JPH11200083A - Electrolytic refining method of copper - Google Patents
Electrolytic refining method of copperInfo
- Publication number
- JPH11200083A JPH11200083A JP10002644A JP264498A JPH11200083A JP H11200083 A JPH11200083 A JP H11200083A JP 10002644 A JP10002644 A JP 10002644A JP 264498 A JP264498 A JP 264498A JP H11200083 A JPH11200083 A JP H11200083A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- copper
- anode plate
- solution
- electrolytic cell
- 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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Classifications
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- 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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅の電解精錬方法
に係わり、特に電解製錬時に発生するツブの低減に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for electrolytic refining of copper, and more particularly, to a method for reducing lumps generated during electrolytic refining.
【０００２】[0002]
【従来の技術】本発明でいう「ツブ」とは、電解精錬時
に陰極板（精錬銅）の表面に生成する突起物、あるいは
コブ状析出物のことで、電解精錬時には極板間の短絡事
故を起こして電力原単位を上昇させ、また、製品（電気
銅）となったあとでもその形状面からハンドリングを困
難ならしめる等、銅の電解精錬において早急に解決すべ
き問題点の１つとして知られている。2. Description of the Related Art "Tube" in the present invention refers to protrusions or bumps formed on the surface of a cathode plate (refined copper) during electrolytic refining. It is known as one of the problems to be solved promptly in the electrolytic refining of copper, such as raising the power consumption per unit and making it difficult to handle the product (electrolytic copper) even after it has become a product (electrolytic copper). Have been.
【０００３】従来、銅電解精錬時の陰極板（精錬銅）の
表面でのツブの低減方法として、膠、チオ尿素等の有機
物を、電解槽内に添加する方法が広く実施されている。
しかし、この方法では添加剤の濃度、均一拡散等に難点
があり、その上、添加剤自体に含まれるＣ、Ｓ等が陰極
板（製品）に電着して品質の低下を招くため添加量に限
界があり、ツブの発生を完全に解決するには至っていな
い。さらに、電解液中の添加有機物の濃度測定が困難な
こともツブの発生の防止を困難にしている。Heretofore, as a method of reducing lumps on the surface of a cathode plate (refined copper) during copper electrolytic refining, a method of adding an organic substance such as glue or thiourea into an electrolytic cell has been widely practiced.
However, in this method, there are difficulties in the concentration, uniform diffusion, etc. of the additive, and in addition, C, S, etc. contained in the additive itself are electrodeposited on the cathode plate (product) to cause deterioration in quality, so that the amount of the additive is reduced. There is a limit, and it has not yet been possible to completely resolve the occurrence of groves. Further, the difficulty in measuring the concentration of the added organic substance in the electrolyte also makes it difficult to prevent the occurrence of bumps.
【０００４】また、電解通電条件を、パルス〜間欠通電
とする電解方法も検討されているが、ツブの発生を完全
に防止するには至っていない。さらに、陽極板の品位、
陰極（種板）のサイズ、電極間隔、電解時の電流密度、
電解液の液温、銅濃度、酸濃度等、種々の要因面から改
善方法が検討されている。例えば、特開平８−296080号
公報には、陽極の酸素品位により定まる陰極電流効率と
陽極電流効率が一定する電解電流で電解する方法が開示
されているが、いまだにツブの発生を完全に防止するに
は至っていない。[0004] Further, an electrolysis method in which the electrolysis energization conditions are pulsed to intermittent energization has been studied, but it has not yet been possible to completely prevent occurrence of bumps. In addition, the quality of the anode plate,
The size of the cathode (seed plate), electrode spacing, current density during electrolysis,
Improvement methods are being studied from various factors such as the electrolyte temperature, copper concentration, and acid concentration. For example, Japanese Patent Application Laid-Open No. 8-296080 discloses a method in which electrolysis is performed with an electrolytic current in which the cathode current efficiency and the anode current efficiency determined by the oxygen quality of the anode are constant, but still prevents the occurrence of bumps completely. Has not been reached.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、以上のよう
な技術の現状に鑑みてなされたものであって、ツブの発
生を低減できる銅の電解精錬方法を提供することを目的
とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and an object of the present invention is to provide a copper electrolytic refining method capable of reducing the occurrence of bumps.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、銅の電解
精錬時のツブの低減方法について鋭意検討を重ねた結
果、銅電解精錬時の陰極板（精錬銅）表面でのツブの発
生は、陽極板の電解槽への装入から通電までの間に陽極
板から発生する銅粉、亜酸化銅、酸化銅、介在物等が核
となって成長することに着目し、電解槽に装入後、通電
開始までに発生する陽極板からの汚れを電解槽内から除
去すること、および、通電開始時に汚染物質を陰極板に
付着させないことが重要であるとの知見をえ、この知見
に基づいて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method for reducing lumps during copper electrolytic refining, and as a result, the generation of lumps on the surface of a cathode plate (refined copper) during copper electrolytic refining. Focusing on the fact that copper powder, cuprous oxide, copper oxide, inclusions, etc. generated from the anode plate grow from the anode plate during the period from charging of the anode plate to the electrolytic cell until energization, it grows as a core. After charging, it was found that it was important to remove the dirt from the anode plate that occurred before the start of energization from the inside of the electrolytic cell, and that it was important to prevent contaminants from adhering to the cathode plate at the start of energization. Based on the above, the present invention has been completed.
【０００７】すなわち、第一の本発明は、陽極板を電解
槽外で硫酸液で洗浄後、電解槽に装入し、電解すること
を特徴とする銅の電解精錬方法であり、また、第二の本
発明は、陽極板を電解槽に装入後、一旦電解液を給液し
た後に、全量液抜きし、その後再度、電解液を給液し
て、電解することを特徴とする銅電解精錬方法であり、
また、第三の本発明は、陽極板を電解槽に装入後、一旦
電解液を給液した後に、通電前にオーバーフローによっ
て電解槽内の電解液の一部を置換し、電解することを特
徴とする銅の電解精錬方法であり、また、本発明では、
前記電解は、電解槽への電解液の給液終了後、通電を開
始し、通電開始後の５〜３０分間の電流値を通常の４０
〜６０％として、それ以降は通常の電流値とするのが好
ましい。That is, the first invention is a copper electrolytic refining method characterized by washing an anode plate with a sulfuric acid solution outside an electrolytic cell, and then loading the anode plate into the electrolytic cell and performing electrolysis. The present invention is characterized in that after the anode plate is inserted into the electrolytic cell, the electrolytic solution is once supplied, the entire amount is drained, and then the electrolytic solution is supplied again to perform the electrolytic process. Refining method,
Further, the third invention is that, after the anode plate is inserted into the electrolytic cell, the electrolytic solution is once supplied, and then a part of the electrolytic solution in the electrolytic cell is replaced by overflow before energization, thereby performing the electrolysis. Characteristic copper electrolytic refining method, and in the present invention,
In the electrolysis, after the supply of the electrolytic solution to the electrolytic cell is completed, the energization is started, and the current value for 5 to 30 minutes after the start of the energization is increased to a normal value of 40 minutes.
After that, it is preferable to set a normal current value thereafter.
【０００８】[0008]
【発明の実施の形態】第一の本発明では、陽極板の予備
洗浄として、電解槽外で陽極板の硫酸液による洗浄を行
う。硫酸液による洗浄は、鋳造したままの陽極板表面の
付着物、酸化膜、銅粉などの洗浄除去のために行うもの
で、電解槽外で実施する。この際の硫酸濃度は５０〜３
００ｇ／ｌ、より望ましくは１００〜２００ｇ／ｌ程
度、洗浄時間は３０秒〜６０分、より望ましくは２〜１
５分程度が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the first invention, as a preliminary cleaning of an anode plate, the anode plate is washed with a sulfuric acid solution outside the electrolytic cell. The cleaning with the sulfuric acid solution is performed for cleaning and removing deposits, oxide films, copper powder, etc. on the surface of the as-cast anode plate, and is performed outside the electrolytic cell. The sulfuric acid concentration at this time is 50 to 3
00 g / l, more preferably about 100 to 200 g / l, and the washing time is 30 seconds to 60 minutes, more preferably 2 to 1
About 5 minutes is preferable.
【０００９】洗浄効果は、硫酸濃度×洗浄時間に比例
し、硫酸濃度５０ｇ／ｌ未満、洗浄時間３０秒未満では
十分な洗浄効果は得られず、硫酸濃度を３００ｇ／ｌ超
としても硫酸量に比して効果は大きくならず、洗浄時間
６０分を超えると陽極板の入替時間が長くなり、電解槽
の稼働率が低下する。なお、この予備洗浄は、硫酸液に
浸積する方法、硫酸液を噴射する方法等いずれの方法を
採用してもよい。The cleaning effect is proportional to the sulfuric acid concentration × the cleaning time. If the sulfuric acid concentration is less than 50 g / l and the cleaning time is less than 30 seconds, a sufficient cleaning effect cannot be obtained. The effect is not so large, and if the cleaning time exceeds 60 minutes, the replacement time of the anode plate becomes longer, and the operation rate of the electrolytic cell decreases. This pre-cleaning may employ any method such as a method of dipping in a sulfuric acid solution or a method of spraying a sulfuric acid solution.
【００１０】また、第二の本発明では、陽極板の予備洗
浄として、陽極板を電解槽に装入後、一旦電解液を給液
した後で、約２〜１５分後に、電解液の全量を電解槽槽
底の抜孔から液抜きをして、鋳造したままの陽極板表面
の介在物、酸化物あるいは浸漬によって発生する銅粉な
どを予備洗浄し、電解槽外に排出する。その後再度、電
解液を給液して電解精錬を行う。In the second aspect of the present invention, as a preliminary cleaning of the anode plate, after the anode plate is inserted into the electrolytic cell, the electrolytic solution is once supplied, and after about 2 to 15 minutes, the total amount of the electrolytic solution is reduced. Is drained from a hole at the bottom of the electrolytic cell, and the inclusions, oxides, copper powder generated by immersion, etc. on the surface of the as-cast anode plate are preliminarily washed and discharged out of the electrolytic cell. Thereafter, an electrolytic solution is supplied again to perform electrolytic refining.
【００１１】この予備洗浄では、電解槽において陽極板
を電解液で洗浄している時間は通常１０分である。この
時間は、サイズが横：９９０ｍｍ、縦：９７０ｍｍ、重
量：３６０ｋｇ／枚である陽極板を、幅：１２００ｍ
ｍ、長さ：４８５０ｍｍ、深さ：１３００ｍｍの電解槽
に装入して、陽極板に付着物等が全く観察されなくなっ
た時間である。In this preliminary cleaning, the time for cleaning the anode plate with the electrolytic solution in the electrolytic cell is usually 10 minutes. During this time, an anode plate having a width of 990 mm, a length of 970 mm, and a weight of 360 kg / sheet was placed at a width of 1200 m.
m, length: 4850 mm, depth: 1300 mm. This is the time during which no deposits or the like were observed on the anode plate at all after being charged in the electrolytic cell.
【００１２】また、第三の本発明では、陽極板の予備洗
浄として、陽極板を電解槽に装入後、一旦電解液を給液
してから、約３０〜１８０分後に、電解液の全量の約３
０〜１００％をオーバーフローによって置換する。この
置換によって鋳造したままの陽極板表面の付着物、酸化
物あるいは浸漬によって発生する銅粉などを予備洗浄
し、電解槽外に排出する。その後再度、電解液を給液し
て電解精錬を行う。In the third aspect of the present invention, as a preliminary cleaning of the anode plate, after the anode plate is inserted into the electrolytic cell, the electrolyte is once supplied, and after about 30 to 180 minutes, the total amount of the electrolyte is reduced. About 3
Replace 0-100% by overflow. By this replacement, deposits on the surface of the anode plate as cast, oxides, copper powder generated by immersion, and the like are preliminarily washed and discharged out of the electrolytic cell. Thereafter, an electrolytic solution is supplied again to perform electrolytic refining.
【００１３】この予備洗浄では、一旦電解液を給液した
後で、約９０分後に、電解液の全量の約５０％をオーバ
ーフローによって置換する。この方法によっても、第
一、第二の発明と同様の効果が得られた。以上のよう
に、予備的な洗浄を施した陽極板を電解槽に装入してセ
ットし、あるいは、電解槽内で予備洗浄した場合はその
ままの状態で電解液を給液し、通電して電解精錬を開始
する。[0013] In this pre-cleaning, after the electrolyte is once supplied, about 50% of the total amount of the electrolyte is replaced by overflow about 90 minutes later. According to this method, effects similar to those of the first and second inventions were obtained. As described above, the anode plate that has been subjected to preliminary cleaning is set in the electrolytic bath by inserting it into the electrolytic bath, or if the preliminary cleaning has been performed in the electrolytic bath, the electrolytic solution is supplied as it is, and the current is supplied. Start electrolytic refining.
【００１４】ここで、電解通電開始後の５〜３０分間の
電流値を通常の通電の４０〜６０％とし、その後、通常
の電流値として電解精錬する。通電時間、電流値を限定
した理由は汚染物質を陰極板に付着させないことを目的
とするものである。すなわち、電解通電開始後の５〜３
０分間の電流値を抑制することによって、前述の電解液
の汚染防止効果を増大することができる。また、電流値
は通常値の４０〜６０％がよい。４０％未満では電解液
の汚染防止効果が充分でなく、また、６０％を超えると
汚染防止効果が得られなくなるおそれがある。Here, the current value for 5 to 30 minutes after the start of electrolytic energization is set to 40 to 60% of normal energization, and thereafter, electrolytic refining is performed as a normal current value. The reason for limiting the energizing time and the current value is to prevent contaminants from adhering to the cathode plate. That is, 5 to 3 after the start of electrolysis.
By suppressing the current value for 0 minute, the above-described effect of preventing the electrolytic solution from being contaminated can be increased. The current value is preferably 40 to 60% of the normal value. If it is less than 40%, the effect of preventing contamination of the electrolytic solution is not sufficient, and if it exceeds 60%, the effect of preventing contamination may not be obtained.
【００１５】[0015]
【実施例】（実施例１および比較例１）先ず、第一の発
明による陽極板の硫酸液による洗浄効果を確認するた
め、次のテストを行った。すなわち、表１に示す不純物
（いずれも重量ｐｐｍ）を含有する陽極板（粗銅）を使
用して硫酸液による洗浄効果の確認テストを実施した。EXAMPLES (Example 1 and Comparative Example 1) First, the following test was conducted to confirm the cleaning effect of the anode plate according to the first invention with a sulfuric acid solution. That is, a test for confirming the cleaning effect of the sulfuric acid solution was performed using an anode plate (blown copper) containing the impurities shown in Table 1 (both in ppm by weight).
【００１６】[0016]
【表１】 [Table 1]
【００１７】同一ブロック全１１槽内の偶数Noの槽につ
いて第一の発明による予備洗浄を行ったものを実施例１
とし、奇数Noの槽での予備洗浄なしを比較例１とした。
予備洗浄には濃度１２０ｇ／ｌの硫酸液を用いて１０分
間、第一の発明の予備洗浄方法を実施した。次いで電解
槽への給液を開始し、給液終了後、電解通電を開始し
た。電解通電開始後の１５分間は、電流値を通常の５０
％（１６ＫＡｍｐ、電流密度１６０Ａｍｐ／ｍ2 ）で電
解精錬を実施し、以降通常の電流値（３２ＫＡｍｐ、電
流密度３２０Ａｍｐ／ｍ2 ）で９日間電解精錬を実施し
た。In the first embodiment, the pre-cleaning according to the first invention was performed on the even numbered tanks in all 11 tanks of the same block.
Comparative Example 1 was performed without preliminary cleaning in the odd-numbered tanks.
For the pre-cleaning, the pre-cleaning method of the first invention was carried out for 10 minutes using a sulfuric acid solution having a concentration of 120 g / l. Then, liquid supply to the electrolytic cell was started, and after the liquid supply was completed, electrolytic energization was started. For 15 minutes after the start of the electrolysis,
% (16 KAmp, current density 160 Amp / m 2 ), and thereafter, electrolytic refining was performed at a normal current value (32 KAmp, current density 320 Amp / m 2 ) for 9 days.
【００１８】その他の電解条件としては、サイズが横：
９９０ｍｍ、縦：９７０ｍｍ、重量：３６０ｋｇ／枚で
ある陽極板４７枚を、極間距離が１００ｍｍとなるよう
に電解槽（幅：１２００ｍｍ、長さ：４８５０ｍｍ、深
さ：１３００ｍｍ）に装入して電解精錬を実施した。そ
の際の電解液は、Ｃｕ４７ｇ／ｌ、硫酸１６５ｇ／ｌ、
液温６５℃とし、添加材として膠とチオ尿素を併せて、
電着銅当り２２０ｇ／ｔｏｎで使用した。Other electrolysis conditions are as follows:
47 anode plates of 990 mm, length: 970 mm, and weight: 360 kg / sheet were placed in an electrolytic cell (width: 1200 mm, length: 4850 mm, depth: 1300 mm) such that the distance between the electrodes was 100 mm. Electrolytic refining was performed. The electrolyte at that time was Cu 47 g / l, sulfuric acid 165 g / l,
The liquid temperature was 65 ° C, and glue and thiourea were added as additives.
Used at 220 g / ton per electrodeposited copper.
【００１９】実施例１および比較例１で得られた陰極板
（電気銅）のツブの発生率（％）の調査結果をまとめて
表２に示した。なお、ツブの発生率（％）は、陰極板枚
数４６枚のうち１０ｍｍ径以上のツブの発生があった陰
極板枚数の比率で表した。Table 2 summarizes the results of a survey on the occurrence rate (%) of bumps of the cathode plate (electrolytic copper) obtained in Example 1 and Comparative Example 1. In addition, the occurrence rate (%) of the jaws was represented by the ratio of the number of cathode plates having a jaw with a diameter of 10 mm or more out of 46 cathode plates.
【００２０】[0020]
【表２】 [Table 2]
【００２１】（実施例２、３および比較例２、３）次
に、予備洗浄と、電流値等の電解条件とを組み合わせた
効果を確認するため、次の電解精錬を実施した。なお、
予備洗浄方法は、第一、第二および第三のいずれの方法
でもその効果は同一である。したがって、電解槽内の電
解液を抜液後、再度、供給する第二の発明の方法を採用
した。(Examples 2 and 3 and Comparative Examples 2 and 3) Next, the following electrolytic refining was carried out in order to confirm the effect of combining pre-cleaning and electrolysis conditions such as a current value. In addition,
The pre-cleaning method has the same effect in any of the first, second and third methods. Therefore, the method of the second invention was adopted in which the electrolytic solution in the electrolytic cell was drained and then supplied again.
【００２２】すなわち、第二の方法による予備洗浄を行
って、電解通電開始後の１５分間の電流値を通常の５０
％とした電解精錬を実施例２とし、電解通電開始後直ち
に通常の電流値とした電解精錬を実施例３とした。ここ
で、実施例２、３の電解条件でかつ、予備洗浄を行わな
い電解精錬をそれぞれ比較例２、３とした。That is, the pre-cleaning is performed by the second method, and the current value for 15 minutes after the start of the energization of the electrolytic solution is reduced to a normal value of 50%.
% Was used in Example 2, and immediately after the start of electrolysis, electrolytic refining was performed with a normal current value. Here, the electrolytic refining under the electrolysis conditions of Examples 2 and 3 and without performing the preliminary cleaning was referred to as Comparative Examples 2 and 3, respectively.
【００２３】なお、その他の電解条件は実施例１と同様
とし、陽極板（粗銅）は表１の組成のものを使用した。
以上の条件で電解精錬を実施したときの陰極板表面での
ツブの発生状況の調査結果を電解条件とともに表３にま
とめて示した。The other electrolysis conditions were the same as in Example 1, and the anode plate (blown copper) used had the composition shown in Table 1.
Table 3 summarizes the results of an investigation of the occurrence of lumps on the surface of the cathode plate when electrolytic refining was performed under the above conditions, together with the electrolytic conditions.
【００２４】[0024]
【表３】 [Table 3]
【００２５】ここで、50％電流値での通電時間（分）が
０（分）となっている例は、通電開始から通常の電流値
で電解精錬していることを示す。表３から明らかなよう
に本発明の方法によると、ツブの発生率（％）が大幅に
低減していることが分かる。Here, an example in which the energizing time (minute) at a 50% current value is 0 (minute) indicates that electrolytic refining is performed at a normal current value from the start of energization. As is clear from Table 3, according to the method of the present invention, the occurrence rate (%) of the lumps is greatly reduced.
【００２６】[0026]
【発明の効果】以上述べたように、本発明のツブの低減
方法によると、銅の電解精錬時における陰極板の表面で
のツブの発生を大幅に低減することか可能となり、得ら
れる電気銅の品質およびその後の製品のハンドリング性
の向上等の大きな効果を得ることができる。As described above, according to the method for reducing bumps of the present invention, it is possible to greatly reduce the occurrence of bumps on the surface of the cathode plate during electrolytic refining of copper. A great effect such as improvement of the quality of the product and the subsequent handling of the product can be obtained.
Claims (4)
解槽に装入し、電解することを特徴とする銅の電解精錬
方法。An electrolytic refining method for copper, comprising: washing an anode plate with a sulfuric acid solution outside an electrolytic tank;
給液した後に、全量液抜きし、その後再度、電解液を給
液して、電解することを特徴とする銅の電解精錬方法。2. The method according to claim 1, wherein after the anode plate is inserted into the electrolytic cell, the electrolytic solution is once supplied, then the entire amount is drained, and then the electrolytic solution is supplied again to carry out the electrolysis. Refining method.
給液した後に、通電前にオーバーフローによって電解槽
内の電解液の一部を置換して、電解することを特徴とす
る銅の電解精錬方法。3. The method according to claim 1, wherein after the anode plate is inserted into the electrolytic cell, an electrolytic solution is once supplied, and then a part of the electrolytic solution in the electrolytic cell is replaced by overflow before the energization to perform electrolysis. Copper electrolytic refining method.
了後、通電を開始し、通電開始後の５〜３０分間の電流
値を通常の４０〜６０％として、それ以降は通常の電流
値とする電解であることを特徴とする請求項１ないし３
のいずれかに記載の銅の電解精錬方法。4. In the electrolysis, after the supply of the electrolytic solution to the electrolytic cell is completed, energization is started, and a current value for 5 to 30 minutes after the start of energization is set to 40 to 60% of a normal value. 4. An electrolysis having a current value of:
The method for electrolytic refining of copper according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00264498A JP4041571B2 (en) | 1998-01-08 | 1998-01-08 | Copper electrolytic refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00264498A JP4041571B2 (en) | 1998-01-08 | 1998-01-08 | Copper electrolytic refining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11200083A true JPH11200083A (en) | 1999-07-27 |
| JP4041571B2 JP4041571B2 (en) | 2008-01-30 |
Family
ID=11535084
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00264498A Expired - Fee Related JP4041571B2 (en) | 1998-01-08 | 1998-01-08 | Copper electrolytic refining method |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864471A (en) * | 2012-08-29 | 2013-01-09 | 张家港市江城冶化科技有限公司 | Composite cathode plate |
-
1998
- 1998-01-08 JP JP00264498A patent/JP4041571B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102864471A (en) * | 2012-08-29 | 2013-01-09 | 张家港市江城冶化科技有限公司 | Composite cathode plate |
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| Publication number | Publication date |
|---|---|
| JP4041571B2 (en) | 2008-01-30 |
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