S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila

Detalhes bibliográficos
Autor(a) principal: Vieira, Michele Oliveira
Data de Publicação: 2015
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da PUC_RS
Texto Completo: http://tede2.pucrs.br/tede2/handle/tede/6269
Resumo: The need for the synthesis improvement resulting in process less aggressive to the environment and the use of reusable raw materials are some of the principles of Green Chemistry. Thus, the goal of this work was to study an alternative route of dimethyl carbonate synthesis from CO2, using the working conditions of a CO2 capture plant for the pre-combustion process. Different ionic liquid imidazolium and pyridine cations combined with the anions [Cl]-, [BF4]-, [PF6]-, and [NTf2]- were tested as catalysts. The characterization of the produced ionic liquid was carried out using infrared spectroscopy with Fourier transform (FTIR) and nuclear magnetic resonance spectroscopy of proton (1H-NMR) confirming that the structure of these materials. The purity was determined by assay of the residual chlorides. For the dimethyl carbonate identification and quantification a gas chromatography equipped with a flame ionization detector (GC-FID) was used.For optimizing synthesis parameters were tested the temperatures of 140 ?C and 175 ?C and reaction time of 12 h, 24 h and 48 h, as well as changes in the cation of the ionic liquids with addition of branching and decreased of alkyl side chain. Herewith the results of methanol conversion and selectivity for DMC showed that these materials can be used as catalysts, but the use of a drying agent to overpass the thermodynamics barrier of the reaction is critical. The most important anions for this synthesis follow the order [BF4]- > [Cl]- > [PF6]- > [NTf2]- for both cations in DMC synthesis. The methanol conversion is maintained constant for all ILs, but the selectivity for dimethyl carbonate reached 81% when [bmim][BF4] was used as catalyst and the loss of this activity after 5 recycles is 8,5 %.
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spelling Einloft, Sandra Mara Oliveira403.158.860-72834.571.600-82http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4474549Y4Vieira, Michele Oliveira2015-08-25T11:59:39Z2015-08-06http://tede2.pucrs.br/tede2/handle/tede/6269The need for the synthesis improvement resulting in process less aggressive to the environment and the use of reusable raw materials are some of the principles of Green Chemistry. Thus, the goal of this work was to study an alternative route of dimethyl carbonate synthesis from CO2, using the working conditions of a CO2 capture plant for the pre-combustion process. Different ionic liquid imidazolium and pyridine cations combined with the anions [Cl]-, [BF4]-, [PF6]-, and [NTf2]- were tested as catalysts. The characterization of the produced ionic liquid was carried out using infrared spectroscopy with Fourier transform (FTIR) and nuclear magnetic resonance spectroscopy of proton (1H-NMR) confirming that the structure of these materials. The purity was determined by assay of the residual chlorides. For the dimethyl carbonate identification and quantification a gas chromatography equipped with a flame ionization detector (GC-FID) was used.For optimizing synthesis parameters were tested the temperatures of 140 ?C and 175 ?C and reaction time of 12 h, 24 h and 48 h, as well as changes in the cation of the ionic liquids with addition of branching and decreased of alkyl side chain. Herewith the results of methanol conversion and selectivity for DMC showed that these materials can be used as catalysts, but the use of a drying agent to overpass the thermodynamics barrier of the reaction is critical. The most important anions for this synthesis follow the order [BF4]- > [Cl]- > [PF6]- > [NTf2]- for both cations in DMC synthesis. The methanol conversion is maintained constant for all ILs, but the selectivity for dimethyl carbonate reached 81% when [bmim][BF4] was used as catalyst and the loss of this activity after 5 recycles is 8,5 %.A necessidade de aperfei?oamento de s?nteses menos agressivas ao meio ambiente e a utiliza??o de insumos reutiliz?veis s?o alguns dos princ?pios da Qu?mica Verde. Sendo assim, neste trabalho foi estudada uma rota alternativa de s?ntese do carbonato de dimetila (DMC) a partir do CO2, utilizando as condi??es de trabalho de uma planta de captura de CO2 pelo processo de pr?-combust?o. Diferentes l?quidos i?nicos de c?tions imidaz?lios e pirid?nicos com ?nions [Cl]-, [BF4]-, [PF6]- e [NTf2]- foram testados como catalisadores. A caracteriza??o dos l?quidos i?nicos produzidos foi poss?vel com a utiliza??o de espectroscopia no infravermelho com transformada de Fourier (FTIR) e espectroscopia de resson?ncia magn?tica nuclear de pr?ton (1H-RMN) que comprovaram a estrutura destes materiais. A pureza foi determinada atrav?s do ensaio residual de cloretos. Para o carbonato de dimetila, a identifica??o e quantifica??o foram realizadas por cromatografia gasosa equipada com um detector de ioniza??o de chama (CG-FID).Para otimiza??o dos par?metros de s?ntese foram testadas vari?veis de temperatura de 140 ?C e 175 ?C e tempo de rea??o de 12 h, 24 h e 48 h, assim como varia??es no c?tion dos l?quidos i?nicos com adi??o de ramifica??es e diminui??o da cadeia lateral alquila. Com isto os resultados de convers?o de metanol e seletividade para DMC demonstraram que estes materiais podem ser utilizados como catalisadores, mas que ? fundamental a utiliza??o de um agente secante para transpor a barreira termodin?mica da rea??o. Os ?nions mais relevantes para esta s?ntese seguem a seguinte ordem [BF4]- > [Cl]- > [PF6]- > [NTf2]- para ambos os c?tions na seletividade para DMC. A convers?o de metanol se mant?m constante para todos os LIs, mas a seletividade para carbonato de dimetila chegou a 81 % quando utilizando o [bmim][BF4] como catalisador e a perda de atividade ap?s 5 reciclos ? de 8,5 %.Submitted by Setor de Tratamento da Informa??o - BC/PUCRS (tede2@pucrs.br) on 2015-08-25T11:59:39Z No. of bitstreams: 1 474057 - Texto Completo.pdf: 1517260 bytes, checksum: 1d622d94e3f6f6c0eb26eeb6bbca2dc8 (MD5)Made available in DSpace on 2015-08-25T11:59:39Z (GMT). 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dc.title.por.fl_str_mv S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
title S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
spellingShingle S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
Vieira, Michele Oliveira
ENGENHARIA DE MATERIAIS
L?QUIDOS I?NICOS
CATALISADORES
S?NTESE (QU?MICA)
CARBONO
CAPTURA DE CARBONO
DI?XIDO DE CARBONO
ENGENHARIAS
title_short S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
title_full S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
title_fullStr S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
title_full_unstemmed S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
title_sort S?ntese e utiliza??o de l?quidos i?nicos como catalisadores na transforma??o qu?mica de CO2 em carbonato de dimetila
author Vieira, Michele Oliveira
author_facet Vieira, Michele Oliveira
author_role author
dc.contributor.advisor1.fl_str_mv Einloft, Sandra Mara Oliveira
dc.contributor.advisor1ID.fl_str_mv 403.158.860-72
dc.contributor.authorID.fl_str_mv 834.571.600-82
dc.contributor.authorLattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4474549Y4
dc.contributor.author.fl_str_mv Vieira, Michele Oliveira
contributor_str_mv Einloft, Sandra Mara Oliveira
dc.subject.por.fl_str_mv ENGENHARIA DE MATERIAIS
L?QUIDOS I?NICOS
CATALISADORES
S?NTESE (QU?MICA)
CARBONO
CAPTURA DE CARBONO
DI?XIDO DE CARBONO
topic ENGENHARIA DE MATERIAIS
L?QUIDOS I?NICOS
CATALISADORES
S?NTESE (QU?MICA)
CARBONO
CAPTURA DE CARBONO
DI?XIDO DE CARBONO
ENGENHARIAS
dc.subject.cnpq.fl_str_mv ENGENHARIAS
description The need for the synthesis improvement resulting in process less aggressive to the environment and the use of reusable raw materials are some of the principles of Green Chemistry. Thus, the goal of this work was to study an alternative route of dimethyl carbonate synthesis from CO2, using the working conditions of a CO2 capture plant for the pre-combustion process. Different ionic liquid imidazolium and pyridine cations combined with the anions [Cl]-, [BF4]-, [PF6]-, and [NTf2]- were tested as catalysts. The characterization of the produced ionic liquid was carried out using infrared spectroscopy with Fourier transform (FTIR) and nuclear magnetic resonance spectroscopy of proton (1H-NMR) confirming that the structure of these materials. The purity was determined by assay of the residual chlorides. For the dimethyl carbonate identification and quantification a gas chromatography equipped with a flame ionization detector (GC-FID) was used.For optimizing synthesis parameters were tested the temperatures of 140 ?C and 175 ?C and reaction time of 12 h, 24 h and 48 h, as well as changes in the cation of the ionic liquids with addition of branching and decreased of alkyl side chain. Herewith the results of methanol conversion and selectivity for DMC showed that these materials can be used as catalysts, but the use of a drying agent to overpass the thermodynamics barrier of the reaction is critical. The most important anions for this synthesis follow the order [BF4]- > [Cl]- > [PF6]- > [NTf2]- for both cations in DMC synthesis. The methanol conversion is maintained constant for all ILs, but the selectivity for dimethyl carbonate reached 81% when [bmim][BF4] was used as catalyst and the loss of this activity after 5 recycles is 8,5 %.
publishDate 2015
dc.date.accessioned.fl_str_mv 2015-08-25T11:59:39Z
dc.date.issued.fl_str_mv 2015-08-06
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