Method for recovering valuable metals

Abstract

The present invention relates to a method for recovering a copper (Cu) by-product from a solid copper by-product raw material obtained by adding an alloy raw material containing a valuable metal to a leachate obtained by adding a raw material obtained from a waste battery to an acidic solution and leaching the raw material, the method comprising the steps of: preparing the copper by-product raw material; selectively leaching the valuable metal by adding the copper by-product raw material and an oxidizing agent to the acidic solution; and separating, from the copper by-product raw material, a purified filtrate in which the valuable metal is dissolved and the copper by-product from which the valuable metal has been removed, wherein the amount of the oxidizing agent added is 1.1 to 2.8 equivalents with respect to the content of the valuable metal contained in the copper by-product, and in the step of selectively leaching the valuable metal, the hydrogen ion concentration of the leached filtrate is 0.0001 M to 5 M.

Description

Method for recovering valuable metals

[0001] The present invention relates to waste battery recycling and to a method for recovering valuable metals.

[0002] This application claims priority to Korean Patent Application No. 10-2024-0191950 filed on December 19, 2023, the entire contents of which are incorporated herein by reference.

[0003] Battery demand is rapidly increasing as they are widely used not only in electronic devices such as smartphones and mobile devices but also in electric vehicles. The demand for these batteries is expected to rise further as the demand for electric vehicles increases as the next-generation mode of transportation.

[0004] Since the aforementioned electric vehicle requires a battery with a large electrical capacity, it is installed and used in the vehicle in units of multiple battery cells, modules composed of multiple battery cells, and packs composed of multiple modules. As the usage of the electric vehicle increases rapidly, the amount of waste generated from batteries used in the electric vehicle is also increasing.

[0005] Although various types of batteries are utilized, lithium-ion batteries are the most widely used in the market due to their high energy density. The lithium-ion battery has a structure comprising a positive electrode, a negative electrode, a separator, and an electrolyte, among which the positive electrode accounts for the largest share of the economy. The positive electrode utilizes metal oxides as materials that allow lithium ions to insert into and exit the lattice structure during oxidation and reduction reactions; NCM-based ternary oxides of nickel, manganese, and cobalt are the most widely used. However, the production of these raw materials for metal oxides is concentrated in specific regions, resulting in poor price stability and requiring measures to ensure their stable supply.

[0006] Recycling technology for recovering valuable metals such as lithium, nickel, cobalt, and manganese from waste batteries is attracting attention as a promising method for supplying raw materials for lithium secondary batteries, and wet processes for recovering valuable metals from pre-treated waste batteries have reached the commercialization stage. This process is carried out by discharging, crushing / grinding, and classifying / selecting waste batteries to form black mass, followed by a leaching process in which valuable metals are dissolved in an acidic solution, and then separation / purification processes such as solvent extraction.

[0007] The components within the aforementioned waste batteries include valuable metals such as nickel, cobalt, manganese, or copper. Copper is present as an impurity element among the components of the waste batteries. Conventional technology for separating and purifying copper from nickel raw materials involves dissolving the nickel-containing raw material in an acidic solution, such as sulfuric acid, and separating and purifying it from the nickel solution using solvent extraction or hydroxide precipitation. However, methods such as solvent extraction and hydroxide precipitation generate large amounts of wastewater, and environmental treatment is difficult due to the leaching of non-target metals resulting from the use of substances like caustic soda.

[0008] The technical problem that the present invention aims to solve is to provide a highly concentrated purified liquid by additionally recovering a high-purity copper residue when recovering copper from an acid leaching solution of a nickel-containing raw material.

[0009] A method for recovering a valuable metal according to one embodiment of the present invention is a method for recovering a copper (Cu) byproduct from a solid copper byproduct raw material obtained by introducing an alloy raw material containing a valuable metal into a leachate obtained by introducing a raw material obtained from a waste battery into an acidic solution and leaching it, the method comprising the steps of: preparing the copper byproduct raw material; introducing the copper byproduct raw material and an oxidizing agent into an acidic solution to selectively leach the valuable metal; and separating a purified filtrate in which the valuable metal is dissolved from the copper byproduct raw material and the copper byproduct from which the valuable metal has been removed, wherein the amount of the oxidizing agent introduced is 1.1 to 2.8 equivalents relative to the content of the valuable metal contained in the copper byproduct, and the hydrogen ion concentration of the leachate filtrate in the step of selectively leaching the valuable metal may be 0.0001 M to 5 M.

[0010] In one embodiment, the oxidizing agent may be a substance that includes oxygen atoms and oxidizes the valuable metal. In one embodiment, the oxidizing agent may include at least one of Air, O2, O3, H2O2, Na2S2O5, KMnO4, HNO3, and Na2S2O8.

[0011] In one embodiment, the copper byproduct may be a residue obtained by the steps of: introducing a raw material obtained from a waste battery into an acidic solution to leach it; introducing an alloy raw material containing at least one of nickel, cobalt, and manganese into the leachate to precipitate copper (Cu) in a solid state; and separating a purified filtrate and a precipitated residue from the solution obtained through the precipitation step.

[0012] In one embodiment, the alloy raw material may be an alloy containing the valuable metal. In one embodiment, the average particle size (D50) of the alloy raw material may be 500 μm or less. In one embodiment, the alloy raw material may be obtained by high-temperature reduction heat treatment of a raw material obtained from the waste battery.

[0013] In one embodiment, the oxidation-reduction potential (ORP) of the purified filtrate can be controlled to 300 mV or less. In one embodiment, the step of precipitating copper (Cu) as a solid phase in the leaching step can precipitate the solid phase in the form of metallic copper (Metallic Cu).

[0014] In one embodiment, the metallic copper may be in the form of a powder. In one embodiment, the metallic copper may not contain hydroxyl groups. In one embodiment, the step of selectively leaching valuable metals by adding the copper byproduct raw material and the oxidizing agent to an acidic solution may be performed at a temperature of 20 to 120 °C. In one embodiment, the step of selectively leaching valuable metals by adding the copper byproduct raw material and the oxidizing agent to an acidic solution may be performed by stirring for 1 to 5 hours.

[0015] A method for recovering valuable metals according to one embodiment of the present invention can prevent the removal of valuable metals along with auxiliary materials by precipitating copper ions from a leachate containing valuable metals into a sparingly soluble solid phase and thereby improving the efficiency of recovering valuable metals.

[0016] FIG. 1 is a schematic diagram of a method for recovering valuable metals according to one embodiment of the present invention.

[0017] Terms such as first, second, and third are used to describe various parts, components, regions, layers, and / or sections, but are not limited thereto. These terms are used solely to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, the first part, component, region, layer, or section described below may be referred to as the second part, component, region, layer, or section without departing from the scope of the present invention.

[0018] The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of "comprising" specifies certain characteristics, areas, integers, steps, actions, elements, and / or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and / or components.

[0019] When it is stated that one part is "on" or "on" another part, it may be directly on or on the other part, or another part may be involved in between. In contrast, when it is stated that one part is "directly on" another part, no other part is interposed in between.

[0020] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with relevant technical literature and the present disclosure, and are not interpreted in an ideal or highly formal sense unless otherwise defined.

[0021] FIG. 1 is a schematic diagram of a method for recovering valuable metals according to one embodiment of the present invention.

[0022] Referring to FIG. 1, a method for recovering valuable metals according to one embodiment of the present invention is a method for removing copper (Cu) byproducts from solid copper byproduct raw materials obtained by adding an alloy raw material containing a valuable metal to a leachate obtained by adding a raw material obtained from waste batteries to an acidic solution and leaching it. The inventors have discovered that by adding an alloy raw material containing a valuable metal as a reducing agent, the alloy containing the valuable metal can be selectively removed from the copper residue obtained, thereby improving the recovery rate of the valuable metal, which is the target metal, and the purity of the copper residue, which is the recovered material, can be improved through the purification of the copper-containing material.

[0023] The method for recovering valuable metals according to the present invention may include the steps of preparing a copper byproduct raw material, introducing the copper byproduct raw material and an oxidizing agent into an acidic solution to selectively leach the valuable metal, and separating a purified filtrate in which the valuable metal is dissolved from the copper byproduct raw material and the copper byproduct from which the valuable metal has been removed.

[0024] In the step of preparing a copper byproduct raw material, the copper byproduct is obtained through the steps of: leaching a raw material obtained from waste batteries by adding it to an acidic solution; precipitating copper (Cu) in a solid state by adding an alloy raw material containing at least one of nickel, cobalt, and manganese to the leaching solution; and separating a purified filtrate and a precipitated residue from the solution obtained through the precipitation step.

[0025] The step of leaching raw materials obtained from waste batteries by introducing them into an acidic solution may be performed to obtain valuable metals from the raw materials obtained from waste batteries. Specifically, the raw materials are obtained from waste batteries and may be materials that have undergone a pretreatment process such as crushing or grinding of the waste batteries. Specifically, the raw materials may be crushed materials containing at least a portion of lithium-ion battery positive electrode active materials, negative electrode active materials, plastics, copper, and / or current collectors such as aluminum, and may refer to, for example, black mass. More specifically, the raw materials may include black mass supplied from discarded lithium-containing batteries, discarded parts of said batteries, and / or materials discarded from the battery production process, or black powder obtained through pretreatment such as heat treatment of said black mass.

[0026] The step of leaching a raw material into an acidic solution may be a step of leaching the raw material into an acidic solution to obtain a leachate containing a valuable metal. The acidic solution may be a solution introduced to leach the leachate containing the valuable metal into a solution phase. The acidic solution may include, for example, at least one of an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, or hydrofluoric acid, or an organic acid such as phosphoric acid or acetic acid. Specifically, the acidic solution may be a sulfuric acid or nitric acid solution, and more specifically, the acidic solution may be a sulfuric acid solution.

[0027] In one embodiment, the concentration of hydrogen ions in the acidic solution can be maintained at 0.00005 M to 5 M, specifically 0.001 M to 2 M, and more specifically 0.1 M to 0.2 M. By satisfying the aforementioned range of the initial hydrogen ion concentration of the acidic solution, copper residue can be easily removed through a reaction with the alloy raw material described later.

[0028] The step of precipitating copper (Cu) in a solid state by adding an alloy raw material containing at least one of nickel, cobalt, and manganese to the leaching solution may be a step of precipitating copper ions in a solid state by adding the alloy raw material to the leaching solution.

[0029] The above alloy raw material may include a valuable metal. The above valuable metal may include at least one of nickel, cobalt, and manganese. The above alloy raw material may be obtained by high-temperature reduction heat treatment of the above raw material.

[0030] The above alloy raw material may be obtained by dry heat treating the above raw material. As previously mentioned, the above raw material may be a material that has been crushed, such as black powder.

[0031] The step of dry heat treating the raw material may involve introducing the raw material into a furnace capable of raising it to a high temperature, thereby raising the raw material to a temperature above its melting point. The step of dry heat treating the raw material may involve heat treatment conditions that perform a high-temperature reduction reaction without undergoing a melting step.

[0032] In one embodiment, the heat treatment conditions may be carried out in a range of 900 to 1,800 ℃. Specifically, the range may be 1,200 to 1,800 ℃, and more specifically, 1,300 to 1,700 ℃. If the upper limit of the range is exceeded, there is a problem of loss due to lithium vaporization, and if the lower limit of the range is exceeded, there is a problem that the sintering and reduction of alloy elements cannot proceed. Within the above temperature range, the carbon in the crushed material can be burned minimally, allowing the reduction reaction to be carried out in a state where carbon dioxide generation is almost non-existent.

[0033] In one embodiment, the step of dry heat treating the raw material may be performed in a gas atmosphere of at least one of an inert gas, carbon dioxide, carbon monoxide, and hydrocarbon gas. The inert gas may include, for example, at least one of argon and nitrogen. By performing a reduction reaction of the raw material in the gas atmosphere, an alloy raw material comprising valuable metals contained within the raw material can be effectively recovered.

[0034] In one embodiment, a portion of the gas atmosphere may contain impurities containing residual oxygen. If the oxygen content among the impurities is high, it may combine with the components of the raw material during the reduction reaction process to form carbon dioxide, which then gasifies together with lithium, causing a problem that recovery is difficult.

[0035] In one embodiment, the average oxygen partial pressure in the dry heat treatment step may be in the range of 0.01 to 1 atm. Specifically, if the oxygen partial pressure is higher than the above value, there is a problem of lithium loss and a large amount of carbon dioxide being generated under localized high-temperature conditions. If the oxygen partial pressure is lower than the lower limit of the above range, there is a problem of reduced Li recovery rate due to the inferiority of LiAlO2 formation.

[0036] Specifically, in the dry heat treatment step, the alloy raw material alloyed with components such as nickel, cobalt, manganese, and lithium-containing oxides in the raw material may contain valuable metals and a remainder of impurities. The alloy raw material may include, for example, aluminum (Al), manganese (Mn), lithium (Li), copper (Cu), cobalt (Co), nickel (Ni), carbon (C), and a remainder of impurities.

[0037] In one embodiment, the alloy raw material may undergo at least one of particle size separation and magnetic separation after the dry heat treatment step. This is a non-limiting example, and impurities remaining in the alloy raw material containing valuable metals can be pretreated through various separation methods.

[0038] In one embodiment, the average particle size (D50) of the alloy raw material may be 500 μm or less. Specifically, the average particle size (D50) may be 450 μm or less, more specifically, 100 to 450 μm. The average particle size of the alloy raw material can control the average particle size of the precipitated metallic copper.

[0039] By satisfying the aforementioned range for the average particle size of the alloy raw material, the precipitation efficiency of copper ions can be improved. Specifically, by satisfying the aforementioned range for the average particle size of the alloy raw material, the precipitation efficiency can be improved by controlling it to 500 μm or less. If the average particle size is excessively large, there is a problem in that the reaction efficiency used as a copper ion precipitating agent decreases.

[0040] In one embodiment, the alloy raw material may be added in an amount of 1.1 equivalents or more relative to the copper (Cu) content in the leaching solution. Specifically, the alloy raw material may be added in an amount of 1.2 equivalents or more. By satisfying the aforementioned range of the equivalent amount of the alloy raw material, there is an advantage in that the redox potential of the purified liquid is appropriately controlled. If the equivalent amount of the alloy raw material is added in an amount of 1.0 equivalents or less, there is a problem in that the redox potential of the purified liquid becomes very high, and the copper concentration in the purified liquid becomes very high.

[0041] In one embodiment, a pH adjuster may be further added to adjust the pH of the leachate. The pH adjuster may be added as a non-limiting example, such as various types of adjusters including sulfuric acid, sodium hydroxide, citric acid, sodium bicarbonate, or phosphoric acid.

[0042] In one embodiment, the step of precipitating copper (Cu) as a solid phase in the leaching step may precipitate the solid phase in the form of metallic copper (Metallic Cu). The metallic copper is in the form of a powder with hydroxyl groups (OH). - It may not include ).

[0043] In the above leaching step, nickel, cobalt, or manganese on the surface of the alloy raw material reacts with metallic nickel, cobalt, or manganese, and through elemental substitution, a solid phase of metallic copper can be formed on the surface of the alloy raw material.

[0044] In one embodiment, the hydrogen ion concentration of the purified liquid from which the residue of metallic copper has been removed in the leaching step may be 0.00005 M to 4 M. Specifically, the hydrogen ion concentration may be 0.001 M to 2 M. By satisfying the aforementioned range of hydrogen ion concentration in the leaching step, a purified solution containing valuable metals such as nickel can be easily obtained, and metallic copper can be easily formed and easily separated.

[0045] In one embodiment, the metallic copper may have a combined amount of nickel, cobalt, and manganese of 30% by weight or less based on 100% by weight of the metallic copper. Specifically, the combined amount may be 15% by weight or less, and more specifically, 9% by weight or less. By including the content of valuable metals within the aforementioned range, the purity of copper can be increased, and since the valuable metals do not dissolve together with copper, the concentration of valuable metals in the purified liquid can be increased.

[0046] In one embodiment, the step of precipitating copper (Cu) in a solid state may be performed at a temperature of 20 to 120 ℃. Specifically, the temperature may be 30 to 90 ℃. By satisfying the aforementioned range, the copper can easily react with the surface of the alloy raw material to form the metallic copper.

[0047] The step of separating the purified filtrate and the precipitated residue from the solution that has undergone the above-mentioned precipitation step may be a solid-liquid separation step. The above-mentioned solid-liquid separation step may be a step of separating the purified filtrate and the solid phase, which is the precipitate, separately using a component such as a filter. The above-mentioned purified filtrate may refer to a filtrate containing valuable metals and in which copper has been purified, and the above-mentioned precipitated residue may refer to the aforementioned solid phase metallic copper.

[0048] In one embodiment, the step of separating the purified liquid and the precipitated residue may utilize a filter press. The filter press may be a component that separates a solid phase and a liquid phase using pressure filtration. Specifically, by applying a predetermined pressure and filtering the purified liquid during the separation step, the solid phase, which is the residue, can be removed more easily.

[0049] In one embodiment, the average particle size (D50) of the metallic copper residue, which is the residue after the step of separating the purified liquid and the precipitated residue, may be 1 to 500 μm. The average particle size (D50) of the solid phase is controlled by the average particle size of the alloy raw material introduced, and must satisfy the aforementioned range to facilitate the precipitation of copper.

[0050] In one embodiment, the oxidation-reduction potential (ORP) of the purified liquid may be controlled to 300 mV or less. Specifically, the oxidation-reduction potential may be controlled to -200 to 200 mV or less, more specifically, -200 to 100 mV, and even more specifically, 0 to 100 mV or less.

[0051] By satisfying the aforementioned range of redox potential, copper ions can be easily precipitated as metallic copper during the leaching process, thereby minimizing the copper concentration in the purified filtrate.

[0052] In one embodiment, the copper (Cu) concentration of the purified liquid may be 80 mg / L or less. Specifically, the copper concentration of the purified liquid may be 500 ppm or less. By satisfying the aforementioned range of copper concentration of the purified liquid, valuable metals from the leaching solution can be easily concentrated into the purified liquid, and copper, which is an impurity, can be easily removed as a residue.

[0053] In the step of selectively leaching valuable metals by introducing the copper byproduct raw material and the oxidizing agent into an acidic solution, the acidic solution may be a solution introduced to leach the leaching liquid containing the valuable metals into the solution phase. The acidic solution may include, for example, at least one of an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, or hydrofluoric acid, or an organic acid such as phosphoric acid or acetic acid. Specifically, the acidic solution may be a sulfuric acid or nitric acid solution, and more specifically, the acidic solution may be a sulfuric acid solution.

[0054] In one embodiment, the hydrogen ion concentration of the acidic solution can be controlled to 0.001 M to 2 M. Specifically, the hydrogen ion concentration can be controlled to 0.05 to 1 M. By satisfying the aforementioned range, valuable metals such as nickel, cobalt, and manganese can be selectively removed from the copper mixed residue contained in the alloy containing the valuable metals, thereby obtaining a high-purity copper residue.

[0055] If the hydrogen ion concentration exceeds the upper limit of the aforementioned range, there is a problem in that the recovery rate decreases due to the ionization of copper, which is the recovered material, at that hydrogen ion concentration. If the hydrogen ion concentration exceeds the lower limit of the aforementioned range, there is a problem in that the ionization of nickel, cobalt, and manganese from the alloy containing valuable metals is inhibited, thereby lowering the quality of the copper mixed residue.

[0056] In one embodiment, the oxidizing agent may include oxygen atoms. Specifically, the oxidizing agent may be a substance that oxidizes valuable metals. For example, the oxidizing agent may be at least one of Air, O2, O3, H2O2, Na2S2O5, KMnO4, HNO3, and Na2S2O8.

[0057] In one embodiment, the amount of the oxidizing agent added may be 1.1 to 2.8 equivalents with respect to the content of valuable metal contained in the copper byproduct. Specifically, the content may be 1.1 to 2 equivalents. By including the content within the aforementioned range, the valuable metal in the copper byproduct is oxidized and removed, and the copper residue can be recovered with high purity.

[0058] In one embodiment, the oxidation-reduction potential (ORP) of the leaching filtrate can be controlled to 300 mV or less. Specifically, the oxidation-reduction potential may be -200 to 300 mV, specifically 0 to 250 mV.

[0059] Specifically, when an oxidizing agent is added in the aforementioned amount, the redox potential of the leaching filtrate can be controlled within the aforementioned range. As the redox potential is controlled within the aforementioned range, copper can be easily removed from the leaching filtrate. If the redox potential is excessively large, there is a problem in that the amount of oxidizing agent added is excessive, causing solid copper to dissolve into the liquid and resulting in loss. If the redox potential is excessively small, there is a problem in that the amount of oxidizing agent added is insufficient, causing nickel or cobalt ions not to dissolve in the purification filtrate, thereby reducing the recovery rate.

[0060] In one embodiment, in the step of selectively leaching the valuable metal, the hydrogen ion concentration of the leaching filtrate may be 0.0001 M to 5 M. Specifically, the hydrogen ion concentration may be 0.001 M to 2 M. By controlling the hydrogen ion concentration of the leaching filtrate to the aforementioned range, a leaching filtrate containing a highly concentrated valuable metal such as nickel can be obtained, and metal by-products can be easily separated.

[0061] The step of separating the leaching filtrate in which valuable metals are dissolved from the copper byproduct raw material and the copper byproduct from which the valuable metals have been removed may be a step of solid-liquid separation between the leaching filtrate and the high-purity copper byproduct. For example, the solid-liquid separation step may separate the solid phase and the liquid phase using a component such as a filter press. Through this, the leaching filtrate containing valuable metals and the copper byproduct can be separated respectively.

[0062] <Experimental Example>

[0063] (Example 1)

[0064] (Byproduct preparation step) 100 g of byproduct was prepared by using an NCM alloy manufactured by performing a high-temperature reduction heat treatment process on black mass to precipitate copper (Cu) in a metallic phase. The byproduct was prepared as a byproduct raw material containing Cu in a metallic phase and containing Ni, Co, and Mn. The byproduct raw material had a Cu content of 62%, and contained 2.5%, 0.7%, and 0.3% of Ni, Co, and Mn, respectively.

[0065]

[0066] (Selective leaching step)

[0067] A sulfuric acid solution and Na2S2O8 were prepared as an oxidizing agent to selectively leach Ni, Co, and Mn. The concentration of the sulfuric acid for the leaching was set to 1 M. The sulfuric acid solution, a byproduct containing NCM alloy and Cu, and the oxidizing agent were mixed and stirred for 2 hours at a temperature of 60 ℃ to obtain a leaching filtrate containing Cu residue and valuable metals from which Ni, CO, and Mn were selectively removed.

[0068] The above oxidizing agent was mixed in an amount of 1.1 equivalents relative to the Ni, CO, and Mn content for the NCM Alloy and the byproduct containing Cu and reacted.

[0069]

[0070] (Example 2)

[0071] In the above selective leaching step, the Cu byproduct in which Ni, Co, and Mn were selectively leached out was recovered using the same process as in Example 1, except that the oxidizing agent introduced was changed to H2O2.

[0072]

[0073] (Example 3)

[0074] In the above selective leaching step, the Cu byproduct in which Ni, Co, and Mn were selectively leached out was recovered using the same process as Example 1, except that the amount of oxidizing agent added was 2 equivalents relative to the Ni, Co, and Mn content contained in the Cu-containing byproduct.

[0075]

[0076] (Comparative Example 1)

[0077] In the above selective leaching step, the Cu byproduct in which Ni, Co, and Mn were selectively leached out was recovered using the same process as in Example 1, except that the amount of oxidizing agent added was 0.5 equivalents relative to the Ni, Co, and Mn content contained in the Cu-containing byproduct.

[0078]

[0079] (Comparative Example 2)

[0080] In the above selective leaching step, the Cu byproduct in which Ni, Co, and Mn were selectively leached out was recovered using the same process as Example 1, except that the amount of oxidizing agent added was 5 equivalents relative to the Ni, Co, and Mn content contained in the Cu-containing byproduct.

[0081]

[0082] (Comparative Example 3)

[0083] In the above selective leaching step, the Cu byproduct in which Ni, Co, and Mn were selectively leached out was recovered using the same process as in Example 1, except that the hydrogen ion concentration of the leaching filtrate after selective leaching was 0.00004 M.

[0084]

[0085] Redox potential (mV): Measured using the potentiometric method. A standard hydrogen electrode was used as the reference electrode, and a platinum electrode, acting as the working electrode, was inserted into the purified filtrate to measure the potential difference between the electrodes.

[0086] Cu concentration (mg / L): Measured using inductively coupled plasma mass spectrometry (ICP-MS).

[0087] Ni content (%) in Cu residue after leaching: Measured using inductively coupled plasma mass spectrometry (ICP-MS).

[0088] Classification Process Conditions Result Oxidizing Agent Type Oxidizing Agent Input Amount Hydrogen Ion Concentration of Leaching Filter (M) ORP (mV) Cu Concentration of Leaching Filter (mg / L) Ni Content in Cu Residue After Leaching (%) Example 1 Na2S2O 8 1.1 equivalents 1.084 ND < 1% Example 2 H2O 2 1.1 equivalents 1.037 ND < 1% Example 3 Na2S2O 8 2 equivalents 1.0245 ND < 1% Comparative Example 1 Na2S2O 8 0.5 equivalents 1.0-173 N.D 1.7% Comparative Example 2 Na2S2O 8 3 equivalents 1.0835792 < 1% Comparative Example 3 Na2S2O 8 1.1 equivalents 0.000047834682.2%

[0089] Referring to Table 1 above, in the examples where the amount of oxidizing agent added is 1.1 equivalents or more and less than 3 equivalents, and the hydrogen ion concentration of the purified filtrate satisfies the scope of the present invention, it can be confirmed that the ORP of the leaching filtrate is 300 mV or less, and the copper (Cu) concentration of the leaching filtrate is trace at an unmeasurable level (ND). In addition, in the examples, it can be confirmed that the Ni content in the Cu residue after leaching is small, at less than 1%. In contrast, in Comparative Example 1 and Comparative Example 2, when the equivalent amount of the oxidizing agent added is excessively high or low, it can be confirmed that the redox potential, the Cu concentration in the leaching filtrate, or the Ni content in the Cu residue after leaching does not satisfy the scope of the present invention.

[0090] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the invention can be implemented in other specific forms without changing the technical concept or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A method for recovering copper (Cu) by-products from solid copper by-product raw materials obtained by adding an alloy raw material containing a valuable metal to a leachate obtained by adding a raw material obtained from waste batteries to an acidic solution to leach the material, Step of preparing the above copper byproduct raw material; A step of selectively leaching valuable metals by introducing the copper byproduct raw material and oxidizing agent into an acidic solution; and A step of separating the leaching filtrate in which valuable metals are dissolved from the copper byproduct raw material and the copper byproduct from which the valuable metals have been removed; Includes, The amount of the oxidizing agent added is 1.1 to 2.8 equivalents with respect to the content of valuable metals contained in the copper byproduct, and A method for recovering valuable metals in which, in the step of selectively leaching the valuable metals, the hydrogen ion concentration of the leaching filtrate is 0.0001 M to 5 M.

2. In Paragraph 1, The above oxidizing agent contains oxygen atoms, and A method for recovering valuable metals, which is a substance that oxidizes the above valuable metals.

3. In Paragraph 2, A method for recovering valuable metals, wherein the oxidizing agent comprises at least one of Air, O2, O3, H2O2, Na2S2O5, KMnO4, HNO3, and Na2S2O8.

4. In Paragraph 1, The above copper byproduct is, A step of leaching raw material obtained from waste batteries by introducing it into an acidic solution; A step of introducing an alloy raw material containing at least one of nickel, cobalt, and manganese into a leaching solution to precipitate copper (Cu) in a solid state; and A step of separating the purified filtrate and the precipitated residue from the solution that has undergone the above-mentioned precipitation step; Method for recovering valuable metal residue obtained through the process.

5. In Paragraph 4, A method for recovering valuable metals, wherein the alloy raw material is an alloy containing the valuable metal.

6. In Paragraph 4, A method for recovering valuable metals in which the average particle size (D50) of the above alloy raw material is 500 μm or less.

7. In Paragraph 4, The above alloy raw material is a method for recovering valuable metals obtained by high-temperature reduction heat treatment of raw material obtained from the above waste battery.

8. In Paragraph 1, A method for recovering valuable metals in which the oxidation-reduction potential (ORP) of the above-mentioned purified liquid is controlled to 300 mV or less.

9. In Paragraph 4, The step of precipitating copper (Cu) in a solid state during the above-mentioned leaching step is, A method for recovering valuable metals by precipitating the above-mentioned solid phase in the form of metallic copper (Metallic Cu).

10. In Paragraph 7, A method for recovering valuable metals in which the above-mentioned metal copper is in powder form.

11. In Paragraph 7, The above metal copper is a method for recovering valuable metals that do not contain hydroxyl groups.

12. In Paragraph 1, A method for recovering valuable metals, wherein the step of selectively leaching valuable metals by introducing the copper byproduct raw material and oxidizing agent into an acidic solution is performed at a temperature of 20 to 120 ℃.

13. In Paragraph 1, A method for recovering valuable metals in which the step of selectively leaching valuable metals by adding the copper byproduct raw material and oxidizing agent to an acidic solution is performed by stirring for 1 to 5 hours.

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