Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/14334 |
Resumo: | One-pot catalytic processes using heterogeneous acid catalysts have been a promising strategy for the valorization of platform molecules from lignocellulosic biomass, such as the transformation of furfural (Fur) to γ-valerolactone (GVL), levulinic acid (AL), levulinate esters, angelic lactones, etc., which can be used for the production of biofuels and additives, "green" solvents and chemical intermediates. Among the catalysts used in these processes, zeolites with Lewis acidity (L) and Brønsted (B) have demonstrated remarkable activities for coupling reactions by Meerwein Ponndorf-Verley transfer hydrogenation (MPV), hydrolysis/ alcoholysis and lactonization, which are routes of synthesis used in the conversion of molecules derived from lignocellulosic biomass. However, in the conversion of Fu, there are still limitations to be overcome, such as the development of more selective heterogeneous catalysts and with more active and accessible sites capable of performing the stages of hydrogenation by MPV and hydrolysis/alcoholysis. For MPV transfer hydrogenation reactions, zeolites with incorporated tetravalent metals (Ti, Sn, Zr, and Hf) have shown high activities, with those Hf-incorporated being the most active. In this context, this work proposes to develop hierarchical ZSM-5 zeolites containing L acid sites generated by Hf and B acid sites to be used as catalysts for the conversion of Fur in the presence of 2-propanol to more valuable products. For this purpose, hierarchical ZSM-5 zeolites with acidity of L and B were prepared by post-synthesis strategies of desilication, dealumination, and incorporation in liquid phase of Hf4+ cations. Analyses from XRD, DRS-UV-Vis, N2 physisorption, and FTIR in situ with adsorbed pyridine proved that the synthesis methods employed are capable to obtain micro-mesoporous ZSM-5 zeolites with both types of acid sites. In the catalytic tests, the hierarchical zeolites were able to catalyze the Fur conversion by in series reactions, generating mainly products such as GVL, AL, isopropyl levulinate (LI), β-angelic lactone (β AgL), and 2-(isopropoxymethyl)furan (2-IPF). The distribution of these products was strongly affected by the textural and acidic properties of the materials. The control of the B/L ratio proved to be essential in obtaining more efficient catalysts. To make this control, different strategies were used, such as heat treatments, changes in the degree of incorporation of the metallic cation, and physical mixtures of solids with L or B acidity. For the thermally treated mesoporous zeolites (Hf, Al)-ZSM-5, the selectivity to GVL decreased with the increase of the calcination temperature of the catalyst, and up to 450 °C its selectivity remained constant. The adjustment of the B/L ratio obtained with the change in the textural properties of the zeolite and subsequent insertion of Hf allowed changing the accessibility of the precursor of the metallic cation and its degree of incorporation, resulting in catalysts with different activities and selectivities. Physical mixtures of protonic hierarchical zeolites with HfO2 were also efficient for controlling the B/L ratio in a simpler and faster way. Using 30 mg of a micro-mesoporous zeolite (Hf, Al)-ZSM-5 containing 1.53 μmol of L and 4.14 μmol of B, it was possible to convert about 200 μmol of Fur after 40 h of reaction at 120 °C, obtaining GVL and LI yields of 35 and 23%, respectively. Catalytic tests varying the reaction conditions allowed to verify that the yields and selectivities to products of interest for the sectors of biofuels and chemical intermediates such as GVL and LI can be improved with the increase of the reaction temperature, catalyst mass and adjustment of the B/L ratio. In addition, catalyst reuse tests showed that the micro-mesoporous ZSM-5 zeolite having B and L sites generated by Hf maintained its catalytic activity until at least four consecutive reaction cycles. In general, the strategies presented were promising for the development of potential catalysts for the reactions of transformation of furan molecules into highly demanded products, such as biofuels, additives and chemical intermediates. |
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Silva, Domingos Sérgio AraújoUrquieta-González, Ernesto Antoniohttp://lattes.cnpq.br/2389975677904655http://lattes.cnpq.br/9207614236832829477e33a5-881e-46a2-b289-5bec9bba45c32021-06-02T12:16:36Z2021-06-02T12:16:36Z2021-04-29SILVA, Domingos Sérgio Araújo. Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14334.https://repositorio.ufscar.br/handle/ufscar/14334One-pot catalytic processes using heterogeneous acid catalysts have been a promising strategy for the valorization of platform molecules from lignocellulosic biomass, such as the transformation of furfural (Fur) to γ-valerolactone (GVL), levulinic acid (AL), levulinate esters, angelic lactones, etc., which can be used for the production of biofuels and additives, "green" solvents and chemical intermediates. Among the catalysts used in these processes, zeolites with Lewis acidity (L) and Brønsted (B) have demonstrated remarkable activities for coupling reactions by Meerwein Ponndorf-Verley transfer hydrogenation (MPV), hydrolysis/ alcoholysis and lactonization, which are routes of synthesis used in the conversion of molecules derived from lignocellulosic biomass. However, in the conversion of Fu, there are still limitations to be overcome, such as the development of more selective heterogeneous catalysts and with more active and accessible sites capable of performing the stages of hydrogenation by MPV and hydrolysis/alcoholysis. For MPV transfer hydrogenation reactions, zeolites with incorporated tetravalent metals (Ti, Sn, Zr, and Hf) have shown high activities, with those Hf-incorporated being the most active. In this context, this work proposes to develop hierarchical ZSM-5 zeolites containing L acid sites generated by Hf and B acid sites to be used as catalysts for the conversion of Fur in the presence of 2-propanol to more valuable products. For this purpose, hierarchical ZSM-5 zeolites with acidity of L and B were prepared by post-synthesis strategies of desilication, dealumination, and incorporation in liquid phase of Hf4+ cations. Analyses from XRD, DRS-UV-Vis, N2 physisorption, and FTIR in situ with adsorbed pyridine proved that the synthesis methods employed are capable to obtain micro-mesoporous ZSM-5 zeolites with both types of acid sites. In the catalytic tests, the hierarchical zeolites were able to catalyze the Fur conversion by in series reactions, generating mainly products such as GVL, AL, isopropyl levulinate (LI), β-angelic lactone (β AgL), and 2-(isopropoxymethyl)furan (2-IPF). The distribution of these products was strongly affected by the textural and acidic properties of the materials. The control of the B/L ratio proved to be essential in obtaining more efficient catalysts. To make this control, different strategies were used, such as heat treatments, changes in the degree of incorporation of the metallic cation, and physical mixtures of solids with L or B acidity. For the thermally treated mesoporous zeolites (Hf, Al)-ZSM-5, the selectivity to GVL decreased with the increase of the calcination temperature of the catalyst, and up to 450 °C its selectivity remained constant. The adjustment of the B/L ratio obtained with the change in the textural properties of the zeolite and subsequent insertion of Hf allowed changing the accessibility of the precursor of the metallic cation and its degree of incorporation, resulting in catalysts with different activities and selectivities. Physical mixtures of protonic hierarchical zeolites with HfO2 were also efficient for controlling the B/L ratio in a simpler and faster way. Using 30 mg of a micro-mesoporous zeolite (Hf, Al)-ZSM-5 containing 1.53 μmol of L and 4.14 μmol of B, it was possible to convert about 200 μmol of Fur after 40 h of reaction at 120 °C, obtaining GVL and LI yields of 35 and 23%, respectively. Catalytic tests varying the reaction conditions allowed to verify that the yields and selectivities to products of interest for the sectors of biofuels and chemical intermediates such as GVL and LI can be improved with the increase of the reaction temperature, catalyst mass and adjustment of the B/L ratio. In addition, catalyst reuse tests showed that the micro-mesoporous ZSM-5 zeolite having B and L sites generated by Hf maintained its catalytic activity until at least four consecutive reaction cycles. In general, the strategies presented were promising for the development of potential catalysts for the reactions of transformation of furan molecules into highly demanded products, such as biofuels, additives and chemical intermediates.Processos catalíticos one-pot a partir de reações em série utilizando catalisadores heterogêneos ácidos têm sido uma estratégia promissora para a valorização de moléculas plataforma oriundas da biomassa lignocelulósica, tais como a transformação do furfural (Fur) a γ-valerolactona (GVL), ácido levulínico (AL), ésteres levulinatos, angélicas lactonas etc., as quais podem ser empregadas para a produção de biocombustíveis e aditivos, solventes “verdes” e intermediários químicos. Dentre os catalisadores utilizados nesses processos, zeólitas com acidez de Lewis (L) e Brønsted (B) têm apresentado atividades notáveis para acoplamentos de reações de hidrogenação por transferência de Meerwein Ponndorf-Verley (MPV), hidrólise/alcoólise e lactonização, as quais são rotas de síntese usadas na conversão de moléculas derivadas da lignocelulose. Entretanto, na conversão do Fur, ainda há limitações a serem superadas, tais como o desenvolvimento de catalisadores heterogêneos mais seletivos e com sítios mais ativos e acessíveis capazes de executar as etapas de hidrogenação por MPV e hidrólise/alcoólise. Para as reações de hidrogenação por transferência MPV, zeólitas com metais tetravalentes incorporados (Ti, Sn, Zr e Hf) têm exibido atividades elevadas, sendo que dentre elas, as contendo Hf estão entre as mais ativas. Nesse contexto, este trabalho propõe desenvolver zeólitas ZSM-5 hierárquicas contendo sítios ácidos de L gerados por Hf e sítios de B para serem empregadas como catalisadores para a conversão do Fur na presença de 2 propanol a produtos mais valiosos. Para esse propósito, zeólitas ZSM 5 hierárquicas com acidez de L e B foram preparadas por estratégias pós-síntese de dessilicalização, desaluminização e incorporação em fase líquida de cátions Hf 4+. Análises de DRX, DRS UV Vis, fisissorção de N2 e FTIR in situ com piridina adsorvida comprovaram que os métodos de síntese empregados permitiram obter zeólitas ZSM-5 micro-mesoporosas com ambos os tipos de sítios. Nos testes catalíticos, as zeólitas hierárquicas foram capazes de catalisar a conversão em série do Fur, gerando, principalmente, produtos como GVL, AL, levulinato de isopropila (LI), β-angélica lactona (β-AgL) e 2 (isopropoximetil)furano (2-IPF). A distribuição desses produtos foi bastante afetada pelas propriedades texturais e ácidas dos materiais. O controle da relação de B/L se mostrou essencial na obtenção de catalisadores mais eficientes. Para fazer esse controle, diferentes estratégias foram utilizadas, tais como tratamentos térmicos, mudanças no grau de incorporação do cátion metálico e misturas físicas de sólidos com acidez de L ou B. Para zeólitas (Hf, Al)-ZSM-5 mesoporosas tratadas termicamente, a seletividade a GVL diminuiu com o aumento da temperatura de calcinação do catalisador, sendo que até 450 °C sua seletividade se manteve constante. O ajuste da relação B/L obtido com a mudança nas propriedades texturais da zeólita e posterior inserção de Hf permitiu alterar a acessibilidade do precursor do cátion metálico e seu grau de incorporação, resultando em catalisadores com diferentes atividades e seletividades. Misturas físicas de zeólitas hierárquicas protônicas com HfO2 também se mostraram promissoras para o controle da relação B/L de maneira mais simples e rápida. Empregando-se 30 mg de uma zeólita (Hf, Al)-ZSM-5 micro-mesoporosa contendo 1,53 μmol de L e 4,14 μmol de B, foi possível converter cerca de 200 μmol do Fur após 40 h de reação a 120 °C, obtendo se rendimentos a GVL e LI de 35 e 23%, respectivamente. Testes catalíticos variando as condições reacionais permitiram verificar que os rendimentos e seletividades a produtos de interesse para os setores de biocombustíveis e intermediários químicos como a GVL e LI podem ser melhorados com o aumento da temperatura reacional, massa de catalisador e ajuste da relação B/L. Além disso, testes de reuso de catalisador mostraram que a zeólita ZSM-5 micro-mesoporosa com sítios ácidos de B e L gerados por Hf manteve sua atividade catalítica até, pelo menos, quatro ciclos reacionais consecutivos. De modo geral, as estratégias apresentadas se mostraram promissoras para o desenvolvimento de potenciais catalisadores para as reações de transformação de moléculas furânicas em produtos de alto valor para a sociedade, tais como biocombustíveis, aditivos e intermediários químicos.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)CAPES: Código de Financiamento 001porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Engenharia Química - PPGEQUFSCarAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessZeólitaZSM-5Sítios ácidos de Lewis e BrønstedCatálise heterogêneaConversão de furfuralMoléculas-plataformaBiomassa lignocelulósicaZeoliteLewis and Brønsted acid sitesHeterogeneous catalysisFurfural conversionPlatform moleculesLignocellulosic biomassENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICAENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICAENGENHARIAS::ENGENHARIA QUIMICAConversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtosFurfural conversion over hierarchical (Hf, Al)-ZSM-5 zeolites: control of Lewis and Brønsted acid sites and their effect on selectivity to productsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis6006000fecd90c-2648-4551-9f5a-7b6c106679b1reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese_Domingos_Versão final.pdfTese_Domingos_Versão final.pdfTeseapplication/pdf6805889https://repositorio.ufscar.br/bitstream/ufscar/14334/1/Tese_Domingos_Vers%c3%a3o%20final.pdf974a2fe7dbd053b4fb3f7da4a4422ecaMD51Carta comprovante Tese D S A Silva - 01-06-21_Assinada.pdfCarta comprovante Tese D S A Silva - 01-06-21_Assinada.pdfCarta comprovanteapplication/pdf92899https://repositorio.ufscar.br/bitstream/ufscar/14334/2/Carta%20comprovante%20Tese%20D%20S%20A%20Silva%20-%2001-06-21_Assinada.pdfad364176bc4ec5071ac34ebfc5799587MD52CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/14334/3/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD53TEXTTese_Domingos_Versão final.pdf.txtTese_Domingos_Versão final.pdf.txtExtracted texttext/plain353069https://repositorio.ufscar.br/bitstream/ufscar/14334/4/Tese_Domingos_Vers%c3%a3o%20final.pdf.txt292060f6f581cb21ad26f6129bf85360MD54Carta comprovante Tese D S A Silva - 01-06-21_Assinada.pdf.txtCarta comprovante Tese D S A Silva - 01-06-21_Assinada.pdf.txtExtracted texttext/plain1059https://repositorio.ufscar.br/bitstream/ufscar/14334/6/Carta%20comprovante%20Tese%20D%20S%20A%20Silva%20-%2001-06-21_Assinada.pdf.txtaed0b6c3513068952774b817637a9d63MD56THUMBNAILTese_Domingos_Versão final.pdf.jpgTese_Domingos_Versão final.pdf.jpgIM Thumbnailimage/jpeg8884https://repositorio.ufscar.br/bitstream/ufscar/14334/5/Tese_Domingos_Vers%c3%a3o%20final.pdf.jpge004d6ccf6b28699a3fb7ce67f81e4f7MD55Carta comprovante Tese D S A Silva - 01-06-21_Assinada.pdf.jpgCarta comprovante Tese D S A Silva - 01-06-21_Assinada.pdf.jpgIM Thumbnailimage/jpeg5722https://repositorio.ufscar.br/bitstream/ufscar/14334/7/Carta%20comprovante%20Tese%20D%20S%20A%20Silva%20-%2001-06-21_Assinada.pdf.jpgb093072151ef8155454418a0245facdcMD57ufscar/143342023-09-18 18:32:11.323oai:repositorio.ufscar.br:ufscar/14334Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:11Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
dc.title.alternative.eng.fl_str_mv |
Furfural conversion over hierarchical (Hf, Al)-ZSM-5 zeolites: control of Lewis and Brønsted acid sites and their effect on selectivity to products |
title |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
spellingShingle |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos Silva, Domingos Sérgio Araújo Zeólita ZSM-5 Sítios ácidos de Lewis e Brønsted Catálise heterogênea Conversão de furfural Moléculas-plataforma Biomassa lignocelulósica Zeolite Lewis and Brønsted acid sites Heterogeneous catalysis Furfural conversion Platform molecules Lignocellulosic biomass ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
title_full |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
title_fullStr |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
title_full_unstemmed |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
title_sort |
Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos |
author |
Silva, Domingos Sérgio Araújo |
author_facet |
Silva, Domingos Sérgio Araújo |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/9207614236832829 |
dc.contributor.author.fl_str_mv |
Silva, Domingos Sérgio Araújo |
dc.contributor.advisor1.fl_str_mv |
Urquieta-González, Ernesto Antonio |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2389975677904655 |
dc.contributor.authorID.fl_str_mv |
477e33a5-881e-46a2-b289-5bec9bba45c3 |
contributor_str_mv |
Urquieta-González, Ernesto Antonio |
dc.subject.por.fl_str_mv |
Zeólita ZSM-5 Sítios ácidos de Lewis e Brønsted Catálise heterogênea Conversão de furfural Moléculas-plataforma Biomassa lignocelulósica |
topic |
Zeólita ZSM-5 Sítios ácidos de Lewis e Brønsted Catálise heterogênea Conversão de furfural Moléculas-plataforma Biomassa lignocelulósica Zeolite Lewis and Brønsted acid sites Heterogeneous catalysis Furfural conversion Platform molecules Lignocellulosic biomass ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Zeolite Lewis and Brønsted acid sites Heterogeneous catalysis Furfural conversion Platform molecules Lignocellulosic biomass |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA::PROCESSOS INDUSTRIAIS DE ENGENHARIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
description |
One-pot catalytic processes using heterogeneous acid catalysts have been a promising strategy for the valorization of platform molecules from lignocellulosic biomass, such as the transformation of furfural (Fur) to γ-valerolactone (GVL), levulinic acid (AL), levulinate esters, angelic lactones, etc., which can be used for the production of biofuels and additives, "green" solvents and chemical intermediates. Among the catalysts used in these processes, zeolites with Lewis acidity (L) and Brønsted (B) have demonstrated remarkable activities for coupling reactions by Meerwein Ponndorf-Verley transfer hydrogenation (MPV), hydrolysis/ alcoholysis and lactonization, which are routes of synthesis used in the conversion of molecules derived from lignocellulosic biomass. However, in the conversion of Fu, there are still limitations to be overcome, such as the development of more selective heterogeneous catalysts and with more active and accessible sites capable of performing the stages of hydrogenation by MPV and hydrolysis/alcoholysis. For MPV transfer hydrogenation reactions, zeolites with incorporated tetravalent metals (Ti, Sn, Zr, and Hf) have shown high activities, with those Hf-incorporated being the most active. In this context, this work proposes to develop hierarchical ZSM-5 zeolites containing L acid sites generated by Hf and B acid sites to be used as catalysts for the conversion of Fur in the presence of 2-propanol to more valuable products. For this purpose, hierarchical ZSM-5 zeolites with acidity of L and B were prepared by post-synthesis strategies of desilication, dealumination, and incorporation in liquid phase of Hf4+ cations. Analyses from XRD, DRS-UV-Vis, N2 physisorption, and FTIR in situ with adsorbed pyridine proved that the synthesis methods employed are capable to obtain micro-mesoporous ZSM-5 zeolites with both types of acid sites. In the catalytic tests, the hierarchical zeolites were able to catalyze the Fur conversion by in series reactions, generating mainly products such as GVL, AL, isopropyl levulinate (LI), β-angelic lactone (β AgL), and 2-(isopropoxymethyl)furan (2-IPF). The distribution of these products was strongly affected by the textural and acidic properties of the materials. The control of the B/L ratio proved to be essential in obtaining more efficient catalysts. To make this control, different strategies were used, such as heat treatments, changes in the degree of incorporation of the metallic cation, and physical mixtures of solids with L or B acidity. For the thermally treated mesoporous zeolites (Hf, Al)-ZSM-5, the selectivity to GVL decreased with the increase of the calcination temperature of the catalyst, and up to 450 °C its selectivity remained constant. The adjustment of the B/L ratio obtained with the change in the textural properties of the zeolite and subsequent insertion of Hf allowed changing the accessibility of the precursor of the metallic cation and its degree of incorporation, resulting in catalysts with different activities and selectivities. Physical mixtures of protonic hierarchical zeolites with HfO2 were also efficient for controlling the B/L ratio in a simpler and faster way. Using 30 mg of a micro-mesoporous zeolite (Hf, Al)-ZSM-5 containing 1.53 μmol of L and 4.14 μmol of B, it was possible to convert about 200 μmol of Fur after 40 h of reaction at 120 °C, obtaining GVL and LI yields of 35 and 23%, respectively. Catalytic tests varying the reaction conditions allowed to verify that the yields and selectivities to products of interest for the sectors of biofuels and chemical intermediates such as GVL and LI can be improved with the increase of the reaction temperature, catalyst mass and adjustment of the B/L ratio. In addition, catalyst reuse tests showed that the micro-mesoporous ZSM-5 zeolite having B and L sites generated by Hf maintained its catalytic activity until at least four consecutive reaction cycles. In general, the strategies presented were promising for the development of potential catalysts for the reactions of transformation of furan molecules into highly demanded products, such as biofuels, additives and chemical intermediates. |
publishDate |
2021 |
dc.date.accessioned.fl_str_mv |
2021-06-02T12:16:36Z |
dc.date.available.fl_str_mv |
2021-06-02T12:16:36Z |
dc.date.issued.fl_str_mv |
2021-04-29 |
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 |
SILVA, Domingos Sérgio Araújo. Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14334. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/14334 |
identifier_str_mv |
SILVA, Domingos Sérgio Araújo. Conversão de furfural sobre zeólitas (Hf, Al)-ZSM-5 hierárquicas: controle da relação de sítios ácidos de Lewis e Brønsted e seu efeito na seletividade a produtos. 2021. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2021. Disponível em: https://repositorio.ufscar.br/handle/ufscar/14334. |
url |
https://repositorio.ufscar.br/handle/ufscar/14334 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.confidence.fl_str_mv |
600 600 |
dc.relation.authority.fl_str_mv |
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Universidade Federal de São Carlos Câmpus São Carlos |
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Programa de Pós-Graduação em Engenharia Química - PPGEQ |
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UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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UFSCAR |
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