Lithium extraction from brines with solid sorbents

Abstract

The present disclosure provides sorbents that contained a crosslinked polymer binder that shows improved robustness and stability to repeated loading and elution. The present disclosure also provides methods of making the polymer-containing sorbent as well as methods of using the sorbent in the separation of lithium and lithium ions for a brine.

Description

LITHIUM EXTRACTION FROM BRINES WITH SOLID SORBENTS

[0001] The present disclosure claims the benefit of priority to United States Provisional Application No. 63 / 687,966, filed on August 28, 2024, the entire contents of which are hereby incorporated by reference.BACKGROUND1. Technical Field

[0002] The present disclosure generally relates to the preparation and use of solid sorbents for the separation or extraction of lithium from brine solutions. The present disclosure provides solid compositions that may contain one or more polymeric compounds that have been crosslinked to form a complex with lithium aluminum layered double hydroxide.2. Description of Related Art

[0003] Solid compositions of sorbents are known to be highly effective at removing lithium from a brine solution. Unfortunately, these sorbents generally readily degrade in their ability to separate lithium from a brine over time and after multiple extraction cycles. This loss of activity results in the need to replace the solid sorbent frequently and leads to increased cost of processing.

[0004] Therefore, there remains a need to develop new solid sorbents for lithium extraction such as lithium aluminum layered double hydroxide (Li / Al LDH) that show improved properties such as enhanced robustness and stability leading to a longer useful life cycle.

[0005] Capacity of solid sorbents material disclosed in the prior arts is low (mg of Li adsorbed per gr of sorbent material), causing to use of more solid sorbents in the adsorption equipment for a given amount of lithium to be produced. This will increase the cost of lithium production. Therefore, there is a need to prepare sorbents in a way to have higher working lithium adsoiption capacity.SUMMARY

[0006] The present disclosure relates to sorbent compositions, preparation of sorbent, and methods of using those sorbents to selectively extract lithium from a brine solution.

[0007] In some aspects, the present disclosure relates to compositions comprising:(A) a lithium aluminum layer double hydroxide; and(B) a polymer; wherein the composition comprises a uniform mixture of the lithium aluminum layer double hydroxide and the polymer.

[0008] In some embodiments, an amount of the polymer is from about 5% w / w to about 50% w / w of the total weight of the composition. In some embodiments, the amount of the polymer is from about 10% w / w to about 40% w / w of the total weight of the composition. In some embodiments, the amount of the polymer is from about 15% w / w to about 30% w / w of the total weight of the composition.

[0009] In some embodiments, the composition comprises a plurality of pellets. In some embodiments, the plurality of pellets comprises a mixture of pellets with an average diameter of 0.05 mm to about 20 mm. In some embodiments, the average diameter of the mixture of the pellets is from about 0.1 mm to about 10 mm. In some embodiments, the average diameter of the mixture of the pellets is from about 0.25 mm to about 5 mm. In some embodiments, the average diameter of the mixture of the pellets is from about 0.25 mm to about 2 mm. In some embodiments, the average diameter of the mixture of the pellets is from about 0.3 mm to about 1.0 mm. In some embodiments, the average diameter of the mixture of the pellets is from about 0.3 mm to about 0.5 mm.

[0010] In some embodiments, the composition comprises less than 10% of solvent or water. In some embodiments, the composition comprises less than 5% of solvent or water. In some embodiments, the composition comprises less than 2.5% of solvent or water. In some embodiments, the composition comprises less than 1 % of solvent or water.

[0011] In some embodiments, the polymer is a copolymer. In some embodiments, the polymer is an acrylate copolymer. In some embodiments, the acrylate copolymer is a styrene copolymer. In some embodiments, the acrylate copolymer is a polymer comprising two or more different acrylate monomers. In some embodiments, the polymer has a Tg from about 1 °C to about 50 °C. In some embodiments, the Tg is from about 5 °C to about 40 °C. In some embodiments, the Tg is from about 10 °C to about 30 °C.

[0012] In some embodiments, the polymer comprises one or more cross linking units. In some embodiments, the polymer comprises an amount of crosslinking from about 5% to about 60% of the total polymer. In some embodiments, the amount of crosslinking is from about 10% to about 50% of the total polymer. In some embodiments, the amount of crosslinking is from about 20% to about 40% of the total polymer.

[0013] In some embodiments, the composition is resistant to thermal degradation at a temperature before 150 °C.

[0014] In yet another aspect, the present disclosure provides methods of preparing a lithium extracting sorbent composition comprising admixing a lithium aluminum double layer hydroxide composition with a polymer to form a lithium extracting sorbent composition. In some embodiments, the lithium aluminum double layer hydroxide composition with a polymer is a composition described herein. In some embodiments, the lithium aluminum double layer hydroxide composition is prepared using a lithium chloride solution that was prepared using a direct lithium extraction process. In some embodiments, the lithium chloride solution prepared in a direct lithium extraction process. In some embodiments the lithium chloride salt comprises oneor more impurities. In some embodiments, the lithium chloride salt is present in a concentration from about 1 wt.% to about 50 wt%. In some embodiments, the polymer and lithium aluminum double layer hydroxide are mixed continuously to prepare the desired composition that is typically done in large-scale sorbent composition preparation.

[0015] In some embodiments, the methods further comprises a filtration step. In some embodiments, the filtration step comprises processing the lithium extracting composition through a belt filtration, a drum filter, a disc filter, or centrifugation to obtain a filtered lithium extracting composition. In some embodiments, the method comprises dissolving or suspending the filtered lithium extracting composition two, three, four, or five times and subjecting to a second, third, fourth, or fifth filtration. In some embodiments, the second, third, fourth, or fifth filtration is processed through a belt filtration, a drum filter, a disc filter, or centrifugation. In some embodiments, the filtration step comprises admixing the lithium extracting composition with a flocculant. In some embodiments, the flocculant is a cationic flocculant. In other embodiments, the flocculant is an anionic flocculant. In other embodiments, the flocculant is a neutral flocculant.

[0016] In some embodiments, the methods further comprises a drying step. In some embodiments, the drying step is performed at a temperature from about 25 °C to about 150 °C. In some embodiments, the temperature is from about 30 °C to about 120 °C. In some embodiments, the temperature is from about 40 ° C to about 100 °C. In some embodiments, the temperature is from about 50 °C to about 80 °C. In some embodiments, the drying step is caried out in a batch vacuum dryer. In some embodiments, the drying step is carried out using a tray dryer, a ribbon dryer, a paddle dryer, conical screw dryer, or thermal screw vacuum dryer.

[0017] In some embodiments, the polymer is added in two or more portions to the lithium aluminum double layer hydroxide composition. In some embodiments, the amount of the polymer is from about 5% w / w to about 50% w / w of the total weight of the composition. In some embodiments, the amount of the polymer is from about 5% w / w to about 40% w / w of the total weight of the composition. In some embodiments, the amount of the polymer is from about 10% w / w to about 30% w / w of the total weight of the composition.

[0018] In some embodiments, the methods further comprise a curing step. In some embodiments, the polymer comprises an amount of crosslinking from about 5% to about 60% of the total polymer. In some embodiments, the amount of crosslinking is from about 10% to about 50% of the total polymer. In some embodiments, the amount of crosslinking is from about 20% to about 40% of the total polymer.

[0019] In some embodiments, the methods further comprise a pelletizing step to form a pelletizing lithium extracting composition. In some embodiments, the pelletizing step comprises a continuous pelleting run. In some embodiments, the pelletizing step comprises a continuous pin mixer. In some embodiments, the pelletizing step further comprises a rotary drum pelletizer.

[0020] In some embodiments, the pelletizing step further comprises one or more pellet drying steps. In some embodiments, the pellet drying steps comprise using a dryer in direct configuration. In otherembodiments, the pellet drying steps comprise using a dryer in indirect configuration. In some embodiments, the pellet drying steps comprise using a dryer in a co-current mode. In other embodiments, the pellet drying steps comprise using a dryer in a counter-current mode. In some embodiments, the pellet drying steps comprise using a rotary drum dryer, fluidized bed dryer, tray dryer, or a continuous turbo tray dryer. In some embodiments, the pelletizing step further comprises using a second pelletizer. In some embodiments, the second pelletizer is disc pelletizer or a rotary drum pelletizer.

[0021] In some embodiments, the pelletizing step comprises adding one or more compounds into a pelletizer. In some embodiments, the one or more compounds are added into the pelletizer through one port. In some embodiments, the one or more compounds are added into the pelletizer through two or more ports. In some embodiments, the two or more ports are two, three, four, or five ports. In some embodiments, the one or more compounds are a solvent. In some embodiments, the solvent is water. In some embodiments, the solvent is an alcoholic or ketone solvent. In some embodiments, the alcoholic or ketone solvent is methanol, ethanol, propanol, butanol, or acetone.

[0022] In some embodiments, the pelletizing step further comprises adding a sacrificial porogen during the pelletizing step. In some embodiments, the sacrificial porogen is a sugar alcohol. In some embodiments, the sacrificial porogen is a water or alcohol soluble organic polymer. In some embodiments, the water or alcohol soluble organic polymer is triblock copolymer of polyethylene glycol and polypropylene glycol. In some embodiments, the water or alcohol soluble organic polymer is polyethylene glycol. In some embodiments, the sacrificial porogen is an organic compound such as camphor. In some embodiments, the sacrificial porogen is resin such as rosin or shellac. In some embodiments, the sacrificial porogen is ammonium bicarbonate. In some embodiments, the pelletizing step comprises adding the sacrificial porogen in an amount of 0.1 wt.% to about 25 wt.%. In some embodiments, the amount of the sacrificial porogen is from about 0.5 wt.% to about 20 wt.%. In some embodiments, the amount of the sacrificial porogen is from about 1 wt.% to about 15 wt.%. In some embodiments, the sacrificial porogen has a particle size is from about 0.5 pm to about 250 pm. In some embodiments, the particle size is from about 1 pm to about 100 pm. In some embodiments, the particle size is from about 5 pm to about 50 pm.

[0023] In some embodiments, the lithium extracting composition comprises a single -pellet crush strength of at least 5 LBF. In some embodiments, the crush strength is at least 10 LBF.

[0024] In some embodiments, the lithium extracting composition comprises a bulk pellet bed crush strength of at least 33 psi and up to 50 psi with no generation of fines.

[0025] In some embodiments, the lithium extracting composition comprises an attrition resistance that generates only less than 1 % fines upon exposure to a standard attrition test.

[0026] In some embodiments, the sorbent composition is prepared in a controlled conditions and addition mode of polymer and water to the LDH powder, such as spraying through one port or multiple ports across thepelletizer, to have stronger pellets and higher porosity within the pellets to increase working capacity of the sorbent for lithium extraction from brine.

[0027] In some embodiments, the sorbent composition is prepared using a specific type of granulation / pelletization equipment, such as pin-mixer or rotary drum pelletizer or combination of both, to have stronger pellets and higher porosity within the pellets to increase working capacity of the sorbent for lithium extraction from brine.

[0028] In some other embodiments, controlled microporosity are created within the pellets by addition of compound or compounds as sacrificial porogens during granulation process that are not soluble during granulation step. Once the pellets are dried, these porogens will be removed from the pellets leaving a controlled porous structure within the pellets that will increase working capacity of the sorbent for lithium extraction from brine.

[0029] In some embodiments, the sacrificial porogens may be removed by dissolution in water at conditions different than granulation step, or in readily available solvent such as methanol or ethanol or acetone. Some examples of these porogens are: mannitol; erythritol; Pluronic also known as Poloxamer that is a synthetic, non-ionic triblock copolymer composed of polyethylene oxide (PEO) and polypropylene oxide (PPO); low-molecular weight polyethylene glyocol (PEG) for example PEG 1000, all of which are partially soluble in water or alcohol.

[0030] In other embodiments, the sacrificial porogen is Shellac, Rosin, Camphor or Zein (corn protein) that are insoluble in water but soluble in ethanol. Synthetic similar resins such as ethyl cellulose may also be used.

[0031] In another embodiments, the sacrificial porogen is ammonium bicarbonate.

[0032] In some embodiments, particle size range of the sacrificial porogen material is from 5 to 50 micrometers. In some embodiments, the amount of sacrificial porogen varies between 1% to 15% of LDH powder.

[0033] In still another aspect, the present disclosure provides compositions prepared using the method described herein.

[0034] In yet another aspect, the present disclosure provides methods of extracting lithium from a composition comprising treating a solution comprising lithium with a composition described herein. In some embodiments, the lithium is a lithium ion.

[0035] In one aspect, the present disclosure uses partially purified lithium chloride solution produced in Direct Lithium Extraction (DLE) process, to synthesize LDH powder, instead of using commercially available lithium chloride solids. Alternatively, the lithium chloride solution can be purchased from another producer at a concentration ranging between 1 to 50 wt.%.

[0036] Other objects, features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specificexamples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

[0038] Figure 1 shows a 10 minute load and elution cycles using granulated LDH with methacrylate binders.

[0039] Figure 2 shows a 10 minute load and elution cycles using granulated LDH with styrene acrylic binders.DETAILED DESCRIPTION

[0040] The present disclosure relates to solid sorbents designed for efficient extraction of lithium from brines. These sorbents offer an approach to lithium extraction, providing enhanced selectivity, capacity, and recyclability compared to traditional methods. By employing specific chemistries and structures, the sorbents efficiently capture lithium ions from brine solutions while minimizing interference from other ions. Furthermore, the sorbents exhibit robustness and durability, enabling multiple cycles of extraction without significant loss of performance. The present disclosure represents a promising advancement in lithium extraction technology, offering economic and environmental benefits for the growing demand in lithium-ion battery production and other applications. Additionally, the present disclosure relates to compositions that result in an increased lithium capacity as measured as mg of lithium per g of absorbent. These and more details are provided belowI. Sorbent

[0041] The present disclosure relates to agglomeration methods by utilizing polymeric binders to enhance the interparticle cohesion of lithium aluminum layered double hydroxide (Li / Al-LDH). This approach fortifies the framework of the powder sorbent, enabling it to withstand the rigors of the column adsorption process. This combination of component results in a high-capacity sorbent pellets that can be used for lithium extraction with one or more desirable mechanical properties such as mechanical strength and attrition resistance against compression and shear during its production and handling and usage inside adsorption equipment while extracting lithium from brines.

[0042] The inclusion of polymeric binders addresses key challenges encountered during the adsorption process, such as maintaining structural integrity and preventing particle disintegration. This technique improves not only the mechanical strength of the sorbent but also its overall performance and longevity. Through meticulous optimization of the agglomeration process, the presently described lithium sorbent has superior stability and efficiency.

[0043] The polymers used for agglomeration are emulsified water-insoluble copolymers, specifically acrylic and styrene-acrylic copolymers, with variable solids by weight percentages, glass transition temperatures (Tg), pH, and viscosity. These polymers cure at temperatures below 60 °C, making them ideal for the agglomeration process of Li / Al-LDH. Furthermore, the absence of additives in these polymer structures ensures their suitability at high temperatures, as additives could diffuse into the solution and adversely affect the polymer structure. The present compositions described herein may show resistance to temperatures such that it may be used in high temperature separations. For example, the present composition may resist degradation at a temperature below 80 °C, 100 °C, 125 °C, 150 °C, or 200 °C.

[0044] The use of these polymeric binders significantly improves the mechanical strength of the sorbent, ensuring it remains intact during the adsorption process. Li / Al-LDH agglomerated with these polymers shows excellent lithium adsorption performance due to the hydrophilicity of the polymers, which enhances lithium pore diffusion into the active sites of the sorbent.

[0045] The agglomerated sorbents exhibit good adhesion, flexibility, and abrasion resistance, alongside outstanding low-temperature film formation. The pellets formed with these binders may demonstrate physical strength exceeding 5 lbs in a single-pellet crush test and 50 psi strength in a bed crush test. These polymers are tunable, allowing for easy adjustment of the copolymer ratios to meet specific requirements. The sorbents may comprise less than 5%, 4%, 3%, 2%, 1%, or 0.5% of water or solvent.A. Lithium Aluminum Layered Double Hydride

[0046] The present method uses lithium aluminum layered double hydrides as the main extractant for lithium ions. The structure of Li / Al LDHs is a two-dimensional structure formed by the insertion of lithium ions into ordered octahedral spaces in the A1(OH)3 layer. In order to balance the charge, both monovalent anions such as Cl" and water molecules are associated with structure. In the layers of Li / Al LDHs, Al3+occupy two-thirds of the octahedrons vacancies generated by close-packed metal-oxygen octahedral layers. The remaining vacancies with radius of ca. 0.70 A are filled by Li+(~0.68 A). These vacancies created from the deintercalation of primordial Li+during the desorption process serve as Li+active sorption sites with high selectivity. In particular a wide range of monovalent anions may be used in the Li / Al LDHs such as halides, especially chloride, phosphate, sulfate, and nitrate. In particular, chloride is commonly used to balance the charge of the complex.

[0047] The present disclosure relates to formation of the Li / Al LDH through the addition of a lithium salt and an aluminum salt in the presence of strong base. In some aspects, each of these salts may be an aluminum or lithium salt with the appropriate counter ion to balance the charge of the composition. For example, the aluminum or lithium salt may each or may both be halide salts. The method comprises using a strong base such as a hydroxide. The present method may relate to the use of a strong base such as an alkali metal hydroxide such as sodium or potassium hydroxide. The addition of the aluminum and lithium salts may be added in any order, but the strong base is added after the aluminum and lithium salts. The resultant Li / Al LDH precipitates out of solution and the reaction is exothermic producing heat as the reaction proceeds. This reaction may be run in a protic solvent such as water or alcohol or ketone. In some embodiments, the method is run in water such as deionized water.

[0048] Even though in most cases commercially available lithium chloride solids may be used to produce LDH, partially purified lithium chloride solution produced in Direct Lithium Etraction (DLE) process may be used, for which LDH sorbent disclosed here is used to prepare. Additionally, lithium chloride solution may be also purchased from another producer at a concentration ranging between 1 to 50 wt.%. Either of these methods will reduce the cost of LDH production significantly.

[0049] The method may also further comprise one or more filtration steps. The filtration steps may comprise one, two, three, four, five, or six filtration steps. In particular, the filtration step may be two, three, or four consecutive filtration steps. Between filtration steps, a re-pulping of cake in water or another solvent may be required. The filtration step may comprise using a belt filtration, a drum filter, a disc filter, vacuum or pressure filtration, hyper-baric filtration or through centrifugation. During the filtration step, the sorbent maybe admixed with a coagulant or flocculant. A coagulant or flocculant or clarifying agent is an agent that causes the induction of floc or larger aggregates. Coagulants can be multivalent cations such as aluminum, iron, calcium, or magnesium. The flocculants may be cationic, anionic, or neutral organic polymers. Additionally, polyacrylamides may be used a polymeric flocculants. Some non-limiting examples of coagulants include alum, aluminum chlorohydrate, aluminum sulfate, calcium oxide, calcium hydroxide, iron(II) sulfate, iron(III) chloride, sodium aluminum, sodium silicate. Some non-limiting example of anionic flocculants include anionic polyacrylamides and their copolymers with varying molecular weight and charge densities, Poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), Poly(styrene sulfonic acid) based flocculants, Poly(vinyl alcohol-co-vinyl acetate) based flocculants, Some non-limiting examples of cationic flocculants are poly(DADMAC) polydiallyldimethylammonium chloride, cationic polyacrylamindes and copolymers such as Poly(acrylamide-diallyldimethylammonium chloride) (PAM-DADMAC), Poly (acrylamideacryloyloxyethyltrimethylammonium chloride) (PAM-AETAC), Poly(acrylamide- methacryloyloxyethyltrimethylammonium chloride) (PAM-METAC), Poly(acrylamide- acrylamidopropyltrimethylammonium chloride) (PAM-APTAC), Quaternary Ammonium polymers such asPoly(ethyleneimine) (PEI) and Poly(dimethylamine-epichlorohydrin). Some non-limiting examples of nonionic flocculants are Polyethylene oxide polymers and co-polymers (PEO), Polypropylene oxide polymers and co-polymers (PPO), and Polyvinylpyrrolidone polymers and copolymers (PVP). Some non-limiting examples of natural polymeric flocculants are carboxymethyl cellulose (CMC), starch, chitosan, isinglass, gelatin, guar gum, or alginate.

[0050] Additionally, the methods may comprise one or more drying steps that are performed before or after pelletization. The drying steps may be carried out using a tray dryer, a ribbon dryer, a paddle dryer, a conical screw dryer, or a thermal screw vacuum dryer. The drying steps may be performed either at atmospheric pressure or under a vacuum. Furthermore, the composition may be heated for a time period. The heat added to the composition may be from about 25 °C to about 150 °C, from about 30 °C to about 120 °C, from about 40 °C to about 100 °C, or from about 50 °C to about 80 °C. In some embodiments, the heat is a temperature from about 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45°C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 130 °C, 140 °C, 150 °C, to about 160 °C, or any range derivable therein.B. Polymers

[0051] In some aspects, the Li / Al LDHs may be further modified with one or more polymers. In particular, the polymers that are used are hydrophobic polymers such as styrene and acrylate polymers. In particular, the polymers used show hydrophobic character. Furthermore, the polymer may be selected based upon glass transition temperatures (Tg), pH, and viscosity of the polymer. For example, the polymer may be one having a Tgfrom about 0 °C to about 75 °C, from about 1 °C to about 50 °C, from about 5 °C to about 40 °C, or from about 10 °C to about 30 °C. In some embodiments, the polymer has a Tgfrom about 0 °C, 1 °C, 2.5 °C, 5 °C, 7.5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, to about 75 °C, or any range derivable therein.

[0052] In particular, the present compositions may comprise from about 1 % to about 80% by total weight of the composition of tire polymer. In some embodiments, the amount of the polymer is from about 2.5% to about 60%, from about 5% to about 50%, from about 10% to about 40%, or from about 15% to about 30%. The amount of polymer in the composition may be from about 1%, 2.5%, 5%, 7.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, to about 80%, or any range derivable therein.

[0053] The polymers used in the present disclosure may be polymerized using a radical polymerization process such as photolysis or thermal degradation to initiate the polymerization. These polymers may be further crosslinked with one or more crosslinking agents that undergo the same type of polymerization. For example, the polymers used herein may contain an amount of the cross linker in the polymer from about 1% to about 60%, from about 2.5% to about 40%, or from about 5% to about 30% of the total weight of the polymer.The amount of cross linker in the polymer is from about 1%, 2.5%, 5%, 7.5%, 10%, 12.5%, 15%, 17.5%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, to about 60%, or any range derivable therein.II. Methods of Preparing Sorbents

[0054] In some aspects, the present disclosure also provides methods of preparing the relevant compositions including obtaining a Li / Al LDH as described above and adding it in the presence of water and one or more polymeric binders comprising one or more monomers and optionally, one or more crosslinking reagents. This combination of elements is done in the presence of a mixing or agglomeration apparatus such as a pin mixer, disc pelletizer, pug mill, drum granulator, ribbon mixer, paddle mixer, tumbler mixer, emulsifier, drum mixer, static mixer, or planetary mixer.

[0055] After mixing, the composition may be pelletized. Pelletization can be done through any appropriate apparatus such as a continuous pin mixer, a pan pelletizer, a rotary drum pelletizer, a pellet machine, disc pelletizer, or an extruder. During or after pelletization, the composition may also be dried in order to remove excess solvent. The dryer can be in either direct or indirect configuration as well as either in co-current or counter-current mode. The solvent may be either an organic solvent, water, or combination of both. The solvent may be an alcoholic solvent such as methanol, ethanol, propanol, or butanol. The solvent may be a ketone solvent such as acetone. The addition of the solvent or water may be added through one or through two or more ports. In some embodiments, the compositions are mixed and pelletized without the use of an additional solvent. Furthermore, the composition may be heated for a time period. The heat added to the composition may be from about 25 °C to about 150 °C, from about 30 °C to about 120 °C, from about 40 °C to about 100 °C, or from about 50 °C to about 80 °C. In some embodiments, the heat is a temperature from about 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45°C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 130 °C, 140 °C, 150 °C, to about 160 °C, or any range derivable therein.

[0056] During the pelletization, the method may further comprise the use of one or more sacrificial porogens. Some non-limiting examples of sacrificial porogens include sugars or sugar alcohols such as mannitol, erythritol, or lactose, a water or solvent soluble polymer such as triblock copolymer like a Plutonic or polaxmer, wherein the blocks are polypropylene glycol or polyethylene glycol, or a low molecular weight (e.g. less than 1000 MW) polyethylene glycol, or organic compounds or polymers such as camphor or a resin such as rosin or shellac, and ammonium salts such as ammonium bicarbonate. The sacrificial porogen is added in an amount from about 0.1 wt.%, 0.25 wt.%, 0.5 wt.%, 0.75 wt.%, 1 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 12.5 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 17.5 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 22.5 wt.%, to about 25 wt.%, or any range derivable therein. The sacrificial porogen may have a particle size from about 0.1 pm, 0.5 pm, 1pm, 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm, 125 pm, 150 pm, 175 pm, 200 pm, to about 250 pm, or any range derivable therein.

[0057] In some aspects, the presently described methods may result in a composition that exists as one or more pellets. These pellets comprise an average diameter from 0.01 mm to about 50 mm, 0.05 mm to about 20 mm, 0.1 mm to about 10 mm, 0.25 mm to about 5 mm, or 0.5 mm to about 2 mm. The size of the pellets may be from about 0.01 mm, 0.05 mm, 0.1 mm, 0.25 mm, 0.5 mm, 0.75 mm, 1 mm, 2 mm, 2.5 mm, 3 mm, 4 mm, 5 mm, 7.5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 40 mm, to about 50 mm, or any range derivable therein.III. Definitions

[0058] The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0059] Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects or patients. When used in other contexts, the term “about” is used to indicate a value of ±10% of the reported value, preferably a value of ±5% of the reported value. It is to be understood that, whenever the term “about” is used, a specific reference to the exact numerical value indicated is also included.”

[0060] The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps.

[0061] A “repeat unit” is the simplest structural entity of certain materials, for example, frameworks and / or polymers, whether organic, inorganic or metal-organic. In the case of a polymer chain, repeat units are linked together successively along the chain, like the beads of a necklace. For example, in polyethylene, -[- CH2CH2-]n-, the repeat unit is -CH2CH2-. The subscript “n” denotes the degree of polymerization, that is, the number of repeat units linked together. When the value for “n” is left undefined or where “n” is absent, it simply designates repetition of the formula within the brackets as well as the polymeric nature of the material. The concept of a repeat unit applies equally to where the connectivity between the repeat units extends three dimensionally, such as in metal organic frameworks, modified polymers, thermosetting polymers, etc.

[0062] The above definitions supersede any conflicting definition in any reference that is incorporated by reference herein. The fact that certain terms are defined, however, should not be considered as indicative thatany term that is undefined is indefinite. Rather, all terms used are believed to describe the disclosure in terms such that one of ordinary skill can appreciate the scope and practice the present disclosure.V. EXAMPLES

[0063] The following examples are included to demonstrate preferred embodiments of the disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the disclosure, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the disclosure.Example 1: Preparation of Lithium Aluminum Layered Double HydrideA. Synthesis

[0064] 4.5 Kg of AICI3.6H2O (18.6389 mol, 1 equiv) and 562.9 g of LiCl.HiO (9.3194 mol, 0.5 equiv) were dissolved in 18 Kg of DI water with a mechanical stirrer. The concentration of Li+in solution should be around 0.4 M. The sequence of addition of AICI3.6H2O and LiCLH2O into the DI water is not important. The temperature of the water increases to ~40 °C upon slowly addition and dissolution of the salts. 2.236 Kg of NaOH (55.916 mol, 3 equiv) was dissolved in 4 Kg of water and added slowly to the solution of the AICI3.6H2O and LiCl.H2O while stirring. White lithium aluminum layered double hydroxide (Li / Al LDH) precipitated and temperature increased to ~ 65 °C (no external heat source) due to exothermic acid and base reaction. The suspension was stirred for 30 minutes after completion of adding the NaOH solution. After stirring the suspension for 30 minutes, 41 Kg of water was added and the suspension was stirred for another 15 min to make sure all the formed NaCl are dissolved. Adding water will help the filtration step to avoid forming the sticky cake. The stirring was turned off and the suspension was allowed to sit overnight to settle down all the solids. The next day, all the solids settled. The upper transparent aqueous layer was removed by a peristaltic pump and the remaining solids were filtered with a Buchner funnel and a Whatman grade GF6 filter paper with the help of diaphragm pump. After filtration, solids were transferred to glass dish and was put in the oven for drying at temperature not higher than 60 °C. The drying time depends on the thickness of the cake spread on the dish. The thinner the layer, the faster the drying time will be. After drying the solids, they were grinded to yield a powder with particle sizes less than 500 microns. The weight of dry ground powder was 2.8 Kg.B. Agglomeration i. Test 1

[0065] Fed 2,000 grams of (Li / ALLDH) into the hatch Pin Mixer with about 550 grams of a Styrene Acrylic copolymer binder. The binder is a styrene acrylic emulsion

[0066] Binder was added slowly in multiple additions with the Pin Mixer running for a few seconds after binder addition. This resulted in a uniform blend of mostly 0.5 - 2.0 mm pellets that appeared smooth and dense. Half of the wet pellets were put on a Pan Pelletizer and rotated to simulate a rotary dryer.

[0067] The discharge moisture from the pin mixer was measured at 28.9%. The pellets were dried in a static oven at 60 degrees Celsius for several hours. Average crush strength on the 3.0 mm pellets was 12.3 LBF. The attrition testing resulted in 6.1 % of material below 0.5 mm. ii. Test 2:

[0068] Fed 2,000 grams of (Li / AI-LDH) into the batch Pin Mixer with about 555 grams of Acrylic copolymer binder. The binder is an acrylic emulsion.

[0069] Binder was added slowly in multiple additions with the Pin Mixer running for a few seconds after binder addition. This resulted in a uniform blend of mostly 0.5 - 2.0 mm pellets that appeared smooth and dense. Half of the wet pellets were put on a Pan Pelletizer and rotated to simulate a rotary dryer.

[0070] The discharge moisture from the pin mixer was measured at 27.2%. The pellets were dried in a static oven at 60 degrees Celsius for several hours. Average crush strength on the 3.0 mm pellets was 10.8 LBF. The attrition testing resulted in 9.2% of material below 0.5 mm.

[0071] The composition in Test #1 and Test #2 were prepared and run through a load and elution cycles of lithium separated by the sorbent in Figures 1 and 2.C. Li Capacity Tested By Rotating Basket Reactor

[0072] The Li capacity was tested in rotating basket reactor of 1 liter capacity. Sorbent made by this method is tested against a known high quality commercially available one. The sorbent of two particle size ranges were tested, 0.3-1 mm and 0.5-2 mm.

[0073] Test method: 35g of adsorbent was placed in the 69 ml rotating cylindrical basket, with screen pore size of 100 pm to retain the sorbent pellets. The bed of adsorbent was exposed to 0.35 liter of synthetic brine for 10 minutes at 800 RPM rotation speed as loading step, followed by exposure to 0.35 liter of eluent for 10 minutes at 800 RPM rotation speed as elution step. The load-elution cycles were repeated 8 times and the amount of Li adsorbed and desorbed were calculated. The test was conducted at room temperature and 80C.Results and discussion:Table 1: Sorbent capacity tested in rotating basket reactor at room temperatureTable 2: Sorbent capacity tested in rotating bed reactor at 80 °C

[0074] Adsorbent made by the method showed higher capacity than the commercial ones at both testing temperatures and both size ranges. It suggested the Li adsorbent made in this method had higher Li adsorption and desorption dynamic capacity at room temperature and elevated temperature.D. Mechanical Test

[0075] The mechanical strength and physical durability of the adsorbent were evaluated using two standardized physical tests: the Attrition Test and the Bed Crush Test. Sorbent of two particle size ranges were tested, 0.3-lmm and 0.5-2 mm. i. Attrition Test

[0076] This test is according to IFDC S-116 test method for fertilizers, that is modified for this application. Approximately a few hundred grs of adsorbent was subdivided to a few 75 grs sub-samples as control and test samples using the cone and quarter method. In the test condition, 75 g of the sample was placed on a 0.5 mm sieve and dry-sieved for 5 minutes with the addition of 75 stainless steel beads (2g each, 7.88 mm diameter) to simulate mechanical attrition. For the control test, 75 g of the sample was placed on a 0.5 mm sieve and dry-sieved for 5 minutes without any beads. After sieving, the fines passing through the 0.5 mm mesh were collected and weighed for both control and test samples. The extent of the attrition was quantified by calculating the percentage of fines generated using the formula: Percent Fines = (Weight of Fines (<0.5 mm) / 75 g) x 100.

[0077] Higher percentage of fines formation indicated that the sorbent was prone to attrition, which would lead to long-term degradation and a shorter life time of the sorbent. ii. Bed Crush Test

[0078] This test is according to ASTM D7084 - 18, but it is slightly modified for this application. Approximately a few hundred grs of adsorbent was subdivided to a few 45 g sub-samples as control and test samples using the cone and quarter method. For both conditions, the test material volume was measured by a 50-ml graduated cylinder, tapped gently to settle, and the corresponding weight was recorded. In the control test, the measured volume of material was sieved through a 0.5 mm mesh for 1 minute without any applied pressure. For the bed crush test sample, the same volume of material was placed in a Bed Crush apparatus, where a compressive load was applied using a Mark-10 force gauge at either 100 Ibf or 150 Ibf for 30 seconds to generate 33 psi and 50 psi compression pressure, respectively. This method was used to simulate the exposure of the sorbent to pressure within the adsorption columns.

[0079] The compressed material was then sieved through a 0.5 mm mesh for 1 minute. Fines passing through the sieve (<0.5 mm) were collected, weighed, and used to calculate the percentage fines generated using the same method as described in Attrition Test.Table 3: Mechanical test results compared with commercial resin A

[0080] As shown in Table 3, adsorbents made in this method demonstrated higher mechanical strength. It had higher bed crush strength at two different sizes ranges, indicating they can maintain their integrity and performance under pressure in the adsorption columns, preventing fine generating that could lead to bed compaction and pressure buildup in the column. Adsorbent produced in our method had very low attrition%, but higher than the commercial sorbent in comparison. This may just be due to the commercial sorbent being already exposed to attrition during bulk packing, loading, transport, unloading and handling.Example 2: Large-scale demo production of LDH powder

[0081] Total of 1000 kg (dry basis) of LDH slurry was produced in two batches using a large-demo scale batch production plant. In each batch, 897 kg of AICI3.6H2O and 78.7 kg of LiCl.H2O were dissolved in 6340 kg of water in a 4000-gal jacketed agitated reactor. Temperature increased from 16 °C to 26 °C by dissolution of raw material. Once the mixture became clear, indicating complete dissolution of the raw material, a 50 wt% solution of sodium hydroxide was dosed to agitated solution to adjust the pH to 7.0 to 7.8, during which temperature increased to 42 °C. Total of 895 kg of 50 wt% sodium hydroxide was added. Using steam in the reactor jacket, mixture temperature increased to 65 °C and maintained for about one hour. Steam flow was stopped and using the cooling coil inside the reactor mixture was cooled gradually to about 45 °C.

[0082] Produced slurry was stored in a holding tank and was filtered using a batch pressure belt filter in multiple batches producing cakes with moisture contents of 50 to 80 wt%. Once entire slurry was filtered, the collected cake was re-slurried in about 2000 to 3000 kg water to wash away residual reactants and contaminants including sodium chloride. The slurry was filtered, and cake was re-slurried again in 1500 to 2000 kg of water. After filtration for the third time, the cake was dried in a batch tray dryer at 60 to 70 °C. The drying was done under atmospheric or vacuum conditions.

[0083] The final LDH product quality was checked. Moisture content, measured gravimetrically, was about 1 to 5 wt%. Molar ratio of Al: Li was calculated after analyzing the LDH powder using ICP and it was in the target 1.9 to 2.7 range, residual NaCl content, measured by ICP was less than 5 wt%.

[0084] The produced dried chunks of the LDH was milled using different milling methods, such as a Jet mill to produce fine LDH powder with size ranging 10 to 125 pm.

[0085] The effect of drying temperature of the LDH on its Li uptake capacity was also tested. Results show that drying temperature can be as high as 100 °C or even 140 °CA. Quasi-equilibrium LDH powder Li Adsorption Test

[0086] Adsorption and desorption capacity of produced LDH powder was tested using a tube-test method to determine quasi-equilibrium capacity of the LDH, that is an approximation of LDH isotherm capacity.

[0087] Test method: 5g of LDH powder was placed in a 50-ml test tube and treated with 45-ml of 50 °C DI water four times to remove intercalated lithium from the LDH structure. The tube tumbled on a roller for 10 min in each step and centrifuged to collect the supernatant. Concentration of lithium in the supernatants was measured by NMR or ICP in each of eluted samples as de-intercalation capacity. The eluted LDH inside the tube was then exposed to brine with 500 mg / L Li and tumbled on the roller for 30 min, after which it was centrifuged and Li concentration in supernatant was measured by NMR. The tube was tumbled for next 30 min and centrifuged again to measure Li concentration. After second step, the spent brine was replaced with fresh brine containing 500 mg / L Li and two-step tumbling and centrifugation was repeated and Li in the supernatant was measured after each 30 min. The loading capacity was calculated using initial Li concentration of brine, 500 mg / L, Li concentration of supernatant measured after 60 min and 120 min.

[0088] In some tests, after loading, the adsorbent was eluted in the same way as Li de-intercalation explained above and eluted capacity was calculated based on mass of LDH used, measurement of lithium concentration and volume of supernatant.

[0089] The eluted capacity of LDH, produced at the 1000 kg scale, before loading was 4.8 to 6.6 mg Li / gr LDH and loading capacity ranged between 6.65 to 8 mg Li / gr LDH. The capacity was satisfactorily high.Example 3: Large Demo-Scale Continuous Granulation to Produce Adsorbent Pellets

[0090] About 430 kg of produced and milled LDH in example above was used to produce adsorbent pellets. The granulation (or pelletization) process was run continuously using a continuous pin-mixer and rotary drum pelletizer at a throughput of 180-200 kg / h LDH powder. Acrylic copolymer binder and water dosed continuously into the pin-mixer to form the wet pellets. Total consumed binder was 105 kg and water was 89-103 kg. The wet pellets discharged from pin-mixer were further pelletized to improve their mechanical properties and spherical shape in a rotary drum pelletizer. Produced wet spherical pellets in the rotary drum pelletizer were dried using flue gas produced from burning liquid fuel or natural gas working as a direct-contact rotary drum dryer. The flue gas and wet pellets were contacted in direct (as this example) or can be contacted in an indirect rotary drum dryer.

[0091] While gas and pellet flows can be counter-current or co-current, in this example wet pellets and gas flows were in co-current configuration to have better temperature control and prevent overheating the pellets. Wet pellets were dried to target temperature of 65 °C to achieve moisture content of 3 to 5 wt%. Dried pellets were screened through different screen mesh sizes to have various size cuts ranging from 0.3 to 2.0 mm.

[0092] Bulk density of produced pellets was 770 to 790 kg / m3and tapped density was about 830-850 kg / m3.

[0093] Some of these pellets were used for continuous 3 -column bench and 3 -column pilot testing programs, explained below.A. Continuous Adsorption Column Tests - Bench Top

[0094] Adsorption performance and dynamic capacity of the produced adsorbent in the example above was tested in a three-column bench set-up that was run in lead-lag and elution merry-go-round configuration. Each column was 50-mm in diameter and filled with 330-mm of adsorbent to have a bed of 1.35 Liter of adsorbent bed in each column. Two sorbent particle size ranges of 0.3-1 mm and 0.5-2 nun were tested. Various loading flow rates for lead-lag columns in series and elution flow rates were tested. Example below is for the loading flow rate of 8 BV / hr (equivalent of 187.2 ml / min) and elution rate of 9 BV / hr (equivalent of 198.1 ml / min).

[0095] The feed brine with lithium concentration of 400-440 mg Li / L was pumped to column 1, as lead column and its effluent was directed to column 2, as lag column, to capture residual lithium remaining in the brine leaving the lead column. Lithium concentrations exiting the lead and lag column outlets were intermittently measured by NMR. The spent or delithiated brine was collected, and its composite concentration was measured at the end of each cycle, which ranged between 5 to 30 mg Li / L. The loading cycle was stopped when the concentration of lithium in the lag column outlet exceeded 15 to 30 mg Li / L. In parallel, column 3, that was the lead column in the previous cycle, was eluted with water to recover the adsorbed lithium from previous cycle. Once this cycle ended, the lag column (column 2) was used as in the lead column for the next cycle and eluted column (column 3) was used as lag column, while column 1 was eluted. This merry-go-round configuration continued to have re-producible and statistically meaningful data.

[0096] Table 4 shows the summary of results. As seen, the presently described claimed adsorbent had higher loading and eluting capacities than commercial adsorbent A in both size ranges.Table 4: Performance of Adsorbent - Continuous Bench Column TestsB. Continuous adsorption column tests - Pilot for Scale-up purposes

[0097] For the scale-up purposes, adsorption performance and dynamic capacity of the produced adsorbent in the example above was further tested in a larger scale system, consisting of three-columns that were run in a similar lead-lag and elution merry-go-round configuration described above. Each column was 0.15 m in diameter and filled with 1.83 m of adsorbent to have about 30 Liter of adsorbent bed volume in each column. Adsorbent particle size range of 0.3-1 mm was tested. Various loading flow rates for lead-lag columns in series and elution flow rates were tested. Example below is for the loading flowrate of 8 to 12 BV / hr (equivalent of 4.0 to 6 L / min) and similar range of flow rate for elution rate. Capacities in the pilot-scale were similar to those observed on the bench scale.Table 5: Performance of Adsorbent - Continuous Pilot Column TestsC. Quasi-equilibrium Adsorbent Capacity Test

[0098] Similar to the tube test explained above for the LDH powder, adsorption and desorption capacity of the produced adsorbent was tested using the tube-test method to determine quasi-equilibrium capacity of the adsorbent.

[0099] Test method: See above, 5g of adsorbent was used.

[0100] The loading capacity of the adsorbent produced in the demo-scale, ranged between 5.7 to 7.3 mg Li / gr adsorbent. The loading capacity of the pellets in various sizes was only slightly lower than LDH powder itself, that was 6.65 to 8 mg Li / gr LDH, see above, which is attributed to mass of polymeric binder reducing gr of LDH per gr of adsorbent pellet. This indicates the adsorbent produced with this method had a good porosity, which did not cause undesired diffusion resistance through the pellets for 2- hrs contact time during quasit-equilibrium test. The capacity was satisfactorily high. In comparison, commercial adsorbent A of size 0.5-2.0 mm, had loading capacity of 4.98 mg Li / gr which was lower than 5.76 mg Li / gr of our adsorbent of same size.Table 6: Performance of adsorbent - Quasi equilibrium adsorbent capacity

[0101] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the disclosure may have focused on several embodiments or may have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications may be applied to the compositions and methods without departing from the spirit, scope, and concept of the disclosure. All variations and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the disclosure as defined by the appended claims.

Claims

CLAIMSWhat is claimed is:

1. A composition comprising:(A) a lithium aluminum layer double hydroxide; and(B) a polymer; wherein the composition comprises a uniform mixture of the lithium aluminum layer double hydroxide and the polymer.

2. The composition of claim 1, wherein an amount of the polymer is from about 5% w / w to about 50% w / w of the total weight of the composition.

3. The composition of either claim 1 or claim 2, wherein the amount of the polymer is from about 10% w / w to about 40% w / w of the total weight of the composition.

4. The composition according to any one of claims 1-3, wherein the amount of the polymer is from about 15% w / w to about 30% w / w of the total weight of the composition.

5. The composition according to any one of claims 1-4, wherein the composition comprises a plurality of pellets.

6. The composition of claim 5, wherein the plurality of pellets comprises a mixture of pellets with an average diameter of 0.05 mm to about 20 mm.

7. The composition of either claim 5 or claim 6, wherein the average diameter of the mixture of the pellets is from about 0.1 mm to about 10 mm.

8. The composition according to any one of claims 5-7, wherein the average diameter of the mixture of the pellets is from about 0.25 mm to about 5 mm.

9. The composition according to any one of claims 5-8, wherein the average diameter of the mixture of the pellets is from about 0.5 mm to about 2 mm.

10. The composition according to any one of claims 1-9, wherein the composition comprises less than 5% of solvent or water.

11. The composition of claim 10, wherein the composition comprises less than 2.5% of solvent or water.

12. The composition of either claim 10 or claim 11, wherein the composition comprises less than 1% of solvent or water.

13. The composition according to any one of claims 1-12, wherein the polymer is a copolymer.

14. The composition according to any one of claims 1-12, wherein the polymer is an acrylate copolymer.

15. The composition of claim 14, wherein the acrylate copolymer is a styrene copolymer.

16. The composition of claim 14, wherein the acrylate copolymer is a polymer comprising two or more different acrylate monomers.

17. The composition according to any one of claims 1-16, wherein the polymer has a Tgfrom about 1 °C to about 50 °C.

18. The composition of claim 17, wherein the Tgis from about 5 °C to about 40 °C.

19. The composition of either claim 17 or claim 18, wherein the Tgis from about 10 °C to about 30 °C.

20. The composition according to any one of claims 1-19, wherein the polymer comprises one or more cross linking units.

21. The composition according to any one of claims 1-20, wherein the polymer comprises an amount of crosslinking from about 5% to about 60% of the total polymer.

22. The composition of claim 21, wherein the amount of crosslinking is from about 10% to about 50% of the total polymer.

23. The composition of either claim 21 or claim 22, wherein the amount of crosslinking is from about 20% to about 40% of the total polymer.

24. The composition according to any one of claims 1-23, wherein the composition is resistant to thermal degradation at a temperature before 150 °C.

25. A method of preparing a lithium extracting composition comprising admixing a lithium aluminum double layer hydroxide composition with a polymer to form a lithium extracting composition.

26. The method of claim 25, wherein the lithium aluminum double layer hydroxide composition with a polymer is a composition according to any one of claims 1-24.

27. The method of claim 25, wherein the lithium aluminum double layer hydroxide composition is prepared using a lithium chloride solution that was prepared using a direct lithium extraction process.

28. The method of claim 27, wherein the lithium chloride solution prepared in a direct lithium extraction process.

29. The method of claim 27, wherein the lithium chloride salt comprises one or more impurities.

30. The method of either claim 27 or claim 29, wherein the lithium chloride salt is present in a concentration from about 1 wt.% to about 50 wt%.

31. The method according to any one of claims 25-30, wherein the method further comprises a filtration step.

32. The method of claim 31, wherein the filtration step comprises processing the lithium extracting composition through a belt filtration, a drum filter, a disc filter, or centrifugation to obtain a filtered lithium extracting composition.

33. The method of either claim 31 or claim 32, wherein the method comprises dissolving or suspending the filtered lithium extracting composition two, three, four, or five times and subjecting to a second, third, fourth, or fifth filtration.

34. The method of claim 33, wherein the second, third, fourth, or fifth filtration is processed through a belt filtration, a drum filter, a disc filter, or centrifugation.

35. The method according to any one of claims 27-34, wherein the filtration step comprises admixing the lithium extracting composition with a flocculant.

36. The method of claim 35, wherein the flocculant is a cationic flocculant.

37. The method of claim 35, wherein the flocculant is an anionic flocculant.

38. The method of claim 35, wherein the flocculant is a neutral flocculant.

39. The method according to any one of claims 25-38, wherein the method further comprises a drying step.

40. The method of claim 39, wherein the drying step is performed at a temperature from about 25 °C to about 150 °C.

41. The method of claim 40, wherein the temperature is from about 30 °C to about 120 °C.

42. The method of claim 41, wherein the temperature is from about 400C to about 100 °C.

43. The method of either claim 41 or claim 42, wherein the temperature is from about 50 °C to about 80°C.

44. The method according to any one of claims 39-43, wherein the drying step is caried out in a batch vacuum dryer.

45. The method of claim 44, wherein the drying step is earned out using a tray dryer, a ribbon dryer, a paddle dryer, conical screw dryer, or thermal screw vacuum dryer.

46. The method according to any one of claims 25-45, wherein the polymer is added in two or more portions to the lithium aluminum double layer hydroxide composition.

47. The method according to any one of claims 25-46, wherein an amount of the polymer is from about 5% w / w to about 50% w / w of the total weight of the composition.

48. The method according to any one of claims 25-47, wherein the amount of the polymer is from about 10% w / w to about 40% w / w of the total weight of the composition.

49. The method according to any one of claims 25-48, wherein the amount of the polymer is from about 15% w / w to about 30% w / w of the total weight of the composition.

50. The method according to any one of claims 25-49, wherein the method further comprises a curing step.

51. The method according to any one of claims 25-50, wherein the polymer comprises an amount of crosslinking from about 5% to about 60% of the total polymer.

52. The method of claim 51, wherein the amount of crosslinking is from about 10% to about 50% of the total polymer.

53. The method of either claim 51 or claim 52, wherein the amount of crosslinking is from about 20% to about 40% of the total polymer.

54. The method according to any one of claims 25-53, wherein the method further comprises a pelletizing step to form a pelletized lithium extracting composition.

55. The method of claim 54, wherein the pelletizing step comprises a continuous pelleting run.

56. The method of either claim 54 or claim 55, wherein the pelletizing step comprises a continuous pin mixer.

57. The method according to any one of claims 54-56, wherein the pelletizing step further comprises a rotary drum pelletizer.

58. The method according to any one of claims 54-57, wherein the pelletizing step further comprises one or more pellet drying steps.

59. The method of claim 58, wherein the pellet drying steps comprise using a dryer in direct configuration.

60. The method of claim 58, wherein the pellet drying steps comprise using a dryer in indirect configuration.

61. The method according to any one of claims 58-60, wherein the pellet drying steps comprise using a dryer in a co-current mode.

62. The method according to any one of claims 58-60, wherein the pellet drying steps comprise using a dryer in a counter-current mode.

63. The method according to any one of claims 58-62, wherein the pellet drying steps comprise using a rotary drum dryer, fluidized bed dryer, tray dryer, or a continuous turbo tray dryer.

64. The method according to any one of claims 54-63, wherein the pelletizing step further comprises using a second pelletizer.

65. The method of claim 64, wherein the second pelletizer is disc pelletizer or a rotary drum pelletizer.

66. The method according to any one of claims 54-65, wherein the pelletizing step comprises adding one or more compounds into a pelletizer.

67. The method of claim 66, wherein the one or more compounds are added into the pelletizer through one port.

68. The method of claim 66, wherein the one or more compounds are added into the pelletizer through two or more ports.

69. The method of claim 68, wherein the two or more ports are two, three, four, or five ports.

70. The method according to any one of claims 66-69, wherein the one or more compounds are a solvent.

71. The method of claim 70, wherein the solvent is water.

72. The method of claim 70, wherein the solvent is an alcoholic or ketone solvent.

73. The method of claim 72, wherein the alcoholic or ketone solvent is methanol, ethanol, propanol, butanol, or acetone.

74. The method of claim 54-73, wherein the pelletizing step further comprises adding a sacrificial porogen during the pelletizing step.

75. The method of claim 74, wherein the sacrificial porogen is a sugar alcohol.

76. The method of claim 74, wherein the sacrificial porogen is a water or alcohol soluble organic polymer.

77. The method of claim 76, wherein the water or alcohol soluble organic polymer is triblock copolymer of polyethylene glycol and polypropylene glycol.

78. The method of claim 76, wherein the water or alcohol soluble organic polymer is polyethylene glycol.

79. The method of claim 74, wherein the sacrificial porogen is an organic compound.

80. The method of claim 79, wherein the organic compound is camphor.

81. The method of claim 74, wherein the sacrificial porogen is resin.

82. The method of claim 81, wherein the resin is rosin or shellac.

83. The method of claim 74, wherein the sacrificial porogen is ammonium bicarbonate.

84. The method according to any one of claims 74-83, wherein the pelletizing step comprises adding the sacrificial porogen in an amount of 0.1 wt.% to about 25 wt.%.

85. The method of claim 84, wherein the amount of the sacrificial porogen is from about 0.5 wt.% to about 20 wt.%.

86. The method of either claim 84 or claim 85, wherein the amount of the sacrificial porogen is from about 1 wt.% to about 15 wt.%.

87. The method according to any one of claims 74-86, wherein the sacrificial porogen has a particle size is from about 0.5 pm to about 250 pm.

88. The method of claim 87, wherein the particle size is from about 1 pm to about 100 pm.

89. The method of either claim 87 or claim 88, wherein the particle size is from about 5 pm to about 50 pm.

90. The method according to any one of claims 25-89, wherein the lithium extracting composition comprises a single-pellet crush strength of at least 5 LBF.

91. The method according to any one of claims 25-90, wherein the single-pellet crush strength is at least 10 LBF.

92. The method according to any one of claims 25-91, wherein the lithium extracting composition comprises a bed crush strength of at least 33 psi and higher such as 50 psi.

93. A composition prepared using the method according to any one of claims 25-92.

94. A method of extracting lithium from a composition comprising treating a solution comprising lithium with a composition according to any one of claims 1-19 and 93.

95. The method of claim 94, wherein the lithium is a lithium ion.

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