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WO2025198668A1 - Compositions et procédés pour extraire un ou plusieurs métaux d'une solution - Google Patents

Compositions et procédés pour extraire un ou plusieurs métaux d'une solution

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Publication number
WO2025198668A1
WO2025198668A1 PCT/US2024/057489 US2024057489W WO2025198668A1 WO 2025198668 A1 WO2025198668 A1 WO 2025198668A1 US 2024057489 W US2024057489 W US 2024057489W WO 2025198668 A1 WO2025198668 A1 WO 2025198668A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
reagent composition
extractant
urea
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/057489
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English (en)
Inventor
Jack Bender
Richelle LYNDON
Aruna EARLA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Exploration Technologies Inc
Original Assignee
Energy Exploration Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Energy Exploration Technologies Inc filed Critical Energy Exploration Technologies Inc
Publication of WO2025198668A1 publication Critical patent/WO2025198668A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01D11/0492—Applications, solvents used
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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 disclosure relates to reagent compositions and methods for extracting one or more metals from a solution using such reagent compositions.
  • Lithium batteries are at the forefront of electricity storage technologies because inter alia they charge faster, last longer and have a higher power density to provide more battery life in a lighter package than conventional batteries. Lithium storage devices are useful for electrification of the transportation sector, electric vehicles, battery storage for electric utilities and in many other applications to reduce carbon emissions and store electricity.
  • Lithium including lithium metal, lithium compounds, and/or lithium salts, is typically extracted from underground deposits of brine water and lithium-containing ore. Brines from salars and salt lakes, as well as spodumene ores, are the primary sources of lithium, while geothermal brines represent secondary sources.
  • Classical methods of lithium extraction rely on brine evaporation in open ponds to maximize element concentration for further purification; however, these methods are very slow (evaporation of ponds to the desired level can take up to 24 months) and strongly dependent on region-specific weather conditions that vary throughout the year.
  • Newer technologies based on precipitation, adsorption, solvent extraction, and membranes can be used for brine concentration and may increase the economic viability of minerals extracted from seawater and other geothermal brines.
  • reagent compositions comprising: at least one urea extractant capable of selectively extracting one or more metals, compounds (i.e., other than salts) thereof, salts thereof, or combinations thereof, from an aqueous solution; and at least one non-urea extractant capable of selectively extracting one or more metals, compounds thereof, salts thereof, or combinations thereof, from the aqueous solution.
  • the at least one urea extractant and the at least one non-urea extractant may be suitable extract the same or different metals, compounds thereof, salts thereof, or combinations thereof.
  • the one or more metals comprise lithium, magnesium, calcium, boron, potassium, sodium, or combinations thereof.
  • the one or more metals comprise a lithium salt, magnesium salt, calcium salt, boron salt, potassium salt, sodium salt or combinations thereof.
  • the one or more metals comprise lithium or a lithium salt (e.g., lithium chloride).
  • the at least one urea extractant comprises one or more urea compound chosen from the following Formula (I), Formula (II) (i. e. , a thiourea), or combinations thereof: wherein R 1 , R 2 , R 3 and R 4 is each independently hydrogen, a methyl group, an ethyl group, a straight or branched C3-C20 alkyl group, a C3-C12 cycloalkyl group having a single ring structure, a CT-C 10 aromatic ring group, a C3-C20 alkylphenyl group, a straight or branched C3-C20 alkenyl group, a straight or branched C3-C20 alkynyl group, a thiol group, wherein each of the C3-C20 alkyl, alkenyl or alkynyl groups may be interrupted with N, 0 or S.
  • Formula (I), Formula (II) i. e. , a thiour
  • the at least one non-urea extractant comprises an amide compound chosen from the following Formula (III), Formula (IV), Formula (V) (i.e., a sulfonamide), or combinations thereof: wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 and R 15 is each independently hydrogen, a methyl group, an ethyl group, a straight or branched C3-C20 alkyl group, a C3-C12 cycloalkyl group having a single ring structure, a Ce-Cio aromatic ring group, a C1-C20 alkylphenyl group, a dihydrobenzodioxene group, a straight or branched C1-C20 alkanol group, a straight or branched C1-C20 alkyldiol group, a straight or branched C3-C20 alkenyl group, a straight or amide compound chosen
  • reagent compositions according to embodiments herein may further include diluent.
  • Suitable diluents include, but are not limited to, an alcohol, an organophosphorous solvent, or a combination thereof.
  • the at least one diluent may be chosen from octanol, trideconal, 2-ethyl-l -hexanol, 3-methyl-l-butanol, isoamyl alcohol, 2-hexyl decanol, octanoic acid, trioctylphosphine oxide (e.g., Cyanex® 923), petroleum distillates solvent (e.g., Orform® SX80), aromatic C9-C10 solvent (e.g., Shellsol® A150), a kerosene (e.g., Orform® SX11), dibutyl carbitol, dichloromethane, trioctylmethylammonium chloride (e.g., Ali
  • the reagent compositions can include at least one modifier, wherein the at least one modifier comprises one or more functional group having a dipole moment and/or that is attached to a highly polar ionic bond.
  • the at least one modifier comprises an aliphatic component that is attracted to non-polar moieties of the at least one urea extractant and/or the at least one non-urea extractant.
  • the at least one modifier may include one or more functional group chosen from a diether, amide, imide, ketone, alcohol, ether, alkyl phosphine, phosphate, ester, phosphonic acid, phosphonic acid, phosphoric acid and/or nitrile.
  • the at least one modifier is chosen from 1,6-di-t-butoxy hexane, di(ethylene glycol) dibutyl ether, 1,4-bis-t-butoxy butane, 2-ethylhexyl succinimide, 4-t-butylcyclohexanone, l-butyl-3-methylimidazolium methyl sulfate, iminodiacetic acid (IDA), dodecanol, 2, 2, 4-trimethyl- 1,3 -pentanediol diisobutyrate (TXIB), ethyoxylated isotridecyl phosphate (TDA), cy decanol, l-methyl-3-octylimidazolium chloride, trihexyltetradecylphosphonium chloride, 1 -decyl-3 -methylimidazolium tetrafluoroborate, 7-ethyl-2-methyl-undecanol
  • IDA im
  • the at least one non-urea extractant is present in the reagent composition in an amount of greater than 0 wt%, or about 1 wt% to about 99 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the at least one non-urea extractant is present in the reagent composition in an amount of greater than 0 wt%, or about 1 wt% to about 99 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the reagent composition comprises a weight ratio of the at least one urea extractant to the at least one non-urea extractant of about 1: 10 to about 100:1
  • the at least one modifier and/or diluent is present in the reagent composition in an amount of greater than 0 wt%, or about 1 wt% to about 99 wt%, based on the total weight of the reagent composition.
  • a weight ratio of the at least one urea extractant to the at least one modifier and/or diluent is about 1 : 10 to about 100: 1.
  • aqueous solution may be a metal-containing brine (e.g., a lithium- containing brine), brine from a salar, product stream from a pond evaporation process, product stream from a processing plant, or combinations thereof.
  • a metal-containing brine e.g., a lithium- containing brine
  • the aqueous solution is contacted with a magnesium selective reagent composition, a boron selective reagent composition, or combinations thereof, prior to contacting the aqueous solution with the reagent composition to extract the one or more lithium salts.
  • the one or more lithium salts comprised in the aqueous solution comprises lithium chloride, lithium sulfate, lithium hydroxide, lithium nitrate or combinations thereof.
  • Methods described herein can further include contacting the metal depleted aqueous phase with fresh reagent composition and further extracting the one or more metals from the aqueous solution into the metal rich organic phase until reaching equilibrium.
  • methods include repeating the further extracting with fresh reagent composition until the metal depleted aqueous phase is free or substantially free of metal.
  • the methods further include emulsifying the metal rich organic phase.
  • the methods include separating the metal depleted aqueous phase from the metal rich organic phase.
  • the methods may further comprise stripping the one or more metals from the metal rich organic phase. In one or more embodiments, about 70% to about 99%, or about 95% of the one or more metals (e.g., lithium as the target metal) is stripped from the metal rich organic phase.
  • Methods as described herein are suitable to provide an overall extraction of one or more target metal (e.g., lithium, one or more lithium salt) from the aqueous solution of greater than about 70%, greater than about 80%, greater than about 90%, greater than about 92%, or about 70% to about 99%, or about 80% to about 93%.
  • the selectivity of the urea extractant for lithium over magnesium in the described methods is about 1 to about 50, about 5 to about 30, or about 10 to about 25.
  • FIG. 1 shows a schematic representation of a zwitterionic extractant when contacted with a solution containing inorganic salts forming an inorganic-organic double salt (IODS) can be formed using lithium chloride (LiCl) as an example.
  • IODS inorganic-organic double salt
  • a depurator vessel includes a single depurator vessel as well as more than one depurator vessel.
  • the term “about” in connection with a measured quantity refers to the normal variations in that measured quantity as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment.
  • the term “about” includes the recited number ⁇ 10%, such that “about 10” would include from 9 to 11.
  • the term “at least about” in connection with a measured quantity refers to the normal variations in the measured quantity, as expected by one of ordinary skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and precisions of the measuring equipment and any quantities higher than that.
  • the term “at least about” includes the recited number minus 10% and any quantity that is higher such that “at least about 10” would include 9 and anything greater than 9. This term can also be expressed as “about 10 or more.”
  • the term “less than about” typically includes the recited number plus 10% and any quantity that is lower such that “less than about 10” would include 11 and anything less than 11. This term can also be expressed as “about 10 or less.”
  • Weight percent if not otherwise indicated, is based on an entire composition free of any volatiles, that is, based on dry solids content.
  • metal refers to the recited metal element and includes compounds (other than salts) containing the metal, salts containing the metal and/or combinations thereof.
  • lithium refers to lithium compounds, lithium salts and lithium-containing molecules.
  • trace or “trace amount” as used herein refers to the amount of a component in a solution being less than about 1 part per million by weight (ppmw).
  • substantially free refers to trace amounts of a component in a fluid, less than trace amounts of the component in the fluid or a non-detectable amount of the component in the fluid.
  • the reagent compositions include zwitterionic urea extractants and nonurea extractants for use in methods of solvent extraction of one or more alkali metals (e.g., lithium and/or lithium containing compounds such as lithium salts including lithium chloride).
  • the extractants and methods described herein can be highly selective for one or more target metals or metal containing compounds such as metal salts (e.g., lithium chloride).
  • it was determined that the reagent compositions as described herein are suitable to concentrate the metal and/or metal compounds (e.g., LiCl) dramatically with a selectivity that was far greater than expected.
  • the solvent extraction methods according various embodiments herein are operable using a conventional solvent extraction process and the system is suitable for stripping with water to a relatively high concentration of metal or metal compounds (e.g., lithium chloride) in the recovery solution. It has been found that the extraction of the metals and metal-containing compounds and the production of a recovery stream containing the concentrated metals and/or compounds is suitable for downstream use as battery grade (e.g., lithium salt) production.
  • metal or metal compounds e.g., lithium chloride
  • Urea extractants and non-urea extractants as described herein may be zwitterionic extractants having a positive charge and a negative charge on the same organic molecule. This makes these compounds intra-ion organic salts, and are often self-associating in the bulk organic.
  • an inorganic-organic double salt can be formed as shown in FIG. 1 using lithium chloride (LiCl) as an example. Without being bound by any particular theory, it is believed that transfer of the LiCl occurs by making an emulsion to increase the surface area.
  • the extractant is suitable to bond with the lithium salt at the interface forming the IODS.
  • the emulsion may be allowed to coalesce once extraction is complete so the phases can be separated.
  • the organic solution is typically washed or scrubbed to remove entrained water or loaded impurities. It is then stripped with water. This is considered an aty pical liquid-liquid solvent extraction process due to the lack of an activation/deactivation mechanism using acid/base.
  • the unloaded formulation is a three-component system: at least one urea extractant, at least one non-urea extractant and at least one modifier.
  • the urea extractant, nonurea extractant, modifier and their respective concentrations may be chosen based on a particular aqueous solution containing one or more target metals, compounds thereof, salts thereof, or combinations thereof.
  • reagent compositions comprising one or more extractant(s) that are selective for one or more target metals including compounds thereof, salts thereof, and/or combinations thereof.
  • the reagent compositions contain at least one urea extractant and at least one non-urea extractant both suitable to extract lithium and/or lithium salts.
  • Suitable extractants include urea extractants, for example, containing a urea compound and/or a urea base structure including a thiourea, and non-urea extractants such as amide extractants, for example, containing an amide compound and/or an amide base structure including sulfonamides.
  • the urea and non-urea extractants do not use a proton transfer mechanism. Without being bound by any particular theory, it is believed that extractants as described herein work by inducing a zwitterionic charge based on resonance structures.
  • the extractants described herein may be suitable to extract lithium as a salt (e.g., lithium chloride, etc.).
  • the reagent compositions may be free of an extractant that uses a proton transfer mechanism.
  • the one or more target metals or metal compounds may be dissolved and/or dispersed within a solvent (e.g., an aqueous solution).
  • a solvent e.g., an aqueous solution
  • the solvent is a metalcontaining aqueous solution, for example, a metal-containing brine, brine from a salar, product stream from a pond evaporation process, product stream from a processing plant, or combinations thereof.
  • the aqueous solution is a brine containing greater than about 60,000 ppm of magnesium, compounds thereof, salts thereof, or combinations thereof, and at least about 150 ppm of lithium, compounds thereof, salts thereof, or combinations thereof.
  • the at least one urea extractant and the at least one non-urea extractant are independently capable of selectively extracting lithium, magnesium, calcium, boron, potassium, or sodium, or combinations thereof.
  • the at least one urea extractant and at least one non-urea extractant are independently capable of selectively extracting one or more lithium compounds, one or more magnesium compounds, one or more calcium compounds, one or more boron compounds, one or more potassium compounds, or one or more sodium compounds, or combinations thereof.
  • suitable extractants may be capable of extracting one or more lithium salt, one or more magnesium salt, one or more calcium salt, one or more boron salt, one or more potassium salt, or one or more sodium salt, or combinations thereof.
  • suitable extractants are capable of selectively extracting, lithium, one or more lithium compounds such as one or more lithium salts, or combinations thereof.
  • the at least one urea extractant and at least one non-urea extractant selectively extract a lithium salt over one or more magnesium salts, one or more calcium salts, one or more boron salts, one or more potassium salts, or one or more sodium salts, and/or combinations thereof.
  • Suitable urea extractants for use in reagent compositions as described herein include one or more urea compound having the following formula (I), formula (II), or combinations thereof: wherein R 1 , R 2 , R 3 and R 4 is each independently hydrogen, a methyl group, an ethyl group, a straight or branched C3-C20 alkyl group, a C3-C12 cycloalkyl group having a single ring structure, a Cs-Cio aromatic ring group, a C3-C20 alkylphenyl group, a straight or branched C3-C20 alkenyl group, a straight or branched C3-C20 alkynyl group, a thiol group, wherein each of the C3-C20 alkyl, alkenyl or alkynyl groups may be interrupted with N, 0 or S.
  • At least one urea extractant is of Formula (I) wherein R 3 and R 4 are H. In one or more embodiments, at least one urea extractant is of Formula (I) wherein R 1 , R 2 or both are a Ce aromatic ring structure. In some embodiments, R 1 is a branched Cs alkyl or a branched Cs alkyl. [0035] In some embodiments, at least one urea extractant in the reagent composition is of Formula (I), wherein R 1 is a branched Cs-Cs alkyl, R 2 is a Ce aromatic ring and R 3 and R 4 are H.
  • At least one urea extractant is of Formula (I) wherein R 1 and R 2 are a Ce aromatic ring and R 3 and R 4 are H. In one or more embodiments, at least one urea extractant is of Formula (I) wherein R 1 and R 2 are independently a straight or branched Ce-Cs alkyl and R 3 and R 4 are H. In some embodiments, at least one urea extractant in the reagent composition is of Formula (II) wherein R 1 and R 3 are a straight or branched Cs-Cs alkyl, and R 2 and R 4 are H.
  • the at least one urea extractant may be present in the reagent composition in an amount of about 5 wt% to about 100 wt%, about 10 wt% to about 90 wt%, about 20 wt% to about 800 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 50 wt%, about 10 wt% to about 50 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the urea extractant is present in the reagent composition in an amount of at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or any individual value or subrange within these ranges.
  • the urea extractant is present in the reagent composition in an amount of about 45 wt%, about 46 wt%, about 47 wt%, about 48 wt%, about 49 wt%, about 50 wt%, about 51 wt%, about 52 wt%, about 53 wt%, about 54 wt, or about 55 wt%. In some embodiments, the urea extractant is present in the reagent composition in an amount of about 50 wt%.
  • Suitable non-urea extractants for use in reagent compositions as described herein include one or more urea compound having the following Formula (III), Formula (IV), Formula (V), or combinations thereof: wherein each independently hydrogen, a methyl group, an ethyl group, a straight or branched C3-C20 alkyl group, a C3-C12 cycloalkyl group having a single ring structure, a CV-C 10 aromatic ring group, a C1-C20 alkylphenyl group, a dihydrobenzodioxene group, a straight or branched C1-C20 alkanol group, a straight or branched C1-C20 alkyldiol group, a straight or branched C3-C20 alkenyl group, a straight or branched C3-C20 alkynyl group, a thiol group, wherein at least one carbon atom of R 5 , R 6 , R 7
  • R 6 is H.
  • R 5 , R 7 or both are a straight or branched C3-C8 alkyl.
  • R 5 is a branched Cs alkyl or a branched Cs alkyl.
  • R 7 may be a branched C4 alkyl.
  • at least one non-urea extractant in the reagent composition is of Formula (III), wherein R 5 and R 7 are each independently a straight or branched C3-C8 alkyl and R 6 is H.
  • At least one non-urea extractant is of Formula (IV) wherein R 8 and R 10 are each independently a straight or branched C3-C8 alkyl, R 9 and R 11 are H, and R 12 is a Cs-Ce cycloalkyl.
  • at least one non-urea extractant is of Formula (III) wherein R 5 is a straight or branched C3-C8 alkyl, R 6 is H and R 7 is methyl.
  • at least one non-urea extractant in the reagent composition is of Formula (III) wherein R 5 is H, R 6 and R7 is each independently a straight or branched C3-C8 alkyl.
  • At least one non-urea extractant is of Formula (III) wherein R 5 is a straight or branched C3-C8 alkyl, R 6 is H, and R 7 is an ethyl group.
  • at least one non-urea extractant is of Formula (III) wherein R 5 is a CR aromatic ring group, R 6 is H, and R 7 is a methyl group.
  • at least one non-urea extractant is of Formula (III) wherein R? is H, R 6 a Ci alkylphenyl group, and R 7 is a straight or branched C3-C8 alkyl group.
  • At least one non-urea extractant is of Formula (IV) wherein R 8 , R 9 and R 10 are H, R 12 is a bond, and R 11 is a straight or branched C3-C8 alkyl.
  • at least one non-urea extractant is of Formula (III) wherein R 5 is a straight or branched Cs-Cs alkyl, R 6 is H and R 7 is a dihydrobenzodioxene group.
  • at least one non-urea extractant is of Formula (III) wherein R 5 is a Ce aromatic ring group, R 6 is H, and R 7 is a straight or branched C3-C8 alkyl.
  • At least one non-urea extractant is of Formula (III), wherein R 5 and R 6 are H, and R 7 is a C3-C8 alkyldiol group.
  • at least one non-urea extractant is of Formula (III) wherein R 5 is an 0 substituted C3-C8 alkanol, R 6 is H, and R 7 is a straight or branched Cs-Cs alkyl.
  • at least one non-urea extractant is of Formula (V) wherein R 13 is H and R 14 and R 15 is each independently a straight or branched Ci-Cs alkyl.
  • the at least one non-urea extractant may be present in the reagent composition in an amount of about 5 wt% to about 100 wt%, about 10 wt% to about 90 wt%, about 20 wt% to about 800 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 50 wt%, about 10 wt% to about 50 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the non-urea extractant is present in the reagent composition in an amount of at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or any individual value or sub-range within these ranges.
  • the non-urea extractant is present in the reagent composition in an amount of about 45 wt%, about 46 wt%, about 47 wt%, about 48 wt%, about 49 wt%, about 50 wt%, about 51 wt%, about 52 wt%, about 53 wt%, about 54 wt, or about 55 wt%.
  • the non-urea extractant is present in the reagent composition in an amount of about 50 wt%.
  • the reagent composition comprises a weight ratio of the at least one urea extractant to the at least one non- urea extractant of about 1: 10 to about 100: 1
  • the reagent compositions described herein further include at least one modifier, at least one diluent, or a combination thereof.
  • “Modifiers” refer to chemical compounds designed to affect the properties of other molecules, materials and/or solutions.
  • “Diluents” refer to one or more substance that is added to the reagent compositions to alter the concentration of other components (e.g., one or more extractant, one or more modifier) contained therein and/or to alter the viscosity of the reagent composition.
  • Modifiers as described herein may be used to stabilize the IODS. This can be helpful as the polarity of the organic solvent is not high enough to stabilize the highly ionic character of the IODS.
  • Suitable modifiers for inclusion in reagent compositions as described herein include compounds having one or more functional group with a dipole moment and/or that are attached to a highly polar ionic bond. This may “shield’' the ionic moieties and helps to solubilize the IODS.
  • the at least one modifier has an aliphatic component that is attracted to non-polar moieties of the at least one urea extractant and/or at least one non-urea extractant.
  • the at least one modifier includes one or more functional group chosen from a diether, imide, ketone, alcohol, ether, alkyl phosphine, phosphate, ester, phosphonic acid, phosphonic acid, phosphoric acid and/or nitrile.
  • Suitable modifiers for use in reagent compositions as described herein may be chosen from 1,6-di-t-butoxy hexane, di(ethylene glycol) dibutyl ether, 1,4-bis-t-butoxy butane, 2- ethylhexyl succinimide, 4-t-butylcyclohexanone, l-butyl-3-methylimidazolium methyl sulfate, iminodiacetic acid (IDA), dodecanol, 2,2,4-trimethyl-l,3-pentanediol diisobutyrate (TXIB), ethoxylatedisotridecyl phosphate (TDA), cy decanol, l-methyl-3-octylimidazolium chloride, trihexyltetradecylphosphonium chloride, l-decyl-3-methylimidazolium tetrafluoroborate, 7- eth
  • the at least one modifier is present in the reagent composition in an amount of about 0 wt% to about 95 wt%, about 5 wt% to about 80 wt%, about 10 wt% to about 80 wt%, about 20 wt% to about 70 wt%, about 30 wt% to about 60 wt%, about 50 wt% to about 90 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the modifier is present in the reagent composition in an amount of at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, or any individual value or sub-range within these ranges. In one or more embodiments, the modifier is present in the reagent composition in an amount of about 40 wt%, about 41 wt%, about 42 wt%, about 43 wt%, about 44 wt%, about 45 wt%, about 46 about 47 wt%, about 48 wt%, about 49 wt%, about 50 wt%, about 51 wt%, or about 52 wt%. In some embodiments, the modifier is present in the reagent composition in an amount of about 50 wt%.
  • the weight ratio of the urea extractant to the modifier in the reagent composition is about 1: 100 to about 100:1, about 1:90 to about 90: 1, about 1 :80 to about 80: 1, about 1: 70 to about 70:1, about 1:60 to about 60:1, about 1:50 to about 50: 1, about 1:40 to about 40: 1, about 1 :30 to about 30: 1, about 1:25 to about 25: 1, about 1:20 to about 20: 1, about 1:15 to about 15:1, about 1: 10 to about 10: 1, about 1:5 to about 5: 1, about 1:2 to about 1 :2, about 1: 10 to about 100: 1, or any individual value or sub-range within these ranges.
  • the weight ratio of the urea extractant to the modifier is at least about 1: 10, at least about 1:5, at least about 1:2, at least about 1: 1, at least about 2:1, at least about 5: 1, at least about 10: 1, or any individual value or sub-range within these ranges.
  • the weight ratio of the non-urea extractant to the modifier in the reagent composition is about 1 :100 to about 100:1, about 1:90 to about 90: 1, about 1:80 to about 80: 1, about 1: 70 to about 70:1, about 1:60 to about 60:1, about 1:50 to about 50: 1, about 1:40 to about 40: 1, about 1 :30 to about 30: 1, about 1:25 to about 25: 1, about 1:20 to about 20: 1, about 1:15 to about 15:1, about 1: 10 to about 10: 1, about 1:5 to about 5: 1, about 1:2 to about 1 :2, about 1: 10 to about 100: 1, or any individual value or sub-range within these ranges.
  • the weight ratio of the non-urea extractant to the modifier is at least about 1:10, at least about 1:5, at least about 1:2, at least about 1 : 1, at least about 2: 1, at least about 5:1, at least about 10:1, or any individual value or sub-range within these ranges.
  • Suitable diluents include, but are not limited to, an alcohol, an organophosphorous solvent, or a combination thereof.
  • the at least one diluent may be chosen from octanol, trideconal, 2-ethyl-l -hexanol, 3-methyl-l-butanol, isoamyl alcohol, 2- hexyl decanol, octanoic acid, trioctylphosphine oxide (e.g., Cyanex® 923), petroleum distillates solvent (e.g., Orform® SX80), aromatic C9-C10 solvent (e.g., Shellsol® A150), a kerosene (e.g., Orform® SX11), dibutyl carbitol, di chloromethane, trioctylmethylammonium chloride (e.g., Aliquat 336), chloroform, or a combination of any two or more thereof.
  • octanol tri
  • the at least one diluent is present in the reagent composition in an amount of about 0 wt% to about 90 wt%, about 5 wt% to about 80 wt%, about 10 wt% to about 70 wt%, about 20 wt% to about 60 wt%, about 40 wt% to about 50 wt%, or any individual value or sub-range within these ranges, based on the total weight of the reagent composition.
  • the diluent is present in the reagent composition in an amount of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt%. In some embodiments, the diluent is present in the reagent composition in an amount of about 0 wt% or less than about 1 wt%.
  • Reagent compositions are comprised of a urea extractant, a non-urea extractant and optionally may be combined with at least one modifier and/or at least one diluent.
  • a diluent is combined with the urea extractant and/or the non-urea extractant, for example, to provide atarget reagent concentration and/or to provide a target viscosity.
  • Suitable reagent concentrations for a urea extractant or a non-urea extractant in a diluent are about 1 wt% to about 99 wt%, or any individual value or sub-range within these ranges.
  • the viscosity of the urea extractant and/or the non-urea extractant, alone or in combination is adjusted by combining the extractant(s) with a diluent while mixing at about 20°C to about 50°C, about 30°C to about 50°C, or any individual value or sub-range within these ranges, to form one or more reagent having a low viscosity of about 0.1 cP to about 15 cP, or any individual value or sub-range within this range.
  • the urea extractant and the non-urea extractant are combined to form an extractant mixture.
  • Each extractant or the extractant mixture may be combined with a modifier while mixing at about 20°C to about 50°C, about 30°C to about 50°C, or any individual value or sub-range within these ranges, to form the reagent composition.
  • a diluent may or may not be present and/or combined with the urea extractant, the non-urea extractant and/or the mixture of the extractants with the modifier.
  • the urea extractant and the non-urea extractant may be combined with the modifier over a range of suitable concentrations and ratios to form the reagent composition.
  • the viscosity of the resulting reagent composition may be about 0. 1 cP to about 100 cP, or any individual value or sub-range within this range.
  • Reagent compositions according to embodiments herein are suitable for use in a liquid-liquid solvent extraction process.
  • an aqueous feed solution e.g., a lithium-containing brine
  • an organic solution e.g., a large organic to aqueous ratio
  • a target metal, compound thereof, salt thereof, or combinations thereof e.g., lithium, lithium salt, lithium chloride, etc.
  • the molar ratio of the extractant to the target metal may be 1 : 1.
  • the aqueous solution may be a metal-containing brine (e.g., a lithium-containing brine), brine from a salar, product stream from a pond evaporation process, product stream from a processing plant, or combinations thereof.
  • the aqueous feed solution contains lithium, magnesium, calcium, boron, potassium, sodium, or combinations thereof.
  • the aqueous feed solution comprises a lithium salt, magnesium salt, calcium salt, boron salt, potassium salt, sodium salt, or combinations thereof.
  • the aqueous feed solution comprises lithium or a lithium salt.
  • the one or more target metals, compounds thereof, salts thereof, or combinations for extraction using the described methods may be lithium chloride, lithium sulfate, lithium hydroxide, lithium nitrate, or combinations thereof.
  • the aqueous solution is a brine containing greater than about 60,000 ppm of magnesium, compounds thereof, salts thereof, or combinations thereof, and at least about 150 ppm of lithium, compounds thereof, salts thereof, or combinations thereof.
  • the aqueous solution may be contacted with a magnesium selective reagent composition, a calcium selective reagent composition, a boron selective reagent composition, or combinations thereof, prior to contacting the aqueous solution with the reagent composition to extract the one or more metals.
  • Removing magnesium, calcium, and/or boron metals, compounds thereof, salts thereof, or combinations thereof may improve the selectivity of a downstream lithium, compounds thereof, salts thereof, or combinations thereof solvent extraction process.
  • the inventive reagent compositions may be combined with an organic solvent (e.g., a kerosene) to form the organic solution.
  • the at least one urea extractant and the at least one non-urea extractant in the reagent composition are suitable to selectively extract one or more target metals including compounds thereof, salts thereof, or combinations thereof from the aqueous solution into the organic solution.
  • adding one or more reagent composition to the organic solution increases the extraction efficiency, selectivity and/or extraction rate for one or more target metal including compounds thereof, salts thereof, and/or combinations thereof.
  • the metal depleted aqueous solution may be recycled to the combine with the aqueous feed solution and/or sent to another process for purification or removal of one or more additional metal, compounds thereof, salts thereof, or combinations thereof using solvent extraction and/or another metal removal process.
  • the metal rich organic phase may be sent to one or more downstream processes (e.g., stripping, electro winning, etc.) to recover the one or more target metals that have been extracted from the aqueous solution.
  • the methods include stripping the one or more metals from the metal rich organic phase.
  • the stripping of the reagent can be accomplished with water.
  • the metal depleted organic solvent may be returned to the solvent extraction process for further contact with incoming aqueous feed.
  • the metal depleted organic solvent is replenished with fresh reagent composition to ensure efficiency of the continuous process.
  • the concentration of lithium salt e.g., lithium chloride
  • the concentration of lithium salt can be increased to at least 20,000 ppm at which point the stripping efficiency drops below 90%. This does not limit the concentration of the strip solution but may alter the amount of extractant necessary to keep extraction efficiency in an effective range.
  • about 70% to about 99%, or at least about 95%, or any individual value or subrange within these ranges of the one or more metals is stripped from the metal rich organic phase.
  • the methods include contacting the aqueous solution with the reagent composition as described herein.
  • the reagent composition may be contained in an organic solvent to form an organic solution.
  • the method further include extracting the one or more metals, compounds thereof, salts thereof, or combinations thereof from the aqueous solution into the organic solution containing the reagent composition until reaching equilibrium to form a metal depleted aqueous phase and a metal rich organic phase.
  • the methods include separating the metal depleted aqueous phase from the metal compound rich organic phase.
  • the methods may further include contacting the metal depleted aqueous phase with fresh reagent composition and further extracting the one or more metals, compounds thereof, salts thereof, or combinations thereof, from the aqueous solution into the metal rich organic phase (or fresh organic solution) until reaching equilibrium. This process may be repeated to further extract more target metal(s) from the aqueous phase using fresh reagent composition until the metal compound depleted aqueous phase is free or substantially free of the one or more target metals, compounds thereof, salts thereof, or combinations thereof.
  • the methods further include emulsifying the metal rich organic phase.
  • Emulsifying the organic phase can increase the surface area of the extractants to provide more bonding sites for the urea extractant and/or non-urea extractant to bond with the one or more target metals, compounds thereof, salts thereof, or combinations thereof.
  • the above methods may provide an overall extraction of the one or more metals, compounds thereof, salts thereof, or combinations thereof, from the aqueous solution of greater than about 70%, greater than about 80%, greater than about 90%, greater than about 92%, or about 70% to about 99%, or about 80% to about 93%, or any individual value or sub-range within these ranges.
  • selectivity for the inventive reagent compositions is very high for lithium over sodium, potassium, magnesium, calcium, boron, and sulfate.
  • emulsions may be controlled to keep selectivity high, which may be addressed by controlling viscosity of the organic. Selection of suitable equipment maintain low entrainment mixing also may assist in emulsion control.
  • the target metal is lithium, lithium-containing compounds, lithium salts, or combinations thereof
  • the selectivity of the urea extractant, the non-urea extractant, or a mixture thereof for lithium over magnesium is about 1 to about 50, about 5 to about 30, or about 10 to about 25.
  • Example 1 Performance of lithium extraction of a brine using an amide extractant El of Formula (III) spiked with a urea extractant E2 and/or E3 of Formula (I) in a tributyl phosphate modifier (Ml)
  • Amide extractant El of Formula (III) was spiked with either a urea extractant E2 of Formula (I) or a urea extractant E3 of Formula (I) in a mixture with a tributyl phosphate modifier Ml . Varying ratios of amide extractant El to urea extractant E2 or E3 were evaluated.
  • the extraction tests were conducted at an O: A of 5: 1 for one (1) hour at room temperature. Strip tests were conducted after each extraction stage at an O: A of 1: 1 using deionized (DI) water for one (1) hour at about 50°C. Both extraction and strip experiments were conducted using a shaker at a low setting. Nuclear magnetic resonance (NMR) imaging was used to measure Li and Na values in aqueous samples, while inductively coupled plasma (ICP) mass spectrometry was used to measure other elements in the strip solutions. Table 1 shows the composition of the feed solution.
  • NMR nuclear magnetic resonance
  • ICP inductively coupled plasma
  • Table 2 shows the extraction and strip results for the various extractant formulations.
  • the urea-spiked amide extractant El improved the LiCl extraction performance by up to 40% and improved the Li/Mg selectivity by up to 180% as compared to an amide extractant El on its own. Lower amounts of extractants can be used with this formulations, which would further reduce the cost of the reagent. With a higher selectivity (Li/Mg mass ratio of 8-9), the LiCl product stream is of higher purity, which requires less Mg polishing for LiCl conversion.
  • a urea extractant E2 was spiked with amide extractant El. Different El :E2 ratios were evaluated. The extraction tests were conducted at an 0: A of 5: 1 for one (1) hour at room temperature. Strip tests were conducted after each extraction stage at O:A of 1: 1 using DI water for one (1) hour at about 50°C. Both extraction and strip experiments were performed using a shaker at a low setting. NMR was used to measure Li and Na values in aqueous samples, while ICP was used to measure other elements in strip solutions.
  • Table 3 shows the composition of the feed solution.
  • composition of the formulations contains the extractants and the residual volume is modifier.
  • Table 4 shows the extraction and strip performance results for the extractant combinations.
  • Solvent extraction was conducted using extractant solutions containing extractant El, extractant E2 and modifier Ml together with amide extractant E15 or E17 of Formula (III) or urea extractant E16 of Formula (II) as the organic phase. Extraction tests were conducted at an O:A of 5: 1 at room temperature using a shaker at a low setting. Strip tests were conducted using DI water at an O:A of 1: 1 at about 50°C. NMR was used to measure Li values in aqueous samples, while ICP was used to measure other elements in strip solutions.
  • Table 5 shows the composition of the feed solution for the various extraction reactions.
  • Table 6 shows the extraction test results for various mixtures of extractants and modifiers.
  • Solvent extraction experiments were conducted using a mixture of a urea extractant E3 and/or E16 with an amide extractant E18 or E19 of Formula (III). Extraction tests were conducted at an O:A of 5:1 for one (1) hour at room temperature. Strip tests were conducted at an 0: A of 1 : 1 using DI water for one (1) hour at about 50°C. All experiments were performed using a shaker at a low setting. NMR was used to measure Li and Na values in aqueous samples, while ICP was used to measure other elements in strip solutions.
  • Table 7 shows the composition of the feed solution for the various extraction reactions.
  • Table 8 shows the solvent extraction results when employing various mixtures of extractants and modifiers in the organic phase.

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Abstract

L'invention concerne des compositions de réactif contenant au moins un agent d'extraction à base d'urée et au moins un agent d'extraction non à base d'urée permettant d'extraire d'une solution aqueuse, de manière sélective, un ou plusieurs métaux, composés de ceux-ci, sels de ceux-ci ou combinaisons de ceux-ci ; et éventuellement au moins un modificateur et/ou un diluant. L'invention concerne en outre des procédés pour extraire un ou plusieurs métaux d'une solution aqueuse, comprenant les étapes consistant à mettre en contact la solution aqueuse avec une composition de réactif telle que décrite ci-dessus ; et à extraire le ou les métaux, composés de ceux-ci, sels de ceux-ci ou combinaisons de ceux-ci, de la solution aqueuse dans la composition de réactif jusqu'à atteindre l'équilibre pour former une phase aqueuse appauvrie en métal et une phase organique riche en métal.
PCT/US2024/057489 2024-03-20 2024-11-26 Compositions et procédés pour extraire un ou plusieurs métaux d'une solution Pending WO2025198668A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306712A (en) * 1963-12-30 1967-02-28 Dow Chemical Co Extraction of lithium halides from calcium-containing brines in the presence of urea and alcohol-ketone
US8753594B1 (en) * 2009-11-13 2014-06-17 Simbol, Inc. Sorbent for lithium extraction
US20210324495A1 (en) * 2018-07-10 2021-10-21 Basf Se Process for the recycling of spent lithium ion cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306712A (en) * 1963-12-30 1967-02-28 Dow Chemical Co Extraction of lithium halides from calcium-containing brines in the presence of urea and alcohol-ketone
US8753594B1 (en) * 2009-11-13 2014-06-17 Simbol, Inc. Sorbent for lithium extraction
US20210324495A1 (en) * 2018-07-10 2021-10-21 Basf Se Process for the recycling of spent lithium ion cells

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