JPS6116000A - Method for regenerating spent silver plating solution - Google Patents
Method for regenerating spent silver plating solutionInfo
- Publication number
- JPS6116000A JPS6116000A JP13634884A JP13634884A JPS6116000A JP S6116000 A JPS6116000 A JP S6116000A JP 13634884 A JP13634884 A JP 13634884A JP 13634884 A JP13634884 A JP 13634884A JP S6116000 A JPS6116000 A JP S6116000A
- Authority
- JP
- Japan
- Prior art keywords
- silver plating
- silver
- solution
- soln
- chamber
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
Landscapes
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は銀めっき廃液の再生方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a method for recycling silver plating waste liquid.
従来の技術
最近、ＩＣ，ＬＳＩ関連産業の成長と相俟ってＩＣ５Ｌ
ＳＩ基板への貴金属めっきが急激に増大している。なお
、貴金属の中でも銀の使用量が多く、電解浴としてはシ
アン公害問題の発生が懸念されるため、低シアン化の方
向にあり、シアン化カリウムの使用量を極力おさえ、ピ
ロリン酸カリウムを支持電解質とした銀めっき浴に変シ
つつある。Conventional technology Recently, with the growth of IC and LSI related industries, IC5L
Precious metal plating on SI substrates is rapidly increasing. Furthermore, among the precious metals, silver is used in a large amount, and there is a concern that it may cause cyanide pollution problems in electrolytic baths, so the trend is toward lower cyanide, minimizing the amount of potassium cyanide used, and using potassium pyrophosphate as the supporting electrolyte. It is changing into a silver-plated bath.
発明が解決しようとする問題点
しかし、ピロリン酸カリウムを支持電解質にした低シア
ン銀めっき浴ではＩＣ基板に銀めっきする前に、下地を
まず銅めっきするため、銀めっき時における銅の溶解が
問題となり、銀めっき不良発生の原因となっている。現
在のところ、銅のみを選択的に除去する方法は発見され
ておらず、銅が一定濃度に達した場合、銀めっき液とし
て使用できないため、電析により金属銀として回収後、
回収業者に引き渡すか、または、廃液のまま回収・ 業
者に引き渡している場合がほとんどである。しかしなが
ら、銀めっき廃液の銀濃度は高いため、銅除去処理を行
い、銀めっき液として再利用することが、経済的効果は
はるかに大きい。Problems to be Solved by the Invention However, in the low cyanide silver plating bath using potassium pyrophosphate as the supporting electrolyte, the base is first plated with copper before silver plating on the IC substrate, so dissolution of copper during silver plating is a problem. This causes silver plating defects. At present, no method has been discovered to selectively remove only copper, and if copper reaches a certain concentration, it cannot be used as a silver plating solution, so after recovering it as metallic silver by electrodeposition,
In most cases, the liquid is handed over to a collection company, or it is handed over to a collection/collection company as waste liquid. However, since the silver concentration of the silver plating waste solution is high, performing copper removal treatment and reusing it as a silver plating solution has a much greater economic effect.
問題点を解決するだめの手段
この発明は、この様な問題点を解消する目的において銀
めっき廃液から−価イオン選択性強塩基性陰イオン交換
膜を介して電気透析を行い、選択的に銀を回収し、銀め
っき液として再利用する方法であって、再生しためつき
液の品質も何ら変ることなく、銀めっきのコストダウン
を企図し得ることを特徴とするものである０
以下、実施用例図を引例しながら本発明の詳細な説明す
る。Means to Solve the Problems In order to solve these problems, the present invention conducts electrodialysis from silver plating waste liquid through a valence ion-selective strongly basic anion exchange membrane to selectively remove silver. This is a method of collecting and reusing silver plating solution as a silver plating solution, which is characterized by the fact that the quality of the recycled plating solution does not change in any way and it is possible to reduce the cost of silver plating. The present invention will be described in detail with reference to example figures.
第１図に示す様に槽体１内を２組の一価イオン選択性強
塩基性陰イオン交換膜２ａ、２ｂで区分して中央部を銀
めっき廃液室３、両側部を陽極室４と陰極室５となして
陽極板６と陰極板７とを垂下し、銀めっき廃液室３内に
ビロリン酸カリウムを支持電解質とした低シアン化銀め
っき廃液を収容して陽極板６と陰極板７とを直流電源８
に接続して電気透析を行い、銀めっき廃液中に存在する
シアン化銀錯イオンＡｇ（ＣＮ）； とピロ′リン酸銅
錯イオンＣｕ（Ｐ２Ｏ３）ニーとのうち、シアン化銀錯
イオンＡｇ（ＣＮ）２を一価イオン選択性強塩基性陰イ
オン交換膜２ａで容易にイオン交換して陽極室４内へ移
動させながら陽極室４内の回収液を槽体１外へ取り出し
、該回収液に苛性カリ溶液とシアン化カリウムを添加す
べくなして成るものである０作用、効果
つぎに、実施用例図により本発明の作用効果を説明する
。As shown in Fig. 1, the inside of the tank body 1 is divided into two sets of monovalent ion-selective strong basic anion exchange membranes 2a and 2b, with the central part being a silver plating waste liquid chamber 3 and the both sides being an anode chamber 4. An anode plate 6 and a cathode plate 7 are suspended as a cathode chamber 5, and a low cyanide silver plating waste liquid with potassium birophosphate as a supporting electrolyte is stored in the silver plating waste liquid chamber 3, and an anode plate 6 and a cathode plate 7 are formed. and the DC power supply 8
Among the silver cyanide complex ion Ag (CN) present in the silver plating waste solution and the copper pyro'phosphate complex ion Cu (P2O3), silver cyanide complex ion Ag ( CN) 2 is easily ion-exchanged with the monovalent ion-selective strongly basic anion exchange membrane 2a and moved into the anode chamber 4, while the recovered liquid in the anode chamber 4 is taken out to the outside of the tank body 1. Next, the functions and effects of the present invention will be explained with reference to practical example diagrams.
銀めっき廃液の組成は表１に示す通りで、不純物である
銅は建浴時には全く含まれていないが、銀めっきと共に
下地の銅が溶解し、銀めっき時間が長くなるにつれ銅溶
解量が多くなシ、１ｏｇ７を以上になると製品に不良が
認められ、めっき液として使用できなくなる。The composition of the silver plating waste solution is shown in Table 1. Although there is no copper as an impurity at the time of bath preparation, the underlying copper dissolves along with the silver plating, and as the silver plating time increases, the amount of dissolved copper increases. However, if it exceeds 1og7, the product will be found to be defective and cannot be used as a plating solution.
表１ 銀めっき廃液の成分（ｇ／７）
そこで、第１図に示す様な銀回収用の電析槽を用い、−
価イオン選択性強塩基性陰イオン交換膜２ａ、２ｂを用
いて銀めっき液を再生させるものである。なお、陰極室
５側のイオン交換膜２ｂを一価イオン選択性、強塩基性
陰イオン交換膜、強塩基性陰イオン交換膜並びに強酸性
陽イオン交換膜となし、銀めっき廃液を純水で１０倍希
釈後１００ｒｎＡ、０，５Ｖの電流、電圧で約２０時間
電気透析を行い、陰極膜の性能により銀、銅の陽極室４
内への移動率を比較すると表２の様になる。Table 1 Components of silver plating waste liquid (g/7) Therefore, using an electrodeposition tank for silver recovery as shown in Figure 1, -
A silver plating solution is regenerated using valence ion selective strongly basic anion exchange membranes 2a and 2b. In addition, the ion exchange membrane 2b on the cathode chamber 5 side is a monovalent ion selective, strongly basic anion exchange membrane, strongly basic anion exchange membrane, and strongly acidic cation exchange membrane, and the silver plating waste liquid is purified with pure water. After 10-fold dilution, electrodialysis was performed for about 20 hours at a current and voltage of 100 rnA and 0.5 V. Depending on the performance of the cathode membrane, silver and copper anode chambers 4
A comparison of the inward migration rates is shown in Table 2.
表２ 陽極室（回収液）への銀及び銅の移動率（％′）
こあ表２より明らかなようにミ釧、銅の移動率に異いが
認められる。この事について銀及び銅はめつき液中では
次の様な錯イオン
Ａｇ（ＣＮ）″ ％ Ｃｕ（Ｐ Ｏ）”として存在し
、−価と六価の陰イオンとしてｉ動し、両イオン共に陽
極に移動する。しかし１、陽極膜が一価イオン選択性強
塩基性陰イオン交換膜２ａであるため一価のＡｇ（ＣＮ
）；イオンが、六価のＣｕ（Ｐ２０□）２イオ／よシ選
択的にイオン交換し易いと共にイオン式量が、１５９．
５と４１１．５となって銀錯イオンが小さいため膜通過
抵抗が小さくなり、移動が容易となる。Table 2 Transfer rate of silver and copper to the anode chamber (recovered liquid) (%')
As is clear from Table 2, there is a difference in the transfer rate of copper and copper. Regarding this matter, silver and copper exist in the plating solution as the following complex ion Ag(CN)%Cu(PO), which moves as -valent and hexavalent anions, and both ions are present at the anode. Move to. However, 1. Since the anode membrane is a monovalent ion selective strongly basic anion exchange membrane 2a, monovalent Ag (CN
); ions are easily ion-exchanged selectively to hexavalent Cu(P20□)2 ions, and the ionic content is 159.
5 and 411.5, and since the silver complex ions are small, the membrane passage resistance becomes small and the movement becomes easy.
また、陰極膜に一価選択性強塩基性陰イ′オン交換膜を
使用すれば銅錯イオンの陽極室４内への移動は少々χ良
好である。Furthermore, if a monovalent selective strongly basic anion exchange membrane is used as the cathode membrane, the movement of copper complex ions into the anode chamber 4 will be slightly better.
従って、陽極膜と陰極膜とを共に一価選択性強塩基性陰
イオン交換膜を使用した場合が銀回収を能率的になし得
るものである。Therefore, it is possible to efficiently recover silver when monovalently selective strongly basic anion exchange membranes are used as both the anode membrane and the cathode membrane.
そこで、本発明方法を用いて銀めっき廃液を１２０時間
処理した場合の銀めっき廃液と陽極室液との銀濃度と銅
濃度とを表わしだのが第３図のグラフであシ、このグラ
フよ９８０時間の電析処理でもってめっき廃液の銀濃度
は３４．７ｇ／ｌから８．５ｇ／を以下となダ、一方、
陽極室液（回収液）の銀は４０ｇ／を以上で、７５％以
上回収されたことになる。また、銅は１１．６ｇ／ｌか
ら１１ ｇ／ｌとなシ、約５−程度陽極室に移動したに
すぎないことがわかる。Therefore, the graph in Figure 3 shows the silver concentration and copper concentration of the silver plating waste solution and the anode chamber solution when the silver plating waste solution is treated for 120 hours using the method of the present invention. After 980 hours of electrodeposition treatment, the silver concentration of the plating waste solution decreased from 34.7 g/l to 8.5 g/l.
The amount of silver in the anode chamber solution (recovered solution) was 40 g/or more, which means that 75% or more was recovered. It can also be seen that copper moved from 11.6 g/l to 11 g/l by only about 5 degrees to the anode chamber.
なお、陰極室液には銀、銅ともほとんど含まれておらず
、また両極板への銀析出も軽微である。Note that the cathode chamber solution contains almost no silver or copper, and silver precipitation on both electrode plates is slight.
回収した陽極室液中のどロリン酸濃度変化はほとんどな
いが、通電時間と共に水素イオン濃度が上昇しｐＨが下
るため苛性カリ溶液を滴加して所定の水素イオン濃度に
すると共に、表１に示した濃度になる様にシアン化カリ
ウムを添加して銀めっき液として再生させるものであシ
、試験の結果、従来の銀めっき液と何ら変ることなく使
用できることが確認された。Although there was almost no change in the concentration of dorophosphoric acid in the collected anode chamber solution, the hydrogen ion concentration increased and the pH decreased with the energization time, so a caustic potash solution was added dropwise to bring the hydrogen ion concentration to the specified level, and the pH was adjusted as shown in Table 1. The silver plating solution is regenerated by adding potassium cyanide to the desired concentration, and tests have confirmed that it can be used in the same way as conventional silver plating solutions.
この様にして銀めっき廃液を電気透析して銀めっき液と
して再生し得ることによって、銀めっきのコストダウン
、並びに経済的省力化を企図し得る等、前記した顕著な
諸効果を奏するものである０By electrodialyzing the silver plating waste solution and regenerating it as a silver plating solution in this way, the above-mentioned remarkable effects can be achieved, such as reducing the cost of silver plating and economical labor saving. 0
第１図は本発明方法の実施例に係る電気透析槽を示した
断面図、第２図はその説明図、第３図は銀めっき廃液を
電気透析した場合の銀と銅・の・濃度変化グラフである
。Fig. 1 is a sectional view showing an electrodialysis tank according to an embodiment of the method of the present invention, Fig. 2 is an explanatory view thereof, and Fig. 3 is a change in concentration of silver and copper when silver plating waste liquid is electrodialyzed. It is a graph.
Claims (1)
銀めっき廃液から一価イオン選択性強塩基性陰イオン交
換膜を介して電気透析を行い選択的に銀を移動させ、該
移動液に苛性カリ溶液やシアン化カリウムを添加するこ
とを特徴として成る、銀めっき廃液の再生方法。1 Electrodialysis is performed to selectively transfer silver from a low-cyanide silver plating waste solution using potassium pyrophosphate as a supporting electrolyte through a monovalent ion-selective strongly basic anion exchange membrane, and the transfer solution is mixed with a caustic potassium solution or A method for recycling silver plating waste liquid, characterized by adding potassium cyanide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13634884A JPS6116000A (en) | 1984-06-30 | 1984-06-30 | Method for regenerating spent silver plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13634884A JPS6116000A (en) | 1984-06-30 | 1984-06-30 | Method for regenerating spent silver plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6116000A true JPS6116000A (en) | 1986-01-24 |
| JPH026840B2 JPH026840B2 (en) | 1990-02-14 |
Family
ID=15173090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13634884A Granted JPS6116000A (en) | 1984-06-30 | 1984-06-30 | Method for regenerating spent silver plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6116000A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636130A (en) * | 2018-05-29 | 2018-10-12 | 浙江师范大学 | Polymer-metal composite separating film preparation method and application |
| JP7037023B1 (en) * | 2021-07-22 | 2022-03-16 | 生態環境部華南環境科学研究所 | Copper Pyrophosphate Plating How to Recycle Copper and Phosphorus Resources in Wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321049A (en) * | 1976-08-11 | 1978-02-27 | Mitsubishi Electric Corp | Low cyanide* high speed electroosilver plating solution |
-
1984
- 1984-06-30 JP JP13634884A patent/JPS6116000A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321049A (en) * | 1976-08-11 | 1978-02-27 | Mitsubishi Electric Corp | Low cyanide* high speed electroosilver plating solution |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636130A (en) * | 2018-05-29 | 2018-10-12 | 浙江师范大学 | Polymer-metal composite separating film preparation method and application |
| JP7037023B1 (en) * | 2021-07-22 | 2022-03-16 | 生態環境部華南環境科学研究所 | Copper Pyrophosphate Plating How to Recycle Copper and Phosphorus Resources in Wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH026840B2 (en) | 1990-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3764503A (en) | Electrodialysis regeneration of metal containing acid solutions | |
| KR100207041B1 (en) | Method of recovering antimony and bismuth from copper electrolyte | |
| US5804057A (en) | Method of removing metal salts from solution by electrolysis an electrode closely associated with an ion exchange resin | |
| JPH06256999A (en) | Method for recovering and regenerating tin plating liquid | |
| US3406108A (en) | Regeneration of spent ammonium persulfate etching solutions | |
| CN104651880B (en) | The method that a kind of decopper(ing) point cyanogen simultaneous PROCESS FOR TREATMENT silver smelts the lean solution containing cyanogen | |
| JPS6116000A (en) | Method for regenerating spent silver plating solution | |
| JPH0780253A (en) | Electrodialytic purifying method | |
| WO2007115530A1 (en) | Electrodeionization method for treating washwaters resulting from the chemical and/or electrochemical surface treatment of metals | |
| JPH1018073A (en) | Electrolysis with addition of ultrasonic vibration | |
| JPS6254875B2 (en) | ||
| JP6703661B2 (en) | Method and apparatus for producing copper ion-containing aqueous solution | |
| JPH06346299A (en) | Method for recovering and reproducing tin plating solution | |
| JPH0824586A (en) | Method for electrodialysis-treating nitric acid and hydrofluoric acid washing waste liquid and device therefor | |
| GB2385061A (en) | Process water treatment using electrodialysis | |
| JPS6018760B2 (en) | Electrolytic recovery method of metallic zinc from acid solution containing zinc and iron generated from a metallic galvanizing factory | |
| JPH08966A (en) | Purification by electrodialysis | |
| CN113912225B (en) | Method for treating and recycling wastewater containing copper coke | |
| JP2965457B2 (en) | Regeneration method of iron chloride waste liquid containing nickel | |
| JPH1121689A (en) | Production of high-purity silver | |
| JPS588306B2 (en) | Metal salt waste liquid purification equipment | |
| JP3653944B2 (en) | Method for selective recovery of Sb and Bi from copper electrolyte | |
| SU1585357A1 (en) | Method of purifying flushing water of electroplating shops from ions of heavy and nonferrous metals | |
| JPS6160148B2 (en) | ||
| JPH06146098A (en) | Method for recovering and reproducing sn plating liquid |