Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol

Detalhes bibliográficos
Ano de defesa: 2015
Autor(a) principal: Barros, Fernando José Soares
Orientador(a): Vieira, Rodrigo Silveira
Banca de defesa: Não Informado pela instituição
Tipo de documento: Dissertação
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Não Informado pela instituição
Programa de Pós-Graduação: Não Informado pela instituição
Departamento: Não Informado pela instituição
País: Não Informado pela instituição
Palavras-chave em Português:
Link de acesso: http://www.repositorio.ufc.br/handle/riufc/12531
Resumo: Glycerol is a by-product of the biodiesel obtaining process and is highlighted due to its availability in the market and its high chemical functionality, presenting itself as a possible forerunner of a number of value-added compounds, e.g., their oligomers (di- and triglycerol). The characteristics of heterogeneous catalysts favor the transformation of glycerol valorization processes in even more sustainable routes. In this context, this paper proposes to evaluate the use of dolomite and eggshell as heterogeneous catalysts in the solventless oligomerization of glycerol. The materials were tested as catalysts in natural and calcined forms. The thermal process has modified the structure and morphology of the materials and their textural properties. Calcination was effective in increasing their catalytic activity. The calcined dolomite showed better catalytic performance, being capable of producing glycerol conversion around 97% with selectivity to diglycerol about 6,7% by reactions with a catalyst/glycerol mass ratio of 0,02; at 220 ° C, nitrogen flow and 24 hours. Using eggshells the best conditions were catalyst/glycerol mass ratio of 0,01 at 220 ° C and 24 hours, obtaining a conversion of approximately 75% and selectivity of 10,9 %. In both cases, there was formation of a high molecular weight product with non-newtonian and pseudoplastic fluid rheological behavior. Dolomite reusing tests pointed to its dissolution in the reaction product with consequent appearance of Ca and Mg in the samples, detected by ICP. There was a significant change in conversion and selectivity to diglycerol with two reuse cycles. The reaction conditions found are less severe than those reported in the literature with the use of synthetic catalysts, which added to the low cost of the material make its utilization promising in the glycerol oligomerization process
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spelling Barros, Fernando José SoaresLuna, Francisco Murilo Tavares deVieira, Rodrigo Silveira2015-05-28T17:53:06Z2015-05-28T17:53:06Z2015BARROS, F. J. S. Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol. 2015. 94 f. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015.http://www.repositorio.ufc.br/handle/riufc/12531Glycerol is a by-product of the biodiesel obtaining process and is highlighted due to its availability in the market and its high chemical functionality, presenting itself as a possible forerunner of a number of value-added compounds, e.g., their oligomers (di- and triglycerol). The characteristics of heterogeneous catalysts favor the transformation of glycerol valorization processes in even more sustainable routes. In this context, this paper proposes to evaluate the use of dolomite and eggshell as heterogeneous catalysts in the solventless oligomerization of glycerol. The materials were tested as catalysts in natural and calcined forms. The thermal process has modified the structure and morphology of the materials and their textural properties. Calcination was effective in increasing their catalytic activity. The calcined dolomite showed better catalytic performance, being capable of producing glycerol conversion around 97% with selectivity to diglycerol about 6,7% by reactions with a catalyst/glycerol mass ratio of 0,02; at 220 ° C, nitrogen flow and 24 hours. Using eggshells the best conditions were catalyst/glycerol mass ratio of 0,01 at 220 ° C and 24 hours, obtaining a conversion of approximately 75% and selectivity of 10,9 %. In both cases, there was formation of a high molecular weight product with non-newtonian and pseudoplastic fluid rheological behavior. Dolomite reusing tests pointed to its dissolution in the reaction product with consequent appearance of Ca and Mg in the samples, detected by ICP. There was a significant change in conversion and selectivity to diglycerol with two reuse cycles. The reaction conditions found are less severe than those reported in the literature with the use of synthetic catalysts, which added to the low cost of the material make its utilization promising in the glycerol oligomerization processO glicerol, subproduto do processo de obtenção do biodiesel, encontra-se em evidência dada sua alta disponibilidade no mercado e por possuir alta funcionalidade química, apresentando-se como possível precursor de uma série de compostos de valor agregado, por exemplo, seus oligômeros (di e triglicerol). As características dos catalisadores heterogêneos favorecem a transformação dos processos de valorização do glicerol em rotas ainda mais sustentáveis. Neste contexto, este trabalho propõe-se a avaliar o uso da dolomita e da casca de ovo como catalisadores básicos heterogêneos na oligomerização do glicerol na ausência de solvente. Os materiais foram testados como catalisadores nas formas natural e calcinada. O processo térmico modificou a estrutura e a morfologia dos materiais bem como suas propriedades texturais. A calcinação foi efetiva no aumento da atividade catalítica dos mesmos. A dolomita calcinada mostrou melhor desempenho catalítico permitindo a obtenção de conversão do glicerol em torno de 97 % com seletividade ao diglicerol de cerca de 6,7 %, em reações com 2 % de catalisador, 220 ºC, fluxo de nitrogênio e 24 horas de duração. Quanto à casca de ovo as melhores condições foram: carga de catalisador de 1 %, 220 ºC e 24 horas, obtendo-se uma conversão de aproximadamente 75 % e seletividade de 10,9 %. Em ambos casos, houve a formação de um produto de elevada massa molecular e comportamento reológico não-newtoniano e pseudoplástico. Os testes de reuso da dolomita apontaram para a dissolução da mesma no produto reacional, com consequente aparecimento de teores de Ca e Mg nas amostras, detectados por ICP. Houve significativa alteração da conversão e da seletividade ao diglicerol com 2 ciclos de reuso. As condições reacionais encontradas são menos severas que as reportadas na literatura com o uso de catalisadores sintéticos, o que somado ao baixo custo do material tornam promissora sua aplicação no processo de oligomerização do glicerolEngenharia químicaCatálise heterogêneaGlicerol - ProduçãoAvaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerolEvaluation of dolomite and eggshell as catalysts in oligomerization of glycerolinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisporreponame:Repositório Institucional da Universidade Federal do Ceará (UFC)instname:Universidade Federal do Ceará (UFC)instacron:UFCinfo:eu-repo/semantics/openAccessORIGINAL2015_dis_fjsbarros.pdf2015_dis_fjsbarros.pdfapplication/pdf3993273http://repositorio.ufc.br/bitstream/riufc/12531/1/2015_dis_fjsbarros.pdfcc424af6940b78faa68bc31c1bf3d191MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81786http://repositorio.ufc.br/bitstream/riufc/12531/2/license.txt8c4401d3d14722a7ca2d07c782a1aab3MD52riufc/125312022-02-23 11:11:51.311oai:repositorio.ufc.br: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Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2022-02-23T14:11:51Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false
dc.title.pt_BR.fl_str_mv Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
dc.title.en.pt_BR.fl_str_mv Evaluation of dolomite and eggshell as catalysts in oligomerization of glycerol
title Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
spellingShingle Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
Barros, Fernando José Soares
Engenharia química
Catálise heterogênea
Glicerol - Produção
title_short Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
title_full Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
title_fullStr Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
title_full_unstemmed Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
title_sort Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol
author Barros, Fernando José Soares
author_facet Barros, Fernando José Soares
author_role author
dc.contributor.co-advisor.none.fl_str_mv Luna, Francisco Murilo Tavares de
dc.contributor.author.fl_str_mv Barros, Fernando José Soares
dc.contributor.advisor1.fl_str_mv Vieira, Rodrigo Silveira
contributor_str_mv Vieira, Rodrigo Silveira
dc.subject.por.fl_str_mv Engenharia química
Catálise heterogênea
Glicerol - Produção
topic Engenharia química
Catálise heterogênea
Glicerol - Produção
description Glycerol is a by-product of the biodiesel obtaining process and is highlighted due to its availability in the market and its high chemical functionality, presenting itself as a possible forerunner of a number of value-added compounds, e.g., their oligomers (di- and triglycerol). The characteristics of heterogeneous catalysts favor the transformation of glycerol valorization processes in even more sustainable routes. In this context, this paper proposes to evaluate the use of dolomite and eggshell as heterogeneous catalysts in the solventless oligomerization of glycerol. The materials were tested as catalysts in natural and calcined forms. The thermal process has modified the structure and morphology of the materials and their textural properties. Calcination was effective in increasing their catalytic activity. The calcined dolomite showed better catalytic performance, being capable of producing glycerol conversion around 97% with selectivity to diglycerol about 6,7% by reactions with a catalyst/glycerol mass ratio of 0,02; at 220 ° C, nitrogen flow and 24 hours. Using eggshells the best conditions were catalyst/glycerol mass ratio of 0,01 at 220 ° C and 24 hours, obtaining a conversion of approximately 75% and selectivity of 10,9 %. In both cases, there was formation of a high molecular weight product with non-newtonian and pseudoplastic fluid rheological behavior. Dolomite reusing tests pointed to its dissolution in the reaction product with consequent appearance of Ca and Mg in the samples, detected by ICP. There was a significant change in conversion and selectivity to diglycerol with two reuse cycles. The reaction conditions found are less severe than those reported in the literature with the use of synthetic catalysts, which added to the low cost of the material make its utilization promising in the glycerol oligomerization process
publishDate 2015
dc.date.accessioned.fl_str_mv 2015-05-28T17:53:06Z
dc.date.available.fl_str_mv 2015-05-28T17:53:06Z
dc.date.issued.fl_str_mv 2015
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.citation.fl_str_mv BARROS, F. J. S. Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol. 2015. 94 f. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015.
dc.identifier.uri.fl_str_mv http://www.repositorio.ufc.br/handle/riufc/12531
identifier_str_mv BARROS, F. J. S. Avaliação da dolomita e da casca de ovo como catalisadores na oligomerização do glicerol. 2015. 94 f. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2015.
url http://www.repositorio.ufc.br/handle/riufc/12531
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