WO2024035944A1

WO2024035944A1 - Extraction of critical minerals using polyanions

Info

Publication number: WO2024035944A1
Application number: PCT/US2023/030099
Authority: WO
Inventors: Reza Barati GHAHFAROKHI
Original assignee: University Of Kansas
Priority date: 2022-08-12
Filing date: 2023-08-11
Publication date: 2024-02-15

Abstract

A method of extracting a critical mineral cation from a composition is provided. The composition can be any type of composition having critical minerals. The method can include contacting a polyanion to a composition, wherein the composition includes the critical mineral cation. The method includes complexing the critical mineral cation with the polyanion to form a polyanion/cation complex in the composition. The method can include separating the polyanion/cation complex from the composition. The method can also include releasing the critical mineral cation from the polyanion.

Description

EXTRACTION OF CRITICAL MINERALS USING POLYANIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims priority to U.S. Provisional Application No. 63/397,624 filed August 12, 2022, which provisional is incorporated herein by specific reference in its entirety.

BACKGROUND

Field:

[0002] The present disclosure relates to polyanions (e.g., anionic poly electrolytes) and/or materials prepared from poly anions for use in extraction of critical minerals (e.g., lithium) from various sources, whether a natural, industrial, or recyclable source.

Description of Related Art:

[0003] Critical minerals are essential natural resources that play a crucial role in various industries, particularly in the domains of technology, energy, and defense. These minerals are considered critical due to their significant economic and strategic importance, as well as their limited availability and potential supply chain vulnerabilities. Critical minerals may be defined under the US Department of Energy (DOE) designation, which at the time of filing of this application includes aluminum, cobalt, copper, dysprosium, electrical steel, fluorine, gallium, iridium, lithium, magnesium, natural graphite, neodymium, nickel, platinum, praseodymium, terbium, silicon, and silicon carbide, where strontium also may be considered a critical even though it is not on the official list.

[0004] Lithium is one of the important critical minerals. Lithium ion extraction is a crucial process in the production of lithium-ion batteries, which are widely used in portable electronics, electric vehicles, and renewable energy storage systems. These lithium-ion batteries have proven to be highly efficient and reliable power sources. However, the extraction of lithium ions is not without its challenges, both technical and environmental.

[0005] Lithium ion (Li+) is a positively charged ion, belonging to the alkali metal group on the periodic table. It has the lowest density of all metals, making it highly lightweight. Lithium ions exhibit exceptional electrochemical performance, producing high energy density and extending battery life, which is the key reason for their wide application. Additionally, lithium is highly reactive and can store and release large amounts of energy with remarkable efficiency. [0006] One prominent and available source of critical minerals is production water from oil and gas, as well as carbon capture, utilization and storage (CCUS) and geothermal projects. These waters have the tendency to contain critical minerals in large enough concentrations that can be economically feasible to separate them along with other minerals.

[0007] However, despite the wide availability of lithium, concerns about its supply chain have emerged. The mining and refining processes required to extract lithium can be economically and environmentally challenging. Ensuring a secure and sustainable supply of critical minerals like lithium has become a priority for many countries, especially those heavily reliant on technologies and industries that require these resources. Efforts are being made to diversify the sources of lithium and invest in advanced extraction technologies to optimize production. Additionally, recycling and recovery initiatives are being promoted to minimize resource depletion and waste generation.

[0008] Polyelectrolytes are polymers with charged functional groups along their molecular chains. Polyanions are a significant class of chemical compounds of polyelectrolytes that are characterized by multiple negatively charged ions (or atoms) within their structure. These highly versatile anionic polymers play a crucial role in various scientific fields, including chemistry, materials science, and biology. The preparation of polyanions involves the combination of elements or molecules that can donate multiple electrons, leading to the formation of several negatively charged ions on the polymer backbone, where each monomer can have at least one negative charge. Common methods for producing polyanions include chemical reactions, such as redox reactions, where an element undergoes oxidation, resulting in the formation of multiple negatively charged species.

SUMMARY

[0009] In some embodiments, a method of extracting a critical mineral cation from a composition is provided. The method can include contacting a polyanion to a composition, wherein the composition includes the critical mineral cation. The critical mineral cation can be complexed with the polyanion to form a polyanion/cation complex in the composition, and the polyanion/cation complex can be separated from the composition. The critical mineral cation can be released from the polyanion. In some aspects, the critical mineral cation is a metal ion that is a monovalent ion, a divalent ion, or a trivalent ion. In some aspects, the critical mineral ion is lithium. In some aspects, the critical mineral ion is strontium. In some aspects, the critical mineral ion is selected from the group consisting of aluminum, cobalt, fluorine, gallium, iridium, lithium, magnesium, natural graphite, neodymium, nickel, platinum, praseodymium, terbium, silicon, and bromine, or combinations thereof.

[0010] In some embodiments, the polyanion is an anionic dextran, anionic cellulose, anionic polysaccharide, negative polymers, or combinations thereof. In some aspects, the polyanion is dextran sulfate, dextran phosphate, carboxymethyl cellulose, sodium alginate, pectin, kappa carrageenan, iota carrageenan, lambda carrageenan, hyaluronic acid, fucoidan, polystyrene sulfonate, polyvinyl sulfonic acid, polyacrylic acid, polymethyl acrylic acid sodium salt, or 3-sulfopropyl methacrylate potassium salt, or combinations thereof.

[0011] In some embodiments, the polyanion is conjugated to a particle, bead, substrate, flow path surface, or other body. In other embodiments, the polyanion is not bound to another body.

[0012] In some embodiments, the composition is a processing solution or is prepared from a processing solution, or waste from an industrial facility. The method can include obtaining the composition from an industrial facility, an oil processing facility, a gas processing facility, a geothermal energy facility, or from a carbon capture, utilization and storage (CCUS) facility.

[0013] In some embodiments, the complexing is performed under mixing. In some aspects, the polyanion has an entrapment efficiency for the critical mineral cation of at least about at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

[0014] In some embodiments, the separating is performed by centrifugation, precipitation, filtration or charged membrane separation.

[0015] In some embodiments, the releasing is by changing pH, salinity, or composition of the separated polyanion/ion complex. In some aspects, the method includes separating the released critical mineral cation from the polyanion, and collecting the released critical mineral cation without the polyanion.

[0016] The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description. BRIEF DESCRIPTION OF THE FIGURES

[0017] The foregoing and following information as well as other features of this disclosure will become more fully apparent from the following description and appended claims, taken in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be considered limiting of its scope, the disclosure will be described with additional specificity and detail through use of the accompanying drawings.

[0018] Fig. 1 includes a flow chart of a method for extracting a critical mineral cation from a source material.

[0019] Fig. 2A includes an illustration of a schematic representation of a polyanionic particle (e.g., formed by crosslinking polyanion) that can be used for extracting a critical mineral cation; however, the particle may have an irregular shape such as a strand with or without crosslinking, where crosslinking can form a 3D conformation of a particle.

[0020] Fig. 2B includes an illustration of a schematic representation of a polyanionic monolayer formed from a plurality of poly anionic polymers.

[0021] Fig. 2C includes an illustration of a poly anionic multilayer, each layer formed by a plurality of poly anionic polymers.

[0022] Fig. 2D includes an illustration of a polyanion linked to a substrate.

[0023] Fig. 3 includes a graph illustrating a calibration curve for lithium concentration.

[0024] Fig. 4 includes a graph illustrating a calibration curve for dextran sulfate (DS) concentration.

[0025] Fig. 5 includes a graph illustrating the particle size versus final dextran sulfate concentration for different systems.

[0026] Fig. 6A includes an illustration of a schematic representation of a polyanionic polyelectrolyte, where dextran sulfate is provided as an example.

[0027] Fig. 6B includes an illustration of a schematic representation of a polyanionic monolayer.

[0028] Fig. 6C includes an illustration of a polyanionic multilayer.

[0029] Fig. 6D includes an illustration of a polyanion linked to a substrate.

[0030] The elements and components in the figures can be arranged in accordance with at least one of the embodiments described herein, and which arrangement may be modified in accordance with the disclosure provided herein by one of ordinary skill in the art. DETAILED DESCRIPTION

[0031] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.

[0032] Generally, the present technology relates to using anionic polyelectrolytes (e.g., polyanions) for binding with critical elements, such as lithium, for extraction purposes. The polyanion can be present in compositions and systems adapted for extraction of the critical element from a source material. The polyanion can use the negative charges to electrostatically associate with cations of the critical elements to form complexes thereof. The complexes can then be separated out of the extraction system, such as by centrifugation, precipitation or filtration. Then, the critical element ions can be pulled from the polyanions, such as by adding counter anions to compete with and dissociate the poly anions from the critical element cations, such a lithium.

[0033] Polyelectrolytes are highly important compounds in various fields, including environmental remediation and waste management. The complex formation between critical mineral ions and polyelectrolytes holds great promise in the realm of industrial waste management and the synthesis of secondary compositions. Techniques for critical mineral ions to complex with polyelectrolytes, particularly polyanions complexing with cationic critical minerals, involve several steps. The first step typically involves identifying different sources of the critical mineral (e.g., lithium), whether in aqueous solutions, solid residues, or wastewater from industrial processes. Once the source is determined, the polyanion is selected based on its ability to form stable complexes with lithium or other critical mineral cations, specifically polyanions are used for lithium cations. To initiate complex formation, the polyanions are introduced to the composition containing the critical mineral cations. The polyanions interact and bind to the critical mineral cations, forming stable complexes. This complex formation can occur through various mechanisms, including electrostatic interactions between the positive charges of the critical mineral cation and each anionic polyelectrolyte polymer. The choice of polyelectrolyte and the conditions under which complexation is carried out strongly influence the efficiency and stability of the resulting complex.

[0034] Polyanions (e.g., negatively charged polyelectrolytes) and their complexes with overall negative charge tend to electro-sterically attract or entrap cationic critical minerals, such as lithium, strontium, and other metal cations. These complexes, which are with the polyanion and cationic critical mineral, make the cationic critical mineral in a form of a particle (e.g., nanoparticle) that is suitable for separation via centrifugation, precipitation, filtration, or charged membranes. Such complexes can also be easily disassembled by changing the pH or salinity of the environment, or adding anionic counter ions. Formulated and optimized polyanions can be mixed with brines or other source materials that carry lithium and other divalent or trivalent cationic critical minerals to generate nanoparticle complexes that can be easily separated out from the source or working composition, and disassembled for release of both polyanions and cationic critical minerals.

[0035] The charge of polyanions enables them to readily participate in electrostatic interactions with positively charged species, such as cations, metal ions, or positively charged regions on proteins or other macromolecules. These interactions can contribute to the stabilization of molecular structures, the formation of complexes, and the regulation of various biological processes.

[0036] In industrial waste management, the ability to complex and capture lithium ions using polyanions provides an effective solution for the removal and recovery of valuable lithium resources. By introducing polyanions to waste streams, the polyanions can complex with the lithium ions present in the waste, allowing for their subsequent separation and potential reuse. This process not only helps mitigate the environmental impact of industrial waste but also offers the opportunity for recycling and resource recovery.

[0037] Moreover, the complex formation between lithium ions and polyanions can also be utilized in the preparation of secondary compositions. By selectively capturing lithium ions using poly anions, the resulting complex can serve as a precursor for the preparation of useful materials. This approach provides a sustainable and economically viable method for obtaining lithium-based secondary compositions, which can find applications in diverse fields, including energy storage, catalysis, and materials science. [0038] In the context of lithium ion extraction, poly anions are employed as ionically - associating ligands to aid the selective binding of lithium ions, thereby facilitating their separation from other metals present in the source material. In lithium ion extraction, polyanions play a significant role by forming strong complexes with lithium ions. Polyanions show a strong affinity for lithium ions due to the electrostatic interaction between their negative charge and the positive charge of the lithium ion.

[0039] Fig. 1 shows an example of a method 100 for extracting critical mineral cations from a composition, which can be performed using a polyanion. The method 100 includes a step of providing a poly anion composition at block 102. The method 100 includes a step of contacting the polyanion with a composition containing a critical mineral at block 104. The method 100 includes a step of allowing for complexing of the critical mineral cation with the polyanion to form a polyanion/cation complex at block 106. The method 100 includes a step of separating the complex from the composition at block 108. The method 100 includes a step of releasing the critical mineral cation from the polyanion at block 110. Additional steps or actions may be added to the method 100, as generally known in the arts of polyanions, mixing, complex formation, complex separation, and complex dissociation into its constituent parts, such as those described herein.

[0040] In some embodiments, the method 100 of Fig. 1 can be used for extracting lithium ions from a composition, which can be performed using a polyanion. The method involves contacting the polyanion with the composition having the lithium ion, complexing the lithium ion with the polyanion to form a polyanion/cation complex, separating the complex from the composition, and releasing the lithium ion from the polyanion.

[0041] In some embodiments, the polyanion can be used for capturing and separating other critical mineral cations than lithium. Accordingly, the polyanion can be used for extraction of a metal cation, such as a monovalent cation, divalent cation, or trivalent ion, where specific examples include strontium, aluminum, cobalt, fluorine, gallium, iridium, lithium, magnesium, natural graphite, neodymium, nickel, platinum, praseodymium, terbium, silicon, and bromine, or critical minerals that are positively charged.

[0042] The source material can be a composition having lithium ions for extraction. Examples of the source material can be a processing solution or industrial wastewater obtained from various facilities. The complexing between the polyanion and metal cation can be performed under mixing, and the separation can be achieved through centrifugation, precipitation, filtration, or charged membrane separation. The released metal cation can be collected without the polyanion. The polyanion can be tailored with a range of anionic moieties in order to have an entrapment efficiency of at least a certain percentage. Accordingly, the molecular weight of the polyanion and the concentration or amount thereof can be modulated in accordance with the target metal cation.

[0043] Formulated and optimized polyanion complexes can be provided to be mixed with compositions having monovalent an multivalent ions, such as lithium and other monovalent ions (sodium, potassium, rubidium, cesium, francium), strontium and other divalent ions (beryllium, magnesium, calcium, barium, radium), or chromium and other trivalent ions (aluminum, iron [III], gold,) in order to generate nanoparticle complexes of poly anion and cation that can be easily separated from each other so that the ion can be removed.

[0044] To achieve this separation, various techniques such as precipitation, filtration, or the utilization of charged membranes can be employed. The negatively charged polyanions and their complexes exert an electro- steric attractive force or entrapment upon the targeted cations, thereby rendering them more amenable to separation. Notably, the polyanion/cation complexes can be readily disassembled, allowing for the liberation of both polyanions and cations. This disassembly can be accomplished through alterations in pH or salinity, commonly referred to as tonicity, such as with counter anions. The polyanion may be recycled and reused for further lithium ion (or other critical mineral cation) extraction.

[0045] There are several techniques that have been developed to facilitate the release of positive lithium ions from negative polyanions. Precipitation methods involve the addition of reagents to the complex in order to form insoluble compounds that can be easily separated, thereby facilitating the extraction of lithium. One way to release lithium from negative poly anions is by utilizing secondary compositions. These compositions can be designed to possess anions with a higher affinity towards lithium ions than the original polyanions. By introducing such secondary compositions, the lithium ions can be selectively captured and released from the polyanions, allowing for their separation and recovery. The complexes can also be subjected to different conditions, such as changes in pH or temperature, to disrupt the complex and release the lithium ions.

[0046] In some embodiments, the negatively charged polyanion can include anionic dextran like dextran sulfate or dextran phosphate, an anionic cellulose such as carboxymethyl cellulose, an anionic polysaccharide such as sodium alginate, pectin, kappa carrageenan, iota carrageenan, lambda carrageenan, hyaluronic acid, or fucoidan, negative polymers such as polystyrene sulfonate, polyvinyl sulfonic acid, polyacrylic acid, polymethyl acrylic acid sodium salt, or 3-sulfopropyl methacrylate potassium salt, or combinations thereof. In some aspects, the polyanion is dextran sulfate, dextran phosphate, carboxymethyl cellulose, or combinations thereof. However, it should be recognized that other polyanions of similar charge and characteristics can be used for extracting critical mineral cations.

[0047] In some embodiments, the polyanion can have an average molecular weight, such as Number average Molecular weight (Mn), Weight average molecular weight (Mw) and viscosity average molecular weight (Mv), suitable for being a capture agent for critical mineral cations. In some aspects, the average molecular weight can be at least 2 about kDa, at least about 5 kDa, at least about 10 kDa, at least about 20 kDa, at least about 30 kDa, or at least about 50 kDa.

[0048] In some embodiment, the system may or may not use an additional crosslinker in order to crosslink the polyanion. The crosslinker can be a glutaraldehyde, epoxy, isocyanate, or other. The crosslinking percent can range in an amount sufficient for forming particles, such as nanoparticles. For example, the crosslinking percentage can be from about 0% to about 10% of crosslinker, and can vary depending on the target goals of the polycation, from nanoparticles to layers.

[0049] In some embodiments, the polyanion can be formed into nanoparticles. The nanoparticles can be formed by crosslinking or other way to link the particles together.

[0050] In some embodiments, the polyanions can be formulated to as to form a particle 202 (Fig. 2A) a single layer 204 (Fig. 2B) or a multi-layer material 206 (Fig. 2C). This can be useful when the lithium source composition is passed through or over the single layer or multi-layer material. For example, this layered material can function as a barrier, flow surface, or membrane for capture of the lithium ions. In some aspects, mixed polymers can be used for forming a single layer or a multi-layer material before interacting with the target critical mineral. However, the polyanion can be formulated into the appropriate concentration.

[0051] In some embodiments, centrifugation, precipitation, filtration, and charged membrane separation are all effective techniques for separating complexes, including those formed by lithium ions and systems having only polyanions or both polyanions and polycations. These techniques utilize different physical principles to isolate the desired species, providing researchers with flexible options to meet their specific separation needs. Centrifugation, a widely used technique, relies on the application of centrifugal force to separate particles in a liquid according to their density. In the case of lithium ion-polyanion complexes, centrifugation could effectively separate them based on their different mass and buoyancy properties. By subjecting the complex solution to high speeds of rotation, the heavier complexes can be forced to sediment, while the lighter supernatant can be removed and collected.

[0052] In contrast, precipitation involves the formation of insoluble solid particles from a solution. By manipulating the solution’s chemical environment, researchers can induce the formation of a solid phase, effectively separating the lithium ion-polyanion complexes from the remaining solution. Subsequent filtration can then be used to isolate the precipitate. Filter membranes with specific pore sizes can selectively retain the complexes while allowing the clear filtrate to pass through, ensuring a high degree of separation and purity. [0053] Charged membrane separation, a technique leveraged when the separation is based on the electrical charge of the complex, can be employed to isolate lithium ion-polyanion complexes. This method uses a membrane with specific charge properties to selectively bind and retain one component of the complex, while allowing the other components to pass through. By manipulating the electrostatic interactions between the complex and the charged membrane, researchers can achieve a highly effective separation. The polyanions can be part of the charged membrane, such as being formed into the membrane, or can be attached to a membrane, which can form a charged membrane due to the charge of the polyanion.

[0054] In some embodiments, an extraction system can include a polyanion (e.g., dextran sulfate) with concentrations ranges of about 0.05% v/v to about 20% v/v, about 0.75% v/v to about 15% v/v, about 0.1% to about 10% v/v, about 0.5% v/v to about 5% v/v, about 0.75% v/v to about 2.5% v/v, or about 1% v/v.

[0055] In some embodiments, the polyanion can be formulated into a capture composition at the concentrations described herein at various pH values of 1-12. In some aspects, it can be desirable to have an acidic pH value. In other aspects, it can be desirable to have an alkaline pH value. In some aspects, the pH can range from 3-8, 4-7, or from 5-6.

[0056] In some embodiments, the polyanion capture compositions can be used to separate lithium from an aqueous composition (e.g., water) at a concentration of down to about 10 ppm, about 20 ppm, about 30, ppm, about 40 ppm, about 50 ppm, about 60 ppm, about 100 ppm, about 125 ppm, or about 150 ppm. [0057] In some embodiments, the polyanions can be formulated into a composition as the polyanion in solution, which is then interacted with the lithium containing source material. [0058] In some embodiments, the polyanions 208 may also be conjugated to a surface of a substrate 210 (e.g., membrane, bead, flow channel, separation member, column filer, etc.), as shown in Fig. 2D. As such, the polyanions 208 may be covalently linked to a substrate 210. The linkage can be by any linking agent, such as a crosslinking agent as described herein. The polyanion-bound membranes can be used to separate the target critical material (e.g., lithium) by injecting the source material through the membrane. The polyanion can be a negatively charged material that may be conjugated to a particle or other body. Alternatively, the Fig. 2D illustration can substitute the substrate with any type of body, such as a flow path surface (e.g., microfluidic channel), or other extraction substrate. For example, a column packing material may be used for the substrate so that the polyanions can function in the column for binding with the critical mineral.

[0059] As noted in Fig. 2D, some of the polyanions 208 appear to be longer than other polyanions 208. In part, this because of polydispersity in the molecular weight of the polyanion. Here, the polyanion 208 can have any desirable polydispersity.

[0060] In some embodiments, the polyanions can be formulated to as to form a polyelectrolyte chain 602 (Fig. 6A) (e.g., dextran sulfate), a single layer 604 (Fig. 6B) or a multi-layer material 606 (Fig. 6C). In some embodiments, the polyanions 608 may also be conjugated to a surface of a substrate 610 (e.g., membrane, bead, flow channel, separation member, column filer, etc.), as shown in Fig. 6D. As such, the polyanions 608 may be covalently linked to a substrate 610. The linkage can be by any linking agent, such as a crosslinking agent as described herein. The polyanion-bound membranes can be used to separate the target critical material (e.g., lithium) by injecting the source material through the membrane. The polyanion can be a negatively charged material that may be conjugated to a particle or other body. Alternatively, the Fig. 6D illustration can substitute the substrate with any type of body, such as a flow path surface (e.g., microfluidic channel), or other extraction substrate. For example, a column packing material may be used for the substrate so that the polyanions can function in the column for binding with the critical mineral.

[0061] Polyanionic complexation with lithium is demonstrated in the lab by adjusting the pH of the polyanion solution using IM NaOH for a batch that can be diluted and pH adjusted for different applications. Solutions of various concentration of polyanion can be added to a brine of salinity from 0 to 300,000 mg/L and lithium content of 10-600 ppm under shear that is applied using stir bars at 100-1,200 rpm. In some aspects, the lithium content in the source material may range from about 10 ppm to about 600 ppm, or about 50 ppm to about 400 ppm, or about 100 ppm to about 200 ppm, or about 125 ppm to about 175 ppm, or any range between any of the end points recited herein.

[0062] Preliminary results indicate that our polyanion systems can interact with lithium and entrap about 81% of the lithium in water solution at pH 3. Therefore, it is reasonable to tailor the system to trap up to about 25% of available lithium, up to about 50% of available lithium, up to about 75% of available lithium, up to about 80% of available lithium, up to about 85% of available lithium, or up to about 90% of available lithium, and possibly higher with tailoring and optimization. The pH may also range as described herein. EXAMPLES

[0063] A calibration curve was developed for lithium using single beam UV. The method for measuring lithium was reported by Quartarolli et al. (2021). Fig. 3 includes a calibration curve for lithium concentration. Fig. 4 includes a calibration curve for dextran sulfate (DS) concentration.

[0064] A 1% solution of DS and 150 ppm lithium were prepared in reverse osmosis (R.O.) water. A mixture with 1 : 1 ratio of the two solutions was prepared and mixed under 600 rpm for 20 minutes to form DS-Li complexes. Part of the solution was centrifuged for 12 minutes under 15000 rpm to separate the DS-Li complex nanoparticles.

[0065] Particle size and zeta potential measurement was conducted for the rest of the solution as well as on the supernatants. Supernatant solutions showed 1-2 kcps count rate of particles, which represents successful separation of nanoparticles during centrifuge. The main DS-Li solution had a pH of 7 and showed average particle size of 147 nm with 3 nm standard deviation on three sample measurements and count rate of 300-500 kcps. This system showed average zeta potential of -30 mV.

[0066] The centrifuge pellet was dissolved in R.O. water and the concentration of lithium in it was measured to be 0.067%. The concentration of lithium in the source solution was 0.083%. Therefore, the calculated entrapment efficiency for these particles is 81.5%. Table 1 shows the lithium and DS concentration in supernatant and nanoparticle system.

Table 1

[0067] Fig. 5 shows the particle size of the DS-Li complexes, versus the Final DS concentration. Accordingly, Fig. 5 shows the particle size versus final dextran sulfate concentration for different systems.

[0068] One skilled in the art will appreciate that, for the processes and methods disclosed herein, the functions performed in the processes and methods may be implemented in differing order. Furthermore, the outlined steps and operations are only provided as examples, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations without detracting from the essence of the disclosed embodiments. [0069] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0070] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.

SUBSTITUTE SHEET ( RULE 26) [0071] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0072] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0073] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.

[0074] From the foregoing, it will be appreciated that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

[0075] All references recited herein are incorporated herein by specific reference in their entirety.

Lucas F. Quartarolli, Alceu T. Silveira and Henrique E. Toma, “Overcoming lithium analysis difficulties with a simple colorimetric/spectrophotometric method.”, Anal. Methods, 2021,13, 3627-3631

Claims

1. A method of extracting a critical mineral cation from a composition, comprising: contacting a polyanion to a composition, wherein the composition includes the critical mineral cation; complexing the critical mineral cation with the polyanion to form a polyanion/cation complex in the composition; separating the polyanion/cation complex from the composition; and releasing the critical mineral cation from the polyanion.

2. The method of claim 1 , wherein the critical mineral cation is a metal ion that is a monovalent ion, a divalent ion, or a trivalent ion.

3. The method of claim 1, wherein the critical mineral cation is lithium.

4. The method of claim 1, wherein the critical mineral cation is strontium.

5. The method of claim 1, wherein the critical mineral cation is selected from the group consisting of aluminum, cobalt, fluorine, gallium, iridium, lithium, magnesium, natural graphite, neodymium, nickel, platinum, praseodymium, terbium, silicon, bromine, or combinations thereof.

6. The method of claim 1, wherein the polyanion is an anionic dextran, an anionic cellulose, an anionic polysaccharide, a negative polymer, or combinations thereof.

7. The method of claim 1, wherein the poly anion is dextran sulfate, dextran phosphate, carboxymethyl cellulose, sodium alginate, pectin, kappa carrageenan, iota carrageenan, lambda carrageenan, hyaluronic acid, fucoidan, polystyrene sulfonate, polyvinyl sulfonic acid, polyacrylic acid, polymethyl acrylic acid sodium salt, 3- sulfopropyl methacrylate potassium salt, or combinations thereof.

8. The method of claim 1, wherein the polyanion is conjugated to a particle, bead, substrate, flow path surface, membrane, or other body.

9. The method of claim 1 , wherein the polyanion is not bound to another body.

10. The method of claim 1, wherein the composition is a processing solution, prepared from a processing solution, or waste from an industrial facility.

11. The method of claim 1, further comprising obtaining the composition, wherein the composition is from an industrial facility, an oil processing facility, a gas processing facility, a geothermal energy facility, or from a carbon capture, utilization and storage (CCUS) facility.

12. The method of claim 1 , wherein the complexing is performed under mixing.

13. The method of claim 1, wherein the separating is performed by centrifugation, precipitation, filtration or charged membrane separation.

14. The method of claim 1, wherein the releasing is by changing pH, salinity, or composition of the separated polyanion/ion complex.

15. The method of claim 1, wherein the poly anion has an entrapment efficiency for the critical mineral cation of at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

16. The method of claim 1, further comprising: separating the released critical mineral cation from the polyanion; and collecting the released critical mineral cation without the polyanion.