JPH0527695B2 - - Google Patents
Info
- Publication number
- JPH0527695B2 JPH0527695B2 JP61262670A JP26267086A JPH0527695B2 JP H0527695 B2 JPH0527695 B2 JP H0527695B2 JP 61262670 A JP61262670 A JP 61262670A JP 26267086 A JP26267086 A JP 26267086A JP H0527695 B2 JPH0527695 B2 JP H0527695B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- silver
- solution
- purity
- ppm
- 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 48
- 229910052802 copper Inorganic materials 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 46
- 229910052709 silver Inorganic materials 0.000 claims description 41
- 239000004332 silver Substances 0.000 claims description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- ZQMUTZKOOPWXJE-UHFFFAOYSA-L copper silver sulfate Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].[Ag+] ZQMUTZKOOPWXJE-UHFFFAOYSA-L 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydrochloric acid Chemical compound 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BKTOCNXVWZYIMH-UHFFFAOYSA-N [Cu++].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Cu++].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BKTOCNXVWZYIMH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、高純度銅の製造方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing high-purity copper.
（従来の技術及び問題点）
従来、水溶液中の銀の除去方法として、簡易簡
便な方法が、提供されていない。さらに詳しく
は、例えば高純度銅を得るためには、その電解液
中の好ましいAgの除去方法が望まれている。(Prior Art and Problems) Conventionally, no simple and convenient method has been provided as a method for removing silver from an aqueous solution. More specifically, in order to obtain high-purity copper, for example, a preferable method for removing Ag from the electrolyte is desired.
通常の電気銅中には、10ppm前後の銀が含まれ
ている。この銀は、前記銅の溶解時には溶存銀と
なり、銅イオン還元時には優先的に還元される。
従つて、通常の電気銅を溶解した銅塩溶液は銀含
優量が1ppm以下の金属銅及び又は銅化合物を得
るための出発原料となる銅塩水溶液とならない。 Ordinary electrolytic copper contains around 10 ppm of silver. This silver becomes dissolved silver when the copper is dissolved, and is preferentially reduced when copper ions are reduced.
Therefore, a copper salt solution in which ordinary electrolytic copper is dissolved cannot be used as a copper salt aqueous solution that is a starting material for obtaining metallic copper and/or copper compounds having a silver content of 1 ppm or less.
すなわち、電気銅を溶解して得られる銅塩水溶
液中には、銅濃度約50ｇ／のときで約0.5mg／
の銀が溶存している。この含銀水溶液に適量の
塩化物例えば塩酸添加で脱銀処理を行つても銀濃
度は0.05mg／程度であり、これを原料として得
られる金属銅及び又は銅化合物中の銀を1ppm以
下にすることは困難である。近年技術の高純度に
伴い、それらに利用される基幹素材である銅につ
いても高純度化の要請が強まつており、不純物と
しての銀品位の低下も強く望まれている。 That is, in the copper salt aqueous solution obtained by dissolving electrolytic copper, when the copper concentration is about 50 g/, about 0.5 mg/
of silver is dissolved. Even if this silver-containing aqueous solution is desilvered by adding an appropriate amount of chloride, such as hydrochloric acid, the silver concentration is about 0.05 mg/, and the silver content in metallic copper and/or copper compounds obtained using this as a raw material is reduced to 1 ppm or less. That is difficult. In recent years, with the increasing purity of technology, there has been an increasing demand for higher purity of copper, which is the core material used in these technologies, and there is also a strong desire to reduce the quality of silver as an impurity.
（発明の構成）
上記問題点を解決するため、種々検討した結
果、電気銅（99.99wt％Cu）をアノードとし高純
度銅を得る方法において、電解液中の１〜0.05
mg／の銀を、塩化物を添加し、さらに金属銅と
も接触させ、浮遊物を除去することににより、銀
濃度0.005mg／以下とし、含銀量が1ppm以下の
電気銅を得ることを特徴とする高純度銅の製造方
法によつて更に低下させ得ることを見い出した。(Structure of the Invention) In order to solve the above problems, as a result of various studies, in a method for obtaining high purity copper using electrolytic copper (99.99wt% Cu) as an anode, 1 to 0.05
mg/mg of silver is added with chloride and further brought into contact with metallic copper to remove suspended matter, thereby reducing the silver concentration to 0.005 mg/ or less and obtaining electrolytic copper with a silver content of 1 ppm or less. It has been found that this can be further reduced by a method for producing high-purity copper.
（発明の具体的説明） 以下本発明について、具体的に説明する。(Specific description of the invention) The present invention will be specifically explained below.
本発明の対象とする液は、銀を含有する銅電解
液である。例えば、硫酸溶液、硝酸溶液等の液中
の銀の除去方法である。 The liquid targeted by the present invention is a copper electrolyte containing silver. For example, it is a method for removing silver from a solution such as a sulfuric acid solution or a nitric acid solution.
上記対象の中で、銅の電解液中の浄液方法に関
して、本発明を具体的に説明する。 Among the above objects, the present invention will be specifically explained with respect to a method for purifying a copper electrolyte.
上記電解液としては、通常の銅の電解精錬の場
合だけでなく、好ましくは態様としては、高純度
銅を製造するための再電解における電解液であ
る。またさらには、電気銅を酸性溶液で再溶解し
た含銅溶液をも含むものである。 The above-mentioned electrolytic solution is not only used in ordinary electrolytic refining of copper, but also preferably in re-electrolysis to produce high-purity copper. Furthermore, it also includes a copper-containing solution in which electrolytic copper is redissolved in an acidic solution.
電解液としては、例えば銅の濃度は30〜60ｇ／
、フリーの硝酸は20〜200ｇ／、銀の濃度は
0.02〜0.1ｇ／程度である。 For example, the electrolyte has a copper concentration of 30 to 60 g/
, free nitric acid is 20-200g/, silver concentration is
It is about 0.02 to 0.1 g/.
前記の液に金属銅及び塩化物を単に接触するの
みで銀が晶出し、これを過処理等で除去するこ
とにより、脱銀が効率的に行われる。 Silver crystallizes by simply bringing metal copper and chloride into contact with the above solution, and by removing it by overtreatment or the like, desilvering is efficiently performed.
この場合、金属銅は表面積0.1〜0.5m2／であ
ることが好ましい、液との接触面積をできる限り
得るためである。 In this case, the metal copper preferably has a surface area of 0.1 to 0.5 m 2 /, in order to obtain as much contact area with the liquid as possible.
また、反応上は、銅粉でもよいが、未反応の金
属銅が脱銀された銀と混つてしまうため使用上好
ましくない。従つて、銅の細線であることが好ま
しい。 Further, from the viewpoint of reaction, copper powder may be used, but it is not preferable in terms of use because unreacted metallic copper will be mixed with desilvered silver. Therefore, it is preferable to use a thin copper wire.
脱銀処理の時間は、30〜90分前後である。 The time for desilvering treatment is approximately 30 to 90 minutes.
さらに、脱銀効率を高めるために塩化物に添加
する。例えば、塩酸を適当量添加する。 その
後、浮遊物を除去する。 Furthermore, it is added to chloride to increase desilvering efficiency. For example, add an appropriate amount of hydrochloric acid. Then, remove floating matter.
その除去には、例えば、ミリポアヌイルターが
用いられる。 For its removal, for example, a millipore nullator is used.
この結果得られる処理液中の銀濃度は、0.005
mg／以下となる。 The silver concentration in the resulting processing solution is 0.005
mg/or less.
このように脱銀された銅溶液を電解することに
より、銀の少ない電気銅が回収できる。 By electrolyzing the copper solution desilvered in this way, electrolytic copper containing less silver can be recovered.
通常の電気銅であればAgは10ppm前後である
が、本発明により得られる電気銅は、銀濃度が
0.05〜0.3ppmと極めて低い値となる。 In ordinary electrolytic copper, the Ag content is around 10 ppm, but in the electrolytic copper obtained by the present invention, the silver concentration is
The value is extremely low at 0.05 to 0.3 ppm.
実施例 １
銀0.5mg／、銅50ｇ／、遊離硫酸50ｇ／
の含銀硫酸銅水溶液を１調整した。塩酸純分
0.1ｇを添加し、混合したのち直径0.01mmの金属
銅線を表面積が約0.2m2となる様に添加し、室温
にて100ml／分の循環量で約60分間脱銀処理を行
つた。引き続きミリポアフイルターで過し、低
銀硫酸銅水溶液を得た。銀濃度は0.002mg／で
あつた。更に、上記低銀硫酸銅水溶液を濃縮し、
５水塩の硫酸銅の結晶を得た。結晶中の銀含有量
は0.1ppm以上であつた。Example 1 Silver 0.5mg/, copper 50g/, free sulfuric acid 50g/
A silver-containing copper sulfate aqueous solution was prepared. Hydrochloric acid purity
After adding 0.1 g and mixing, a metal copper wire with a diameter of 0.01 mm was added so that the surface area was about 0.2 m 2 , and desilvering was carried out at room temperature for about 60 minutes at a circulation rate of 100 ml/min. Subsequently, it was filtered through a Millipore filter to obtain a low silver copper sulfate aqueous solution. The silver concentration was 0.002 mg/. Furthermore, the above-mentioned low silver copper sulfate aqueous solution is concentrated,
Crystals of pentahydrate copper sulfate were obtained. The silver content in the crystals was 0.1 ppm or more.
実施例 ２
銀0.5mg／、銅50ｇ／、遊硫酸酸1.0ｇ／
の含銀硝酸銅水溶液を１調整した。塩酸純分
0.1ｇを添加し、混合したのち、実施例１同様に
脱銀処理を行つて、低銀硝酸銅水溶液を得た。銀
濃度は0.003mg／であつた。Example 2 Silver 0.5mg/, copper 50g/, free sulfuric acid 1.0g/
One silver-containing copper nitrate aqueous solution was prepared. Hydrochloric acid purity
After adding 0.1 g and mixing, desilvering treatment was performed in the same manner as in Example 1 to obtain a low silver copper nitrate aqueous solution. The silver concentration was 0.003 mg/.
実施例 ３
通常の電気銅（99.99％Cu、13ppmAg）を再電
解を行い、その電解液中に含まれるAgを除去す
べく電解液の一部を抜き出し、塩酸を電解液１
当たり0.1ｇになるように添加し、銅の極細線を
前記液に接触させ銀を晶出させた。その後ミリポ
アフイルターで過した後、電解槽に戻し電解液
中の銀の濃度を低く保持しつつ、再電解を継続し
た。再電解後得られた電気銅中の銀は0.5ppmと
低い値であつた。Example 3 Ordinary electrolytic copper (99.99% Cu, 13ppmAg) was re-electrolyzed, a part of the electrolyte was extracted to remove Ag contained in the electrolyte, and hydrochloric acid was added to the electrolyte 1.
A fine copper wire was added to the solution in an amount of 0.1 g, and silver was crystallized by contacting the solution with an ultrafine copper wire. After passing through a Millipore filter, it was returned to the electrolytic cell and re-electrolysis was continued while keeping the silver concentration in the electrolyte low. The silver content in the electrolytic copper obtained after re-electrolysis was as low as 0.5 ppm.
比較例
銀0.5mg／、銅50ｇ／、遊離硫酸50ｇ／
の含銀硫酸銅水溶液を１調整し、塩酸純分0.1
ｇを添加し、脱銀処理行つた。引き続きミリポア
フイルターで過し、脱銀後液を得た。溶存銀は
0.05mg／であつた。更に、この脱銀後液を用い
て、実施例３同様電解採取を行つた。得られた電
気銅中の銀含有量は1.2ppmであつた。Comparative example Silver 0.5mg/, copper 50g/, free sulfuric acid 50g/
Prepare a silver-containing copper sulfate aqueous solution, and add hydrochloric acid purity to 0.1.
g was added to perform desilvering treatment. Subsequently, it was passed through a Millipore filter to obtain a desilvered solution. Dissolved silver is
It was 0.05mg/. Furthermore, electrowinning was performed in the same manner as in Example 3 using this post-desilvering solution. The silver content in the obtained electrolytic copper was 1.2 ppm.
（発明の効果）
以上説明したように、本発明では、含銀銅電解
液を金属銅との接触に先立ち塩素イオンを添加す
ることによつて溶存銀濃度を大巾に低下せしめら
れる。これにより電解後に含銀量が1ppm以下の
高純度の金属銅が得られる。(Effects of the Invention) As explained above, in the present invention, the dissolved silver concentration can be significantly reduced by adding chlorine ions to the silver-containing copper electrolyte prior to contact with metal copper. As a result, high-purity metallic copper with a silver content of 1 ppm or less can be obtained after electrolysis.
Claims (1)
度銅を得る方法において、電解液中の１〜0.05
mg／の銀を、塩化物を添加し、さらに金属銅と
も接触させ、浮遊物を除去することににより、銀
濃度0.005mg／以下とし、含銀量が1ppm以下の
電気銅を得ることを特徴とする高純度銅の製造方
法。1 In the method of obtaining high-purity copper using electrolytic copper (99.99wt%Cu) as an anode, 1 to 0.05
mg/mg of silver is added with chloride and further brought into contact with metallic copper to remove suspended matter, thereby reducing the silver concentration to 0.005 mg/ or less and obtaining electrolytic copper with a silver content of 1 ppm or less. A method for producing high-purity copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26267086A JPS63118024A (en) | 1986-11-06 | 1986-11-06 | Method for desilverization or silver recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26267086A JPS63118024A (en) | 1986-11-06 | 1986-11-06 | Method for desilverization or silver recovery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63118024A JPS63118024A (en) | 1988-05-23 |
| JPH0527695B2 true JPH0527695B2 (en) | 1993-04-22 |
Family
ID=17378970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26267086A Granted JPS63118024A (en) | 1986-11-06 | 1986-11-06 | Method for desilverization or silver recovery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63118024A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2777955B2 (en) * | 1992-12-07 | 1998-07-23 | 株式会社ジャパンエナジー | Desilvering or silver recovery method |
| JP2015183204A (en) * | 2014-03-20 | 2015-10-22 | Jx日鉱日石金属株式会社 | Method for recovering silver |
| JP6457039B2 (en) * | 2017-09-13 | 2019-01-23 | Ｊｘ金属株式会社 | Silver recovery method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS527322A (en) * | 1975-07-08 | 1977-01-20 | Stanley Electric Co Ltd | Process for recovery of noble metals from waste liquid |
| JPS5743628A (en) * | 1980-08-29 | 1982-03-11 | Kousuke Kawabata | Water purifying , oxygen enriching and temperature raising apparatus for fish breeding pond |
-
1986
- 1986-11-06 JP JP26267086A patent/JPS63118024A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS527322A (en) * | 1975-07-08 | 1977-01-20 | Stanley Electric Co Ltd | Process for recovery of noble metals from waste liquid |
| JPS5743628A (en) * | 1980-08-29 | 1982-03-11 | Kousuke Kawabata | Water purifying , oxygen enriching and temperature raising apparatus for fish breeding pond |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63118024A (en) | 1988-05-23 |
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