WO2021231597A1 - Systèmes et procédés de récupération de lithium à partir de saumures - Google Patents

Systèmes et procédés de récupération de lithium à partir de saumures Download PDF

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Publication number
WO2021231597A1
WO2021231597A1 PCT/US2021/032027 US2021032027W WO2021231597A1 WO 2021231597 A1 WO2021231597 A1 WO 2021231597A1 US 2021032027 W US2021032027 W US 2021032027W WO 2021231597 A1 WO2021231597 A1 WO 2021231597A1
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Prior art keywords
lithium
brine
pond
precipitation
stream
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PCT/US2021/032027
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English (en)
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WO2021231597A9 (fr
Inventor
Amit PATWARDHAN
Teague Egan
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Energy Exploration Technologies, Inc.
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Priority to AU2021254665A priority Critical patent/AU2021254665B2/en
Priority to PE2021001898A priority patent/PE20220205A1/es
Priority to IL287465A priority patent/IL287465B2/en
Priority to US17/602,808 priority patent/US20230192503A1/en
Priority to JOP/2021/0311A priority patent/JOP20210311A1/ar
Priority to MX2021013733A priority patent/MX2021013733A/es
Priority to EP21789600.0A priority patent/EP3947756A4/fr
Priority to CA3136247A priority patent/CA3136247C/fr
Application filed by Energy Exploration Technologies, Inc. filed Critical Energy Exploration Technologies, Inc.
Priority to CN202180003093.1A priority patent/CN113924375B/zh
Priority to PCT/US2021/032027 priority patent/WO2021231597A1/fr
Priority to US17/529,492 priority patent/US20220136081A1/en
Publication of WO2021231597A1 publication Critical patent/WO2021231597A1/fr
Publication of WO2021231597A9 publication Critical patent/WO2021231597A9/fr
Priority to US17/862,090 priority patent/US20240067530A1/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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/06—Sulfates; Sulfites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/38—Magnesium nitrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/40—Magnesium sulfates
    • 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
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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 provides systems and methods for efficient extraction of lithium from brines, particularly high salt brines containing significant concentrations of sodium (Na/Na + ), potassium (K/K + ), magnesium (Mg/Mg 2+ ), calcium (Ca/Ca 2 ), chloride (Cl/Cl ), sulfate (SO4/SO4 2 ), boron (B, ionic or molecular) and /or other ions that can lead to lithium (Li/Li + ) losses in new and existing processes for Li extraction from brine due to Li co-precipitation with such other ions.
  • nanofiltration and reverse osmosis processes require high pressures which represent a major operating cost.
  • Shortcomings of ion exchange and ion sorption processes reside in the limited selectivity and specific capacities offered. These are also batch processes and require chemicals for elution of ions and large amounts of water for washing the resin or media beds. Disposal of this contaminated effluent is another problem.
  • moderate selectivity membranes against a very high background of impurities results in excessive current and energy requirements to move the impurity ions along with lithium.
  • Co-precipitation losses are when a lithium salt solid precipitates as itself or as a double salt with other cations and anions. This is the co-precipitation loss. Lithium co precipitation losses from such processes can be as large as 40-60%, depending on the specific process and brine chemistry.
  • the systems and methods described herein can eliminate the lithium co-precipitation losses by application of a separator at a specific location(s) in the evaporation sequence.
  • Applications of the systems and methods provided herein can be seamlessly incorporated into existing operations or be utilized as design features in new operations.
  • the preferred systems and methods require treatment of as little as 1-5% of the total brine flow, require low energy and fresh water input, increase lithium recovery by absolute 40-70%, and thus greatly reduce lithium extraction costs and environmental impact.
  • the present disclosure provides a system for efficiently extracting lithium from brines by reducing lithium losses due to co-precipitation and/or allowing significantly higher lithium concentration.
  • the preferred system includes a sequence of two or more solar evaporation ponds configured to allow evaporation of brine to occur in each pond and for brine to flow from a first pond to one or more other ponds in the sequence; and a conduit configured to remove at least a portion of the brine at a brine removal location and transmit the removed brine to a separator whereby one or more impurities are separated from lithium to form a high impurity stream (i.e., the impure stream) and a low impurity stream (i.e., the pure stream).
  • a high impurity stream i.e., the impure stream
  • a low impurity stream i.e., the pure stream
  • the high impurity stream is optionally recycled to the sequence of evaporation ponds at a location the same as or upstream from the brine removal location and the low impurity stream is fed to one or more of the removal location, to a subsequent pond in the sequence, or to a lithium plant or concentration facility.
  • the brine removal location is positioned such that lithium co-precipitation together with the one or more impurities is reduced as compared to an amount of lithium co-precipitation that would occur in the preceding or succeeding ponds in the absence of the separation system. As a result, lithium loss due to co-precipitation is reduced or eliminated.
  • the low impurity stream may have a higher or lower concentration of lithium than the high impurity stream but will have a lower concentration of the one or more impurities that are selected for separation from lithium in the separator.
  • impurities herein, we mean components such as Na + , K + , Mg 2+ , Ca 2+ , CT, S04 2 , B (ionic or molecular) and other ions (i.e., “impurity ions”) or components that, unless separated and/or removed, can form co-precipitates with lithium.
  • the present disclosure provides a system wherein feed to a first pond in the sequence of ponds is a high lithium, low sulfate brine (e.g., Chilean-type) brine.
  • the high impurity stream is recycled to a pond precipitating a salt selected from the group consisting of bischofite and carnallite and the low impurity stream is fed to a pond that is substantially free of co-precipitated Li in the form of lithium carnallite.
  • the present disclosure provides a system wherein feed to a first pond in the sequence of ponds is a low lithium, high magnesium, high sulfate (e.g., Venezuelan-type) brine.
  • the high impurity stream is recycled to a pond precipitating a salt selected from the group consisting of bischofite, carnallite, hexahydrite and kieserite, and the low impurity stream is fed to a pond that is substantially free of co-precipitated Li in the form of lithium sulfate monohydrate.
  • the feed to a first pond in the sequence of ponds is a low lithium, low magnesium, high sulfate (e.g., Argentinian-type) brine.
  • the high impurity stream is recycled to a pond precipitating a salt selected from the group consisting of NaCl and Glauber’s salt, and the low impurity stream is fed to a pond that is substantially free of co-precipitated Li in the form of lithium potassium double salt or lithium schoenite.
  • the high impurity stream is evaporated in a separate pond sacrificing the contained lithium or harvesting precipitated lithium salt for further processing.
  • the high impurity stream could also be reinjected to the aquifer.
  • the low impurity stream can be processed as described in paragraphs [0010] to [0012] or taken directly to precipitation or downstream processing plant either together with the concentrated brine or separately from it.
  • the portion of brine removed at the brine removal location is about 1 to about 50%, 1 to 25% and preferably 1 to 5% of the total brine flow in the ponds.
  • the increase in lithium recovery is from about 10 to about 70% (absolute units).
  • the lithium containing brine is pre concentrated by solar evaporation to a point at the brine removal location at which further concentration would co-precipitate lithium salts.
  • the separator is configured to at least partially separate lithium from impurity cations and anions which have a propensity to form lithium salts that can precipitate under further brine concentration, and which impurity cations and anions are suitable for earlier precipitation with each other in preceding evaporation ponds in the sequence.
  • the separation may be, for example, selected from the group consisting of a selective ion separation membrane, nanofiltration, ion sorption, ion exchange, and electrodialysis.
  • a particularly preferred separator is a LiTASTM selective ion separation membrane.
  • the membrane separator can be operated in a dialysis or electrodialysis mode.
  • the present disclosure provides a system further including removal of borate ions or boric acid in the separation process and recycling and precipitating borate ions or boric acid in previous ponds in the sequence as calcium borate or boric acid, thereby eliminating or substantially reducing a potential requirement for further boron treatment.
  • the systems provide for recycle of the high impurity stream to a point in one or more preceding evaporation ponds in the sequence where conditions are favorable for precipitation and thus removal of one or more impurity ions without lithium co-precipitation.
  • the systems provide for advancing the low impurity stream to a downstream pond, mechanical evaporator, or precipitation plant for further concentration. This further concentration can now occur substantially without lithium co-precipitation and the associated lithium loss.
  • the systems provide for the high impurity stream diverted to a separate pond for evaporation or re-injection into the aquifer. Precipitated salts containing lithium could be processed together or separately with the brine in the processing plant. In another aspect, the systems provide for advancing the low impurity stream directly to the downstream processing plant.
  • the present disclosure provides a method for improving efficiency in extracting lithium from brines using a sequence of solar evaporation ponds, by reducing lithium losses due to co-precipitation, the method including separating at least a portion of the brine at a brine removal location to obtain a removed brine, and transmitting the removed brine through a separator such that one or more impurities are separated from lithium to form a high impurity stream (i.e., the impure stream) and a low impurity stream (i.e., the pure stream).
  • a separator such that one or more impurities are separated from lithium to form a high impurity stream (i.e., the impure stream) and a low impurity stream (i.e., the pure stream).
  • the method can next recycle at least a portion of the high impurity stream to the sequence of evaporation ponds at a location the same as or upstream from the brine removal location, and transfer the low impurity stream to one or more of the removal location (i.e., the pond from which the brine was removed), to a downstream (i.e., subsequent) pond in the sequence, or to a lithium recovery facility.
  • the brine removal location is positioned such that lithium co-precipitation with one or more impurities is reduced from the brine flow and higher concentration of lithium is attained due to lithium co precipitation reduction or elimination.
  • the method may include further concentrating the low impurity stream by, such as, evaporation without co-precipitation loss of lithium even at higher concentrations.
  • the method of separating is conducted via a selective monovalent-multivalent and/or a monovalent-monovalent ion separation system.
  • the separator comprises a LiTASTM Technology Membrane.
  • the membrane may be operated in a dialysis or electrodialysis mode.
  • the method of separating is conducted via a solvent extraction, ion exchange or ion adsorption technique to selectively separate lithium from impurity ions.
  • the method can attain an increase in lithium concentration in a range from about 50% to about 400%.
  • Figure 1 illustrates typical solar evaporation and concentration of lithium from brines as well as precipitations of salts at different points in the evaporation sequence. Lithium precipitation losses in such systems can be in the 40-60% range.
  • Figure 2 illustrates embodiments of the present disclosure using separator applications in the evaporation pond cascade to exploit natural brine chemistry for removal of impurities and concentration of lithium without lithium co-precipitation losses.
  • Figure 2 (a) represents typical Chilean and Perun brines, (b) typical Argentinian brines, and (c) typical Venezuelan and some Argentinian brines.
  • Figure 3 illustrates increases in Li recovery using aspects of the presently disclosed methods and systems while attaining high lithium concentrations from a typical Venezuelan brine.
  • Figure 4 shows aspects of a preferred embodiment using ion separation after camallite / bischofite ponds from a typical Chilean or Venezuelan brine.
  • Figure 5 illustrates an aspect of seamless integration of the presently disclosed systems in an existing operation.
  • Figure 6 depicts a mass balance and simulation results of the conventional brine (Chilean Brine High Lithium, Low Sulfate) evaporation process for production of lithium.
  • Figure 7 depicts a mass balance and simulation results of the brine evaporation process of Figure 6 using preferred aspects of the present disclosure.
  • Figure 8 depicts a mass balance and simulation results of another conventional brine (Bolivian Brine, Low Lithium, High Magnesium, High Sulfate) evaporation process for production of lithium.
  • Figure 9 depicts a mass balance and simulation results of the brine evaporation process of Figure 8 using preferred aspects of the present disclosure.
  • Figure 10 depicts a mass balance and simulation results of another conventional brine (Argentinian Brine, Low Lithium, Low Magnesium, High Sulfate) evaporation process.
  • Argentinian Brine Low Lithium, Low Magnesium, High Sulfate
  • Figure 11 depicts a mass balance and simulation results of the brine evaporation process of Figure 10 using preferred aspects of the present disclosure.
  • the systems and methods described herein advantageously eliminate or minimize lithium co-precipitation losses by application of a separator, preferably a selective monovalent-multivalent and/or a selective monovalent-monovalent separation process applied at a selected location in the evaporation cycle.
  • the methods comprise one or more of the following steps: solar evaporation to preconcentrate the brine to the point of lithium saturation; apply selective separation to separate lithium from the impurities at a selected location (preferably, a point such that lithium would otherwise reach saturation and co-precipitation with impurity ions); return separated impurities to a location in the evaporation sequence where conditions are favorable for their precipitation; and then further concentrate lithium by, such as evaporation, as the accompanying impurities do not favor lithium co-precipitation.
  • natural evaporation-concentration-precipitation processes are allowed to occur to, at, or near the point of lithium saturation, the “saturation point.”
  • this point may be reached after the carnallite/bischofite pond as shown in Figure 1, or earlier with saturation of lithium sulfate monohydrate (LhSOr.H O). Evaporation beyond the lithium saturation point will start lithium co-precipitation and losses.
  • Application of the systems and methods described herein after natural solar evaporation can reduce the overall volume of brine to be treated by 95-99%.
  • locations for application of separation can also be viewed as a location for removal of a portion of the brine stream from the sequence of evaporation ponds. This location is preferably a point at which the concentration of lithium is within a range of minus 50%, minus 25%, preferably plus or minus 10%, or up to plus 50% of its saturation concentration in the brine.
  • the recycle location can be at the location for removal (e g., the same pond from which removal occurred) of at least a portion of the brine stream or can be upstream of this location where conditions are favorable for precipitation of impurities without lithium co precipitation, or a separate pond for partial or total evaporation or re-injected to the aquifer.
  • Such recycle and precipitation of the impurities prevents them from building up in the system and altering the chemistry in the evaporation ponds.
  • Figure 2a depicts a brine in which continued evaporation results in lithium co-precipitation as LiCl.MgCl2.7H2O.
  • the previous pond in the evaporative sequence however has conditions favorable for, and thus is precipitating, MgCl2.6H20. This is a very typical situation in Chilean and Venezuelan brines as well as other high magnesium brines.
  • Mg 2+ is prevented from advancing forward; we have found that lithium co-precipitation as LiCl.MgCl2.7H20 will thus be prevented.
  • Magnesium can be prevented from advancing by utilizing, for example, a suitable monovalent-divalent (Li + /Mg 2+ ) cation selective separator.
  • the blocked Mg 2+ may then be recycled to the previous pond(s) where conditions remain favorable for its precipitation as MgCl2.6H20.
  • the lithium passing the separator and advancing now does not have magnesium to co-precipitate and hence can be concentrated to much higher levels without incurring any lithium losses.
  • the brine is typical of Argentinian and Venezuelan brines as well as other high sulfate brines, wherein the concentration of Li results in precipitation of LriSCri.ftO.
  • the previous pond is favorable for precipitating Na2SO4.10H2O.
  • separator blocks SO4 2 from advancing, L12SO4.H2O will not precipitate in subsequent evaporation.
  • an equivalent amount of cation also is blocked, to maintain electroneutrality.
  • Na + is preferred cation to block, as it is favored for precipitation in the previous pond to which, preferably, it is recycled.
  • Na + and SO4 2' are thus recycled back to the previous pond where they are precipitated as additional Na2SC>4.10H2O.
  • Na + and SO4 2 can be blocked by a suitable monovalent-monovalent (Li-Na) cationic separator and a monovalent-divalent anionic separator (Cl -SOr 2 ) ⁇ [0041]
  • Li-Na monovalent-monovalent
  • Cl -SOr 2 monovalent-divalent anionic separator
  • the recycle is alternatively to the first pond in the sequence where conditions are also favorable for precipitating, for example, sulfate as sodium sulfate decahydrate.
  • sulfate as sodium sulfate decahydrate.
  • the impurity ions co-precipitated with Li, resulting in significant Li losses.
  • an optional separator configured to block the borate anion from advancing and thus recycling it back to the previous ponds where conditions are favorable for precipitation of calcium or sodium borate or boric acid also is beneficial.
  • boron is removed from the concentrated brine by expensive and environmentally undesirable methods, such as solvent extraction using organic solvents.
  • separators useful in embodiments of the present disclosure can include any separators which can achieve separation of at least a portion of lithium from one or more impurities in the brine, and preferably targeted monovalent-monovalent and/or monovalent- multivalent separations.
  • suitable separators utilize nanofiltration, ion sorption, or ion exchange, with preferred embodiments utilizing LiTASTM membrane separation technology as shown in Figure 4.
  • LiTASTM membrane separation technology we mean lithium-ion transport and/or separation using metal organic framework (MOF) nanoparticles.
  • MOFs have exceptionally high internal surface area and adjustable apertures that achieve separation and transport of ions while only allowing certain ions to pass through.
  • MOF nanoparticles are materialized like a powder, but when combined with polymer to create a tangible product, utilizing a proprietary processing method, the combined MOF and polymer create a mixed matrix membrane embedded with the nanoparticles.
  • the MOF particles create a percolation network, or channels, that allow selected ions to pass through.
  • the membrane When extracting lithium, the membrane is placed in a module housing. Brine is pumped through the system with one or more layers of membranes that conduct effective separation even at high salinities. While current separator technology can fall short in one area or another, LiTASTM is particularly preferred and effective. LiTASTM Membrane Technology U.S. Patent Application No. 62/892,439, filed August 27, 2019, U.S. Patent Application No. 62/892,440, filed August 27, 2019, and International Patent WO Publication Number 2019/113649 A 1 , published June 20, 2019, are hereby incorporated by reference in their entireties.
  • Dialysis mode is suitable for ionic separation subsystems herein as very low energy costs are incurred as the transfer of ions through the membranes relies on concentration driving forces rather than electrical or pressure driving forces.
  • concentration driving forces rather than electrical or pressure driving forces.
  • osmotic pressures are too large to be overcome by practical or economically feasible means.
  • Li extraction is conducted in a source of fresh water or a low Li - containing water source to maintain a suitable concentration gradient across the membrane.
  • the extractant or sweep fluid may also advantageously constitute return mother liquor from the downstream precipitation plant which is low in lithium and high in Na and Cl. High Na concentration may also enhance monovalent-monovalent selectivity between Li and Na, as the concentration driving force for Na would be lower.
  • a dialysis approach would slightly reduce the lithium concentration compared to the feed to the separator. This can be overcome by application of electrodialysis to selectively concentrate lithium or by reverse osmosis to reject water.
  • the TDS of the pure stream is around 10% which can allow a small concentration using reverse osmosis before osmotic pressures become too large.
  • An electrodialysis mode of operation with Li-selective membranes is particularly preferred as fresh water use is minimized, and the process stream can be cleaned and concentrated simultaneously.
  • molecular boric acid in acidic conditions remains with the impurity stream allowing its simultaneous removal with other impurities rather than needing a separate step for its removal.
  • the separators advance lithium forward and recycle the impurities to the preceding ponds.
  • the return location of the impurities is preferred to be the same pond from which the feed to the separator is drawn. This can however also be recycled to earlier stages of evaporation if the chemistry is favorable for ion impurity precipitation is such ponds.
  • the impurities could also be evaporated partially or completely in a separate pond or injected to the aquifer.
  • the lithium advance stream could be concentrated during separation such as with electrodialysis or other separation methods and advance directly to the downstream processing plant.
  • the systems and methods taught herein can be integrated seamlessly in existing operations.
  • the brine advances from one pond to the next in sequence.
  • the advancing brine instead passes through a separator at a selected location based on brine chemistry and lithium saturation at that point.
  • Part of the brine with reduced impurities then advances to the next pond in the series, and the other part with higher impurities is recycled to the pond feeding the separator or optionally to one or more previous ponds in the sequence.
  • the recycle feed pond precipitates the excess impurities recycled by the separator, thus keeping the advancing brine composition substantially constant.
  • New ponds and evaporation concentration systems can also be designed to incorporate aspects of the presently disclosed systems and methods in new operations.
  • the impurities-depleted brine from the separator can advance normally to the next pond in the series where lithium concentration can increase significantly without co-precipitation as double salts with impurities.
  • the first salt to precipitate is halite followed by sylvinite (mixture of halite and sylvite), kainite, calcium borate and gypsum. Further evaporation precipitates carnallite, bischofite, kainite, sylvinite, gypsum, kieserite and boric acid. The precipitation of salts varies and is dependent on the starting brine compositions and evaporation conditions. This proceeds until a lithium concentration of about 0.5-2% is reached. Further evaporation from this level starts precipitation of lithium sufate monohydrate, lithium carnallite or lithium schoenite, again dependent on the brine composition, potentially resulting in significant lithium losses from prior systems.
  • Example A is a single stage separation while Example B utilizes two stage separation.
  • Example A represents monovalent selective membrane dialysis
  • Example B monovalent selective membrane electrodialysis
  • Example C a lithium selective membrane dialysis process.
  • Example A Chilean Brine (High Li, Low Sulfate )
  • Figure 6 represents the conventional brine evaporation process simplified to four pond stages.
  • the starting brine composition is indicated by Stream 1 composition and the final concentrated brine by Stream 11 compositions. All streams are numbered and the flow rates in tons per hour are indicated. The salt species precipitating in each pond are also indicated with their amounts in tons per hour.
  • the starting lithium brine concentration is high at 0.19%.
  • the Mg/Li ratio is moderately low at 6.6.
  • Sulfate is low at 0.2%.
  • the major precipitate is halite (NaCl).
  • Pond II precipitates NaCl and KC1 (sylvinite) in major amounts.
  • Pond III conditions are favorable for precipitation of magnesium as bischofite (MgCh.bFhO) and carnallite (KCl.MgCl2.6H2O). These conditions are exploited in this Example to recycle additional magnesium and precipitate the same.
  • Lithium concentration after this pond reaches 1.65%. This point was determined such that any concentration beyond this will result in lithium co precipitation.
  • further evaporation starts to precipitate lithium and magnesium together as lithium carnallite (LiCl. MgCh.7H20) resulting in large lithium losses.
  • the point of application for the separator was determined.
  • the separator would be applied after Pond III and before Pond IV as lithium precipitation and losses do not occur in Pond III but start in Pond IV.
  • the co-precipitating element of interest is also now determined to be Mg as lithium co-precipitates with magnesium in Pond IV.
  • a suitable location to remove this magnesium is also now known to be Pond III where conditions are favorable to precipitation of magnesium but not lithium.
  • the lithium content in the final concentrated stream with the application of a preferred method according to the present disclosure is more than doubled, as lithium losses do not occur in Pond IV due to now low levels of magnesium there.
  • the lithium concentration then advantageously proceeds from 1.65% to 6% without any lithium precipitation losses in Pond IV.
  • Stream 16 in Figure 7 shows any water addition that may be required by the separator operation. It could be zero where the separator does not require it without impacting the method. This additional water, if any, can be evaporated in the preceding pond where the impurity enriched stream is recycled.
  • Figure 8 represents the conventional brine evaporation process simplified to four pond stages for a Venezuelan brine.
  • the starting brine composition is indicated by Stream 1 composition, and the final concentrated brine by Stream 11 composition. All streams are numbered and the flow rates in tons per hour are indicated. The salt species precipitating in each pond are also indicated with their amounts in tons per hour.
  • the starting lithium brine concentration is very low at 0.07%.
  • the Mg/Li ratio is very high at 19.
  • Sulfate/Li ratio is also very high at 29.
  • the major precipitate is halite (NaCl) and polyhalite (K2SO4.MgSO4.2CaSO4.2H2O).
  • Pond II precipitates NaCl+KCl (Sylvinite) and minor amounts of polyhalite.
  • Pond III halite, sylvinite, kainite (KCl.MgSO4.3H2O) and carnallite (KCl.MgCl2.6H2O) precipitate.
  • Li concentration reaches 0.49%.
  • Further evaporation in Pond IV starts lithium sulfate monohydrate precipitation along with increasing amounts of carnallite and other salts.
  • the separator would be applied after Pond III and before Pond IV as lithium precipitation and losses do not occur in Pond III but start in Pond IV.
  • the co-precipitating ion of interest is also now determined to be sulfate as lithium precipitates as L12SO4.H2O in Pond IV.
  • the separation used here grossly separates all impurities from Li.
  • a suitable location to remove this sulfate ion is also now known to be Pond III as it is already precipitating Mg, K and sulfate as carnallite and kainite and boric acid, but not lithium.
  • Magnesium is the counter-ion to sulfate that is selected in this Example as sulfate precipitates with magnesium in the preceding ponds.
  • the brines in this Example are Argentinian type brines which are characterized by low Li and Mg contents but high sulfate.
  • Figure 10 represents the conventional brine evaporation process simplified to four pond stages.
  • the starting brine composition is indicated by Stream 1 composition and the final concentrated brine by Stream 11 composition.
  • the starting lithium brine concentration is very low at 0.07%.
  • the Mg/Li ratio is also very low at ⁇ 3.
  • Sulfate/Li ratio is however very high at 20.
  • the major precipitate is halite (NaCl) along with Glauber’s salt (NaiSCri.lOFLO).
  • Pond II continues to precipitate halite.
  • Pond III precipitates halite and sylvite (Sylvinite, NaCl+KCl). These ponds also precipitate minor amounts of syngenite (K2SO4.CaSO4.H2O).
  • the major sink to remove the high levels of sulfate in this brine type is in Pond I.
  • Pond III reaches a lithium concentration of 0.69%. Further concentration beyond this in Pond IV results in lithium co-precipitation losses as lithium potassium double salt (lithium schoenite, L12SO4.K2SO4). Hence, the selected location for the separator application would be after Pond III. It is also now determined that reducing sulfate levels along with an associated counter ion such as K or Na would prevent lithium co-precipitation losses in Pond IV. A suitable sink for sulfate was already determined to be Pond I. Hence, recirculating the impure sulfate concentrated stream from the separator to Pond I, would remove the excess sulfate. A separator was modelled at the selected location, achieving monovalent-monovalent and monovalent-multivalent separation with selectivities as shown in Table 4.
  • FIG 11 shows the steady-state mass balance of the entire pond sequence after introduction of the separator and recycle of the separator impure stream to Pond I.
  • Some of the excess sulfate recycled by the separator would be precipitated in Pond I as NaiSC lOFEO, which can be seen to be an increase from the conventional case.
  • the excess recycling sulfates alters the chemistry of the pond sequence resulting in different solid-liquid equilibrium conditions in the ponds. Due to the high levels of recirculating sulfates, conditions become favorable for the precipitation of epsomite (MgSCE.TFEO) in Pond III. This is where the major proportion of remaining excess sulfate would be removed.
  • MgSCE.TFEO epsomite

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Abstract

La présente invention concerne des systèmes et des procédés faisant appel à l'évaporation solaire pour préconcentrer des saumures contenant du lithium jusqu'à ce qu'elles soient saturées ou quasi-saturées en lithium, puis à des procédés de séparation pour séparer le lithium des impuretés. Un courant d'impuretés séparés est recyclé vers un point dans la séquence d'évaporation où les conditions sont favorables pour leur précipitation et leur élimination ou disposé dans un bassin d'évaporation séparé ou réinjecté sous terre, tandis qu'un courant d'impuretés inférieur est transféré vers l'emplacement d'élimination et/ou un bassin ultérieur dans la séquence et/ou une installation pour lithium ou une installation de concentration. Une concentration supplémentaire du lithium par évaporation peut alors avoir lieu étant donné que les impuretés sont éliminées, ce qui permet d'éliminer les pertes de lithium par co-précipitation et d'obtenir des concentrations en lithium significativement plus élevées.
PCT/US2021/032027 2020-05-12 2021-05-12 Systèmes et procédés de récupération de lithium à partir de saumures WO2021231597A1 (fr)

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EP21789600.0A EP3947756A4 (fr) 2020-05-12 2021-05-12 Systèmes et procédés de récupération de lithium à partir de saumures
IL287465A IL287465B2 (en) 2020-05-12 2021-05-12 Systems and methods for recovering lithium from brines
US17/602,808 US20230192503A1 (en) 2020-05-12 2021-05-12 Systems and Methods for Recovering Lithium from Brines
JOP/2021/0311A JOP20210311A1 (ar) 2020-05-12 2021-05-12 أنظمة وطرق استرداد الليثيوم من المحاليل الملحية
MX2021013733A MX2021013733A (es) 2020-05-12 2021-05-12 Sistemas y metodos para recuperar litio de salmueras.
AU2021254665A AU2021254665B2 (en) 2020-05-12 2021-05-12 Systems and methods for recovering lithium from brines field
CA3136247A CA3136247C (fr) 2020-05-12 2021-05-12 Systemes et methodes pour recuperer le lithium des saumures
PE2021001898A PE20220205A1 (es) 2020-05-12 2021-05-12 Sistemas y metodos para recuperar litio de salmueras
CN202180003093.1A CN113924375B (zh) 2020-05-12 2021-05-12 用于从盐水中回收锂的系统和方法
PCT/US2021/032027 WO2021231597A1 (fr) 2020-05-12 2021-05-12 Systèmes et procédés de récupération de lithium à partir de saumures
US17/529,492 US20220136081A1 (en) 2020-05-12 2021-11-18 Systems and Methods for Recovering Lithium from Brines Field
US17/862,090 US20240067530A1 (en) 2020-05-12 2022-07-11 Systems and Methods for Recovering Lithium from Brines Field

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PE20220205A1 (es) 2022-02-01
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CN113924375B (zh) 2023-04-04
AU2021254665B2 (en) 2022-04-21

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