A SYSTEM FOR EXTRACTLING LITHIUM IONS FROM A LIQUID

Abstract

A system for extracting lithium ions from a liquid, characterized in that it comprises a loaded ion exchange material in one or more tanks, or a loaded ion exchange material in one or more columns, wherein said one or more tanks or said one or more columns comprise one or more injection ports; and a pH modulating device for increasing the pH of the liquid present in the system, wherein the pH modulating device is connected to said one or more injection ports and is configured to modulate the pH of the liquid.

Description

A SYSTEM FOR EXTRACTING LITHIUM IONS FROM A REFERENCE LIQUID [1] This application claims the benefit of U.S. Provisional Application Nos. 62 / 540,511, filed August 2, 2017, and 62 / 582,208, filed November 6, 2017, which applications are incorporated herein by reference in their entirety. BACKGROUND OF THE INVENTION [2] Lithium is an essential element for high-energy rechargeable batteries and other technologies. Lithium can be found in a variety of liquid solutions, including natural and synthetic brines and leachates from minerals and recycled products. SUMMARY OF THE INVENTION [3] Lithium can be extracted from liquids using an ion exchange process based on inorganic ion exchange materials. Inorganic ion exchange materials absorb lithium ions from a liquid while releasing hydrogen ions, and then elute lithium ions into acid while absorbing hydrogen ions. The ion exchange process can be repeated to extract lithium ions from a liquid and give a concentrated lithium ion solution. The concentrated lithium ion solution can be further processed into chemicals for the battery industry or other industries. [4] One aspect described herein is a system for extracting lithium ions from a liquid, comprising: a) an ion exchange material; and b) pH modulating equipment for increasing the pH of the liquid present in the system. 2047634 of 163 [5] In some embodiments, the ion exchange material is loaded into a vessel. In some embodiments, the ion exchange material is loaded into a plurality of vessels. In some embodiments, the pH modulating equipment is connected to the vessel loaded with the ion exchange material. In some embodiments, the vessel further comprises a plurality of injection ports, where the plurality of injection ports are used to increase the pH of the liquid present in the system. In some embodiments, the pH modulating equipment further comprises one or more tanks. [6] In some embodiments, the pH modulating apparatus comprises a tank comprising: a) one or more compartments; and b) means for moving liquid through the one or more compartments. In some embodiments, ion exchange material is loaded into at least one compartment. In some embodiments, the tank further comprises means for circulating liquid throughout the tank. In some embodiments, the means for circulating liquid throughout the tank is a mixing device. In some embodiments, the tank further comprises an injection port. [7] One aspect described herein is a system for extracting lithium ions from a liquid, comprising a tank, the tank further comprising: a) one or more compartments; b) an ion exchange material; c) a mixing device; and d) pH modulating equipment for changing the pH of the system, the ion exchange material being used to extract lithium ions from the liquid. [8] In some embodiments, the ion exchange material 2047634 of 163 is loaded into at least one of the one or more compartments. In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is an injection port. In some embodiments, the tank further comprises a porous partition. In some embodiments, the porous partition is a porous partition made of a polymer. [9] One aspect described herein is a system for extracting lithium ions from a liquid comprising an ion exchange material and a plurality of columns, wherein each of the plurality of columns is configured to transport the ion exchange material along the length of the column and the ion exchange material is used to extract lithium ions from the liquid.

[10] In some embodiments, at least one of the plurality of columns comprises an acid solution. In some embodiments, at least one of the plurality of columns comprises the liquid. In some embodiments, each of the plurality of columns is configured to transport the ion exchange material via a piping system or an internal transport system.

[11] In some embodiments, the ion exchange material comprises a plurality of ion exchange particles. In some embodiments, the plurality of ion exchange particles present in the ion exchange material is selected from uncoated ion exchange particles, coated ion exchange particles, and 2047634 of 163 combinations thereof. In some embodiments, the ion exchange material is a porous ion exchange material. In some embodiments, the porous ion exchange material comprises a network of pores that allows liquids to rapidly move from the surface of the porous ion exchange material toward the plurality of ion exchange particles. In some embodiments, the ion exchange material is in the form of porous ion exchange beads.In some embodiments, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, an oil field brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or a combination of ores, a leachate from a mineral or a combination of minerals, a leachate from a clay or a combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof.

[12] One aspect described herein is a device for extracting lithium from a liquid comprising one or more vessels independently configured to simultaneously accommodate porous ion exchange beads moving in one direction and alternately acid solutions, brine, and optionally other solutions moving in the net opposite direction.

[13] In some embodiments, at least one of the one or more containers is equipped with a transport system equipped 2047634 of 163 appropriately to displace the porous ion exchange beads in an upward direction and simultaneously allow a net downward flow of acidic solutions, brine, and optionally others. In some embodiments, the porous ion exchange beads comprise ion exchange particles that reversibly exchange lithium and hydrogen and a material that acts as a structural matrix, and have a network of pores.In some embodiments, the liquid comprises a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a filtered brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, ore leachate, mineral leachate, clay leachate, recycled product leachate, recycled material leachate, or combinations thereof.

[14] One aspect described herein is a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a system as described herein to produce a lithiated ion exchange material; and b) treating the lithiated ion exchange material obtained in a) with an acid solution to produce a salt solution comprising lithium ions.

[15] One aspect described herein is a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a tank of a system as described herein to produce a lithiated ion exchange material; and b) treating the lithiated ion exchange material obtained in a) with an acid solution to produce a 2047634 of 163 salt solution comprising lithium ions.

[16] An aspect described herein consists of a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a system comprising a tank to produce a lithiated ion exchange material, where the tank further comprises (i) one or more compartments, (ii) an ion exchange material, (iii) a mixing device, and (iv) a pH modulating equipment to change the pH of the liquid; and b) treating the lithiated ion exchange material obtained in a) with an acidic solution to produce a hydrogen-rich ion exchange material and a salt solution comprising lithium ions. In some embodiments, the method further comprises, before b), washing the lithiated ion exchange material with an aqueous solution. In some embodiments, the method further comprises, after ab), washing the hydrogen-rich ion exchange material with an aqueous solution.In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is a pipe. In some embodiments, the inlet is an injection port. In some embodiments, the method further comprises, during a), measuring a change in pH by the pH modulating apparatus. In some embodiments, the change in pH triggers the addition of a base to maintain lithium uptake. In some embodiments, changing the pH below a pH value of between about 2 and about 9 triggers the addition of base to maintain uptake. 2047634 of 163 lithium.

[17] In some embodiments of the methods described herein, the tank further comprises a porous partition. In some embodiments, the porous partition is a porous partition made of a polymer.

[18] An aspect described herein consists of a method for extracting lithium ions from a liquid, comprising: a) providing a system comprising an ion exchange material, a tank comprising one or more compartments; and a mixing device, where (i) the ion exchange material is based on oxides and exchanges hydrogen ions for lithium ions, and (ii) the mixing device is capable of moving the liquid through the tank comprising one or more compartments; b) flowing the liquid inside the system of a) thereby causing the liquid to come into contact with the ion exchange material, where the ion exchange material exchanges hydrogen ions for lithium ions in the liquid to produce a lithiated ion exchange material; c) removing the liquid from the system of b);d) flowing an acid solution through the system c) thereby causing the acid solution to come into contact with the lithiated ion exchange material, where the lithiated ion exchange material exchanges lithium ions for hydrogen ions present in the acid solution to produce the ion exchange material and a salt solution comprising lithium ions from the lithiated ion exchange material; and e) collecting the salt solution comprising the lithium ions for further processing;

[19] In some embodiments of the methods described herein, the liquid is a natural brine, a dissolved saline salt, water, 2047634 of 163 sea, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, an oil field brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or combination of ores, a leachate from a mineral or combination of minerals, a leachate from a clay or combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof.

[20] In some embodiments of the methods described herein, the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof.

[21] One aspect described herein is a process for extracting lithium from a liquid comprising treating the ion exchange material alternately with acid solutions, brine, and optionally others, in a configuration where the material moves in the net opposite direction to the acid solutions, brine, and optionally other components, to thereby produce a lithium-enriched solution from the liquid.

[22] In some embodiments of the process for extracting lithium from a liquid, the process comprising: a) treating the ion exchange material with acid under appropriate conditions to absorb hydrogen to generate a hydrogen-enriched material and release lithium to generate a lithium-enriched solution; b) optionally, washing with 2047634 of 163 water the hydrogen-enriched material to obtain a hydrogen-enriched material substantially free of residual acid; c) treating the hydrogen-enriched material with the liquid under conditions appropriate to absorb lithium to generate a lithium-enriched material; d) optionally, washing the lithium-enriched material with water to generate a lithium-enriched material substantially free of the liquid; and e) repeating the cycle to produce a lithium-enriched solution from the liquid. In some embodiments, the ion exchange material comprises ion exchange particles that reversibly exchange lithium and hydrogen and a material that acts as a structural matrix, and have a network of pores.In some embodiments of the processes described herein, the liquid comprises a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a filtered brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, ore leachate, mineral leachate, clay leachate, recycled product leachate, recycled material leachate, or combinations thereof.

[23] One aspect described herein is a process for extracting lithium ions from a liquid, comprising: a) contacting an ion exchange material with the liquid; and b) increasing the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof. In some embodiments, the ion exchange material is loaded into one or more 2047634 of 163 compartments of a tank. In some embodiments, the process further comprises moving the liquid through the one or more compartments of the tank. In some embodiments, the tank comprises injection ports. In some embodiments, the process further comprises using the injection ports to increase the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof. In some embodiments, the ion exchange material is loaded into one or more containers. In some embodiments, the one or more containers also comprise a plurality of injection ports.In some embodiments, the process further comprises using the plurality of injection ports to increase the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof.

[24] In some embodiments of the processes described herein, the ion exchange material comprises a plurality of ion exchange particles. In some embodiments, the plurality of ion exchange particles present in the ion exchange material are selected from uncoated ion exchange particles, coated ion exchange particles, and combinations thereof. In some embodiments, the ion exchange material is a porous ion exchange material. In some embodiments, the porous ion exchange material comprises a network of pores that allows 2047634 of 163 to rapidly move liquids from the surface of the porous ion exchange material toward the plurality of ion exchange particles. In some embodiments, the porous ion exchange material is in the form of porous ion exchange beads. INCORPORATION AS A REFERENCE

[25] All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference. BRIEF DESCRIPTION OF THE FIGURES

[26] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by referring to the following detailed description, which sets forth illustrative embodiments in which the principles of the invention are utilized, and the accompanying figures, where:

[27] Figure 1 illustrates a batch recirculation system comprising an ion exchange column, a mixing tank, a settling tank, and a recirculation tank.

[28] Figure 2 illustrates a batch recirculation system comprising an ion exchange column, a mixing tank, and a recirculation tank.

[29] Figure 3 illustrates a column exchange system comprising a brine circuit, a water wash circuit, and a 2047634 of 163 acid circuit.

[30] Figure 4 illustrates a column exchange system comprising a brine circuit, a water wash circuit, and an acid recirculation circuit.

[31] Figure 5 illustrates a stirred tank system comprising a tank, a base mixing tank, and a permeable compartment for containing the ion exchange beads.

[32] Figure 6 illustrates a ported ion exchange column system comprising an ion exchange column with multiple ports along the length of the column for injecting base.

[33] Figure 7 illustrates a coated ion exchange particle.

[34] Figure 8 illustrates a porous ion exchange bead.

[35] Figure 9 illustrates an ion exchange column with a moving bed of beads moving in the opposite direction to the flows of brine, acid, and other solutions.

[36] Figure 10 illustrates the assembly of a column for the acid and a column for the brine, which moves the ion exchange beads in the opposite direction to the liquid flows.

[37] Figure 11 illustrates the assembly of an acid column, a water wash column, a brine column, and another water wash column.

[38] Figure 12 illustrates the assembly of various columns for acid, brine, and water wash with various flow rates of the liquid solutions and beads, various column heights, and various residence times of the beads and brine. 2047634 of 163

[39] Figure 13 illustrates an elevator system with a conveyor belt having fins attached to the conveyor belt.

[40] Figure 14 illustrates a lifting system with a sliding surface whose position is maintained fixed and which has fins attached to a separate transport system.

[41] Figure 15 illustrates a porous bead containing ion exchange particles, matrix material, and pores formed by removing filler material.

[42] Figure 16 illustrates a stirred tank reactor with pH modulating equipment.

[43] Figure 17 illustrates a stirred tank reactor with pH modulating equipment and a compartment to contain the ion exchange particles.

[44] Figure 18 illustrates a pair of stirred tank reactors including a large stirred tank reactor with pH modulating equipment and a small stirred tank reactor.

[45] Figure 19 illustrates a stirred tank reactor network with a circuit for a liquid that is operated continuously.

[46] Figure 20 illustrates a network of stirred tank reactors, each operating in a batch mode and operating together in a switched network. DETAILED DESCRIPTION OF THE INVENTION

[47] In this specification, the terms “lithium”, “lithium ion”, and “Li+” are used interchangeably and said terms are synonymous unless specifically stated otherwise. In this specification 2047634 of 163 descriptive, the terms “hydrogen”, “hydrogen ion”, “proton”, and “H+” are used interchangeably and said terms are synonymous unless specifically stated otherwise.

[48] ​​As used herein, the words “column” and “vessel” are used synonymously. In some embodiments described herein, when reference is made to a “vessel,” the vessel is a column. In some embodiments described herein, when reference is made to a “column,” the column is a vessel.

[49] The terms “the pH of the system” or “the pH of” a component of a system, for example in one or more tanks, vessels, columns, pH modulating equipment, or pipes, that are used to establish fluid communication between one or more tanks, vessels, columns, or pH modulating equipment, refers to the pH of the liquid medium contained in or present in the system, or contained in or present in one or more components thereof. In some embodiments, the liquid medium contained in the system, or one or more components thereof, is a liquid. In some embodiments, the liquid medium contained in the system, or one or more components thereof, is a brine.In some embodiments, the liquid medium contained in the system, or one or more components thereof, is an acid solution, an aqueous solution, a wash solution, a salt solution, a salt solution comprising lithium ions, or a lithium-enriched solution.

[50] Lithium is an essential element for batteries and other technologies. Lithium is found in a variety of liquids, including natural and synthetic brines and leachates from minerals, clays, and other mineral products. 2047634 of 163 recycled. Optionally, lithium is extracted from said liquids using an ion exchange process based on inorganic ion exchange materials. Said inorganic ion exchange materials absorb lithium from a liquid while releasing hydrogen, and then elute the lithium in acid while absorbing hydrogen. This ion exchange process is optionally repeated to extract lithium from a liquid and obtain a concentrated lithium solution. The concentrated lithium solution is optionally further processed to obtain chemicals for the battery industry or other industries.

[51] Optionally, the ion exchange materials are formed into beads and the beads are optionally loaded into ion exchange columns for lithium extraction. Optionally, alternating streams of brine, acid, and other solutions are flowed through an ion exchange column to extract lithium from the brine and produce a lithium concentrate, which is eluted from the column using the acid. As the brine flows through the ion exchange column, the beads adsorb lithium while releasing hydrogen, where both lithium and hydrogen are cations. The release of hydrogen during lithium adsorption will acidify the brine and limit lithium adsorption unless the pH of the brine is optionally maintained within an appropriate range to thermodynamically facilitate favorable lithium adsorption and concomitant hydrogen release.

[52] To control the pH of the brine and maintain the pH within a range that is appropriate for lithium absorption in an ion exchange column, bases such as NaOH are optionally added. 2047634 of 163 Ca(OH)2, CaO, KOH, or NH3 to the brine in the form of solids, aqueous solutions, or in other forms. For brines containing divalent ions such as Mg, Ca, Sr, or Ba, the addition of base to the brine can cause the precipitation of solids, such as Mg(OH)2 or Ca(OH)2, which can cause problems for the ion exchange reaction. Such precipitates cause problems in at least three ways. First, the precipitation can remove base from the solution, leaving less base in solution available to neutralize protons and maintain the pH within an appropriate range for lithium adsorption on the ion exchange column. Second, the precipitates that form due to the addition of base can clog the ion exchange column, including clogging the surfaces and pores of the ion exchange beads and the void spaces between the ion exchange beads.This clogging can prevent lithium from entering the beads and being adsorbed by the ion exchange material. The clogging can also cause high pressures at the top of the column. Third, precipitates in the column dissolve during acid elution and thus contaminate the lithium concentrate produced by the ion exchange system. For ion exchange beads to adsorb lithium from the brine, an ideal pH range for the brine is optionally between 6 and 9, a preferred pH range is optionally between 4 and 9, and an acceptable pH range is optionally between 2 and 9. pH modulation system for lithium extraction

[53] An aspect of the invention described herein consists of an ion exchange reactor for lithium extraction with a shape that 2047634 of 163 allows pH control during lithium absorption from a brine or other liquid containing lithium ions. This reactor works by neutralizing the hydrogen released during lithium absorption, while also solving the problems associated with precipitation due to base addition.

[54] An aspect of the invention described herein is a system for extracting lithium ions from a liquid, comprising: a) an ion exchange material; and b) pH modulating equipment for increasing the pH of the liquid present in the system. The ion exchange material extracts lithium ions from a liquid. During the extraction of lithium ions from a liquid by the ion exchange material, the pH of the liquid is optionally decreased. Increasing the pH of the liquid present in the system by the use of pH modulating equipment maintains the pH within a range that is appropriate for the absorption of lithium ions by the ion exchange material. In one embodiment, the pH modulating scheme comprises measuring the pH of the system and adjusting the pH of the system to bring it into and maintain it within a pH range ideal for lithium extraction.In one embodiment, for the ion exchange material to absorb lithium from the brine, an ideal pH range for the brine is optionally between 6 and 9, a preferred pH range is optionally between 4 and 9, and an acceptable pH range is optionally between 2 and 9. In one embodiment, the pH modulation scheme comprises measuring the pH of the system and that the pH of the system is less than 6, less than 4, or less than 2, the pH of the system is brought and maintained at a pH between 2 and 9, a pH between 4 and 9, or a pH between 6 and 9. Batch recirculation system 2047634 of 163

[55] In one embodiment of the system, the ion exchange material is loaded into a column. In one embodiment of the system, pH modulating equipment is connected to the column loaded with the ion exchange material. In one embodiment of the system, the pH modulating equipment comprises one or more tanks.

[56] In some embodiments of the systems described herein, the ion exchange material is loaded into a vessel. In some embodiments, the pH modulating equipment is in fluid communication with the vessel loaded with the ion exchange material. In some embodiments, the pH modulating equipment is in fluid communication with the column loaded with the ion exchange material.

[57] In one embodiment of the system, one or more ion exchange columns are loaded with a fixed or fluidized bed of ion exchange beads. In one embodiment of the system, the ion exchange column is a cylindrical construction with inlet and outlet ports. In a further embodiment, the ion exchange column is optionally a non-cylindrical construction with inlet and outlet ports. In a further embodiment, the ion exchange column optionally has inlet and outlet ports for pumping brine, and additional gates or hatches for loading and unloading ion exchange beads into and from the column. In a further embodiment, the ion exchange column is optionally equipped with one or more safety devices to reduce the risk of theft of the ion exchange beads. In one embodiment, 2047634 of 163 said beads contain ion exchange material that can reversibly absorb lithium from the brine and release the lithium in an acidic medium. In one embodiment, the ion exchange material comprises particles that are optionally protected with a coating material such as SiO2, ZrO2, or TiO2 to limit dissolution or degradation of the ion exchange material. In one embodiment, said beads contain a structural component such as an acid-resistant polymer that binds the ion exchange materials. In one embodiment, the beads contain pores that facilitate penetration of brine, acid, and aqueous and other solutions into the beads to deliver lithium and hydrogen to the bead and to extract them from the bead or to wash the bead.In one embodiment, the pore structure of the bead allows them to form a connected pore network with a pore size distribution and are structured by incorporating filler materials during bead formation and then removing said filler material with a liquid or gas.

[58] In one embodiment of the system, the system consists of a batch recirculation system, comprising an ion exchange column that is connected to one or more tanks for mixing the base with the brine, settling out any precipitates after the base is added, and storing the brine prior to reinjection into the ion exchange column or the other tanks. In one embodiment of the batch recirculation system, the brine is loaded into one or more tanks, pumped through the ion exchange column, pumped through a series of tanks, and then looped back to the ion exchange column. In one embodiment, the 2047634 of 163 brine optionally repeatedly passes through this loop. In one embodiment, the brine is recirculated through the ion exchange column to allow for optimal lithium uptake by the beads. In one embodiment, the base is added to the brine in a manner that maintains the pH at a level suitable for lithium uptake and in a manner that minimizes the amount of base-related precipitates in the ion exchange column.

[59] In one embodiment, as brine is pumped through the batch recirculation system, the pH of the brine in the ion exchange column drops due to the release of hydrogen from the ion exchange beads during lithium uptake, and the pH of the brine is adjusted upward by the addition of base as a solid, an aqueous solution, or other form. In one embodiment, the ion exchange system drives the ion exchange reaction to near completion, and the pH of the brine exiting the ion exchange column approaches the pH of the brine entering the ion exchange column. In one embodiment, the amount of base optionally added is controlled so as to neutralize the hydrogen released by the ion exchange beads such that basic precipitates do not form.In one embodiment, an excess of base or a transient excess of base is optionally added such that basic precipitates form. In one embodiment, basic precipitates form transiently and are then partially or completely redissolved by hydrogen released from the ion exchange column. In one embodiment of the system, base is optionally added to the brine flow before the. 2047634 of 163 ion exchange column, after the ion exchange column, before one or more tanks, or after one or more tanks.

[60] In one embodiment of the batch recirculation system, the tanks include a mixing tank where the base is mixed with the brine. In one embodiment, the tanks include a settling tank, where optionally some precipitates such as Mg(OH)2 settle to the bottom of the settling tank to prevent injection of the precipitates into the ion exchange column. In one embodiment, the tanks include a storage tank where brine is stored prior to reinjection into the ion exchange column, the mixing tank, the settling tank, or other tanks. In one embodiment, the tanks include an acid recirculation tank.In one embodiment, some tanks of the batch recirculation reactor optionally serve a variety of purposes, including: base mixing tank, settling tank, acid recirculation tank, or storage tank. In any embodiment, a tank optionally does not serve two functions simultaneously. For example, a tank is not both a base mixing tank and a settling tank.

[61] In one embodiment of the batch recirculation system, base is added to a mixing tank, which is optionally a continuous stirred tank reactor, a confluence of acidified brine flow and base flow followed by a static mixer, a confluence of acidified brine flow and base flow followed by a paddle mixer, a confluence of acidified brine flow and base flow followed by a 2047634 of 163 turbine mixer in the form of a paddle wheel, or a continuous stirred tank reactor in the form of a vertical column with good mixing at the bottom and settling near the top. In one embodiment, the base is optionally added as a solid or as an aqueous solution. In one embodiment, the base is optionally added continuously at a constant or variable rate. In one embodiment, the base is optionally added as separate aliquots or batches in a constant or variable manner. In one embodiment, the base is optionally added in accordance with one or more pH meters, which optionally sample the brine downstream of the ion exchange column or elsewhere in the batch recirculation system. In one embodiment, filters are optionally used to prevent precipitates from exiting the mixing tank.In one embodiment, the filters are optionally plastic mesh sieves, columns with small packings containing granular media such as sand, silica, or alumina, columns with small packings containing porous filter media, or a membrane.

[62] In one embodiment of the batch recirculation system, the settling tank is optionally a bottom-inflow, top-effluent settling tank or a one-end, top-effluent settling tank. In one embodiment, chambered dams are used to completely settle the precipitates before the brine is recirculated into the reactor. In one embodiment, solid-based precipitates are collected at the bottom of the settling tank and recirculated to the mixer. In a In one embodiment, precipitates such as Mg(OH)2 optionally settle near the bottom of the tank. In one embodiment, brine is withdrawn from the top of the settling tank where the amount of suspended precipitates is minimal. In one embodiment, the precipitates optionally settle under forces such as gravity, centrifugal action, or other forces. In one embodiment, filters are optionally used to prevent precipitates from exiting the settling tank. In one embodiment, the filters are optionally plastic mesh sieves, columns with small packings containing granular media such as sand, silica, or alumina, columns with small packings containing porous filter media, or a membrane.In one embodiment, baffles are optionally used to ensure sedimentation of the precipitate and to prevent the precipitate from leaving the sedimentation tank and entering the column.

[63] In one embodiment of the batch recirculation system, basic precipitates are optionally collected from the settling tank and re-injected into the brine located in a mixing tank or elsewhere to adjust the pH of the brine.

[64] In one embodiment of the batch recirculation system, one or more ion exchange columns are optionally connected to one or more tanks or a set of tanks. In one embodiment of the batch recirculation system, there are optionally multiple ion exchange columns that recirculate brine through a set of shared mixing, settling, and storage tanks. In one embodiment of the batch recirculation system, there are optionally a 2047634 of 163 ion exchange column that recirculates the brine through multiple sets of mixing, settling, and storage tanks. Column exchange system

[65] An aspect of the invention described herein is a system wherein ion exchange material is loaded into a plurality of columns. In one embodiment, the pH modulating equipment comprises a plurality of tanks connected to the plurality of columns, where each tank of the plurality of tanks is directly connected to a column of the plurality of columns. In one embodiment, two or more tanks of the plurality of tanks are connected to the plurality of columns form at least one circuit. In one embodiment, three or more tanks of the plurality of tanks connected to the plurality of columns form at least two circuits. In one embodiment, three or more tanks of the plurality of tanks connected to the plurality of columns form at least three circuits. In one embodiment, at least one circuit is a liquid circuit.In one embodiment, at least one circuit is a water wash circuit. In one embodiment, at least one circuit is a circuit for the acid solution. In one embodiment, at least two circuits are water wash circuits.

[66] In one embodiment of the ion exchange system, the system is a column exchange system wherein there are a plurality of ion exchange columns connected to form a brine circuit, an acid circuit, a water wash circuit, and optionally other circuits. In one embodiment of the brine circuit, brine flows through a first column via the brine circuit, 2047634 of 163 then to the next column in the brine circuit, and so on, such that lithium is extracted from the brine as the brine flows through one or more columns. In one embodiment of the brine circuit, the base is added to the brine before or after each or certain ion exchange columns of the brine circuit to maintain the pH of the brine within a range appropriate for lithium uptake by the ion exchange beads. In one embodiment of the acid circuit, the acid flows through a first column via the acid circuit, then to the next column in the acid circuit, and so on, such that the lithium is eluted with acid from the columns to produce a lithium concentrate.In one embodiment of the acid circuit, acid flows through a first column of the acid circuit, then optionally to the next column of the acid circuit, and so on, such that lithium is eluted with acid from the columns to produce a lithium concentrate. In one embodiment of the water wash circuit, water flows through a first column of the water wash circuit, then optionally to the next column of the water wash circuit, and so on, such that brine present in the void spaces, pore space, or headspace of the water wash circuit columns is washed away.

[67] In one embodiment of the column exchange system, ion exchange columns are exchanged between the brine circuit, the water wash circuit, and the acid circuit. In one embodiment, the first column in the brine circuit is loaded with lithium and then exchanged with another within the water wash circuit to 2047634 of 163 remove brine from the voids, pore space, or headspace of the column. In one embodiment, the first column in the water wash circuit is washed to remove brine and then exchanged with another column in the acid circuit, where the lithium is eluted with acid to form a lithium concentrate. In one embodiment, the first column in the acid circuit is eluted with acid and then exchanged with another column within the brine circuit to absorb lithium from the brine. In one embodiment of the column exchange system, two water wash circuits are used to wash the columns after both the brine and acid circuits.In one embodiment of the column exchange system, only a water wash circuit is used to wash the columns after the brine circuit, while excess acid is neutralized with base or removed by washing the columns in the brine circuit.

[68] In one embodiment of the column exchange system, the first column in the brine circuit is exchanged to become the last column in the water wash circuit. In one embodiment of the column exchange system, the first column in the water wash circuit is exchanged to become the last column in the acid circuit. In one embodiment of the column exchange system, the first column in the acid circuit is exchanged to become the last column in the brine circuit.

[69] In one embodiment of the column exchange system, each column of the brine circuit contains one or more tanks or couplings for mixing the base with the brine and optionally for the 2047634 of 163 settling of any basic precipitate that forms after the addition of base. In one embodiment of the column exchange system, each column of the brine circuit has one or more associated tanks or couplings for removing basic precipitates or other particles by sedimentation or filtration. In one embodiment of the column exchange system, each column or various groups of columns have one or more associated settling tanks or filters that remove particles, including particles that are released from the ion exchange beads.

[70] In one embodiment of the column exchange system, the number of columns in the brine circuit is optionally less than about 3, less than about 10, less than about 30, or less than about 100. In one embodiment of the column exchange system, the number of columns in the acid circuit is optionally less than about 3, less than about 10, less than about 30, or less than about 100. In one embodiment of the column exchange system, the number of columns in the water wash circuit is optionally less than about 3, less than about 10, less than about 30, or less than about 100. In certain embodiments, the number of columns in the brine circuit is between 1 and 10. In some embodiments, the number of columns in the acid circuit is between 1 and 10.In some embodiments, the number of columns in the washing circuit is between 1 and 10.

[71] In one embodiment of the exchange system in 2047634 of 163 column, optionally there are one or more brine circuits, one or more acid circuits, and one or more water wash circuits. In one embodiment of the column exchange system, the ion exchange columns are optionally supplied with fresh ion exchange beads without interruption in the operation of the columns. In one embodiment of the column exchange system, ion exchange columns with beads whose capacity has been depleted are optionally replaced with ion exchange columns with fresh ion exchange beads without interruption in the operation of the columns.

[72] In one embodiment of the column exchange system, the columns contain fluidized beds of ion exchange material. In one embodiment of the column exchange system, the columns have means for creating a fluidized bed of ion exchange material such as overhead stirrers or pumps. In one embodiment of the column exchange system, the columns contain fluidized beds of ion exchange material. In one embodiment of the ion exchange system, where the system is an exchange system and the vessels are stirred tank reactors. In one embodiment of the exchange system, the base may be added directly to the columns or to other tanks containing the ion exchange material.In one embodiment of the exchange system, base may be added to the brine or other solution in a separate mixing tank and then this may be added to the columns or other tanks containing the ion exchange material.

[73] In one embodiment of the ion exchange system, 2047634 of 163 ion exchange beads are loaded onto ion exchange columns and after absorption of lithium from the brine, said lithium is eluted from the ion exchange columns using an acid recirculation loop. In one embodiment of the acid recirculation loop, acid is flowed through an ion exchange column, to a tank, and then recirculated through the ion exchange column to optimize lithium elution. In one embodiment of the ion exchange system, ion exchange beads are loaded onto ion exchange columns and after absorption of lithium from the brine, said lithium is eluted from each ion exchange column using a single pass flow of acid.In one embodiment of the ion exchange system, ion exchange beads are loaded onto an ion exchange column and after absorption of lithium from the brine, the lithium is eluted from the ion exchange column using a circuit of exchange columns.

[74] In one embodiment of the ion exchange system, ion exchange columns are charged with lithium by flowing brine through the columns using a batch recirculation system and then lithium is eluted from the columns using an in-column exchange system. In one embodiment of the ion exchange system, ion exchange columns are charged with lithium by flowing brine through the columns using an in-column exchange system and then lithium is eluted from the columns using a batch recirculation system. In one embodiment of the ion exchange system, ion exchange columns are charged with lithium by flowing brine through the columns using a batch recirculation system and then lithium is eluted from the columns. 2047634 of 163 columns using a batch recirculation system. In one embodiment of the ion exchange system, the ion exchange columns are loaded with lithium by flowing brine through the columns using an in-column exchange system and then eluting the lithium from the columns using an in-column exchange system. Stirred tank system

[75] One aspect of the invention described herein is a system wherein the pH modulating device is a tank comprising: a) one or more compartments; and b) a means for moving liquid through the one or more compartments. In one embodiment, ion exchange material is loaded into at least one compartment. In one embodiment, the means for moving liquid through the one or more compartments is a pipe. In a further embodiment, the means for moving liquid through the one or more compartments is a pipe and an appropriately configured pump. In one embodiment, the tank further comprises a means for circulating liquid throughout the tank. In one embodiment, the means for circulating liquid throughout the tank is a mixing device. In one embodiment, the tank further comprises an injection port.

[76] In some embodiments, the tank further comprises one or more injection ports. In some embodiments, the tank further comprises a plurality of injection ports.

[77] One aspect described herein is a system for extracting lithium ions from a liquid, comprising a tank, the tank further comprising: a) one or more compartments; b) a material of 2047634 of 163 ion exchange; c) a mixing device; and d) a pH modulating device for changing the pH of the system, where the ion exchange material is used to extract lithium ions from the liquid. In one embodiment, the pH modulating device changes the pH of the liquid present in the system.

[78] In some embodiments, the ion exchange material is loaded into at least one of the one or more compartments. In some embodiments, the ion exchange material is fluidized in at least one of the one or more compartments. In some embodiments, the ion exchange material is not fluidized in at least one of the one or more compartments. In some embodiments, the ion exchange material occupies a fixed position in at least one of the one or more compartments.

[79] In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is a pipe. In some embodiments, the inlet is an injection port.

[80] In some embodiments, the tank further comprises a porous partition. In some embodiments, the porous partition is a porous partition made of a polymer. In some embodiments, the porous partition is a mesh or a membrane. In some embodiments, the porous partition is a polymer mesh or a polymer membrane. In some embodiments, the porous partition comprises one or more layers of mesh, membrane, or other porous structure. In some embodiments, the porous partition comprises one or more coarse meshes that 2047634 of 163 provide structural support and one or more fine meshes and / or membranes that provide filtration. In some embodiments, the porous partition comprises a polyetheretherketone mesh, a polypropylene mesh, a polyethylene mesh, a polysulfone mesh, a polyester mesh, a polyamide mesh, a polytetrafluoroethylene mesh, an ethylene tetrafluoroethylene polymer mesh, a stainless steel mesh, a polymer-coated stainless steel mesh, a ceramic-coated stainless steel mesh, or a combination thereof, where the mesh is a coarse mesh, a fine mesh, or a combination thereof. In some embodiments, the porous partition made of a polymer comprises a mesh comprising one or more blends of two or more of: a polyetheretherketone, a polypropylene, a polyethylene, a polysulfone, a polyester, a polyamide, a polytetrafluoroethylene, or an ethylene tetrafluoroethylene polymer.In some embodiments, the porous partition comprises a polyether ether ketone membrane, a polypropylene membrane, a polyethylene membrane, a polysulfone membrane, a polyester membrane, a polyamide membrane, a polytetrafluoroethylene membrane, an ethylene tetrafluoroethylene polymer membrane, or combinations thereof.

[81] In one embodiment of the ion exchange system, wherein the system is a stirred tank system comprising a brine tank containing permeable compartments for the beads such as pallets, pans, permeable boxes, or other vessels that are loaded with ion exchange beads, and the brine is agitated through the tank in a batch process. In one embodiment of the stirred tank system, optionally the base is added directly to the tank so that the brine is added to the tank. 2047634 of 163 gradually or all at once as a solid or as an aqueous solution. In one embodiment of the stirred tank system, after completing a brine absorption step, the permeable bead containers are optionally transferred to another tank for acid elution. In one embodiment of the stirred tank system, the permeable bead compartments are located at the bottom of the stirred tank during the brine step and after completing the brine step, the brine is then removed, and the bottom of the stirred tank is filled with acid to elute the lithium in such a way that the permeable bead compartments are covered with an optimal volume of acid.

[82] In one embodiment of the stirred tank system, ion exchange beads are suspended using plastic structural supports in a tank with an internal mixing device. In one embodiment of the stirred tank system, a brine stream is withdrawn from the tank and passed through a column where hydrogen ions in the brine produced by ion exchange are neutralized using sacrificial bases in solution or added as a solid, or by an ion exchange resin. This pH corrected stream is sent back to the system where lithium can be further extracted. In one embodiment of the stirred tank system, the brine that has been passed through the bead compartment is sent back to the opposite end of the tank through a pipe that is optionally internal or external to the tank.In one embodiment of the stirred tank system, base is optionally added to the brine located inside the tank or in a base addition tank outside the tank. 2047634 of 163

[83] In one embodiment of the stirred tank system, fresh brine is fed to the system so as to operate in a continuous stirred tank reactor mode rather than in a batch mode. In one embodiment of the batch recirculation system, it is fed to the system so as to operate in a continuous stirred tank reactor mode rather than in a batch mode.

[84] In one embodiment of the ion exchange system, the ion exchange material is mixed with a liquid in a stirred tank reactor. In one embodiment, the ion exchange material may comprise coated particles, uncoated particles, porous beads, or combinations thereof.

[85] In one embodiment of the ion exchange system, a stirred tank reactor is used to fluidize the ion exchange material in a liquid to allow absorption of lithium from the liquid into the ion exchange material. In one embodiment, a stirred tank reactor is used to fluidize the ion exchange material in a wash fluid to remove residual brine, acid, or other contaminants from the ion exchange materials. In one embodiment, a stirred tank reactor is used to fluidize the ion exchange material in an acidic solution to elute lithium from the ion exchange material while replacing the lithium in the ion exchange material with protons. In one embodiment, a single stirred tank reactor is used to mix the ion exchange material with a liquid, a wash fluid, and the acidic solution.

[86] In some embodiments, the system for extracting ions from 2047634 of 163 lithium from a liquid, comprising a tank, wherein the tank further comprises: a) one or more compartments; b) an ion exchange material; c) a mixing device; and d) pH modulating equipment for changing the pH of the liquid present in the system, where the ion exchange material is used to extract lithium ions from the liquid, further comprises another tank, where the other tank further comprises: a) one or more compartments; b) an ion exchange material; c) a mixing device; and d) pH modulating equipment for changing the pH of the liquid present in the system. In some embodiments, the tank is in fluid communication with the other tank.

[87] In some embodiments, the system for extracting lithium ions from a liquid, comprising a tank, the system further comprising another tank, the other tank further comprising: a) one or more compartments; b) an ion exchange material; c) a mixing device; and d) an acid inlet for adding acid to the system. In a further embodiment, the ion exchange material travels between the tank and the other tank.

[88] In some embodiments, the system for extracting lithium ions from a liquid, comprising a tank, the tank further comprising: a) one or more compartments; b) an ion exchange material; c) a mixing device; and d) pH modulating equipment for changing the pH of the liquid present in the system, the ion exchange material being used to extract lithium ions from the liquid, further comprising a plurality of tanks, each tank further comprising: a) one or more compartments; b) an ion exchange material; c) a mixing device; 2047634 of 163 mixer; and d) a pH modulating device for changing the pH of the liquid present in the system. In some embodiments, each tank in the system is in fluid communication with each of the other tanks in the system.

[89] In some embodiments, the system further comprises another plurality of tanks, where each tank further comprises: a) one or more compartments; b) an ion exchange material; and c) a mixing device.

[90] In some embodiments, the system is configured to operate in a batch mode. In some embodiments, the system is configured to operate in a continuous mode. In some embodiments, the system is configured to operate in both a batch mode and a continuous mode. In some embodiments, one or more tanks of the system are configured to operate in a batch mode, and one or more tanks of the system are configured to operate in a continuous mode. In some embodiments, one or more tanks of the system are configured to operate in a batch mode, and one or more tanks of the system are configured to operate in a semi-continuous mode. In some embodiments, one or more tanks of the system are configured to operate in a semi-continuous mode, and one or more tanks of the system are configured to operate in a continuous mode.In some embodiments, one or more tanks of the system are configured to operate in a batch mode, one or more tanks of the system are configured to operate in a semi-continuous mode, and one or more tanks of the system are configured to operate in a continuous mode. In some embodiments. 2047634 of 163 embodiment, the system is configured to operate in a semi-continuous mode, a batch mode, a continuous mode, or combinations thereof.

[91] In one embodiment of the ion exchange system, a plurality of stirred tank reactors are used to mix the ion exchange material with a liquid, a wash fluid, and the acid solution. In one embodiment, the stirred tank reactors may have different sizes and may contain different volumes of a liquid, a wash fluid, and the acid solution. In one embodiment, the stirred tanks may be cylindrical, conical, rectangular, pyramidal, or a combination thereof. In one embodiment of the ion exchange system, the ion exchange material may travel through the plurality of stirred tank reactors in the direction opposite that of the liquid, the wash fluid, or the acid solution.

[92] In one embodiment of the ion exchange system, a plurality of stirred tank reactors may be used where one or more stirred tank reactors mix the ion exchange material with a liquid, one or more stirred tank reactors mix the ion exchange material with a wash fluid, and one or more stirred tank reactors mix the ion exchange material with an acid solution.

[93] In one embodiment of the ion exchange system, the stirred tank reactors may be operated in a continuous, semi-continuous, or batch mode where a liquid flows continuously, semi-continuously, or batchwise through the stirred tank reactor. In one embodiment of the ion exchange system, the stirred tank reactors may be operated in a continuous, semi-continuous, or batch mode where a liquid flows continuously, semi-continuously, or batchwise through the stirred tank reactor. 2047634 of 163 stirred tank reactors can be operated in a continuous, semi-continuous, or batch mode, where the ion exchange material flows continuously, semi-continuously, or in batches through the stirred tank reactor. In one embodiment of the ion exchange system, the stirred tank reactors can be operated in a mode in which the ion exchange material remains in the tank while the liquid, wash fluid, or acid solution is flowed through the tank in continuous, semi-continuous, or batch flows.

[94] In one embodiment, the ion exchange material may be loaded into or removed from the stirred tank reactors through the top, bottom, or side of the tank.

[95] In one embodiment of the ion exchange system, stirred tank reactors may comprise one or more compartments. In one embodiment, the compartments may contain ion exchange material in a bed that is fluidized, fixed, partially fluidized, partially fixed, alternately fluidized, alternately fluidized, or combinations thereof. In one embodiment, the compartments may comprise a porous support at the bottom of the compartment, on the sides of the compartment, at the top of the compartment, or combinations thereof. In one embodiment, the compartments may be conical, cylindrical, rectangular, pyramidal, or may have other shapes, or combinations thereof. In one embodiment, the compartment may be located at the bottom of the tank.In one embodiment, the shape of the compartment may conform to the shape of the stirred-tank reactor. In one embodiment, the. 2047634 of 163 compartment may be partially or completely composed of the stirred tank reactor tank.

[96] In one embodiment, the compartment may comprise a porous structure. In one embodiment, the compartment may comprise a polymer, a ceramic, a metal, or combinations thereof. In one embodiment, the compartment may be partially or completely comprised of a porous material or mesh. In one embodiment, the compartment may be at the top of the tank. In one embodiment, the compartment may be separated from the remainder of the tank by one or more porous materials. In one embodiment, the compartment may be at the top of the tank. In one embodiment, the compartment may be separated from the remainder of the tank by a bi-layer mesh comprising a coarse mesh layer for strength and a fine mesh layer to contain smaller particles in the compartment.In one embodiment, the compartment may allow liquid to flow freely through the stirred tank reactor and through the compartment. In one embodiment, the compartment may be open at the top. In one embodiment, the compartment may contain the ion exchange material in the tank but may allow the ion exchange material to move throughout the tank. In one embodiment, the compartment may comprise most or least of the volume of the tank. In one embodiment, the compartment may represent a fraction of the tank volume that is greater than 1 percent, greater than 10 percent, greater than 50 percent, greater than 90 percent. 2047634 of 163 greater than 99 percent, or greater than 99.9 percent. In one embodiment, one or more agitation, mixing, or pumping devices may be used to move the fluid through the compartment of the stirred-tank reactor, or combinations thereof.

[97] In one embodiment of the ion exchange system, the stirred tank reactors may be arranged in a network where flows of brine, wash fluid, and acid solutions are directed through different columns. In one embodiment, a network of stirred tank reactors may include physical movement of ion exchange material through the various stirred tank reactors. In one embodiment, a network of stirred tank reactors may not include physical movement of ion exchange material through the various stirred tank reactors. In one embodiment, a network of stirred tank reactors may include switching flows of brine, wash fluid, and acid solutions through the various stirred tank reactors. In one embodiment, the brine may be directed to the stirred tank reactors in a continuous or batch fashion.In one embodiment, the brine may be mixed with the ion exchange material in one or more reactors before exiting the system. In one embodiment, a stirred-tank reactor network may include a brine circuit with countercurrent exposure of the ion exchange material to brine flows. In one embodiment, a stirred-tank reactor network may include a wash circuit with countercurrent exposure of the ion exchange material to wash fluid flows. In one embodiment, a tank reactor network. 2047634 of 163 agitated may include an acid circuit with countercurrent exposure of the ion exchange material to the acid solution flows. In one embodiment, the wash fluid may be water, an aqueous solution, or a solution containing an antiscalant.

[98] In one embodiment of the stirred tank reactor, the acid is added at the beginning of the elution. In one embodiment of the stirred tank reactor, the acid is added at the beginning of the elution and again during the elution. In one embodiment of the stirred tank reactor, a lower concentration acid is added at the beginning of the elution and an additional amount of high concentration acid is added to continue the elution.

[99] One aspect described herein is a system for extracting lithium ions from a liquid, comprising: a) an ion exchange material; b) a tank comprising one or more compartments; and c) a mixing device, wherein the ion exchange material is used to extract lithium ions from the liquid.

[100] In some embodiments, the ion exchange material is loaded into at least one of the one or more compartments. In some embodiments, the ion exchange material is fluidized or partially fluidized in at least one of the one or more compartments. In some embodiments, the ion exchange material occupies a fixed position in at least one of the one or more compartments. In some embodiments, the ion exchange material is mounted in at least one of the one or more compartments.

[101] One aspect described here is a system for 2047634 of 163 extracting lithium ions from a liquid, comprising: a) a column comprising an ion exchange material; and b) pH modulating equipment for changing the pH of the liquid present in the system, where the pH modulating equipment is in fluid communication with the column, where the ion exchange material is used to extract lithium ions from the liquid. Other types of systems

[102] One aspect described herein is a system for extracting lithium ions from a liquid, comprising: a) a plurality of columns, each of the plurality of columns comprising an ion exchange material; and b) pH modulating equipment for changing the pH of the liquid present in the system, the pH modulating equipment being in fluid communication with each of the plurality of columns, the ion exchange material being used to extract lithium ions from the liquid.

[103] In some embodiments, the pH modulating equipment comprises a plurality of tanks, where each of the plurality of tanks is directly connected to one of the plurality of columns. In one embodiment, the pH modulating equipment comprises a plurality of tanks, where each of the plurality of tanks is in direct liquid communication with one of the plurality of columns. In some embodiments, two or more of the plurality of tanks are connected to two or more of the plurality of columns forming at least one circuit. In some embodiments, two or more of the plurality of tanks are 2047634 of 163 connected to two or more of the plurality of columns, forming at least two circuits. In some embodiments, three or more of the plurality of tanks connected to three or more of the plurality of columns form at least two circuits. In some embodiments, three or more of the plurality of tanks connected to three or more of the plurality of columns form at least three circuits.

[104] In some embodiments, at least one circuit is a liquid circuit. In some embodiments, at least one circuit is a water wash circuit. In some embodiments, at least two circuits are water wash circuits. In some embodiments, at least one circuit is an acid solution circuit.

[105] One aspect described herein is a system for extracting lithium ions from a liquid comprising an ion exchange material and a plurality of vessels, wherein each of the plurality of vessels is configured to transport the ion exchange material along a length of the vessel and the ion exchange material is used to extract lithium ions from the liquid. In some embodiments, at least one of the plurality of vessels comprises an acid solution. In some embodiments, at least one of the plurality of vessels comprises the liquid. In some embodiments, each of the plurality of vessels is configured to transport the ion exchange material via a piping system or an internal transport system.

[106] One aspect described herein is a system for extracting lithium ions from a liquid comprising an exchange material. 2047634 of 163 ionic and a plurality of columns, where each column of the plurality of columns is configured to transport the ion exchange material along the length of the column and the ion exchange material is used to extract lithium ions from the liquid.

[107] In some embodiments, at least one of the plurality of columns comprises an acid solution. In some embodiments, at least one of the plurality of columns comprises the liquid. In some embodiments, each of the plurality of columns is configured to transport the ion exchange material via a piping system or an internal transport system.

[108] In some embodiments, the ion exchange material comprises ion exchange particles. In some embodiments, at least a portion of the ion exchange material is in the form of ion exchange particles. In some embodiments, the ion exchange particles are selected from: uncoated ion exchange particles, coated ion exchange particles, and combinations thereof. In some embodiments, the ion exchange particles comprise uncoated ion exchange particles. In some embodiments, the ion exchange particles comprise coated ion exchange particles. In some embodiments, the ion exchange particles comprise a mixture of uncoated and coated ion exchange particles.

[109] In some embodiments, the coated ion exchange particles comprise an ion exchange material and a coating material. 2047634 of 163

[110] In some embodiments, the coating material of the coated ion exchange particles comprises a carbide, a nitride, an oxide, a phosphate, a fluoride, a polymer, carbon, a carbonaceous material, or combinations thereof. In some embodiments, the coating material of the coated ion exchange particles is selected from the group consisting of: TiO, ZrO, MoO, SnO, NbO, TaO, SiO, LiTiO, LiZrO, LiSiO, LiMnO, LiMoO, LiNbO, LiTaO, AlPO, LaPO, ZrPO, MoPO, MoPO, BaSO, AlFe, SiC, TiC, ZrC, SiN, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon, solid solutions thereof, and combinations thereof.

[111] In some embodiments, the ion exchange material of the coated ion exchange particles comprises an oxide, a phosphate, an oxyfluoride, a fluorophosphate, or combinations thereof. In some embodiments, the ion exchange material of the coated ion exchange particles is selected from the group consisting of: Li4Mn5O12, Li4Ti5Oi2, Li2TiO3, Li2MnO3, Li2SnO3, LiMn2O4, Li1,eMn1,eO4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7TiiiO24, U3VO4, Li2Si3O7, LiFePO4, LiMnPO4, Li2CuP2O7, Al(OH)3, LiCl.xAl(OH)3.yH2O, SnO2.xSb2O5.yH2O, TiO2.xSb2O5.yH2O, solid solutions thereof, and combinations thereof; where x is between 0.1-10; and y is between 0.1-10.

[112] In some embodiments, the uncoated ion exchange particles comprise an ion exchange material. In some embodiments, the ion exchange material of the 2047634 of 163 uncoated ion exchange particles comprises an oxide, a phosphate, an oxyfluoride, a fluorophosphate, or combinations thereof. In some embodiments, the ion exchange material of the uncoated ion exchange particles is selected from the group consisting of: Li4Mn5O12, Li4Ti5O12, Li2TiO3, Li2MnO3, Li2SnO3, LiMn2O4, Li1,eMn1,eO4, LiAlO2, LiCuO2, LiTiO2, Li4TiO4, Li7TiO24, Li3V04, Li2Si3O7, LiFePO4, LiMnPO4, Li2CuP2O7, Al(OH)3, LiCl.xAl(OH)3.yH2O, SnO2.xSb2O5.yH2O, TiO2.xSb2O5.yH2O, solid solutions thereof, and combinations thereof; where x is between 0.1-10; and y is between 0.1-10.

[113] In some embodiments, the ion exchange material is porous. In some embodiments, the porous ion exchange material comprises a network of pores that allows liquids to rapidly move from the surface of the porous ion exchange material toward a plurality of ion exchange particles. In some embodiments, the porous ion exchange material comprises a network of pores that allows a liquid to move from the surface of the porous ion exchange material toward a plurality of ion exchange particles. In some embodiments, the porous ion exchange material comprises a network of pores that allows a liquid to rapidly move from the surface of the porous ion exchange material toward a plurality of ion exchange particles.In some embodiments, the porous ion exchange material is porous ion exchange beads. In some embodiments, the porous ion exchange material comprises porous ion exchange beads.

[114] In some embodiments of the systems described 2047634 of 163 herein, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, waste brine from a bromine extraction process, an oil field brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or a combination of ores, a leachate from a mineral or a combination of minerals, a leachate from a clay or a combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof. In some embodiments of the systems described herein, the liquid is a brine.In some embodiments of the systems described herein, the liquid comprises a natural brine, a synthetic brine, or a mixture of a natural and a synthetic brine. In some embodiments of the systems described herein, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, waste brine from a bromine extraction process, an oilfield brine, a liquid from an ion exchange process, or combinations thereof.

[115] An aspect of the invention described herein consists of a system, wherein the column further comprises a plurality of injection ports, where the plurality of injection ports are used to increase the pH of the liquid present in the system. 2047634 of 163

[116] In an embodiment of the ion exchange system, where the system is a mixed base system comprising an ion exchange column and a mixing chamber where the base is mixed with the brine immediately prior to injecting the brine into the column.

[117] In one embodiment of the ion exchange system, the system is a ported ion exchange column system having multiple ports for injecting aqueous base spaced at intervals along the direction of brine flow through the column. As the brine flows through the column, there is a region of the column where the beads experience the highest rate of lithium uptake, and this region travels through the column in the direction of brine flow. In the ported ion exchange column system, base is injected near that region to neutralize the protons released by the ion exchange reaction. In regions of the columns where the beads have become saturated with lithium and the rate of proton release has slowed, base injection is reduced or terminated to prevent the formation of basic precipitates.

[118] In one embodiment of the ion exchange system, the system has a moving bed of beads traveling in a direction opposite to the flow of the brine and the base is injected at one or more fixed points in the column in a region close to where the ion exchange reaction occurs with a maximum rate to neutralize the protons released by the ion exchange reaction. In one embodiment of the ion exchange system, the base that is added to the brine is optionally NaOH, KOH, Mg(OH)2, Ca(OH)2, CaO, NH3, Na2SO4, K2SO4, NaHSO4, KHSO4, 2047634 of 163 NaOCl, KOCl, NaClO4, KCIO4, NaH2BO4, Na2HBO4, Na3BO4, KH2BO4, K2HBO4, K3BO4, MgHBO4, CaHBO4, NaHCO3, KHCO3, NaCO3, KCO3, MgCO3, CaCO3, Na2O, K2O, Na2CO3, K2CO3, Na3PO4, Na2HPO4, NaH2PO4, K3PO4, K2HPO4, KH2PO4, CaHPO4, MgHPO4, sodium acetate, potassium acetate, magnesium acetate, poly(vinylpyridine), poly(vinylamine), polyacrylonitrile, other bases, or combinations thereof. In one embodiment, the base is optionally added to the brine in its neat form or as an aqueous solution. In one embodiment, the base is optionally added in a gaseous state, such as gaseous NH3. In one embodiment, the base is optionally added to the brine in a constant stream, a variable stream, in constant aliquots, or in variable aliquots.In one embodiment, the base is optionally created in the brine using an electrochemical cell to remove gaseous H2 and Cl2, which are optionally combined in a separate system to create HCl acid for use in elution of lithium from the system or for other purposes.

[119] In some embodiments, a solid base is mixed with a liquid to create a basic solution. In some embodiments, a solid base is mixed with a liquid to create a basic solution, and the resulting basic solution is added to a second volume of a liquid to increase the pH of the second volume of the liquid. In some embodiments, the solid base is mixed with a liquid to create a basic solution, where the resulting basic solution is used to adjust or control the pH of a second solution. In some embodiments, a solid base is mixed with a liquid to create a basic slurry. In some embodiments, a 2047634 of 163 solid base with a liquid to create a basic slurry, and the resulting basic slurry is added to a second volume of a liquid to increase the pH of the second volume of the liquid. In some embodiments, the solid base is mixed with a liquid to create a basic slurry, where the resulting basic slurry is used to adjust or control the pH of a second solution. In some embodiments, the base may be added to a liquid as a mixture or slurry of base and liquid.

[120] In one embodiment of the ion exchange system, brine flows through a pH control column containing sacrificial base solid particles such as NaOH, CaO, or Ca(OH)2, which dissolve in the brine and raise the pH of the brine. In one embodiment of the ion exchange system, brine flows through a pH control column containing regenerable ion exchange resins containing immobilized OH groups that react with hydrogen ions, or regenerable basic species such as immobilized polypyridine, which conjugate with HCl, thereby neutralizing the acidified brine. When the ion exchange resin has become depleted of its OH groups or saturated with HCl, it is optionally regenerated with a base such as NaOH.

[121] In one embodiment of the ion exchange system, pH meters are optionally installed in the tanks, pipes, columns, and other components of the system to monitor pH and control base addition rates and amounts at various locations throughout the system. 2047634 of 163

[122] In one embodiment of the ion exchange system, the columns, tanks, pipes, and other components of the system are optionally constructed using plastic, metal with a plastic coating, or other materials that are resistant to corrosion caused by brine or acid.

[123] In one embodiment of the ion exchange system, the ion exchange columns are optionally washed with mildly acidic water, optionally including a pH buffer, to remove all basic precipitates from the column prior to acid elution.

[124] After saturating or near saturating the ion exchange column with lithium, the lithium is rinsed from the ion exchange column using acid. Optionally, the acid is flowed through the column one or more times to elute the lithium. In one embodiment, optionally, the acid is flowed through the ion exchange column using a batch recirculation system comprising connecting a tank to the ion exchange column. In one embodiment, the tank used for the acid flows is optionally the same tank used for the brine flows. In a further embodiment, the tank used for the acid flows is optionally a different tank than the one used for the brine flows.In a further embodiment, the acid is distributed over the top of the ion exchange column and is allowed to percolate through the column and is immediately recirculated thereto without the use of an additional tank. In one embodiment, the acid addition optionally occurs without the use of a tank for the acid flows. 2047634 of 163

[125] In one embodiment of the ion exchange system, the column is optionally washed with water after the brine and / or acid steps, and the wash water effluent is optionally treated using pH neutralization and reverse osmosis to obtain process water.

[126] In one embodiment of the ion exchange system, the ion exchange column optionally has a cylindrical, rectangular, or other shape. In one embodiment, the ion exchange column optionally has a cylindrical shape with a height greater or less than its diameter. In one embodiment, the ion exchange column optionally has a cylindrical shape with a height less than 10 cm, less than 1 meter, or less than 10 meters. In one embodiment, the ion exchange column optionally has a cylindrical shape with a diameter less than 10 cm, less than 1 meter, or less than 10 meters.

[127] In one embodiment of the ion exchange system, the system may optionally be resupplied with fresh ion exchange beads by exchanging one ion exchange column with a new column loaded with fresh ion exchange beads. In one embodiment of the ion exchange system, the system may optionally be resupplied with fresh ion exchange beads by removing the beads from the column and loading new beads onto the column. In one embodiment of the ion exchange system, new beads are optionally supplied to all columns in the system simultaneously. In one embodiment of the ion exchange system, new beads are optionally supplied to one or more 2047634 of 163 columns at a time. In one embodiment of the ion exchange system, fresh beads are optionally supplied to one or more columns without interrupting the operation of other columns, which optionally continue operating.

[128] In one embodiment of the ion exchange system, pumping brine optionally continues until the ion exchange beads approach a lithium saturation point for a period of time that is optionally less than about 1 hour, less than about 2 hours, less than about 4 hours, less than about 8 hours, less than about 24 hours, less than about 48 hours, or less than about one week. In one embodiment of the ion exchange system, pumping brine optionally continues until the ion exchange beads approach a lithium saturation point for a period of time that is optionally greater than about one week.In certain embodiments of the ion exchange system, pumping of brine optionally continues until the ion exchange beads approach a lithium saturation point for a period of time that is optionally between 30 minutes and 24 hours. In one embodiment of the ion exchange system, pumping of acid optionally continues until the ion exchange beads approach a hydrogen saturation point for a period of time that is optionally less than about 1 hour, less than about 2 hours, less than about 4 hours, less than about 8 hours, less than about 24 hours, or less. 2047634 of 163 approximately 48 hours. In one embodiment of the ion exchange system, pumping of brine optionally continues until the ion exchange beads approach a hydrogen saturation point for a period of time that is optionally greater than between about one and 48 hours. In certain embodiments of the ion exchange system, pumping of brine optionally continues until the ion exchange beads approach a hydrogen saturation point for a period of time that is optionally between 30 minutes and 24 hours. Ion exchange material

[129] One aspect of the invention described herein is a system wherein the ion exchange material comprises a plurality of ion exchange particles. In one embodiment, the plurality of ion exchange particles present in the ion exchange material are selected from uncoated ion exchange particles, coated ion exchange particles, and combinations thereof. In one embodiment, the ion exchange material is a porous ion exchange material. In one embodiment, the porous ion exchange material comprises a network of pores that allows liquids to rapidly move from the surface of the porous ion exchange material to the plurality of ion exchange particles. In one embodiment, the ion exchange material is in the form of porous ion exchange beads.In one embodiment, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine. 2047634 of 163 a processed brine, an oilfield brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or combination of ores, a leachate from a mineral or combination of minerals, a leachate from a clay or combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof.

[130] Ion exchange materials are typically small particles, which together constitute a fine powder. In some embodiments, a small particle size minimizes the diffusion distance that lithium must travel within the core of the ion exchange particles. In some containers, such particles are optionally coated with protective surface coatings to minimize dissolution of the ion exchange materials while allowing efficient transfer of lithium and hydrogen to and from the particles.

[131] In one embodiment, the coated ion exchange particles comprise an ion exchange material and a coating material wherein the ion exchange material comprises Li4Mn5O12, Li1,eMn1,eO4, Li2MO3 (M = Ti, Mn, Sn), LiFePO4, solid solutions thereof, or combinations thereof and the coating material comprises TiO2, ZrO2, MoO2, Li2TiO3, Li2ZrO3, LiNbO3, AlF3, SiC, Si3N4, graphitic carbon, amorphous carbon, diamond-like carbon, or combinations thereof. The coated ion exchange particles have an average diameter of less than about 100 nm, less than 2047634 of 163 about 1,000 nm, or less than about 10,000 nm, and the coating thickness is less than about 1 nm, less than about 10 nm, or less than about 100 nm. The particles are created by first synthesizing the ion exchange material by a method such as a hydrothermal, solid state, or microwave method. The coating material is then deposited onto the surface of the ion exchange material using a method such as chemical vapor deposition, a hydrothermal, solvothermal, sol-gel, precipitation, or microwave method. The coated ion exchange particles are treated with an acid solution prepared with hydrochloric acid, sulfuric acid, nitric acid, or combinations thereof where the concentration of the acid solution is greater than about 0.1 M, greater than about 1.0 M, greater than about 5 M, greater than about 10 M, or combinations thereof.During acid treatment, the particles absorb hydrogen while releasing lithium. The ion exchange material converts to a hydrated state with a hydrogen-rich composition. The coating material allows diffusion of hydrogen and lithium, respectively, into and out of the ion exchange material, while providing a protective barrier that limits dissolution of the ion exchange material. After acid treatment, the coated and hydrated ion exchange particles are treated with a liquid, where the liquid is a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a synthetic brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, or a leachate from minerals. 2047634 of 163 leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. The coated ion exchange particles absorb lithium while releasing hydrogen. The lithium salt solution is then collected. The coated ion exchange particles are then capable of repeatedly carrying out the ion exchange reaction for a number of cycles greater than about 10 cycles, greater than about 30 cycles, greater than about 100 cycles, or greater than about 300 cycles.

[132] A major challenge in lithium extraction using inorganic ion exchange particles is loading the particles into an ion exchange column in such a way that brine and acid can be pumped efficiently through the column with minimal clogging. Optionally, the materials are shaped into beads, and the beads are loaded into the column. This loading of the beads creates void spaces between the beads, and these void spaces facilitate pumping through the column. The beads hold the ion exchange particles in place and prevent the particles from moving freely through the entire column. When the materials are shaped into beads, the penetration of brine and acid solutions into the beads becomes slow and difficult.A slow rate of convection and diffusion of the acid and brine solutions into the bead demonstrates the kinetics of lithium absorption and release. Such slow kinetics can create problems for column operation. Slow kinetics may require the use of slow pumping rates. 2047634 of 163 of the column. Slow kinetics can also lead to low lithium recovery from the brine and inefficient use of acid to elute lithium.

[133] In some embodiments, the ion exchange beads are porous ion exchange beads with pore networks that facilitate transport into the beads of solutions being pumped through an ion exchange column. Optionally, the pore networks are strategically controlled to provide rapid and distributed access for penetration of brine and acid solutions into the bead interior and delivery of lithium and hydrogen to the ion exchange particles. An example of a porous ion exchange bead is shown in Figure 8.

[134] In some embodiments, ion exchange beads are formed by mixing ion exchange particles, a matrix material, and a filler material. These components are mixed and formed into beads. The filler material is then removed from the bead to leave pores. The filler material is dispersed within the bead to leave a pore structure that allows for rapid kinetic transport of lithium and hydrogen. This method optionally includes multiple ion exchange materials, multiple polymeric materials, and multiple filler materials.

[135] Another major challenge in lithium extraction using inorganic ion exchange materials is the dissolution and degradation of the materials, especially during the elution of lithium in acid but also during the absorption of lithium present in liquids. To obtain a concentrated lithium solution by the ion exchange process, it is desirable to use a concentrated acid solution to elute the lithium. However, concentrated acid solutions dissolve and degrade the materials. 2047634 of 163 inorganic ion exchange beads, which reduces the performance and lifetime of the materials. Therefore, porous ion exchange beads optionally contain coated lithium extraction ion exchange particles comprising an ion exchange material and a coating material that protects the particle surface. The coating protects the ion exchange material from dissolution and degradation during the elution of lithium in acid, during the absorption of lithium from a liquid, and during other aspects of an ion exchange process. These coated particles allow the use of concentrated acids in the ion exchange process to give concentrated lithium solutions. An example of a coated ion exchange particle is shown in Figure 7.

[136] In the present invention, the ion exchange material is selected to have a high lithium absorption capacity, high selectivity for lithium in a liquid relative to other ions such as sodium and magnesium, strong absorption of lithium present in liquids including those with low lithium concentrations, easy elution of lithium with a small excess of acid, and rapid ionic diffusion. Optionally, a coating material is selected to protect the particle from dissolution and chemical degradation during the recovery of lithium in acid and also during the absorption of lithium present in various liquids. Optionally, a coating material is also selected to facilitate diffusion of lithium and hydrogen between the particles and the liquids, to allow adhesion of the particles to a structural support, and to suppress structural and mechanical degradation of the particles.

[137] When porous ion exchange beads are used in a 2047634 of 163 ion exchange column, the lithium-containing liquid is pumped through the ion exchange column such that the ion exchange particles absorb the lithium from the liquid while releasing hydrogen. After the beads have absorbed the lithium, an acid solution is pumped through the column such that the particles release the lithium into the acid solution while absorbing hydrogen. Optionally, the column is operated in a co-flow mode by alternating between the liquid and the acid solution flowing through the column in the same direction, or optionally, the column is operated in a counterflow mode by alternating between the liquid and the acid solution flowing through the column in opposite directions.Between the liquid and acid solution flows, the column is optionally treated or washed with water or other solutions for purposes such as adjusting the pH in the column or removing potential contaminants. Optionally, the beads form a fixed or moving bed, and the moving bed optionally moves countercurrent to the brine and acid flows. Optionally, the beads are carried between multiple moving bed columns where different columns are used for the brine, acid, water, or other flows. Before or after the liquid flows through the column, the pH of the liquid is optionally adjusted with NaOH or other chemicals to facilitate the ion exchange reaction as well as the handling or disposal of the spent liquid.Before or after the liquid has flowed through the column, the liquid optionally undergoes other processes including other ion exchange processes, solvent extraction, evaporation, chemical treatment, or precipitation to remove lithium, to remove other chemical species, or. 2047634 of 163 to treat the brine in another way.

[138] When ion exchange particles are treated with acid, a lithium solution is produced. This lithium solution is optionally further processed to produce lithium chemicals. Such lithium chemicals are optionally used as feedstock for an industrial application. In some embodiments, the ion exchange material is selected from the following list: an oxide, a phosphate, an oxyfluoride, a fluorophosphate, or combinations thereof. In some embodiments, the ion exchange material is selected from the following list: LiFePO4, LiMnPO4, U2MO3 (M = Ti, Mn, Sn), Li4Ti5Oi2, Li4Mn5O12, LiMn2O4, Li1,eMn1,eO4, LiMO2 (M = Al, Cu, Ti), Li4TiO4, Li7TiO24, U3VO4, Li2Si3O7, Li2CuP2O7, Al(OH)3, LiCl.xAl(OH)3.yH2O, SnO2.xSb2O5.yH2O, TiO2.xSb2O5.yH2O, solid solutions thereof, or combinations thereof. In a further aspect, the ion exchange material comprises LiFePO4, Li2SnO3, Li2MnO3, Li2TiO3, Li4Ti5O12, Li4Mn5O12, Li1.6Mn1.6O4, solid solutions thereof, or combinations thereof.

[139] In a further aspect described herein, the coating material permits diffusion to and from the ion exchange material. In particular, the coating material facilitates diffusion of lithium and hydrogen between the particles and liquids, permits adhesion of the particles to a structural support, and suppresses structural and mechanical degradation of the particles. In a further aspect described herein, the coating material comprises a carbide, a nitride, an oxide, a phosphate, a fluoride, a polymer, carbon, a carbonaceous material, or combinations thereof. In a further aspect, the coating material 2047634 of 163 coating comprises polyvinylidene difluoride, polyvinyl chloride, a fluorinated polymer, a chlorinated polymer, or a fluoro-chlorinated polymer. In a further aspect, a coating material comprises NbO, TaO, MoO, TiO, ZrO, SnO, SiO, LiO, LiTiO, LiZrO, LiMoO, LiNbO, LiTaO, LiSiO, LiSiO, LiMnO, ZrSiO, AlPO, LaPO, ZrPO, MoPO, MoPO, BaSO, AlF, SiC, TiC, ZrC, SiN, ZrN, BN, carbon, graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon, solid solutions thereof, or combinations thereof. In a further aspect, a coating material comprises TiO2, ZrO2, SiO2, Li2TiO3, Li2ZrO3, Li2MnO3, ZrSiO4, or LiNbO3. In a further aspect, a coating material comprises a chlorinated polymer, a fluorinated polymer, a chlorinated fluorinated polymer, a hydrophilic polymer, a hydrophobic polymer, copolymers thereof, mixtures thereof, or combinations thereof.In a further aspect, a coating material comprises a copolymer, a block copolymer, a linear polymer, a branched polymer, a crosslinked polymer, a heat-treated polymer, a solution-processed polymer, copolymers thereof, blends thereof, or combinations thereof. In a further aspect, a coating material comprises low density polyethylene, high density polyethylene, polypropylene, polyester, polytetrafluoroethylene (PTFE), certain types of polyamide, polyetheretherketone (PEEK), polysulfone, polyvinylidene fluoride (PVDF), poly(4-vinylpyridine-co-styrene) (PVPCS), polystyrene (PS), polybutadiene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC), ethylene tetrafluoroethylene polymer (ETFE), poly(chlorotrifluoroethylene) (PCTFE), ethylene chlorotrifluoroethylene (Halar), polyvinyl fluoride (PVF), ethylene-propylene. 2047634 of 163 fluorinated (FEP), perfluorinated elastomer, chlorotrifluoroethylenevinylidene fluoride (FKM), perfluoropolyether (PFPE), perfluoro3,6-dioxa-4-methyl-7-octenesulfonic acid (NAFION® (copolymer of perfluoro3,6-dioxa-4-methyl-7-octenesulfonic acid and tetrafluoroethylene)), polyethylene oxide, polyethylene glycol, sodium polyacrylate, polyethylene-block-poly(ethylene glycol), polyacrylonitrile (PAN), polychloroprene (neoprene), polyvinyl butyral (PVB), expanded polystyrene (EPS), polydivinylbenzene, copolymers thereof, mixtures thereof, or combinations thereof.In a further aspect, a coating material comprises polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), ethylene chlorotrifluoroethylene (Halar), poly(4-vinyl pyridine-co-styrene) (PVPCS), polystyrene (PS), acrylonitrile butadiene styrene (ABS), expanded polystyrene (EPS), polyphenylene sulfide, sulfonated polymer, carboxylated polymer, other polymers, copolymers thereof, mixtures thereof, or combinations thereof. In a further aspect, a coating is deposited on an ion exchange particle by dry mixing, solvent mixing, emulsification, extrusion, bubbling one solvent into another, casting, heating, evaporation, vacuum evaporation, spray drying, vapor deposition, chemical vapor deposition, microwave treatment, hydrothermal synthesis, polymerization, co-polymerization, crosslinking, irradiation, catalysis, foaming, other deposition methods, or combinations thereof.In a further aspect, a coating is deposited using a solvent comprising N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, ethanol, acetone, other solvents, or combinations thereof. In a further aspect, a coating is deposited using a solvent comprising N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, ethanol, acetone, other solvents, or combinations thereof. 2047634 of 163 coating using a solvent comprising N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, ethanol, acetone, or combinations thereof.

[140] In a further aspect described herein, the coated ion exchange particles have an average diameter of less than about 10 nm, less than about 100 nm, less than about 1,000 nm, less than about 10,000 nm, or less than about 100,000 nm. In a further aspect, the coated ion exchange particles have an average size of less than about 100 nm, less than about 1,000 nm, or less than about 10,000 nm. In a further aspect, the coated ion exchange particles are optionally secondary particles comprising smaller sized primary particles having an average diameter of less than about 10 nm, less than about 100 nm, less than about 1,000 nm, less than about 10,000 nm, or less than about 100,000 nm. In a further aspect, the coating optionally overlies the primary ion exchange particles.In a further aspect, the coating optionally coats the secondary ion exchange particles. In a further aspect, the coating optionally coats the secondary ion exchange particles. In a further aspect, the coating optionally coats both the primary ion exchange particles and the secondary ion exchange particles. In a further aspect, the primary ion exchange particles optionally have a first coating and the secondary ion exchange particles optionally have a second coating. 2047634 of 163 have a second coating that optionally has an identical, similar, or different composition to that of the first coating.

[141] In some embodiments described herein, the coating material has a thickness of less than about 1 nm, less than about 10 nm, less than about 100 nm, less than about 1,000 nm, or less than about 10,000 nm. In still other embodiments, the coating material has a thickness of less than about 5 nm, less than about 50 nm, or less than about 500 nm. In some embodiments, the ion exchange particles have a coating material with a thickness selected from the following list: less than 1 nm, less than 10 nm, less than 100 nm, or less than 1,000 nm. In some embodiments, the coating material has a thickness selected from the following list: less than 1 nm, less than 10 nm, or less than 100 nm.In certain embodiments, the coating material has a thickness between about 0.5 nm and about 1000 nm. In some embodiments, the coating material has a thickness between about 1 nm and about 100 nm.

[142] In a further aspect described herein, the ion exchange material and the coating material form one or more concentration gradients where the chemical composition of the particle lies within the range between two or more components. In a further aspect, the chemical composition optionally varies between the ion exchange materials and the coating in a manner that is continuous, discontinuous, or 2047634 of 163 continuous and discontinuous in different regions of the particle. In a further aspect, the ion exchange materials and the coating materials form a concentration gradient extending over: a thickness of less than about 1 nm, less than about 10 nm, less than about 100 nm, less than about 1,000 nm, less than about 10,000 nm, or less than about 100,000 nm. In a further aspect, the ion exchange materials and the coating materials form a concentration gradient extending over: a thickness of between about 1 nm and about 1,000 nm.

[143] In a further aspect described herein, the ion exchange material is synthesized by a method such as a hydrothermal, solvothermal, sol-gel, solid state, molten salt flow, ion exchange, microwave, ball mill grinding, chemical precipitation, coprecipitation, vapor deposition, or combinations thereof. In a further aspect, the ion exchange material is synthesized by a method such as a chemical precipitation, hydrothermal, solid state, or combinations thereof.

[144] In a further aspect described herein, the coating material is deposited by a method such as chemical vapor deposition, atomic layer deposition, physical vapor deposition, hydrothermal, solvothermal, sol-gel, solid state, molten salt flow, ion exchange, microwave, chemical precipitation, coprecipitation, ball mill grinding, pyrolysis, or combinations thereof. In a further aspect, the coating material is deposited by a method such as sol-gel, chemical precipitation, or combinations thereof. In one aspect 2047634 of 163 additional, the coating materials are deposited in a reactor that is optionally a batch tank reactor, a continuous tank reactor, a batch furnace, a continuous furnace, a tube furnace, a rotary tube furnace, or combinations thereof.

[145] In some embodiments, a coating material is deposited with physical characteristics that can be selected from the following list: it can be crystalline, amorphous, have a complete coating, a partial coating, uniform, non-uniform, or combinations thereof.

[146] In some embodiments, multiple coatings are optionally deposited on the ion exchange material in an arrangement that can be selected from the following list: concentric, patchy, or combinations thereof.

[147] In some embodiments, the matrix is ​​selected from the following list: a polymer, an oxide, a phosphate, or combinations thereof. In some embodiments, the structural support is selected from the following list: polyvinyl fluoride, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonated polytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, sulfonated polymer, carboxylated polymer, Nafion, copolymers thereof, and combinations thereof. In some embodiments, the structural support is selected from the following list: polyvinylidene difluoride, polyvinyl chloride, sulfonated polytetrofluoroethylene, polystyrene, polydivinylbenzene, copolymers thereof, or combinations thereof. In some 2047634 of 163 embodiments, the structural support is selected from the following list: titanium dioxide, zirconium dioxide, silicon dioxide, solid solutions thereof, or combinations thereof. In some embodiments, the matrix material is selected to have heat resistance, acid resistance, and / or other chemical resistance.

[148] In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and the filler material together at once. In some embodiments, the porous beads are formed by first mixing the ion exchange particles and the matrix material, and then mixing with the filler material. In some embodiments, the porous beads are formed by first mixing the ion exchange particles and the filler material, and then mixing with the matrix material. In some embodiments, the porous beads are formed by first mixing the matrix material and the filler material, and then mixing with the ion exchange particles.

[149] In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material with a solvent that dissolves one or more of the components. In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material as dry powders in a mixer or ball mill. In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material in a spray dryer.

[150] In some embodiments, the matrix material is a 2047634 of 163 polymer that is dissolved in and mixed with the ion exchange particles and / or the filler material using a solvent from the following list: N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, or combinations thereof. In some embodiments, the filler material is a salt that is dissolved in and mixed with the ion exchange particles and / or the matrix material using a solvent from the following list: water, ethanol, isopropyl alcohol, acetone, or combinations thereof.

[151] In some embodiments, the filler material is a salt that dissolves out of the bead and forms pores by using a solution that may be selected from the following list: water, ethanol, isopropyl alcohol, a surfactant mixture, an acid or a base, or combinations thereof. In some embodiments, the filler material is a material that thermally decomposes to form a gas at a high temperature such that the gas can exit the bead forming pores, where the gas is selected from the following list: water vapor, oxygen, nitrogen, chlorine, carbon dioxide, nitrogen oxides, organic vapors, or combinations thereof.

[152] In some embodiments, the porous ion exchange beads are formed from a dry powder using a mechanical press, a pellet press, a tablet press, a pill press, a rotary press, or combinations thereof. In some embodiments, the porous ion exchange beads are formed from a solvent slurry by dripping the slurry into a different liquid solution. The solvent slurry is optionally formed using a 2047634 of 163 solvent of N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, or combinations thereof. The different liquid solution is optionally formed using water, ethanol, isopropyl alcohol, acetone, or combinations thereof.

[153] In some embodiments, the porous ion exchange bead is approximately spherical, with an average diameter that may be selected from the following list: less than 10 um, less than 100 um, less than 1 mm, less than 1 cm, or less than 10 cm. In some embodiments, the porous ion exchange bead is approximately spherical, with an average diameter that may be selected from the following list: less than 200 um, less than 2 mm, or less than 20 mm. In certain embodiments, the porous ion exchange bead is approximately spherical, with an average diameter between 10 um and 2 mm.

[154] In some embodiments, the porous ion exchange bead is pellet-shaped with a diameter of less than 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, or less than 20 mm and with a height of less than 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, or less than 20 mm. In certain embodiments, the porous ion exchange bead is pellet-shaped with a diameter between 500 um and 10 mm.

[155] In some embodiments, the porous ion exchange bead is included in a support structure, which is optionally a membrane, a spiral wound membrane, a hollow fiber membrane, or a mesh. In some embodiments, the porous ion exchange bead is included in a support structure comprising a polymer, a ceramic, or combinations thereof. In some embodiments, 2047634 of 163 embodiment, the porous ion exchange beads are loaded directly onto an ion exchange column without an additional support structure.

[156] In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a geothermal brine, seawater, concentrated seawater, desalination effluent, a concentrated brine, a processed brine, liquid from an ion exchange process, liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof.In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a synthetic brine, a geothermal brine, liquid from an ion exchange process, liquid from a solvent extraction process, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. In some embodiments, the liquid is optionally pretreated prior to entering the ion exchange reactor to remove suspended solids, hydrocarbons, or organic molecules. In some embodiments, the liquid optionally enters the ion exchange reactor without any pretreatment from its source.

[157] In some embodiments, a liquid is selected with a lithium concentration that can be selected from the following list: less than 100,000 ppm, less than 10,000 ppm, less than 1,000 ppm, less than 100 2047634 of 163 ppm, less than 10 ppm, or combinations thereof. In some embodiments, a liquid with a lithium concentration that can be selected from the following list is selected: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, or combinations thereof. Device for extracting lithium from a liquid

[158] One aspect described herein is a device for extracting lithium from a liquid comprising one or more vessels independently configured to simultaneously accommodate porous ion exchange beads moving in one direction and alternately acid solutions, brine, and optionally other solutions moving in the net opposite direction.

[159] In one aspect described herein, there is a device for extracting lithium from a liquid comprising a stirred tank reactor, an ion exchange material, and pH modulating equipment for increasing the pH of the liquid in the stirred tank reactor.

[160] One aspect disclosed herein is a device for extracting lithium from a liquid comprising a stirred tank reactor, an ion exchange material, pH modulating equipment for increasing the pH of the liquid in the stirred tank reactor, and a compartment for containing the ion exchange material in the stirred tank reactor while allowing for removal of liquid, wash fluid, and acid solutions from the stirred tank reactor.

[161] In one embodiment, at least one of the one or more containers is equipped with a transport system appropriately equipped to move the porous ion exchange beads in 2047634 of 163 upward direction and simultaneously allow a net downward flow of acidic solutions, brine, and optionally others. In one embodiment, the conveyor system comprises fins with perforations. In one embodiment, where the fins slide in an upward direction on a sliding surface that is held fixed in place. In one embodiment, the fins slide in an upward direction on a sliding surface that is held fixed in place. In one embodiment, all of the one or more vessels are equipped with a conveyor system appropriately equipped to move the porous ion exchange beads in an upward direction and simultaneously allow a net downward flow of acidic solutions, brine, and optionally others. In one embodiment, there are an even number of vessels. In one embodiment, there are an odd number of vessels.In one embodiment, the containers are columns.

[162] In some embodiments, structures with perforations are used to move ion exchange material through one or more vessels. In some embodiments, the perforations in the structures may be less than 10 microns, less than 100 microns, less than 1,000 microns, or less than 10,000 microns. In some embodiments, the structures may be attached to a transport system. In some embodiments, the structures may comprise a porous compartment, a porous septum, or other porous structure. In some embodiments, the structures may contain a fixed or fluidized bed of ion exchange material. In some embodiments, the structures may contain ion exchange material while 2047634 of 163 allow brine, aqueous solution, or acid solution to pass through the structures.

[163] In one embodiment, the porous ion exchange beads comprise ion exchange particles that reversibly exchange lithium and hydrogen and a material acting as a structural matrix and having a network of pores. In one embodiment, the liquid comprises a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a filtered brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, ore leachate, mineral leachate, clay leachate, recycled product leachate, recycled material leachate, or combinations thereof. Methods for modulating pH for lithium extraction

[164] An aspect of the invention described herein is a method for extracting lithium ions from a liquid, comprising: flowing the liquid through the column of the system described above to produce a lithiated ion exchange material; and treating the resulting lithiated ion exchange material with an acid solution to produce a salt solution comprising lithium ions.

[165] An aspect of the invention described herein is a method for extracting lithium ions from a liquid, comprising: flowing the liquid through the plurality of columns of the system described above to produce a lithiated ion exchange material; and treating the resulting lithiated ion exchange material with an acid solution. 2047634 of 163 to produce a salt solution comprising lithium ions.

[166] One aspect of the invention described herein is a method for extracting lithium ions from a liquid, comprising: flowing the liquid through the tank of the system described above to produce a lithiated ion exchange material; and treating the resulting lithiated ion exchange material with an acid solution to produce a salt solution comprising lithium ions.

[167] An aspect of the invention described herein is a method for extracting lithium ions from a liquid, comprising: flowing the liquid through the column of the system described above to produce a lithiated ion exchange material; and treating the resulting lithiated ion exchange material with an acid solution to produce a salt solution comprising lithium ions.

[168] In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a geothermal brine, seawater, concentrated seawater, desalination effluent, a concentrated brine, a processed brine, liquid from an ion exchange process, liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a synthetic brine, a geothermal brine, liquid from an ion exchange process, liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. 2047634 of 163 ion exchange, liquid from a solvent extraction process, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. In some embodiments, the liquid is optionally pretreated before entering the ion exchange reactor to remove suspended solids, hydrocarbons, or organic molecules. In some embodiments, the liquid is optionally entered into the ion exchange reactor without any pretreatment from its source.

[169] In one embodiment, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, an oil field brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or a combination of ores, a leachate from a mineral or a combination of minerals, a leachate from a clay or a combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof.

[170] In some embodiments, a liquid is selected having a lithium concentration that may be selected from the following list: less than 100,000 ppm, less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than 10 ppm, or combinations thereof. In some embodiments, a liquid is selected having a lithium concentration that may be selected from the following list: less than 5,000 ppm, less than 500 ppm, or combinations thereof. 2047634 of 163 ppm, less than 50 ppm, or combinations thereof.

[171] In some embodiments, the acid used to recover lithium from the ion exchange reactor is selected from the following list: hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof. In some embodiments, the acid used to recover lithium from the porous ion exchange beads is selected from the following list: hydrochloric acid, sulfuric acid, nitric acid, or combinations thereof.

[172] In one embodiment, the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof.

[173] In some embodiments, the acid used to recover lithium from the ion exchange system has a concentration that can be selected from the following list: less than 0.1 M, less than 1.0 M, less than 5 M, less than 10 M, or combinations thereof. In some embodiments, the acid used to recover lithium from the porous ion exchange beads has a concentration greater than 10 M.

[174] In one embodiment, acids with different concentrations are used during the elution process. In one embodiment, acid with a lower concentration is added first to elute lithium from the ion exchange material and then an additional amount of acid of a higher concentration is added to elute more lithium into the solution and increase the lithium concentration in the eluate. 2047634 of 163

[175] In some embodiments, the ion exchange beads perform the ion exchange reaction repeatedly while maintaining a suitable lithium uptake capacity for a number of cycles that may be selected from the following list: greater than 10 cycles, greater than 30 cycles, greater than 100 cycles, greater than 300 cycles, or greater than 1,000 cycles. In some embodiments, the porous ion exchange beads perform the ion exchange reaction repeatedly for a number of cycles that may be selected from the following list: greater than 50 cycles, greater than 100 cycles, or greater than 200 cycles. In some embodiments, a suitable lithium uptake capacity is optionally defined as a percentage of the initial uptake capacity that may be selected from the following list: greater than 95%, greater than 90%, greater than 80%, greater than 60%, or greater than 20%.In some embodiments, a suitable lithium absorption capacity is optionally defined as a percentage of the initial absorption capacity such as less than 20%.

[176] In some embodiments, the concentrated lithium solution obtained from the ion exchange reactor is further processed to obtain lithium feedstocks using methods that may be selected from the following list: solvent extraction, ion exchange, chemical precipitation, electrodialysis, electrowinning, electrolysis, evaporation with direct solar energy, evaporation with concentrated solar energy, evaporation with a heat transfer medium heated with concentrated solar energy, evaporation with heat from a geothermal brine, heat from combustion, pH neutralization, or combinations thereof. In some embodiments, the solution 2047634 of 163 lithium concentrate obtained from the ion exchange reactor is concentrated using reverse osmosis or membrane technologies.

[177] In some embodiments, the concentrated lithium solution obtained from the ion exchange reactor is further processed to obtain lithium chemicals that may be selected from the following list: lithium chloride, lithium carbonate, lithium hydroxide, lithium metal, lithium metal oxide, lithium metal phosphate, lithium sulfide, or combinations thereof. In some embodiments, the concentrated lithium solution obtained from the porous ion exchange beads is further processed to obtain lithium chemicals that are solid, liquid, hydrated, or anhydrous.

[178] In some embodiments, the lithium chemicals produced using the ion exchange reactor are used in an industrial application that may be selected from the following list: lithium batteries, metal alloys, glasses, greases, or combinations thereof. In some embodiments, the lithium chemicals produced using the coated ion exchange particles are used in an application that may be selected from the following list: lithium batteries, lithium-ion batteries, lithium sulfide batteries, solid-state lithium batteries, and combinations thereof.

[179] In some embodiments, the ion exchange materials are synthesized in a lithiated state with a crystalline sublayer occupied entirely or partially by lithium. In some embodiments, the ion exchange materials are synthesized in a hydrated state with a crystalline sublayer occupied entirely or partially by hydrogen. 2047634 of 163

[180] In some embodiments, the ion exchange material extracts lithium ions from a liquid. During the extraction of lithium ions from a liquid by the ion exchange material, the pH of the liquid is optionally decreased. Increasing the pH of the liquid present in the system through the use of pH modulating equipment maintains the pH within a range that is appropriate for uptake of the lithium ions by the ion exchange material. In one embodiment, the pH modulating scheme comprises measuring the pH of the system and adjusting the pH of the system to bring it into and maintain it within a pH range ideal for lithium extraction. In one embodiment, for the ion exchange material to uptake lithium from brine, an ideal pH range for the brine is optionally between 6 and 9, a preferred pH range is optionally between 4 and 9, and an acceptable pH range is optionally between 2 and 9.In one embodiment, the pH modulation scheme comprises measuring the pH of the system and the pH of the system being less than 6, less than 4, or less than 2, the pH of the system being brought and maintained at a pH between 2 and 9, a pH between 4 and 9, or a pH between 6 and 9.

[181] Another aspect described herein consists of a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a system comprising a tank to produce a lithiated ion exchange material, where the tank further comprises (i) one or more compartments, (ii) an ion exchange material, (iii) a mixing device, and (iv) a pH modulating equipment to change the pH of the liquid present in the system; and b) treating the lithiated ion exchange material obtained in a) with an acid solution to produce a lithiated ion exchange material. 2047634 of 163 hydrogen-rich ion exchange and a salt solution comprising lithium ions.

[182] In some embodiments, the method further comprises, before b), washing the lithiated ion exchange material with an aqueous solution. In some embodiments, the method further comprises, after b), washing the hydrogen-rich ion exchange material with an aqueous solution. In some embodiments, the aqueous solution is water.

[183] ​​In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a washing system. In some embodiments, the method also comprises, before b), transferring a slurry comprising the lithiated ion exchange material. In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a washing system and washing the lithiated ion exchange material with a solution. In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a washing system and washing the lithiated ion exchange material with a solution comprising water.In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a washing system and washing the lithiated ion exchange material with an aqueous solution. In some embodiments, the lithiated ion exchange material is washed with an aqueous solution.

[184] In some embodiments, the method further comprises, before b), flowing the lithiated ion exchange material through a system 2047634 of 163 separation. In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a separation system and separating the lithiated ion exchange material. In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a separation system and separating volatile components from the lithiated ion exchange material. In some embodiments, the method also comprises, before b), flowing the lithiated ion exchange material through a separation system and separating volatile components comprising water from the lithiated ion exchange material.

[185] In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base to the tank. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is a pipe. In some embodiments, the inlet is an injection port.

[186] In some embodiments, the method further comprises, during a), measuring a change in the pH of the liquid using the pH modulating apparatus. In some embodiments, the measured pH change triggers the addition of a base to maintain lithium uptake. In some embodiments, a change in pH to below a pH value of between about 2 and about 9 triggers the addition of a base to maintain lithium uptake. In some embodiments, a change in pH to below a pH value of about 2, about 3, about 4, about 5, about 6, about 7, about 8, or 2047634 of 163 about 9 triggers the addition of a base to maintain lithium uptake. In some embodiments, a change in pH to a pH value below between about 2 and about 4, between about 3 and about 5, between about 4 and about 6, between about 5 and about 7, between about 6 and about 8, or between about 7 and about 9 triggers the addition of a base to maintain lithium uptake. In some embodiments, base is added to the liquid to maintain the pH of the liquid within a range of about 2-3, 3-4, 4-5, 5-6, 6-7, 7-8, or 8-9. In some embodiments, base is added to the liquid to maintain the pH of the liquid within a range of about 4-5, 5-6, 6-7, or 7-8.In some embodiments, base is added to the liquid to maintain the pH of the liquid within a range of about 4.0-4.5, 4.5-5.0, 5.0-5.5, 5.5-6.0, 6.0-6.5, 6.5-7.0, 7.0-7.5, or 7.5-8.0. In some embodiments, the pH of a liquid is maintained within a target range high enough to facilitate lithium uptake and low enough to prevent precipitation of metal salts from the liquid. In some embodiments, the pH of the liquid is maintained below a pH of about 8 to prevent precipitation of Mg salts.In some embodiments, the pH of the liquid is maintained below a pH of about 2, below a pH of about 3, below a pH of about 4, below a pH of about 5, below a pH of about 6, below a pH of about 7, below a pH of about 8, or below a pH of about 9 to prevent precipitation of. 2047634 of 163 metal salts. In some embodiments, the pH of the liquid may drop outside a target pH range due to the release of protons from the ion exchange material, and a pH modulating device may adjust the pH of the liquid to return it to the target pH range. In some embodiments, the pH of the liquid may be adjusted to a value above a target pH range prior to the liquid entering the system, and then protons released by the ion exchange material may reduce the pH of the system to within the target range. In some embodiments, the pH of the liquid may be controlled to maintain it within a certain range, and the range may be changed over time. In some embodiments, the pH of the liquid may be controlled to maintain it within a certain range, and then the pH of the liquid may be dropped.In some embodiments, the pH of the liquid can be controlled to maintain it within a certain range, and then the pH of the liquid can be dropped to solubilize colloids or solids. In some embodiments, base can be added to a liquid to neutralize protons without measuring the pH. In some embodiments, base can be added to a liquid to neutralize protons with monitoring of the volumes or amounts of base. In some embodiments, the pH of the liquid can be measured to monitor lithium uptake by the ion exchange material. In some embodiments, the pH of the liquid can be monitored to determine when to separate a liquid from an ion exchange material. In some embodiments, the rate of change of the pH of the liquid can be measured to monitor the rate of lithium uptake.In some embodiments, the rate of change in the pH of the liquid can be measured to determine when it is. 2047634 of 163 must separate a liquid from an ion exchange material.

[187] In some embodiments, the tank further comprises a porous partition. In some embodiments, the porous partition is a porous partition made of a polymer. In some embodiments, the porous partition is a mesh or a membrane. In some embodiments, the porous partition is a polymer mesh or a polymer membrane. In some embodiments, the porous partition comprises one or more layers of mesh, membrane, or other porous structure. In some embodiments, the porous partition comprises one or more coarse meshes that provide structural support and one or more fine meshes and / or membranes that provide filtration.In some embodiments, the porous partition comprises a polyetheretherketone mesh, a polypropylene mesh, a polyethylene mesh, a polysulfone mesh, a polyester mesh, a polyamide mesh, a polytetrafluoroethylene mesh, an ethylene tetrafluoroethylene polymer mesh, a stainless steel mesh, a polymer coated stainless steel mesh, a ceramic coated stainless steel mesh, or a combination thereof, where the mesh is a coarse mesh, a fine mesh, or a combination thereof. In some embodiments, the porous partition made of a polymer comprises a mesh comprising one or more blends of two or more of: a polyetheretherketone, a polypropylene, a polyethylene, a polysulfone, a polyester, a polyamide, a polytetrafluoroethylene, or an ethylene tetrafluoroethylene polymer.In some embodiments, the porous partition comprises a polyether ether ketone membrane, a polypropylene membrane, a polyethylene membrane, a polysulfone membrane, a polyester membrane, a membrane of. 2047634 of 163 polyamide, a polytetrafluoroethylene membrane, an ethylene tetrafluoroethylene polymer membrane, or combinations thereof.

[188] In some embodiments, the method further comprises, after a), draining the liquid through the porous septum after producing the lithiated ion exchange material.

[189] In some embodiments, the method further comprises, after b), draining the salt solution comprising lithium ions through the porous septum after producing the hydrogen-rich ion exchange material.

[190] In some embodiments, the method further comprises, after a), flowing the lithiated ion exchange material through another system comprising a tank to produce the hydrogen-rich ion exchange material and the salt solution comprising lithium ions, where the tank of the other system further comprises (i) one or more compartments, and (ii) a mixing device.

[191] In some embodiments, the system comprises a plurality of tanks and each tank of the plurality of tanks further comprises (i) one or more compartments, (ii) an ion exchange material, (iii) a mixing device, and (iv) pH modulating equipment for changing the pH of the system.

[192] One aspect described herein is a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a first system comprising a tank, the tank of the first system further comprising (i) one or more compartments, (ii) an ion exchange material, (iii) a mixing device, and (iv) a modulating device. 2047634 of 163 pH to change the pH of the liquid in the first system, to produce a lithiated ion exchange material; b) flowing the lithiated ion exchange material from a) through a second system comprising a tank, where the tank of the second system further comprises (i) one or more compartments, and (ii) a mixing device; and c) treating the lithiated ion exchange material from b) with an acid solution to produce a hydrogen-rich ion exchange material and a salt solution comprising lithium ions.

[193] In some embodiments, the method further comprises, after a), washing the lithiated ion exchange material with an aqueous solution.

[194] In some embodiments, the method also comprises, before b), adding an aqueous solution to the lithiated ion exchange material to form a fluidized lithiated ion exchange material.

[195] In some embodiments, the method further comprises, after c), washing the hydrogen-rich ion exchange material with an aqueous solution. In some embodiments, the aqueous solution is water.

[196] In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is a pipe. In some embodiments, the inlet is an injection port.

[197] In some embodiments, the method further comprises, during a), measuring a change in the pH of the liquid using the pH modulating equipment. 2047634 of 163 pH. In some embodiments, the change in pH triggers the addition of a base to maintain lithium absorption.

[198] One aspect disclosed herein is a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a first system comprising a plurality of tanks to produce a lithiated ion exchange material, each of the plurality of tanks in the first system being in fluid communication with each of the other tanks in the plurality of tanks in the first system, and each of the plurality of tanks in the first system further comprising (i) one or more compartments, (ii) an ion exchange material, (iii) a mixing device, and (iv) pH modulating equipment for changing the pH of each of the plurality of tanks in the first system;b) flowing the lithiated ion exchange material through a second system comprising a plurality of tanks, each tank of the plurality of tanks of the second system being in fluid communication with each of the other tanks of the plurality of tanks of the second system, and each tank of the plurality of tanks of the second system further comprising (i) one or more compartments, and (ii) a mixing device; and c) treating the lithiated ion exchange material from b) with an acid solution in at least one of the plurality of tanks of the second system to produce a hydrogen-rich ion exchange material and a salt solution comprising lithium ions.

[199] In some embodiments, the method further comprises, after c), washing the hydrogen-rich ion exchange material with an aqueous solution in at least one tank of the plurality of tanks of the 2047634 of 163 second system.

[200] In some embodiments, the method is operated in a batch mode. In some embodiments, the method is operated in a continuous mode. In some embodiments, the method is operated in both continuous and batch modes. In some embodiments, the method is operated in a continuous mode, in a batch mode, in a semi-continuous mode, or in combinations thereof.

[201] In some embodiments, the pH modulating apparatus comprises a pH measuring device and an inlet for adding base. In some embodiments, the pH measuring device is a pH probe. In some embodiments, the inlet is a pipe. In some embodiments, the inlet is an injection port.

[202] In some embodiments, the method further comprises, during a), measuring a change in the pH of the liquid using the pH modulating apparatus. In some embodiments, the change in pH triggers the addition of a base to maintain lithium absorption.

[203] An aspect described herein consists of a method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a first system comprising a tank to produce a lithiated ion exchange material, where the tank further comprises (i) one or more compartments, (ii) ion exchange material, and (iii) a mixing device; b) flowing the lithiated ion exchange material obtained in a) through a second system comprising a tank, where the tank further comprises (i) one or more compartments, (ii) an acid solution, and (iii) a mixing device; and c) separating the ion exchange material 2047634 of 163 lithiated to produce hydrogen-rich ion exchange material and a salt solution comprising lithium ions.

[204] In some embodiments, before b), the lithiated ion exchange material is washed. In some embodiments, the lithiated ion exchange material is washed with an aqueous solution.

[205] One aspect disclosed herein is a method for extracting lithium ions from a liquid, comprising: a) providing a system comprising an ion exchange material, a tank comprising one or more compartments; and a mixing device, wherein (i) the ion exchange material is oxide-based and exchanges hydrogen ions for lithium ions, and (ii) the mixing device is capable of moving the liquid through the tank comprising one or more compartments; b) flowing the liquid within the system of a), thereby bringing the liquid into contact with the ion exchange material, the ion exchange material exchanges hydrogen ions for lithium ions in the liquid to produce a lithiated ion exchange material; c) removing the liquid from the system of b);d) flowing an acid solution through the system c) thereby causing the acid solution to come into contact with the lithiated ion exchange material, where the lithiated ion exchange material exchanges lithium ions for hydrogen ions present in the acid solution to produce the ion exchange material and a salt solution comprising lithium ions from the lithiated ion exchange material; and e) collecting the salt solution comprising the lithium ions for further processing;

[206] In some embodiments, the salt solution that 2047634 of 163 comprises lithium ions undergoing crystallization.

[207] A method for extracting lithium ions from a liquid, comprising: a) flowing the liquid through a system comprising an ion exchange material and a plurality of columns, wherein the plurality of columns are configured to transport the ion exchange material along the length of the column, to produce a lithiated ion exchange material; and b) treating the lithiated ion exchange material obtained in a) with an acid solution to produce a salt solution comprising lithium ions.

[208] One aspect disclosed herein is a method for extracting lithium ions from a liquid, comprising: a) providing a system comprising an ion exchange material and a plurality of columns, each of the plurality of columns configured to transport the ion exchange material along the length of the column; b) flowing the liquid through a first of the plurality of columns to produce a lithiated ion exchange material; c) flowing the lithiated ion exchange material from b) through a second of the plurality of columns; and d) treating the lithiated ion exchange material from c) with an acid solution to produce a hydrogen-rich ion exchange material and a salt solution comprising lithium ions.

[209] In some embodiments, the method further comprises, after b), flowing the lithiated ion exchange material through another column of the plurality of columns and washing the lithiated ion exchange material with an aqueous solution. In some embodiments, the method 2047634 of 163 also comprises, after d), flowing the hydrogen-rich ion exchange material through another column of the plurality of columns and washing the hydrogen-rich ion exchange material with an aqueous solution.

[210] One aspect disclosed herein is a method for extracting lithium ion from a liquid, comprising: a) providing a system comprising an ion exchange material and a plurality of columns, each of the plurality of columns configured to transport the ion exchange material along the length of the column; b) flowing the liquid through a first of the plurality of columns to produce a lithiated ion exchange material; c) flowing the lithiated ion exchange material from b) through a second of the plurality of columns; d) washing the lithiated ion exchange material from c) with an aqueous solution; e) flowing the lithiated ion exchange material from d) through a third of the plurality of columns;and f) treating the lithiated ion exchange material from e) with an acid solution to produce a hydrogen-rich ion exchange material and a salt solution comprising lithium ions;

[211] In some embodiments, the method further comprises: g) flowing the hydrogen-rich ion exchange material through a fourth column of the plurality of columns; and h) washing the hydrogen-rich ion exchange material with an aqueous solution. In some embodiments, each column of the plurality of columns is configured to transport the ion exchange material via a piping system or an internal transport system. In some embodiments, each column of the plurality of columns is configured to transport the ion exchange material via a piping system or an internal transport system. 2047634 of 163 columns is configured to transport the ion exchange material via a piping system. In some embodiments, each column of the plurality of columns is configured to transport the ion exchange material via an internal transport system.

[212] In some embodiments of the methods described herein, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, waste brine from a bromine extraction process, an oil field brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or a combination of ores, a leachate from a mineral or a combination of minerals, a leachate from a clay or a combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof. In some embodiments of the methods described herein, the liquid is a brine.In some embodiments of the methods described herein, the liquid comprises a natural brine, a synthetic brine, or a mixture of a natural and a synthetic brine. In some embodiments of the methods described herein, the liquid is a natural brine, a dissolved saline salt, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, waste brine from a bromine extraction process, an oilfield brine, or a liquid. 2047634 of 163 from an ion exchange process, or combinations thereof.

[213] In some embodiments of the methods described herein, the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof. In some embodiments of the methods described herein, the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, or combinations thereof. In some embodiments of the methods described herein, the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, or combinations thereof. In some embodiments of the methods described herein, the acid solution comprises hydrochloric acid. In some embodiments of the methods described herein, the acid solution comprises sulfuric acid.In some embodiments of the methods described herein, the acid solution comprises phosphoric acid. Process for extracting lithium from a liquid

[214] One aspect described herein is a process for extracting lithium from a liquid comprising treating porous ion exchange beads alternately with acid solutions, brine, and optionally others, in a configuration where the beads travel in the net opposite direction to the acid solutions, brine, and optionally other components, to thereby produce a lithium-enriched solution from the liquid. In one embodiment, the process comprises: (a) treating the porous ion exchange beads with acid under appropriate conditions 2047634 of 163 to absorb hydrogen to generate hydrogen-enriched beads and release lithium to generate a lithium-enriched solution; (b) optionally, washing the hydrogen-enriched beads with water to generate hydrogen-enriched beads substantially free of residual acid; (c) treating the hydrogen-enriched beads with the liquid under conditions appropriate to absorb lithium to generate lithium-enriched beads, (d) optionally, washing the lithium-enriched beads with water to generate lithium-enriched beads substantially free of the liquid; and (e) repeating the cycle to produce a lithium-enriched solution from the liquid.

[215] One aspect disclosed herein is a process for extracting lithium from a liquid comprising treating the ion exchange material alternately with acidic solutions, brine, and optionally others, in a configuration where the ion exchange material travels in the net opposite direction to the acidic solutions, the brine, and optionally other components, to thereby produce a lithium enriched solution from the liquid. One aspect disclosed herein is a process for extracting lithium from a liquid comprising treating the ion exchange material alternately with acid, the liquid, and optionally other solutions, in a configuration where the ion exchange material travels in the net opposite direction to the acid, the liquid, and optionally other solutions, to thereby produce a lithium enriched solution from the liquid.One aspect described herein is a process for extracting lithium from a liquid comprising treating the ion exchange material alternately with acid solutions, brine, and optionally others, in a configuration where the material. 2047634 of 163 ion exchange moves in the net opposite direction to that of the acid solutions, the brine, and optionally other components, to thereby produce a lithium-enriched solution from the brine.In one embodiment, the process comprises: (a) treating the ion exchange material with acid under conditions appropriate to absorb hydrogen to generate a hydrogen-enriched material and release lithium to generate a lithium-enriched solution; (b) optionally, washing the hydrogen-enriched material with water to obtain a hydrogen-enriched material substantially free of residual acid; (c) treating the hydrogen-enriched material with the liquid under conditions appropriate to absorb lithium to generate a lithium-enriched material; (d) optionally, washing the lithium-enriched beads with water to generate lithium-enriched beads substantially free of the liquid; and (e) repeating the cycle to produce a lithium-enriched solution from the liquid.

[216] In one embodiment, the porous ion exchange beads comprise ion exchange particles that reversibly exchange lithium and hydrogen and a material that acts as a structural matrix, and have a network of pores. In one embodiment, the liquid comprises a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a filtered brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, ore leachate, mineral leachate, clay leachate, recycled product leachate, recycled material leachate, or combinations thereof. 2047634 of 163

[217] Some embodiments of the present invention comprise a process for extracting lithium from a liquid comprising treating porous ion exchange beads alternately with acidic solutions, brine, and optionally others, in a configuration where the beads travel in the net opposite direction to the acidic solutions, brine, and optionally other components, to thereby produce a lithium-enriched solution from the liquid, the process comprising: a) treating the porous ion exchange beads with acid under conditions appropriate to absorb hydrogen to generate hydrogen-enriched beads and release lithium to generate a lithium-enriched solution; b) optionally washing the hydrogen-enriched beads with water to generate hydrogen-enriched beads substantially free of residual acid;c) treating the hydrogen-enriched beads with the liquid under conditions appropriate to absorb lithium to generate lithium-enriched beads, d) optionally, washing the lithium-enriched beads with water to generate lithium-enriched beads substantially free of the liquid; and e) repeating the cycle to produce a lithium-enriched solution from the liquid.

[218] One aspect described herein is a process for extracting lithium from a liquid comprising alternately treating ion exchange particles with the liquid, washing fluid, and acid, in a system for extracting lithium ions from a liquid, comprising: a. An ion exchange material; b. A stirred tank reactor; and c. pH modulating equipment for increasing the pH of the liquid present in the system.

[219] One aspect described herein is a process for extracting lithium from a liquid comprising treating ion exchange particles 2047634 of 163 alternatively with the liquid, a wash fluid, and an acid solution, with a system for extracting lithium ions from a liquid, comprising a stirred tank reactor, an ion exchange material, pH modulating equipment for increasing the pH of the liquid in the stirred tank reactor, and a compartment for containing the ion exchange material in the stirred tank reactor while allowing removal of the liquid, wash fluid, and acid solutions from the stirred tank reactor. pH modulation process for lithium extraction

[220] One aspect of the invention described herein is a process for extracting lithium ions from a liquid, comprising: a) contacting an ion exchange material with the liquid; and b) increasing the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, and combinations thereof.

[221] Another aspect described herein is a process for extracting lithium ions from a liquid, comprising: a) contacting an ion exchange material with the liquid; and b) increasing the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof. In some embodiments of the process, increasing the pH of the liquid is performed before contacting the ion exchange material with the liquid. In some embodiments of the process, increasing the pH of the liquid is performed during contact of the ion exchange material with the liquid. In some embodiments of the process, increasing the pH of the liquid is performed 2047634 of 163 after contacting the ion exchange material with the liquid. In some embodiments of the process, the pH of the liquid is increased before and during contact of the ion exchange material with the liquid. In some embodiments of the process, the pH of the liquid is increased before and after contact of the ion exchange material with the liquid. In some embodiments of the process, the pH of the liquid is increased during and after contacting the ion exchange material with the liquid. In some embodiments of the process, the pH of the liquid is increased before, during, and after contact of the ion exchange material with the liquid.

[222] An aspect of the invention described herein is a process, wherein the ion exchange material is loaded into a column. In one embodiment, the process further comprises: a) loading a liquid into one or more liquid tanks, b) connecting the column to the one or more liquid tanks, and c) passing the liquid from the one or more liquid tanks through the column, where the passage of the liquid occurs at least once. In one embodiment, the process further comprises increasing the pH of the liquid in the one or more pH increasing tanks. In one embodiment, the process further comprises settling the precipitates in one or more settling tanks. In one embodiment, the process further comprises storing the liquid in one or more storage tanks before or after circulating the liquid through the column.

[223] An aspect of the invention described herein consists of a process, wherein the process further comprises: a) loading the liquid into one or 2047634 of 163 more liquid tanks, b) connecting the column to the one or more liquid tanks, c) passing the liquid from the one or more liquid tanks through the column, where the passage of the liquid occurs at least once; d) increasing the pH of the liquid obtained as a result of c). In one or more pH increasing tanks, e) settling the precipitates of the liquid obtained as a result of d. In one or more sedimentation tanks; and f) storing the liquid obtained as a result of e. In one or more storage tanks.

[224] An aspect of the invention described herein is a process wherein ion exchange material is loaded into a plurality of columns. In one embodiment, a plurality of tanks are connected to the plurality of columns, each tank of the plurality of tanks being directly connected to one of the plurality of columns. In one embodiment, two or more of the plurality of columns form at least one circuit. In one embodiment, at least one circuit is selected from a liquid circuit, a water wash circuit, and an acid solution circuit. In one embodiment, the pH of the liquid is increased in the plurality of tanks connected to the plurality of columns of the liquid circuit.In one embodiment, the circuit for the liquid includes a plurality of columns connected to a plurality of tanks, where each tank of the plurality of tanks is directly connected to a column of the plurality of columns.

[225] An aspect of the invention described herein is a process, the process further comprising: a) passing the liquid through a plurality of columns of the liquid circuit, b) passing 100 2047634 100 of 163 an acid solution through a plurality of columns of the circuit for the acid solution one or more times; and c) passing water through a plurality of columns of the water washing circuit. In one embodiment, the process further comprises exchanging a plurality of columns between the circuit for the liquid, the water washing circuit and the circuit for the acid solution, such that: a) at least one of the plurality of columns in the circuit for the liquid becomes at least one of the plurality of columns in the water washing circuit and / or at least one of the plurality of columns in the circuit for the acid solution, b) at least one of the plurality of columns in the water washing circuit becomes at least one of the plurality of columns in the circuit for the acid solution and / or at least one of the plurality of columns in the circuit for the liquid,and / or c) at least one of the plurality of columns in the circuit for the acid solution becomes at least one of the plurality of columns in the circuit for the liquid and / or at least one of the plurality of columns in the water washing circuit.

[226] An aspect of the invention described herein is a process, wherein ion exchange material is loaded into one or more compartments of a tank. In one embodiment, the process further comprises moving liquid through the one or more compartments of the tank. In one embodiment, the tank comprises injection ports. In one embodiment, the process further comprises using the injection ports to increase the pH of the liquid prior to contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, and / or to increase the pH of the liquid prior to contact with the ion exchange material. 101 2047634 101 of 163 ion exchange and combinations of such situations.

[227] In some embodiments, the process further comprises using the injection ports to increase the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof.

[228] An aspect of the invention described herein is a process, wherein the column further comprises a plurality of injection ports. In one embodiment, the process further comprises using the plurality of injection ports to increase the pH of the liquid prior to contact with the ion exchange material, during contact with the ion exchange material, following contact with the ion exchange material, and combinations thereof.

[229] In some embodiments, the process further comprises using the plurality of injection ports to increase the pH of the liquid before contact with the ion exchange material, during contact with the ion exchange material, after contact with the ion exchange material, or combinations thereof.

[230] In one embodiment, the ion exchange material comprises a plurality of ion exchange particles. In one embodiment, the plurality of ion exchange particles present in the ion exchange material is selected from uncoated ion exchange particles, coated ion exchange particles, and combinations thereof. In one embodiment, the ion exchange material is a porous ion exchange material. In one embodiment, 102 2047634 102 of 163 embodiments, the porous ion exchange material comprises a network of pores that allows liquids to rapidly move from the surface of the porous ion exchange material toward the plurality of ion exchange particles. In one embodiment, the ion exchange material is in the form of porous ion exchange beads.

[231] In one embodiment, the ion exchange material extracts lithium ions from a liquid. During the extraction of lithium ions from a liquid by the ion exchange material, the pH of the liquid is optionally decreased. Increasing the pH of the liquid present in the system maintains the pH within a range that is appropriate for the uptake of lithium ions by the ion exchange material. In one embodiment, increasing the pH comprises measuring the pH of the system and adjusting the pH of the system to bring it to and maintain a pH range ideal for lithium extraction. In one embodiment, for the ion exchange material to uptake lithium from brine, an ideal pH range for the brine is optionally between 6 and 9, a preferred pH range is optionally between 4 and 9, and an acceptable pH range is optionally between 2 and 9.In one embodiment, increasing the pH comprises measuring the pH of the system and the pH of the system is less than 6, less than 4, or less than 2, the pH of the system is brought and maintained at a pH between 2 and 9, a pH between 4 and 9, or a pH between 6 and 9. Continuous process for lithium extraction

[232] Lithium is an essential element for batteries and other technologies. Lithium is found in a variety of liquids, including natural and synthetic brines and leachates from minerals, clays, and recycled products. 103 2047634 103 of 163 Lithium can be extracted from such liquids using an ion exchange process based on inorganic ion exchange materials. These inorganic ion exchange materials absorb lithium from a liquid while releasing hydrogen, and then elute the lithium in an acidic medium while absorbing hydrogen. This ion exchange process can be repeated to extract lithium from a liquid and obtain a concentrated lithium solution. The concentrated lithium solution can then be further processed into chemical products for the battery industry or other industries.

[233] Ion exchange materials can be formed into beads and the beads can be loaded into ion exchange columns for lithium extraction. In an ion exchange column with a fixed bed, the beads at one end of the column rapidly approach saturation, while the beads at the other end of the column never approach saturation. This saturation can be with lithium during brine flow or with hydrogen during acid flow. When a bead at the top of a fixed bed is saturated, it must remain in place until the entire column has been adequately saturated. As long as a bead remains in place after approaching saturation, it is not able to contribute substantially to the sorption capacity of the column.In this situation, using beads in ion exchange columns is inefficient because saturated beads must wait additional time before the next processing step. Furthermore, due to this waiting period, the beads are exposed to longer flows of acid and brine solutions, which accelerate their dissolution and degradation.

[234] The present invention consists of a continuous process for the 104 2047634 104 of 163 lithium extraction using columns with moving beds of ion exchange beads. Multiple columns can be used in this process. In one column, acid is pumped through the column, and the beads travel through the column in the opposite direction to the acid. During this acid flow, the beads absorb hydrogen from the acid while releasing lithium. Optionally, in another column, the beads are washed with water to remove residual acid. In another column, brine is pumped through the column, and the beads travel through the column in the opposite direction to the brine. During this brine flow, the beads absorb lithium from the brine while releasing hydrogen. The hydrogen can be neutralized by adding base before, during, or after the brine flow through the column. Optionally, in another column, the beads are washed with water to remove residual brine.The beads are then sent back to the acid column, and the cycle is repeated. Figure 9 illustrates a continuous-mode column with a moving bed of ion exchange beads. Figure 10 illustrates a continuous-mode column assembly that includes two types of ion exchange columns for the brine and acid streams. Figure 11 illustrates a continuous-mode column assembly that includes two types of ion exchange columns for the brine and acid streams, and two types of water wash columns to wash away residual brine and acid. Figure 12 illustrates a column assembly where individual columns can process various flow rates of the liquid solutions and beads with various residence times and column heights.

[235] Ion exchange materials are typically particles 105 2047634 105 of 163 small particles, which together constitute a fine powder. The small particle size is necessary to minimize the diffusion distance that lithium must travel within the core of the ion exchange particles. In some containers, such particles can be coated with protective surface coatings to minimize dissolution of the ion exchange materials while allowing efficient transfer of lithium and hydrogen to and from the particles, as disclosed in co-pending U.S. Provisional Application 62 / 421,934, filed November 14, 2016, entitled “Lithium Extraction with Coated Ion Exchange Particles,” which is incorporated by reference throughout.

[236] A major challenge in lithium extraction using inorganic ion exchange particles is loading the particles onto an ion exchange column in such a way that brine and acid can be efficiently pumped through the column with minimal clogging. Materials can be shaped into beads, and the beads can be loaded onto the column. This loading of the beads creates void spaces between the beads, and these void spaces facilitate pumping through the column. The beads hold the ion exchange particles in place and prevent the particles from moving freely through the entire column. When materials are shaped into beads, the penetration of brine and acid solutions into the beads may become slow and difficult.A slow rate of convection and diffusion of the acid and brine solutions into the bead demonstrates the kinetics of lithium absorption and release. Such slow kinetics can create problems for column operation. Slow kinetics may require the use of velocities. 106 2047634 106 of 163 slow pumping through the column. Slow kinetics can also lead to low lithium recovery from the brine and inefficient use of acid to elute lithium.

[237] In some embodiments, the ion exchange beads are porous ion exchange beads with pore networks that facilitate transport into the beads of solutions being pumped through an ion exchange column. The pore networks can be strategically controlled to provide rapid and distributed access for penetration of brine and acid solutions into the bead interior and delivery of lithium and hydrogen to the ion exchange particles. An example of a porous ion exchange bead is shown in Figure 15.

[238] In some embodiments, ion exchange beads are formed by mixing ion exchange particles, a matrix material, and a filler material. These components are mixed and formed into beads. The filler material is then removed from the bead to leave pores. The filler material is dispersed within the bead in a manner that leaves a pore structure that allows for rapid kinetic transport of lithium and hydrogen. This method may include multiple ion exchange materials, multiple polymeric materials, and multiple filler materials.

[239] Another major challenge of lithium extraction using inorganic ion exchange materials is the dissolution and degradation of the materials, especially during the elution of lithium in acid but also during the absorption of lithium present in the liquids. To obtain a concentrated lithium solution from the ion exchange process, it is desirable to use a concentrated acid solution to elute the lithium. However, the 107 2047634 107 of 163 concentrated acid solutions dissolve and degrade inorganic ion exchange materials, reducing the performance and useful lifetime of the materials. Therefore, porous ion exchange beads may contain coated lithium extraction ion exchange particles comprising an ion exchange material and a coating material that protects the particle surface. The coating protects the ion exchange material from dissolution and degradation during the elution of lithium in acid, during the absorption of lithium from a liquid, and during other aspects of an ion exchange process. These coated particles allow the use of concentrated acids in the ion exchange process to give concentrated lithium solutions.

[240] In one aspect described herein, the ion exchange material is selected to have a high lithium adsorption capacity, high selectivity for lithium in a liquid relative to other ions such as sodium and magnesium, strong adsorption of lithium present in liquids including those with low lithium concentrations, easy elution of lithium with a small excess of acid, and rapid ionic diffusion. In one aspect described herein, the coating material is selected to protect the particle from dissolution and chemical degradation during recovery of lithium in acid and also during adsorption of lithium present in various liquids.In some embodiments, the coating material may also be selected to facilitate one or more of the following objectives: diffusion of lithium and hydrogen between the particles and liquids, allowing adhesion of the particles to a structural support, and suppressing structural and mechanical degradation of the particles. 108 2047634 108 of 163

[241] In some embodiments, the continuous mode ion exchange column may be loaded with beads at the top and then the beads may travel through the top ion exchange to the bottom. In some embodiments, the continuous mode ion exchange column may be loaded with beads at the bottom and then the beads may travel through the bottom ion exchange to the top. In some embodiments, the continuous mode ion exchange column may be loaded with beads at the bottom of the column using a pipe or transport system that is flooded with solution at the bottom but extends upward to a height greater than the height of the solution in the ion exchange column.This pipe or transport system allows the beads to be fed through the bottom of the ion exchange column, where they are immersed in the liquid solution, while preventing leakage of the liquid solution to the outside of the column. In some embodiments, the beads are ion exchange particles, ion exchange particles with a coating, ion exchange particles without a coating, ion exchange particles embedded in a porous matrix, or combinations thereof. In some embodiments, a continuous ion exchange column is loaded with ion exchange material at the top or bottom of the column, and the material is removed at the bottom or top of the column.In some embodiments, a continuous mode ion exchange column is loaded with ion exchange material at the top of the column, and the ion exchange material is removed from the bottom of the column. In some embodiments, a 109 2047634 109 of 163 ion exchange column for continuous mode with ion exchange material at the bottom of the column and the ion exchange material is removed from the top of the column.

[242] In some embodiments, an internal transport system is used in continuous mode columns to move beads through the column from the bottom up or from top to bottom. In some embodiments, a screw mechanism is used in continuous mode columns to move beads through the column from the bottom up or from top to bottom. In some embodiments, a screw mechanism is used in continuous mode columns that slides under the beads while forcing them upward. In some embodiments, a screw mechanism is used in continuous mode columns that rotates the beads upward using friction or structures on the screw that form ridges, notches, steps, fins, supports, or fins.Such structures can be rigid or flexible, and can be made of materials such as metal, plastic, or ceramic. The material selected for the acid column must be acid-resistant. In some embodiments, gravity is used to move the ion exchange material through a column from the top to the bottom. In some embodiments, liquid is caused to flow upward through a column while the ion exchange material descends through the column or is suspended in the column by gravity. In some embodiments, the rate at which the liquid is pumped upward through the column is controlled to suspend the ion exchange material. 110 2047634 110 of 163 present in the column. In some embodiments, the ion exchange material present in a column comprises particles, uncoated particles, coated particles, porous material, porous beads, or porous beads comprising a structural matrix. In some embodiments, the ion exchange material is transported from one column to another column using a pipe, a conveyor belt, a hopper, a vessel, a funnel, an elevator, or combinations thereof. In some embodiments, the column may be cylindrical, conical, rectangular, pyramidal, non-cylindrical, or may have combinations of these shapes.

[243] In some embodiments, continuous mode columns are vertically oriented hollow cylinders with vertical flows of liquid solutions and beads in opposite directions. In some embodiments, continuous mode columns are horizontally oriented, with horizontal flows of liquid solutions and beads in opposite directions. In some embodiments, continuous mode columns are diagonally upward with a stepped transport system. In some embodiments, the liquid solutions and beads may sometimes flow in the same direction through the columns.

[244] In some embodiments, each column is a conveying system that may not be cylindrical or may not be completely contained. In some embodiments, the column is a lift system where the beads are transported in an upward direction, while the liquid solution flows downward through the beads. The lift has a finned conveyor belt. The fins have perforations to allow 111 2047634 111 of 163 allows the brine to flow downward through the fins. The fins move upward, carrying the pearls from the bottom to the top. Figure 13 illustrates this elevator system, which has fins attached to a moving conveyor belt.

[245] In some embodiments, each column is a non-cylindrical lift system with fins that move upwardly over a smooth sliding surface, which is held fixed in position. The fins are not attached to the sliding surface but are attached to a separate transport system. The fins have perforations to allow downward flow of liquid solutions, and the fins move the beads upward from the bottom of the transport system to the top. This allows the beads to become saturated with the flowing liquid and then be removed from the top of the transport system. Such a lift system having a fixed sliding surface and separately mounted fins is illustrated in Figure 14.

[246] In some embodiments, the fin perforations may measure less than 0.5 mm, less than 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, less than 16 mm, or less than 32 mm. In some embodiments, a continuous process may utilize conveying systems that move at different velocities for the brine, acid, and other liquid flows. In some embodiments, a continuous process may utilize conveying systems with fins of different sizes for the brine, acid, or other liquid solution flows.

[247] When porous ion exchange beads are used in an ion exchange column, the lithium-containing liquid is pumped through 112 2047634 112 of 163 of the ion exchange column such that the ion exchange particles absorb lithium from the liquid while releasing hydrogen. After the beads have absorbed the lithium, an acid solution is pumped through the column such that the particles release the lithium to the acid solution while absorbing hydrogen. The column may be operated in a co-flow mode with the liquid and acid solution flowing alternately through the column in the same direction, or the column may be operated in a counter-flow mode with a liquid and an acid solution flowing alternately through the column in opposite directions. Between the flows of the liquid and acid solution, the column may be treated or washed with water or other solutions for purposes such as adjusting the pH in the column or removing potential contaminants.The beads may form a fixed or moving bed, and the moving bed may move countercurrent to the brine and acid flows. The beads may be moved between multiple moving bed columns where different columns are used for the brine, acid, water, or other flows. Before or after the liquid has flowed through the column, the pH of the liquid may be adjusted with NaOH or other chemicals to facilitate the ion exchange reaction as well as the handling or disposal of the spent liquid. Before or after the liquid has flowed through the column, the liquid may be subjected to other processes including other ion exchange processes, solvent extraction, evaporation, chemical treatment, or precipitation to remove lithium, to remove other chemical species, or to otherwise treat the brine.

[248] When ion exchange particles are treated with acid, they 113 2047634 113 of 163 produces a lithium solution. This lithium solution can be further processed to produce lithium chemicals. These lithium chemicals can then be supplied to an industrial application.

[249] In some embodiments, an ion exchange material is selected from the following list: an oxide, a phosphate, an oxyfluoride, a fluorophosphate, or combinations thereof. In some embodiments, an ion exchange material is selected from the following list: Li4Mn5O12, Li4TI50i2, U2MO3 (M = Ti, Mn, Sn), LiMn2O4, Li1,eMn1,6O4, LiMO2 (M = Al, Cu, Ti), LithiumO4, Li7TiiiO24, U3VO4, Li2Si3O7, LiFePO4, LiMnPO4, Li2CuP2O7, Al(OH)3, LiCl.xAl(OH)3.yH2O, SnO2.xSb2O5.yH2O, TiO2.xSb2O5.yH2O, solid solutions thereof, or combinations thereof. In some embodiments, an ion exchange material is selected from the following list: Li4Mn5O12, Li4Ti50i2, Li1.6Mn1.6O4, Li2MO3 (M = Ti, Mn, Sn), LiFePO4, solid solutions thereof, or combinations thereof.

[250] In some embodiments, the coating material for protecting the surface of the ion exchange material is selected from the following list: a carbide, a nitride, an oxide, a phosphate, a fluoride, a polymer, carbon, a carbonaceous material, or combinations thereof. In some embodiments, a coating material is selected from the following list: TiO , ZrO , MoO , SnO , Nb O , Ta O , SiO , Li TiO , Li ZrO , Li SiO , Li MnO , Li MoO , LiNbO , LiTaO , AlPO , LaPO , ZrP O , MoP O , MoP O , BaSO , AlF , SiC, TiC, ZrC, Si N , ZrN , BN, carbon, graphitic carbon, amorphous carbon, hard carbon, diamond-like carbon, solid solutions thereof, or combinations thereof. ... 114 2047634 In 114 of 163 embodiments, a coating material is selected from the following list: TiO2, ZrO2, MoO2, SiO2, LiO2, Li2ZrO3, Li2SiO3, Li2MnO3, LiNbO3, AlF3, SiC, Si3N4, graphitic carbon, amorphous carbon, diamond-like carbon, or combinations thereof.

[251] In some embodiments, the ion exchange particles may have an average diameter selected from the following list: less than 10 nm, less than 100 nm, less than 1,000 nm, less than 10,000 nm, or less than 100,000 nm. In some embodiments, the ion exchange particles may have an average size selected from the following list: less than 200 nm, less than 2,000 nm, or less than 20,000 nm.

[252] In some embodiments, the ion exchange particles may be secondary particles comprising smaller primary particles that may have an average diameter that may be selected from the following list: less than 10 nm, less than 100 nm, less than 1,000 nm, or less than 10,000 nm.

[253] In some embodiments, the ion exchange particles have a coating material with a thickness selected from the following list: less than 1 nm, less than 10 nm, less than 100 nm, or less than 1,000 nm. In some embodiments, the coating material has a thickness selected from the following list: less than 1 nm, less than 10 nm, or less than 100 nm.

[254] In some embodiments, the ion exchange material and a coating material may form one or more concentration gradients where the chemical composition of the particle is 115 2047634 115 of 163 within the range between two or more components. In some embodiments, the ion exchange materials and coating materials may form a concentration gradient extending over: a thickness selected from the following list: less than 1 nm, less than 10 nm, less than 100 nm, less than 1,000 nm, less than 10,000 nm, or less than 100,000 nm.

[255] In some embodiments, the ion exchange material is synthesized by a method that may be selected from the following list: hydrothermal, solvothermal, sol-gel, solid state, molten salt flow, ion exchange, microwave, ball mill grinding, precipitation, or vapor deposition. In some embodiments, the ion exchange material is synthesized by a method that may be selected from the following list: hydrothermal, solid state, or microwave.

[256] In some embodiments, a coating material is deposited by a method that may be selected from the following list: chemical vapor deposition, atomic layer deposition, physical vapor deposition, hydrothermal, solvothermal, sol-gel, solid state, molten salt flow, ion exchange, microwave, wet impregnation, precipitation, titration, parking, ball mill grinding, or combinations thereof. In some embodiments, the coating material is deposited by a method that may be selected from the following list: chemical vapor deposition, hydrothermal, titration, solvothermal, wet impregnation, sol-gel, precipitation, microwave, or combinations thereof.

[257] In some embodiments, a material is deposited 116 2047634 116 of 163 coating with physical characteristics that can be selected from the following list: it may be crystalline, amorphous, have a complete coating, a partial coating, uniform, non-uniform, or combinations thereof.

[258] In some embodiments, the multiple coatings may be deposited on the ion exchange material in an arrangement that may be selected from the following list: concentric, patchy, or combinations thereof.

[259] In some embodiments, the matrix is ​​selected from the following list: a polymer, an oxide, a phosphate, or combinations thereof. In some embodiments, the structural support is selected from the following list: polyvinyl fluoride, polyvinylidene difluoride, polyvinyl chloride, polyvinylidene dichloride, polyethylene, polypropylene, polyphenylene sulfide, polytetrafluoroethylene, polytetrofluoroethylene, sulfonated polytetrofluoroethylene, polystyrene, polydivinylbenzene, polybutadiene, sulfonated polymer, carboxylated polymer, Nafion, copolymers thereof, and combinations thereof. In some embodiments, the structural support is selected from the following list: polyvinylidene difluoride, polyvinyl chloride, sulfonated polytetrofluoroethylene, polystyrene, polydivinylbenzene, copolymers thereof, or combinations thereof.In some embodiments, the structural support is selected from the following list: titanium dioxide, zirconium dioxide, silicon dioxide, solid solutions thereof, or combinations thereof. In some embodiments, the matrix material is selected to have heat resistance, acid resistance, and / or other chemical resistance. 117 2047634 117 of 163

[260] In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and the filler material together at once. In some embodiments, the porous beads are formed by first mixing the ion exchange particles and the matrix material, and then mixing with the filler material. In some embodiments, the porous beads are formed by first mixing the ion exchange particles and the filler material, and then mixing with the matrix material. In some embodiments, the porous beads are formed by first mixing the matrix material and the filler material, and then mixing with the ion exchange particles.

[261] In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material with a solvent that dissolves one or more of the components. In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material as dry powders in a mixer or ball mill. In some embodiments, the porous beads are formed by mixing the ion exchange particles, the matrix material, and / or the filler material in a spray dryer.

[262] In some embodiments, the matrix material is a polymer that is dissolved and mixed with the ion exchange particles and / or the filler material using a solvent from the following list: N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, or combinations thereof. In some embodiments, the filler material is a salt ... 118 2047634 118 of 163 mixed with the ion exchange particles and / or matrix material using a solvent from the following list: water, ethanol, isopropyl alcohol, acetone, or combinations thereof.

[263] In some embodiments, the filler material is a salt that dissolves out of the bead forming pores by using a solution that can be selected from the following list: water, ethanol, isopropyl alcohol, a surfactant mixture, an acid or a base, or combinations thereof. In some embodiments, the filler material is a material that thermally decomposes to form a gas at a high temperature such that the gas can exit the bead forming pores, where the gas is selected from the following list: water vapor, oxygen, nitrogen, chlorine, carbon dioxide, nitrogen oxides, organic vapors, or combinations thereof.

[264] In some embodiments, the porous ion exchange beads are formed from a dry powder using a mechanical press, a pellet press, a tablet press, a pill press, a rotary press, or combinations thereof. In some embodiments, the porous ion exchange beads are formed from a solvent slurry by dripping the slurry into a different liquid solution. The solvent slurry can be formed using a solvent of N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, dimethylacetamide, methyl ethyl ketone, or combinations thereof. The different liquid solution can be formed using water, ethanol, isopropyl alcohol, acetone, or combinations thereof.

[265] In some embodiments, the porous exchange bead 119 2047634 119 of 163 ionic is approximately spherical, with an average diameter that can be selected from the following list: less than 10 um, less than 100 um, less than 1 mm, less than 1 cm, or less than 10 cm. In some embodiments, the porous ion exchange bead is approximately spherical, with an average diameter that can be selected from the following list: less than 200 um, less than 2 mm, or less than 20 mm.

[266] In some embodiments, the porous ion exchange bead is pellet-shaped with a diameter of less than 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, or less than 20 mm and with a height of less than 1 mm, less than 2 mm, less than 4 mm, less than 8 mm, or less than 20 mm.

[267] In some embodiments, the porous ion exchange bead is included in a support structure, which may be a membrane, a spiral wound membrane, a hollow fiber membrane, or a mesh. In some embodiments, the porous ion exchange bead is included in a support structure comprising a polymer, a ceramic, or combinations thereof. In some embodiments, the porous ion exchange beads are loaded directly into an ion exchange column without an additional support structure.

[268] In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a geothermal brine, seawater, concentrated seawater, desalination effluent, a concentrated brine, a processed brine, liquid from an ion exchange process, liquid from a solvent extraction process, a synthetic brine, leachate from ores, leachate 120 2047634 120 of 163 from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof. In some embodiments, the liquid is selected from the following list: a natural brine, a dissolved saline salt, a concentrated brine, a processed brine, a synthetic brine, a geothermal brine, liquid from an ion exchange process, liquid from a solvent extraction process, leachate from minerals, leachate from clays, leachate from recycled products, leachate from recycled materials, or combinations thereof.

[269] In some embodiments, a liquid is selected with a lithium concentration that can be selected from the following list: less than 100,000 ppm, less than 10,000 ppm, less than 1,000 ppm, less than 100 ppm, less than 10 ppm, or combinations thereof. In some embodiments, a liquid is selected with a lithium concentration that can be selected from the following list: less than 5,000 ppm, less than 500 ppm, less than 50 ppm, or combinations thereof.

[270] In some embodiments, the acid used to recover lithium from the porous ion exchange beads is selected from the following list: hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof. In some embodiments, the acid used to recover lithium from the porous ion exchange beads is selected from the following list: hydrochloric acid, sulfuric acid, nitric acid, or combinations thereof. 121 2047634 121 of 163

[271] In some embodiments, the acid used to recover lithium from the porous ion exchange beads has a concentration that can be selected from the following list: less than 0.1 M, less than 1.0 M, less than 5 M, less than 10 M, or combinations thereof.

[272] In some embodiments, the porous ion exchange beads perform the ion exchange reaction repeatedly for a number of cycles that may be selected from the following list: more than 10 cycles, more than 30 cycles, more than 100 cycles, more than 300 cycles, or more than 1,000 cycles. In some embodiments, the porous ion exchange beads perform the ion exchange reaction repeatedly for a number of cycles that may be selected from the following list: more than 50 cycles, more than 100 cycles, or more than 200 cycles.

[273] In some embodiments, the concentrated lithium solution obtained from the porous ion exchange beads is further processed to obtain lithium feedstocks using methods that may be selected from the following list: solvent extraction, ion exchange, chemical precipitation, electrodialysis, electrowinning, evaporation with direct solar energy, evaporation with concentrated solar energy, evaporation with a heat transfer medium heated with concentrated solar energy, evaporation with heat from a geothermal brine, heat from combustion, or combinations thereof.

[274] In some embodiments, the concentrated lithium solution obtained from the porous ion exchange beads is continued 122 2047634 122 of 163 processing to obtain lithium chemicals that can be selected from the following list: lithium chloride, lithium carbonate, lithium hydroxide, lithium metal, lithium metal oxide, lithium metal phosphate, lithium sulfide, or combinations thereof. In some embodiments, the concentrated lithium solution obtained from the porous ion exchange beads is further processed to obtain lithium chemicals that are solid, liquid, hydrated, or anhydrous.

[275] In some embodiments, the lithium chemicals produced using the porous ion exchange beads are used in an industrial application that may be selected from the following list: lithium batteries, metal alloys, glass, greases, or combinations thereof. In some embodiments, the lithium chemicals produced using the coated ion exchange particles are used in an application that may be selected from the following list: lithium batteries, lithium-ion batteries, lithium sulfide batteries, solid-state lithium batteries, and combinations thereof.

[276] In some embodiments, the ion exchange materials are synthesized in a lithiated state with a crystalline sublayer occupied entirely or partially by lithium. In some embodiments, the ion exchange materials are synthesized in a hydrated state with a crystalline sublayer occupied entirely or partially by hydrogen. EXAMPLES Example 1: Lithium extraction using coated ion exchange particles

[277] Lithium is extracted from brine using exchange particles 123 2047634 123 of 163 coated ion exchange particles. The brine is an aqueous solution containing 50,000 ppm Na and 1,000 ppm Li. The coated ion exchange particles comprise an ion exchange material and a coating material. The ion exchange material is Li4Mn5O12 and the coating material is ZrO2. The particles comprise 98% by weight of active material and 2% by weight of the coating. The particles have an average diameter of 1.0 microns, and the coating thickness is approximately 2 nm.

[278] The particles are created by first synthesizing Li4Mn5O12 and then depositing the coating on the surface of the Li4Mn5O12. The particles are treated with HCl acid to give LiCl in solution. During the acid treatment, the particles absorb hydrogen while releasing lithium. The active material of formula Li4Mn5O12 is converted to a hydrated state with a hydrogen-rich composition. The ZrO2 coating allows diffusion of hydrogen and lithium respectively to and from the active material while providing a protective barrier that limits the dissolution of manganese and oxygen from the active material. The solution is collected for elemental analysis to measure the lithium yield.

[279] After acid treatment, the hydrated particles are treated with brine, where the particles absorb lithium while releasing hydrogen. The particles are converted from a hydrated state to a lithiated state with a lithium-rich composition. The solution is collected for elemental analysis to measure lithium uptake.

[280] The lithiated material is then treated again with acid to obtain lithium in solution as described above. The hydration and lithiation cycle is repeated to extract the lithium from the brine and obtain a 124 2047634 124 of 163 LiCl solution. Dissolution and degradation of the active material in acid is limited because the coating provides a protective barrier. The dissolution of the active material is measured by elemental analysis of the acid solution after stirring. Example 2: Extraction of lithium using an ion exchange column loaded with beads comprising coated ion exchange particles

[281] Lithium is extracted from the brine using an ion exchange column packed with beads containing coated ion exchange particles. The brine is a natural brine containing approximately 500 ppm Li, 50,000 ppm Na, and other chemical species including K, Mg, Ca, and sulfates. The beads comprise 10 wt % polyvinylidene fluoride (PVDF) matrix and 90 wt % coated ion exchange particles. The coated ion exchange particles comprise an active material and a surface protective coating. The active material is Li4MnsO12 and the coating is ZrO2. The particles comprise 98 wt % active material constituents and 2 wt % coating. The particles have an average diameter of 1.0 microns, and the coating thickness is approximately 2 nm.

[282] The particles are created by first synthesizing Li4MnsO12 and then depositing the coating onto the surface of the Li4MnsO12. The beads are created by dissolving PVDF in N-methyl-2-pyrrolidone (NMP) to form a solution. This solution is then mixed with the coated ion exchange particles to form a slurry. The slurry is then dropped into deionized water to form beads. The beads have an average diameter of 2 125 2047634 125 of 163 mm and a porosity of 35%.

[283] The ion exchange column is 2 meters long and 50 cm in diameter. The column is loaded with beads. 10 M HCl is pumped through the bottom of the column to elute a LiCl solution through the top of the column. The particles absorb hydrogen while releasing lithium to give LiCl. The active material of formula Li4Mn5O12 is converted to a hydrated state with the hydrogen-rich composition Li4-xHxMn5O12. Lithium recovery from the column is monitored using pH measurements and elemental analysis. After lithium recovery, the column is rinsed with water.

[284] After acid treatment, brine is pumped downward through the column. The particles absorb lithium while releasing hydrogen. The hydrated material is converted to a lithiated state with the lithium-rich composition Li4-xHxMn5O12. Lithium uptake by the ion exchange beads in the column is monitored using pH measurements and elemental analysis. The brine exiting the column is brought to neutral pH using NaOH and then re-injected into a brine reservoir. After lithium uptake, the column is rinsed with water.

[285] The column is operated by repeating the steps described above of alternately pumping acid and brine. This operation of the column functions to extract lithium from the brine and produce a concentrated LiCl solution. During column operation, the ion exchange particles are protected from dissolution and degradation due to the surface coating, which provides a protective barrier.

[286] The LiCl solution obtained by the operation of the 126 2047634 126 of 163 columns are processed to obtain lithium feedstocks, including Li2CO3, LiOH, and metallic Li. These lithium feedstocks are marketed for use in batteries, alloys, and other products. Example 3: Lithium extraction using a batch recirculation system with mixing tanks, settling tanks, and recirculation tanks

[287] Lithium is extracted from the brine using a batch recirculation system (Figure 1) comprising an ion exchange column (101), a base mixing tank (102), a settling tank for base precipitates (103), a brine recirculation tank (104), and an acid recirculation tank (105). The brine is a natural aqueous chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange column is loaded with a packed bed of porous ion exchange beads (Figure 8). The porous ion exchange beads comprise ion exchange particles and a polymer matrix. Ion exchange particles are coated ion exchange particles comprising a Li4Mn5O12 core with a ZrO2 coating (Figure 7).The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is approximately 4.0 nm. The polymer matrix comprises polyvinylidene difluoride. The porous beads contain pore networks with a controlled pore size distribution that provides diffusion channels from the bead surface to the interior of the bead and the ion exchange particles. The beads have a shape distribution with an average diameter of 2.0 mm. 127 2047634 127 of 163

[288] The ion exchange column is 50 cm high and 1.3 cm in diameter. 200 ml of acid (1.0 M HCl) is loaded into the acid recirculation tank. The acid is pumped through the ion exchange column at a flow rate of 10 ml per minute. The acid solution flows through the ion exchange column where the protons of the acid enter the ion exchange beads and are exchanged for lithium. In this way, the lithium is released from the beads and enters the acid solution. The acid solution flows back to the acid recirculation tank and is recirculated through the column over a period of 6 hours. After this 6-hour time period, the acid solution has been converted into a lithium chloride solution with some HCl remaining. The lithium chloride solution with some HCl remaining is removed from the system and further processed to produce lithium carbonate powder.

[289] 500 ml of water is loaded into the acid recirculation tank. The water is pumped through the ion exchange column at a flow rate of 20 ml per minute to wash residual acid from the column. The water flows through the ion exchange column, then back to the acid recirculation tank, and is then recirculated through the ion exchange column. After 2 hours of water washing, the water is removed from the acid recirculation tank, the water is pH neutralized, and the water is discarded.

[290] 10 liters of brine are loaded into the brine recirculation tank. The brine is pumped through the ion exchange column at a flow rate of 40 ml per minute. As the brine flows through the column, the ion exchange beads absorb lithium from the column. 128 2047634 128 of 163 brine while releasing protons. The acidified brine stream exits the ion exchange column and enters a mixing tank, where base as aqueous NaOH is injected from an aqueous base tank (106) to bring the pH of the brine to approximately 7.5. In the mixing tank, the base is mixed with the brine. The brine stream from the mixing tank goes to the settling tank, where the Mg(OH)2 precipitates optionally settle to the bottom. The Mg(OH)2 precipitates, forming an aqueous slurry, are pumped from the bottom of the settling tank and reinjected into the mixing tank. The pH of the brine entering and exiting the mixing tank is monitored to control base injection rates into the mixing tank. The brine exits the settling tank and enters the brine recirculation tank. The brine is then recirculated back to the ion exchange column.After 36 hours, the lithium uptake rate of the ion exchange beads slows, pumping through the system is terminated, and the spent brine is drained from the system and discarded. The system is then washed again with 500 ml of water as described above. The system is then eluted with acid as described above to recover a lithium concentrate.

[291] Such system operations are repeated to extract lithium from the brine and give a lithium chloride concentrate to produce lithium carbonate or other lithium chemicals. Example 4: Lithium extraction using a batch recirculation system with mixing tanks and recirculation tanks

[292] Lithium is extracted from the brine using a recirculation system 129 2047634 129 of 163 batches (Figure 2) comprising an ion exchange column (201), a base mixing tank (202), a brine recirculation tank (203), and an acid recirculation tank (204). The brine is a natural aqueous chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange column is packed with a packed bed of porous ion exchange beads. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles are coated ion exchange particles comprising a Li4Mn5O12 core with a ZrO2 coating. The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is approximately 4.0 nm. The polymer matrix comprises polyvinylidene fluoride.Porous beads contain pore networks with a controlled pore size distribution that provides diffusion channels from the bead surface to the bead interior and toward the ion exchange particles. The beads have a shape distribution with an average diameter of 2.0 mm.

[293] The ion exchange column is 50 cm high and 1.3 cm in diameter. 200 ml of acid (1.0 M HCl) are loaded into the acid recirculation tank. The acid is pumped through the ion exchange column at a flow rate of 10 ml per minute. The acid solution flows through the ion exchange column, where the protons of the acid enter the ion exchange beads and are exchanged for lithium. In this way, the lithium is released from the beads and enters the acid solution. The acid solution is flowed back to the acid recirculation tank and recirculated through the 130 2047634 130 of 163 column for a period of 6 hours. After this 6-hour period, the acid solution has converted into a lithium chloride solution with some HCl remaining. The lithium chloride solution, with some HCl remaining, is removed from the system and further processed to produce powdered lithium carbonate.

[294] 500 ml of water is loaded into the acid recirculation tank. The water is pumped through the ion exchange column at a flow rate of 20 ml per minute to rinse residual acid from the column. The water flows through the ion exchange column, then back to the acid recirculation tank, and is then recirculated through the ion exchange column. After 2 hours of water washing, the water is removed from the acid recirculation tank, the water is pH neutralized, and the water is discarded.

[295] Ten liters of brine are loaded into the brine recirculation tank. Water is pumped through the ion exchange column at a flow rate of 40 ml per minute. As the brine flows through the column, the ion exchange beads absorb lithium from the brine while releasing protons. The acidified brine flow exits the ion exchange column and enters the mixing tank, where aqueous NaOH base is injected from an aqueous base tank (205) to bring the pH of the brine to approximately 7.0 while limiting the formation of basic precipitates. In the mixing tank, the base is mixed with the brine. The pH of the brine entering and leaving the mixing tank is monitored to control the base injection rates into the mixing tank. The brine exits the mixing tank and enters the brine recirculation tank. 131 2047634 131 of 163 brine. The brine is then recirculated back to the ion exchange column. After 36 hours, the lithium uptake rate of the ion exchange beads slows, pumping through the system is terminated, and the spent brine is drained from the system and discarded. The system is then washed again with 500 ml of water as described above. The system is then eluted with acid as described above to recover a lithium concentrate.

[296] Such system operations are repeated to extract lithium from the brine and give a lithium chloride concentrate to produce lithium carbonate or other lithium chemicals. Example 5: Lithium extraction using a column exchange system with brine circuit, acid circuit, and water wash circuit

[297] Lithium is extracted from the brine using a column exchange system (Figure 3) comprising six ion exchange columns, which are divided into a brine circuit, a water wash circuit, and an acid circuit. The brine is a natural aqueous chloride solution containing approximately 50 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange columns are loaded with packed beds of porous ion exchange beads. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles are coated ion exchange particles comprising a Li4MnsO12 core with a ZrO2 coating. The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is 0.1 microns. 132 2047634 132 of 163 approximately 4.0 nm. The polymer matrix comprises polyvinylidene fluoride. The porous beads contain pore networks with a controlled pore size distribution that provides diffusion channels from the bead surface to the bead interior and toward the ion exchange particles. The beads have a shape distribution with an average diameter of 2.0 mm.

[298] Each of the six ion exchange columns is 150 cm high and 75 cm in diameter (303, 305, 307, 311, 314, 316). Each ion exchange column has an associated mixing tank to mix the base with the brine before injecting the brine into the column (302, 304, 306, 310, 313, 315). Three of the columns (303, 305, 307) together with the associated mixing tanks (302, 304, 306) are connected to form a brine circuit. Brine flows from a brine pipe (301) through a first mixing tank (302), a first ion exchange column (303), a second mixing tank (304), a second ion exchange column (305), a third mixing tank (306), a third ion exchange column (307), and then to a discard pipe (308). To the brine circuit mixing tanks (303, 305, 307), a basic aqueous NaOH solution is added to increase the pH of the brine to 7.5.The pH of the brine is monitored before and after each mixing tank in the brine circuit to control the rate of addition of the aqueous base solution. In the first mixing tank (302) of the brine circuit, the brine enters the mixing tank through the brine pipe at a pH of 6.5, and a relatively small amount of base is added. In the other mixing tanks in the brine circuit (304, 306), the brine enters the mixing tank. 133 2047634 133 of 163 mixture from the outlet of the previous ion exchange columns with a pH of 3.5, and a relatively larger amount of base is added to neutralize the protons that are released in the previous ion exchange columns.

[299] The water wash circuit includes pumping water from a water pipe (309), through an ion exchange column that is saturated with lithium (311), and then pumping the water to a discard pipe. This water wash circuit removes residual brine from the column to prepare for acid elution with minimal impurity content.

[300] The acid circuit comprises two ion exchange columns, which are eluted with 1.0 M sulfuric acid to give a lithium sulfate concentrate. The acid solution flows from an acid storage tank (312), into a first acid circuit ion exchange column (314) and then into a second acid circuit ion exchange column (316). The mixing tanks associated with the acid circuit are inactive (313, 315). As the acid flows through the acid circuit, the ion exchange beads absorb protons while releasing lithium to form a lithium sulfate solution. The resulting lithium sulfate concentrate flows through a lithium concentrate pipe (317) and is then taken to a conversion plant for processing into battery grade lithium hydroxide.

[301] The flow rates of the brine circuit, the water wash circuit, and the acid circuit are coordinated for an exchange event, which is punctuated by the exchange of values ​​to redirect the flow through the system. During the exchange event, the first column of the acid circuit 134 2047634 134 of 163 brine is switched to the water wash circuit, the column of the water wash circuit is switched to the acid circuit, and the first column of the acid circuit is switched to the brine circuit.

[302] As the brine flows through the brine circuit, lithium is absorbed onto the ion exchange beads in the ion exchange columns. The first ion exchange column in the brine circuit is first saturated with lithium, and then this first column is switched to the water wash circuit. As the acid solution flows through the acid circuit, lithium is released from the ion exchange beads in the ion exchange columns. The first ion exchange column in the acid circuit is first saturated with protons, and then this first column is exchanged at the end of the brine circuit. Residual acid in the ion exchange column at the end of the brine circuit is washed away with the brine and the pH is neutralized before being discarded.

[303] After the exchange event, the brine circuit comprises three ion exchange columns (320, 322, 324) and three mixing tanks for the base aggregate (319, 321, 323). The acid circuit comprises two ion exchange columns (331, 333). The mixing tanks associated with the acid circuit are inactive (330, 332). The water wash circuit comprises an ion exchange column (328). After the exchange event, the brine pipe (318), the water pipe (326), the acid tank (329), the discard pipe (325), and the pipe for the lithium concentrate (324) are exchanged to the new circuits using valves.

[304] In other alternative versions of this example, the circuit 135 2047634 135 of 163 brine optionally comprises fifty or more ion exchange columns with associated base mixing tanks for each column. This large number of ion exchange columns and mixing tanks allows for high lithium recoveries from brines with lithium concentrations greater than 50 ppm, while maintaining the brine pH within the range of 4-8. Such a large number of ion exchange columns is difficult to illustrate, and therefore a brine circuit with only three columns is used in this example for ease of description and illustration. Example 6: Lithium extraction using a column exchange system with brine circuit, acid recirculation circuit, and water wash circuit

[305] Lithium is extracted from the brine using a column exchange system (Figure 4) comprising five ion exchange columns, which are divided into a brine circuit, a water wash circuit, and an acid recirculation circuit. The brine is a natural aqueous chloride solution containing approximately 50 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange columns are loaded with packed beds of porous ion exchange beads. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles are coated ion exchange particles comprising a Li4MnsO12 core with a ZrO2 coating. The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is approximately 4.0 nm. The polymer matrix comprises polyvinylidene fluoride.Porous pearls contain networks of. 136 2047634 136 of 163 pores with a controlled pore size distribution provide diffusion channels from the bead surface to the bead interior and toward the ion exchange particles. The beads have a shape distribution with an average diameter of 2.0 mm.

[306] Each of the five ion exchange columns is 150 cm high and 75 cm in diameter (403, 405, 407, 411, 414). Each ion exchange column has an associated mixing tank to mix the base with the brine before injecting the brine into the column (402, 404, 406, 410, 413). Three of the columns (403, 405, 407) are connected together with the associated mixing tanks (402, 404, 406) to form a brine circuit. Brine flows from a brine pipe (401) through a first mixing tank (402), a first ion exchange column (403), a second mixing tank (404), a second ion exchange column (405), a third mixing tank (406), a third ion exchange column (407), and then to a discard pipe (408). To the brine circuit mixing tanks (403, 405, 407), a basic aqueous NaOH solution is added to increase the pH of the brine to 7.5.The pH of the brine is monitored before and after each mixing tank in the brine circuit to control the rate of addition of the aqueous base solution. In the first mixing tank (402) of the brine circuit, brine enters the mixing tank from the brine pipe at a pH of 6.5, and a relatively small amount of base is added. In the other mixing tanks of the brine circuit (404, 406), brine enters the mixing tank from the outlet of the above ion exchange columns at a pH of 3.5, and a relatively larger amount of base is added. 137 2047634 137 of 163 base to neutralize the protons released in the previous ion exchange columns.

[307] The water wash circuit includes pumping water from a water pipe (409), through an ion exchange column that is saturated with lithium (411), and then pumping the water to a discard pipe. This water wash circuit removes residual brine from the column to prepare for acid elution with minimal impurity content.

[308] The acid recirculation circuit comprises an ion exchange column (414) and an acid recirculation tank (412). The tank is charged with acid (1.0 M HCl), which is pumped into the ion exchange column, then back to the tank, and then recirculated through the column. As the acid solution flows through the column, the ion exchange beads absorb protons while releasing lithium. Over time, the acid solution becomes a lithium chloride concentrate. The mixing tanks associated with the ion exchange column are inactive (413). The resulting lithium chloride concentrate is then pH neutralized, concentrated by reverse osmosis, subjected to a final treatment to remove trace amounts of divalent ions, and processed by carbonation to give a powdered battery grade lithium carbonate.

[309] The flow rates of the brine circuit, the water wash circuit, and the acid recirculation circuit are coordinated for a switchover event, which is punctuated by the exchange of values ​​to redirect the flow through the system. During the switchover event, the first column of the brine circuit is switched to the water wash circuit, the second column is switched to the acid recirculation circuit. 138 2047634 138 of 163 of the water wash circuit is switched to the acid recirculation circuit, and the column of the acid circulation circuit is switched to the brine circuit.

[310] As brine flows through the brine circuit, lithium is adsorbed by the ion exchange beads in the ion exchange columns. First, the first ion exchange column in the brine circuit is saturated with lithium, and then this first column is switched to the water wash circuit. The ion exchange column in the acid recirculation circuit is saturated with protons, and then this column is exchanged with another one at the end of the brine circuit. Brine washes away residual acid in the ion exchange column at the end of the brine circuit, and the pH is neutralized before it is discarded.

[311] After the swapping event, the brine pipe (401), water pipe (409), acid tank (412), and waste pipe (408) are swapped to the new circuits using valves.

[312] In other alternative versions of this example, the brine circuit optionally comprises fifty or more ion exchange columns with base mixing tanks associated with each column. This large number of ion exchange columns and mixing tanks allows high lithium recoveries to be obtained from brines with lithium concentrations greater than 50 ppm, while maintaining the pH of the brine in the range of 4-8. Such a large number of ion exchange columns is difficult to illustrate, and therefore a brine circuit with only three columns is used in this example for ease of description and illustration. Example 7: Lithium extraction using a stirred tank system 139 2047634 139 of 163

[313] Lithium is extracted from the brine using a stirred tank system (Figure 5) comprising a tank (501), a mixing tank for base addition (502), a brine recirculation pipe (503), a permeable compartment serving as a support for ion exchange beads inside the tank (504), and an acid recirculation pipe (505). The brine is a natural aqueous chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange column is loaded with a packed bed of porous ion exchange beads. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. Ion exchange particles are coated ion exchange particles comprising a Li4Mn5O12 core with a ZrO2 coating.The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is approximately 4.0 nm. The polymer matrix comprises polyvinylidene fluoride. The porous beads contain pore networks with a controlled pore size distribution that provides diffusion channels from the bead surface to the interior of the bead and toward the ion exchange particles. The beads have a shape distribution with an average diameter of 2.0 mm.

[314] The tank is 3.5 meters high and 2.5 meters in diameter (501). The permeable compartment that serves as a support for the ion exchange beads is mounted inside the tank near the bottom of the tank. The compartment is mounted in a sufficiently low position in the tank such that the compartment will be submerged by the 140 2047634 140 of 163 minimum volume of acid that is necessary to elute the lithium from the beads. The bead-containing compartment is loaded into the tank with the beads in a lithiated state. Acid (1.0 M HCl) is then loaded into the tank and recirculated through the acid circulation tube (505). This acid solution delivers protons to the beads while they absorb lithium from the beads. The acid solution is pumped out of the tank at a point above the compartment, through the acid circulation tube, and then reinjected through the bottom of the tank. The acid solution then percolates through the compartment where it comes into contact with the ion exchange beads, eluting the lithium from the beads.As lithium elution slows, the resulting lithium concentrate is removed from the system and processed to a battery-grade lithium carbonate product by neutralization, concentration using reverse osmosis, carbonation, and recrystallization.

[315] Water is charged to the tank and recirculated through the acid circulation pipe to wash away residual acid.

[316] Brine is charged to the tank and pumped out the top of the tank into the base mix tank (502). The brine then flows through the brine circulation pipe and is re-injected through the bottom of the tank below the compartment. The brine flows upward through the tank and percolates through the compartment. The brine comes into contact with the ion exchange beads, and the beads absorb lithium by extracting it from the brine while releasing protons. The acidified brine flows upward over the compartment and is then pumped into the base mix tank. In the base mix tank, an aqueous NaOH base solution is added to neutralize the lithium. 141 2047634 141 of the 163 protons released by the beads and maintaining the brine pH in the range of 6-8. The neutralized brine then flows through the brine recirculation pipe and is recirculated back through the tank for additional lithium absorption. When lithium absorption slows, the depleted brine is removed from the tank. The tank is then washed again with water as described above. The acid step is then repeated to give a lithium chloride concentrate. The cycle is repeated to obtain a lithium concentrate, which is further processed to give battery-grade lithium carbonate. Example 8: Lithium extraction using a ported ion exchange column system

[317] Lithium is extracted from the brine using a ported ion exchange column system (Figure 6) comprising a column (602) with multiple base injection ports (604). The brine is a natural aqueous chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The ion exchange column is loaded with a packed bed of porous ion exchange beads. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles are coated ion exchange particles comprising a Li4Mn5O12 core with a ZrO2 coating. The particles are approximately spherical with an average diameter of 3.0 microns, and the coating thickness is approximately 4.0 nm. The polymer matrix comprises polyvinylidene fluoride.Porous beads contain pore networks with a controlled pore size distribution. 142 2047634 142 of 163, which provides diffusion channels from the pearl surface to the pearl interior and toward the ion exchange particles. The pearls have a shape distribution with an average diameter of 2.0 mm.

[318] Ion exchange beads are loaded onto the ported ion exchange column system. 1.0 M HCl acid is flowed through the system to elute a lithium chloride concentrate. The system is then acid washed to remove residual acid. Brine is flowed through the bottom of the system from a brine pipe (601). As the brine flows through the column, the beads adsorb lithium from the brine and release protons into the brine, acidifying the brine. To maintain the pH of the brine within a pH range of 4-8, a basic aqueous NaOH solution is injected through the base injection ports. First, as the brine penetrates the column and comes into contact with the fresh beads near the bottom of the column, the ion exchange reaction is faster near the bottom of the column, and therefore base is initially injected at a higher flow rate through the bottom ports of the column.As the beads become saturated near the bottom of the column, the region of the column with the highest ion exchange rate moves upward through the column. To neutralize protons being released into the brine at higher elevations, base is then injected into a higher portion of the column, and base injection is slowed near the bottom of the column and finally terminated. Base injection at the bottom of the column is terminated to prevent precipitation of Mg(OH)2 and other basic precipitates in the column in regions where protons are no longer being released at rates sufficient to neutralize the base. As. 143 2047634 143 of 163 As the brine moves upward through the column, the pH is maintained within a range of 4-8 while the beads absorb lithium and release protons, while limiting the formation of basic precipitates. When the beads throughout the column have become saturated or nearly saturated with lithium, the column is washed with water, and the lithium is eluted with sulfuric acid to form a lithium sulfate concentrate. The lithium concentrate is then processed to yield a lithium hydroxide product. Example 9: Lithium extraction with two types of moving bed columns

[319] Lithium is extracted from the brine using an ion exchange column packed with a moving bed of porous ion exchange particles. The brine is a natural chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles comprise a Li4Mn5O12 core with a ZrO2 coating. The ion exchange particles contain 99% by weight Li4Mn5O12 and 1% by weight ZrO2. The particles are approximately spherical with an average diameter of 1.0 microns, and the coating thickness is approximately 1.0 nm. The polymer matrix comprises PVC.Porous beads contain pores with a pore size distribution that provides diffusion channels from the bead surface to the bead interior and toward the ion exchange particles. When porous beads are immersed in aqueous or other solutions, the solutions infiltrate the pores. The beads have a pore size distribution. 144 2047634 144 of 163 shapes that on average are approximately spherical with an average diameter of 1.0 mm.

[320] Porous ion exchange beads are created by combining three components: ion exchange particles, a polymer, and a removable filler material. The filler material is potassium sulfate. The three components are mixed together using a solvent mixture composed of N-methyl-2-pyrrolidone, ethanol, and water, and then the solvent is removed. The resulting mixture is ground and shaped into beads using a mechanical press. The beads are then heated to alter the polymer structure and improve mechanical strength. The filler is removed using water, which dissolves the filler and thus creates pores throughout the bead. The bead is then heated again to alter the polymer structure and further improve mechanical strength.

[321] Lithium is extracted from brine by a continuous process with porous beads moving between two types of ion exchange columns. One type of ion exchange column is an acid column, where acid is pumped through the column. The other type of ion exchange column is a brine column, where brine is pumped through the column.

[322] The acid columns are 2.0 meters long and 1.0 meters in diameter. Each column is packed with a moving bed of porous beads. Acid (1.0 M HCl) is pumped through the column from the bottom to the top at a flow rate of 0.5 bed volumes per hour to elute a LiCl solution. The pores in the beads allow the acid solution to penetrate inside the bead and access the ion exchange particles. 145 2047634 145 of 163 Therefore, the ion exchange particles can absorb hydrogen from the acid while releasing lithium into the acid. The active material of formula Li4Mn5O12 is converted to a hydrogenated state with a hydrogen-rich composition with the formula Li4-xHxMn5O12 where x can be close to 2. The ZrO2 coating allows diffusion of hydrogen and lithium respectively to and from the active material while providing a protective barrier that limits the dissolution of manganese and oxygen from the active material. The beads release lithium to give a LiCl solution with a lithium in solution concentration of approximately 0.8 M. Lithium recovery from the column is monitored using pH measurements and elemental analysis. The beads are loaded on top of the column and a screw mechanism causes them to move to the bottom of the column.At the bottom of the column, the beads are removed from the column using another screw-like mechanism. The beads are then washed with water and transferred to a brine column.

[323] The brine columns are 3.0 meters long and 1.0 meters in diameter. Each column is loaded with a moving bed of porous beads. Brine is pumped through the column from the bottom to the top at a flow rate of 4.0 bed volumes per hour. The beads absorb lithium while releasing hydrogen. The pores in the beads allow the brine solution to penetrate the bead and access the ion exchange particles. Therefore, the ion exchange particles can absorb lithium from the brine while releasing hydrogen into the brine. The beads are converted from a hydrogenated state to a lithiated state with a lithium-rich composition with the formula Li4Mn5O12 where x 146 2047634 146 of 163 may be close to 0. Lithium uptake by the beads in the column is monitored using pH measurements and elemental analysis. The brine exiting the column is brought to neutral pH using NaOH and then reinjected into a brine reservoir. The beads are loaded onto the top of the column, and a screw-like mechanism moves them to the bottom of the column. At the bottom of the column, the beads are removed from the column using another screw-like mechanism. The beads are then washed with water and transferred back to a column for the acid.

[324] The acid and brine columns are operated in a continuous process by continuously flowing acid and brine through the respective columns. Beads travel continuously through the columns. In the brine column, each bead is removed from the column as the lithium uptake into the bead begins to slow due to partial saturation. In the acid column, each bead is removed from the column as the lithium release from the bead begins to slow due to partial saturation. Removing the bead from the acid column minimizes the time the bead spends in the acid medium while ensuring adequate lithium extraction from the bead. This protects the lifetime of the bead. Such column operations function to extract lithium from the brine and produce a concentrated LiCl solution.During column operations, the porous beads allow acid and brine solutions to penetrate the beads and deliver hydrogen and lithium to the ion exchange particles. The ion exchange particles are protected from dissolution and degradation by the ZrO2 surface coating, which provides a protective barrier. 147 2047634 147 of 163

[325] The LiCl solution obtained from the column operations is processed to obtain lithium feedstocks including Li2CO3, LiOH, LiCl, and metallic Li. These lithium feedstocks are marketed for use in batteries, alloys, and other products. Example 10: Lithium extraction with four types of moving bed columns

[326] Lithium is extracted from the brine using an ion exchange column packed with a moving bed of porous ion exchange particles. The brine is a natural chloride solution containing approximately 100 ppm Li, 40,000 ppm Na, 30,000 ppm Ca, and 3,000 ppm Mg. The porous ion exchange beads comprise ion exchange particles and a polymer matrix. The ion exchange particles comprise a Li4Mn5O12 core with a ZrO2 coating. The ion exchange particles contain 99% by weight Li4Mn5O12 and 1% by weight ZrO2. The particles are approximately spherical with an average diameter of 1.0 microns, and the coating thickness is approximately 1.0 nm. The polymer matrix comprises PVC.Porous beads contain pores with a pore size distribution that provides diffusion channels from the bead surface to the bead interior and toward the ion exchange particles. When porous beads are immersed in aqueous or other solutions, the solutions infiltrate the pores. The beads have a shape distribution that averages approximately spherical with an average diameter of 1.0 mm.

[327] Porous ion exchange beads are created by combining 148 2047634 148 of 163 three components: ion-exchange particles, a polymer, and a removable filler material. The filler material is potassium sulfate. The three components are mixed together using a solvent mixture composed of N-methyl-2-pyrrolidone, ethanol, and water, and then the solvent is removed. The resulting mixture is ground and shaped into beads using a mechanical press. The beads are heated to alter the polymer structure and improve mechanical strength. The filler is removed using water, which dissolves the filler and thereby creates pores throughout the bead. The bead is heated again to alter the polymer structure and further improve mechanical strength.

[328] Lithium is extracted from brine by a continuous process with porous beads moving between four types of columns. The first type of column is an ion-exchange acid column, where acid is pumped through the column to supply hydrogen to the beads and release lithium. The second type of column is a water column, where residual acid is washed from the beads. The third type of column is an ion-exchange brine column, where brine is pumped through the column to supply lithium to the beads while releasing hydrogen. The fourth type of column is a water column, where residual brine is washed from the beads.

[329] The acid columns are 2.0 meters long and 1.0 meters in diameter. Each column is packed with a moving bed of porous beads. Acid (1.0 M HCl) is pumped through the column from the bottom to the top at a flow rate of 0.5 bed volumes per hour to elute a LiCl solution. The pores in the beads allow the solution to 149 2047634 149 of 163 acid to penetrate the bead and access the ion exchange particles. Therefore, the ion exchange particles can absorb hydrogen from the acid while releasing lithium into the acid. The active material of formula Li4Mn5O12 is converted to a hydrogenated state with a hydrogen-rich composition with the formula Li4-xHxMn5O12 where x can be close to 2. The ZrO2 coating allows diffusion of hydrogen and lithium respectively to and from the active material while providing a protective barrier that limits the dissolution of manganese and oxygen from the active material. The beads release lithium to give a LiCl solution with a lithium in solution concentration of approximately 0.8 M. Lithium recovery from the column is monitored using pH measurements and elemental analysis.The beads are loaded at the top of the column, and a screw-like mechanism moves them to the bottom of the column. At the bottom of the column, the beads are removed from the column using another screw-like mechanism.

[330] The beads are then transferred to another column with a moving bed of beads, where the beads are washed with water to remove residual acid. The water flows in the opposite direction to the movement of the beads. The beads are then transferred to a brine column.

[331] The brine columns are 3.0 meters long and 1.0 meters in diameter. Each column is loaded with a moving bed of porous beads. Brine is pumped through the column from the bottom to the top at a flow rate of 4.0 bed volumes per hour. The beads absorb lithium while releasing hydrogen. The pores in the beads allow the brine solution to penetrate into the bead and access the 150 2047634 150 of 163 ion exchange particles. Therefore, the ion exchange particles can absorb lithium from the brine while releasing hydrogen into the brine. The beads are converted from a hydrogenated state to a lithiated state with a lithium-rich composition with the formula Li4Mn5O12 where x can be close to 0. Lithium uptake by the beads in the column is monitored using pH measurements and elemental analysis. The brine exiting the column is brought to a neutral pH using NaOH and then reinjected into a brine reservoir. The beads are loaded onto the top of the column and a screw-like mechanism causes them to move to the bottom of the column. At the bottom of the column, the beads are removed from the column using another screw-like mechanism.

[332] The beads are then transferred to another column with a moving bed of beads, where the beads are washed with water to remove residual brine. The water flows in the opposite direction to the movement of the beads. The beads are then transferred back to a column for the acid.

[333] The acid and brine columns are operated in a continuous process by continuously flowing acid and brine through the respective columns. Beads travel continuously through the columns. In the brine column, each bead is removed from the column as lithium uptake into the bead begins to slow due to partial saturation. In the acid column, each bead is removed from the column as lithium release from the bead begins to slow due to partial saturation. Removing the bead from the acid column minimizes the time the bead spends in the acid medium while ensuring adequate lithium extraction from the bead. This protects the 151 2047634 151 of 163 bead lifetime. These column operations serve to extract lithium from the brine and produce a concentrated LiCl solution. During column operations, the porous beads allow the acid and brine solutions to penetrate the beads and deliver hydrogen and lithium to the ion exchange particles. The ion exchange particles are protected from dissolution and degradation by the ZrO2 surface coating, which provides a protective barrier.

[334] The LiCl solution obtained from the column operations is processed to obtain lithium feedstocks including Li2CO3, LiOH, LiCl, and metallic Li. These lithium feedstocks are marketed for use in batteries, alloys, and other products. Example 11: Lithium extraction using a stirred tank reactor

[335] Lithium was extracted from a brine using a stirred tank reactor packed with a fluidized bed of ion exchange particles. The brine was a natural chloride solution containing 500 ppm Li, 60,000 ppm Na, 17,000 ppm Ca, and 3,000 ppm Mg. The ion exchange particles comprised a Li4MnsO12 core with a titanium dioxide coating. The ion exchange particles contained 98 wt % Li4MnsO12 and 2 wt % titanium dioxide. The particles were approximately spherical, with an average diameter of 50 microns.

[336] The ion exchange particles were loaded into a stirred tank reactor (Figure 16) comprising a tank (2101), an overhead stirrer (2102), a pH probe (2103), and a pipe for adding base to the tank (2104). The particles were successively stirred with brine, water, 0.75 N sulfuric acid, and again with water. When the particles were 152 2047634 152 of 163 particles were agitated with brine, absorbing lithium from the brine while simultaneously releasing protons into the brine. As the protons were released, the brine pH dropped. The pH probe measured the change in pH and injected base through the tube into the brine. This base neutralized the protons released by the particles and maintained a strong thermodynamic force driving lithium uptake by the particles. The particles were then washed with water to remove residual brine. The particles were then eluted with sulfuric acid, and the particles released lithium to form a lithium sulfate solution while absorbing protons. The particles were then washed again to remove residual acid. The particles were then returned to a brine step, and the cycle was repeated. The cycle served to extract lithium from the brine and produce a lithium sulfate solution. Example 12: Lithium extraction using a compartmented stirred tank reactor

[337] Lithium was extracted from the brine using a stirred tank reactor packed with a fluidized bed of ion exchange particles. The brine was a natural chloride solution containing 500 ppm Li, 60,000 ppm Na, 17,000 ppm Ca, and 3,000 ppm Mg. The ion exchange particles comprised Li4MnsO12 in a polystyrene matrix. The particles contained approximately 90% Li4MnsO12 and 10% polystyrene. The particles had a typical size of 100 microns.

[338] The ion exchange particles were loaded into a stirred tank reactor (Figure 17) comprising a tank (2201), an overhead stirrer (2202), a pH probe (2203), a pipe for adding base to the tank 153 2047634 153 of 163 (2204), and a compartment containing the ion exchange particles with a porous polymer support (2205). The porous polymer support was a polyetheretherketone mesh with a pore size of 35 microns. The porous polymer support divided the bottom of the tank from the top of the tank, containing the ion exchange particles at the top of the tank, and allowing fluid to drain out of the tank through the mesh and to a pipe connected at the bottom of the tank. The compartment accounted for approximately 99% of the tank volume.

[339] The particles were agitated consecutively with brine, water, 0.75 N hydrochloric acid, and again with water. When the particles were agitated with brine, the particles adsorbed lithium from the brine while releasing protons into the brine. As the protons were released, the pH of the brine dropped. The pH probe measured the change in pH and triggered the addition of base through the tube into the brine. This base neutralized the protons released by the particles and maintained a strong thermodynamic force driving lithium adsorption onto the particles. The brine was drained from the tank through the bottom, leaving the ion exchange particles in the compartment, separated by the porous mesh. The particles were then washed with water three times to remove residual brine, each time draining the water through the bottom of the tank.The particles were then eluted with hydrochloric acid, and the particles released lithium to form a lithium chloride solution while absorbing protons. The lithium chloride solution was then drained from the bottom of the tank. The particles were then washed again to remove residual acid. After that, the particles were returned to a brine step, and the cycle was repeated. 154 2047634 154 of 163 The cycle served to extract lithium from the brine and produce a lithium chloride solution. The lithium chloride was concentrated by evaporation, purified, and reacted with sodium carbonate to form lithium carbonate powder. Example 13: Lithium extraction using a pair of stirred tank reactors

[340] Lithium is extracted from the brine using a stirred tank reactor packed with a fluidized bed of ion exchange particles. The brine is a natural chloride solution containing approximately 500 ppm Li, 60,000 ppm Na, 20,000 ppm Ca, and 5,000 ppm Mg. The ion exchange particles comprise a Li4MnsO12 material. The particles are approximately spherical with an average diameter of 30 microns.

[341] Ion exchange particles are loaded into an ion exchange system (Figure 18) comprising a large stirred tank reactor and a small stirred tank reactor. The large stirred tank reactor comprises a large tank (2301), an overhead stirrer (2302), a pH probe (2303), a pipe for adding base to the tank (2304), and a compartment containing the ion exchange particles with a porous polymer support (2305). The small stirred tank reactor comprises a small tank (2306), an overhead stirrer (2307), and a compartment containing the ion exchange particles with a porous polymer support (2308). The porous polymer supports are formed with a bilayer structure, with a coarse mesh of polypropylene (750 micron pores) and a fine mesh of polyetheretherketone (20 micron pores). The porous polymer support separates the bottom from the 155 2047634 155 of the 163 tanks at the top of the tanks, keeping the ion exchange particles at the top of the tanks and allowing the fluid to drain out of the tanks through the mesh and into connected pipes at the bottom of the tanks. The compartments represent 99% of the tanks' volume.

[342] In the large stirred tank reactor compartment, particles are agitated with brine and water. As the particles are agitated with brine, they absorb lithium from the brine while releasing protons into the brine. As protons are released, the pH of the brine drops. The pH probe measures the change in pH and triggers the addition of base through the tube into the brine. This base neutralizes the protons released from the particles and maintains a strong thermodynamic force driving lithium uptake by the particles. The brine drains from the tank through the screen and out the bottom, leaving the ion exchange particles in the compartment, separated by the porous screen. The particles are then washed with water to remove residual brine, and the water is drained out the bottom of the tank.Water is then added to the tank to form a slurry, which is pumped out of the large stirred tank reactor and into the small stirred tank reactor compartment.

[343] In the small stirred tank reactor, the particles are washed again with water, and then the water is drained from the bottom of the tank through the mesh to the outside. The particles are then stirred with hydrochloric acid, and the particles release lithium to form a lithium chloride solution while absorbing protons. The lithium chloride solution is then drained from the bottom of the tank. The particles are then washed again. 156 2047634 156 of 163 to remove residual acid. Water is then added to form a slurry, and the slurry is pumped back to the large stirred-tank reactor.

[344] Lithium chloride is concentrated by evaporation and purified. The lithium chloride solution is then mixed with a sodium carbonate solution to precipitate lithium carbonate. Example 14: Lithium extraction using a network of continuous stirred tank reactors

[345] Lithium is extracted from the brine using a stirred tank reactor packed with a fluidized bed of ion exchange particles. The brine is a natural chloride solution containing approximately 500 ppm Li, 60,000 ppm Na, 20,000 ppm Ca, and 5,000 ppm Mg. The ion exchange particles comprise a Li4MnsO12 material with a titanium dioxide coating embedded in a polyvinylidene difluoride (PVDF) matrix. The ion exchange particles contain 75 wt % Li4MnsO12, 5 wt % titanium dioxide, and 20 wt % PVDF. The particles are approximately spherical with an average diameter of 80 microns.

[346] The ion exchange particles are loaded into a network of stirred tank reactors, which are operated in a continuous mode (Figure 19). The system comprises three large stirred tank reactors (2401, 2402, 2403) and three small stirred tank reactors (2404, 2405, 2406). Each large stirred tank reactor comprises a large tank, an overhead stirrer, a pH probe, a pipe for adding base to the tank, and a compartment containing the exchange particles. 157 2047634 157 of 163 ionic with a porous polymer support. Each of the small stirred-tank reactors comprises a small tank, an overhead stirrer, and a compartment containing the ion exchange particles with a porous polymer support. The porous polymer supports are formed with a bilayer structure having a coarse polypropylene mesh (750 micron pores) and a fine polyester mesh (20 micron pores). The porous polymer support separates the bottom of the tanks from the top of the tanks, keeps the ion exchange particles at the top of the tanks, and allows fluid to drain out of the tanks through the mesh and into connected pipes at the bottom of the tanks. In each tank, the compartment represents approximately 98% of the tank volume.

[347] Brine is continuously flowed from a well field through an ultrafiltration unit to remove suspended solids and into the first large stirred tank reactor (2401). In the first stirred tank reactor, the brine is agitated with the ion exchange particles for a residence time of 20 minutes and is continuously withdrawn from the reactor at the bottom of the reactor and then pumped into the second large stirred tank reactor (2402). In the second stirred tank reactor, the brine is agitated with the ion exchange particles for a residence time of 20 minutes and is continuously withdrawn from the reactor at the bottom of the reactor and then pumped into the third large stirred tank reactor (2403). In the third stirred tank reactor, the brine is agitated with the ion exchange particles for a residence time of 20 minutes and is continuously withdrawn from the reactor at the bottom of the reactor and then pumped into the third large stirred tank reactor (2404). 158 2047634 158 of 163 reactor continuously through the bottom of the reactor and then filtered to remove all ion exchange particle fragments and sent through a return pipe to the well field for reinjection. When the particles are agitated with the brine, they absorb lithium from the brine while simultaneously releasing protons into the brine. As protons are released, the brine pH drops. The pH probe measures the change in pH and triggers the addition of base into the brine through the pipe. This base neutralizes the protons released from the particles and maintains a strong thermodynamic force driving lithium absorption onto the particles.

[348] The ion exchange particles are continuously removed from the first stirred tank reactor as a slurry and sent to a pH buffer tank and loaded in batches into a small stirred tank reactor (2406) for washing to remove residual brine. The particles are then batch transferred to another small stirred tank reactor (2405) for eluting with 1.0 N sulfuric acid to produce lithium sulfate solution, which is drained from the compartment and the bottom of the tank. The particles are then transferred to another small stirred tank reactor (2404) for washing to remove residual acid. The particles are then transferred to a pH buffer tank, from where they are continuously fed to the first large stirred tank reactor to repeat the cycle.

[349] Lithium sulfate is concentrated by reverse osmosis and purified. The lithium sulfate solution is then mixed with a sodium carbonate solution to precipitate lithium carbonate. Example 15: Lithium extraction using a switched-mode network 159 2047634 159 of 163 stirred tank reactors

[350] Lithium is extracted from the brine using a stirred tank reactor packed with a fluidized bed of ion exchange particles. The brine is a natural chloride solution containing approximately 300 ppm Li, 80,000 ppm Na, 1,000 ppm Ca, and 3,000 ppm Mg. The ion exchange particles comprise a polystyrene-coated Li4Mn5O12 material. The ion exchange particles contain 95 wt% Li4Mn5O12 and 5 wt% polystyrene. The particles are approximately spherical with an average diameter of 50 microns.

[351] Ion exchange particles are loaded into a network of six stirred tank reactors, forming a switched network (Figure 20). Each stirred tank reactor comprises a large tank, an overhead stirrer, a pH probe, a pipe for adding base to the tank, and a compartment containing the ion exchange particles with a porous polymer support. The porous polymer supports are formed with a bilayer structure having a coarse polypropylene mesh (500 micron pores) and a fine polyetheretherketone mesh (20 micron pores). The porous polymer support separates the bottom of the tanks from the top of the tanks, keeps the ion exchange particles at the top of the tanks, and allows fluid to drain out of the tanks through the mesh and into connected pipes at the bottom of the tanks. In each tank, the compartment accounts for approximately 99% of the tank volume.

[352] In each stirred tank reactor, the particles are stirred consecutively with brine, water, 0.75 N sulfuric acid, and again 160 2047634 160 of 163 with water. When the particles are agitated with brine, they absorb lithium from the brine while simultaneously releasing protons into the brine. As protons are released, the brine's pH drops. The pH probe measures the change in pH and triggers the addition of base into the brine through the tube. This base neutralizes the protons released from the particles and maintains a strong thermodynamic force driving lithium adsorption onto the particles. The brine drains from the compartment through the porous mesh and exits the tank through a tube at the bottom, leaving the ion exchange particles in the compartment. The particles are then washed with water three times to remove residual brine, with the water draining out the bottom of the tank each time. The particles are then eluted with sulfuric acid, and the particles release lithium to form a lithium sulfate solution while absorbing protons.The lithium sulfate solution is then drained from the bottom of the tank. The particles are then washed again to remove residual acid. The particles are then returned to a brine step, and the cycle is repeated. The cycle extracts lithium from the brine and produces a lithium sulfate solution.

[353] The stirred tank reactor network is operated in a batch mode by switching reactors such that at any given time, one reactor is being eluted with acid (2501), one reactor is being washed with water to remove residual acid (2502), three reactors are being treated with brine to cause particulate to adsorb lithium (2503, 2504, 2505), and one reactor is being washed with water to remove residual brine (2506).

[354] Lithium sulfate is concentrated by reverse osmosis, 161 2047634 161 of 163 is purified and electrolyzed to form a lithium hydroxide solution. The lithium hydroxide solution crystallizes to form lithium hydroxide powder.

[355] Although preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are given by way of example only. Now, those skilled in the art will conceive numerous variations, changes, and substitutions without departing from the invention. It should be understood that in practicing the invention, various alternatives to the embodiments of the invention described herein may optionally be employed. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of said claims and their equivalents shall be covered thereby. 162 2047634 162 of 163 CLARKE MODET & CO. (ARGENTINA) SA - 30540437455 Digitally signed by PORTALTRAMITES - INPI Date: 2022.11.25 12:37:30 -03:00 Reason: Digitally signed by the INPI Location: Buenos Aires, Argentina 2047634 163 of 163

Claims

1. A system for extracting lithium ions from a liquid, characterized in that it comprises: i) an ion exchange material loaded in one or more tanks, or ii) an ion exchange material loaded in one or more vessels, wherein said one or more tanks or vessels comprise one or more injection ports; and a pH modulating unit for increasing the pH of the liquid present in the system, wherein the pH modulating unit is connected to said one or more injection ports and is configured to modulate the pH of the liquid by dosing a base into the liquid, and wherein the liquid is i) contained in one or more tanks or vessels comprising the ion exchange material; or ii) circulated within one or more second tanks for pH modulation. 29 Claims follow