Metal separation method

Abstract

In one embodiment, provided is a metal separation method with which it is possible to efficiently separate and / or recover a metal intended to be separated and / or recovered from an aqueous solution containing a metal. The present disclosure, in one embodiment, relates to a metal separation method for separating, or separating and recovering, a metal from an aqueous solution containing the metal, the method includes a step in which an aqueous solution containing a metal is brought into contact with a metal separation agent containing a salt (component A) represented by formula (I), thiocyanic acid (component B), and a water-insoluble organic solvent (component C) to separate the metal from an aqueous phase to an organic phase. In formula (I), R1 is a C6-22 hydrocarbon group which may have an ester group, an amide group and / or an ether group, R2 and R3 are each independently a C6-22 hydrocarbon group which may have an ester group, an amide group and / or an ether group, or a C1-4 alkyl group which may have a hydroxyl group, R4 is a C1-6 alkyl group or a hydrogen atom, and X-is an anion.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a metal separation method for separating or separating and recovering a metal from an aqueous solution containing the metal, a metal separation reagent kit, a metal recovery method, a manufacturing method of a lithium ion battery, and a metal separation reagent. BACKGROUND

[0002] Rare metals, noble metals are widely used in business, industry, and thus are important metals. On the other hand, in order to avoid emission of hazardous residues, it is necessary to develop an efficient recovery process of these metals in industrial products. Recovery of metals from electronic waste, natural resources is generally achieved by applying a process of dry metallurgy, wet metallurgy. However, the dry metallurgy method consumes a large amount of energy, and generates a contaminated gas in the process, and thus can cause great damage to the human body, the environment. The wet metallurgy method dissolves the desired metal by leaching with an alkali or an acid. After the leaching process, the resulting metal solution is further subjected to a separation process such as chemical precipitation, solvent extraction, electrolytic deposition. Among them, the solvent extraction method is widely used because of its good efficiency and universality. In the solvent extraction method, a metal capturing agent (metal separation reagent) that captures metals contained in an aqueous solution is used. As a metal capturing agent, a nitrogen-containing compound such as an amine compound is generally used.

[0003] For example, in Japanese Patent Application Publication No. 2015-183282 (Patent Literature 1), a technology is disclosed in which, in the production of metal nickel and metal cobalt based on a wet refining method, in order to separate and recover cobalt from a cobalt-containing nickel chloride aqueous solution, a tertiary amine is used as an extractant, and an aromatic hydrocarbon solvent is used as a diluent to extract cobalt. Also, in the examples, tri-n-octylamine is used as the tertiary amine.

[0004] In Japanese Patent Application Publication No. 2015-168858 (Patent Literature 2), as a solvent extraction method for extracting cobalt from an aqueous solution containing cobalt ions, a technology is disclosed in which the solubility of a quaternary ammonium-based ionic liquid in water is greatly reduced by mixing a certain organic solvent, and ions are extracted from an aqueous solution containing cobalt with the quaternary ammonium-based ionic liquid as an extractant. In addition, in the examples, trioctylmethylammonium chloride is used. SUMMARY

[0005] The present disclosure relates to a metal separation method for separating or separating and recovering a metal from an aqueous solution containing the metal, a metal separation reagent kit, a metal recovery method, a manufacturing method of a lithium ion battery, and a metal separation reagent.

[0006] [Chemical Formula 1]

[0007]

[0008] In formula (I), R 1 is a hydrocarbon group having 6 or more and 22 or less carbon number optionally having an ester group, an amide group and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having 6 or more and 22 or less carbon number optionally having an ester group, an amide group and / or an ether group, or an alkyl group having 1 or more and 4 or less carbon number optionally having a hydroxyl group, R 4 is an alkyl group having 1 or more and 6 or less carbon number or a hydrogen atom, and X - is an anion.

[0009] The present disclosure relates to, in one embodiment, a metal separation reagent kit for separating or separating and recovering a metal from an aqueous solution containing the metal, comprising a first agent containing a salt represented by the following formula (I) (component A) and a second agent containing thiocyanic acid (component B).

[0010] [Chemical 2]

[0011]

[0012] In formula (I), R 1 is a hydrocarbon group having 6 or more and 22 or less carbon number optionally having an ester group, an amide group and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having 6 or more and 22 or less carbon number optionally having an ester group, an amide group and / or an ether group, or an alkyl group having 1 or more and 4 or less carbon number optionally having a hydroxyl group, R 4 is an alkyl group having 1 or more and 6 or less carbon number or a hydrogen atom, and X - is an anion.

[0013] The present disclosure relates to, in one embodiment, a metal recovery method for separating and recovering a metal from an aqueous solution containing the metal, the metal recovery method comprising: a step of separating the metal from an aqueous phase to an organic phase by bringing an aqueous solution containing the metal into contact with an agent prepared by combining a metal separation reagent kit of the present disclosure; and a step of recovering the metal from the organic phase.

[0014] The present disclosure relates to, in one embodiment, a method for manufacturing a lithium ion battery, the method for manufacturing a lithium ion battery comprising: a step of separating a metal from an aqueous phase to an organic phase by bringing an aqueous solution containing the metal into contact with an agent prepared by combining a metal separation reagent kit of the present disclosure; a step of recovering the metal from the organic phase; and a step of manufacturing a battery using the metal recovered in the step.

[0015] This disclosure relates in one manner to a metal separating agent for separating or separating and recovering metal from an aqueous solution containing metal, comprising a salt (component A) as shown in formula (I) and thiocyanate (component B).

[0016] This disclosure relates in one manner to a metal separating agent for separating or separating and recovering metals from an aqueous solution containing metals, which is prepared by combining a salt (component A) and thiocyanate (component B) as shown in formula (I).

[0017] [Chemistry 3]

[0018]

[0019] In equation (I), R 1 R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0020] In one aspect, this disclosure relates to a metal separation method for separating metals from an aqueous solution containing metals, the metal separation method comprising the step of contacting the aqueous solution containing metals with the metal separating agent of this disclosure to separate the metals from the aqueous phase to the organic phase.

[0021] This disclosure relates, in one aspect, to a metal recovery method for separating and recovering metal from an aqueous solution containing metal, the metal recovery method comprising: a step of contacting the aqueous solution containing metal with a metal separating agent of this disclosure to separate the metal from the aqueous phase to an organic phase; and a step of recovering the metal from the organic phase. Detailed Implementation

[0022] However, alkylammonium salts such as trioctylmethylammonium chloride tend to exhibit reduced cobalt separation and recovery performance at low hydrochloric acid concentrations or in the presence of sulfate ions. Furthermore, high concentrations of hydrochloric acid impose a significant environmental burden and are difficult to dispose of. Additionally, the variation in separation and recovery performance with the types of acids present in the mixture contributes to the reduced versatility of the extractant.

[0023] Therefore, this disclosure provides a metal separation method capable of efficiently separating and / or recovering metals intended to be separated and / or recovered from aqueous solutions containing metals.

[0024] According to this disclosure, in one embodiment, a metal separation method can be provided that is capable of efficiently separating and / or recovering metals intended to be separated and / or recovered from an aqueous solution containing metals.

[0025] [Metal Separation Methods]

[0026] This disclosure is based on the insight that, by using a metal separating agent comprising a salt (component A) of the above formula (I), thiocyanate (component B) and a water-insoluble organic solvent (component C), or a metal separating agent comprising a salt (component A) of the above formula (I) and thiocyanate (component B), it is possible to efficiently separate and / or recover metals intended to be separated and / or recovered from aqueous solutions containing metals.

[0027] That is, in one aspect, this disclosure relates to a metal separation method (hereinafter also referred to as "the metal separation method of this disclosure"), which is a metal separation method for separating or separating and recovering metal from an aqueous solution containing metal. The metal separation method includes a step (hereinafter also referred to as "contact step") of contacting the aqueous solution containing metal with a metal separating agent (hereinafter also referred to as "the metal separating agent of this disclosure") containing a salt (component A) of the above formula (I), thiocyanate (component B) and a water-insoluble organic solvent (component C) to separate the metal from the aqueous phase to the organic phase.

[0028] According to the metal separation method of this disclosure, in one or more embodiments, a metal separation method can be provided that can efficiently separate and / or recover metals intended to be separated and / or recovered from aqueous solutions containing metals. According to the metal separation method of this disclosure, in one or more embodiments, a metal separation method with excellent metal separation and recovery performance from aqueous solutions containing metals can be provided.

[0029] This disclosure relates in other ways to a metal separation method (hereinafter also referred to as "the metal separation method of this disclosure"), which is a metal separation method for separating metal from an aqueous solution containing metal, the metal separation method comprising a step of contacting the aqueous solution containing metal with a metal separating agent (hereinafter also referred to as "the metal separating agent of this disclosure") containing a salt (component A) and thiocyanate (component B) as shown in formula (I) above to separate the metal from the aqueous phase to the organic phase (hereinafter also referred to as "the contact step").

[0030] According to the metal separation method disclosed herein, it is possible to efficiently separate the intended metal from an aqueous solution containing the metal.

[0031] Furthermore, in one or more embodiments of the metal separation method disclosed herein, the cobalt recovery efficiency is excellent. Additionally, in one or more embodiments of the metal separation method disclosed herein, the Co-Ni separation capability is excellent. That is, in one or more embodiments of the metal separation method disclosed herein, it is a metal separation method for separating or separating and recovering cobalt from an aqueous solution containing cobalt. In one or more embodiments of the metal separation method disclosed herein, it is a metal separation method for separating or separating and recovering cobalt from an aqueous solution containing both cobalt and nickel.

[0032] While some details regarding the mechanism by which the effects of this disclosure manifest are unclear, they can be speculated as follows.

[0033] In aqueous solutions (aqueous phase), metal ions are stabilized by accepting electrons primarily with water molecules or other hydrophilic compounds. This stabilized structure is called a metal ion cluster. To facilitate the movement of these metal ion clusters into oil (organic phase), greater stabilization is required. The salt (component A) of formula (I) of this disclosure, due to its high charge density and positive charge, exhibits electrostatic interaction with the negatively charged metal ion cluster in aqueous solutions (aqueous phase), thus forming a more stable structure. Therefore, component A of this disclosure shows a certain effect as a metal separation agent in oil (organic phase).

[0034] Furthermore, by using thiocyanate (component B), component B forms complexes with structures specific to different metals compared to general ligands. For example, it is believed to form a linear bidentate complex with nickel and a tetrahedral tetradentate complex with cobalt. The structural differences in these thiocyanate complexes result in variations in the reactivity of component A with each metal, thus suggesting a greater likelihood of achieving highly precise metal separation.

[0035] This disclosure supplements the oil (organic phase) with metal ions by the presence of component B in the oil (organic phase). Furthermore, component A helps to stably contain the interacting metal ions and component B in the oil (organic phase), thereby enabling the extraction of specific metal ions with far greater efficiency compared to the use of the salt (component A) and thiocyanate (component B) shown in formula (I) alone.

[0036] The salt (component A) shown in formula (I) of this disclosure can be an alkylammonium salt or an amine salt having polar groups such as ester groups. It is believed that when the alkylammonium salt or amine salt has polar groups, it shares electrons with metal ions due to its electron-withdrawing properties, thereby forming more stable covalent bonds. The formation rate of these covalent bonds varies with various metal ions, resulting in increased selectivity and the ability to separate negatively charged metal ion clusters. Therefore, it is believed that when component A of this disclosure has polar groups (specific alkylammonium salts or amine salts), it can provide superior metal separation and recovery capabilities.

[0037] However, this disclosure may also be interpreted in ways other than those described above.

[0038] <Aqueous solutions containing metals>

[0039] As a "metal-containing aqueous solution" of this disclosure, in one or more embodiments, an aqueous solution obtained by treating electronic waste can be cited. Electronic waste, in one or more embodiments, can include waste from electronic components of lithium-ion batteries. As a metal-containing aqueous solution, in one or more embodiments, an aqueous solution (leaching solution) obtained by treating waste electronic components with acid can be cited.

[0040] The "metal-containing aqueous solution" obtained from electronic waste can be obtained, for example, by separating the positive electrode component of a lithium-ion battery into ferrous metals, plastics, and electrode powder BM (black matrix) through crushing and heat treatment, and then dissolving the electrode powder BM in an acidic aqueous solution of sulfuric acid or hydrochloric acid. The electrode powder BM may contain, for example, lithium (Li), cobalt (Co), nickel (Ni), and manganese (Mn). In one or more embodiments, examples of metal-containing aqueous solutions include an aqueous solution containing cobalt and an aqueous solution containing both cobalt and nickel.

[0041] In this disclosure, an aqueous solution containing metal can be cited as an example of a leachate obtained by leaching battery residue containing positive electrode active material from a lithium-ion battery with an acidic aqueous solution.

[0042] <Contact Process>

[0043] In one or more embodiments, the contacting process described above is a process in which an aqueous solution containing metal, which is an aqueous phase, is contacted with an organic phase of the metal separating agent of this disclosure, thereby dispensing (extracting) the metal to be separated into the organic phase, and thus separating the metal from the aqueous phase.

[0044] As the organic phase in the above-mentioned process, the organic phase contained in oil-continuous or bicontinuous emulsion systems can be used.

[0045] The metal separating agent of this disclosure, which contains an organic phase, is in one or more embodiments in the form of a water-insoluble organic solvent (component C) described later.

[0046] The operating steps of the above-mentioned contact process are not particularly limited, and any known operating steps used in liquid phase extraction can be appropriately selected. For example, the following steps can be taken: adding the metal separating agent of this disclosure, which contains an aqueous solution of the metal as an aqueous phase and an organic phase, to any container; thoroughly mixing the aqueous phase and the organic phase using a shaker or the like; and then separating the phases by centrifugation to perform liquid-liquid separation. Alternatively, known extraction devices or apparatuses such as countercurrent extraction apparatus or separatory funnels can be used instead of containers.

[0047] The pH of the aqueous solution containing the metal is not particularly limited and can be appropriately selected according to the type of metal intended to be separated and / or recovered, the purpose, etc. In one or more embodiments, the pH of the aqueous solution containing the metal is generally 6.0 or less, preferably 5.5 or less, more preferably 5.0 or less or 5 or less. For example, when the metal intended to be separated and / or recovered is, for example, cobalt (Co), the pH of the aqueous solution containing the metal is preferably 7.0 or less or 7 or less, more preferably 4.0 or less or 4 or less. In this disclosure, the pH of the aqueous solution is a value at 25°C and can be measured using a pH meter, specifically, using the methods described in the examples.

[0048] In the above contact process, there is no particular limitation on the contact time between the aqueous phase and the organic phase, and it can be appropriately selected according to the purpose. For example, 1 to 10 minutes can be used as the contact time.

[0049] In the above-described contacting process, the temperature at which the aqueous phase contacts the organic phase is not particularly limited. However, from the viewpoint of the solubility of the metal separating agent, it is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher. Furthermore, from the viewpoint of operability, it is preferably 100°C or lower, more preferably 75°C or lower, and even more preferably 50°C or lower. More specifically, the temperature in the above-described contacting process is preferably 0°C or higher and 100°C or lower, more preferably 10°C or higher and 75°C or lower, and even more preferably 20°C or higher and 50°C or lower.

[0050] In one or more embodiments, the metal separating agent of this disclosure that comes into contact with the aqueous phase during the above-described contact process comprises an organic phase. In one or more embodiments, the organic phase is derived from a water-insoluble organic solvent (component C) of the metal separating agent of this disclosure.

[0051] In the above contact process, the volume ratio of the aqueous phase to the organic phase (volume of aqueous phase / volume of organic phase) is not particularly limited and can be appropriately selected according to the purpose. It is usually 1 or more, and preferably 1 to 10.

[0052] Regarding the amount (mol%) of the salt (component A) of formula (I) in the metal separating agent of this disclosure that comes into contact with the aqueous phase in the above-described contacting process, from the viewpoint of the separability of the metal to be separated, it is preferably 100 mol% or more, more preferably 500 mol% or more, and even more preferably 1000 mol% or more, and preferably 10000 mol% or less, more preferably 5000 mol% or less, and even more preferably 2500 mol% or less, relative to the concentration of the metal in the aqueous solution containing the metal (100 mol%). More specifically, the amount of the salt (component A) of formula (I) in the metal separating agent of this disclosure is preferably 100 mol% or more and 10000 mol% or less, more preferably 500 mol% or more and 5000 mol% or less, and even more preferably 1000 mol% or more and 2500 mol% or less, relative to the concentration of the metal in the aqueous solution containing the metal (100 mol%).

[0053] Regarding the amount of thiocyanate (component B) in the metal separating agent of this disclosure that comes into contact with the aqueous phase in the above-described contacting process, from the viewpoint of the separability of the metal to be separated, it is preferably 100 mol% or more, more preferably 500 mol% or more, and even more preferably 1000 mol% or more, and preferably 20000 mol% or less, more preferably 10000 mol% or less, and even more preferably 5000 mol% or less, relative to the concentration of the metal (100 mol%) in the aqueous solution containing the metal. More specifically, the amount of thiocyanate (component B) in the metal separating agent of this disclosure is preferably 100 mol% or more and 20000 mol% or less, more preferably 500 mol% or more and 10000 mol% or less, and even more preferably 1000 mol% or more and 5000 mol% or less, relative to the concentration of the metal (100 mol%) in the aqueous solution containing the metal.

[0054] Regarding the amount of water-insoluble organic solvent (component C) in the metal separating agent of this disclosure that comes into contact with the aqueous phase in the above-described contacting process, from the viewpoint of the recovery efficiency of the metal to be recovered, it is preferably 1000 mol% or more, more preferably 5000 mol% or more, and even more preferably 10000 mol% or more, and preferably 100000 mol% or less, more preferably 50000 mol% or less, and even more preferably 25000 mol% or less, relative to the concentration of the metal (100 mol%) in the aqueous solution containing the metal. More specifically, the amount of water-insoluble organic solvent (component C) in the metal separating agent of this disclosure is preferably 1000 mol% or more and 100000 mol% or less, more preferably 5000 mol% or more and 50000 mol% or less, and even more preferably 10000 mol% or more and 25000 mol% or less, relative to the concentration of the metal (100 mol%) in the aqueous solution containing the metal.

[0055] [Metal separating agent]

[0056] In one embodiment, this disclosure relates to a metal separating agent (hereinafter also referred to as "the metal separating agent of this disclosure") for separating or separating and recovering metals from an aqueous solution containing metals, comprising a salt (component A) as shown in formula (I) above and thiocyanate (component B).

[0057] According to this disclosure, in one or more embodiments, a metal separating agent capable of efficiently separating and / or recovering a metal intended to be separated and / or recovered from an aqueous solution containing a metal can be provided. According to this disclosure, in one or more embodiments, a metal separating agent with excellent metal separation and recovery performance from an aqueous solution containing a metal can be provided.

[0058] The metal separating agent disclosed herein is used in one or more embodiments to separate or recover metals from aqueous solutions containing metals. In one or more embodiments, the metals targeted for separation and / or recovery include catalyst metals used in lithium-ion batteries, etc. Catalyst metals include fourth-period metals, such as at least one metal selected from cobalt, nickel, and manganese. The metals in the aqueous solution are preferably in an ionic state. In one or more embodiments, the metal separating agent disclosed herein exhibits excellent cobalt recovery efficiency. Furthermore, in another or more embodiments, the metal separating agent disclosed herein exhibits excellent Co-Ni separation capability. That is, in one or more embodiments, the metal separating agent disclosed herein is used to separate or recover cobalt from aqueous solutions containing cobalt. In one or more embodiments, the metal separating agent disclosed herein is used to separate or recover cobalt from aqueous solutions containing both cobalt and nickel.

[0059] <Component A: Salt represented by formula (I)>

[0060] The metal separating agent disclosed herein comprises a salt (hereinafter also referred to as "component A") as shown in formula (I). In formula (I), R... 4 In the case where the alkyl group has 1 or more but less than 6 carbon atoms, component A is a quaternary ammonium salt. In the following formula (I), R... 4 When the hydrogen atom is present, component A is a tertiary amine salt. That is, component A is the salt shown in formula (I), which includes quaternary ammonium salt and tertiary amine salt. Component A can be one type or a combination of two or more types.

[0061] [Chemistry 4]

[0062]

[0063] In equation (I), R 1 R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0064] In the above equation (I), R 1 R 2 and R 3 Each is independently a hydrocarbon group having 6 or more but less than 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, regarding R 1 R 2 and R 3 The hydrocarbon group, from the viewpoint of the separability of the metal to be separated, is a hydrocarbon group with 6 or more and 22 carbon atoms, preferably a hydrocarbon group with 8 or more and 18 carbon atoms, and more preferably a hydrocarbon group with 8 or more and 16 carbon atoms. The hydrocarbon group can be straight-chain or branched; however, from the viewpoint of suppressing foaming when in contact with aqueous solution, a branched chain is preferred. The hydrocarbon group can be a saturated chain or an unsaturated chain; however, from the viewpoint of suppressing foaming when in contact with aqueous solution, an unsaturated chain is preferred.

[0065] From the perspective of the separability of metals intended to be separated, R 1 R 2 and R 3 At least one of them preferably has an ester group, an amide group and / or an ether group, more preferably has an ester group or an ether group, and even more preferably has an ester group.

[0066] In R 1R 2 and R 3 In the case where the hydrocarbon group having 6 or more carbon atoms and 22 or fewer has an ester group, an amide group, and / or an ether group, in one or more embodiments, examples of hydrocarbon groups with -R can be cited. 5 -XR 6 It means that R 5 An alkyl group with 1 or more but less than 4 carbon atoms, where X is -OC (=O)-, -NH-C (=O)-, or an oxygen atom. From the viewpoint of the separability of the metal to be separated, R 6 It is a hydrocarbon group with 6 or more carbon atoms and 18 or fewer. Regarding R... 5 The number of carbon atoms, from the viewpoint of the separability of the metals to be separated, is preferably 1 or 2. Regarding R... 6 From the viewpoint of the separability of the metals to be separated, the carbon number is preferably 6 or more and 18 or less. 6 The hydrocarbon group can be saturated or unsaturated; however, in one or more embodiments, from the viewpoint of suppressing foaming when in contact with aqueous solution, it is preferred to have an unsaturated chain. In one or more embodiments, from the viewpoint of the separability of the metal intended to be separated, X is preferably -OC (=O)-.

[0067] Regarding R 2 and R 3 From the viewpoint of the separability of the metal to be separated, the alkyl group having 1 or more carbon atoms and 4 or less with hydroxyl groups is preferred, the alkyl group having 1 or more carbon atoms and 3 or less with hydroxyl groups is more preferred, the alkyl group having 1 or 2 or less with hydroxyl groups is more preferred, and hydroxyethyl is even more preferred.

[0068] Regarding R 4 From the viewpoint of the separability of the metal to be separated, the alkyl group is an alkyl group or hydrogen atom with 1 or more and 6 or less carbon atoms, preferably an alkyl group with 1 or more and 6 or less carbon atoms, more preferably an alkyl group with 1 or more and 4 or less carbon atoms, even more preferably an alkyl group with 1 or more and 2 or less carbon atoms, and even more preferably methyl.

[0069] X - Examples of opposite ions include alkyl sulfate ions, sulfate ions, phosphate ions, carboxylate ions (formate ions, acetate ions, propionate ions), and halide ions, which have 1 or more but less than 3 carbon atoms. Among these, from the viewpoint of ease of manufacture and availability of raw materials, X... - Preferably, it is selected from at least one of methyl sulfate ions, ethyl sulfate ions, chloride ions, and bromide ions, more preferably methyl sulfate ions. X - It can be a single type or two or more types.

[0070] In one or more embodiments, component A is R in formula (I). 1 R 2 and R 3 A compound having at least one ester group having 6 or more carbon atoms and less than 22 carbon atoms (hereinafter also referred to as "component A1"). Component A1 in one or more embodiments is R in formula (I). 1 R 2 and R 3 Compounds containing at least two ester groups having 6 or more carbon atoms and fewer than 22 carbon atoms, and R in formula (I). 1 R 2 and R 3 Compounds having ester groups with 6 or more carbon atoms and 22 or fewer carbon atoms.

[0071] As component A1, R in formula (I) can be cited as an example in one or more embodiments. 1 R 2 and R 3 These are compounds containing hydrocarbon groups with 6 or more but fewer than 22 carbon atoms and an ester group; R in formula (I) 1 and R 2 They are hydrocarbon groups with 6 or more but less than 22 carbon atoms that have an ester group, and R 3 Compounds can be alkyl groups having 1 or more but less than 4 carbon atoms and containing a hydroxyl group, such as methyltris[2-ethylhexanoate]-ammonium salt and (2-hydroxyethyl)-methylbis[2-oleate]-ammonium salt. Examples of the opposite ions of these salts include methyl sulfate ions, ethyl sulfate ions, chloride ions, and bromide ions. Examples of component A1 include methyltris[2-ethylhexanoate]-ammonium methyl sulfate and (2-hydroxyethyl)-methylbis[2-oleate]-ammonium methyl sulfate. It should be noted that there is no particular limitation on the number of carbon atoms in the hydrocarbon group interrupted by the ester group and the nitrogen atom; for example, compounds with 0 or more or 4 or less carbon atoms can be included.

[0072] In one or more embodiments, component A is R in formula (I). 1 R 2 and R 3 At least one of the compounds having an ether group having 6 or more carbon atoms and 22 or fewer carbon atoms (hereinafter also referred to as "component A2"). As component A2, in one or more embodiments, R in formula (I) can be cited as an example. 1 R 2 and R 3Compounds having an ether group and a hydrocarbon group having 6 or more but 22 or fewer carbon atoms, such as tris[2-hexyloxyethyl]-hexyl-ammonium salts, are examples. Examples of the opposite ions of these salts include methyl sulfate ions, ethyl sulfate ions, chloride ions, and bromide ions. Examples of component A2 include tris[2-hexyloxyethyl]-hexyl-ammonium hydrochloride. It should be noted that there is no particular limitation on the number of carbon atoms in the hydrocarbon group interrupted by the ether group and the nitrogen atom; for example, compounds with 0 or more or 4 or fewer carbon atoms can be included.

[0073] In one or more embodiments, component A is R in formula (I). 1 R 2 and R 3 At least one of the compounds having an amide group having 6 or more carbon atoms and 22 or fewer carbon atoms (hereinafter also referred to as "component A3"). As component A3, in one or more embodiments, R in formula (I) can be cited as an example. 1 R 2 and R 3 Compounds having an amide group and a hydrocarbon group having 6 or more but less than 22 carbon atoms are examples of such compounds, such as tris[2-(oleamide)ethyl]-methyl-ammonium methyl salt. Examples of the opposite ions of these salts include methyl sulfate ions, ethyl sulfate ions, chloride ions, and bromide ions. Examples of component A3 include tris[2-(oleamide)ethyl]-methyl-ammonium methyl sulfate. It should be noted that there is no particular limitation on the number of carbon atoms in the hydrocarbon group interrupted by the amide group and the nitrogen atom; examples of 0 or more or 4 or less are acceptable.

[0074] Regarding component A, from the viewpoint of the separability of the metals to be separated, it is preferred to be selected from at least one of components A1, A2 and A3, more preferably from at least one of components A1 and A2, and even more preferably from component A1.

[0075] From the same point of view, component A is preferably selected from at least one of methyltri[2-ethylhexanoate ethyl]-ammonium salt, (2-hydroxyethyl)-methylbis[2-oleate ethyl]-ammonium salt, tri[2-hexyloxyethyl]-hexyl-ammonium salt, and tri[2-(oleamide)ethyl]-methyl-ammonium methyl salt, more preferably selected from at least one of methyltri[2-ethylhexanoate ethyl]-ammonium salt, (2-hydroxyethyl)-methylbis[2-oleate ethyl]-ammonium salt, and tri[2-hexyloxyethyl]-hexyl-ammonium salt, further preferably selected from at least one of methyltri[2-ethylhexanoate ethyl]-ammonium salt and (2-hydroxyethyl)-methylbis[2-oleate ethyl]-ammonium salt, even more preferably selected from methyltri[2-ethylhexanoate ethyl]-ammonium salt, and even more preferably selected from methyltri[2-ethylhexanoate ethyl]-ammonium methyl sulfate.

[0076] Regarding the amount (mass %) of component A in the metal separating agent of this disclosure, from the viewpoint of the separability of the metal to be separated, it is preferably 1.0% by mass or more or 1% by mass, more preferably 5.0% by mass or more or 5% by mass, further preferably 10.0% by mass or more or 10% by mass, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. More specifically, the amount (mass %) of component A in the metal separating agent of this disclosure is preferably 1.0% by mass or more and 50% by mass or 1% by mass or more and 50% by mass or less, more preferably 5.0% by mass or more and 40% by mass or 5% by mass or more and 40% by mass or less, further preferably 10.0% by mass or more and 30% by mass or 10% by mass or more and 30% by mass or less. When there is a combination of two or more components A, the amount of component A refers to their total amount.

[0077] The metal separating agent disclosed herein is, in one or more embodiments, a composition comprising component A and component B.

[0078] <Thiocyanate (Component B)>

[0079] In one or more embodiments, the metal separating agent of this disclosure is, from the viewpoint of the separability of the metal to be separated, formed by or containing component A and thiocyanate (hereinafter also referred to as "component B"). That is, in one or more embodiments, the metal separating agent of this disclosure is formed by combining component A and thiocyanate (component B).

[0080] In the metal separating agent disclosed herein, in one or more embodiments, component A and component B exist in a miscible state.

[0081] In this disclosure, the term "combined" means not only combining component A and thiocyanate (component B), but also further combining optional components as needed.

[0082] In this disclosure, the proportions of each component in the metal separating agent can be read as the content of each component in the metal separating agent.

[0083] From the perspective of the separability of the metals to be separated, examples of component B include ammonium thiocyanate and sodium thiocyanate. Component B can be one type or a combination of two or more types.

[0084] Regarding the amount (mass %) of component B in the metal separating agent of this disclosure, from the viewpoint of the separability of the metal to be separated, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less. More specifically, the amount (mass %) of component B in the metal separating agent of this disclosure is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, even more preferably 0.5% by mass or more and 10% by mass or 1.0% by mass or more and 10% by mass or less. When component B is a combination of two or more types, the amount of component B refers to their total amount.

[0085] Regarding the mass ratio A / B (amount of component A / amount of component B) of component A to component B in the metal separating agent of this disclosure, from the viewpoint of the separability of the metal to be separated, it is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1.0 or more. Moreover, from the same viewpoint, it is preferably 50 or less, 40 or less, or 20 or less, more preferably 10 or less, and even more preferably 5.0 or less. More specifically, the mass ratio A / B (amount of component A / amount of component B) is preferably 0.01 or more and 50 or less, 0.01 or more and 30 or less, or 0.01 or more and 20 or less, more preferably 0.1 or more and 10 or less, and even more preferably 1.0 or more and 5.0 or less.

[0086] <Water-insoluble organic solvent (component C)>

[0087] The metal separating agent disclosed herein is formed or contains, in one or more embodiments, component A, thiocyanate (component B) and water-insoluble organic solvent (component C).

[0088] In this disclosure, "water-insoluble organic solvent" refers to an organic solvent whose solubility is less than 0.01 g per 100 g of water at 25°C.

[0089] Examples of water-insoluble organic solvents (component C) include petroleum-based solvents such as kerosene; aliphatic hydrocarbon solvents such as hexane, isooctane, and dodecane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogen solvents such as chloroform and dichloromethane; higher alcohol solvents such as dodecyl alcohol and octanol; and higher fatty acid solvents such as oleic acid. Among these, from the perspective of the recovery efficiency of the metal to be recovered, petroleum-based solvents such as kerosene are preferred. Component C can be one type or a combination of two or more types (mixed solvent).

[0090] In this disclosure, the phase derived from component C when the metal separating agent of this disclosure is mixed with an aqueous solution is sometimes referred to as the "organic phase".

[0091] When the metal separating agent of this disclosure contains component C, from the viewpoint of the recovery efficiency of the metal to be recovered, the amount (mass%) of component C in the metal separating agent of this disclosure is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 99.9% by mass or less, more preferably 99% by mass or less, and further preferably 95% by mass or less. More specifically, the amount (mass%) of component C in the metal separating agent of this disclosure is preferably 50% by mass or more and 99.9% by mass or less, more preferably 60% by mass or more and 99% by mass or less, and further preferably 70% by mass or more and 95% by mass or less. When there is a combination of two or more components C, the amount of component C refers to their total amount.

[0092] When the metal separating agent of this disclosure contains component C, the mass ratio A / C (amount of component A / amount of component C) of component A to component C in the metal separating agent of this disclosure, from the viewpoint of the recovery efficiency of the metal to be recovered, is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. Moreover, from the same viewpoint, it is preferably 10 or less, more preferably 5.0 or less or 5 or less, and even more preferably 1.0 or less or 1 or less. More specifically, the mass ratio A / C (amount of component A / amount of component C) is preferably 0.01 or more and 10 or less, more preferably 0.05 or more and 5.0 or less or 0.05 or more and 5 or less, and even more preferably 0.1 or more and 1.0 or less or 0.1 or more and 1 or less.

[0093] When the metal separating agent of this disclosure contains component C, the mass ratio B / C (amount of component B / amount of component C) of component B to component C in the metal separating agent of this disclosure is preferably 0.001 or more, more preferably 0.01 or more, and even more preferably 0.05 or more, and from the same viewpoint, preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less. More specifically, the mass ratio B / C (amount of component B / amount of component C) is preferably 0.001 or more and 10 or less, more preferably 0.01 or more and 5 or less, and even more preferably 0.01 or more and 1 or less.

[0094] <Other Ingredients>

[0095] The metal separating agent disclosed herein may contain other components as needed, without impairing the effects of this disclosure. Examples of such other components include, for instance, defoamers and demulsifiers.

[0096] [Metal Separator Kit]

[0097] This disclosure relates, in one embodiment, to a metal separation kit (hereinafter also referred to as "the metal separation kit of this disclosure") for separating, or separating and recovering metals from an aqueous solution containing metals, comprising a first agent and a second agent, wherein the first agent comprises component A and the second agent comprises component B.

[0098] The first agent and the second agent are mixed during use in one or more embodiments.

[0099] The first and second doses may contain the above-mentioned optional ingredients (ingredient C, other ingredients) as needed.

[0100] The reagent prepared in conjunction with the metal separating agent kit of this disclosure, i.e., the reagent obtained by mixing the first agent and the second agent, is the metal separating agent of this disclosure in one or more embodiments.

[0101] The metal separator kit disclosed herein is, in one or more embodiments, a kit for manufacturing the metal separator of this disclosure.

[0102] The metal separating agent kit disclosed herein is, in one or more embodiments, a metal separating agent kit for separating or separating and recovering cobalt.

[0103] The metal separating agent kit disclosed herein is, in one or more embodiments, a metal separating agent kit for separating or separating and recovering cobalt from an aqueous solution containing cobalt and nickel.

[0104] [Metal Recycling Methods]

[0105] This disclosure relates, in one embodiment, to a metal recovery method (hereinafter also referred to as the "metal recovery method of this disclosure"), which is a method for separating and recovering metal from an aqueous solution containing metal. The metal recovery method includes: a step of contacting the aqueous solution containing metal with an agent formulated with the metal separating agent of this disclosure or a metal separating agent kit of this disclosure to separate the metal from the aqueous phase to an organic phase (hereinafter also referred to as the "contact step"); and a step of recovering the metal from the organic phase (hereinafter also referred to as the "recovery step"). According to the metal recovery method of this disclosure, the metal intended to be separated and recovered can be efficiently separated and recovered from the aqueous solution (aqueous phase) containing metal.

[0106] Furthermore, in one or more embodiments of the metal recovery method disclosed herein, the cobalt recovery efficiency is excellent. Additionally, in one or more embodiments of the metal recovery method disclosed herein, the Co-Ni separation capability is excellent. That is, in one or more embodiments of the metal recovery method disclosed herein, it is a metal recovery method for separating and recovering cobalt from an aqueous solution containing cobalt. In one or more embodiments of the metal recovery method disclosed herein, it is a metal recovery method for separating and recovering cobalt from an aqueous solution containing both cobalt and nickel.

[0107] <Contact Process>

[0108] The contact method and contact conditions in the contact process of the metal recycling method disclosed herein can be set to be the same as those in the metal separation method disclosed herein.

[0109] <Recycling Process>

[0110] In the above-mentioned recycling process, methods for recovering metals separated (distributed, extracted) into the organic phase include, for example, crystallization and electrolysis.

[0111] <Liquid extraction and reverse extraction processes>

[0112] The metal separation method and metal recovery method disclosed herein may further include the following liquid separation step (1) and reverse extraction step (2) in one or more embodiments.

[0113] (1) Separation process: The aqueous phase and organic phase that were in contact during the contact process are separated.

[0114] (2) The reverse extraction process involves contacting the organic phase separated in the liquid-liquid separation process with an aqueous phase that is different from the aqueous phase in the liquid-liquid separation process to perform reverse extraction.

[0115] The aqueous solution used in the separation step (1) is not particularly limited as long as it can be used in the reverse extraction; however, an acidic aqueous solution or an aqueous solution containing a complexing agent such as ethylenediaminetetraacetic acid (EDTA) or thiourea is preferred. It should be noted that, in the case of an acidic aqueous solution, its pH is preferably adjusted to be lower than that of the aqueous solution used in the contact step. It should also be noted that the acid used is not particularly limited; however, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, and hypophosphite can be cited.

[0116] <Preparation Process>

[0117] The metal separation method and metal recovery method disclosed herein may further include a step of preparing an aqueous solution containing the metal (hereinafter also referred to as the "preparation step") in one or more embodiments. The preparation method is not particularly limited; the aqueous solution containing the metal may be purchased or prepared in-house.

[0118] The aqueous solution containing metal is not particularly limited as long as it contains the metal intended to be separated and / or recovered. Generally speaking, the aqueous solution is prepared under conditions that enable the separation (extraction) of the metal to be separated and / or recovered (in the case that it also contains metals other than the metal to be separated and / or recovered, the conditions under which the extraction rate of the metal to be separated and / or recovered differs from the extraction rate of the metals other than the metal to be separated and / or recovered). The aqueous solution is preferably prepared as an acidic aqueous solution.

[0119] Examples of aqueous solutions containing metals include aqueous solutions obtained from the treatment of the aforementioned electronic waste.

[0120] In the case of preparing an acidic aqueous solution containing the metal to be separated and / or recovered, the preparation method is not particularly limited. Acid (to adjust the pH) may be added to the aqueous solution containing the metal to be separated and / or recovered, or the acidic aqueous solution may be prepared to dissolve the metal to be separated and / or recovered. It should be noted that the acid used in the preparation of the acidic aqueous solution may include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, and hypophosphorous acid.

[0121] [Manufacturing method of lithium-ion battery]

[0122] This disclosure relates, in one embodiment, to a method for manufacturing a lithium-ion battery (hereinafter also referred to as the "lithium-ion battery manufacturing method of this disclosure"), the method comprising: a step of contacting an aqueous solution containing metal with an agent prepared in accordance with the metal separation agent kit of this disclosure to separate the metal from the aqueous phase to an organic phase (hereinafter also referred to as the "contact step"); a step of recovering the metal from the organic phase (hereinafter also referred to as the "recovery step"); and a step of manufacturing a battery using the metal recovered in the above steps.

[0123] The contact method and contact conditions in the contact process of the lithium-ion battery manufacturing method disclosed herein can be set to be the same as the contact method and contact conditions in the metal separation method of the present disclosure described above.

[0124] The recycling method in the recycling process of the lithium-ion battery manufacturing method disclosed herein can be set to be the same as the recycling method in the metal recycling method of the present disclosure described above.

[0125] The lithium-ion battery manufacturing method disclosed herein may further include the above-described liquid separation process (1) and reverse extraction process (2) in one or more embodiments.

[0126] The lithium-ion battery manufacturing method disclosed herein may further include the above-described preparation steps in one or more embodiments.

[0127] This disclosure further relates, in one or more embodiments, to the following metal separation methods, metal separation agent kits, metal separation agents, and metal recovery methods.

[0128] <1> A metal separation method, which is used to separate or separate and recover metals from an aqueous solution containing metals.

[0129] The above-mentioned metal separation method includes a step of contacting an aqueous solution containing metal with a metal separating agent containing a salt (component A) as shown in formula (I), thiocyanate (component B) and a water-insoluble organic solvent (component C) to separate the metal from the aqueous phase to the organic phase.

[0130] [Chemistry 5]

[0131]

[0132] In equation (I), R 1 R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0133] <2> According to the metal separation method described in <1>, component A is R in formula (I). 1 R 2 and R 3 Compounds having at least one ester group having 6 or more carbon atoms and less than 22 carbon atoms.

[0134] <3> According to the metal separation method described in <1>, component A is R in formula (I). 1 R 2 and R 3 Compounds containing at least two ester groups with 6 or more carbon atoms and less than 22 carbon atoms.

[0135] <4> According to the metal separation method described in <1>, component A is R in formula (I). 1 R 2 and R 3 Compounds having ester groups with 6 or more carbon atoms and 22 or fewer carbon atoms.

[0136] <5> According to any one of <1> to <4>, the metal separation method, wherein, with respect to component A, R in formula (I) 4 It is a methyl group.

[0137] <6> The metal separation method according to any one of <1> to <5>, wherein the mass ratio of component A to component B in the metal separating agent, A / B, is 0.01 or more and 50 or less.

[0138] <7> The metal separation method according to any one of <1> to <5>, wherein the mass ratio of component A to component B in the metal separating agent, A / B, is 0.01 or more and 30 or less, or 0.01 or more and 20 or less, or 0.1 or more and 10 or less, or 1.0 or more and 5.0 or less.

[0139] <8> A metal separation method according to any one of <1> to <7>, wherein the content of component A in the metal separating agent is 1% by mass or more and 50% by mass or less.

[0140] <9> The metal separation method according to any one of <1> to <7>, wherein the content of component A in the metal separating agent is 5.0% by mass or more and 40% by mass or less, or 5% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less.

[0141] <10> The metal separation method described in any one of <1> to <9>, wherein the content of component B in the metal separating agent is 0.5% by mass or more and 10% by mass or less.

[0142] <11> According to any one of <1> to <9>, the content of component B in the metal separating agent is 0.1% by mass or more and 40% by mass or less, or 0.5% by mass or more and 20% by mass or less, or 0.5% by mass or more and 10% by mass or less, or 1.0% by mass or more and 10% by mass or less.

[0143] <12> The metal separation method described in any one of <1> to <11> is a metal separation method for separating or separating and recovering cobalt.

[0144] <13> The metal separation method described in any one of <1> to <12> is a metal separation method for separating or separating and recovering cobalt from an aqueous solution containing cobalt and nickel.

[0145] <14> A metal separation reagent kit for separating or separating and recovering metals from an aqueous solution containing metals, comprising a first agent and a second agent, wherein the first agent comprises a salt (component A) as shown in formula (I) and the second agent comprises thiocyanate (component B).

[0146] [Chemistry 6]

[0147]

[0148] In equation (I), R 1 R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0149] <15> According to the metal separation agent kit described in <14>, component A is R in formula (I). 1 R 2 and R 3 Compounds having at least one ester group having 6 or more carbon atoms and less than 22 carbon atoms.

[0150] <16> According to the metal separation agent kit described in <14>, component A is R in formula (I). 1 R 2 and R 3 Compounds containing at least two ester groups with 6 or more carbon atoms and less than 22 carbon atoms.

[0151] <17> According to the metal separation agent kit described in <14>, component A is R in formula (I). 1 R 2 and R 3 Compounds having ester groups with 6 or more carbon atoms and 22 or fewer carbon atoms.

[0152] <18> According to any one of <14> to <17>, the metal separating agent kit, wherein, with respect to component A, R in formula (I) 4 It is a methyl group.

[0153] <19> The metal separating agent kit according to any one of <14> to <18>, wherein the mass ratio A / B of component A to component B in the metal separating agent is 0.01 or more and 50 or less, or 0.01 or more and 30 or less, or 0.01 or more and 20 or less, or 0.1 or more and 10 or less, or 1.0 or more and 5.0 or less.

[0154] <20> The metal separating agent kit according to any one of <14> to <19>, wherein the content of component A in the metal separating agent is 1.0% by mass or more and 50% by mass or less, or 1% by mass or more and 50% by mass or less, or 5.0% by mass or more and 40% by mass or less, or 5% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less.

[0155] <21> The metal separating agent kit according to any one of <14> to <20>, wherein the content of component B in the metal separating agent is 0.1% by mass or more and 40% by mass or less, or 0.5% by mass or more and 20% by mass or less, or 0.5% by mass or more and 10% by mass or less, or 1.0% by mass or more and 10% by mass or less.

[0156] <22> A metal separating agent kit according to any one of <14> to <21>, which is a metal separating agent kit for separating or separating and recovering cobalt.

[0157] <23> The metal separating agent kit described in any one of <14> to <22> is a metal separating agent kit for separating or separating and recovering cobalt from an aqueous solution containing cobalt and nickel.

[0158] <24> A metal recovery method is a method for separating and recovering metals from an aqueous solution containing metals.

[0159] The above-mentioned metal recovery method includes: a step of separating the metal from the aqueous phase to the organic phase by contacting an aqueous solution containing the metal with a reagent prepared in combination with any one of the metal separation agent kits described in <14> to <23>; and a step of recovering the metal from the organic phase.

[0160] <25> A method for manufacturing a lithium-ion battery, the method comprising: a step of separating the metal from the aqueous phase to the organic phase by contacting an aqueous solution containing a metal with an agent prepared in combination with a metal separation agent kit described in any one of <14> to <23>; a step of recovering the metal from the organic phase; and a step of manufacturing a battery using the metal recovered in the above steps.

[0161] <26> A metal separating agent for separating or separating and recovering metals from an aqueous solution containing metals, comprising a salt (component A) as shown in formula (I) and thiocyanate (component B).

[0162] [Chemistry 7]

[0163]

[0164] In equation (I), R 1R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0165] <27> A metal separating agent for separating or separating and recovering metals from an aqueous solution containing metals is prepared by combining a salt (component A) and thiocyanate (component B) as shown in formula (I).

[0166] [Chemistry 8]

[0167]

[0168] In equation (I), R 1 R is a hydrocarbon group having 6 or more carbon atoms and less than 22, optionally having an ester group, an amide group, and / or an ether group. 2 and R 3 Each is independently a hydrocarbon group having 6 or more and 22 carbon atoms, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having 1 or more and 4 carbon atoms, optionally having a hydroxyl group, R 4 X is an alkyl group or a hydrogen atom having 1 or more carbon atoms and 6 or fewer carbon atoms. - It is an anion.

[0169] <28> According to the metal separating agent described in <26> or <27>, wherein component A is R in formula (I) 1 R 2 and R 3 Compounds having at least one ester group having 6 or more carbon atoms and less than 22 carbon atoms.

[0170] <29> According to any one of <26> to <28>, the metal separating agent, wherein component A is R in formula (I) 1 R 2 and R 3 Compounds having at least one ester group having 6 or more carbon atoms and less than 22 carbon atoms.

[0171] <30> According to any one of <26> to <28>, the metal separating agent, wherein component A is R in formula (I) 1 R 2 and R 3 Compounds containing at least two ester groups with 6 or more carbon atoms and less than 22 carbon atoms.

[0172] <31> According to any one of <26> to <28>, the metal separating agent, wherein component A is R in formula (I) 1 R 2 and R 3 Compounds having ester groups with 6 or more carbon atoms and 22 or fewer carbon atoms.

[0173] <32> According to any one of <26> to <31>, the metal separating agent, wherein, with regard to component A, R in formula (I) 4 It is a methyl group.

[0174] <33> The metal separating agent described in any one of <26> to <32>, wherein the mass ratio of component A to component B, A / B, is 0.01 or more and 50 or less.

[0175] <34> The metal separating agent described in any one of <26> to <33>, wherein the mass ratio of component A to component B, A / B, is 0.01 or more and 30 or less, or 0.01 or more and 20 or less, or 0.1 or more and 10 or less, or 1.0 or more and 5.0 or less.

[0176] <35> The metal separating agent described in any of <26> to <34> is prepared by combining component A, thiocyanate (component B) and a water-insoluble organic solvent (component C).

[0177] <36> The metal separating agent described in any one of <26> to <35>, wherein the content of component A is 1% by mass or more and 50% by mass or less.

[0178] <37> The metal separating agent described in any one of <26> to <35>, wherein the content of component A in the metal separating agent is 5.0% by mass or more and 40% by mass or less, or 5% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less.

[0179] <38> The metal separating agent described in any one of <26> to <37>, wherein the content of component B is 0.5% by mass or more and 10% by mass or less.

[0180] <39> The metal separating agent described in any one of <26> to <37>, wherein the content of component B in the metal separating agent is 0.1% by mass or more and 40% by mass or less, or 0.5% by mass or more and 20% by mass or less, or 0.5% by mass or more and 10% by mass or less, or 1.0% by mass or more and 10% by mass or less.

[0181] <40> The metal separating agent described in any one of <26> to <39> is a metal separating agent used for separating or separating and recovering cobalt.

[0182] <41> The metal separating agent described in any one of <26> to <39> is a metal separating agent used for separating or separating and recovering cobalt from an aqueous solution containing cobalt and nickel.

[0183] <42> A metal separation method is a method for separating metals from an aqueous solution containing metals.

[0184] The above-mentioned metal separation method includes the step of contacting an aqueous solution containing metal with a metal separating agent described in any one of <26> to <41> to separate the metal from the aqueous phase to the organic phase.

[0185] <43> A metal recovery method is a method for separating and recovering metals from an aqueous solution containing metals.

[0186] The above-mentioned metal recycling methods include:

[0187] A process of separating a metal from an aqueous phase to an organic phase by contacting an aqueous solution containing a metal with any of the metal separating agents described in <26> to <41>; and

[0188] The process of recovering metals from the above organic phase.

[0189] Example

[0190] The present disclosure will now be described in detail with reference to the embodiments; however, the present disclosure is not limited to these embodiments in any way.

[0191] 1. Preparation of Metal Separating Agent I (Organic Phase)

[0192] Quaternary ammonium salt (component A shown in Table 1) and organic solvent (component C shown in Table 1) were miscible at a ratio of 0 to 30 vol%. Then, ammonium thiocyanate (component B shown in Table 1) was added to the aforementioned miscible at a ratio of 0.5 mol / L to prepare metal separating agent I (Examples 1-9, Comparative Examples 1-2). The proportions (mass %) of each component in the metal separating agent of this disclosure are shown in Table 1.

[0193] The following substances are used as components of the metal separating agent.

[0194] (ingredient A)

[0195] <Example of the manufacture of triester-methylammonium methyl sulfate>

[0196] Triester-methylammonium methyl sulfate (compound name: methyltri[2-ethylhexanoate ethyl]-ammonium methyl sulfate) [in formula (I), R 1 R 2 R 3 Ethyl 2-ethylhexanoate, R4 [A compound in which methyl is methyl and X is methyl sulfuric acid] is obtained as shown below.

[0197] 2-Ethylhexanoic acid, triethanolamine, hypophosphorous acid as a catalyst, and butylated hydroxytoluene as an antioxidant were added to a four-necked flask connected to a condenser. After nitrogen purging, the mixture was heated to 170°C over 1.5 hours and stirred for 2 hours. Subsequently, the pressure was reduced to 13.3 kPa over 1.5 hours, and the mixture was allowed to mature for 7 hours. After cooling, the esterified amine was obtained. The obtained esterified amine was added to a 2 L separable flask, and after nitrogen purging, dimethyl sulfate was added dropwise over 1 hour while the mixture was heated to 65°C. The mixture was allowed to mature at 65°C for 4 hours. After cooling to room temperature, trimethylammonium methyl sulfate was obtained.

[0198] <Example of manufacturing diester-methylammonium methyl sulfate>

[0199] Diester-methylammonium methyl sulfate (compound name: (2-hydroxyethyl)-methylbis[2-oleoethyl]-ammonium methyl sulfate) [R in formula (I)] 1 R 2 Ethyl oleate, R 3 Hydroxyethyl, R 4 [A compound in which methyl is methyl and X is methyl sulfuric acid] is obtained as shown below.

[0200] Oleic acid, triethanolamine, hypophosphite as a catalyst, and butylated hydroxytoluene as an antioxidant were added to a four-necked flask connected to a condenser. After nitrogen purging, the mixture was heated to 170°C over 1.5 hours and stirred for 2 hours. Subsequently, the pressure was reduced to 13.3 kPa over 1.5 hours, and the mixture was allowed to mature for 7 hours. After cooling, the esterified amine was obtained. The obtained esterified amine was added to a separable flask, and after nitrogen purging, dimethyl sulfate was added dropwise over 1 hour while the mixture was heated to 65°C. The mixture was allowed to mature at 65°C for 4 hours. After cooling to room temperature, diesteryl methylammonium methyl sulfate was obtained.

[0201] <Example of manufacturing trietherhexylammonium hydrochloride>

[0202] Trietherhexylammonium hydrochloride (compound name: tri[2-hexyloxyethyl]-hexyl-ammonium hydrochloride) [R in formula (I)] 1 R 2 R 3 For hexoxyethyl, R 4 [A compound in which X is a hexyl group and X is a chloride group] was obtained as shown below.

[0203] Triethanolamine, hexanol, and sodium hydroxide were added to a four-necked flask, and after nitrogen purging, the temperature was raised to 160°C. The pressure was then reduced to below 1.3 kPa and stirred for 24 hours. After cooling to room temperature, water was added to stop the reaction, yielding trietheramine. The obtained trietheramine was added to a separable flask, and after nitrogen purging, the temperature was raised to 65°C while chlorohexane was added dropwise over 1 hour. The mixture was then aged at 65°C for 4 hours. After cooling to room temperature, trietherhexylammonium hydrochloride was obtained.

[0204] The synthetic raw materials used in the manufacture of component A are listed below.

[0205] <Synthetic Raw Materials>

[0206] Triethanolamine [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0207] 2-Ethylhexanoic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0208] Oleic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0209] Hypophosphoric acid [Sigma Aldrich]

[0210] BHT [Made by Tokyo Chemical Industry Co., Ltd.]

[0211] Dimethyl sulfate [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0212] Hexanol [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0213] Sodium hydroxide [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0214] Chlorohexane [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0215] <Trioctylmethylammonium methyl sulfate>

[0216] The compound in which trioctylmethylammonium hydrochloride is washed with an aqueous solution of methylsulfuric acid and replaced with methylsulfate.

[0217] (Ingredient B)

[0218] Ammonium thiocyanate [manufactured by Tokyo Chemical Industry Co., Ltd.]

[0219] (Component C)

[0220] Kerosene [Made by Tokyo Chemical Industry Co., Ltd.]

[0221] 2. Preparation of Aqueous Solution II (Aqueous Phase, Metal-Containing Aqueous Solution)

[0222] Co sulfate and Ni sulfate were dissolved in 1 mol / L sulfuric acid to prepare aqueous solution II containing Co and Ni (Co concentration: 3.0 g / L, Ni concentration: 3.0 g / L). The pH of aqueous solution II is shown in Table 1. Regarding the content of each metal in aqueous solution II, Co is 0.3% by mass and Ni is 0.3% by mass.

[0223] [pH Measurement Method]

[0224] The pH of aqueous solution II is the pH value at 25°C, measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is the value after the electrode has been immersed in the grinding slurry composition for 1 minute. The results are shown in Table 1.

[0225] 3. Evaluation of metal separating agents (Examples 1-9, Comparative Examples 1-2)

[0226] The metal separating agent I (organic phase) was contacted with aqueous solution II (aqueous phase) to evaluate the extraction capacity of Co and the separation capacity of Co-Ni. The specific steps are as follows.

[0227] [Metal Extraction Method]

[0228] Metal separating agent I (organic phase) and aqueous solution II (aqueous phase) are added to a separatory funnel and shaken at 20°C for 10 minutes to bring them into contact, allowing the metal to transfer (partition) into metal separating agent I (organic phase) for metal extraction (separation). It should be noted that the volume ratio (volume of aqueous phase / volume of organic phase) of the contacting aqueous solution II to metal separating agent I (organic phase) is 1.0. Regarding the proportions of each component in metal separating agent I in contact with aqueous solution II, relative to the Co concentration in aqueous solution II, component A is 1500 mol%, component B is 2500 mol%, and component C is 25000 mol%.

[0229] The concentrations of Co and Ni in the extracted metal separating agent I (organic phase) and aqueous solution II (aqueous phase) were quantitatively analyzed using ICP-OES to calculate the Co extraction rate and the Co-Ni separation capability. The results are presented in Table 1. The Co extraction rate and Co-Ni separation capability are defined as follows.

[0230] [Co extraction rate]

[0231] Co extraction rate is obtained by dividing the Co concentration (g / L) in the extracted metal separating agent I by the Co concentration (g / L) in the initial (before extraction) aqueous solution I.

[0232] Co extraction rate = (Co concentration in metal separating agent I after extraction) / (Co concentration in aqueous solution I before extraction)

[0233] It should be noted that in ICP-OES, cases below the detection limit are indicated as "below the detection limit" in Table 1.

[0234] [Co-Ni separation capability]

[0235] The Co-Ni separation capability is obtained by dividing the ratio of Co concentration (g / L) to Ni concentration (g / L) in the extracted metal separating agent I (Co / Ni) by the ratio of Co concentration (g / L) to Ni concentration (g / L) in the extracted aqueous solution II (Co / Ni).

[0236] Co-Ni separation capacity = (Co / Ni concentration ratio in metal separating agent I after extraction) / (Co / Ni concentration ratio in aqueous solution II after extraction)

[0237] It should be noted that since the Co-Ni separation capacity was not calculated for Examples 2 and 5, it is represented as "-" in Table 1.

[0238] [Table 1]

[0239]

[0240] As shown in Table 1, the Co extraction rates of Examples 1-9, which used the quaternary ammonium salt (component A) and ammonium thiocyanate (component B) represented by formula (I), were all above 94%. Furthermore, Examples 1, 3-4, 6-9 exhibited superior Co-Ni separation capabilities compared to Comparative Examples 1-2, which did not use component B. Additionally, the Co-Ni separation capabilities of Examples 1, 3, and 4 were superior to those of Example 9. Thus, it can be confirmed that the metal separating agents of Examples 1-9 possess high separation and recovery performance. In particular, Example 1, which used triesterified methylammonium methyl sulfate as component A, achieved a Co extraction rate of over 99% and a separation capacity of over 1300, indicating even higher separation and recovery performance.

[0241] Industrial availability

[0242] The metal separating agent disclosed herein can be used as a recovery agent for rare and precious metals.

Claims

1. A metal separation method which is a metal separation method for separating, or separating and recovering, a metal from an aqueous solution containing the metal, the metal separation method comprising a step of separating the metal from an aqueous phase to an organic phase by bringing an aqueous solution containing the metal into contact with a metal separation agent containing a salt represented by the following formula (I) as component A, thiocyanic acid as component B, and a water-insoluble organic solvent as component C, In formula (I), R 1 is a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having a carbon number of 1 or more and 4 or less, optionally having a hydroxyl group, R 4 is an alkyl group having a carbon number of 1 or more and 6 or less, or a hydrogen atom, and X - is an anion.

2. The metal separation method according to claim 1, wherein The component A is a compound in which at least one of R 1 , R 2 , and R 3 has an ester group having a carbon number of 6 or more and 22 or less.

3. The metal separation method according to claim 1 or 2, wherein Component A is a compound in which at least two of R 1 , R 2 , and R 3 have an ester group having a carbon number of 6 or more and 22 or less.

4. The metal separation method according to any one of claims 1 to 3, wherein Component A is R in formula (I) 1 , R 2 and R 3 a compound having an ester group with a carbon number of 6 or more and 22 or less.

5. The metal separation method according to any one of claims 1 to 4, wherein the mass ratio A / B of component A to component B in the metal separation agent is 0.01 or greater and 50 or less.

6. The metal separation method according to any one of claims 1 to 5, wherein the content of component A in the metal separation agent is 1 mass% or greater and 50 mass% or less.

7. The metal separation method according to any one of claims 1 to 6, wherein the content of component B in the metal separation agent is 0.5 mass% or greater and 10 mass% or less.

8. The metal separation method according to any one of claims 1 to 7, which is a metal separation method for separating, or separating and recovering, cobalt.

9. The metal separation method according to any one of claims 1 to 8, which is a metal separation method for separating, or separating and recovering, cobalt from an aqueous solution containing cobalt and nickel.

10. A metal separation agent kit for separating, or separating and recovering, a metal from an aqueous solution containing the metal, the metal separation agent kit containing a first agent containing a salt represented by the following formula (I) as component A and a second agent containing thiocyanic acid as component B; In formula (I), R 1 is a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having a carbon number of 1 or more and 4 or less, optionally having a hydroxyl group, R 4 is an alkyl group having a carbon number of 1 or more and 6 or less, or a hydrogen atom, X - is an anion.

11. The metal separation agent kit according to claim 10, which is a metal separation agent kit for separating, or separating and recovering, cobalt.

12. The metal separation agent kit according to claim 10 or 11, which is a metal separation agent kit for separating, or separating and recovering, cobalt from an aqueous solution containing cobalt and nickel.

13. A metal recovery method which is a metal recovery method for separating and recovering a metal from an aqueous solution containing the metal, the metal recovery method comprising: a step of separating the metal from an aqueous phase to an organic phase by bringing an aqueous solution containing the metal into contact with a reagent prepared by combining the metal separation agent kit according to any one of claims 10 to 12; and a step of recovering the metal from the organic phase.

14. A method for manufacturing a lithium ion battery, comprising: a step of separating a metal from an aqueous phase to an organic phase by bringing an aqueous solution containing the metal into contact with a reagent prepared by combining the metal separation agent kit according to any one of claims 10 to 12; a step of recovering the metal from the organic phase; and a step of manufacturing a battery using the metal recovered in the step.

15. A metal separation agent for separating or separating and recovering a metal from an aqueous solution containing the metal, comprising a salt represented by the following formula (I) as component A and thiocyanic acid as component B. In formula (I), R 1 is a hydrocarbon group having 6 or more and 22 or less carbon number, optionally having an ester group, an amide group and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having 6 or more and 22 or less carbon number, optionally having an ester group, an amide group and / or an ether group, or an alkyl group having 1 or more and 4 or less carbon number, optionally having a hydroxyl group, R 4 is an alkyl group having 1 or more and 6 or less carbon number or a hydrogen atom, X - is an anion.

16. A metal separation agent for separating or separating and recovering a metal from an aqueous solution containing the metal, which is prepared by combining a salt represented by the following formula (I) as component A and thiocyanic acid as component B. In formula (I), R 1 is a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, R 2 and R 3 are each independently a hydrocarbon group having a carbon number of 6 or more and 22 or less, optionally having an ester group, an amide group, and / or an ether group, or an alkyl group having a carbon number of 1 or more and 4 or less, optionally having a hydroxyl group, R 4 is an alkyl group having a carbon number of 1 or more and 6 or less, or a hydrogen atom, X - is an anion.

17. The metal separation agent according to claim 15 or 16, wherein Component A is a compound in which at least one of R 1 , R 2 , and R 3 has an ester group having a carbon number of 6 or more and 22 or less.

18. The metal separation agent according to any one of claims 15 to 17, wherein the mass ratio A / B of component A to component B is 0.01 or more and 50 or less.

19. The metal separation agent according to any one of claims 15 to 18, which is prepared by combining component A, a thiocyanate salt as component B and a water-insoluble organic solvent as component C.

20. The metal separation agent according to any one of claims 15 to 19, wherein the content of component A is 1 mass% or more and 50 mass% or less.

21. The metal separation agent according to any one of claims 15 to 20, wherein the content of component B is 0.5 mass% or more and 10 mass% or less.

22. The metal separation agent according to any one of claims 15 to 21, which is a metal separation agent for separating or separating and recovering cobalt.

23. The metal separation agent according to any one of claims 15 to 22, which is a metal separation agent for separating or separating and recovering cobalt from an aqueous solution containing cobalt and nickel.

24. A metal separation method for separating a metal from an aqueous solution containing the metal, the metal separation method comprising a step of separating the metal from an aqueous phase to an organic phase by bringing the aqueous solution containing the metal into contact with the metal separation agent according to any one of claims 15 to 23.

25. A metal recovery method for separating and recovering a metal from an aqueous solution containing the metal, the metal recovery method comprising: a step of separating the metal from an aqueous phase to an organic phase by bringing the aqueous solution containing the metal into contact with the metal separation agent according to any one of claims 15 to 23; and a step of recovering the metal from the organic phase. ​

Images