JPH0753213A - Production of copper sulfate solution - Google Patents
Production of copper sulfate solutionInfo
- Publication number
- JPH0753213A JPH0753213A JP5198717A JP19871793A JPH0753213A JP H0753213 A JPH0753213 A JP H0753213A JP 5198717 A JP5198717 A JP 5198717A JP 19871793 A JP19871793 A JP 19871793A JP H0753213 A JPH0753213 A JP H0753213A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- sulfuric acid
- leaching
- raw material
- solution
- 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.)
- Pending
Links
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
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅原料中の銅分を硫酸
水溶液で浸出することによって硫酸銅溶液を製造する方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper sulfate solution by leaching the copper content in a copper raw material with an aqueous sulfuric acid solution.
【０００２】[0002]
【従来の技術】銅メッキ工場や種々の化学工業から発生
する含銅スラッジなどの回収銅は産出量が多く、回収銅
を原料とした銅のリサイクルは産業上重要な技術であ
る。これら回収銅は、種々の形態をとるが、現実に回収
銅として提供される銅原料中には、酸化第二銅のほかに
酸化第一銅を含む場合が多い。銅原料中の銅分を浸出し
て硫酸銅溶液を得る方法としては、硫酸水溶液を用い、
酸化第二銅の浸出を促す為にエアレーションをしたり、
エアレーションの代わりに酸化剤として、過酸化水素や
次亜塩素酸を添加する方法が行われている。通常空気の
使用が最も安価なので反応容器内の銅原料に硫酸水溶液
を送入し、得られるスラリーに対し、ただちにエアレー
ションを行いながら該スラリーの攪拌を継続することに
よって、銅原料中の銅分を浸出する。2. Description of the Related Art A large amount of recovered copper such as copper-containing sludge generated from copper plating plants and various chemical industries is produced, and recycling of copper from recovered copper is an industrially important technology. Although these recovered coppers take various forms, the copper raw material actually provided as recovered copper often contains cuprous oxide in addition to cupric oxide. As a method of leaching the copper content in the copper raw material to obtain a copper sulfate solution, an aqueous sulfuric acid solution is used,
Aeration to promote the leaching of cupric oxide,
A method of adding hydrogen peroxide or hypochlorous acid as an oxidant instead of aeration is performed. Since the use of air is usually the cheapest, the aqueous sulfuric acid solution is fed into the copper raw material in the reaction vessel, and the resulting slurry is immediately aerated while continuing to agitate the slurry to remove the copper content in the copper raw material. Leach out.
【０００３】[0003]
【発明が解決しようとする課題】しかし、エアレーショ
ンしながら攪拌し、銅原料を硫酸水溶液で浸出すると発
泡が著しく、さらに浸出を継続すると、銅原料スラリー
が浸出槽から溢れ出すという欠点がある。この溢れを防
ぐ為に、エアレーションを中断しながら浸出操作を断続
的に行う必要があり、その結果浸出反応が終了するまで
には長時間かかることになり、時間的ロスは極めて多大
であるという欠点もある。本発明は、上記欠点を伴わな
い、硫酸銅溶液の製造方法を提供することを目的とす
る。However, when the copper raw material is leached with an aqueous sulfuric acid solution while stirring while aerating, foaming is remarkable, and when the leaching is continued, the copper raw material slurry overflows from the leaching tank. In order to prevent this overflow, it is necessary to intermittently perform the leaching operation while interrupting aeration, and as a result it takes a long time to complete the leaching reaction, and the time loss is extremely large. There is also. It is an object of the present invention to provide a method for producing a copper sulfate solution without the above drawbacks.
【０００４】[0004]
【課題を解決するための手段】本発明は、銅原料を硫酸
水溶液中に浸漬した後、エアレーションしながら攪拌し
て銅原料中の銅分を硫酸水溶液で浸出することを特徴と
するものであり、また硫酸水溶液の硫酸濃度が９０〜１
８０ｇ／ｌ、温度が３０℃以上であることを特徴とする
ものである。The present invention is characterized by immersing a copper raw material in a sulfuric acid aqueous solution and then agitating while aerating to leaching the copper content in the copper raw material with the sulfuric acid aqueous solution. Also, the sulfuric acid concentration of the sulfuric acid aqueous solution is 90 to 1
It is characterized in that it is 80 g / l and the temperature is 30 ° C. or higher.
【０００５】[0005]
【作用】本発明は、銅原料を硫酸水溶液でエアレーショ
ンを行いながら浸出する時の発泡の原因が銅原料中に含
まれる酸化第一銅にあることを見いだしたことにある。
エアレーション下で酸化第一銅が発泡するのは、酸化第
一銅粒子表面の疎水性が強い為であると考えられる。と
くに酸化第一銅の含有量が２５重量％以上で発泡し易く
なる傾向を示す。The present invention is based on the finding that the cause of foaming when the copper raw material is leached while performing aeration with a sulfuric acid aqueous solution is cuprous oxide contained in the copper raw material.
It is considered that the cuprous oxide foams under aeration because the cuprous oxide particles have a strong hydrophobic surface. Especially when the content of cuprous oxide is 25% by weight or more, foaming tends to occur easily.
【０００６】本発明において、エアレーションを行いな
がら浸出する前に、銅原料を浸出用の硫酸水溶液中に浸
漬するのは、酸化第一銅に不均一化反応を起こさせるこ
とができるからである。この不均一化反応を式で示せば
次のように表される。 Ｃｕ2 Ｏ→ＣｕＯ＋Ｃｕ° たとえば、酸化第一銅（Ｃｕ2 Ｏ）試薬をＨ2 ＳＯ4 濃
度１３０ｇ／ｌ、温度４０℃の硫酸溶液中に浸漬する
と、図１に示すように銅原料中に存在していた酸化第一
銅が浸漬時間の経過と共に図２に示すように減少し、そ
の代わりに図３に示すように生成期の金属銅（Ｃｕ°）
が生じる。この不均一化反応によって生成する酸化第二
銅（ＣｕＯ）は硫酸水溶液中にただちに溶解する。また
同時に生成する生成期の金属銅は、エアレーションしな
がら攪拌することによって硫酸水溶液に溶解する。In the present invention, the reason why the copper raw material is immersed in the sulfuric acid aqueous solution for leaching before leaching while performing aeration is that cuprous oxide can cause a heterogeneous reaction. This heterogeneous reaction can be expressed by the following equation. Cu 2 O → CuO + Cu ° For example, when a cuprous oxide (Cu 2 O) reagent is immersed in a sulfuric acid solution having an H 2 SO 4 concentration of 130 g / l and a temperature of 40 ° C., it is present in the copper raw material as shown in FIG. As shown in FIG. 2, the amount of cuprous oxide that had been formed decreased as the immersion time passed, and instead, as shown in FIG.
Occurs. The cupric oxide (CuO) produced by this heterogeneous reaction is immediately dissolved in the aqueous sulfuric acid solution. Further, the metallic copper in the production period which is produced at the same time is dissolved in the sulfuric acid aqueous solution by stirring while aerating.
【０００７】図１に示される浸漬時間６０分の状態の酸
化第一銅をエアレーションしながら浸出すると、発泡は
全く見られない。また浸漬時間３０分の状態の酸化第一
銅をエアレーションしながら浸出すると、発泡がわずか
に見られるが反応容器から溢れ出ることはなかった。さ
らに浸漬時間を取らずにただちにエアレーションしなが
ら浸出した場合には、発泡が極めて激しく反応容器から
スラリーが溢れ出し浸出を継続することはできなかっ
た。このことから、エアレーションによる浸出の前にエ
アレーションを伴わない浸漬工程を設けることによっ
て、浸出する際に発泡することがないことから、上述の
不均一化反応により銅原料中に含む酸化第一銅が発泡す
る事なく、浸出されると考えられる。When leaching cuprous oxide in the state shown in FIG. 1 for 60 minutes with aeration, no foaming is observed at all. Further, when the cuprous oxide in the state of the immersion time of 30 minutes was leached while aerating, a slight foaming was observed, but it did not overflow from the reaction vessel. Furthermore, when leaching was immediately performed by aeration without taking soaking time, the foaming was so severe that the slurry overflowed from the reaction vessel and the leaching could not be continued. From this, by providing a dipping step without aeration before leaching by aeration, since there is no foaming during leaching, cuprous oxide contained in the copper raw material by the above-mentioned non-uniformization reaction It is considered to be leached without foaming.
【０００８】本発明において、硫酸水溶液の硫酸濃度を
９０〜１８０ｇ／ｌとするのは、９０ｇ／ｌ未満では、
銅原料中の銅分の浸出率が低くなるからであり、１８０
ｇ／ｌを越えても浸出率は変らず硫酸の消費量が増える
からである。また硫酸水溶液の温度を３０℃以上とする
のは、３０℃未満では浸出率が低くなるからである。In the present invention, the sulfuric acid concentration of the aqueous sulfuric acid solution is set to 90 to 180 g / l when it is less than 90 g / l.
This is because the leaching rate of the copper content in the copper raw material becomes low.
Even if it exceeds g / l, the leaching rate does not change and the consumption of sulfuric acid increases. The reason why the temperature of the aqueous sulfuric acid solution is set to 30 ° C. or higher is that the leaching rate becomes lower at less than 30 ° C.
【０００９】[0009]
（実施例１）銅原料（Ｃｕ７５．０重量％、Ｆｅ７．６
重量％：平均粒径０．１０ｍｍ）１０６６ｇと、Ｈ2 Ｓ
Ｏ4 濃度１３０ｇ／ｌの硫酸水溶液１０リットルで作成
した４０℃のスラリーを容量１５ｌの反応槽内で、６０
分間浸漬した。浸漬した後、空気量１０００ｍｌ／ｍｉ
ｎでエアレーションしながら３時間浸出を行った。その
結果、反応槽での発泡は見られなかった。そして得られ
た浸出液の銅濃度、浸出残渣量、残渣中の銅含有率及び
銅の浸出率を測定した。その結果を表１に示す。(Example 1) Copper raw material (Cu 75.0% by weight, Fe 7.6)
% By weight: average particle size 0.10 mm) 1066 g, H 2 S
A slurry at 40 ° C. prepared with 10 liters of an aqueous sulfuric acid solution having an O 4 concentration of 130 g / l was placed in a reaction vessel having a volume of 15 liters,
Soaked for a minute. After soaking, air volume 1000ml / mi
Leaching was performed for 3 hours while aerating with n. As a result, no foaming was observed in the reaction tank. Then, the copper concentration of the obtained leachate, the amount of the leach residue, the copper content in the residue, and the leach rate of copper were measured. The results are shown in Table 1.
【００１０】（実施例２）実施例１の方法において、浸
漬時間を３０分として浸漬した以外は、実施例１と同様
に浸出を行った。そのとき発泡がわずかに見られた。実
施例１と同様に測定し、その結果を表１に示す。Example 2 Leaching was performed in the same manner as in Example 1 except that the immersion time was 30 minutes in the method of Example 1. A slight bubbling was then seen. The measurement was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００１１】（比較例１）実施例１の方法において、硫
酸水溶液に浸漬せずに、最初からエアレーション（空気
量１０００ｍｌ／ｍｉｎ）しながら浸出を行った。その
結果、浸出開始後１分で、反応槽液面に泡が発生し始め
た。そのため、断続的に反応を行い、浸出時間が８時間
であった。実施例１と同様に測定し、その結果を表１に
示す。(Comparative Example 1) In the method of Example 1, leaching was carried out from the beginning while aeration (air amount of 1000 ml / min) without immersing in the sulfuric acid aqueous solution. As a result, one minute after the start of leaching, bubbles started to be generated on the liquid surface of the reaction tank. Therefore, the reaction was carried out intermittently, and the leaching time was 8 hours. The measurement was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００１２】（比較例２）実施例１の方法において、浸
漬時間を３時間としエアレーションをしないこと以外は
実施例１と同様に行った。実施例１と同様に測定し、そ
の結果を表１に示す。(Comparative Example 2) The same procedure as in Example 1 was carried out except that the immersion time was 3 hours and no aeration was carried out. The measurement was performed in the same manner as in Example 1, and the results are shown in Table 1.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１よりエアレーションを伴う浸出の前
に、浸漬する工程を設けることによって、発泡を起こす
ことなく、従来の方法による銅浸出率と同じ浸出率が得
られることが分かる。これに対して、エアレーションの
ないまま浸出を行うと、発泡は起こらないが、銅浸出率
が低い。これは、酸化第一銅の不均一化反応で生成する
Ｃｕ°が浸出されないまま浸出残渣中に残留してしまっ
たためと考えられる。浸出液への浸漬時間を設けた後
に、エアレーションしながら浸出を行う場合は、前半で
Ｃｕ2 Ｏの不均一化反応によってＣｕ°が生成し、後半
でのエアレーション下でこのＣｕ°が酸化浸出されるも
のと考えられる。本来Ｃｕ°は硫酸浸出され難いもので
あるが、不均一化反応によって生成されるＣｕ°は極め
て微粒子で且つ、表面活性が高いために、エアレーショ
ンによって酸化浸出されるものと考えられる。It can be seen from Table 1 that the same leaching rate as the copper leaching rate obtained by the conventional method can be obtained by providing the step of immersing before the leaching involving aeration without causing foaming. On the other hand, when leaching is performed without aeration, foaming does not occur, but the copper leaching rate is low. It is considered that this is because Cu ° generated by the heterogeneous reaction of cuprous oxide remained in the leaching residue without being leached. When leaching is performed while aeration is performed after the immersion time in the leaching solution, Cu ° is generated by the heterogeneous reaction of Cu 2 O in the first half, and this Cu ° is oxidized and leached under aeration in the second half. It is considered to be a thing. Originally, Cu ° is difficult to be leached with sulfuric acid, but Cu ° generated by the heterogeneous reaction is considered to be oxidatively leached by aeration because it is extremely fine particles and has high surface activity.
【００１５】[0015]
【発明の効果】本発明の方法によれば、酸化第一銅によ
る発泡、更には浸出反応容器からの銅原料スラリーの溢
れ出しを防止できるので、浸出反応を断続的に実施する
必要がなく、継続的に浸出を行わせることができるの
で、極めて短時間で従来法と同等の浸出結果を得ること
ができる。According to the method of the present invention, it is possible to prevent foaming by cuprous oxide and further overflow of the copper raw material slurry from the leaching reaction vessel, so that it is not necessary to carry out the leaching reaction intermittently. Since leaching can be performed continuously, leaching results equivalent to those of the conventional method can be obtained in an extremely short time.
【図１】酸化第一銅試薬のＸ線回折パターンを示す図で
ある。FIG. 1 is a diagram showing an X-ray diffraction pattern of a cuprous oxide reagent.
【図２】硫酸水溶液に３０分浸漬後の酸化第一銅試薬の
Ｘ線回折パターンを示す図である。FIG. 2 is a view showing an X-ray diffraction pattern of a cuprous oxide reagent after being immersed in a sulfuric acid aqueous solution for 30 minutes.
【図３】硫酸水溶液に６０分浸漬後の酸化第一銅試薬の
Ｘ線回折パターンを示す図である。FIG. 3 is a view showing an X-ray diffraction pattern of a cuprous oxide reagent after being immersed in a sulfuric acid aqueous solution for 60 minutes.
Ａ 酸化第一銅（Ｃｕ2 Ｏ） Ｂ 生成期の金属銅（Ｃｕ°）A Cuprous oxide (Cu 2 O) B Metallic copper in the production period (Cu °)
Claims (2)
液で浸出して、硫酸銅溶液を製造する方法において、該
銅原料を該硫酸水溶液中に浸漬した後、エアレーション
しながら攪拌して該銅原料中の銅分を該硫酸水溶液で浸
出することを特徴とする硫酸銅溶液の製造方法。1. A method for producing a copper sulfate solution by leaching a copper raw material containing cuprous oxide with a sulfuric acid aqueous solution, which comprises immersing the copper raw material in the sulfuric acid aqueous solution and then stirring while aerating. A method for producing a copper sulfate solution, which comprises leaching the copper content in the copper raw material with the aqueous sulfuric acid solution.
／ｌ、温度が３０℃以上であることを特徴とする請求項
１に記載の製造方法。2. A sulfuric acid solution having a sulfuric acid concentration of 90 to 180 g.
/ L, the temperature is 30 ℃ or more, the manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198717A JPH0753213A (en) | 1993-08-11 | 1993-08-11 | Production of copper sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198717A JPH0753213A (en) | 1993-08-11 | 1993-08-11 | Production of copper sulfate solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0753213A true JPH0753213A (en) | 1995-02-28 |
Family
ID=16395840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5198717A Pending JPH0753213A (en) | 1993-08-11 | 1993-08-11 | Production of copper sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753213A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022486A1 (en) * | 2002-09-05 | 2004-03-18 | Nikko Materials Co., Ltd. | High purity copper sulfate and method for production thereof |
| EP1695938A4 (en) * | 2003-09-04 | 2007-06-06 | Nippon Mining Co | High purity copper sulfate and method for production thereof |
| CN105923966A (en) * | 2016-04-20 | 2016-09-07 | 广东省稀有金属研究所 | Method for leaching out nickel, copper and sulfur from electroplating sludge |
-
1993
- 1993-08-11 JP JP5198717A patent/JPH0753213A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022486A1 (en) * | 2002-09-05 | 2004-03-18 | Nikko Materials Co., Ltd. | High purity copper sulfate and method for production thereof |
| EP1695938A4 (en) * | 2003-09-04 | 2007-06-06 | Nippon Mining Co | High purity copper sulfate and method for production thereof |
| US7695527B2 (en) | 2003-09-04 | 2010-04-13 | Nippon Mining & Metals Co., Ltd | High purity copper sulfate and method for production thereof |
| CN105923966A (en) * | 2016-04-20 | 2016-09-07 | 广东省稀有金属研究所 | Method for leaching out nickel, copper and sulfur from electroplating sludge |
| CN105923966B (en) * | 2016-04-20 | 2018-07-27 | 广东省稀有金属研究所 | A method of leaching ambrose alloy sulphur from electroplating sludge |
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