WO2024203328A1 - 金属抽出剤、及びこの金属抽出剤を用いた金属イオンの分離回収方法、並びに、化合物 - Google Patents

金属抽出剤、及びこの金属抽出剤を用いた金属イオンの分離回収方法、並びに、化合物 Download PDF

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WO2024203328A1
WO2024203328A1 PCT/JP2024/009753 JP2024009753W WO2024203328A1 WO 2024203328 A1 WO2024203328 A1 WO 2024203328A1 JP 2024009753 W JP2024009753 W JP 2024009753W WO 2024203328 A1 WO2024203328 A1 WO 2024203328A1
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group
metal
metal ions
groups
substituent
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French (fr)
Japanese (ja)
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陽 串田
宏顕 望月
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Fujifilm Corp
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Fujifilm Corp
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Priority to EP24779457.1A priority Critical patent/EP4692383A1/en
Priority to CN202480022670.5A priority patent/CN120958151A/zh
Priority to JP2025510432A priority patent/JPWO2024203328A1/ja
Priority to KR1020257031461A priority patent/KR20250152647A/ko
Publication of WO2024203328A1 publication Critical patent/WO2024203328A1/ja
Priority to US19/333,270 priority patent/US20260015371A1/en
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    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • 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
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • 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)]
    • 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
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
    • 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
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C07F9/4028—Esters of poly(thio)phosphonic acids containing no further substituents than -PO3H2 groups in free or esterified form
    • 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
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a metal extractant that extracts metal ions present in an aqueous phase into an oil phase, a method for separating and recovering metal ions using this metal extractant, and a compound.
  • Valuable metals such as precious metals and rare earth metals are essential elements for precision instruments, and a stable supply and securing of high-purity valuable metals is a major challenge. These valuable metals are usually mined as a mixture with multiple metals, so it is necessary to isolate and refine (highly purify) the desired valuable metal from the mined mixture. In addition, since there is a limit to the amount of valuable metals that can be mined from mines, technology to recover valuable metals from industrial waste without relying on mining is also considered important. In particular, with the spread of electric vehicles, the amount of discarded lithium-ion batteries (LiBs) is increasing year by year.
  • LiBs lithium-ion batteries
  • LiBs use positive electrode active materials containing metal elements such as cobalt and nickel, and the demand for cobalt and nickel is expected to increase significantly. In order to meet the increasing demand for valuable metals associated with this trend, it is desirable not only to increase the amount of mining, but also to establish metal recycling technology from discarded LiBs.
  • wet extraction is used as a method for isolating and refining the desired valuable metals from mining mixtures, and as a method for recycling metals from waste materials.
  • an organic phase containing a metal extractant is brought into contact with an aqueous solution (aqueous phase) containing ions of metal elements (simply called metal ions), mixed, and allowed to stand to separate the two phases, causing the metal ions coordinated with the metal extractant to migrate (be extracted) into the organic phase.
  • This organic phase is then removed, and the metal ions are back-extracted and purified as necessary, making it possible to isolate and purify the desired metal, and to recycle it as a (high-purity) metal.
  • Patent Document 1 describes a metal extractant used in such wet extraction methods that is a phenylphosphonic acid monoester of a hydrocarbon group with 4 to 6 branched carbon atoms and a total of 16 to 20 carbon atoms.
  • Patent Document 2 describes a metal extractant used in wet extraction methods in which an organic phase containing a metal extractant is contacted with an aqueous phase in multiple stages, the metal extractant being an alkylphosphonic acid monoalkyl ester in which both alkyl groups have 8 to 10 carbon atoms (excluding cases in which both alkyl groups are the same alkyl group with 8 carbon atoms).
  • Patent Document 2 requires contacting the aqueous phase and the oil phase in multiple stages, which causes productivity problems. Therefore, there is also a need for a metal extractant that can increase the phase separation speed to quickly separate the aqueous phase and the oil phase into liquid phases after contacting and mixing the aqueous phase and the oil phase.
  • Patent Documents 1 and 2 make no consideration whatsoever about further improving the selectivity for metal ions or improving the phase separation rate.
  • the present invention aims to provide a metal extractant that can extract specific metal ions present in the aqueous phase into the oil phase with high selectivity while rapidly separating the aqueous phase containing the metal ions from the oil phase, and a method for separating and recovering metal ions using this metal extractant.
  • Another objective of the present invention is to provide a compound that can be used as a metal extractant that exhibits the above-mentioned excellent properties.
  • the present invention has been completed through further investigation based on these findings.
  • a metal extractant for extracting metal ions present in an aqueous phase into an oil phase comprising: A metal extractant represented by the following formula (I):
  • R 1 and R 2 each represent a substituent having a molecular weight of 100 or more, and at least one of the substituents has a molecular weight of 160 or more.
  • YP represents an oxygen atom or a sulfur atom.
  • Z represents a hydroxy group, a sulfanyl group or a hydroxyaryl group.
  • L represents a single bond, provided that when n is 2 or more, the L sandwiched between two adjacent P's represents a single bond or a linking group.
  • n is an integer from 1 to 6.
  • ⁇ 5> The metal extractant according to any one of ⁇ 1> to ⁇ 4>, wherein at least one of R 1 and R 2 is a substituent containing a hydrocarbon group having 3 or more branched carbon atoms, or a substituent containing a hydrocarbon group having 9 or more carbon atoms.
  • At least one of R 1 and R 2 is a substituent containing a hydrocarbon group having one or more branched carbon atoms and having 9 or more carbon atoms.
  • ⁇ 7> The metal extractant according to any one of ⁇ 1> to ⁇ 6>, wherein at least one of R 1 and R 2 is a substituent containing a ring structure.
  • ⁇ 8> The metal extractant according to any one of ⁇ 1> to ⁇ 7>, wherein the metal ion is an ion of a metal element belonging to Groups 1 to 14 of the periodic table.
  • the metal extractant according to any one of ⁇ 1> to ⁇ 8> which is used for extracting and separating two or more kinds of metal ions belonging to different groups in the periodic table.
  • a method for separating and recovering metal ions comprising mixing an aqueous phase containing a plurality of kinds of metal ions with an oil phase containing the metal extractant according to any one of ⁇ 1> to ⁇ 9>.
  • R1 and R2 each represent a substituent having a molecular weight of 100 or more, and at least one of the substituents has a molecular weight of 160 or more. At least one of R1 and R2 represents a substituent having a branched structure.
  • YP represents an oxygen atom or a sulfur atom.
  • Z represents a hydroxy group, a sulfanyl group or a hydroxyaryl group.
  • L represents a single bond, provided that when n is 2 or more, the L sandwiched between two adjacent P's represents a single bond or a linking group.
  • n is an integer from 1 to 6.
  • the present invention provides a metal extractant capable of extracting specific metal ions present in an aqueous phase into an oil phase with high selectivity while rapidly separating the aqueous phase containing the metal ions from the oil phase, and a method for separating and recovering metal ions using the metal extractant.
  • the present invention also provides a compound that can be used as a metal extractant exhibiting the above-mentioned excellent properties.
  • FIG. 1 is a 1 H-NMR chart of compound E-1 synthesized in the example.
  • any of the upper limit and lower limit can be appropriately combined to form a specific numerical range.
  • the upper limit and lower limit forming the numerical range are not limited to the specific combination described before and after " ⁇ " as a specific numerical range, and can be a numerical range obtained by appropriately combining the upper limit and lower limit of each numerical range.
  • a numerical range expressed using " ⁇ ” means a range including the numerical values described before and after " ⁇ " as the upper limit and lower limit.
  • the expression of a compound is used to mean not only the compound itself, but also its salts and ions. It also means to include derivatives that have been partially modified by introducing a substituent or the like within the scope that does not impair the effects of the present invention.
  • the substituents, linking groups, etc. hereinafter referred to as substituents, etc.
  • substituents, etc. may have an appropriate substituent. Therefore, even if the present invention is simply described as a YYY group, this YYY group includes an embodiment that has a substituent in addition to an embodiment that has no substituent.
  • substituents include, for example, a group selected from the substituents GZ described below.
  • substituents GZ a group selected from the substituents GZ described below.
  • a "metal element belonging to a different group in the periodic table of elements” may be referred to as a "different group metal element", and in particular, a “different group metal element in the same period in the periodic table” may be referred to as a “different group metal element in the same period”. Furthermore, an “ion of a different group metal element” and an “ion of a different group metal element in the same period” may be referred to as a “different group metal ion” and an “different group metal ion in the same period”, respectively.
  • ppm indicating the content and the like is based on mass and represents “mass ppm” unless otherwise specified.
  • the metal extractant of the present invention contains a compound represented by formula (I) described later, and may contain other components as appropriate within the scope of not impairing the action and effect of the present invention.
  • the metal extractant of the present invention may contain other compounds (other metal extractants) that function as extractants for metal ions other than the compound represented by formula (I), but since the compound represented by formula (I) exhibits the above-mentioned excellent properties as a metal extractant as described later, it is preferable to contain the compound represented by formula (I) alone.
  • the metal extractant of the present invention containing the compound represented by formula (I) alone includes an embodiment containing only the compound represented by formula (I) and an embodiment containing the other metal extractant in a content of 10 mass% or less with respect to the total of the compound represented by formula (I).
  • the form of the metal extractant of the present invention and the compound represented by formula (I) are not particularly limited, and may be a solid such as powder or granules, or a liquid (solution) dissolved in an organic solvent described below.
  • the metal extractant of the present invention exhibits the function of extracting metal ions present in the aqueous phase into the oil phase, and can be particularly suitably used in wet extraction methods.
  • a specific metal ion present in the aqueous phase can be extracted into the oil phase with high selectivity, preferably with a high recovery rate (high extraction rate).
  • this metal extractant can extract a specific metal ion from a plurality of metal ions present in the aqueous phase into the oil phase with high selectivity, preferably with a high recovery rate.
  • the metal ions that can be extracted into the oil phase are ideally one specific metal ion, but may be two or more metal ions.
  • one of the metal ions can be extracted (separated and recovered) into the oil phase with high selectivity and preferably with a high recovery rate relative to the other metal ions (including those extracted into the oil phase).
  • two or more different metal ions for example, two or more metal ions belonging to Groups 1 to 14 of the periodic table, preferably two or more different metal ions, particularly preferably cobalt ions and nickel ions, which are different metal ions of the same period, can be extracted into the oil phase with high selectivity and preferably with a high recovery rate.
  • the present invention which uses a compound represented by formula (I) as a metal extractant, it is possible to extract both metal ions belonging to the same period and different groups, which have similar physical and chemical behaviors, particularly metal ions belonging to group 9 (particularly cobalt ions) and metal ions belonging to group 10 (particularly nickel ions), which are required due to the rapid spread of lithium ion batteries in recent years, while recovering one of the metal ions with high selectivity and preferably with a high recovery rate. Therefore, the present invention can greatly contribute to the further spread of electric vehicles and the construction of a sustainable society.
  • being able to extract metal ions with high selectivity means being able to extract only one specific metal ion from among multiple types of metal ions present in the aqueous phase.
  • being able to extract metal ions with high selectivity means that, among the two or more types of metal ions extracted, the amount of the specific metal ion (usually one type) to be extracted can be extracted and separated from the other metal ions at a ratio (separation ability, selectivity ratio) of 3.0 or more relative to the total amount of the other metal ions extracted [(amount of specific metal ion extracted)/(total amount of other metal ions extracted)].
  • the above ratio (selectivity ratio) is preferably 4.0 or more, more preferably 5.0 or more, and even more preferably 6.0 or more. There is no particular limit to the upper limit, but it can be set to 50, for example.
  • the term "high recovery rate of metal ions” means that, for the metal ions extracted in the maximum amount (specific metal ions to be extracted) among the extracted metal ions, the amount of the metal ions extracted into the oil phase can be extracted at a ratio of 60% or more to the content of the metal ions in the aqueous phase (before extraction) [(amount of metal ions extracted into the oil phase)/(content of the metal ions in the aqueous phase)].
  • the above ratio (recovery rate) is preferably 80% or more, and more preferably 90% or more.
  • the upper limit is the total amount (100%) of the metal ions present in the aqueous phase, and for example, it is preferably 99% or less, and can also be 95% or less or 90% or less.
  • the specific amount of extraction depends on the content of the metal ions present in the aqueous phase, but can be, for example, 30,000 ppm by mass or less, and preferably 20,000 ppm by mass or less.
  • the time required for rapid liquid phase separation (phase splitting) after contact and mixing of the aqueous phase and the oil phase is not uniquely determined by the content of metal ions or metal extractant, the liquid volumes of the aqueous phase and the oil layer, the mixing conditions, etc.
  • Rapid liquid phase separation of the aqueous phase and the oil phase means, for example, that the aqueous phase and the oil phase separate to a state where the phase interface can be visually confirmed within 5 minutes (at the time when 5 minutes have passed) after mixing of the aqueous phase and the oil phase is stopped under the conditions in the examples described below.
  • the time required for liquid phase separation of the aqueous phase and the oil phase to be completed after contact and mixing of the aqueous phase and the oil phase is referred to as the phase separation time
  • the speed at which the aqueous phase and the oil phase separate after contact and mixing of the aqueous phase and the oil phase is referred to as the phase separation speed.
  • the metal extractant of the present invention comprises a compound having a chemical structure represented by the following formula (I) (sometimes referred to as the compound of the present invention). As described above, this compound exhibits excellent properties as a metal extractant.
  • R 1 and R 2 each represent a substituent having a molecular weight of 100 or more, at least one of which has a molecular weight of 160 or more. That is, R 1 and R 2 each represent a substituent having a molecular weight of 100 or more, at least one of which has a molecular weight of 160 or more.
  • Compounds represented by formula (I) having the above basic structure include a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, and further compounds having 1 to 6 acid groups in which at least one oxygen atom of these acid groups is replaced with a sulfur atom.
  • compounds in which n is 1 in formula (I) include phosphoric acid compounds such as phosphoric acid ester compounds (R 1 O-P( ⁇ O)(Z)-OR 2 ), phosphonic acid ester compounds (R 1 -P( ⁇ O)(Z)-OR 2 , R 1 O-P( ⁇ O)(Z)-R 2 ) and phosphinic acid compounds (R 1 -P( ⁇ O)(Z)-R 2 ), and thiophosphoric acid compounds in which at least one oxygen atom in each of the above phosphoric acid compounds is converted to a sulfur atom.
  • "Z" in each of the above compounds has the same meaning as Z in formula (I).
  • the compound represented by formula (I) in which n is 1 is preferably a phosphoric acid compound, more preferably a phosphoric acid ester compound or a phosphonic acid ester compound, even more preferably a phosphonic acid ester compound, and particularly preferably a phosphonic acid monoester compound, in that it can achieve both the selectivity of the metal extractant and the phase separation rate at a higher level.
  • the substituents that can be taken as R 1 and R 2 are all those having a molecular weight of 100 or more.
  • the molecular weight of at least one of the substituents that can be taken as R 1 and R 2 is set to 160 or more.
  • the substituents that can be taken as R 1 and the substituents that can be taken as R 2 are both 100 or more in molecular weight, and at least one of them has a molecular weight of 160 or more, so that the compound represented by the above formula (I) becomes a metal extractant that shows high selectivity even when the phase separation rate is fast.
  • the molecular weight of the substituents that can be R1 and R2 is preferably 120 or more, more preferably 160 or more, and even more preferably 200 or more, in terms of the selectivity and phase separation rate of the metal extractant.
  • the upper limit of the molecular weight of the substituent is not particularly limited and can be appropriately determined, and can be, for example, 400 or less, and preferably 350 or less. In order to achieve a high level of compatibility between the selectivity and phase separation rate of the metal extractant, it is preferable that the molecular weight of both substituents that can be taken as R 1 and R 2 is 160 or more.
  • the substituents having a molecular weight of 160 or more preferably have a molecular weight of 200 or more, more preferably have a molecular weight of 220 or more, and even more preferably have a molecular weight of 240 or more, in order to achieve a high level of compatibility between the selectivity and phase separation rate of the metal extractant.
  • the upper limit of the molecular weight of the substituent having a molecular weight of 160 or more is not particularly limited, and can be the above upper limit of the molecular weight of the substituents that can be taken as R 1 and R 2.
  • the molecular weight of a substituent refers to the total atomic weight of the atoms constituting the substituent, provided that when the substituent has a polymer chain in its structure, the number average molecular weight is calculated as the standard polystyrene equivalent by gel permeation chromatography (GPC) as described below.
  • the total number of carbon atoms constituting each of the substituents that can be taken as R 1 and R 2 is not particularly limited and can be appropriately determined as long as it satisfies the above-mentioned molecular weight.
  • the total number of carbon atoms (hereinafter simply referred to as the number of carbon atoms) of the substituents that can be taken as R 1 and R 2 is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and particularly preferably 14 or more, in terms of the selectivity and phase separation rate of the metal extractant.
  • the upper limit of the number of carbon atoms is not particularly limited and can be appropriately determined, for example, it can be 30 or less, and preferably 24 or less.
  • the number of carbon atoms of the substituents having a molecular weight of 160 or more among the substituents that can be taken as R1 and R2 is preferably 12 or more, more preferably 14 or more, even more preferably 15 or more, and particularly preferably 16 or more, in order to achieve a higher level of compatibility between the selectivity and phase separation rate of the metal extractant.
  • the upper limit of the number of carbon atoms in the substituents having a molecular weight of 160 or more is not particularly limited, and can be set to the above-mentioned upper limit of the number of carbon atoms of the substituents that can be taken as R1 and R2 .
  • R 1 and R 2 are not particularly limited, and include various substituents and groups that combine substituents.
  • the above-mentioned "various substituents” refers to a substituent that is R 1 and R 2 alone
  • the above-mentioned “group that combines substituents” refers to a substituent that is composed of a combination of multiple substituents.
  • a composite substituent is formed by combining multiple single substituents by removing hydrogen atoms from a required number of single substituents among the single substituents that constitute it.
  • the position at which a specific substituent is substituted with another substituent is not particularly limited and can be appropriately determined.
  • the substitution position may be any of the 2-position to 4-position with respect to the bonding position of the phenyl group.
  • the substituents that can be taken as R1 and R2 are interpreted as single substituents whenever possible.
  • a 2-ethylhexyl group can be interpreted as a composite substituent in which an ethyl group replaces a hexyl group, but is interpreted as a branched alkyl group.
  • a hexyloxy group can be interpreted as a composite substituent combining a hexyl group and an oxygen atom, but is interpreted as an alkoxy group.
  • the substituents (including single and composite substituents) that can be taken as R 1 and R 2 may be a hydrocarbon group composed of only carbon atoms and hydrogen atoms, or may be a heteroatom-containing substituent containing at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. It is preferable that at least one of the substituents that can be taken as R 1 and R 2 is a heteroatom-containing substituent.
  • the heteroatom-containing substituent preferably contains an oxygen atom or a sulfur atom as a heteroatom, and preferably contains an oxygen atom.
  • the number of heteroatoms contained in the heteroatom-containing substituent is not particularly limited, and can be 1 to 4, and is preferably 1.
  • the heteroatom may be present in any of the substituents, for example, inside or at the end of the atomic chain that constitutes the substituent. In the present invention, it is preferable that one of the heteroatoms is present at the end of the atomic chain that constitutes the substituent and is bonded to P in the above formula (I).
  • the heteroatom-containing substituent is not particularly limited, and examples thereof include single substituents such as alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthio groups, arylthio groups, and heterocyclic thio groups, as well as composite substituents such as groups combining these single substituents with an aryl group (substituents containing a ring structure), as described below.
  • the single substituent that can be taken as R 1 and R 2 is not particularly limited, and includes appropriate substituents, for example, a group selected from the substituent GZ described later (however, the carbon number and molecular weight are not adopted from those of the substituent GZ, but are as described above).
  • alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon groups such as aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, amino groups, etc. are preferred, and in terms of the selectivity and phase separation rate of the metal extractant, alkyl groups, alkoxy groups, and alkylthio groups are more preferred, and alkyl groups or alkoxy groups are even more preferred.
  • the alkyl group, alkenyl group, and alkynyl group that can be used as a single substituent may be any of linear, branched, and cyclic chains, but branched chains are more preferable in that they can achieve a higher level of both selectivity and phase separation rate of the metal extractant.
  • the molecular weight and number of carbon atoms of the alkyl group, alkenyl group, and alkynyl group all satisfy the above-mentioned ranges.
  • the aryl group, heterocyclic group, aryloxy group, heterocyclic oxy group, arylthio group, heterocyclic thio group and amino group which can be used as a single substituent are the same as the corresponding groups in the substituent GZ described later.
  • the alkyl groups constituting the alkoxy group and alkylthio group which may be the sole substituent are the same as the alkyl groups which may be the sole substituent.
  • the composite substituents that can be taken as R 1 and R 2 are not particularly limited, and include (single) substituents, for example, groups in which a plurality of substituents selected from the substituents G and Z are combined.
  • the number of single substituents constituting the composite substituent is not particularly limited, and can be 2 to 6, and is preferably 2 to 4.
  • composite substituents include groups in which hydrocarbon groups are combined (groups in which an alkyl group, an alkenyl group, or an alkynyl group is combined with an aryl group), groups in which an alkoxy group or an alkylthio group is combined with an aryl group, and groups in which an alkyl group, an alkenyl group, or an alkynyl group is combined with an amino group.
  • groups in which hydrocarbon groups are combined groups in which an alkyl group, an alkenyl group, or an alkynyl group is combined with an aryl group
  • groups in which an alkoxy group or an alkylthio group is combined with an aryl group
  • groups in which an alkyl group, an alkenyl group, or an alkynyl group is combined with an amino group.
  • the composite substituent "alkyl group-oxygen atom-phenyl group-" in compounds E-4 and E-5 synthesized in the examples is interpreted as a group in which an alkoxy group and a phenyl group are combined, not as a group in which an alkyl group and a phenoxy group are combined, and not as a group in which an alkyl group, an oxygen atom, and a phenyl group are combined.
  • the above interpretation is the same when an oxygen atom or the like bonded to an alkenyl group or an alkynyl group is contained in the composite substituent.
  • the composite substituent those containing a ring structure are preferred in that they can achieve a higher level of both the selectivity and phase separation rate of the metal extractant.
  • the ring structure contained in the composite substituent is not particularly limited, and examples include ring structures derived from cycloalkyl groups, aryl groups, heterocyclic groups, etc., and ring structures derived from aryl groups and aromatic heterocyclic groups are preferred, and in terms of the selectivity and phase separation rate of the metal extractant, ring structures derived from aryl groups are more preferred.
  • composite substituents containing a ring structure are preferred groups combining an alkyl group with an aryl group, groups combining an alkoxy group or an alkylthio group with an aryl group, etc., and alkoxyaryl groups are more preferred, with alkoxyphenyl groups being even more preferred.
  • substituents that can be taken by R1 and R2 among those mentioned above, from the viewpoint of the selectivity and phase separation rate of the metal extractant, a single substituent of an alkyl group, an alkoxy group, or an alkylthio group, or a composite substituent containing a ring structure combining an alkoxy group or an alkylthio group with an aryl group, is preferred.
  • the alkoxy group, the alkylthio group, and the composite substituent containing a ring structure are preferably substituents having a molecular weight of 160 or more in terms of the selectivity and phase separation rate of the metal extractant.
  • the combination of the substituent that can be taken as R 1 and the substituent that can be taken as R 2 is not particularly limited, and the above-mentioned substituents that can be taken as R 1 and R 2 can be appropriately combined.
  • the molecular structure of the substituent is not particularly limited, but the substituents that can be taken as R 1 and R 2 are preferably a combination containing a substituent having a branched structure (a combination in which at least one of the substituents is a substituent having a branched structure) in terms of the selectivity and phase separation rate of the metal extractant, and more preferably a combination of the substituents having a branched structure with each other, and a combination of a substituent having a branched structure and a substituent containing a ring structure (particularly a composite substituent).
  • the substituent having a branched structure is not particularly limited, but among the above, examples include hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and single or composite substituents containing hydrocarbon groups, and preferred are single substituents such as alkyl groups, alkoxy groups, and arylthio groups, or composite substituents such as a group combining an alkoxy group or an alkylthio group with an aryl group, and more preferred are alkyl groups, alkoxy groups, or groups combining an alkoxy group and an aryl group.
  • hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups
  • single or composite substituents containing hydrocarbon groups and preferred are single substituents such as alkyl groups, alkoxy groups, and arylthio groups, or composite substituents such as a group combining an alkoxy group or an alkylthio group with an aryl group, and more preferred are alkyl groups,
  • the substituent having a branched structure does not have to be a substituent having a molecular weight of 160 or more or a substituent having 12 or more carbon atoms.
  • the substituent in terms of the selectivity and phase separation rate of the metal extractant, it is preferable that the substituent have a molecular weight of 160 or more or a substituent having 12 or more carbon atoms.
  • the type of the substituent is not particularly limited, but as a combination of the substituents that can be taken as R1 and R2 , a combination of single substituents or a combination of a single substituent and a composite substituent is preferable in terms of the selectivity and phase separation rate of the metal extractant.
  • the combination of single substituents the same (type) of substituents may be combined, or different (type) of substituents may be combined. Examples of the combination of the same substituents include the combination of alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, or alkylthio groups.
  • the carbon chains of the single substituents to be combined may be the same or different, but it is preferable that they are all branched chains.
  • the number of carbon atoms of the single substituents to be combined may be the same or different.
  • a combination in which one of the substituents is an alkoxy group or an alkylthio group is preferred, and in terms of the selectivity and phase separation rate of the metal extractant, a combination of an alkyl group, an alkenyl group, or an alkynyl group with an alkoxy group or an alkylthio group is more preferred, and a combination of an alkyl group and an alkoxy group is even more preferred.
  • the carbon chain of the alkyl group, the alkenyl group, or the alkynyl group and the carbon chain of the alkyl group constituting the alkoxy group or the alkylthio group may be the same or different, but it is preferable that both are branched chains.
  • the number of carbon atoms of the alkyl group, the alkenyl group, or the alkynyl group and the number of carbon atoms of the alkyl group constituting the alkoxy group or the alkylthio group may be the same or different.
  • the alkoxy group and the alkylthio group preferably have a larger molecular weight and carbon number than the alkyl group, the alkenyl group, and the alkynyl group, in terms of being able to achieve a higher level of both the selectivity and the phase separation rate of the metal extractant, and more preferably correspond to a substituent with a molecular weight of 160 or more.
  • a combination of an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an alkylthio group with a composite substituent containing a ring structure is preferred, and a combination of an alkyl group, an alkoxy group, or an alkylthio group with an alkoxy group and an aryl group is more preferred.
  • a combination of the substituent that can be taken as R1 and the substituent that can be taken as R2 among the above-mentioned combinations, a combination of alkoxy groups, a combination of an alkyl group and an alkoxy group, and a combination of an alkoxy group and an alkoxyaryl group are particularly preferable.
  • the substituents that can be taken by R 1 and R 2 can each be appropriately selected from the above-mentioned substituents.
  • at least one of R 1 and R 2 is a substituent containing a hydrocarbon group having 3 or more branched carbon atoms, or a substituent containing a hydrocarbon group having 9 or more carbon atoms, and it is more preferable that both R 1 and R 2 are a substituent containing a hydrocarbon group having 3 or more branched carbon atoms, or a substituent containing a hydrocarbon group having 9 or more carbon atoms.
  • the substituent containing a specific group or ring structure includes a substituent consisting of only the specific group or ring structure, and a substituent consisting of the specific group or ring structure and other groups, atoms, or structures (described in detail below).
  • the substituent containing a hydrocarbon group includes a substituent consisting of only a hydrocarbon group (the hydrocarbon group itself) and a hydrocarbon oxy group consisting of this hydrocarbon group and, for example, an oxygen atom.
  • Hydrocarbon groups having three or more branched carbon atoms are not particularly limited, but typically include alkyl groups, alkenyl groups, or alkynyl groups having a branched structure, which have three or more branched carbon atoms (tertiary carbon atoms).
  • the number of branched carbon atoms present in this hydrocarbon group is not particularly limited as long as it is three or more, and can be, for example, 3 to 8. In terms of the selectivity and phase separation rate of the metal extractant, it is preferable that it is 3 to 6, and more preferably 4 to 6.
  • the molecular weight and number of carbon atoms of the hydrocarbon group having three or more branched carbon atoms are not particularly limited and are appropriately selected within the above ranges, but it is preferable that the molecular weight is 160 or more and the number of carbon atoms is 12 or more.
  • a hydrocarbon group having three or more branched carbon atoms it is preferable that it is an alkyl group having a branched structure, which has three or more branched carbon atoms, and examples thereof include 2,5,7,7-tetramethyloctane, 2-(1,3,3-trimethyl-1-butyl)-5,7,7-trimethyl-octane, etc.
  • the hydrocarbon group having 9 or more carbon atoms is not particularly limited, but among the above-mentioned hydrocarbon groups, an alkyl group, an alkenyl group, or an alkynyl group is preferable, and an alkyl group is more preferable.
  • the molecular weight of the hydrocarbon group having 9 or more carbon atoms is not particularly limited as long as it is 127 or more, but it is preferable to appropriately select it within the above range.
  • the hydrocarbon group having 9 or more carbon atoms may be linear or branched, but is preferably branched.
  • the number of branched carbon atoms is not particularly limited as long as it is 1 or more, and examples thereof include an embodiment having 1 or 2 branched carbon atoms and an embodiment having 3 or more branched carbon atoms. In an embodiment having 3 or more branched carbon atoms, the number of branched carbon atoms is preferably the same as the number of branched carbon atoms of the hydrocarbon group having 3 or more branched carbon atoms in terms of the selectivity and phase separation rate of the metal extractant.
  • hydrocarbon group having 9 or more carbon atoms an alkyl group having 9 or more carbon atoms is preferred, and a branched chain alkyl group having one or more branched carbon atoms and having 9 or more carbon atoms is more preferred.
  • linear alkyl groups having 9 or more carbon atoms include n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, and n-hexadecyl group.
  • alkyl groups having 9 or more carbon atoms and one or two branched carbon atoms include 1-ethyl-1-methylhexane, 8-methylnonane, 2-butyloctane, 2-hexyldecane, 2-ethyldecane, 2-octyldecane, 2-hexyldodecane, 2-octyldodecane, and 2-decyltetradecane.
  • alkyl groups having 9 or more carbon atoms and three or more branched carbon atoms include 2-(1,3,3-trimethyl-1-butyl)-5,7,7-trimethyl-octane.
  • the atoms, groups, etc. other than the hydrocarbon group that constitute the substituent containing the above-mentioned hydrocarbon group are not particularly limited, and examples thereof include a group selected from the substituents GZ described below (substituents other than hydrocarbon groups), the above-mentioned heteroatoms, etc.
  • a group containing the above-mentioned hydrocarbon group and an oxygen atom or a sulfur atom is preferred, and specific examples thereof include an alkoxy group and an alkylthio group.
  • the combination of the substituent that can be taken as R 1 and the substituent that can be taken as R 2 is not particularly limited, and it is sufficient that either one of the substituents is a substituent containing a hydrocarbon group having 3 or more branched carbon atoms or a substituent containing a hydrocarbon group having 9 or more carbon atoms, and these substituents can be appropriately combined with a substituent that does not fall into either the substituent containing a hydrocarbon group having 3 or more branched carbon atoms or the hydrocarbon group having 9 or more carbon atoms among the above-mentioned substituents that can be taken as R 1 and R 2.
  • Y 1 P represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • Z represents a hydroxy group, a sulfanyl group (mercapto group), or a hydroxyaryl group.
  • a preferred first embodiment of the group that can be taken as Z is preferably a hydroxy group or a sulfanyl group, and more preferably a hydroxy group.
  • a preferred second embodiment of the group that can be taken as Z is preferably a hydroxy group or a hydroxyaryl group.
  • the hydroxyaryl group that can be taken as Z may be an aryl group having at least one hydroxy group, and examples of the aryl group include the aryl group in the substituent GZ described below, with a phenyl group being preferred.
  • the number of hydroxy groups to be introduced into the aryl group is not particularly limited, and can be 1 to 4, with one or two being preferred.
  • the position of the aryl group to which the hydroxy group is introduced is not particularly limited, and can be appropriately set with respect to the bonding position of the aryl group.
  • it may be any of the 2- to 4-positions with respect to the bonding position, with the 2-position being preferred.
  • hydroxyaryl group examples include a 2-, 3-, or 4-hydroxyphenyl group, a dihydroxyphenyl group, a trihydroxyphenyl group, and a tetrahydroxyphenyl group, and in terms of the selectivity and phase separation rate of the metal extractant, a 2-, 3-, or 4-hydroxyphenyl group is preferred.
  • Each group that can be taken as Z may form a salt.
  • the cation that forms the salt is not particularly limited, and examples thereof include metal cations, particularly metal cations of Group 1 or Group 2, and organic cations.
  • the organic cation is not particularly limited, and examples thereof include ammonium cations and alkylammonium cations.
  • L represents a single bond, provided that when n is 2 or more, L sandwiched between two adjacent P represents a single bond or a linking group.
  • the linking group that can be taken as L is not particularly limited, and examples thereof include an alkylene group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 4 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms, and more preferably having 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, an imino group (-NR N -: R N represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms), a carbonyl group, or a group related to a combination thereof.
  • an alkylene group, an arylene group, a carbonyl group, an oxygen atom, a sulfur atom, or an imino group, or a group related to a combination thereof is preferable, and an alkylene group is more preferable.
  • the alkylene group and the alkenylene group may be any of a straight chain, a branched chain, and a cyclic chain, but a straight chain or a branched chain is preferable.
  • the number of groups, linking groups, or atoms to be combined is not particularly limited, but can be, for example, 2 to 15, preferably 2 to 10, and more preferably 2 to 5.
  • the number of types of groups, linking groups, or atoms to be combined is not particularly limited, but can be, for example, 2 or more, and preferably 2 or 3.
  • the number of linking atoms of the linking group is not particularly limited, but is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less, and particularly preferably 4 or less.
  • the lower limit is 1 or more.
  • the number of linking atoms refers to the minimum number of atoms connecting two adjacent P.
  • the number of atoms constituting the linking group is not particularly limited, but can be, for example, 3 to 30, preferably 3 to 20, and more preferably 3 to 10.
  • the linking group is -CH 2 -CH 2 -
  • the number of atoms constituting the molecular structure is 6, but the number of linking atoms is 2.
  • the compound represented by formula (I) has two or more linking groups, it is sufficient that at least one linking group satisfies the above-mentioned number of linking atoms and number of constituent atoms, and it is preferable that all of the linking groups satisfy the above-mentioned number of linking atoms and number of constituent atoms.
  • n is an integer from 1 to 6. In a first preferred embodiment, n is an integer of 1 to 3. As a second preferred embodiment of n, n is preferably 1 or an integer of 3 to 6. In the first and second embodiments, n is more preferably 1. When n is an integer of 2 to 6, the n Y P s , Zs and Ls may be the same or different.
  • the compound represented by formula (I) can be formed by appropriately combining R1 and R2 , YP , Z, L, and n in the formula, and it is preferable to form the compound by combining preferred ones of each symbol.
  • the compound represented by formula (I) may be a basic compound, but is preferably an acidic compound having at least one active hydrogen atom, that is, the compound represented by formula (I) corresponds to an acidic metal extractant, in terms of excellent selectivity and high phase separation rate as a metal extractant.
  • active hydrogen atoms in the compound include hydrogen atoms in hydroxyl groups (including phenolic hydroxyl groups) and sulfanyl groups.
  • the active hydrogen atom may be present in any of R 1 , R 2 and L, but is preferably present in the above Z.
  • the number of hydroxyl groups present in the compound may be one or more, may be 1 to 4, and is preferably one or two.
  • a group containing an active hydrogen atom may form a salt, and the active hydrogen atom may be converted into a cation.
  • Such a cation is not particularly limited, and may be the cation described above for Z.
  • the compound represented by formula (I) may function as a polydentate ligand with respect to a specific metal ion (metal ion to be extracted) present in the aqueous phase, but it is preferable that it functions as a monodentate ligand in terms of selectivity and phase separation rate.
  • the molecular weight of the compound represented by formula (I) is not particularly limited, but can be, for example, 350 to 50,000, and from the viewpoint of solubility in an oil phase, etc., it is preferably 400 to 10,000, and more preferably 500 to 1,000.
  • the molecular weight refers to the number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC), unless otherwise specified.
  • GPC gel permeation chromatography
  • Molecular weight measurement The molecular weight of an oligomer is basically measured by the method under Condition 1 or Condition 2 (preferential) below. However, depending on the type of oligomer, an appropriate eluent may be selected and used.
  • the pKa of the compound represented by formula (I) is not particularly limited and may take any appropriate value, and is preferably 0.1 to 12.
  • the pKa can be measured by neutralization titration.
  • the compound represented by formula (I) may have a substituent, and examples of the substituent that may be had include groups selected from the substituents GZ described below.
  • the compound represented by formula (I) can be synthesized by referring to known synthesis methods, for example, the synthesis method described in Patent Document 1, or the synthesis method described in the Examples below.
  • Substituent GZ - alkyl groups (preferably alkyl groups having 1 to 20 carbon atoms, for example, 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, for example, vinyl, allyl, oleyl, etc.), alkynyl groups (preferably alkynyl groups having 2 to 20 carbon atoms, for example, ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.),
  • Heterocyclic groups include aromatic heterocyclic groups and aliphatic heterocyclic groups. Examples of such groups include a tetrahydropyran ring group, a tetrahydrofuran ring group, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, and pyrrolidone groups, alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, and benzyloxy), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, and 4-methoxyphenoxy), heterocyclic oxy groups (groups in which the above-mentioned heterocyclic groups are bonded to an -O- group), and alkoxycarbonyl groups ( Preferably, the alkoxycarbonyl group
  • acylamino groups such as acetylamino and benzoylamino
  • alkylthio groups preferably alkylthio groups having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio and benzylthio
  • arylthio groups preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio and 4-methoxyphenylthio
  • heterocyclic thio groups groups in which the above-mentioned heterocyclic groups are bonded to an -S- group
  • alkylsulfonyl groups preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl and ethylsulfonyl
  • arylsulfonyl groups preferably arylsulfonyl groups having 6 to
  • R P is a hydrogen atom or a substituent (preferably a group selected from the substituents G and Z). Each of the groups given as examples of the substituent GZ may be further substituted with the above-mentioned substituent GZ.
  • the above alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group and/or alkynylene group may be cyclic or chain-like, and may be straight-chain or branched.
  • the method for separating and recovering metal ions of the present invention (hereinafter, sometimes referred to as the separation and recovery method of the present invention) is a method for mixing an aqueous phase containing multiple kinds of metal ions with an oil phase containing the metal extractant of the present invention, whereby a specific metal ion coordinated with the metal extractant of the present invention can be transferred (extracted) from the aqueous phase to the oil phase, and separated and recovered with high selectivity, preferably with a high recovery rate.
  • the metal ions extracted into the oil phase may be a part of the multiple kinds of metal ions contained in the aqueous phase, or may be all kinds of heterogeneous metal ions contained in the aqueous phase.
  • the separation and recovery method of the present invention can extract one kind of metal ion as an ion of a valuable metal element into the oil phase with high selectivity, preferably with a high recovery rate, but can extract two or more kinds of heterogeneous metal ions, for example, one kind of metal ion among two or more kinds of heterogeneous metal ions belonging to Groups 1 to 14 of the periodic table, into the oil phase with high selectivity, preferably with a high recovery rate.
  • the separation and recovery method of the present invention can extract one of two or more different metal ions belonging to Groups 9 to 12 of the periodic table, particularly preferably cobalt ions and nickel ions which are different metal ions from the same period, into an oil phase with high selectivity and preferably with a high recovery rate.
  • the separation and recovery method of the present invention is based on the discovery of the characteristics and functions of the metal extractant of the present invention, which is capable of extracting one of a plurality of metal ions (groups) present in an aqueous phase in a wet extraction method, with high selectivity and preferably with a high recovery rate, out of the two or more metal ions that are extracted together into an oil phase, and is applied to a new application of separating and recovering two or more metal ions, particularly heterogeneous metal ions.
  • the water that forms the aqueous phase is not particularly limited, but (ultra)pure water, ion-exchanged water, etc. can be used.
  • the metal ions contained in the aqueous phase may contain at least two types of ions of metal elements belonging to Groups 1 to 14 of the periodic table, preferably at least two types of metal ions belonging to Groups 3 to 14, and may contain metal ions belonging to Groups 15 to 17.
  • the metal ion contains two or more kinds of metal ions belonging to groups 1 to 14, more preferably two or more kinds of metal ions belonging to groups 3 to 14, and even more preferably at least one transition metal element (metal element belonging to groups 3 to 12).
  • the metal ion contains two or more kinds of metal ions belonging to groups 4 to 12, more preferably two or more kinds of metal ions belonging to groups 4 to 10, even more preferably two or more kinds of metal ions belonging to groups 8 to 12, particularly preferably two or more kinds of metal ions belonging to groups 9 to 12, and most preferably two or more kinds of metal ions belonging to groups 9 and 10.
  • the metal ions belonging to each group are not particularly limited, but are preferably metal ions belonging to periods 4 to 6 in the periodic table, and more preferably metal ions belonging to periods 4 or 5.
  • the number of types of metal ions is not particularly limited as long as it is two or more, and can be, for example, 2 to 15 types, preferably 2 to 8 types, and more preferably 2 to 5 types.
  • the combination of multiple metal ions is not particularly limited, and examples of combinations of groups include combinations including Group 9 and Group 10, combinations including Group 9 and Group 12, combinations including Group 9 and Group 11, combinations including Group 9, Group 10 and Group 12, combinations including Group 4 and Group 9, combinations including Group 7, Group 9 and Group 10, combinations including Group 7, Group 8, Group 9 and Group 10, and combinations including Group 7, Group 8, Group 9 and Group 10.
  • the number of metal ions belonging to each group may be two or more, but it is preferred that the number be one, in view of high selectivity.
  • the combination of metal ions include a combination including Co and Ni, a combination including Co and Zn, a combination including Co and Cu, a combination including Rh and Ni, a combination including Zr and Rh, a combination including Mn, Co and Ni, and a combination of Mn, Fe, Co and Ni.
  • the multiple types of metal ions contained in the aqueous phase may include metal ions of the same group or different metal ions of different groups.
  • the number of different metal ions contained in the aqueous phase may be two or more, and is preferably, for example, two to four, and more preferably two.
  • the metal elements belonging to each group are not particularly limited, and appropriate atoms can be used.
  • Preferred examples of metal elements belonging to Group 1 include Li, Na, Rb, and Cs.
  • Preferred examples of the metal elements belonging to Group 2 include Mg, Ca, Sr, and Ba.
  • Preferred examples of the metal elements belonging to Group 3 include Sc and Y.
  • Preferred examples of the metal elements belonging to Group 4 include Ti, Zr, and Hf.
  • Preferred examples of the metal elements belonging to Group 5 include V, Nb, and Ta.
  • Preferred examples of the metal elements belonging to Group 6 include Cr, Mo, and W.
  • Preferred examples of the metal elements belonging to Group 7 include Mn and Tc.
  • Preferred examples of the metal elements belonging to Group 8 include Fe, Ru, and Os.
  • Preferred examples of the metal elements belonging to Group 9 include Co, Rh, and Ir.
  • Preferred examples of the metal elements belonging to Group 10 include Ni, Pd, and Pt.
  • Preferred examples of metal elements belonging to Group 11 include Cu, Ag, and Au.
  • Preferred examples of metal elements belonging to Group 12 include Zn, Cd, and Hg.
  • Preferred examples of metal elements belonging to Group 13 include Al, Ga, In, and Tl.
  • Preferred examples of metal elements belonging to Group 14 include Ga, Sn, and Pb.
  • Preferred examples of the metal elements belonging to Group 15 include Sb and Bi.
  • the metal element belonging to Group 16 is not particularly limited, and a preferred example is Tellurium.
  • metal ions can be prepared as appropriate, and examples of such materials that can be used include various metal salts (salts of typical elements with inorganic acids such as nitric acid and sulfuric acid, or organic acids such as acetic acid), mixtures of mined metals (ions), materials recovered from metal waste, metals recovered from other waste such as waste batteries (LiB), and mixtures of these.
  • metal salts salts of typical elements with inorganic acids such as nitric acid and sulfuric acid, or organic acids such as acetic acid
  • ions materials recovered from metal waste
  • metals recovered from other waste such as waste batteries (LiB)
  • Metals recovered from waste LiB can be recovered by known methods such as wet processing, electrolysis, etc.
  • the total content of the multiple types of metal ions in the aqueous phase is not particularly limited and may be set as appropriate.
  • the total content may be 1,000 to 1,000,000 ppm by mass, preferably 1,000 to 100,000 ppm by mass, more preferably 1,000 to 80,000 ppm by mass, and even more preferably 2,000 to 60,000 ppm by mass.
  • the total content of metal ions belonging to Groups 9 to 12 among the metal ions is not particularly limited and may be set as appropriate, but may be, for example, 1,000 to 80,000 ppm by mass, preferably 1,000 to 60,000 ppm by mass, and more preferably 2,000 to 60,000 ppm by mass.
  • the total content of metal ions belonging to groups 3 to 7 and groups 13 to 16 among the metal ions is not particularly limited and may be set appropriately, but may be, for example, 1,000 to 60,000 ppm by mass, and preferably 1,000 to 30,000 ppm by mass.
  • the content of the metal ions belonging to each group is not particularly limited and may be appropriately set, but may be, for example, 1,000 to 60,000 ppm by mass, preferably 1,000 to 50,000 ppm by mass, and more preferably 2,000 to 30,000 ppm by mass.
  • the content of the metal ions belonging to each group is the total content.
  • the content of metal ions belonging to a certain group may be greater or less than the content of metal ions belonging to other groups. Since the separation and recovery method of the present invention can separate and recover metal ions with high selectivity, it is not necessary to set the content of metal ions belonging to different groups to a specific ratio.
  • the mass ratio of the content of metal ions belonging to a certain group (e.g., metal ions extracted at the maximum extraction amount) to the content of metal ions belonging to another group (e.g., metal ions other than the metal ions extracted at the maximum extraction amount (including metal ions that are not extracted)) [content of metal ions belonging to a certain group: content of metal ions belonging to another group] can be, for example, 100:1 to 10,000, preferably 100:10 to 5,000, more preferably 100:50 to 1,000, and even more preferably 100:70 to 250.
  • the pH of the aqueous phase is not particularly limited and may be appropriately set. Taking into consideration the solubility of metal ions, the formation of complex ions, and the like, the pH is preferably, for example, 0.1 to 10, and more preferably 2.0 to 9.0.
  • the pH of the aqueous phase can be adjusted, for example, by using an acid or an alkali.
  • known acids can be used without any particular limitation, and examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, oxalic acid, organic phosphoric acid, and organic sulfonic acid.
  • alkali known acids can be used without any particular limitation, and examples thereof include inorganic alkalis and organic alkalis, and inorganic alkalis are preferred.
  • inorganic alkali examples thereof include metal alkalis such as hydroxides and carbonates of metals of Group 1 or Group 2, as well as ammonia water and ammonium chloride.
  • organic alkali examples thereof include organic ammonium salts.
  • the temperature of the aqueous phase is not particularly limited and can be, for example, 10 to 60°C.
  • the aqueous phase may contain, as necessary, a ligand (compound) that coordinates with a metal ion, or a compound that generates a ligand.
  • the aqueous phase can be prepared by dissolving metal ions in water.
  • the conditions for preparing the aqueous phase are not particularly limited.
  • the preparation temperature can be 10 to 60°C.
  • the aqueous phase may contain a masking agent in addition to the metal ions. Any known masking agent can be used without any particular limitation. Examples of the masking agent include monodentate ligands such as ammonia, and chelating agents such as dithizone.
  • an oil phase (organic phase) containing one or more kinds of the metal extractants of the present invention is used in combination with the above-mentioned aqueous phase.
  • the metal extractant of the present invention exhibits solubility in an organic solvent, is present in the oil phase, and coordinates with metal ions present in the vicinity of the interface between the aqueous phase and the oil phase, thereby transferring the metal ions to the oil phase.
  • solubility in an organic solvent means the property of the metal extractant being soluble in an organic solvent at the content described below.
  • the organic solvent forming the oil phase is not particularly limited, and any suitable organic solvent can be used. Examples include alcohol solvents, ether solvents, hydrocarbon solvents (aromatic solvents, aliphatic solvents), halogenated solvents, etc. Among these, hydrocarbon solvents are preferred, and various solvents that are fractions of petroleum are more preferred, with aromatic, paraffinic, naphthenic, kerosene, gasoline, naphtha, kerosene, and diesel hydrocarbon solvents being even more preferred.
  • the content of the metal extractant in the oil phase is appropriately set in consideration of the content of metal ions, the amount of coordination to the metal ions, etc.
  • the content in the oil phase can be 20 to 10,000 mmol/L (mM), preferably 50 to 1,000 mmol/L, and more preferably 100 to 500 mmol/L.
  • the temperature of the oil phase is not particularly limited and can be, for example, 10 to 60°C.
  • the oil phase may contain other appropriate components in addition to the acidic metal extractant of the present invention.
  • the oil phase can be prepared by dissolving a metal extractant in an organic solvent.
  • the preparation conditions for the oil phase are not particularly limited, and the preparation temperature can be, for example, 10 to 60°C.
  • the above-mentioned aqueous phase and oil phase are mixed and allowed to stand.
  • the mixing conditions and the standing conditions at this time are not particularly limited and can be set appropriately.
  • the mixing can be performed using various mixing devices. Examples of the mixing device include a method using a magnetic stirrer (stirrer tip), a method using a mechanical stirrer, and a method using a mixer.
  • the stirring conditions are sufficient as long as they are conditions that allow the aqueous phase and the oil phase to be mixed (conditions under which the metal extractant is coordinately bonded to the metal ion), and are set appropriately according to the combination of the metal ion and the metal extractant, the mixing temperature, and further the mixing device.
  • the stirring speed can be 80 rpm or more as the rotation speed of the magnetic stirrer, etc., and is preferably 100 to 200 rpm.
  • the stirring time is not uniquely determined by the stirring conditions, etc., but can be, for example, 10 minutes to 24 hours.
  • the stirring speed can be set to a high speed and the stirring time can be set to a long time.
  • the mixing temperature is not particularly limited and can be, for example, 10 to 60°C.
  • the standing conditions are not particularly limited and can be appropriately set as long as the aqueous phase and the oil phase are separated into two layers.
  • the standing time in the wet extraction method is usually set to 10 minutes to 24 hours after mixing is stopped.
  • the standing time can be set to a shorter time than usual to increase the productivity of the wet extraction method. In this case, the standing time can be, for example, less than 5 minutes, and preferably less than 4 minutes, after mixing is stopped.
  • the standing temperature is 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 depending on the content (concentration) of the metal ions, the content (concentration) of the metal extractant, etc., and is not uniquely determined.
  • the ratio of the oil phase to 100 mL of the aqueous phase can be 50 to 2,000 mL, preferably 80 to 1,000 mL, and more preferably 80 to 200 mL.
  • the metal ions that can be coordinated with the metal extractant refer to metal ions that are coordinated with the metal extractant 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 unique, but is appropriately determined in consideration of the pKa of the metal extractant, the complex formation constant of the metal extractant and the metal ion, the coordination number of the metal ion, and the like.
  • the pH of the mixed system is preferably 0.01 to 14, more preferably 0.1 to 10, and from the viewpoints of selectivity and phase separation speed, and furthermore, recovery rate, it is more preferably 0.5 to 7.0, particularly preferably 1.0 to 6.5, and most preferably 2.5 to 6.5.
  • the pH of the aqueous phase is most preferably 3.0 to 6.5 within the above range.
  • the pH can be adjusted using the above-mentioned acids or alkalis, or aqueous solutions thereof, but in one preferred embodiment, ammonia or an ammonium salt is not used.
  • the above-mentioned mixing of the aqueous phase and the oil phase and leaving to stand after mixing are carried out after adjusting the pH.
  • the aqueous phase and the oil phase are mixed in this way, and the mixture is allowed to stand to obtain a two-phase separation fluid (solvent extraction phase, solvent extraction system) in which the aqueous phase and the oil phase are separated from each other in layers while in contact with each other.
  • solvent extraction phase solvent extraction system
  • the metal ions coordinated with the metal extractant are present (moved) in the oil phase.
  • the number of types of metal ions extracted into the oil phase is ideally one type, but may be two or more types, in which case it can be, for example, 2 to 10 types, preferably 2 to 6 types, and more preferably 2 or 3 types.
  • the two or more types of metal ions extracted into the oil phase among the multiple types of metal ions are not particularly limited, but are preferably, for example, the same as the two or more types (combination) of different metal ions contained in the aqueous phase described above.
  • the simple method of mixing the aqueous phase and oil phase and allowing them to stand in the separation and recovery method of the present invention allows specific metal ions from among multiple types of metal ions to be extracted, separated and recovered with high selectivity and preferably with a high recovery rate, and in particular, while extracting ions of two or more metal elements, it is possible to separate and recover one of the metal ions with high selectivity and preferably with a high recovery rate.
  • a type of metal ion that can be separated and recovered with high selectivity and preferably with high recovery is not uniquely determined by the group or period of the metal ion, the content, the type of metal extractant, etc.
  • the metal ion belonging to group 9 can be separated and recovered with high selectivity and preferably with high recovery
  • the Co ions can be separated and recovered with high selectivity and preferably with high recovery.
  • the metal ion belonging to group 11 can be separated and recovered with high selectivity and preferably with high recovery.
  • the metal ions belonging to Group 9, Group 10, and Group 12 are extracted into the oil phase, the metal ions belonging to Group 10 are usually not extracted, but the metal ions belonging to Group 12 can be separated and recovered with high selectivity and preferably with a high recovery rate.
  • the separation and recovery method of the present invention can extract and recover one or more metal ions from a plurality of metal ions present in an aqueous phase into an oil phase with high selectivity, preferably with a high recovery rate.
  • the separation and recovery method of the present invention can extract two or more metal ions while recovering one of the metal ions with high selectivity, preferably with a high recovery rate. Therefore, by subjecting the aqueous phase containing two or more metal ions stripped from the oil phase to the separation and recovery method of the present invention, the selectivity of one metal ion can be further increased without significantly impairing the recovery rate, and as a result, high-purity metal ions can be recovered, preferably with a high recovery rate.
  • Such a separation and recovery method of the present invention can also be said to be a method for extracting two or more types of metal ions.
  • the metal extractant can coordinate to the metal ion alone and extract the metal ion into the oil phase, so the aqueous phase and the oil phase do not need to contain compounds that cooperate with the metal extractant of the present invention to extract the metal ion, such as compounds that coordinate to the metal ion or compounds that generate ligands, such as known metal extractants.
  • an aqueous phase containing a specific metal ion as an essential component and an oil phase containing the metal extractant of the present invention as an essential component are usually used.
  • the separation and recovery method of the present invention may have a step other than the step of mixing the aqueous phase and the oil phase and leaving them to stand as described above.
  • the separation and recovery method may include a step of premixing the aqueous phase and the oil phase before adjusting the pH, a step of back-extracting (isolating) metal ions from the oil phase obtained in the step of mixing the aqueous phase and the oil phase and leaving them to stand (a step of back-extracting metal ions from the oil phase and recovering a metal extractant), a step of recovering the back-extracted metal ions as a compound (salt), a step of purifying the back-extracted metal ions or their compounds, a step of purifying the recovered metal extractant, and a step of removing ions of metal elements belonging to Group 1 or Group 2 in the periodic table of elements in advance.
  • any known method can be applied without particular limitation, and for example, it can be performed by making the liquid phase acidic, for example, pH 2 to 4, using an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid.
  • an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid.
  • any known method can be applied without particular limitation.
  • the separation and recovery method of the present invention may be carried out as a batch process or a continuous process.
  • the apparatus for carrying out the separation and recovery method of the present invention is not particularly limited, and known equipment can be used. Examples include a separating funnel, a mixer settler, and the like.
  • a contacting and mixing apparatus using a liquid delivery device such as a flow synthesis device or an emulsion flow device can also be used.
  • the above-mentioned conditions can be applied to the contacting, mixing, and standing conditions in the continuous treatment.
  • the amount of the aqueous phase to be circulated can also be set to be greater than the above-mentioned mixing ratio of the aqueous layer and the oil phase.
  • each sulfate salt was dissolved in ultrapure water in the combination of metal ions shown in the column "Metal ion concentration (ppm) in aqueous phase before extraction" in Table 2-1 to prepare metal ion-containing aqueous solutions (W2) to (W4).
  • the pH of each of the prepared metal ion-containing aqueous solutions (W1) to (W4) was measured using a pH meter (SK-620pHII, manufactured by Satotec Co., Ltd.) and the results are shown below.
  • Metal ion-containing aqueous solution (W1): 6.6 Metal ion-containing aqueous solution (W2): 6.2 Metal ion-containing aqueous solution (W3): 6.5 Metal ion-containing aqueous solution (W4): 7.0
  • Example 1 In a 30 mL vial, 10 mL of the extractant solution (Y1) was added to 10 mL of the prepared metal ion-containing aqueous solution (W1), and the mixture was stirred at 25 ° C. for 30 minutes (rotation speed: 150 rpm) with a stirrer tip (diameter 6 mm, length 20 mm) (premixing). At this time, the mixed amount (unit: equivalent) of compound E-1 relative to the total content of the metal ions that can be coordinated (synonymous with the extracted metal ions, Co and Ni in Example 1) was 0.78.
  • Example 2 ⁇ Examples 2 to 12 and Comparative Examples 1 to 4>
  • the metal ion-containing aqueous solution and the extractant solution were changed to the combination shown in the "Aqueous Phase” column of Table 2-1 and the "Oil Phase” column of Table 2-2 (hereinafter, Table 2-1 and Table 2-2 are collectively referred to as Table 2), and the pH when the aqueous phase and the oil phase were mixed was set to the value shown in the "pH at mixing" column of Table 2-2, and the mixture was allowed to stand.
  • Example 2 In the same manner as in Example 1, the metal ions extracted in each Example are shown in the "Type” column of the “Extracted metal ions” column of Table 2-2, and the metal ions extracted in the maximum amount are shown in the "Maximum extracted ions” column of the same column of Table 2-2.
  • ICP-OES inductively coupled plasma optical emission spectroscopy
  • Optima 7300D product name
  • the measured values of the dissolved metal ion content of each aqueous phase used in the Examples and Comparative Examples are shown in the "Metal ion concentration (ppm) in aqueous phase before extraction” column of Table 2-1
  • the measured values of the dissolved metal ion content of each aqueous phase after mixing in each Example and Comparative Example are shown in the "Metal ion concentration (ppm) in aqueous phase after extraction” column of Table 2-1.
  • the ",” in the metal ion concentrations in the table indicates a digit separator and does not indicate a decimal point
  • Examples 1 to 12 in which compounds E-1 to E-9 of the present invention were used as metal extractants, two types of metal ions present in the metal ion-containing aqueous solution were all extracted into the oil phase.
  • the metal ion with the maximum extraction amount (Examples 1 to 5, 8, and 10 to 12: Co ion, Example 6: Zn ion, Example 7: Cu ion, Example 9: Rh ion) was extracted almost entirely (with a high recovery rate) from the aqueous phase into the oil phase with a high selectivity to metal ions other than the metal ion with the maximum extraction amount.
  • the time elapsed until separation into two phases was short (phase separation rate was high), which increased the productivity of the wet extraction method.
  • the present invention can extract almost all of one of two different metal ions from the aqueous phase to the oil phase with high selectivity using a simple method and high productivity. Therefore, in view of the above-mentioned situation, the present invention has a great technical significance in that one metal ion can be recovered from the obtained oil phase with a high recovery rate and further improved selectivity, with a simple method and a small number of steps, and with high productivity, by a back extraction step or the like.

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PCT/JP2024/009753 2023-03-27 2024-03-13 金属抽出剤、及びこの金属抽出剤を用いた金属イオンの分離回収方法、並びに、化合物 Ceased WO2024203328A1 (ja)

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EP24779457.1A EP4692383A1 (en) 2023-03-27 2024-03-13 Metal extractant, method for separating and recovering metal ions using said metal extractant, and compound
CN202480022670.5A CN120958151A (zh) 2023-03-27 2024-03-13 金属萃取剂及使用该金属萃取剂的金属离子的分离回收方法以及化合物
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