KR100423350B1 - Method for processing anode slime of copper electrolysis - Google Patents

Abstract

An object of the present invention is to develop a copper electrolyte wet treatment process capable of efficiently separating platinum group, gold, selenium and tellurium, and efficiently separating and recovering selenium and tellurium.

As a solution, the copper electrolytic material is subjected to pretreatment via a decopper process, a chloride leaching process, and a gold extraction process, and the obtained gold extract liquid has a concentration of chlorine ion of 1.5 mol / l or less. Platinum sulfide, gold, selenium, and sulfur remaining in the rear liquid by blowing at a temperature of 60 to 90 ° C. and diluting sulfurous acid gas diluted to 8 to 12% by air at an amount of 8 to 15 times the concentration of platinum group and gold mol. The tellurium is separated to obtain a platinum group-containing gold reducing product. Subsequently, the sulfurous acid gas was kept at a temperature of 60 to 90 ° C. while maintaining the chlorine ion concentration in the liquid at 2.0 mol or less and the selenium concentration in the solution at 3 g / l or more. Blowing is performed at twice the molar concentration of selenium, and selenium and tellurium are separated to obtain a selenium-containing reduced product. Furthermore, sulfuric acid gas is blown to the after-separating selenium at the temperature of 60-90 degreeC, and a tellurium-containing reduced product is obtained.

Description

Treatment method of copper electrolytic material {METHOD FOR PROCESSING ANODE SLIME OF COPPER ELECTROLYSIS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating copper electrolysates, and in particular, a gold extraction liquid from copper electrolysates subjected to pretreatment via a decopper process, a chloride leaching process and a gold extraction process. By treating sulfur dioxide under specific conditions, the method of efficiently separating and recovering the gold and platinum groups from selenium tellurium, and then performing sulfite gas reduction treatment under specific conditions, thereby reducing selenium (Se) in tellurium (Te). It relates to a method for efficiently separating and recovering.

The present invention is characterized by efficiently separating and recovering the gold, platinum group, selenium, and tellurium refining raw materials through a wet process in the gold extraction after-liquor.

In electrolytic refining of copper, roughly 99.5% of the crude copper from the converter is refined in a refining furnace, and a cast anode (anode) and an end plate as a cathode are formed by alternating dozens of sheets in the electrolytic cell. Electrolytic purification is carried out. Copper electrodeposited on the end plate is called electric copper, and is processed and commercialized in a well-known aspect after that. Impurities contained in the anode are deposited on the bottom of the electrolytic cell in the form of mud, which is called a copper anode. In addition to copper, a copper electrolytic material is enriched with precious metals in raw materials including gold, and is a major raw material for recovering precious metals. It also contains selenium and tellurium. An analysis example of the copper electrolytic precursor is shown in Table 1 below.

Example of analysis of copper electrolyte (unit:%) Au Ag Cu Pt Pd As Bi Sb Pb Se Te 1.9 17.5 25.7 0.03 0.2 3.7 0.4 2.0 4.7 8.4 4.5

The treatment of copper electrolytic materials has been put into practical use in either the dry method or the wet method, but the wet method appears to be more useful in terms of equipment cost and processing flow. In the wet method, the copper electrolytic material is repulped with an electrolyte solution, dissolves soluble impurities such as copper, tellurium, and arsenic remaining in the whole material, and separates the insoluble material mainly composed of noble metals and selenium with solid / liquid to separate the precious metals. Concentrate and purify. The main components of the insolubles are silver, selenium, platinum group, tellurium and lead. This is oxidized and dissolved in a solution containing hydrochloric acid, silver is solid / liquid separated as chloride, and is made of high purity silver in the silver purification process. In this way, selenium, gold, platinum group, etc. are dissolved in the solid / liquid separated liquid, and gold is extracted from the liquid by solvent extraction. After extracting gold, a large amount of selenium and trace amounts of gold and platinum groups are contained. Since this liquid contains a large amount of selenium, selenium needs to be recovered. As a selenium recovery method, a method of reducing the liquid and simultaneously reducing the selenium and the platinum group has been used.

As a method of concentrating this large amount of selenium and the platinum group contained therein, JEHoffmann, for example, wet-processes copper electrolysates in "Proceedings of COPPER 95-COBRE 95 Innternationaru Connference", and selenium and platinum groups. It reports the following ways to recover gold:

`` Selenium is reduced and recovered from the liquid after recovery of gold. The reduction reaction is reduced by sulfurous acid gas above 85 ° C. Platinum, palladium, silver and tellurium are also reduced simultaneously. The selenium is distilled off and the platinum group and gold are concentrated in the distillation residue, but these recovered products are ground to 200 mesh or less and repeated in the original process. Gold and silver are recovered in the upstream process, and platinum and palladium are treated when concentrated to a concentration suitable for recovery.

5 shows a process flow sheet according to this conventional method.

In this process, since all the valuables are recovered simultaneously with selenium and are repeated in the original process, there are the following problems:

(1) Since the concentration of platinum groups in the distillation residues of selenium is low, it is necessary to repeat the distillation residues in the original step and concentrate until a certain concentration can be secured.

(2) Selenium and tellurium, which are impurities in the refining of platinum group and gold, are repeated with the platinum group and gold in the original process.

③ The repeat is a distillation residue of selenium, which is a glassy mass and must be pulverized to 200 mesh or less in order to be repeated in the original process and to be efficiently dissolved in a hydrochloric acid solution. Selenium grinding has problems such as low melting point of selenium, glass shape depending on shape, and sufficient environmental response for dust protection.

④ It cannot be commercialized early because the process is repeated to concentrate palladium and platinum.

Consequently, in the prior art methods including the above, there is a fundamental problem that separation of the platinum group, gold and selenium tellurium of gold, platinum and palladium is incomplete. The selenium in the copper electrolytic material is about 15%, compared with 0.2% for platinum and 0.02% for platinum. Therefore, in the after-liquid solution which collect | dissolves the whole thing in the liquid and collect | recovers gold, it becomes about 0.5 g / l for palladium, and about 0.06 g / l for platinum about 20-40 g / l of selenium. This difference in concentration is 80 times that of palladium and 800 times that of platinum. In a typical reducing agent, these elements are reduced at a ratio close to the concentration ratio in the solution, so that the reducing product becomes a platinum group-gold material having a very high selenium content. Therefore, in the case where palladium is subsequently purified by solvent extraction, solid selenium precipitates at the time of extraction, filling the reaction tank to close the pipe and worsening the phase separation. It also worsens the phase separation during back extraction and worsens the quality of palladium.

The second problem is that the separation of selenium and tellurium is incomplete. The content of tellurium in selenium becomes high, and tellurium separation during selenium distillation becomes difficult, and high-quality selenium cannot be recovered.

In view of such a situation, an object of the present invention is to develop a wet process that completely solves the above problems and makes it possible to efficiently recover the platinum group and gold from the gold extraction after the copper electrolytic pretreatment. In addition, the present invention also addresses the development of a wet process that enables efficient recovery of selenium and tellurium.

1 shows a process flow sheet of the present invention,

2 is a graph showing the relationship between the chlorine ion concentration (mol / L) in the reducing whole liquid and the Pd concentration in the reducing liquid;

3 is SO ₂ concentration: 100% (diluted mu) of the case and the SO ₂ concentration in the air: in the case of diluting to 10%, reduced Pd concentration (㎎ / ℓ) in the huaek and SO ₂ blow fineness: SO ₂ Graph showing the relationship of / (Pt + Pd) (mol / mol),

4 is a graph showing the relationship between selenium concentration in reduced after-liquor and tellurium concentration in reduced selenium;

5 shows a process flow sheet of the conventional method.

The reason why the separation of the platinum group, gold and selenium tellurium by the reduction is difficult is that the reduction potential of the platinum group, gold, and tetravalent selenium (Se (4+)) is similar. On the other hand, selenium exists as valence of tetravalent (Se (4+)) and hexavalent (Se (6+)) in a conventional solution. Se (6+) is reduced to Se (4+) followed by Se. The reduction potential of Se (6+) → Se (4+) is higher than that of platinum group and gold. Therefore, the present inventors have found that when platinum group and gold are reduced in parallel with the reaction of Se (6+) → Se (4+), less selenium can be incorporated into the platinum group and gold. As a result of repeated examination, it is determined whether selenium is present as a Se (4+) or Se (6+) entity depending on the Cl concentration, and when the hydrochloric acid concentration is set to 1.5 mol / l or less, Se (6+) may be increased. It has been found that it can reduce the coprecipitation of selenium. In addition, sulfuric acid (SO ₂ ) gas alone is not completely separated, and platinum group, gold, especially palladium cannot be less than 100 mg / l, and it is necessary to dilute the sulfurous acid concentration to 8-12% by air. It has also been found that sulfurous acid gas needs to be blown at an amount of 8 to 15 times the concentration of platinum group and gold mol.

Based on this knowledge, the present invention provides (1) pretreatment of (A) the copper electrolytic material via a decopper process, a chloride leaching process and a gold extraction process, and (B) a chlorine ion in liquid to the obtained gold extraction liquid. The thick liquor is maintained by maintaining the concentration at 1.5 mol / l or less and blowing sulfurous acid gas diluted to 8 to 12% by air at a temperature of 60 to 90 ° C at an amount of 8 to 15 times the concentration of platinum group and gold mol. Provided is a method for treating a copper electrolytic precursor, characterized by separating a platinum group, gold, selenium and tellurium remaining in the mixture to obtain a platinum group, a gold-containing reducing product.

In the present invention, the "platinum group" refers to a platinum group element represented by palladium or platinum. The "chlorine ion concentration" is not limited to chlorine ions as hydrochloric acid and chlorine ions forming a compound with a metal, and for example, chlorine involved in chlorine temperature generated by dissociation of chlorides such as platinum chloride. Means the total ion concentration. "Sulfite gas" used also includes smelting exhaust gas.

Subsequently, selenium must be recovered by sulfur dioxide reduction, so that when the selenium concentration in the reducing liquid is lowered, the reduction of tellurium also begins to proceed. It has been found that co-precipitation of tellurium can be prevented by managing the selenium concentration in the reduced after-treatment at the time of selenium reduction not to be less than 3 g / l. As a result of examining other reaction conditions, it was successful to reduce the concentration of tellurium in the reduced selenium to 100 ppm or less, particularly 10 ppm or less.

Based on the results of this study, the present invention further provides (2) pretreatment of (A) the copper electrolytic material via the decoppering step, the chloride leaching step, and the gold extraction step, and (B) the obtained gold extraction rear solution, (A) The sulfuric acid gas, which is kept at a concentration of 1.5 mol / l or less in a liquid and diluted to 8 to 12% by air at a temperature of 60 to 90 ° C, is 8 to 15 times the concentration of platinum group and mol of gold. Blowing in a quantity, the first reduction treatment to separate the platinum group, gold and selenium tellurium remaining in the rear liquid to obtain a platinum group, gold-containing reduction product; and (b) Chlorine ions in the liquid after separating the platinum group, gold. Selenium and tellurium are blown at a temperature of 60 to 90 ° C. at a temperature of 60 to 90 ° C. while maintaining the concentration at 2.0 mol or less and maintaining the selenium concentration in the solution at 3 g / l or more. 2nd reduction to obtain selenium-containing reduced product by separating To carry out processing including an electrolytic copper-based, characterized in providing a full water treatment.

Since tellurium can be easily reduced by sulfur dioxide reduction. Thus, the present invention further provides (3) pretreatment of (A) the copper electrolytic material via the decoppering step, the chloride leaching step, and the gold extraction step, and (B) the obtained gold extraction back liquid, (A) chlorine in liquid By keeping the ion concentration at 1.5 mol / l or less and blowing sulfurous acid gas diluted to 8-12% by air at a temperature of 60-90 ° C. at an amount of 8-15 times the platinum group-gold mol concentration, A first reduction treatment in which the platinum group, gold and selenium tellurium remaining in the rear liquid are separated to obtain a platinum group and gold-containing reducing product, and (b) the chlorine ion concentration in the liquid is 2.0 mol or less. And selenium are separated from the selenium by blowing the sulfurous acid gas at twice or less than the mol concentration of selenium at a temperature of 60 to 90 ° C. while maintaining the selenium concentration in the solution at 3 g / l or more. A second reduction step of obtaining the containing reduction product, and (c) phase Provided is a method for treating a copper electrolytic material, comprising treating a sulfite gas at a temperature of 60 to 90 ° C. with a selenium separated from the group selenium, and carrying out a treatment including a third reduction step of obtaining a tellurium-containing reduced product. .

In a preferred embodiment, the following operation is carried out in the method for treating copper electrolyte: (4) The copper removal step is performed by using copper sulfate in sulfuric acid solution of copper electrolysis step under normal pressure and air blow. It is carried out by leaching and removing 70-85 degreeC and 18-24 hours, and (5) The leaching liquid after decoppering is sulfuric acid concentration: 230-450 g / L, temperature: 70-90 degreeC, and reaction time: 16-24 hours Under the reaction conditions, tellurium is precipitated as copper telluride by copper plate / copper powder, and (6) in the chloride leaching step, the pre-copper slurry slurry repulped with hydrochloric acid using hydrogen peroxide in combination with chloride is leached into the platinum group in the whole product after decopper. • Dissolve the gold in the solution, and at the same time mainly separate silver, lead, etc. as chlorides. (7) After leaching chloride, the solids of the silver chloride are sent to silver reduction / purification process after repulping with water and iron powder is added. Silver is reduced from silver chloride, (8) In the gold extraction process, the solution after the chloride leaching is cooled to 5 ° C. and the hydrochloric acid concentration is adjusted for gold extraction, and gold only is used in the chloride leaching solution using DBC (dibutylcarfitol). (9) The platinum group / gold-containing reduced product was recovered from the platinum group as a raw material of the platinum group refining step, and the gold was recovered from the gold-containing solution from the refining step. After repulping with water and washing, vacuum drying is used as the raw material of the selenium distillation machine, distilled selenium is continuously added dropwise onto the casting drum, and the selenium is recovered as a dry shot, while the distillation residue is dried solid. The remaining selenium is completely distilled off by a distiller to obtain a dry solid residue containing platinum group and gold, and the dry solid residue is recovered as a raw material of the platinum group refining process. Gold is recovered from the gold-containing solution from this refining process, and (11) a tellurium-containing reduced product is used as a raw material for the recovery of tellurium, together with copper telluride from the de-tellurization process, if necessary, followed by alkali leaching and neutralization. Tellurium is produced and tellurium is recovered by alkali leaching and electrowinning.

Embodiment of the Invention

As shown in Table 1, the copper electrolytic material is a main raw material for recovering precious metals because, in addition to copper, precious metals in the raw material including gold are concentrated. It also contains selenium and tellurium.

First, a copper electrolytic material is dissolved using a copper electrolytic process solution, and impurities such as copper, tellurium, and arsenic are leached. The leaching residue is dissolved using a hydrochloric acid solution and an oxidizing agent, and then silver and the like are separated into solids and liquids as chlorides. Gold is solvent-separated from the after-separation liquid and separated.

After this pretreatment, according to the present invention, the gold, platinum, and platinum group, gold, selenium, and tellurium of the sediment are separated. Also selenium and tellurium are separated.

1 shows a flow sheet of the process of the present invention. This will be described below in detail.

(A) pretreatment

(1) Decopper, taltellur process

The decoppering step is a step of leaching and removing about 25% of copper contained in the whole product with sulfuric acid solution of the copper electrolysis step to 1% or less. The telomerization step is a process for removing the tellurium in the leach solution in advance by copper substitution because telure is also leached into the solution leaching copper, and returning it directly to the copper electrolysis process contaminates the quality of copper. The whole product sent in the electrolytic process is repulped by the electrolytic conveyance liquid after Ni removal from the copper electrolytic semen process, for example. The mold release agent contained in the whole product is removed by a wet net and sent to a decopper leaching tank. The decopper leaching is carried out at 70 to 85 ° C., especially at 80 ° C. under normal pressure and air blow, and the copper quality in the whole product decreases from about 25% to about 0.5% for 18 to 24 hours. In addition, Te and As in whole thing elute at 50% and 85%, respectively.

The decopper leaching scheme is shown below:

Cu + 1 / 2O ₂ + H ₂ SO ₄ → CuSO ₄ + H ₂ O

Cu ₂ Se + O ₂ + 2H ₂ SO ₄ → 2CuSO ₄ + Se + 2H ₂ O

The leachate contains about 1 g / l Fe and the following reaction also contributes to the decopper leaching:

4FeSO ₄ + O ₂ + 2H ₂ SO ₄ → 2Fe ₂ (SO ₄ ) ₃ + 2H ₂ O

Cu ₂ Se + 2Fe ₂ (SO ₄ ) ₃ → 2CuSO ₄ + Se + 4FeSO ₄

After decoppering, the solid / liquid is separated by a filter press. The leaching liquor precipitates tellurium as copper telluride by a copper plate and / or copper powder in a tal tellurium. Sulfuric acid concentration is 230 ~ 450 g / ℓ, temperature is 70 ~ 90 ℃ and reaction time is 16 ~ 24 hours. The end point of the reaction is confirmed by analyzing the Te concentration in the rear solution. The scheme is as follows:

H ₂ TeO ₃ + 4Cu + 2H ₂ SO ₄ → Cu ₂ Te + 2CuSO ₄ + 3H ₂ O

The precipitated copper telluride is separated into solid / liquid by a filter press and then sent to a tellurium recovery step described later. The thick liquid is returned to the copper electrolytic semen process.

The whole thing after decoppering is sent to a chloride leaching tank after repulping with hydrochloric acid in a repulping tank.

(2) Chloride leaching process

The chloride leaching step is a step in which gold is dissolved in a solution in all the decoppered materials and silver and the like are separated as chlorides.

In the chlorine leaching tank, chlorine leaching of the entire copper decopper slurry repulped with hydrochloric acid is carried out. It is preferable to use hydrogen peroxide together. The dissolution reaction involves a reaction of consuming hydrochloric acid and hydrogen peroxide, a reaction consuming only hydrochloric acid, and a reaction consuming only hydrogen peroxide, as shown below.

(A) Reactions that consume hydrochloric acid and hydrogen peroxide:

Au: 2Au + 3H ₂ O ₂ + 8HCl → 2HAuCl ₄ + 6H ₂ O

Ag: Ag ₂ Se + 3H ₂ O ₂ + 2HCl → 2AgCl + H ₂ SeO ₃ + 3H ₂ O

Pt: Pt + 2H ₂ O ₂ + 6HCl → H ₂ PtCl ₆ + 4H ₂ O

Pd: Pd + H ₂ O ₂ + 4HCl → H ₂ PdCl ₄ + 2H ₂ O

Cu: Cu + H ₂ O ₂ + 2HCl → CuCl ₂ + 2H ₂ O

(B) reactions that consume only hydrochloric acid:

Pb: PbSO ₄ + 2HCl → PbCl ₂ + H ₂ SO ₄

Bi: BiAsO ₄ + 3HCl → BiCl ₃ + H ₃ AsO ₄

(C) reactions that consume only hydrogen peroxide:

Se: Se + 2H ₂ O ₂ → H ₂ SeO ₃ + H ₂ O

Te: Te + 2H ₂ O ₂ → H ₂ TeO ₃ + H ₂ O

Sb: H ₃ SbO ₃ + H ₂ O ₂ → H ₃ SbO ₄ + H ₂ O

It is preferable to perform chlorine leaching reaction by adding hydrogen peroxide gradually. In order to suppress decomposition by the disproportionation reaction of hydrogen peroxide, the reaction temperature needs to be appropriately controlled. By chloride / oxidation the chloride and oxide are dissolved or precipitated by their respective solubility. Silver chloride is precipitated because of its low solubility in hydrochloric acid solution and is separated from other platinum groups and gold. Most lead chloride is also precipitated. In addition, most antimony compounds and tellurium compounds are precipitated.

After leaching the chloride, the solid / liquid is separated by a filter press, the solid of the silver chloride is sent to the silver reduction and purification process after repulping with water, and the solution is sent to an acid concentration adjusting tank equipped with cooling means.

The silver refining process is a process of reducing and refining silver from silver chloride. Conventionally, the process by the wet method has been performed, but the removal of the accompanying lead was difficult and required a complicated process. Here, a very efficient method combining the wet method and the dry method will be described. This is a process of reducing silver chloride with lead chloride, purifying and commercializing it by oxidation and silver electrolysis.

According to this preferred method, iron powder is added to this slurry in a silver reduction bath to reduce it. The reaction is promoted in an acidic solution, but since the chloride leaching residue contains adherent hydrochloric acid, the slurry becomes acidic by repulping with water. The reactor may take into account the direct reduction reaction with iron powder and the reduction reaction with hydrogen of the generator produced by hydrolysis of iron powder as follows:

2AgCl + Fe → 2Ag + FeCl ₂

2AgCl + 2H → 2Ag + 2HCl

The reaction is initiated at room temperature, which is raised to near the boiling point by the heat of reaction. Lead chloride in the chloride leaching residue also becomes metal lead, and chlorine in the reducing silver is about 0.5%. Iron acts advantageously as a slug in dry tablets in the oxidation furnace in subsequent processes even if it remains.

After reduction, the solid / liquid is separated by a filter press, and the rear liquid becomes a waste liquid after reduction by hydrazine. Reduction silver is processed in an oxidation furnace, cast as a raw silver plate, and refine | purified by silver electrolysis. Electrodeposited silver is cast with electrolytic silver after cleaning and dissolving.

(3) Gold extraction and reduction process

After leaching the chloride, the solution is sent to an acid concentration adjusting tank equipped with cooling means. In this adjustment tank, it cools to 5 degreeC in order to prevent the precipitation of impurities by the solubility in a gold extraction process. In addition, the concentration of hydrochloric acid is adjusted to the gold extraction conditions. After adjustment, after solid / liquid separation by filter press, the solution is sent to the gold extraction process. Precipitation precipitates mainly composed of lead chloride are returned to the smelting process.

Gold extraction process is the process of extracting only gold from the chloride leaching solution in the solvent. After the gold solvent extraction, gold is reduced and precipitated in a solvent from which gold is extracted in the gold commercialization process to be commercialized.

As a solvent for gold extraction, a known solvent may be used, but the use of DBC (dibutylcarfitol ((C ₄ H ₉ OC ₂ H ₄ ) ₂ O) is preferable. DBC is gold (HAuCl ₄ to AuCl ₃ ) Because it is easy to make and compounds, gold can be extracted from aqueous solutions, and the DBC has a very high selectivity for gold and a distribution coefficient of gold as high as 1000.

Gold extraction is fast, so it is carried out in a continuous operation using a mixer setler. In the DBC after extraction, a very small amount of aqueous solution or sediment is present and finally causes deterioration or non-uniformity of the product gold. Thus, the debris is removed from the DBC by a centrifuge. After centrifugation, the DBC is scrubbed in a continuous operation with a mixer setler using a weak hydrochloric acid solution. Scrub removes impurities such as Fe extracted in the DBC. After scrubbing, the DBC is sent to the gold removal aid after removal of the entrainment by a centrifuge. The scrubbing after-liquor is used as washing water and dilution water in the chloride leaching process.

Since the gold extract is dissolved in about 3 g / L of water solubility in the aqueous phase, the distillation tank is distilled off with about 20% water. The gold extraction after removal of DBC is sent to the reduction process using sulfurous acid gas. The distilled DBC is repeated in the gold extraction process.

In the gold reduction bath, gold in DBC is directly reduced by mixing oxalic acid aqueous solution and DBC. The scheme is as follows:

2HAuCl ₄ + 3 (COOH) ₂ → 2Au + 6CO ₂ + 8HCl

The reduction reaction is carried out at 80 ~ 90 ℃ for 2 hours of stirring time. After reduction, DBC is sedimented and separated into aqueous solution and used for circulation back to the gold extraction process. The reduced gold and aqueous solution are vacuum filtered, and the reduced gold is washed, dried, melted and cast to produce a gold ingot or gold short. Since the filtered liquid contains a small amount of gold and unreacted oxalic acid, it is treated with hydrazine reduction and deoxalic acid to obtain waste liquid. The oxalic acid residue is repeated in the smelting process and the rear liquid is used as the waste liquid. Deoxalic acid treatment is a method of fixing oxalic acid as calcium oxalate by calcium hydroxide by the following reaction:

(COOH) ₂ + Ca (OH) ₂ → Ca (COO) ₂ + 2H ₂ O

(B) Platinum group, gold, selenium and tellurium reduction processes

A first reduction step of obtaining a platinum group / gold-containing reducing product from a thick solution after gold extraction by extracting gold by solvent extraction; a second reduction step of obtaining a selenium-containing reducing product; and a third reduction of obtaining a tellurium-containing reducing product thereafter. By passing through the three steps of the step, the recovery of the platinum group / gold-containing reduced product can be efficiently performed, and the selenium-containing reduced product can be recovered efficiently. Thereafter, the tellurium-containing reduced product can be easily recovered.

(A) Separation of platinum groups, gold, selenium and tellurium;

Platinum groups, gold and tetravalent selenium (Se (4+)) have similar reduction potentials as follows:

Au (+) + e → Au +1.68 V

Pd (2+) + 2e → Pd +0.83 V

PtCl ₄ (2-) + 2e → Pt + 4Cl (-) +0.73 V

H ₂ SeO ₃ + 4H (-) + 4e → Se + 3H ₂ O +0.74 V

On the other hand, selenium is present as a valence of tetravalent (Se (4+)) and hexavalent (Se (6+)) in the usual gold extraction solution. Se (6+) is reduced to Se (4+) and then to Se. The reduction potential of Se (6+) → Se (4+) is SeO ₄ (2-) + 4H (−) + 2e → H ₂ SeO ₃ + H ₂ O (+1.19 V), and the reduction of platinum group and gold Higher than the transition.

Therefore, when the platinum group and gold are reduced in parallel with the reaction of Se (6+) → Se (4+), the incorporation of selenium into the platinum group and the gold can be reduced.

However, whether selenium is present as Se (4+) or Se (6+) is dependent on the concentration of chlorine ions in the gold extract liquid. When the chlorine ion concentration is low or high, selenium increases Se (6+) and at medium concentrations Se (4+) increases. The actual ratio of Se (4+) and Se (6+) changes in the coexisting ion and oxidation state. When the chlorine ion concentration is 1.5 mol / L or less, Se (6+) can be increased and selenium co-precipitation can be reduced. Here, the chlorine ion concentration is not limited to chlorine ions as hydrochloric acid and chlorine ions forming a compound with a metal, and for example, chlorine ions involved even including chlorine ions generated by dissociation of chlorides such as platinum chloride. It means the total concentration.

Table 2 shows the relationship between the gold extraction after-liquid (liquid amount: 15 m 3), that is, the chlorine ion concentration (mol / l) in the reducing preliminary liquid and the reduction post-reduction liquid after completion of the reduction, that is, the Pd concentration at the end point. Data. The initial concentration of Pd was about 500 mg / l. The initial concentration of Pt was about 50 mg / l, and all in the rear liquor was less than 5 mg / l (not shown). Here, the blowing of sulfurous acid gas was performed for 10 to 30 minutes at a flow rate of 260 to 350 (l / min). In this case, the ratio SO ₂ / Pt + Pd mol was 469 mol / 75 mol = 6.3 mol / mol. It was found that when the chlorine ion concentration was 1.5 mol / l or less, the Pd concentration at the end point could be greatly reduced.

FIG. 2 is a graph showing the relationship between the chlorine ion concentration (mol / L) in the reduction total liquid and the Pd concentration in the reducing liquid corresponding to Table 2. FIG.

Table 3 is an analysis value of typical reducing products (platinum group, gold recovery raw materials) at this time. It was found that the selenium / palladium ratio was improved from 4.76 to 2.62 by setting the chloride ion concentration to 1.5 mol or less.

Table 4 shows Pd, Pt, and Se grades which are reduction products in reduction which normally do not perform such an operation. Se / Pd is very high at 62.4.

Liquid amount (㎥) Cl concentration (mol / l) Pd concentration at the end point (mg / l) 15151515151515 1.551.601.701.741.791.801.87 14.018.012.016.019.021.034.0 1515151515151515151515151515 1.481.311.421.321.531.311.421.551.381.391.491.341.361.44 4.81.00.31.57.36.69.06.91.92.98.25.04.25.8

FP-801 Cake Cl Concentration> 1.5 M, Pd <10 mg / l Pd Classy (%) Pt grace (%) Se grace (%) 15.9416.1112.1018.00 1.952.570.751.30 70.971.677.576.0 Se / Pd = 4.76

FP-801 Cake Cl Concentration <1.5 M, Pd <10 mg / l Pd Classy (%) Pt grace (%) Se grace (%) 22.1422.1722.3922.4322.5722.7523.9724.0224.4424.7428.27 2.812.893.002.803.203.023.083.203.362.922.92 64.759.264.961.765.064.761.761.661.360.955.3 Se / Pd = 2.62

When more than 15 times of SO ₂ is added, precious metal recovered raw material reducing material (還 元 滓) Pd Classy (%) Pt grace (%) Se grace (%) 2.161.271.371.43 0.670.210.260.19 98.096.097.297.3 Se / Pd = 62.4

In addition, in the sulfurous acid (SO ₂ ) gas alone, the separation is not complete, and the platinum group, gold, in particular, palladium cannot be 100 mg / l or less. The sulfur dioxide dilution concentration by air needs to be 8 to 12%. When platinum group and gold are reduced in this way, mixing of selenium with platinum group and gold can be reduced.

In addition, it is necessary to blow sulfurous acid gas diluted to 8 to 12% by air in an amount of 8 to 15 times the mol concentration of the platinum group and gold mol concentration. If the amount of sulfurous acid gas blow (SO ₂ / platinum group, gold = mol / mol) is less than 8, the reduction is not efficient, and if it exceeds 15, the concentration of platinum group and gold in the reducing liquid is reduced. Selenium is also highly reduced, which is undesirable (see Table 4).

FIG. 3 and Table 5 show the reduced aftertreatment in the case of SO ₂ concentration: 100% (diluent free) and when diluted to SO ₂ concentration: 10% by air (two columns and plots are repeated). in the Pd concentration (㎎ / ℓ) and SO ₂ blow fineness: SO ₂ / a graph showing the relation between (Pt + Pd) (㏖ / ㏖). If it is not diluted with air, the palladium concentration does not become 100 mg / l or less. When the sulfurous acid gas diluted to 8 to 12% by air is blown to a mol concentration of 8 to 15 times that of the platinum group and gold mol concentrations, the concentration of palladium in the reduced liquid is increased.

The implementation temperature is in the range of 60 to 90 ° C. Outside this range, the reduction efficiency is reduced or the reduction cannot be managed well.

As a standard practice, for example, sulfurous acid gas is blown at a blow amount of, for example, 260 to 350 (L / min) at 80 to 82 ° C for 10 to 30 minutes. As a SO ₂ gas, copper smelting exhaust gas is used (SO ₂ concentration: 8 to 10%). SO ₂ gas is dissolved in water and reacts as sulfurous acid as follows:

SO ₂ gas 10% SO ₂ gas 100% [Cl] = 1.5M [Cl] = 1.5M [Cl] = 1.0M [Cl] = 1.3M [Cl] = 1.6M SO ₂ / (Pt + Pd) mol / mol Ptmg / ℓ Pdmg / L Ptmg / ℓ Pdmg / L SO ₂ / (Pt + Pd) mol / mol Ptmg / ℓ Pdmg / L Ptmg / ℓ Pdmg / L Ptmg / ℓ Pdmg / L 059141823 386 <1 <1 <1 <1 34011071 <1 <1 38 <1 <1 <1 <1 34081 <1 <1 013467910121518 57534235271910 <1 <1 <1 <1 595557521421331231169149144143143 76705845352818101 <1 <1 790754677581482408297243208209192 8181706155443728197 <1 912944915802712655591460391265177

H ₂ PtCl ₆ + 2H ₂ SO ₃ + 2H ₂ O → Pt + 2H ₂ SO ₄ + 6HCl

H ₂ PdCl ₄ + H ₂ SO ₃ + H ₂ O → Pd + H ₂ SO ₄ + 4HCl

(B) Separation of selenium and tellurium

The reduction potentials of selenium and tellurium differ as follows:

TeO ₂ + 4H (+) + 4e → Te + 2H ₂ O +0.53 V

H ₂ SeO ₃ + 4H (-) + 4e → Se + 3H ₂ O +0.74 V

However, when the selenium concentration in the reducing after-treatment is lowered to recover selenium, the reduction of tellurium also begins to proceed. Tellurium in selenium is an impurity. Thereafter, even if distillation or the like is operated to purify selenium, it is difficult to separate tellurium. Therefore, it is important to separate selenium and tellurium in the step of reduction operation.

By controlling the selenium concentration in the reduced after-treatment at the time of selenium reduction to be less than 3 g / l, co-precipitation of tellurium can be prevented, and the tellurium concentration in the reduced selenium can be 100 ppm or less, usually 10 ppm or less. have. This is because, while the selenium concentration is high, the reduction of selenium is predominant, and the reduction of tellurium does not occur because the reduction potential is low. When the selenium concentration is lowered, the reduction potential for reducing the selenium remaining in the liquid is lowered, and approaches the reduction potential of tellurium. The selenium concentration immediately before this tellurium reduction potential is 3 g / L.

4 is a graph showing the relationship between selenium concentration in the reduced after-liquor and tellurium concentration in the reduced selenium. In this case, SO ₂ gas was blown for 600 to 800 minutes at a flow rate of 250 to 350 (l / min). It can be seen that the co-precipitation of tellurium can be prevented by managing the selenium concentration in the reduced after-treatment to be less than 3 g / l.

In order to promote the reduction of selenium, it is also necessary to maintain the concentration of chlorine ions in the liquid after separating the platinum group and the gold to 2.0 mol or less.

The reaction temperature is in the range of 60 to 90 ° C, preferably 80 to 85 ° C in order to obtain good selenium reduction action.

Blowing sulfurous acid gas at a molar concentration no greater than twice the molar concentration of selenium is also necessary to avoid the reduction of tellurium.

In this way, sulfite gas is kept at twice the mol concentration of selenium at a temperature of 80 to 85 ° C. while maintaining the chlorine ion concentration in the rear liquid at 2.0 mol or less and maintaining the selenium concentration in the liquid at 3 g / l or more. The selenium tellurium can be satisfactorily separated by blowing sulfurous acid gas at a blow amount of, for example, 260 to 350 (l / min) for 600 to 800 minutes.

The selenium reduction reaction is as follows:

H ₂ SeO ₃ + 2H ₂ SO ₃ + H ₂ O → Se + 2H ₂ SO ₄ + 2H ₂ O

(C) Tellurization reduction

After reducing the platinum group, gold and selenium in this manner, tellurium is blown by blowing the sulfurous acid gas at a blow amount of 500 to 700 (l / min) at 60 to 90 ° C, preferably 80 to 82 ° C for 500 to 700 minutes. Can be reduced. Tellurization reactions are as follows:

H ₂ TeO ₃ + 2H ₂ SO ₃ + H ₂ O → Te + 2H ₂ SO ₄ + 2H ₂ O

After completion of each step, the solid / liquid separation solution by the filter press is transferred to the next step.

The platinum group-gold containing reducing material becomes a raw material of the platinum and palladium refining process. Purification of palladium can be carried out by conventional methods using solvent extraction. Gold-containing solutions from the refining process are treated separately to recover gold.

The selenium-containing reduced product is further repulped and washed with water, followed by vacuum drying to become a raw material of the selenium distillation machine. Selenium distillation is carried out with a continuous vacuum distillation. Distillation temperature is 350 ~ 380 ℃. Distilled selenium is dripped continuously on a casting drum, and it becomes a dry shot. The distillation residue is again distilled off the remaining selenium with a dry solid distiller to obtain a dry solid residue containing Au, Pt and Pd. The dry solid residue is a raw material of the platinum and palladium refining process. Gold is recovered separately.

Tellurium-containing reduced extracts are a raw material for tellurium recovery. The thick liquid becomes waste liquid. The tellurium recovery step uses copper telluride from the de-tellurization process described in the pretreatment process and the reduced product as a reduced precipitate as a raw material to recover tellurium dioxide by alkali leaching and neutralization, and further by alkaline leaching electrolytic extraction. Commercialize tellurium. Along with this, the tellurium recovery process will be described below.

Tellurium recovery process:

The copper telluride and the tellurium-containing reduced product are leached to tellurium by blowing air into a sodium hydroxide solution in a telluric leaching tank. The leaching reaction is as follows:

Leaching Copper Tellurium:

Cu ₂ Te + 3 / 2O ₂ + ₂ NaOH → Cu ₂ O + Na ₂ TeO ₃ + H ₂ O

Leaching of Tellurium-Containing Reducts:

Te + O ₂ + ₂ NaOH → Na ₂ TeO ₃ + H ₂ O

Se + O ₂ + ₂ NaOH → Na ₂ SeO ₃ + H ₂ O

Leaching is performed at the temperature of 75-85 degreeC. After leaching, the solid / liquid separation is carried out by a filter press, the leaching residue of the main sulfurous acid gas is returned to the copper smelting process, the leaching liquor is sent to a neutralization tank, and the tellurium is separated and recovered as tellurium dioxide by neutralization of sulfuric acid.

EXAMPLE

(Example 1)

The copper electrolyte having the analytical value shown in Table 1 was leached using a sulfuric acid solution of the copper electrolytic process in the decopper process. The decopper leaching was carried out at 80 ° C. under normal pressure and an air blow, and the copper quality in the whole product decreased to about 0.5% for 18 to 24 hours. The decopper leaching rates were Cu: 98,5%, Te: 50%, Sb: 3%, Bi: 2%, As: 85%, and Au, Ag, Pt, Pd, Se, and Pb contained in all materials It was not leached, but the leaching rate was 0%.

The decopper leaching liquor was treated under a condition of a sulfuric acid concentration of 250 g / L, a temperature of 80 DEG C, and a reaction time of about 18 hours using a copper plate and a copper powder in a detellurizing bath to precipitate copper telluride.

The whole decopper was repulped with hydrochloric acid and sent to a chlorine leaching tank. Chloride leaching was performed by slowly adding hydrogen peroxide. It cooled so that reaction temperature might be 60-70 degreeC. After the leaching of chlorine, the solid / liquid was separated by a filter press, the solid of the silver chloride was repulped with water, and then the silver reduction process was used, and the solution was sent to a cooling acid concentration adjusting tank for use in the gold extraction process. The chloride leaching rate was as follows; Au: 97.5%, Ag: 1%, Pt: 99%, Pd: 98%, Se: 93%, Te: 70%, Pb: 5%, Sb: 30%, Bi: 69%

The chloride leaching solution and the DBC of the gold extraction solvent were contacted using a mixer setler, and gold was extracted from the aqueous solution. The gold extraction DBC was centrifuged, scrubbed and centrifuged with a weak hydrochloric acid solution, mixed with an oxalic acid solution in a gold reducing bath, and the gold in the DBC was directly reduced. The reduction reaction was carried out at 85 ° C. for 2 hours. The reduced analytical value was <1 ppm for any of Pd, Ag, Cu, Pb, Fe, Pt, Ti, Te, Se, Sn.

On the other hand, the gold extract was sent to the reduction step after distilling off the DBC, and separated the platinum group, gold and selenium tellurium.

Reduction was carried out under the following conditions:

Gold Extraction Liquid Pd Initial Concentration: Approx. 500 mg / l

Gold Extraction Pt Initial Concentration: Approx. 50 mg / l

Gold extract after-chlorine concentration: 1.31 mol / l

Blow flow rate of sulfur dioxide: 300 (ℓ / min)

SO ₂ / (Pt + Pd) mol ratio: 6.3 mol / mol

Blow time: 20 minutes

Temperature: 80 ~ 82 ℃

The following results were obtained:

Liquid concentration (unit g / ℓ) Se Te Au Pd Pt Full amount of treatment 20.0 1.20 0.010 0.340 0.038 After reduction treatment 20.0 1.20 <0.001 0.008 <0.001

Reduction product composition (%) Au Pt Pd Te Se Reduction Recovery 0.4 2.7 25.0 0.2 64.0

(Example 2)

Then selenium and tellurium were separated.

Reduction was carried out under the following conditions:

Example 1 Reduced Lateral Se Concentration: 20 g / l

Example 1 Reducing Tate Te Concentration: 1.20 g / l

Chlorine ion concentration: 1.5 mol / l

Blow flow rate of sulfur dioxide: 300 (ℓ / min)

SO ₂ / Se mol ratio: 1.8 mol / mol

Blow time: 700 minutes

Temperature: 80 ~ 82 ℃

The following results were obtained:

Liquid concentration (unit g / ℓ) Se Te Au Pd Pt Example 1 After Treatment 20.0 1.20 <0.001 0.008 <0.001 Example 2 After Treatment 3.07 1.20 <0.001 <0.001 <0.001

Reduction product composition (%) Au Pt Pd Te Se Recovery reduction composition - 0.009 0.046 0.0004 99

(Example 3)

Reduction was carried out under the following conditions:

Temperature: 80 ~ 82 ℃,

SO ₂ blow amount: 600 l / min

Time: 10 hours

The following operation results were obtained (together the results of Examples 1 and 2):

Liquid concentration (unit g / ℓ) Se Te Au Pd Pt Full amount of treatment 20.0 1.20 0.010 0.340 0.038 After the first stage treatment 20.0 1.20 <0.001 0.008 <0.001 After the second stage treatment 3.07 1.20 <0.001 <0.001 <0.001 After the third stage treatment 0.013 0.007 <0.001 <0.001 <0.001

Reduction product composition (%) Au Pt Pd Te Se 1st stage separation recovery composition 0.4 2.7 25.0 0.2 64.0 Second stage separation recovery composition - 0.009 0.046 0.0004 99 Third stage separation recovery composition - <0.1 <0.1 63 27.0

(A) The platinum group, gold, selenium, and tellurium were separated easily and efficiently. Platinum group and gold can be recovered from a high concentration of selenium. Therefore, there is no need to remove selenium beforehand. Usually, to remove the selenium in advance, it needs to be heated and oxidized, and a washing tower is required to volatilize selenium in the gas phase. Therefore, the environment is deteriorated, and equipment is needed to completely remove the selenium in the gas phase. And waste liquid treatment such as washing.

Since selenium is satisfactorily separated, selenium does not interfere with the operation of the process in the platinum group and gold recovery process. If the selenium concentration is too high (Se / Pd exceeds 3.5), the metal selenium reduced by the slight potential change in the liquid, the contact with organics, etc. becomes coke-phase selenium, filling the reaction phase, clogging the piping, and in solvent extraction There have been harms that inhibit the phase, but these harms are resolved.

Platinum group and gold such as platinum group remaining after the recovery can be concentrated to an intermediate raw material which can be effectively treated immediately in the platinum group refining process, and the amount of selenium can be kept to a minimum. Therefore, even if the platinum group concentration of the raw material precursor is low, it is unnecessary to repeat the selenium residue containing platinum group in the original process due to the platinum group concentration.

(B) The platinum group and the gold-containing material, which have been separated and recovered in the first step, are not only concentrated in the platinum group and the gold, but also precipitated, so that they are suitable for dissolution in the next step. It can be used without pretreatment in the platinum group and gold recovery process.

(C) Since selenium is recovered from a liquid containing less platinum group or gold, such as platinum group, even if selenium is distilled and purified, there are few distillation residues and the treatment of distillation residues is easy.

(D) Separation of selenium and tellurium is good, which facilitates selenium purification. Until now, the separation of tellurium, which is a major impurity, has been necessary, but the tellurium can be 100 ppm or less, usually 10 ppm or less.

(E) Tellurium may be sent directly to the Tellurium purification process. In addition, the burden on the phase purification process by repetition can be reduced.

Claims (12)

As a method of treating a copper electrolytic material, (A) The copper electrolytic material is subjected to pretreatment via a decopper process, a chloride leaching process and a gold extraction process, (B) In the obtained gold extraction liquid (i), the sulfuric acid gas which maintained the chlorine ion concentration in liquid below 1.5 mol / L, and was diluted to 8-12% concentration with air at the temperature of 60-90 degreeC, is platinum group. Blowing for 10 to 30 minutes at a flow rate of 260 to 350 (l / min) at an amount of 8 to 15 times the concentration of gold mol, thereby separating the platinum group, gold, selenium, and tellurium remaining in the rear liquid to contain the platinum group and gold content. A reduction method of obtaining a reducing product, wherein the copper electrolytic precursor is treated. As a method for treating copper electrolytic material, (A) The copper electrolytic material is subjected to pretreatment via a decopper process, a chloride leaching process and a gold extraction process, (B) In the obtained gold extraction liquid, (A) platinum sulfide gas which kept the chlorine ion concentration in liquid below 1.5 mol / l, and was diluted to 8-12% concentration with air at the temperature of 60-90 degreeC. By blowing for 10 to 30 minutes at a flow rate of 260 to 350 (l / min) at an amount of 8 to 15 times the concentration of gold mol, the platinum group, gold, selenium and tellurium remaining in the rear liquid are separated to reduce the platinum group and gold content. In the first reduction treatment to obtain water, and (b) after separating the platinum group and gold, the chlorine ion concentration in the liquid is maintained at 2.0 mol or less, and the selenium concentration in the solution is maintained at 3 g / l or more. , Selenium and tellurium are separated by blowing the sulfurous acid gas at a temperature of 60 to 90 ° C. for 600 to 800 minutes at a flow rate of 250 to 350 (l / min) at not more than twice the molar concentration of selenium. A copper electrolytic material, characterized in that the treatment comprising a second reduction step to obtain Method. As a method for treating copper electrolytic material, (A) The copper electrolytic material is subjected to pretreatment via a decopper process, a chloride leaching process and a gold extraction process, (B) In the obtained gold extraction liquid, (A) platinum sulfide gas, which was maintained at a concentration of 1.5 mol / l or less in a liquid and diluted to 8 to 12% by air at a temperature of 60 to 90 ° C. By blowing for 10 to 30 minutes at a flow rate of 260 to 350 (l / min) at an amount of 8 to 15 times the molar concentration, the platinum group, gold, selenium and tellurium remaining in the rear liquid are separated to form a platinum group and gold-containing reduced product. (B) while maintaining the chlorine ion concentration in the liquid at 2.0 mol or less and the selenium concentration in the solution at 3 g / l or more, At a temperature of 60 to 90 ° C., sulfurous acid gas is blown for 600 to 800 minutes at a flow rate of 250 to 350 (l / min) at less than twice the molar concentration of selenium, thereby separating selenium and tellurium, thereby reducing the selenium-containing reducing product. (2) Sulfurous acid at a temperature of 60 to 90 DEG C in a second liquid obtained after the separation step; To 500 ~ 700 (l / min) flow rate of 500 ~ 700 minutes blow tellurium-containing tailings third copper electrolytic reduction method before water treatment, characterized in that for performing step processing including obtaining a while by the switch. The decoppering step is performed by using copper sulfate contained in the whole product at 70 to 85 ° C. and 18 to 80 ° C. under an atmospheric pressure and an air blower using a sulfuric acid solution of a copper electrolysis step. A method for treating copper electrolytic material by leaching and removing for 24 hours. 5. The tellurium solution of claim 4, wherein the leaching liquor after decoppering is tellurized by copper plate / copper powder at the reaction conditions of sulfuric acid concentration: 230-450 g / L, temperature: 70-90 ° C and reaction time: 16-24 hours. A method for treating copper electrolytic material, which precipitates as copper. The chloride leaching process according to any one of claims 1 to 3, wherein in the chloride leaching step, the platinum-prevented slurry, which is repulped with hydrochloric acid using hydrogen peroxide in combination, is dissolved in the solution, thereby dissolving the platinum group and gold in the solution after decoppering. And, at the same time, a method of treating copper electrolyte, which mainly separates silver, lead, etc. as chloride. 7. The method for treating a copper electrolytic electrolyte according to claim 6, wherein after the leaching of chloride, the solid of the silver chloride main body is sent to a silver reduction / purification step after repulping with water, and iron powder is added to reduce silver from silver chloride. The method of any one of claims 1 to 3, wherein, in the gold extraction step, the solution after the chloride leaching is cooled to 5 ° C, and the hydrochloric acid concentration is adjusted for gold extraction, and the chloride is prepared using DBC (dibutylcarbitol). A method for treating copper electrolyte, in which solvent is extracted only gold from a leach solution. The copper electrolytic material according to any one of claims 1 to 3, wherein the platinum group / gold-containing reducing product recovers the platinum group as a raw material of the platinum group refining step and recovers gold from the gold-containing solution from the refining step. Treatment method. 4. The selenium-containing reducing substance is washed with repulping with water, followed by vacuum drying to form a raw material for the selenium distillation, and distilled selenium is continuously dropped onto the casting drum, and selenium is used as a dry shot. After the distillation residue was recovered, the remaining selenium was completely distilled off with a dry solid still, to obtain a dry solid residue containing platinum group and gold, and the dry solid residue as a raw material of the platinum group refining process. A method for treating copper electrolyte, which recovers gold and recovers gold from the gold-containing solution from this purification step. 4. The method for treating copper electrolyte according to claim 3, wherein the tellurium-containing reducing product is used as a raw material for recovering tellurium, and the tellurium dioxide is produced by alkali leaching and neutralization, and the tellurium is recovered by alkali leaching and electrowinning. 12. The tellurium according to claim 11, wherein the tellurium-containing reducing product is used as a raw material for recovering tellurium together with copper telluride from the de-tellurization process, and tellurium dioxide is produced by alkali leaching and neutralization. Method of treating copper electrolytic material to be recovered.