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18-membered macrocycle appended on resin for selective rare earth element extraction and separation

The rare earth elements are critically important for a wide range of modern technologies. However, obtaining them selectively and efficiently from natural sources and recycled materials is challenging and often requires harsh or wasteful conditions. Here we show that a macrocyclic chelator appended to a solid resin can overcome this challenge by acting as a robust platform for both the extraction and separation of these elements. This resin preferably captures the large rare earth elements in mixtures of these ions, giving rise to higher extraction efficiencies for them over the smaller ions. We further demonstrate that this resin can be used to separate rare earth elements. As a proof-of-principle validation, this resin was demonstrated to selectively extract rare earth elements in the presence of many different types of competing metal ions in a bioleachate solution obtained from autoslag waste, leading to their enrichment.

Coordination chemistry

Picolinate-based acyclic ligand for rare earth element extraction and separation

The rare earth elements (REEs) play an important role in many modern technologies, particularly those relevant to clean energy. Despite their increasing importance, obtaining them in elementally pure forms suitable for downstream applications is challenging due to their similar chemical properties. This problem has impeded efforts to efficiently and selectively extract them from end-of-life materials and electronic waste. Here, we report a cost-efficient acyclic picolinate-based chelator H 4 aapa. The REE stability constants (log K ML ) of this chelator were measured via pH potentiometric and UV-Visible spectrophotometric titrations, revealing it to preferably bind light over heavy REEs like many recently reported 18-membered macrocycles. Its REE complexes were characterized by X-ray crystallography and NMR spectroscopy, demonstrating that this chelator can attain different conformations. The unique properties of aapa were subsequently used to separate REEs via the dissolution of insoluble REE oxalate mixtures. This dissolution-based separation led to large separation factors, the most significant being that for the Ce 3+ /Lu 3+ pair (38.6) at pH 4. Leveraging the strong REE binding affinity of aapa, we further demonstrated this chelator can leach REEs from authentic end-of-life materials in the form of magnet waste and autocatalyst smelting (autocat) slag. With this approach, exposure of these materials to a 20 mM solution of aapa at neutral pH generates a metal-containing solution enriched in Nd 3+ and Dy 3+ by 56.9 wt% and 3.0 wt%, marking a 4-fold improvement over the use of 4 M HNO 3 .

Gao, Yangyang [University of California, Santa Bar

A Novel Continuous Ultrasound-Assisted Leaching Process for Rare Earth Element Extraction: Environmental and Economic Assessment

Rare earth elements (REEs) make up integral components in personal electronics, healthcare instrumentation, and modern energy technologies. REE leaching with organic acids is an environmentally friendly alternative to traditional extraction methods. Our previous study demonstrated that batch ultrasound-assisted organic acid leaching of REEs can significantly decrease environmental impacts compared to traditional bioleaching. The batch method is limited to small volumes and is unsuitable for industrial implementation. This study proposes a novel approach to increase reaction volume using a continuous ultrasound-assisted organic acid leaching method. Laboratory experiments showed that continuous ultrasound-assisted leaching increased the leaching rate (µg/h) 11.3–24.5 times compared to our previously reported batch method. Techno-economic analysis estimates the cost of the continuous approach using commercially purchased organic acids is $\$$9465/kg of extracted REEs and $\$$4325/kg of extracted REEs, using gluconic acid and citric acid, respectively. The sensitivity analysis reveals that substituting commercially purchased organic acids with microbially produced biolixiviant can reduce the process cost by approximately 99% while minimally increasing energy consumption. Environmental assessment shows that most of the emissions stemmed from the energy required to power the ultrasound reactor. We concluded that increased leaching capacity using a continuous ultrasound-assisted approach is feasible, but process modifications are needed to reduce the environmental impact.

54 - ENVIRONMENTAL SCIENCES/GLOBAL CLIMATE CHANGE

Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem

Impact of organic acids on extraction of rare earth elements: Mechanisms and optimization

Organic acids are increasingly recognized as an environmentally friendly and efficient selective leaching agent of critical minerals. However, their impact on subsequent extraction processes remains unclear. This study investigates the extraction behavior of rare earth elements (REEs), representative of critical minerals, in the presence of various organic acids, including citric acid, maleic acid, malonic acid, DL-malic acid, L(+)-tartaric acid, and L-ascorbic acid. The results show that organic acids slightly reduce the extraction of REEs but greatly increase the extraction of aluminum (Al³⁺), making it harder to separate REEs from other elements. To avoid this, it is best to keep organic acid concentrations as low as possible in practical applications. However, by optimizing extraction conditions, these negative effects can be minimized. Specifically, adjusting the contact time between solutions allows for efficient REE extraction while limiting unwanted aluminum extraction. Among the acids tested, malonic acid and L(+)-tartaric acid were found to be the most effective for selectively extracting REEs. Mechanistically, organic acids are likely to form complexes with REEs and D2EHPA during extraction, except for Y (III), offering practical guidelines for optimizing REE recovery. Beyond extraction, this study also highlights a way to recover organic acids by precipitating REEs from stripping solutions using oxalic acid, which adds both environmental and economic benefits. Furthermore, these findings provide useful insights for optimizing REE recovery and offer a reference for extracting other critical minerals from solutions containing organic acids.

D2EHPA

Mechanically and Chemically Robust Lanmodulin-Functionalized Silk Sponges for Rare Earth Element Sequestration

The extraction of rare-earth elements (REEs) from low-grade sources like electronic waste (E-waste) could supplement current unsustainable mining practices. REEs are crucial for various industries, but supply struggles to meet growing demand. Herein, we present an environmentally friendly method for REE extraction using silk protein sponges functionalized with lanmodulin (LanM), a protein that selectively binds REEs. These sponges are relatively facile to fabricate and scale, while offering highly selective REE binding. The REEs can then be recovered via simple acid leaching, allowing sponge reuse for multiple cycles as well as specific desorption of different REEs by changing the pH of the desorption buffer. Finally, this method avoids harmful solvents used in traditional extraction and enables recycling of REEs from industrial and E-waste.

REEs

Process design for recovering rare-earth elements from mine tailings with low rare-earth concentrations via sequential leaching and solvent extraction

Rare earth elements (REEs) are essential for advanced technologies and yet face significant supply chain risks due to their concentrated global production and limited domestic availability. Addressing this challenge requires efficient processes capable of upgrading low-grade secondary resources such as mine tailings. In this study, we developed a novel separation flowsheet that integrates sequential leaching and 2-stage solvent extraction (SX) processes to recover high-purity heavy REEs (HREEs) and light REEs (LREEs) from a simulated mine-tailing concentrate containing 2.4 wt% total REEs (TREEs; 0.6 wt% LREEs and 1.8 wt% HREEs). Sequential leaching with controlled pH adjustment selectively precipitated REEs while retaining the large amount of impurities in the solution, producing an REE-enriched leachate by following leaching processes with roughly twice the REE concentration and half the impurity concentration compared to that of single-step leaching. The optimized SX flowsheet employed Cyanex 572 to extract HREEs and Fe over LREEs, followed by Fe removal using tributyl phosphate (TBP), while the raffinate stream was processed by SX with di(2-ethylhexyl)phosphoric acid (D2EHPA) to recover LREEs under optimized conditions balancing both extraction efficiency and purity. Although increased extractant availability in the organic phase improved LREE recovery, it also increased co-extraction of Ca, underscoring trade-offs in process optimization. Both HREE- and LREE-rich solutions were subsequently precipitated into solid products via oxalate precipitation, resulting in high-purity REE solids containing ∼92.0 wt% HREEs (∼95.7 wt% TREEs) and ∼92.8 wt% LREEs (∼94.0 wt% TREEs). In conclusion, this proof-of-concept study using simulated mine tailings demonstrates a promising approach for upgrading low-grade REE resources, while highlighting the need for future validation with real materials.

Mine tailings

Sustainable extraction of rare earth elements from coal fly ash leachates using a recyclable ionic liquid

The growing demand for rare earth elements (REEs) has prompted interest in their recovery from alternative sources such as coal fly ash (CFA). This study explores the ionic liquid (IL) betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf 2 N], for selective extraction of REEs from leachates of a Class C CFA. While previous studies have demonstrated the effectiveness of using [Hbet][Tf 2 N] to extract REEs from different types of CFA in direct ash-IL systems, this study investigates four CFA leachates prepared using HCl, HNO 3 , H 2 SO 4 , and citrate. Extraction experiments were conducted across varying pH levels and with additives such as ascorbic acid and betaine. Among the systems tested, [Hbet][Tf 2 N] achieved REE recoveries of 51% and 47% from the HCl and citrate leachates, respectively, comparable to 49% REE recovery in ash-IL extraction. Co-extraction of bulk elements was significantly reduced in the leachate-IL systems. Optimal REE extraction occurred near pH 11, and addition of ascorbic acid effectively suppressed iron co-extraction without compromising REE recovery. Recycling experiments demonstrated that [Hbet][Tf₂N] retains its performance over five cycles with manageable losses. These results reveal the promise of [Hbet][Tf 2 N] for effectively recovering REEs from leachates of solid wastes, highlighting its applicability as a sustainable strategy for other aqueous REE feedstocks.

chemistry

Adsorption of hydroxamic acid ligands for improved extraction of rare earth elements from monazite ores

Efficient separation of rare earth element (REE) ores via froth flotation requires the development of novel ligands with enhanced adsorption capacity and selectivity. To realize these advances, understanding the mechanisms underlying interactions between the ligand and mineral surfaces is essential. This study systematically evaluates the adsorption behavior of alkyl- and aromatic alkyl-substituted hydroxamic acid ligands on monazite surfaces using complementary spectroscopic techniques, including UV–visible (UV–vis) spectroscopy, Raman spectroscopy, infrared spectroscopy, and vibrational sum frequency generation (SFG) spectroscopy, together with the ab initio molecular dynamics (AIMD) simulations. Among the studied ligands, octanohydroxamic acid (OHA) and 4-ethoxy-N,2-dihydroxybenzamide (EDHBA) exhibit high adsorption capacity under basic pH (8–10) by forming multilayers on the surface. OHA has a higher equilibrium adsorption capacity compared to EDHBA, but it forms a less stable multilayer susceptible to disruption in the presence of interfering ions. AIMD results show that OHA adopts a single stable chelating geometry, while EDHBA exhibits multiple binding modes involving distinct interactions with La surface atoms and phosphate-bound oxygens, resulting in more complex adsorption kinetics. The variations in surface binding and intermolecular interactions observed between alkyl and aromatic molecules influence the differences in adsorption kinetics, equilibrium adsorption capacities on the mineral surface, and their flotation performance. This work provides valuable insight into the adsorption mechanism of ligands at mineral interfaces, which is crucial for guiding the design of new ligands with enhanced separation performance.

Zhou, Muchu [ORNL] (ORCID:0000000182650215)

Extraction and separation of rare earth elements using LN resins in hydrochloric acid

The separation of the rare earth elements is essential for numerous scientific applications but remains a significant challenge due to the nearly identical chemical properties of the adjacent lanthanide elements. Eichrom’s LN series of extraction chromatographic resins feature organophosphorus extractants and are widely used to achieve adjacent lanthanide separations. While extensive characterization of these resins has been completed for nitric acid matrices, the use of hydrochloric acid is preferred for a variety of applications. Further, the extraction of the rare earth elements, La–Lu and Y, has been characterized on LN and LN2 resins in hydrochloric acid via batch uptake and column chromatographic studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA

Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte

Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.

coal fly ash

Ion-Specific Precipitation of Extractants Enables Rare-Earth Separation and Wastewater Remediation from Solvent Extraction of Critical Elements

The increasing demand for rare-earth elements (REEs) necessitates sustainable recovery strategies, particularly from secondary sources, such as electronic waste. Solvent extraction is the primary industrial method for REE separation; however, the unintentional dissolution of extractants into wastewater poses serious environmental risks, leading to organic contamination and process inefficiencies. Existing wastewater treatment methods struggle to remove these persistent pollutants, underscoring the need for innovative recovery approaches. Herein, we present a ligand-mediated precipitation strategy that simultaneously recovers REEs and removes dissolved extractants from solvent extraction wastewater. We show that residual extractants in the aqueous phase can selectively bind REEs, inducing their precipitation while leaving transition metals in solution. By integrating FTIR spectroscopy, EDS, XPS, EXAFS, and SAXS, we elucidate the mechanism of ion-specific precipitation and the local coordination environment of metal ions in the precipitate. Importantly, we demonstrate that the precipitated extractants can be efficiently recovered and reused, providing a closed-loop solution that enhances sustainability. Applying this method to leachates from samarium–cobalt (Sm–Co) and neodymium–iron–boron (NdFeB) mixed magnets, we achieve highly selective REE precipitation under mild conditions, demonstrating a scalable and cost-effective pathway for REE recovery, wastewater purification, and extractant recycling. In conclusion, by integrating element-specific ligand-mediated precipitation with extractant reuse, this work offers a transformative approach to REE separation that reduces the environmental impact while improving resource efficiency.

E-waste

Separation and Recovery of High-Purity Dysprosium from Electric Vehicle Scrap Permanent Magnets Using Cyanex 572, a Cationic Extractant in a Membrane Solvent Extraction Process

Rare earth elements (REEs), especially heavy rare earth elements such as dysprosium (Dy), have gained immense attention globally due to their widespread use in many state-of-the-art technologies. Consequently, demand for REEs is increasing rapidly in comparison to their supply. Recycling of REEs from end-of-life (EoL) electronic waste (e-waste) can help to mitigate the increasing gap between the demand and supply of REEs. This study reports the separation and recovery of high-purity Dy from various feedstocks such as scrap permanent magnets (SPMs), electric vehicle (EV) magnets, and mixed rare earth oxides (REOs) using an economically viable and scalable membrane solvent extraction (MSX) process. First, the optimized conditions (organic phase composition and feed solution acid concentration) for the separation of Dy from light REEs such as neodymium (Nd) and praseodymium (Pr) were evaluated using liquid–liquid extraction. Thereafter, a multistage MSX process was developed to separate high purity (>99.5 wt %) Dy from Nd and Pr using Cyanex 572, a cationic extractant. Using feedstocks with varying initial compositions, the MSX process obtained 100% pure Dy with 63–96% Dy recovery in three to six stages with a maximum extraction rate of 2.9 g m–2 h –1 . Purity of the recovered Dy was confirmed via additional characterization such as scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. This novel MSX process holds immense potential for industry deployment for the separation of heavy and light rare REEs from a wide range of e-waste.

electrical vehicle magnets