JPS6312150B2 - - Google Patents
Info
- Publication number
- JPS6312150B2 JPS6312150B2 JP19658884A JP19658884A JPS6312150B2 JP S6312150 B2 JPS6312150 B2 JP S6312150B2 JP 19658884 A JP19658884 A JP 19658884A JP 19658884 A JP19658884 A JP 19658884A JP S6312150 B2 JPS6312150 B2 JP S6312150B2
- Authority
- JP
- Japan
- Prior art keywords
- anode
- electrolysis
- cathode
- container
- electrolytic
- 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.)
- Expired
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
- Electroplating Methods And Accessories (AREA)
- Electrolytic Production Of Metals (AREA)
Description
【発明の詳細な説明】
技術分野
Sn，Pbの精錬工程におけるこれらの金属の電
解精製やSnメツキやハンダメツキおよびスクラ
ツプからのSnおよびPbを回収する際のSn，Pbハ
ンダ材などの電解法に関する。[Detailed Description of the Invention] Technical Field The present invention relates to electrolytic refining of these metals in the refining process of Sn and Pb, and electrolytic methods for Sn and Pb solder materials when recovering Sn and Pb from Sn plating, solder plating, and scrap.
従来技術
Sn，Pbの電解精製や回収はメツキ用硼弗酸や
珪弗酸を電解液とし、Sn，Pb、ハンダなどの鋳
造板をアノードとして行われている。Prior Art Electrolytic refining and recovery of Sn and Pb is carried out using borofluoric acid or silicic acid for plating as an electrolyte and a cast plate of Sn, Pb, solder, etc. as an anode.
発明の背景
従来法ではアノードを完全に電解溶出させるこ
とは不可能で必ず残分を生ずる。これを回収する
ためには電解を止めて取出し作業が必要であり、
かつ回収した残分の再鋳造作業が必要となる。BACKGROUND OF THE INVENTION In conventional methods, it is impossible to completely electrolytically elute the anode and a residue always remains. In order to recover this, it is necessary to stop the electrolysis and take it out.
In addition, it is necessary to recast the recovered residue.
このような不便は、例えば銅メツキの場合には
ステンレス鋼またはチタンの篭に銅ボールを保持
させ、これをアノードとすることにより、残分の
発生をなくし、かつ銅ボールの追加により長時間
の電解も可能にする等の改良がなされ解決されて
いる（特公昭53―47215号）。しかしSn，Pb電解
のように硼弗酸、珪弗酸浴を使う場合、アノード
篭として使える材料がなかつた。チタンやステン
レス鋼も腐食して寿命が短い。プラスチツクを使
つても通電のためのリード線部分の消耗は避けら
れない。 For example, in the case of copper plating, holding the copper ball in a stainless steel or titanium cage and using this as an anode eliminates the generation of residue, and the addition of copper balls reduces the time required for a long time. Improvements such as making electrolysis possible were made and the problem was solved (Special Publication No. 47215-1973). However, when using a borofluoric acid or silifluoric acid bath, such as in Sn and Pb electrolysis, there was no material that could be used as an anode cage. Titanium and stainless steel also corrode and have a short lifespan. Even if plastic is used, wear and tear on the lead wires for conducting electricity cannot be avoided.
炭素繊維製の篭が前記の酸溶液中でまつたく腐
食を受けず、しかも高い導電性と強い機械強度を
有することを見い出し、Sn，Pb，ハンダでも、
小塊つぎたし電解が可能なことを確認した。 It was discovered that carbon fiber baskets were not easily corroded in the acid solution mentioned above, and had high electrical conductivity and strong mechanical strength.
It was confirmed that electrolysis could be performed by splicing small lumps.
発明の構成
本発明によればSnまたはPbまたはSn，Pbを含
む合金をアノードとし、前記金属のイオンの珪弗
酸または硼弗酸溶液を電解液として、精製または
メツキを行なう電気分解法において、前記の金属
の小塊を炭素繊維製の容器に保持してアノードを
形成させ電解することを特徴とする電気分解法が
提供される。Structure of the Invention According to the present invention, in an electrolysis method in which refining or plating is carried out using Sn or Pb or an alloy containing Sn, Pb as an anode and a silicic acid or borofluoric acid solution of metal ions as an electrolyte, There is provided an electrolysis method characterized in that the aforementioned small lump of metal is held in a container made of carbon fiber to form an anode and electrolyzed.
発明の効果利点
本発明の方法はSn，Pbの電解精製やハンダメ
ツキに利用できる。Effects and Advantages of the Invention The method of the present invention can be used for electrolytic refining of Sn and Pb and solder polishing.
本発明の方法は次の利点を有する。 The method of the invention has the following advantages.
(1) Sn，Pbで継ぎ足し電解が可能となり長時間
連続化が実現した。(1) Replenishment electrolysis with Sn and Pb has become possible, allowing continuous operation over long periods of time.
(2) アノードの鋳造が不要となり、どんな形状の
ものも使える。(2) There is no need to cast anodes, and any shape can be used.
(3) アノード残分の発生がなく再生工程が不要で
ある。(3) There is no generation of anode residue and no regeneration process is required.
実施態様
実施例 １
市販のカーボンフアイバー製織布（東邦レーヨ
ン高強度ベスフアイトHTA）を所定形状に裁断
し、同質のカーボンフアイバー糸を用いて縫製し
10cm×10cm×10cmの上部が開放の升状容器を作製
した。この容器は自由に液体を通過させる程度の
目の粗い間隙をもつた容器であつた。第１図に示
すようにこの容器１をPVC樹脂製の保持架台２
（保持架台側面には20mmの穴が多数うがつてある）
に保持させ、容器１中に組成がSn60％，Pn40％
のハンダ塊３（約0.5cm角）20Kgを充填してアノ
ードとし、カソード側には通常の銅製保持具８に
10cm×10cm角の鉄板を保持させた（銅は液にひた
されない）。下記の組成の電解液を用い液温を30
℃に調節しつつカソード電流密度2.0A／ｄm2で
電解を行なつた。被メツキ物（カソード鉄板）は
４分毎に新規なものと交換し、８時間連続通電し
て電解を行ない、この間２時間毎にアノード側容
器中に前記の原料ハンダ塊15ｇを補充した。すな
わち原料ハンダの合計投入量は65Kgである。（但
し実際に溶解したハンダは46Kgであつた）この結
果表面に組成がSn60％，Pb40％で、厚さ40μmの
良好なメツキ層を有する鉄板120枚が得られ、し
かも電解初期の電着物と８時間後の電着物の間に
は何らの差異も認められないことが確認され、安
定した長時間の連続電解が行われたことが明らか
になつた。Embodiment Example 1 A commercially available carbon fiber woven fabric (Toho Rayon High Strength Besuphite HTA) was cut into a predetermined shape and sewn using carbon fiber thread of the same quality.
A square-shaped container measuring 10 cm x 10 cm x 10 cm with an open top was prepared. This container had a gap that was wide enough to allow the liquid to pass through freely. As shown in Figure 1, this container 1 is placed on a PVC resin holding stand 2.
(There are many 20mm holes on the side of the holding frame.)
The composition is 60% Sn and 40% Pn in container 1.
20 kg of solder mass 3 (approximately 0.5 cm square) is filled to form an anode, and a normal copper holder 8 is attached to the cathode side.
A 10cm x 10cm square iron plate was held (copper cannot be immersed in liquid). Use an electrolytic solution with the following composition and set the solution temperature to 30
Electrolysis was carried out at a cathode current density of 2.0 A/dm 2 while adjusting the temperature to . The object to be plated (cathode iron plate) was replaced with a new one every 4 minutes, and electricity was continuously applied for 8 hours to perform electrolysis. During this period, 15 g of the raw material solder mass was replenished into the anode side container every 2 hours. In other words, the total input amount of raw material solder is 65 kg. (However, the actual melted solder was 46 kg) As a result, 120 iron plates with a composition of 60% Sn and 40% Pb and a good plating layer with a thickness of 40 μm on the surface were obtained. It was confirmed that no difference was observed between the electrodeposits after 8 hours, and it became clear that stable continuous electrolysis had been carried out over a long period of time.
実解液組成
硼弗化錫 （Sn（BF4）2）
60ｇ／（Snとして）
硼弗化鉛 （Pb（BF4）2）
25ｇ／（Pbとして）
遊離硼弗化水素酸（Ｆ・HBF4）
100ｇ／
遊離硼酸 （Ｆ・H3BO3）
25ｇ／
にかわ ５ｇ／
実施例 ２
第２図の装置を用いて粗錫（品位98％）の電解
精製を行なつた。第２図の装置は実質的に第１図
の装置と同じであるがカソードには絶縁性樹脂板
上に10cm×10cmのステンレススチール電着板を帖
付したものを用い、その４枚を第２図に示すよう
にアノード保持架台の各側面に対面するように配
置した。下記の組成の電解液を用い、液温を30℃
に調節してカソード電流密度2A／ｄm2で約45時
間連続電解を行なつた。この間約15時間毎にカソ
ード板を新規なものと交換し、アノード側には
400ｇの粗錫塊を補給した。Actual solution composition: Tin fluoride (Sn( BF4 ) 2 )
60g/(as Sn) Lead borofluoride (Pb( BF4 ) 2 )
25g/(as Pb) Free borohydrofluoric acid (F・HBF 4 )
100g/free boric acid (F・H 3 BO 3 )
25g/glue 5g/Example 2 Crude tin (grade 98%) was electrolytically refined using the apparatus shown in FIG. The apparatus shown in Figure 2 is substantially the same as the apparatus shown in Figure 1, but the cathode is made of a 10 cm x 10 cm stainless steel electrodeposited plate attached to an insulating resin plate, and the four sheets are attached to the cathode. As shown in Figure 2, they were arranged so as to face each side of the anode holding frame. Use an electrolytic solution with the following composition, and keep the solution temperature at 30℃.
Continuous electrolysis was carried out for about 45 hours at a cathode current density of 2 A/dm 2 . During this period, the cathode plate was replaced with a new one approximately every 15 hours, and the anode side
400g of crude tin ingot was supplied.
この結果、カソード板上に厚さ約10mmの平滑な
電着面を有する錫が、カソード一枚当り平均66ｇ
得られた。この錫の品位を検定したところ純度約
99.96％の精製された電気錫であることがわかつ
た。またこの品位は電解の初期から終期までほぼ
一定であつた。 As a result, an average of 66g of tin, which has a smooth electrodeposited surface approximately 10mm thick, is deposited on each cathode plate.
Obtained. When the quality of this tin was tested, the purity was approx.
It was found to be 99.96% refined electrolytic tin. Moreover, this quality remained almost constant from the beginning to the end of electrolysis.
電解液組成
硼弗化錫 （Sn（BF4）2）
80ｇ／（Snとして）
遊離硼弗化水素酸（Ｆ・HBF4）
100ｇ／
遊離硼酸 （Ｆ・H3BO3）
25ｇ／
にかわ ８ｇ／
βナフトール １ｇ／
電解終了後アノード容器中には粗錫87ｇスライ
ム32ｇが残留していたスライムの組成は錫14％、
銀37％、銅10％他であつた。この実験からアノー
ド残分の発生なしに長時間の電解精製が可能なこ
とがわかつた。Electrolyte composition: Tin fluoride (Sn( BF4 ) 2 )
80g/(as Sn) Free borohydrofluoric acid (F・HBF 4 )
100g/free boric acid (F・H 3 BO 3 )
25g / Glue 8g / β-naphthol 1g / After electrolysis, 87g of crude tin and 32g of slime remained in the anode container.The composition of the slime was 14% tin,
It was composed of 37% silver and 10% copper. This experiment revealed that long-term electrolytic refining is possible without generating anode residue.
実施例 ３
市販のカーボンフアイバー製織布（東邦レーヨ
ン高強度ベスフアイトHTA）を所定形状に裁断
し、同質のカーボンフアイバー糸を用いて縫製し
12cm×12cm×２cm厚の上部が開放の升状容器１を
作製した。この容器を第３図に示すようにPVC
製の保持架台２に保持させ、該アノード容器中に
10cm×10cm×１cmの板状に鋳造した粗鉛板（品位
98％）５を入れ、10cm×10cm×２mm厚の電気鉛板
を絶縁性樹脂板に帖付したものをカソードとして
第３図に示すように配置し、下記組成の電解液を
用い、液温を35℃にコントロールしつつカソード
電流密度1A／ｄm2で約２日間連続電解を行なつ
た。この間、約５時間毎にカソード板を新規なも
のに交換し、アノード側にも新規な粗鉛板を補給
した。Example 3 A commercially available carbon fiber woven fabric (Toho Rayon High Strength Besuphite HTA) was cut into a predetermined shape and sewn using carbon fiber thread of the same quality.
A square-shaped container 1 with an open top and 12 cm x 12 cm x 2 cm thick was prepared. This container is made of PVC as shown in Figure 3.
The anode container is held on a holding frame 2 made of
Crude lead plate cast into a 10cm x 10cm x 1cm plate (quality
A 10cm x 10cm x 2mm thick electrolytic lead plate attached to an insulating resin plate was placed as a cathode as shown in Figure 3, and an electrolytic solution with the following composition was used. Continuous electrolysis was carried out for about 2 days at a cathode current density of 1 A/dm 2 while controlling the temperature at 35°C. During this period, the cathode plate was replaced with a new one approximately every 5 hours, and a new crude lead plate was also supplied to the anode side.
この結果カソードの片面当り約２mm厚の平滑な
電着面を有する鉛が得られた。この鉛の品位は純
度99.97％の精製された電気鉛であることがわか
つた。また電解中アノード容器に保持された粗鉛
板は、全面一様に溶解して薄くなり完全に溶解す
るため残分の発生が皆無で新規アノードの補充も
きわめて簡単なのでPbの電解精製がきわめて容
易に長時間連続して行なえるようになつた。 As a result, lead having a smooth electrodeposited surface with a thickness of approximately 2 mm was obtained on each side of the cathode. The quality of this lead was found to be refined electrolytic lead with a purity of 99.97%. In addition, the crude lead plate held in the anode container during electrolysis melts uniformly over the entire surface, becomes thinner, and completely dissolves, so there is no residue and it is extremely easy to replenish new anodes, making electrolytic refining of Pb extremely easy. I was able to do this continuously for a long time.
電解液組成
珪弗化鉛 PbSiF6 65ｇ／（Pbとして）
遊離珪弗化水素酸Ｆ・H2SiF6
103ｇ／
にかわ 0.5ｇ／Electrolyte composition Lead silicofluoride PbSiF 6 65g/(as Pb) Free hydrosilicofluoride F・H 2 SiF 6
103g/ glue 0.5g/
第１図は本発明方法を実施するために使用する
装置の１例の概念図である。第２図は本発明方法
を実施するために使用する装置の別の態様の概念
図である。第３図は本発明方法を実施するために
使用する装置の別の態様の概念図である。
１：炭素繊維製アノード容器、２：樹脂製架
台、３：原料金属または合金、４：電解槽、５：
カソード、６：電解液、７：整流器。
FIG. 1 is a conceptual diagram of an example of an apparatus used to carry out the method of the present invention. FIG. 2 is a conceptual diagram of another embodiment of the apparatus used to carry out the method of the invention. FIG. 3 is a conceptual diagram of another embodiment of the apparatus used to carry out the method of the invention. 1: Carbon fiber anode container, 2: Resin frame, 3: Raw metal or alloy, 4: Electrolytic cell, 5:
Cathode, 6: Electrolyte, 7: Rectifier.
Claims (1)
ードとし、前記金属のイオンの珪弗酸または硼弗
酸溶液を電解液として、精製またはメツキを行な
う電気分解法において、前記の金属の小塊を炭素
繊維製の容器に保持してアノードを形成させ電解
することを特徴とする電気分解法。1. In an electrolysis method in which refining or plating is carried out using Sn or Pb or an alloy containing Sn or Pb as an anode and a silifluoric acid or borofluoric acid solution of ions of the metal as an electrolyte, small lumps of the metal are An electrolysis method characterized by holding in a carbon fiber container to form an anode and electrolyzing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59196588A JPS6176695A (en) | 1984-09-21 | 1984-09-21 | Electrolyzing method of tin, lead or tin-lead containing alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59196588A JPS6176695A (en) | 1984-09-21 | 1984-09-21 | Electrolyzing method of tin, lead or tin-lead containing alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6176695A JPS6176695A (en) | 1986-04-19 |
| JPS6312150B2 true JPS6312150B2 (en) | 1988-03-17 |
Family
ID=16360232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59196588A Granted JPS6176695A (en) | 1984-09-21 | 1984-09-21 | Electrolyzing method of tin, lead or tin-lead containing alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6176695A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4935910B2 (en) * | 2010-01-07 | 2012-05-23 | 大日本印刷株式会社 | Organic thin film solar cell |
| KR101199513B1 (en) * | 2010-10-21 | 2012-11-09 | 한국지질자원연구원 | Valuable metal recovery method from waste solder |
| CN104562084A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Method for preparing electrolytic solution for refining lead bullion |
| CN104562085A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Crude lead electrolytic refining method |
| CN104562093A (en) * | 2014-12-22 | 2015-04-29 | 芜湖金龙模具锻造有限责任公司 | Method for preparing cathode used in refining of lead bullion |
| FR3060610B1 (en) * | 2016-12-19 | 2020-02-07 | Veolia Environnement-VE | ELECTROLYTIC PROCESS FOR EXTRACTING TIN AND / OR LEAD INCLUDED IN A CONDUCTIVE MIXTURE |
| CN109778230B (en) * | 2019-01-22 | 2021-03-12 | 河套学院 | A kind of method for electrolytic separation of lead and copper with high lead matte |
-
1984
- 1984-09-21 JP JP59196588A patent/JPS6176695A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6176695A (en) | 1986-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5024737A (en) | Process for producing a reactive metal-magnesium alloy | |
| US6379512B1 (en) | Combination for electrolytic reduction of alumina | |
| Moskalyk et al. | Anode effects in electrowinning | |
| JPS6312150B2 (en) | ||
| Howie et al. | The electrodeposition of aluminium from molten aluminium chloride/sodium chloride | |
| US1465034A (en) | Process for the electrolytic deposition of copper | |
| US3864227A (en) | Method for the electrolytic refining of copper | |
| US3855089A (en) | Process for the electrolytic refining of heavy metals | |
| EP0058506B1 (en) | Bipolar refining of lead | |
| CN101148773B (en) | Method for producing magnesium-lithium-calcium alloy by fused salt electrolytic ion eutectoid method | |
| US4483752A (en) | Valve metal electrodeposition onto graphite | |
| JPH09316678A (en) | Metal recovery method from spent nickel-cadmium secondary battery | |
| US679824A (en) | Art or process of refining lead by electrolysis. | |
| JP5804920B2 (en) | Electrolytic extraction of metals | |
| RU2361967C1 (en) | Method of compacted nickel electro-extraction | |
| CA1265470A (en) | Manufacture of self supporting members of copper containing phosphorus | |
| JPS63307291A (en) | Manufacturing method of high purity copper | |
| US3002914A (en) | Preparation of electrodes for electrolysis of aqueous solutions by the mercury process | |
| US3389063A (en) | Process for electrolytic recovery and refining of metals | |
| US3251756A (en) | Electrolytic process for making phosphine | |
| JP7042641B2 (en) | Aluminum foil manufacturing method and manufacturing equipment | |
| US2845387A (en) | Method of electrodepositing metals | |
| US3326644A (en) | Electrowinning copper and product thereof | |
| KR100229165B1 (en) | Process for electrodepositing a metallic coating of a nickel-cobalt alloy on an object and electrolytic solution used therein | |
| US2341244A (en) | Electrolytic production of alloys |