Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4

Detalhes bibliográficos
Autor(a) principal: Silva, Nathacha Kare Gonçalves
Data de Publicação: 2018
Tipo de documento: Tese
Idioma: eng
Título da fonte: Repositório Institucional da UFU
Texto Completo: https://repositorio.ufu.br/handle/123456789/27281
http://dx.doi.org/10.14393/ufu.te.2019.15
Resumo: Problems arising from fossil fuels combustion, such as local air pollution, the global climate change, and the conflicts between countries for finite fossil reserves stimulated the pursuit for renewable sources of energy. Lignocellusic biomass has the potential to be transformed in fuels, fuels additives, and sustainable chemicals in the perspective of non-competition with food production. The raw product thermochemically treated by fast pyrolysis of lignocellulosic biomass shows undesired properties derived from the high oxygen content and needs to be upgraded, in an analogue way as occurs with crude petroleum. Hydrodeoxygenation (HDO) is one of the processes that can be applied to upgrade the non-condensed or condensed (bio-oil) pyrolysis vapors. In this work, the HDO of guaiacol (2-methoxyphenol, C7H8O2), model compound representative of the lignin portion of biomass, was evaluated to function as foundation for the development of more complex studies. Initially, a thermodynamic analysis of the guaiacol conversion was carried out using the software UniSim Design R400. The results of the chemical equilibrium revealed that most of the reactions were exothermic and that the HDO of guaiacol did not show thermodynamic restriction to occur. The experimental part of this study involved the guaiacol reaction with hydrogen at atmospheric pressure using niobium-based catalysts. The catalytic system tested was comprised by platinum supported on niobium oxide (Nb2O5), alumina (Al2O3), niobia-alumina (5%Nb2O5/Al2O3; 20%Nb2O5/Al2O3), and niobium phosphate (NbOPO4). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, CO chemisorption, and temperature-programmed desorption of isopropylamine. The influence of operating conditions such as hydrogen partial pressure, temperature, and space velocity on both activity and selectivity were analyzed. It was observed that the higher the niobia loading in the niobia-alumina mixed support the higher was the selectivity for phenol. The Pt/NbOPO4 catalyst formed less deoxygenated products than Pt/Nb2O5. Pt/Nb2O5 prepared using ammonium niobium oxalate as precursor was superior to the catalyst prepared using niobic acid. The Pt/Nb2O5 was the best performance catalyst, which was attributed to the interaction between Pt and NbOx species (metal-support interface).
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spelling Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4Study of guaiacol hydrodeoxygenation in vapor phase over platinum catalysts supported on niobium-based matrices: xNb2O5 / (100-x) Al2O3 (x = 0, 5, 20, 100, wt%) and NbOPO4Engenharia QuímicaChemical EngineeringHidrodesoxigenaçãoHydrodeoxygenationHDOGuaiacolMelhoramento da biomassaBiomass upgradingFosfato de nióbioNiobium phosphateNióbiaNiobiaCatalisadores de platinaPlatinum catalystsCNPQ::ENGENHARIAS::ENGENHARIA QUIMICAProblems arising from fossil fuels combustion, such as local air pollution, the global climate change, and the conflicts between countries for finite fossil reserves stimulated the pursuit for renewable sources of energy. Lignocellusic biomass has the potential to be transformed in fuels, fuels additives, and sustainable chemicals in the perspective of non-competition with food production. The raw product thermochemically treated by fast pyrolysis of lignocellulosic biomass shows undesired properties derived from the high oxygen content and needs to be upgraded, in an analogue way as occurs with crude petroleum. Hydrodeoxygenation (HDO) is one of the processes that can be applied to upgrade the non-condensed or condensed (bio-oil) pyrolysis vapors. In this work, the HDO of guaiacol (2-methoxyphenol, C7H8O2), model compound representative of the lignin portion of biomass, was evaluated to function as foundation for the development of more complex studies. Initially, a thermodynamic analysis of the guaiacol conversion was carried out using the software UniSim Design R400. The results of the chemical equilibrium revealed that most of the reactions were exothermic and that the HDO of guaiacol did not show thermodynamic restriction to occur. The experimental part of this study involved the guaiacol reaction with hydrogen at atmospheric pressure using niobium-based catalysts. The catalytic system tested was comprised by platinum supported on niobium oxide (Nb2O5), alumina (Al2O3), niobia-alumina (5%Nb2O5/Al2O3; 20%Nb2O5/Al2O3), and niobium phosphate (NbOPO4). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, CO chemisorption, and temperature-programmed desorption of isopropylamine. The influence of operating conditions such as hydrogen partial pressure, temperature, and space velocity on both activity and selectivity were analyzed. It was observed that the higher the niobia loading in the niobia-alumina mixed support the higher was the selectivity for phenol. The Pt/NbOPO4 catalyst formed less deoxygenated products than Pt/Nb2O5. Pt/Nb2O5 prepared using ammonium niobium oxalate as precursor was superior to the catalyst prepared using niobic acid. The Pt/Nb2O5 was the best performance catalyst, which was attributed to the interaction between Pt and NbOx species (metal-support interface).Tese (Doutorado)Problemas oriundos da combustão de combustíveis fósseis, tais como a poluição local do ar, a mudança climática global e os conflitos entre países pelas finitas reservas fósseis estimularam a busca por fontes renováveis de energia. A biomassa lignocelulósica tem o potencial de ser transformada em combustíveis, aditivos de combustíveis e químicos sustentáveis na perspectiva de não-competição com a produção de alimentos. O produto bruto termoquimicamente tratado pela pirólise rápida da biomassa lignocelulósica apresenta propriedades indesejáveis derivadas do alto conteúdo de oxigênio e precisa ser refinado, de maneira análoga ao que acontece com o petróleo. A hidrodesoxigenação (HDO) é um dos processos que pode ser aplicado para refinar os vapores de pirólise não-condensados ou condensados (bio-óleo). Neste trabalho, a HDO de guaiacol (2-metóxifenol, C7H8O2), composto modelo representativo da porção de lignina da biomassa, foi avaliado para funcionar como uma base para o desenvolvimento de estudos mais complexos. Inicialmente, uma análise termodinâmica da conversão de guaiacol foi realizada usando o software UniSim Design R400. Os resultados do equilíbrio químico revelaram que a maioria das reações era exotérmica e que a HDO de guaiacol não mostrou restrição termodinâmica para ocorrer. A parte experimental deste estudo envolveu a reação de guaiacol com hidrogênio à pressão atmosférica usando catalisadores à base de nióbio. O sistema catalítico testado foi composto por platina suportada em óxido de nióbio (Nb2O5), alumina (Al2O3), nióbia-alumina (5%Nb2O5/Al2O3; 20%Nb2O5/Al2O3) e fosfato de nióbio (NbOPO4). Os catalisadores foram caracterizados por difração de raios X (DRX), fisissorção de nitrogênio, quimissorção de CO e dessorção à temperatura programada de isopropilamina. A influência das condições operacionais como pressão parcial de hidrogênio, temperatura e velocidade espacial na atividade e seletividade foram analisadas. Foi observado que quanto maior o conteúdo de nióbia no suporte misto de nióbia-alumina maior foi a seletividade para fenol. O catalisador Pt/NbOPO4 formou menos produtos desoxigenados do que Pt/Nb2O5. Pt/Nb2O5 preparado usando oxalato amoniacal de nióbio como precursor foi superior ao catalisador preparado usando ácido nióbico. Pt/Nb2O5 mostrou-se como o catalisador de melhor desempenho, o que foi atribuído à interação entre Pt e espécies NbOx (interface metal-suporte).Universidade Federal de UberlândiaBrasilPrograma de Pós-graduação em Engenharia QuímicaBarrozo, Marcos Antonio de SouzaSoares, Ricardo ReisRossa, ViniciusMonteiro, Robson de SouzaNoronha, Fábio BellotSilva, Victor Luis dos Santos Teixeira daSilva, Nathacha Kare Gonçalves2019-11-06T13:06:31Z2019-11-06T13:06:31Z2018-06-07info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfSILVA, Nathacha Kare Gonçalves. Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4. 2018. 95f. Tese (Doutorado em Engenharia Química) - Universidade Federal de Uberlândia, Uberlândia, 2018. DOI http://dx.doi.org/10.14393/ufu.te.2019.15https://repositorio.ufu.br/handle/123456789/27281http://dx.doi.org/10.14393/ufu.te.2019.15enghttp://creativecommons.org/licenses/by-nc-nd/3.0/us/info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFUinstname:Universidade Federal de Uberlândia (UFU)instacron:UFU2021-11-26T14:20:23Zoai:repositorio.ufu.br:123456789/27281Repositório InstitucionalONGhttp://repositorio.ufu.br/oai/requestdiinf@dirbi.ufu.bropendoar:2021-11-26T14:20:23Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)false
dc.title.none.fl_str_mv Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
Study of guaiacol hydrodeoxygenation in vapor phase over platinum catalysts supported on niobium-based matrices: xNb2O5 / (100-x) Al2O3 (x = 0, 5, 20, 100, wt%) and NbOPO4
title Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
spellingShingle Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
Silva, Nathacha Kare Gonçalves
Engenharia Química
Chemical Engineering
Hidrodesoxigenação
Hydrodeoxygenation
HDO
Guaiacol
Melhoramento da biomassa
Biomass upgrading
Fosfato de nióbio
Niobium phosphate
Nióbia
Niobia
Catalisadores de platina
Platinum catalysts
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
title_short Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
title_full Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
title_fullStr Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
title_full_unstemmed Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
title_sort Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4
author Silva, Nathacha Kare Gonçalves
author_facet Silva, Nathacha Kare Gonçalves
author_role author
dc.contributor.none.fl_str_mv Barrozo, Marcos Antonio de Souza
Soares, Ricardo Reis
Rossa, Vinicius
Monteiro, Robson de Souza
Noronha, Fábio Bellot
Silva, Victor Luis dos Santos Teixeira da
dc.contributor.author.fl_str_mv Silva, Nathacha Kare Gonçalves
dc.subject.por.fl_str_mv Engenharia Química
Chemical Engineering
Hidrodesoxigenação
Hydrodeoxygenation
HDO
Guaiacol
Melhoramento da biomassa
Biomass upgrading
Fosfato de nióbio
Niobium phosphate
Nióbia
Niobia
Catalisadores de platina
Platinum catalysts
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
topic Engenharia Química
Chemical Engineering
Hidrodesoxigenação
Hydrodeoxygenation
HDO
Guaiacol
Melhoramento da biomassa
Biomass upgrading
Fosfato de nióbio
Niobium phosphate
Nióbia
Niobia
Catalisadores de platina
Platinum catalysts
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
description Problems arising from fossil fuels combustion, such as local air pollution, the global climate change, and the conflicts between countries for finite fossil reserves stimulated the pursuit for renewable sources of energy. Lignocellusic biomass has the potential to be transformed in fuels, fuels additives, and sustainable chemicals in the perspective of non-competition with food production. The raw product thermochemically treated by fast pyrolysis of lignocellulosic biomass shows undesired properties derived from the high oxygen content and needs to be upgraded, in an analogue way as occurs with crude petroleum. Hydrodeoxygenation (HDO) is one of the processes that can be applied to upgrade the non-condensed or condensed (bio-oil) pyrolysis vapors. In this work, the HDO of guaiacol (2-methoxyphenol, C7H8O2), model compound representative of the lignin portion of biomass, was evaluated to function as foundation for the development of more complex studies. Initially, a thermodynamic analysis of the guaiacol conversion was carried out using the software UniSim Design R400. The results of the chemical equilibrium revealed that most of the reactions were exothermic and that the HDO of guaiacol did not show thermodynamic restriction to occur. The experimental part of this study involved the guaiacol reaction with hydrogen at atmospheric pressure using niobium-based catalysts. The catalytic system tested was comprised by platinum supported on niobium oxide (Nb2O5), alumina (Al2O3), niobia-alumina (5%Nb2O5/Al2O3; 20%Nb2O5/Al2O3), and niobium phosphate (NbOPO4). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, CO chemisorption, and temperature-programmed desorption of isopropylamine. The influence of operating conditions such as hydrogen partial pressure, temperature, and space velocity on both activity and selectivity were analyzed. It was observed that the higher the niobia loading in the niobia-alumina mixed support the higher was the selectivity for phenol. The Pt/NbOPO4 catalyst formed less deoxygenated products than Pt/Nb2O5. Pt/Nb2O5 prepared using ammonium niobium oxalate as precursor was superior to the catalyst prepared using niobic acid. The Pt/Nb2O5 was the best performance catalyst, which was attributed to the interaction between Pt and NbOx species (metal-support interface).
publishDate 2018
dc.date.none.fl_str_mv 2018-06-07
2019-11-06T13:06:31Z
2019-11-06T13:06:31Z
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.uri.fl_str_mv SILVA, Nathacha Kare Gonçalves. Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4. 2018. 95f. Tese (Doutorado em Engenharia Química) - Universidade Federal de Uberlândia, Uberlândia, 2018. DOI http://dx.doi.org/10.14393/ufu.te.2019.15
https://repositorio.ufu.br/handle/123456789/27281
http://dx.doi.org/10.14393/ufu.te.2019.15
identifier_str_mv SILVA, Nathacha Kare Gonçalves. Estudo da hidrodesoxigenação do guaiacol em fase vapor sobre catalisadores de platina suportados em matrizes à base de nióbio: xNb2O5/(100-x)Al2O3 (x = 0, 5, 20, 100, % peso) e NbOPO4. 2018. 95f. Tese (Doutorado em Engenharia Química) - Universidade Federal de Uberlândia, Uberlândia, 2018. DOI http://dx.doi.org/10.14393/ufu.te.2019.15
url https://repositorio.ufu.br/handle/123456789/27281
http://dx.doi.org/10.14393/ufu.te.2019.15
dc.language.iso.fl_str_mv eng
language eng
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info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/3.0/us/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Engenharia Química
publisher.none.fl_str_mv Universidade Federal de Uberlândia
Brasil
Programa de Pós-graduação em Engenharia Química
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFU
instname:Universidade Federal de Uberlândia (UFU)
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instname_str Universidade Federal de Uberlândia (UFU)
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institution UFU
reponame_str Repositório Institucional da UFU
collection Repositório Institucional da UFU
repository.name.fl_str_mv Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)
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