JPH0726222B2 - High-purity copper manufacturing method - Google Patents
High-purity copper manufacturing methodInfo
- Publication number
- JPH0726222B2 JPH0726222B2 JP3166295A JP16629591A JPH0726222B2 JP H0726222 B2 JPH0726222 B2 JP H0726222B2 JP 3166295 A JP3166295 A JP 3166295A JP 16629591 A JP16629591 A JP 16629591A JP H0726222 B2 JPH0726222 B2 JP H0726222B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- electrolysis
- hydrogen peroxide
- electrolytic bath
- nitric acid
- 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
- 239000010949 copper Substances 0.000 title claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 29
- 229910052802 copper Inorganic materials 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 44
- 238000005868 electrolysis reaction Methods 0.000 claims description 32
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 23
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 18
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000011282 treatment 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
【０００１】[0001]
【産業上の利用分野】本発明は高純度銅の湿式製造法に
関し、さらに詳しくは、硝酸酸性硝酸銅溶液を電解液と
する効率の良い、安定した電解精製法により高純度銅を
製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet production method of high-purity copper, and more specifically, a method for producing high-purity copper by an efficient and stable electrolytic refining method using a nitric acid-acidic copper nitrate solution as an electrolytic solution. Regarding
【０００２】[0002]
【従来の技術】従来、高純度銅の製造法としては、硫酸
酸性硫酸銅溶液を用いて陰極上に銅を析出させる硫酸銅
浴電解法が主として用いられてきたが、近年、除去が困
難な硫黄を排除する目的から硫酸酸性硫酸銅浴に代えて
硝酸酸性硝酸銅浴を用いる硝酸酸性硝酸銅浴電解法が注
目されている。2. Description of the Related Art Conventionally, as a method for producing high-purity copper, a copper sulfate bath electrolysis method of depositing copper on a cathode using a sulfuric acid-acidified copper sulfate solution has been mainly used, but in recent years, removal thereof is difficult. For the purpose of eliminating sulfur, a nitric acid-acidified copper nitrate bath electrolysis method using a nitric acid-acidified copper nitrate bath instead of the sulfuric acid-acidified copper sulfate bath is drawing attention.
【０００３】しかしながら、現在行われている硝酸酸性
硝酸銅浴電解法では、硝酸酸性電解浴中の析出銅陰極面
上に、硝酸の還元により生成される亜硝酸に起因すると
考えられる酸化銅（Ｃｕ2 Ｏ）の析出、並びにＮＯx ガ
スの発生などが生じ、陰極析出銅面の荒れ、電解の進行
妨害などと共に析出銅の品位低下をもたらし、安定した
電解を長時間継続することが困難である。However, in the currently performed nitric acid-acidic copper nitrate bath electrolysis method, copper oxide (Cu) (Cu), which is considered to be caused by the reduction of nitric acid, is formed on the deposited copper cathode surface in the nitric acid-acidic electrolytic bath. 2 O) precipitation, NO x gas generation, etc. occur, the copper surface deposited on the cathode becomes rough, the progress of electrolysis is impaired, and the quality of the deposited copper deteriorates, making it difficult to continue stable electrolysis for a long time. .
【０００４】硝酸の還元により生成される亜硝酸を除去
するために、電解液中にアセトアミドを添加して亜硝酸
を窒素ガスに分解して陰極面から放出しながら電解を行
う方法も行われているが、分解されたアセトアミドが亜
硝酸と反応してカルボン酸となり、電解液中に蓄積され
る等の問題があった。In order to remove nitrous acid produced by the reduction of nitric acid, a method is also used in which acetamide is added to an electrolytic solution to decompose nitrous acid into nitrogen gas and discharge it from the cathode surface to perform electrolysis. However, there is a problem that decomposed acetamide reacts with nitrous acid to form a carboxylic acid, which is accumulated in the electrolytic solution.
【０００５】上記硝酸酸性硝酸銅電解法における陰極反
応は、主反応としての Ｃｕ2+＋２ｅ＝Ｃｕ （Ｅ0 ＝0.34V ） (1) に対し、 ＮＯ3 - ＋３Ｈ+ ＋２ｅ＝ＨＮＯ2 ＋Ｈ2 Ｏ (2) ＨＮＯ2 ＋Ｈ+ ＋ｅ＝ＮＯ＋Ｈ2 Ｏ (3) の合成反応として、 ＮＯ3 - ＋４Ｈ+ ＋３ｅ＝ＮＯ＋２Ｈ2 Ｏ (Ｅ0 ＝0.99−0.06pHV ） (4) という副反応が進行しているものと考えられており、こ
のような副反応によって陰極上に析出する亜硝酸が、Ｃ
ｕ2 Ｏの析出、並びにＮＯx ガスの発生の原因となり、
電流効率の低下や析出電着銅の電着荒れを発生させる。The cathodic reaction in the above-described nitric acid-acidified copper nitrate electrolysis method is as follows: Cu 2+ + 2e = Cu (E 0 = 0.34 V ) (1) as the main reaction, whereas NO 3 − + 3H + + 2e = HNO 2 + H 2 O (2) As a synthetic reaction of HNO 2 + H + + e = NO + H 2 O (3), a side reaction of NO 3 − + 4H + + 3e = NO + 2H 2 O (E 0 = 0.99-0.06pH V ) (4) progresses. It is believed that the nitrous acid deposited on the cathode by such a side reaction is C
causing precipitation of u 2 O and generation of NO x gas,
It causes a decrease in current efficiency and electrodeposition of deposited electrodeposited copper.
【０００６】また、上記 (2)式の反応における部分反応
として、次のような諸反応が進行しているものと考えら
れている。 Ｈ+ ＋ＮＯ3 - ＝ＨＮＯ3 (5) ＨＮＯ3 ＋ＨＮＯ2 ＝Ｎ2 Ｏ4 ＋Ｈ2 Ｏ (6) Ｎ2 Ｏ4 ＝２ＮＯ2 (7) ２ＮＯ2 ＋２ｅ＝２ＮＯ2 - (8) ２ＮＯ2 - ＋２Ｈ+ ＝２ＨＮＯ2 (9) Further, as the partial reaction in the reaction of the above formula (2), it is considered that the following reactions are in progress. H + + NO 3 - = HNO 3 (5) HNO 3 + HNO 2 = N 2 O 4 + H 2 O (6) N 2 O 4 = 2NO 2 (7) 2NO 2 + 2e = 2NO 2 - (8) 2NO 2 - + 2H + = 2HNO 2 (9)
【０００７】すなわち、上記部分反応が進行するために
は亜硝酸の存在が不可欠であり、この亜硝酸が存在する
がゆえに陰極上におけるＣｕ2 Ｏの析出およびＮＯx ガ
スの発生は避けられないものであった。That is, the presence of nitrous acid is indispensable for the above partial reaction to proceed, and because of the presence of this nitrous acid, the precipitation of Cu 2 O and the generation of NO x gas on the cathode are inevitable. Met.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、硝酸酸性硝
酸銅溶液の電解時に、電解液中から亜硝酸を除去するこ
とによって、陰極上にＣｕ2 Ｏを主成分とする銅酸化物
が蓄積したりＮＯx ガスが発生したりすることを防止
し、安定した電解をより長く継続させることができる高
純度銅の製造法を提供することを目的とする。DISCLOSURE OF THE INVENTION According to the present invention, copper oxide containing Cu 2 O as a main component is accumulated on the cathode by removing nitrous acid from the electrolytic solution during electrolysis of a nitric acid-acidified copper nitrate solution. It is an object of the present invention to provide a method for producing high-purity copper capable of preventing stable generation of NO x gas and continuing stable electrolysis for a longer period of time.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究したところ、好ましくはpHを2.
5より小さい値に維持しながら、硝酸酸性硝酸銅溶液中
に過酸化水素を添加することにより、電解溶液中におけ
る亜硝酸が除去され、安定した電解が継続されることを
見い出し、本発明を達成することができた。[Means for Solving the Problems] The inventors of the present invention have conducted diligent research to solve the above problems.
While maintaining a value lower than 5, while adding hydrogen peroxide to the nitric acid acidic copper nitrate solution, found that nitrous acid in the electrolytic solution was removed and stable electrolysis was continued, and the present invention was achieved. We were able to.
【００１０】すなわち、本発明は、硝酸酸性硝酸銅電解
浴を用い、該電解浴における陰極面上に高純度銅を析出
させて得る電解法であって、好ましくはpHを 2.5より小
さい値に維持した上記電解浴に、電解開始前または電解
進行中に該電解浴中の陰極面で生成される亜硝酸に対し
て当量以上の過酸化水素を添加することを特徴とする高
純度銅の製造法を提供するものである。That is, the present invention is an electrolytic method using a nitric acid-acidified copper nitrate electrolytic bath to deposit high-purity copper on the cathode surface of the electrolytic bath, preferably maintaining the pH at a value lower than 2.5. A method for producing high-purity copper, characterized in that hydrogen peroxide in an amount equal to or more than the amount of nitrous acid generated on the cathode surface of the electrolytic bath before the start of electrolysis or during the progress of electrolysis is added to the above electrolytic bath. Is provided.
【００１１】[0011]
【作用】過酸化水素は、 Ｈ2 Ｏ2 ＋２Ｈ+ ＋２ｅ＝２Ｈ2 Ｏ （Ｅ0 ＝ 1.776V ）および Ｈ2 Ｏ2 ＝Ｏ2 ＋２Ｈ+ ＋２ｅ（Ｅ0 ＝ 0.699V ） という酸化および還元作用を行う能力を併有しているた
め、亜硝酸を含有する溶液中に過酸化水素を添加するこ
とにより生じる亜硝酸の分解反応として、次の２通りの
反応が考えられる。一つは、 Ｈ2 Ｏ2 ＋２Ｈ+ ＋２ｅ＝２Ｈ2 Ｏ、および ＨＮＯ2 ＋Ｈ2 Ｏ＝ＮＯ3 - ＋３Ｈ+ ＋２ｅより、 Ｈ2 Ｏ2 ＋ＨＮＯ2 ＝ＮＯ3 - ＋Ｈ+ ＋Ｈ2 Ｏ (10) という酸化反応、もう一つは、 Ｈ2 Ｏ2 ＝Ｏ2 ＋２Ｈ+ ＋２ｅ、および ２ＨＮＯ2 ＋２Ｈ+ ＋２ｅ＝２ＮＯ＋２Ｈ2 Ｏより、 ２ＨＮＯ2 ＋Ｈ2 Ｏ2 ＝２ＮＯ（ｇ）＋Ｏ2 ＋２Ｈ2 Ｏ (11) という還元反応である。Action Hydrogen peroxide has an oxidizing and reducing action of H 2 O 2 + 2H + + 2e = 2H 2 O (E 0 = 1.776 V ) and H 2 O 2 ═O 2 + 2H + + 2e (E 0 = 0.699 V ). Since it has both the ability to perform, the following two reactions are conceivable as the decomposition reaction of nitrous acid that occurs when hydrogen peroxide is added to a solution containing nitrous acid. One is from H 2 O 2 + 2H + + 2e = 2H 2 O and HNO 2 + H 2 O = NO 3 − + 3H + + 2e, and it is called H 2 O 2 + HNO 2 = NO 3 − + H + + H 2 O (10). oxidation reaction and another, H 2 O 2 = O 2 + 2H + + 2e, and 2HNO 2 + 2H + + 2e = from 2NO + 2H 2 O, 2HNO 2 + H 2 O 2 = 2NO (g) + O 2 + 2H 2 O (11) Is a reduction reaction.
【００１２】本発明者等は、亜硝酸が既知量溶存してい
るpH＝ 0.5〜2.5 の硝酸酸性硝酸銅溶液中に過酸化水素
を定量添加したところ、［ＨＮＯ2 ］／［Ｈ2 Ｏ2 ］＝
１なる反応、すなわち上記亜硝酸の酸化反応が進行する
ことを確認した。したがって、pH＝ 0.5〜2.5 の硝酸酸
性硝酸銅溶液電解浴中に、電解前または電解進行中に、
電解により生成する亜硝酸に対して当量以上の過酸化水
素を添加することにより、溶存する亜硝酸は酸化分解さ
れて消失し、ＮＯx ガスの発生やＣｕ2 Ｏを主成分とす
る銅酸化物の蓄積が防止される。また、過酸化水素は、
金属元素を含まないため高純度精製には都合が良く、し
かも自己消失するため電解に与える影響が極めて少な
く、極めて好適な添加剤であると言える。The present inventors have found that when hydrogen peroxide is quantitatively added to a nitric acid-acidified copper nitrate solution having a pH of 0.5 to 2.5 in which a known amount of nitrous acid is dissolved, [HNO 2 ] / [H 2 O 2 ] =
It was confirmed that the reaction No. 1, that is, the above oxidation reaction of nitrous acid proceeds. Therefore, in a nitric acid acidic copper nitrate solution electrolytic bath with pH = 0.5 to 2.5, before or during electrolysis,
By adding an equivalent amount or more of hydrogen peroxide to nitrous acid generated by electrolysis, dissolved nitrous acid is oxidatively decomposed and disappears, and NO x gas is generated or copper oxide containing Cu 2 O as a main component. Accumulation is prevented. Also, hydrogen peroxide is
Since it does not contain a metal element, it is convenient for high-purity purification, and since it self-disappears, it exerts very little influence on electrolysis and can be said to be an extremely suitable additive.
【００１３】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
【００１４】[0014]
【実施例１】硝酸酸性硝酸銅溶液３リットル（銅濃度 2
5g/l）を十分に煮沸し、溶液中の窒素酸化物（ＮＯ、Ｎ
Ｏ2 、ＨＮＯ2 ）を除去した後、窒素酸化物として亜硝
酸ソーダ（ＮａＮＯ2 10 mg/ml）溶液を用いて該硝酸酸
性硝酸銅溶液の亜硝酸濃度を30mg/lに調整した。これら
の処理を施した硝酸酸性硝酸銅溶液のpHを 1.5、 2.0お
よび 2.5とし、これら３種類の溶液をそれぞれスターラ
ーを用いて撹拌した後、25℃の液温を維持したまま濃度
が35 g/lの過酸化水素を 0.2mlずつ添加していった。過
酸化水素を添加するたびごとに吸光光度法によって該硝
酸銅溶液中の亜硝酸濃度を調べ、その結果を図１に示し
た。Example 1 Nitric acid acidic copper nitrate solution 3 liters (copper concentration 2
5g / l) is thoroughly boiled and nitrogen oxides (NO, N
O 2, HNO 2) after removal of the nitrite concentration of the nitric acid acidic copper nitrate solution was adjusted to 30 mg / l as nitrogen oxides with sodium nitrite (NaNO 2 10 mg / ml) solution. The pH of the nitric acid-acidified copper nitrate solution subjected to these treatments was adjusted to 1.5, 2.0, and 2.5, and these three types of solutions were stirred using a stirrer, respectively, and then the concentration was 35 g / l of hydrogen peroxide was added in 0.2 ml increments. Each time hydrogen peroxide was added, the concentration of nitrous acid in the copper nitrate solution was examined by an absorptiometric method, and the results are shown in FIG.
【００１５】図１からもわかるように、過酸化水素添加
量に対し、pH＝1.5 および 2.0の溶液中のＨＮＯ2 の濃
度はほぼ［ＨＮＯ2 ］／［Ｈ2 Ｏ2 ］＝１の当量で減少
し、当量点であるＨ2 Ｏ2 ＝２mlでＮＯ2 - は消失し
た。これに対してpH＝ 2.5の溶液では、亜硝酸の濃度は
ほとんど減少しなかった。As can be seen from FIG. 1, the concentration of HNO 2 in the solution of pH = 1.5 and 2.0 is approximately [HNO 2 ] / [H 2 O 2 ] = 1 equivalent to the amount of hydrogen peroxide added. It decreased, and NO 2 − disappeared at the equivalence point of H 2 O 2 = 2 ml. On the other hand, in the solution of pH = 2.5, the concentration of nitrite hardly decreased.
【００１６】一方、過酸化水素を添加したpH＝ 1.5の硝
酸酸性硝酸銅溶液（銅濃度＝25 g/l、ＨＮＯ2 濃度＝１
mg/l未満）３リットルを用い、６Ｎ電気銅を陽極および
４Ｎ無酸素銅板を陰極とし、陰極電流密度＝ 100Ａ／ｍ
2 、撹拌回転数＝150rpmおよび浴温＝25℃という電解条
件で72時間電解を行い、溶液中の亜硝酸濃度および析出
した銅の品位と電着状態を調べた。On the other hand, a nitric acid-acidified copper nitrate solution of pH = 1.5 to which hydrogen peroxide was added (copper concentration = 25 g / l, HNO 2 concentration = 1)
less than mg / l) 3 liters, using 6N electrolytic copper as an anode and 4N oxygen-free copper plate as a cathode, cathode current density = 100 A / m
2. Electrolysis was carried out for 72 hours under the electrolysis conditions of stirring rpm = 150 rpm and bath temperature = 25 ° C., and the nitrite concentration in the solution and the quality and electrodeposition of the deposited copper were investigated.
【００１７】その結果、電解後の電解浴中の亜硝酸濃度
は１mg/l未満であり、亜硝酸の増加は認められなかっ
た。また、得られた電着銅は平滑かつ緻密な７Ｎグレイ
ドの高純度銅であった。As a result, the nitrite concentration in the electrolytic bath after electrolysis was less than 1 mg / l, and no increase in nitrite was observed. The obtained electrodeposited copper was smooth and dense 7N grade high-purity copper.
【００１８】[0018]
【比較例１】過酸化水素を添加しないこと以外は実施例
１と同様にして電解を行い、電解浴中の亜硝酸濃度、電
着状態および析出した銅の品位を調べた。その結果、72
時間後に浴中の亜硝酸濃度は上昇し、陰極にＮＯx ガス
の発生が認められた。また、電着状態については、ＮＯ
x ガスによる電着荒れが生じており、析出した銅は酸化
銅であった。Comparative Example 1 Electrolysis was performed in the same manner as in Example 1 except that hydrogen peroxide was not added, and the nitrite concentration in the electrolytic bath, the electrodeposition state, and the quality of the deposited copper were examined. As a result, 72
After a lapse of time, the concentration of nitrous acid in the bath increased, and generation of NO x gas was observed at the cathode. Regarding the electrodeposition state, NO
Electrodeposition was caused by x gas, and the deposited copper was copper oxide.
【００１９】[0019]
【実施例２】実施例１と同様にして硝酸酸性硝酸銅溶液
の亜硝酸濃度を30mg/lに調整し、実施例１で示した電解
条件で電解を行い、電解進行中に過酸化水素を連続的に
添加し、電解浴中の亜硝酸濃度および析出した銅の品位
を調べた。なお、過酸化水素は、比較例１であらかじめ
調べた亜硝酸増加量(1.54 mg/hr)に対して当量(1.1mg/h
r)ずつ添加した。Example 2 In the same manner as in Example 1, the nitrite concentration of the nitric acid-acidified copper nitrate solution was adjusted to 30 mg / l, electrolysis was performed under the electrolysis conditions shown in Example 1, and hydrogen peroxide was added during the progress of electrolysis. After continuous addition, the nitrite concentration in the electrolytic bath and the quality of the deposited copper were examined. It should be noted that hydrogen peroxide is equivalent to the nitrite increase amount (1.54 mg / hr) previously examined in Comparative Example 1 (1.1 mg / h).
r) was added each.
【００２０】その結果、72時間後に亜硝酸濃度は２mg/l
まで減少し、得られた電着銅は平滑かつ緻密な７Ｎグレ
イドの高純度銅であった。As a result, after 72 hours, the nitrite concentration was 2 mg / l.
The obtained electrodeposited copper was a smooth and dense 7N grade high-purity copper.
【００２１】[0021]
【実施例３】電解進行中に過酸化水素を2.2mg/hrずつ添
加したこと以外は実施例２と同様にして電解浴中の亜硝
酸濃度および析出した銅の電着状態と品位を調べた。そ
の結果、電解前には30mg/lであった亜硝酸濃度は１mg/l
未満まで減少した。また、得られた電着銅は平滑かつ緻
密な７Ｎグレイドの高純度銅であった。[Example 3] The nitrite concentration in the electrolytic bath and the electrodeposited state and quality of the deposited copper were examined in the same manner as in Example 2 except that hydrogen peroxide was added in an amount of 2.2 mg / hr during the electrolysis. . As a result, the nitrite concentration was 1 mg / l, which was 30 mg / l before electrolysis.
Reduced to less than. The obtained electrodeposited copper was smooth and dense 7N grade high-purity copper.
【００２２】以上の結果より、電解浴中に添加された過
酸化水素は、析出する亜硝酸と速やかに反応して消失
し、残存した過酸化水素は自己分解して消失するため、
電解には影響を与えないことが確認された。また、過酸
化水素添加量および添加時期とその結果についての評価
を表１に示した。なお、表１における評価の欄は、No．
１、２および３については過酸化水素添加による亜硝酸
の減少度についての評価であり、No．４、５、６および
７については電解継続が可能であるか否かについての評
価である。また、Ｈ2 Ｏ2 添加量の欄における当量と
は、硝酸酸性硝酸銅電解浴中に析出する亜硝酸に対する
当量のことである。From the above results, the hydrogen peroxide added to the electrolytic bath rapidly reacts with the precipitated nitrous acid and disappears, and the remaining hydrogen peroxide self-decomposes and disappears.
It was confirmed that it does not affect electrolysis. Table 1 shows the evaluation of the amount of hydrogen peroxide added, the timing of addition, and the results. The evaluation column in Table 1 is No.
Nos. 1, 2 and 3 are evaluations regarding the degree of reduction of nitrous acid by the addition of hydrogen peroxide, and No. Nos. 4, 5, 6 and 7 are evaluations as to whether electrolysis can be continued. In addition, the equivalent in the column of the amount of H 2 O 2 added is the equivalent to the nitrous acid deposited in the nitric acid-acidified copper nitrate electrolytic bath.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明の開発により、硝酸酸性硝酸銅電
解法において電解浴中の陰極面上に析出する亜硝酸を消
失させることができるようになった。そのため、電解浴
中における陰極上にＣｕ2 Ｏを主成分とする銅酸化物が
蓄積したりＮＯx ガスが発生することが防止され、安定
した電解をより長く継続させることができるようになっ
た。また、本発明において電解浴中に添加する過酸化水
素は金属元素を含まず、かつ自己消失するため電解に与
える影響が極めて少ない。As a result of the development of the present invention, it has become possible to eliminate the nitrous acid deposited on the cathode surface in the electrolytic bath in the nitric acid-acidic copper nitrate electrolysis method. Therefore, accumulation of copper oxide containing Cu 2 O as a main component and generation of NO x gas on the cathode in the electrolytic bath were prevented, and stable electrolysis could be continued for a longer time. . Further, in the present invention, hydrogen peroxide added to the electrolytic bath does not contain a metal element and self-disappears, so that it has very little influence on electrolysis.
【図１】電解浴に添加する過酸化水素の添加量と、電解
浴に溶存する亜硝酸の濃度との関係を示したグラフであ
る。FIG. 1 is a graph showing the relationship between the amount of hydrogen peroxide added to an electrolytic bath and the concentration of nitrous acid dissolved in the electrolytic bath.
Claims (2)
電解精製において、電解により上記電解浴中に生成され
る亜硝酸に対して当量以上の過酸化水素を電解開始前ま
たは電解進行中に該電解浴中に添加することを特徴とす
る高純度銅の製造法。1. In the electrolytic refining of copper using a nitric acid-acidified copper nitrate electrolytic bath, an amount of hydrogen peroxide equal to or more than the amount of nitrous acid generated in the electrolytic bath by electrolysis is used before or during electrolysis. A method for producing high-purity copper, characterized in that it is added to the electrolytic bath.
さい値に保つ請求項１記載の方法。2. The method according to claim 1, wherein the pH value of the electrolytic bath during electrolysis is kept below 2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3166295A JPH0726222B2 (en) | 1991-06-11 | 1991-06-11 | High-purity copper manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3166295A JPH0726222B2 (en) | 1991-06-11 | 1991-06-11 | High-purity copper manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04365888A JPH04365888A (en) | 1992-12-17 |
| JPH0726222B2 true JPH0726222B2 (en) | 1995-03-22 |
Family
ID=15828696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3166295A Expired - Fee Related JPH0726222B2 (en) | 1991-06-11 | 1991-06-11 | High-purity copper manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0726222B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111364068A (en) * | 2020-04-27 | 2020-07-03 | 阳谷祥光铜业有限公司 | Preparation method of micron copper powder |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906644B (en) * | 2010-07-20 | 2012-11-28 | 福达合金材料股份有限公司 | Method for recycling copper from copper nitrate waste water |
| CN105132944B (en) * | 2014-06-06 | 2017-08-11 | 东北大学 | A kind of method and device for preparing high purity copper |
-
1991
- 1991-06-11 JP JP3166295A patent/JPH0726222B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111364068A (en) * | 2020-04-27 | 2020-07-03 | 阳谷祥光铜业有限公司 | Preparation method of micron copper powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04365888A (en) | 1992-12-17 |
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