Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

Detalhes bibliográficos
Ano de defesa: 2014
Autor(a) principal: Duarte, Kahildete Rodrigues Forte
Orientador(a): Não Informado pela instituição
Banca de defesa: Não Informado pela instituição
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal do Rio Grande do Norte
BR
UFRN
Programa de Pós-Graduação em Engenharia Química
Pesquisa e Desenvolvimento de Tecnologias Regionais
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: https://repositorio.ufrn.br/jspui/handle/123456789/15933
Resumo: The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market
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spelling Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsõesNew alyernatives for removal of sulfur from diesel fuel using surfactants and microemulsionsDiesel. Remoção de enxofre. Adsorção. Vermiculita. Tensoativos. MicroemulsãoDiesel. Sulfur removal. Adsorption. Vermiculite. Surfactants. microemulsionCNPQ::ENGENHARIAS::ENGENHARIA QUIMICAThe diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the marketOs óxidos de enxofre formados pela combustão do óleo diesel podem ser descarregados para a atmosfera sob a forma de particulados e poluentes primários como SO2 e SO 3, acarretando grandes prejuízos ao meio ambiente e à saúde humana e, ainda, podem se transformar em ácidos na câmara de combustão, causando danos aos motores. A preocupação mundial com o meio ambiente saudável e despoluído tem levado à instituição de normas e leis no sentido de reduzir os níveis de emissão de poluentes no ar, estabelecendo teores de enxofre cada vez mais baixos nos combustíveis, de modo a seter produtos menos agressivos ao meio ambiente e à saúde pública. Os métodos convencionais de remoção de enxofre do diesel têm custo elevado, além de não serem capazes de produzir combustíveis com nível zero de enxofre. Assim, este trabalho tem como objetivo desenvolver novos métodos de remoção de enxofre do diesel utilizando tensoativos e sistemas microemulsionados, procurando associar novas tecnologias e viabilidade econômica aos processos. Para escolha do tensoativo, foi feito um estudo de extração na região de Winsor I, com cloreto de dodecilamônio (DDACl) e nonil fenol etoxilado (RNX 95). A partir dos resultados foi escolhido o RNX 95, como constituinte dos sistemas microemulsionados utilizados na modificação dos adsorventes, para os processos de adsorção e, como extratante, para extração líquido-líquido. Utilizou-se como adsorvente a vermiculita tratada com uma microemulsão constituída por RNX 95 (tensoativo), n-butanol (cotensoativo), hexano (fase oleosa) e água destilada, solução salina de CaCl220 ppm, solução salina de CaCl2 1500 ppm (fase aquosa), nos processos de adsorção, em banho finito e em coluna, cuja fase fluida foi o óleo diesel comercial (1233 ppm de enxofre). Na etapa de adsorção em banho finito aplicaram-se duas abordagens estatísticas pelo método do planejamento fatorial completo (23), com três variáveis (temperatura, concentração da solução salina de CaCl2 e granulometria da vermiculita) em dois níveis experimentais (superior e inferior), variando a razão vermiculita:diesel, sendo um planejamento fatorial para a razão igual a 1:2 e outro para razão igual a 1:5. A resposta experimental foi a capacidade da vermiculita em adsorver o enxofre. Os melhores resultados, tanto para a razãovermiculita/diesel de 1:5 como para a razão 1:2, foram obtidos a uma temperatura de 60°C, concentração de CaCl 2 1500 ppm e granulometria da vermiculita 65 mesh, obtendo-se capacidades de adsorção de 4,24 mg/g para a razão 1:5 e 2,87 mg/g, para a razão 1:2, indicando que a variável mais significativa, em ambas as razões, foi a concentração da solução salina de CaCl2. Na extração líquido-líquido, realizada em duas e em seis etapas, utilizou-se a mesma proporção de tensoativoe diesel e obtiveram-se percentuais de extração de 46,8% e 73,15%, respectivamente. Foi realizado também um estudo alternativo de modificação de outros adsorventes para fins de comparação. Os ensaios foram feitos em banho finito com bentonita e diatomita, modificadas com microemulsão. Os agentes modificadores foram os já estudados neste trabalho acrescidos de soluções salinas de BaCl220 ppm e 1500 ppm, como fases aquosas dos sistemas microemulsionados. Para a bentonita a melhor capacidade de adsorção foi de 7,53 mg/g utilizando o sistema microemulsionado com água destilada na fase aquosa e para a diatomita o melhor resultado ocorreu com a microemulsão contendo solução salina de CaCl2 20ppm, obtendo-se uma capacidade de adsorção de 17,04 mg/g. A realização deste estudo permite concluir que, dentre as alternativas testadas, a adsorção utilizando adsorventes impregnados por microemulsões foi considerado o melhor processo de remoção do enxofre do diesel e que a sua otimização e scale upconstitui-se em uma alternativa viável e de custo compatível comas necessidades do mercadoUniversidade Federal do Rio Grande do NorteBRUFRNPrograma de Pós-Graduação em Engenharia QuímicaPesquisa e Desenvolvimento de Tecnologias RegionaisDantas Neto, Afonso Avelinohttp://lattes.cnpq.br/5211954491266744http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783215D9Dantas, Tereza Neuma de Castrohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783139Z0&dataRevisao=nullPeres, Antônio Eduardo Clarkhttp://lattes.cnpq.br/8666548473150908Leite, Ricardo Henrique de Limahttp://lattes.cnpq.br/3801476460958779Medeiros, Gilson Gomes dehttp://lattes.cnpq.br/9423866978987831Moura, Maria Carlenise Paiva de Alencarhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702157Y9Barros Neto, Eduardo Lins dehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4798645D3Duarte, Kahildete Rodrigues Forte2014-12-17T15:01:57Z2014-09-192014-12-17T15:01:57Z2014-03-12info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfDUARTE, Kahildete Rodrigues Forte. New alyernatives for removal of sulfur from diesel fuel using surfactants and microemulsions. 2014. 128 f. Tese (Doutorado em Pesquisa e Desenvolvimento de Tecnologias Regionais) - Universidade Federal do Rio Grande do Norte, Natal, 2014.https://repositorio.ufrn.br/jspui/handle/123456789/15933porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRN2017-11-02T09:21:33Zoai:repositorio.ufrn.br:123456789/15933Repositório InstitucionalPUBhttp://repositorio.ufrn.br/oai/repositorio@bczm.ufrn.bropendoar:2017-11-02T09:21:33Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false
dc.title.none.fl_str_mv Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
New alyernatives for removal of sulfur from diesel fuel using surfactants and microemulsions
title Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
spellingShingle Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
Duarte, Kahildete Rodrigues Forte
Diesel. Remoção de enxofre. Adsorção. Vermiculita. Tensoativos. Microemulsão
Diesel. Sulfur removal. Adsorption. Vermiculite. Surfactants. microemulsion
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
title_short Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
title_full Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
title_fullStr Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
title_full_unstemmed Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
title_sort Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões
author Duarte, Kahildete Rodrigues Forte
author_facet Duarte, Kahildete Rodrigues Forte
author_role author
dc.contributor.none.fl_str_mv Dantas Neto, Afonso Avelino

http://lattes.cnpq.br/5211954491266744

http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783215D9
Dantas, Tereza Neuma de Castro

http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783139Z0&dataRevisao=null
Peres, Antônio Eduardo Clark

http://lattes.cnpq.br/8666548473150908
Leite, Ricardo Henrique de Lima

http://lattes.cnpq.br/3801476460958779
Medeiros, Gilson Gomes de

http://lattes.cnpq.br/9423866978987831
Moura, Maria Carlenise Paiva de Alencar

http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4702157Y9
Barros Neto, Eduardo Lins de

http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4798645D3
dc.contributor.author.fl_str_mv Duarte, Kahildete Rodrigues Forte
dc.subject.por.fl_str_mv Diesel. Remoção de enxofre. Adsorção. Vermiculita. Tensoativos. Microemulsão
Diesel. Sulfur removal. Adsorption. Vermiculite. Surfactants. microemulsion
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
topic Diesel. Remoção de enxofre. Adsorção. Vermiculita. Tensoativos. Microemulsão
Diesel. Sulfur removal. Adsorption. Vermiculite. Surfactants. microemulsion
CNPQ::ENGENHARIAS::ENGENHARIA QUIMICA
description The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market
publishDate 2014
dc.date.none.fl_str_mv 2014-12-17T15:01:57Z
2014-09-19
2014-12-17T15:01:57Z
2014-03-12
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.uri.fl_str_mv DUARTE, Kahildete Rodrigues Forte. New alyernatives for removal of sulfur from diesel fuel using surfactants and microemulsions. 2014. 128 f. Tese (Doutorado em Pesquisa e Desenvolvimento de Tecnologias Regionais) - Universidade Federal do Rio Grande do Norte, Natal, 2014.
https://repositorio.ufrn.br/jspui/handle/123456789/15933
identifier_str_mv DUARTE, Kahildete Rodrigues Forte. New alyernatives for removal of sulfur from diesel fuel using surfactants and microemulsions. 2014. 128 f. Tese (Doutorado em Pesquisa e Desenvolvimento de Tecnologias Regionais) - Universidade Federal do Rio Grande do Norte, Natal, 2014.
url https://repositorio.ufrn.br/jspui/handle/123456789/15933
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.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Universidade Federal do Rio Grande do Norte
BR
UFRN
Programa de Pós-Graduação em Engenharia Química
Pesquisa e Desenvolvimento de Tecnologias Regionais
publisher.none.fl_str_mv Universidade Federal do Rio Grande do Norte
BR
UFRN
Programa de Pós-Graduação em Engenharia Química
Pesquisa e Desenvolvimento de Tecnologias Regionais
dc.source.none.fl_str_mv reponame:Repositório Institucional da UFRN
instname:Universidade Federal do Rio Grande do Norte (UFRN)
instacron:UFRN
instname_str Universidade Federal do Rio Grande do Norte (UFRN)
instacron_str UFRN
institution UFRN
reponame_str Repositório Institucional da UFRN
collection Repositório Institucional da UFRN
repository.name.fl_str_mv Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)
repository.mail.fl_str_mv repositorio@bczm.ufrn.br
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