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.

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.

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

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.

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.

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.

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.

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. / text