Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica

Detalhes bibliográficos
Autor(a) principal: Martins, Maria Inês
Data de Publicação: 2015
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFU
Texto Completo: https://repositorio.ufu.br/handle/123456789/15089
https://doi.org/10.14393/ufu.te.2015.65
Resumo: Due to social and environmental issues, considerable attention has been given to the production of biodiesel in substitution or addition of petroleum diesel. Biodiesel a mixture of fatty acids methyl esters is a renewable fuel obtained from a transesterification of vegetable oils and animal fats, in which alkaline hydroxides are used as catalyst. This process presents two main disadvantages: the catalyst cannot be reutilized or regenerated and there is a high quantity of residual water being produced during the separation fases. In this way, the production of biodiesel by means of heterogeneous catalytic transesterification becomes an interesting alternative in order to minimize the problems associated with homogeneous catalytic. In this respect, this study evaluates the production process of biodiesel by means of soybean oil methanolysis utilizing free and supported solid alkaline catalysts in a polymeric matrix. Initially, three distinct mixed oxides (Hidrotalcita de Mg/Al; CaO-CeO2 e CaZrO3) have been synthesized. These oxides were also supported in polysulphone (PS) and polyvinyl alcohol (PVA). The catalysts samples were physically and chemically characterized by different technics. These samples were then evaluated for their catalytic performance in the transesterification reaction, for pre-established conditions. It has been found that the CaZrO3 free and supported in PVA showed the best performance, attaining conversions greater than 90% in all conditions investigated. Thus, these two catalysts were selected for further experiments. It has been analyzed the influence of the operational conditions (methanol/oil molar ratio, temperature, amount of catalyst and time reaction) in the conversion of soybean oil into fatty acids methyl esters (% FAME). These conditions were optimized applying artificial neural network methodology in order to obtain the highest %FAME. Furthermore, it has been studied the behavior of different configurations of reactors (magnetic agitation, ultrasonic agitation with and without recirculation), the biodiesel synthesis in a spiral catalytic membrane and the stability of CaZrO3 free and supported in PVA. It is worth mentioning that under the studied conditions all variables presented significant influence in the %FAME. It is possible to conclude that under optimal conditions conversion above 96% FAME can be obtained for both catalysts under mild conditions of temperature and pressure (64°C and at atmospheric pressure). It was also found that the transesterification reaction under magnetic agitation resulted in higher mass transfer coefficients, either for the free catalyst or the supported one. This magnetic agitation prove to be more efficient then the ultrasonic agitation. The fact that the use of CaZrO3 in its free form has given the possibility of eight consecutive batch reaction cycles, which shows a high reuse capacity, without lixiviation, demonstrates its capability to be used successfully in continuous processes of biodiesel production. In conclusion, the use of a spiral catalytic membrane as a reactor presented satisfactory results (92,7 %FAME and 24 h reaction time) and thus confirming its viability to be used in the industrial production of biodiesel.
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spelling 2016-06-22T18:41:27Z2015-12-302016-06-22T18:41:27Z2015-04-29MARTINS, Maria Inês. Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica. 2015. 126 f. Tese (Doutorado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2015. Disponível em: https://doi.org/10.14393/ufu.te.2015.65.https://repositorio.ufu.br/handle/123456789/15089https://doi.org/10.14393/ufu.te.2015.65Due to social and environmental issues, considerable attention has been given to the production of biodiesel in substitution or addition of petroleum diesel. Biodiesel a mixture of fatty acids methyl esters is a renewable fuel obtained from a transesterification of vegetable oils and animal fats, in which alkaline hydroxides are used as catalyst. This process presents two main disadvantages: the catalyst cannot be reutilized or regenerated and there is a high quantity of residual water being produced during the separation fases. In this way, the production of biodiesel by means of heterogeneous catalytic transesterification becomes an interesting alternative in order to minimize the problems associated with homogeneous catalytic. In this respect, this study evaluates the production process of biodiesel by means of soybean oil methanolysis utilizing free and supported solid alkaline catalysts in a polymeric matrix. Initially, three distinct mixed oxides (Hidrotalcita de Mg/Al; CaO-CeO2 e CaZrO3) have been synthesized. These oxides were also supported in polysulphone (PS) and polyvinyl alcohol (PVA). The catalysts samples were physically and chemically characterized by different technics. These samples were then evaluated for their catalytic performance in the transesterification reaction, for pre-established conditions. It has been found that the CaZrO3 free and supported in PVA showed the best performance, attaining conversions greater than 90% in all conditions investigated. Thus, these two catalysts were selected for further experiments. It has been analyzed the influence of the operational conditions (methanol/oil molar ratio, temperature, amount of catalyst and time reaction) in the conversion of soybean oil into fatty acids methyl esters (% FAME). These conditions were optimized applying artificial neural network methodology in order to obtain the highest %FAME. Furthermore, it has been studied the behavior of different configurations of reactors (magnetic agitation, ultrasonic agitation with and without recirculation), the biodiesel synthesis in a spiral catalytic membrane and the stability of CaZrO3 free and supported in PVA. It is worth mentioning that under the studied conditions all variables presented significant influence in the %FAME. It is possible to conclude that under optimal conditions conversion above 96% FAME can be obtained for both catalysts under mild conditions of temperature and pressure (64°C and at atmospheric pressure). It was also found that the transesterification reaction under magnetic agitation resulted in higher mass transfer coefficients, either for the free catalyst or the supported one. This magnetic agitation prove to be more efficient then the ultrasonic agitation. The fact that the use of CaZrO3 in its free form has given the possibility of eight consecutive batch reaction cycles, which shows a high reuse capacity, without lixiviation, demonstrates its capability to be used successfully in continuous processes of biodiesel production. In conclusion, the use of a spiral catalytic membrane as a reactor presented satisfactory results (92,7 %FAME and 24 h reaction time) and thus confirming its viability to be used in the industrial production of biodiesel.Devido a questões sócio-ambientais, considerada atenção tem sido dada à produção de biodiesel em substituição ou adição ao diesel de petróleo. O biodiesel, mistura de ésteres de ácidos graxos, é um combustível renovável, obtido principalmente a partir da transesterificação catalítica homogênea de óleos vegetais e gordura animal, empregando-se hidróxidos alcalinos como catalisadores. Este processo apresenta como principais desvantagens o fato de o catalisador não poder ser reutilizado ou regenerado e a produção de grande quantidade de água residual durante as etapas de separação. Desta forma, a produção de biodiesel por meio de transesterificação catalítica heterogenea se torna uma alternativa interessante para minimizar os problemas associados com a catálise homogênea. Neste contexto, este estudo avalia o processo de produção de biodiesel por meio da metanólise de óleo de soja usando-se catalisadores sólidos alcalinos, livres e suportados em matriz polimérica. Inicialmente, foram sintetizados três óxidos mistos distintos (Hidrotalcita de Mg/Al; CaO-CeO2 e CaZrO3). Estes óxidos foram também suportados em polissulfona (PS) e polivinil álcool (PVA). As amostras de catalisadores foram caracterizadas físico-quimicamente por diferentes técnicas e avaliadas quanto ao desempenho catalítico na reação de transesterificação em condições pré-estabelecidas, sendo que o uso dos catalisadores CaZrO3 livre e suportado em PVA levaram a obtenção de conversões do óleo de soja em biodiesel maiores que 90% nas condições estudadas. Assim, estes dois catalisadores foram selecionados e utilizados nos ensaios posteriores. Foi, então, verificada a influência das condições operacionais (razão molar metanol/óleo, temperatura, quantidade de catalisador e tempo de reação) na conversão em monoésteres de ácidos graxos (% FAME). Estas condições foram também otimizadas para a obtenção dea máxima %FAME, usando-se redes neuronais artificiais (RNA s) e o método heurístico de colônia de formigas (ACO). Posteriormente avaliou-se o comportamento da reação de transesterificação em configurações distintas de reatores (agitação magnética, agitação ultrassônica com e sem recirculação), a síntese de biodiesel em reator de membrana catalítica espiral e a estabilidade dos catalisadores CaZrO3 livre e suportado em PVA. Dentre os resultados obtidos pode se destacar que nas condições estudadas, todas as variáveis apresentaram efeitos significativos na %FAME. A partir das condições reacionais ótimas foram alcançadas conversões acima de 96 %FAME em condições amenas de temperatura e pressão (64°C e pressão atmosférica) para ambos os catalisadores. A condução da reação de transesterificação em reator com agitação magnética resultou em maiores coeficientes de transferência de massa tanto para o catalisador livre, como para o suportado, proporcionando uma agitação mais eficiente quando comparada a agitação ultrassônica. Devido a sua não lixiviação e alta capacidade de reuso em processo batelada, suportando um ciclo de 08 reações consecutivas, o uso de CaZrO3 em processos contínuos de produção de biodiesel pode ser promissor. Finalizando, a proposta inovadora de um reator com membrana catalítica espiral levou a resultados satisfatórios (92,7 %FAME em 24 h de reação), apresentando-se como uma configuração de reator viável para a produção de biodiesel em escala industrial.Doutor em Engenharia Químicaapplication/pdfporUniversidade Federal de UberlândiaPrograma de Pós-graduação em Engenharia QuímicaUFUBREngenhariasTransesterificação catalítica heterogêneaCatalisadores sólidos alcalinosZirconato de cálcioMembrana catalíticaCatalisadoresTransesterificaçãoBiodieselHeterogeneous transesterification reactionSolid alkaline catalystCalcium zirconateCatalytic membraneCNPQ::ENGENHARIAS::ENGENHARIA QUIMICAProdução de biodiesel empregando catalisadores livres e suportados em matriz poliméricainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisReis, Miria Hespanhol Mirandahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4773556J4Cardoso, Vicelma Luizhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787074J7Kamimura, Eliana Setsukohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723412J9Pires, Ricardo Franciscohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4230803J8Santos, Líbia Dinizhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4774604P3Coutinho Filho, Ubirajarahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797915J2http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4798601D8Martins, Maria Inês81757072info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFUinstname:Universidade Federal de Uberlândia (UFU)instacron:UFUTHUMBNAILProducaoBiodieselEmpregando.pdf.jpgProducaoBiodieselEmpregando.pdf.jpgGenerated Thumbnailimage/jpeg1202https://repositorio.ufu.br/bitstream/123456789/15089/4/ProducaoBiodieselEmpregando.pdf.jpgbc1f15d1be64be1f4b498c9671d27215MD54ORIGINALProducaoBiodieselEmpregando.pdfProducaoBiodieselEmpregando.pdfapplication/pdf8969081https://repositorio.ufu.br/bitstream/123456789/15089/3/ProducaoBiodieselEmpregando.pdfad2e07b2d979ed8ad5744d05180f57c5MD53TEXTProducaoBiodieselEmpregando.pdf.txtProducaoBiodieselEmpregando.pdf.txtExtracted texttext/plain254786https://repositorio.ufu.br/bitstream/123456789/15089/2/ProducaoBiodieselEmpregando.pdf.txt272a52e52502e52e6196ba6713ac2eeeMD52123456789/150892021-03-03 12:42:57.619oai:repositorio.ufu.br:123456789/15089Repositório InstitucionalONGhttp://repositorio.ufu.br/oai/requestdiinf@dirbi.ufu.bropendoar:2024-04-26T15:05:40.071841Repositório Institucional da UFU - Universidade Federal de Uberlândia (UFU)false
dc.title.por.fl_str_mv Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
title Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
spellingShingle Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
Martins, Maria Inês
Transesterificação catalítica heterogênea
Catalisadores sólidos alcalinos
Zirconato de cálcio
Membrana catalítica
Catalisadores
Transesterificação
Biodiesel
Heterogeneous transesterification reaction
Solid alkaline catalyst
Calcium zirconate
Catalytic membrane
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
title_short Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
title_full Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
title_fullStr Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
title_full_unstemmed Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
title_sort Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica
author Martins, Maria Inês
author_facet Martins, Maria Inês
author_role author
dc.contributor.advisor-co1.fl_str_mv Reis, Miria Hespanhol Miranda
dc.contributor.advisor-co1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4773556J4
dc.contributor.advisor1.fl_str_mv Cardoso, Vicelma Luiz
dc.contributor.advisor1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4787074J7
dc.contributor.referee1.fl_str_mv Kamimura, Eliana Setsuko
dc.contributor.referee1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723412J9
dc.contributor.referee2.fl_str_mv Pires, Ricardo Francisco
dc.contributor.referee2Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4230803J8
dc.contributor.referee3.fl_str_mv Santos, Líbia Diniz
dc.contributor.referee3Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4774604P3
dc.contributor.referee4.fl_str_mv Coutinho Filho, Ubirajara
dc.contributor.referee4Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797915J2
dc.contributor.authorLattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4798601D8
dc.contributor.author.fl_str_mv Martins, Maria Inês
contributor_str_mv Reis, Miria Hespanhol Miranda
Cardoso, Vicelma Luiz
Kamimura, Eliana Setsuko
Pires, Ricardo Francisco
Santos, Líbia Diniz
Coutinho Filho, Ubirajara
dc.subject.por.fl_str_mv Transesterificação catalítica heterogênea
Catalisadores sólidos alcalinos
Zirconato de cálcio
Membrana catalítica
Catalisadores
Transesterificação
Biodiesel
topic Transesterificação catalítica heterogênea
Catalisadores sólidos alcalinos
Zirconato de cálcio
Membrana catalítica
Catalisadores
Transesterificação
Biodiesel
Heterogeneous transesterification reaction
Solid alkaline catalyst
Calcium zirconate
Catalytic membrane
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
dc.subject.eng.fl_str_mv Heterogeneous transesterification reaction
Solid alkaline catalyst
Calcium zirconate
Catalytic membrane
dc.subject.cnpq.fl_str_mv CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
description Due to social and environmental issues, considerable attention has been given to the production of biodiesel in substitution or addition of petroleum diesel. Biodiesel a mixture of fatty acids methyl esters is a renewable fuel obtained from a transesterification of vegetable oils and animal fats, in which alkaline hydroxides are used as catalyst. This process presents two main disadvantages: the catalyst cannot be reutilized or regenerated and there is a high quantity of residual water being produced during the separation fases. In this way, the production of biodiesel by means of heterogeneous catalytic transesterification becomes an interesting alternative in order to minimize the problems associated with homogeneous catalytic. In this respect, this study evaluates the production process of biodiesel by means of soybean oil methanolysis utilizing free and supported solid alkaline catalysts in a polymeric matrix. Initially, three distinct mixed oxides (Hidrotalcita de Mg/Al; CaO-CeO2 e CaZrO3) have been synthesized. These oxides were also supported in polysulphone (PS) and polyvinyl alcohol (PVA). The catalysts samples were physically and chemically characterized by different technics. These samples were then evaluated for their catalytic performance in the transesterification reaction, for pre-established conditions. It has been found that the CaZrO3 free and supported in PVA showed the best performance, attaining conversions greater than 90% in all conditions investigated. Thus, these two catalysts were selected for further experiments. It has been analyzed the influence of the operational conditions (methanol/oil molar ratio, temperature, amount of catalyst and time reaction) in the conversion of soybean oil into fatty acids methyl esters (% FAME). These conditions were optimized applying artificial neural network methodology in order to obtain the highest %FAME. Furthermore, it has been studied the behavior of different configurations of reactors (magnetic agitation, ultrasonic agitation with and without recirculation), the biodiesel synthesis in a spiral catalytic membrane and the stability of CaZrO3 free and supported in PVA. It is worth mentioning that under the studied conditions all variables presented significant influence in the %FAME. It is possible to conclude that under optimal conditions conversion above 96% FAME can be obtained for both catalysts under mild conditions of temperature and pressure (64°C and at atmospheric pressure). It was also found that the transesterification reaction under magnetic agitation resulted in higher mass transfer coefficients, either for the free catalyst or the supported one. This magnetic agitation prove to be more efficient then the ultrasonic agitation. The fact that the use of CaZrO3 in its free form has given the possibility of eight consecutive batch reaction cycles, which shows a high reuse capacity, without lixiviation, demonstrates its capability to be used successfully in continuous processes of biodiesel production. In conclusion, the use of a spiral catalytic membrane as a reactor presented satisfactory results (92,7 %FAME and 24 h reaction time) and thus confirming its viability to be used in the industrial production of biodiesel.
publishDate 2015
dc.date.available.fl_str_mv 2015-12-30
2016-06-22T18:41:27Z
dc.date.issued.fl_str_mv 2015-04-29
dc.date.accessioned.fl_str_mv 2016-06-22T18:41:27Z
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dc.identifier.citation.fl_str_mv MARTINS, Maria Inês. Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica. 2015. 126 f. Tese (Doutorado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2015. Disponível em: https://doi.org/10.14393/ufu.te.2015.65.
dc.identifier.uri.fl_str_mv https://repositorio.ufu.br/handle/123456789/15089
dc.identifier.doi.por.fl_str_mv https://doi.org/10.14393/ufu.te.2015.65
identifier_str_mv MARTINS, Maria Inês. Produção de biodiesel empregando catalisadores livres e suportados em matriz polimérica. 2015. 126 f. Tese (Doutorado em Engenharias) - Universidade Federal de Uberlândia, Uberlândia, 2015. Disponível em: https://doi.org/10.14393/ufu.te.2015.65.
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