JP2014162982A - Method of separating and recovering metal from metal mixed solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a separation recovery method which separates the metal group B efficiently from a metal mixed aqueous solution containing a metal group A consisting of lithium, manganese, nickel and cobalt and a metal group B comprising copper, aluminum and iron and separates and recovers individually lithium, manganese, nickel and cobalt of the metal group A.SOLUTION: A separation recovery method comprises a primary extraction of separating mainly iron, aluminum and copper by using an extraction agent consisting of a mixture of a phosphonic ester type extraction agent and a carboxylic acid type extraction agent, a secondary extraction of separating mainly manganese, copper and aluminum by using an extraction agent consisting of a mixture of a phosphoric ester type extraction agent and an oxime-based extraction agent, a tertiary extraction of separating cobalt from the extraction residue of the secondary extraction by using a phosphonic ester type extraction agent and a quaternary extraction of separating nickel from the extraction residue of the tertiary extraction by using a carboxylic acid type extraction agent, carried out in this order.

Description

  The present invention relates to a method for separating and recovering metal from a mixed metal solution. In particular, the present invention relates to a method for recovering valuable metals such as lithium, manganese, nickel and cobalt from a metal mixed solution obtained by acid leaching of a waste cathode material of a lithium ion battery.

  Lithium ion batteries are rapidly expanding their applications for hybrid vehicles. Furthermore, the production volume of large batteries is expected to increase rapidly as the capacity of the unit increases. Further, with the growing demand for lithium ion batteries, establishment of a method for recovering valuable metals from lithium ion batteries is required.

  Lithium ion batteries mainly consist of a positive electrode, a negative electrode, a separator, and a casing, and the positive electrode is a positive electrode active material containing manganese, cobalt, nickel, lithium, etc. on a current collector such as an aluminum foil. It has a structure bonded via.

  As a recycling method for lithium ion batteries, acid leaching is performed using raw materials after incineration, crushing and sorting used lithium ion batteries, and then each metal is extracted and separated by solvent extraction from the obtained leachate. A method has been proposed. However, when copper, iron, and aluminum are contained as impurities in the raw material, copper, iron, and aluminum are leached by acid leaching, and the quality of manganese, cobalt, nickel, and lithium, which are target collections, is reduced. Therefore, when copper, iron and aluminum are contained in the leachate obtained by acid leaching of the raw material, it is necessary to remove them.

For example, JP 2010-180439 A (Patent Document 1) describes a method of removing iron and aluminum by neutralization treatment. Specifically, it is a method for recovering nickel from a sulfuric acid aqueous solution containing nickel and cobalt and iron, aluminum, manganese and other impurity elements, and includes the following steps (1) to (5). A characteristic nickel recovery method from sulfuric acid aqueous solution is disclosed.
Process (1): Precipitation containing iron and aluminum produced by adding calcium carbonate to the acidic aqueous sulfuric acid solution while blowing a mixed gas composed of sulfurous acid gas and air or oxygen gas, and subjecting to oxidation neutralization treatment. Product (a) is removed.
Step (2): Calcium hydroxide is added to the post-oxidation neutralized solution obtained in the above step (1) and subjected to neutralization to separate and recover the mixed hydroxide containing nickel and cobalt. .
Step (3): The mixed hydroxide obtained in the step (2) is subjected to a dissolution treatment in a sulfuric acid solution having a concentration of 50% by mass or more, and a precipitate (b) containing manganese and gypsum produced. Is removed to obtain a nickel and cobalt concentrate.
Step (4): The concentrated solution obtained in the step (3) is subjected to solvent extraction using a phosphoric acid ester-based acidic extractant, and an extraction residual solution containing nickel and a back extract containing cobalt are obtained. obtain.
Step (5): A neutralizing agent is added to the extraction residual liquid obtained in the step (4) and subjected to neutralization treatment, and the produced nickel hydroxide is separated and recovered.

JP 2010-180439 A

  However, when the method of removing iron and aluminum by neutralization treatment as in the method of Japanese Patent Application Laid-Open No. 2010-180439 (Patent Document 1), the ratio of cobalt and nickel co-precipitated and lost during neutralization is high. There's a problem. In addition, aluminum hydroxide, iron hydroxide, cobalt hydroxide and nickel hydroxide produced by the neutralization treatment have poor filterability and have a very long time for solid-liquid separation. It is necessary to adjust the overall processing speed slowly.

  Therefore, the present invention efficiently separates the metal group B from the metal mixed aqueous solution containing the metal group A composed of lithium, manganese, nickel, and cobalt and the metal group B composed of copper, aluminum, and iron, and Another object of the present invention is to provide a method for separating and recovering lithium, manganese, nickel and cobalt constituting the metal group A.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, when a specific extraction agent is combined and solvent extraction is performed in two stages, it is possible to economically and efficiently separate copper, aluminum, and iron. I found it. Specifically, a primary extraction that mainly separates iron, aluminum and copper using an extractant mixed with a phosphonate extractant and a carboxylic acid extractant, a phosphate extractant and an oxime extract By using the extraction agent mixed with the extraction agent and performing the secondary extraction mainly separating manganese, copper and aluminum in this order, the metal group B can be removed with high efficiency. The purity of each metal when lithium, manganese, nickel, and cobalt constituting A are separated and recovered is also significantly improved.

The present invention completed on the basis of the above knowledge, in one aspect,
Step (1): Phosphonate extractant and carboxylic acid for aqueous metal mixture containing metal group A composed of lithium, manganese, nickel and cobalt and metal group B composed of copper, aluminum and iron Solvent extraction using a first mixed extractant containing a system extractant, and separating a metal component belonging to metal group B from the metal mixed solution,
Step (2): The extraction residue after step (1) is subjected to solvent extraction using a second mixed extract containing a phosphate ester type extractant and an oxime type extractant, and further extracted from the extraction residue. A step of separating manganese belonging to metal group B and separating manganese.
Step (3): a step of subjecting the extraction residue after step (2) to solvent extraction using a phosphonate ester extractant and separating cobalt from the extraction residue.
Step (4): a step of solvent extraction using a carboxylic acid-based extractant with respect to the extraction residue after step (3), and separating nickel from the extraction residue,
Is a method for separating and recovering a metal from a mixed metal aqueous solution.

  In one embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, step (1) is carried out at an equilibrium pH of 2.5 to 4.0.

  In another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, the step (2) is performed with the equilibrium pH of the mixed metal aqueous solution being 2.5 to 4.0.

  In still another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, the first mixed extractant contains 2-ethylhexyl 2-ethylhexylphosphonate and neodecanoic acid.

  In still another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, in the first mixed extractant, the phosphonate extractant: carboxylic acid extractant = 1: 10-4: 1 (volume ratio).

  In still another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, the second mixed extractant contains di-2-ethylhexyl phosphate and an adoxime extractant.

  In still another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, in the second mixed extractant, phosphate ester extractant: oxime extractant = 1: 1 to 1:50 ( Volume ratio).

  In yet another embodiment of the method for separating and recovering metal from the mixed metal aqueous solution according to the present invention, the leached solution obtained by acid leaching the waste material containing the positive electrode active material of the lithium ion battery. It is.

  According to the present invention, the metal group B is efficiently separated from the metal mixed aqueous solution containing the metal group A composed of lithium, manganese, nickel, and cobalt and the metal group B composed of copper, aluminum, and iron, and The lithium, manganese, nickel, and cobalt constituting the metal group A can be separated and recovered. In particular, the present invention can be applied to a recycling technique for waste materials containing a positive electrode active material of a lithium ion battery.

It is a flowchart which shows one Embodiment of the separation-and-recovery method of the metal which concerns on this invention.

In one embodiment of the method for separating and recovering metal from the mixed metal solution according to the present invention,
Step (1): Phosphonate extractant and carboxylic acid for aqueous metal mixture containing metal group A composed of lithium, manganese, nickel and cobalt and metal group B composed of copper, aluminum and iron Extracting the metal group B from the metal mixed solution by solvent extraction using the first mixed extractant containing a system extractant;
Step (2): The extraction residue after step (1) is subjected to solvent extraction using a second mixed extract containing a phosphate ester type extractant and an oxime type extractant, and further extracted from the extraction residue. A step of separating the metal group B and manganese,
Step (3): a step of subjecting the extraction residue after step (2) to solvent extraction using a phosphonate ester extractant and separating cobalt from the extraction residue.
Step (4): a step of solvent extraction using a carboxylic acid-based extractant with respect to the extraction residue after step (3), and separating nickel from the extraction residue,
In order.

(Process 1)
The mixed metal aqueous solution to be treated by the present invention contains a metal group A composed of lithium, manganese, nickel, and cobalt and a metal group B composed of copper, aluminum, and iron. Although it does not have a restriction | limiting in particular as long as the said requirement is satisfied, Typically, it is the liquid after leaching obtained by acid leaching the waste material containing the positive electrode active material of a lithium ion battery with a sulfuric acid etc. Specific examples include incinerating waste positive electrode active materials from positive electrode active material manufacturers and positive electrode active materials from battery manufacturers (in some cases, negative electrode active materials and solvents (PVDF and NMP) are kneaded). Incinerated dry materials, positive electrode materials with positive electrode active material bonded to a current collector such as aluminum foil, binder, separated positive electrode active material from the positive electrode material, and the battery itself, generally called battery cage or battery crushed powder -It is a liquid after leaching obtained by acid leaching with a sulfuric acid or the like from which the positive electrode active material has been separated by crushing or sieving.

  Thus, in an exemplary embodiment, the post leaching solution is acidic. Such post-leaching solution is typically 0.001-50 g / L lithium, 0.1-100 g / L manganese, 0.1-100 g / L nickel, 0.1-100 g / L lithium. Contains cobalt, 0.001-20 g / L copper, 0.001-20 g / L aluminum, 0.001-20 g / L iron. Such post-leaching solution is more typically 0.01-20 g / L lithium, 1-80 g / L manganese, 1-80 g / L nickel, 1-80 g / L cobalt, 0.01 Contains 10 to 10 g / L copper, 3 to 10 g / L aluminum, and 0.01 to 10 g / L iron. In the present invention, even after a leaching solution containing aluminum at a high concentration, solvent extraction can be performed with high separation efficiency without removing aluminum in advance.

  Although iron is easily extracted by solvent extraction, it needs to be contacted with an acid with a very high acid concentration (low pH) for back extraction after extraction, and an acid concentration of about 200 g / L (about pH-0.6). However, since it remains in the solvent and accumulates in the solvent, it is necessary to separately extract the extractant and remove iron, so it is not suitable for solvent extraction when high concentrations of iron are included. The neutralization process was performed. However, the present inventor can efficiently extract a metal component belonging to the metal group B from the metal mixed solution while suppressing the extraction of iron in a low pH region by using a predetermined mixed extractant. I found out. Since no neutralization treatment is involved, it is possible to avoid loss of cobalt and nickel co-precipitated during neutralization. Moreover, the problem of the delay of the process resulting from bad filterability, such as the hydroxide obtained after the neutralization process, is also solved.

  Specifically, in the step (1), the metal mixed aqueous solution described above is subjected to solvent extraction using a first mixed extractant containing a phosphonate extractant and a carboxylic acid extractant, and the metal A metal component belonging to metal group B is separated from the mixed solution. On the other hand, iron is easily extracted in a low pH region with only the phosphonic acid ester-based extractant, whereas it is difficult to extract aluminum and copper with only the carboxylic acid-based extractant. However, by using an extractant in which both are mixed, the pH region where iron is back-extracted shifts to the high pH side, and aluminum can also be extracted in a single extraction operation. Although extraction rates are not as high as iron and aluminum, copper can also be extracted. Therefore, there are obtained advantages that the amount of acid used for pH adjustment at the time of back extraction is reduced and the recovery process is shortened and the cost is reduced.

  Examples of the phosphonate extractant include, but are not limited to, 2-ethylhexyl phosphonate 2-ethylhexyl (trade name: PC-88A, Ionquest 801). Examples of the carboxylic acid-based extractant include, but are not limited to, neodecanoic acid and naphthenic acid. Among them, neodecanoic acid is preferred for the reason of iron back extraction on the high pH side. Various extraction agents other than phosphonic acid ester extraction agents and carboxylic acid extraction agents can be considered, but in the present invention, high separation efficiency can be obtained without the need for other extraction agents.

  The volume ratio of the phosphonic acid ester extractant and the carboxylic acid extractant is not particularly limited, but for reasons of aluminum and copper extraction and iron back extraction, phosphonic acid ester extractant: carboxylic acid extractant = 1: It is preferably 10 to 4: 1 (volume ratio), more preferably phosphonate extractant: carboxylic acid extractant = 1: 5 to 3: 2 (volume ratio), and phosphonate ester It is even more preferable that the extractant: carboxylic acid-based extractant = 1: 4 to 1: 1 (volume ratio).

  The extractant can typically be used after diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic, paraffinic and naphthenic solvents. In one embodiment of the present invention, it can be diluted such that the total concentration of the first extractant and the second extractant in the mixed extractant is 10-30% by volume, viscosity, phase separation, extraction speed, It is preferable to dilute so that it may become 20-25 volume% for the reason of extraction capacity | capacitance.

  The extraction procedure may follow a conventional method. For example, the metal mixed aqueous solution (aqueous phase) and the extractant (organic phase) are brought into contact, and these are typically stirred and mixed with a mixer (eg, 200 to 500 rpm for 5 to 60 minutes), and the metal group The ions of B are reacted with the extractant. Extraction is preferably performed at room temperature (eg, 15 to 25 ° C.) to 60 ° C. or less, and is preferably performed at 35 to 45 ° C. for reasons of extraction speed, phase separation, and evaporation of the organic solvent. Thereafter, the mixed organic phase and aqueous phase are separated by a difference in specific gravity with a settler. The solvent extraction may be repeated, for example, a multi-stage system in which the organic phase and the aqueous phase are in countercurrent contact. The O / A ratio (volume ratio of the oil phase to the aqueous phase) depends on the content of the metal to be extracted, but is generally set to 0.1 to 10 in consideration of the operation with the mixer settler. Is preferred.

  The equilibrium pH at the time of extraction is preferably 2.5 to 4.0, more preferably 2.8 to 3.3 for reasons of separation efficiency and generation of Al hydroxide.

  Back extraction can be performed on the extraction agent (organic phase) containing metal group B after extraction. Back extraction can be performed by using an acidic aqueous solution such as sulfuric acid or hydrochloric acid and stirring and mixing with a mixer or the like (eg, 5 to 60 minutes at 200 to 500 rpm). It is preferable to use sulfuric acid as the back extract for reasons of product quality, prevention of equipment corrosion, and chloride ion concentration in the waste water. The acid concentration of the back extract is 0.5 to 200 g / l (pH: -0.6 to 2.0) due to the back extraction of the extracted metal and the reason for reducing the amount of acid transferred to the subsequent process. It is preferable to adjust, and it is more preferable to adjust to 25-100 g / l (pH: -0.3-0.3). Back extraction can be performed at room temperature (eg, 15 to 25 ° C.) to 60 ° C. or less, and is preferably performed at 35 to 45 ° C. for reasons of back extraction speed, phase separation, and evaporation of the organic solvent. By reverse extraction, most of the metal group B can be moved to the water phase side. Thereby, the metal group B which has moved to the aqueous phase side can be further processed by neutralization or the like.

  In general, scavenging can be performed on the extractant (organic phase) after back extraction for the purpose of removing the metal remaining in the extractant (organic phase). Scavenging can be performed by using an acidic aqueous solution such as sulfuric acid and hydrochloric acid and stirring and mixing with a mixer or the like (eg, 5 to 60 minutes at 200 to 500 rpm). As the scavenging liquid, it is preferable to use sulfuric acid for the reasons of product quality, prevention of equipment corrosion, and chloride ion concentration in the waste water. The acid concentration of the scavenging liquid is 25 to 400 g / l (pH: due to the reason for removing much of the metal remaining in the extractant (organic phase) after back extraction and reducing the amount of acid transferred to the subsequent step. It is preferable to adjust to -0.9 to 0.3), and it is more preferable to adjust to 100 to 250 g / l (pH: -0.7 to -0.3). Scavenging can be carried out at room temperature (for example, 15 to 25 ° C.) to 60 ° C. or less, and is preferably carried out at 35 to 45 ° C. for the reasons of scavenging speed, phase separation, and evaporation of the organic solvent. By scavenging, most of the metal remaining in the extractant (organic phase) after back extraction of the metal group B can be moved to the aqueous phase side. Thereby, the extractant can be reused.

  The back-extracted metal group B on the water phase side can be recovered as a solid content by solid-liquid separation by filtration or the like after the neutralization treatment. Iron, aluminum, and copper can be recovered as hydroxides. As a neutralization method, for example, the pH is adjusted to 7.0 or higher with sodium hydroxide.

  The copper content in the remaining liquid can be precipitated as copper sulfide by sulfidation and recovered as a solid content by solid-liquid separation. For sulfurization, hydrogen sulfide gas can be used, and hydrogen sulfide gas can be generated from an alkali sulfide such as sodium sulfide or sodium hydrosulfide and used. It is easier to handle hydrogen sulfide gas generated from alkali sulfide than to handle hydrogen sulfide gas, which is a toxic gas, directly. A liquid temperature above room temperature is sufficient. The pH of the solution is preferably 4.5 or less, and more preferably 0.1 to 2.0. The amount of hydrogen sulfide gas generated from hydrogen sulfide gas or alkali sulfide is preferably slightly larger than the equivalent of copper in the solution. That is, it is preferable to set it as 1.05 or more of copper equivalents, and 1.05-1.5 times is preferable from a viewpoint of economical efficiency.

(Process 2)
The present invention is characterized in that the metal group B is separated by a two-stage solvent extraction operation. By carrying out the step (1), most of the metal group B is separated from the metal mixed aqueous solution, but the step (2) is further carried out on the extraction residual liquid (aqueous phase) after the step (1). Thereby, the advantage of improving the separability between the metal group B and the metal group A excluding manganese is obtained.

  Specifically, in the step (2), the extraction residual liquid (aqueous phase) after the step (1) is a solvent using a second mixed extract containing a phosphate ester extractant and an oxime extractant. The metal group B is further separated from the extraction residual liquid. At this time, manganese is also separated at the same time. By using the phosphate ester-based extractant and the oxime-based extractant in combination, the separation efficiency of the metal group B from the metal mixed aqueous solution is significantly improved. In particular, in step (2), most of copper can be extracted.

  Examples of the phosphate ester extractant include, but are not limited to, di-2-ethylhexyl phosphoric acid (trade name: D2EHPA or DP8R).

  Preferred examples of the oxime-based extractant include aldoxime and aldoximes. Specifically, but not limited to, 2-hydroxy-5-nonylacetophenone oxime (trade name: LIX84), 5-dodecyl salicylaldoxime (trade name: LIX860), a mixture of LIX84 and LIX860 (trade name: LIX984) and 5-nonylsalicylaldoxime (trade name: ACORGA M5640). Among them, 5-nonylsalicylaldoxime is preferred mainly from the viewpoint of price.

  The volume ratio of the phosphate ester extractant and the oxime extractant is not particularly limited, but the oxime extractant is originally an extractant that selectively extracts copper, and the oxime extractant promotes copper extraction. The volume of the oxime extractant is small compared to the phosphate ester extractant because it plays a role and a large proportion of the oxime extractant requires a lot of acid to back-extract copper. preferable. For example, the volume ratio of the phosphate ester extractant and the oxime extractant is preferably phosphate ester extractant: oxime extractant = 1: 1 to 50: 1, preferably 5: 1 to 15: 1. Is more preferable.

  The extractant can typically be used after diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic, paraffinic and naphthenic solvents. In one embodiment of the present invention, it can be diluted such that the total concentration of the first extractant and the second extractant in the mixed extractant is 10-30% by volume, viscosity, phase separation, extraction speed, It is preferable to dilute so that it may become 20-25 volume% for the reason of extraction capacity | capacitance.

  The extraction procedure may be in accordance with a conventional method, as in step (1). However, the equilibrium pH at the time of extraction is preferably 2.5 to 4.0, more preferably 2.8 to 3.3 for the purpose of avoiding precipitation of aluminum.

  Back extraction can be performed on the extractant (organic phase) containing metal group B and manganese after solvent extraction, as in step (1). Thereby, the metal group B and manganese moved to the aqueous phase side can be further processed by neutralization. It can also be combined with the back extract of step (1). Metal group B and manganese in the back extract are separated by neutralization. For example, the pH is adjusted to 7.0 with sodium hydroxide to produce iron, aluminum, and copper hydroxides. The liquid after solid-liquid separation contains manganese, and can be recovered by a method of producing manganese carbonate by blowing carbon dioxide into the liquid. Manganese can also be recovered as manganese sulfate by heating and concentrating the sulfuric acid acidic post-extraction solution (aqueous phase side). For the extractant (organic phase) after back extraction, scavenging can be performed in the same manner as described in the step (1).

(Process 3)
At the stage where the step (2) is finished, the metal group B is almost separated and removed from the metal mixed solution. Manganese is also largely separated. Therefore, the extraction residual liquid after the step (2) mainly contains lithium, cobalt, and nickel. After the step (3), the metals belonging to the metal group A are separated and recovered.

  In the step (3), the extraction residual liquid (aqueous phase) after the step (2) is subjected to solvent extraction using a phosphonic ester extractant, and cobalt is separated from the extraction residual liquid. The phosphonate extractant is not particularly limited, but 2-ethylhexyl phosphonate 2-ethylhexyl (trade name: PC-88A, Ionquest 801) is preferable from the viewpoint of separation efficiency of nickel and cobalt.

  The extractant can typically be used after diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic, paraffinic and naphthenic solvents. In one embodiment of the present invention, it can be diluted such that the total concentration of the first extractant and the second extractant in the mixed extractant is 10-30% by volume, viscosity, phase separation, extraction speed, It is preferable to dilute so that it may become 20-25 volume% for the reason of extraction capacity | capacitance.

  The extraction procedure may be in accordance with a conventional method, as in step (1). However, the equilibrium pH at the time of extraction is preferably 4.5 to 5.5, more preferably 4.8 to 5.2 for reasons of separation between nickel and cobalt.

  Back extraction can be performed on the extractant (organic phase) containing cobalt after solvent extraction, as in step (1). Cobalt that has moved to the aqueous phase can be recovered by electrowinning or the like.

  In order to concentrate lithium and nickel between step (3) and step (4), both are once solvent extracted from the extraction residual liquid (aqueous phase) after step (3) and then back-extracted. It is also possible to perform operations. Examples of the extractant at this time include 2-ethylhexyl 2-ethylhexylphosphonate and di-2-ethylhexylphosphoric acid. By repeating back-extraction of these organic phases from which nickel and lithium have been extracted in the same manner as in step (1), the nickel and lithium concentrations in the back-extracted solution are increased, and nickel and lithium can be concentrated. The equilibrium pH at the time of back extraction is preferably 2-4. If the pH is lower than this, it becomes a wasteful acid for back-extracting lithium and nickel, and costs increase. Moreover, when pH is higher than this, transfer to the aqueous phase of nickel and lithium will become inadequate, and the nickel and lithium density | concentration of a back extract will not fully rise. The back extract obtained by concentrating nickel and lithium can be used in step (4) to separate nickel and lithium. However, since the concentration operation causes an increase in chemical cost due to pH adjustment, it is preferable not to perform the concentration operation from the viewpoint of economy.

(Process 4)
The extraction residue after step (3) is subjected to solvent extraction using a carboxylic acid-based extractant, and nickel is separated from the extraction residue. Examples of the carboxylic acid-based extractant include, but are not limited to, neodecanoic acid and naphthenic acid, and neodecanoic acid is preferred for the reason of nickel extraction ability.

  The extraction procedure may be in accordance with a conventional method, as in step (1). However, if the equilibrium pH at the time of extraction is too high, nickel hydroxide is generated. On the other hand, if it is too low, the extraction rate of nickel decreases, so 6-8 is preferable, and 6.8-7. 2 is more preferable. During nickel extraction, hydrogen ions are released from the extractant, and the pH of the solution decreases. Therefore, it is desirable to add nickel and extract nickel while maintaining the pH. As the alkaline agent to be used, aqueous ammonia or sodium hydroxide can be used.

  Back extraction can be performed on the extractant (organic phase) containing nickel after solvent extraction, as in step (1). It is desirable from the viewpoint of cost that the nickel moved to the aqueous phase side is recovered by electrowinning. There is a method in which the carbonic acid is first recovered and then recovered, and then reduced to metallic nickel.

  For aqueous solution containing lithium (extraction residue) after separating nickel, after adding an alkali agent, it is possible to precipitate and recover lithium carbonate by blowing carbon dioxide or adding a carbonating agent. It is. Sodium hydroxide or aqueous ammonia can be used as the alkaline agent. The production of lithium carbonate efficiently proceeds by setting the pH at the time of blowing carbon dioxide or charging the carbonating agent to 8-11. Moreover, since pH falls with the production | generation of lithium carbonate at the time of carbon dioxide blowing, the recovery rate of lithium can be improved by adding an alkali suitably and hold | maintaining the pH of carbonation to 8-11.

  Examples of the present invention will be described below, but the examples are for illustrative purposes and are not intended to limit the invention.

<Example 1: Verification of effect by first mixed extractant>
Pre-extraction solutions (pH: 2.2) containing various metals simulating the post-leaching solution obtained by leaching the battery crushed powder of a lithium ion battery with sulfuric acid were prepared. The concentration of each metal is shown in Table 1.
The concentration of each metal was measured by ICP.

The following three types of extractants were prepared.
(1) 2-ethylhexyl phosphonate 2-ethylhexyl (trade name: PC-88A) 5.0% by volume, neodecanoic acid (hexion specialty chemicals trade name: VA-10) 20.0% by volume, linear Extractant (2) 2-ethylhexylphosphonate 2-ethylhexyl (trade name: PC-88A) containing 75.0% by volume of an organic solvent (trade name: Shellsol D70) whose main component is a hydrocarbon based on 25.0 Extractant containing 35.0% by volume of organic solvent (trade name: Shellsol D70) containing 3% by volume of linear hydrocarbon as a main component (3) Neodecanoic acid (Hexion Specialty Chemicals trade name: VA-10) 25.0% by volume, and an organic solvent (product name: Shellsol D70) containing 75.0% by volume of a linear hydrocarbon-based organic solvent. It was prepared.

The pre-extraction solution and each extraction agent were mixed and shaken (200 rpm) using a separatory funnel so that the O / A ratio = 3, and solvent extraction was performed. The reaction time in the extraction was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. For each extractant, the change in extraction rate when the equilibrium pH during extraction was changed was investigated.
In the extractant using PC-88A alone, the pH was changed from 1 to 6.5. Al and Fe showed almost the same extraction rate, and increased rapidly when the pH exceeded 2, reaching almost 100% at pH 3.0. Cu was extracted from pH 2.0 and was almost 100% at pH 3.5. The extraction rate of Mn increased with pH, about 50% in the vicinity of pH 3, and almost 100% from around pH 4. Co was hardly extracted up to around pH 3, but the extraction rate increased before pH 4 and reached nearly 100% from around pH 5. Ni was hardly extracted until pH 4 was exceeded, the extraction rate reached 50% near pH 5, and reached nearly 100% when pH 6 was exceeded. Li was hardly extracted up to around pH 6.
In the extractant using VA-10 alone, the pH was changed from 1.5 to 3.25. The extraction rate of Fe gradually increased from around pH 2, about 20% at pH 2.5, and hydroxide was generated at pH 2.8, and the extraction rate was unknown. On the other hand, the extraction rate of metal components other than Fe was extremely low regardless of pH.
On the other hand, when an extractant mixed with PC-88A and VA-10 was used, the pH region where Fe was extracted moved to the low pH side. Specifically, an extraction rate of about 80% could be obtained even at pH 2.5, and an extraction rate of 95% or more was obtained at pH 3. Al increased to about 40% at pH 2.5, and reached about 80% at pH 3.0. On the other hand, the pH region where Mn, Co and Ni are extracted moved to the high pH side. Specifically, Mn has an extraction rate of 20% or less even when the pH is raised to 4, Co has an extraction rate of 5% or less even if the pH is raised to 4, Ni rises to 4.5 Almost no extraction was made. Cu began to be extracted from around pH 3, and about 70% was extracted at pH 4. Li was hardly extracted up to around pH 6.
From the viewpoint of the separation efficiency of the metal group A (Li, Mn, Ni, Co) and the metal group B (Cu, Al, Fe), it can be seen that the equilibrium pH = 3 ± 0.2 is preferable.

<Example 2: Verification of effect by second mixed extractant>

The following three types of extractants were prepared.
(1) Di-2-ethylhexyl phosphoric acid (trade name: D2EHPA) is 21.0% by volume, 5-nonylsalicylaldoxime (trade name: ACORGA M5640) is 4.0% by volume, and linear hydrocarbons are mainly used. Extractant containing 25.0% by volume of organic solvent (trade name: Shellsol D70) (2) Di-2-ethylhexyl phosphate (trade name: D2EHPA) 25.0% by volume, linear hydrocarbon Is an extractant containing 75.0% by volume of an organic solvent (trade name: Shellsol D70), 25.0% by volume of 5-nonylsalicylaldoxime (trade name: ACORGA M5640), and 75 of kerosene. 0.0% by volume extractant

For the same pre-extraction solution as in Example 1, the pre-extraction solution and each extraction agent were mixed and stirred (200 rpm) using a separatory funnel so that the O / A ratio = 3, and solvent extraction was performed. The shaking time for extraction was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. For each extractant, the change in extraction rate when the equilibrium pH during extraction was changed was investigated.
For the extractant using D2EHPA alone, the pH was changed from 2.0 to 4.0. The extraction rates of Mn, Al and Cu were relatively high. Mn had an extraction rate of about 65% at pH 2 and was 95% or more at pH 4. Al had an extraction rate of about 45% at pH 2 and 95% or more at pH 4. Cu had an extraction rate of about 20% at pH 2 and 90% or more at pH 4. Fe was extracted at nearly 90% at pH 2.0, and the extraction rate was almost 100% at pH 2.5, while Ni and Li had an extraction rate of 10% or less in the range of pH 2.0 to 4.0. there were. Co was hardly extracted up to around pH 3, but the extraction rate exceeded 20% from around pH 3.5.
For the extractant using ACORGA M5640 alone, the pH was varied from 0.5 to 4.0. The extraction rate of Cu increased with pH and reached nearly 100% at pH 2.0. Fe began to be extracted from around pH 2, and increased to about 20% at pH 2.5 and to about 50% at pH 3.5. The other metal components were hardly extracted.
On the other hand, even when an extractant in which D2EHPA and ACORGA M5640 are mixed is used, the copper extraction rate exceeds 80% at pH 3.0, and it can be seen that copper can be extracted with the mixed extractant. Moreover, it is thought that Cu can be extracted at a lower pH side than D2EHPA, and mixing of Cu into the post-process due to the remaining of Cu can also be reduced.
From the viewpoint of separation efficiency from Li, Ni, and Co, it can be seen that an equilibrium pH of around 3 is preferable.

<Example 3: Verification of overall process>
(Process 1)
Solvent extraction was performed on the pre-extraction solution shown in Table 2 using the same extractant as (1) of Example 1 with an equilibrium pH of 3.0. The solvent extraction was carried out by mixing and stirring (400 rpm) the pre-extraction solution and the extractant using a countercurrent multistage mixer settler (extraction stage number: 2 stages) so that the O / A ratio = 3. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 3 shows the concentration of each metal in the extraction residual liquid (aqueous phase) after the step (1) and the extraction rate of each metal. The extraction rate was calculated by the following formula.
Extraction rate (%) = {1- (Amount of metal in extraction residual liquid) / (Amount of metal in liquid before extraction)} × 100

  From the above results, it can be seen that most of Al, Fe and Cu have moved to the oil phase side. And even after solvent extraction, it turns out that Mn, Co, Ni, and Li remain on the water phase side with almost no loss.

(Process 2)
The extraction residue after step (1) was subjected to solvent extraction using the same extractant as in Example 2 (1) with an equilibrium pH of 3.0. The solvent extraction is performed by mixing and stirring (400 rpm) using a countercurrent multistage mixer settler (extraction stage number: 3 stages) so that the extraction residual liquid after step (1) and the extractant become O / A ratio = 3. It went by. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 4 shows the concentration of each metal in the extraction residual liquid (aqueous phase) after step (2) and the extraction rate of each metal.

  From the above results, it can be seen that most of Mn and Al, Fe and Cu remaining in the step (1) have moved to the oil phase side. And even after solvent extraction, it turns out that Co, Ni, and Li remain on the water phase side with almost no loss.

(Process 3)
2-ethylhexyl phosphonate 2-ethylhexyl (trade name: PC-88A) 25.0% by volume, linear hydrocarbon-based organic solvent (trade name: Shellsol D70) 75.0% by volume An extractant was prepared. The extraction residue after step (2) was subjected to solvent extraction using this extractant with an equilibrium pH of 5.0. The solvent extraction is performed by mixing and stirring (400 rpm) using a countercurrent multi-stage mixer settler (number of extraction stages: 5 stages) so that the extraction residual liquid after step (2) and the extractant become O / A ratio = 3. It went by. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 5 shows the concentration of each metal in the extraction residual liquid (aqueous phase) after step (3) and the extraction rate of each metal.

  From the above results, it can be seen that most of Co has moved to the oil phase side. And even after solvent extraction, it turns out that Ni and Li remain on the water phase side with almost no loss.

(Process 4)
Extraction containing 25.0% by volume of neodecanoic acid (Hexion Specialty Chemicals trade name: VA-10) and 75.0% by volume of organic solvent (trade name: Shellsol D70) mainly composed of linear hydrocarbons An agent was prepared. The extraction residue after step (3) was subjected to solvent extraction using this extractant with an equilibrium pH of 7.0. The solvent extraction is performed by mixing and stirring (400 rpm) using a countercurrent multi-stage mixer settler (number of extraction stages: 2 stages) so that the extraction residual liquid after step (3) and the extractant become O / A ratio = 3. It went by. The stirring time in each extraction stage was 15 minutes. The liquid temperature during extraction was maintained at 25-30 ° C. Table 6 shows the concentration of each metal in the extraction residual liquid (aqueous phase) after the step (4) and the extraction rate of each metal.

  From the above results, it can be seen that most of Ni has shifted to the oil phase side. And even after solvent extraction, it turns out that Li remains on the water phase side with almost no loss.

Claims (8)

Step (1): Phosphonate extractant and carboxylic acid for aqueous metal mixture containing metal group A composed of lithium, manganese, nickel and cobalt and metal group B composed of copper, aluminum and iron Solvent extraction using a first mixed extractant containing a system extractant, and separating a metal component belonging to metal group B from the metal mixed solution,
Step (2): The extraction residue after step (1) is subjected to solvent extraction using a second mixed extract containing a phosphate ester type extractant and an oxime type extractant, and further extracted from the extraction residue. A step of separating manganese belonging to metal group B and separating manganese.
Step (3): a step of subjecting the extraction residue after step (2) to solvent extraction using a phosphonate ester extractant and separating cobalt from the extraction residue.
Step (4): a step of solvent extraction using a carboxylic acid-based extractant with respect to the extraction residue after step (3), and separating nickel from the extraction residue,
A method for separating and recovering a metal from a mixed metal aqueous solution, comprising sequentially performing steps.   The method for separating and recovering a metal from an aqueous metal mixture according to claim 1, wherein step (1) is carried out at an equilibrium pH of 2.5 to 4.0.   The method for separating and recovering a metal from an aqueous metal mixed solution according to claim 1, wherein step (2) is carried out by setting the equilibrium pH of the aqueous metal mixed solution to 2.5 to 4.0.   The method for separating and recovering metal from the aqueous metal mixture solution according to any one of claims 1 to 3, wherein the first mixed extractant contains 2-ethylhexyl 2-ethylhexylphosphonate and neodecanoic acid.   In the first mixed extractant, the phosphonate extractant: carboxylic acid extractant = 1: 10 to 4: 1 (volume ratio). From the metal mixed aqueous solution according to any one of claims 1 to 4. Metal separation and recovery method.   The method for separating and recovering metal from the aqueous metal mixture solution according to any one of claims 1 to 5, wherein the second mixed extractant contains di-2-ethylhexyl phosphate and an adoxime extractant.   The metal from the metal mixed aqueous solution according to any one of claims 1 to 6, wherein the second mixed extractant is phosphate ester extractant: oxime extractant = 1: 1 to 1:50 (volume ratio). Separation and recovery method.   The metal mixed solution is a liquid after leaching obtained by acid leaching of a waste material containing a positive electrode active material of a lithium ion battery. Separation and recovery of metal from the metal mixed aqueous solution according to any one of claims 1 to 7. Method.