WO2023215002A1 - Récupération de lithium à l'aide de sources aqueuses - Google Patents

Récupération de lithium à l'aide de sources aqueuses Download PDF

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Publication number
WO2023215002A1
WO2023215002A1 PCT/US2022/051500 US2022051500W WO2023215002A1 WO 2023215002 A1 WO2023215002 A1 WO 2023215002A1 US 2022051500 W US2022051500 W US 2022051500W WO 2023215002 A1 WO2023215002 A1 WO 2023215002A1
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WIPO (PCT)
Prior art keywords
stream
lithium
concentration
feed
extraction
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PCT/US2022/051500
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English (en)
Inventor
Dominic Vincent PERRONI
Gary W. Sams
Prasanna Nirgudkar
Florence Binet
Rod Shampine
Original Assignee
Schlumberger Technology Corporation
Schlumberger Canada Limited
Services Petroliers Schlumberger
Schlumberger Technology B.V.
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.)
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Application filed by Schlumberger Technology Corporation, Schlumberger Canada Limited, Services Petroliers Schlumberger, Schlumberger Technology B.V. filed Critical Schlumberger Technology Corporation
Priority to PCT/US2023/020954 priority Critical patent/WO2023215448A1/fr
Priority to US18/311,966 priority patent/US20230364560A1/en
Priority to US18/311,975 priority patent/US20230356107A1/en
Priority to US18/311,956 priority patent/US20230366062A1/en
Priority to PCT/US2023/020957 priority patent/WO2023215450A1/fr
Publication of WO2023215002A1 publication Critical patent/WO2023215002A1/fr
Priority to US18/430,935 priority patent/US20240165539A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/263—Chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/24—Counter-current operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series

Definitions

  • This patent application describes methods and apparatus for lithium recovery from aqueous sources. Specifically, effective processes for concentrating and recovering lithium from dilute sources are described.
  • Lithium is a key element in energy storage. Electrical storage devices, such as batteries, supercapacitors, and other devices commonly use lithium to mediate the storage and release of chemical potential energy as electrical current. As demand for renewable, but non-transportable, energy sources such as solar and wind energy grows, demand for technologies to store energy generated using such sources also grows.
  • the disclosure relates to a method of recovering lithium from a lithium source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed.
  • the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • At least one of the concentration operations includes a counter-flow reverse osmosis operation.
  • the method also includes generating a low TDS stream as a permeate from any of the one or more concentration operations, wherein the low TDS stream is recycled or used as fresh water
  • the disclosure also relates to a method of recovering lithium from a lithium source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations includes a first membrane separation operation, having a first semi-permeable membrane, yielding from the input stream a preconcentrated stream and a permeate stream, and a second membrane separation operation.
  • the preconcentrated stream flows into a plurality of reactors in series, each containing a semi- permeable membrane separating the reactor into a first volume and a second volume.
  • the preconcentrated stream flows sequentially as a non-permeating stream into the first volume of each reactor, and the non-permeating stream exiting the plurality of reactors yields the output stream.
  • the second membrane separation operation yields a dilute brine stream that exits the second volume of at least one of the reactors, and the dilute brine stream is recycled into the first membrane separation operation.
  • the disclosure also relates to a method of recovering lithium from a brine source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate.
  • the method also includes performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations includes at least a membrane separation operation, wherein at least one the membrane separation operation includes a plurality of reactors in series each having a semi-permeable membrane, yields a lithium concentrate and a dilute brine stream, and is configured so that the lithium concentrate has a TDS over 120,000mg/l, preferably over 200, 000mg/l.
  • the method also includes separating the dilute brine stream using a semi-permeable membrane into two streams including a permeate stream, wherein the permeate stream has a TDS under 2,000 mg/l, preferably under 500 mg/l, and recycling the permeate stream into another stream.
  • Fig. 1 is a schematic process diagram of a lithium recovery process, according to one embodiment.
  • FIG. 2 is a schematic diagram of a vaporizer usable during a concentration stage of the process shown in Fig. 1
  • FIG. 3 is a process diagram summarizing a concentration stage of a lithium recovery process according to an embodiment.
  • FIG. 4 is a process diagram of a portion of a concentration stage of a lithium recovery process according to another embodiment.
  • Direct extraction of lithium is commonly used in lithium recovery from aqueous lithium sources.
  • Direct extraction processes typically employ a solid material to withdraw lithium selectively from a lithium source onto or into the withdrawal material.
  • a recovery fluid is then contacted with the loaded withdrawal material to remove the lithium from the withdrawal material to form a lithium intermediate stream.
  • the quantity of recovery fluid generally determines the concentration of lithium in the lithium intermediate stream, but unloading rate of ions from the withdrawal material can provide an effective upper limit to the concentration achievable.
  • the withdrawal material is generally chosen to be selective to lithium. That means many cations are removed from the source, but lithium is removed more readily than other cations.
  • the ions removed by the withdrawal material include lithium along with other impurities, such as monovalent cations sodium and potassium and divalent cations calcium and magnesium.
  • the withdrawal material will age with use because ion removal is not quantitative in each cycle. Longer recovery processing can enhance ion removal in each cycle, but such measures are subject to diminishing returns as throughput declines.
  • recovery fluid application rate is subject to an optimum which trades lithium intermediate stream concentration, recovery time, and degradation of loading capacity.
  • the direct lithium extraction process may be an ion exchange or ion replacement process, where the withdrawal medium is pre-loaded with ions that are exchanged to the feed fluid while withdrawing other ions from the feed fluid.
  • the withdrawal and recovery processes are typically both ion exchange or ion replacement processes, but an ion exchange process where the recovery fluid does not replace ions can also be used, where ions are replaced for the withdrawal step by exposing the withdrawal medium to a third fluid for the purpose of preloading exchange ions.
  • the direct lithium extraction process may be an adsorption process where ions are adsorbed from the aqueous lithium stream solution onto the surface of a solid adsorbent material that is selective to lithium, such as metal oxide, metal hydroxide or such material mixed with a resin.
  • a desorbent solution is used to recover the withdrawn ions.
  • the direct lithium extraction process may be an absorption process where ions are absorbed from the brine solution into the bulk of a solid absorbent material that is selective to lithium.
  • a desorbent solution is used in these cases, as well.
  • FIG. 1 is a schematic process diagram of a lithium recovery process 100, according to one embodiment.
  • the process 100 uses an extraction stage 104 that performs direct lithium extraction, as described above.
  • An extraction feed 105 is provided to the extraction stage for withdrawal of ions to produce a lithium-depleted stream 107.
  • the extraction stage 104 is most effective where lithium concentration in the extraction feed 105 is at least about 70 ppm, for example at least about 100.
  • Lithium sources having higher concentrations, for example as high as 1 ,000-3,000 ppm, of lithium can also be used.
  • the adsorbent material may be stationary or fluidized within the vessel, or conveyed through one or more vessels or zones for contacting with the brine, for example in a counter-current format.
  • the adsorbent material may be contained in a plurality of vessels in flow communication with one another and the vessels may be fluidly connected with a plurality of zones (ie inlets/outlets) during the extraction process.
  • the extraction 102 may therefore take place continuously, for instance loading resin in a first vessel with lithium by fluidly connecting this vessel with the brine source while unloading resin in a second vessel by fluidly connecting the second vessel with the eluent and washing a third vessel using a strip solution.
  • the extraction may be continuous counter-current adsorption desorption (CCAD).
  • An exemplary counter-current adsorption desorption that may be used is for instance described in US patent number 11365128 from EnergySource Minerals hereby incorporated by reference.
  • the lithium-depleted stream 107 may be separated into a reject stream and a fresh water stream using at least a membrane separation operation having a semi- permeable membrane, or a thermal vaporizer such as vaporizer 200 disclose in the following.
  • the reject stream may be returned to the environment (ie reinjected into the geological formation) and the fresh water stream may be recycled into another stream of the method, such as the eluent.
  • a membrane separation operation When a membrane separation operation is deployed it may be configured to perform electrodialysis, reverse osmosis, counter-flow reverse osmosis, a combination of both reverse osmosis and counter-flow reverse osmosis such as described in relationship with operation 500. In that case, the lithium-depleted stream takes place of the lithium extract, the reject stream takes place of the lithium concentrate and the fresh water stream corresponds to the permeate stream.
  • the process 100 is configured to use dilute lithium sources.
  • the sources can be salar brines, water leached from rock and clay formations and/or leaching resins, produced water from wells, mines, and geothermal installations, seawater, pre-treated aqueous lithium sources such as desalinator or electrochemical process effluents, recycled lithium from previous industrial applications, and other sources.
  • These sources can have very low concentrations of lithium (seawater, for example, averages about 0.4 ppm lithium) and very high relative concentrations of impurity ions such as sodium. Most of the impurity ions have solubility in water lower than lithium, so bringing concentration of lithium up in these materials generally precipitates solids, which must be managed.
  • the process 100 uses a feed preparation stage 102 to prepare a feed for the extraction stage 104.
  • the feed preparation stage 102 generally raises lithium concentration and TDS to an effective range for the extraction stage 104. Any known way of raising concentration in an aqueous fluid may be used during feed preparation stage. A few examples are provided below.
  • Membrane processes such as reverse osmosis (“RO”), nanofiltration (“NF,” sometimes also referred to as “loose” RO), and counter-flow reverse osmosis (such as CFRO® that is a counter-flow reverse osmosis product available from Gradient Corp, of Boston, Massachusetts, USA) can be used to remove water from an aqueous source.
  • RO reverse osmosis
  • NF nanofiltration
  • CAO® counter-flow reverse osmosis product available from Gradient Corp, of Boston, Massachusetts, USA
  • Thermal methods using heat pumps, hot exhaust, solar radiation, and multi-effect evaporators can also be used. Evaporation, for example using cooling towers, atomizers, sprayers, and Carrier Gas Extraction® (also available from Gradient Corp.), can also be used to precipitate impurities and evaporate water. Combinations of such processes can also be used. Various modes of filtration can also be used to remove unwanted larger solids from brine sources.
  • the feed preparation stage 102 may be configured to provide a lithium concentration ratio between the stream exiting the preparation stage and the feed entering the preparation stage of at least 10, or 20.
  • the feed preparation stage may be configured as a function of the lithium source, so that it generally provides a lithium feed stream having at least about 70 ppm, for example about 100 ppm, such as about 150-200 ppm lithium ions, predominantly countered by chloride ions, for direct extraction in the extraction stage 104, but higher concentrations of lithium could be used.
  • the direct extraction stage 104 generally operates as described above.
  • the withdrawal material is typically a resin with a composition or surface preparation that increases affinity for lithium ions relative to other ions.
  • the withdrawal material is typically housed in a vessel, and multiple vessels of withdrawal material are typically used so some resin beds can be regenerated without stopping production.
  • Regeneration typically involves treatment with a hot fluid to achieve substantial removal of all ions from the resin. Where surface treatments or exchange ions are used, the regeneration can also include re-application of the surface treatment or exchange ions prior to placing the withdrawal bed back into service.
  • a recovery stream 109 is provided to the extraction stage to remove ions from the withdrawal material, thus forming a lithium intermediate 111.
  • Flow rate of the recovery stream 109 is selected to concentrate lithium to a selected range, for instance of about 1 ,500 ppm to 3,000 ppm. Concentration of impurity ions can increase in the extraction stage 104 as well.
  • the recovery stream 109 can be a water stream, which may be deionized, or a dilute brine stream having a low level of lithium ions, for example around 100 ppm. Selectivity for lithium ensures that impurity concentration rises less than lithium concentration.
  • Impurities are removed at an impurity stage 108.
  • Sodium, calcium, and magnesium are typically removed or reduced in the impurity stage 108. Any combination of membrane separation, ion exchange, and precipitation can be used.
  • concentration of the impurities Prior to removing impurities, concentration of the impurities can be increased to a level that optimizes the volume of water handled by the impurity stage. For most aqueous lithium streams, impurity removal is found to be most effective where impurity concentration is higher, so the lithium intermediate 111 can be treated in an impurity preparation stage 106 prior to treatment at the impurity stage 108.
  • the impurity preparation stage 106 water is first removed from some or all of the lithium intermediate 111 to form an impurity stage feed 113 having elevated ion (/.e. lithium and impurity) concentration, along with a first removed stream 121 , which may be a water stream or brine stream.
  • the impurity preparation stage 106 is generally operated to increase concentration of one or more impurities in the impurity stage feed to a value near the solubility limit of the one or more impurities in the impurity stage feed for example about 90% or 95% of the solubility limit.
  • the impurity preparation stage 106 is operated to raise calcium concentration in the impurity stage feed 113 to near the solubility limit of calcium in the eluent, for example about 90% or 95% of the solubility limit of calcium in the eluent. Removal of calcium, and other divalent ions, is then performed in the impurity stage 108 at near-optimal conditions to maximize removal of divalent impurities.
  • the impurity stage 108 results in a purified lithium stream 115 with high lithium concentration and very low concentration of divalent impurities.
  • any known way of raising concentration in an aqueous fluid may be used during impurity preparation stage 106.
  • Membrane processes such as reverse osmosis (“RO”), nanofiltration (“NF,” sometimes also referred to as “loose” RO), and counter-flow reverse osmosis (CFRO® is a counter-flow reverse osmosis product available from Gradient Corp, of Boston, Massachusetts, USA) can be used to remove water from an aqueous source.
  • Thermal methods using heat pumps, hot exhaust, solar radiation, and multi-effect evaporators can also be used.
  • the impurity preparation stage 106 may be configured to provide a lithium concentration ratio between the stream exiting the preparation stage and the feed entering the preparation stage of at least 10, or 20.
  • the impurity preparation stage may be configured as a function of the lithium intermediate stream, to have a concentration ratio enabling to increase concentration of one or more impurities in the impurity stage feed to a value near the solubility limit of the one or more impurities, as set forth above.
  • Monovalent impurities can remain in the purified lithium stream 115, so the purified lithium stream 115 is routed to a concentration stage 110 to remove any monovalent impurities prior to a conversion step that converts lithium chloride to lithium carbonate by adding sodium carbonate or directly to lithium hydroxide by electrochemical reaction.
  • the concentrator also generally raises lithium concentration by a factor of about 10.
  • Sodium and potassium have lower solubility limits in water than lithium, so concentrating the purified lithium stream 115 can precipitate sodium and potassium, which can be removed as solids.
  • the concentration stage 110 can be a multi-stage concentrator with solids removal between stages. Each concentration stage can be configured to raise the concentration of lithium until sodium solids become a burden. Solids can then be removed and further concentration can proceed.
  • the aqueous lithium sources contemplated for use in the process 100 can have sodium concentration several orders of magnitude higher than lithium concentration, for example at least 100 or at least 1 ,000 times the lithium concentration, so the concentration stage 110 can be quite effective in removing large quantities of sodium with relative ease.
  • solubility of sodium ions declines, so each absolute increment of increased lithium concentration yields more sodium precipitation.
  • Sodium solubility also declines more with temperature than lithium solubility, so elevated temperature can enhance removal of sodium in the concentration stage 110.
  • Sodium overwhelmingly precipitates as chloride in the concentration stage 110, and solids can be removed by any suitable process including settling, centrifugation, vortex separation, and the like.
  • the most extreme filtration processes may become untenable due to the concentration of lithium ions, but processes such as evaporation and seeding can be used to remove water and precipitate sodium and potassium.
  • the concentration stage 110 produces a lithium concentrate 117 and one or more removed streams 119 that can be water streams, brine streams, and/or salt slurries.
  • the water and brine streams can be recycled to parts of the process 100 where ion concentrations are lower to facilitate processing.
  • a portion of the lithium concentrate 117 can also be recycled and added to a lithium source to raise the lithium concentration of the lithium source and/or dilute impurities at the brine source.
  • a series of membrane separations is performed during the concentration stage 110 to separate the lithium concentrate 117 with high lithium concentration, as a non-permeating stream, from a stream with low lithium concentration, as a permeating stream.
  • the permeating stream in this case, will also contain most impurities from the purified lithium stream 115.
  • a vaporizer may alternatively or additionally be used during concentration stage to further concentrate the lithium salt in the lithium concentrate 117.
  • the vaporizer yields a vaporizer water stream, which can be recycled to parts of the process, as explained below, an impurity stream, which contains non-lithium cations such as sodium, potassium, magnesium, manganese, calcium, and the like.
  • the vaporizer also yields the lithium concentrate 117, which can then be routed to the conversion stage 112.
  • Fig. 2 is a schematic process diagram of a vaporizer 200 that can be used as, or as part of, the concentration stage 110.
  • the example vaporizer 200 allows concentration of lithium and removal of solids.
  • the vaporizer 200 includes a vaporization vessel 202 that receives the purified lithium stream 115. Heat is applied to the purified lithium stream 115 within the vaporization vessel 202 to vaporize water and concentrate lithium and other ions within the vessel 202.
  • a heater 204 is coupled to the vessel 202 to apply heat to the fluid within the vessel 202.
  • the heater 204 is shown here schematically as an element inserted into the interior of the vessel 202, but heat input can be accomplished in any convenient manner.
  • the vessel 202 generally has a vaporization section 206 and a precipitation section 208. Solids precipitate from the fluid as water is vaporized and solubility limits are reached.
  • the vaporizer 200 is therefore also a precipitator of solids. Sodium precipitates as chloride, and potentially other salts due to trace amounts of other anions. Lithium generally remains in a concentrated solution, but some lithium salts can precipitate if enough water is removed by evaporation. Sodium solids generally settle below the lithium-rich solution due to density. The lithium solution is removed as the lithium concentrate 117, which is removed from a lower part of the vaporization section 206. Vaporized water is removed in an overhead stream 210 of the vaporization section 206.
  • Heat is recovered from the vaporized water by thermally contacting the vaporized water with the purified lithium stream 115 in a heat exchanger 212.
  • the heated purified lithium stream 115 is provided to the vaporization section 206 of the vessel 202, optionally using a valve or orifice to flash the heated purified lithium stream 115 within the vaporization section 206.
  • the vaporized water is at least partially condensed in the heat exchanger 212, and a portion 250 of the vaporized water may be added to the lithium concentrate 117 to ensure all solids are dissolved prior to routing the lithium concentrate 117 to the conversion stage 112.
  • the remaining vaporized water exits as the vaporizer water stream 252, which can be, or can be included in, one of the removed streams 119.
  • the vaporization section 206 of the vessel 202 is sized to provide residence time for sodium precipitates to settle into the precipitation section 208.
  • a precipitate stream 214 is withdrawn from a lower portion of the precipitation section 208 and pumped to a settling vessel 216.
  • Separated water or brine may be withdrawn from the settling vessel 216 and returned to the vaporization vessel 202 as a vaporization return stream 218 or recycled to any other location in the process (as explained below).
  • vaporization return stream may be, or may be another part of, the removed stream 119.
  • the water or brine is returned at the bottom of the precipitation section 208 to fluidize solids that may collect at the bottom of the precipitation section 208.
  • the water or brine, or a portion thereof, can be returned to the vaporization vessel 202 at other points, or may be routed to other uses.
  • the concentration stage includes two different membrane separation operations in series : a reverse osmosis operation 502 and a counter-flow reverse osmosis operation 504.
  • the reverse osmosis operation 502 is upstream from the counter-flow reverse osmosis operation 504
  • the lithium intermediate 111 is pressurized to a target pressure (preferably less than or equal to 2000 psi) using a pump 501 before flowing to the membrane separations operations.
  • the counter-flow reverse osmosis operation uses a plurality of n reactors in series 5081 - ... - 508n each comprising a semi-permeable membrane 510i - ... - 51 On , optionally a lithium selective membrane.
  • the semi-permeable membrane may be a reverse osmosis membrane, a nanofiltration membrane or more generally any type of membrane that enables water molecules to go through while lithium ions do not go through.
  • the reactors may all comprise the same type of membranes or different reactors may have a different type of membranes.
  • Each membrane 510i - ... - 51 On separates each reactor into a first volume 512i - ...
  • Each reactor comprises a first inlet 5161 - ... - 516 n to receive the stream to be concentrated (or non-permeating stream) and a first outlet 5181 - ... - 518 n to exit the concentrated stream from the reactor.
  • Each reactor also comprises a second inlet 520i - ... - 520 n to receive the permeating stream and a second outlet 522i - ...
  • the nonpermeating stream 534 derived from the purified lithium stream 115 and permeating stream flow counter-current, ie the non-permeating stream flows from reactor 1 to n while the permeating stream flows from reactor n to 1 .
  • the non-permeating stream is collected at the first outlet of the n th reactor 508 n and forms the lithium concentrate 117.
  • the permeating stream is collected at the second outlet of the first reactor and forms the dilute brine stream 535 may be recycled into the counter-flow reverse osmosis operation and/or recycled to one or more other stages of the process, for instance as a strip solution or as an eluent in the extraction stage.
  • the number of stages n may be between 2 and 10, optionally between 3 and 6 to limit the costs while concentrating the stream to a target concentration.
  • the concentration stage may also include a plurality of counterflow reverse osmosis operation 504 in parallel, each handling a portion of the flow to be concentrated.
  • the reverse osmosis operation 502 is represented as including a RO container 524 also including a semi-permeable membrane 526 , optionally a lithium selective membrane.
  • the semi-permeable membrane may be a reverse osmosis membrane, a nanofiltration membrane or more generally any type of membrane that enables water molecules to go through while lithium ions do not go through.
  • the membrane 526 separates the RO container into a first volume 528 to receive a stream to be concentrated, here the purified lithium stream 115 and a second volume 530.
  • the purified lithium stream 115 enters the RO container via an inlet 531 situated in the first volume and the container comprises a first outlet 532 in the first volume through which a preconcentrated stream 534 containing a higher concentration of lithium than the purified lithium stream 115exits the RO container and a second outlet 536 in the second volume through which the stream 538 with a lower concentration of lithium that passed through the membrane (ie permeate stream) exits the RO container.
  • the reverse osmosis operation 502 is represented in one stage with one container but it can also be in several stages, including a plurality of containers with identical or different semi-permeable membranes therein in series, ie the preconcentrated stream 534 exiting a first RO container is directed to the inlet of a second RO container to further concentrate the preconcentrated stream before counter-flow reverse osmosis operation, and/or the permeate stream 538 is directed to the inlet of an additional RO to container to desalinate the brine.
  • the reverse osmosis operation may also include several RO containers in parallel.
  • FIG. 4 Another configuration for the reverse osmosis operation 502 with a first stage having two RO containers 602, 604 in parallel and a second stage having a RO container 606 in series and receiving the concentrated stream of both RO containers as an input for further concentration is represented as an example in FIG. 4.
  • Using RO containers in series during reverse osmosis operation 502 can reduce the number of stages of the counter-flow reverse osmosis operation 504 as well as maximize permeate recovery, that can be re-used into the process as explained above, therefore reducing fresh water demand. Indeed, the permeate of each container in this case may be recycled to one or more stages of the process, in particular as eluent of the lithium extraction stage 102.
  • the concentration stage first comprises the reverse osmosis operation 502.
  • the preconcentrated stream 534 is then directed to the counter-flow reverse osmosis operation 504, while the permeate stream 538 that has a low TDS (less than 2,000mg/l, preferably less than 500mg/l and preferably around 100 mg/l) is recycled to another stream of the method, for instance in the extraction stage 102 as eluent, or any other stage of the process where fresh water is needed.
  • the preconcentrated stream 534 passes through the n reactors 508i - ... - 508 n and is collected at the exit of the n th reactor 508 n .
  • the counter-flow reverse osmosis output stream is depressurized and separated into a first portion that forms the lithium concentrate 117 and a second portion that is sent back to the reactors 508i - ... - 508 n as a permeating stream.
  • Using a lithium concentrate portion as a permeating stream in counter-flow reverse osmosis 504 increases operation efficiency.
  • the depressurization may enable to recover energy by converting the pressure into energy, using for instance a generator associated to a turbine.
  • the lithium concentration of the preconcentrated stream 534 increases while the lithium concentration of the dilute brine stream decreases.
  • the dilute brine stream 115 may be recycled to the concentration stage 104, ie mixed with the lithium extract stream 114 to be further concentrated.
  • the concentration stage 104 may include only the counter-flow reverse osmosis operation 504 and no reverse osmosis operation 502 depending on lithium intermediate 111 concentration and target concentration of lithium concentrate 117. In that case, a portion or all of the dilute brine stream may be recycled to another stage of the process.
  • Such a concentration stage including counter-flow reverse osmosis operation 504 enables a concentration ratio between the stream exiting the n th reactor and the stream entering the first reactor, of 2 to 20.
  • the concentration of the dilute brine 115 may be reduced so that a concentration ratio between the stream exiting the first reactor and the stream entering the nth reactor, of 2 to 20,
  • the stream entering the counter-flow reverse osmosis operation 504 has preferably a lithium concentration between 0.05% and 6 % weight, preferably between 0.5 and 3%.
  • the lithium concentrate stream 117 at the exit of the counter-flow reverse osmosis operation 504 has a TDS (total dissolved solids) over 120,000mg/l preferably over 200, 000mg/l and a lithium concentration over 2%, preferably over 3.3% and the dilute brine 115 at the exit of the counter-flow reverse osmosis operation 504 has preferably a lithium concentration of less than 2 % weight, preferably less than 1.5% weight.
  • the counter-flow reverse osmosis operation 504 enables to increase the lithium concentration in the lithium concentrate 117 compared to a more conventional method such as simple reverse osmosis operation in an order of magnitude of about 3 to 4, enabling to recover more than 80%, preferably more than 90% of the lithium intermediate 111 as the dilute brine stream 5355.
  • the counter-flow reverse osmosis is an example of a second membrane separation operation that enables to go up to a TDS over 120,000mg/l.
  • a second membrane separation operation having different configuration and setup may enable to reach such concentration, using for instance different equipment, or flow pattern, etc. Such operation is also covered by the current disclosure.
  • Combining a reverse osmosis operation 502 and a counter-flow reverse osmosis operation 504 limits the cost necessary for the concentration stage by limiting the number of reactors in the counter-flow reverse osmosis operation. Furthermore, combining those operations enables to generate a permeate of the reverse osmosis operation 502 that can be recycled as an eluent in the lithium extraction operation, significantly limiting the fresh water needed in the extraction operation (fresh water being mainly used as eluent). Indeed, the permeate stream 538 has a low lithium concentration and low TDS and is an efficient eluent whereas the dilute brine stream 115 may have a higher TDS that may not directly enable to extract lithium efficiently from the extraction stage.
  • the dilute brine stream may be treated using a specific reverse osmosis operation independently from the lithium concentration stage (downstream of the counter-flow reverse osmosis operation) - the reverse osmosis 502 being then optional.
  • a specific reverse osmosis operation independently from the lithium concentration stage (downstream of the counter-flow reverse osmosis operation) - the reverse osmosis 502 being then optional. Any configuration or variation that enables to concentrate lithium up to a certain concentration and obtain fresh water (ie stream with TDS below 2,000 mg/l) that can be recycled elsewhere is part of the disclosure.
  • the dilute brine stream 535 may however be recycled as an eluent by being mixed with an additional stream, for instance a fresh water stream and/or by undergoing an impurity removal operation before being recycled as eluent.
  • FIG. 3 and 4 described in relationship with the concentration stage 110 may be also used to increase lithium concentration as part of the feed preparation stage 102 or impurity removal 106.
  • the aqueous lithium source is the inlet stream to the RO container and the feed for extraction is collected exiting the counter-flow reverse osmosis operation.
  • a permeate stream obtained from the reverse osmosis operation may also be recycled to other stages of the process as described elsewhere in the application.
  • the lithium intermediate 111 is the inlet stream to the RO container and the impurity stage feed 113 is collected exiting the counter-flow reverse osmosis operation.
  • the first removed stream 121 corresponds to the permeate stream obtained from the reverse osmosis operation that may also be recycled to other stages of the process as described elsewhere in the application.
  • Multiple streams can be recycled in the process 100 to manage the concentration of lithium at each stage of the process 100 and to manage a ratio of lithium ions to impurity ions at each stage of the process, so that each stage of the process 100 can operate in an optimal range.
  • the composition of each stream transferred from one unit of the process 100 to another can be targeted to improve performance of the receiving unit.
  • the impurity preparation stage 106 and the concentration stage 110 produce respective removed streams 121 and 119, which can be recycled to the recovery stream 109.
  • Each of the removed streams 121 and 119 can be water or dilute brine streams.
  • the impurity stage 108 can also generate a water or dilute brine removed stream 123, depending on the type of impurity reduction processes performed in the impurity stage 108.
  • Each of the removed streams 119, 121 , and 123, or portions thereof, can, independently be returned to any stage of the process 100 to manage composition profile of lithium and impurity ions across the process 100 for optimal operation. All or part of any of the removed streams 119, 121 , and 123 can, independently, be routed to the recovery stream 109 or to a first return 135 located in the lithium intermediate 111 between the extraction stage 104 and the impurity preparation stage 106. All or part of any of the removed streams 119 and 123 can, independently, be routed to a second return located in the impurity stage feed 113 between the impurity preparation stage 106 and the impurity stage 108.
  • the removed stream 119, or portion thereof, can be routed back to a third return located in the lithium intermediate stream 115 between the impurity stage 108 and the concentration stage 110.
  • the removed streams are generally recycled backward in the process 100 to avoid sending streams with higher quantities of impurities forward in the process 100 toward the finished product end of the process 100. Recycling the removed streams 119, 121 , and 123 can manage water loading in the process 100 and minimize the need to make up water for processing.
  • Each of the intermediate streams 113, 115, and 117, or portions thereof, can also be returned to any stage of the process 100 in an impurity feed recycle 125, a concentrator feed recycle 127, and a lithium concentrate recycle 129, respectively. All or part of any of the recycle streams 125, 127, and 129 can be returned to a fourth return 133 located in the extraction feed 105 between the feed preparation stage 102 and the extraction stage 104. All or part of any of the recycle streams 125, 127, and 129 can be returned to a fifth return 131 located in the lithium intermediate 111 between the extraction stage 104 and the impurity preparation stage 106.
  • All or part of any of the recycle streams 127 and 129 can be returned to a sixth return 141 located in the impurity feed stream 113 between the impurity preparation stage 106 and the impurity stage 108. All of part of the recycle stream 129 can be returned to a seventh return 143 located in the concentrator feed 115 between the impurity stage 108 and the concentration stage 110.
  • the recycle streams 125, 127, and 129 have increasing lithium concentration and decreasing impurity concentration.
  • the removed streams 119, 123, and 121 are generally water or dilute brine streams. These various streams are used to tune compositions at targeted locations in the process 100 to optimize performance of the individual units of the process 100. For example, where a ratio of lithium to impurities in a particular process stream is lower or higher than optimal for performance of the unit immediately downstream, a low- or high-ion-concentration stream from a downstream location of the process can be selected to blend with the process stream to optimize the composition of the process stream.
  • the lithium concentrate 117 is routed to a conversion stage 112 to convert lithium chloride to lithium carbonate or lithium hydroxide, yielding a lithium product 145.
  • the conversion can be performed by known chemical, electrochemical, and hybrid processes.
  • the lithium product 145 can be a lithium hydroxide product or a lithium carbonate product.
  • the lithium product 145 can be a liquid solution of lithium hydroxide or lithium carbonate, a slurry of solid lithium hydroxide in a solution of lithium hydroxide, or a slurry of lithium carbonate in a solution of lithium carbonate.
  • a method having a preparation stage 102 and an extraction stage 104 only is part of the scope of this disclosure, as well as a method having a preparation stage 102, an extraction stage 104 directly followed by an impurity removal 108 without impurity preparation 106 (ie the lithium intermediate being fed to the impurity removal 108) or a concentration stage 110 without impurity preparation 106 and removal 108 (ie the lithium intermediate being fed to the concentration stage 110).
  • a method having an extraction stage 104, an impurity preparation 106, an impurity removal and a concentration stage 110 followed by a conversion stage 112 is part of the scope of this disclosure.
  • the disclosure relates to a method of recovering lithium from a lithium source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed.
  • the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • At least one of the concentration operations includes a counter-flow reverse osmosis operation.
  • the method also includes generating a low TDS stream as a permeate from any of the one or more concentration operations, wherein the low TDS stream is recycled, ie directed to any operation of the method, especially having a fresh water need, or used as fresh water.
  • the low TDS stream has a TDS under 2,000 mg/l, preferably under 500 mg/l.
  • One or more concentration operations may include a reverse osmosis operation upstream of a counter-flow reverse osmosis operation.
  • the reverse osmosis separates the input stream into a preconcentrated stream and a permeate stream using a semi- permeable membrane, wherein the permeate stream is the low TDS stream.
  • the counter-flow reverse osmosis operation may include flowing the preconcentrated stream into a plurality of reactors in series, each containing a semi- permeable membrane separating the reactor into a first volume and a second volume.
  • the preconcentrated stream flows sequentially as a non-permeating stream into the first volume of each reactor and a permeating stream flows sequentially into the second volume of each reactor counter-current to the non-permeating stream.
  • the nonpermeating stream exiting the plurality of reactors yields a concentrated stream and the permeating stream exiting the plurality of reactors yields a dilute brine stream.
  • the dilute brine stream may be recycled into the reverse osmosis operation.
  • the at least one concentration operation may include pressurizing the input stream, especially before the counter-flow reverse osmosis operation, and preferably at a target pressure lower than membrane threshold pressure, in particular below 2000 psi.
  • the at least one concentration operation may include pressurizing the input stream before the reverse osmosis operation and depressurizing the permeating stream before flowing it into the second volume of the plurality of reactors.
  • the at least one concentration operation may include a feed preparation operation, wherein the input stream is an aqueous lithium source and the output feed is the extraction feed.
  • the feed preparation operation takes place upstream of the extraction stage.
  • the at least one concentration operation may include concentrating a stream derived from the lithium intermediate as the input stream to yield a lithium concentrate as the output feed. Such a concentration operation takes place downstream of the extraction stage, directly on the lithium intermediate or on a stream corresponding to the lithium intermediate that has undergone one or more additional operations.
  • the stream derived from the lithium intermediate is a first stream
  • the method further comprises treating a second stream derived from the lithium intermediate in an impurity stage to remove impurities, and forming a purified lithium stream, wherein the first stream is the purified lithium stream.
  • impurity treatment operation ie impurity stage
  • the one or more concentration operations may further include an impurity preparation stage.
  • the input stream is the lithium intermediate and the output feed is an an impurity stage feed
  • the second stream ie undergoing the impurity stage
  • concentrating the lithium intermediate in the impurity preparation stage comprises increasing concentration of one or more impurities in the lithium intermediate to at least 90% of the solubility limit of the one or more impurities in the lithium intermediate
  • the method may further comprise converting lithium in the lithium concentrate to a lithium product.
  • the lithium chloride in the lithium concentrate is converted to lithium carbonate and/or hydroxide.
  • At least a portion of the low TDS stream is recycled into the extraction stage.
  • Extracting lithium from the extraction feed includes contacting the extraction feed with a lithium selective medium to load the medium with lithium and contacting an eluent stream with the lithium-loaded medium to form the lithium intermediate, low TDS stream may then be recycled into the eluent stream.
  • the brine source stream yields a lithium depleted brine stream after having contacting the lithium selective medium, and using at least a membrane separation operation or thermal vaporizer to yield a reject stream and a fresh water stream, wherein the fresh water stream is recycled, ie directed to any operation of the method, especially having a fresh water need.
  • the reject stream may be returned to the environment, ie reinjected in the geological formation.
  • the extraction stage may include a continuous counter-current adsorption desorption process.
  • the plurality of reactors may include 2 to 10, preferable 3 to 6, reactors.
  • the lithium concentration range between the lithium concentrate and non-permeating stream may be between 2 and 20.
  • the lithium concentration range between the lithium concentrate and dilute brine stream may be between 2 and 20.
  • the TDS of the lithium concentration is over 120,000mg/l and preferably over 200,000 mg/l.
  • the lithium concentration of the lithium concentrate may be over 2.%, preferably over 3.3 % weight.
  • At least a portion of the low TDS stream is recycled as a permeate target feed into another stream used in any stage of the method.
  • the permeate target feed may for instance be one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • At least a portion of the dilute brine stream is recycled into a dilute brine target feed, and the dilute brine target feed is one one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • the at least one portion of the low TDS stream recycled into the permeate target feed and/or the at least one portion of the dilute brine stream recycled into the dilute brine target feed is adjusted to manage the concentration of lithium or to manage a ratio of lithium ions to impurity ions into the permeate, respectively dilute brine, target feed.
  • the disclosure also relates to a method of recovering lithium from a lithium source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations includes concentrating a non-permeating stream derived from the input stream to form the output feed using at least a membrane separation operation.
  • the membrane separation operation include flowing the non-permeating stream in a plurality of reactors in series, wherein each reactor contains a semi-permeable membrane separating the reactor into a first and a second volumes, wherein the non-permeating stream flows into the first volume of the plurality of reactors. It also includes collecting the non-permeating stream at the outlet of the plurality of the reactors. A first portion of the non-permeating stream forms the output feed and a second portion of the non-permeating stream is recycled into the membrane separation operation as a permeating stream. It further includes flowing the permeating stream into a second volume of the plurality of reactors counter-current to the non-permeating stream.
  • the membrane separation operation is a first membrane separation operation
  • the at least one concentration operation includes a second membrane separation operation to concentrate the inlet stream upstream from the first membrane separation operation.
  • the second membrane separation operation includes separating the inlet stream into a preconcentrated stream and a permeate stream using at least a semi-permeable membrane.
  • the preconcentrated stream is the non-permeating stream of the first membrane separation operation.
  • the method may also include collecting the permeating stream at the outlet of the plurality of the reactors.
  • the collected permeating stream forms a dilute brine stream.
  • the at least one concentration operation may also include pressurizing the nonpermeating stream, especially before flowing it into the first volume of the plurality of reactors, preferably at a target pressure lower than membrane threshold pressure, in particular below 2000 psi, and depressurizing the permeating stream before flowing it into the second volume of the plurality of reactors.
  • the at least one concentration operation may also include a feed preparation operation that concentrates the aqueous lithium source to yield the extraction feed.
  • the at least one concentration operation may include concentrating a stream derived from the lithium intermediate as the input stream to yield a lithium concentrate as the output feed. Such a concentration operation takes place downstream of the extraction stage, directly on the lithium intermediate or on a stream corresponding to the lithium intermediate that has undergone one or more additional operations.
  • the stream derived from the lithium intermediate is a first stream
  • the method further comprises treating a second stream derived from the lithium intermediate in an impurity stage to remove impurities, and forming a purified lithium stream, wherein the first stream is the purified lithium stream.
  • impurity treatment operation ie impurity stage
  • the one or more concentration operations may further include an impurity preparation stage.
  • the input stream is the lithium intermediate and the output feed is an an impurity stage feed
  • the second stream ie undergoing the impurity stage
  • concentrating the lithium intermediate in the impurity preparation stage comprises increasing concentration of one or more impurities in the lithium intermediate to at least 90% of the solubility limit of the one or more impurities in the lithium intermediate
  • the method may further comprise converting lithium in the lithium concentrate to a lithium product.
  • the lithium chloride in the lithium concentrate is converted to lithium carbonate and/or hydroxide.
  • At least a portion of the low TDS stream is recycled into a permeate target feed, and the permeate target feed may be used in any stage of the method, and may for instance correspond to one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • At least a portion of the dilute brine stream is recycled into a dilute brine target feed, and the dilute brine target feed is one one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • the at least one portion of the low TDS stream recycled into the permeate target feed and/or the at least one portion of the dilute brine stream recycled into the dilute brine target feed is adjusted to manage the concentration of lithium or to manage a ratio of lithium ions to impurity ions into the permeate, respectively dilute brine, target feed.
  • At least a portion of the low TDS stream is recycled, preferably into the extraction stage.
  • Extracting lithium from the extraction feed includes contacting the extraction feed with a lithium selective medium to load the medium with lithium and contacting an eluent stream with the lithium-loaded medium to form the lithium intermediate, low TDS stream may then be recycled into the eluent stream.
  • the brine source stream yields a lithium depleted brine stream after having contacting the lithium selective medium, and using at least a membrane separation operation or thermal vaporizer to yield a reject stream and a fresh water stream, wherein the fresh water stream is recycled, ie directed to any operation of the method, especially having a fresh water need.
  • the reject stream may be returned to the environment, ie reinjected in the geological formation.
  • the extraction stage may include a continuous counter-current adsorption desorption process.
  • the plurality of reactors may include 2 to 10, preferable 3 to 6, reactors.
  • the lithium concentration range between the lithium concentrate and non-permeating stream may be between 2 and 20.
  • the lithium concentration range between the lithium concentrate and dilute brine stream may be between 2 and 20.
  • the TDS of the lithium concentration is over 120,000mg/l and preferably over 200,000 mg/l.
  • the lithium concentration of the lithium concentrate may be over 2.%, preferably over 3.3 % weight.
  • the disclosure also relates to a method of recovering lithium from a lithium source.
  • the method comprises extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; and performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations includes a first membrane separation operation, having a first semi-permeable membrane, yielding from the input stream a preconcentrated stream and a permeate stream, and a second membrane separation operation.
  • the preconcentrated stream flows into a plurality of reactors in series, each containing a semi-permeable membrane separating the reactor into a first volume and a second volume, and the preconcentrated stream flows sequentially as a non-permeating stream into the first volume of each reactor.
  • the non-permeating stream exiting the plurality of reactors yields the output stream.
  • the second membrane operation yields a dilute brine stream that exits the second volume of at least one of the reactors, wherein the dilute brine stream is recycled into the first membrane separation operation.
  • the second membrane separation operation may include a permeating stream that flows sequentially into the second volume of the plurality of reactors, counter-current to the permeating stream, wherein at least a portion of the non-permeating stream is recycled into the permeating stream, wherein the permeating stream yields the dilute brine stream.
  • the at least one concentration operations may also include pressurizing the non-permeating stream, especially before flowing it into the first volume of the plurality of reactors, preferably at a target pressure lower than membrane threshold pressure, in particular below 2000 psi, and depressurizing the permeating stream before flowing it into the second volume of the plurality of reactors.
  • the at least one concentration operation may also include a feed preparation operation that concentrates the aqueous lithium source to yield the extraction feed.
  • the at least one concentration operation may include concentrating a stream derived from the lithium intermediate as the input stream to yield a lithium concentrate as the output feed. Such a concentration operation takes place downstream of the extraction stage, directly on the lithium intermediate or on a stream corresponding to the lithium intermediate that has undergone one or more additional operations.
  • the stream derived from the lithium intermediate is a first stream
  • the method further comprises treating a second stream derived from the lithium intermediate in an impurity stage to remove impurities, and forming a purified lithium stream, wherein the first stream is the purified lithium stream.
  • impurity treatment operation ie impurity stage
  • the one or more concentration operations may further include an impurity preparation stage.
  • the input stream is the lithium intermediate and the output feed is an an impurity stage feed
  • the second stream ie undergoing the impurity stage
  • concentrating the lithium intermediate in the impurity preparation stage comprises increasing concentration of one or more impurities in the lithium intermediate to at least 90% of the solubility limit of the one or more impurities in the lithium intermediate
  • At least a portion of the permeate stream may be recycled into is a permeate target feed.
  • the permeate target feed may be any stream used in one or more stages of the method, for instance one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • At least a portion of the permeate stream may be recycled into the extraction stage.
  • Extracting lithium from the extraction feed includes contacting the extraction feed with a lithium selective medium to load the medium with lithium and contacting an eluent stream with the lithium-loaded medium to form the lithium intermediate, low TDS stream may then be recycled into the eluent stream.
  • the brine source stream yields a lithium depleted brine stream after having contacting the lithium selective medium, and using at least a membrane separation operation or thermal vaporizer to yield a reject stream and a fresh water stream, wherein the fresh water stream is recycled, ie directed to any operation of the method, especially having a fresh water need.
  • the reject stream may be returned to the environment, ie reinjected in the geological formation.
  • the extraction stage may include a continuous counter-current adsorption desorption process.
  • the plurality of reactors may include 2 to 10, preferable 3 to 6, reactors.
  • the lithium concentration range between the lithium concentrate and non-permeating stream may be between 2 and 20.
  • the lithium concentration range between the lithium concentrate and dilute brine stream may be between 2 and 20.
  • the TDS of the lithium concentration is over 120,000mg/l and preferably over 200,000 mg/l.
  • the lithium concentration of the lithium concentrate may be over 2.%, preferably over 3.3 % weight.
  • the disclosure also relates to a method of recovering lithium from a brine source.
  • the method comprises extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; and performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations may include a first membrane separation operation, having a first semi-permeable membrane, yielding from the input stream a preconcentrated stream and a permeate stream, and concentrating the preconcentrated stream using a second membrane separation operation, wherein the second membrane operation includes a plurality of reactors in series each having a semi-permeable membrane to yield the output stream, wherein the second membrane separation operation is configured so that the lithium concentrate has a TDS over 120,000mg/l, preferably over 200, 000mg/l.
  • each semi-permeable membrane separate the associated reactor into a first volume and a second volume, wherein the preconcentrated stream flows sequentially as a non-permeating stream into the first volume of each reactor, and wherein the second membrane operation yields a dilute brine stream that exits the second volume of at least one of the reactors, wherein the dilute brine stream is recycled into the first membrane separation operation.
  • the second membrane separation operation may include a permeating stream that flows sequentially into the second volume of the plurality of reactors, counter-current to the permeating stream, wherein at least a portion of the non-permeating stream is recycled into the permeating stream, wherein the permeating stream yields the dilute brine stream.
  • the at least one concentration operations may also include pressurizing the nonpermeating stream, especially before flowing it into the first volume of the plurality of reactors, preferably at a target pressure lower than membrane threshold pressure, in particular below 2000 psi, and depressurizing the permeating stream before flowing it into the second volume of the plurality of reactors.
  • the at least one concentration operation may also include a feed preparation operation that concentrates the aqueous lithium source to yield the extraction feed.
  • the at least one concentration operation may include concentrating a stream derived from the lithium intermediate as the input stream to yield a lithium concentrate as the output feed. Such a concentration operation takes place downstream of the extraction stage, directly on the lithium intermediate or on a stream corresponding to the lithium intermediate that has undergone one or more additional operations.
  • the stream derived from the lithium intermediate is a first stream
  • the method further comprises treating a second stream derived from the lithium intermediate in an impurity stage to remove impurities, and forming a purified lithium stream, wherein the first stream is the purified lithium stream.
  • impurity treatment operation ie impurity stage
  • the one or more concentration operations may further include an impurity preparation stage.
  • the input stream is the lithium intermediate and the output feed is an an impurity stage feed
  • the second stream ie undergoing the impurity stage
  • concentrating the lithium intermediate in the impurity preparation stage comprises increasing concentration of one or more impurities in the lithium intermediate to at least 90% of the solubility limit of the one or more impurities in the lithium intermediate
  • At least a portion of the permeate stream may be recycled into is a permeate target feed.
  • the permeate target feed may be used in any stage of the method and for instance may be one of the aqueous lithium source, extraction feed, lithium intermediate, impurity stage feed or purified lithium stream.
  • At least a portion of the permeate stream may be recycled into the extraction stage.
  • Extracting lithium from the extraction feed includes contacting the extraction feed with a lithium selective medium to load the medium with lithium and contacting an eluent stream with the lithium-loaded medium to form the lithium intermediate, low TDS stream may then be recycled into the eluent stream.
  • the brine source stream yields a lithium depleted brine stream after having contacting the lithium selective medium, and using at least a membrane separation operation or thermal vaporizer to yield a reject stream and a fresh water stream, wherein the fresh water stream is recycled, ie directed to any operation of the method, especially having a fresh water need.
  • the reject stream may be returned to the environment, ie reinjected in the geological formation.
  • the extraction stage may include a continuous counter-current adsorption desorption process.
  • the plurality of reactors may include 2 to 10, preferable 3 to 6, reactors.
  • the lithium concentration range between the lithium concentrate and non-permeating stream may be between 2 and 20.
  • the lithium concentration range between the lithium concentrate and dilute brine stream may be between 2 and 20.
  • the TDS of the lithium concentration is over 120,000mg/l and preferably over 200,000 mg/l.
  • the lithium concentration of the lithium concentrate may be over 2.%, preferably over 3.3 % weight.
  • the disclosure also relates to a method of recovering lithium from a brine source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate.
  • the method also includes performing one or more concentration operations, each concentration operation concentrating an input stream to yield an output feed, wherein the input stream is obtained from the lithium intermediate and/or the extraction feed is obtained from the output feed.
  • the at least one concentration operations includes at least a membrane separation operation, wherein at least one the membrane separation operation includes a plurality of reactors in series each having a semi-permeable membrane, yields a lithium concentrate and a dilute brine stream, and is configured so that the lithium concentrate has a TDS over 120,000mg/l, preferably over 200,000mg/l.
  • the method also includes separating the dilute brine stream using a semi-permeable membrane into two streams including a permeate stream, wherein the permeate stream has a TDS under 2,000 mg/l, preferably under 500 mg/l, and recycling the permeate stream, ie directing it to any operation of the method, especially having a fresh water need.
  • the one or more concentration operations include a first membrane separation operation yielding a preconcentrated stream and a diluted stream from the input stream, a second membrane operation, wherein the at least one membrane separation is the second membrane operation.
  • the method also includes providing the dilute brine stream into the first membrane separation operation, wherein the diluted stream is the permeate stream.
  • each semi-permeable membrane separate the associated reactor into a first volume and a second volume, wherein a stream derived from the input stream flows sequentially as a non-permeating stream into the first volume of each reactor, and wherein the dilute brine stream that exits the second volume of at least one of the reactors, wherein the dilute brine stream is recycled into the first membrane separation operation.
  • the second membrane separation operation may also have a permeating stream that flows sequentially into the second volume of the plurality of reactors, counter-current to the permeating stream, wherein at least a portion of the non-permeating stream is recycled into the permeating stream, wherein the permeating stream yields the dilute brine stream.
  • the at least one concentration operation may include a feed preparation operation that concentrates the aqueous lithium source to yield the extraction feed.
  • the at least one concentration operation may include concentrating a stream derived from the lithium intermediate to yield a lithium concentrate. Such a concentration operation takes place downstream of the extraction stage, directly on the lithium intermediate or on a stream corresponding to the lithium intermediate that has undergone one or more additional operations.
  • the stream derived from the lithium intermediate is a first stream
  • the method further comprises treating a second stream derived from the lithium intermediate in an impurity stage to remove impurities, and forming a purified lithium stream, wherein the first stream is the purified lithium stream.
  • impurity treatment operation ie impurity stage
  • the one or more concentration operations may further include an impurity preparation stage.
  • the input stream is the lithium intermediate and the output feed is an an impurity stage feed
  • the second stream ie undergoing the impurity stage
  • concentrating the lithium intermediate in the impurity preparation stage comprises increasing concentration of one or more impurities in the lithium intermediate to at least 90% of the solubility limit of the one or more impurities in the lithium intermediate
  • At least a portion of the permeate stream may recycled into the extraction stage.
  • extracting lithium from the extraction feed includes contacting the extraction feed stream with a lithium selective medium to load the medium with lithium and contacting an eluent stream with the lithium-loaded medium to form the lithium intermediate.
  • the permeate stream may be recycled into the eluent stream.
  • the brine source stream yields a lithium depleted brine stream after having contacting the lithium selective medium, and using at least a membrane separation operation or thermal vaporizer to yield a reject stream and a fresh water stream, wherein the fresh water stream is recycled, ie directed to any operation of the method, especially having a fresh water need.
  • the extraction stage may include a continuous counter-current adsorption desorption process.
  • the plurality of reactors may include 2 to 10, preferable 3 to 6, reactors.
  • the lithium concentration range between the lithium concentrate and non-permeating stream may be between 2 and 20.
  • the lithium concentration range between the lithium concentrate and dilute brine stream may be between 2 and 20.
  • the lithium concentration of the lithium concentrate may be over 2.%, preferably over 3.3 % weight.
  • the method may also include pressurizing the input stream, especially before the at least one membrane separation operation, preferably at a target pressure lower than membrane threshold pressure, in particular below 2000 psi.

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Abstract

Sont décrits ici des procédés de récupération de lithium à partir de sources de lithium diluées. Les procédés consistent à concentrer une source de lithium aqueuse diluée pour obtenir une charge d'alimentation d'extraction ayant une concentration en lithium d'extraction ; extraire du lithium de la charge d'alimentation d'extraction à l'aide d'une extraction directe de lithium lors d'une étape d'extraction pour obtenir un intermédiaire de lithium ; concentrer un flux obtenu à partir de l'intermédiaire de lithium lors d'une étape de concentration pour obtenir un concentré de lithium ; et convertir le lithium dans le concentré de lithium en hydroxyde de lithium.
PCT/US2022/051500 2022-05-04 2022-12-01 Récupération de lithium à l'aide de sources aqueuses WO2023215002A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/US2023/020954 WO2023215448A1 (fr) 2022-05-04 2023-05-04 Récupération de lithium à l'aide de sources aqueuses
US18/311,966 US20230364560A1 (en) 2022-05-04 2023-05-04 Lithium recovery using aqueous sources
US18/311,975 US20230356107A1 (en) 2022-05-04 2023-05-04 Lithium recovery using aqueous sources
US18/311,956 US20230366062A1 (en) 2022-05-04 2023-05-04 Lithium recovery using aqueous sources
PCT/US2023/020957 WO2023215450A1 (fr) 2022-05-04 2023-05-04 Récupération de lithium à l'aide de sources aqueuses
US18/430,935 US20240165539A1 (en) 2022-05-04 2024-02-02 Lithium recovery using aqueous sources

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WO2021061343A1 (fr) * 2019-09-25 2021-04-01 Veolia Water Solutions & Technologies Support Procédé écoénergétique destiné à la concentration et la récupération de lithium à partir d'une saumure contenant du lithium

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US20210087697A1 (en) * 2019-09-25 2021-03-25 Ecostar-Nautech Co., Ltd. Method for producing lithium hydroxide monohydrate from brines
WO2021061343A1 (fr) * 2019-09-25 2021-04-01 Veolia Water Solutions & Technologies Support Procédé écoénergétique destiné à la concentration et la récupération de lithium à partir d'une saumure contenant du lithium

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