Formação do carbonato de glicerol por transesterificação catalítica heterogênea
Autor(a) principal: | |
---|---|
Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/16945 |
Resumo: | The industrial production of biodiesel has generated large amounts of glycerol, transforming this co-product into raw material for other processes. Notably, glycerol carbonate has emerged as a promising substance for the chemical industry, since it is a biomass-derived product and has several applications. Glycerol carbonate can be produced by different processes, with the transesterification between glycerol and dimethyl carbonate being the most widely studied reaction. However, despite being considered the simplest and greenest possible route, other esters can be used, which makes the transesterification process chemically and operationally complex, despite this complexity not being properly disclosed. Therefore, in order to understand the process from a molecular catalysis perspective, this work investigated the reactions between glycerol and different carbonic acid esters (dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate), using CTA MCM-41 hybrid silica as basic catalyst. Furthermore, for comparison with the hybrid silica, the catalytic potential of calcium oxide (CaO) and magnesium oxide (MgO) was evaluated. The hybrid silica was synthesized according to a well-established method and the high-purity oxides were commercially purchased. The reactions for formation of glycerol carbonate were performed in a batch reactor, in the presence of dimethylformamide (DMF) as solvent. Experiments were performed to study the effects of different operational parameters on the formation of glycerol carbonate and co-products. The reaction products were analyzed by GC-FID and GC-MS and all chemical species produced during the reactions were identified. Reaction steps and reaction mechanisms were proposed for these reactions, together with determination of the conditions to produce glycerol carbonate with maximum efficiency in terms of conversion, selectivity, and yield. The results showed that hybrid silica has high catalytic activity, being more active than commercial catalysts. The main products of the reactions were glycerol carbonate and glycidol, with small amounts of glycerol monocarbonates, glycerol tricarbonates and glycidol carbonates being produced. Cyclic-chain esters showed greater reactivity than straight chain esters, forming fewer co-products. Finally, cyclic-chain esters and straight-chain esters formed the products following different reaction mechanisms. |
id |
SCAR_56f2becc09e06e0f15710c7e6765688e |
---|---|
oai_identifier_str |
oai:repositorio.ufscar.br:ufscar/16945 |
network_acronym_str |
SCAR |
network_name_str |
Repositório Institucional da UFSCAR |
repository_id_str |
4322 |
spelling |
de Paula, Gustavo MedeirosCardoso, Dilsonhttp://lattes.cnpq.br/2462847535959232http://lattes.cnpq.br/89900205032586540398b482-2427-4894-8966-0e572c08d7a12022-10-27T12:38:57Z2022-10-27T12:38:57Z2022-04-29DE PAULA, Gustavo Medeiros. Formação do carbonato de glicerol por transesterificação catalítica heterogênea. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/16945.https://repositorio.ufscar.br/handle/ufscar/16945The industrial production of biodiesel has generated large amounts of glycerol, transforming this co-product into raw material for other processes. Notably, glycerol carbonate has emerged as a promising substance for the chemical industry, since it is a biomass-derived product and has several applications. Glycerol carbonate can be produced by different processes, with the transesterification between glycerol and dimethyl carbonate being the most widely studied reaction. However, despite being considered the simplest and greenest possible route, other esters can be used, which makes the transesterification process chemically and operationally complex, despite this complexity not being properly disclosed. Therefore, in order to understand the process from a molecular catalysis perspective, this work investigated the reactions between glycerol and different carbonic acid esters (dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate), using CTA MCM-41 hybrid silica as basic catalyst. Furthermore, for comparison with the hybrid silica, the catalytic potential of calcium oxide (CaO) and magnesium oxide (MgO) was evaluated. The hybrid silica was synthesized according to a well-established method and the high-purity oxides were commercially purchased. The reactions for formation of glycerol carbonate were performed in a batch reactor, in the presence of dimethylformamide (DMF) as solvent. Experiments were performed to study the effects of different operational parameters on the formation of glycerol carbonate and co-products. The reaction products were analyzed by GC-FID and GC-MS and all chemical species produced during the reactions were identified. Reaction steps and reaction mechanisms were proposed for these reactions, together with determination of the conditions to produce glycerol carbonate with maximum efficiency in terms of conversion, selectivity, and yield. The results showed that hybrid silica has high catalytic activity, being more active than commercial catalysts. The main products of the reactions were glycerol carbonate and glycidol, with small amounts of glycerol monocarbonates, glycerol tricarbonates and glycidol carbonates being produced. Cyclic-chain esters showed greater reactivity than straight chain esters, forming fewer co-products. Finally, cyclic-chain esters and straight-chain esters formed the products following different reaction mechanisms.A produção industrial de biodiesel tem gerado grandes quantidades de glicerol, transformando este coproduto em matéria-prima para outros processos. Notavelmente, o carbonato de glicerol tem se tornado uma substância promissora para a indústria química, uma vez que é um produto derivado de biomassa e possui diversas aplicações. O carbonato de glicerol pode ser produzido por diferentes processos, sendo a reação de transesterificação entre o glicerol e o carbonato de dimetila a mais estudada. Entretanto, embora essa reação seja considerada como a rota mais simples e verde possível, outros ésteres podem ser utilizados, o que torna o processo de transesterificação química e operacionalmente complexo, apesar dessa complexibilidade não ser devidamente divulgada. Nesse sentido, com o intuito de entender o processo do ponto de vista da catálise molecular, este trabalho investigou as reações entre o glicerol e diferentes ésteres do ácido carbônico (carbonato de dimetila, carbonato de dietila, carbonato de etileno e carbonato de propileno), utilizando a sílica híbrida CTA-MCM-41 como catalisador básico. Além disso, para efeito comparativo com a sílica híbrida, avaliou o potencial catalítico do óxido de cálcio e do óxido de magnésio (CaO e MgO). A sílica híbrida foi sintetizada a partir de um método já consolidado e os óxidos de elevada pureza foram adquiridos comercialmente. As reações para formação do carbonato de glicerol foram realizadas em um reator batelada, na presença de dimetilformamida (DMF) como solvente. Os experimentos foram realizados a fim de estudar a influência de diferentes parâmetros operacionais na formação do carbonato de glicerol e coprodutos. Os produtos reacionais foram analisados por GC-FID e GC-MS e todas as espécies químicas produzidas durante as reações foram devidamente identificadas. Etapas reacionais e mecanismos reacionais foram propostos para essas reações, juntamente com a determinação das condições para produzir carbonato de glicerol com máxima eficiência em termos de conversão, seletividade e rendimento. Os resultados mostraram que a sílica híbrida possui elevada atividade catalítica, sendo mais ativa que os catalisadores comerciais. Os principais produtos das reações foram o carbonato de glicerol e glicidol, com pequenas quantidades de monocarbonatos de glicerol, tricarbonatos de glicerol e carbonatos de glicidol sendo produzidas. Ésteres de cadeia cíclica apresentaram maior reatividade do que ésteres de cadeia linear, formando menos coprodutos. Finalmente, os ésteres de cadeia cíclica e ésteres de cadeia linear formaram os produtos seguindo mecanismos reacionais distintos.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)141307/2018-8porUniversidade 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/openAccessCarbonato de glicerolCTA-MCM-41Ésteres do ácido carbônicoGlicerolTransesterificaçãoCarbonic acid estersGlycerolGlycerol carbonateTransesterificationENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICAENGENHARIAS::ENGENHARIA QUIMICAFormação do carbonato de glicerol por transesterificação catalítica heterogêneaGlycerol carbonate formation by heterogeneous catalytic transesterificationinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis60060045193456-2aac-47ce-8120-3995d1ca2a46reponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdfTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdfTeseapplication/pdf4196163https://repositorio.ufscar.br/bitstream/ufscar/16945/3/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf1003541cab172a7d61cac8230d274cd4MD53Carta_Comprovante_Gustavo_24.10.2022.pdfCarta_Comprovante_Gustavo_24.10.2022.pdfCarta comprovante da versão final de teseapplication/pdf156769https://repositorio.ufscar.br/bitstream/ufscar/16945/2/Carta_Comprovante_Gustavo_24.10.2022.pdf1ee2bb2d96d346c2ad0ad15628c129baMD52CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufscar.br/bitstream/ufscar/16945/4/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD54TEXTTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.txtTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.txtExtracted texttext/plain199599https://repositorio.ufscar.br/bitstream/ufscar/16945/5/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.txt16b0360e7ce0098fef83bc11ecece3a6MD55Carta_Comprovante_Gustavo_24.10.2022.pdf.txtCarta_Comprovante_Gustavo_24.10.2022.pdf.txtExtracted texttext/plain1392https://repositorio.ufscar.br/bitstream/ufscar/16945/7/Carta_Comprovante_Gustavo_24.10.2022.pdf.txt1d141b55fa6b10b20076720d2850cba1MD57THUMBNAILTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.jpgTese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.jpgIM Thumbnailimage/jpeg6591https://repositorio.ufscar.br/bitstream/ufscar/16945/6/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.jpg8efa1c22f4c9da33c809df35a7ffad8eMD56Carta_Comprovante_Gustavo_24.10.2022.pdf.jpgCarta_Comprovante_Gustavo_24.10.2022.pdf.jpgIM Thumbnailimage/jpeg11699https://repositorio.ufscar.br/bitstream/ufscar/16945/8/Carta_Comprovante_Gustavo_24.10.2022.pdf.jpg4605302eb98110d5d89bd961b36d6b57MD58ufscar/169452023-09-18 18:32:34.569oai:repositorio.ufscar.br:ufscar/16945Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:32:34Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
dc.title.alternative.eng.fl_str_mv |
Glycerol carbonate formation by heterogeneous catalytic transesterification |
title |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
spellingShingle |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea de Paula, Gustavo Medeiros Carbonato de glicerol CTA-MCM-41 Ésteres do ácido carbônico Glicerol Transesterificação Carbonic acid esters Glycerol Glycerol carbonate Transesterification ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
title_short |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
title_full |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
title_fullStr |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
title_full_unstemmed |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
title_sort |
Formação do carbonato de glicerol por transesterificação catalítica heterogênea |
author |
de Paula, Gustavo Medeiros |
author_facet |
de Paula, Gustavo Medeiros |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8990020503258654 |
dc.contributor.author.fl_str_mv |
de Paula, Gustavo Medeiros |
dc.contributor.advisor1.fl_str_mv |
Cardoso, Dilson |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/2462847535959232 |
dc.contributor.authorID.fl_str_mv |
0398b482-2427-4894-8966-0e572c08d7a1 |
contributor_str_mv |
Cardoso, Dilson |
dc.subject.por.fl_str_mv |
Carbonato de glicerol CTA-MCM-41 Ésteres do ácido carbônico Glicerol Transesterificação |
topic |
Carbonato de glicerol CTA-MCM-41 Ésteres do ácido carbônico Glicerol Transesterificação Carbonic acid esters Glycerol Glycerol carbonate Transesterification ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
dc.subject.eng.fl_str_mv |
Carbonic acid esters Glycerol Glycerol carbonate Transesterification |
dc.subject.cnpq.fl_str_mv |
ENGENHARIAS::ENGENHARIA QUIMICA::TECNOLOGIA QUIMICA ENGENHARIAS::ENGENHARIA QUIMICA |
description |
The industrial production of biodiesel has generated large amounts of glycerol, transforming this co-product into raw material for other processes. Notably, glycerol carbonate has emerged as a promising substance for the chemical industry, since it is a biomass-derived product and has several applications. Glycerol carbonate can be produced by different processes, with the transesterification between glycerol and dimethyl carbonate being the most widely studied reaction. However, despite being considered the simplest and greenest possible route, other esters can be used, which makes the transesterification process chemically and operationally complex, despite this complexity not being properly disclosed. Therefore, in order to understand the process from a molecular catalysis perspective, this work investigated the reactions between glycerol and different carbonic acid esters (dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate), using CTA MCM-41 hybrid silica as basic catalyst. Furthermore, for comparison with the hybrid silica, the catalytic potential of calcium oxide (CaO) and magnesium oxide (MgO) was evaluated. The hybrid silica was synthesized according to a well-established method and the high-purity oxides were commercially purchased. The reactions for formation of glycerol carbonate were performed in a batch reactor, in the presence of dimethylformamide (DMF) as solvent. Experiments were performed to study the effects of different operational parameters on the formation of glycerol carbonate and co-products. The reaction products were analyzed by GC-FID and GC-MS and all chemical species produced during the reactions were identified. Reaction steps and reaction mechanisms were proposed for these reactions, together with determination of the conditions to produce glycerol carbonate with maximum efficiency in terms of conversion, selectivity, and yield. The results showed that hybrid silica has high catalytic activity, being more active than commercial catalysts. The main products of the reactions were glycerol carbonate and glycidol, with small amounts of glycerol monocarbonates, glycerol tricarbonates and glycidol carbonates being produced. Cyclic-chain esters showed greater reactivity than straight chain esters, forming fewer co-products. Finally, cyclic-chain esters and straight-chain esters formed the products following different reaction mechanisms. |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-10-27T12:38:57Z |
dc.date.available.fl_str_mv |
2022-10-27T12:38:57Z |
dc.date.issued.fl_str_mv |
2022-04-29 |
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 |
DE PAULA, Gustavo Medeiros. Formação do carbonato de glicerol por transesterificação catalítica heterogênea. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/16945. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/16945 |
identifier_str_mv |
DE PAULA, Gustavo Medeiros. Formação do carbonato de glicerol por transesterificação catalítica heterogênea. 2022. Tese (Doutorado em Engenharia Química) – Universidade Federal de São Carlos, São Carlos, 2022. Disponível em: https://repositorio.ufscar.br/handle/ufscar/16945. |
url |
https://repositorio.ufscar.br/handle/ufscar/16945 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.confidence.fl_str_mv |
600 600 |
dc.relation.authority.fl_str_mv |
45193456-2aac-47ce-8120-3995d1ca2a46 |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Engenharia Química - PPGEQ |
dc.publisher.initials.fl_str_mv |
UFSCar |
publisher.none.fl_str_mv |
Universidade Federal de São Carlos Câmpus São Carlos |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFSCAR instname:Universidade Federal de São Carlos (UFSCAR) instacron:UFSCAR |
instname_str |
Universidade Federal de São Carlos (UFSCAR) |
instacron_str |
UFSCAR |
institution |
UFSCAR |
reponame_str |
Repositório Institucional da UFSCAR |
collection |
Repositório Institucional da UFSCAR |
bitstream.url.fl_str_mv |
https://repositorio.ufscar.br/bitstream/ufscar/16945/3/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf https://repositorio.ufscar.br/bitstream/ufscar/16945/2/Carta_Comprovante_Gustavo_24.10.2022.pdf https://repositorio.ufscar.br/bitstream/ufscar/16945/4/license_rdf https://repositorio.ufscar.br/bitstream/ufscar/16945/5/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.txt https://repositorio.ufscar.br/bitstream/ufscar/16945/7/Carta_Comprovante_Gustavo_24.10.2022.pdf.txt https://repositorio.ufscar.br/bitstream/ufscar/16945/6/Tese_Gustavo_Medeiros_de_Paula_27.10.2022.pdf.jpg https://repositorio.ufscar.br/bitstream/ufscar/16945/8/Carta_Comprovante_Gustavo_24.10.2022.pdf.jpg |
bitstream.checksum.fl_str_mv |
1003541cab172a7d61cac8230d274cd4 1ee2bb2d96d346c2ad0ad15628c129ba e39d27027a6cc9cb039ad269a5db8e34 16b0360e7ce0098fef83bc11ecece3a6 1d141b55fa6b10b20076720d2850cba1 8efa1c22f4c9da33c809df35a7ffad8e 4605302eb98110d5d89bd961b36d6b57 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR) |
repository.mail.fl_str_mv |
|
_version_ |
1802136413641113600 |