KR100866824B1 - Method for processing electro-precipitation copper - Google Patents

Abstract

(Problem) Provides a more convenient method for separating and recovering copper, arsenic, bismuth, and antimony from electrolytic precipitated copper, respectively.

(Solution) (1) After optionally washing with electrolytic precipitation copper, at least 90% by weight of the As component contained in the electrolytic precipitated copper is oxidized to pentavalent while introducing an oxygen-containing gas into the electrolytic precipitated copper in the sulfuric acid acidic solution. A sulfuric acid leaching comprising stirring the solution at a liquid temperature and time sufficient to make a solid, followed by solid-liquid separation into a sulfuric acid leaching liquid containing a leach residue containing a Sb component and a Bi component and a pentavalent As component. 1 process,

(2) After adding trivalent iron to the sulfuric acid leaching solution to form crystalline scorodite (FeAsO ₄ .2H ₂ O), the residue containing the crystalline scorodite and after deabrasion A second step of solid-liquid separation into a liquid,

(3) If unreacted Fe or unreacted Fe and As remain in the solution after the de-aeration, an alkali is added to form a Fe salt, and when the As component remains, the As component is coprecipitated with the Fe salt ( Iii) an optional third step of solid-liquid separation of precipitates containing Fe salts and As components (if the As component remains) and post-decarburization liquid;

(4) A method for treating electrolytic precipitated copper, comprising an optional fourth step of precipitating a Cu salt by adding alkali to the liquid after the degassing, followed by solid-liquid separation into a precipitate containing the Cu salt and a decopper after-liquid solution.

Description

Treatment method of electrolytic precipitation copper {METHOD FOR PROCESSING ELECTRO-PRECIPITATION COPPER}

1 shows one aspect of the processing flow of the present invention.

2 is XRD of scorodite crystals obtained in Examples.

3 is a diagram showing the pH dependence of deironing neutralization.

4 is a diagram showing the pH dependence of decopper neutralization.

The present invention relates to a method for treating electrolytic precipitated copper, which is produced in a copper smelting step. More specifically, the present invention relates to a method for separating and recovering copper, arsenic, bismuth, antimony and the like from electrolytic precipitated copper, respectively.

Various impurities are mixed in copper ore, and 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 of them are mixed in the copper bath and brought into the electrolytic refining process of copper.

As, Sb, Bi, and the like contained in the crude copper (copper anode) are partially eluted in the electrolytic solution, and the undissolved fraction is precipitated at the bottom of the electrolytic cell as anode slime. In addition, since the amount of copper eluted from the positive electrode is generally larger than the amount of copper deposited on the negative electrode, the copper concentration in the electrolyte is gradually increased. Therefore, a part of electrolyte solution is taken out to another electrolytic cell, and the quality of electrolyte solution is controlled. The extracted electrolytic solution is decopperized, and Cu and the impurities are precipitated at the cathode, and Cu and the impurities are separated and recovered by precipitating them on the bottom of the electrolytic cell. In the field, what is deposited in these electrolytic cell bottoms and what is deposited in a cathode is called electrolytic precipitation copper.

The electrolytic precipitated copper is usually repeated in the copper smelting process, but for this purpose, it is preferable to separate impurities from the electrolytic precipitated copper. In addition, methods for using As, Sb, Bi, and the like as valuables remain. Therefore, a technique for separating and recovering Cu, As, Sb, Bi, and the like from electrolytic precipitated copper is desired.

For example, Japanese Laid-Open Patent Publication No. 2002-249827 describes a method of separating bismuth and antimony from electrolytic precipitated copper by a wet method. Specifically, the alkali treated product of electrolytic precipitated copper containing copper oxide, bismuth and antimony is leached in sulfuric acid at a liquid temperature of 40 to 90 ° C., a processing time of 2 to 5 hours, and 50 to 200 g / L, and copper, arsenic, nickel The bismuth, antimony, and copper are separated by eluting and leaving bismuth and antimony in the residue. On the other hand, it is described that the recovery of copper, arsenic and nickel leached from sulfuric acid can be repeated, for example, in a dry step of copper smelting after neutralization treatment.

Also, Japanese Patent Publication No. 3212875 describes a method for recovering arsenic from a smelting intermediate. Specifically, it is a method for recovering arsenic including a step of adding copper and copper oxide or copper or copper oxide to an aqueous solution containing arsenic, and further generating arsenic acid by oxidation. Fly acid is recovered as a precipitate of calcium arsenate by slaked lime.

However, if there are many impurities in the electrolytic precipitated copper repeated in the copper smelting process, the burden on the dry process or electrosmelting cannot be increased. However, if arsenic can be recovered in a form suitable for long-term storage rather than calcium arsenate, There are still many challenges, such as being desirable. That is, the conventionally proposed treatment system for electrolytic precipitated copper is not an optimal system in terms of separation order, stability of recovered material, recyclability, and the like, and there is still room for improvement.

Thus, one of the problems of the present invention is to provide a more convenient method for separating and recovering copper, arsenic, bismuth, antimony and the like from electrolytic precipitated copper, respectively.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining the treatment system of electrolytic precipitation copper, the present inventors discovered that the following treatment systems which combined a series of operation were more effective than the process of electrolytic precipitation copper.

That is, the present invention in one aspect,

(1) Sufficient to oxidize at least 90% by weight of the As component contained in the electrolytic precipitated copper to pentavalent while introducing an oxygen-containing gas into the electrolytic precipitated copper in the sulfuric acid acidic solution after optionally washing the electrolytic precipitated copper with water. A first step of carrying out sulfuric acid leaching comprising stirring the solution at a liquid temperature and time, and then solid-liquid separation into a sulfuric acid leaching liquid containing a leach residue containing a Sb component and a Bi component and a pentavalent As component;

(2) By adding trivalent iron to the sulfuric acid leaching solution to form crystalline scorodite (FeAsO ₄ .2H ₂ O), the solid-liquid separation from the residue containing the crystalline scorodite and the degreasing liquid With the second process,

(3) When unreacted Fe or unreacted Fe and As remain in the solution after the de-aeration, an alkali is added to form a Fe salt. When the As component remains, the As component is co-precipitated with the Fe salt. And an optional third step of solid-liquid separation into a precipitate containing a Fe salt and an As component (if the As component remains) and a de-ironing solution;

(4) A method for treating electrolytic precipitated copper comprising an optional fourth step of precipitating a Cu salt by adding alkali to the liquid after the de-ironing, followed by solid-liquid separation into a precipitate containing the Cu salt and the de-coppering liquid. .

In one embodiment of the present invention, sulfuric acid leaching in the first step involves stirring at 70 to 95 ° C for 4.5 to 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 leaching liquid in the first step is 0.3 to 2.2 pH.

In one embodiment of the present invention, 95% by weight or more of the As component is oxidized to pentavalent by leaching sulfuric acid in the first step.

In one Embodiment of this invention, crystalline scorodite in a 2nd process is produced by heating at 60-95 degreeC.

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, crystalline scorodite in the second step is produced 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 liquid after degreasing 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 liquid after the removal is in the range of 4.0 to 8.0.

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

Best Mode for Carrying Out the Invention

Electrolytic precipitation copper

The target raw material of the treatment method according to the present invention mainly comprises electrolytic precipitated copper produced in the copper smelting process as described above, but the treatment method according to the present invention can be applied as long as it is a material having substantially the same composition as the electrolytic precipitated copper. have. Therefore, the "electrolytic precipitation copper" used in this invention shall also contain the chemical substance which has a composition substantially the same as electrolytic precipitation copper, regardless of the origin. For example, the electrolytic precipitated copper contains Cu: 30 to 70% by weight, As: 20 to 50% by weight, Bi: 0.1 to 6% by weight, Sb: 0.5 to 8% by weight, Pb: 0.1 to 10% by weight, and the like. It is common to have a substance having such a composition as electrolytic precipitated copper, which is the subject of the present invention.

Flush treatment

Before the first step, a water washing treatment may be optionally performed on the electrolytic precipitated copper. The water washing treatment repulps the electrolytic precipitated copper in water, stirred for 0.5 to 6 hours, and contains a trace amount of the electrolytic solution (containing copper sulfate, Ni, Fe, etc.) adhered during the preparation of the electrolytic precipitated copper, and the electrolytic precipitated copper. After dissolving Ni, Fe, etc., it can carry out by filtering a slurry and solid-liquid separation. In this process, most of Fe and Ni can be separated from the electrolytic precipitated copper.

However, this operation clarifies the amount of zero-valent (not dissolved in water) copper excluding copper sulfate among the amount of copper in the electrolytic precipitated copper, and the sulfuric acid required for sulfuric acid leaching of the electrolytic precipitated copper carried out in the next step. It is an operation whose main purpose is to obtain an amount more accurately. In the case where the trace elements such as Ni and Fe are not particularly concerned, or the content of copper sulfate is already known or the amount of the electrolyte solution into the electrolytic precipitated copper is small, it is not necessary to perform this step.

1st process

In the first step, while introducing an oxygen-containing gas into the electrolytic precipitated copper in the acidic sulfuric acid solution, stirring the solution at a liquid temperature and time sufficient to oxidize at least 90% by weight of the As component contained in the electrolytic precipitated copper to pentavalent. The sulfuric acid leaching containing is performed, and solid-liquid separation is carried out by the leaching residue containing Sb component and Bi component, and the sulfuric acid leaching liquid containing pentavalent As component.

The leaching reaction occurring at this time is generally oxidized to Cu up to Cu ²⁺ and As up to As ⁵⁺ according to the following equation.

Cu + H ₂ SO ₄ + 1 / 2O ₂ → CuSO ₄ + H ₂ O. (One)

2As + 5 / 2O 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. If it is less than 1.0 equivalent, the leaching liquid is weakly acidic, precipitates such as Cu ₃ AsO ₄ are formed, and the leaching rates of Cu and As are lowered. If it exceeds 1.2 equivalents, it does not affect the leaching rates of Cu and As, but the amount of sulfuric acid used increases. The concentration in the sulfuric acid solution of Cu and As is not particularly limited. However, when the solubility is exceeded, the leaching rates of Cu and As are lowered, so that the solubility of Cu ²⁺ and As ⁵⁺ is preferably less.

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 formation of crystalline scorodite. Furthermore, at pH 2.2 or higher, the added iron precipitates as iron hydroxide, and iron is not effectively used for the synthesis of scorodite. For this reason, it is preferable to set it as pH of 0.3-2.2 range, and it is more preferable to set it as 0.4-1.2 range.

In sulfuric acid leaching, the oxidation of As reliably proceeds by stirring at 70 to 95 ° C. for 4.5 to 11 hours, preferably at 80 to 95 ° C. for 7 to 11 hours, and preferably 90% by weight or more of the As component. Can oxidize at least 95% by weight, more preferably at least 98% by weight. Since sulfuric acid leaching is an exothermic reaction, it is also possible to carry out especially without heating externally. The stirring time may be longer, and may be appropriately determined so as to balance the economy and the effect.

In order to increase the oxidation efficiency of As, it is preferable to supply a sufficient amount (for example, 10 equivalents of oxygen to copper / 7 hours with respect to copper) by making bubbles of the oxygen-containing gas to be introduced fine. Therefore, it is preferable to perform stirring vigorously, for example, it is preferable to introduce | transduce and / or agitate an oxygen containing gas by jet injection. This value is a case of jet injection (jet agitator brand name), and in the case of a stirrer using a conventional turbine blade, the reaction efficiency is lowered, even if the amount of oxygen-containing gas is introduced 3.5 times or more of this value, the reaction time is two times or more. This is necessary. By performing the mantissa control of As in this step, scorodite production in the second step is facilitated. Cu ²⁺ also has the effect of promoting the oxidation of As.

The oxygen-containing gas is not particularly limited so long as it does not significantly affect the reaction, but for example, a mixture of pure oxygen, oxygen and an inert gas can be used. It is preferable to set it as air from a viewpoint of handleability and cost.

Further, in order to efficiently separate Sb and Bi from the electrolytic precipitated copper, the solubility of Sb and Bi in the sulfuric acid leaching liquid is constant, so that (1) increasing the concentration of the electrolytic precipitated copper pulp at the time of sulfuric acid leaching, (2) It is preferable to use electrolytic precipitated copper having a high Sb and Bi quality. Bi and Sb separated from the electrolytic precipitated copper can also be separated and recovered separately, for example, by an electric furnace treatment.

2nd process

In the second step, trivalent iron is added to the sulfuric acid leaching solution obtained in the first step to produce crystalline scorodite (FeAsO ₄ .2H ₂ O), and the residue containing the crystalline scorodite next. Separate the solid with water and degreased solution.

Crystalline scorodite can be produced by heating to 60-95 degreeC under atmospheric pressure, for example, and sufficient amount of scorodite is produced by reacting, for example for 8 to 72 hours. In the first step, As is sufficiently oxidized to pentavalent, so that crystalline scorodite is produced with trivalent iron and high reaction efficiency. Skorodite is chemically stable and suitable for long term storage.

Examples of the trivalent iron include iron oxide, iron sulfate, iron chloride, and the like. However, the trivalent iron is preferably provided in the form of an acidic aqueous solution from the viewpoint of reacting in an aqueous solution. It is preferable that it is provided in the form of an aqueous solution of ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) in view of the most effective. 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 to add the pH of the sulfuric acid leaching solution to which the aqueous solution is added is maintained at 0.3 to 2.2, preferably 0.4 to 1.2. Since As is fully oxidized to pentavalent in the first step, scorodite is easily generated even at such low pH. In addition, since there is no need to increase the pH at this stage, there is an advantage in that it is not necessary to add alkali such as caustic soda. Therefore, in the method for treating electrolytic precipitated copper according to the present invention, smooth linkage can be performed without waste between the first step and the second step.

The amount of trivalent iron used is preferably 1.0 equivalent or more relative to the amount of As from the viewpoint of removing As, and from 1.1 to 1.5 equivalents from an economic point of view.

3rd process

The third step is an optional step carried out when unreacted Fe or unreacted Fe and As remain in the liquid after the de-carburizing solution. An alkali is added to generate a Fe salt, and when As component remains, The component is co-precipitated with this, and then solid-liquid separation is carried out with a precipitate containing the Fe salt and the As component (if the As component remains) and the de-iron solution.

The alkali to be used is not particularly limited as long as it can produce insoluble Fe salts (insoluble Fe salts capable of co-precipitation of As when As is present). For example, sodium carbonate, calcium carbonate, sodium hydroxide and calcium hydroxide. And magnesium hydroxide.

Returning the solution after the reaction to the electrolytic smelting solution is most effective in the copper smelting process. In view of this point, the sodium in the electrolytic solution is difficult to remove, so its use is not preferable. Calcium, on the other hand, does not have a strong limitation because coexisting sulfuric acid and gypsum are generated and removed. From this viewpoint, it is preferable to use calcium compounds, such as calcium carbonate and calcium hydroxide, as alkali, and calcium carbonate is preferable at the point which is easy to control pH especially.

Alkali has a pH of 2.2 when precipitation of iron hydroxide becomes remarkable, and copper is more likely to precipitate when it exceeds 4.0. Therefore, the addition of the alkali salt until the pH of the liquid after fertilization is in the range of 2.2 to 4.0 is more effective than the precipitation efficiency of the Fe salt and the Cu salt. It is preferable for the reason of avoiding precipitation, and it is more preferable to add it until the pH is in the range of 3.0 to 3.5.

This precipitate is returned to the second step after dissolving in sulfuric acid, and can be reused as an iron source and As (as an As component remaining) as a treatment target. In addition, copper sulfate, which is mainly contained in the liquid after the removal of iron, has few impurities and can be used as an electrolytic solution for electrosmelting. However, the liquid after iron removal may further recover Cu as a precipitate by the following fourth step.

4th process

The fourth step is an optional step carried out when recovering Cu as a precipitate. The alkali salt is added to the post-dehydration solution to precipitate the Cu salt, followed by solid-liquid separation into a precipitate containing the Cu salt and the post-copper solution. . In order to improve the filterability, it is effective to mature the precipitate by heating at 40 to 70 ° C for 30 to 90 minutes, for example.

The alkali to be used is not particularly limited as long as it can produce insoluble Cu salts. Examples thereof include sodium carbonate, calcium carbonate, sodium hydroxide, calcium hydroxide, magnesium hydroxide and the like. When calcium salts are used, gypsum is mixed and copper quality during precipitation is lowered. Therefore, it is preferable to use sodium alkali or calcium alkali which can be obtained inexpensively if the cost is important to reduce the deposit.

Alkali is preferably added until the pH of the liquid after de-ironing is in the range of 4.0 to 8.0, for reasons such as the precipitation efficiency of the Cu salt, the alkali cost, the copper quality in the precipitate, the drainage standard, and the like. It is more preferable to add until it is.

Since the decopper solution is mainly composed of calcium or sodium and sulfate sulfate used for neutralization, and heavy metals are removed, it can be treated as general general drainage.

Example

EXAMPLES Hereinafter, although an Example for better understanding this invention and its advantages is described, this invention is not limited to it.

1 shows one aspect of the processing flow of the present invention.

Water treatment of electrolytic precipitated copper

1000 g (wet weight) of electrolytic precipitated copper having the composition shown in Table 1 was repulped in 2000 ml of water and stirred for 4 hours to dissolve the electrolyte solution (copper sulfate, nickel, iron, etc.) attached at the time of preparation of the electrolytic precipitated copper. The slurry was filtered and separated into solid and liquid. The obtained residue was dried and then introduced into 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: sulfuric acid leaching of electrolytic precipitated copper

228.6 g (1.1 equivalents to the copper contained in the electrolytic precipitated copper) was added to 200 g (dry weight) of the electrolytic precipitated copper which had been washed with water, and water was further added to make the slurry amount 2000 ml ( PH 0.07 before initiation of the reaction).

The mixture was leached for 7 hours while introducing air at 700 ml / min. A jet agitator (JET AJITER made by SHIMAZAKI) was used for introduction and stirring of air. In addition, although liquid temperature was not specifically controlled, since sulfuric acid leaching is an exothermic reaction, liquid temperature rose to 88 degreeC after 4 hours of a leaching start, and it gradually fell after that, and was 70 degreeC after 7 hours. By reaction, the color of the liquid changed from black to blue (pH 0.85 after completion of the reaction). After sulfuric acid leaching, the leaching was filtered and solid-liquid separated. The residue was washed with water, and the washing water was added to the sulfuric acid leaching liquid. Table 2 shows the contents of the obtained sulfuric acid leaching liquid and sulfuric acid leaching residue.

In terms of the amount of the residue, 87.1% bismuth in the electrolytic precipitated copper was used as the residue and could be removed from the leaching liquid. Moreover, since only 1.6% of arsenic and 0.4% of copper remain in the residue, the reaction efficiency is high.

Second Process: Synthesis of Skorodite

To arsenic contained in 425 ml of sulfuric acid leaching solution obtained in the first step, 43 g of ferric sulfate solution (ferric sulfate solution (n hydrochloride, ferric iron content, 21.3%)) dissolved in hot water, sulfuric acid leaching solution 225 ml of ferric iron (1.45 equivalents) was added, the liquid amount was 650 ml, and then heated to 95 ° C. to synthesize scorodite for 24 hours.

Immediately after mixing the sulfuric acid leaching solution and the ferric sulfate solution at room temperature, the reaction did not proceed, but with heating, precipitation of scorodite was observed around 60 ° C. The pH of the synthesis liquid was 0.63 (room temperature) before the start of the reaction, but was 0.58 (room temperature) after the reaction was finished. After the synthesis of scorodite, the scorodite crystals were filtered off and solid-liquid separated.

The scorodite crystals were washed with water, and the washing water was added to the liquid after deaeration. Table 3 shows the quantities of the obtained scorodite crystal and the solution after degumming. The XRD of the obtained scorodite crystal is shown in FIG. Elution of arsenic is small and stable crystalline scorodite is obtained.

In addition, elution of arsenic from scorodite obtained by this synthesis was 0.2 mg / L (using an acetic acid buffer solution of TCLP pH 5), and it was confirmed that arsenic was stable. Regarding the amount of scorodite crystal, the reaction efficiency is high because 98.0% of arsenic is distributed to the scorodite crystal.

Considering that trivalent arsenic does not contribute to scorodite synthesis, it can be said that 98% or more of the dissolved arsenic is pentavalent by sulfuric acid leaching of electrolytic precipitated copper. The sulfuric acid leaching solution of electrolytic precipitated copper was shown to be effective as a raw material for scorodite synthesis.

Third Process: Neutralizing

26.6 g of calcium carbonate (10.64 g in the amount of Ca) was added to 1370 ml of the deaerated solution obtained in the second step, neutralized to pH 3.48, and arsenic and iron were co-precipitated as iron hydroxide. Thereafter, in order to improve the filterability, the precipitates were 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 sulfate added during neutralization.

This precipitate was filtered off and the solid was separated. The precipitate was washed with water, and the washing water was added to the liquid after degassing. The amount of the obtained precipitate (hereinafter, referred to as decarburized sludge) and the liquid after decarburization is shown in Table 4. In the liquid after iron removal, arsenic is not detected and it is removed efficiently. On the other hand, only 0.3% of copper in the decarburized sludge is distributed, indicating that it remains in the liquid after decarburization.

In addition, the result at the time of changing a pH and carrying out deironing neutralization in order to investigate pH dependence is shown in FIG.

4th process: neutralize copper

9.2 g of calcium carbonate (3.68 g in the amount of Ca) was added to 2315 ml of the solution after iron removal obtained in the third step, neutralized to pH 5.59, and precipitated as copper hydroxide. Thereafter, in order to improve the filterability, the precipitates were aged by heating at 60 ° C. for 30 minutes. This precipitate was filtered off and the solid was separated. The amount of the obtained precipitate (hereinafter, referred to as decopper sludge) and decoppered liquid is shown in Table 5. Copper is well separated from bismuth and arsenic with high recovery.

In addition, the result when decopper neutralization was performed by changing pH in order to investigate pH dependence is shown in FIG.

According to the present invention, Cu, As, Bi, and Sb can be separated and recovered from the electrolytic precipitated copper, respectively. At this time, As is fixed as stable scorodite. This is a form suitable for long-term storage because it is less soluble in water and stable than calcium arsenate. Cu can be returned to the copper smelting process in a state where impurities are reduced, and the limit of the amount of repetition caused by the dry process and the purification ability of electrosmelting is greatly reduced. Therefore, the residence time in the smelting process of copper in the electrolytic precipitated copper as an intermediate product can be shortened.

Claims (16)

(1) stirring the solution at a liquid temperature and time sufficient to oxidize at least 90% by weight of the As component contained in the electrolytic precipitated copper to pentavalent while introducing an oxygen-containing gas into the electrolytic precipitated copper in the sulfuric acid acidic solution; A first step of solid-liquid separation with a sulfuric acid leaching solution containing a leach residue containing a Sb component and a Bi component and a valent As component; (2) By adding trivalent iron to the sulfuric acid leaching solution to form crystalline scorodite (FeAsO ₄ .2H ₂ O), the solid-liquid separation from the residue containing the crystalline scorodite and the degreasing liquid The processing method of the electrolytic precipitation copper containing the 2nd process to carry out. The method of claim 1, The sulfuric acid leaching in a 1st process is a method of treating electrolytic precipitated copper, which involves stirring at 70 to 95 ° C for 4.5 to 11 hours. The method according to claim 1 or 2, Sulfuric acid leaching in the first step is performed without heating externally. The method according to claim 1 or 2, The oxygen-containing gas in the first step is air. The method for treating electrolytic precipitated copper. The method according to claim 1 or 2, A method for treating electrolytic precipitated copper, wherein the introduction or stirring of the oxygen-containing gas in the first step or both are carried out by jet injection. The method according to claim 1 or 2, The sulfuric acid leaching solution in the first step is a treatment method of electrolytic precipitated copper having a pH of 0.3 to 2.2. The method according to claim 1 or 2, A method for treating electrolytic precipitated copper in which the As component is 95% by weight or more oxidized to pentavalent by leaching sulfuric acid in the first step. The method according to claim 1 or 2, Crystalline scorodite in a 2nd process is the processing method of the electrolytic precipitated copper produced by heating at 60-95 degreeC. The method according to claim 1 or 2, A method for treating electrolytic precipitated copper, wherein trivalent iron in the second step is provided as ferric sulfate. The method according to claim 1 or 2, Crystalline scorodite in a 2nd process is the processing method of the electrolytic precipitated copper produced at pH 0.4-1.2. The method according to claim 1 or 2, The treatment method of electrolytic precipitation copper which washes with electrolytic precipitation copper before leaching sulfuric acid in a 1st process. The method of claim 1, When unreacted Fe or unreacted Fe and As remain in the deaerated solution obtained in the second step, alkali salts are added to form Fe salts, and when the As component remains, the As component is co-precipitated with the Fe salt. And a third step of solid-liquid separation into a precipitate containing a Fe salt and an As component (when the As component remains) and a de-ironing solution. The method of claim 12, A method for treating electrolytic precipitated copper, comprising a fourth step of precipitating a Cu salt by adding alkali to the post-de-dehydration liquid obtained in the third step, and then solid-liquid separation into a precipitate containing the Cu salt and the de-copper post-solution. The method according to claim 12 or 13, Alkali in a 3rd process is a treatment method of the electrolytic precipitated copper added until the pH of a liquid after degrating becomes 2.2-4.0. The method of claim 13, Alkali in a 4th process is a treatment method of the electrolytic-precipitated copper added until the pH of a liquid after iron removal becomes 4.0-8.0 range. The method of claim 13, 2. The method of treating electrolytic precipitated copper, wherein the alkali in the third or fourth process, or both, is provided as calcium carbonate.

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