Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre

Detalhes bibliográficos
Autor(a) principal: Ferrari, Tatiane Caroline
Data de Publicação: 2015
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)
Texto Completo: http://repositorio.uem.br:8080/jspui/handle/1/3744
Resumo: The water gas shift reaction (WGSR), has been widely used as a way to remove the poisonous CO from the hydrogen current from methanol reforming. In this study, Cu/ZnO/ Al2O3 catalysts were used to study this reaction. The catalysts used were commercial HiFUEL W220 and one prepared by the sol-gel method. The materials were dried, and the calcination temperature was determined by DSC-TGA analysis. The materials were calcined and characterized according to the BET area, pore diameter and pore volume, TPR, S-TPR, XRD, TPD, SEM. After calcination, the catalysts were loaded into the reactor, then reduced and tested in the WGSR at low temperatures (200-250°C). Long duration tests have been performed (in which the temperature and the CO/steam molar ratio were kept at 200°C and 1/2, respectively). Short duration tests have been carried out temperature (between 200 and 250°C) and CO/steam molar ratio (between 1/4 and 1/2). Conversion of CO and H2 yield were examined. Gaseous and liquid products leaving the reactor were analyzed by gas chromatography. CO2 and H2 were produced, along with small quantities of coke. The conversions obtained for the long-term tests were higher when the catalyst synthesized by the sol-gel method was used. The coke was analyzed by SEM for the industrial catalyst. A carbon balance for identification of coke was also carried out. According to this carbon balance, the sol-gel catalyst yielded less. A mathematical model was developed for a CO reduction reactor and four kinetic expressions from the literature have been applied to this model (elementary, AYASTUY et al. (2005), AMADEO and LABORDE (1995), and Criscuoli et al. (2000)). The proposed mathematical model was solved in MATLAB. The behavior obtained for the CO conversion were compared with experimental data. The kinetics showed a better fit for the sol-gel catalyst data was proposed by AYASTUY et al. (2005) to the molar ratios CO / water vapor ½ and 1/3 and proposed by Criscuoli et al. (2000) molar ratio to 1/4. In the best results obtained for the same contact time, the reactor was determined length required for the CO concentration decreases to 4000 mg L-1, which according MENECHINI Neto et al. (2014) is the average concentration of CO at the exit of a reactor for methanol steam reforming, CO to the acceptable limit for application in fuel cells (50 mg L-1).
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spelling Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobreStudy of carbon monoxide removal reaction with copper-based industrial and sol-gel catalystsCatálise heterogêneaCatalisador sol-gelCélulas a combustivelHidrogênioMonóxido de carbonoBrasil.EngenhariasEngenharia QuímicaThe water gas shift reaction (WGSR), has been widely used as a way to remove the poisonous CO from the hydrogen current from methanol reforming. In this study, Cu/ZnO/ Al2O3 catalysts were used to study this reaction. The catalysts used were commercial HiFUEL W220 and one prepared by the sol-gel method. The materials were dried, and the calcination temperature was determined by DSC-TGA analysis. The materials were calcined and characterized according to the BET area, pore diameter and pore volume, TPR, S-TPR, XRD, TPD, SEM. After calcination, the catalysts were loaded into the reactor, then reduced and tested in the WGSR at low temperatures (200-250°C). Long duration tests have been performed (in which the temperature and the CO/steam molar ratio were kept at 200°C and 1/2, respectively). Short duration tests have been carried out temperature (between 200 and 250°C) and CO/steam molar ratio (between 1/4 and 1/2). Conversion of CO and H2 yield were examined. Gaseous and liquid products leaving the reactor were analyzed by gas chromatography. CO2 and H2 were produced, along with small quantities of coke. The conversions obtained for the long-term tests were higher when the catalyst synthesized by the sol-gel method was used. The coke was analyzed by SEM for the industrial catalyst. A carbon balance for identification of coke was also carried out. According to this carbon balance, the sol-gel catalyst yielded less. A mathematical model was developed for a CO reduction reactor and four kinetic expressions from the literature have been applied to this model (elementary, AYASTUY et al. (2005), AMADEO and LABORDE (1995), and Criscuoli et al. (2000)). The proposed mathematical model was solved in MATLAB. The behavior obtained for the CO conversion were compared with experimental data. The kinetics showed a better fit for the sol-gel catalyst data was proposed by AYASTUY et al. (2005) to the molar ratios CO / water vapor ½ and 1/3 and proposed by Criscuoli et al. (2000) molar ratio to 1/4. In the best results obtained for the same contact time, the reactor was determined length required for the CO concentration decreases to 4000 mg L-1, which according MENECHINI Neto et al. (2014) is the average concentration of CO at the exit of a reactor for methanol steam reforming, CO to the acceptable limit for application in fuel cells (50 mg L-1).A reação de deslocamento gás-água (water gas shift reaction - WGSR) tem sido muito utilizada como forma de remover o CO venenoso da corrente de hidrogênio proveniente da reforma de metanol, para aplicação em células a combustível. No presente trabalho, catalisadores de Cu/ZnO/Al2O3 foram utilizados para estudo dessa reação. Os catalisadores utilizados foram o comercial HiFUEL W220 e um preparado pelo método sol-gel. Os materiais foram secos e, por meio da obtenção da temperatura de calcinação pela análise de TGA-DSC, foram calcinados e caracterizados em relação a Medidas de adsorção e dessorção de N2 que inclui: área BET, volume de poros, diâmetro de poros e isotermas de adsorção, TPR, STPR, DRX, TPD, MEV. Depois de calcinados, os catalisadores foram carregados no reator, reduzidos e então testados na WGSR a baixas temperaturas (200 - 250°C). Foram realizados testes de longa duração (nos quais a temperatura e a razão molar CO/vapor d'água foram mantidas em 200°C e 1/2, respectivamente) e testes de curta duração (nos quais a temperatura foi variada entre 200 e 250°C e a razão molar CO/vapor d'água entre 1/4 e 1/2). Foram analisados a conversão de CO e o rendimento de H2. Os produtos gasosos e líquidos que efluentes do reator foram analisados por cromatografia gasosa. Houve produção de CO2, H2 e de coque em pequenas quantidades. As conversões obtidas para os testes de longa duração foram superiores para o catalisador sintetizado pelo método sol-gel. O coque foi analisado por MEV para o catalisador industrial. Também foi realizado um balanço de carbono para identificação de coque. O catalisador sol-gel, segundo o balanço de carbono, formou menos coque. Um modelo matemático foi desenvolvido para um reator de abatimento de CO, e quatro cinéticas presentes em literatura foram aplicadas a esse modelo (elementar; AYASTUY et. al., 2005; AMADEO e LABORDE, 1995 e CRISCUOLI et al., 2000). O modelo matemático proposto foi resolvido no MATLAB. Os comportamentos obtidos para a conversão de CO foram comparados com os dados experimentais. A cinética que apresentou um melhor ajuste para os dados do catalisador sol-gel foi a proposta por AYASTUY et al. (2005), para as razões molares CO/vapor d'água de ½ e 1/3 e a proposta por CRISCUOLI et al. (2000) para a razão molar de 1/4. Com o melhor resultado obtido, para o mesmo tempo de contato, foi determinado o comprimento do reator necessário para que a concentração de CO decresça de 4000 mg L-1, que segundo MENECHINI NETO et al. (2014) é a concentração média de CO na saída de um reator de reforma a vapor de metanol, até o limite de CO aceitável para aplicação em células a combustível (50 mg L-1).1 CD-ROM (xvii, 116 f.)Universidade Estadual de MaringáBrasilDepartamento de Engenharia QuímicaPrograma de Pós-Graduação em Engenharia QuímicaUEMMaringá, PRCentro de TecnologiaLuiz Mário de Matos JorgeRoberta Carolina Pelissari Rizzo Domingues - UTFPROnélia Aparecida Andreo dos Santos - UEMPaulo Roberto Paraíso - UEMValmir Calsavara - UEMFerrari, Tatiane Caroline2018-04-17T17:42:55Z2018-04-17T17:42:55Z2015info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesishttp://repositorio.uem.br:8080/jspui/handle/1/3744porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)instname:Universidade Estadual de Maringá (UEM)instacron:UEM2018-10-15T18:19:45Zoai:localhost:1/3744Repositório InstitucionalPUBhttp://repositorio.uem.br:8080/oai/requestopendoar:2024-04-23T14:56:53.845138Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM)false
dc.title.none.fl_str_mv Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
Study of carbon monoxide removal reaction with copper-based industrial and sol-gel catalysts
title Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
spellingShingle Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
Ferrari, Tatiane Caroline
Catálise heterogênea
Catalisador sol-gel
Células a combustivel
Hidrogênio
Monóxido de carbono
Brasil.
Engenharias
Engenharia Química
title_short Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
title_full Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
title_fullStr Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
title_full_unstemmed Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
title_sort Estudo da reação de remoção do monóxido de carbono com catalisadores industrial e sol-gel à base de cobre
author Ferrari, Tatiane Caroline
author_facet Ferrari, Tatiane Caroline
author_role author
dc.contributor.none.fl_str_mv Luiz Mário de Matos Jorge
Roberta Carolina Pelissari Rizzo Domingues - UTFPR
Onélia Aparecida Andreo dos Santos - UEM
Paulo Roberto Paraíso - UEM
Valmir Calsavara - UEM
dc.contributor.author.fl_str_mv Ferrari, Tatiane Caroline
dc.subject.por.fl_str_mv Catálise heterogênea
Catalisador sol-gel
Células a combustivel
Hidrogênio
Monóxido de carbono
Brasil.
Engenharias
Engenharia Química
topic Catálise heterogênea
Catalisador sol-gel
Células a combustivel
Hidrogênio
Monóxido de carbono
Brasil.
Engenharias
Engenharia Química
description The water gas shift reaction (WGSR), has been widely used as a way to remove the poisonous CO from the hydrogen current from methanol reforming. In this study, Cu/ZnO/ Al2O3 catalysts were used to study this reaction. The catalysts used were commercial HiFUEL W220 and one prepared by the sol-gel method. The materials were dried, and the calcination temperature was determined by DSC-TGA analysis. The materials were calcined and characterized according to the BET area, pore diameter and pore volume, TPR, S-TPR, XRD, TPD, SEM. After calcination, the catalysts were loaded into the reactor, then reduced and tested in the WGSR at low temperatures (200-250°C). Long duration tests have been performed (in which the temperature and the CO/steam molar ratio were kept at 200°C and 1/2, respectively). Short duration tests have been carried out temperature (between 200 and 250°C) and CO/steam molar ratio (between 1/4 and 1/2). Conversion of CO and H2 yield were examined. Gaseous and liquid products leaving the reactor were analyzed by gas chromatography. CO2 and H2 were produced, along with small quantities of coke. The conversions obtained for the long-term tests were higher when the catalyst synthesized by the sol-gel method was used. The coke was analyzed by SEM for the industrial catalyst. A carbon balance for identification of coke was also carried out. According to this carbon balance, the sol-gel catalyst yielded less. A mathematical model was developed for a CO reduction reactor and four kinetic expressions from the literature have been applied to this model (elementary, AYASTUY et al. (2005), AMADEO and LABORDE (1995), and Criscuoli et al. (2000)). The proposed mathematical model was solved in MATLAB. The behavior obtained for the CO conversion were compared with experimental data. The kinetics showed a better fit for the sol-gel catalyst data was proposed by AYASTUY et al. (2005) to the molar ratios CO / water vapor ½ and 1/3 and proposed by Criscuoli et al. (2000) molar ratio to 1/4. In the best results obtained for the same contact time, the reactor was determined length required for the CO concentration decreases to 4000 mg L-1, which according MENECHINI Neto et al. (2014) is the average concentration of CO at the exit of a reactor for methanol steam reforming, CO to the acceptable limit for application in fuel cells (50 mg L-1).
publishDate 2015
dc.date.none.fl_str_mv 2015
2018-04-17T17:42:55Z
2018-04-17T17:42:55Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/masterThesis
format masterThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://repositorio.uem.br:8080/jspui/handle/1/3744
url http://repositorio.uem.br:8080/jspui/handle/1/3744
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade Estadual de Maringá
Brasil
Departamento de Engenharia Química
Programa de Pós-Graduação em Engenharia Química
UEM
Maringá, PR
Centro de Tecnologia
publisher.none.fl_str_mv Universidade Estadual de Maringá
Brasil
Departamento de Engenharia Química
Programa de Pós-Graduação em Engenharia Química
UEM
Maringá, PR
Centro de Tecnologia
dc.source.none.fl_str_mv reponame:Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)
instname:Universidade Estadual de Maringá (UEM)
instacron:UEM
instname_str Universidade Estadual de Maringá (UEM)
instacron_str UEM
institution UEM
reponame_str Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)
collection Repositório Institucional da Universidade Estadual de Maringá (RI-UEM)
repository.name.fl_str_mv Repositório Institucional da Universidade Estadual de Maringá (RI-UEM) - Universidade Estadual de Maringá (UEM)
repository.mail.fl_str_mv
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