Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures

Detalhes bibliográficos
Autor(a) principal: Santos, Leonardo Leandro dos
Data de Publicação: 2018
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFRN
Texto Completo: https://repositorio.ufrn.br/jspui/handle/123456789/26932
Resumo: The expected increase in demand for lithium salts raises a growing concern regarding this metal scarcity and environmental issues in the national industry of lithium extraction in tilled reserves. The methodologies applied in lithium extraction are associated with the use of sulfates, organic and actinide-based solvents that leads to the formation of sulfated silico-aluminum by-products and radioactive waste. Therefore, this study aimed to develop and to design environmentally efficient routes in order to extract lithium in salt form from beta-spodumene (β-LiAlSi2O6) and technologically feasible routes to simultaneously obtain zeolites as a by-product. A literature review describes techniques to extract lithium using sulfated additives with by-product recovery after the synthesis process, which indicates that this research is considered unprecedented for having obtained zeolitic crystalline structures formed in the lithium extraction route. In order to elaborate efficient and economically feasible extraction routes, a prior understanding of the attributes of molecular sieves was necessary, in particular, the zeolite types. Thus, the efficiency of lithium extraction using Na2CO3, NaOH e NaCl additives was evaluated through the measurement of atomic absorption in the supernatant, based on chemoselective ion exchange between Li+ from β-LiAlSi2O6 and Na+ from Na2CO3 and NaCl, resulting in up to 85% of extracted lithium. The addition of NaOH promoted the mineralization for the dissolution of β-LiAlSi2O6, enabling the recovery of Li and the availability of Si and Al for the nucleation and the development of zeolite structures. As a result, two routes were developed operating in the closed and continuous circuit (HTS: high-throughput screening). Each route consisted of different stages such as calcination, hydrothermal treatment, and the use of bicarbonate for the dissolution and precipitation of the associated lithium salt, besides the recovery of new materials like as by-products of cage (LTA and FAU) or channel (LTT, MOR, and MFI) zeolitic topology. At last, in order to validate the strategies used, the materials were categorized applying techniques such as XRD, XRF, TGA, ICP, N2 adsorption isotherms, SEM, TEM and FT-IR with adsorbed pyridine.
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spelling Santos, Leonardo Leandro dosNascimento, Rubens Maribondo doBraga, Tiago PinheiroBieseki, LindianeSapag, Manuel KarimPergher, Sibele Berenice Castella2019-04-11T18:45:50Z2019-04-11T18:45:50Z2018-07-25SANTOS, Leonardo Leandro dos. Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures. 2018. 161f. Tese (Doutorado em Ciência e Engenharia de Materiais) - Centro de Ciências Exatas e da Terra, Universidade Federal do Rio Grande do Norte, Natal, 2018.https://repositorio.ufrn.br/jspui/handle/123456789/26932The expected increase in demand for lithium salts raises a growing concern regarding this metal scarcity and environmental issues in the national industry of lithium extraction in tilled reserves. The methodologies applied in lithium extraction are associated with the use of sulfates, organic and actinide-based solvents that leads to the formation of sulfated silico-aluminum by-products and radioactive waste. Therefore, this study aimed to develop and to design environmentally efficient routes in order to extract lithium in salt form from beta-spodumene (β-LiAlSi2O6) and technologically feasible routes to simultaneously obtain zeolites as a by-product. A literature review describes techniques to extract lithium using sulfated additives with by-product recovery after the synthesis process, which indicates that this research is considered unprecedented for having obtained zeolitic crystalline structures formed in the lithium extraction route. In order to elaborate efficient and economically feasible extraction routes, a prior understanding of the attributes of molecular sieves was necessary, in particular, the zeolite types. Thus, the efficiency of lithium extraction using Na2CO3, NaOH e NaCl additives was evaluated through the measurement of atomic absorption in the supernatant, based on chemoselective ion exchange between Li+ from β-LiAlSi2O6 and Na+ from Na2CO3 and NaCl, resulting in up to 85% of extracted lithium. The addition of NaOH promoted the mineralization for the dissolution of β-LiAlSi2O6, enabling the recovery of Li and the availability of Si and Al for the nucleation and the development of zeolite structures. As a result, two routes were developed operating in the closed and continuous circuit (HTS: high-throughput screening). Each route consisted of different stages such as calcination, hydrothermal treatment, and the use of bicarbonate for the dissolution and precipitation of the associated lithium salt, besides the recovery of new materials like as by-products of cage (LTA and FAU) or channel (LTT, MOR, and MFI) zeolitic topology. At last, in order to validate the strategies used, the materials were categorized applying techniques such as XRD, XRF, TGA, ICP, N2 adsorption isotherms, SEM, TEM and FT-IR with adsorbed pyridine.O aumento previsto na demanda por sais de lítio traz uma crescente preocupação com a escassez desse metal e problemas ambientais na indústria nacional de extração litinífera cujas metodologias empregadas estão associadas a sulfatos, solventes orgânicos e a base de actinídeos, consequentemente formando rejeitos silicoaluminosos sulfatados e radioativos. Portanto, o objetivo deste estudo foi desenvolver rota ambientalmente eficiente para extração de lítio na forma de sal a partir de beta-espodumênio (β-LiAlSi2O6) e tecnologicamente viável para obtenção simultânea de zeólitas como subproduto. Estudos da literatura descrevem metodologias para extração de lítio utilizando aditivos sulfatados, com recuperação do resíduo pós-síntese. O presente estudo, entretanto, é inédito em razão de obter estruturas cristalinas zeolíticas como subproduto em rota para extração de lítio. Em princípio, ao elaborar meios de extração eficiente e economicamente viável, foi importante entender as características das peneiras moleculares, especificamente as zeólitas. Como resultado, a eficiência para extração de lítio com o uso dos aditivos Na2CO3, NaOH e NaCl foi avaliada por meio de medidas de absorção atômica no sobrenadante, resultando em até 85% de lítio extraído, baseado na troca iônica quimiosseletiva entre Li+ de β-LiAlSi2O6 e Na+ de Na2CO3 e NaCl. A adição de NaOH promoveu ação mineralizante com vistas à dissolução de β-LiAlSi2O6, viabilizando a recuperação de Li e disponibilidade de Si e Al para nucleação e crescimento de estruturas zeolíticas. Como resultado, foram desenvolvidas duas rotas, cada qual operando em circuito cíclico e contínuo (HTS: High-throughput Screening), compreendido por etapas como calcinação, tratamento hidrotérmico e bicarbonatação, para extração de lítio e obtenção de subproduto com topologia zeolítica tipo gaiola (LTA e FAU) e tipo canal (LTT, MOR e MFI). Os materiais foram caracterizados por diversas técnicas como DRX, FRX, TG, Espectrometria de emissão atômica por plasma acoplado indutivamente, isotermas de adsorção de N2, MEV, MET e Espectroscopia na região do infravermelho por transformada de Fourier com piridina adsorvida.CNPQ::ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICABeta-spodumeneLithium extractionLi2CO3High-throughput screeningZeolitesExtraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structuresExtração de lítio de beta-espodumênio através de rotas para obtenção simultânea de estruturas zeolíticasinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisPROGRAMA DE PÓS-GRADUAÇÃO EM CIÊNCIA E ENGENHARIA DE MATERIAISUFRNBrasilinfo:eu-repo/semantics/openAccessporreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRNTEXTExtractionlithiumfrom_Santos_2018.pdf.txtExtractionlithiumfrom_Santos_2018.pdf.txtExtracted texttext/plain278963https://repositorio.ufrn.br/bitstream/123456789/26932/2/Extractionlithiumfrom_Santos_2018.pdf.txta1326b71fc3d4ce19fc9c69da2a970b1MD52THUMBNAILExtractionlithiumfrom_Santos_2018.pdf.jpgExtractionlithiumfrom_Santos_2018.pdf.jpgGenerated Thumbnailimage/jpeg1453https://repositorio.ufrn.br/bitstream/123456789/26932/3/Extractionlithiumfrom_Santos_2018.pdf.jpgc43731f9af270b84abfe85dae70b2b82MD53ORIGINALExtractionlithiumfrom_Santos_2018.pdfapplication/pdf8745437https://repositorio.ufrn.br/bitstream/123456789/26932/1/Extractionlithiumfrom_Santos_2018.pdf3e09f28ed9e073f0eca8d20c8113fc54MD51123456789/269322020-02-20 10:07:44.483oai:https://repositorio.ufrn.br:123456789/26932Repositório de PublicaçõesPUBhttp://repositorio.ufrn.br/oai/opendoar:2020-02-20T13:07:44Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false
dc.title.pt_BR.fl_str_mv Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
dc.title.alternative.pt_BR.fl_str_mv Extração de lítio de beta-espodumênio através de rotas para obtenção simultânea de estruturas zeolíticas
title Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
spellingShingle Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
Santos, Leonardo Leandro dos
CNPQ::ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA
Beta-spodumene
Lithium extraction
Li2CO3
High-throughput screening
Zeolites
title_short Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
title_full Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
title_fullStr Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
title_full_unstemmed Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
title_sort Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures
author Santos, Leonardo Leandro dos
author_facet Santos, Leonardo Leandro dos
author_role author
dc.contributor.authorID.pt_BR.fl_str_mv
dc.contributor.advisorID.pt_BR.fl_str_mv
dc.contributor.advisor-co1ID.pt_BR.fl_str_mv
dc.contributor.referees1.none.fl_str_mv Braga, Tiago Pinheiro
dc.contributor.referees1ID.pt_BR.fl_str_mv
dc.contributor.referees2.none.fl_str_mv Bieseki, Lindiane
dc.contributor.referees2ID.pt_BR.fl_str_mv
dc.contributor.referees3.none.fl_str_mv Sapag, Manuel Karim
dc.contributor.referees3ID.pt_BR.fl_str_mv
dc.contributor.author.fl_str_mv Santos, Leonardo Leandro dos
dc.contributor.advisor-co1.fl_str_mv Nascimento, Rubens Maribondo do
dc.contributor.advisor1.fl_str_mv Pergher, Sibele Berenice Castella
contributor_str_mv Nascimento, Rubens Maribondo do
Pergher, Sibele Berenice Castella
dc.subject.cnpq.fl_str_mv CNPQ::ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA
topic CNPQ::ENGENHARIAS::ENGENHARIA DE MATERIAIS E METALURGICA
Beta-spodumene
Lithium extraction
Li2CO3
High-throughput screening
Zeolites
dc.subject.por.fl_str_mv Beta-spodumene
Lithium extraction
Li2CO3
High-throughput screening
Zeolites
description The expected increase in demand for lithium salts raises a growing concern regarding this metal scarcity and environmental issues in the national industry of lithium extraction in tilled reserves. The methodologies applied in lithium extraction are associated with the use of sulfates, organic and actinide-based solvents that leads to the formation of sulfated silico-aluminum by-products and radioactive waste. Therefore, this study aimed to develop and to design environmentally efficient routes in order to extract lithium in salt form from beta-spodumene (β-LiAlSi2O6) and technologically feasible routes to simultaneously obtain zeolites as a by-product. A literature review describes techniques to extract lithium using sulfated additives with by-product recovery after the synthesis process, which indicates that this research is considered unprecedented for having obtained zeolitic crystalline structures formed in the lithium extraction route. In order to elaborate efficient and economically feasible extraction routes, a prior understanding of the attributes of molecular sieves was necessary, in particular, the zeolite types. Thus, the efficiency of lithium extraction using Na2CO3, NaOH e NaCl additives was evaluated through the measurement of atomic absorption in the supernatant, based on chemoselective ion exchange between Li+ from β-LiAlSi2O6 and Na+ from Na2CO3 and NaCl, resulting in up to 85% of extracted lithium. The addition of NaOH promoted the mineralization for the dissolution of β-LiAlSi2O6, enabling the recovery of Li and the availability of Si and Al for the nucleation and the development of zeolite structures. As a result, two routes were developed operating in the closed and continuous circuit (HTS: high-throughput screening). Each route consisted of different stages such as calcination, hydrothermal treatment, and the use of bicarbonate for the dissolution and precipitation of the associated lithium salt, besides the recovery of new materials like as by-products of cage (LTA and FAU) or channel (LTT, MOR, and MFI) zeolitic topology. At last, in order to validate the strategies used, the materials were categorized applying techniques such as XRD, XRF, TGA, ICP, N2 adsorption isotherms, SEM, TEM and FT-IR with adsorbed pyridine.
publishDate 2018
dc.date.issued.fl_str_mv 2018-07-25
dc.date.accessioned.fl_str_mv 2019-04-11T18:45:50Z
dc.date.available.fl_str_mv 2019-04-11T18:45:50Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.citation.fl_str_mv SANTOS, Leonardo Leandro dos. Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures. 2018. 161f. Tese (Doutorado em Ciência e Engenharia de Materiais) - Centro de Ciências Exatas e da Terra, Universidade Federal do Rio Grande do Norte, Natal, 2018.
dc.identifier.uri.fl_str_mv https://repositorio.ufrn.br/jspui/handle/123456789/26932
identifier_str_mv SANTOS, Leonardo Leandro dos. Extraction of lithium from beta-spodumene using routes with simultaneous acquisition of zeolitic structures. 2018. 161f. Tese (Doutorado em Ciência e Engenharia de Materiais) - Centro de Ciências Exatas e da Terra, Universidade Federal do Rio Grande do Norte, Natal, 2018.
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