JPS6054397B2 - Copper electrolytic refining method - Google Patents
Copper electrolytic refining methodInfo
- Publication number
- JPS6054397B2 JPS6054397B2 JP57184662A JP18466282A JPS6054397B2 JP S6054397 B2 JPS6054397 B2 JP S6054397B2 JP 57184662 A JP57184662 A JP 57184662A JP 18466282 A JP18466282 A JP 18466282A JP S6054397 B2 JPS6054397 B2 JP S6054397B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrolytic
- refining method
- electrolytic refining
- added
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052802 copper Inorganic materials 0.000 title claims description 39
- 239000010949 copper Substances 0.000 title claims description 39
- 238000007670 refining Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 9
- 229920002472 Starch Polymers 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 9
- 229920001353 Dextrin Polymers 0.000 claims description 8
- 239000004375 Dextrin Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019425 dextrin Nutrition 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- -1 Avitone (trade name Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000010936 titanium Substances 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
【発明の詳細な説明】
本発明は硫酸酸性硫酸銅溶液を電解液として、電気分
解により粗銅から純銅を回収する銅の電解精製法に関す
るもので、特に硫黄並びに砒素、ビスマス、アンチモン
等の不純物が少ない電気銅を製造するための銅の電解精
製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrolytic refining method for copper in which pure copper is recovered from blister copper by electrolysis using a sulfuric acid copper sulfate solution as an electrolyte. This invention relates to a copper electrolytic refining method for producing a small amount of electrolytic copper.
従来、粗銅を陽極とし、純銅、チタンまたはステンレ
スを陰極として、硫酸酸性硫酸銅溶液中で電気分解する
ことにより電気銅を製造する銅の電解精製において陰極
に析出する銅への不純物の混入を防止し、かつ陽極、陰
極間の短絡の原因となる樹枝状または瘤状析出物の発達
を抑制して平滑で緻密な電気銅を得るため電解液に有機
化合物を主体とする電解添加剤を加えている。Conventionally, electrolytic copper is produced by electrolysis in a sulfuric acidic copper sulfate solution using blister copper as an anode and pure copper, titanium, or stainless steel as a cathode. Preventing the contamination of impurities into the copper deposited on the cathode during electrolytic refining of copper. In order to obtain smooth and dense electrolytic copper by suppressing the development of dendritic or knob-like precipitates that cause short circuits between the anode and cathode, electrolytic additives mainly consisting of organic compounds are added to the electrolytic solution. There is.
電解添加剤は一般に膠とチオ尿素を組み合せたものが
基本的で、これにに第３の添加剤、例えばアビトン（商
品名、石油系スルフォン化物）、セパラン（商品名、ア
クリルアミド誘導体）、グーラツク（リグニンピッチ生
成物）等が併用されている。Generally, electrolytic additives are basically a combination of glue and thiourea, in addition to which a third additive such as Avitone (trade name, petroleum-based sulfonated product), Separan (trade name, acrylamide derivative), Goulak (trade name), etc. lignin pitch products) etc. are used in combination.
膠及びチオ尿素、場合によつては第３の添加剤を補足
的に添加することによつて陰極に析出する銅の樹枝状ま
たは瘤状の電着を抑制し平滑な電気銅を得ることができ
る。By supplementarily adding glue, thiourea, and in some cases a third additive, it is possible to suppress the dendritic or knob-like electrodeposition of copper deposited on the cathode and obtain smooth electrolytic copper. can.
電解添加剤として、チオ尿素等の硫黄含有添加剤を用い
た場合、含有硫黄原子の一部が電気銅の結晶粒界に析出
し、結晶微細化の効果が現われるようになる。 しかし
、その代償として電気銅中の硫黄品位が１０ｐμｍ程度
と比較的高くなり、最近、電気銅の各種用途において、
硫黄含有量の少ない電気銅を望む声が強い斯界において
、硫黄品位をこれ以下に下げるには、硫黄を含まない電
解添加剤を見い出すことが必要となつてきた。When a sulfur-containing additive such as thiourea is used as an electrolytic additive, some of the sulfur atoms contained are precipitated at the crystal grain boundaries of electrolytic copper, resulting in the effect of crystal refinement. However, as a trade-off, the sulfur content in electrolytic copper has become relatively high, around 10 pμm, and recently, in various uses of electrolytic copper,
In this industry, where there is a strong demand for electrolytic copper with a low sulfur content, it has become necessary to find electrolytic additives that do not contain sulfur in order to lower the sulfur grade below this level.
本発明は、上記に鑑み種々検討の結果、表面が平滑緻
密で硫黄含有量の少ない電気銅を製造し得る銅の電解精
製法を提供するものである。 さらに本発明は、硫黄含
有量が少ないことに加えて、他の有害不純物である砒素
、ビスマス、アンチモンの含有量が少ない電気銅を製造
し得る銅の電解精製法を提供するものである。As a result of various studies in view of the above, the present invention provides an electrolytic refining method for copper that can produce electrolytic copper having a smooth, dense surface and a low sulfur content. Furthermore, the present invention provides a copper electrolytic refining method that can produce electrolytic copper that has a low sulfur content and also a low content of other harmful impurities such as arsenic, bismuth, and antimony.
すなわち本発明は、硫酸酸性硫酸銅溶液を電解液とし
て電気分解することにより粗銅から純銅を回収する銅の
電解精製法において、硫酸酸性硫酸銅溶液にデンプンま
たはデキストリンを添加して電気分解することを特徴と
する銅の電解精製法に関するものである。That is, the present invention provides a method for electrolytically refining copper in which pure copper is recovered from blister copper by electrolyzing a sulfuric acid acidic copper sulfate solution as an electrolytic solution, in which starch or dextrin is added to the sulfuric acid acidic copper sulfate solution for electrolysis. This article relates to the characteristic method of electrolytic refining of copper.
本発明の電解添加剤であるデンプンは、植物組織から
工業的に分離精製されたものであり、ジヤガイモ、サツ
マイモなどの地下デンプン、トウモロコシ、小麦などの
地上デンプンのいずれも適用し得る。The starch that is the electrolytic additive of the present invention is industrially separated and purified from plant tissue, and any of underground starches such as potato and sweet potato, and above ground starches such as corn and wheat can be used.
またデキストリンはデンプンを加水分解して麦芽糖に至
るまでの分解中間生成物であり、加水分解の方法及び程
度により種々のものが得られるが、本発明の目的に対し
てほとんどのものが適用し得る。Dextrin is a decomposition intermediate product of starch hydrolysis to maltose, and various types can be obtained depending on the method and degree of hydrolysis, but most of them can be applied to the purpose of the present invention. .
上記デンプン及びデキストリンは、いずれも非イオン性
であり、銅の電解液中への添加量は１０ｍ９／ｅ〜５０
ｍ９／ｅ１好ましくは１５ｍ９／ｅ〜３０ｍ９／１１析
出銅トン当たり４０ｙ〜１５０ｆ１好ましくは６０ｙ〜
１００ｙで、これより少量では効果は薄く、またこれよ
り多く添加しても効果に変りはなく、不経済である。The above starch and dextrin are both nonionic, and the amount of copper added to the electrolyte is 10 m9/e to 50 m9/e.
m9/e1 preferably 15m9/e to 30m9/11 40y to 150f1 preferably 60y to 30m9/11 per ton of deposited copper
If the amount is less than 100y, the effect is weak, and if it is added in a larger amount, the effect remains the same and is uneconomical.
上記電解添加剤はデンプンまたはデキストリン単独で使
用しても良いが、膠、ゼラチン等従来使用されている水
溶性タンパク質と併用するとさらに効果は増大し特に表
面が平滑緻密な電気銅が得られる。The above-mentioned electrolytic additive may be used alone with starch or dextrin, but when used in combination with conventionally used water-soluble proteins such as glue and gelatin, the effect is further increased and electrolytic copper with a smooth and dense surface can be obtained.
また本発明の電解添加剤を使用する際の電解条件は、通
常実施されているものと特に変ソーはなく、例えば電解
液組成ＣＵ４Ｏｙ／′〜５５ｙ／Ｅ．．Ｈ２ｓＯ４ｌ８
Ｏｙ／′〜２２０ｆ／ｅ１液温関゜Ｃ〜６５℃、電流密
度２００Ａ／イ〜３００Ａ／イ、膠を併用する場合には
膠添加量６０ｙ〜１００ｆ１（析出銅トン当たり）なる
条件で行えば良い。以上説明したように本発明によれば
硫黄及び他の有害不純物である砒素、ビスマス、アンチ
モンの含有量が少ない電気銅の製造が可能であり、最近
の斯界の要求の十分応え得る銅の電解精製法を提供し得
る。以下本発明を実施例に基づいて説明する。実施例
ＣＵ５４ｙ／Ｅ，．Ｈ２ｓＯ４ｌ９８ｆ／ＥｌＮｉｌ６
ｆＩ／ｅを含有する銅電解液に、電解添加剤としてデン
プン（Ｓｔａｒｃｈ）またはデキストリン（Ｄｅｘｔｒ
ｉｎｅ）を（９）］１１！９／ｅ加え、液温槃℃、電流
密度３００Ａ／イで電解精製を行なつた。Further, the electrolytic conditions when using the electrolytic additive of the present invention are not particularly different from those normally practiced, and for example, the electrolytic solution composition is CU4Oy/' to 55y/E. ．． H2sO4l8
Oy/'~220f/e1 Liquid temperature: C~65℃, current density: 200A/a~300A/e, if glue is used, the amount of glue added is 60y~100f1 (per ton of deposited copper). good. As explained above, according to the present invention, it is possible to produce electrolytic copper with a low content of sulfur and other harmful impurities such as arsenic, bismuth, and antimony, and the electrolytic refining of copper can fully meet the recent demands of the industry. law can be provided. The present invention will be explained below based on examples. Example CU54y/E, . H2sO4l98f/ElNil6
Starch or dextrin is added as an electrolytic additive to the copper electrolyte containing fI/e.
(9)]11!9/e was added, and electrolytic refining was carried out at a liquid temperature of 300° C. and a current density of 300 A/e.
電解開始と同時に、デンプンまたはデキストリンを析出
銅トン当たり１００ｆ補加した。Simultaneously with the start of electrolysis, 100 f of starch or dextrin was added per ton of deposited copper.
また同時にデンプンまたはデキストリンと膠の併用試験
も行なつた。At the same time, a combination test of starch or dextrin and glue was also conducted.
この時の膠の添加量は１５１９／ｅとし、析出銅トン当
たりの補加量を８０ｆとした。また比較例として、電解
添加剤無添加及び膠とチオ尿素を析出銅トン当たり各々
８０ｙ１１００ｙ添加した場合についても併せて試験を
行なつた。The amount of glue added at this time was 1519/e, and the supplementary amount per ton of deposited copper was 80f. As comparative examples, tests were also conducted in which no electrolytic additive was added and in which 80y1100y of glue and thiourea were added per ton of deposited copper.
この結果得られた電気銅中の不純物品位をまとめて表１
に示す。表より本発明の電解添加剤を使用すると、電気
銅中の硫黄品位はもとより、他の有害不純物である砒素
、ビスマス、アンチモンの品位もまた低下することが明
らかである。Table 1 summarizes the impurity levels in electrolytic copper obtained as a result.
Shown below. It is clear from the table that when the electrolytic additive of the present invention is used, not only the sulfur level in electrolytic copper but also the levels of other harmful impurities such as arsenic, bismuth, and antimony are reduced.
本発明により得られた電気銅の表面は全て満足すべき緻
密平滑性を有していた。All the surfaces of the electrolytic copper obtained according to the present invention had satisfactory denseness and smoothness.
Claims (1)
ことにより粗銅から純銅を回収する銅の電解精製法にお
いて、硫酸酸性硫酸銅溶液にデンプンまたはデキストリ
ンを添加して電気分解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 pure copper is recovered from blister copper by electrolysis using a sulfuric acid acidic copper sulfate solution as an electrolyte, which is characterized by adding starch or dextrin to the sulfuric acid acidic copper sulfate solution and performing electrolysis. Electrolytic refining method of copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57184662A JPS6054397B2 (en) | 1982-10-22 | 1982-10-22 | Copper electrolytic refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57184662A JPS6054397B2 (en) | 1982-10-22 | 1982-10-22 | Copper electrolytic refining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5976886A JPS5976886A (en) | 1984-05-02 |
| JPS6054397B2 true JPS6054397B2 (en) | 1985-11-29 |
Family
ID=16157150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57184662A Expired JPS6054397B2 (en) | 1982-10-22 | 1982-10-22 | Copper electrolytic refining method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6054397B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6455394A (en) * | 1987-08-26 | 1989-03-02 | Nippon Mining Co | Production of high-purity electrolytic copper |
| JPH11223421A (en) | 1998-02-10 | 1999-08-17 | Denso Corp | Refrigerant evaporator |
-
1982
- 1982-10-22 JP JP57184662A patent/JPS6054397B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5976886A (en) | 1984-05-02 |
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