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Recovery of lithium from Uyuni salar brine
Abstract
A hydrometallurgical process was developed to recover lithium from a brine collected from Salar de Uyuni, Bolivia, which contains saturated levels of Na, Cl and sulphate, low Li (0.7–0.9 g/L Li) and high Mg (15–18 g/L Mg). Unlike other commercial salar brines currently being processed, the high levels of magnesium and sulphate in Uyuni brine would create difficulties during processing if conventional techniques were used. A two-stage precipitation was therefore first adopted in the process using lime to remove Mg and sulphate as Mg(OH)2 and gypsum (CaSO4.2H2O). Boron (at 0.8 g/L in the raw brine), a valuable metal yet deleterious impurity in lithium products, could also be mostly recovered from the brine by adsorption at a pH lower than pH11.3 in this first stage. The residual Mg and Ca (including that added from lime) which were subsequently precipitated as Ca–Mg oxalate could be roasted to make dolime (CaO ∙ MgO) for re-use in the first stage of precipitation. Evaporation of the treated brine up to 30 folds would produce 20 g/L Li liquors. The salt produced during evaporation was a mixture of NaCl and KCl, containing acceptable levels of sulphate, Mg, Ca, etc. The final precipitation of lithium at 80–90 °C produced a high purity (99.55%) and well crystalline lithium carbonate.
... To effectively utilize and recover liquid lithium resources, it is crucial to develop efficient extraction methods. The main methods for extracting lithium from liquid lithium resources include precipitation [4], solvent extraction [5,6], membrane separation [7], electrochemical methods [8,9], and adsorption [10]. Among them, the adsorption technique has attracted significant research attention for its straightforward operation and economic efficiency. ...
Titanium lithium ion sieve (Ti-LIS) has attracted much attention due to their excellent adsorption properties and easy preparation process. In this study, the Li2TiO3 with different doping amounts of W (LTWO) was synthesized by the hydrothermal method. Then, the LTWO was washed with HCl to obtain the adsorbent of W-doped H2TiO3 (HTWO). The structure and adsorption properties of HTWO-4 were tested and the results showed that the introduction of W into HTWO leads to lattice defects, which increase oxygen vacancies and promote Li⁺ diffusion in the adsorbent. The effects of adsorption time, initial Li⁺ concentration, and pH on the adsorption properties of Li⁺ were systematically evaluated. The adsorption process of HTWO was confirmed as chemisorption and monolayer adsorption by simulating the pseudo-second-order kinetic model and Langmuir model. Among them, HTWO-4 exhibits a higher adsorption capacity than others, with a value of 34.68 mg/g in a LiCl solution (Li⁺ = 210 mg/L). Additionally, the HTWO-4 exhibits superior adsorption selectivity of Li⁺ over Mg²⁺, Ca²⁺, K⁺, and Na⁺, maintaining a high Li⁺ adsorption capacity after five regeneration cycles. This work provides an ideal candidate adsorbent in the field of lithium resource utilization.
... At this stage, various salts precipitate as water is removed. Ion salts that do not precipitate spontaneously, such as boron, calcium, magnesium, and sulfates, must be removed through chemical treatment [32,33]. ...
The rapid expansion of lithium-ion battery (LIB) markets for electric vehicles and renewable energy storage has exponentially increased lithium demand, driving research into sustainable extraction methods. Traditional lithium recovery from brine using evaporation ponds is resource intensive, consuming vast amounts of water and causing severe environmental issues. In response, Direct Lithium Extraction (DLE) technologies have emerged as more efficient, eco-friendly alternatives. This review explores two promising electrochemical DLE methods: Electrodialysis (ED) and Capacitive Deionization (CDI). ED employs ion-exchange membranes (IEMs), such as cation exchange membranes, to selectively transport lithium ions from sources like brine and seawater and achieves high recovery rates. IEMs utilize chemical and structural properties to enhance the selectivity of Li⁺ over competing ions like Mg²⁺ and Na⁺. However, ED faces challenges such as high energy consumption, membrane fouling, and reduced efficiency in ion-rich solutions. CDI uses electrostatic forces to adsorb lithium ions onto electrodes, offering low energy consumption and adaptability to varying lithium concentrations. Advanced variants, such as Membrane Capacitive Deionization (MCDI) and Flow Capacitive Deionization (FCDI), enhance ion selectivity and enable continuous operation. MCDI incorporates IEMs to reduce co-ion interference effects, while FCDI utilizes liquid electrodes to enhance scalability and operational flexibility. Advancements in electrode materials remain crucial to enhance selectivity and efficiency. Validating these methods at the pilot scale is crucial for assessing performance, scalability, and economic feasibility under real-world conditions. Future research should focus on reducing operational costs, developing more durable and selective electrodes, and creating integrated systems to enhance overall efficiency. By addressing these challenges, DLE technologies can provide sustainable solutions for lithium resource management, minimize environmental impact, and support a low-carbon future.
... Many of the salt-lake brines that have high potential for resource recovery using solar evaporation have high concentrations of divalent cations. For example, in lithium containing brines the concentration of magnesium can be as high as 3 wt % and the concentration of calcium can be as high as 2.4 wt %. 39,40 Table S1 summarizes the ion concentrations of selected lithium containing brines throughout the world. In commercialized processes, such as the chemical precipitation method currently used for lithium mining, reducing the concentration of the divalent cations is the costliest step as they can prevent high lithium recoveries from some brines. ...
In this work, we analyzed the effects of mineral scaling on the performance of a 3D interfacial solar evaporator, with a focus on the cations relevant to lithium recovery from brackish water. The field has been rapidly moving toward resource recovery applications from brines with higher cation concentrations. However, the potential complications caused by common minerals in these brines other than NaCl have been largely overlooked. Therefore, in this study, we thoroughly examined the effects of two common cations (calcium and magnesium) on the long-term solar evaporation performance of a 3D graphene oxide stalk. The 3D stalk can achieve an evaporation flux as high as 17.8 kg m–2 h–1 under one-sun illumination, and accumulation of NaCl on the stalk surface has no impact. However, the presence of CaCl2 and MgCl2 significantly reduces the evaporative flux even in solutions lacking scale-forming anions. A close examination of scale formation during long-term evaporation experiments revealed that CaCl2 and MgCl2 tend to precipitate out within the stalk, thus blocking water transport through the stalk and significantly dropping the evaporation rates. These findings imply that research attention is needed to modify and optimize the internal water transport channels for 3D evaporators. Additionally, we emphasize the importance of testing realistic mixtures—including prominent divalent cations— and testing long-term operations in interfacial solar evaporation research and investigating approaches to mitigate the negative impacts of divalent cations.
... Under specified conditions, the extraction of boron reach a rate of 99.07%, and water is employed as a stripping agent to recover the solvent. The effluent stream then proceeds to the first precipitation stage (Pr 1) to remove Mg 2+ and other ions such as Fe 2+ and Ni 2+ (Chagnes and Swiatowska, 2015;Karidakis et al., 2005;An et al., 2012). Lithium recovery processes face difficulties with handling large quantities of magnesium as it needs to be recovered as a by-product to enhance the economic efficiency of the process while minimizing the loss of lithium. ...
Lithium demand is surging, necessitating efficient extraction methods. Geothermal brines offer a promising alternative feedstock, yet comprehensive systems-level analyses are lacking. We developed an industrial process model for a plant processing 2000 ton/h geothermal brine using chemical precipitation to produce lithium carbonate, coupled with techno-economic and life cycle assessments to evaluate process economics and environmental impacts. A novel recycling process for on-site reuse of precipitating agents is also proposed, increasing total investment cost by 23% while reducing CO2 emissions by nearly 50% without extending the payback period. Additionally, we investigated the impact of feedstock concentration and water costs on process economics. Our findings show that low-concentration lithium brines (less than 200 mg/L) are economically viable only at high lithium carbonate selling prices. This study highlights the potential of geothermal brines as a sustainable lithium source and the benefits of integrating recycling processes to mitigate environmental concerns.
... Due to the similar chemical compositions, the recovery of lithium from the waste liquid of rock salt brine can refer to salt lake brine methods that contain precipitation (Wang et al. 2017;han et al 2018), adsorption (Li et al. 2020), solar pond , solvent extraction (Song et al. 2020), membrane (Chung et al. 2008) and electrodialysis methods (Xiong et al. 2021). The precipitation method is a traditional method that uses carbonate (An et al. 2012), aluminate (Zhong et al. 2021), and phosphate (he et al. 2017) to precipitate lithium. In this study, the amorphous Al(Oh) 3 produced by AlCl 3 · 6h 2 O and NaOh was used to precipitate Li + in the waste liquid from rock salt brine with the formation of LiCl · 2Al(Oh) 3 · xh 2 O salt (Kotsupalo et al. 2013;Paranthaman et al. 2017). ...
An integrated process consisting of Li+ precipitation by Al(OH)3, roasting, water leaching, evaporation, and Li2CO3 precipitation was used to recycle Li+ from the waste liquid of rock salt brine (0.099 g/L Li+). Waste liquid from roc salt brine was discharged wastewater after NaCl crystallization and the removal of impurities in the salt manufacturing plant of the good rock salt mine. The influences of Al3+/Li+ mole ratio, Na+/Al3+ mole ratio, precipitation temperature, and time on the recovery of Li+ were investigated during Li+ precipitation by Al(OH)3 stage. The results showed that the optimal condition was Al3+/Li+ mole ratio = 2.5, Na+/Al3+ mole ratio = 2.2, precipitation temperature of 60℃ (333.15 K) for more than 20 min, whose recovery of Li+ reached 97.25%. The thermodynamic analyses of the simulated Li+–Al+–Mg2+–Cl––H2O system were conducted to construct the potential-pH (φ-pH) diagrams. The results showed that the pH value should be located in the LiCl · 2Al(OH)3 · 2H2O salt region with no formation of Mg(OH)2, which started at pH = ~6.5 and ended at pH from 10.09 to 8.55 as the temperature changed. Subsequently, the Li+precipitate was roasting for the transformation of insoluble LiCl · 2Al(OH)3 · xH2O salt to soluble LiCl, followed by the water leaching to obtain the enriched Li+ solution (1.951 g/L Li+) with Li+ recovery of 85.52%. To meet the requirement of Li2CO3 precipitation, the enriched Li+ solution was evaporated, and Na2CO3 was added to precipitate the Li2CO3 product after SO4 2–, Ca2+, and Mg2+ removal. The total recovery of Li+ was 66.69% after the experimental process, and the purity of Li2CO3 product was 99.3%, which can be regarded as industrial-grade Li2CO3. In conclusion, the success in lithium recovery using the aluminum hydroxide precipitation method provided a new perspective for preparing Li2CO3 from the waste liquid of rock salt brine, which could be considered as a newly developing lithium resource to meet the dramatically increasing demand for lithium in new energy vehicle industry.
... Lime softening is also used in industry to reduce Mg 2 + concentrations through the addition of limewater, Ca(OH) 2 or simply CaO, to raise the pH and precipitate Mg 2 + as Mg(OH) 2 . [50,51] Based on the K sp of Mg(OH) 2 (1.5×10 À 11 ), we reasoned that increasing the sample pH from 7.4 to 11 ([OH À ] = 10 À 3 M) would promote Mg(OH) 2 precipitation to yield a final Mg 2 + concentration in solution of~15 μM. As demonstrated in Supporting Information, Figure S7, there is little decrease in the fluorescence signal in the presence of 5 mM level of Mg 2 + in comparison with that of non-target metal ions. ...
The global demand for lithium has soared in recent years due to the wide use of lithium batteries. To meet this demand, we herein report developing novel on‐site sample preparation methods for the extraction of Li⁺ from relevant materials, including brine water, spodumene rock, as well as lithium‐ion battery electrodes, and a DNAzyme‐based fluorescent sensor for sensitive and robust detection of Li⁺ in these samples down to 1.4 mM (10 ppm) using a portable fluorometer. The system can distinguish key threshold lithium levels that indicate economic value across several industries, including 200 ppm Li⁺ for brine mining, 6 % Li2O or SC6 for rock mining, and Li⁺‐specific aging in LIBs. The methods developed and demonstrated in this work will allow highly selective, on‐site, portable detection of lithium in both environmental samples to identify new lithium resources and in battery electrodes to guide recycling strategies in order to meet the global demand for lithium.
... It involves the calcium hydroxide and sodium oxalate usage in a two-step precipitation method. This eliminates magnesium, along with other impurities such as boron and sulfur [133]. According to a proposed double-drop technique, deionized water was combined with AlCl 3 ·6H 2 O and introduced into the brine. ...
The escalating demand for lithium has intensified the need to process critical lithium ores into battery-grade materials efficiently. This review paper overviews the transformation processes and cost of converting critical lithium ores, primarily spodumene and brine, into high-purity battery-grade precursors. We systematically examine the study findings on various approaches for lithium recovery from spodumene and brine. Dense media separation (DMS) and froth flotation are the most often used processes for spodumene beneficiation. Magnetic separation (MS) and ore gravity concentration techniques in spodumene processing have also been considered. To produce battery-grade lithium salts, the beneficiated-concentrated spodumene must be treated further, with or without heat, in the presence of acidic or alkaline media. As a result, various pyro and hydrometallurgical techniques have been explored. Moreover, the process of extracting lithium from brine through precipitation, liquid–liquid extraction, and polymer inclusion membrane separation employing different organic, inorganic, and composite polymer sorbents has also been reviewed.
... During the lithium concentration process, one of the main impurities is magnesium, which, in excess, in the most concentrated ponds, generates the precipitation of lithium carnallite, and therefore, lithium yield losses. On the other hand, magnesium presents drawbacks in subsequent purification stages, which makes it necessary to remove it to ensure a high-purity lithium carbonate or lithium hydroxide product [37]. ...
Citation: Torres, D.; Pérez, K.; Galleguillos Madrid, F.M.; Leiva, W.H.; Gálvez, E.; Salinas-Rodríguez, E.; Gallegos, S.; Jamett, I.; Castillo, J.; Saldana, M.; et al. Salar de Atacama Lithium and Potassium Productive Process. Metals 2024, 14, 1095. Abstract: The average lithium content in the Earth's crust is estimated at about 0.007%. Despite this, lithium is considered abundant and widely distributed, with significant extraction from various sources. Notably, the brines in the Salar de Atacama are highlighted for their high lithium concen-tration~1800 mg/L. Lithium is currently recovered from these brines through a solar evaporation process. The brine is transferred through a series of ponds, increasing the lithium concentration from 0.2% to 6% over 18 months, while decanting other minerals like potassium, magnesium, and boron. This method is the most efficient and cost-effective globally due to the Salar de Atacama's high lithium concentration of approximately 1800 ppm and the region's intense solar radiation, which facilitates evaporation at no economic cost. This manuscript describes in detail the lithium and potassium extraction processes used in the Salar de Atacama.
... CaO is the most commonly used precipitant, which tends to be combined in a two-stage precipitation process with Na 2 C 2 O 4 , Na 2 CO 3 , NaOH, or evaporation. An et al. (2012) reported the extraction of high-purity lithium carbonate from Uyuni Salar with a Li concentration of 0.7-0.9 g/L and a high Mg concentration of 15-18 g/L on a two-stage precipitation process. ...
Lithium has been a critical metal for energy transition, mainly because of its application as an energy storage matrix, which has seen its demand increasing exponentially in the last decades. To supply the current demand chain and overcome the geographical and technological limitations of lithium extraction from Salt Lake brines, the present article investigates the possibility of lithium extraction from non-conventional resources, such as Oilfields and Geothermal brines. Thus, our investigation seeks to answer the following research questions: (1) Are there identified lithium-rich subsurface brine resources? (2) Could the conventional lithium extraction precipitation method be successfully applied to those resources? (3) What are the state-of-the-art of alternative technologies that can economically be applied for efficient lithium recovery from those subsurface brine re-sources? First, our investigation identifies and distributes geographically lithium-rich subsurface brine resources worldwide, with the American continent being abundant on Oilfield brine. Europe, on the other hand, was much more abundant in Geothermal water. The UK possesses lithium-rich oilfields at relatively low concentrations and highly enriched geothermal brine, with an abundance of other lithium-rich brine sites possible across Africa and Asia. Secondly, it was established through a critical evaluation that conventional precipitation methods are insufficient for lithium extraction when applied to subsurface brines. Thus, it leads us to survey the state-of-the-art of novel extraction technologies with data from 1960 to the present, with the highest information density covering the last 22 years. Out of the reviewed extraction technologies, ion-sieve adsorbent and nanofiltration were found to be the best ally for lithium extraction from subsurface brine in the present and near future with low energy consumption, excellent lithium recovery, high extraction rate, outstanding selectivity, and forming adaptability.
... Similar observations were noted in [42], where it was shown that at concentration ratios up to 20, lithium losses are negligible, but above this value, they can reach up to 60%, depending on the final lithium concentration in the brine. Other authors [43], investigating the evaporation of real brines under natural sunlight, demonstrated minimal lithium losses (<0.004%), although the concentration ratio was rather low, i.e., around 5. ...
In recent years, the demand for lithium, essential to the high-tech and battery sectors, has increased rapidly. The majority of lithium carbonate is now sourced from continental brines in Latin America, owing to the lower production costs and reduced environmental impact. In Europe, often overlooked but promising lithium resources could include highly mineralized underground waters. Therefore, this study investigates the enrichment of these low-grade solutions (<100 mg/L Li) through evaporation followed by solvent extraction (SX) processes under specific conditions. The effectiveness and the technical feasibility of lithium extraction were evaluated using binary synthetic, multicomponent semi-synthetic, and real brine samples. The popular tributyl phosphate/methyl isobutyl ketone (TBP/MIBK) system, supplemented with FeCl3 and AlCl3 as co-extractants, was employed as the organic phase. Evaporation resulted in significant lithium losses (up to 80%), reduced to ~10% by washing the crystallisate obtained during evaporation with ethanol. The results from SX tests revealed differences between the synthetic and real brines. While the synthetic brines exhibited satisfactory lithium extraction yields (91%), the real brines showed a significantly lower extraction efficiency (~32%), rendering the tested system ineffective. Solid phase precipitation during the SX trials was observed for both the synthetic and real brines, which were concentrated before the SX stage, highlighting the challenges in lithium-recovery processes. However, semi-synthetic brine trials yielded promising results, with a satisfactory extraction efficiency (76%), and the absence of physical problems (emulsion, long disengagement, etc.). This reveals the importance of the chemical composition of brines and emphasizes the need for varied procedural approaches in lithium-recovery processes.
... Moreover, a high lithium loading leads to rapid saturation of the adsorbent and increases the cost of adsorbent regeneration [33]. The recovery of lithium as Li 2 CO 3 by chemical precipitation from Uyuni salar brine wastewater from the aluminum anode industry was reported by Álvarez-Ayuso et al. [34]. Wei et al., in 2005, applied the selective precipitation to produce purified Li 2 CO 3 from dilute Li-rich brine to increase the practical value of Li-rich brine that is obtained using the conventional treatment method. ...
In this study, a novel fluidized-bed homogeneous granulation (FBHo-G) process was developed to recover lithium (Li) from industrial Li-impacted wastewater. Five important operational variables (i.e., temperatures, pH, [P] 0 /[Li] 0 molar ratios, surface loadings, and up-flow velocities (U mf)) were selected to optimize the Li recovery (TR%) and granulation ratio (GR%) efficiencies of the process. The optimal operational conditions were determined as the following: a temperature of 75 • C, pH of 11.5, [P] 0 /[Li] 0 of 0.5, surface loading of 2.5 kg/m 2 ·h, and U mf of 35.7 m/h). The TR% and GR% at optimal condition could be as much as 90%. The material characterization of the recovery pellet products showed that they were highly crystallized Li 3 PO 4 (purity~88.2%). The pellets had a round shape and smooth surface with an average size of 0.65 mm, so could easily be stored and transported. The high purity enables them to be further directly reused as raw materials for a wide range of industrial applications (e.g., in the synthesis of cathode materials). Our calculation shows that the FBHo-G process could recover up to 0.1845 kg of lithium per cubic meter of Li-containing wastewater, at a recovery rate of~90%. A brief technoeconomic analysis shows that FBHG process had economic viability, with an estimate production cost of USD 26/kg Li removed, while the potential gained profit for selling lithium phosphate pellets could be up to USD 48 per the same volume of wastewater and the net profit up to USD 22/m 3 Li treated. In all, fluidized-bed homogeneous granulation, a seedless one-step recovery process, opens a promising pathway toward a green and sustainable recycling industry for the recovery and application of the resource-limited lithium element from nonconventional water sources.
The proliferation of Li‐related technologies, especially in the electronic devices and transportation sectors, has exacerbated the global Li resource gap. In response, significant efforts have been directed toward enhancing access to this valuable resource. Recently, numerous studies have highlighted solvent extraction as a straightforward, economical, and environmentally friendly approach for Li extraction and separation. Among them, ionic liquids (ILs) as highly tunable design solvents have garnered considerable attention for their exceptional properties compared to traditional organic solvents, yet their associated extraction systems have albeit with only moderate advancements over the past few decades. To this end, this review initiates an investigation into the pioneering research on the utilization of ILs as diluents, primary extractants, and co‐extractants for Li extraction and separation. Afterward, a comprehensive review is presented on the extraction behaviors of diverse ILs, primarily encompassing cation‐exchange and ion‐association mechanisms. The challenges faced in the application of ILs by solvent extraction are discussed. Meanwhile, Industrial technology such as patents and prospects of ILs are examined, paving the way for future directions in the development and application of ILs within Li solvent extraction technologies.
The global demand for lithium has surged in recent years due to its wide applications in industry and medicine. We have achieved selective solid-liquid extraction of LiCl using a heteroditopic receptor with an ether linker as a cation recognition site and two urea functionalities as cooperative anion recognition sites. The receptor exhibits high selectivity for LiCl from 1H NMR spectra by complexation in CD3CN and CDCl3. The solid-liquid extraction, followed by stripping to neutral aqueous phase using with the receptor revealed recovery of LiCl about 90% by ion chromatography and ICP-MS analyses, with a slight competition with MgCl2. LiCl was also recovered from the artificially prepared salt mixture and natural one from the Salar de Uyuni by the solid-liquid extraction with less competitive recovery of MgCl2.
Salt lake resources are unique and valuable minerals on Earth associated with specific elements. The advancement of technology and the rise of new industries are progressively showcasing their strategic significance for economic development. This study used bibliometrics and visualization techniques to analyze the current state and developmental trends of research on salt lake resource exploitation, both domestically and globally. A total of 760 articles from Science Citation Index Expanded (SCIE) were analyzed. The research findings reveal that the processes of salt lake separation and extraction have progressed through three distinct stages: the germination stage, the stable development stage, and the rapid development stage. China has offered robust policy support for research in this domain at the national level. China possesses a centrality score of 1.08 in the separation and extraction of salt lakes, with 50% of the 10 most active nations in this domain situated in Asia and South America. The prominent institutions comprise the Chinese Academy of Sciences (centrality score of 0.32), the Qinghai Salt Lake Study Institute (centrality score of 0.22), and the University of the Chinese Academy of Sciences (centrality score of 0.14), encompassing a diverse array of study subjects. Keywords from 2003 signify the initial advancement of lithium extraction from saline lakes, whereas those from 2011 underscore the heightened focus on integrated resource utilization and multidisciplinary study. Keywords from 2015 indicate an intensified emphasis on the extraction of lithium and other elements. The terms “tributyl phosphate” (citation strength of 6.05) and “nanofiltration” (citation strength of 4.29) exhibit significant interest in magnesium–lithium separation research and water treatment technologies employed in salt lake separation and extraction, receiving the highest number of citations. The persistent emphasis on “lithium ions” signifies the increasing demand for raw materials propelled by advancements in the new energy sector. Research trend analysis indicates that sodium resource utilization has stabilized, whereas magnesium, a byproduct of lithium extraction, is presently a key focus for downstream product applications. Rare elements remain at the experimental research stage. The industrialization of salt lake resources, including potassium, lithium, and boron, is notably advanced. Future research should focus on the mineralization and enrichment patterns of potassium resources, developing improved extraction methods for lithium, and advancing technologies for the cost-effective and environmentally friendly separation of boron resources. The future objective for resource extraction in salt lakes is to transition from a crude methodology to a refined, sustainable, and intelligent development framework.
Selective lithium extraction (DLE) from natural surface and geothermal brines is very challenging due to the low ratio of lithium to other metals, and the lack of suitable materials that...
From high-entropy systems to quasi-stable equilibrium of simple complementary components.
The growing demand for lithium, driven by its critical role in lithium-ion batteries (LIBs) and other applications, has intensified the need for efficient extraction methods from aqua-based resources such as seawater. Among various approaches, 2D channel membranes have emerged as promising candidates due to their tunable ion selectivity and scalability. While significant progress has been made in achieving high Li ⁺ /Mg ²⁺ selectivity, enhancing Li ⁺ ion selectivity over Na ⁺ ion, the dominant monovalent cation in seawater, remains a challenge due to their similar properties. This review provides a comprehensive analysis of the fundamental mechanisms underlying Li ⁺ selectivity in 2D channel membranes, focusing on the dehydration and diffusion processes that dictate ion transport. Inspired by the principles of biological ion channels, we identify key factors—channel size, surface charge, and binding sites—that influence energy barriers and shape the interplay between dehydration and diffusion. We highlight recent progress in leveraging these factors to enhance Li ⁺ /Na ⁺ selectivity and address the challenges posed by counteracting effects in ion transport. While substantial advancements have been made, the lack of comprehensive principles guiding the interplay of these variables across permeation steps represents a key obstacle to optimizing Li ⁺ /Na ⁺ selectivity. Nonetheless, with their inherent chemical stability and fabrication scalability, 2D channel membranes offer significant potential for lithium extraction if these challenges can be addressed. This review provides insights into the current state of 2D channel membrane technologies and outlines future directions for achieving enhanced Li ⁺ ion selectivity, particularly in seawater applications.
Graphical Abstract
In the quest for environmental sustainability, the rising demand for electric vehicles and renewable energy technologies has substantially increased the need for efficient lithium extraction methods. Traditional lithium production, relying on geographically concentrated hard-rock ores and salar brines, is associated with considerable energy consumption, greenhouse gas emissions, groundwater depletion and land disturbance, thereby posing notable environmental and supply chain challenges. On the other hand, low-quality brines-such as those found in sedimentary waters, geothermal fluids, oilfield-produced waters, seawater and some salar brines and salt lakes-hold large potential owing to their extensive reserves and widespread geographical distribution. However, extracting lithium from these sources presents technical challenges owing to low lithium concentrations and high magnesium-to-lithium ratios. This Review explores the latest advances and continuing challenges in lithium extraction from these demanding yet promising sources, covering a variety of methods, including precipitation, solvent extraction, sorption, membrane-based separation and electrochemical-based separation. Furthermore, we share perspectives on the future development of lithium extraction technologies, framed within the basic principles of separation processes. The aim is to encourage the development of innovative extraction methods capable of making use of the substantial potential of low-quality brines.
The global demand for lithium has soared in recent years due to the wide use of lithium batteries. To meet this demand, we herein report developing novel on‐site sample preparation methods for the extraction of Li+ from relevant materials, including brine water, spodumene rock, and lithium‐ion battery electrodes, and a DNAzyme‐based fluorescent sensor for sensitive and robust detection of Li+ in these samples down to 1.4 mM (10 ppm) using a portable fluorometer. The system can distinguish key threshold lithium levels that indicate economic value across several industries, including 200 ppm Li+ for brine mining, 6% Li2O or SC6 for rock mining, and Li+‐specific aging in LIBs. The methods developed and demonstrated in this work will allow highly selective, on‐site, portable detection of lithium in both environmental samples to identify new lithium resources and in battery electrodes to guide recycling strategies in order to meet the global demand for lithium.
Lithium is a vital energy storage material in high demand, but its excess in water bodies poses environmental risks, necessitating rigorous monitoring and remediation. Currently, there are no reports on...
Energy storage plays a crucial role in the modern energy landscape, with its applications spanning from renewable energy integration to the electrification of transportation and microgrids. Lithium is a key component of lithium-ion batteries at the core of energy storage technologies. Increasing demand for lithium has challenged supply chains and required a rethinking of how we source it. This comprehensive review presents a critical and holistic assessment of the opportunities and challenges of sourcing lithium from diverse feedstocks, such as seawater, geothermal, produced water (oilfield), and salt lake brines. We assess various lithium extraction technologies (precipitation, extraction, electrochemical techniques, and membrane processes) considering these three feedstocks. A quantitative comparative analysis is conducted across all technologies, considering factors such as cost, commercial maturity, operation duration, and other relevant parameters to determine the most promising technologies for each feedstock while identifying remaining research and technological gaps. Our analysis reveals that Direct Lithium Extraction (DLE) technologies, characterized by higher selectivity and lower environmental impact, demonstrate significant promise for enhancing lithium yields from geothermal brines. In contrast, membrane processes are identified as more suited for seawater and salt lake brines, offering cost-effective scalability despite challenges with selectivity and membrane fouling. Ultimately, the efficient integration of these technologies is illustrated for harvesting lithium from each unconventional resource. The analysis shows that adsorption and chemical precipitation are the commercial technologies for lithium recovery from geothermal, salt lake, and oilfield brine.
A method for selectively extracting lithium from lithium sulfate solution is proposed by using a synergistic DBM/TBP extraction system and employing linear analysis and DFT calculations to explore the synergistic extraction mechanism of lithium. The experimental results showed that, for a simulated solution containing 2.0 g/L lithium and 50 g/L sodium, and 0.5 mol/L DBM + 1 mol/L TBP + sulfonated kerosene as the organic phase, at an O/A phase ratio of 1:1, an equilibrium pH of 13, a temperature of 25°C, and a reaction time of 3 min, the single-stage extraction rate of lithium reached 94.5%, with a βLi/Na ratio of 210. Through three-stage simulated countercurrent extraction under an O/A phase ratio of 1:3 and an equilibrium pH of 13, more than 99% of the lithium was extracted. Washing with 0.5 mol/L H2SO4 at a phase ratio of 2:1 removed nearly 98% of the sodium. After washing, the loaded organic phase was subjected to three-stage countercurrent re-extraction using 1.5 mol/L H2SO4 under an O/A phase ratio of 3:1, achieving a lithium re-extraction rate greater than 99%. The DBM/TBP synergistic extraction system can effectively selectively recover lithium from lithium sulfate solution, achieve deep separation of lithium and sodium, and achieve high-concentration recovery of lithium.
Lithium, a critical material for the global development of green energy sources, is anomalously enriched in some coal deposits and coal by-products to levels that may be considered economically viable. Recovering lithium from coal, particularly from coal gangue or coal ashes, offers a promising alternative for extracting this element. This process could potentially lead to economic gains and positive environmental impacts by more efficiently utilizing coal-based waste materials. This review focuses on lithium concentrations in coal and coal by-products, modes of lithium occurrence, methods used to identify lithium-enriched phases, and currently available hydrometallurgical recovery methods, correlated with pretreatment procedures that enable lithium release from inert aluminosilicate minerals. Leaching of raw coal appears inefficient, whereas coal gangue and fly ash are more feasible due to their simpler composition and higher lithium contents. Lithium extraction can achieve recovery rates of over 90%, but low lithium concentrations and high impurity levels in the leachates require advanced selective separation techniques. Bottom ash has not yet been evaluated for lithium recovery, despite its higher lithium content compared to feed coal.
As a key ingredient of batteries for electric vehicles (EVs), lithium plays a significant role in climate change mitigation, but lithium has considerable impacts on water and society across its life cycle. Upstream extraction methods—including open‐pit mining, brine evaporation, and novel direct lithium extraction (DLE)—and downstream processes present different impacts on both the quantity and quality of water resources, leading to water depletion and contamination. Regarding upstream extraction, it is critical for a comprehensive assessment of lithium's life cycle to include cumulative impacts related not only to freshwater, but also mineralized or saline groundwater, also known as brine. Legal frameworks have obscured social and ecological impacts by treating brine as a mineral rather than water in regulation of lithium extraction through brine evaporation. Analysis of cumulative impacts across the lifespan of lithium reveals not only water impacts in conventional open‐pit mining and brine evaporation, but also significant freshwater needs for DLE technologies, as well as burdens on fenceline communities related to wastewater in processing, chemical contaminants in battery manufacturing, water use for cooling in energy storage, and water quality hazards in recycling. Water analysis in lithium life cycle assessments (LCAs) tends to exclude brine and lack hydrosocial context on the environmental justice implications of water use by life cycle stage. New research directions might benefit from taking a more community‐engaged and cradle‐to‐cradle approach to lithium LCAs, including regionalized impact analysis of freshwater use in DLE, as well as wastewater pollution, cooling water, and recycling hazards from downstream processes.
This article is categorized under: Human Water > Human Water
Human Water > Water Governance
Human Water > Water as Imagined and Represented
Science of Water > Water and Environmental Change
Forward osmosis (FO) using deep eutectic solvents (DESs) as the draw solution (DS) was used in liquid mining of lithium from a synthesized brine, which was used as the feed...
Processing of petalite concentrate from the Bikita deposits in Zimbabwe for production of high-purity Li2CO3 has been studied. XRF and ICP-OES analysis showed that the concentrate consists of oxides of Li, Si, and Al as major components, with an average Li2O content of 4.10%. XRD examination confirmed that the sample is a petalite. Processing of the petalite involves roasting the pre-heated concentrate with concentrated H2SO4 followed by water leaching of the resulting Li2SO4, solution purification and precipitation of Li2CO3. The effects of roasting temperature, stirring speed, solid to liquid ratio, leaching temperature and time on the lithium dissolution are reported. The dissolution rates are significantly influenced by roasting temperature and stirring speed. Water-washed lithium carbonate with a purity of 99.21% (metal basis) was produced. Synthesised and commercial Li2CO3 samples were characterised and compared using X-ray diffraction (XRD) and thermogravimetric analysis (TGA).
The granites of South-West England are a potential source of lithium which is generally found within the mica mineral, zinnwaldite. It is mainly found in the central and western end of the St. Austell granite. When kaolin extraction occurs in these areas a mica-rich waste product is produced which is currently disposed of in tailings storage facilities. In this study a tailings sample containing 0.84% Li2O was upgraded by a combination of froth flotation, using dodecylamine as the collector, and wet high intensity magnetic separation (WHIMS) to 2.07% Li2O. The concentrate was then roasted with various additives, including limestone, gypsum and sodium sulphate, over a range of temperatures. The resulting products were then pulverised before being leached with water at 85°C. Analysis of these products by XRD revealed that the water-soluble sulphates, KLiSO4 and Li2KNa(SO4)2, were produced under specific conditions. A maximum lithium extraction of approximately 84% was obtained using gypsum at 1050°C. Sodium sulphate produced a superior lithium extraction of up to 97% at 850°C. In all cases iron extraction was very low.Preliminary tests on the leach solution obtained by using sodium sulphate as an additive have shown that a Li2CO3 product with a purity of >90% could be produced by precipitation with sodium carbonate although more work is required to reach the industrial target of >99%.
The demand for lithium is expected to increase by almost 60% from 102,000t to 162,000t, with batteries accounting for more than 40,000t of the growth. Lithium ion batteries offer exceptional power-to-weight ratios suitable for small applications such as laptops and digital cameras. Several elements are combined with lithium to make a safe cathode for automotive applications such as Vanadium with Li3V2(PO4)3 providing the highest voltage and specific energy. Vanadium is most commonly used as a steel hardener and strengthener, and is added to construction and other steels at a level of from one to four per cent. Lithium can be obtained from evaporated brines, hard rock minerals and clays. The least expensive source of lithium carbonate is brine recovered from salars in the Andes of South America, where high winds and solar energy evaporate brines to economic levels.
A zinnwaldite concentrate with 1.40% Li processed in this study was prepared from zinnwaldite wastes (0.21% Li) using dry magnetic and grain size separations. Zinnwaldite wastes originated from dressing Sn-W ores, which were mined in the past in the Czech Republic in Cínovec area. The extraction process of lithium, so-called gypsum method consisted of sintering the concentrate with CaSO4 and Ca(OH)2, subsequent leaching of the sinters obtained in H2O, solution purification and precipitation of Li2CO3. It was observed that almost 96% lithium extraction was achieved if sinters prepared at 950°C were leached at 90°C, liquid-to-solid ratio = 10: 1, reaction time of 10 min. The weight ratio of the concentrate to CaSO4 to Ca(OH)2 was 6 : 4.2 : 2. Lithium carbonate product containing almost 99% Li2CO3 was separated from the condensed leach liquor, from which calcium was removed by carbonate precipitation.
There are several saline waters which contain large amount of Mg2+, such as sea water, natural brine, ore leaching, process stream, geothermal brine, bittern, etc. Typically, magnesium chloride aqueous is rejected during the potash process and disposal of this can comprise significant environmental issues. Thus the aimed extraction of this salt can avail environmentally and economically. In this study, main facets of the recovery process for pilot plant probe were studied in a laboratory scale. The magnesium chloride was extracted from concentrate with help of the chemical precipitation and evaporation-crystallization processes. For more extraction efficiency carnalit water washing and added recycle stream methods were investigated, separately. The recovery yield and magnesium chloride purity was obtained 75% and 98%, respectively.
The precipitation of magnesium hydroxide from aqueous solutions by reaction with calcium hydroxide has been studied in agarose gel by electron microscopy and diffraction. The first stage, which dominates at very low Mg2+ concentrations, is the formation of thin single crystals of magnesium hydroxide, some 500 nm or less in diameter. At higher concentrations, these are overgrown to produce larger particles, thicker towards the outside, and generally consisting of several crystallites, with a common c-axis, but imperfectly aligned in the ab plane. The implications for growth mechanisms, and for the production of magnesium hydroxide from seawater, are discussed.
Precipitation of magnesium hydroxide is the first step in the production of various magnesium compounds from seawater. Although the process is well known, kinetic data for the precipitation reaction using slaked lime and dolomite is not available in the literature. In this study, the global kinetics of precipitation of magnesium hydroxide from seawater were investigated by monitoring the total calcium and magnesium composition of species smaller than 2 μm. The effects of temperature and dolomite particle size were also investigated.
In this study, Li2CO3 was extracted from a zinnwaldite concentrate with 1.21% Li and 0.84% Rb prepared from zinnwaldite wastes (0.21% Li, 0.20% Rb). These wastes originated from dressing of Sn–W ores, which were mined in the Czech Republic in the past. Processing of the zinnwaldite concentrate consisted of roasting the concentrate with CaCO3 followed by water leaching of the resulting calcines. This method made it possible to extract about 90% of Li as well as Rb. Lithium carbonate products were separated from leach liquor using two different procedures. The first one comprised conversion of the original alkaline leach liquor to carbonated solution by CO2 bubbling, solution purification and Li2CO3 crystallization during water evaporation. The second procedure consisted of lithium solvent extraction from the original leach liquor using LIX 54 and TOPO as an extraction agent followed by stripping with diluted H2SO4, solution purification and lithium carbonate precipitation with K2CO3. Water-washed lithium carbonate salts were produced in both procedures and contained almost 99.5% Li2CO3 with the first method providing higher yield. Mother liquors after Li2CO3 crystallization and/or inorganic phases after lithium solvent extraction are suitable intermediates for production of rubidium compounds, such as Rb2CO3, Rb2SO4 or RbOH.
Magnesium hydroxide is a valuable chemical produced almost in pure form from seawater and its bitterns through precipitation process. Product size distribution of magnesium hydroxide affects the ease of downstream processes of filtration and drying. Therefore, gaining insight into kinetic information in order to improve the size distribution of product particles is essential. In this work, a mechanistic model has been developed for precipitation of magnesium hydroxide from sea bittern. The parameters of model equations based on the population balance concept have been determined using the experimental data of precipitation from a pure synthetic solution containing 3% Mg2+ and a sea bittern from salt production unit of a local petrochemical complex. The model suggests a higher nucleation rate coefficient and a lower growth rate coefficient for precipitation from the sea bittern compared to that from pure synthetic solution. The nucleation increase and growth decrease which were attributed to the effects of impurities in the bittern, would decrease the settling velocity of the product particles and therefore make the filtration process in industrial use more difficult. However, a larger coefficient of agglomeration rate was predicted by the model for precipitation from the bittern favor to product settling.
Endothermically decomposing mineral fillers, such as aluminium or magnesium hydroxide, magnesium carbonate, or mixed magnesium/calcium carbonates and hydroxides, such as naturally occurring mixtures of huntite and hydromagnesite are in heavy demand as sustainable, environmentally benign fire retardants. They are more difficult to deploy than the halogenated flame retardants they are replacing, as their modes of action are more complex, and are not equally effective in different polymers. In addition to their presence (at levels up to 70%), reducing the flammable content of the material, they have three quantifiable fire retardant effects: heat absorption through endothermic decomposition; increased heat capacity of the polymer residue; increased heat capacity of the gas phase through the presence of water or carbon dioxide. These three contributions have been quantified for eight of the most common fire retardant mineral fillers, and the effects on standard fire tests such as the LOI, UL 94 and cone calorimeter discussed. By quantifying these estimable contributions, more subtle effects, which they might otherwise mask, may be identified.
Precipitation of magnesium hydroxide from hard coal mine brine, which contained 2.84 kg/m[sup 3] Mg[sup 2+] and 68.06 kg/m[sup 3] Cl[sup [minus]], by means of sodium hydroxide was tested. In order to increase the sedimentation and filtration rates of the acquired Mg(OH)[sub 2] a so-called forming (of the precipitate) was applied which consisted in introduction of NaOH to a solution containing Mg[sup 2+] ions without stirring. The mixture was then left to stand for some time (called time of forming) and then stirred in order to get quantitative reaction. Within the time of forming, [tau] = 0--24 h, the sedimentation rate increased about 5 times and the filtration rate increased about 60 times. Humidity of the filter cake was also reduced. The microscopic observation showed an increase of particles, and X-ray structural analysis showed an increase in degree of order of Mg(OH)[sub 2] crystal structure when the time of forming increased.
The chemical precipitation of magnesium from sulphate solution, resulting from heap leaching of nickeliferous laterites with sulphuric acid, was studied. Magnesium was removed as hydroxide using calcium hydroxide (Ca(OH)2) and the precipitate produced was a mixture of magnesium hydroxide (Mg(OH)2) and gypsum (CaSO4·2H2O). The variables studied were the temperature and the stoichiometric quantity of Ca(OH)2. The responses measured were magnesium removal and the specific surface of the precipitate. Design of the experiments and statistical analysis of the data were used in order to determine the main effects and interactions of the factors. Scanning electron microscopy (SEM) was also used to investigate the effect of precipitation conditions on the morphological characteristics of the Mg(OH)2–CaSO4·2H2O mixture. Kinetic analysis with the aid of Nielsen theory allowed the determination of the Mg(OH)2 formation mechanism. The use of a magnesium hydroxide–gypsum mixture as a filler material was also examined. The suitability of the precipitate was evaluated by measuring a set of properties that can characterize a material as a filler and by measuring mechanical properties of polymers filled with the precipitate at various addition levels. The magnesium hydroxide–gypsum precipitate proved to be promising for this application, as it was found to have similar properties with other commercial products.
Among other applications, magnesium hydroxide is commonly used as a flame-retardant filler in composite materials, as well as a precursor for magnesium oxide refractory ceramic. The microstructure of the powder is of prime importance in both technical applications. The influence of synthesis parameters on the morphological characteristics of magnesium hydroxide nanoparticles precipitated in dilute aqueous medium was studied. Several parameters were envisaged such as chemical nature of the base precipitant, type of counter-ion, temperature and hydrothermal treatment. Special attention was given to the obtaining of platelet-shaped, nanometric and de-agglomerated powders. The powders were characterized in terms of particle size distribution, crystal habits, morphology and ability to be re-dispersed in water. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and laser diffusion analyses were used for this purpose.
The cumulative availability curve shows the quantities of a mineral commodity that can be recovered under current conditions from existing resources at various prices. The future availability of a mineral commodity depends on the shape of its cumulative availability curve (determined by geologic considerations, such as the nature and incidence of the available mineral deposits), the speed at which society moves up the curve (determined by future demand and the extent to which this demand is satisfied by recycling), and shifts in the curve (determined by cost-reducing technological change and other factors). While the shape of the curve for any given mineral commodity may or may not be known, it is knowable since the geologic processes responsible for the curve's shape took place many years ago. In contrast, the factors governing how fast society moves up the curve and how the curve shifts over time are not only unknown but also unknowable. Using lithium as an example, this article shows that knowledge about the shape of the cumulative availability curve can by itself provide useful insights for some mineral commodities regarding the potential future threat of shortages due to depletion. Despite the inherent uncertainties surrounding the future growth in lithium demand as well as the uncertainties regarding the future cost-reducing effects of new production technologies, the shape of the lithium cumulative availability curve indicates that depletion is not likely to pose a serious problem over the rest of this century and well beyond.