Made available in DSpace on 2016-08-19T12:56:30Z (GMT). No. of bitstreams: 1 Lyzette Goncalves de Moura.pdf: 21773601 bytes, checksum: b72a0b464ec701d6ed3a2f71444b3e58 (MD5) Previous issue date: 2007-09-18 / In this work, among the main models developed and applied for pure crude oils stability prediction and for the compatibility between crude oils/fractions; the Toluene Equivalence (TE) performance, the Heithaus parameter (Parameter P) of the crude compatibility model, the Crude Compatibility Model, the Colloidal Instability Index (CII) and the one of the Bureau of Mines Correlation Index - Toluene Equivalence (BMCI-TE) were valuated. For their implementation, except the CII, is necessary the determination of the asphaltenes precipitation onset, obtained by adding n-heptane to the pure crude until the occurrence of precipitation. It was not possible to get that measurement in part of the estimated crude oils; due to that fact we were unable to analyze the model efficiency for these samples stability/compatibility. The CII results refer to the total number of samples, but the rest refer only to those presenting precipitation when added with n-heptane end their mixtures. In the stability evaluation, the TE furnished only a stability order related classification, while with the P parameter it was attained 89% of prediction target hitting; with the Crude Compatibility Model together with the BMCI-TE, the prediction target hitting was 95%, whereas with the CII the prediction target hitting was 3%. With respect to mixture compatibility the TE, P parameter and the Crude Compatibility Model revealed 83% of the prediction target hitting, and in the BMCI-TE the prediction target hitting 50%. The CII presented 39% prediction target hitting for binary mixtures and for ternary mixtures, which could only be evaluated according to this parameter, the prediction target hitting was 80%. Except the CII, the parameters presented as main limitation the impossibility of its application to systems involving samples that do not precipitate when added with n-heptane; but the CII, which does not have this relation, revealed the worst performance. Classical models of stability and compatibility of crude oils proved to be little efficient for analyzing systems that include the Brazilian crude oils considered in this study, This strongly suggests the necessity of deeper studies to enhance the already existing models and indices or to develop new ones. / Dentre os principais modelos desenvolvidos e aplicados à predição da estabilidade de petróleos puros e da compatibilidade entre petróleos/frações, neste trabalho avaliou-se o desempenho do Tolueno Equivalente (TE), do Parâmetro de Heithaus (Parâmetro P), do Modelo de Compatibilidade do Petróleo, do Índice de Instabilidade Coloidal (IIC) e do Índice de Correlação do Bureau of Mines - Tolueno Equivalente (BMCI-TE). Para a implementação dos mesmos, com exceção do IIC, é necessária a determinação do início de precipitação dos asfaltenos, obtido adicionando-se n-heptano ao petróleo puro até que ocorra a precipitação. Em parte dos petróleos avaliados não foi possível obter essa medida e, devido a isso, não se conseguiu analisar a eficiência dos modelos na predição da estabilidade/compatibilidade destas amostras. Os resultados do IIC são relativos ao total de amostras, mas os demais se referem apenas àquelas que apresentam precipitação na presença de n-heptano e às misturas entre elas. Na avaliação da estabilidade, o TE proporcionou somente uma classificação quanto à ordem de estabilidade; já com o Parâmetro P, obteve-se 89% de acerto na predição; com Modelo de Compatibilidade do Petróleo e com o BMCI-TE, o acerto foi de 95%, enquanto que com o IIC, foi de 3%. Em relação à compatibilidade das misturas, o TE, o Parâmetro P e o Modelo de Compatibilidade do Petróleo revelaram um percentual de acerto de 83% e no BMCI-TE o acerto foi de 50%. O IIC apresentou um acerto de 39% para as misturas binárias; e para as ternárias, que só puderam ser avaliadas segundo este parâmetro, o acerto foi de 80%. Excetuando-se o IIC, os parâmetros apresentam como principal limitação, a impossibilidade de aplicação a sistemas envolvendo amostras que não apresentam precipitação mediante o acréscimo de n-heptano; porém o IIC, que não possui esta restrição, revelou o pior desempenho. Os modelos clássicos de predição de estabilidade e compatibilidade de petróleos mostraram-se pouco eficientes na análise dos sistemas envolvendo os petróleos brasileiros considerados neste estudo, suscitando a necessidade de um estudo mais profundo para o aprimoramento dos modelos e índices existentes ou desenvolvimento de novos.

Made available in DSpace on 2016-08-19T12:56:41Z (GMT). No. of bitstreams: 1 DISSERTACAO DAVID23042011.pdf: 1761533 bytes, checksum: 8afdff9f67c0685d536bb3b816b3f286 (MD5) Previous issue date: 2011-04-23 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The starting point of precipitation of asphaltenes, IP, is defined as the minimum amount of precipitant, in general n-heptane added to oil to the occurrence of precipitation of asphaltenes. It is observed that this phenomenon is related to kinetic factors inherent in the system, fact not previously measured in models of behavior of asphaltenes. In this context, the abundantly used technique for determining the onset of precipitation of asphaltenes using NIR spectroscopy is investigated. Are demonstrated significant amounts of additional information about using this technique, for example, the effect of the rate of addition of n-heptane to oil. This work used two samples of oil named P1 and P2, with different physical and chemical characteristics, which provides that the IP values ranged from 2.59 to 3.25 and 0.56 to 1.2 ml of heptane / g of oil, respectively, depending on the flow used. From the data obtained, it was possible to establish a standard procedure that minimizes significantly the measurement variation due to the dilution rate. This analysis therefore provides the equilibrium condition required for the correct measure of the onset of asphaltene precipitation, providing clues to a better understanding of the frequent disagreements reported in the literature. Aiming to better characterize this phenomenon, it is a comparison between two techniques well diffused in the literature, namely, optical microscopy and NIR spectroscopy. It is observed that both techniques are equivalent with respect to determining the point of beginning of precipitation of asphaltenes indicating that sometimes disagreements trial may be associated with only the choice of experimental parameters. Moreover, in general, are given some recommendations on this type of experiment. / O ponto de início de precipitação dos asfaltenos, IP, é definido como a quantidade mínima do precipitante, em geral n-heptano, adicionado ao petróleo para que ocorra a precipitação dos asfaltenos. É observado que este fenômeno está associado a fatores cinéticos inerentes ao sistema, fato até então não mensurado adequadamente nas modelagens de comportamento dos asfaltenos. Neste contexto, a abundantemente usada técnica de determinação de inicio de precipitação dos asfaltenos utilizando espectroscopia de NIR (near infrared) é investigada. São demonstradas quantidades significativas de informações adicionais acerca da utilização desta técnica, como por exemplo, o efeito da taxa de adição de n-heptano ao petróleo. Neste trabalho são utilizadas duas amostras de petróleo denominadas P1 e P2, com distintas características físico-químicas, onde se determina que os valores de IP variaram entre 2,59 3,25 e 0,56 1,2 ml de heptano/g de petróleo, respectivamente, a depender da vazão utilizada. A partir dos dados obtidos, foi possível estabelecer um procedimento padrão que minimiza significativamente a variação das medidas em função da taxa de diluição. Esta análise, portanto, estabelece a condição de equilíbrio necessária para a correta medida do inicio de precipitação dos asfaltenos, fornecendo indícios para uma melhor compreensão dos frequentes desacordos experimentais relatados na literatura. Ainda com o objetivo de melhor caracterização deste fenômeno, é realizada uma comparação entre duas técnicas bastante difundidas na literatura, a saber, microscopia óptica e espectroscopia de NIR. É observado que ambas as técnicas se equivalem no que diz respeito à determinação do ponto do inicio de precipitação dos asfaltenos indicando que, por vezes, os desacordos experimentais podem estar associados apenas à escolha dos parâmetros experimentais. Além do mais, em geral, são dadas algumas recomendações acerca deste tipo de experimento.

The behavior of sulfur compounds in asphalt cements can be studied in a more comprehensive way through the separation of maltenes and asphaltenes and their respective fractions. Thus, the ASTM D4124 method was applied for the separation of maltenes and asphaltenes in acidic, basic and neutral fractions of súlfur compounds. Herein, it could be observed that the sulfur heteroatom appears in higher levels as a less reactive fraction (neutral compounds) for virgin asphalts. The aging process lead to an increase of at least 20% for the polar fractions of sulfur, which is related to here to acidic and basic sulfur compounds. From this speciation results, a classification of the asphalt samples can be proposed taking into account the calculated reactivity in terms of polar (acidic/basic) and neutral compounds. These results permit to infer that a higher content of asphaltenes does not necessarily imply in a higher reactivity of the asphaltic binder. So the presence of specific functional groups related to these heteroatoms (e.g. sulfur) may be definitive for a greater or lesser susceptibility of the binder to the aging processes. / O estudo do comportamento de compostos sulfurados no cimento asfáltico de petróleo (CAP) pode ser melhor entendido através da separação em maltenos, asfaltenos e suas respectivas frações. Com esta finalidade, foi utilizado a ASTM D4124 para o fracionamento de amostras de asfalto em maltenos e asfaltenos. Por conseguinte, maltenos e asfaltenos foram fracionados em suas respectivas frações ácida, básica e neutra para a especiação dos compostos sulfurados. Em se tratando de maltenos e asfaltenos, observou-se que o enxofre aparece em maior quantidade na fração menos reativa (fração neutra) para amostras virgens, sendo que com o processo envelhecimento leva a um aumento (>20%) da fração mais polar do asfalto relacionada a compostos sulfurados ácidos e básicos. A partir dessa especiação, uma classificação das amostras estudadas foi proposta levando em consideração a reatividade calculada em termos de compostos polares e neutros. Estes resultados permitem inferir que um maior teor de asfaltenos não implica necessariamente em uma maior reatividade do ligante asfáltico. A presença de grupos funcionais específicos relacionados a seus heteroátomos (a exemplo do enxofre) deve ser definitiva para uma maior ou menor suscetibilidade do ligante ao envelhecimento.

Le géochronomètre Re-Os a fait ses preuves dans son application aux huiles et bitumes pétroliers. Cependant, l’application de ce système sur les fluides pétroliers souffre d’un manque de compréhension de la géochimie pétrolière de Re et Os, des mécanismes de remise à zéro du géochronomètre et par conséquent des évènements réellement datés. Plus précisément, l’utilisation du géochronomètre Re-Os nécessite de comprendre la manière dont le comportement du système Re-Os permet de remplir les conditions nécessaire au développement d’une isochrone. Ces conditions sont : 1) l’homogénéisation isotopique des huiles à l’échelle d’un champ pétrolier ; 2) le fractionnement de Re par rapport à Os pour obtenir des échantillons ayant différents rapport Re/Os ; 3) la fermeture du système jusqu’au moment de la datation. Des protocoles expérimentaux ont ainsi été mis au point afin de comprendre le comportement géochimique de Re et Os dans les huiles afin d’évaluer l’utilisation du système Re-Os en tant que géochronomètre dans le cadre d’une application directe sur les pétroles. Le fractionnement de Re et Os a été vérifié dans le cas de la perte d’asphaltènes au cours de l’évolution de l’huile par précipitation séquentielle en laboratoire. Des expériences de contact entre solutions aqueuses de Re et Os et huiles ont été conduites afin d’étudier la possibilité d’un transfert des métaux entre ces deux phases sur une large gamme de concentrations et de températures. Enfin, l’étude de spéciation de Re et Os dans les huiles artificiellement enrichies en Re et Os par spectroscopie d’absorption X (rayonnement synchrotron) a permis de proposer un mécanisme d’incorporation de Re et Os dans les huiles / The Re-Os radiogenic system is well adapted to the dating of oils and bitumen. However the meaning of the obtained age is ambiguous. This is mainly due to gaps in our knowledge of the geochemical behavior and the speciation of Re and Os in oils. Specifically, use of the Re-Os system requires an understanding of how Re-Os behavior can lead to the fulfillment of the conditions necessary for the development of an isochron. These conditions are: 1) the isotopic homogenization of oils at the scale of a petroleum field 2) the fractionation of Re from Os so as to obtain samples with various Re/Os ratios 3) the closure of the system during the period of radiogenic ingrowth of the daughter isotope, that is, from the time of the event of interest to the present day. Experimental investigation of the organic geochemical behavior of Re and Os in oils under various conditions, designed as analogs of the different stages of petroleum generation and evolution, were performed in order to evaluate the use of the Re-Os system as a geochronometer in the context of a direct use on petroleum. The possibility of Re-Os fractionation resulting from asphaltene loss during oil evolution was investigated by sequential asphaltene precipitation in the laboratory. The possibility of metal transfer from formation waters to petroleum was studied by performing contact experiments between oils and aqueous solutions of Re and Os of various concentrations over a wide range of temperatures and for varying periods of time. Finally, the study by X-ray absorption spectroscopy of Re and Os in oils artificially enriched in these elements contributed to the proposal of a mechanism for Re and Os incorporation at the oil-water interface

Dans un contexte où la demande énergétique ne cesse de croître et où les réserves pétrolières sont limitées, il est nécessaire de développer des sources énergétiques alternatives ainsi que de ransformer celles existantes afin de satisfaire les besoins croissants notamment dans les secteurs du transport et de la pétrochimie. Un des objectifs de l’IFP est de concevoir et d’améliorer des procédés de raffinages existants afin d’optimiser l’utilisation des ressources conventionnelles tout en les diversifiant afin de produire notamment du carburant à partir des produits lourds du pétrole. L'enjeu des prochaines décennies est de convertir efficacement des bruts lourds en produits légers valorisables tels que l'essence, le kérosène et le gazole. Pour cela, il est indispensable de disposer d'une connaissance précise des produits présents dans la charge, principalement des asphaltènes, afin d'adapter le catalyseur utilisé et obtenir les meilleurs résultats de conversion possibles. L’objectif de la thèse visait à obtenir une meilleure caractérisation physico-chimique des asphaltènes en solution. Le manuscrit décrit une nouvelle application de la technique RMN DOSY (Diffusion Ordered Spectroscopy) à la caractérisation des produits lourds du pétrole. Des asphaltenes de cinq origines différentes ont été analysées sur une large gamme de concentration afin d’étudier leur agrégation en solution. Les résultats révèlent l’existence de deux familles d’agrégats en régime semidilué : une famille diffusant rapidement appelée nanoagrégats et un type d’agrégats diffusant plus lentement nommée macroagrégats dans ce manuscrit. L’influence du solvant a été étudiée sur une charge analysée dans le toluène, le tetra-hydrofurane et le chloroforme. Des informations physiques moyennes sur la taille et la masse moléculaire des nanoagrégats des asphaltènes ont été calculées à partir de leur diffusion en solution. Il a ainsi été possible de mettre en évidence des familles de produits caractérisées par une structure et une masse moléculaire en une seule expérience. Le manuscrit propose également une discussion sur le caractère continental ou/et archipel des asphaltènes. L’hypothèse de départ est basée sur la co-existence des deux types d’asphaltènes avec un caractère archipel (ou continental) plus ou moins marqué suivant l’origine des échantillons / New energy supplies need to be developed to face the growing worldwide energy demand. Heavy oils have attracted attention since their represent an important energy reserve. The problem to deal with during their upgrading is the presence of asphaltenes, representing the heaviest and the most resistant fraction of the crude oil. It is worth getting a better understanding into the physico-chemistry of asphaltenes to develop new catalysts and new conversion processes. The manuscript describes a new application of Diffusion Ordered Spectroscopy (1H-DOSY) NMR experiment. It is evaluated as a potential tool to investigate the physico-chemistry of asphaltenes from five different origins in just one experiment. Asphaltenes were studied over a wide range of concentrations in different solvents to get a deeper insight into their aggregation behaviour. For the first time, two different aggregates were observed in the semi-dilute regime and reported in this manuscript. Average size and molecular weight are estimated from diffusion measurements at infinite dilution. Based on different results, a discussion about continental and archipelago type is also provided. Asphaltenes are expected to be a distribution of the two types of asphaltenes with a more pronounced archipelago (or continental) type depending on the origin of the sample

Ce est consacré à l’élaboration et à l’étude de mélanges de type polymères/maltènes (MP) et polymères/asphaltes (AMP). Les polymères sont des copolymères à blocs de styrène et de butadiène (SBS) présentant une architecture ramifiée en étoile à quatre branches. Ils ont été partiellement hydrogénés en SBEBS grâce à l’utilisation d’un catalyseur type Ziegler-Natta. Dans les conditions expérimentales utilisées, les analyses physico-chimiques des SBEBS ont clairement montré que l’hydrogénation a été réalisée sans dégradation ni réticulation des chaînes macromoléculaires. Les mélanges, fabriqués sous agitation à l’état fondu, ont ensuite été caractérisés par rhéologie et microscopie de fluorescence. Les résultats obtenus permettent d’établir que : - selon la teneur en copolymère, les AMP présentent soit une morphologie de type émulsion soit une structure de type macroréseau, - les mélanges polymères/maltènes sont des systèmes bi-phasiques constitués par une phase de copolymère gonflé et une phase de maltènes, tandis que les mélanges polymères/asphaltes sont des systèmes tri-phasiques constitués d’une phase de copolymère gonflé, d’une phase de maltènes et d’une phase d’asphaltènes stabilisés par des maltènes. Dans tous les cas, ces effets sont la conséquence directe du gonflement du copolymère dans les mélanges. Cette étude a donc permis d’établir que la microstructure des copolymères a une influence notoire sur leur gonflement et sur les performances rhéologiques des mélanges résultants / A study of maltenes/polymer and asphalt/polymer blends, with two styrene-butadiene-styrene (SBS) polymers with four-branch star-like chain architecture is reported in this work. The employed polymers, with the same overall composition and distribution, were in-situ partially hydrogenated using a Nickel II Ziegler-Natta type catalyst without cross-linking or chain scission reactions. Blends were prepared by a melt mixing procedure and studied by fluorescence microscopy and rheological measurements. Results indicate that maltene/polymers blends are bi-phase heterogeneous systems with swollen polymer-rich and maltenes-rich phases, while asphalt/polymers blends are tri-phase systems with swollen polymer-rich, maltenes-rich and stabilized asphaltenes phases. In both cases, the rheological behavior of blends is mainly affected by the swollen polymer rich phase. It was confirmed that the rheological properties of PMM depend on the molecular characteristics of the copolymer such as the total molecular weight and molecular architecture, which determine the material behavior

Cette thèse porte sur l'étude de la diffusion des asphaltènes dans les catalyseurs d'hydrotraitement. La revue bibliographique met en évidence d'importantes lacunes dans les connaissances, d'une part sur l'impact sur les processus de diffusion des fortes températures rencontrées dans les procédés de raffinage et d'autre part, sur la dynamique des asphaltènes dans les réseaux poreux des catalyseurs. Ainsi, une double approche expérimentale a été développée, s'articulant dans un premier temps autour d'une étude de diffusion et d'adsorption dans des conditions proches de celles des procédés, puis dans un second temps une étude de la diffusion en milieu confiné par Résonance Magnétique Nucléaire (RMN) à travers des techniques de mesure de temps de relaxation ainsi que la RMN à gradient de champ pulsé (DOSY). Les résultats obtenus montrent que même à haute température, la diffusion des asphaltènes dans les catalyseurs est un processus très lent, plusieurs jours étant nécessaires pour que le coeur soit atteint. Les techniques de RMN utilisées montrent le caractère fortement confiné des asphaltènes dans le milieu poreux ainsi que de fortes interactions entre les asphaltènes et la surface alumine des catalyseurs, à l'origine d'une très faible dynamique bien que le processus d'adsorption soit dans une certaine mesure quand même réversible / This PhD thesis deals with the diffusion of asphaltenes in hydrotreatment catalysts. The literature review shows weaknesses in knowledge about both, how does the high temperature impact the diffusion phenomena and, what is the dynamic of asphaltenes in the porous media. Therefore, a double experimental approach has been developed, first the diffusion and the adsorption of asphaltenes near process conditions have been studied, and then the dynamic in porous media has been studied by Nuclear Magnetic Resonance (NMR) technics which involves relaxation times measurements and Diffusion Ordered SpectroscopY (DOSY). Results show that even at high temperature, the diffusion of asphaltenes in catalysts is relatively slow; several days are needed to reach the center. The NMR results highlight a slow dynamic of asphaltenes in the porous media, since they are in confined environment and they are in strong interactions with alumina, even if the adsorption is to a certain extent reversible

La formation d'émulsions eau-dans-huile stables est un problème majeur rencontré par les pétroliers au niveau de la production mais aussi du raffinage. Afin d'essayer de prévoir ce phénomène, Total a développé une méthode de classement des huiles qui permet, à partir de leurs propriétés physico-chimiques, de déterminer a priori leur capacité à former ou non des émulsions stables. Cependant, les mécanismes interfaciaux sous-jacents ainsi que l’influence des molécules tensioactives du brut sur la stabilité des émulsions n’est pas très clair. Notre travail a consisté à étudier la contribution des acides naphténiques et des asphaltènes dans les phénomènes observés. L’étude d’huiles réelles a permis d’établir un lien entre la stabilité des émulsions et la formation à l'interface d'un gel 2D. Les études menées sur les huiles réelles dont les acides naphténiques ont été extraits ont permis de montrer que ces derniers, en compagnie de leurs formes ionisées, les naphténates, ont la capacité de réduire la stabilité des émulsions en diminuant la résistance du gel interfacial, ou même en empêchant sa formation. Les expériences réalisées sur les huiles réelles dépourvues d’asphaltènes ont permis de confirmer le rôle stabilisant des asphaltènes. Les résultats obtenus suggèrent que les asphaltènes s’adsorbent sur le gel 2D déjà formé par des tensioactifs passés de l’huile vers l’eau et le rapprochent ainsi de sa transition vitreuse. La résistance du gel interfacial s'en trouve alors augmentée, ce qui conduit à la formation d'émulsions plus stables. En croisant le classement industriel des bruts opéré par Total et les résultats de l’étude, un mécanisme global, régi par la compétition entre les acides naphténiques, les naphténates et les asphaltènes à l’interface E/H est proposé pour expliquer les différences de stabilité observées avec les différentes huiles. Lorsque les acides et les naphténates sont suffisamment concentrés, ils empêchent la formation du gel interfacial et les émulsions sont peu stables. Lorsqu’ils sont moins concentrés le rôle des asphaltènes peut alors devenir prépondérant en donnant une cohésion plus importante au gel qui se rapproche de sa transition vitreuse, ce qui conduit en général au renforcement de la stabilité des émulsions formées. / Water-in-crude oil emulsions are a major issue for oil companies in both production and refining facilities. Thanks to physical and chemical characterizations, Total set a classification which allows the decision of a crude oil ability to create stable emulsions. However the interfacial mechanisms implied and the influence of the indigenous surfactants of crude oil remain unclear. Our work consists in studying the naphthenic acids and asphaltenes contribution to the w/o emulsion stability. The study of realistic crude oils enabled the discovery of a link between the emulsion stability with the formation of a very particular interfacial behavior: a two-imensional gel. Experiments with desacidified oils have proven the destabilizing ability of naphthenic acids and their ionized form, naphthenates. They actually decrease the interfacial gel strength and can even prevent the gel formation. Asphaltenes-free crude oils have permitted to confirm the stabilizing role of asphaltenes. Rather than adsorbing directly on the interface, asphaltenes seem to adsorb on the interfacial gel already formed. The gel strength is thus increased and lead to higher emulsion stability. Thanks to these results and the industrial classification of crude oil developed by Total, a global mechanism explaining the emulsion stability process has been proposed. This mechanism is governed by the competition between asphaltenes, naphthenates and naphthenic acids at the water/oil interface. If the concentration of naphthenic acids and naphthenates is high enough, the interfacial gel cannot be formed and the emulsions are unstable. If the crude oil is not acidic enough, the asphaltenes influence increases dramatically and implies the strengthening of the gel which becomes closer to his glass transition. This generally leads to the formation of more stable emulsions.

La construction des routes avec des techniques d'enrobage à chaud (T=160 °C) implique une consommation d'énergie fossile et des rejets de gaz à effet de serre importants. Une production plus écologique du bitume nécessite de diminuer les températures d'enrobage en conservant les propriétés mécaniques des enrobés ainsi obtenus. Le développement de techniques permettant de réduire les températures est donc un enjeu majeur de l'industrie routière. Dans ce travail, nous avons joué à la fois sur la composition et le procédé pour moduler les propriétés du bitume et atteindre l’objectif fixé.Nous avons décomposé le bitume en ses différentes fractions en utilisant des techniques de séparation asphaltènes/maltènes à l'aide d'un alcane (pentane et heptane). Nous avons formulé des bitumes à différentes proportions et natures d'asphaltènes en introduisant des protocoles de préparation originaux. A l’aide de techniques de caractérisation variées telles que la rhéologie, la diffusion des rayons X ou encore des techniques de microscopies et d'analyses thermiques, nous avons déterminéles rôles des différentes fractions du bitume. Nous avons ainsi montré l'impact important des asphaltènes, mais également des fractions que nous avons qualifiées « d'intermédiaires », sur les comportements rhéologiques. Enfin, nous avons élaboré des objets coeur-écorce, composés d’une écorce rigide, non collante, riche en asphaltènes et d’un coeur mou, riche en maltènes. Ces objets sont particulièrement intéressants pour le transport du bitume à température ambiante. / The classic manufacture of hot mix asphalt for road construction is associated with a high consumption of fossil fuels and a high level of emissions of greenhouse gases into the atmosphere. A cleaner production of bitumen requires lowering the manufacturing temperature of these products without impoverishing their level of mechanical performances. The development of technologies that enable temperature reduction had thus become a major objective in the field of road engineering. In this work, we are playing on both composition and process in order to control the final properties of the material and propose an interesting way to reduce temperature during transportation. We have been interested in the different fractions composing the bitumen. We have there by employed a separation technique with alkane (heptane and pentane) to segregate the maltenes and asphaltenes. We could therefore realize diverse reconstituted bitumen using original protocols. Using various characterization techniques (such as rheology, X-ray scattering, optic, electronic and atomic force microscopy, infrared spectroscopy, thermal analysis...), we get insight into the effect of asphaltenes content and nature on bitumen properties. Our results show the huge impact of asphaltenes and other fractions called "intermediate fractions" on bitumen rheological properties. Finally, we propose an innovative processing of bitumen via the elaboration of core/shell objects composed of a rigid, nonsticky and asphaltenes-rich corona and a soft maltenes-rich core. These objects are very interesting for transporting bitumen at ambient temperature.

The main objective of this research was to exploit the interrelations between the rheological behavior and nano-microstructure of complex fluids in solving two state-of-the-art problems, one in the field of biomedical engineering: controlling the amount and characteristics of bioaerosol droplets generated during coughing, and the other in the bitumen-heavy oil industry: characterizing the nano-microstructure of asphaltene particles in bitumen and heavy oil from their rheological behavior. For the first problem, effect of viscoelastic and surface properties of artificial mucus simulant gels on the size distribution and amount of airborne bioaerosol droplets generated during simulated coughing were investigated. The results revealed that suppressing the generation of bioaerosol droplets and/or reducing the number of emitted droplets to a minimum during coughing are practically achievable through modulation of mucus viscoelastic properties. While variation of surface tension did not show any change in the droplet size distribution, an increase in particle size was observed as the samples changed from elastic solid type to viscoelastic type to viscous fluid type samples. This knowledge will help in the development of a new class of drugs being developed at the University of Alberta, aimed at controlling the transmission of airborne epidemic diseases by modifying the viscoelastic properties of mucus. For the second problem, studies of viscoelastic behavior of Athabasca bitumen (Alberta) and Maya crude (Mexico) oil samples, along with their Nano-filtered and chemically separated-plus-reconstituted samples were performed. The results revealed that the rheological behaviors of the bitumen-heavy oil samples are governed by their multiphase nature. The rheological behavior of all feeds, permeates and retentate samples followed a single master curve over the entire temperature interval, consistent with that of a slurry comprising a Newtonian liquid plus a dispersed solid comprising non-interacting hard spheres. The behavior of asphaltenes in the reconstituted samples, however, was found to be significantly different from that in nanofiltered samples. The information about the characteristics and behaviors of asphaltenes obtained in this study will help better understand the asphaltene structures, and support the effort to determine solutions for numerous asphaltene-related industrial problems. In the long run, this knowledge will help to create more efficient extraction and upgrading processes for bitumen and heavy oils. / Thermo Fluids