Estudo de adsorção de tiofeno em carbono ativado

Detalhes bibliográficos
Ano de defesa: 2010
Autor(a) principal: Rocha, Ana Vívian Parente
Orientador(a): Azevedo, Diana Cristina Silva de
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/15762
Resumo: Concerns with environmental protection and human health have had a remarkable impact on vehicle emissions regulations. Following similar policies of governmental agencies worldwide, Brazilian Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP) has established a timetable for drastic reduction of sulfur content in diesel and gasoline in the last few years. Hydrodesulfurization (HDS) is the industrial process being currently employed for this matter. However, the HDS process is costly and, to achieve deeper desulfurization levels, it would require higher hydrogen pressure, which may eventually lead to the saturation of olefinic compounds, causing a decrease in gasoline octane number. Therefore, special attention has been given to the use of adsorption for additional removal of sulfur compounds from effluent streams of existing hydrotreatment (HDT) plants. Adsorption processes may operate under mild temperature and pressure conditions. In the present work, desulfurization in thiophene/n-hexane, thiophene/n-octane and thiophene/toluene/n-octane mixtures were conducted, together with a study of thiophene/toluene selectivity, all experiments using activated carbon 830 W by Norit (Netherlands) as sorbent. The adsorbent was characterized texturally by adsorption/desorption of N2 at 77 K and results showed it to be a microporous material. Adsorption of thiophene from n-hexane solutions and thiophene/toluene selectivity were carried out using the experimental technique of headspace chromatography finite bath. Adsorption isotherms thus obtained showed unfavorable behavior and the adsorbent selectively adsorbs toluene as compared to thiophene, reaching maximum selectivity on liquid/solid ratio of less than 4%. Adsorption of thiophene in n-octane and n-octane/toluene (4:1 vol.) was assessed by fixed bed experiments performed under a flow rate of 0.5 mL/min, two different temperatures and sulfur concentration in the feed ranging from 275 to 1000 ppm. Adsorption isotherms thus measured fall within the Henry’s Law region (linear) with dimensionless adsorption constants of 3.7 and 3.0 at 30 ºC and 45 ºC, respectively. For the feed concentration of 1000 ppm in n-octane, the measured dynamic adsorption capacity was 0.035 mmolS/gads, which was reduced to 0.020 mmolS/gads when toluene was present. Regardless the inlet sulfur concentration, the amount of adsorbed thiophene decreased considerably in the presence of the aromatic compound. Breakthrough curves of thiophene in n-octane were simulated according to a mathematical model that assumed axially dispersed flow and mass transfer described by a linear driving force approximation (LDF). The model was solved numerically by orthogonal collocation in finite elements, using the commercial solver gPROMS. The proposed model matched experimental data reasonably well, especially for the feed concentration of 1000 ppm. The LDF time constant was the tunable parameter between simulations and experimental data and the best average values were found to be 3.3 and 2.2 min-1 at 30 and 45 ºC, respectively.
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spelling Rocha, Ana Vívian ParenteCavalcante Júnior, Célio LoureiroAzevedo, Diana Cristina Silva de2016-03-28T17:38:54Z2016-03-28T17:38:54Z2010ROCHA, A. V. P. Estudo de adsorção de tiofeno em carbono ativado. 102 f. 2010. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2010.http://www.repositorio.ufc.br/handle/riufc/15762Concerns with environmental protection and human health have had a remarkable impact on vehicle emissions regulations. Following similar policies of governmental agencies worldwide, Brazilian Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP) has established a timetable for drastic reduction of sulfur content in diesel and gasoline in the last few years. Hydrodesulfurization (HDS) is the industrial process being currently employed for this matter. However, the HDS process is costly and, to achieve deeper desulfurization levels, it would require higher hydrogen pressure, which may eventually lead to the saturation of olefinic compounds, causing a decrease in gasoline octane number. Therefore, special attention has been given to the use of adsorption for additional removal of sulfur compounds from effluent streams of existing hydrotreatment (HDT) plants. Adsorption processes may operate under mild temperature and pressure conditions. In the present work, desulfurization in thiophene/n-hexane, thiophene/n-octane and thiophene/toluene/n-octane mixtures were conducted, together with a study of thiophene/toluene selectivity, all experiments using activated carbon 830 W by Norit (Netherlands) as sorbent. The adsorbent was characterized texturally by adsorption/desorption of N2 at 77 K and results showed it to be a microporous material. Adsorption of thiophene from n-hexane solutions and thiophene/toluene selectivity were carried out using the experimental technique of headspace chromatography finite bath. Adsorption isotherms thus obtained showed unfavorable behavior and the adsorbent selectively adsorbs toluene as compared to thiophene, reaching maximum selectivity on liquid/solid ratio of less than 4%. Adsorption of thiophene in n-octane and n-octane/toluene (4:1 vol.) was assessed by fixed bed experiments performed under a flow rate of 0.5 mL/min, two different temperatures and sulfur concentration in the feed ranging from 275 to 1000 ppm. Adsorption isotherms thus measured fall within the Henry’s Law region (linear) with dimensionless adsorption constants of 3.7 and 3.0 at 30 ºC and 45 ºC, respectively. For the feed concentration of 1000 ppm in n-octane, the measured dynamic adsorption capacity was 0.035 mmolS/gads, which was reduced to 0.020 mmolS/gads when toluene was present. Regardless the inlet sulfur concentration, the amount of adsorbed thiophene decreased considerably in the presence of the aromatic compound. Breakthrough curves of thiophene in n-octane were simulated according to a mathematical model that assumed axially dispersed flow and mass transfer described by a linear driving force approximation (LDF). The model was solved numerically by orthogonal collocation in finite elements, using the commercial solver gPROMS. The proposed model matched experimental data reasonably well, especially for the feed concentration of 1000 ppm. The LDF time constant was the tunable parameter between simulations and experimental data and the best average values were found to be 3.3 and 2.2 min-1 at 30 and 45 ºC, respectively.A qualidade do ar e a preocupação com o meio ambiente e a saúde da população têm influenciado as regulamentações de emissões veiculares. A exemplo de órgãos governamentais em todo o mundo, a Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP) do Brasil tem estabelecido cronogramas de redução drástica de sulfurados no diesel e na gasolina nos últimos anos. A hidrodessulfurização (HDS) é o processo classicamente utilizado atualmente para reduzir o teor de enxofre em correntes de hidrocarbonetos. No entanto, o processo HDS é caro, pois requer elevadas temperaturas e pressões e hidrogênio, podendo levar à saturação de compostos olefínicos, o que compromete a octanagem da gasolina. Dessa forma, atenção especial vem sendo dada ao uso da adsorção para remoção de compostos sulfurados que poderá complementar ou – em alguns casos – substituir os processos existentes de hidrotratamento (HDT). Esse processo de adsorção pode ser realizado a temperatura e pressão ambiente. Neste trabalho foi realizado um estudo de remoção de enxofre a partir de soluções tiofeno/n-hexano, tiofeno/n-octano e tiofeno/tolueno/n-octano e um estudo de seletividade tiofeno/tolueno utilizando como adsorvente o carbono ativado 830 W da Norit (Holanda). O material foi caracterizado texturalmente por adsorção de N2 a 77 K. Os resultados indicaram ser um material microporoso. A adsorção do tiofeno em n-hexano e a seletividade tiofeno/tolueno foi avaliada usando a técnica experimental de banho finito com cromatografia headspace. A isoterma de adsorção obtida em headspace apresentou um comportamento desfavorável para o tiofeno e o adsorvente estudado foi seletivo pelo tolueno em relação ao tiofeno, sendo observado um ponto de saturação em razões líquido/sólido inferiores a 4%. Já a adsorção do tiofeno em n-octano e em n-octano/tolueno foi avaliada através de um estudo dinâmico de adsorção usando uma coluna de leito fixo com uma vazão de 0,5 mL/min a duas temperaturas distintas com concentração de alimentação na faixa de 275 a 1000 ppm. As isotermas de equilíbrio assim obtidas encontram-se na região de Henry (linear) com a constante de adsorção K = 3,7 e 3,0 para temperaturas de 30 ºC e 45 ºC, respectivamente. Obteve-se para concentração de 1000 ppm sem tolueno uma quantidade adsorvida de 0,035 mmolS/gads, que se reduz para 0,020 mmolS/gads na presença do aromático (20 % vol.). Pode-se observar que – em toda a faixa de concentrações de sulfurado estudada – a quantidade de tiofeno adsorvida diminuiu consideravelmente na presença do tolueno. Curvas de breakthrough do tiofeno em n-octano foram simuladas segundo um modelo matemático que considera fluxo axialmente disperso e transferência de massa descrita por uma aproximação de força motriz linear (LDF). O modelo foi resolvido numericamente por colocação ortogonal em elementos finitos, utilizando o software comercial gPROMS. O modelo matemático proposto representou razoavelmente os dados experimentais, especialmente para concentração de 1000 ppm. A constante de tempo de transferência de massa foi o parâmetro de ajuste entre as simulações e os dados experimentais, estimando-se valores médios de 3,3 e 2,2 min-1 a 30 e a 45 ºC, respectivamente.Engenharia químicaAdsorçãoEnxofreToluenoEstudo de adsorção de tiofeno em carbono ativadoStudy thiophene adsorption in activated carboninfo: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/openAccessORIGINAL2010_dis_avprocha.pdf2010_dis_avprocha.pdfapplication/pdf1076626http://repositorio.ufc.br/bitstream/riufc/15762/1/2010_dis_avprocha.pdf78f4b3f060df066223834be502c9b69fMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81786http://repositorio.ufc.br/bitstream/riufc/15762/2/license.txt8c4401d3d14722a7ca2d07c782a1aab3MD52riufc/157622020-10-27 09:49:18.722oai:repositorio.ufc.br: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Repositório InstitucionalPUBhttp://www.repositorio.ufc.br/ri-oai/requestbu@ufc.br || repositorio@ufc.bropendoar:2020-10-27T12:49:18Repositório Institucional da Universidade Federal do Ceará (UFC) - Universidade Federal do Ceará (UFC)false
dc.title.pt_BR.fl_str_mv Estudo de adsorção de tiofeno em carbono ativado
dc.title.en.pt_BR.fl_str_mv Study thiophene adsorption in activated carbon
title Estudo de adsorção de tiofeno em carbono ativado
spellingShingle Estudo de adsorção de tiofeno em carbono ativado
Rocha, Ana Vívian Parente
Engenharia química
Adsorção
Enxofre
Tolueno
title_short Estudo de adsorção de tiofeno em carbono ativado
title_full Estudo de adsorção de tiofeno em carbono ativado
title_fullStr Estudo de adsorção de tiofeno em carbono ativado
title_full_unstemmed Estudo de adsorção de tiofeno em carbono ativado
title_sort Estudo de adsorção de tiofeno em carbono ativado
author Rocha, Ana Vívian Parente
author_facet Rocha, Ana Vívian Parente
author_role author
dc.contributor.co-advisor.none.fl_str_mv Cavalcante Júnior, Célio Loureiro
dc.contributor.author.fl_str_mv Rocha, Ana Vívian Parente
dc.contributor.advisor1.fl_str_mv Azevedo, Diana Cristina Silva de
contributor_str_mv Azevedo, Diana Cristina Silva de
dc.subject.por.fl_str_mv Engenharia química
Adsorção
Enxofre
Tolueno
topic Engenharia química
Adsorção
Enxofre
Tolueno
description Concerns with environmental protection and human health have had a remarkable impact on vehicle emissions regulations. Following similar policies of governmental agencies worldwide, Brazilian Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP) has established a timetable for drastic reduction of sulfur content in diesel and gasoline in the last few years. Hydrodesulfurization (HDS) is the industrial process being currently employed for this matter. However, the HDS process is costly and, to achieve deeper desulfurization levels, it would require higher hydrogen pressure, which may eventually lead to the saturation of olefinic compounds, causing a decrease in gasoline octane number. Therefore, special attention has been given to the use of adsorption for additional removal of sulfur compounds from effluent streams of existing hydrotreatment (HDT) plants. Adsorption processes may operate under mild temperature and pressure conditions. In the present work, desulfurization in thiophene/n-hexane, thiophene/n-octane and thiophene/toluene/n-octane mixtures were conducted, together with a study of thiophene/toluene selectivity, all experiments using activated carbon 830 W by Norit (Netherlands) as sorbent. The adsorbent was characterized texturally by adsorption/desorption of N2 at 77 K and results showed it to be a microporous material. Adsorption of thiophene from n-hexane solutions and thiophene/toluene selectivity were carried out using the experimental technique of headspace chromatography finite bath. Adsorption isotherms thus obtained showed unfavorable behavior and the adsorbent selectively adsorbs toluene as compared to thiophene, reaching maximum selectivity on liquid/solid ratio of less than 4%. Adsorption of thiophene in n-octane and n-octane/toluene (4:1 vol.) was assessed by fixed bed experiments performed under a flow rate of 0.5 mL/min, two different temperatures and sulfur concentration in the feed ranging from 275 to 1000 ppm. Adsorption isotherms thus measured fall within the Henry’s Law region (linear) with dimensionless adsorption constants of 3.7 and 3.0 at 30 ºC and 45 ºC, respectively. For the feed concentration of 1000 ppm in n-octane, the measured dynamic adsorption capacity was 0.035 mmolS/gads, which was reduced to 0.020 mmolS/gads when toluene was present. Regardless the inlet sulfur concentration, the amount of adsorbed thiophene decreased considerably in the presence of the aromatic compound. Breakthrough curves of thiophene in n-octane were simulated according to a mathematical model that assumed axially dispersed flow and mass transfer described by a linear driving force approximation (LDF). The model was solved numerically by orthogonal collocation in finite elements, using the commercial solver gPROMS. The proposed model matched experimental data reasonably well, especially for the feed concentration of 1000 ppm. The LDF time constant was the tunable parameter between simulations and experimental data and the best average values were found to be 3.3 and 2.2 min-1 at 30 and 45 ºC, respectively.
publishDate 2010
dc.date.issued.fl_str_mv 2010
dc.date.accessioned.fl_str_mv 2016-03-28T17:38:54Z
dc.date.available.fl_str_mv 2016-03-28T17:38:54Z
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dc.identifier.citation.fl_str_mv ROCHA, A. V. P. Estudo de adsorção de tiofeno em carbono ativado. 102 f. 2010. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2010.
dc.identifier.uri.fl_str_mv http://www.repositorio.ufc.br/handle/riufc/15762
identifier_str_mv ROCHA, A. V. P. Estudo de adsorção de tiofeno em carbono ativado. 102 f. 2010. Dissertação (Mestrado em Engenharia Química)–Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2010.
url http://www.repositorio.ufc.br/handle/riufc/15762
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