴とする請求項８に記載の電解金属回収装置。9. The electrolytic metal recovery apparatus according to claim 8, wherein the solution contains thiosulfate to dissolve silver ions and the electrolysis voltage is 0.7 to 1.5V.
とする請求項１〜７の何れか１項に記載の電解金属回収
装置。10. The electrolytic metal recovery apparatus according to claim 1, wherein the metal is gold or platinum.
装置を使用して100ppm以下の低濃度金属含有溶液からの
金属回収を行う電解金属回収方法。11. An electrolytic metal recovery method for recovering a metal from a low-concentration metal-containing solution of 100 ppm or less by using the electrolytic metal recovery device according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30005993A JPH07150384A (en) | 1993-11-30 | 1993-11-30 | Electrolytic metal recovering method and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30005993A JPH07150384A (en) | 1993-11-30 | 1993-11-30 | Electrolytic metal recovering method and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07150384A true JPH07150384A (en) | 1995-06-13 |
Family
ID=17880208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30005993A Pending JPH07150384A (en) | 1993-11-30 | 1993-11-30 | Electrolytic metal recovering method and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07150384A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017110269A (en) * | 2015-12-17 | 2017-06-22 | アサヒプリテック株式会社 | Negative electrode for electrolytic device, and electrolytic device including the same |
| JP2017193761A (en) * | 2016-04-21 | 2017-10-26 | 大成建設株式会社 | Recovery method of arsenic and purification method and purification device of sewage containing arsenic |
| CN109097792A (en) * | 2018-10-29 | 2018-12-28 | 东北大学 | A kind of electrolysis unit from low concentration cupric cyanide barren solution recycling copper and cyanide |
-
1993
- 1993-11-30 JP JP30005993A patent/JPH07150384A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017110269A (en) * | 2015-12-17 | 2017-06-22 | アサヒプリテック株式会社 | Negative electrode for electrolytic device, and electrolytic device including the same |
| JP2017193761A (en) * | 2016-04-21 | 2017-10-26 | 大成建設株式会社 | Recovery method of arsenic and purification method and purification device of sewage containing arsenic |
| CN109097792A (en) * | 2018-10-29 | 2018-12-28 | 东北大学 | A kind of electrolysis unit from low concentration cupric cyanide barren solution recycling copper and cyanide |
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