Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-01-27T12:21:52Z No. of bitstreams: 1 MarcilioDosSantosTavares_TESE.pdf: 4345486 bytes, checksum: 8f84f78e0923aad2b8781e75eb8573ea (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-01-30T12:18:04Z (GMT) No. of bitstreams: 1 MarcilioDosSantosTavares_TESE.pdf: 4345486 bytes, checksum: 8f84f78e0923aad2b8781e75eb8573ea (MD5) / Made available in DSpace on 2017-01-30T12:18:04Z (GMT). No. of bitstreams: 1 MarcilioDosSantosTavares_TESE.pdf: 4345486 bytes, checksum: 8f84f78e0923aad2b8781e75eb8573ea (MD5) Previous issue date: 2016-07-29 / O conhecimento da composi??o do petr?leo e seus produtos ? uma necessidade imprescind?vel numa refinaria para o ajuste das condi??es do processo. Desta forma a otimiza??o do refino de petr?leo ? fundamental para a predi??o da distribui??o dos produtos e sua qualidade. Realizar o estudo cin?tico da degrada??o t?rmica e catal?tica na presen?a da ze?lita H ?Beta e avaliar os produtos obtidos por PY - CG/ MS de petr?leo leve foi o objetivo principal deste trabalho. Contudo, foram feitas correla??es de dados obtidos atrav?s da destila??o Simulada por Cromatografia a G?s (SIMDIST), da an?lise termogravim?trica (TG/DTG) e da pir?lise acoplada a um espectr?metro de massas (GC/MS), para auxiliar nas an?lises dos dados obtidos. Atrav?s da t?cnica de Fluoresc?ncia de Raios X por Energia Dispersiva (EDX), seguindo o m?todo ASTM D4294 foi poss?vel determinar o teor de enxofre contido na amostra. A termogravimetria (TG/DTG) apresentou tr?s etapas de perdas de massa, onde a primeira etapa est? relacionada ? remo??o de hidrocarbonetos e compostos org?nicos leves. Na segunda etapa ocorre a decomposi??o de arom?ticos de alta massa molecular. E na terceira etapa, ocorreu a degrada??o de coque. Atrav?s da t?cnica de PY ? GC/MS foram detectados os produtos de degrada??o da amostra de petr?leo nas temperaturas de 250?C, 350?C e 450?C, com e sem a presen?a da ze?lita H-Beta. A degrada??o t?rmica e catal?tica da amostra de petr?leo leve foi realizada da temperatura ambiente at? 900?C, nas raz?es de aquecimento de 5, 10 e 20oC min-1. As curvas geradas pela TG/DTG apresentaram uma degrada??o mais acelerada na amostra de petr?leo sem catalisador H-Beta. Esses resultados foram ratificados pela energia de ativa??o, calculada atrav?s do m?todo cin?tico ? Livre (Vyazovkin modelfree Kinetic), em que a presen?a do catalisador reduziu a energia, em especial na faixa de craqueamento, mostrando a efici?ncia do processo, principalmente para a obten??o de materiais leves da composi??o da amostra de petr?leo leve, como diesel e gasolina. / Knowledge of the oil composition and its products is an absolute necessity in a refinery for adjusting the process conditions. Thus the optimization of petroleum refining is essential for predicting the distribution of products and their quality. Perform the kinetic study of the thermal and catalytic degradation in the presence of zeolite H -Beta and evaluate the products obtained by PY-GC/MS of light oil was the main objective of this work. However, data correlations were made obtained by Simulated Distillation by Gas Chromatography (SIMDIST), the thermal gravimetric analysis (TG / DTG) and pyrolysis coupled to a mass spectrometer (GC/MS), to assist in the analysis of data. Through Fluorescence technique of X-ray energy dispersive (EDX) following the ASTM D4294 method it was possible to determine the sulfur content in the sample. Thermogravimetry (TG/DTG) showed three-step weight loss, where the first stage relates to the removal of light hydrocarbons and organic compounds. The second step is decomposition of aromatic high molecular weight. And the third stage was the degradation of coke. Through the technique PY-GC/MS were detected degradation products of the oil sample at temperatures of 250?C, 350?C and 450?C, with and without the presence of zeolite H-Beta. The thermal and catalytic degradation of light oil sample was carried out from room temperature to 900C, the heating rates of 5, 10 and 20 ? C min-1. The curves generated by TG/DTG showed a faster degradation in the sample oil without H-Beta catalyst. These results were confirmed by activation energy calculated using the kinetic method - Free (Vyazovkin modelfree Kinetic) in the presence of the catalyst decreased energy, in particular in cracking band, showing the process efficiency, particularly for obtaining lightweight materials of light oil sample composition, such as diesel and gasoline.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-01-14T20:06:38Z No. of bitstreams: 1 CamilaGiseleDamascenoPeixoto_DISSERT.pdf: 4730926 bytes, checksum: d89e75f06427057e5b75359107c6228a (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-01-18T22:06:35Z (GMT) No. of bitstreams: 1 CamilaGiseleDamascenoPeixoto_DISSERT.pdf: 4730926 bytes, checksum: d89e75f06427057e5b75359107c6228a (MD5) / Made available in DSpace on 2016-01-18T22:06:35Z (GMT). No. of bitstreams: 1 CamilaGiseleDamascenoPeixoto_DISSERT.pdf: 4730926 bytes, checksum: d89e75f06427057e5b75359107c6228a (MD5) Previous issue date: 2014-09-24 / Um dos principais problemas relacionados ? utiliza??o do ?leo diesel como combust?vel ? a presen?a de enxofre (S) que provoca polui??o no meio ambiente e corros?o nos motores. Com o intuito de minimizar as consequ?ncias decorrentes da libera??o deste poluente, a legisla??o brasileira estabeleceu limites m?ximos de teor de enxofre que os combust?veis podem apresentar. Para atender ?s exig?ncias, o ?leo diesel com concentra??o m?xima de enxofre igual a 10 mg/kg (S10) vem sendo amplamente comercializado no pa?s. Entretanto, a redu??o no teor de enxofre pode acarretar mudan?as nas propriedades f?sico-qu?micas do combust?vel, as quais s?o essenciais para o desempenho dos ve?culos. Este trabalho tem como objetivo a identifica??o das principais mudan?as nas propriedades f?sico-qu?micas do ?leo diesel e como elas est?o relacionadas ? redu??o do teor de enxofre. Foram testadas amostras de ?leo diesel dos tipos S10, S500 e S1800 de acordo com as metodologias da American Society for Testing and Materials (ASTM). As propriedades f?sico-qu?micas de massa espec?fica, ponto de fulgor, viscosidade cinem?tica e propriedades a baixa temperatura foram determinadas. Os ?leos tamb?m foram caracterizados por termogravimetria (TG) e submetidos ? destila??o f?sica (ASTM D86) e destila??o simulada por cromatografia gasosa (ASTM D2887). Os resultados da caracteriza??o f?sico-qu?mica mostraram que a redu??o do enxofre tornou os combust?veis mais leves e fluidos, permitindo uma maior aplicabilidade a ambientes com baixas temperaturas e uma maior seguran?a para o transporte e armazenamento. Atrav?s dos dados de destila??o simulada foi observado que a diminui??o do teor de enxofre provocou aumento das temperaturas de ebuli??o das fra??es iniciais e a redu??o das temperaturas de ebuli??o das fra??es m?dias e pesadas. A TG revelou um evento de perda de massa, atribu?do ? volatiliza??o ou destila??o de hidrocarbonetos leves e m?dios. A partir destes dados, o comportamento cin?tico das amostras foi estudada e verificou-se que as energias de ativa??o (Ea) pouco variaram ao longo da convers?o. v Considerando a m?dia dessas energias, o S1800 apresentou a Ea mais elevada no decorrer da convers?o e o S10 os menores valores / One of the main problems related to the use of diesel as fuel is the presence of sulfur (S) which causes environmental pollution and corrosion of engines. In order to minimize the consequences of the release of this pollutant, Brazilian law established maximum sulfur content that diesel fuel may have. To meet these requirements, diesel with a maximum sulfur concentration equal to 10 mg/kg (S10) has been widely marketed in the country. However, the reduction of sulfur can lead to changes in the physicochemical properties of the fuel, which are essential for the performance of road vehicles. This work aims to identify the main changes in the physicochemical properties of diesel fuel and how they are related to reduction of sulfur content. Samples of diesel types S10, S500 and S1800 were tested according with the methods of the American Society for Testing and Materials (ASTM). The fuels were also characterized by thermogravimetric analysis (TG) and subjected to physical distillation (ASTM D86) and simulated distillation gas chromatography (ASTM D2887). The results showed that the reduction of sulfur turned the fuel lighter and fluid, allowing a greater applicability to low temperature environments and safer for transportation and storage. Through the simulated distillation data was observed that decreasing sulfur content resulted in higher initial boiling point temperatures and the decreasing of the boiling temperature of the medium and heavy fractions. Thermogravimetric analysis showed a loss event mass attributed to volatilization or distillation of light and medium hydrocarbons. Based on these data, the kinetic behavior of the samples was investigated and it was observed that the activation energies (Ea) did not show significant changes throughout conversion. Considering the average of these energies, the S1800 had the highest Ea during the conversion and the S10 the lowest values