Asphaltenic crude oil is a complex fluid containing various components with different chemical properties. When it comes in contact with water, its polar components adsorb at the oil/water interface, reducing the interfacial tension and eventually developing viscoelastic films. The interfacial films impact emulsion stability and adhere to the oil-bearing reservoirs rocks, altering their wettability and thus hindering oil mobilization. Here, we investigate the formation of crude oil/water interfacial films. We measure both the time-dependent shear and extensional interfacial rheology moduli, and we relate it to the chemical composition of the films, highlighting the role of polar aromatic molecules in film formation. Varying chemical composition of the aqueous phase, we show that the properties of the interfacial films depend not only on the concentration of ionic species in water but also on their chemical nature. In particular, we highlight the role of sulfate salt in promoting interfacial viscoelasticity and in altering the composition of fully developed films. To study the rock/fluid interaction, we fabricate mixed-wet capillaries with angular cross-sections inspired by the naturally occurring primary drainage of pore-filling brine by invading crude oil. After employing our novel coating procedure, we experimentally investigate water invasion in mixed-wet capillaries and compare it with predictions of dynamic and quasi-static (Mayer-Stowe-Princen (MSP)) meniscus-invasion models. None of the dynamic models built for uniformly-wet pores can fully describe our experimental data in mixed-wet capillaries. However, the experimental results agree with predictions of MSP theory. To our knowledge, this is the first direct experimental validation of MSP theory under mixed-wet conditions. We confirm the possibility of spontaneous piston-type imbibition with high ($> 90^{\circ}$) advancing contact angles into mixed-wet pores, given that the contact angle is lowered below a critical value that is a function of pore geometry and residual water saturation. In oil reservoirs, injection of specific brines would be required to change the contact angle to values below the imbibition threshold. Finally, we extend our study and introduce a powerful 3D high-speed laser imaging of dynamic fluid flow in angular capillaries and investigate its capability to capture non-equilibrium shapes of fluid interfaces.

No description available.

Ce travail porte sur la compréhension du phénomène d'instabilité qui se produit dans le procédé d'hydroconversion des résidus sous vide (RSV). Au delà de 60% de conversion du RSV, l'instabilité se manifeste par un dépôt solide d'hydrocarbures lourds dans les unités industrielles de conversion des résidus, ce qui empêche d'atteindre un niveau de conversion du RSV plus élevé. L'objectif de cette thèse consiste à mieux comprendre l'influence du catalyseur utilisé dans le procédé d'hydroconversion sur l'apparition du phénomène d'instabilité. Des catalyseurs dopés au fluor et sodium ont été préparés par ajout de dopants à la surface d'un catalyseur NiMo/Al2O3 de référence. Après leur caractérisation, les catalyseurs ont été testés sur charge réelle RSV en réacteur autoclave. Les tests catalytiques ont été réalisés à haute température dans les conditions industrielles (430°C) et à plus basse température (390°C), afin de favoriser les réactions catalytiques par rapport aux réactions thermiques. Les tests catalytiques réalisés à 390 et 430°C montrent une teneur en sédiments deux fois moins importante avec le catalyseur F-NiMo, ce qui est expliqué par une amélioration de la conversion des asphaltènes. Celle-ci est expliquée par l'amélioration des réactions d'hydrogénation et de l'acidité, et par une meilleure résistance au cokage à 390°C. L'effet de la température sur la stabilité a également été étudié. Les résultats démontrent que la teneur en sédiments des effluents est deux fois supérieure pour les tests réalisés à 430°C par rapport aux tests réalisés à 390°C. Cet accroissement de l'instabilité est attribué à un caractère plus aromatique et condensé des molécules qui précipitent (asphaltènes), qui ont en conséquence une tendance accrue à s'agréger, et par la désalkylation des molécules qui stabilisent (résines). / This work focuses on the instability phenomena occurring during vacuum residue hydroconversion. At high level of residue conversion, carbonaceous sediments (sediments) are formed and have detrimental effects on the industrial units during the hydroprocessing operations. The aim of this work is investigate the influence of the catalyst used inhydroconversion process on the sediments formation. Modified catalysts have been prepared by sodium and fluorine deposition on a NiMo/Al2O3 reference catalyst. After having been characterized, the catalysts have been tested in a perfectly stirred batch reactor. Catalytic tests have been performed at high temperature (430°C) in industrial conditions and at lower temperature (390°C) in order to favor catalytic reactions rather thermic reactions. The catalytic tests at the two temperatures show that the amount of sediments is two times lower with F-NiMo catalyst. This is explained by the improvement of asphaltenes conversion due to an increase of catalyst acidity and hydrogenation reactions. At 390°C, coking with F-NiMo catalyst is reduced so that porous volume is higher. The temperature effect on effluents stability has also been studied. Results show that the amount of sediments is twice lower at 390°C for a same catalyst. The increase of instability at 430°C is attributed to more condensed and aromatic asphaltenes and resins dealkylation which increase selfaggregation tendency of asphaltenes.

Le travail de thèse effectué a porté sur l'applicabilité et la compréhension d’un système catalytique bifonctionnel acide et hydro/déshydrogénante sur l'hydroconversion et l’hydrotraitement d'un Résidu Sous Vide. En amont de ce travail, il est rappelé qu'au-delà de 400 °C (régime thermique), la forte conversion du RSV conduit à des phénomènes indésirables de précipitation et d’instabilité, liés à l'augmentation de la polarité des asphaltènes. L’objectif de la thèse était donc de favoriser les réactions de craquage et d’hydrogénolyse à plus faible température (370 °C), grâce à la fonction acide du catalyseur, et d’étudier la nature des structures asphalteniques résultantes. Des catalyseurs modèles, de formulation NiMo, supportés sur des aluminosilicates préparés par greffage de silicium à la surface d'une alumine, ont été utilisés. Ces catalyseurs développent une acidité faible, apportée par le support. Cette acidité a été quantifiée et caractérisée sur les aluminosilicates synthétisés, comme sur le catalyseur fini. La phase hydrogénante, ainsi que la texture des solides, ont aussi été caractérisées en détail. Des catalyseurs, dont les trois paramètres précités ont pu être modifiés indépendamment, ont ainsi été obtenus.Les performances catalytiques ont ensuite été évaluées en hydroconversion d’un RSV Safaniya, en réacteur batch. Les résultats révèlent un impact limité de l’acidité sur les grandeurs globales du test. Les modifications successives des phases hydrogénantes, et l’apport de macroporosité, n’ont pas permis d’améliorer cet impact par la suite. L’analyse détaillée conduite sur les asphaltènes après conversion a mis en relief des modifications de structures moléculaires nettes. Celles-ci ont pu être illustrées via une méthode de reconstitution moléculaire. L'introduction d’acidité a ainsi favorisé les réactions de craquage des chaines aliphatiques ou naphténique des asphaltènes, sans pour autant augmenter l'aromaticité de la molécule. / The aim of this work was to study and investigated bifunctional sulfided and acidic catalyst for the hydroconversion and the hydrotraitment of a Vacuum Residue. Upstream works have already demonstrate that high level of residue conversion, at high temperatures ( > 400 °C), leads to create carbonaceous sediments (sediments), link to asphaltenes polarity and aromaticity. Thus, our objective was to promote hydrocracking reactions at lower temperatures (370 °C), by enhancing acidity of conventional sulfided catalysts. Structures of consequent asphaltenes, modified by acidity, were also studied. Model NiMo catalysts were obtained by grafting silica on the surface of alumina carriers. Characterization on carriers and sulfided catalysts reveal the improvement of a weak acidity. Hydrogenating phase and textures properties have also been characterized in this work. In the end, we have obtained catalysts with same texture, same hydrogenating power, but also different level of acidity strength. Catalytic performances were evaluated in batch reactor, for the hydroconversion reaction of a Safaniya Vacuum Residue. Results reveal no changes in hydroconversion or hydrotraitment reactions parameters with acidity. No improvement was observed by enhancing the hydrogenating power or by adding macroporosity on textures with acidic sulfided catalysts. Nonetheless, combinated asphaltenes analysis and molecular reconstructions methods have shown that acidity can modify asphaltènes structures and properties. Acidity enhances cracking reactions of aliphatic chains and naphthenic units, without improving the aromaticity of the molecules.

A decomposição térmica dos asfaltenos é a principal responsável pela formação de coque no processamento de petróleos. O fenômeno não é claramente entendido, pelas dificuldades ainda existentes na caracterização de tais componentes pesados do óleo. Este trabalho apresenta informações sobre os produtos da decomposição térmica dos asfaltenos isolados de um petróleo da Bacia de Campos, maior bacia produtora de petróleo no Brasil. A abordagem envolveu: 1) estudos da decomposição térmica dos asfaltenos por termogravimetria (TG) em condições controladas; 2) caracterização dos produtos voláteis dessa decomposição por termogravimetria acoplada à cromatografia gasosa e espectrometria de massas (TG/DTA-CG-EM) e 3) caracterização dos produtos sólidos obtidos em diferentes temperaturas pela reação de oxidação catalisada pelo íon rutênio (RICO) que converte seletivamente alquil aromáticos em ácidos alcanóicos. A decomposição térmica dos asfaltenos foi estudada por termogravimetria. Os asfaltenos se decompõem drasticamente entre 320 e 650ºC produzindo 54% de produtos voláteis e 46% de coque. O material volátil liberado dos asfaltenos a 700°C foi analisado por TG/DTA acoplado a CG-EM. Foi identificada uma série de alcanos contendo de C3 a C10. Esse resultado causou grande surpresa, pois na análise da pirólise de diferentes asfaltenos são observados alcanos com maior número de átomos de carbono. Outro experimento foi realizado, agora em duas etapas: coleta do material volátil e injeção desta no sistema GC-EM. Desta vez foi possível identificar a série homóloga de alcanos de C11 até C33. Para o maior conhecimento da decomposição térmica dos asfaltenos, foram obtidos, em escala preparativa, produtos sólidos de decomposição térmica destes nas temperaturas de 320, 380, 400, 440, 480, 550 e 580°C. As análises realizadas nesses produtos - elementar, espectroscopia na região do infravermelho, ressonância magnética nuclear de carbono 13 no estado sólido - indicaram que quanto maior a temperatura de obtenção dos produtos sólidos, menor é o conteúdo de hidrogênio e carbono alifático. Os asfaltenos e os seus produtos de pirólise foram submetidos a reação de oxidação seletiva. Os ácidos gerados foram metilados para análise por CG-EM. Nos asfaltenos e nos produtos obtidos a 320, 380, 400 e 440°C foram identificados ésteres metílicos lineares que indicaram a presença de hidrocarbonetos alifáticos contendo de 5 a 25 átomos de carbono, ésteres metílicos de ácidos dicarboxílicos que indicaram a presença de pontes alquilicas entre os grupamentos aromáticos contendo de 3 a 15 átomos de carbono e alguns ésteres metílicos de ácidos benzenodicarboxílicos. Comparando-se o teor total desses ésteres metílicos presentes em cada produto de reação, foi verificado que a concentração dos ésteres metílicos lineares diminui lentamente a 320, 380, 400ºC, e drasticamente a partir de 400ºC. O mesmo ocorrendo com os ésteres dos ácidos dicarboxílicos e benzeno dicarboxílicos, em menor concentração que os ésteres metílicos lineares. / The thermal decomposition of asphaltenes is mainly responsible for the formation of coke in petroleum processing. The phenomena involved are not clearly understood, due to the difficulties in characterizing such heavy components. This research reports the application of thermal analysis techniques to study the thermal behavior of asphaltenes from Brazilian oil (Campos Basin). The approach involves: 1) studies of the thermal decomposition of asphaltenes under controlled conditions by thermogravimetry (TG); 2) characterization of volatile fractions by thermogravimetry and differential thermal analysis coupled with gas chromatography and mass spectrometry (TG/DT-GC-MS); 3) solid products from the thermal decomposition of asfaltenes where subjected to ruthenium (VIII) ion catalyzed oxidation reaction (RICO) that converts selectively and efficiently, alkyl aromatics to alkanoic acids. Thermogravimetry was used to study the asphaltenes thermal decomposition. The asphaltenes drastically decomposes from 320 to 650ºC to produce 54% of volatile products and 46% of coke. The volatile products of the asphaltenes at 700ºC were done by TG/DTA coupled to GC-MS. The volatile material was identified as a series of straight chain of normal alkyl ranging from C3 to C10. This result indicated limitations of the apparatus employed n-alkyl chains longer than these were expected. However, it worked well for lighter components. Another experiment, in which gaseous products from pyrolysis procedure were recovered by bubbling in CH2Cl2, accounted for the heavier components. The solution obtained this time can be analyzed by syringe injection in a CG-MS. The majority of the volatile material is constituted of straight chain alkanes ranging from C13 to C33. Knowing more about the thermal decomposition conversion of asphaltenes, the solid pyrolysis products of them were obtained in larger quantities at 320, 380, 400, 440, 480, 550 e 580ºC. They were characterized by elemental analysis and solid state 13C nuclear magnetic resonance. It was observed that at higher pyrolysis temperatures, lower the hydrogen and aliphatic carbon contents were obtained for the solid products. So, to improve knowledge on these systems, asphaltenes and their solid products from thermal decomposition were oxidized with ruthenium (VIII) ion. The acids formed were mixed with excess of ethereal diazomethane and submitted to GC-MS in order to identify the correspondent methyl esters. It was observed three homologous series: methyl esters of linear carboxylic acids ranging from C6 to C27, corresponding to chain alkyl length from C5 to C26 substituent on aromatic carbon; small amounts of dimethyl esters were also present in a homologous series, ranging from C5 to C17 indicating bridge polymethylenes between aromatics from C3 to C15 and benzene dicarboxilic acids from C10 to C12. The total content of methyl ester of each reaction products was compared. It was observed that the linear esters content decreased slowly at a 320, 380, 400°C and drastically up to 400ºC. The same occurred with the dimethyl aliphatic esters and dimethyl benzyl esters.

Les activités de production des hydrocarbures sont fortement dépendantes du comportement thermodynamique des fluides produits. La précipitation d'asphaltènes, entités qui constituent les principaux composants de la fraction la plus lourde et la plus polaire du pétrole, peut conduire à la formation d'un dépôt solide. Nous avons mis en oeuvre et évalué plusieurs méthodologies expérimentales appliquées à la détermination des diagrammes de phase de fluides asphalténiques dans les conditions de haute pression et haute température. Nous avons mis au point une technique utilisant un résonateur à cristal de quartz (RCQ), capable d'identifier les conditions thermodynamiques de changement de phase, sous haute pression, dans des fluides avec une teneur faible en asphaltènes. Les données obtenues avec le RCQ ont été validées par filtration isobare et par microscopie haute pression (MHP). Les effets sur la floculation de l'ajout de gaz, des conditions thermodynamiques imposées au fluide et de la vitesse de dépressurisation ont été étudiés expérimentalement à l'aide des trois techniques susmentionnées. Les résultats obtenus par MHP sur différentes live oils suggèrent l'existence de quatre types de comportement de fluides lors d'une dépressurisation isotherme, avec dans certains cas l'apparition d'un équilibre liquide-liquide dans des conditions de températures et de pressions élevées. Enfin, nous avons établi, avec la caractérisation physico-chimique des asphaltènes obtenus (nC7) à partir des huiles mortes, que la différence d'aromaticité entre cette fraction et celle de son huile d'origine, pouvait être un indicateur utile afin d'anticiper un possible phénomène de précipitation. / Oil production activities are strongly dependent on the phase behavior of produced fluids. The flocculation of asphaltenes, the major components of the heaviest and most polar fraction of crude oil, can lead to solids formation in several steps of oil production. In this thesis, we evaluated several methodologies applied for asphaltenes phase behavior assessment under high-pressure conditions. Among the methodologies, we had developed an apparatus based on the quartz crystal resonator (QCR), able to identify thermodynamic conditions of phase changes in pressurized fluids containing low asphaltenes content. The data obtained with the QCR were validated by isobaric filtration and high pressure microscopy (HPM) tests. Applying the three aforementioned techniques, the influence of gas addition, kinetic factors, thermodynamic conditions and the influence of depressurization rate on the onset of asphaltenes flocculation were studied. Live oils were evaluated by the HPM technique. The results from HPM suggest the existence of four phase behavior patterns for isothermal depressurization experiments, highlighting the existence of a liquid-liquid equilibrium at elevated temperatures and pressures. The physico-chemical characterization of asphaltenes extracted with n-heptane from dead oil suggests that the difference of aromaticity between this fraction and its referred oils could be a parameter to indicate possible problems of asphaltenes flocculation during the oil production.

Ce travail porte sur la compréhension des paramètres du catalyseur (texture, effet de support) permettant d’améliorer la réaction de conversion de liquéfiats de charbon. En effet, le catalyseur actuellement employé est un catalyseur du type conversion de résidu sous vide de brut de pétrole. Or ces matrices sont différentes en termes de poids moléculaires et de teneur en hétéroélément (O et N). Pour atteindre l’objectif de cette thèse, une caractérisation poussée du liquéfiat a été menée à l’aide de diverses techniques (GCxGC, HR-13C-RMN, FT-ICR/MS,…). Cette analyse détaillée du liquéfiat a mis avant son caractère fortement aromatique. Les extractions aux solvants ont permis d’isoler les asphaltènes et préasphaltènes de ce liquéfiat. Leurs analyses montrent que ces familles de composés sont de plus faible masse moléculaire que les asphaltènes des résidus pétroliers, et que leur teneur en hétéroélément est plus importante. Les tests catalytiques de conversion de liquéfiat ont été réalisés à 420°C 15MPa d’H2 pendant 8h. Ils montrent que l’augmentation de la taille de pore (mésoporeux) ainsi que l’apport d’une bimodalité du support (méso+macroporosité) permettent d’augmenter le transfert de matière et donc d’augmenter le coefficient de diffusion ce qui a pour conséquence d’améliorer le rendement en produits plus légers. Concernant la nature du support, de part sa capacité à favoriser les réactions d’HDO le TiO2 (vs Al2O3) permet de limiter la compétition entre les composés oxygénés et les composés hydrocarbonés. En conclusion, ce travail montre que plusieurs paramètres sont susceptibles d’améliorer les performances des catalyseurs de conversion des liquéfiats de charbon / This work focuses on the comprehension of the catalyst parameters (textural properties and support effect) that increase the yield of the coal liquid upgrading. The current in use catalyst was design for the petroleum vacuum residue conversion. However, these two feeds present different characteristics such as the average molecular weight and the amount of heteroelement (especially O and N). To reach our goal, an in-depth characterization of the coal liquid was carried out using techniques such as GCxGC, HR-13C-NMR, FT-ICR/MS. This coal liquid analysis pointed out its strong aromatic character. Extractive solvent experiments isolated the asphaltenes and preasphaltenes and their analysis show that they have a smaller average molecular weight distribution than that of petroleum asphaltenes. Catalytic experiments were carried out at 420°C, 15MPa of H2 for 8h. It shows that the increasing mesoporous size and the bimodality (meso + macroporosity) enable to raise the mass transfer thus the diffusion coefficient which enhances the yield in lighter products. The capability of TiO2 (as a support vs Al2O3) to promote HDO reaction, enables to restrain the competition between oxygen containing compounds and pure hydrocarbons. To conclude, this work demonstrates that several parameters can enhance catalyst’s performance for the coal liquid upgrading

This thesis explored how asphaltene and naphthenic amphiphile species influence the formation (morphology and size) and stability of heavy crude oil (bitumen) emulsions. It was experimentally shown that asphaltenes produce water-in-oil emulsions. Naphthenic amphiphiles on the other hand flip the emulsion morphology to oil-in-water. It was further demonstrated that the size and stability of these emulsions is influenced by physicochemical effects such as the pH, solvent-bitumen-water ratios, solvent aromaticity, and temperature. In view of these findings, the hydrophilic-lipophilic deviation (HLD) and net-average curvature (NAC) models were looked at as potential means for predicting the formation and stability of emulsions. Owing to the complexity of bitumen emulsions, however, the HLD and NAC models were instead tested against well-defined sodium dihexyl sulfosuccinate-toluene-water emulsions. The morphologies of these emulsions were predicted as a function of the formulation salinity whereas corresponding droplet sizes were predicted as a function of the continuous phase density and interfacial tension (γow). Emulsion stability trends were in turn predicted using a collision-coalescence-separation assumption. From this assumption, emulsion stability was expressed as a function of the emulsion droplet collision frequency and activation energy. The key parameters of the highly scrutinized activation energy term included the γow, interfacial rigidity, and critical film thickness. In applying the same modeling approach to the stability of other emulsions already published in the literature, it was found that the rigidity of adsorbed multilayer/liquid crystal films cannot yet be fully accounted for. This shortcoming was the reason for which only minimum stability times were reported for bitumen emulsions.

This thesis explored how asphaltene and naphthenic amphiphile species influence the formation (morphology and size) and stability of heavy crude oil (bitumen) emulsions. It was experimentally shown that asphaltenes produce water-in-oil emulsions. Naphthenic amphiphiles on the other hand flip the emulsion morphology to oil-in-water. It was further demonstrated that the size and stability of these emulsions is influenced by physicochemical effects such as the pH, solvent-bitumen-water ratios, solvent aromaticity, and temperature. In view of these findings, the hydrophilic-lipophilic deviation (HLD) and net-average curvature (NAC) models were looked at as potential means for predicting the formation and stability of emulsions. Owing to the complexity of bitumen emulsions, however, the HLD and NAC models were instead tested against well-defined sodium dihexyl sulfosuccinate-toluene-water emulsions. The morphologies of these emulsions were predicted as a function of the formulation salinity whereas corresponding droplet sizes were predicted as a function of the continuous phase density and interfacial tension (γow). Emulsion stability trends were in turn predicted using a collision-coalescence-separation assumption. From this assumption, emulsion stability was expressed as a function of the emulsion droplet collision frequency and activation energy. The key parameters of the highly scrutinized activation energy term included the γow, interfacial rigidity, and critical film thickness. In applying the same modeling approach to the stability of other emulsions already published in the literature, it was found that the rigidity of adsorbed multilayer/liquid crystal films cannot yet be fully accounted for. This shortcoming was the reason for which only minimum stability times were reported for bitumen emulsions.

A decomposição térmica dos asfaltenos é a principal responsável pela formação de coque no processamento de petróleos. O fenômeno não é claramente entendido, pelas dificuldades ainda existentes na caracterização de tais componentes pesados do óleo. Este trabalho apresenta informações sobre os produtos da decomposição térmica dos asfaltenos isolados de um petróleo da Bacia de Campos, maior bacia produtora de petróleo no Brasil. A abordagem envolveu: 1) estudos da decomposição térmica dos asfaltenos por termogravimetria (TG) em condições controladas; 2) caracterização dos produtos voláteis dessa decomposição por termogravimetria acoplada à cromatografia gasosa e espectrometria de massas (TG/DTA-CG-EM) e 3) caracterização dos produtos sólidos obtidos em diferentes temperaturas pela reação de oxidação catalisada pelo íon rutênio (RICO) que converte seletivamente alquil aromáticos em ácidos alcanóicos. A decomposição térmica dos asfaltenos foi estudada por termogravimetria. Os asfaltenos se decompõem drasticamente entre 320 e 650ºC produzindo 54% de produtos voláteis e 46% de coque. O material volátil liberado dos asfaltenos a 700°C foi analisado por TG/DTA acoplado a CG-EM. Foi identificada uma série de alcanos contendo de C3 a C10. Esse resultado causou grande surpresa, pois na análise da pirólise de diferentes asfaltenos são observados alcanos com maior número de átomos de carbono. Outro experimento foi realizado, agora em duas etapas: coleta do material volátil e injeção desta no sistema GC-EM. Desta vez foi possível identificar a série homóloga de alcanos de C11 até C33. Para o maior conhecimento da decomposição térmica dos asfaltenos, foram obtidos, em escala preparativa, produtos sólidos de decomposição térmica destes nas temperaturas de 320, 380, 400, 440, 480, 550 e 580°C. As análises realizadas nesses produtos - elementar, espectroscopia na região do infravermelho, ressonância magnética nuclear de carbono 13 no estado sólido - indicaram que quanto maior a temperatura de obtenção dos produtos sólidos, menor é o conteúdo de hidrogênio e carbono alifático. Os asfaltenos e os seus produtos de pirólise foram submetidos a reação de oxidação seletiva. Os ácidos gerados foram metilados para análise por CG-EM. Nos asfaltenos e nos produtos obtidos a 320, 380, 400 e 440°C foram identificados ésteres metílicos lineares que indicaram a presença de hidrocarbonetos alifáticos contendo de 5 a 25 átomos de carbono, ésteres metílicos de ácidos dicarboxílicos que indicaram a presença de pontes alquilicas entre os grupamentos aromáticos contendo de 3 a 15 átomos de carbono e alguns ésteres metílicos de ácidos benzenodicarboxílicos. Comparando-se o teor total desses ésteres metílicos presentes em cada produto de reação, foi verificado que a concentração dos ésteres metílicos lineares diminui lentamente a 320, 380, 400ºC, e drasticamente a partir de 400ºC. O mesmo ocorrendo com os ésteres dos ácidos dicarboxílicos e benzeno dicarboxílicos, em menor concentração que os ésteres metílicos lineares. / The thermal decomposition of asphaltenes is mainly responsible for the formation of coke in petroleum processing. The phenomena involved are not clearly understood, due to the difficulties in characterizing such heavy components. This research reports the application of thermal analysis techniques to study the thermal behavior of asphaltenes from Brazilian oil (Campos Basin). The approach involves: 1) studies of the thermal decomposition of asphaltenes under controlled conditions by thermogravimetry (TG); 2) characterization of volatile fractions by thermogravimetry and differential thermal analysis coupled with gas chromatography and mass spectrometry (TG/DT-GC-MS); 3) solid products from the thermal decomposition of asfaltenes where subjected to ruthenium (VIII) ion catalyzed oxidation reaction (RICO) that converts selectively and efficiently, alkyl aromatics to alkanoic acids. Thermogravimetry was used to study the asphaltenes thermal decomposition. The asphaltenes drastically decomposes from 320 to 650ºC to produce 54% of volatile products and 46% of coke. The volatile products of the asphaltenes at 700ºC were done by TG/DTA coupled to GC-MS. The volatile material was identified as a series of straight chain of normal alkyl ranging from C3 to C10. This result indicated limitations of the apparatus employed n-alkyl chains longer than these were expected. However, it worked well for lighter components. Another experiment, in which gaseous products from pyrolysis procedure were recovered by bubbling in CH2Cl2, accounted for the heavier components. The solution obtained this time can be analyzed by syringe injection in a CG-MS. The majority of the volatile material is constituted of straight chain alkanes ranging from C13 to C33. Knowing more about the thermal decomposition conversion of asphaltenes, the solid pyrolysis products of them were obtained in larger quantities at 320, 380, 400, 440, 480, 550 e 580ºC. They were characterized by elemental analysis and solid state 13C nuclear magnetic resonance. It was observed that at higher pyrolysis temperatures, lower the hydrogen and aliphatic carbon contents were obtained for the solid products. So, to improve knowledge on these systems, asphaltenes and their solid products from thermal decomposition were oxidized with ruthenium (VIII) ion. The acids formed were mixed with excess of ethereal diazomethane and submitted to GC-MS in order to identify the correspondent methyl esters. It was observed three homologous series: methyl esters of linear carboxylic acids ranging from C6 to C27, corresponding to chain alkyl length from C5 to C26 substituent on aromatic carbon; small amounts of dimethyl esters were also present in a homologous series, ranging from C5 to C17 indicating bridge polymethylenes between aromatics from C3 to C15 and benzene dicarboxilic acids from C10 to C12. The total content of methyl ester of each reaction products was compared. It was observed that the linear esters content decreased slowly at a 320, 380, 400°C and drastically up to 400ºC. The same occurred with the dimethyl aliphatic esters and dimethyl benzyl esters.