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Orientadores: Rahoma Sadeg Mohamed, Watson Loh / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T20:10:23Z (GMT). No. of bitstreams: 1 Santos_RonaldoGoncalvesdos_M.pdf: 2592752 bytes, checksum: 0b29b2d43cb92bfcf2b5329b8efb1f8c (MD5) Previous issue date: 2003 / Resumo: O alto custo de produção e transporte dos óleos pesados é a principal barreira para a exploração das suas abundantes reservas mundiais. Tecnologias de fluxo de petróleo em oleodutos baseadas no confinamento do óleo em uma seção anular aquosa, conhecidas como core-flows, têm surgido como alternativa viável para o transporte desses óleos. O efeito lubrificante do filme aquoso conduz à reduzidos valores de viscosidade e, conseqüentemente, ao baixo consumo de energia. Um possível problema associado com esta tecnologia é o acumulo gradual do óleo sobre a superfície interna da tubulação, requerendo o uso de procedimentos de limpeza. Este trabalho é baseado na investigação dos efeitos de componentes polares do petróleo sobre a molhabilidade de tais superfícies por óleos crus através de medidas de ângulo do contato em sistemas óleo pesado/fase aquosa/superfície metálica. Asfaltenes e ácidos naftênicos foram removidos do óleo cru por floculação com n-alcanos e por tratamento com solução alcalina, respectivamente. Como superfícies metálicas modelos, aço comercial e aço galvanizado foram utilizados, e as fases aquosas estudadas compreenderam água para e soluções de cloreto de sódio e de meta-silicate de sódio a 1%. Ângulos de contato estáticos foram determinados através da deposição de uma gora de óleo sob a superfície metálica na presença de uma fase aquosa... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: High cost of recovery and transport of heavy crude oils is the main barrier for the exploration of their abundant reserves worldwide. The technology of oil flow in pipelines assisted by its confinement within an annular aqueous section, known as core-flow, represent a viable alternative for the transport of these oils. The lubricating effect of the aqueous film leads to reduced equivalent viscosities and, hence, low energy consumption. One of the possible problems associated with this technique is the gradual accumulation of oil on the inner pipeline surfaces, requiring the use of cleaning procedures. This work is aimed at investigating the roles of the oil polar components on the wetting of such surfaces by crude oil through contact angle measurements in systems containing heavy oil/aqueous phase/metallic surfaces. Asphaltenes and naphthenic acids were removed from the crude oil, respectively, by flocculation with alkanes and by washing with alkaline solution. As model metallic surfaces, commercial and galvanized steel were used; and the studied aqueous phases comprised pure water, 1% sodium chloride and sodium meta-silicate solutions. Static contact angles were determined via the placement of an oil droplet under the metallic surface in the presence of an aqueous phase. These measurements revealed small influence of the nature of the metallic surfaces on the observed wettability... Note: The complete abstract is available with the full electronic digital thesis or dissertations / Mestrado / Mestre em Engenharia Química

Le but de cette thèse est d’étudier le comportement des asphaltènes dans des condition de hydrotraitement, y compris les propriétés de transport et d’adsorption. La chromatographie d'exclusion stérique inverse (ISEC) ainsi que la spectroscopie d'impédance sont utilisées pour déterminer des paramètres topologiques de solides poreux d’alumine (porosité, taille de pores, tortuosité). Des coefficients de diffusion effectifs de polystyrènes de différentes tailles sont aussi étudiés par chromatographie liquide en conditions non-adsorbantes: les molécules de petites tailles pénètrent plus profondément dans le milieu poreux donc elles prennent plus de temps pour traverser la colonne, tandis que les molécules ayant une taille supérieure à la taille du pore ne sondent que la macroporosité. Avec l'utilisation des méthodes dynamique et «peak parking», il est possible de modéliser le transport des molécules de différentes tailles, et cela aidera à prédire le comportement de molécules d’une taille quelconque. Les colonnes ont été assemblées au laboratoire à partir de poudres et de monolithes d’alumine. Les caractéristiques d'adsorption des asphaltènes modèles sont déterminées et comparées avec une fraction d’asphaltènes extraite d’un brut. Un phénomène de dimérisation ainsi qu’une très forte adsorption sur la surface de l’alumine sont observés avec la molécule modèle. La méthode dynamique a été utilisée avec des colonnes courtes dans des conditions de saturation. Une influence apparente du débit dans l’importance et le mécanisme d’adsorption a pu être constatée. / This work aims to study the complex behaviors of asphaltenes within the hydrotreatment catalytic porous system including transport properties and adsorption. Inverse size-exclusion chromatography (ISEC) and impedance spectroscopy are used to determine the topological characteristics of different alumina porous solids (porosity, pore size, tortuosity). The effective diffusion coefficient of polystyrenes of different sizes was studied via chromatography in non-adsorbing conditions. Elution peaks are used to determine the effect of molecule size on the accessible pore volume and the transport properties therein: molecules of relatively small sizes penetrate further into the porous medium, thus taking more time to navigate the chromatographic setup, while larger molecules traverse much faster, through the macroporosity. The liquid chromatography technique is divided in two different methods. Both methods yield diffusion coefficient values which are modelled, predicting the behavior of molecules of any size. Columns were assembled manually from alumina powders or monoliths. A synthesized asphaltene model molecule was used and its adsorption behavior was determined and compared to an asphaltene fraction recovered from crude oil. The asphaltene model molecule shows a dimerization behavior as well as extremely strong interactions with the alumina surface. Dynamic method was attempted in short alumina columns at saturation conditions and an apparent influence of the flow rate on the extent and mechanics of adsorption was observed.

Le but de ce travail est de fournir des informations qui peuvent aider à clarifier le mécanisme par lequel se produit la précipitation d’asphaltènes afin d'optimiser les modèles qui prédisent ce phénomène. Premièrement, la composition chimique des fractions aromatiques et saturées est analysée au regard à la stabilité des asphaltènes dans le brut. Plus précisément, la composition SARA de différents bruts vénézuéliens est corrélée au seuil de floculation des asphaltènes. Nos résultats mettent en évidence que les saturées, semblables aux résines, ont un effet significatif sur la stabilité des asphaltènes dans le brut. Deuxièmement, la teneur en Ni et V dans les asphaltènes et leurs sous fractions A1 et A2 a été déterminé par spectroscopie d'émission atomique avec plasma inductif. Les données expérimentales établissent que A1 a une concentration en V et en Ni supérieure à celle de A2, quelque soit la stabilité des bruts. Nous interprétons ces données comme l’illustration d’interactions fortes, telles que des liaisons covalentes entre pétroporphyrines et les molécules d’asphaltènes. Finalement, un dispositif haut pression est utilisé pour détecter visuellement la pression seuil de floculation d'un système modèle correspondant à une solution d’asphaltènes dans un mélange toluène/heptane/CO2. Les résultats confirment, pour ces systèmes gazés, que les augmentations de pression conduisent à une augmentation de la solubilité des asphaltènes et que pour la température il y a deux régimes opposés. Le premier correspond à une diminution de la stabilité du fluide avec l’augmentation de la température et le second, passé une valeur seuil proche de 80°C, conduit au phénomène inverse. / The purpose of this work is to provide information that can help in clarifying the mechanism by which asphaltene precipitation occurs in order to optimize the models that predict the phenomenon. The study is divided into three chapters. In the first one, the constituents of aromatic and saturate fractions of some Venezuelan crude oils were associated with the asphaltenes stability. SARA composition was correlated with asphaltene flocculation onsets and the results showed that saturates, similar to resins, have a significant effect on the flocculation process of the asphaltenes. In the second chapter, the concentration of Ni and V was determined in asphaltenes and their fractions A1 and A2. The samples were analyzed using inductively coupled plasma atomic emission spectrometry and elemental combustion analysis. Results show that A1 presents higher Ni and V concentrations than A2, in both stable and unstable crude oils. These results can be explained by strong interactions, such as covalent bonds between the petroporphyrins and the asphaltene molecules. In the final section, the asphaltenes phase envelopes were obteined for a system consisting of asphaltene in a mixture toluene/heptane/CO2. The temperature ranges 10-150 °C with varying concentrations of CO2 between 10 and 20 wt%. The experimental results confirm that increase of pressure leads to increase of solubility of the asphaltenes in the medium. Also, there are two temperature regimes having opposite trends. First, the solubility of the asphaltenes increases with the temperature, then after a threshold value of 80 °C, the stability is getting worse with the temperature

Le développement des outils analytiques pour l'analyse de la matière organique complexe en géochimie organique a connu de nombreuses avancées ces dernières années. Ce développement a permis de répondre à un grand nombre de questions quant à la composition de la matière organique. Cependant, beaucoup des points restent encore à élucider comme notamment la caractérisation des fractions de hauts poids moléculaires ainsi que le suivi de la réactivité de la matière organique. Ce travail de thèse a eu pour objectif (i) d'adapter les techniques de spectrométrie de masse déjà existantes pour l'analyse de la matière organique fossile (notamment par la sélection de la source d'ionisation atmosphérique la plus adaptée) mais également (ii) de développer un nouveau type de couplage entre la chromatographie d'exclusion stérique (SEC) et la spectrométrie de masse APPI-QTOF pour l'analyse des fractions peu polaires de hauts poids moléculaires. L'adaptation du l'APPI-QTOF a tout d'abord permis de mieux comprendre la réactivité de contaminants organiques polyaromatiques en présence de phases minérales. Le couplage SEC-APPI-QTOF a, quant à lui, permis d'améliorer les connaissances sur la structure des asphaltènes. Cependant, malgré la « simplification » rendue possible par la SEC, la très grande quantité d'informations reste difficile à interpréter et prend beaucoup de temps. Un modèle mathématique a donc été développé basé sur des analyses numériques et statistiques des spectres de masse, permettant de les comparer entre eux afin de distinguer l'origine des échantillons et de suivre l'impact de processus physico-chimiques (altérations naturelles - traitements de remédiation). / The development of analytical tools for organic geochemistry analysis has increased these past years. This development has allowed answering many questions about organic matter composition. However, many issues remain to be clarified including the characterization of high molecular weight fractions and monitoring the reactivity of organic matter. This thesis has focused on both (i) existing method improvements for fossil organic geochemistry analysis but also on (ii) developing a new type of coupling between the size exclusion chromatography (SEC) and the APPI-QTOF mass spectrometry for high molecular weight weakly polar fractions. Adjustments on APPI-QTOF mass spectrometry have allowed a better understanding of polyaromatic organic contaminant reactivity in presence of mineral matrices. The success of this coupling has allowed a better understanding of the structure of asphaltenes. However despite the "simplification" obtained by the SEC, the large amount of information remains difficult to interpret and time-consuming. A mathematical model has been developed based on numerical and statistical analysis of mass spectra, allowing direct comparison of mass spectra and being able to identify several types of information such as origins of samples, monitoring of physico-chemical processes and also the efficiency of soil recovery treatments as well as the identification of analytical protocols.

La thèse est une contribution expérimentale et théorique à la modélisation d'écoulements de bruts pétroliers produits par dépressurisation du réservoir. Il s'agit de produire l'huile en dessous du point de bulle et de profiter de l'expansion de la phase gaz pour déplacer l'huile (procédé appelé "Solution Gas Drive"). Jusqu'à présent les simulateurs de réservoir permettaient la simulation d'un tel mécanisme pour les huiles légères. Un problème se pose avec les huiles lourdes dont la forte viscosité et la physico-chimie intensifient l'état hors d'équilibre dû au mécanisme de changement de phase. Les simulateurs numériques classiques ne prennent pas en compte ce type de mécanisme hors équilibre, ni l'écoulement du gaz sous forme dispersée. Bien qu'un grand nombre de travaux aient déjà été réalisés essentiellement à l'échelle des pores, l'étude bibliographique montre qu'il est nécessaire d'avoir un modèle décrit par des équations continues (approche de Darcy). L'étude expérimentale des propriétés physico-chimiques (tension dynamique, élasticité de surface) des principaux constituants des bruts montre que les asphaltènes ont un effet tensioactif favorisant la formation de mousse au dessus d'une concentration seuil. Enfin, l'étude théorique des différents processus physiques permet d'établir un modèle d'écoulement continu, ne faisant intervenir que des grandeurs macroscopiques mesurables. La nucléation et le transfert de masse sont modélisés par une fonction volumique de transfert, la nucléation étant basée sur le modèle de bulles préexistantes. Deux phases gaz peuvent coexister : l'une continue à l'échelle du milieu, l'autre dispersée dans l'huile sous forme de bulles. Les simulations de plusieurs expériences, réalisées avec des roches et des fluides différents, montrent que le modèle permet d'interpréter et de prédire les productions de gaz et d'huile.

Made available in DSpace on 2016-12-23T14:41:52Z (GMT). No. of bitstreams: 1 Thieres Magaive Costa Pereira.pdf: 7173330 bytes, checksum: 5a2aee56b5048351ab0fc838877f8030 (MD5) Previous issue date: 2013-08-23 / O petróleo é uma mistura complexa, sendo uma das misturas mais desafiadoras para as análises químicas. Muitas técnicas são empregadas para a caracterização dos constituintes do óleo. Entretanto, quando combinamos o altíssimo poder de resolução e exatidão da espectrometria de massas, em especial a Ressonância Ciclotrônica de Íons com Transformada de Fourier, (FT-ICR MS) com fontes de ionização a pressão atmosférica, uma atribuição precisa de mais de 20 000 compostos orgânicos do petróleo pode ser obtida. Na indústria do petróleo existe um grande interesse na análise de ácidos naftênicos e asfaltenos devido a problemas como corrosão e formação de depósitos, que aumentam os custos de produção. Portanto este trabalho tem como objetivo a avaliação da termodegradação de ácidos naftênicos, além do emprego das fontes de ESI, APCI, APPI, LDI e MALDI para aquisição de novos dados relativos a caracterização de asfaltenos. Dois petróleos foram utilizados nos ensaios de termodegradação, o petróleo A com acidez de 2,38 mg KOH g-1 e o petróleo B com 4,79 mg KOH g-1 os quais foram tratados a 280, 300 e 350 ºC pelo período de 2, 4 e 6 horas. De uma maneira geral, as principais classes identificadas para ambas às amostras foram O2, N e NO2, respectivamente. Uma leve redução do NAT e da abundância relativa referente à classe O2 foram observado em função da temperatura e do tempo de envelhecimento (T = 280 → 300 oC e t = 2 → 6 h), sendo que a temperatura de tratamento térmico a 350 ºC demonstrou-se determinante na remoção de compostos da classe O2. O perfil químico de amostras de asfaltenos brasileiros foi avaliado utilizando-se cinco diferentes métodos de ionização em ambos os modos de ionização: positivo e negativo, depois, a distribuição de peso molecular, distribuição de classe, parcelas típicas de número de carbono contra DBE e diagramas van Krevelen foram obtidos e discutidos. Um comportamento atípico foi observado para a fonte de LDI e MALDI (±) FT-ICR MS. Um amplo perfil, de m/z 500-3000, apresentando espaçamento de 24 Da foi observado, e este corresponde a formas alotrópicas de fulereno, C60. Em geral, os asfaltenos apresentaram um elevada proporção de espécies heteroatómicas como: HC, HC [H], N, N [H], N2O, N2O [H], N2, N2 [H], O, O[H] para o modo (+) e N, N [H], NO, NO [H], NO, NO2[H], N2O, N2O[H] para o modo negativo. Nos diagramas de DBE contra o número de carbono, os asfaltenos mostraram para cada valor de DBE uma pequena amplitude de compostos com respeito à NC, proporcionando assim, imagens que formam uma linha de 45 ° entre os eixos CN e DBE. Isto indica que estes compostos não exibem grandes cadeias de alquílicas, sendo composta principalmente por anéis aromáticos. Em geral os diagramas de van Krevelen mostraram alta proporção de compostos com razão H/C ~0,7, corroborando com a existência de espécies altamente aromáticas / Petroleum is a complex mixture, being one of the most challenging mixtures for chemical analyzes. Many techniques are employed to characterize constituents of the oil. However , when we combine the highest resolving power and accuracy of mass spectrometry , especially Ion Cyclotron Resonance Fourier Transform ( FT - ICR MS ) with sources of atmospheric pressure ionization , an assignment need more than 20 000 organic compounds in the oil can be obtained. In the oil industry there is a great interest in the analysis of asphaltenes and naphthenic acids due to problems such as corrosion and deposit formation, which increases production costs. Therefore this study aims to evaluate the thermodegradation of naphthenic acids, besides the use of sources of ESI, APCI, APPI, MALDI and LDI for the acquisition of new data on the characterization of asphaltenes . Two test oils were used in thermodegradation of the oil with an acidity of 2.38 mg KOH g -1 and Oil B with 4.79 mg KOH g- 1 which were treated at 280 , 300 and 350 ° C for a period of 2 , 4 and 6 hours. Generally, the major classes identified for both samples O2, NO2, and C, respectively. A slight reduction of NAT and relative abundance refers to the class O2 were observed as a function of temperature and aging time (T = 280 → 300 ° C t = 2 → 6 h), and the heat treatment temperature at 350 ° C showed a determinant for the removal of class O2. The chemical asphaltenes Brazilian samples was evaluated using five different methods of ionization in both modes of ionization: positive and negative, then the molecular weight distribution, distribution class, typical plots versus carbon number and DBE van Krevelen diagrams were obtained and discussed. An unusual behavior was observed for the LDI and MALDI source ( ± ) FT - ICR MS . A comprehensive profile of m / z 500-3000, with spacing of 24 Da was observed, and this corresponds to allotropes of fullerene C60. In general, the asphaltenes had an heteroatómicas high proportion of species such as HC , HC [ H] , N, [ H] , N2O N2O [ H] N2, N2 [ M ] O O [ H] to mode (+) and N, [ H ] , NO [ H] , NO , NO2, [ H] , N2O N2O [ H ] for the negative mode . In the diagrams DBE against the carbon number , the asphaltenes shown for each value of DBE composed of a small amplitude with respect to NC, thus providing images that form a line of 45 ° between the axes CN and DBE. This indicates that these compounds do not exhibit large chain alkyl, composed mainly of aromatic rings. In general diagrams van Krevelen showed a high proportion of compounds ratio H / C ~ 0.7, confirming the existence of highly aromatic species

This work presents the use of analytical techniques, conventional and advanced for the chemical characterization of four samples of blends crude oils from the PETROBRAS station, Oiteirinhos II (Carmópolis-SE). These samples, which have different exploration characteristics, were identified as CEOL 1, CEOL 2, CEOL 3 and CEOL 4. After the collection in the field and subsequently separation of water residue through centrifugation at 2500 rpm, the blends were characterized by density, asphaltenes content, fractionation SARA (saturates, aromatics, resins and asphaltenes) and by the application of micropyrolisys off-line. The advanced characterization to elucidate the chemical relationship between the samples were made using the Thermogravimetry (TGA), Infrared Spectroscopy (IR), Spectroscopy in Ultraviolet (UV), Matrix Assisted Laser Desorption Ionization - Time of Flight - Mass Spectrometry (MALDI-TOF-MS), Gas Chromatography Mass Spectrometry (GC/MS), Gas Chromatography with Flame Ionization Detector (GC-FID) and Comprehensive Two-Dimensional Gas Chromatography (GC x GC). The blends CEOL 3 presented the highest density (0.9737 g mL-1), confirming the results of MALDI-TOF-MS, that shows predominantly high molecular mass compounds in the composition. The SARA fractionation indicates the Saturated fraction as the largest fraction in all oils (> 50%). The analysis of TGA explained similar bands of mass loss in all blends and their asphaltenes. The characterization by IR showed bands related to the hydrocarbon composition and the UV showed the presence of mono, di and tri aromatics structures in the blends as well in their respective asphaltenes. The chromatographic analysis (GC/MS, GC-FID and GC x GC) showed that all blends have a paraffinic profile, with the predominance of n-alkanes of low molecular weight (n-C10 to n-C40) and characteristics of oxide depositional environment (Pr/Ph>1) and lacustrine origin (CPI>1). The analysis by GC/MS showed that the distribution area relating to the free n-alkanes in the CEOL 3 blends is approximately 30% lower than the other samples, and that after the micropyrolysis process these areas become approximately the same. For biomarkers, GC/MS was possible to identify the majority presence of tri- and tetracyclic terpanes (m/z 191) and regular steranes (m/z 217) as the major constituents of the blends, pointing also to the release of occluded biomarkers in asphaltenic structures after the micropyrolysis process. The identification and subsequent correlation between biomarkers indicated that the blends crude oils studied have partial biodegradation characteristics, with a blend of mature and immature oils from terrigenous and/or algal organic matter. / Este trabalho apresenta o emprego de diversas técnicas analíticas, convencionais e avançadas, para a caracterização química de quatro blendas de óleos brutos provenientes da estação da Petrobras de Oiteirinhos II (Carmópolis-SE). Estas amostras, que apresentam diferentes características de exploração, foram identificadas como CEOL 1, CEOL 2, CEOL 3 e CEOL 4. Após a coleta em campo e posterior separação dos resíduos de água por centrifugação a 2500 rpm, as blendas foram caracterizados a partir da determinação da densidade, do teor de asfaltenos, fracionamento SARA (Saturados, Aromáticos, Resinas e Asfaltenos) e aplicação da micropirólise off-line. A caracterização avançada, aplicada para elucidar a relação química entre as amostras, foram realizadas utilizando as técnicas de Termogravimetria (TGA), Espectroscopia no Infravermelho (IV), Espectroscopia no Ultravioleta (UV), Espectrometria de Massa por Tempo de voo com Desorção-Ionização a Laser Assistida por Matriz (MALDI-TOF-MS), Cromatografia Gasosa acoplada a Espectrometria de Massas (CG/EM), Cromatografia Gasosa com Detector de Ionização de Chama (CG-DIC) e Cromatografia Gasosa Bidimensional Abrangente (CG x CG). A blenda CEOL 3 apresentou a maior densidade (0,9737 g mL-1) corroborando com os resultados de MALDI-TOF-MS, mostrando a predominância de compostos de alta massa molecular em sua composição. O fracionamento SARA aponta a fração de Saturados como a maior fração em todos as blendas (>50%). A análise de TGA expôs faixas de perdas de massas semelhantes em todas as amostras e seus asfaltenos. A caracterização por IV apresentou estiramentos referentes à composição de hidrocarbonetos e o UV a presença de estruturas mono, di e tri aromáticos tanto nas blendas como em seus respectivos asfaltenos. As análises cromatográficas (CG/EM, CG-DIC e CG x CG) mostraram que todos as blendas possuem um perfil parafínico, com predominância de n-alcanos de baixo peso molecular (n-C10 a n-C40) com características de ambiente deposicional óxido (Pr/Ft>1) de origem lacustre (CPI>1). A análise por CG/EM mostrou ainda que a distribuição em área referente a n-alcanos livres presentes na blenda CEOL 3 é cerca de 30% menor do que as outras amostras, e que após o processo de micropirólise essas áreas passam a ser aproximadamente iguais. Para biomarcadores, por CG/EM foi possível identificar a presença majoritária de terpanos tri e tetracíclicos (m/z 191) e esteranos regulares (m/z 217), como constituintes majoritários das blendas em estudo, apontando ainda, a liberação de biomarcadores ocluídos nas estruturas asfaltênicas após o processo de micropirólise. A identificação e posterior correlação entre os biomarcadores indicaram que as blendas de óleos brutos possuem características de biodegradação parcial, com uma mistura de muito e pouco evoluídos termicamente, provenientes de matéria orgânicas terrígenas e/ou algas.