Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
  • C22B3/40—Mixtures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/04—Solvent extraction of solutions which are liquid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/03—Monoamines
  • C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/09—Diamines
  • C07C211/10—Diaminoethanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
  • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
  • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C335/02—Thiourea
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/126—Acids containing more than four carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/54—Reclaiming serviceable parts of waste accumulators

Definitions

• the present invention relates to a method for separating and recovering metal ions and a two-phase separated fluid.
• a wet extraction method (solvent extraction method) is used as a method for recycling metals from waste.
• an organic phase containing a metal extractant is brought into contact with an aqueous solution (aqueous phase) containing metal element ions, mixed, and allowed to stand to separate the two phases. Elemental ions can be transferred (extracted) to the organic phase. This organic phase can be taken out, the ions of the metal elements are back-extracted, and the ions can be purified as necessary to be recycled as metals.
• LiB lithium-ion batteries
• Patent Document 1 discloses that "a valuable metal, cobalt and a method for recovering at least cobalt out of nickel, comprising: a first extraction step for recovering Co, in which cobalt ions are extracted by solvent extraction from the acidic solution and back-extracted; and a first extraction step for recovering Co.
• the first extraction step for recovering Co includes cobalt in the acidic solution Recovery of valuable metals comprising a solvent extraction process for extracting ions into a solvent, a scrubbing process for scrubbing said solvent from which cobalt ions have been extracted, and a back extraction process for back extracting cobalt ions in said solvent after scrubbing into a solution. method is proposed.
• Patent Document 2 describes "A method for producing cobalt sulfate for batteries from nickel-containing electrolytic cobalt obtained by electrolysis, comprising a dissolving step of dissolving the electrolytic cobalt with an acid, and a dissolving step.
• the pH is adjusted by adding ammonia ions to the cobalt solution during, before or after contacting the cobalt solution with the extractant, and the cobalt ions are extracted and back-extracted.
• a crystallization step for obtaining cobalt sulfate by crystallizing cobalt ions in the post-extraction liquid after the extraction step.
• the method described in WO 2005/030003 uses the extractant alone or ammonia ions as a masking agent for nickel ions in the extraction step for Co recovery, and in addition, as described above, cobalt This is a method of recovering ions. Therefore, from a productive point of view, a simpler recovery method is required.
• the method described in Patent Document 2 is a method of extracting cobalt ions by using both ammonium ions as a masking agent for nickel ions and an extractant, but the nickel content is usually about 100 to 1000 mass ppm. It is a method of recovering cobalt using relatively little electrolytic cobalt, and its scope of application is limited.
• the method described in any of the patent documents is a method for recovering cobalt and nickel, and when other metals coexist, it cannot be applied to a method for recovering other metals, and is limited to these metals. It is desired to establish a collection method that does not
• the present invention provides ions of metal elements belonging to groups 8 to 12 in the periodic table of the elements from two or more kinds of metal ions including ions of metal elements belonging to groups 3 to 16 in the periodic table of the elements. It is an object of the present invention to provide a method for separating and recovering metal ions and a two-phase separation fluid that can separate and recover metal ions with high separation performance (purity) even by a simple method.
• the present inventors have found that in a wet extraction method for separating and recovering specific metal ions from two or more metal ions including ions of metal elements belonging to Groups 3 to 16, water containing two or more metal ions
• the phase contains an organic compound (B) having a coordinating functional group that coordinates to at least one of two or more metal ions, and is brought into contact with the oil phase (organic phase) containing the extractant (C). It was found that by a simple mixing operation, the metal ions in which the extractant (C) is coordinated with the ions of the metal elements belonging to Groups 8 to 12 can be selectively transferred to the oil phase and extracted.
• the present invention has been completed through further studies based on these findings.
• R 1 represents an alkyl group
• R 2 and R 3 represent an organic group, and may be the same or different.
• X represents a carboxy group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group or an oxime group.
• Y represents a phosphinic acid group, phosphonic acid group, phosphoric acid group, sulfonic acid group or oxime group.
• ⁇ 4> The separation and recovery method according to any one of ⁇ 1> to ⁇ 3>, wherein the organic compound (B) is a chelating agent.
• ⁇ 5> The separation and recovery method according to any one of ⁇ 1> to ⁇ 4>, wherein the organic compound (B) contains at least one element of N, O, S and P in its molecular structure.
• ⁇ 6> The separation and recovery method according to any one of ⁇ 1> to ⁇ 5>, wherein the organic compound (B) is represented by the following formula (III).
• L 1 represents a divalent organic group
• L 2 represents a single bond or a divalent organic group
• A represents a hydroxy group, amino group, carboxy group, sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphonic acid, cyano group, carbamoyl group or thiol group, and two A's may be different.
• B represents a monovalent organic group or a hydrogen atom, and when a plurality of B's are included, they may be different from each other.
• n is an integer of 0-8.
• ⁇ 7> The separation and recovery method according to any one of ⁇ 1> to ⁇ 6>, wherein the two or more metal ions (A) contain at least one transition metal element.
• the metal ions to be transferred to the oil phase are ions of two metal elements belonging to groups different from each other among ions of metal elements belonging to groups 8 to 11 in the periodic table of the elements ⁇ 1>.
• ⁇ 9> The separation and recovery method according to any one of ⁇ 1> to ⁇ 8>, wherein the two or more kinds of metal ions (A) are recovered metals from waste batteries.
• the aqueous phase containing the organic compound (B) having a coordinating functional group and the oil phase containing the extractant (C) are in contact with each other and are phase-separated from each other,
• fluid ⁇ 11>
• the extractant (C) is represented by the following formula (I) or formula (II).
• R 1 represents an alkyl group
• R 2 and R 3 represent an organic group, and may be the same or different.
• X represents a carboxy group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphonic acid group or an oxime group.
• Y represents a phosphinic acid group, phosphonic acid group, phosphoric acid group, sulfonic acid group or oxime group.
• ⁇ 13> The two-phase separation fluid according to any one of ⁇ 10> to ⁇ 12>, wherein the organic compound (B) is a chelating agent.
• ⁇ 14> The two-phase separation fluid according to any one of ⁇ 10> to ⁇ 13>, wherein the organic compound (B) contains at least one element of N, O, S and P in its molecular structure.
• ⁇ 15> The two-phase separation fluid according to any one of ⁇ 10> to ⁇ 14>, wherein the organic compound (B) is represented by the following formula (III).
• L 1 represents a divalent organic group
• L 2 represents a single bond or a divalent organic group
• A represents a hydroxy group, amino group, carboxy group, sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphonic acid, cyano group, carbamoyl group or thiol group, and two A's may be different.
• B represents a monovalent organic group or a hydrogen atom, and when a plurality of B's are included, they may be different from each other.
• n is an integer of 0-8.
• the metal ions present in the oil phase are ions of two metal elements belonging to groups different from each other among ions of metal elements belonging to groups 8 to 11 in the periodic table of the elements ⁇ 10>.
• the present invention provides ions of metal elements belonging to groups 8 to 12 in the periodic table of the elements from two or more kinds of metal ions including ions of metal elements belonging to groups 3 to 16 in the periodic table of the elements. It is possible to provide a method for separating and recovering metal ions and a two-phase separation fluid that can separate and recover metal ions with high separation performance (purity) even by a simple method.
• a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
• the upper limit and lower limit forming the numerical range are described before and after "-" as a specific numerical range. It is not limited to a specific combination, and can be a numerical range in which the upper limit value and the lower limit value of each numerical range are appropriately combined.
• the expression of a compound (for example, when it is called with a compound at the end) is used to mean the compound itself, its salt, and its ion.
• substituents, linking groups, etc. for which substitution or non-substitution is not specified are intended to mean that the group may have an appropriate substituent. Therefore, in the present invention, even when the YYY group is simply described, this YYY group includes not only the embodiment having no substituent but also the embodiment having a substituent. This also applies to compounds that are not specified as substituted or unsubstituted.
• Preferred substituents include, for example, groups selected from substituents Z described later.
• the respective substituents, etc. may be the same or different from each other. means that Further, even if not otherwise specified, when a plurality of substituents and the like are adjacent to each other, they may be connected to each other or condensed to form a ring.
• "ppm" indicating the content or the like is based on mass and represents "mass ppm”.
• the method for separating and recovering metal ions of the present invention uses two or more ions of metal elements belonging to Groups 3 to 16 in the periodic table of the elements.
• ions of metal elements belonging to groups 8 to 12 in the periodic table of the elements are transferred from the water phase to the oil phase, and separated from the metal ions existing (remaining) in the water phase. It is a method of recovery.
• ions of metal elements belonging to Groups 8 to 12 existing in the aqueous phase can be separated and recovered with high resolution (high purity).
• Ions of metal elements present in the aqueous phase include metal ions to which the organic compound (B) is coordinated and metal ions to which the organic compound (B) is not coordinated. considered to coexist.
• metal ions to which the organic compound (B) is coordinated
• metal ions to which the organic compound (B) is not coordinated. considered to coexist.
• the organic compound (B) coordinated to the metal ion is exchanged with the extractant (C), or the metal ion to which the organic compound (B) is not coordinated It is thought that the extractant (C) is coordinated to the organic compound (B), and the metal ions preferentially or selectively coordinated with the organic compound (B) are selectively transferred to the oil phase and extracted.
• the ease of coordination with the metal ions belonging to Groups 3 to 16, especially the metal ions belonging to Groups 8 to 12, stability, etc. are determined by the organic compound ( It can be controlled by choosing B) and extractant (C).
• ⁇ Aqueous phase> In the separation and recovery method of the present invention, two or more metal ions (A) including ions of metal elements belonging to groups 3 to 16 in the periodic table of the elements and an organic compound are added to the oil phase described later. An aqueous phase containing (B) is used.
• the two or more metal ions (A) present in the aqueous phase are two or more metal ions belonging to Groups 3 to 16, and Groups 8 to 12 to be extracted, preferably It contains at least one metal ion belonging to Groups 8 to 11.
• Such two or more metal ions (A) may contain at least one metal ion belonging to Groups 3 to 16, and may contain metal ions belonging to groups other than Groups 3 to 16.
• the metal ion (A) contains two or more metal ions belonging to groups 8 to 12, preferably metal ions belonging to groups 8 to 11.
• the number of types of metal ions is not particularly limited as long as it is 2 or more, and can be, for example, 2 to 15 types, preferably 2 to 8 types, and preferably 2 to 5 types. more preferred.
• Combinations of metal ions are not particularly limited. combinations comprising Group 9, or combinations comprising Groups 7 and 10.
• two or more kinds of metal ions belonging to each group may be used, but one kind is preferable in terms of high separation performance.
• Specific combinations of metal ions include, for example, a combination containing Co and Ni, a combination containing Fe and Zn, a combination containing Mn and Co, and a combination containing Mn and Ni.
• a combination of Fe and Zn, a combination of Co and Ni, a combination of Mn, Co and Ni, a combination of Co, Ni and Zn, a combination of Fe, Co, Ni and Zn, and in each combination further combinations containing In, and the like.
• Metal elements belonging to each group are not particularly limited, and appropriate atoms can be used. for example, As metal elements belonging to Group 3, Sc and Y are preferred. Preferred examples of metal elements belonging to Group 4 include Ti, Zr, and Hf. Preferred metal elements belonging to Group 5 include V, Nb, and Ta. As metal elements belonging to Group 6, Cr, Mo, and W are preferred. Preferred metal elements belonging to Group 7 include Mn and Tc. Fe, Ru, and Os are preferably mentioned as the metal elements belonging to Group VIII. As metal elements belonging to Group 9, Co, Rh, and Ir are preferable. Preferred metal elements belonging to Group 10 include Ni, Pd, and Pt. Cu, Ag, and Au are preferably mentioned as the metal element belonging to Group 11.
• Zn, Cd, and Hg are preferably mentioned as metal elements belonging to Group 12.
• Al, Ga, In, and Tl are preferable as the metal elements belonging to Group 13.
• Sb and Bi are preferably exemplified as the metal elements belonging to Group 15.
• the metal element belonging to Group 16 is not particularly limited, and Te is preferably mentioned.
• the metal elements belonging to each group the metal elements of the 4th period or the 5th period are preferable.
• metal ions Two or more kinds of metal ions (A) can be appropriately prepared. Mixtures of metals (ions), recovered metals from waste metals, other wastes such as recovered metals from waste batteries (LiB), and mixtures thereof can be used. Examples of metals recovered from waste LiB include those recovered by wet processing described in Patent Document 1, electrolytic cobalt described in Patent Document 2, and the like. Reference can be made, the content of which is incorporated as part of the description herein.
• Organic compound (B) is a compound having a coordinating functional group that coordinates to at least one metal ion belonging to Groups 3 to 16. This organic compound (B) exhibits water solubility and coordinates with at least one metal ion present in the aqueous phase and coexisting therewith, and inhibits the extraction agent (C) described later from coordinating. Therefore, it is considered that the organic compound (B) has a function of keeping the metal ion coordinated to the water phase without moving it to the oil phase. That is, in the present invention, as the organic compound (B), a compound having a coordinating functional group that coordinates with the metal ion that is to remain in the aqueous phase without being transferred to the oil phase is selected.
• water-soluble means the property that the organic compound (B) can be dissolved in water at the content described later.
• the organic compound (B) is not particularly limited as long as it is a compound exhibiting the above functions, and ligands having coordinating functional groups are preferred.
• the organic compound (B) may be a monodentate ligand, it is preferably a multidentate ligand (chelating agent), more preferably a didentate to hexadentate ligand, from the viewpoint of separation ability.
• the organic compound (B) preferably contains at least one element of N, O, S and P in its molecular structure, and more preferably contains the above elements in its coordinating functional group. It is more preferable to contain the above element in the coordinating functional group of .
• the number of the above elements contained in the organic compound (B) is not particularly limited, and can be, for example, 1 to 20, preferably 2 to 14, more preferably 4 to 12.
• the organic compound (B) contains a plurality of the above elements, they may be the same element or different elements.
• the coordinating functional group containing the above element is not particularly limited, and preferably includes, for example, a group that can be taken as A in formula (III) described later.
• the organic compound (B) is more preferably a compound represented by the following formula (III) in that it can achieve high separation performance together with the extractant (C) described later.
• L 1 represents a divalent organic group and L 2 represents a single bond or a divalent organic group.
• the organic group that can be taken as L 1 or L 2 is not particularly limited, and examples thereof include groups derived from aromatic compounds, aliphatic compounds, or compounds in which these are combined. Specifically, an alkylene group ( The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3), an alkenylene group (the number of carbon atoms is preferably 2 to 6, more preferably 2 to 3), an arylene group (the number of carbon atoms is 6 to 24 are preferred, and 6 to 10 are more preferred), or groups related to combinations thereof.
• the alkylene group and alkenylene group may be straight chain, branched chain or cyclic chain, preferably straight chain or branched chain, and have at least one, preferably two or more oxygen, sulfur or nitrogen atoms in the carbon chain. may contain.
• the number of groups to be combined should be two or more, preferably two or three.
• a combination of an alkylene group or an alkenylene group and an arylene group is preferable, and a combination of alkylene group-arylene group-alkylene group is more preferable.
• the organic group that can be taken as L 1 is preferably an alkylene group, more preferably a linear alkylene group, and more preferably a linear chain in which N in the formula (III) is bonded to both ends of the longest carbon chain, A 1,2-ethylene group is particularly preferred.
• the number of carbon atoms in the alkylene group that can be taken as L 1 is more preferably 1 to 3, particularly preferably 2, within the above range.
• the organic group that can be taken as L 2 is preferably an alkylene group, more preferably a linear or branched alkylene group, and a linear alkylene in which N and A in formula (III) are bonded to one end of the carbon chain is more preferred, a 1,1-straight-chain alkanediyl group is particularly preferred, and a methylene group is most preferred.
• the number of carbon atoms in the alkylene group that can be taken as L 2 is more preferably 1 to 3, particularly preferably 1, within the above range.
• L 1 and L 2 may be different from each other or the same, and two L 2 in the formula may be different from each other.
• A is a hydroxy group, an amino group, a carboxy group, a sulfonic acid group (--SO 3 H), a sulfinic acid group (--SO 2 H), a phosphate group (--OPO 3 H 2 ), a phosphonic acid group (--PO 3 H 2 ), a cyano group, a carbamoyl group or a thiol group.
• A is preferably a hydroxy group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group.
• the sulfonic acid group, sulfinic acid group, phosphoric acid group and phosphonic acid group all include groups in which at least one oxygen atom is substituted with a nitrogen atom or a sulfur atom.
• Two A's may be the same or different.
• A may be dissociated or form a salt in the aqueous phase depending on the pH.
• the salt-forming cation is not particularly limited, and examples thereof include metal cations, particularly Group 1 or Group 2 metal cations, organic cations, and the like. Examples of organic cations include, but are not limited to, ammonium cations and alkylammonium cations.
• the two -L 2 -A groups in the compound represented by formula (III) may be different, but are preferably the same.
• B represents a monovalent organic group or a hydrogen atom.
• the organic group that can be taken as B is not particularly limited, and examples thereof include a group derived from an aromatic compound, an aliphatic compound, or a combination thereof, and a -L 2 -A group.
• an alkyl group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3)
• an alkenyl group the number of carbon atoms is preferably 2 to 6, more preferably 2 to 3
• an aryl group having preferably 6 to 24 carbon atoms, more preferably 6 to 10 carbon atoms
• a group related to a combination thereof is not particularly limited, and examples thereof include a group derived from an aromatic compound, an aliphatic compound, or a combination thereof, and a -L 2 -A group.
• an alkyl group (the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3)
• the alkyl group and alkenyl group may be straight chain, branched chain or cyclic chain, preferably straight chain or branched chain.
• the number of groups to be combined should be two or more, preferably two or three.
• the -L 2 -A group that can be taken as B includes a group obtained by appropriately combining the above L 2 and A, and a group obtained by combining mutually preferred groups.
• the -L 2 -A group that can be taken as B may be different from the -L 2 -A group in formula (III), but is preferably the same.
• the plurality of B's may be the same or different.
• it is more preferable that the two -L 2 -A groups and the plurality of B's in the compound represented by formula (III) are the same group.
• n is an integer of 0 to 8, preferably an integer of 1 to 4, more preferably 1 or 2.
• the organic compound (B) may have a substituent, and examples of the substituent that may have are groups selected from substituents Z described later, however, groups not falling under A are preferable.
• Preferred mono- or poly(alkylenediamine) compounds include alkylenediamine compounds, dialkylenetriamine compounds, trialkylenetetramine compounds, tetraalkylenepentamine compounds, and pentaalkylenehexamine compounds.
• Specific examples of the organic compound (B) include those shown below in addition to those used in the examples, but the present invention is not limited thereto.
• the water that forms the aqueous phase is not particularly limited, but (ultra)pure water, ion-exchanged water, etc. can be used.
• the total content of two or more kinds of metal ions (A) in the aqueous phase is not particularly limited and is set as appropriate. ,000 to 100,000 ppm by mass, more preferably 1,000 to 50,000 ppm by mass.
• the total content of metal ions belonging to Groups 8 to 12 among the metal ions is not particularly limited and can be set as appropriate. ,000 to 60,000 ppm by mass, more preferably 1,000 to 30,000 ppm by mass.
• the total content of metal ions belonging to Groups 3 to 7 and Groups 13 to 16 is not particularly limited and can be set as appropriate. ppm, preferably 1,000 to 30,000 ppm by weight.
• the content of metal ions belonging to Group 8 among the metal ions is not particularly limited and can be set as appropriate.
• 000 mass ppm is preferred.
• the content of metal ions belonging to Group 9 among the metal ions is not particularly limited and can be set as appropriate. 000 mass ppm is preferred.
• the content of metal ions belonging to Group 10 among the metal ions is not particularly limited and can be set as appropriate. 000 mass ppm is preferred.
• the content of metal ions belonging to Group 11 among the metal ions is not particularly limited and can be set as appropriate. 000 mass ppm is preferred.
• the content of metal ions belonging to Group 12 among the metal ions is not particularly limited and can be set as appropriate. 000 mass ppm is preferred. When two or more kinds of metal ions belonging to each group are included, the content of metal ions belonging to each group is the total content.
• the content of metal ions belonging to each of Groups 8 to 12 may be larger or smaller than the content of metal ions belonging to a specific group. Since the separation and recovery method of the present invention can separate and recover metal ions with high resolution, it is not necessary to set the content of metal ions belonging to different groups to a specific ratio.
• electrolytic cobalt contains nickel at a rate of 100 to 1,000 mass ppm (0.01 to 0.1 mass%) relative to cobalt. The amount can also be set above the above ratio. This point is not limited to the combination of nickel and cobalt.
• the mass ratio of the content of metal ions belonging to another group to the content of metal ions belonging to a specific group can be, for example, 100:1 to 10,000, preferably 100:10 to 5,000, more preferably 100:50 to 1,000.
• the content of the organic compound (B) in the aqueous phase is appropriately set in consideration of the content of metal ions, the amount of coordination with metal ions, the number of coordinating functional groups, and the like. For example, it can be 10 to 10,000 parts by mass, preferably 40 to 5,000 parts by mass, with respect to 100 parts by mass of the total metal ion content.
• the content of the organic compound (B) with respect to the total content of metal ions that can be coordinated with the organic compound (B) (also referred to as the mixed amount.
• the ratio of the number of moles of the metal extractant to the total number of moles of metal ions: mol The ratio) can be, for example, 0.8 to 5.0 equivalents, preferably 1.0 to 2.0 equivalents.
• the metal ion with which the organic compound (B) can coordinate refers to a metal ion with which the organic compound (B) coordinates preferentially or selectively over other metal ions in the aqueous phase.
• the pH of the aqueous phase is not particularly limited and can be set appropriately. Considering the solubility of metal ions, the formation of complex ions, etc., it is preferably 0.1 to 10, and 0.5 to 7. is more preferable.
• the temperature of the aqueous phase is not particularly limited, and can be, for example, 10 to 60°C.
• the aqueous phase can be prepared by dissolving metal ions and organic compound (B) in water.
• it is prepared by mixing an aqueous solution in which metal ions are dissolved and an aqueous solution in which the organic compound (B) is dissolved.
• it is preferable to mix the two aqueous solutions at the following preparation temperature and pH of 0.1 to 10 for 10 minutes to 6 hours.
• an acid or an alkali can be used.
• the acid known acids can be used without particular limitation, and inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, organic phosphoric acid and organic sulfonic acid; is mentioned.
• the alkali any known alkali can be used without particular limitation, and examples thereof include inorganic alkalis and organic alkalis, with inorganic alkalis being preferred.
• examples of inorganic alkalis include metal alkalis such as hydroxides and carbonates of Group 1 or Group 2 metals, aqueous ammonia, and ammonium chloride.
• organic alkalis include organic ammonium salts and the like.
• the amount of the acid or alkali agent to be used is not particularly limited. 0.5 molar equivalent is preferred.
• Conditions for preparing the aqueous phase are not particularly limited.
• the preparation temperature can be 10-60°C.
• an oil phase (organic phase) containing an extractant (C) is used for the aqueous phase described above.
• the extractant (C) is a compound having a coordinating functional group that coordinates to metal ions belonging to Groups 8 to 12.
• This extractant (C) exhibits solubility in an organic solvent, exists in the oil phase, coordinates with metal ions present in the vicinity of the interface between the water phase and the oil phase, and transfers the metal ions to the oil phase. It is considered to indicate the function of In the present invention, the solubility in an organic solvent means the property that the extractant (C) can be dissolved in an organic solvent at the content described later.
• the extractant (C) is not particularly limited as long as it is a compound exhibiting the above functions, and ligands having coordinating functional groups are preferred.
• the extractant (C) may be a monodentate ligand or a polydentate ligand (chelating agent). In the case of polydentate ligands, di- to octadentate ligands are preferred.
• the extractant (C) is preferably an acidic extractant.
• the acidic extractant refers to a compound having an acidic functional group that dissociates hydrogen ions (H + ) in its molecular structure, and can be specifically defined by the acid dissociation constant pKa.
• the pKa of the extractant (C) is, for example, preferably 1-12, more preferably 2-8. In the present invention, pKa is a value measured by a neutralization titration method.
• the extractant (C) is more preferably a compound represented by the following formula (I) or formula (II), since it can achieve high separation performance together with the organic compound (B) described above.
• R 1 represents an alkyl group.
• the alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited.
• the number of carbon atoms in the alkyl group that can be used as R 1 is not particularly limited.
• R 2 and R 3 represent organic groups.
• Organic groups that can be used as R 2 and R 3 are not particularly limited, and examples thereof include groups derived from aromatic compounds, aliphatic compounds, or compounds in which these are combined. Specifically, alkyl groups (having preferably 1 to 20 carbon atoms, more preferably 4 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms), alkenyl groups (having preferably 1 to 20 carbon atoms and more preferably 4 to 16 carbon atoms) ), an aryl group (having preferably 6 to 24 carbon atoms, more preferably 6 to 10 carbon atoms), or a group related to a combination thereof.
• Alkyl groups and alkenyl groups may be linear, branched or cyclic.
• the number of groups to be combined should be two or more, preferably two or three.
• alkyl groups are preferred as R 2 and R 3 .
• the divalent organic groups that can be taken as R 2 and R 3 may be the same or different.
• all of R 1 to R 3 are preferably alkyl groups, one of which is a long-chain alkyl group having 4 to 16 carbon atoms, and the remaining two is more preferably a single-chain alkyl group having 1 to 3 carbon atoms.
• both R 2 and R 3 are preferably alkyl groups , more preferably long-chain alkyl groups having 4 to 12 carbon atoms. are the same alkyl groups.
• the phosphonic acid group, sulfinic acid group, phosphoric acid group and phosphonic acid group all include groups in which at least one oxygen atom is substituted with a nitrogen atom or a sulfur atom.
• the phosphinic acid group, phosphonic acid group, phosphoric acid group, and sulfonic acid group all include groups in which at least one oxygen atom is substituted with a nitrogen atom or a sulfur atom.
• X and Y may be dissociated or form a salt in the oil phase.
• the salt-forming cation is not particularly limited, and includes, for example, the metal cations and organic cations described above.
• the extractant (C) is preferably a phosphonic acid compound (a compound represented by formula (II) in which Y is a phosphonic acid group).
• the extractant (C) may have a substituent, and examples of the substituent which may be present include a group selected from the substituents Z described later, provided that groups not corresponding to the above X are preferably exemplified. .
• extractant (C) examples include those shown below in addition to those used in the examples, but the present invention is not limited to these.
• the combination of the organic compound (B) and the extractant (C) that are preferably used for the metal ions to be extracted is not unique, and depends on the coordination number of the metal ion, the metal ion and the extractant (C) or the It is appropriately determined in consideration of the complex formation constant with the compound (B), the pH at the time of mixing, the coordinating functional group of the organic compound (B), the pKa of the extractant (C), and the like.
• substituents that the organic compound (B) and the extractant (C) may have include the following substituent Z.
• substituent Z Substituent Z - alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (Preferably a cycloalkyl group having 3 to 20 carbon atoms, for example, cycloprop
• alkyl group usually means including a cycloalkyl group, but here it is separately described ), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, etc.), an aralkyl group (preferably having 7 to 23 aralkyl groups such as benzyl, phenethyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, more preferably 5 or 6 having at least one oxygen, sulfur or nitrogen atom It is a membered heterocyclic group, including aromatic heterocyclic groups and aliphatic heterocyclic groups, such as tetrahydropyran ring group, tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, and 2-imidazolyl.
• an aryl group preferably an aryl group having 6 to 26 carbon
• alkoxy groups preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.
• aryloxy groups Preferably, an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.
• a heterocyclic oxy group bonded to the above heterocyclic group
• alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, etc.
• aryloxycarbonyl group preferably aryl having 6 to 26 carbon atoms Oxycarbonyl group, e.g
• alkylsulfonyl groups preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl and ethylsulfonyl
• arylsulfonyl groups preferably arylsulfonyl groups having 6 to 22 carbon atoms, such as benzenesulfonyl
• alkylsilyl groups preferably carbon 1-20 alkylsilyl groups, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.
• arylsilyl groups preferably C6-42 arylsilyl groups, such as triphenylsilyl, etc
• R P is a hydrogen atom or a substituent (preferably a group selected from substituent Z). Further, each of the groups exemplified for the substituent Z may be further substituted with the substituent Z described above.
• the alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group, etc. may be cyclic or chain, straight chain or branched.
• organic solvent The organic solvent that forms the oil phase is not particularly limited, and any suitable organic solvent can be used. Examples thereof include alcohol solvents, ether solvents, hydrocarbon solvents (aromatic solvents, aliphatic solvents), halogen solvents and the like. Among them, hydrocarbon solvents are preferred, various solvents that are branch components of petroleum are more preferred, and hydrocarbon solvents such as aromatics, paraffins, naphthenes, kerosene, gasoline, naphtha, kerosene, and light oil are more preferred.
• the content of the extractant (C) in the oil phase is appropriately set in consideration of the content of metal ions, the amount of coordination with metal ions, the number of coordinating functional groups, and the like.
• the content in the oil phase can be 20 to 10,000 millimoles/L (mM), preferably 50 to 1,000 millimoles/L.
• the temperature of the oil phase is not particularly limited, and can be, for example, 10 to 60°C.
• the oil phase can be prepared by dissolving the extractant (C) in an organic solvent.
• the preparation conditions for the oil phase are not particularly limited, and for example, the preparation temperature can be 10 to 60°C.
• the aqueous phase and the oil phase are mixed and allowed to stand still.
• the mixing conditions and stationary conditions at this time are not particularly limited and can be set as appropriate.
• mixing can be performed using various mixing devices.
• the mixing device include a method using a magnetic stirrer (stirrer tip), a method using a mechanical stirrer, and a method using a mixer or the like.
• Stirring conditions (stirring speed, stirring time, etc.) may be any conditions under which the aqueous phase and the oil phase can be mixed (conditions under which the extractant (C) coordinates with the metal ions). ) and the extractant (C), the mixing temperature, and the mixing apparatus.
• the stirring time is not uniquely determined depending on the stirring conditions and the like, but can be, for example, 10 minutes to 24 hours.
• the standing condition may be any condition as long as the water phase and the oil phase are separated into two layers.
• the standing time can be 10 minutes to 24 hours after stopping the mixing.
• the mixing temperature and standing temperature are also not particularly limited, and can be, for example, 10 to 60°C.
• the mixing ratio of the aqueous phase and the oil phase is appropriately set according to the concentration of the metal ion, the concentration of the organic compound (B), the concentration of the extractant (C), etc. not determined definitively.
• the ratio of the oil phase to 100 mL of the aqueous phase can be 50 to 2,000 mL, and the ratio can be 80 to 1,000 mL. preferable.
• the oil phase at a ratio of 1 to 20 moles of the extractant (C) with respect to the total content (moles) of the metal ions. It is more preferable to mix the oil phase at a ratio of 1 to 10 mol of the agent (C).
• the content of the extractant (C) with respect to the total content of metal ions that can be coordinated by the extractant (C) (also referred to as the mixed amount.
• the ratio of the number of moles of the metal extractant to the total number of moles of metal ions: mol The ratio) can be, for example, 1.0 to 10.0 equivalents, preferably 1.5 to 6.0 equivalents.
• the metal ion that can be coordinated by the extractant (C) refers to a metal ion that is coordinated by the extractant (C) and extracted into the oil phase.
• the pH of the mixed system can also be adjusted.
• the pH set for a specific metal ion to be extracted is not unambiguous, and the pKa of the metal extractant, the complex formation constant between the metal extractant and the metal ion, the coordination number of the metal ion, etc. are considered. determined as appropriate.
• the pH of the mixed system can be, for example, 0.1 to 14, preferably 2 to 14, more preferably 3 to 10.
• the pH can be adjusted using the acid or alkali described above, or an aqueous solution thereof, but it is one of the preferred embodiments not to use ammonium ions.
• the above-described mixing of the water phase and the oil phase and standing after mixing are performed after adjusting the pH.
• a two-phase separated fluid in which the aqueous phase and the oil phase are phase-separated, obtained by mixing the aqueous phase and the oil phase in this way and leaving The two phases are in contact with each other and are separated into layers. Then, among the two or more kinds of metal ions described above, metal ions in which the extractant (C) is coordinated to a metal element belonging to Groups 8 to 12, preferably Groups 8 to 11, is the oil phase. and the extractant (C) is distributed to two metal ions belonging to groups different from each other among the metal ions belonging to Groups 8 to 12, preferably Groups 8 to 11. Positionally bound metal ions may also be present in the oil phase.
• the combination of metal ions to be transferred to the oil phase is a combination containing two metal ions belonging to Groups 8 to 12, preferably Groups 8 to 11, among the combinations of metal ions described above. , particularly a combination of Co and Ni.
• the metal ions to be extracted into the oil phase are not particularly limited as long as they are not all kinds contained in the aqueous phase, and may be one kind or two or more kinds, preferably one kind or two kinds.
• the concentration of one metal ion is preferably higher than the concentration of the other metal ion, e.g. It is preferably at least twice as high (the concentration of the other metal ion is 50% by mass or less with respect to the concentration of the other metal ion).
• the metal ion (A) and the organic compound (B) may exist separately, and the metal ion (A) is coordinated with the organic compound (B). may exist as
• metal ions belonging to Groups 8 to 12 and metal ions belonging to Groups 3 to 7 or Groups 13 to 16 are present in the aqueous phase, the organic compound (B) and the extraction
• metal ions belonging to Groups 8 to 12 are converted from metal ions belonging to groups other than Groups 8 to 12, and metal ions belonging to Groups 8 to 12. There is a tendency that one or more of the are selectively extracted from other metal ions.
• one of the metal ions belonging to Groups 8 to 12 belonging to any group if there are no metal ions belonging to Groups 3 to 7 or Groups 13 to 16 in the aqueous phase, one of the metal ions belonging to Groups 8 to 12 belonging to any group Alternatively, two or more metal ions are selectively extracted.
• the metal ions belonging to Groups 8 to 12 are Fe, Co, Ni, and Zn, respectively, they are selectively extracted and separated with higher resolution.
• the metal ions belonging to groups 8 and 12 are Fe and Zn, respectively, one of Fe and Zn can be selectively extracted from metal ions belonging to other groups with higher resolution. separated.
• the pH is preferably set between 0.2 and 3.5.
• metal ions belonging to Groups 8 and 12 are not present in the aqueous phase, among the above metal ions, metal ions belonging to Groups 9 and 10 are mixed with metal ions belonging to other groups, and One or more of the metal ions belonging to Groups and Group 10 tend to be selectively extracted from other metal ions.
• the metal ions belonging to Groups 9 and 10 are Co and Ni, respectively, they are selectively extracted and separated with higher resolution.
• Co and Ni when selectively extracting Co, EDTA-OH, DPTA, or EDTA is used as the organic compound (B), and phosphonic acid is used as the extractant (C) to achieve high separation. can be selectively extracted with high efficiency.
• the pH is preferably set between 3.6 and 8.5.
• ions of metal elements belonging to Groups 8 to 12 are selectively separated from two or more kinds of metal ions present in an aqueous phase with high separation ability in an oil phase. can be extracted and recovered. Moreover, even when two or more kinds of metal ions belonging to Groups 8 to 12 are extracted, one kind of metal ion can be selectively extracted at a concentration twice or more that of the other kinds of metal ions.
• Such a separation and recovery method of the present invention can also be called a method for extracting metal ions.
• the separation and recovery method of the present invention may have steps other than the above-described step of mixing the aqueous phase and the oil phase and allowing them to stand.
• a method of back-extracting (isolating) metal ions from the oil phase obtained in the step of mixing and standing the water phase and the oil phase, a step of recovering the back-extracted metal ions as a compound (salt), a reverse Examples include a step of purifying the extracted metal ions or compounds thereof, and a step of previously removing ions of metal elements belonging to Group 1 or Group 2 in the periodic table of the elements.
• a method for back-extracting (isolating) metal ions from the oil phase known methods can be applied without particular limitation.
• Example 1 ⁇ Separation and Recovery of Metal Ions>
• a 30 mL vial tube 1.5 mL of an aqueous solution of thiourea dissolved as an organic compound aqueous solution was added to 10 mL of the prepared metal ion-containing aqueous solution, and the mixture was stirred at 25° C. for 10 minutes.
• an aqueous phase containing five kinds of metal ions (A) and organic compound (B) was prepared.
• the mixing amount (unit: equivalent) of the organic compound (B) with respect to the total content of coordinating metal ions (here, Fe and Zn) is shown in Table 1, "Mixing amount" column.
• the pH of the aqueous phase was 4.1.
• 12 mL of TEHA solution was added as an extractant solution to this aqueous phase, and the mixture was stirred at 25° C. for 30 minutes with a stirrer tip.
• the mixing amount (unit: equivalent) of the extractant (C) with respect to the total content of coordinating metal ions (here, Fe and Zn) is shown in Table 1, "Mixing amount” column.
• 10M sodium hydroxide aqueous solution or 10M hydrochloric acid is added to adjust the pH of the mixed solution to the value shown in the "pH at mixing" column in Table 1, further stirred at 25 ° C. for 30 minutes, and then at the same temperature for 1 hour. left undisturbed. Separation into two layers, an organic phase (oil phase) and an aqueous phase, was confirmed, and the aqueous phase was taken out by liquid separation to separate and recover metal ions.
• Example 2 In Example 1, the metal ion-containing aqueous solution, the extractant solution, and the organic compound aqueous solution were changed to the combinations shown in Table 1, and the mixed amount of the organic compound (B) and the extractant (C) was changed to each "mixed amount" in Table 1. column, and the pH at the time of mixing the aqueous phase and the oil phase was set to the value shown in the "pH at mixing" column in Table 1, and mixed and left to stand. In the same manner, separation and recovery of metal ions in Examples 2 to 14 were carried out.
• the "coordinable metal ion” is as described above, but in each example, it is the metal ion shown in the "extracted metal ion” column of Table 1 (the same applies hereinafter).
• Example 15 ⁇ Separation and Recovery of Metal Ions> To 10 mL of the metal ion-containing aqueous solution containing the metal ions shown in Table 1, 1.5 mL of an organic compound aqueous solution in which EDTA was dissolved was added to a 30-mL vial tube and stirred at 25° C. for 10 minutes. Thus, an aqueous phase containing two kinds of metal ions (A) and an organic compound (B) was prepared. At this time, the mixing amount (unit: equivalent) of the organic compound (B) with respect to the total content of coordinating metal ions (here, Co and Ni) is shown in Table 1 in the "mixing amount" column. The pH of the aqueous phase was 3.1.
• Comparative Examples 1 and 2 In Example 1, 1.5 mL of ultrapure water was added instead of the organic compound aqueous solution, and the combination of the metal ion-containing aqueous solution and the extractant solution was changed to the combination shown in Table 1, and the pH when the aqueous phase and the oil phase were mixed. The separation and recovery of metal ions in Comparative Examples 1 and 2 were carried out in the same manner as in Example 1, except that the mixture was set to the value shown in the "pH during mixing" column in Table 1 and mixed and allowed to stand.
• the concentration of one of the extracted Zn and Fe is about 3.7 times or more the concentration of the other, and the separation ability between Fe and Zn is also high.
• Examples 5, 7 and 8 can separate and recover only Zn or only Fe from other metal ions with high resolution.
• Examples 6 and 9 to 14 in which the aqueous phase containing two kinds of metal ions, Co and Ni, are separated and recovered using a combination of the extractant (C) and the organic compound (B), the extracted Co Alternatively, the concentration of one of Ni is approximately 2.9 times or more the concentration of the other, and one of Co and Ni can be separated and recovered from the other of Co and Ni with high separation performance. From the above results, it can be concluded that by back-extracting the oil phase obtained in each of the above examples using a conventional method and conditions, the metal ions extracted into the oil phase with high resolution can be separated without impairing the high resolution. I know it can be recovered.

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