Tesis sobre el tema "Heavy crude oil"

Energy based on non-renewable resources such as gas, oil, coal and nuclear fission, even with their serious problems of pollution, contributes to 86% of the global energy consumption. Oil will remain the dominant transport fuel: about 87% of transport fuel in 2030 will still be petroleum-based. Discoveries of conventional sources of light easy-to-access crude oil are becoming less common and current oil production levels are struggling to match demand, it is necessary to develop new non-conventional sources of oil in order to supplement conventional oil supply, whose demand is increasing continuously. A possible clue to solve this situation could be to take advantage of the extensive reserves of heavy crude oils existing in different places around the world, which could be an excellent source of more valuable hydrocarbons. In this context, some facilities called upgraders are used to process theses heavy crude oils to both increase the hydrogen-carbon ratio and improve their quality, reducing their density and decreasing their viscosity, sulphur, nitrogen and metals. The main objective in this work is to study the heavy crude oil upgrading processes in order to identify new operation schemes which explore different opportunities of integration between the upgraders and other processes or new schemes for upgraders that can sustain on its own through the production of a wide range of products. Each design alternative has been modelled with state-of-the-art commercial software packages. The crude oil dilution process was evaluated using naphtha and a light crude oil as diluents. Sensitivity analyses were done with the purpose of selecting the type and flow rate of diluent. Once the best diluent was selected, the integration of an upgrader to a refinery was studied. Heavy ends from both the upgrader and the refinery were taken as feedstocks to an integrated gasification combined cycle (IGCC). The best operation schemes for IGCC, in order to achieve the requirements of power and hydrogen for the upgrader and the refinery was determined. Different schemes for heavy crude oil processing to produce transportation fuel instead of syncrude were proposed, too. Finally, economic evaluation of all the schemes was performed to find the best solution for heavy crude oils. The best results for the dilution process of heavy crude oils were obtained when naphtha was used as diluent. The configuration proposed for the upgrader allows producing a synthetic crude oil with 35.5 °API. The integration of the upgrader to a refinery allows the treatment of the heavy streams of the refinery and transforms them into products of higher qualities. The integration of the IGCC to the upgrader and the refinery permits a complete elimination of the heavy residues produced in these units and produces hydrogen and power to be used in the site or to export. Economic evaluation shows that all the proposed processing schemes studied are economically attractive. The proposed processing schemes chosen include the integration between upgrader refinery and IGCC unit with CCS.

The recovery characteristics of Bolu-Himmetoglu, Bolu-Hatildag, Kü
tahya- Seyitö
mer, and Nigde-Ulukisla oil shale samples and Bati Raman, Ç
amurlu, and Garzan crude oil samples were tested experimentally using retort and microwave heating techniques. Many parameters like heating time, porosity, water saturation were studied. To enhance the efficiency of the processes three different iron powders (i.e.
Fe, Fe2O3, and FeCl3) were added to the samples and the doses of the iron powders were optimized. While crude oil viscosities were measured to explain the fluid rheologies, since it is impossible to measure the shale oil viscosity at the laboratory conditions due to its very high viscosity, shale oil viscosities were obtained numerically by using the electrical heating option of a reservoir simulator (CMG, STARS 2007) by matching between the laboratory and numerical oil production and temperature distribution results. Then the field scale simulations for retorting of oil shale and crude oil fields were conducted. Since the microwave heating cannot be simulated by CMG, STARS, microwave heating was modeled analytically. In order to explain the feasibility of heating processes, an economic evaluation was carried out. The experimental, numerical, and analytical results show that field scale oil recovery from oil shales and heavy crude oils by electrical and electromagnetic heating could be economically viable. While microwave heating is advantageous from an operational point of view, retorting is advantageous if the technically feasibility of the study is considered.

The current shortage of crude oil from conventional sources has increased interest in developing unconventional resources such as oil sands. Heavy crudes and bitumen are found in Northern Alberta and their exploration, processing, and transport to market pose challenges in the use of these resources. Part of the solution to these challenges involves the reactive thermal processing of heavy crudes and bitumen. This thesis focused on mild thermal cracking reactions, and two studies regarding these reactions were presented. The first was an experimental study performed in a pilot-scale semi-batch reactor. The three crude oils were heated to 350, 400, 425, and 450°C at 1240 kPa. A five-lump reaction model combined with a process simulator with VLE calculations was fitted with the experimental data obtained. The goodness of fit between the model predicted values and experimental values for the Hardisty (MBL), Albian Heavy Synthetic (AHS), and Christina Lake Dilute Bitumen (CDB) were determined to be 0.99, 0.99, and 0.98, respectively. Moreover, 80, 85, and 89% of the optimized model’s predicted values had less than 10% error for MBL, AHS, and CDB, respectively. The second study described the implementation of a mild thermal cracking reaction model to the development of a train car fire-model for the assessment of safety aspects in the design of train cars used to transport crude oil. Case studies were conducted using the UniSim® depressuring utility and a previously developed mild thermal cracking reaction model to demonstrate the effect of compositional change. Three crude oils with varying properties and representative of the types of crudes transported by rail in Canada were used here: MBL, AHS, and CDB. The case studies conducted showed the performance of a train car fire-model to be dependent on the crude oil characteristics: up to -57% and -99% difference in model predicted variables for AHS and CDB, respectively, when compared to MBL. Furthermore, the model’s performance was also shown to be affected by the compositional change of a given crude oil due to mild thermal cracking reactions: up to 42% difference in model predicted variables when compared to the base case.

Adequate wastewater management is a crucial element to achieve water sustainability in the petroleum refining sector, as their operations produce vast quantities of wastewater with potentially harmful contaminants. Treatment technologies are therefore pivotal for stopping these chemicals from entering the environment and protecting receiving environments. However, refining effluents are still linked to serious pollution problems, partly because little progress has been made in determining the causative agents of the observed biological effects, resulting in non-targeted treatment. Here it is shown that naphthenic acids, which have been reported as toxic and recalcitrant, are important components of refining wastewater resulting from the processing of heavy crude oil and that they have a significant contribution to the toxic effects exerted by these effluents. Furthermore, it was found that their chemical stability makes them highly resistant to remediation using Pseudomonas putida and H2O2/Fe-TAML (TetraAmido Macrocyclic Ligands) systems under laboratory conditions, and only sequential aliquots of Fe-TAML catalysts and H2O2 showed to partially degrade naphthenic acids (50 mg/L) within 72 hours. Results suggest that a combinatorial approach of Fe-TAML/H2O2 followed by biodegradation might improve current treatment options, but further optimisation is required for the biological treatment. These results can serve as a starting point for better environmental regulations relevant to oil refining wastewater resulting from heavy crude oil, as naphthenic acids are not currently considered in the effluent guidelines for the refining sector. Furthermore, the degradation of naphthenic acids under mild conditions using Fe-TAML/H2O2 systems indicates that these catalysts hold promise for the remediation of refining wastewater in real-life scenarios.

Thermal recovery methods are frequently used to enhance the production of heavy crude oils. Steam-based processes are the most economically popular and effective methods for heavy oil recovery for several decades. In general, there are various mechanisms over steam injection to enhance and have additional oil recovery. However, among these mechanisms, steam distillation plays pivotal role in the recovery of crude oil during thermal recovery process. In this study, an experimental investigation was carried out to investigate the role of various minerals present in both sandstone and carbonate formations as well as the effect of steam temperature on steam distillation process. Two different types of dead-heavy crude oils were tested in a batch autoclave reactor with 30 % water and the content of the reactor (crude oil, 10 % rock and mineral). The results were compared as the changes in the density, viscosity and chemical composition (SARA and TPH analyses) of heavy crude oil. Five different mineral types (bentonite, sepiolite, kaolinite, illite and zeolite) were added into the original crude oil and reservoir rocks to observe their effects on the rheological and compositional changes during steam distillation process. Analysis of the results of experiments with Camurlu and Bati Raman heavy crude oils in the presence of different minerals such as Bentonite, Zeolite, Illite, Sepiolite, and Kaolinite in both sandstone and limestone reservoir rocks indicate that steam distillation produces light end condensates which can be considered as solvent or condensate bank during steam flooding operation. It was also illustrated that minerals in reservoir formations perform the function of producing distilled light oil compounds, resulting in enhancement of heavy crude oils recovery in steam flooding. Measurements showed that the remaining oil after steam distillation has higher viscosity and density. On the other hand, the effect of steam distillation is more pronounced in limestone reservoirs compared to sandstone reservoirs for the given heavy crude oil and steam temperature. Among the five different minerals tested, kaolinite found to be the most effective mineral in terms of steam distillation.

Aquatic ecosystems are still being polluted with crude oil and other technogenic contaminants. In order to evaluate genotoxic and cytotoxic impact of this pollutants, micronucleus test and analysis of the other nuclear abnormalities is rather frequently being used. The main objective of the study is assessment of genotoxicity and cytotoxicity effects in different fish and bivalves exposed to the crude oil and other technogenic contaminants discharged from the several oil platforms (Statfjord B, Oseberg C, Minija). Environmental genotoxicity and cytotoxicity was evaluated by measuring the frequencies of micronuclei and other nuclear abnormalities in cells of mussels and fish caged in different oil platforms (Ekofisk, Statfjord B) field zones in situ. The study results provide new information about environmental geno-cytotoxicity in oil platforms field zones. The peculiarities of genotoxicity and cytotoxicity in fish and mussels after experimental treatment with crude oil from the North Sea oil platforms and Minija well in Lithuania and other technogenic contaminants (produced water, mixtures of PAHs, alkylphenols and heavy metals) were assessed. There were determined time-tissue-species-concentration-related relationships in induction of nuclear abnormalities in studied fish and mussels. The study results revealed usefulness of genotoxicity endpoints, as well as cytotoxicity endpoints for the evaluation of damage, caused by the contamination discharged from the marine oil... [to full text]
Į vandens ekosistemas patenka dideli kiekiai žaliavinės naftos bei naftos išgavimo technologinių procesų metu susidarančių teršalų. Šiame darbe analizuotas Šiaurės jūroje veikiančių naftos platformų (Statfjord B, Oseberg C), Barenco jūroje išgaunamos arktinės bei Lietuvoje esančio Minijos naftos gręžinio žaliavinės naftos, taip pat skirtingų gamybinių vandenų atskiedimų, įvairių poliaromatinių angliavandenilių ir alkilfenolių bei sunkiųjų metalų mišinių genotoksinis (pagal mikrobranduolių ir branduolio pumpurų dažnius) bei citotoksinis (pagal fragmentuotų-apoptozinių ir dvibranduolių ląstelių dažnius) poveikis skirtingų rūšių moliuskų ir žuvų ląstelėse. Taikant aktyvaus monitoringo metodą nustatytas Statfjord B ir Ekofisk naftos platformų aplinkos genotoksiškumas ir citotoksiškumas in situ. Šio darbo tyrimų rezultatai suteikė naujos informacijos apie naftos platformų aplinkos geno-citotoksiškumą, taip pat skirtingose platformose išgaunamos žaliavinės naftos, gamybinių vandenų, įvairių alkilfenolių, sunkiųjų metalų mišinių geno-citotoksinį poveikį vandens organizmams. Atlikti tyrimai leido įvertinti genotoksiškumo ir citotoksiškumo dėsningumus skirtingose organizmų grupėse ir jų audiniuose. Eksperimentų metu nustatyta skirtingų žaliavinės naftos, alkilfenolių, sunkiųjų metalų mišinių skirtingų koncentracijų, ekspozijos laiko bei geno-citotoksiškumo indukcijos priklausomybė. Darbe aprašyti metodai gali būti sėkmingai naudojami monitoringe kaip ankstyvieji biožymenys įvairių... [toliau žr. visą tekstą]

Orientador: Antonio Carlos Bannwart
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica e Instituto de Geociencias
Made available in DSpace on 2018-08-12T08:12:48Z (GMT). No. of bitstreams: 1 Karcher_Viviane_M.pdf: 1731022 bytes, checksum: 355de3e34591ff15d14ab367330328f8 (MD5) Previous issue date: 2008
Resumo: Durante a produção de petróleo, é comum o aparecimento de água sob a forma de gotas finamente dispersas no óleo. A água pode ser oriunda de métodos de recuperação avançada e/ou do próprio reservatório (água conata). O cisalhamento turbulento produzido durante o escoamento destes fluidos através de dutos ou dispositivos, como bombas, ou até mesmo no reservatório, pode causar a formação de emulsões de água em óleo (A/O). Para os óleos pesados,estas emulsões permanecem estáveis por um período longo devido à presença de agentes emulsificantes naturais no petróleo cru. Por essa razão, a separação dessas emulsões necessita de equipamentos específicos, o que contribui para o aumento do custo do processo. O objetivo deste estudo é investigar as propriedades interfaciais de emulsões A/O compostas por água e petróleo pesado brasileiro. Para tanto, um aparato experimental foi construído com o objetivo de calcular a energia interfacial dessas emulsões. As emulsões A/O foram geradas através de um aparelho homogeneizador rotativo imerso em um vaso calorimétrico. Dois métodos foram empregados: o método calorimétrico, baseado no balanço de energia da emulsificação, e o método padrão, baseado na medida do tamanho e distribuição das gotas através da técnica de microscopia óptica. As incertezas nas medidas experimentais, em ambos os métodos, foram estudadas a fim de avaliar a viabilidade de cada um. Como principais resultados deste estudo, as magnitudes relativas dos termos do balanço de energia durante a emulsificação foram obtidas. O comportamento reológico destas emulsões também foi estudado.
Abstract: In petroleum production operations, water is commonly present within the oil phase as a finely dispersed phase. This situation originates from enhanced oil recovery methods and/or the presence of connate water inside the own reservoir. The turbulent shear associated with fluid flow during of heavy crude transportation through pipelines may cause the formation of water-in-oil emulsions (W/O). These remain stable for a long time, due the presence of naturally emulsifying agents in the crude oil phase. Therefore, emulsion separation requires specific equipments which contribute to increase the processes costs. The main purpose of this study is to investigate the interfacial properties of W/O emulsions composed by water and a Brazilian heavy crude oil. For that purpose an experimental set-up was built in order to measure the interfacial energy of the emulsions. The W/O emulsions were prepared in a calorimeter vessel by using a rotating impeller. Two methods were used, namely, the calorimetric method based on the energy balance for the emulsification and the standard method of the droplet size and distribution by means of a digital microscope. The uncertainty in experimental measurements was determined for both methods, in order to evaluate their feasibility. The main result of this research is the determination of the relative magnitudes of the different terms in the energy balance during emulsification. Results for the rheological behavior of W/O emulsions are also reported.
Mestrado
Explotação
Mestre em Ciências e Engenharia de Petróleo

Į vandens ekosistemas patenka dideli kiekiai žaliavinės naftos bei naftos išgavimo technologinių procesų metu susidarančių teršalų. Šiame darbe analizuotas Šiaurės jūroje veikiančių naftos platformų (Statfjord B, Oseberg C), Barenco jūroje išgaunamos arktinės bei Lietuvoje esančio Minijos naftos gręžinio žaliavinės naftos, taip pat skirtingų gamybinių vandenų atskiedimų, įvairių poliaromatinių angliavandenilių ir alkilfenolių bei sunkiųjų metalų mišinių genotoksinis (pagal mikrobranduolių ir branduolio pumpurų dažnius) bei citotoksinis (pagal fragmentuotų-apoptozinių ir dvibranduolių ląstelių dažnius) poveikis skirtingų rūšių moliuskų ir žuvų ląstelėse. Taikant aktyvaus monitoringo metodą nustatytas Statfjord B ir Ekofisk naftos platformų aplinkos genotoksiškumas ir citotoksiškumas in situ. Šio darbo tyrimų rezultatai suteikė naujos informacijos apie naftos platformų aplinkos geno-citotoksiškumą, taip pat skirtingose platformose išgaunamos žaliavinės naftos, gamybinių vandenų, įvairių alkilfenolių, sunkiųjų metalų mišinių geno-citotoksinį poveikį vandens organizmams. Atlikti tyrimai leido įvertinti genotoksiškumo ir citotoksiškumo dėsningumus skirtingose organizmų grupėse ir jų audiniuose. Eksperimentų metu nustatyta skirtingų žaliavinės naftos, alkilfenolių, sunkiųjų metalų mišinių skirtingų koncentracijų, ekspozijos laiko bei geno-citotoksiškumo indukcijos priklausomybė. Darbe aprašyti metodai gali būti sėkmingai naudojami monitoringe kaip ankstyvieji biožymenys įvairių... [toliau žr. visą tekstą]
Aquatic ecosystems are still being polluted with crude oil and other technogenic contaminants. In order to evaluate genotoxic and cytotoxic impact of this pollutants, micronucleus test and analysis of the other nuclear abnormalities is rather frequently being used. The main objective of the study is assessment of genotoxicity and cytotoxicity effects in different fish and bivalves exposed to the crude oil and other technogenic contaminants discharged from the several oil platforms (Statfjord B, Oseberg C, Minija). Environmental genotoxicity and cytotoxicity was evaluated by measuring the frequencies of micronuclei and other nuclear abnormalities in cells of mussels and fish caged in different oil platforms (Ekofisk, Statfjord B) field zones in situ. The study results provide new information about environmental geno-cytotoxicity in oil platforms field zones. The peculiarities of genotoxicity and cytotoxicity in fish and mussels after experimental treatment with crude oil from the North Sea oil platforms and Minija well in Lithuania and other technogenic contaminants (produced water, mixtures of PAHs, alkylphenols and heavy metals) were assessed. There were determined time-tissue-species-concentration-related relationships in induction of nuclear abnormalities in studied fish and mussels. The study results revealed usefulness of genotoxicity endpoints, as well as cytotoxicity endpoints for the evaluation of damage, caused by the contamination discharged from the marine oil... [to full text]

Doutoramento em Química
The main objective of this work was to monitor a set of physical-chemical properties of heavy oil procedural streams through nuclear magnetic resonance spectroscopy, in order to propose an analysis procedure and online data processing for process control. Different statistical methods which allow to relate the results obtained by nuclear magnetic resonance spectroscopy with the results obtained by the conventional standard methods during the characterization of the different streams, have been implemented in order to develop models for predicting these same properties. The real-time knowledge of these physical-chemical properties of petroleum fractions is very important for enhancing refinery operations, ensuring technically, economically and environmentally proper refinery operations. The first part of this work involved the determination of many physical-chemical properties, at Matosinhos refinery, by following some standard methods important to evaluate and characterize light vacuum gas oil, heavy vacuum gas oil and fuel oil fractions. Kinematic viscosity, density, sulfur content, flash point, carbon residue, P-value and atmospheric and vacuum distillations were the properties analysed. Besides the analysis by using the standard methods, the same samples were analysed by nuclear magnetic resonance spectroscopy. The second part of this work was related to the application of multivariate statistical methods, which correlate the physical-chemical properties with the quantitative information acquired by nuclear magnetic resonance spectroscopy. Several methods were applied, including principal component analysis, principal component regression, partial least squares and artificial neural networks. Principal component analysis was used to reduce the number of predictive variables and to transform them into new variables, the principal components. These principal components were used as inputs of the principal component regression and artificial neural networks models. For the partial least squares model, the original data was used as input. Taking into account the performance of the develop models, by analysing selected statistical performance indexes, it was possible to conclude that principal component regression lead to worse performances. When applying the partial least squares and artificial neural networks models better results were achieved. However, it was with the artificial neural networks model that better predictions were obtained for almost of the properties analysed. With reference to the results obtained, it was possible to conclude that nuclear magnetic resonance spectroscopy combined with multivariate statistical methods can be used to predict physical-chemical properties of petroleum fractions. It has been shown that this technique can be considered a potential alternative to the conventional standard methods having obtained very promising results.
O principal objetivo deste trabalho foi monitorizar um conjunto de propriedades físico-químicas de correntes processuais pesadas através da espectroscopia de ressonância magnética nuclear, com o intuito de propor um procedimento de análise e processamento de dados em linha para o controlo processual. Vários métodos estatísticos que permitiram relacionar os resultados obtidos por espectroscopia de ressonância magnética nuclear com os resultados obtidos pelos métodos convencionais, aquando da caracterização das diferentes correntes, foram implementados a fim de desenvolver modelos de previsão dessas mesmas propriedades. O conhecimento em tempo real das propriedades físico-químicas dos derivados de petróleo é essencial para otimizar as operações de refinação, garantindo assim operações técnica, económica e ambientalmente adequadas. A primeira parte deste trabalho envolveu a realização de um elevado número de experiências, efetuadas na refinaria de Matosinhos, seguindo métodos convencionais normalizados, importantes para avaliar e caracterizar as correntes de gasóleo de vácuo leve, gasóleo de vácuo pesado e fuel óleo. As propriedades analisadas foram a massa volúmica, viscosidade cinemática, teor em enxofre, ponto de inflamação, resíduo carbonoso, valor P e a destilação atmosférica e de vácuo. Para além da determinação de todas estas propriedades físico-químicas, usando os métodos convencionais, as mesmas amostras foram analisadas por espectroscopia de ressonância magnética nuclear. A segunda parte deste trabalho esteve relacionada com a aplicação de métodos estatísticos multivariáveis que relacionam as propriedades físico-químicas com a informação quantitativa adquirida por espectroscopia de ressonância magnética nuclear. Vários métodos foram aplicados, incluindo a análise por componentes principais, a regressão múltipla por componentes principais, as regressões múltiplas parciais e as redes neuronais artificiais. A análise de componentes principais foi utilizada para reduzir o número de variáveis preditivas e transformá-las em novas variáveis, os componentes principais. Estes componentes principais foram utilizados como variáveis de entrada da regressão múltipla por componentes principais e das redes neuronais artificiais. Na regressão por mínimos quadrados parciais os dados originais foram usados como variáveis de entrada. Tomando em consideração o desempenho dos modelos desenvolvidos, com recurso a parâmetros estatísticos, foi possível concluir que a regressão múltipla por componentes principais contribuiu para piores desempenhos. Melhores desempenhos foram obtidos com a aplicação da regressão por mínimos quadrados parciais e das redes neuronais artificiais. No entanto, foi com os modelos de redes neuronais artificiais que melhores desempenhos foram obtidos em quase todas as propriedades analisadas. Tendo em conta os resultados obtidos, foi possível concluir que a espectroscopia de ressonância magnética nuclear combinada com métodos estatísticos multivariáveis pode ser usada para prever as propriedades físico-químicas de derivados de petróleo. Demonstrou-se que esta técnica pode ser considerada como uma potencial alternativa aos métodos convencionais tendo-se obtido resultados bastantes promissores.

A economia mundial é fortemente dependente da disponibilidade de óleo, no entanto as reservas de óleo leve, mais atrativas ao mercado, tendem nos próximos anos ao esgotamento, trazendo à luz as reservas de óleo pesado para atender as demandas do mercado. No entanto, os processos associados ao transporte e processamento desses óleos viscosos consomem muita energia, impondo um grande desafio para a indústria do petróleo. Nesse contexto, se transportar óleos viscosos com água através de um escoamento bifásico em padrão Core Annular Flow (CAF) é muito promissor. Nessa prática, uma película anular de água envolve o núcleo que contém o óleo, minimizando o contato entre este e a parede do duto e reduzindo as perdas de energia por atrito. Visou o presente estudo mapear os padrões de escoamento de óleo pesado com água em dutos horizontais e verticais, mensurar os fatores de redução de potência e do diferencial de pressão associados à um trecho reto e à uma válvula de gaveta aberta e determinar o holdup para avaliar a eficiência do CAF. Para atingir esses objetivos, uma unidade de bancada foi construída, consistindo de tanques de armazenamento e de separação da mistura. Interligando os tanques, foram dispostos dutos transparentes com 27 mm de diâmetro interno e 8 m de extensão, contendo duas seções horizontais e uma vertical para análise e diversos acessórios hidráulicos. O óleo utilizado possuía viscosidade de 3200 cP a 22 °C e densidade de 945 kg/m3 . Os resultados experimentais demonstraram haver diversas configurações de fluxo segundo o posicionamento do duto, e que a diferença de densidade dos fluidos descentraliza o óleo nos escoamentos horizontais. Além disso, o trecho vertical intercalado entre os trechos horizontais se comportou como um retificador de fluxo, melhorando os índices do CAF. Foi determinado um fator de redução de perda de pressão máximo de 250 vezes para o trecho reto e de 12 vezes para a válvula de gaveta. O fator global máximo de redução de potência foi mensurado em 2,2 vezes. Concluiu-se que, para um trecho reto, o projeto de instalações hidráulicas para o escoamento bifásico deve considerar 15 % a mais de perda de carga em relação ao escoamento de água pura. Já para a válvula de gaveta, esse fator deve ser de 700 %.
The world economy is strongly dependent on the availability of oil, however, light oil reserves, more market-oriented, tend to deplete in coming years, bringing to light the heavy oil reserves to meet the demands of the market. However, the processes associated with the transportation and production of these viscous oils consume a lot of energy and pose a great challenge for the oil industry. In this context, transporting viscous oils through a liquid-liquid two-phase oil-water flow in a core annular pattern (CAF) is very promising. In this method, an annular water film surrounds the oil-containing core, minimizing its contact with the pipe wall and reducing energy losses by friction. The aim of the present work was to map the flow patterns of a biphasic oil-water flow in horizontal and vertical pipes, to evaluate the overall energy savings provided by the CAF technique, to measure the pressure gradient reduction factor along the pipe and in a gate valve and to determine the holdup as a way of assessing the energy efficiency of the biphasic oil-water flow transport. To achieve these goals, an experimental facility was built and it consisted of cargo and separation tanks. Connecting these tanks, approximately 8 m of 27mm-ID clear transparent PVC pipes, two horizontal and one vertical sections and various hydraulic fittings. It was used in the tests lubricating oil with 3200 cP and 945 kg/m3 at 22°C and distilled water. The experimental results showed that there are several flow configurations according to the pipe positioning, and that the oil and the water density difference decentralizes the oil core in horizontal flows. In addition, the vertical section placed between the two horizontal ones behaved like a flow rectifier, improving the core annular flow energy savings basis. An average pressure gradient reduction factor of 250 times in a straight pipe and of 12 times in a gate valve was determined. The maximum overall power reduction factor was measured as being 2.2 times. It was concluded that the design of a hydraulic installation to transport heavy oil with water in a core annular pattern should consider a pressure drop increase by a factor of 15 % in a straight pipe and by a factor of 700 % in a gate valve based on the monophasic water transport at similar flow rates.

Les pétroles utilisés en raffinage étant de plus en plus lourds et chargés en métaux et hétéroélements, il est d’une grande importance pour les activités de raffinage de connaître la spéciation de ces espèces au sein des produits pétroliers et leurs comportements durant les procédés de raffinage. Afin d’apporter des réponses à cette problématique des techniques de caractérisation élémentaire et moléculaire ont été utilisées notamment par ICP MS Haute Résolution et FT ICR MS respectivement. Ces techniques analytiques sont appliquées à différents échantillons pétroliers provenant parfois de procédés de raffinage et les informations obtenues au niveau élémentaire et moléculaire sont utilisées de manières complémentaires pour améliorer notre compréhension des mécanismes se produisant au sein de nos échantillons durant les activités de raffinage
The crude oils available for the refining industry are heavier and heavier and more concentrated in metals and heteroelements. It is thus of great importance to study the speciation of these species within the petroleum products and their behavior during the refining processes. To answer that problematic, elemental and molecular characterization techniques have been used, mainly High Resolution ICP MS and FT ICR MS for the elemental and molecular characterization respectively. The analytical techniques quoted are used for the analysis of several petroleum products sometimes originating from refining processes and the information obtained at the elemental and molecular level are combined to improve our understanding of the mechanisms occurring within our samples during refining activities

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques persistants qui sont présents en mélange complexe dans l’environnement et notamment dans les milieux aquatiques. Ils s’adsorbent sur les particules en suspension, s’accumulent dans les sédiments et dans les premiers maillons de la chaîne trophique. L’objectif de cette étude était de mesurer les effets à long terme d’une contamination par des HAP chez un modèle de vertébrés : le poisson zèbre. Dans un premier temps, des embryons ont été exposés pendant les 4 premiers jours de leur développement sur du sédiment naturel enrobé de 3 HAP individuel (phénanthrène, pyrène et benzo[a]pyrène) puis transférés et élevés en eau propre. Dans un deuxième temps, des poissons ont été exposés par voie alimentaire tout au long du cycle de vie et dès le premier repas à 3 fractions de HAP à doses environnementales enrobées sur les aliments : une fraction pyrolytique (PY) extraite d’un sédiment échantillonné dans la Seine et deux fractions pétrogéniques (un fuel lourd (HO) provenant de l’Erika et un pétrole brut type Arabian light (LO)). Les effets à long terme sur la croissance, la survie, la reproduction et le comportement ont été évalués à différents âges. Ces effets ont pu être observés à plusieurs échelles, i.e. de la molécule, aux tissus et organes puis à l’échelle de l’individu. Globalement, chez les poissons contaminés, la croissance est ralentie, la survie larvaire diminuée chez les HO, la fonction reproduction est altérée fortement à la fois au niveau hormonal, tissulaire et phénotypique ainsi que les réponses comportementales léthargiques ou hyper-réactives selon les cas. L’exposition par voie sédimentaire a révélé des effets visibles lorsque les individus atteignaient 6 mois soulignant l’existence d’effets tardifs, notamment sur les réponses comportementales, d’une exposition très précoce y compris chez la descendance. Quant à l’exposition par voie alimentaire, elle a montré une gradation des effets. Toutes fonctions confondues, les résultats obtenus permettent d'établir une hiérarchie dans la toxicité des fractions étudiées : PY < LO ≈ HO. L'approche multi-échelle utilisée dans ce travail a permis, en partant d'informations acquises au niveau moléculaire, tissulaire et individuel, d'aboutir à une compréhension intégrée des conséquences qu'une exposition à des HAP peut avoir sur l'aptitude à la survie des poissons dans leur milieu naturel ainsi qu'à leur capacité à participer au renouvellement des générations futures
Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) which are found in complex mixtures in the environment including aquatic ecosystems. They adsorb on particles, accumulate in sediment and in the first link of the food web. The aim of this study was to measure long term effects of PAHs contamination on a vertebrate model : the zebrafish. In a first study, embryos were exposed on natural sediment spiked with 3 individual PAH (phenanthrene, pyrene and benzo[a]pyrene) during the first four days of their development. In a second study, to evaluate the consequences of long-term chronic exposure to PAHs, zebrafish were exposed, from their first meal (5 days post fertilisation) until they became reproducing adults, to diets spiked with three PAHs fractions at environmentally relevant concentrations (0.3X, 1X and 3X; with the 1X concentration being in the range of 4.6-6.7 μg.g-1 for total quantified PAHs). The fractions used were representative of PAHs of pyrolytic (PY) origin or of two different oils of differing compositions (a heavy fuel (HO) and a light crude oil (LO)). Long term effects on growth, survival, reproduction and behavior were evaluated at different ages. Effects were observed at molecule, tissue, organ and individual scales. In general, for contaminated fish, growth was reduced, larval survival decreased in HO, and reproduction was strongly impaired at hormonal, tissue and phenotypic levels, and behavioral responses were lethargic or hyperactive depending on fractions and stages. Sediment exposure still revealed visible effects when fish were 6 month old. These results hereby showed significant late effects, especially in behavioral responses after an early exposure, including in larvae issued from contaminated fish. In spiked diets contaminated fish, we observed a gradation of effects. Combining all functions, we established of hierarchy in toxicity in the studied fractions: PY < LO ≈ HO. Finally, our results gathered at a multiscale from molecule, to tissue and individuals, indicate that PAH mixtures of different compositions, representative of situations encountered in the wild, can promote lethal and sublethal effects which are likely to be detrimental for fish survival and recruitment into future generations

La présence d'hétéroatomes et métaux dans des fractions lourdes de pétrole brut peuvent entraîner la désactivation des catalyseurs d’hydrotraitement et d’hydrocraquage. Les composés contenant ces éléments sont connus pour être inclus dans des agrégats macromoléculaires d’asphaltènes, qui sont considérées comme les composants les plus problématiques des produits pétroliers. Ces travaux ont pour objectif d’apporter une meilleure compréhension de l’environnement chimique de ces espèces et des phénomènes d’agrégation pour optimiser les processus de raffinage. Des techniques de séparation comme la chromatographie de perméation de gel ou Gel Permeation Chromatography (GPC), Advanced Polymer chromatographie (APC) et la chromatographie sur couche mince d’haute performance ou High Performance Thin Layer Chromatography (HPTLC) ont été combinées avec des techniques d’analyse élémentaire comme la spectrométrie de masse à plasma à couplage inductif ou Inductively Coupled Plasma Mass Spectrometry (ICP-MS) et la spectrométrie de masse moléculaire d’haute résolution pour la caractérisation des fractions pétrolières lourdes. Les profils de distribution en taille d’espèces qui contiennent du vanadium, du nickel et du soufre, les hétéroatomes et métaux les plus abondants dans les produits pétroliers, ont été déterminés par GPC couplé à une détection élémentaire par ICP MS. Les paramètres ayant le plus d’impact sur la distribution en taille et l’évolution des agrégats dans les solutions de différentes coupes pétrolières ont été optimisés. Cela nous a permis de faire différentes comparaisons, entre de nombreuses charges et effluents de procédés, ainsi que d’autres séries d’échantillons ou de mélanges provenant d’unités-pilotes d’hydrotraitement. Les résultats obtenus ont pu être mis en regard de caractéristiques macroscopiques comme la viscosité. Le couplage du nouveau système APC avec l’ICP MS a été mis au point avec succès. Cette technique a permis de réaliser des cartographies d’échantillons pétroliers plus rapides qu’en GPC tout en consommant moins de solvant. Cependant, les différences des chromatogrammes APC obtenus par rapport aux profils GPC suggèrent des interactions indésirables avec la phase stationnaire, qui ont été l’objet d’une évaluation approfondie.Enfin, un dernier type de séparation a été évaluée. L’HPTLC, qui utilise des plaques à usage unique, peut être appliquée à la séparation de produits lourds par polarité, et ce sans étapes de déasphaltage préalable, contrairement aux colonnes de chromatographie liquide qui peuvent être détériorées à cause de l'adsorption irréversible et de la précipitation des asphaltènes. Différents types de plaques et éluants ont été testés afin de développer une méthode simple pour la séparation des fractions SAR (Saturés, Aromatiques et Résines) des échantillons de distillat sous vide ou Vacuum Gas Oil (VGO). Ce travail avait pour but des migrations en une seule étape et analyse UV qui pourrait être mis en œuvre pour l’analyse de routine dans les laboratoires de contrôle avec une adsorption irréversible réduite. Des résultats très prometteurs ont été obtenus avec l’utilisation de plaques de cellulose pour la séparation des familles de polarité différentes au sein des agrégats d’asphaltènes. Des tests sur l'analyse directe des plaques par Désorption-Ionisation par Électronébulisation (DESI) MS, l'analyse directe en temps réel ou Direct Analysis in Real Time (DART) MS et Ablation Laser (LA) ICP MS ont été effectués
The presence of heteroatoms and metals in heavy fractions of crude oil can cause the deactivation of hydrotreatment and hydrocracking catalysts. Compounds containing these elements are known to be included in macromolecular asphaltene aggregates, which are considered the most problematic components of heavy oil. This thesis aimed for a better understanding of the chemical environment of these species and on the aggregation phenomenon to optimize refining processes. Separation techniques such as Gel Permeation Chromatography (GPC), Advanced Polymer Chromatography (APC) and High Performance Thin Layer Chromatography (HPTLC) were combined with elementary analysis techniques such as Inductively Coupled Plasma Mass Spectrometry (ICP MS) or high-resolution molecular mass spectrometry for the characterization of heavy fractions of crude oil. Here, the size profiles of species that contain vanadium, nickel and sulfur, the most abundant heteroatoms and metals present in petroleum products, were determined by GPC online with elemental detection by ICP MS. The parameters having the most significant impact on size distribution and the evolution over time of aggregates from solutions of different petroleum cuts were optimized. This allowed the comparison between various feeds and effluents and other series of samples and mixtures from pilot units of refining processes by GPC ICP MS. Results obtained could be related to macroscopic characteristics such as viscosity. Hyphenation of the new APC System to ICP MS has been successfully completed. It allowed the mapping of petroleum samples faster than GPC, therefore with less solvent consumption. However, the differences of the APC chromatograms obtained with respect to the GPC profiles suggested significant unwanted interactions of the highly polar compounds of the petroleum samples with the stationary phase, which have been thoroughly studied. Finally, another type of separation was evaluated. HPTLC, of single-use plates, can be applied to the analysis of heavy petroleum products by polarity without prior deasphalting steps while chromatography columns can be deteriorated because of the irreversible adsorption and asphaltene precipitation. To this end, various types of plates and eluents were tested to develop straightforward SAR (Saturates, Aromatics and Resins) separations of Vacuum Gas Oil (VGO) samples. This method, based on single-step migrations with reduced irreversible adsorption and UV monitoring, could be implemented for routine analysis in control laboratories. Very promising results were obtained by the use of cellulose plates for the separation of different families within asphaltene aggregates. Tests on Desorption ElectroSpray Ionization (DESI) MS, Direct Analysis in Real Time (DART) MS and Laser Ablation (LA) ICP MS analyses of the plates have been performed

A research report submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science in Engineering (Metallurgy and Materials Engineering), October 2017
In many crude oil exploitation oil cannot be produced using its own natural drive after many years due to pressure depletion. In order to maintain the reservoir pressure and optimize the oil production, secondary oil recovery methods are usually used i.e. water injection, gas lift and reinjection of natural gas. Although, secondary oil recovery methods increase hydrocarbon production by about 35 - 45 %, they do not provide a definitive solution due to continuous pressure decrease and the excessive amount of water required. An alternative recovery technique known as tertiary recovery or enhanced oil recovery is usually used at this stage and focuses on increasing the mobility of the oil. Chemicals such as surfactants, polymers and nanoparticles are injected to improve recovery. These chemicals help improve properties of the injected fluid and its interactions with the rocks. Surfactants are well known for reducing interfacial tension formed between oil and water and polymers for improving sweep efficiency. Moreover, addition of nanoparticle is said to further reduce interfacial tension between water and oil and help reduce the capillary pressure. This study looked at emulsion stability of crude oil with cationic surfactants and non-ionic surfactants. The objective was to analyse how stable the solution with surfactants only is and also how the stability is affected by temperatures, nanoparticles and stirring mechanism. It further investigates which surfactant type is best suitable to stabilise emulsions and whether or not the combination of surfactant and nanoparticle can provide a more stable emulsion than surfactants only In the study, experiments were conducted to test emulsion stability based on temperature variation, water to oil ratios differences and droplet size formation. Cationic dodecyl trimethyl ammonium bromide (DTAB) and non-ionic Triton®X-100 surfactants were used; nanoparticle zinc oxide (ZnO) was later added into the two types of surfactants aqueous solutions and emulsion stability tests conducted. Temperature was raised from 250C to 60C to look at the effect this will have on emulsion stability. Water/ Oil ratios were analyse the effect/impact the different ratios had on emulsion stability. Droplet size distribution was analysed using a microscope to see how tight the emulsions are. The experimental results suggest that cationic DTAB is not a good candidate for emulsion stability especially at 600C. The potential application of non-ionic surfactant Triton®X-100 alone gave better stability. Addition of nanoparticle ZnO to DTAB did not help stability and when ZnO is added to non-ionic surfactant Triton®X-100 the stability was good at all temperatures but did not last for a longer periods vs having non-ionic surfactant Triton®X-100 only , suggesting that Triton®X-100 is best suitable to keep emulsions formed stable and further microscopic work supported this finding.
XL2018

The rheological properties of heavy crude oil have been investigated using RheoStress RS100 from Haake. The effects of shear rate, temperature and oil concentration on the viscosity have been determined. From the rheological data, it was observed that blending the heavy crude oil with a limited amount of lighter crude oil worked better than using the other alternatives and was considered as the proposed method of reducing the viscosity. Therefore, the theological behavior of heavy crude oil and heavy crude oil-light crude oil (O-light) mixtures has been studied and a series of experiments was conducted. The experiments were performed in terms of studying the effect of shear stress x, shear rate Þ, yield stress x 0 , thixotropic behavior, the storage modulus G' , the loss modulus G" , the complex modulus G* , and the complex viscosity j*. The results showed a significant viscosity reduction of 0.375 Pa.s at room temperature 298 K through which it complies with the desired value required for pumping the heavy crude oil through the pipelines. Moreover, the heavy crude oil showed a thixotropic behavior with hysteresis area of 321.65 KPa.s -1 which decreases with temperature. It was clear that the heavy crude oil required a yield stress of 0.7 Pa, whereas it did not require any yield stress to pump the heavy crude oil-light crude oil mixture. In addition, it was noted that the complex modulus, the storage modulus and the loss modulus showed a direct proportional with frequency and inverse proportional with temperature. The complex viscosity of the heavy crude oil decreased with temperature and fraction of water added, and it reached 225 Pa.s at 338 K.

Thesis (Ph. D.)--Florida State University, 2005.
Advisor: Alan G. Marshall, Florida State University, College of Arts and Sciences, Dept. of Chemistry and Biochemistry. Title and description from dissertation home page (viewed Jan. 26, 2006). Document formatted into pages; contains xxi, 145 pages. Includes bibliographical references.

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

Chemical EOR processes such as polymer flooding and surfactant polymer flooding must be designed and implemented in an economically attractive manner to be perceived as viable oil recovery options. The primary expenses associated with these processes are chemical costs which are predominantly controlled by the crude oil properties of a reservoir. Crude oil viscosity dictates polymer concentration requirements for mobility control and can also negatively affect the rheological properties of a microemulsion when surfactant polymer flooding. High microemulsion viscosity can be reduced with the introduction of an alcohol co-solvent into the surfactant formulation, but this increases the cost of the formulation. Experimental research done as part of this study combined the process of hot water injection with ASP flooding as a solution to reduce both crude oil viscosity and microemulsion viscosity. The results of this investigation revealed that when action was taken to reduce microemulsion viscosity, residual oil recoveries were greater than 90%. Hot water flooding lowered required polymer concentrations by reducing oil viscosity and lowered microemulsion viscosity without co-solvent. Laboratory testing of viscous microemulsions in core floods proved to compromise surfactant performance and oil recovery by causing high surfactant retention, high pressure gradients that would be unsustainable in the field, high required polymer concentrations to maintain favorable mobility during chemical flooding, reduced sweep efficiency and stagnation of microemulsions due to high viscosity from flowing at low shear rates. Rough scale-up chemical cost estimations were performed using core flood performance data. Without reducing microemulsion viscosity, field chemical costs were as high as 26.15 dollars per incremental barrel of oil. The introduction of co-solvent reduced chemical costs to as low as 22.01 dollars per incremental barrel of oil. This reduction in cost is the combined result of increasing residual oil recovery and the added cost of an alcohol co-solvent. Heating the reservoir by hot water flooding resulted in combined chemical and heating costs of 13.94 dollars per incremental barrel of oil. The significant drop in cost when using hot water is due to increased residual oil recovery, reduction in polymer concentrations from reduced oil viscosity and reduction of microemulsion viscosity at a fraction of the cost of co-solvent.
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