Óxido de zinco dopado para produção de biodiesel

Detalhes bibliográficos
Ano de defesa: 2016
Autor(a) principal: Pereira, Maria de Fatima lattes
Orientador(a): Santos, Iêda Maria Garcia dos lattes
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal da Paraíba
Programa de Pós-Graduação: Programa de Pós-Graduação em Química
Departamento: Química
País: Brasil
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: https://repositorio.ufpb.br/jspui/handle/tede/9190
Resumo: Powders of pure zinc oxide (ZnO) and zinc oxide doped with 5% Al3+ (ZNAL) were obtained by the Pechini method using Zn(NO3)2.6H2O and Al(NO3)3.6H2O as precursors. The characterization was performed using XRD, Raman, FTIR and UV-Vis, and stoichiometry was confirmed by XRF. The results obtained by Raman and XRD indicated that Al3+ is completely incorporated into the ZnO crystal lattice. Attempts of doping ZnO with Fe3+ lead to a secondary phase which, according to ICCD 01-070-3377, was assigned to ZnFe2O4, for this reason this oxide was not used as a catalyst. Tests of pH variation with the oxides in acidic and basic media indicated that ZNAL presents a much larger basic character than ZnO. Using a 23 factorial design, ZnO and ZNAL were tested as catalysts for the ethanolic transesterification of cottonseed oil at temperature 130 and 200 °C, alcohol/oil ratio of 6:1 and 12:1 and 3% catalyst (w/w relative to the oil ). The reactions were performed in the Parr reactor for 4 hours and agitation of 600 rpm. 1H NMR and 13C NMR spectroscopies were used to characterize and evaluate the ethyl ester content produced during transesterifications indicating that 5% of Al3+ addition into the crystalline ZnO lattice significantly increased the catalytic potential of the oxide, reaching a higher conversion ratio of 81% when T = 130 °C and greater than 94% when T = 200 °C. The results analyzed by factorial design indicated that the type of catalyst and the temperature were the most determining factors in conversion rates. Using a kinetic study at temperatures of 130, 160, 180 and 200 °C and reaction times of 30, 60, 120 and 240 minutes, it was observed that the reactions catalyzed by ZnO had a linear behavior conversion rate, while reaction catalyzed by ZNAL reached rates greater than 80%of conversion after 30 minutes when T = 200 °C. It was also observed that the rate of ethanolic transesterification of cottonsed oil was influenced by mass transport phenomena when catalyzed by ZnO. For transesterifications catalysed by ZNAL a 1st order behavior was observed at T = 130 ° C and 2nd order was observed for the other temperatures.
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spelling 2017-08-01T11:30:58Z2018-07-21T00:29:59Z2018-07-21T00:29:59Z2016-08-22PEREIRA, Maria de Fátima.Óxido de zinco dopado para produção de biodiesel. 2016. 120F. Tese (Doutorado em Química)- Universidade Federal da Paraíba, João Pessoa, 2016.https://repositorio.ufpb.br/jspui/handle/tede/9190Powders of pure zinc oxide (ZnO) and zinc oxide doped with 5% Al3+ (ZNAL) were obtained by the Pechini method using Zn(NO3)2.6H2O and Al(NO3)3.6H2O as precursors. The characterization was performed using XRD, Raman, FTIR and UV-Vis, and stoichiometry was confirmed by XRF. The results obtained by Raman and XRD indicated that Al3+ is completely incorporated into the ZnO crystal lattice. Attempts of doping ZnO with Fe3+ lead to a secondary phase which, according to ICCD 01-070-3377, was assigned to ZnFe2O4, for this reason this oxide was not used as a catalyst. Tests of pH variation with the oxides in acidic and basic media indicated that ZNAL presents a much larger basic character than ZnO. Using a 23 factorial design, ZnO and ZNAL were tested as catalysts for the ethanolic transesterification of cottonseed oil at temperature 130 and 200 °C, alcohol/oil ratio of 6:1 and 12:1 and 3% catalyst (w/w relative to the oil ). The reactions were performed in the Parr reactor for 4 hours and agitation of 600 rpm. 1H NMR and 13C NMR spectroscopies were used to characterize and evaluate the ethyl ester content produced during transesterifications indicating that 5% of Al3+ addition into the crystalline ZnO lattice significantly increased the catalytic potential of the oxide, reaching a higher conversion ratio of 81% when T = 130 °C and greater than 94% when T = 200 °C. The results analyzed by factorial design indicated that the type of catalyst and the temperature were the most determining factors in conversion rates. Using a kinetic study at temperatures of 130, 160, 180 and 200 °C and reaction times of 30, 60, 120 and 240 minutes, it was observed that the reactions catalyzed by ZnO had a linear behavior conversion rate, while reaction catalyzed by ZNAL reached rates greater than 80%of conversion after 30 minutes when T = 200 °C. It was also observed that the rate of ethanolic transesterification of cottonsed oil was influenced by mass transport phenomena when catalyzed by ZnO. For transesterifications catalysed by ZNAL a 1st order behavior was observed at T = 130 ° C and 2nd order was observed for the other temperatures.Pós de óxido de zinco puro (ZnO) e de óxido de zinco dopado com 5% de Al3+ (ZNAL) foram obtidos pelo método Pechini utilizando Zn(NO3)2.6H2O e Al(NO3)3.6H2O como precursores. A caracterização foi realizada através de DRX, Raman, FTIR e UV-Vis, tendo a estequiometria confirmada por FRX. Os resultados do estudo de caracterização por UV-vis e Raman, indicaram que Al3+ encontra-se completamente incorporado à rede cristalina do ZnO. Tentativas de dopagem com Fe3+ apresentaram fase secundária que, de acordo com a carta ICCD 01-070-3377, foi atribuída a ZnFe2O4, por esse motivo este óxido não foi utilizado como catlisador. Testes de variação de pH com os óxidos em meio ácido e básico indicaram que ZNAL apresenta um caráter básico muito maior do que ZnO. Utilizando um planejamento fatorial 23, ZnO e ZNAL foram testados como catalisadores na transesterificação etanólica do óleo de algodão em temperaturas de 130 e 200 oC, relações álcool/óleo 6:1 e 12:1 e 3% (m/m em relação ao óleo) de catalisador. As reações ocorreram em reator Parr com tempo de 4 horas e rotação de 600 rpm. As espectroscopias RMN 1H e 13C foram utilizadas para caracterizar e avaliar o teor de ésteres etílicos produzidos nas transesterificações indicando que a adição de 5% de Al3+ à rede cristalina do ZnO aumentou significativamente o potencial catalítico do óxido, chegando a um índice de conversão superior a 81% a T = 130 oC e maior que 94% a T = 200 oC. Os resultados analisados pelo planejamento fatorial indicaram que o tipo de catalisador e a temperatura foram os fatores mais determinantes nos índices de conversão. Através de um estudo cinético utilizando temperaturas de 130, 160, 180 e 200 oC e tempos reacionais de 30, 60, 120 e 240 minutos, observou-se que as reações catalisadas por ZnO tiveram um comportamento linear de índice de conversão, enquanto que, as catalisadas por ZNAL chegaram a índices superiores a 80% de conversão em apenas 30 minutos quando T = 200 oC. Também foi possível observar que as transesterificações etanólicas do óleo de algodão foram influenciadas pela transferência de massa, abaixo de 120 minutos de reação, quando catalisadas por ZnO. Para as etanólises catalisadas por ZNAL observou-se um comportamento de 1ª ordem quando T = 130 oC e de 2ª ordem nas demais temperaturas.Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-08-01T11:30:58Z No. of bitstreams: 1 arquivototal.pdf: 3636328 bytes, checksum: ddc2927ae330b27ef4de24fdb3975d47 (MD5)Made available in DSpace on 2017-08-01T11:30:58Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3636328 bytes, checksum: ddc2927ae330b27ef4de24fdb3975d47 (MD5) Previous issue date: 2016-08-22Made available in DSpace on 2018-07-21T00:29:59Z (GMT). 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dc.title.por.fl_str_mv Óxido de zinco dopado para produção de biodiesel
title Óxido de zinco dopado para produção de biodiesel
spellingShingle Óxido de zinco dopado para produção de biodiesel
Pereira, Maria de Fatima
Dopagem
Catálise heterogênea
Transesterificação
Cinética Química
Doping
Heterogeneous catalysis
Transesterification
Chemical kinetics
CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Óxido de zinco dopado para produção de biodiesel
title_full Óxido de zinco dopado para produção de biodiesel
title_fullStr Óxido de zinco dopado para produção de biodiesel
title_full_unstemmed Óxido de zinco dopado para produção de biodiesel
title_sort Óxido de zinco dopado para produção de biodiesel
author Pereira, Maria de Fatima
author_facet Pereira, Maria de Fatima
author_role author
dc.contributor.advisor1.fl_str_mv Santos, Iêda Maria Garcia dos
dc.contributor.advisor1ID.fl_str_mv 50548221015
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/7060067415685353
dc.contributor.advisor-co1.fl_str_mv Pontes, Liliana de Fatima Bezerra Lira de
dc.contributor.advisor-co1ID.fl_str_mv 00756514401
dc.contributor.advisor-co1Lattes.fl_str_mv http://lattes.cnpq.br/0438588394065892
dc.contributor.advisor-co2.fl_str_mv Maia, Ary da Silva
dc.contributor.advisor-co2Lattes.fl_str_mv http://lattes.cnpq.br/0234548596508203
dc.contributor.authorID.fl_str_mv 43980759415
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/4556587620572640
dc.contributor.author.fl_str_mv Pereira, Maria de Fatima
contributor_str_mv Santos, Iêda Maria Garcia dos
Pontes, Liliana de Fatima Bezerra Lira de
Maia, Ary da Silva
dc.subject.por.fl_str_mv Dopagem
Catálise heterogênea
Transesterificação
Cinética Química
topic Dopagem
Catálise heterogênea
Transesterificação
Cinética Química
Doping
Heterogeneous catalysis
Transesterification
Chemical kinetics
CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Doping
Heterogeneous catalysis
Transesterification
Chemical kinetics
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
description Powders of pure zinc oxide (ZnO) and zinc oxide doped with 5% Al3+ (ZNAL) were obtained by the Pechini method using Zn(NO3)2.6H2O and Al(NO3)3.6H2O as precursors. The characterization was performed using XRD, Raman, FTIR and UV-Vis, and stoichiometry was confirmed by XRF. The results obtained by Raman and XRD indicated that Al3+ is completely incorporated into the ZnO crystal lattice. Attempts of doping ZnO with Fe3+ lead to a secondary phase which, according to ICCD 01-070-3377, was assigned to ZnFe2O4, for this reason this oxide was not used as a catalyst. Tests of pH variation with the oxides in acidic and basic media indicated that ZNAL presents a much larger basic character than ZnO. Using a 23 factorial design, ZnO and ZNAL were tested as catalysts for the ethanolic transesterification of cottonseed oil at temperature 130 and 200 °C, alcohol/oil ratio of 6:1 and 12:1 and 3% catalyst (w/w relative to the oil ). The reactions were performed in the Parr reactor for 4 hours and agitation of 600 rpm. 1H NMR and 13C NMR spectroscopies were used to characterize and evaluate the ethyl ester content produced during transesterifications indicating that 5% of Al3+ addition into the crystalline ZnO lattice significantly increased the catalytic potential of the oxide, reaching a higher conversion ratio of 81% when T = 130 °C and greater than 94% when T = 200 °C. The results analyzed by factorial design indicated that the type of catalyst and the temperature were the most determining factors in conversion rates. Using a kinetic study at temperatures of 130, 160, 180 and 200 °C and reaction times of 30, 60, 120 and 240 minutes, it was observed that the reactions catalyzed by ZnO had a linear behavior conversion rate, while reaction catalyzed by ZNAL reached rates greater than 80%of conversion after 30 minutes when T = 200 °C. It was also observed that the rate of ethanolic transesterification of cottonsed oil was influenced by mass transport phenomena when catalyzed by ZnO. For transesterifications catalysed by ZNAL a 1st order behavior was observed at T = 130 ° C and 2nd order was observed for the other temperatures.
publishDate 2016
dc.date.issued.fl_str_mv 2016-08-22
dc.date.accessioned.fl_str_mv 2017-08-01T11:30:58Z
2018-07-21T00:29:59Z
dc.date.available.fl_str_mv 2018-07-21T00:29:59Z
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 PEREIRA, Maria de Fátima.Óxido de zinco dopado para produção de biodiesel. 2016. 120F. Tese (Doutorado em Química)- Universidade Federal da Paraíba, João Pessoa, 2016.
dc.identifier.uri.fl_str_mv https://repositorio.ufpb.br/jspui/handle/tede/9190
identifier_str_mv PEREIRA, Maria de Fátima.Óxido de zinco dopado para produção de biodiesel. 2016. 120F. Tese (Doutorado em Química)- Universidade Federal da Paraíba, João Pessoa, 2016.
url https://repositorio.ufpb.br/jspui/handle/tede/9190
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dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.none.fl_str_mv Universidade Federal da Paraíba
dc.publisher.program.fl_str_mv Programa de Pós-Graduação em Química
dc.publisher.initials.fl_str_mv UFPB
dc.publisher.country.fl_str_mv Brasil
dc.publisher.department.fl_str_mv Química
publisher.none.fl_str_mv Universidade Federal da Paraíba
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