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
Autor(a) principal: | |
---|---|
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). |
id |
UFU_2a5d69547de12e4815bded57037f689d |
---|---|
oai_identifier_str |
oai:repositorio.ufu.br:123456789/27281 |
network_acronym_str |
UFU |
network_name_str |
Repositório Institucional da UFU |
repository_id_str |
|
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 |
dc.rights.driver.fl_str_mv |
http://creativecommons.org/licenses/by-nc-nd/3.0/us/ 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) instacron:UFU |
instname_str |
Universidade Federal de Uberlândia (UFU) |
instacron_str |
UFU |
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) |
repository.mail.fl_str_mv |
diinf@dirbi.ufu.br |
_version_ |
1813711512442765312 |