JP2008081784A - Electrolyzed sediment copper treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly convenient method for separating and recovering copper, arsenic, bismuth, antimony or the like from electrolyzed sediment copper. <P>SOLUTION: The electrolyzed sediment copper treatment mehtod comprises: a first step (1) in which electrolyzed sediment copper is water-washed, thereafter, while introducing oxygen-containing gas into the electrolyzed sediment copper in sulfuric acidity, an As component is oxidized to be pentavalent, sulfuric acid leaching is performed, then it is subjected to solid-liquid separation into leaching residue containing Sb and Bi components and a sulfuric acid decotion containing the As component; a second step (2) in which trivalent iron is added to the sulfuric acid decotion to thereby produce crystalline scorodite, and it is subjected to solid-liquid separation into residue containing the crystalline scorodite and a liquid after the removal of the arsenic; an optional third step (3) in which alkali is added to the liquid after the removal of arsenic to thereby produce an Fe salt, the As component and the Fe salt are coprecipitated, then it is subjected to solid-liquid separation into precipitates containing the Fe salt and the As component, and a liquid after the removal of the iron; and a fourth step in which alkali is added to the liquid after the removal of the iron to precipitate a Cu salt, then it is subjected to solid-liquid separation into precipitates containing the Cu salt and a liquid after the removal of the copper. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for treating electrolytically precipitated copper produced in a copper smelting process. More specifically, the present invention relates to a method for separating and recovering copper, arsenic, bismuth, antimony, and the like from electrolytically precipitated copper.

Various impurities are mixed in the copper ore, and examples of such impurities include arsenic (As), bismuth (Bi), antimony (Sb), and the like. Most of these impurities are volatilized and separated by high heat in the dry process of copper smelting, but some are mixed into the crude copper and brought into the copper electrolytic purification process.
As, Sb, Bi, etc. contained in the crude copper (copper anode) are partly eluted in the electrolytic solution, and the undissolved part is precipitated at the bottom of the electrolytic cell as anode slime. Further, since the amount of copper eluted from the anode is generally larger than the amount of copper deposited on the cathode, the copper concentration in the electrolytic solution gradually increases. Therefore, a part of the electrolytic solution is extracted into another electrolytic cell to control the quality of the electrolytic solution. The extracted electrolytic solution is subjected to copper removal electrolysis, Cu and the impurities are deposited on the cathode, and Cu and the impurities are separated and recovered by depositing them on the bottom of the electrolytic cell. In this field, those precipitated at the bottom of the electrolytic cell and those deposited at the cathode are collectively referred to as electrolytically precipitated copper.

  Electrolytically precipitated copper is usually repeated in the copper smelting process, but it is preferable to separate impurities from the electrolytically precipitated copper. In addition, As, Sb, Bi, etc. still have a way to be used as valuable materials. Therefore, a technique for separating and recovering Cu, As, Sb, Bi, and the like from electrolytically precipitated copper is desired.

  For example, JP 2002-249827 A describes a method of separating bismuth and antimony from electrolytically precipitated copper by a wet method. Specifically, an alkaline treatment of electrolytically precipitated copper containing copper oxide, bismuth, and antimony was leached with 50 to 200 g / L sulfuric acid at a liquid temperature of 40 to 90 ° C., a treatment time of 2 to 5 hours, copper, arsenic, By eluting nickel and leaving bismuth and antimony in the residue, bismuth, antimony and copper are separated. On the other hand, it is described that the recovery of copper, arsenic and nickel leached with sulfuric acid can be repeated, for example, after the neutralization treatment in the dry process of copper smelting.

Japanese Patent No. 3212875 describes a method for recovering arsenic from a smelting intermediate. Specifically, it is a method for recovering arsenic, which includes a step of adding copper and copper oxide or copper or copper oxide to an arsenic-containing aqueous solution and generating arsenic acid by oxidation. Arsenic is recovered by slaked lime as calcium arsenate precipitate.
JP 2002-249827 A Japanese Patent No. 3212875

  However, it is unavoidable that there are a lot of impurities in the electrolytically precipitated copper that is repeated in the copper smelting process, which increases the burden on the dry process and electric smelting. Various problems still exist such that it is more desirable if it can be recovered. That is, the conventionally proposed electrolytic precipitation copper treatment system cannot be an optimal system from the viewpoint of separation procedure, stability of recovered material, and recyclability, and there is still room for improvement.

  Accordingly, one of the objects of the present invention is to provide a more convenient method for separating and recovering copper, arsenic, bismuth, antimony and the like from electrolytically precipitated copper.

In order to solve the above-mentioned problems, the present inventor has eagerly studied a treatment system for electrolytically precipitated copper, and found that the following treatment system combined with a series of operations is more effective than expected for treating electrolytically precipitated copper. I found it.
That is, the present invention in one aspect,
(1) After the electrolytically precipitated copper is optionally washed with water, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced into the electrolytically precipitated copper in sulfuric acid acid while introducing an oxygen-containing gas. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component A first step of solid-liquid separation into sulfuric acid leachate,
(2) By adding trivalent iron to the sulfuric acid leaching solution to produce crystalline scorodite (FeAsO ₄ .2H ₂ O), solid-liquid separation into a residue containing the crystalline scorodite and a post-arsenic-removed solution A second step to perform,
(3) When unreacted Fe or unreacted Fe and As remain in the solution after de-arsenic, an alkali is added to form a Fe salt, and the As component remains when the As component remains An optional third step of co-precipitation with Fe salt, followed by solid-liquid separation into a precipitate containing Fe salt and an As component (if the As component remains) and a solution after deironing;
(4) An optional fourth step of adding an alkali to the post-deironation solution to precipitate a Cu salt, and then solid-liquid separation into a precipitate containing the Cu salt and a post-decopperization solution;
It is a processing method of the electrolytic precipitation copper containing.

  In one embodiment of the invention, sulfuric acid leaching in the first step involves stirring at 70-95 ° C. for 4.5-11 hours.

  In one embodiment of the present invention, sulfuric acid leaching in the first step is performed without heating from the outside.

  In one embodiment of the present invention, the oxygen-containing gas in the first step is air.

  In one embodiment of the present invention, the introduction and / or stirring of the oxygen-containing gas in the first step is performed by jet injection.

  In one embodiment of the present invention, the sulfuric acid leachate in the first step has a pH of 0.3 to 2.2.

  In one embodiment of the present invention, the As component is 95 wt. % Or more is oxidized to pentavalent.

  In one embodiment of the present invention, the crystalline scorodite in the second step is produced by heating to 60-95 ° C.

  In one embodiment of the present invention, the trivalent iron in the second step is provided as ferric sulfate.

  In one embodiment of the present invention, the crystalline scorodite in the second step is generated at a pH of 0.4 to 1.2.

  In one embodiment of the present invention, the alkali in the third step is added until the pH of the dearsenic solution is in the range of 2.2 to 4.0.

  In one embodiment of the present invention, the alkali in the fourth step is added until the pH of the solution after deironing is in the range of 4.0 to 8.0.

  In one embodiment of the present invention, the alkali in the third step and / or the fourth step is provided as calcium carbonate.

  According to the present invention, Cu, As, Bi, and Sb can be separated and recovered from electrolytically precipitated copper. At this time, As is fixed as a stable scorodite. This is a form that is less soluble in water than calcium arsenate, is stable and suitable for long-term storage. Cu can be returned to the copper smelting process in a state in which impurities are reduced, and the limitation on the amount of repetition due to the purification process of the dry process and electric smelting is greatly reduced. Therefore, the residence time in the smelting process of copper in the electrolytically precipitated copper as an intermediate product can be shortened.

Electrolytically precipitated copper The target raw material of the treatment method according to the present invention is mainly the electrolytically precipitated copper produced in the copper smelting process as described above, but if it is a substance having substantially the same composition as the electrolytically precipitated copper The processing method according to the present invention can be applied. Therefore, “electrolytically precipitated copper” as used in the present invention includes chemical substances having substantially the same composition as electrolytically precipitated copper regardless of its origin. For example, electrolytically precipitated copper is Cu: 30 to 70 wt. %, As: 20 to 50 wt. %, Bi: 0.1 to 6 wt. %, Sb: 0.5 to 8 wt. %, Pb: 0.1 to 10 wt. In general, a substance having such a composition is the subject of the present invention as electrolytically precipitated copper.

Prior to the first washing process, the electrolytically precipitated copper may be optionally washed with water. The washing process involves repulping the electrolytically precipitated copper with water and stirring for 0.5 to 6 hours, and is included in the electrolytic solution (including copper sulfate, Ni, Fe, etc.) attached during the production of the electrolytically precipitated copper and the electrolytically precipitated copper After dissolving a trace amount of Ni, Fe, and the like, the slurry can be filtered and solid-liquid separated. In this step, most of Fe and Ni can be separated from the electrolytically precipitated copper.
However, this operation is necessary for the sulfuric acid leaching of the electrolytically precipitated copper in the next step by clarifying the amount of zero-valent (not dissolved in water) copper excluded from the copper amount in the electrolytically precipitated copper. The main purpose of this operation is to obtain a more accurate amount of sulfuric acid. If trace elements such as Ni and Fe are not particularly concerned, or if the content of copper sulfate is known or the electrolytic solution is not brought into the electrolytically precipitated copper, this step is not necessary.

First Step In the first step, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced while introducing an oxygen-containing gas into the electrolytically precipitated copper in sulfuric acid acidity. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component Solid-liquid separation into sulfuric acid leachate.

The leaching reaction occurring at this time generally follows the following equation: Cu is oxidized to Cu ²⁺ and As is oxidized to As ⁺⁵ .
_{Cu + H 2 SO 4 + 1} / 2O 2 → CuSO 4 + H 2 O ···· (1)
2As + 5/2 O ₂ + 3H ₂ O → 2H ₃ AsO ₄ (2)
The amount of sulfuric acid used is preferably 1.0 to 1.2 equivalents relative to the amount of Cu. When it is less than 1.0 equivalent, the leaching solution becomes weakly acidic, precipitates such as Cu ₃ AsO ₄ are generated, and the leaching rate of Cu and As decreases. When it exceeds 1.2 equivalents, the leaching rate of Cu and As is not affected, but the amount of sulfuric acid used is increased. The concentration of Cu and As in the sulfuric acid solution is not particularly limited. However, if the solubility is exceeded, the leaching rate of Cu and As decreases, so that it is preferably not more than the solubility of Cu ²⁺ and As ⁵⁺ .
Further, as the pH of the sulfuric acid leaching solution, the solubility of the crystalline scorodite produced in the second step is rapidly increased at pH 0.3 or less, thereby inhibiting the production of crystalline scorodite. Furthermore, when the pH is 2.2 or more, the added iron is precipitated as iron hydroxide, and iron is not effectively used for the synthesis of scorodite. For these reasons, the pH is preferably in the range of 0.3 to 2.2, more preferably in the range of 0.4 to 1.2.

In sulfuric acid leaching, for example, by stirring at 70 to 95 ° C. for 4.5 to 11 hours, preferably at 80 to 95 ° C. for 7 to 11 hours, the oxidation of As progressed reliably, and 90 wt. % Or more, preferably 95 wt. % Or more, more preferably 98 wt. % Or more can be oxidized to pentavalent. Since sulfuric acid leaching is an exothermic reaction, it can be performed without heating from the outside. The stirring time may be longer, and may be determined as appropriate in consideration of economy and effect.
In order to increase the oxidation efficiency of As, it is preferable to supply a sufficient amount of oxygen-containing gas bubbles to be introduced (for example, 10 equivalents of oxygen to copper for 7 hours). Therefore, it is preferable to vigorously perform stirring, and for example, introduction of oxygen-containing gas and / or stirring is conveniently performed by jet injection. This value is in the case of jet injection (trade name of jet agitator), and in the case of a stirrer using a normal turbine blade, the reaction efficiency is lowered, and even when the amount of oxygen-containing gas is introduced 3.5 times or more, More than twice the reaction time is required. By controlling the valence of As at this stage, scorodite generation in the second step is facilitated. Cu ²⁺ also has the effect of promoting As oxidation.

  The oxygen-containing gas is not particularly limited as long as it does not have a significant adverse effect on the above reaction. For example, pure oxygen or a mixture of oxygen and an inert gas can be used. Air is preferable from the viewpoint of handling and cost.

  Moreover, in order to efficiently separate Sb and Bi from electrolytically precipitated copper, the solubility of Sb and Bi in the sulfuric acid leachate is constant, so (1) increase the electrolytically precipitated copper pulp concentration during sulfuric acid leaching, (2) It is preferable to use electrolytically precipitated copper having high Sb and Bi quality. Bi and Sb separated from the electrolytically precipitated copper can be separately separated and recovered by, for example, electric furnace treatment.

Second Step In the second step, trivalent iron is added to the sulfuric acid leachate obtained in the first step to produce crystalline scorodite (FeAsO ₄ .2H ₂ O), and then the residue containing the crystalline scorodite And solid-liquid separation after de-arsenic.

  Crystalline scorodite can be produced, for example, by heating to 60 to 95 ° C. under atmospheric pressure. For example, a sufficient amount of scorodite is produced by reacting for 8 to 72 hours. Since As is sufficiently oxidized to pentavalent in the first step, crystalline scorodite is produced with trivalent iron and high reaction efficiency. Scorodite is chemically stable and suitable for long-term storage.

Examples of the trivalent iron include iron oxide, iron sulfate, and iron chloride. The trivalent iron is preferably provided in the form of an acidic aqueous solution from the viewpoint of performing a reaction in an aqueous solution. It is preferable that the solution is provided in the form of an aqueous solution of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) from the viewpoint that it is most effective to return the solution to an electrolysis electrolyte. Moreover, the polyferric sulfate aqueous solution used by waste water treatment etc. can also be used. At this time, it is advantageous from the viewpoint of scorodite synthesis that the sulfuric acid leachate to which the aqueous solution is added is added as a pH such that the pH is maintained at 0.3 to 2.2, preferably 0.4 to 1.2. is there. Since As is sufficiently pentavalently oxidized in the first step, scorodite is easily generated even at such a low pH. There is also an advantage that it is not necessary to add an alkali such as caustic soda because it is not necessary to raise the pH at this stage. Therefore, in the method for treating electrolytically precipitated copper according to the present invention, smooth cooperation without waste is possible between the first step and the second step.

  The amount of trivalent iron used is required to be 1.0 equivalent or more with respect to the amount of As from the viewpoint of removing As, and is preferably 1.1 to 1.5 equivalents from an economical viewpoint.

Third step The third step is an optional step performed when unreacted Fe or unreacted Fe and As remain in the post-dearsenic solution, and an alkali is added to produce an Fe salt. When the As component remains, the As component is co-precipitated with it, and then solid-liquid separation into a precipitate containing the Fe salt and As component (when the As component remains) and a solution after deironing To do.

The alkali to be used is not particularly limited as long as it can generate an insoluble Fe salt (an insoluble Fe salt that can co-precipitate As if it remains). Examples thereof include sodium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide, and magnesium hydroxide.
It is most effective for the copper smelting process to return the solution after the reaction to the electrolytic solution of electrolysis. Considering this point, it is difficult to remove sodium in the electrolytic solution, so that it is not preferable to use it. On the other hand, calcium is not subject to strong restrictions because it produces and removes coexisting sulfuric acid and gypsum. From this point of view, it is preferable to use calcium compounds such as calcium carbonate and calcium hydroxide as alkali, and calcium carbonate is particularly preferable because pH can be easily controlled.

  Alkaline has a pH at which precipitation of iron hydroxide is noticeable at 2.2, and copper tends to precipitate when it exceeds 4.0, so the pH of the solution after de-arsenic is in the range of 2.2 to 4.0. It is preferable to add it until it becomes, for reasons of precipitation efficiency of Fe salt and avoidance of precipitation of Cu salt, and it is more preferable to add until the pH is in the range of 3.0 to 3.5.

  This precipitate can be dissolved in sulfuric acid, then returned to the second step, and reused as the iron source and As to be treated (when the As component remains). In addition, copper sulfate is mainly contained in the liquid after deironing and has few impurities, so that it can be used as an electrolytic solution for electric smelting. However, after the iron removal, the Cu may be recovered as a precipitate by the following fourth step.

Fourth Step The fourth step is an optional step that is performed when Cu is recovered as a precipitate. An alkali is added to the solution after deironing to precipitate a Cu salt, and then a precipitate containing the Cu salt is added. Solid-liquid separation after the copper removal. In order to improve the filterability, for example, it is effective to age the precipitate by heating at 40 to 70 ° C. for 30 to 90 minutes.

The alkali to be used is not particularly limited as long as it can generate an insoluble Cu salt, and examples thereof include sodium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. If calcium salt is used, gypsum is mixed and the copper quality in the precipitation is lowered, so in order to reduce the precipitate, sodium-based alkali is used. It is preferable to do this.
Alkaline is preferably added until the pH of the solution after iron removal is in the range of 4.0 to 8.0 for reasons such as Cu salt precipitation efficiency, alkali cost, copper quality in the precipitate, and drainage standards. It is more preferable to add until the pH is in the range of 5.0 to 7.0.

  The solution after copper removal is mainly composed of calcium or sodium and sulfate radicals used for neutralization, and since heavy metals are removed, it can be treated as a general integrated waste water.

Hereinafter, examples for better understanding of the present invention and its advantages will be described, but the present invention is not limited thereto.
FIG. 1 shows one aspect of the processing flow of the present invention.

Electrolytically Precipitated Copper Washing Treatment 1000 g (wet weight) of electrolytically precipitated copper having the composition shown in Table 1 was repulped with 2000 ml of water, stirred for 4 hours, and an electrolyte solution (copper sulfate, nickel deposited during the production of electrolytically precipitated copper) , Iron, etc.), the slurry was filtered and solid-liquid separated. The obtained residue was dried and led to the first step. The residue weight after drying was 733.2 g. Ni and Fe could be removed almost completely. The analytical value of the residue is also shown in Table 1.

First step: 228.6 g of 98% concentrated sulfuric acid (1.1 equivalents to the copper contained in the electrolytically precipitated copper) was added to 200 g (dry weight) of the electrolytically precipitated copper that had been subjected to the sulfuric acid leaching and washing treatment of the electrolytically precipitated copper. Further, water was added to make the slurry amount 2000 ml (pH 0.07 before starting the reaction).
While introducing air at 700 ml / min, the mixture was stirred and leached for 7 hours. A jet agitator (JET AJITER manufactured by SHIMAZAKI) was used for air introduction and stirring. Although the liquid temperature was not particularly controlled, sulfuric acid leaching is an exothermic reaction, so the liquid temperature rose to 88 ° C. 4 hours after the start of leaching, then gradually decreased, and after 7 hours, the temperature was 70 ° C. there were. Due to the reaction, the color of the liquid changed from black to blue (pH 0.85 after completion of the reaction). After leaching with sulfuric acid, the leachate was filtered and solid-liquid separated. The residue was washed with water, and the washing water was added to the sulfuric acid leachate. Table 2 shows the amounts of the obtained sulfuric acid leaching solution and sulfuric acid leaching residue.
In view of the amount of the residue, 87.1% bismuth in the electrolytically precipitated copper could be removed from the leachate as a residue. Moreover, since only 1.6% arsenic and 0.4% copper remain in the residue, the reaction efficiency is high.

Second step: Synthesis of scorodite In 425 ml of sulfuric acid leachate obtained in the first step, 43 g of ferric sulfate solution (ferric sulfate reagent (n-hydrate, ferric content 21.3%)) was dissolved in warm water. 225 ml of ferric iron with respect to arsenic contained in the liquid and sulfuric acid leachate) was added to make the liquid volume 650 ml, heated to 95 ° C., and scorodite was synthesized for 24 hours.
Immediately after mixing the sulfuric acid leachate and the ferric sulfate solution at room temperature, the reaction did not proceed, but precipitation of scorodite was observed at around 60 ° C. with heating. The pH of the synthesis solution was 0.63 (room temperature) before the start of the reaction, but was 0.58 (room temperature) after the completion of the reaction. After the scorodite synthesis, the scorodite crystals were filtered and solid-liquid separated.
The scorodite crystals were washed with water, and the washing water was added to the solution after dearsenization. Table 3 shows the amounts of the obtained scorodite crystals and the liquid after dearsenization. The XRD of the obtained scorodite crystal is shown in FIG. A stable crystalline scorodite with little arsenic elution is obtained.
The elution of arsenic from the scorodite obtained by this synthesis was 0.2 mg / L (using an acetate buffer solution of TCLP pH 5), and it was confirmed that arsenic was stable. From the viewpoint of the quantity of scorodite crystals, the reaction efficiency is high because 98.0% of arsenic is distributed to the scorodite crystals.
Considering that trivalent arsenic does not contribute to scorodite synthesis, it can be said that 98% or more of dissolved arsenic is pentavalent due to sulfuric acid leaching of electrolytically precipitated copper. It was shown that the sulfuric acid leaching solution of electrolytically precipitated copper was effective as a raw material for scorodite synthesis.

Third step: Neutralization of iron removal Add 26.6 g of calcium carbonate (10.64 g of Ca) to 1370 ml of the dearsenic solution obtained in the second step, neutralize to pH 3.48, and arsenic and iron Co-precipitated as iron hydroxide. Thereafter, in order to improve filterability, the precipitate was aged by heating at 60 ° C. for 30 minutes. This precipitation includes iron hydroxide co-precipitated with arsenic and gypsum produced by calcium carbonate and sulfate radicals added during neutralization.
The precipitate was filtered and separated into solid and liquid. The precipitate was washed with water, and the washing water was added to the solution after deironation. Table 4 shows the amount of the obtained precipitate (hereinafter referred to as deironed mud) and the liquid after deironing. Arsenic is not detected from the solution after iron removal and is efficiently removed. On the other hand, only 0.3% of the copper in the iron removal mud is distributed, indicating that it remains in the liquid after the iron removal.
In addition, in order to investigate pH dependence, the result when changing pH and carrying out deiron neutralization is shown in FIG.

Fourth step: Neutralization of copper removal Add 9.2 g of calcium carbonate (3.68 g of Ca) to 2315 ml of the post-deironation solution obtained in the third step, and neutralize to pH 5.59 to obtain copper hydroxide. Precipitated. Thereafter, in order to improve filterability, the precipitate was aged by heating at 60 ° C. for 30 minutes. The precipitate was filtered and separated into solid and liquid. Table 5 shows the amount of the obtained precipitate (hereinafter referred to as decoppered mud) and the post-decopperized liquid. Copper is well separated from bismuth and arsenic with high recovery.
In addition, in order to investigate pH dependence, the result at the time of performing copper removal neutralization by changing pH is shown in FIG.

An aspect of the processing flow of the present invention is shown. It is XRD of the scorodite crystal obtained in the Example. It is a figure showing the pH dependence of iron removal neutralization. It is a figure showing the pH dependence of copper removal neutralization.

Claims (13)

(1) After the electrolytically precipitated copper is optionally washed with water, 90 wt. As of the As component contained in the electrolytically precipitated copper is introduced into the electrolytically precipitated copper in sulfuric acid acid while introducing an oxygen-containing gas. Sulfuric acid leaching including stirring the solution at a temperature and time sufficient to oxidize more than 5% to pentavalent, followed by leaching residue containing Sb component and Bi component and pentavalent As component A first step of solid-liquid separation into sulfuric acid leachate,
(2) By adding trivalent iron to the sulfuric acid leaching solution to produce crystalline scorodite (FeAsO ₄ .2H ₂ O), solid-liquid separation into a residue containing the crystalline scorodite and a post-arsenic-removed solution A second step to perform,
(3) When unreacted Fe or unreacted Fe and As remain in the solution after de-arsenic, an alkali is added to form a Fe salt, and the As component remains when the As component remains An optional third step of co-precipitation with Fe salt, followed by solid-liquid separation into a precipitate containing Fe salt and an As component (if the As component remains) and a solution after deironing;
(4) An optional fourth step of adding an alkali to the post-deironation solution to precipitate a Cu salt, and then solid-liquid separation into a precipitate containing the Cu salt and a post-decopperization solution;
A method for treating electrolytically precipitated copper comprising:   The processing method according to claim 1, wherein the sulfuric acid leaching in the first step involves stirring at 70 to 95 ° C for 4.5 to 11 hours.   The treatment method according to claim 1 or 2, wherein the sulfuric acid leaching in the first step is performed without heating from the outside.   The processing method according to any one of claims 1 to 3, wherein the oxygen-containing gas in the first step is air.   The processing method according to any one of claims 1 to 4, wherein the introduction and / or stirring of the oxygen-containing gas in the first step is performed by jet injection.   The treatment method according to any one of claims 1 to 5, wherein the sulfuric acid leachate in the first step has a pH of 0.3 to 2.2.   As component was 95 wt. % Or more is oxidized to pentavalent, The processing method as described in any one of Claims 1-6.   The processing method according to any one of claims 1 to 7, wherein the crystalline scorodite in the second step is produced by heating to 60 to 95 ° C.   The treatment method according to any one of claims 1 to 8, wherein the trivalent iron in the second step is provided as ferric sulfate.   The processing method according to any one of claims 1 to 9, wherein the crystalline scorodite in the second step is generated at a pH of 0.4 to 1.2.   The treatment method according to any one of claims 1 to 10, wherein the alkali in the third step is added until the pH of the solution after dearsenic is in the range of 2.2 to 4.0.   The treatment method according to any one of claims 1 to 11, wherein the alkali in the fourth step is added until the pH of the solution after iron removal is in the range of 4.0 to 8.0.   The treatment method according to any one of claims 1 to 12, wherein the alkali in the third step and / or the fourth step is provided as calcium carbonate.