<p>  </p> <p>Mass spectrometry (MS) is a powerful tool for the molecular-level characterization of complex mixtures. It is susceptible, selective, versatile, and fast. MS provides molecular weight information for the ionized analytes based on their mass-to-charge (<em>m/z</em>) ratios. Elemental compositions of the ionized analytes can be provided by MS operated at high resolution. In addition, MS provides invaluable information through tandem mass spectrometric approaches. Tandem mass spectrometry (MSn, n ≥ 2, where n is the number of ion-separation steps) utilizing collision-activated dissociation (CAD) has proven especially effective for elucidating the structures of individual compounds in complex mixtures. MS can be coupled with various external desorption/ionization methods. Laser-induced acoustic desorption (LIAD) is a technique that enables the evaporation of nonvolatile and thermally labile compounds into a mass spectrometer from the surface of the metal foil. LIAD is a soft evaporation technique that is a great companion for MS because it causes minimal fragmentation to the desorbed neutral molecules. LIAD can also be coupled with instruments other than mass spectrometers, such as molecular rotational resonance (MRR) spectrophotometer as a versatile evaporation technique. </p> <p>This dissertation focuses on research using high-resolution tandem mass spectrometric methods for the structural characterization of isomeric cations of asphaltene model compounds. The fragmentation behaviors of seven isomeric n-pentylquinoline radical cations are studied. Mechanisms for the formation of several fragment ions are also discussed based on quantum chemical calculations. Additionally, a novel suspension spin coating method is reported to improve LIAD performance. Further discussed in the dissertation is the endeavor of expanding the field of LIAD applications to MRR spectroscopy.</p>

No description available.

La croissance de la demande en produits pétroliers (essence et gazole), en particulier dans les pays développés, et la nature limitée des ressources pétrolières conduisent l’industrie pétrolière à s’intéresser de plus en plus à l’exploitation et la transformation des huiles lourdes et extra-lourdes. Leurs propriétés non conventionnelles du fait de leur forte composition en asphaltènes (particules définies comme l'ensemble de constituants insolubles dans le n-heptane et solubles dans le toluène) nécessitent la mise en oeuvre de procédés de plus en plus sophistiqués à toutes les étapes de leur exploitation et de leur production. Ces bruts, situés principalement au Canada et au Venezuela, sont caractérisés par leur forte viscosité de 1 à 55 Pa.s (1 000 cP à 55 000 cP), qui rend leur transport en surface impossible dans leur état naturel. Le développement de solutions technologiques nouvelles repose sur une meilleure connaissance des propriétés thermo- physiques et du comportement colloïdal de ces produits.Les méthodes de caractérisation expérimentale et de modélisation utilisées pour les bruts conventionnels sont inadaptées pour les bruts lourds et extra lourds. La caractérisation PVT des bruts lourds fait l’objet de nombreux travaux à l’heure actuelle. Les propriétés à déterminer sont les équilibres de phase et les propriétés thermo physiques des phases en équilibre. Dans ce contexte, cette thèse a pour objectifs principaux le développement de méthodes expérimentales et de modèles adaptés aux bruts lourds et aux procédés de récupération envisagés pour ces bruts (production froide, injection de solvant VAPEX, injection de vapeur SAGD, etc...). / Due to increasing demand for fuel, in particular for developed countries, and the limited nature of reserves, petroleum industry is, and will, growing concerned by the heavy and and extra-heavy oil processing. The non-conventional properties of these oils (due to a high asphaltene composition) require specific engineering solutions during the different steps of their processing. These crudes, mainly localized in Canada and Venezuela, are characterized by their strong viscosity, from 1 up to 55 Pa.s, which makes their transport to earth surface impossible. The development of new technological solutions is based on a better knowledge of the thermophysical properties and the colloidal behavior of these products. The methods of experimental characterization and modelling used for the conventional crudes are unsuited for both heavy and extra heavy crudes. To date, characterization PVT of heavy crudes is the subject of numerous studies. The properties to be determined are balances of phase and thermophysical properties of the equilibrium cycles. In this context, the main objectives of this thesis are not only the development of experimental methods and models suitable for heavy crudes, but also the recovery processes envisaged for these crudes (cold production, VAPEX process, SAGD process, etc…).

During the production and transportation of oil and gas, flow assurance issues may occur due to the solid deposits that are formed and carried by the flowing fluid. Solid deposition may cause serious damage and possible failure to production equipment in the flow lines. The major flow assurance problems that are faced in the fields are concerned with asphaltene, wax and scale deposition, as well as hydrate formations. Hydrates, wax and asphaltene deposition are mostly addressed in deep-water environments, where fluid flows through a long path with a wide range of pressure and temperature variations (Hydrates are generated at high pressure and low temperature conditions). In fact, a large change in the thermodynamic condition of the fluid yields phase instability and triggers solid deposit formations. In contrast, scales are formed in aqueous phase when some incompatible ions are mixed. Among the different flow assurance issues in hydrocarbon reservoirs, asphaltenes are the most complicated one. In fact, the difference in the nature of these molecules with respect to other hydrocarbon components makes this distinction. Asphaltene molecules are the heaviest and the most polar compounds in the crude oils, being insoluble in light n-alkenes and readily soluble in aromatic solvents. Asphaltene is attached to similarly structured molecules, resins, to become stable in the crude oils. Changing the crude oil composition and increasing the light component fractions destabilize asphaltene molecules. For instance, in some field situations, CO₂ flooding for the purpose of enhanced oil recovery destabilizes asphaltene. Other potential parameters that promote asphaltene precipitation in the crude oil streams are significant pressure and temperature variation. In fact, in such situations the entrainment of solid particulates in the flowing fluid and deposition on different zones of the flow line yields serious operational challenges and an overall decrease in production efficiency. The loss of productivity leads to a large number of costly remediation work during a well life cycle. In some cases up to $5 Million per year is the estimated cost of removing the blockage plus the production losses during downtimes. Furthermore, some of the oil and gas fields may be left abandoned prematurely, because of the significance of the damage which may cause loss about $100 Million. In this dissertation, we developed a robust wellbore model which is coupled to our in-house developed compositional reservoir model (UTCOMP). The coupled wellbore/reservoir simulator can address flow restrictions in the wellbore as well as the near-wellbore area. This simulator can be a tool not only to diagnose the potential flow assurance problems in the developments of new fields, but also as a tool to study and design an optimum solution for the reservoir development with different types of flow assurance problems. In addition, the predictive capability of this simulator can prescribe a production schedule for the wells that can never survive from flow assurance problems. In our wellbore simulator, different numerical methods such as, semi-implicit, nearly implicit, and fully implicit schemes along with blackoil and Equation-of-State compositional models are considered. The Equation-of-State is used as state relations for updating the properties and the equilibrium calculation among all the phases (oil, gas, wax, asphaltene). To handle the aqueous phase reaction for possible scales formation in the wellbore a geochemical software package (PHREEQC) is coupled to our simulator as well. The governing equations for the wellbore/reservoir model comprise mass conservation of each phase and each component, momentum conservation of liquid, and gas phase, energy conservation of mixture of fluids and fugacity equations between three phases and wax or asphaltene. The governing equations are solved using finite difference discretization methods. Our simulation results show that scale deposition is mostly initiated from the bottom of the wellbore and near-wellbore where it can extend to the upper part of the well, asphaltene deposition can start in the middle of the well and the wax deposition begins in the colder part of the well near the wellhead. In addition, our simulation studies show that asphaltene deposition is significantly affected by CO₂ and the location of deposition is changed to the lower part of the well in the presence of CO₂. Finally, we applied the developed model for the mechanical remediation and prevention procedures and our simulation results reveal that there is a possibility to reduce the asphaltene deposition in the wellbore by adjusting the well operation condition. / text

The dependence on oil and the fact that petroleum conventional reservoirs are becoming depleted direct attentions toward unconventional-and harder to access-reservoirs. Among those, heavy and extremely heavy oil reservoirs and tar sands form a considerable portion of all petroleum resources. Conventional thermal and thermocatalytic refining methods are not affordable choices in some cases, as they demand a considerable energy investment. On the other hand, electron irradiation, as a novel technology, provides more promising results in heavy oil upgrading. Electron irradiation, as a method of delivering energy to a target molecule, ensures that most of the energy is absorbed by the molecule electronic structure. This leads to a very efficient generation of reactive species, which are capable of initiating chemical reactions. In contrast, when using thermal energy, only a small portion of the energy goes into the electronic structure of the molecule; therefore, bond rupture will result only at high energy levels. The effect of electron irradiation on different heavy petroleum fluids is investigated in this study. Radiation-induced physical and chemical changes of the fluids have been evaluated using different analytical instruments. The results show that high energy electron particles intensify the cracking of heavy hydrocarbons into lighter species. Moreover, irradiation is seen to limit any post-treatment reactions, providing products of higher stability. Depending on the characteristics of the radiolyzed fluid, irradiation may change the distribution pattern of the products, or the radiolysis process may follow the same mechanism that thermal cracking does. In addition to that, we have studied the effectiveness of different influencing variables such as reaction temperature, absorbed dose values, and additives on radiolytic reactions. More specifically, the following subjects are addressed in this study: *Radiation?induced chain reactions of heavy petroleum fluids *Complex hydrocarbon cracking mechanism *High and low temperature radiolysis *Synergetic effects of different chemical additives in radiolysis reactions *Time stability of radiation products

Orientadores: Rubens Maciel Filho, Maria Izabel Maretti Silveira Bueno / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T14:39:31Z (GMT). No. of bitstreams: 1 Henriques_ClaudeteBernardo_D.pdf: 9506603 bytes, checksum: 875e508c591361025ae37d3b9ac0f432 (MD5) Previous issue date: 2011 / Resumo: Esta tese tem como objetivo apresentar um estudo detalhado para a caracterização de petróleos, tanto no âmbito do desenvolvimento de modelos capazes de prever propriedades físico-químicas clássicas, como também avaliar os fenômenos associados a instabilidades decorrentes de características químicas. Para alcançar este objetivo, duas ações foram executadas: (1) Obter a curva de destilação do ponto de ebulição verdadeiro (PEV) através de simulação, por espectrometria de espalhamento de raios-X (EERX) aliada ao algoritmo denominado máquina vetor de suporte (SVM), com o propósito de prever o rendimento do processo de refino, e (2) Caracterizar o petróleo em relação ao fenômeno de agregação dos asfaltenos, para assim possibilitar a previsão da qualidade do processo de refino. Foram avaliadas amostras de petróleos com propriedades distintas, com o intuito de fornecer amplitude e robustez ao estudo. A primeira abordagem foi à análise classificatória dos petróleos em relação às suas propriedades intrínsecas (teor de enxofre, Grau API e ponto de ebulição verdadeiro), com aplicação de métodos multivariados de classificação. Com estas classificações em mãos, foram desenvolvidos modelos para previsão da curva PEV e do Grau API, utilizando o algoritmo SVM (segunda abordagem). Os dados tratados por meio deste algoritmo apresentaram um perfil de não linearidade. Os resultados obtidos para a caracterização das cargas a partir dos modelos não foram significativamente diferentes dos valores experimentais, permitindo o desenvolvimento de estudos computacionais usando o software comercial Petro-SIM®, para caracterização, aquisição das curvas das misturas de petróleos e, finalmente, previsão dos rendimentos dos cortes na simulação de uma torre de destilação atmosférica. A partir destes resultados, é muito importante ressaltar que, ao contrário da maioria das modelagens quimiométricas, um pequeno grupo de amostras foi necessário para o desenvolvimento do modelo (13 amostras). Vale também serem mencionadas a alta capacidade de previsão do modelo, a rápida e eficiente previsão de curvas PEV de amostras de petróleos puros, processados nas refinarias e, finalmente, a aplicação com sucesso destes modelos em simuladores de processo. A terceira abordagem do trabalho foi à avaliação dos aspectos relacionados à existência de formas coloidais dos asfaltenos, peptizados por resinas e dos efeitos relacionados à presença de outros solventes nos petróleos, que podem causar mudanças na cinética de floculação dos asfaltenos. A composição dos solventes (petróleos diluentes) e dos petróleos pesados foi correlacionada com os resultados do estudo cinético, obtido por meio da avaliação da transmitância por varredura óptica da camada de precipitação dos particulados e da floculação dos asfaltenos, como também por modelos dinâmicos. Para isto, foram elaboradas misturas de petróleos e observou-se que os efeitos associados ao fenômeno de agregação estão diretamente correlacionados com a composição dos petróleos, assim como com a presença de particulados nas misturas. A caracterização adequada dos constituintes de petróleo é uma informação indispensável para garantir o processamento adequado nas refinarias. A reprodução do cenário real do processo, por meio da simulação, foram promissores, mostrando que a caracterização da carga é possível ao se trabalhar com os modelos desenvolvidos, reforçando a relevância das técnicas aplicadas para descrição dos fenômenos químicos associados ao cenário de produção nacional / Abstract: This work aims to present a detailed study for petroleum characterization, through model developments able to preview physical chemical properties and also to evaluate the associate phenomena due to instability in current chemical characteristics. For this purpose two actions were executed: (1) To obtain the curve true boiling point (TPB) through the simulation by spectrometry X-ray scattering (EERX) combined with the algorithm called support vector machine (SVM), in order to predict the yield of the refining process, and (2) to characterize the petroleum in respect to asphaltene aggregation phenomena, making possible the prediction of the quality of the refining process. For these purposes, the petroleum samples were evaluated with different properties, providing amplitute and robustness to the study. The first approach was the classificatory analisis of petroleum in relation to intrinsic properties (sulfur contents, API degrees and true boiling point curves) with application of classification multivariate methods. With these classifications in hands, models were developed to predict the TBP curve and API gravity, using the algorithm SVM (second approach). The data were processed by this algorithm, showing nonlinear profiles. The results for the blend characterization using the models were not significantly different from the experimental values, allowing the development of computational studies using the commercial software Petro-SIM® for characterization, acquisition of mixtures curves and finally, prediction of the cuts yield in the simulation of an atmospheric distillation tower. From these results, it is important to emphasize that a small group of samples was necessary for the model development (13 samples). It is also worth to mention the high predictive ability of the model, the rapid and efficient prediction of TBP curves of crude oil samples, processed in the refineries and finally, the successful application of these models in process simulators. The third approach of this work was to evaluate the aspects related to the existence of colloidal forms of asphaltenes, peptized by resins and of effects related to the presence of other solvents in oils, which can cause changes in the kinetics of flocculation of asphaltenes. The composition of solvents (thinner oil) and of heavy crude oils were correlated with the results of kinetic study, obtained by evaluating the transmittance for optical scanning of the layer of precipitation of particles and the flocculation of asphaltenes, but also by dynamic models. For this, petroleum mixtures were prepared and it was observed that the effects associated to aggregation phenomena are correlated with the petroleum composition as well as the particulate presence in mixtures. The adequate characterization of petroleum constituents is essential information to ensure proper processing in refineries. The reproduction of real scenario of the process, through the simulation, were promising, showing that the blend characterization is possible when working with these developed models, reinforcing the relevance of the techniques applied for describing the chemical phenomena associated with the setting of national production / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

No description available.

<p> 2-Tetrazens are often used as high energy-density materials. Only a few synthetic methods  exist for making them. Further, their structure-property relationships remain largely unexplored.  Asphaltenes are usually a complex mixture found in the heaviest fraction of heavy crude oil. Their structural characterization and understanding have become a pertinent task for petroleum industry  around the world. Mass spectrometry is a powerful analytical tool for the detection and  characterization of unknown compounds even in complex mixtures. It features high sensitivity and  speed and can provide a variety of valuable information for different types of analytes. This thesis  focuses on the development of an effective synthetic method for 2-tetrazenes and the mass  spectrometry study of the ionized 2-tetrazenes. In addition, the mass spectrometric behavior of  ionized asphaltene model compounds are also discussed in this thesis. Chapter 2 describes the instrumentation and fundamental aspects of the mass spectrometers used in the research discussed in this thesis. Chapter3 introduces an effective synthetic method for  2-tetrazens based on iodine-mediated oxidative N-N coupling reaction of hydrazines. Chapter 4  presents the fragmentation behavior of ionized 2-tetrazenes in tandem mass spectrometry experiments. Upon collision-activated dissociation (CAD), ionized alkyl-substituted linear 2- tetrazenes underwent simpler fragmentation reactions than the ionized aromatic 2-tetrazenes or a  cyclic 2-tetrazene. The observations were rationalized by using quantum chemical calculations.  Chapter 5 presents the fragmentation behavior of ionized asphaltene model compounds under  medium-energy collision-activated dissociation (MCAD). The comparison between the different  behaviors of the molecular radical cations of these compounds provided useful information for the  identification of related unknown compound </p>

Made available in DSpace on 2016-08-19T12:56:39Z (GMT). No. of bitstreams: 1 Maria do Socorro Garreto.pdf: 7283583 bytes, checksum: 2b71ac789d5be27c5154d61dd9dc98cc (MD5) Previous issue date: 2006-05-10 / The crude oil can be understood as a mixture sufficiently polydisperse where its diverse components form a dispersion and/or solution whose original state can be modified in function of variations of temperature, pressure and composition causing, for example, the formation of organic deposits. The asphaltene constitutes heavy fractions of oils with great capacity for precipitation and consequent deposition. Better understanding of the asphaltenes behavior is essential to reduce the negative impacts caused by these fractions in petroleum production and processing. An important subject is the relation between the asphaltenes stability in the oils and the measurements of asphaltenes onset precipitation, which represent the minimum amount of a flocculent (n-alkane of low molar mass) necessary to initiate the formation of the precipitated ones in the oils. These measurements, in general, are executed in different conditions against the found ones during the production, and are found also significant errors for oils with low amounts of asphaltenes and with particles in suspension. Distinct interpretations in relation to the precipitation phenomenon are still verified when comparing the results between diverse techniques. In this work, the results of different techniques in the determination of the asphaltenes onset precipitation have been evaluated by optical microscopy, viscosimetry and impedance spectroscopy in ten samples of Brazilian crude oils with different characteristics. The results of precipitation onset also had been related with the asphaltenes stability in the pure oils and mixtures of oils. The oil samples had been assigned P1-P10, A and B. The precipitation onset was induced by the addition of heptane in the oil and the toluene oil (2:1) mixture. The results showed good agreement with the values of precipitation onset for the three evaluated techniques, indicating that the flocculation and precipitation represent the same phenomenon. The addition of the toluene provoked a displacement of the asphaltene onset precipitation point strengthening the influence of the aromaticity in the solubilization of the asphaltenes. It was still observed that the stability of the asphaltene in the oil depends on a relation between all the physico-chemical parameters, however parameters such as resins and aromatics exert a bigger influence on the stability. The study in oil mixtures had indicated that the precipitation onset is not a parameter that can be used exclusively as indicative of asphaltenes stability. / O petróleo pode ser compreendido como uma mistura bastante polidispersa em que, seus diversos componentes formam uma dispersão e/ou solução cujo estado original pode ser alterado em função de variações de temperatura, pressão e composição, acarretando, por exemplo, a formação de depósitos orgânicos. Os Asfaltenos constituem frações pesadas de petróleos com grande capacidade para a precipitação e conseqüente deposição pelas mudanças no equilíbrio de fases da mistura. Uma melhor compreensão do comportamento dos asfaltenos é essencial para reduzir os impactos negativos causados por estas frações na produção e processamento do petróleo. Um assunto importante e também bastante discutível é a relação entre estabilidade dos asfaltenos nos petróleos e as medidas de início de precipitação dos asfaltenos, que representa a quantidade mínima de um floculante (n-alcano de baixa massa molar) necessária para iniciar a formação dos precipitados nos petróleos. Essas medidas, em geral, são executadas em condições distintas às encontradas durante a produção, e também, verificam-se erros bastante significativos para petróleos com baixos teores de asfaltenos e que apresentam partículas em suspensão. Neste trabalho avaliaram-se os resultados obtidos a partir de diferentes técnicas para a determinação do inicio de precipitação dos asfaltenos, seja a microscopia ótica, viscosimetria e espectroscopia de impedância, para dez amostras de petróleos brasileiros com características diferentes. Os resultados de início de precipitação foram também relacionados com a estabilidade dos asfaltenos nos petróleos puros e em misturas de petróleos. As amostras de petróleos foram designadas P1-P10, A e B. O início de precipitação foi induzido pela adição de n-heptano no petróleo e na mistura petróleo tolueno (2:1). Os resultados revelaram uma boa concordância nos valores de início de precipitação para as três técnicas avaliadas indicando que a floculação e precipitação representam o mesmo fenômeno. A adição do tolueno provocou um deslocamento do ponto de início de precipitação dos asfaltenos reforçando a influência da aromaticidade na solubilização dos asfaltenos. Observou-se ainda que a estabilidade dos asfaltenos no petróleo depende de uma relação entre todos os parâmetros físico-químicos, entretanto os parâmetros resinas e aromáticos exercem uma maior influência sobre a estabilidade. Os resultados obtidos com as misturas dos petróleos indicaram que o início de precipitação não é um parâmetro que possa ser empregado, exclusivamente, como indicativo da estabilidade dos asfaltenos em misturas.

[pt] A adsorção de moléculas de asfalteno na interface óleo-água induz a formação de uma microestrutura complexa, que estabiliza as emulsões e prejudica a eficiência dos processes de refino de petróleo. Neste trabalho, desenvolvemos um conjunto de novos protocolos de reologia de cisalhamento para avaliar o efeito de solventes polares e apolares na adsorção de genuínos asfaltenos brasileiros. Além disso, a morfologia do asfalteno, após a adição de solventes com aromaticidades distintas, é investigada por microscopia de varredura (MEV). Os resultados indicam que os asfaltenos estão organizados em uma estrutura do tipo ilha com unidades aromáticas e policondensadas, que formam filmes interfaciais reversíveis com a adição de solventes polares. O estudo interfacial também revela que solventes apolares podem "prender" os nanoagregados de asfalteno na mistura. Esses agregados, na presença de solventes fracamente polares, podem se consolidar em um padrão mais compactado, sugerindo que o crescimento do filme e o autoarranjo do asfalteno estão diretamente relacionados ao conteúdo aromático. Explora-se as diferenças na estruturação do asfalteno e como afetam a extensão da emulsificação espontânea. É proposto que a taxa de emulsificação está diretamente relacionada à configuração química dos asfaltenos. Finalmente, estuda-se a adição de ácido esteárico (AE) a soluções de asfalteno em conteúdo de água deionizada (AD) e água sintética (AS) para melhor compreender como as propriedades reológicas e superficiais são afetadas pela competição das coespécies. Verifica-se que interfaces formadas puramente por AEs originam filmes mais viscosos do que elásticos na interface ar-água. A atividade interfacial dos asfaltenos brasileiros é evidente e significativa na presença de eletrólitos e dependente da aromaticidade do solvente. / [en] Adsorption of asphaltene molecules at the oil-water interface induces the formation of a complex microstructure, which stabilizes emulsions and impairs the efficiency of crude oil refining. In this work, we design a set of new shear rheology protocols to assess the effect of polar and non-polar solvents on indigenous Brazilian (BR) asphaltene adsorption. Moreover, the asphaltene morphology upon addition of solvents with distinct aromaticities is investigated by SEM microscopy. Our findings indicate that asphaltenes are a polycondensate aromatic island-type structure that forms reversible films when polar solvents are placed on top of the adsorbed film. The interfacial study also reveals that non-polar solvents may lock up asphaltene nanoaggregates in mixture. These aggregates, upon the presence of weakly polar solvents, can consolidate into a more close-packed pattern, suggesting that network growth and asphaltene self-arrangement are directly related to the aromatic content. We explore the differences in asphaltene structuring and how it affects the extent of spontaneous emulsification. We find that the rate of emulsification is directly related to the chemical configuration of asphaltenes. Finally, we study the addition of stearic acid (SA) to asphaltene solutions in deionized water (DW) and synthetic water (SW) to better understand how surface and rheological properties are affected by competitive adsorption. We find that single SA are more prone to form liquid-like rather than solid-like films at the air-water interface. Furthermore, we show that the interfacial activity of our asphaltenes is enhanced in the presence of electrolytes and is dependent of the solvent aromaticity.