JPH034629B2 - - Google Patents
Info
- Publication number
- JPH034629B2 JPH034629B2 JP62034434A JP3443487A JPH034629B2 JP H034629 B2 JPH034629 B2 JP H034629B2 JP 62034434 A JP62034434 A JP 62034434A JP 3443487 A JP3443487 A JP 3443487A JP H034629 B2 JPH034629 B2 JP H034629B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrolytic copper
- desilvering
- anode
- 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 - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
発明の技術分野
本発明は高純度電気銅の製造方法に関する。
発明の従来技術
従来、高純度銅の製法としては、例えば、銀が
８〜14ppm、イオウが５〜15ppm含む電気銅を硝
酸浴で電気分解し、イオウ分の少ない電気銅を得
る方法である。
この方法によれば、通常の電気銅中のイオウが
５〜9ppmあるものがかなり低下するのであるが、
最も高い銀については、好ましく除去することが
できない。
更に塩素源を添加し、電解浴温を規制して、銀
含有量を低下させる方法等が行われているが好ま
しく除去することができていない。
発明の構成
そこで発明者等が鋭意検討した結果、以下の発
明をなした。
即ち、本発明は、予め電気分解により得られた
電気銅及び又は相当品を硝酸浴中で再電解する方
法において、陽、陰極室を隔膜で区別し、陽極室
排出液を金属銅を脱銀剤として用いて、脱銀した
後、該処理液を陰極室に給液することを特徴とす
る高純度電気銅の製造方法を提供する。
発明の具体的説明
本発明で用いる電解浴は硝酸酸性浴である。硝
酸の濃度はPHが３以下に保持されるように調整さ
れる。好ましくはPH＝1.5〜2.0に調整される。ア
ノードは電気銅、無酸素銅等を用いる。これらの
品位は、銀が８〜14ppm、イオウが５〜15ppm、
砒素0.2〜1ppm、アンチモン0.1〜0.6ppm、ビス
マス0.1〜0.5ppm、鉛0.3〜1.0ppm含むものが、
通常である。
これらの不純物を効率的に除くためには、陽、
陰極室を隔膜で区分することが不可欠である。即
ち、隔膜の主目的は陽極の溶解によつて生ずる不
純物と陰極との隔離である。上記不純物は沈降す
る固形物、懸濁する固形物及び溶存物とに大別さ
れる。溶存不純物は電気泳動によつて、陰極室に
到達しようとするので、隔膜を通過する陰極室液
で押し戻し排除しなければならない。従つて、隔
膜の選定に当たつては通液性、給液量、溶存不純
物の電気泳動度等を考慮しなければならない。し
かしながら通常の隔膜材の場合、有孔度、孔径と
もに不明の場合が多く、実験結果によつて選定す
る例が多い。隔膜材としてはイオン交換膜、布
地、セラミツク等があるが耐酸性の布地、例えば
テビロン、テトロン等の化繊布が好ましい。
更に、本発明の方法においては陽極排出液の脱
銀が不可欠である。脱銀方法としては、金属銅片
充填等を通過させる方法である。
又、塩素の添加は脱銀効率を高める。
塩素源としては塩酸、塩素ガス、塩化銅等があ
る。これらの塩素量としてはフリーの塩素が20
mg／〜20ｇ／あると好ましく、より好ましく
は、0.1ｇ／〜1.0ｇ／である。
又、脱銀後液を孔径0.1μ〜2μの材（孔径は小
さいほど好ましい）で過することによつて不純
物がより好ましく除去できることを把握した。
電流密度は0.8〜1.5A／ｄm2で実施される。
実施例 １
電気銅（成分品位 Ag：13.9 Ｓ：11.0 As：
0.5 Sb：0.3 Bi：0.3 Pb：0.7ppm）を陽極とし、
Ti板を陰極として、陽、陰極間にテトロン
（TR84501 商品名、北村製布(株)製）を配し両極
液を区分する隔膜とした。電解浴の流れは、陽極
室より排出された不純電解液が脱銀処理され引き
続き陰極室に給液されるようにした。脱銀処理は
特願（61−262670号）の方法とし、金属銅に接触
する脱銀時間即ち脱銀工程での滞留時間は4.0hと
し、隔膜面当たりの給液量は1.65cm／ｈとした。
電気浴は、銅50ｇ／（10日間電解後は54ｇ／
となつた。）硝酸浴とし、PHは1.7-190.1とした。
電解浴温は特に調整はしなかつた（22〜27℃であ
つた）。
電流密度は1.0A／ｄm2とし、陽、陰極面間距
離40mmで行つた。連続10日間通電後、引き上げ
Ti板から剥がし洗浄乾燥を行つて高純度電気銅
を得た。得られた電気銅の品位は表１の如くであ
つた。
TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing high purity electrolytic copper. Prior Art of the Invention Conventionally, as a method for producing high purity copper, for example, electrolytic copper containing 8 to 14 ppm of silver and 5 to 15 ppm of sulfur is electrolyzed in a nitric acid bath to obtain electrolytic copper with a low sulfur content. According to this method, the sulfur content in ordinary electrolytic copper, which has 5 to 9 ppm, is significantly reduced.
For the highest silvers, it cannot be removed favorably. Furthermore, methods have been used to reduce the silver content by adding a chlorine source and regulating the temperature of the electrolytic bath, but these methods have not been able to remove the silver satisfactorily. Structure of the Invention As a result of intensive study, the inventors made the following invention. That is, the present invention is a method of re-electrolyzing electrolytic copper and/or equivalent products previously obtained by electrolysis in a nitric acid bath, in which the anode and cathode chambers are separated by a diaphragm, and the anode chamber discharge liquid is used to desilver metal copper. Provided is a method for producing high-purity electrolytic copper, which comprises supplying the treatment solution to a cathode chamber after desilvering. DETAILED DESCRIPTION OF THE INVENTION The electrolytic bath used in the present invention is a nitric acid bath. The concentration of nitric acid is adjusted so that the pH is kept below 3. Preferably, the pH is adjusted to 1.5 to 2.0. Electrolytic copper, oxygen-free copper, etc. are used for the anode. The quality of these is 8 to 14 ppm for silver, 5 to 15 ppm for sulfur,
Those containing arsenic 0.2-1ppm, antimony 0.1-0.6ppm, bismuth 0.1-0.5ppm, lead 0.3-1.0ppm,
Normal. In order to efficiently remove these impurities, positive,
It is essential to separate the cathode chamber with a diaphragm. That is, the main purpose of the diaphragm is to separate impurities generated by dissolution of the anode from the cathode. The above impurities are broadly classified into precipitated solids, suspended solids, and dissolved substances. Dissolved impurities try to reach the cathode chamber through electrophoresis, so they must be pushed back and removed by the cathode chamber fluid passing through the diaphragm. Therefore, when selecting a diaphragm, consideration must be given to liquid permeability, amount of liquid supplied, electrophoretic mobility of dissolved impurities, etc. However, in the case of ordinary diaphragm materials, both the porosity and the pore diameter are often unknown, and selection is often made based on experimental results. Examples of the diaphragm material include ion exchange membranes, fabrics, ceramics, etc., but acid-resistant fabrics, such as synthetic fibers such as Teviron and Tetron, are preferable. Furthermore, in the method of the present invention, desilvering of the anode effluent is essential. The desilvering method is a method of passing through a metal copper piece filling or the like. Also, addition of chlorine increases desilvering efficiency. Chlorine sources include hydrochloric acid, chlorine gas, and copper chloride. The amount of chlorine in these is 20% free chlorine.
mg/~20g/, more preferably 0.1g/~1.0g/. It has also been found that impurities can be more preferably removed by passing the desilvering solution through a material with a pore diameter of 0.1 to 2 microns (the smaller the pore diameter is, the better). The current density is carried out at 0.8-1.5 A/ dm2 . Example 1 Electrolytic copper (component quality Ag: 13.9 S: 11.0 As:
0.5 Sb: 0.3 Bi: 0.3 Pb: 0.7 ppm) as the anode,
A Ti plate was used as a cathode, and a Tetron (TR84501 trade name, manufactured by Kitamura Seifu Co., Ltd.) was placed between the anode and cathode to serve as a diaphragm to separate the two electrolytes. The flow of the electrolytic bath was such that the impure electrolyte discharged from the anode chamber was desilvered and then supplied to the cathode chamber. The desilvering treatment was carried out using the method described in the patent application (No. 61-262670), and the desilvering time in contact with metallic copper, that is, the residence time in the desilvering process, was 4.0 h, and the amount of liquid supplied per diaphragm surface was 1.65 cm/h. did. The electric bath contains 50 g of copper (54 g after 10 days of electrolysis)
It became. ) A nitric acid bath was used, and the pH was set to 1.7 -19 0.1.
The electrolytic bath temperature was not particularly adjusted (it was 22 to 27°C). The current density was 1.0 A/dm 2 and the distance between the positive and cathode surfaces was 40 mm. After energizing for 10 consecutive days, withdraw
High purity electrolytic copper was obtained by peeling it off from the Ti plate, washing and drying it. The quality of the obtained electrolytic copper was as shown in Table 1.
【表】
実施例 ２
循環する電解浴中の塩素温度を塩素添加で
100-1910mg／とした以外は全く実施例１同様に
行つて高純度電気銅を得た。銀が実施例１より多
く除去でき0.20ppmであつた。他の成分は変化は
なかつた。
実施例 ３
実施例２の方法において、脱銀処理後液を孔径
0.2μのミリポアーフイルター（商品名 ミリポア
ー社製）で過し、陰極室に給液する方法を実施
した結果、銀が0.08ppmと極めて低い値を示しよ
り好ましい高純度電気銅が得られた。
発明の効果
以上のように本発明を実施することにより以下
の効果を得る。
(1) 99.9999％以上の高純度の銅が得られる。
(2) これにより得られた銅は、オーデイオ用、ビ
デオ配線用等に用いられ、音色あるいは画像の
美しい映像を可能とし得る。[Table] Example 2 Changing the chlorine temperature in the circulating electrolytic bath by adding chlorine
100 -19 High purity electrolytic copper was obtained in the same manner as in Example 1 except that the amount was 10 mg/. More silver than in Example 1 could be removed to 0.20 ppm. There were no changes in other components. Example 3 In the method of Example 2, the solution after desilvering treatment was
As a result of passing through a 0.2μ Millipore filter (trade name, manufactured by Millipore) and supplying the liquid to the cathode chamber, more preferable high-purity electrolytic copper with a very low silver content of 0.08 ppm was obtained. Effects of the Invention By implementing the present invention as described above, the following effects can be obtained. (1) High purity copper of 99.9999% or higher can be obtained. (2) The copper thus obtained can be used for audio and video wiring, etc., and can produce beautiful tones and images.
Claims (1)
相当品を硝酸浴中で再電解する方法において、
陽、陰極室を隔膜で区別し、陽極室排出液を金属
銅を脱銀剤として用いて、脱銀した後、該処理液
を陰極室に給液することを特徴とする高純度電気
銅の製造方法。 ２ 脱銀後液を孔径0.1μ〜2μの材で過するこ
とを特徴とする第１項記載の高純度銅の製造方
法。 ３ 遊離塩素が20mg／〜20ｇ／溶存する電解
液を用いることを特徴とする特許請求の範囲第１
項記載の高純度電気銅の製造方法。[Claims] 1. A method of re-electrolyzing electrolytic copper and/or an equivalent product previously obtained by electrolysis in a nitric acid bath,
High-purity electrolytic copper, characterized in that the anode and cathode chambers are separated by a diaphragm, and the anode chamber discharge liquid is desilvered using metallic copper as a desilvering agent, and then the treated solution is supplied to the cathode chamber. Production method. 2. The method for producing high-purity copper according to item 1, characterized in that the solution after desilvering is passed through a material with a pore size of 0.1 μm to 2 μm. 3. Claim 1, characterized in that an electrolytic solution containing 20 mg/~20 g/dissolved free chlorine is used.
A method for producing high-purity electrolytic copper as described in Section 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62034434A JPS63203784A (en) | 1987-02-19 | 1987-02-19 | Production of high purity electrolytic copper |
| US07/080,336 US4792369A (en) | 1987-02-19 | 1987-07-30 | Copper wires used for transmitting sounds or images |
| US07/237,492 US4874436A (en) | 1987-02-19 | 1988-08-26 | Method for producing high purity electrolytic copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62034434A JPS63203784A (en) | 1987-02-19 | 1987-02-19 | Production of high purity electrolytic copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63203784A JPS63203784A (en) | 1988-08-23 |
| JPH034629B2 true JPH034629B2 (en) | 1991-01-23 |
Family
ID=12414115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62034434A Granted JPS63203784A (en) | 1987-02-19 | 1987-02-19 | Production of high purity electrolytic copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63203784A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9783904B2 (en) | 2012-06-14 | 2017-10-10 | Mitsubishi Materials Corporation | High-purity electrolytic copper and electrolytic refining method thereof |
| KR20210023678A (en) * | 2019-08-23 | 2021-03-04 | 광저우 인스티튜트 오브 에너지 콘버전, 차이니즈 아카데미 오브 사이언시즈 | Novel organic solid waste pyrolysis gasifier |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006134724A1 (en) * | 2005-06-15 | 2006-12-21 | Nippon Mining & Metals Co., Ltd. | Ultrahigh-purity copper and process for producing the same, and bonding wire comprising ultrahigh-purity copper |
| JP5016410B2 (en) * | 2007-08-03 | 2012-09-05 | Ｄｏｗａメタルマイン株式会社 | Copper solution purification method and copper production method |
| JP7454329B2 (en) * | 2017-06-01 | 2024-03-22 | 三菱マテリアル株式会社 | High purity electrical copper plate |
| CN110678582B (en) | 2017-06-01 | 2021-10-29 | 三菱综合材料株式会社 | Method for producing high-purity electrolytic copper |
| WO2018221734A1 (en) * | 2017-06-01 | 2018-12-06 | 三菱マテリアル株式会社 | Method for producing high-purity electrolytic copper |
| CN114293227A (en) * | 2021-12-16 | 2022-04-08 | 虹华科技股份有限公司 | Processing technology of high-purity copper product for aerospace |
-
1987
- 1987-02-19 JP JP62034434A patent/JPS63203784A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9783904B2 (en) | 2012-06-14 | 2017-10-10 | Mitsubishi Materials Corporation | High-purity electrolytic copper and electrolytic refining method thereof |
| KR20210023678A (en) * | 2019-08-23 | 2021-03-04 | 광저우 인스티튜트 오브 에너지 콘버전, 차이니즈 아카데미 오브 사이언시즈 | Novel organic solid waste pyrolysis gasifier |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63203784A (en) | 1988-08-23 |
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