ALLOY TREATMENT METHOD

Abstract

An alloy treatment method is provided, in which a solution containing nickel and/or cobalt is obtained from an alloy containing nickel and/or cobalt and also containing copper and zinc, the method comprising: a leaching step for subjecting the alloy to a leaching treatment with an acid under the condition where a sulfating agent is present to produce a leachate; a reduction step for subjecting the leachate to a reduction treatment using a reducing agent to produce a reduced solution; an oxidation/neutralization step for adding an oxidizing agent and a neutralizing agent to the reduced solution to produce a neutralized solution containing nickel and/or cobalt and also containing zinc; and a solvent extraction step for subjecting the neutralized solution to a solvent extraction procedure using an acidic phosphorus compound-based extractant to produce a solution containing nickel and/or cobalt.

Claims

1. A method for treating an alloy, for obtaining a solution comprising nickel and/or cobalt from an alloy comprising nickel and/or cobalt, copper, and zinc, the method comprising: a leaching step of obtaining a leachate by subjecting the alloy to leaching treatment with acid in a coexistence of a sulfating agent; a reduction step of subjecting the leachate to reduction treatment using a reducing agent; and a solvent extraction step of obtaining a solution comprising nickel and/or cobalt by subjecting the solution obtained in the reduction step to solvent extraction with an acidic phosphorus compound-based extractant to extract zinc, wherein in the leaching step, the sulfating agent is added first to the alloy and the acid is then added.

2. The method for treating an alloy according to claim 1, comprising an oxidation neutralization step of obtaining a solution comprising nickel and/or cobalt, and zinc by adding an oxidizing agent and adding a neutralizing agent to the solution obtained in the reduction step, and subjecting the obtained solution to the solvent extraction step.

3. The method for treating an alloy according to claim 1, wherein the solvent extraction step comprises adding acid to the acidic phosphorus compound-based extractant after solvent extraction to carry out back extraction, and obtaining a post-back-extraction extractant and a post-extraction solution comprising zinc.

4. The method for treating an alloy according to claim 3, wherein the acidic phosphorus compound-based extractant after back extraction is repeatedly used as the acidic phosphorus compound-based extractant in the solvent extraction step.

5. The method for treating an alloy according to claim 1, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

6. The method for treating an alloy according to claim 2, wherein the solvent extraction step comprises adding acid to the acidic phosphorus compound-based extractant after solvent extraction to carry out back extraction, and obtaining a post-back-extraction extractant and a post-extraction solution comprising zinc.

7. The method for treating an alloy according to claim 6, wherein the acidic phosphorus compound-based extractant after back extraction is repeatedly used as the acidic phosphorus compound-based extractant in the solvent extraction step.

8. The method for treating an alloy according to claim 2, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

9. The method for treating an alloy according to claim 3, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

10. The method for treating an alloy according to claim 4, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

11. The method for treating an alloy according to claim 6, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

12. The method for treating an alloy according to claim 7, wherein the alloy is an alloy obtained by melting a waste battery of a lithium ion battery.

Description

PREFERRED MODE FOR CARRYING OUT THE INVENTION

[0043] Hereinafter, a specific embodiment of the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be executed with appropriate modifications within the scope of the object of the present invention. Note here that in this specification, the term “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less”.

[0044] The method for treating an alloy of the present embodiment is a method for obtaining a solution including nickel and/or cobalt from an alloy including nickel and/or cobalt, copper, and zinc.

[0045] Examples of the alloy including nickel and/or cobalt, copper, and zinc as a subject to be treated include an alloy obtained by heating and melting, and reducing wastes from raw materials including wastes from deteriorated automobiles or electronic devices, scrap of a lithium ion battery generated with the lifetime of a lithium ion battery, or waste batteries, and the like, of defective products in battery manufacturing processes.

[0046] In the following, a method for treating an alloy is described taking an alloy obtained by melting a waste battery of a lithium ion battery.

[0047] Specifically, a method for treating an alloy includes: a leaching step S1 of subjecting an alloy to leaching treatment with acid in a coexistence of a sulfating agent to obtain a leachate; a reduction step S2 of subjecting a leachate to a reduction treatment using a reducing agent; an oxidation neutralization step S3 of adding an oxidizing agent and adding a neutralizing agent to the solution (reduced solution) obtained in the reduction step to obtain a solution including nickel and/or cobalt; and a solvent extraction step S4 of subjecting the obtained solution (neutralized solution) to a solvent extraction with an acidic phosphorus compound-based extractant to extract zinc to obtain a solution including nickel and/or cobalt.

[0048] [Leaching Step]

[0049] In the leaching step S1, the alloy is subjected to leaching treatment with acid in a coexistence of a sulfating agent to obtain a leachate. The alloy obtained by melting a waste battery of a lithium ion battery contains various impurities that are not subjects to be recovered in addition to copper, nickel, and cobalt. In the present embodiment, by subjecting such an alloy to a leaching treatment in a state in which the acid and the sulfide agent coexist, the copper leached out of the alloy is precipitated as copper sulfide and separated. On the other hand, by subjecting the alloy to leaching treatment with acid, a leachate is obtained by leaching nickel and/or cobalt. Note here that in this leachate, copper that has not been reacted with the sulfating agent, and impurities such as iron, phosphorus, and/or zinc may remain.

[0050] An alloy obtained by melting a waste battery of a lithium-ion battery to be treated is not particularly limited in shape, and examples thereof include an alloy obtained by casting the obtained alloy into a plate shape, an alloy drawn linearly and appropriately cut into a rod, a powdery material such as alloy powder obtained by applying an atomization method (hereinafter, this alloy powder is also referred to as “atomized powder” for convenience). However, when the subject to be treated is a powdery material such as atomized powder, leaching treatment can be efficiently carried out. Note here that the atomizing method is a method in which high-pressure gas or water is brought into contact with the molten metal to scatter and quench (solidify) the molten metal to obtain powder.

[0051] When the alloy is made into a powder substance, when the particle diameter of the alloy is about 300 μm or less, the leaching treatment can be carried out more effectively. On the other hand, since too fine particles make the cost high, and may cause dust generation or ignition, the particle diameter of the alloy is preferably about 10 μm or more.

[0052] In the leaching treatment, the alloy to be treated is preferably pre-washed with a dilute acid in advance. Thus, the surface of the alloy can be subjected to active treatment, and the leaching reaction can be promoted.

[0053] As the acid, hydrochloric acid, sulfuric acid, nitric acid, or the like, can be used alone or in combination. Furthermore, chloride may be contained in sulfuric acid and used as an acid. In order to achieve a so-called “battery-to-battery” which is an ideal circulation method for recycling waste LIB and reusing it as a LIB raw material, it is preferable to use an acid including sulfuric acid. When sulfuric acid is used as the acid, the leachate can be obtained in the form of sulfate, which is easily used as the positive electrode material of the lithium ion battery.

[0054] The amount of acid used is 1 equivalent or more, preferably, 1.2 equivalents or more, more preferably 1.2 equivalents or more and 11 equivalents or less, relative to the total amount of nickel and/or cobalt included in the alloy. Thus, the reaction rate can be increased by increasing the acid concentration.

[0055] The acid and the alloy may be supplied to a device in which a plurality of stages of mixing portions, such as thickeners, are connected, and the acid and the alloy may be brought into contact with each other in a stepwise manner in a countercurrent. For example, an alloy may be supplied to the mixing portion at the top of the device, an acid may be supplied to the mixing portion at the bottom of the device, and the acid and the alloy may be brought into contact with each other in a stepwise manner in a countercurrent.

[0056] Sodium hydrosulfide or elemental sulfur can be used as the sulfating agent to be added together with the acid. When the elemental sulfur is used, it is preferable that the elemental sulfur is appropriately pulverized so as to facilitate the reaction.

[0057] The amount of the sulfating agent is preferably 1 equivalent or more with respect to the amount of copper included in the alloy.

[0058] The acid and the sulfating agent may be added to the alloy at the same time, but it is preferable that the sulfating agent is added first and the acid is then added. When the acid and the sulfating agent are added to the alloy at the same time, the reaction may proceed rapidly and bumping may occur. By adding the sulfating agent first, and then bringing the acid into contact therewith, a rapid reaction can be suppressed. When the sulfating agent is added first, and then the acid is then added, for example, an alloy and the sulfating agent are charged into a solvent such as water, and then the acid is added. Furthermore, in order to proceed a homogeneous reaction, the leachate may be bubbled with air or the like.

[0059] It is preferable to carry out a preliminary test in advance to determine an appropriate range for temperature, time, and the concentration of slurry obtained by adding an acid and a sulfating agent to the alloy, in the leaching step S1.

[0060] In particular, in the leaching step S1, it is preferable to monitor and control the range of the oxidation-reduction potential (ORP) and pH while the oxidation-reduction potential (ORP) and pH of the leachate are measured. Specifically, the oxidation-reduction potential (ORP) is preferably controlled to 240 mV or more and 280 mV or less on the basis of the silver/silver chloride electrode, and the pH is preferably controlled to 0.8 or more and 1.6 or less. Within such a range, leaching is promoted and re-dissolution due to excessive oxidation of the precipitated copper sulfide can be suppressed.

[0061] The end point of the leaching reaction can be determined by measuring the oxidation-reduction potential (ORP) of the leachate, and determining the end portion of leaching of nickel and/or cobalt.

[0062] Note here that in the leaching treatment, a divalent copper ion may be added. Thus, the divalent copper ion acts as a catalyst, and the leaching reaction can be promoted.

[0063] [Reduction Step]

[0064] In the reduction step S2, the leachate obtained in the leaching step S1 is subjected to reduction treatment using a reducing agent to obtain a reduced solution including nickel and/or cobalt. Herein, in the treatment in the leaching step S1 described above, copper constituting the alloy, together with nickel and/or cobalt, is leached by acid and dissolved in the solution, and a part of the copper remains in the solution without reacting with the sulfating agent. Then, in the reduction step S2, a small amount of copper remaining in the leachate is reduced to produce a precipitate including copper, and the produced precipitate is separated by solid-liquid separation to obtain a reduced solution including nickel and/or cobalt.

[0065] As the reducing agent, for example, a less noble metal than copper can be used. Among them, preferably, metal including nickel and/or cobalt is used, and copper is reduced by bringing the leachate into contact with the metal. The treatment method of the alloy treatment method according to the present embodiment obtains a solution including nickel and/or cobalt, and is industrially advantageous because by using a metal including nickel and/or cobalt to be recovered as a reducing agent, there is no need to recover the reducing agent separately in a subsequent step.

[0066] Note here that as the reducing agent, in addition to the metal mentioned above, sulfide can be used. Sulfide may be solid, liquid or gas (gaseous form). Sulfide may also be a mixture of the powdery substance of the alloy to be treated in the leaching step S1 described above and sulfur. In addition, it is preferable to use atomized powder obtained by quenching and pulverizing the molten metal of the alloy into powder.

[0067] The method for reducing the leachate is not particularly limited, and when a solid or liquid reducing agent is used, the reducing agent may be directly added to the leachate, and when the reducing agent is gas (gaseous form), the reducing agent may be added by bubbling to the leachate.

[0068] It is preferable that the addition amount of the reducing agent and the reaction temperature be tested in advance to select the optimum range. Furthermore, the reduction treatment is preferably controlled by monitoring the oxidation-reduction potential (ORP) and pH and adding a reducing agent or the like as appropriate to control them, and it is preferable to select the optimum range by carrying out a test in advance.

[0069] [Oxidation Neutralization Step]

[0070] In the oxidation neutralization step S3, oxidation neutralization treatment is carried out by adding an oxidizing agent and adding the neutralizing agent to the reduced solution obtained in the reduction step S2 to obtain a solution (neutralized solution) including nickel and/or cobalt, and zinc. Specifically, in the oxidation-neutralization step S3, an oxidizing agent is added to the reduced solution to cause an oxidation reaction, and when a neutralizing agent is added to control the pH of the solution to a predetermined range, at least a precipitate of iron and/or phosphorus included in the reduced solution is produced. Although it is not essential to provide the oxidation neutralization step S3 in the present invention, at least iron and/or phosphorus can be separated as a precipitate through the oxidation neutralization step S3 to obtain a purified solution (neutralized solution) including nickel and/or cobalt and zinc.

[0071] As the oxidizing agent, conventionally known oxidizing agents such as hydrogen peroxide and hypochlorous acid can be used.

[0072] Addition of the oxidizing agent is preferably controlled within a predetermined range by monitoring the oxidation-reduction potential (ORP) of the solution. Specifically, an oxidizing agent is added to the solution to control the ORP (using silver/silver chloride as a reference electrode) in a range of, for example, 380 mV to 430 mV.

[0073] Furthermore, an oxidizing agent is added so as to cause an oxidation reaction, and a neutralizing agent is added so as to control the pH of the solution, preferably, in a range of 3.8 or more and 4.5 or less. When neutralization treatment is carried out by controlling the pH in such a range, impurities such as at least iron and/or phosphorus can be effectively precipitated.

[0074] The neutralizing agent is not particularly limited, but conventionally known alkalis such as sodium hydroxide and potassium hydroxide can be used.

[0075] Herein, in the oxidation neutralization treatment, the oxidizing agent may be added to the reduced solution after addition of the neutralizing agent, but it is preferable that the oxidizing agent and the neutralizing agent are added to the reduced solution at the same time or the neutralizing agent is added after addition of the oxidizing agent, and it is more preferable that the neutralizing agent is added to the reduced solution after addition of the oxidizing agent. For example, when an oxidizing agent is added to the reduced solution having a high pH by the addition of the neutralizing agent, in a case where iron is included in impurities, the iron is not sufficiently oxidized, Fe(OH).sub.3 precipitate (iron sediment) is not sufficiently generated, and separation of the impurities may become insufficient.

[0076] [Solvent Extraction Step]

[0077] In a solvent extraction step S4, zinc is extracted by subjecting the obtained solution to solvent extraction with an acidic phosphorus compound-based extractant to obtain a solution including nickel and/or cobalt. Specifically, the obtained neutralized solution and an organic solvent including an acidic phosphorus compound-based extractant are mixed with each other, and zinc is extracted in an organic solvent to obtain an organic solvent containing zinc and a solution including nickel and/or cobalt. By carrying out solvent extraction treatment using an acidic phosphorus compound-based extractant, zinc is extracted more efficiently and effectively to separate nickel and/or cobalt.

[0078] As the acidic phosphorus compound-based extractant, di-(ethylhexyl phosphate) (D2EHPA), 2-ethylhexyl (2-ethylhexyl) phosphonate, and the like, can be used.

[0079] At the time of extraction, the acidic phosphorus compound-based extractant is preferably diluted with, for example, a hydrocarbon-based organic solvent before used. The concentration of the acidic phosphorus compound-based extractant in an organic solvent is not particularly limited, but it is preferably 1 vol. % or more and 30 vol. % or less, and particularly preferably 10 vol. % or more and 25 vol. % or less when the phase separation property and the like is taken into consideration.

[0080] Furthermore, when the solvent extraction is carried out, prior to the extraction treatment, pH of the neutralized solution to be treated is preferably adjusted to a range of 1.0 or more and 5.0 or less, more preferably 2.0 or more and 4.5 or less, and further preferably 2.5 or more and 4.5 or less.

[0081] Furthermore, by adding acid to the extractant after solvent extraction to carry out back extraction, a post-back-extraction-extractant and a post-back-extraction solution including zinc may be obtained. Specifically, acid is added and mixed to cause reaction opposite to the solvent extraction treatment to back-extract impurities, and a post-back-extraction solution including zinc is obtained.

[0082] As the acid to be added, sulfuric acid with about 1 N, and the like can be used. Furthermore, the acidic phosphorus compound-based extractant after back extraction can be used repeatedly as the acidic phosphorus compound-based extractant in the solvent extraction step.

EXAMPLES

[0083] The present invention will be described in further detail below with reference to Examples, but the present invention is not limited to the Examples below at all.

EXAMPLE

[0084] [Leaching Step]

[0085] A waste lithium ion battery (waste LIB) was subjected to pyrometallurgical treatment of carrying out reduction by heating and melting, and an alloy obtained by reducing and melting was poured into a small crucible having a hole in the bottom surface, and the molten metal flowing out of the hole was sprayed with high-pressure gas or water, and the molten metal was scattered and solidified to obtain a powdery material (atomized powder) having a particle diameter of 300 μm or less. The resultant powdery material was used as an alloy to be treated.

[0086] The powdery material was leached with sulfuric acid and sulfur at a slurry concentration of 200 g/L. The temperature was 70° C. and the leaching time was 6 hours. After leaching, solid-liquid separation was carried out by filtration, and the filtrate (leachate) was obtained.

[0087] [Reduction Step]

[0088] Next, a nickel powder (reducing agent) having a particle diameter of 1 μm to 300 μm was added to the resulting leachate, and the leachate was subjected to reduction treatment using a reducing agent, filtered, and solid-liquid separated to obtain a filtrate (reduced solution).

[0089] [Oxidation Neutralization Step]

[0090] Next, while the obtained reduced solution was maintained at liquid temperature of 60° C. to 70° C., a hydrogen peroxide solution (oxidizing agent) having a concentration of 30% was added. After the hydrogen peroxide solution (oxidizing agent) was added, a sodium hydroxide solution (neutralizing agent) was added. Thus, the reduced solution was subjected to an oxidation neutralization reaction. After the reaction, solid-liquid separation by filtration was carried out to obtain filtrate (neutralized solution). This filtrate (neutralized solution) was analyzed by an ICP analyzer. Analysis value (g/L) of each element component is shown in Table 1.

TABLE-US-00001 TABLE 1 Ni Co Mn Zn (g/L) (g/L) (g/L) (g/L) Neutralized 80.4 41.8 1.06 0.16 solution

[0091] [Solvent Extraction Step]

[0092] To a 200 ml beaker, 50 ml of a neutralized solution (pre-extraction stock solution) obtained in the oxidation neutralization step and 100 ml of a solution obtained by diluting an acidic phosphorus compound-based extractant (2-diethylhexyl phosphate (D2EHPA)) to 20 vol. % with Teclean N20 were transferred, and subjected to solvent extraction treatment by stirring for 10 minutes while pH was adjusted with NaOH. Thereafter, a water phase (raffinate) and an extracted organic phase are separated from each other, and the raffinate and the extracted organic phase were respectively analyzed by an ICP emission spectroscopic analyzer (Agilent 5100 SVDV). The analyzed value (g/L) and pH in the water phase (raffinate) of each element component are shown in Table 2, and extraction rate (%) of each element component in the extracted organic phase is shown in Table 3.

TABLE-US-00002 TABLE 2 Ni Co Mn Zn pH (g/L) (g/L) (g/L) (g/L) Example1 2.01 82.2 42.5 0.82 0.015 Example2 3.02 81.9 42.0 0.51 <0.001 Example3 4.10 77.2 37.3 0.46 <0.001

TABLE-US-00003 TABLE 3 Ni Co Mn Zn Extractant pH (%) (%) (%) (%) Example1 D2EHPA 2.01 0.0 0.0 22.8 90.6 Example2 3.02 0.0 0.0 52.3 99.3 Example3 4.10 4.0 10.7 56.8 99.4

[0093] As is apparent from Tables 2 and 3, it is shown that when the neutralized solution is subjected to solvent extraction with an acidic phosphorus compound-based extractant, zinc is extracted from a solution (neutralized solution) including nickel and/or cobalt, and zinc, and the nickel and/or cobalt can be obtained.

[0094] In particular, Examples 2 and 3 in which pH was controlled to 3 or more, and solvent extraction treatment was carried out, the concentration of zinc (Zn) in the water phase (raffinate) is lower than 0.001 g/L, showing that when solvent extraction with an acidic phosphorus compound-based extractant is carried out, a larger amount of zinc can be extracted.