JPH089790B2 - Copper electrolytic refining method - Google Patents
Copper electrolytic refining methodInfo
- Publication number
- JPH089790B2 JPH089790B2 JP62170266A JP17026687A JPH089790B2 JP H089790 B2 JPH089790 B2 JP H089790B2 JP 62170266 A JP62170266 A JP 62170266A JP 17026687 A JP17026687 A JP 17026687A JP H089790 B2 JPH089790 B2 JP H089790B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrolytic refining
- refining method
- electrolytic
- purity
- 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 - Fee Related
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
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は銅の電解精製法に関し、特に硫酸銅と硝酸銅
を主成分とする水溶液を電解液にすることによって電析
物への不純物の混入を防止するようにした銅の電解精製
法に関する。TECHNICAL FIELD The present invention relates to an electrolytic refining method for copper, and in particular, by using an aqueous solution containing copper sulfate and copper nitrate as main components as an electrolytic solution, impurities in electrodeposits can be reduced. The present invention relates to a method for electrolytically refining copper so as to prevent contamination.
従来の銅の電解精製法として、電解浴に硫酸銅と硫酸
を主成分とする硫酸銅浴を使用する方法がある。この方
法は安価で管理し易く、比較的良質の電析物が得られ
る。電解条件を制御することにより現在99.999％の純度
の銅が得られている。電解精製後の帯溶精製の回数を増
加すると電析Cu中に吸蔵される硫黄の量を減少させるこ
とができる。As a conventional electrolytic refining method of copper, there is a method of using copper sulfate and a copper sulfate bath containing sulfuric acid as a main component in an electrolytic bath. This method is inexpensive and easy to manage, and relatively high quality electrodeposits can be obtained. By controlling the electrolysis conditions, copper with a purity of 99.999% is currently obtained. The amount of sulfur occluded in the electrodeposited Cu can be decreased by increasing the number of zonal refining after electrolytic refining.
一方、近年、先端技術の分野の拡大に伴い、超高純度
の銅材の需要が増加しており、99.999％以上の純度の銅
材の経済的製法の確立が急務となっている。銅純度の指
標として残留抵抗比RRR（＝室温での比抵抗/4.2゜Kでの
比抵抗）が用いられるが、99.9999％以上の純度を得る
ためにはRRR値を少なくとも7000以上にする必要があ
る。On the other hand, in recent years, with the expansion of the field of advanced technology, the demand for ultra-high purity copper materials has increased, and there is an urgent need to establish an economical manufacturing method for copper materials with a purity of 99.999% or more. The residual resistance ratio RRR (= resistivity at room temperature / resistivity at 4.2 ° K) is used as an index of copper purity, but in order to obtain a purity of 99.9999% or higher, the RRR value must be at least 7000 or higher. is there.
しかし、従来の硫酸銅浴を使用した銅の電解精製方法
では、硫酸イオン（SO4 --）による電析Cu中へのＳの混
入のため、上記の純度を実現することは極めて困難であ
る。そのうえ、帯溶精製によるＳの排除にも限界があ
り、電析Cu中のＳの量が一定水準よりも多いと、帯溶精
製の回数を増加させても一定値以下に減少させることは
困難であるばかりか、工数増による製造コストの上昇を
招くという不都合がある。However, in the electrolytic refining process of copper using a conventional copper sulfate bath, sulfate ion (SO 4 -) for the incorporation of S into electrodeposition Cu by, it is extremely difficult to realize the purity of the . In addition, there is a limit to the removal of S by zoning refining, and if the amount of S in electrodeposited Cu exceeds a certain level, it is difficult to reduce it to below a certain value even if the number of times of zoning refining is increased. In addition to the above, there is the inconvenience of increasing the manufacturing cost due to the increase in the number of processes.
本発明は上記に鑑みてなされたものであり、工数の増
加による製造コストの上昇を伴わずに電析Cu中のＳの量
を減らして高純度の銅を得る銅の電解精製法を提供す
る。The present invention has been made in view of the above, and provides an electrolytic refining method of copper for obtaining high-purity copper by reducing the amount of S in electrodeposited Cu without increasing the manufacturing cost due to the increase in the number of steps. .
即ち、本発明の銅の電解精製法は硝酸銅と硫酸銅を主
成分とする水溶液を電解液とするものであり、以下の工
程を備えている。That is, the electrolytic refining method for copper of the present invention uses an aqueous solution containing copper nitrate and copper sulfate as main components as an electrolytic solution, and includes the following steps.
（１）電解液を作成する工程 純水中に高純度に精製した硝酸銅結晶（Cu（NO3）２
・3H2O）と硫酸銅結晶（CuSO4・5H2O）を所定のモル比
ｍ（0.23＜ｍ＜150）で溶解させる。モル比ｍが0.23よ
り小さいと電解液中の硫酸イオン（SO4 --）が多くな
り、そのため電析Cu中のＳの量が多くなり銅の純度が低
下する。モル比ｍが150より大きくなると電析Cuが樹枝
状晶になり易く電解後の洗浄が煩雑になり、ひいては銅
の純度の低下を招く。銅イオン濃度から電析Cuの結晶の
形状を見ると、30g/以下では樹枝状晶になり易く、15
0g/以上ではこぶ状になり易い。30g/〜150g/の範
囲では平滑で緻密な結晶が得られる。(1) Process of preparing electrolyte solution Copper nitrate crystal (Cu (NO 3 ) 2 purified to high purity in pure water
・ 3H 2 O) and copper sulfate crystals (CuSO 4 .5H 2 O) are dissolved in a predetermined molar ratio m (0.23 <m <150). Molar ratio m is in 0.23 smaller with the electrolyte sulfuric acid ion (SO 4 -) is increased, therefore the amount of S in the electrodeposition Cu is the purity of many becomes copper decreases. When the molar ratio m is larger than 150, the electrodeposited Cu is likely to become dendrites, which makes cleaning after electrolysis complicated and eventually lowers the purity of copper. Looking at the crystal shape of electrodeposited Cu from the copper ion concentration, dendrites tend to be formed at 30 g / less.
If it is 0 g / g or more, it tends to become a hump. In the range of 30 g / to 150 g /, smooth and dense crystals can be obtained.
（２）電解精製の工程 純度99.996％の無酸素銅を陽極とし、陰極電流密度を
3.4A/dm2、液温を25℃で電解精製を行う。(2) Electrorefining process The oxygen-free copper with 99.996% purity is used as the anode, and the cathode current density is
Perform electrolytic refining at 3.4 A / dm 2 and liquid temperature of 25 ° C.
以下、本発明の銅の電解精製法を詳細に説明する。 Hereinafter, the electrolytic refining method for copper of the present invention will be described in detail.
本発明の実施例は以下の通りである。 Examples of the present invention are as follows.
純水中に予め高純度に精製した硝酸銅結晶（Cu（N
O3）２・3H2O）と硫酸銅結晶（CuSO4・5H2O）を第１表
に示したモル比で溶解した水溶液１を電解液とする。
純度99.996％の無酸素銅を陽極とし、電流密度3.4A/d
m2、液温25℃で電解精製を行い、陰極から精製銅を得
た。電解精製した銅は真空溶解後帯溶精製し、直径10mm
の丸棒とした。この丸棒を伸線して直径0.5mmの線材と
し、550℃で焼鈍後、残留抵抗比RRRを測定した。第１表
は本発明と従来の電解精製法によ る電析Cuの結晶の形状と残留抵抗比RRR値を比較したも
のである。第１表から判るように、モル比ｍが大きくな
るにつれて、電析物はより平滑に、より緻密になるが、
一定値以上になると再び平滑度、緻密度は低下し、形状
は悪くなる。電析物はモル比ｍが大きくなるにつれてRR
R値は増加し、純度が向上することが判る。しかし、モ
ル比ｍがｍ＞150（供試浴No.11のｍ＝1.5/0.01＝150）
では再び減少傾向が著しくなる。硝酸銅を添加すると、
硫酸銅濃度が相対的に減少することによって電析物への
Ｓの混入が減少し、銅の純度が向上する。一方、添加量
が一定値を越えた場合に再度純度の低下がみられるの
は、電析物の析出状態が悪化して樹枝状晶となり易く、
その結果、電解液の捕捉量の増加による汚染が生じたも
のと考えられる。Copper nitrate crystals (Cu (N
O 3) 2 · 3H 2 O ) to the aqueous solution 1 and an electrolytic solution obtained by dissolving in a molar ratio shown copper sulfate crystals (CuSO 4 · 5H 2 O) in Table 1.
Oxygen-free copper with a purity of 99.996% was used as the anode, and current density was 3.4A / d.
Electrolytic refining was performed at m 2 and a liquid temperature of 25 ° C., and purified copper was obtained from the cathode. Electrolytically refined copper is vacuum-melted, then zone-refined and purified, diameter 10 mm
It was a round bar. This round bar was drawn into a wire having a diameter of 0.5 mm, and the residual resistance ratio RRR was measured after annealing at 550 ° C. Table 1 shows the present invention and the conventional electrolytic refining method. 2 is a comparison between the crystal shape of the deposited Cu and the residual resistance ratio RRR value. As can be seen from Table 1, as the molar ratio m increases, the electrodeposit becomes smoother and more dense,
When the value exceeds a certain value, the smoothness and the density are lowered again and the shape is deteriorated. RR increases as the molar ratio m increases.
It can be seen that the R value increases and the purity improves. However, the molar ratio m is m> 150 (sample bath No. 11 m = 1.5 / 0.01 = 150)
Then, the decreasing tendency becomes remarkable again. With the addition of copper nitrate,
The relative decrease in the copper sulfate concentration reduces the incorporation of S into the electrodeposit and improves the purity of copper. On the other hand, when the addition amount exceeds a certain value, a decrease in purity is again observed, which is because the deposition state of the deposit is deteriorated and dendritic crystals are easily formed.
As a result, it is considered that contamination due to an increase in the amount of captured electrolytic solution occurred.
尚、比較のために純硫酸銅浴および純硫酸銅浴による
電解精製の結果を示したが、本発明の実施例に比べいず
れもRRR値は小さい。また、電析物の結晶の形状は純硫
酸銅浴では、概して平滑、緻密であるが、本発明の実施
例による電析物は更に平滑、緻密である。一方、純硝酸
銅浴からの電析物は典型的な樹枝状晶であり、形状的に
は著しく悪い。硝酸銅の硝酸イオン（NO3 -）によるＮは
事実上Cuに固溶度を持たないので硝酸塩が混入してもＳ
と比べ汚染の原因とはならないが、洗浄効率の低下は工
数増を招くためコストアップの要素になる。For comparison, the results of electrolytic refining using a pure copper sulfate bath and a pure copper sulfate bath are shown, but the RRR values are smaller than those of the examples of the present invention. The crystal shape of the deposit is generally smooth and dense in a pure copper sulfate bath, but the deposits according to the examples of the present invention are smooth and dense. On the other hand, the electrodeposits from the pure copper nitrate bath are typical dendrites, which are extremely poor in shape. Of copper nitrate nitrate ion (NO 3 -) because N has no solid solubility in virtually Cu by even nitrate is mixed S
Although it does not cause pollution as compared with the above, the decrease in cleaning efficiency causes an increase in man-hours, which causes an increase in cost.
以上説明した通り、本発明の銅の電解精製法によれ
ば、硝酸銅と硫酸銅を主成分とする特定の組成の水溶液
を電解液としたため、工数の増加による製造コストの上
昇を伴わずに電析Cu中のＳの量を減らして高純度の銅を
得ることができる。As described above, according to the electrolytic refining method for copper of the present invention, since an aqueous solution having a specific composition containing copper nitrate and copper sulfate as a main component is used as the electrolytic solution, without increasing the manufacturing cost due to the increase in the number of steps. High-purity copper can be obtained by reducing the amount of S in electrodeposited Cu.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小野瀬 雅幸 茨城県日立市川尻町1500番地 日立電線株 式会社豊浦工場内 (72)発明者 関田 克男 茨城県日立市川尻町1500番地 日立電線株 式会社豊浦工場内 (72)発明者 瀬谷 武司 茨城県日立市川尻町1500番地 日立電線株 式会社豊浦工場内 (56)参考文献 特開 昭49−39532（ＪＰ，Ａ) 特開 昭49−72122（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Onose, Masayuki Onose, 1500 Kawajiri-cho, Hitachi-shi, Ibaraki, Toyoura Plant, Hitachi Cable Co., Ltd. Company Toraura Factory (72) Inventor Takeshi Seya 1500 Kawajiri-cho, Hitachi City, Ibaraki Prefecture Hitachi Cable Co., Ltd. Toyoura Factory (56) Reference JP-A-49-39532 (JP, A) JP-A-49-72122 ( JP, A)
Claims (2)
を含む水溶液を電解液とし、陰極に精製された銅を析出
させる銅の電解精製法において、前記電解液が硫酸銅と
硝酸銅を主成分とする水溶液にしてモル比で0.23〜150
の硝酸銅と硫酸銅を含み且つ30g/〜150g/の銅イオ
ン濃度を有することを特徴とする銅の電解精製法。1. A copper electrolytic refining method in which copper as a material to be purified is used as an anode, an aqueous solution containing copper ions is used as an electrolytic solution, and purified copper is deposited on a cathode, wherein the electrolytic solution is copper sulfate and copper nitrate. In a molar ratio of 0.23 to 150
And a copper ion concentration of 30 to 150 g /, and an electrolytic refining method for copper.
化雰囲気または真空中で溶解し、鋳塊としたのち、これ
を帯溶精製することを特徴とする特許請求の範囲第１項
記載の銅の電解精製法。2. A copper ingot electrolytically refined by the electrolytic solution is melted in a non-oxidizing atmosphere or vacuum to form an ingot, which is then purified by zoning. Copper electrolytic refining method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62170266A JPH089790B2 (en) | 1987-07-08 | 1987-07-08 | Copper electrolytic refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62170266A JPH089790B2 (en) | 1987-07-08 | 1987-07-08 | Copper electrolytic refining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6415389A JPS6415389A (en) | 1989-01-19 |
| JPH089790B2 true JPH089790B2 (en) | 1996-01-31 |
Family
ID=15901750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62170266A Expired - Fee Related JPH089790B2 (en) | 1987-07-08 | 1987-07-08 | Copper electrolytic refining method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089790B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5417301B2 (en) * | 1972-08-21 | 1979-06-28 | ||
| JPS4972122A (en) * | 1972-09-27 | 1974-07-12 |
-
1987
- 1987-07-08 JP JP62170266A patent/JPH089790B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6415389A (en) | 1989-01-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |