CRUSHING, DISSOLUTION, AND SEPARATION TECHNIQUES FOR LITHIUM-BEARING MATERIALS

Description

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to and the benefit of U.S. Provisional Patent Application No. 63/708,769, filed Oct. 18, 2024, entitled “CRUSHING, DISSOLUTION, AND SEPARATION TECHNIQUES FOR LITHIUM-BEARING MATERIALS,” the disclosure of which is incorporated here by reference in its entirety.

BACKGROUND

The present disclosure generally relates to compositions, systems, and methods for simultaneous crushing, dissolution, and separation of lithium from lithium-bearing materials.

This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the present disclosure, which are described and/or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. Accordingly, it may be understood that these statements are to be read in this light, and not as admissions of prior art.

Lithium (Li) is an important material that is employed in various areas, particularly in development of batteries. Mining techniques are employed to obtain lithium material. However, the extraction of lithium from certain lithium-bearing materials, such as hard or soft materials, such as tuff, mica, or clays like hectorite and montmorillonite, which contain approximately 0.02% to 10.0% lithium by weight, involves several steps. Certain techniques may utilize a relatively high amount of energy and may use a relatively large amount of chemicals and water during crushing, heating, leaching, and precipitation steps associated with lithium extraction. Furthermore, the current steps generate significant quantities of waste material. Accordingly, it is presently recognized that it may be desirable to develop processes that can reduce the energy required for crushing and heating and/or lower the amount of chemicals and water to meet sustainability objectives and provide economical benefits.

SUMMARY

A summary of certain embodiments disclosed herein is set forth below. It should be understood that these aspects are presented merely to provide the reader with a brief summary of these certain embodiments and that these aspects are not intended to limit the scope of this disclosure. Indeed, this disclosure may encompass a variety of aspects that may not be set forth below.

In certain embodiments, the present disclosure relates to a method for obtaining a raw lithium-bearing material. The method includes obtaining a raw lithium-bearing material. The method also includes obtaining one or more additives. The method further includes providing the raw lithium-bearing material and the one or more additives to a mill, wherein the mill is configured to mechanically impact the raw lithium-bearing material. The method also includes obtaining a lithium-bearing material intermediate based on the mechanical impact to the raw lithium-bearing material and the one or more additives. The method includes providing the lithium-bearing material intermediate to a separator. Further, the method includes obtaining the lithium product via the separator.

In certain embodiments, a system includes a controller having a processor, a memory, and instructions stored on the memory and executable by the processor to control a lithium-based extraction system to receiving a raw lithium-bearing material into a mill. The instructions include receiving one or more additives into the mill. The instructions also include crushing the raw lithium-bearing material and the one or more additives to generate an intermediate. Further, the instructions include separating lithium product from the intermediate, thereby generating the lithium product.

Various refinements of the features noted above may exist in relation to various aspects of the present disclosure. Further features may also be incorporated in these various aspects as well. These refinements and additional features may exist individually or in any combination. For instance, various features discussed below in relation to one or more of the illustrated embodiments may be incorporated into any of the above-described aspects of the present disclosure alone or in any combination. The brief summary presented above is intended only to familiarize the reader with certain aspects and contexts of embodiments of the present disclosure without limitation to the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

FIG. 1 is a schematic view of an embodiment of a lithium extraction system with enclosed belt conveyors and a sprinkler system, in accordance with the present disclosure;

FIG. 2 is a schematic view of an embodiment of a lithium extraction system that includes an injection system, in accordance with the present disclosure; and

FIG. 3 is a flowchart of an embodiment of a method for operation of a lithium extraction system, in accordance with present disclosure.

DETAILED DESCRIPTION

One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, all features of an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.

Furthermore, when introducing elements of various embodiments of the present disclosure, the articles “a,” “an,” and “the” are intended to mean that there are one or more of the elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements. Additionally, it should be understood that references to “one embodiment,” “an embodiment,” or “some embodiments” of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features. Furthermore, the phrase A “based on” B is intended to mean that A is at least partially based on B. Moreover, unless expressly stated otherwise, the term “or” is intended to be inclusive (e.g., logical OR) and not exclusive (e.g., logical XOR). In other words, the phrase A “or” B is intended to mean A, B, or both A and B. elements. All numerical values within the detailed description herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. For example, “about” or “approximately” may refer to ±0.5%, ±1%, ±2, ±5%, ±10%, or ±15%.

The term “raw lithium-bearing material” refers to a lithium-containing ore (e.g., include at least about 0.02% lithium by weight, or about 0.02% to 10.0% lithium by weight) that contains earth materials such as clay, tuffs or mica, and lithium products (such as lithium hydroxide, lithium chloride, lithium carbonate, lithium sulfate or lithium phosphate). For example, a raw lithium-bearing material (e.g., lithium-rich liquor) may be converted into Li products, which may be further purified for various applications (e.g., battery grade applications). Accordingly, “raw lithium-bearing material”, “lithium-bearing material”, and “lithium-containing ore” may be used interchangeably.

The term “lithium-free material” refers to a material (e.g., an ore) that does not contain lithium product or is otherwise substantially free of lithium. For example, the lithium-free material may contain less than or equal to about ⅓, about ½, about ¼, or about 1/10 of the original lithium content by weight.

A conventional beneficiation process to treat raw lithium-bearing material (e.g., hard or soft materials, such as tuff, mica, or clays) may include obtaining raw lithium-bearing material that contains 0.02% to 10.0% lithium by weight. Further, the beneficiation process may include reducing the particle size of the raw lithium-bearing material to less than 500 micrometers (μm) using a ball mill and creating a slurry with an aqueous base consisting of sodium or potassium carbonates (e.g., Na₂CO₃, K₂CO₃) or hydroxides (NaOH, KOH). In one example process, resulting slurry is then heated at approximately 50 to 125° C. for 0.1 to 6 hours, after which the solids are separated. The separated clays may then be acidified using, for example, aqueous sulfuric acid (H₂SO4) to reduce the pH value to about 0 to 2. Subsequently, the acidified slurry may be heated to about 50 to 125° C. for about 0.5 to 10 hours, upon which residual solids are separated from the aqueous phase. The liquid portion of the cooled slurry is treated with NaOH, KOH, or calcium hydroxide (Ca(OH)₂) and is followed by treating the slurry with Na₂CO₃ or K₂CO₃ in the presence of heat to eliminate interfering alkaline earth metals. Subsequently, the slurry may be cooled, followed by the separation of the aqueous phase from the slurry. The aqueous phase is treated with alkali carbonate to precipitate the lithium carbonate, upon which the solid lithium carbonate is removed by filtering the hot slurry. In short, the above-mentioned processes may utilize a relatively large amount of chemicals, utilize a relatively large amount of energy to crush raw lithium-bearing material and heating resulting slurries, produce relatively large amounts of waste. It is presently recognized that integrating crushing raw lithium-bearing material with mineral activation and/or separation steps may provide a more efficient process

Accordingly, the present disclosure relates to techniques for integrating crushing with mineral activation and separation steps, which may reduce the amount energy, chemicals, and water utilized for extracting lithium products (e.g., lithium salts in dissolved or precipitated form, lithium hydroxide (LiOH), lithium hydroxide monohydrate (LiOH·H₂O) lithium chloride (LiCl), lithium carbonate (Li₂CO₃), lithium sulfate (Li₂SO₄), lithium phosphate (Li₃PO₄) and to improve the efficiency of recovery. As discussed in more detail herein, the present techniques may combine one or more of particle reduction, mineral dissolution, and selective lithium recovery steps using grinding agents, solvent formulations, mills, and enhanced gravity separators, thereby reducing the number of chemicals and eliminates water for the extraction of lithium products. It is presently recognized that grinding lithium-containing ore with reuseable or recyclable non-aqueous precursors that leach minerals is desirable at locations without water resources or scarcity. Furthermore, mills are designed to impart significant energy to particles being processed, which can lead to localized heating at points of contact. For example, several types of mills, including ball mills, generate high temperature at the contact points of particles due to intense mechanical forces, high friction, and rapid impact. As such, by combining crushing with mineral activation provided by mills, overall energy required to activate the mineral can be lowered. The disclosed techniques may also prevent activated clays from undergoing pozzolanic activity, thereby allowing lithium-free clay particles to be used in geopolymer manufacturing, for instance for use in cement. In this way, the present embodiments described herein provide several advantages, including but not limited to minimizing the use of chemicals, water, and energy for the extraction of lithium products.

Grinding Agents

As described above, the disclosed techniques may combine one or more of particular reduction, mineral dissolution, and selective lithium recovery steps using a grinding agent (e.g., precursors). In general, the grinding agent may facilitate various processes associated with selective lithium recovery from a slurry. In one embodiment, the grinding agents may enable a reduction in particle size of the ore during crushing. For example, grinding agents may exhibit different particle sizes and/or hardness properties relative to ore particles. Accordingly, an aspect of this disclosure includes leveraging the differences in particle sizes and/or hardness of the grinding agents relative to ore particles to reduce particle size of the ore. In another embodiment, the grinding agents may enable dissolution of lithium. For example, grinding agents (e.g., fusion salts) may react with ore particles at high temperatures (e.g., at the contact points), thereby resulting in activation (e.g., chemical activation) of clays to facilitate Li liberation. In an embodiment, the grinding agent composition is selected so that it can both allow particle size reduction and lithium dissolution. The composition of the grinding agent may include a mixture of fusion salts, fluxes, polyionic salts, carbonate salts, ammonium-based salts, cationic salts, chelating agents, etc. The grinding agents may be solid, liquid, or gaseous when provided to raw lithium-bearing materials to dissolve and separate from impurities like quartz during milling. For example, clay particles may be ground with fusion salts in high-energy, high-speed mills, which may generate high temperatures at their contact points, thereby leading to the dissolution of the clay mineral and exposing lithium for easier extraction. As such, two or more fusion salts, polyionic salts, carbonate salts, ammonium-based salts, cationic salts, or any combination thereof, may be blended at different ratios together to fine tune the particle size (i.e., reduction in particle size) based on particle hardness and mechanical activation (e.g., via mechanical impacting, such as dry grinding or dry milling) of lithium-containing ore. This approach would also prevent activated clays from undergoing pozzolanic activity, allowing lithium-free clay particles to be used in geopolymer manufacturing for cement.

In one embodiment, grinding mineral feedstock with fusion salts or fluxes as part of the grinding agent in the mills facilitates in-situ dissolution of lithium-bearing clay minerals and promotes formation of soluble Li compounds. Accordingly, common fusion salts that may be used include but are not limited to cryolite (Na₃AlF₆), sodium carbonate (Na₂CO₃), potassium carbonate (K₂CO₃), or sulfates such as sodium sulfate (Na₂SO₄) or barium sulfate (BaSO₄). For example, it is believed fusion salts, especially molten salts, can reduce the temperature required to melt hard rock during lithium extraction. In one example, molten salts, such as lithium fluoride (LiF) and beryllium fluoride (BeF₂), exhibit superior ionic conductivity properties. This may allow the molten salts to transfer heat, thereby lowering the overall temperature needed for melting ore like illites, which utilize high temperature like hard rock, in liberating lithium. The higher thermal stability of these salts ensures that heat may be consistently applied to the rock, which facilitates melting at lower temperatures relative to traditional melting that would otherwise require higher temperatures. Additionally, the high heat capacity and thermal conductivity of molten salts enables them to absorb and distribute heat more effectively. In this way, the higher heat transfer efficiency of fusion salts reduces overall energy required to reach a mineral's melting point. Molten salts can also chemically interact with the mineral by breaking down its structure and making it easier to melt. This chemical interaction further reduces the temperature needed for melting the mineral and liberating lithium. These reactions can be fluorination, oxidation-reduction, or ion exchange.

For example, molten salts containing fluorides, such as LiF and BeF₂ may react with lithium-bearing minerals like spodumene (LiAl(SiO₃)₂). The fluoride ions attack the mineral structure to form soluble lithium fluoride and other byproducts. An example fluorination reaction is:

Furthermore, molten salts may also facilitate redox reactions. For example, LiCl in its molten state may react with lithium-bearing minerals, thereby reducing the lithium ions and forming soluble lithium chloride (see equation below)

Finally, in the presence of molten salts, lithium ions can be exchanged with other cations in a mineral structure. The ion exchange process may help break down the lattice structure of minerals, thereby releasing Li ions into the molten salt solution. Ion exchange coupled with swelling also leads to effective Li extraction. Additional examples associated with the liberation of lithium ions from a mineral structure include Liu, J., Xu, R., Sun, W., Wang, L. and Zhang, Y., 2024. Lithium extraction from lithium-bearing clay minerals by calcination-leaching method. Minerals, 14(3), p. 248. Accordingly, the fusion salts described herein advantageously facilitate lithium extraction from a lithium-bearing material.

In one embodiment, the grinding agent may include polyionic salts such as sodium polyphosphates (e.g., sodium hexametaphosphate (Na(PO3)₆)), ammonium polyphosphates (e.g., ammonium polyphosphate or (NH₄PO₃)_n), polyacrylic acid salts (e.g., sodium polyacrylate or (C3H3NaO₂)n), polysulfide salts (e.g., sodium polysulfide or Na₂S_x), polyphosphate salts (e.g., sodium tripolyphosphate or Na₅P₃O₁₀), polysilicate salts (e.g., sodium metasilicate (Na₂SiO₃)), etc. In further embodiments, the grinding agent may also include carbonate salts, such as sodium carbonate (Na₂CO₃), potassium carbonate (K₂CO₃), calcium carbonate (CaCO₃), and lithium carbonate (Li₂CO₃), which may facilitate lithium leaching from a highly reactive calcinated ore and subsequent precipitation, purification, and conversion of lithium from a slurry.

In one embodiment, cationic grinding agents, such as magnesium chloride (MgCl₂), calcium chloride (CaCl₂)), sodium chloride (NaCl), potassium chloride (KCl), ammonium salts such as ammonium chloride (NH₄Cl) or ammonium sulfate ((NH₄)₂SO₄), and other cationic species, such as aluminum chloride (AlCl₃) or iron salts (FeCl₂, FeCl₃), may be used to selectively enhance grinding and separation of lithium minerals from gangue. For example, the addition of cationic grinding agents may alter the surface chemistry of the minerals, thereby improving their floatation or leachability during post-grinding processing steps.

In one embodiment, ammonium salts, such as ammonium chloride (NH₄Cl), ammonium sulfate (NH₄)₂SO₄, ammonium bifluoride (NH₄HF₂), ammonium carbonate (NH₄)₂CO₃, ammonium nitrate (NH₄NO₃) may be used to selectively dissolve lithium from the activated lithium-containing ore along with facilitating precipitation and purification of lithium compounds from the slurry or in downstream processes. Accordingly, the salts described herein may be suitable for facilitating the comminution of a material and the liberation of lithium from the material early in an extraction process.

Furthermore, surfactant-type ammonium salts, such as DADMAC (diallydimethylammonium chloride) may also be used as a dispersing agent in the grinding and milling stages to reduce particle size in addition to preventing fine particle agglomeration/aggregation. The surfactant-type ammonium salts may also be used as a collector during froth floatation or selective adsorption to separate lithium compounds from solutions.

In general, employing grinding agents provides several advantages as it enables a reduction in the number of chemicals used in the processing of lithium-containing ore and eliminate water by integrating crushing with mechanical activation in the mill. Furthermore, the grinding agents facilitate dissolution of clay particles and selectively extract lithium from the slurry.

Solvent Formulations

As described above, the disclosed techniques may combine one or more of particular reduction, mineral dissolution, and selective lithium recovery steps using solvent (e.g., one or more solvents (e.g., co-solvent)) formulations. The solvent formulations may be employed as part of the particle reduction, mineral dissolution, selective lithium recovery processes, or a combination thereof, using mills and enhanced gravity separators to improve the beneficiation process. In one embodiment, solvents may be employed to facilitate formation of a slurry (e.g., a lubricant). In another embodiment, solvents (e.g., Li-selective solvents and/or gases) may be employed to facilitate separation of lithium product from a slurry. In one embodiment, the solvent may be selected to both employed to facilitate formation of a slurry and separation of lithium. In some embodiments, the solvent may be selected to additionally facilitate grinding and particle size reduction. In another example, a fusion solvent, a surfactant (e.g., stearic acid), and one or more solvents may be employed to facilitate liberation of lithium. In general, example techniques for using a solvent formulation may include generating, producing, or otherwise obtaining a slurry containing dissolved minerals by mixing raw lithium-bearing material with the solvent formulation. The solvent formulation may include glycols (e.g., ethylene glycol), alcohols (e.g., isopropanol, propanol, butanol), organic acids (e.g., citric acid), supercritical carbon dioxide (CO₂), or molten salts (e.g., ionic liquids, deep eutectic solvents) to separate impurities (e.g., lithium-bearing clay minerals). Additional solvents may include phosphine oxides (e.g., trioctylphosphine oxides), cryolite (Na₃AlF₆), organophosphorus acids, carboxylic acids, propylene carbonates, ionic liquids (e.g., tetrabutylammonium bis(2-ethylhexyl)-phosphates and derivatives). For example, molten salts mixtures such as lithium chloride-potassium chloride (LiCl—KCl) eutectic mixture, lithium chloride-calcium chloride (LiCl—CaCl₂)) mixtures, lithium fluoride-sodium fluoride (LiF—NaF) mixture, lithium chloride-magnesium chloride (LiCl—MgCl₂), ternary and quaternary mixtures (e.g., three or more salts) such as LiCl—KCl—NaCl or LiCl—KCl—CaCl₂), cryolite (Na₃AlF₆) may be used to fine tune the melting point and solubility of lithium-containing ore and lithium compounds to enable selective extraction.

In one embodiment, the solvent formulation may include one or more chelating agents (e.g., green chelating agents). For example, the chelating agents may include one or more of citric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), crown-ethers, nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA) may be mixed with solvents (e.g., glycols, alcohols, organic acids, supercritical CO₂, or molten salt). The chelating agents may selectively bind to lithium metal ions, thereby facilitating in their separation from complex lithium-containing ore or solution matrices. At least in some instances, the chelating agents may form stable complexes, which may improve solubility, transport, and recovery of lithium during separation processes and improve overall sustainability of the lithium extraction process. In some embodiments, surfactants may be employed as part of the solvent formulation, including but not limited to, soaps of fatty acids such as sodium, calcium, magnesium, or aluminum stearates or oleates. For example, the solvent formulation may include between about 0.01 to about 90 wt % of the one or more chelating agents, about 1% to about 90% one or more solvents, or a combination thereof. In another example, additives may be provided at high concentrations that exceed their solubility limit. For example, excess amounts of grinding agents such as stearic acid or aluminum stearate may be provided in the absence of solvents to a ball mill to crush a mineral. In some embodiments, small quantities of solvents may be added to a mixture including grinding agents and the mineral to facilitate dispersion of materials. As such, while the overall concentration of grinding agents may exceed their solubility limit, such a mixture may be sufficient at facilitating liberation of Li from a material.

In one embodiment, one or more types of solvents may be selected to facilitate processing lithium-bearing material. For example, following grinding of the lithium-bearing material, aqueous solvent such as brines, diluted ammonia, etc. may be provided as leaching solutions to release Li from the lithium-bearing material. The aqueous solvent extraction may be associated with an acidic region only. In some embodiments, non-aqueous solvents such as alcohols etc., may be utilized as a leaching solvent to selectively extract Li from the clay minerals. Accordingly, solvents may be chosen to facilitate lithium extraction from a material based on a type of workflow.

In general, employing the solvent formulations provides several advantages as it may reduce or substantially eliminate water from being utilized during the grinding and lithium extraction process. Accordingly, the disclosed techniques may be beneficial for use in mines with limited to no access to water. Furthermore, as the clays present in lithium-containing ore do not have the ability to react with water, unreactive spent clays (i.e., lithium-free clay) may be utilized in geopolymer manufacturing. In this way, the disclosed techniques described herein reduce waste and improve the circularity of the overall process.

Mill Operations and Control Systems

In general, the high shear and temperatures at the contact points between the particles and chemical reaction with salts and/or solvents may facilitate in-situ dissolution of lithium from the clay's surface interlayers, and potentially its crystalline (i.e., framework) structure. Therefore, the lithium-selective grinding agents and solvents as described above may help in separating a portion of soluble lithium products prior to actual roasting and acid-leaching steps, which may necessitate modification to the conventional lithium extraction processes. It should be noted that the shear and/or temperatures generated in a composition including grinding agents and ore at contact points between the grinding agents and ore is inherent to the components within the composition. Accordingly, type of mill and/or mill operations may be modified to obtain lithium products.

The mill(s) that may be used for crushing and grinding the lithium-containing ore may include ball mills, planetary mills, high-energy mills, vibratory ball mills, fluidized bed jet mills, attrition stirred media mills, high-speed pin mills, high-speed hammer mills, or high-shear colloid mills. It should be noted that one or more types of mills may be used in the lithium extraction process, which may vary depending on the composition and/or requirements of the raw lithium-bearing material (e.g., coarse or fine grinding, dry or wet grinding). For example, a process may begin with utilizing jaw crushers to reduce lithium-containing ore size, and then feeding the lithium-containing ore with a reduced size (e.g., particle size) into high-energy mill. As such, the high-energy mills may further break down particles such that additional grinding that may be accommodated by a vibratory mill. In this way, the vibratory mills can generate uniform particles which are suitable for finer grinding in a planetary mill. The operation of the mills may be continuous, intermittent, or variable speeds. For example, continuous milling may be suitable where consistent processing is required like (i.e., coarse crushing of lithium-containing ore), while intermittent milling may be desirable during mechanical activation of finer clay particles, as it enables cooling periods and prevents overheating. In some embodiments, the mills (e.g., one or more mills) may be coupled to and/or use coolants and/or cooling systems for simultaneous cooling and mineral separation from slurry. In further embodiments, lithium-containing ore may be pre-crushed to improve milling efficiency. In this way, the feed quantity may be optimized in a mill, thereby preventing overloading and ensuring consistent milling. Accordingly, the type of milling, number of mills, and associated operations may be customized depending on the type of lithium-containing ore.

In one embodiment, the disclosed techniques may include dry mechanical impacting, such as dry grinding or dry milling). For example, it is presently recognized that it may be advantageous to dry grind lithium-containing ore that does not utilize water or other liquids to enable milling. In this way, grinding may be performed in the absence of any solvent (i.e., no liquid). In some embodiments, wet grinding (e.g., wet milling) may be employed. In contrast, wet grinding (e.g., wet milling) may be employed for lithium-containing ore that utilizes water or other liquids to perform milling. For example, liquid dispersants (e.g., surfactants, sodium silicate) and/or solvent mixtures (e.g., organic solvents, alcohols) may be utilized in wet milling to enable fine grinding processes, prevent agglomeration of the fine clay particles (e.g., clay particle-clay particle attachment), reduce sticking to the grinding machine, and enhance grinding efficiency. Moreover, as wet grinding will generate a slurry including grinding agents, lithium compounds, solvents, impurities, and lithium-bearing clay particles, the slurry can undergo separation. For example, separation techniques such as hydrocyclones, centrifuges, or floatation devices (e.g., froth floatation devices, gravity settlers) may be used to separate the lithium compounds, impurities, and lithium-bearing clay particles.

In one embodiment, operational parameters of the mills may be customized and/or optimized for a specific operation (e.g., coarse crushing, intermediate crushing, fine crushing, mechanical activation) and clay types including soft clays (e.g., hectorite, montmorillonite) and hard clays (e.g., illites). For example, the operational parameters may include rotational speed, energy input, material composition (e.g., chemical properties and/or physical properties), dry or wet milling, or time. Accordingly, in some embodiments, operational parameters may be adjusted based on sensor feedback. In some embodiments, the sensor feedback may indicate one or more physical properties, one or more chemical properties, or both, of the raw lithium-bearing material before mechanical impact via a mill. Additionally, or alternatively, the sensor feedback may indicate the one or more physical properties, the one or more chemical properties, or both, of the lithium-bearing material after mechanical impact. For example, sensor feedback may indicate that the size of a lithium-containing ore is not sufficiently small. Accordingly, milling time may be adjusted to reduce particle size by decreasing or increasing milling time. In other embodiments, sensor feedback may indicate that particles in a mill are not mechanically activated. As such, longer milling time may be employed to mechanically activate the particles, thereby enhancing their reactivity and surface area.

In one embodiment, the operational parameters of the mills may be adjusted based on ratios of lithium-bearing material to additives, wherein the additives may include grinding agents, solvents, or a combination thereof. For example, the ratio between lithium-bearing material: grinding agents: solvents may prompt an adjustment to milling time and/or specific operation (e.g., coarse crushing, intermediate crushing, fine crushing, mechanical activation).

In one embodiment, the rotation speed may be modified of a mill. For example, high rotational speeds may be employed to increase the impact energy and shear forces, which may lead to more effective crushing and mechanical activation (e.g., via mechanical impacting, such as dry grinding or dry milling) of the lithium-containing ore. However, each mill has an optimal speed range for efficient milling, and exceeding this range can reduce efficiency and cause excessive wear. Accordingly, the rotational speed may be adjusted depending on the type of mill and/or lithium-containing ore composition.

In one embodiment, the grinding agent (i.e., salt blends) and solvent formulations (i.e., solvent mixtures) may be mixed with the raw lithium-bearing materials before or during the grinding process (e.g., coarse, intermediate, and fine grinding steps) in mills. Furthermore, the grinding agents may be introduced into the mills though solid, liquid, or gaseous injection systems (e.g., atomizers or nozzles). For example, grinding agents that are harder than the lithium-containing ore may be provided to the raw lithium-bearing material to achieve efficient grinding and prevent contamination. Grinding agents that exhibit a larger size may be more suitable for coarse grinding, but conversely, grinding agents that exhibit a smaller size may be ideal for fine grinding and mechanical activation. In this way, grinding agents and/or solvent formulations may be customized with respect to the lithium-containing ore type (e.g., spodumene, lepidolite, amblygonite, hectorite, and so on) when provided to a mill.

In one embodiment, inert gases may be utilized during the milling process. For example, inert gases (e.g., argon) may prevent oxidation and/or unwanted reactions of the lithium-containing ore during mechanical activation. Furthermore, milling lithium-containing ore under vacuum may also reduce contamination and enhance mechanical activation. Accordingly, one or more gas lines and/or vacuum lines may be coupled to one or more mills.

In one embodiment, the one or more mills described above may be integrated with a controller (e.g., control systems) to perform all aspects of the lithium extraction process. For example, the controller may be coupled to sensors to obtain measurements associated with the lithium extraction process (e.g., material composition (e.g., composition of a feed ore, composition of a liquid portion of an output), feed rate of lithium-containing ore, flow rate of solvents, flow rate of grinding agents, temperature in mill, gas composition). Accordingly, the controller may adjust operation parameters of mills and/or operations based on sensor feedback provided by the sensors. For example, the sensor feedback may be compared to a threshold value. In this way, the controller may adjust operations of the mill and/or other components if sensor feedback deviates from a threshold value.

With the foregoing in mind, FIG. 1 is a schematic view of an embodiment of a lithium extraction system 10 with enclosed belt conveyors and a sprinkler system, in accordance with the present disclosure. The lithium extraction system 10 may include a lithium extraction additives system 12, a housing 14, sprinkler systems 16, a conveyor belt 18, a control system 20 (e.g., controller), mills 22, a separator 24, and sensors 26. In general, the lithium extraction system 10 may receive raw lithium-bearing material 28 (e.g., a first lithium-bearing material) and provide additives using the lithium extraction additives system 12, upon which an intermediate 30 (e.g., a first lithium-bearing intermediate, a second lithium-bearing material) may be generated. As such, the intermediate 30 may be provided to the one or more mills 22 and processed, thereby generating lithium product 32.

In the illustrated embodiment, raw lithium-bearing material 28 may be provided to the lithium extraction system 10 via the conveyor belt 18. The conveyor belt 18 may be covered by the housing 14 such that it is enclosed. Accordingly, the conveyor belt 18 may receive the raw lithium-bearing material 28 and move the material along the conveyor belt 18, wherein the raw lithium-bearing material 28 may contact one or more sprinklers of the sprinklers system 16. In general, the sprinkler system 16 may be coupled to the lithium extraction additives system 12 via one or more conduits such that it may receive one or more additives (e.g., grinding agents 34, solvents 36) from the lithium extraction additives system 12. For example, the sprinkler system 16 may be disposed downstream from the lithium extraction additives system 12 such that it may receive the additives. Although three sprinkler systems 16 are shown, it should be noted that the lithium extraction system 10 may include any suitable number of sprinkler systems, such as one, two, three, four, five, or more than five.

It should be noted that the illustrated embodiment is merely exemplary and that other steps may be used to process the raw lithium-bearing material 28. In one embodiment, a second feed may be provided, wherein the second feed includes additives (e.g., grinding agents 34, solvents 36) that may be provided separately to the mills 22 such that the raw lithium-bearing material 28 may contact the additives in the mills 22. In another embodiment, the raw lithium-bearing material 28 may be provided into a mixer (e.g., a tumbler), upon which the additives (e.g., grinding agents 34, solvents 36) may be provided and allowed to mix with little to no grinding before being transferred to the mills 22.

As described herein, the grinding agents 34 may include one of or a mixture of fusion salts, fluxes, polyionic salts, carbonate salts, ammonium-based salts, cationic salts, etc. The solvents 36 may include glycols, alcohols, organic acids, supercritical CO₂, molten salts, green chelating agents, surfactants, etc. Accordingly, the sprinkler system 16 may provide (e.g., spray, sprinkle) the additives (e.g., grinding agents 34, solvents 36) upon the raw lithium-bearing material 28, thereby generating the intermediate 30. It should be noted that the additives may be provided to the raw lithium-bearing material 28 using solid, liquid, or gaseous systems (e.g., sprinkler system 16, atomizers, nozzles). In general, the intermediate 30 may be a wet intermediate (e.g., slurry, wherein one or more solvents 36 are provided to the mills 22) or a dry intermediate (e.g., one or more solvents 36 are not fed to the mills 22). For example, the wet intermediate (e.g., slurry) may include a mixture of the raw lithium-bearing material 28, grinding agents 34, solvents 36, etc., while the dry intermediate may include a mixture of grinding agents 34 and the raw lithium-bearing material. Accordingly, the lithium extraction system 10 advantageously enables processing raw lithium-bearing materials 28 based on its composition.

The intermediate 30 may be provided to the mills 22. It should be noted that one or more mills 22 may be employed as part of the lithium extraction system 10. The mills 22 may grind the intermediate 30 based on the composition of the intermediate 30. As indicated above, one or more types of mills 22 may be employed to grind the intermediate 30. For example, if the intermediate 30 is a wet intermediate, wet milling techniques may be employed. Alternatively, if the intermediate 30 is a dry intermediate, dry milling techniques may be employed. Furthermore, the operational parameters of the mills 22 may be modified depending on the composition of the intermediate 30. Accordingly, the intermediate 30 may be processed (e.g., crushed) by the mills 22, wherein the intermediate 30 may undergo mechanical activation due to the heat generated by the mills 22. Mechanical forces (e.g., high shear and temperatures) may be generated at the contact points between the intermediate 30 and chemical reaction with grinding agents 34 salts and/or solvents 36 within the mills 22, which enables the dissolution of lithium from the raw lithium-bearing material 28. Accordingly, the mills 22 may generate an additional intermediate 38 (e.g., a second lithium-bearing intermediate, a third lithium-bearing material), which may be provided subsequently to the separator 24. For example, the intermediate 38 may include lithium ions, impurities (e.g., grinding agents 34, solvents 36, side products), and clay particles. Accordingly, the separator 24 (e.g., hydrocyclones, centrifuges, vapor extraction, or floatation devices) may receive the intermediate 38 and separate the unwanted products and perform purification (e.g., raw lithium-bearing material 28, impurities (e.g., grinding agents 34, solvents 36, side products), thereby generating the lithium product 32. Alternative extraction techniques (e.g., vapor extraction techniques) may be employed if solvents 36 includes non-aqueous solvents to separate unwanted products and perform purification. In certain embodiments, the raw lithium-bearing material may include other elements in addition to lithium. For example, the other elements may include uranium (U), magnesium (Mg), potassium (K), boron (B), etc. Once the lithium product 32 has been obtained via the separator, the lithium-deprived material intermediate (i.e., the lithium-bearing material intermediate deprived from the separated lithium) may be further processed by obtaining one or more additional products containing one of the other elements. It should be noted different grinding agents 34 and/or solvents 36 may be selected to facilitate extraction of the secondary and tertiary elements, after lithium product 32 has been generated, relative to the grinding agents 34 and/or solvents 36 used for the lithium product 32.

In some embodiments, the extraction techniques may include direct lithium extraction, for instance, after separation in the separator 24. For example, the separator 24 may generate an additional intermediate (e.g., a lithium-bearing material, second lithium-bearing material intermediate, second lithium-bearing intermediate) that may be mixed with an aqueous stream to generate a lithium source material (e.g., combination of lithium-bearing material and aqueous stream, lithium source) before proceeding to direct lithium extraction. Direct extraction of lithium may be used in lithium recovery from aqueous lithium sources. Direct extraction processes may employ a solid material (e.g., withdrawal material) to withdraw lithium ions selectively from a lithium source onto or into the withdrawal material. Put differently, the solid material may withdraw and retain lithium from the lithium source material to create a loaded withdrawal material. A recovery fluid is subsequently contacted with the loaded withdrawal material to remove the lithium from the withdrawal material to form a lithium intermediate stream. The quantity of recovery fluid generally determines the concentration of lithium in the lithium intermediate stream, but unloading rate of ions from the withdrawal material can provide an effective upper limit to the concentration achievable. This process is referred to as an ion withdrawal lithium extraction process.

During an ion withdrawal lithium extraction process, the withdrawal material utilized may be selective to lithium. This may cause many types of cations to be removed from the source, but lithium is removed more readily than other cations. Thus, the ions removed by the withdrawal material include lithium possibly along with other impurities, such as monovalent cations sodium and potassium and divalent cations calcium and magnesium. Longer recovery processing can enhance ion removal in each cycle, but such measures are subject to diminishing returns as throughput declines. Thus, recovery fluid application rate is subject to an optimum which trades lithium intermediate stream concentration, recovery time, and degradation of loading capacity.

An ion withdrawal direct lithium extraction process may be an ion exchange or ion replacement process, where the withdrawal medium is pre-loaded with ions that are exchanged to the feed fluid while withdrawing other ions from the feed fluid. In such cases, the withdrawal and recovery processes are both typically ion exchange or ion replacement processes, but an ion exchange process where the recovery fluid does not replace ions can also be used, where ions are replaced for the withdrawal step by exposing the withdrawal medium to a third fluid for the purpose of preloading exchange ions. In some cases, the direct lithium extraction process may be an adsorption process where ions are adsorbed from the aqueous lithium stream solution onto the surface of a solid adsorbent material that is selective to lithium, such as metal oxide, metal hydroxide or such material mixed with a resin. A desorbent solution is used to recover the withdrawn ions. In other cases, the direct lithium extraction process may be an absorption process where ions are absorbed from the brine solution into the bulk of a solid absorbent material that is selective to lithium. A desorbent solution is used in these cases, as well. These cases of pure sorption-desorption may utilize regeneration of the withdrawal medium because unloading of ions from medium is not quantitative.

Direct lithium extraction processes may also use a lithium selective electrochemical separation process. The lithium selective electrochemical separation process uses a voltage bias to drive materials through a lithium selective membrane to separate lithium from an aqueous lithium source. The aqueous lithium source is brought into contact with a first side of the lithium selective membrane, and an aqueous eluent material is brought into contact with a second side of the lithium selective membrane, opposite from the first side. The voltage bias is applied within the aqueous lithium source and the aqueous eluent material to form an electric field within both materials and extending across the lithium selective membrane. The electric field provides a driving force to move, or increase movement of, charged species through the lithium selective membrane. The species motivated by the electric field to move through the lithium selective membrane depends on the configuration of the lithium selective membrane. For example, the lithium selective membrane may selectively pass lithium ions more than other ions or the lithium selective membrane may selectively block passage of lithium ions more than other ions.

Direct lithium extraction processes that include lithium selective electrochemical separation processes use lithium selective membranes. Such membranes can include, or be made of, lithium selective materials such as lithium aluminum germanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanates, or a metal organic framework type material such as UiO-66 with acid and amine groups. Such materials can be configured alone in a membrane structure or can be added to a support material, such as a resin, configured into a membrane structure. That is, such lithium selective membranes may include lithium aluminum germanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanates, a metal organic framework material, a resin, or a combination thereof. Additional stages to further remove targeted impurities may be performed before and/or after the direct lithium extraction.

A concentration stage, using evaporation technique (including enhanced evaporation) and/or membrane separation technique, such as reverse osmosis, forward osmosis, counter-flow reverse osmosis, osmotically assisted reverse osmosis, etc. may be used to concentrate a stream exiting the direct lithium extraction stage. An exemplary concentration stage may include a reverse osmosis stage followed by a counter-flow reverse osmosis stage, as disclosed in more details in PCT application WO2023/215002.

The method may include a final stage of conversion to transform the aqueous stream (generally containing mostly lithium chloride) into a lithium product 32, such product being a lithium hydroxide or a lithium carbonate. The conversion can be performed by known chemical, electrochemical, and hybrid processes. or a slurry of lithium carbonate in a solution of lithium carbonate.

In the illustrated embodiment, the lithium extraction system 10 includes a control system 20 that may control all or certain operations of the lithium extraction system 10. As shown, the control system 20 is communicatively coupled to the lithium extraction additives system 12, the sprinkler system 16, the conveyor belt 18, the mills 22, the separator 24, and the sensors 26. The control system 20 includes one or more processors 40, memory 42, instructions 44 stored on the memory 42 and executable by the processor 40, and communication circuitry 46 configured to communicate with sensors 26 and various equipment of the lithium extraction system 10. For example, the control system may receive sensor feedback and/or electrical signals from sensors 26 coupled to the conveyor belt 18, the mills 22, and/or the separator 24 indicating physical and/or chemical properties of the raw lithium-bearing material 28, the intermediate 30, the intermediate 38, the lithium product 32, or a combination thereof. For example, the sensors 26 may include temperature sensors, pressure sensors, flow rate sensors, gas composition sensors, liquid composition sensors, or any combination thereof. In some embodiments, the sensor feedback may include operational parameters of the conveyor belt 18, the mills 22, and/or the separator 24 that correspond to physical and/or chemical properties of the raw lithium-bearing material 28, the intermediate 30, the intermediate 38, the lithium product 32, or a combination thereof. For example, a sensor 26 may indicate an amount of current supplied to the mill and/or a speed of the mill 22. The amount of current supplied to the mill 22 may indicate a degree of milling (e.g., a particle size of the intermediate 38). Accordingly, the control system 20 may utilize the sensor feedback from the sensor 26 to adjust the operations performed by the lithium extraction system 10. Furthermore, the lithium extraction system 10 described herein may also include various sensors 26 positioned along material flow paths (e.g., a conduit providing intermediate 30 to the mills 22), solvents 36 flow paths, grinding agents 34 flow paths, gas flow paths, and/or coolant flow paths.

In certain embodiments, the control system 20 is configured to control operation of the lithium extraction system 10 such by controlling modes of operation (e.g., controlling lithium extraction additives system 12 to provide grinding agents 34 and/or solvents 36, operate the conveyor belt 18, adjust operations of the mills 22 (e.g., continuous milling, intermittent milling, variable speeds), adjust operations of the separator 24). For example, the control system 20 may receive sensor feedback and/or electrical signals indicative of operation parameters to adjust crushing type based on a specific operation (e.g., coarse crushing, intermediate crushing, fine crushing, mechanical activation) and/or clay types (e.g., hard clays, soft clays). The control system 20 may also adjust various operational parameters (e.g., one or more operational parameters) of the one or more mills 22 (e.g., rotational speed, energy input, material composition, dry or wet milling, time). In some embodiments, the control system 20 may be coupled to a gas supply to provide inert gas (e.g., argon), activate and/or adjust cooling system and/or coolants to reduce the high temperatures generated by the mechanical activation of the intermediate 30 in the mills 22, or activate and/or adjust operation of a vacuum pump to reduce contamination and enhance mechanical activation within the mills 22.

In certain embodiments, operational parameters of the mills 22 may be adjusted based on ratios of raw lithium-bearing material 28 to additives, wherein the additives may include grinding agents 34, solvents 36, or a combination thereof. For example, the ratio between raw lithium-bearing material 28: grinding agents 34: solvents 36 may prompt an adjustment to milling time and/or specific operation (e.g., coarse crushing, intermediate crushing, fine crushing, mechanical activation). In another example, a ratio of the raw lithium-bearing material 28: additives may include adjusting loading in the mills 22 (e.g., feed mass/volume). Furthermore, the performance of milling can depend on the amount of material in the mills 22 (e.g., too little raw lithium-bearing material 28: additives or too much raw lithium-bearing material 28: additives may inhibit crushing and heat generation).

As described above, the lithium extraction system 10 may include one or more sensors 26 that measure, receive, or otherwise obtain sensor feedback indicative of operational parameters of components of the lithium extraction system 10 (e.g., the conveyor belt 18 and/or the mill 22). At least in some instances, the sensor feedback may be indicative of physical and/or chemical properties of the raw lithium-bearing material 28, the intermediate 30, the intermediate 38, the lithium product 32, or a combination thereof.

With the foregoing in mind, FIG. 2 is a schematic view of an embodiment of a lithium extraction subsystem 100 with an injection system. The lithium extraction subsystem 100 may be utilized in the lithium extraction system 10 of FIG. 1 (e.g., including at least the conveyor belt 18 and/or sprinkler systems 16) or employed without the conveyor belts 18 and/or sprinkler systems 16 described in FIG. 1. The lithium extraction subsystem 100 may include a lithium extraction additives system 12, an injection system 102, mills 22, a separator 24, and sensors 26. In a generally similar manner as FIG. 1, the lithium extraction subsystem 100 may receive raw lithium-bearing material 28 and provide additives using the lithium extraction additives system 12, upon which an intermediate 38 may be generated. As such, the intermediate 38 may be provided to the mills 22 and processed, thereby generating lithium product 32.

In the illustrated embodiment, raw lithium-bearing material 28 may be provided to the lithium extraction subsystem 100 via a conduit. The conduit may be coupled to one or more mills 22, wherein the one or more mills 22 is disposed downstream to receive the raw lithium-bearing material 28. Furthermore, the one or more mills 22 may be coupled to the injection system 102 via one or more conduits. In general, the injection system 102 is disposed downstream from the lithium extraction additives system 12 such that it may receive the additives (e.g., grinding agents 34 and/or solvents 36). The grinding agents 34 and/or solvents 36 may be provided to the injection system 102 via one or more conduits coupled. Accordingly, the injection system 102 may receive the grinding agents 34 and/or solvents 36 such that it may inject the grinding agents 34 and/or solvents 36 into the mills 22 (e.g., one or more mills 22). In this way, the raw lithium-bearing material 28 may contact the grinding agents 34 and/or solvents 36 within the mills 22. It should be noted that the additives may be provided to the raw lithium-bearing material 28 in the mills using solid, liquid, or gaseous systems (e.g., atomizers, nozzles) via the injection system 102.

The mills 22 may grind, crush, mill, or otherwise mechanically impact the combination of the raw lithium-bearing material 28, grinding agents 34, and/or solvents 36 present and adjust operations based on the composition. In a generally similar manner to FIG. 1, if the composition is “wet” (e.g., wet intermediate of FIG. 1), wet milling techniques may be employed. Alternatively, if the composition is “dry” (e.g., dry intermediate of FIG. 1), dry milling techniques may be employed. As indicated above, one or more types of mills 22 may be employed to grind the intermediate 30. Furthermore, the operations of the mills 22 may be modified depending on the composition within the mills 22. Accordingly, the composition may be processed (e.g., crushed) by the mills 22 such that it can undergo mechanical activation/forces (e.g., mechanical impact and mechanical shear forces generated at contact points between lithium-bearing material and chemical reaction of grinding agents 34 and/or solvents 36 to promote dissolution of lithium from the raw lithium-bearing material 28) due to the heat generated by the mills 22. For example, the mechanical activation may generate localized high temperatures (e.g., hot spots). In this way, the localized heating provided by the hot spots may promote chemical reactions, thereby facilitating dissolution of lithium. Additional descriptions associated with the mechanical forces and/or hot spots include Young-Soon Kwon, Konstantin B Gerasimov, Sok-Keel Yoon, Ball temperatures during mechanical alloying in planetary mills. Journal of Alloys and Compounds, Volume 346, Issues 1-2, 2002, Pages 276-281, ISSN 0925-8388, https://doi.org/10.1016/S0925-8388(02)00512-1 and Andrew W. Tricker, George Samaras, Karoline L. Hebisch, Matthew J. Realff, Carsten Sievers, Hot spot generation, reactivity, and decay in mechanochemical reactors, Chemical Engineering Journal, Volume 382, 2020, 122954, ISSN 1385-8947, https://doi.org/10.1016/j.cej.2019.122954. Accordingly, the mills 22 may generate intermediate 38, which may include unreacted raw lithium-bearing material 28, impurities (e.g., grinding agents 34, solvents 36, side products), and the lithium product 32. The separator 24 (e.g., hydrocyclones, centrifuges, or floatation devices) may be positioned downstream from the mills 22 to receive the intermediate 38 and separate the unwanted products and perform purification (e.g., raw lithium-bearing material 28, impurities (e.g., grinding agents 34, solvents 36, side products), thereby generating lithium product 32. Furthermore, it should be noted that, in some embodiments, direct lithium extraction may be used as an extraction method in a generally similar manner as FIG. 1, for instance, after separation in the separator 24 as part of the lithium extraction subsystem 100, which may be utilized in the lithium extraction system 10 of FIG. 1.

In a generally similar manner to FIG. 1, a control system 20 (e.g., controller) may be configured to control all aspects of the lithium extraction subsystem 100. Accordingly, the control system 20 may be coupled to the lithium extraction additives system 12, the injection system 102, the mills 22, the separator 24, and the sensors 26. In general, the control system 20 includes one or more processors 40, memory 42, instructions 44 stored on the memory 42 and executable by the processor 40, and communication circuitry 46 configured to communicate with sensors 26 and various equipment of the lithium extraction subsystem 100. For example, the control system 20 is configured to receive sensor feedback and/or electrical signals from sensors 26 coupled to the injection system 102, mills 22, and/or the separator 24. Furthermore, the lithium extraction subsystem 100 described herein may also include various sensors 26 positioned along material flow paths (e.g., a conduit providing raw lithium-bearing material 28, a conduit providing intermediate 38 to the separator 24), solvents 36 flow paths, grinding agents 34 flow paths, gas flow paths, and/or coolant flow paths. For example, the sensors 26 may include temperature sensors, pressure sensors, flow rate sensors, gas composition sensors, liquid composition sensors, or any combination thereof.

In certain embodiments, the control system 20 is configured to control operation of the lithium extraction subsystem 100 such by controlling modes of operation (e.g., controlling lithium extraction additives system 12 to provide grinding agents 34 and/or solvents 36, injection rate, amount, and/or type of additives via the injection system 102, adjust operations of the mills 22 (e.g., continuous milling, intermittent milling, variable speeds), adjust operations of the separator 24). For example, the control system 20 may receive sensor feedback and/or electrical signals indicative of operation parameters to adjust crushing type based on a specific operation (e.g., coarse crushing, intermediate crushing, fine crushing, mechanical activation) and/or clay types (e.g., hard clays, soft clays). The control system 20 may adjust various operational parameters of the mills 22, provide a gas supply, activate and/or adjust cooling systems and/or coolants, or activate and/or adjust a vacuum pump in a generally similar manner as the control system 20 of FIG. 1.

With the preceding in mind, FIG. 3 is a flowchart of an embodiment of a method for operation of a lithium extraction system of FIG. 1 and of FIG. 2, in accordance with present disclosure. The method 200 may be performed by the lithium extraction system 10, 100, the control system 20, 122 a computing device, or any other suitable computing device(s) or control systems. Furthermore, the blocks of the method 200 may be performed in the order disclosed herein or in any suitable order. For example, certain blocks of the method 200 may be performed concurrently or consecutively. In addition, in certain embodiments, at least one of the blocks of the method 200 may be omitted. Further, it should be noted, that the lithium extraction systems 10, 100 and/or control system 20, 122 may iteratively perform the blocks outlined in method 200.

At block 202, the method 200 includes obtaining a raw lithium-bearing material 28. As described herein, raw lithium-bearing material may include soft clays or hard clays, tuffs or mica including 0.02% to 10.0% lithium by weight. In some embodiments, the method 200 includes providing one or more additives (e.g., the grinding agents 34 and/or the solvents 36 as described herein above) to the lithium-bearing material 28. For example, the raw lithium-bearing material 28 may be provided to a conveyor belt 18, upon where it may come into contact with grinding agents 34 and/or solvents 36 to form an intermediate 30 (e.g., a first lithium-bearing intermediate).

At block 204, the method 200 includes providing the raw lithium-bearing material 28 to a mill 22 upon where it may come into contact with grinding agents 34 and/or solvents 36 provided via an injection system 102. In some embodiments, the raw lithium-bearing material 28 may be directly provided to the mill 22 (e.g., without adding grinding agents 34 and/or solvents 36 as described in FIG. 1). In other embodiments, an intermediate 30 including the raw lithium-bearing material 28, 112, grinding agents 34, 116, and/or solvents 36, 118 may be provided to the mills 22, 106. As such, the mills 22, 106 may crush and mechanically activate the intermediate 30 and/or a composition including the raw lithium-bearing material 28, 112, grinding agents 34, 116, and/or solvents 36, 118.

At block 206, the method 200 includes obtaining the intermediate product 38 from the mills 22. For example, the raw lithium-bearing material 28 may be subjected to mechanical activation performed by the mills 22, 106, via grinding, milling, crushing, or otherwise mechanically impacting the intermediate 38, thereby generating the intermediate 38. The intermediate 38 may include the raw lithium-bearing material 28, 112, impurities (e.g., grinding agents 34, 116, solvents 36, 118, side products), and the lithium product 32, 114.

At block 208, the method 200 includes providing the intermediate 38, 120 to a separator 24, 108. Accordingly, the separator 24, 108 may separate and remove unwanted products as part of the purification process. In some embodiments, direct lithium extraction may be used as an extraction method, for instance, after separation by the separator 24. As such, at block 210, the method 200 includes obtaining the lithium product 32, 114 from the separation process. In some embodiments, obtaining the lithium product 32 may include performing one or more additional isolation and/or purification steps using the output of the separator 24.

Technical effects of the disclosed embodiments include processing raw lithium-bearing materials by integrating crushing with mineral activation and separation steps to reduce the amount of chemicals, water, and energy to generate lithium products. Accordingly, grinding agents and solvents may be combined with the raw lithium-bearing material in a mill, which combines particle reduction, mineral dissolution, and selective lithium recovery steps to obtain the lithium product. Because the mill will generate heat during the crushing process, the grinding agents and/or solvents are provided to the mill in combination with the raw lithium-bearing material. In this way, the crushing ability and heat generated by the mill may be leveraged to crush and mechanically activate the lithium-containing ore using mechanical forces that are generated at contact points between the raw lithium-bearing material, grinding agents, and/or solvents, thereby reducing the overall energy required to activate the material. The grinding agents and/or solvents described herein enable a reduction in the number of chemicals and eliminate water (e.g., absence of water) in the process of the raw lithium-bearing material. Additionally, a lithium extraction system using an enclosed conveyor belt and sprinkler system and a lithium extraction system using an injection system may be used in addition to the grinding agents, solvents, and processes described herein. The operations of the mills may be adjusted using a control system based on the composition of the lithium-containing ore. In this way, the present embodiments enable tunability over the lithium extraction process.

The subject matter described in detail above may be defined by one or more clauses, as set forth below.

A method includes obtaining a raw lithium-bearing material. The method also includes obtaining one or more additives. Further, the method includes providing the raw lithium-bearing material and the one or more additives to a mill, wherein the mill is configured to mechanically impact the raw lithium-bearing material. The method also includes obtaining a lithium-bearing material intermediate based on the mechanical impact to the raw lithium-bearing material and the one or more additives. The method includes providing the lithium-bearing material intermediate to a separator. Further, the method includes obtaining a lithium product via the separator.

The method of the preceding clause, wherein providing the raw lithium-bearing material and the one or more additives to the mill comprises spraying, via a sprinkler system, the one or more additives onto the raw lithium-bearing material upstream of the mill.

The method of any preceding clause, wherein providing the one or more additives to the mill comprises injecting, via an injection system, the one or more additives directly into the mill.

The method of any preceding clause, wherein the one or more additives comprise grinding agents.

The method of any preceding clause, wherein the one or more grinding agents comprise fusion salts, fluxes, polyionic salts, carbonate salts, ammonium-based salts, cationic salts, or a combination thereof.

The method of any preceding clause, wherein the one or more additives further includes a solvent.

The method of any preceding clause, wherein the one or more solvents comprise glycols, alcohols, organic acids, supercritical carbon dioxide (CO₂), molten salts, or a combination thereof.

The method of any preceding clause including receiving sensor feedback indicative of a physical property of the intermediate and/or raw lithium-bearing material. The method also includes adjusting one or more operational parameters of the mill based on the sensor feedback.

The method of any preceding clause, wherein the one or more operational parameters comprise rotational speed, energy input, material composition, time, or a combination thereof.

The method of any preceding clause, wherein the separator comprises an enhanced gravity separator.

The method of any preceding clause, wherein the raw lithium-bearing material is one of a clay, tuff, or mica.

The method of any preceding clause, wherein the raw lithium-bearing material is clay and wherein clay particles are used as precursors for cement.

The method of any preceding clause, further including further obtaining a lithium-deprived material intermediate via the separator and obtaining at least an additional product containing another element than lithium from the lithium-deprived material intermediate.

The method of any preceding clause, wherein the at least one additional product includes at least one of uranium (U), magnesium (Mg), potassium (K), and boron (B).

The method of any preceding clause, wherein inert gases are provided to the mill.

The method of any preceding clause, wherein the lithium-bearing intermediate is obtained by milling the raw lithium-bearing material in the mill under vacuum.

A system includes a controller having a processor, a memory, and instructions stored on the memory and executable by the processor to control a lithium-based extraction system to receive a raw lithium-bearing material into a mill. The instructions include receiving one or more additives into the mill. The instructions also include crushing the raw lithium-bearing material and the one or more additives to generate an intermediate. The instructions further include separate lithium product from the intermediate, thereby generating the lithium product.

The system of the preceding clause, wherein the one or more additives comprise one or more fusion salts, polyionic salts, carbonate salts, ammonium-based salts, cationic salts, or a combination thereof.

The system of any preceding clause, wherein the one or more additives comprise one or more glycols, alcohols, organic acids, supercritical carbon dioxide, molten salts, chelating agents, or a combination thereof.

The system of any preceding clause, wherein the controller is configured to adjust one or more operational parameters of the mill based on sensor feedback generated from one or more sensors, wherein the one or more operational parameters comprise one or more comprise rotational speed, energy input, material composition, dry milling, wet milling, time, or a combination thereof.

The system of any preceding clause, wherein the controller is configured to control an injection system to inject the one or more additives onto the raw lithium-bearing material to generate the intermediate.

The system of any preceding clause, wherein the controller is configured to receive feedback indicating a physical property of the intermediate or the raw lithium-bearing material.

The system of any preceding clause, wherein clay particles are used as precursors for cement.

The foregoing description, for purpose of explanation, has been described with reference to specific embodiments. However, the illustrative discussions above are not intended to be exhaustive or to limit the disclosure to the precise forms disclosed. Many modifications and variations are possible in view of the above teachings. Moreover, the order in which the elements of the methods described herein are illustrated and described may be re-arranged, and/or two or more elements may occur simultaneously. The embodiments were chosen and described in order to best explain the principals of the disclosure and its practical applications, to thereby enable others skilled in the art to best utilize the disclosure and various embodiments with various modifications as are suited to the particular use contemplated.

Finally, the techniques presented and claimed herein are referenced and applied to material objects and concrete examples of a practical nature that demonstrably improve the present technical field and, as such, are not abstract, intangible or purely theoretical. Further, if any claims appended to the end of this specification contain one or more elements designated as “means for [perform]ing [a function] . . . ” or “step for [perform]ing [a function] . . . ”, it is intended that such elements are to be interpreted under 35 U.S.C. 112(f). However, for any claims containing elements designated in any other manner, it is intended that such elements are not to be interpreted under 35 U.S.C. 112(f).