KR101043398B1 - Copper recovery method using zinc concentrate and copper electrolyte production method - Google Patents

Abstract

In a method for recovering copper according to an embodiment of the present invention, a precipitation step of injecting zinc concentrate into a precipitation stock solution containing copper to generate a first precipitate and a second precipitate by introducing the first precipitate into a refined stock solution containing copper It may comprise a purification step to produce a precipitate.

Zinc concentrate, copper, electrolyte

Description

A method for recovery of copper and manufacturing method for copper electrolyte using Zinc concentrate}

The present invention relates to a copper recovery method, and more particularly, to a copper recovery method using a zinc concentrate and a method for producing a copper electrolyte.

Copper (Cu) is excellent in malleability, ductility and processability, and has excellent electrical conductivity after silver (Ag), so it is widely used in almost all fields such as copper plates, various electrical and electronic products, alloy materials, mechanical parts, and building materials. Copper is one of the most important metals among nonferrous metals, such as aluminum and zinc, and has excellent electrical and thermal conductivity, easy processing, and high chemical resistance, which makes it difficult to corrode. Zinc (Zn), tin (Sn), nickel ( Ni) easily forms alloys and is widely used throughout the electrical industry, brass, bronze, mechanical parts, construction, money and other industries.

Recovery of copper as a high-purity metal from copper concentrate can be largely classified into dry smelting and wet smelting. The dry smelting methods include the self-furnace method, the Mitsubishi continuous method, and the refraction furnace method.The copper matte is melted through the melting of sulfide ore, and then copper matt is formed in the converter. After the process, the final method of producing high-purity copper through electrolytic refining is introduced in most smelters.

Wet smelting methods include Solvent Extraction-Electro-Winning (SX-EW) and bacterial leaching. SX-EW is the most widely used method. In the SX-EW method, the copper contained in the oxide or low grade sulfide is leached into sulfuric acid, and then the solvent is extracted to separate / concentrate the copper, and finally, copper is recovered through electrolytic extraction.

The present invention is to provide a copper recovery method using zinc concentrate. In addition, to recover the copper in the copper recovery step to provide a double target process (Double target process) capable of leaching the zinc contained in the zinc concentrate.

In a method for recovering copper according to an embodiment of the present invention, a precipitation step of injecting zinc concentrate into a precipitation stock solution containing copper to generate a first precipitate and a second precipitate by introducing the first precipitate into a refined stock solution containing copper It may comprise a purification step to produce a precipitate.

In the precipitation step, the zinc concentrate may be added in an amount of 1.5 equivalents or more and 2.0 equivalents or less relative to the copper content. In addition, the zinc concentrate may have an average particle size larger than 1 μm and 10 μm or less. On the other hand, the precipitation step may be carried out in more than 6 hours 10 hours or less than 75 ℃ 100 ℃.

In the purification step, the first precipitate may be added to 50g or more and 100g or less per 1L of the purified stock solution. In addition, the purification step may be performed within 4 hours or more within 8 hours.

The precipitation stock solution contains iron, and at least 40% of the iron may be trivalent iron.

It may further comprise a grinding step of grinding the zinc concentrate before the precipitation step.

The precipitation filtrate may be produced in the precipitation step, and the precipitation filtrate may be used as the purification stock solution in the purification step. Meanwhile, a purification filtrate may be generated in the purification step, and the purification filtrate may be used as the precipitation stock solution in the precipitation step.

After the purification step, the step of oxidizing the ferrous sulfate in the purified filtrate to ferric sulfate may further include, wherein the purified filtrate subjected to the oxidation step may be used as the precipitation stock solution.

The oxidation step may be performed at 60 ° C. or higher and 80 ° C. or lower. In addition, in the oxidation step, oxygen may be supplied to the purified filtrate within 4 hours.

Copper electrolytic solution production method according to an embodiment of the present invention, the precipitation step of producing a first precipitate by injecting zinc concentrate to the precipitation stock solution containing copper, by adding the first precipitate to the purification stock solution containing copper It may include a purification step of producing a second precipitate and a dissolution step of dissolving the second precipitate in the dissolved stock solution.

In the dissolving step, the second precipitate may be added at 100 g or more and 200 g or less per 1 L of the dissolution stock solution. In addition, the dissolution step may be performed at 80 ° C. or higher and 100 ° C. or lower, or 12 hours or more and 16 hours or less.

The dissolution stock solution may be a copper electrolytic fine liquid.

Before the dissolving step, the dissolution stock solution may further include a heating step of heating to 80 ℃ 100 ℃.

According to the present invention, the copper recovery process can be simplified by using zinc concentrate. In addition, a copper electrolyte may be prepared by adding a dissolution step to the copper recovery process according to the present invention.

Hereinafter, with reference to the accompanying drawings, it will be described an embodiment of the present invention in detail so that those skilled in the art can easily carry out. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In order to clearly describe the present invention, parts irrelevant to the description are omitted in the drawings, and like reference numerals designate like parts throughout the specification.

1 is a process chart showing a copper recovery method according to an embodiment of the present invention.

Referring to Figure 1, the copper recovery method according to an embodiment of the present invention includes a precipitation step and a purification step.

Precipitation step (S100) is a step of producing a first precipitate and the precipitate filtrate by adding zinc concentrate (zinc concentrate) to the precipitation stock solution containing copper. The zinc concentrate may be ground before the precipitation step and then added to the precipitation stock solution.

The purified filtrate generated in the purification step (S200) is used as a precipitation stock solution through an oxidation step, and the precipitation stock solution may include iron (Fe), zinc (Zn) and other impurities in addition to copper (Cu).

The main component of zinc concentrate is zinc sulfide (ZnS), with an average particle size of greater than 1 µm and less than 10 µm. Zinc concentrate is added to the precipitation stock solution in an amount of 1.5 equivalents to 2.0 equivalents based on the amount of copper contained in the precipitation stock solution. If the zinc concentrate input is less than 1.5 equivalents, the copper recovery becomes too low. If the concentration of zinc concentrate exceeds 2.0 equivalents, the copper recovery may reach nearly 100%, but the zinc content is increased because many unreacted zinc concentrates remain in the first precipitate without reacting. The zinc concentrate injected in the precipitation step is leached to zinc sulfate by reaction with copper contained in the precipitation stock solution under atmospheric pressure. The precipitate filtrate generated in the precipitation step is a solution having the same composition as the atmospheric leaching filtrate of zinc concentrate and can be used to produce high purity zinc through a series of purification processes.

The reaction occurring in the precipitation step may be represented by the formula (1).

Scheme 1: ZnS + Fe ₂ (SO ₄ ) ₃ → ZnSO ₄ + S + 2FeSO ₄

Scheme 2: CuSO ₄ + S + 2 FeSO ₄ → CuS + Fe ₂ (SO ₄ ) ₃

Scheme 3: CuSO ₄ + ZnS → CuS + ZnSO ₄

Scheme 1 shows that zinc sulfide (ZnS) contained in zinc concentrate reacts with ferric sulfate (Fe ₂ (SO ₄ ) ₃ ). As a result of this reaction, ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) becomes ferrous sulfate (FeSO ₄ ) and zinc sulfate (ZnSO ₄ ) and sulfur (S) are produced.

Scheme 2 shows that sulfur (S) produced in Scheme 1 reacts with copper sulfate (CuSO ₄ ) and ferrous sulfate (FeSO ₄ ). As a result of this reaction, ferrous sulfate (FeSO ₄ ) becomes ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) and copper sulfide (CuS) is produced.

Scheme 1 and Scheme 2 represent two reactions that proceed simultaneously, and both schemes are summarized in Scheme 3. However, the reaction in which zinc concentrate is decomposed by ferric sulfate is an initiation reaction, which is represented by Scheme 1. For this initiation reaction to occur, the content of trivalent iron (Fe (III)) must be at least 0.2 times the mass ratio to the copper content.

The precipitation step may be performed at 75 ° C. or more and 100 ° C. or less for 6 hours or more and within 10 hours. If the reaction temperature is less than 75 ℃ copper recovery is too low, if it exceeds 100 ℃ it is too expensive. In addition, if the reaction time is less than 6 hours, the copper recovery is too low, if more than 12 hours is too expensive.

The main component of the first precipitate is copper sulfide (CuS). Zinc concentrate that has not reacted in the precipitation step may be included in the first precipitate.

The purification step (S200) is a step of generating a second precipitate and a purified filtrate by inputting the first precipitate to the refined stock solution containing copper.

The first precipitate may be added to 50 g or more and 100 g or less per 1 L of the purified stock solution. If the amount of the first precipitate is less than 50g, a large-capacity purification facility and a precipitation facility are required to process the entire amount of the first precipitate generated in the precipitation step, which requires a lot of investment and operating costs. When the amount of the first precipitate added is more than 100 g, the second precipitate may contain a large amount of zinc, which may increase the zinc content in the dissolved filtrate in the later dissolution step.

The purification step can be performed at least 4 hours and no more than 8 hours. If the reaction time is less than 4 hours, the reaction does not occur sufficiently and the zinc content in the second precipitate is increased. If the reaction time exceeds 8 hours, there is a problem in that the operation and maintenance costs are high due to the residence time more than necessary.

In this step, the zinc sulfide contained in the first precipitate may be reacted with the purified stock solution to dissolve unreacted zinc concentrate and remove it from the first precipitate. As the purified stock solution, the wet leaching filtrate of copper concentrate contains ferric sulfate and sulfuric acid, so that unreacted zinc concentrate according to Scheme 1 of Chemical Formula 1 can be dissolved and removed from the first precipitate. Can be.

In addition, referring to Chemical Formula 2, zinc sulfide may be removed using dilute sulfuric acid as a purified stock solution. In this case, hydrogen sulfide (H ₂ S), which is a toxic gas, is generated and separate equipment such as a scrubber needs to be installed. It is not recommended to use dilute sulfuric acid as the purification stock because it is harmful to the environment and expensive.

ZnS + H ₂ SO 4 → ZnSO ₄ + H ₂ S

The main component of the second precipitate is copper sulfide (CuS). That is, copper is recovered in the form of copper sulfide through a precipitation step and a purification step. In this copper sulfide, copper may be 35% or more and 55% or less and sulfur may be 25% or more and 40% or less. The second precipitate may be a fine powder, with an average particle size of 1 μm or more and 3 μm or less and a maximum particle size of 10 μm.

If the zinc concentrate introduced during the precipitation step contains less than 5% iron, the second precipitate may contain less than 3% iron.

In the purification step, a purification filtrate is also produced along with the second precipitate. Since the purified filtrate may contain 20 g / L or more and 30 g / L or less, the purified filtrate may be used to recover the copper by using the precipitation filtrate in the precipitation step.

As mentioned above, since at least 40% of iron in the precipitation stock solution must be present as ferric sulfate, it is difficult to use the purified filtrate as a precipitation stock solution as it is. Through a separate oxidation step, the content of ferric sulfate must be increased by oxidizing ferrous sulfate in the purified filtrate.

In the oxidation step, ferrous sulfate is oxidized to ferric sulfate by adding oxygen to the purified filtrate. This step can be performed within 4 hours at 60 ° C. or higher and 80 ° C. or lower. If the temperature is below 60 ° C, the oxidation efficiency is too low. If the temperature exceeds 80 ° C, the energy cost increases. In addition, since the reaction temperature of the precipitation step increases, there is a problem that a separate cooling device such as a heat exchanger is required to control the reaction temperature of the precipitation step.

The purified filtrate which has undergone this oxidation step can be used as the precipitation stock liquor in the precipitation step.

2 is a process chart showing a method for producing a copper electrolyte according to an embodiment of the present invention.

Referring to Figure 2, the copper electrolyte preparation method according to an embodiment of the present invention includes a precipitation step, a purification step and a dissolution step.

Precipitation step (S300) and purification step (S400) is the same as described in the copper recovery method, so a description thereof will be omitted.

Dissolution step (S500) is a step of producing a dissolution filtrate by dissolving the second precipitate into the dissolution stock solution.

As the dissolution stock solution, copper electrolytic fine liquid may be used and the dissolution filtrate may be used as copper electrolyte. For example, copper electrolytic tailings may include copper, iron, zinc and sulfuric acid. In this case, copper may be 35 g / L to 45 g / L, iron may be 4 g / L to 10 g / L, zinc may be 15 g / L to 45 g / L, and sulfuric acid may be 160 g / L to 200 g / L.

After melt | dissolution stock is previously heated to 80 degreeC or more and 100 degrees C or less, a 2nd sediment can be thrown in.

The second precipitate is produced in the purification step (S400). The second precipitate may be added at 100 g or more and 200 g or less per 1 L of the dissolved stock solution.

If the amount of the second precipitate is less than 100g, the copper concentration in the dissolved filtrate is lowered to less than 84.6g / L, while the iron contained in the second precipitate is dissolved in a lot of the dissolved filtrate, there is a problem that the iron content is increased.

If the amount of the second precipitate exceeds 200 g, the copper concentration in the dissolved filtrate is 130 g / L or more, and the dissolved filtrate may be supersaturated. In the process of transferring the supersaturated dissolved filtrate to the electrolytic cell, copper sulfide crystals may precipitate, causing copper loss or clogging.

The reaction taking place in the dissolution step can be represented by the formula (3).

Scheme 4: CuS + Fe ₂ (SO ₄ ) ₃ → CuSO ₄ + S + 2FeSO ₄

Scheme 5: 4FeSO4 + 2H ₂ SO ₄ + O ₂ → 2Fe (SO ₄ ) ₃ + 2H ₂ O

Scheme 6: CuS + H ₂ SO ₄ + 0.5O ₂ → CuSO ₄ + S + H ₂ O

Here, Scheme 4 shows that copper sulfide (CuS) contained in the second precipitate reacts with ferric sulfate (Fe ₂ (SO ₄ ) ₃ ). As a result of this reaction, ferric sulfate (Fe ₂ (SO ₄ ) ₃ ) becomes ferrous sulfate (FeSO ₄ ) and copper sulfate (CuSO ₄ ) and sulfur (S) are produced.

Scheme 5 shows that ferrous sulfate (FeSO ₄ ) generated in Scheme 4 is oxidized to ferric sulfate by reacting with sulfuric acid and oxygen. As a result of this reaction, ferrous sulfate (FeSO ₄ ) becomes ferric sulfate (Fe ₂ (SO ₄ ) ₃ ).

Scheme 4 and Scheme 5 represent two reactions that proceed simultaneously, and the two schemes are summarized in Scheme 6.

The dissolution step may be performed at 80 ° C. or higher and 100 ° C. or lower for 12 hours or more and within 16 hours.

If the temperature is lower than 80 ° C, the reaction time needs to be long, which consumes a lot of energy and increases the cost. If the temperature exceeds 100 ℃, the reactor must be made of a material that can withstand the high temperature and high pressure state also increases the cost.

If the reaction time is less than 12 hours, the reaction does not occur sufficiently, so less copper is dissolved into the dissolution filtrate. If the reaction time is more than 16 hours, there is a lot of dissolved copper, but it is expensive.

At the end of the dissolution step, the dissolution filtrate and the dissolution residue are separated. The dissolved filtrate can be used as a copper electrolyte. The dissolved residue may contain at least 1% of lead sulfate, up to 15%, sulfur 40% to 70%, less than 0.5% copper, and small amounts of valuable metals.

Experimental Example 1

2 L of a purified filtrate containing 30 g / L copper, 20 g / L ferric acid, and 50 g / L sulfuric acid was placed in a 3 L reactor, heated to the reaction temperature, and oxygen was added thereto. The oxidation rate of ferrous sulfate was calculated by quantitative analysis of ferric sulfate content by wet titration. The experimental conditions and results are shown in Table 1 below.

Reaction temperature
(℃) Oxygen
(NL / min) Oxidation rate of ferrous sulfate by reaction time (%) 0 hours 0.25 hours 0.5 hours 1 hours 2 hours 4 hours Example 1 60 5 0 10.8 22.3 40.8 52.5 58.2 Example 2 70 5 0 13.2 26.0 43.6 54.9 61.9 Example 3 80 5 0 14.8 28.5 46.4 57.3 64.4 Comparative Example 1 40 5 0 2.1 4.3 7.9 14.1 17.7 Comparative Example 2 50 5 0 5.4 9.9 16.1 21.3 23.9 Comparative Example 3 90 5 0 14.9 28.8 46.7 57.5 65.2

Example 1 Experiment result of ~ 3

After 4 hours in Example 1, the oxidation rate of ferrous sulfate was 58.2%.

After 4 hours in Example 2, the oxidation rate of ferrous sulfate was 61.9%.

In Example 3, after 4 hours, the oxidation rate of ferrous sulfate was 64.4%.

Comparative Example 1 Experiment result of ~ 3

After 4 hours in Comparative Example 1, the oxidation rate of ferrous sulfate was 17.7%.

After 4 hours in Comparative Example 2, the oxidation rate of ferrous sulfate was 23.9%.

After 4 hours in Comparative Example 3, the oxidation rate of ferrous sulfate was 65.2%, which is higher than that of Example 3, 64.4%. However, the reaction temperature of the comparative example 3 is 90 degreeC, and is higher than the 80 degreeC of Example 3. If the reaction temperature is high, the temperature of the purified filtrate must be lowered by using a separate cooling facility such as a heat exchanger before sending the purified filtrate oxidized in the oxidation step to the precipitation step. This is undesirable because of the high cost.

Experimental Example 2

Example 4

2 L of a purified filtrate containing 30 g / L copper, 20 g / L ferric acid and 50 g / L sulfuric acid was put in a 3 L reactor and oxygen was added at 60 ° C. for 1 hour. The purified filtrate was then heated to 80 ° C. 1.5 wt% of zinc concentrate containing 0.2wt% of copper, 58.1wt% of zinc, 1.5wt% of iron, and 33.0wt% of sulfur and having an average particle size and a maximum particle size of 3 µm and 10 µm, respectively, was added to the filtrate for reaction for 8 hours. did. The resulting precipitate filtrate was filtered to investigate the copper recovery. The content of copper, zinc and iron in the first precipitate and the precipitate filtrate was quantitatively analyzed by atomic absorption spectrophotometry.

Example 5

Except that 1.7 equivalents of zinc concentrate was tested in the same manner as in Example 4.

Example 6

Except that 2.0 equivalents of zinc concentrate was tested in the same manner as in Example 4.

Example 7

The experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 75 ° C.

Example 8

The experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 85 ° C.

Example 9

Experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 90 ℃.

Example 10

Experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 95 ℃.

Example 11

Experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 100 ℃.

Example 12

Experiment was carried out in the same manner as in Example 6, except that the reaction time was 6 hours.

Example 13

Experiment was carried out in the same manner as in Example 6 except that the reaction time was 10 hours.

Comparative Example 4

Experiment was carried out in the same manner as in Example 4, except that 1.0 equivalent of zinc concentrate was added.

Comparative Example 5

The experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 75 ° C.

Comparative Example 6

Experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 70 ℃.

Comparative Example 7

Experiment was carried out in the same manner as in Example 6 except that the reaction temperature was 60 ℃.

Comparative Example 8

Experiment was carried out in the same manner as in Example 6, except that the reaction time was 2 hours.

Comparative Example 9

Experiment was carried out in the same manner as in Example 6, except that the reaction time was 4 hours.

The results of the experiment as described above are shown in Table 2 below.

Zinc concentrate
(equivalent weight) Reaction temperature
(℃) Reaction time
(time) First precipitate Copper recovery
(%) Copper (wt%) Zinc (wt%) Example 4 1.5 80 8 33.4 8.5 96.3 Example 5 1.7 80 8 35.9 13.2 99.9 Example 6 2.0 80 8 32.8 18.7 100 Example 7 1.7 75 8 26.4 18.7 93.8 Example 8 1.7 85 8 35.9 13.2 99.9 Example 9 1.7 90 8 35.9 13.1 99.9 Example 10 1.7 95 8 36.0 13.0 100 Example 11 1.7 100 8 35.9 13.1 99.9 Example 12 1.7 80 6 31.4 19.4 92.6 Example 13 1.7 80 10 36.0 12.9 100 Comparative Example 4 1.0 80 8 19.4 4.7 78.4 Comparative Example 5 1.3 80 8 31.7 6.2 89.7 Comparative Example 6 1.7 70 8 19.4 25.4 68.3 Comparative Example 7 1.7 60 8 8.3 51.7 10.4 Comparative Example 8 1.7 80 2 11.0 38.4 35.1 Comparative Example 9 1.7 80 4 22.9 25.3 68.3

Example 4 Experimental result of ~ 13

In Example 4, the copper recovery was measured and found to be 96.3%.

In Example 5, the copper recovery was measured and found to be 99.9%.

In Example 6, the copper recovery was measured and found to be 100%.

In Example 7, the copper recovery was found to be 93.8%.

In Example 8, the copper recovery was measured and found to be 99.9%.

In Example 9, the copper recovery was measured and found to be 99.9%.

In Example 10, the copper recovery was measured and found to be 100%.

In Example 11, the copper recovery was measured and found to be 99.9%.

In Example 12, the copper recovery was measured and found to be 92.6%.

In Example 13, the copper recovery was measured and found to be 100%.

Comparative Example 4 Experimental result of ~ 9

In Comparative Example 4, the copper recovery was measured and found to be 78.4%. The zinc remaining in the first precipitate without reacting was relatively low at 4.7 wt%.

Copper recovery was measured in Comparative Example 5 as a result of 89.7%. The zinc remaining in the first precipitate without reacting was relatively low at 6.2 wt%.

Copper recovery was measured in Comparative Example 6 as a result of 68.3%.

Copper recovery was measured in Comparative Example 7 as a result of 10.4%. This low copper recovery indicates little precipitation progress.

In Comparative Example 8, the copper recovery was measured and found to be 35.1%.

Copper recovery was measured in Comparative Example 9 as a result of 68.3%.

Experimental Example 3

Example 14

50 g of a first precipitate was added to 1 L of an atmospheric leaching filtrate of copper concentrate containing 40 g of copper, 20 g / L of iron (40% or more of trivalent iron), and 60 g / L of sulfuric acid to react for 8 hours. The first precipitate was produced in Example 5. After the second precipitate formed, it was washed with a small amount of pure water to remove soluble copper. Thereafter, the second precipitate was dried in a drier at 100 ° C. for 12 hours. The contents of copper and zinc in the second precipitate and the purified filtrate were quantitatively analyzed by atomic absorption spectrophotometry.

Example 15

Experiment was carried out in the same manner as in Example 14, except that 100 g of the first precipitate was added.

Example 16

Experiment was carried out in the same manner as in Example 15, except that the reaction time was 4 hours.

Example 17

Experiment was carried out in the same manner as in Example 15 except that the reaction time was 6 hours.

Example 18

Experiment was carried out in the same manner as in Example 15, except that the reaction time was 10 hours.

Comparative Example 10

Experiment was carried out in the same manner as in Example 14, except that 200 g of the first precipitate was added.

Comparative Example 11

Experiment was carried out in the same manner as in Example 14, except that 300 g of the first precipitate was added.

Comparative Example 12

Experiment was carried out in the same manner as in Example 15, except that the reaction time was 2 hours.

Comparative Example 13

Experiment was carried out in the same manner as in Example 16, except that copper was 0 g / L in the purified stock solution.

Comparative Example 14

Experiment was carried out in the same manner as in Example 17, except that copper was 0 g / L in the purified stock solution.

Comparative Example 15

Experiment was carried out in the same manner as in Example 15, except that copper was 0 g / L in the purified stock solution.

The results of the experiment as described above are shown in Table 3 below.

Reactant Reaction time
(time) product Refined Stock Solution First precipitate Purified filtrate Second Settlement Copper
(g / L) input
(g) Copper
(wt%) zinc
(wt%) Copper
(g / L) Copper
(wt%) zinc
(wt%) Example 14 40 50 35.9 13.2 8 34.2 47.2 1.3 Example 15 40 100 35.9 13.2 8 29.1 45.6 3.8 Example 16 40 100 35.9 13.2 4 31.3 42.9 6.0 Example 17 40 100 35.9 13.2 6 30.1 44.1 4.7 Example 18 40 100 35.9 13.2 10 28.5 45.7 3.1 Comparative Example 10 40 200 35.9 13.2 8 20.7 41.5 7.2 Comparative Example 11 40 300 35.9 13.2 8 13.8 38.6 9.3 Comparative Example 12 40 100 35.9 13.2 2 34.1 40.1 8.9 Comparative Example 13 0 100 35.9 13.2 4 0 41.7 8.3 Comparative Example 14 0 100 35.9 13.2 6 0 45.2 6.7 Comparative Example 15 0 100 35.9 13.2 8 0 48.3 5.2

Example 14 Experimental Results of ~ 18

In Example 14, when comparing the first precipitate and the second precipitate, the copper content increased from 35.9 wt% to 47.2 wt% and the zinc content decreased from 13.2 wt% to 1.3 wt%. This is because the zinc contained in the first precipitate was dissolved into the purified stock solution while the copper in the purified stock solution was recovered as the second precipitate.

In Example 15 the copper content was 45.6 wt% and the zinc content was 3.8 wt%.

In Example 16 the copper content was 42.9 wt% and the zinc content was 6.0 wt%.

In Example 17 the copper content was 44.1 wt% and the zinc content was 4.7 wt%.

In Example 18 the copper content was 45.7 wt% and the zinc content was 3.1 wt%.

Comparative Example 10 Experimental result of ~ 15

In Comparative Example 10 and Comparative Example 11, the zinc content of the second precipitate was somewhat higher, at 7.2 wt% and 9.3 wt%, respectively. This is because the input amount of the first precipitate was 200g and 300g, respectively, compared with Examples 1 to 18.

In Comparative Example 12, the zinc content of the second precipitate was 8.9 wt%. This is because the reaction time was relatively short at 2 hours, and zinc in the first precipitate was not sufficiently dissolved in the purified stock solution.

In Comparative Examples 13 to 15, the zinc content in the second precipitate was varied to 8.3 wt%, 6.7 wt% and 5.2 wt%, respectively. However, a large amount of hydrogen sulfide was generated because dilute sulfuric acid containing no copper was used as a purified stock solution.

Experimental Example 4

Example 19

1 L of copper electrolytic fine liquid containing 40 g / L of copper, 8 g / L of iron, and 180 g / L of sulfuric acid was put into a 2 L reactor and heated to 90 ° C. 100 g of the second precipitate produced in Example 15 was added to the reactor. Oxygen was continuously added to the reactor, and the final redox potential after the reaction was adjusted to be 450 mV or more with respect to the silver / silver chloride reference electrode, and the mixed solution was leached and filtered for 16 hours. The dissolved residue produced in this process was washed with a small amount of pure water to remove soluble copper and dried in a drier at 100 ° C. for 12 hours. The contents of copper and zinc in the second precipitate and the purified filtrate were quantitatively analyzed by atomic absorption spectrophotometry.

Example 20

Experiment was carried out in the same manner as in Example 21, except that 150 g of the second precipitate was added.

Example 21

The same procedure as in Example 21 was carried out except that 200 g of the second precipitate was added.

Example 22

Experiment was carried out in the same manner as in Example 20 except that the reaction time was 12 hours.

Comparative Example 16

Experiment was carried out in the same manner as in Example 20, except that the reaction time was 4 hours.

Comparative Example 17

Experiment was carried out in the same manner as in Example 20 except that the reaction time was 8 hours.

Comparative Example 18

Experiment was carried out in the same manner as in Example 20 except that the reaction time was 20 hours.

Comparative Example 19

The same procedure as in Example 20 was carried out except that 250 g of the second precipitate was added.

Comparative Example 20

Experiment was carried out in the same manner as in Example 20, except that 300 g of the second precipitate was added.

Comparative Example 21

The same procedure as in Example 20 was carried out except that 400 g of the second precipitate was added.

Comparative Example 22

The same procedure as in Example 20 was carried out except that 50 g of the second precipitate was added.

The results of the experiment as described above are shown in Table 4 below.

Reactant Reaction time
(time) product Melt Stock Second Settlement Soluble filtrate Dissolved residue Copper
(g / L) input Copper
(wt%) zinc
(wt%) Copper
(g / L) Copper
(wt%) zinc
(wt%) Example 19 40 100 45.6 3.8 16 84.6 2.6 0.3 Example 20 40 150 45.6 3.8 16 106.0 2.8 0.5 Example 21 40 200 45.6 3.8 16 126.7 4.2 0.6 Example 22 40 150 45.6 3.8 12 103.9 5.9 0.5 Comparative Example 16 40 150 45.6 3.8 4 66.1 40.9 1.1 Comparative Example 17 40 150 45.6 3.8 8 90.3 20.7 0.8 Comparative Example 18 40 150 45.6 3.8 20 106.8 2.2 0.4 Comparative Example 19 40 250 45.6 3.8 16 130.3 18.5 0.6 Comparative Example 20 40 300 45.6 3.8 16 133.6 19.5 0.8 Comparative Example 21 40 400 45.6 3.8 16 133.9 28.9 1.0 Comparative Example 22 40 50 45.6 3.8 16 62.7 0.7 0.3

Example 19 Experimental result of ~ 22

Comparing the second precipitate and the dissolved residue in Example 19, copper was reduced from 45.6 wt% to 2.6 wt%. About 94.3% of the copper contained in the second precipitate was dissolved in the dissolution stock solution.

In Example 20 copper was reduced from 45.6 wt% to 2.8 wt%.

In Example 21 copper decreased from 45.6 wt% to 4.2 wt%.

In Example 22 copper decreased from 45.6 wt% to 5.9 wt%.

Experimental results of Comparative Examples 16-22

In Comparative Example 16, the copper was reduced from 45.6 wt% to 40.9 wt%. Only about 10.3% of the copper contained in the second precipitate was dissolved in the dissolved stock solution.

In Comparative Example 17, the copper was reduced from 45.6 wt% to 20.7 wt%. Only about 54.6% of the copper contained in the second precipitate was dissolved in the dissolution stock solution.

In Comparative Example 18, the copper was reduced from 45.6 wt% to 2.2 wt%, and mostly dissolved in the dissolution stock solution. However, the reaction time was 20 hours, which was expensive.

In Comparative Examples 19 to 21, copper decreased from 45.6 wt% to 18.5 wt%, 19.5 wt%, and 28.9 wt%, respectively.

In Comparative Example 22, the copper was reduced from 45.6 wt% to 0.7 wt%, and mostly dissolved in the dissolution stock solution. However, the copper concentration of the dissolved stock solution was 62.7 g / L, which was less than that of 84.6 g / L of Example 19.

 Although the embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it is within the scope of the present invention.

1 is a process chart showing a copper recovery method according to an embodiment of the present invention.

2 is a process chart showing a method for producing a copper electrolyte according to an embodiment of the present invention.

Claims (20)

A precipitation step of generating zinc concentrate by injecting zinc concentrate into the precipitation stock solution containing copper; and A purification step of generating a second precipitate by injecting the first precipitate into the purification stock solution containing copper Copper recovery method comprising a. In claim 1, In the precipitation step A copper recovery method for injecting the zinc concentrate in an amount of 1.5 equivalents or more and 2.0 equivalents or less relative to the copper content. 3. The method of claim 2, The zinc concentrate has a mean particle size of greater than 1 µm and less than or equal to 10 µm. The method according to any one of claims 1 to 3, Copper recovery method of performing the precipitation step within 6 hours to 10 hours. The method according to any one of claims 1 to 3, Copper recovery method which performs the said precipitation step at 75 degreeC or more and 100 degrees C or less. The method according to any one of claims 1 to 3, In the purification step, A method for recovering copper, wherein 50 g or more and 100 g or less of the first precipitate is added per 1 L of the purified stock solution. In claim 6, Copper recovery method of performing the purification step within 4 hours to 8 hours. The method according to any one of claims 1 to 3, The precipitation stock solution contains iron, At least 40% of the iron is trivalent iron. In claim 1, Copper recovery method further comprising a grinding step of grinding the zinc concentrate before the precipitation step. In claim 1, In the precipitation step to produce a precipitate filtrate, Copper recovery method using the precipitated filtrate in the purification step in the purification step. In claim 1, In the purification step to produce a purified filtrate, Copper recovery method using the purified filtrate as the precipitation stock solution in the precipitation step. 12. The method of claim 11, An oxidation step of oxidizing ferrous sulfate to ferric sulfate in the purification filtrate after the purification step; Copper purification method using the purified filtrate subjected to the oxidation step as the precipitation stock solution. The method of claim 12, Copper recovery method to perform the oxidation step at 60 ℃ 80 ℃. The method of claim 13, In the oxidation step, Copper recovery method for supplying oxygen to the purified filtrate within 4 hours. A precipitation step of generating zinc concentrate by injecting zinc concentrate into the precipitation stock solution containing copper; A purification step of generating a second precipitate by adding the first precipitate to a purification stock solution containing copper; and Dissolving step of dissolving the second precipitate into the dissolution stock solution Copper electrolyte manufacturing method comprising a. 16. The method of claim 15, In the dissolution step A method for producing a copper electrolyte in which the second precipitate is introduced at 100 g or more and 200 g or less per 1 L of the dissolved stock solution. The method of claim 15 or 16, The copper electrolyte solution manufacturing method which performs the said dissolution step at 80 degreeC or more and 100 degrees C or less. The method of claim 17, Copper dissolution step of performing the dissolution step within 12 hours to 16 hours. The method of claim 18, The dissolution stock solution is a copper electrolytic solution production method. The method of claim 19, Before the dissolution step, The copper electrolyte solution manufacturing method further including the heating step of heating the said melt | dissolution stock solution to 80 to 100 degreeC.

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