JPH0132316B2 - - Google Patents
Info
- Publication number
- JPH0132316B2 JPH0132316B2 JP59147642A JP14764284A JPH0132316B2 JP H0132316 B2 JPH0132316 B2 JP H0132316B2 JP 59147642 A JP59147642 A JP 59147642A JP 14764284 A JP14764284 A JP 14764284A JP H0132316 B2 JPH0132316 B2 JP H0132316B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- lead
- holding container
- phosphor bronze
- concentration
- 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
- Electrolytic Production Of Metals (AREA)
Description
技術分野
本発明は電気伝導材料としてのリン青銅と鉄−
ニツケル合金から、付着しているハンダ材料を除
去して該材料を回収する方法に関する。
従来技術
リン青銅と高ニツケル−鉄−ニツケル合金は電
気接点材料、リードフレーム等の材料として今日
多量に使用されており、ますます増加の傾向にあ
り、多量のスクラツプが出る。これらの材料は、
いわゆる高付加価値合金であるが、ハンダ等の付
着したスクラツプからそのままの形で回収する適
当な方法が知られていない。本発明者らは前記の
スクラツプに含まれる不純物は錫鉛の合金である
ことに着目して、錫鉛めつきの手法を応用してこ
の合金を除去し、リン青銅および鉄−ニツケル合
金を回収する方法を開発した。
発明の構成
本発明によれば、リン青銅または鉄ベースニツ
ケル合金を母材とし、鉛錫合金を不純物として含
む金属スクラツプを電解槽中の保持容器に装入し
て、ケイフツ化浴、またはホウフツ化浴の電解浴
に浸漬し、前記保持容器側を陽極とする一方、電
解槽中の金属板を陰極として電解することにより
不純物を溶出させてリン青銅または鉄ベースニツ
ケル合金の母材を回収する方法であつて、ケイフ
ツ化水素濃度又はホウフツ化水素濃度100〜130
ｇ／、錫イオン濃度30〜50ｇ／、鉛濃度20〜
50ｇ／の電解浴を用い、錫鉛合金のめつき時よ
り僅かに長い電解時間または僅かに高い電流密度
の条件下で、上記スクラツプ母材のリン青銅また
は鉄−ニツケル合金が僅かに溶出するように電解
することを特徴とする有価金属回収方法が提供さ
れる。
本発明の好適な実施態様においては、陽極の母
材回収と同時に陰極における不純物の析出回収が
なされる。
本発明の実施装置としては、一般に錫鉛合金め
つきに用いられる装置おいて、その電気的接続を
変換したものを利用することができる。
保持容器は導電性材料でできたかご状のもので
あり、従来錫鉛合金めつきにおいて陰極として使
用されていたものと同様のものである。
回収された原料スクラツプは大小さまざまの大
きさのものが含まれているので、実際にはおおよ
そ一定の大きさに揃えるために、切断処理するこ
とが好ましい。
また多くのスクラツプは成形工程で潤滑油など
が付着しているので、これを除去するためアルカ
リ洗浄等の脱脂処理を施すことが好ましい。電解
は40℃程度の液温で、0.5〜1.0A／ｄm2の電流密
度で実施する。
本発明においては、錫鉛合金のめつき時より僅
かに長い電解時間または僅かに高い電流密度の条
件下で電解を行ない付着している錫鉛合金の量を
推定して、それが全部溶出するだけでなく、スク
ラツプの基材、即ち、リン青銅または鉄−ニツケ
ル合金を多少溶出させることにより、錫鉛不純物
を確実に除去し、錫鉛不純物の入らない高品位の
スクラツプを回収する。また同時に錫鉛合金を陰
極金属板上に析出させて回収する。またこのた
め、通常の電解浴組成とは異なる次の組成の電解
浴を用いる。
ケイフツ化水素濃度 100〜130ｇ／
ホウフツ化水素濃度 〃
錫イオン濃度 30〜50ｇ／
鉛濃度 20〜50ｇ／
電解操作終了後、保持容器を浴から上げて洗浄
し、融解鋳造する。
尚、SnPbまたはそれらの合金を陰極板上にス
ポンジ状または針状を呈することなく平滑なシー
ト状に析出させるためには、従来のこれらの金属
の電解法において用いられる、にかわ、ゼラチ
ン、βナフトールなどの添加剤がすべて有効に使
用できる。
実施態様
以下本発明の実施例を示す。
参考例
第１図および第２図に示す装置を用いて本発明
を実施した。同図において、１は電解槽であり、
電解槽１の内部にかご状保持容器２が収納されて
いる。３は架台、４は保持容器の支持棒であり、
１０は回転用のモータである。保持容器２は導電
性材料でできた回転するかご状の容器であり、水
平方向に置かれた回転軸に相当する固定軸５には
垂直に下方に向つて通電棒６が設けられている。
かご状保持容器２には蓋７が設けられ、処理すべ
きスクラツプを出し入れできる。保持容器２は駆
動モータ１０に連動するチエーン１１によつて回
転される。一方、保持容器２の両側には金属板８
が配設されている。本装置構成においては上記保
持容器２側を陽極とし、該金属板８側を陰極とす
る点が従来のめつき用装置構成と異なる。即ち、
保持容器２を支持する支持棒４の上部にはコネク
タ９が設けられ、該コネクタ９を介して外部電源
の陽極に接続される。これにより保持容器２に外
部電源から通電すると、保持容器２に入れられた
スクラツプは容器自身および前記通電棒６との接
触によつて、それ自身が陽極として作用する状態
になる。
尚、保持容器２および陰極板８の材質はいずれ
もステンレス鋼（SUS 304）であり、また保持
容器２の陰極板８に相対する面は20メツシユの金
網である。この保持容器２即ちバレル状の陽極篭
にハンダメツキが付着したリン青銅300ｇを充填
し、電解液として下記の組成の珪弗化水素酸溶液
を用い40℃に温度調節してバレルを回転しながら
1A、12時間の通電終了後、陽極篭とカソー
電解液組成
H2SiF6 128ｇ／
Sn（） 72.6ｇ／
Pb（） 23.1ｇ／
にかわ １ｇ／
βナフトール 0.5ｇ／
ド板を引き上げ、陽極篭中から取り出した回収リ
ン青銅とカソード板から剥離した回収ハンダを洗
浄乾燥して各回収物質の量と品位を求めたところ
表１に示す結果が得られた。尚カソード板上には
平滑でかつ緻密なシート状のハンダが得られた。
またこの電流効率は約95％であつた。
Technical field The present invention relates to phosphor bronze and iron as electrically conductive materials.
The present invention relates to a method for removing adhering solder material from a nickel alloy and recovering the material. BACKGROUND OF THE INVENTION Phosphor bronze and high nickel-iron-nickel alloys are used in large quantities today as materials for electrical contacts, lead frames, etc., and the number of such materials is increasing, resulting in a large amount of scrap. These materials are
Although it is a so-called high value-added alloy, there is no known suitable method for recovering it as it is from scrap to which solder and the like have adhered. The present inventors focused on the fact that the impurity contained in the scrap was a tin-lead alloy, and applied a tin-lead plating method to remove this alloy and recover phosphor bronze and iron-nickel alloy. developed a method. Structure of the Invention According to the present invention, metal scrap containing phosphor bronze or iron-based nickel alloy as a base material and containing lead-tin alloy as an impurity is charged into a holding container in an electrolytic bath, and is then processed into a silting bath or a housting bath. A method of recovering the base material of phosphor bronze or iron-based nickel alloy by immersing it in an electrolytic bath, using the holding container side as an anode, and electrolyzing the metal plate in the electrolytic bath as a cathode, thereby eluting impurities. and the hydrogen silicate concentration or hydrogen borofluoride concentration is 100 to 130
g/, tin ion concentration 30~50g/, lead concentration 20~
Using an electrolytic bath of 50 g/mt, under conditions of a slightly longer electrolytic time or a slightly higher current density than when plating tin-lead alloys, the phosphor bronze or iron-nickel alloy of the scrap base material is slightly eluted. Provided is a method for recovering valuable metals characterized by electrolyzing the metals. In a preferred embodiment of the present invention, impurities are precipitated and recovered from the cathode at the same time as the anode base material is recovered. As an apparatus for carrying out the present invention, it is possible to use an apparatus generally used for tin-lead alloy plating, whose electrical connections have been converted. The holding container is a cage-shaped container made of a conductive material, similar to that used as a cathode in conventional tin-lead alloy plating. Since the recovered raw material scraps include scraps of various sizes, it is actually preferable to cut them into roughly uniform sizes. Further, since many scraps have lubricating oil and the like attached to them during the molding process, it is preferable to perform degreasing treatment such as alkaline cleaning to remove this. Electrolysis is carried out at a liquid temperature of about 40° C. and a current density of 0.5 to 1.0 A/dm 2 . In the present invention, electrolysis is performed under conditions of slightly longer electrolysis time or slightly higher current density than when tin-lead alloy is plated, and the amount of attached tin-lead alloy is estimated and all of it is eluted. In addition, the base material of the scrap, ie, phosphor bronze or iron-nickel alloy, is slightly eluted to ensure the removal of tin-lead impurities and to recover high-quality scrap free of tin-lead impurities. At the same time, tin-lead alloy is deposited on the cathode metal plate and recovered. Further, for this purpose, an electrolytic bath having the following composition different from the usual electrolytic bath composition is used. Hydrogen silicide concentration: 100 to 130 g / Hydrogen borofluoride concentration: Tin ion concentration: 30 to 50 g / Lead concentration: 20 to 50 g / After the electrolytic operation is completed, the holding container is lifted from the bath, washed, and melted and cast. In order to deposit SnPb or its alloys on the cathode plate in the form of a smooth sheet without forming a spongy or acicular shape, glue, gelatin, and β-naphthol, which are used in conventional electrolytic methods for these metals, must be used. All additives such as can be used effectively. Embodiments Examples of the present invention will be shown below. Reference Example The present invention was carried out using the apparatus shown in FIGS. 1 and 2. In the figure, 1 is an electrolytic cell;
A cage-shaped holding container 2 is housed inside the electrolytic cell 1 . 3 is a pedestal, 4 is a support rod for the holding container,
10 is a rotation motor. The holding container 2 is a rotating cage-shaped container made of a conductive material, and a current-carrying rod 6 is provided vertically downward on a fixed shaft 5 corresponding to a rotating shaft placed in a horizontal direction.
The basket-shaped holding container 2 is provided with a lid 7, through which scraps to be processed can be taken in and taken out. The holding container 2 is rotated by a chain 11 that is linked to a drive motor 10. On the other hand, metal plates 8 are provided on both sides of the holding container 2.
is installed. This apparatus configuration differs from the conventional plating apparatus configuration in that the holding container 2 side is used as an anode and the metal plate 8 side is used as a cathode. That is,
A connector 9 is provided on the upper part of the support rod 4 that supports the holding container 2, and is connected to the anode of an external power source via the connector 9. As a result, when the holding container 2 is energized from an external power source, the scrap contained in the holding container 2 comes into contact with the container itself and the current-carrying rod 6, thereby acting as an anode. The holding container 2 and the cathode plate 8 are both made of stainless steel (SUS 304), and the surface of the holding container 2 facing the cathode plate 8 is made of 20-mesh wire mesh. This holding container 2, that is, the barrel-shaped anode cage, was filled with 300 g of phosphor bronze with solder plating attached, and the temperature was adjusted to 40°C using a hydrosilicofluoric acid solution with the composition shown below as the electrolyte, and the barrel was rotated.
After 1A and 12 hours of electricity, the anode cage and catholyte composition H 2 SiF 6 128g / Sn () 72.6g / Pb () 23.1g / Glue 1g / β-naphthol 0.5g / The plate was pulled up and placed in the anode cage. The recovered phosphor bronze taken out from the cathode plate and the recovered solder peeled off from the cathode plate were washed and dried, and the amount and quality of each recovered substance were determined, and the results shown in Table 1 were obtained. A smooth and dense sheet-like solder was obtained on the cathode plate.
Moreover, this current efficiency was about 95%.
【表】
表１に示すように97.9％＋2.1％＝100％の純度
のリン青銅が高い回収率で回収され、同時にスク
ラツプに付着していたPbの全量とSnの大部分が
後処理の容易な平滑なシート状で回収された。
実施例
バレル状陽極篭をPVCで作製した以外は参考
例と同様の装置を用いて以下の回収を行つた。
陽極篭にハンダ付着のジユメツト線（42％Ni、
残りFe）の500ｇを投入し、グラフアイト電極で
通電を保ちつつ電解液として下記の組成のホウフ
ツ化水素酸を用い、40℃に温度調節して1A、9.5
時間の電解を行なつた。
電解液組成
HBF4：100ｇ／
Sn（）：45ｇ／
Pb（）：40ｇ／
にかわ：0.5ｇ／
通電終了後参考例と同様にして物質収支を求め
た。結果を表２に示した。電流効率は約94％であ
つた。[Table] As shown in Table 1, phosphor bronze with a purity of 97.9% + 2.1% = 100% was recovered with a high recovery rate, and at the same time, the entire amount of Pb and most of the Sn attached to the scrap were removed by the post-treatment. It was easily recovered in the form of a smooth sheet. Example The following collection was carried out using the same equipment as in the reference example except that the barrel-shaped anode cage was made of PVC. A composite wire (42% Ni,
Add 500 g of the remaining Fe), keep the current flowing through the graphite electrode, use hydroborofluoric acid with the composition shown below as the electrolytic solution, adjust the temperature to 40°C, and heat at 1 A, 9.5
Electrolyzed time. Electrolyte composition HBF 4 : 100g/Sn(): 45g/Pb(): 40g/Glue: 0.5g/After energization, the material balance was determined in the same manner as in the reference example. The results are shown in Table 2. The current efficiency was about 94%.
【表】
表２に示すように本実施例において、100％純
度のジユメツト線が高い回収率で回収され、かつ
不純物として含まれるハンダもシート状で回収さ
れた。
以上説明したように本発明の回収方法によれ
ば、従来適当な回収処理方法が無いため乾式製錬
工程に送られ、各成分金属の単体に戻されていた
リン青銅や鉄ベースニツケル合金を合金組成のま
ま高純度でかつ高い回収率にて回収することがで
き、しかも不純物である錫鉛合金をも同時に回収
できる。[Table] As shown in Table 2, in this example, a 100% pure composite wire was recovered at a high recovery rate, and the solder contained as an impurity was also recovered in the form of a sheet. As explained above, according to the recovery method of the present invention, phosphor bronze and iron-based nickel alloys, which were conventionally sent to a pyrometallurgical process and returned to individual component metals due to the lack of an appropriate recovery treatment method, can be alloyed. The composition can be recovered with high purity and high recovery rate, and the impurity tin-lead alloy can also be recovered at the same time.
第１図および第２図は本発明の実施装置を示す
概略図であり、第１図はその部分切欠正面図、第
２図はその部分切欠側面図である。
図中、１……電解槽、２……保持容器、８……
金属板である。
1 and 2 are schematic diagrams showing an apparatus for implementing the present invention, with FIG. 1 being a partially cutaway front view thereof, and FIG. 2 being a partially cutaway side view thereof. In the figure, 1...electrolytic cell, 2...holding container, 8...
It is a metal plate.
Claims (1)
とし、鉛錫合金を不純物として含む金属スクラツ
プを電解槽中の保持容器に装入して、ケイフツ化
浴、またはホウフツ化浴の電解浴に浸漬し、前記
保持容器側を陽極とする一方、電解槽中の金属板
を陰極として電解することにより不純物を溶出さ
せてリン青銅または鉄ベースニツケル合金の母材
を回収する方法であつて、ケイフツ化水素濃度又
はホウフツ化水素濃度100〜130ｇ／、錫イオン
濃度30〜50ｇ／、鉛濃度20〜50ｇ／の電解浴
を用い、錫鉛合金のめつき時より僅かに長い電解
時間または僅かに高い電流密度の条件下で、上記
スクラツプ母材のリン青銅または鉄−ニツケル合
金が僅かに溶出するように電解することを特徴と
する有価金属回収方法。1. A metal scrap having a base material of phosphor bronze or iron-based nickel alloy and containing a lead-tin alloy as an impurity is placed in a holding container in an electrolytic bath, and immersed in an electrolytic bath of a silicidation bath or a boufization bath, A method for recovering a base material of phosphor bronze or iron-based nickel alloy by eluting impurities by electrolyzing the holding container side as an anode and a metal plate in an electrolytic tank as a cathode, the method comprising: reducing hydrogen silicate concentration; Alternatively, using an electrolytic bath with a hydrogen borofluoride concentration of 100 to 130 g/, a tin ion concentration of 30 to 50 g/, and a lead concentration of 20 to 50 g/, the electrolysis time is slightly longer or the current density is slightly higher than when plating tin-lead alloys. A method for recovering valuable metals, characterized in that electrolysis is carried out under such conditions that the phosphor bronze or iron-nickel alloy of the scrap base material is slightly eluted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59147642A JPS6126800A (en) | 1984-07-18 | 1984-07-18 | Method for recovering valuable metal from metal scrap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59147642A JPS6126800A (en) | 1984-07-18 | 1984-07-18 | Method for recovering valuable metal from metal scrap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6126800A JPS6126800A (en) | 1986-02-06 |
| JPH0132316B2 true JPH0132316B2 (en) | 1989-06-30 |
Family
ID=15434949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59147642A Granted JPS6126800A (en) | 1984-07-18 | 1984-07-18 | Method for recovering valuable metal from metal scrap |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6126800A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06272098A (en) * | 1993-03-19 | 1994-09-27 | Ebara Yuujiraito Kk | Electrolytic peeling solution and peeling method of coating film made of tin or tin alloy |
| JP7780702B2 (en) * | 2020-05-22 | 2025-12-05 | 日本製鉄株式会社 | Ni-based alloy seamless pipes and welded joints |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA988879A (en) * | 1972-11-06 | 1976-05-11 | Cominco Ltd. | Electrolytic lead refining |
| US4056450A (en) * | 1975-06-30 | 1977-11-01 | M & T Chemicals Inc. | Continuous detinning system |
-
1984
- 1984-07-18 JP JP59147642A patent/JPS6126800A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6126800A (en) | 1986-02-06 |
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