Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)

Lithium, declared critical raw material by the European Union in 2020, is a competitor to hydrogen as alternative to petroleum. Its use is increasing while reserves are declining, boosting new sources, as seawater desalination concentrates. In this work, a computational study of the most promising e...

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Autores: Coterillo Ruisánchez, Raúl, Gallart Tauler, Lien Ester, Fernández-Escalante Barquín, Elena, Junquera Quintana, Francisco Javier|||0000-0002-9957-8982, García Fernández, Pablo (físico)|||0000-0002-4901-0811, Ortiz Uribe, Inmaculada|||0000-0002-3257-4821, Ibáñez Mendizábal, Raquel|||0000-0002-0432-1827, San Román San Emeterio, María Fresnedo|||0000-0002-3638-2448
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad de Cantabria (UC)
Repositorio:UCrea Repositorio Abierto de la Universidad de Cantabria
Idioma:inglés
OAI Identifier:oai:repositorio.unican.es:10902/28314
Acceso en línea:https://hdl.handle.net/10902/28314
Access Level:acceso abierto
Palabra clave:Lithium
Extraction
Seawater desalination concentrates
Density Functional Theory (DFT)
Equilibrium and selectivity
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spelling Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)Coterillo Ruisánchez, RaúlGallart Tauler, Lien EsterFernández-Escalante Barquín, ElenaJunquera Quintana, Francisco Javier|||0000-0002-9957-8982García Fernández, Pablo (físico)|||0000-0002-4901-0811Ortiz Uribe, Inmaculada|||0000-0002-3257-4821Ibáñez Mendizábal, Raquel|||0000-0002-0432-1827San Román San Emeterio, María Fresnedo|||0000-0002-3638-2448LithiumExtractionSeawater desalination concentratesDensity Functional Theory (DFT)Equilibrium and selectivityLithium, declared critical raw material by the European Union in 2020, is a competitor to hydrogen as alternative to petroleum. Its use is increasing while reserves are declining, boosting new sources, as seawater desalination concentrates. In this work, a computational study of the most promising extractants, B-diketones and organophosphates and combinations thereof, towards lithium in presence of metal ions found in the concentrates, Na+, K+, Mg2+, Ca2+ and Sr2+ was carried out, via molecular simulation using ab initio Density Functional Theory (DFT). The geometries, reaction energies, and thermodynamic parameters have been evaluated. Using the square of the electronic wave function an electrostatic interaction was confirmed as cation-extractant/s bonding. The complexation reaction energies of the systems formed by a cation and a single extractant display negative [delta]E and [delta]G values, pointing towards stable complexes and spontaneous reactions. The synergic effect of extractants was studied by combining the [beta]-diketones with TOPO (1:1) leading to an increase of [delta]E and [delta]G (absolute value). The extraction coefficient, K, follows the order K(K+) > K(Na+) > K(Li+) > K(Sr2+) > K(Ca2+) > K(Mg2+). In consequence, selectivity Li+ towards cations of the group II was higher, S(Li+/Mg2+) > S(Li+/Ca2+) > S(Li+/Sr2+) for the combined mixtures BTA TOPO and FDOD TOPO and lower towards group I cations, S(Li+/Na+) > S(Li+/K+) for DBM TOPO and LIX54 TOPO. The selectivity of Li+ regarding the rest of the cations and the 16 extractants and mixtures of extractants was lower than the selectivity of Li+ with respect to each cation, being the best value for the DBM TOPO and LIX54 TOPO systems. The results obtained are expected to provide a tool on the behaviour of the most promising of extractants towards Li+ in seawater desalination concentrates.This research was developed in the framework of the project PID2020-115409RB-I00 financed by the Ministry of Science and Innovation (Spain).ElsevierUniversidad de Cantabria20222022-06-15journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articlehttps://hdl.handle.net/10902/28314Desalination, 2022, 532, 115704reponame:UCrea Repositorio Abierto de la Universidad de Cantabriainstname:Universidad de Cantabria (UC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:repositorio.unican.es:10902/283142026-06-02T12:39:31Z
dc.title.none.fl_str_mv Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
title Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
spellingShingle Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
Coterillo Ruisánchez, Raúl
Lithium
Extraction
Seawater desalination concentrates
Density Functional Theory (DFT)
Equilibrium and selectivity
title_short Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
title_full Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
title_fullStr Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
title_full_unstemmed Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
title_sort Selective extraction of lithium from seawater desalination concentrates: study of thermodynamic and equilibrium properties using Density Functional Theory (DFT)
dc.creator.none.fl_str_mv Coterillo Ruisánchez, Raúl
Gallart Tauler, Lien Ester
Fernández-Escalante Barquín, Elena
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
García Fernández, Pablo (físico)|||0000-0002-4901-0811
Ortiz Uribe, Inmaculada|||0000-0002-3257-4821
Ibáñez Mendizábal, Raquel|||0000-0002-0432-1827
San Román San Emeterio, María Fresnedo|||0000-0002-3638-2448
author Coterillo Ruisánchez, Raúl
author_facet Coterillo Ruisánchez, Raúl
Gallart Tauler, Lien Ester
Fernández-Escalante Barquín, Elena
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
García Fernández, Pablo (físico)|||0000-0002-4901-0811
Ortiz Uribe, Inmaculada|||0000-0002-3257-4821
Ibáñez Mendizábal, Raquel|||0000-0002-0432-1827
San Román San Emeterio, María Fresnedo|||0000-0002-3638-2448
author_role author
author2 Gallart Tauler, Lien Ester
Fernández-Escalante Barquín, Elena
Junquera Quintana, Francisco Javier|||0000-0002-9957-8982
García Fernández, Pablo (físico)|||0000-0002-4901-0811
Ortiz Uribe, Inmaculada|||0000-0002-3257-4821
Ibáñez Mendizábal, Raquel|||0000-0002-0432-1827
San Román San Emeterio, María Fresnedo|||0000-0002-3638-2448
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad de Cantabria
dc.subject.none.fl_str_mv Lithium
Extraction
Seawater desalination concentrates
Density Functional Theory (DFT)
Equilibrium and selectivity
topic Lithium
Extraction
Seawater desalination concentrates
Density Functional Theory (DFT)
Equilibrium and selectivity
description Lithium, declared critical raw material by the European Union in 2020, is a competitor to hydrogen as alternative to petroleum. Its use is increasing while reserves are declining, boosting new sources, as seawater desalination concentrates. In this work, a computational study of the most promising extractants, B-diketones and organophosphates and combinations thereof, towards lithium in presence of metal ions found in the concentrates, Na+, K+, Mg2+, Ca2+ and Sr2+ was carried out, via molecular simulation using ab initio Density Functional Theory (DFT). The geometries, reaction energies, and thermodynamic parameters have been evaluated. Using the square of the electronic wave function an electrostatic interaction was confirmed as cation-extractant/s bonding. The complexation reaction energies of the systems formed by a cation and a single extractant display negative [delta]E and [delta]G values, pointing towards stable complexes and spontaneous reactions. The synergic effect of extractants was studied by combining the [beta]-diketones with TOPO (1:1) leading to an increase of [delta]E and [delta]G (absolute value). The extraction coefficient, K, follows the order K(K+) > K(Na+) > K(Li+) > K(Sr2+) > K(Ca2+) > K(Mg2+). In consequence, selectivity Li+ towards cations of the group II was higher, S(Li+/Mg2+) > S(Li+/Ca2+) > S(Li+/Sr2+) for the combined mixtures BTA TOPO and FDOD TOPO and lower towards group I cations, S(Li+/Na+) > S(Li+/K+) for DBM TOPO and LIX54 TOPO. The selectivity of Li+ regarding the rest of the cations and the 16 extractants and mixtures of extractants was lower than the selectivity of Li+ with respect to each cation, being the best value for the DBM TOPO and LIX54 TOPO systems. The results obtained are expected to provide a tool on the behaviour of the most promising of extractants towards Li+ in seawater desalination concentrates.
publishDate 2022
dc.date.none.fl_str_mv 2022
2022-06-15
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
NA
http://purl.org/coar/version/c_be7fb7dd8ff6fe43
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10902/28314
url https://hdl.handle.net/10902/28314
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv Desalination, 2022, 532, 115704
reponame:UCrea Repositorio Abierto de la Universidad de Cantabria
instname:Universidad de Cantabria (UC)
instname_str Universidad de Cantabria (UC)
reponame_str UCrea Repositorio Abierto de la Universidad de Cantabria
collection UCrea Repositorio Abierto de la Universidad de Cantabria
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301629

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