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Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep...
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Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Processing and Extractive Metallurgy".

Deadline for manuscript submissions: closed (31 October 2024) | Viewed by 10938

Special Issue Editors

Dr. Esteban Quijada-Maldonado

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Guest Editor
Laboratory of Separation Processes Intensification (SPI), Department of Chemical Engineering, University of Santiago de Chile, Av. Lib. Bdo. O’Higgins 3363, Estación Central, Santiago 9170020, Chile
Interests: liquid–liquid extractions of metal ions; separation technologies; ionic liquids; deep eutectics solvents
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Julio Romero

E-Mail Website
Guest Editor
Chemical and Bioprocess Engineering Department, University of Santiago de Chile, Santiago 71783-5, Chile
Interests: membrane separations; ionic liquids; deep eutectic solvents
Special Issues, Collections and Topics in MDPI journals
Dr. Ricardo Abejón

E-Mail Website
Guest Editor
Chemical and Bioprocess Engineering Department, University of Santiago de Chile, Santiago 71783-5, Chile
Interests: membrane technologies; wastewater treatment; life cycle analysis

Special Issue Information

Dear Colleagues,

Lanthanides or so-called rare earth elements (REEs) have attracted much attention in the scientific community due to their increasing number of technological applications, especially those related to the low carbon economy, such as hybrid vehicles, electric vehicles, and wind turbines. Recovery from leached minerals and, more recently, from recycled technological wastes is carried out through solvent extraction (SX), where the purification of REEs is not straightforward and uses toxic solvents. In this sense, ionic liquids (ILs) are a novel and outstanding class of solvents which have been proposed for SX of metal ions due to their excellent properties, such as negligible vapor pressure, non-flammability, and wide solvating power, but also an increased performance (distribution ratios and selectivity) over toxic solvents, opening many opportunities for these solvents to be applied in the REE purification industry. However, recently, deep eutectic solvents (DES) have gained much attention due to their ability to keep the same green characteristics as ILs but with simpler, cheaper, and less toxic synthesis.

This Special Issue is dedicated to collecting the most recent achievements on SX of REEs with ILs or DES, while papers on processes such as leaching of REEs containing mineral (or electronic waste) with these solvents, electrodeposition of lanthanides after SX or other processes associated with the recovery of metal ions using these solvents, such as supported liquid membranes (SLM), perstraction, structurally modified membranes, and solvent impregnated resins (SIR), are also welcome.

Dr. Esteban Quijada-Maldonado
Prof. Dr. Julio Romero
Dr. Ricardo Abejón
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • recovery of electronic wastes containing REEs
  • leaching of REEs containing minerals with ILs or DES
  • solvent extractions of REEs
  • selective separations of REEs
  • ionic liquids
  • deep eutectic solvents
  • extraction stoichiometry
  • ILs and/or des electrolytes
  • supported liquid membranes
  • structurally modified membranes
  • perstraction using ILs or DES
  • solvent impregnated resins

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Published Papers (6 papers)

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Research

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27 pages, 6065 KiB  
Article
Extraction of Lanthanides(III) from Nitric Acid Solutions with N,N′-dimethyl-N,N′-dicyclohexyldiglycolamide into Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids and Their Mixtures with Molecular Organic Diluents
by Alexander N. Turanov, Vasilii K. Karandashev, Vladimir E. Baulin, Yury M. Shulga and Dmitriy V. Baulin
Minerals 2024, 14(11), 1167; https://doi.org/10.3390/min14111167 - 17 Nov 2024
Viewed by 399
Abstract
The extraction of lanthanides(III) from aqueous nitric acid solutions with novel unsymmetrical diglycolamide extactant, N,N′-dimethyl-N,N′-dicyclohexyldiglycolamide (DMDCHDGA) into bis(trifluoromethylsulfoyl)imide-based ionic liquids (ILs), namely 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][Tf2N]), benzyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N222Bn][Tf2N]) [...] Read more.
The extraction of lanthanides(III) from aqueous nitric acid solutions with novel unsymmetrical diglycolamide extactant, N,N′-dimethyl-N,N′-dicyclohexyldiglycolamide (DMDCHDGA) into bis(trifluoromethylsulfoyl)imide-based ionic liquids (ILs), namely 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][Tf2N]), benzyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N222Bn][Tf2N]) methyltrioctylammonium bis(trifluoromethylsulfonyl)imide ([N1888][Tf2N]), and their mixtures with molecular organic diluent 1,2-dichloroethane (DCE), is studied. DMDCHDGA has been shown to interact with components of the IL [C4mim][Tf2N]. The effect of HNO3 concentration in the aqueous phase on the extraction of Ln(III) ions is studied. The stoichiometry of the extracted complexes is determined, and the mechanism of Ln(III) extraction in a system with [C4mim][Tf2N] is discussed. It is shown that the efficiency and intragroup selectivity of the extraction of Ln(III) ions with DMDCHDGA into [C4mim][Tf2N] is significantly higher than when using its symmetric analog TODGA. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
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17 pages, 48563 KiB  
Article
Molecular Dynamic Simulation of the Interaction of a Deep Eutectic Solvent Based on Tetraethylammonium Bromide with La3+ in Acidic Media
by Luver Echeverry-Vargas, Luz M. Ocampo-Carmona and Leopoldo Gutiérrez
Minerals 2024, 14(7), 711; https://doi.org/10.3390/min14070711 - 13 Jul 2024
Viewed by 812
Abstract
In recent years, noticeable progress has been made in the development of alternative extraction systems characterized by greater sustainability. In this context, deep eutectic solvents (DESs) have emerged as a promising alternative to the conventional solvents commonly used in metal extraction. This work [...] Read more.
In recent years, noticeable progress has been made in the development of alternative extraction systems characterized by greater sustainability. In this context, deep eutectic solvents (DESs) have emerged as a promising alternative to the conventional solvents commonly used in metal extraction. This work focuses on investigating the extraction of lanthanum in an aqueous solution of sulfuric acid using a deep eutectic solvent, employing molecular dynamics simulations (MD). The structural characteristics of the solvent and its interactions with the components of the aqueous solution are explored. In this study, tetraethylammonium bromide (TEABr) is combined with ethylene glycol (EG) to form a DES, in which sodium cyanide (NaCN) is subsequently solubilized. According to the results obtained from the MD simulation, the primary interactions in the DESs are established through hydrogen bonds between the bromine and the hydrogens of the methyl group of tetraethylammonium at 3.5 Å, as well as between the bromine and the hydrogens of the methylene group of ethylene glycol at 3.5 Å. Similarly, the main interactions between the binary DES and sodium cyanide occur through the hydrogens of the hydroxyl group of EG and the carbon of cyanide at 1.7 Å, and between the oxygen of the hydroxyl group of EG and the sodium at 2.5 Å. In the acidic solution, the primary interaction is highlighted between the lanthanum ion and the oxygen of the bisulfate at 2.8 Å. Additionally, it is observed that the interaction between the DES and the aqueous solution occurs between the lanthanum and the oxygen of the hydroxyl group of EG, as well as between the lanthanum and the carbon of cyanide at 4.4 Å. It is important to note that, when increasing the temperature from 25 to 80 °C, the interaction distance between the lanthanum and the carbon of cyanide decreases to 2.4 Å, suggesting a possible correlation with the increase in lanthanum extraction, as experimentally observed. Overall, this study underscores the importance of considering the fundamental structural interactions of the DES with the lanthanum acid solution, providing an essential theoretical basis for future experimental investigations. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
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14 pages, 3749 KiB  
Article
Extraction of Lanthanides(III) from Aqueous Nitric Acid Solutions with Tetra(n-octyl)diglycolamide into Methyltrioctylammonium Bis(trifluoromethanesulfonul)imide Ionic Liquid and Its Mixtures with Molecular Organic Diluents
by Alexander N. Turanov, Vasilii K. Karandashev and Vladimir E. Baulin
Minerals 2023, 13(6), 736; https://doi.org/10.3390/min13060736 - 29 May 2023
Cited by 6 | Viewed by 1457
Abstract
The extraction of lanthanides(III) from aqueous nitric acid solutions with tetra(n-octyl)diglycolamide into methyltrioctylammonium bis(trifluoromethanesulfonul)imide ([N1888][Tf2N]) ionic liquid and its mixtures with molecular organic diluents is investigated in this study. This study also investigates the effect of HNO [...] Read more.
The extraction of lanthanides(III) from aqueous nitric acid solutions with tetra(n-octyl)diglycolamide into methyltrioctylammonium bis(trifluoromethanesulfonul)imide ([N1888][Tf2N]) ionic liquid and its mixtures with molecular organic diluents is investigated in this study. This study also investigates the effect of HNO3 concentration in the aqueous phase on the extraction of Ln(III) ions. Subsequently, the stoichiometry of the extracted complexes is determined, and the mechanism of Ln(III) extraction in a system with [N1888][Tf2N] is discussed. It is shown that the intragroup selectivity of the extraction of Ln(III) ions is significantly higher when using [N1888][Tf2N] than when using the imidazolium-based ionic liquid [C4mim][Tf2N]. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
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24 pages, 3191 KiB  
Article
Simulation of Solvent Extraction Circuits for the Separation of Rare Earth Elements
by Keven Turgeon, Jean-François Boulanger and Claude Bazin
Minerals 2023, 13(6), 714; https://doi.org/10.3390/min13060714 - 23 May 2023
Cited by 1 | Viewed by 3640
Abstract
The separation of Rare Earth Elements (REEs) is an important step in the valorization of REE ore and aims at producing individual rare earth compounds for the market. The separation is carried out industrially by solvent extraction (SX) using interconnected circuits consisting of [...] Read more.
The separation of Rare Earth Elements (REEs) is an important step in the valorization of REE ore and aims at producing individual rare earth compounds for the market. The separation is carried out industrially by solvent extraction (SX) using interconnected circuits consisting of cascades of mixer-settlers. The design of a REE separation circuit implies the selection of the operating conditions and of the number of mixer-settlers required to achieve a target degree of purity for the separated elements. This design work is either carried out by piloting a circuit or using a mathematical simulation. Independent of the method, the world expertise in this area is limited. This paper describes a simulation method requiring a minimum of calibration effort, which can be used to design a complete REE separation plant. The simulation enables assessment of the effect of the number of mixer-settlers per extraction, the scrubbing and stripping stage, as well as the pH of the aqueous solution and organic-phase contents of free and loaded extractant on the purity of the separated REEs. The simulation tool presented here has been developed from a fundamental analysis of the chemical reactions involved in the solvent extraction process. Unlike most of the simulation methods documented in the literature, the method requires no empirical calibration. The proposed method is validated using data from laboratory batch tests and with published data from continuous pilot and industrial REE separation circuits. The application of the simulation tool is illustrated with the planning of the test conditions for a forthcoming pilot test work and with the simulation of a 9-REE product SX separation plant. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
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Review

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27 pages, 380 KiB  
Review
Recent Uses of Ionic Liquids in the Recovery and Utilization of Rare Earth Elements
by Francisco Jose Alguacil, Jose Ignacio Robla and Olga Rodriguez Largo
Minerals 2024, 14(7), 734; https://doi.org/10.3390/min14070734 - 22 Jul 2024
Viewed by 1156
Abstract
The importance of rare earth elements as a basis for the development of new technologies or the improvement of existing ones makes their recovery from raw and waste materials necessary. In this recovery, hydrometallurgy and its derivative solvometallurgy play key roles due to [...] Read more.
The importance of rare earth elements as a basis for the development of new technologies or the improvement of existing ones makes their recovery from raw and waste materials necessary. In this recovery, hydrometallurgy and its derivative solvometallurgy play key roles due to their operational characteristics, which are emphasized with the use of ionic liquids. This manuscript reviews the most recent advances (2023 and 2024) in the use of ionic liquids in unit operations (leaching and separation technologies) aimed at the recovery of these valuable and strategic metals. Moreover, a comprehensive review is presented of the use of these chemicals in the development of advanced materials containing some of these rare earth elements. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
14 pages, 426 KiB  
Review
Recent Work on the Recovery of Rare Earths Using Ionic Liquids and Deep Eutectic Solvents
by Francisco Jose Alguacil and Jose Ignacio Robla
Minerals 2023, 13(10), 1288; https://doi.org/10.3390/min13101288 - 30 Sep 2023
Cited by 4 | Viewed by 2179
Abstract
With the development of smart technologies, the use of rare-earth elements (REEs) has been widespread; thus, their importance as valuable and strategic metals has been boosted to levels never known before. Due to their scarcity in the Earth’s crust, the recovery of these [...] Read more.
With the development of smart technologies, the use of rare-earth elements (REEs) has been widespread; thus, their importance as valuable and strategic metals has been boosted to levels never known before. Due to their scarcity in the Earth’s crust, the recovery of these elements from secondary resources has also witnessed further developments. Traditional pyrometallurgical and hydrometallurgical processing techniques, though widely used in the recovery of these REEs, have some environmental drawbacks; thus, new recovery approaches are under development. Here, Solvometallurgy has emerged as an environmentally friendly technology, and ionic liquids and deep eutectic solvents have turned out to be first-line chemicals to be used in the different unit operations employed in solvometallurgical processing, i.e., leaching, liquid–liquid extraction, ion exchange (adsorption), precipitation, and electrolysis. This manuscript reviews the most recent literature (2002–June 2023) concerning the use of ionic liquids and deep eutectic solvents in the recovery of REEs from various sources. Full article
(This article belongs to the Special Issue Solvent Extraction of Rare-Earth Elements with Ionic Liquids and Deep Eutectic Solvents)
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