Patent Application
20250223667
This application relates generally to systems, methods, and apparatuses for isolating and extracting target elements, minerals, and salts from a variety of saline sources.
Minerals like lithium, magnesium, sodium, potassium, calcium, cobalt, manganese, nickel, rare earth elements, and graphite are key components for many technologies and, therefore, have intrinsic value. These minerals are found in many products, including computers, household appliances, and, particularly in clean energy technologies like batteries, electric vehicles, wind turbines, and solar panels helping to drive the move away from fossil fuels. As the world continues to create a more sustainable future, many of these industries will depend on critical minerals raising the global demand, which is expected to grow to 600 percent over the next several decades. The global lithium-ion battery market, for example, is estimated at USD 48.19 billion in 2022 and is expected to be 182.53 billion in 2030 with a compound annual growth rate (CAGR) of 18.1%. Unfortunately, the U.S. depends on foreign sources for many of these minerals. Accordingly, identifying domestic sources has become a national security concern.
A primary challenge to securing a robust U.S. lithium (Li) supply chain is a lack of domestic production opportunities. Existing methods for obtaining lithium include direct lithium extraction (DLE) which encompasses emerging technologies designed to extract lithium from brine resources more efficiently and sustainably than traditional evaporation methods because those traditional methods are known for their intense water consumption, long processing times, and limitation to continental brines as feedstocks. DLE can be categorized into five main approaches: adsorption, ion exchange, solvent extraction, (electro-)membrane, and electrochemical methods, with each approach exhibiting both advantages and disadvantages. Each approach aims to separate lithium from other elements in brine solutions, offering advantages such as faster extraction times, higher recovery rates, smaller environmental footprints, and the ability to process lower-grade and geographically diverse lithium resources.
Adsorption DLE, utilizing aluminum-based sorbents with water as the eluent, currently stands as the most commercially viable technology and is more effective with higher quality brine (lithium concentrations≥300 pm). Following closely is ion exchange DLE, which employs coated manganese or titanium-based sorbents and dilute hydrochloric acid (HCl) as the eluent. Unlike the Adsorption approach, Ion exchange technologies excel with lower quality brines (lithium concentrations below 100 ppm). Solvent extraction currently ranks third in commercial viability and combines adsorption for initial extraction. Alternative methods at lower technology readiness levels include electromembrane processes (such as nanofiltration and electrodialysis) and electrochemical approaches. While these methods demonstrate promising characteristics, including high recovery rates, efficiency, selectivity, and lower energy consumption and water consumption rates from low lithium concentration solutions, their economic viability remains uncertain.
Clean water security is another problem becoming more urgent around the world. According to the United National Water organization, 1.42 billion people, including 450 million children, live in high or extremely high-water vulnerability areas. Clean water security is mainly impacted by droughts, wildfires, civil conflict, agricultural deficits, and antiquated water distribution channels. By 2025, two-thirds of the world's population may be facing water shortages making clean water availability one of the direst environmental issues of our time. Climate change and bio-energy demands are expected to amplify the already complex relationship between world development and water demand. In the future, water must be treated as a scarce resource with a stronger focus on managing demand. Water scarcity and demand require low-cost, environmentally friendly, and energy-efficient water production and supply technologies.
One such process for meeting fresh water demands is seawater desalination, a process that converts seawater to fresh water and has the opportunity to be a significant source of potable water production. Desalinated water is necessary to meet the demands in regions impacted by freshwater scarcity and is expected to narrow the water demand/supply gap. Globally, approximately 15,906 operational desalination plants produce 95 million m3/day of desalinated water. Reverse osmosis (RO) is the most commonly used process, with up to 55% recovery. As a result, seawater desalination globally generates up to 125.5 million m3/day of brine that is left over after the available fresh water is separated. That brine is up to three times saltier than seawater. The brine is treated as waste and discharged back into the ocean where it can unfortunately detrimentally impact the aquatic ecosystem and marine life.
Systems and methods of the invention recognize that concentrated seawater, along with other waste feeds or industrial process streams (e.g., battery e-waste, oil and gas produce waters, industrial wastewater, food and beverage wastewater, fertilizer production, mining tailings, leachates, and synthesized brines) contain many of the valuable minerals discussed above. The processes described herein provide for more efficient and environmentally-friendly separation, purification, and concentration of valuable minerals from a variety of waste feeds including concentrated brine from seawater desalination.
Multiple elements have been identified in many unconventional brine sources, including valuable elements like lithium (Li). However, recovery and concentration of lithium is challenging and requires high energy input for successful recovery. Traditionally, hydrometallurgy and ion exchange membranes have been used to extract minerals from brine. However, these methods can only extract one ion at a time and require strong acids as input for extraction. This presents many challenges for commercializing these technologies and exacerbates environmental concerns. Accordingly, the systems and methods described herein, allowing for efficient extraction of multiple minerals from brine (including unconventional waste sources and combined feeds) without the need for strong acids, is a significant advancement over existing technologies addressing an unmet need.
In certain embodiments, the present invention leverages zwitterionic chromatography processes to allow multi-mineral extraction that can continuously harvest essential compounds without ancillary chemicals, enabling a more energy-efficient and improved environmental footprint and reduced operational requirements.
Current lithium extraction technologies, including hydrometallurgy and direct lithium extraction, that mine lithium from brine sources rely on brine concentrations where the ratios of magnesium to lithium and calcium to lithium are 4:1 or lower. This is because higher concentrations of magnesium and calcium mean either more chemical leaching, which results in lower lithium yields, or the membranes being used to filter these minerals will become inoperable and need to be cleaned frequently, slowing down production. In contrast, the systems and methods described herein allow for multiple minerals to be filtered simultaneously, thereby avoiding the aforementioned problems found with other methods. Additionally, the present systems and methods can be applied to brines with higher magnesium and calcium concentrations and are not limited to the 4:1 ratios required for hydrometallurgical and direct lithium extraction methods. Accordingly, the systems and methods of the invention can allow of extraction from new sources such as geothermal brines in the United States that have been previously overlooked due to their high concentrations of magnesium and calcium at ratios higher than 4:1.
Systems and methods described herein provide an integrated system to extract monovalent, divalent, transition metals, and rare earth elements from natural and waste saline sources with a reduced chemical footprint, lower water consumption, and improved energy efficiency compared to current treatment and recovery methods. Furthermore, the systems and methods described herein can recover salt complexes at rates of 90% or greater while maintaining purity of 90% or higher at much faster rates than current evaporative methods. Other advantages of the present system include flexibility in brine composition and the ability to combine multiple feed sources along with multiplex recovery of different minerals in a single system. In various embodiments, systems and methods of the invention have been applied using chromatographic technology with lithium recovery rates exceeding 95% through a chemical-free, continuous process. Furthermore, the systems and methods herein have achieved selective lithium recovery from oil and gas industry waste waters containing lithium concentrations as low as 15 ppm. This approach overcomes key limitations of existing methods by eliminating chemical additives, enabling low-concentration feedstock processing, providing flexibility for multi-mineral recovery, while promoting environmentally responsible resource management practices in domestic operations.
A single system of the invention can accept feeds comprising desalination brine, battery e-waste, byproducts from oil and gas production, industrial wastewater, food and beverage wastewater, mining tailings, leachates, synthesized brines and other salty feed sources, including combined feeds of any of the above. Systems and methods can use zSMB chromatography and other apparatuses including multiple adsorption, ion-exchange, and surface chemistries such as zwitterion, zeolites, metal organic frameworks, heavy metal sorbents (chalcogenides), ceramic wicks, and others alone or in combination to maximize extraction efficiency and/or minimize environmental impacts. The single system can recover multiple by-products through directed flow of the feed through various extraction apparatuses including lithium chloride, calcium chloride, magnesium chloride, potassium chloride, transition metals, and rare earth elements.
Aspects of the invention can include a system for extraction of target minerals from a feed. The system can include an inlet operable to receive a feed mixture: one or more pre-treatment apparatuses in fluidic communication with the inlet and operable to prepare the feed mixture for mineral extraction; a plurality of mineral extraction apparatuses in fluidic communication with the one or more pre-treatment apparatuses and each operable to separate one or more target minerals from the pre-treated feed mixture, wherein the plurality of mineral extraction apparatuses comprise a plurality of zwitterionic simulated moving bed chromatographic separators each having a zwitterion with an affinity selected to separate a different target mineral from the feed, wherein the plurality of mineral extraction apparatuses are operable to produce one or more concentrated target mineral liquid and reclaimed water; one or more post-treatment apparatuses in fluidic communication with the plurality of mineral extraction apparatuses and operable to receive the one or more concentrated target mineral liquid and distill and purify the one or more target minerals from the concentrated target mineral liquid; a system of valves operable to direct fluid flow between the inlet, the one or more pre-treatment apparatuses, the plurality of mineral extraction apparatuses, and the one or more post-treatment apparatuses; and a controller operable to control the system of valves in a determined sequence.
The feed mixture can comprise one or more selected from the group consisting of seawater, batter e-waste, oil and gas production byproducts, industrial wastewater, food and beverage wastewater, mining tailings, leachates, geothermal brines, hard-rock acid mine drainage, and synthesized brines. In certain embodiments the feed mixture may comprise two or more selected from the group consisting of seawater, batter e-waste, oil and gas production byproducts, industrial wastewater, food and beverage wastewater, mining tailings, leachates, and synthesized brines.
The one or more pre-treatment apparatuses can be operable to perform one or more processes selected from the group of pH adjustment, adsorption, activated carbon filtration, bi-polar membrane electrodialysis, distillation, mechanical vapor recompression, reverse osmosis, nanofiltration, electrolysis, membrane distillation crystallography, carbonation, ceramic wicking, and layered heavy metal sulfide filtration. One or more of the plurality of mineral extraction apparatuses may be operable to perform direct lithium extraction, electrodialysis, membrane and ion-exchange filtration, organic sorbent filtration, or inorganic sorbent filtration. Two or more of the plurality of mineral extraction apparatuses can be arranged in parallel. In some embodiments, two or more of the plurality of mineral extraction apparatuses can be arranged in series. Systems of the invention can include one or more sensors operable to measure pressure, flow rate, temperature, pH, conductivity, or concentration of target mineral in a fluid in the system. The controller may be operable to receive data from the one or more sensors and define the determined sequence based on the received data.
In various embodiments, the one or more target minerals can be selected from the group consisting of lithium, sodium, magnesium, calcium, cobalt, manganese, potassium, rare earth elements, gallium, and transition metals. The one or more pretreatment apparatuses can comprise a brine characterization apparatus operable to determine presence of one or more elements, concentration of one or more elements, presence of cations or anions, total organic compounds, alkalinity, salinity, total dissolved solids, conductivity, density and/or specific gravity, or volatile organic content in the feed mixture. The controller may be operable to receive data from the brine characterization apparatus and define the determined sequence based on the received data. The brine characterization apparatus can be operable to perform inductively coupled plasma optical emission spectroscopy, elemental analysis, or ion chromatography on the feed mixture.
In certain aspects, the invention can include methods for extraction of target minerals from a feed, the method comprising: receiving at an inlet of a system, a feed mixture: pre-treating the received feed mixture in one or more pre-treatment apparatuses of the system to prepare for mineral extraction; separating one or more target minerals from the pre-treated feed mixture in a plurality of mineral extraction apparatuses wherein the plurality of mineral extraction apparatuses comprise a plurality of zwitterionic simulated moving bed chromatographic separators each having a zwitterion with an affinity selected to separate a different target mineral from the feed, wherein the plurality of mineral extraction apparatuses are operable to produce one or more concentrated target mineral liquid and reclaimed water; distilling and purifying the one or more target minerals from the concentrated target mineral liquid in one or more post-treatment apparatuses; directing, using a controller and a system of valves, fluid flow between the inlet, the one or more pre-treatment apparatuses, the plurality of mineral extraction apparatuses, and the one or more post-treatment apparatuses in a determined sequence.
Methods can include separation of various target minerals and/or reclaimed water using the systems described herein.
The advantages of the invention described above, together with further advantages, may be better understood by referring to the following description taken in conjunction with the accompanying drawings. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention.
As depicted in
The heart of process depicted in
In certain embodiments, amorphous metal chalcogenides can be used as sorbents in a pre-treatment or extraction step to isolate a target mineral as described, for example, in U.S. Pat. Pub. No. 2019/0055136, incorporated herein by reference. In some embodiments, lithium or other minerals may be extracted in a pre-treatment or extraction step/apparatus using a 3D nanostructured hybrid inorganic-gel framework electrode as described, for example, in Zhao, et al., 2020, Efficient Lithium Extraction from Brine Using a Three-Dimensional Nanostructured Hybrid Inorganic-Gel Framework Electrode, ACS Sustainable Chem. Eng. 2020, 8, 4827-4837, incorporated herein by reference.
Activated carbon filtration uses an adsorption medium with its function being to adsorb organic molecules in its micropores. It is activated using thermal or chemical processes to extend its adsorption capacity.
Bipolar membrane electrodialysis (BMED) is a well-developed, efficient, and environmentally friendly technology, which can be used to produce bases and acids from neutral salts. The BMED technique is an integration of bipolar membrane (BM) with conventional electrodialysis.
Selectrodialysis with Bipolar Membranes (BMSED) is an electrically driven membrane desalination technology, which has high potential to selectively remove specific ions from the solution (Chen, et al., 2018, Selectrodialysis with bipolar membrane for the reclamation of concentrated brine from RO plant, Desalination, 442:8-15, incorporated herein by reference). An electrodialysis cell consists of two electrodes and alternatingly placed ion exchange membranes between them.
Mineral carbonation is based on the reaction of CO2 with metal oxide bearing materials to form insoluble carbonates, with calcium and magnesium being the most attractive metals. In nature such a reaction is called silicate weathering and takes place on a geological time scale.
Electrodialysis (ED) is a membrane process of separation under the action of an electric field, where ions are selectively transported across ion-exchange membranes. Separating the cation-and anion-exchange membranes alternatively, ED can successfully produce two streams of different concentrations in the separated compartments. ED is cost-effective due to its a limited need of chemicals while still allowing for substantial product recovery.
Electrolysis utilizes electrical energy to cause the reduction of ionic metal species into the elemental, metallic state.
Membrane distillation-crystallization (MDC) is a popular technique for near zero liquid discharge (near-ZID) applications, as it has the ability to treat brines at near saturation to further reduce their volume. MDC combines membrane distillation (MD) with crystallization to recover solid salts and produce high-quality water.
Nanofiltration (NF) is a pressure driven membrane separation process between ultrafiltration and reverse osmosis and is particularly useful in separating Li from Mg.
Depending on the source(s) of the starting feed, pre-treatment can include pH adjustment to achieve the desired pH for subsequent processes.
Pre-treatment can include brine characterization in certain embodiments. In some embodiments, subsequent pre-treatment measure may be selected based on brine characterization. Brine characterization can include determining the brine's composition and how to properly treat it to recover ions. This can be done through a variety of testing that is possible via in-lab equipment and external testing facilities or, in some embodiments, through apparatuses included in the flow of the extraction system wherein the brine characterization is an initial pre-treatment step and feeds information to a computer controller operable to select a flow path for the brine including pre-treatment, mineral extraction, and post-treatment steps and apparatuses based on the brine composition. Exemplary brine characterization techniques can include inductively coupled plasma optical emission spectroscopy and/or any known form of mass or other spectroscopy to determine the elemental composition and concentration of a brine feed. Brine characterization can include High-Performance Liquid Chromatography (HPLC) simulation, anion chromatography, cation chromatography, x-ray fluorescence and/or crystallography, scanning electron microscopy, ultraviolet fluorescence, and Fourier transform infrared spectroscopy. Other brine characterization techniques can include elemental analysis to determine the amount of carbon, hydrogen, oxygen, nitrogen, and/or sulfur in a feed brine and/or ion chromatography to determine cations and anions present in the feed. Brine characterization can include total organic carbon measurements to determine the total amount of organic compounds present in the feed. In various embodiments, physical properties of the brine feed can be determined including alkalinity, salinity, total dissolved solids, resistivity, pH, viscosity, turbidity, and conductivity of the brine feed along with the volatile organic compound (VOC) content of the brine. As shown in
After the optional pre-treatment(s), the feed can proceed to mineral separation and recovery. An advantage of the present system and methods is the available combination of multiple different extraction methods to target a variety of minerals in a single continuous method or apparatus. A primary mineral separation and recovery method is simulated moving bed (SMB) chromatography as described in Kim, et al., 2020, Journal of Industrial and Engineering Chemistry 88 (2020) 328-338; Zhang, et al., 2023, Research Progress on the Typical Variants of Simulated Moving Bed: From the Established Processes to the Advanced Technologies, Processes 2023, 11, 508; and, more specifically, zwitterionic SMB (zSMB) chromatography as discussed with respect to lithium extraction in PCT publication WO2021/119208, the content of each of which is incorporated herein by reference in its entirety. The use of simulated moving bed chromatographic with zwitterionic resins provides some of the advantages over direct lithium extraction discussed above, specifically avoiding the need for mineral acids (used to elute adsorbed lithium in direct lithium extraction) instead using only water used as an eluent. In various embodiments, zSMB extraction can be combined in a hybrid extraction method using, for example, thermal processes such multistage flash, mechanical vapor recompression, and/or multi-effect distillation (see WO2021/119208).
As discussed in the above-referenced PCT publication, target-specific zwitterionic sorbents have been previously developed for mineral salt separation. Those materials allow mineral salt fractionation under water elution, which differs from conventional ion exchange approaches requiring additional chemicals for the salt separations, particularly lithium chloride separation. Conventional IX (CIX) is in many respects inferior to the Zwitterionic Ion Chromatography (ZIC) methods discussed herein. CIX-based technology is a multi-step process. In Step 1, the brine is loaded onto a packed bed that can selectively bind Li+ cations. Step 2 washes the unbound salts out of the column. Step 3 elutes the Li+ cations through the addition of a mineral acid such as hydrochloric acid, and then Step 4 regenerates the column with water to remove any acids in the bed.
Such IX/adsorption technology is the current approach for Li recovery from U.S.-based saline resources. Therefore, the zwitterionic SMB (zSMB) technology discussed herein can be compared to these currently practiced DLE processes to assess viability. The ZIC method intercalates the entire salt between the zwitterion stationary phases under water elution, partitioning mineral salts. This allows the separation of many different salts simultaneously without other added chemicals (e.g. HCl). In contrast to CIX/adsorption, ZIC operates in isocratic elution mode using only water as the eluent, thus it can be easily scaled with SMB technology and requires no added chemicals. This improves environmental stewardship and decreases operating expenses compared to currently practiced DLE technology. Furthermore, in various embodiments, the throughput, yields, and chemical/water footprints can be improved based on machine-learning (ML) model optimization.
Additional methods that can be used alone or in combination with zSMB chromatography in systems and methods of the invention to increase mineral yield can include DLE, electrodialysis methods, membrane and ion-exchange methods, and organic and inorganic sorbents. In certain embodiments, CO2 injection techniques such as described in U.S. Pat. No. 10,315,926, incorporated herein by reference in its entirety. Additionally, a variety of resins, polymers, zeolites, and/or metal-organic frameworks (MOFs) can be used to improve zSMB chromatographic techniques.
Furthermore, any combination of the above pre-treatment techniques for mineral separation can be applied at any point of the process including after zSMB treatment to further extract desired minerals. Additionally, those methods and zSMB can be applied more than once to the feed including redirecting effluent or other post-treatment products through the zSMB apparatus or other filtration or pre-treatment apparatuses multiple times to ensure maximum mineral recovery. After critical target mineral extraction the reaming depleted brine can be exited from the system. Throughout the process, any water generated can be reused or recycled for water needs of the user or sent back through the process along with or substituted for untreated mineral water streams to further purify and/or extract any remaining target minerals.
After mineral separation, concentration and water recovery steps can be performed. These can include distillation, electrowinning, reverse osmosis, and mechanical evaporation. The resulting recovered water can be used as a new source of fresh water, thereby addressing the growing demand for potable water worldwide while simultaneously providing a source for valuable minerals with a reduced environmental impact compared to existing methods of mineral mining and water production.
The isolated minerals (e.g., lithium) can then be purified through, for example, crystallization and converted to a final product via carbonation, electrolysis, or other methods depending on the desired final product and the extracted mineral. The resulting end-use product (e.g., battery-grade lithium) can then be delivered to industry for use.
Returning to
As shown in the example depicted in
Various liquids including unconventional waste sources and desalination brines can be subjected to an initial reverse osmosis filtration step followed by pH adjustment depending on the target mineral to be extracted. For example, chromatographic fractionation of sodium. potassium, calcium, and magnesium may require a pH of 10 while lithium requires a pH of 9. After fractionation of the target mineral which, as described above, can be driven by selection of specific zwitterions in the stationary phase, the resulting product can be distilled and the resulting target salt can be crystallized to form the desired product (e.g., sodium chloride lithium chloride, potassium chloride, calcium chloride, or magnesium chloride).
While the treatments shown are separated for clarity, it should be appreciated that any combination of the mineral extraction methods depicted can be applied to a single feed from one or more combined waste sources or brines serially or in parallel to extract multiple target minerals in a single process. To accomplish this, systems and methods of the invention can include valves, which may be computer controlled, to direct the flow of liquid from the brine or waste source(s) to and between the various pretreatment, mineral extraction, and post treatment apparatuses. As will be appreciated, various in-line sensors may be included to monitor, for example, temperature, pressure, pH, or other characteristics as well as to identify target minerals and/or contaminants in recovered water. In certain embodiments the information from such sensors can be received by a computing device comprising a non-transient memory and a processor in order for that computer to control flow (via, pumps, valves, and other mechanisms) of the fluids within the system based on feedback received from the sensors. For example, identification of magnesium or lithium in a waste source via the one or more sensors may cause the computer to execute instructions to open valves and/or pump the waste source into one of the aforementioned apparatuses specifically configured to extract those minerals. Alternatively, if a specific target mineral is not detected, the system may bypass an apparatus for extraction of that mineral (via pumps and/or valves) that would otherwise be in fluidic communication with the overall system.
Additionally, sensors information can be used by the computer to control timing of movement between pre-treatment, extraction, and/or post-treatment apparatuses. For example, a pH sensor in a pre-treatment apparatus may provide continuous feedback to the computer during pH adjustment and the computer can time the movement of the fluid from that pre-treatment apparatus based on the target pH being achieved. Similarly, mineral concentration of a specific target mineral can be measured in, for example, a raffinate, an eluent, reclaimed water, or other apparatus product and, based on the concentration of the target mineral in that fluid, pumps and/or valves controlled by the computer can be used to either redirect that fluid back through the extraction or other apparatus or onward to a subsequent step and/or apparatus in the process or system.
ZIC technology provides a different separation approach and mechanism compared to the methods in current use (adsorption, ion exchange, solvent extraction). One advantageous aspect of ZIC is its flexibility in mineral recovery, even for high TDS saline resources that are not exploitable with current DLE technologies. Specifically, ZIC has the potential to selectively fraction LiCl from other divalent mineral salts (MgCl2, CaCl2). This allows a more universal stationary phase for the recovery of minerals from saline resources simply by changing the switching sequence of the SMB, which can be done by efficient optimization using a machine learning model.
This Application claims the benefit of and priority to U.S. Provisional Application Ser. No. 63/618,128, filed Jan. 5, 2024, the content of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63618128 | Jan 2024 | US |
