Aplicação de microemulsões na solubilização de frações pesadas de petróleo

This work presents studies related to the use of microemulsions in the solubilization of heavy crude oil fractions responsible by the formation of deposits. The first stage of the work was addressed to the construction of phases diagrams, with the intention of determining the area within which the microemulsion is formed. The following systems were studied: UNITOL L 90 n-Butanol - Water - Kerosene (system 1); UNITOL L 90 - n-Butanol - Water - Xylene (system 2); UNITOL L 90 n-Butanol - Water - Kerosene/Xylene 10% (system 3); UNITOL L 90 - Sec-Butanol - Water - Xylene (system 4). In parallel experiments of physical adsorption were carried out by the static method, with the intention of simulating natural conditions of reservoirs. Crude oil of the Fazenda Belém field (Rio Grande do Norte), was used as solute, xylene as solvent and the Assu sandstone (Rio Grande do Norte, Brazil) and Botucatu sandstone (Paraná, Brazil) as rock reservoirs. The curves of adsorption presented the S format type, in agreement with the classification proposed by Giles, Smith and Huitson (1974). The solubilization process was accomplished in the batch method, by varying the time of agitation, the microemulsions and the solid/solution ratio. The experiments showed that the microemulsions presented high efficiency in the solubilization of the crude oil adsorbed on the sandstones. System 2 presented an efficiency of 99% for the Assu sandstone and 97% for the Botucatu sandstone

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Fractais e Percolação na Recuperação de Petróleo

The complex behavior of a wide variety of phenomena that are of interest to physicists, chemists, and engineers has been quantitatively characterized by using the ideas of fractal and multifractal distributions, which correspond in a unique way to the geometrical shape and dynamical properties of the systems under study. In this thesis we present the Space of Fractals and the methods of Hausdorff-Besicovitch, box-counting and Scaling to calculate the fractal dimension of a set. In this Thesis we investigate also percolation phenomena in multifractal objects that are built in a simple way. The central object of our analysis is a multifractal object that we call Qmf . In these objects the multifractality comes directly from the geometric tiling. We identify some differences between percolation in the proposed multifractals and in a regular lattice. There are basically two sources of these differences. The first is related to the coordination number, c, which changes along the multifractal. The second comes from the way the weight of each cell in the multifractal affects the percolation cluster. We use many samples of finite size lattices and draw the histogram of percolating lattices against site occupation probability p. Depending on a parameter, ρ, characterizing the multifractal and the lattice size, L, the histogram can have two peaks. We observe that the probability of occupation at the percolation threshold, pc, for the multifractal is lower than that for the square lattice. We compute the fractal dimension of the percolating cluster and the critical exponent β. Despite the topological differences, we find that the percolation in a multifractal support is in the same universality class as standard percolation. The area and the number of neighbors of the blocks of Qmf show a non-trivial behavior. A general view of the object Qmf shows an anisotropy. The value of pc is a function of ρ which is related to its anisotropy. We investigate the relation between pc and the average number of neighbors of the blocks as well as the anisotropy of Qmf. In this Thesis we study likewise the distribution of shortest paths in percolation systems at the percolation threshold in two dimensions (2D). We study paths from one given point to multiple other points

Fractais e percolação na recuperação de Petróleo

The complex behavior of a wide variety of phenomena that are of interest to physicists, chemists, and engineers has been quantitatively characterized by using the ideas of fractal and multifractal distributions, which correspond in a unique way to the geometrical shape and dynamical properties of the systems under study. In this thesis we present the Space of Fractals and the methods of Hausdorff-Besicovitch, box-counting and Scaling to calculate the fractal dimension of a set. In this Thesis we investigate also percolation phenomena in multifractal objects that are built in a simple way. The central object of our analysis is a multifractal object that we call Qmf . In these objects the multifractality comes directly from the geometric tiling. We identify some differences between percolation in the proposed multifractals and in a regular lattice. There are basically two sources of these differences. The first is related to the coordination number, c, which changes along the multifractal. The second comes from the way the weight of each cell in the multifractal affects the percolation cluster. We use many samples of finite size lattices and draw the histogram of percolating lattices against site occupation probability p. Depending on a parameter, ρ, characterizing the multifractal and the lattice size, L, the histogram can have two peaks. We observe that the probability of occupation at the percolation threshold, pc, for the multifractal is lower than that for the square lattice. We compute the fractal dimension of the percolating cluster and the critical exponent β. Despite the topological differences, we find that the percolation in a multifractal support is in the same universality class as standard percolation. The area and the number of neighbors of the blocks of Qmf show a non-trivial behavior. A general view of the object Qmf shows an anisotropy. The value of pc is a function of ρ which is related to its anisotropy. We investigate the relation between pc and the average number of neighbors of the blocks as well as the anisotropy of Qmf. In this Thesis we study likewise the distribution of shortest paths in percolation systems at the percolation threshold in two dimensions (2D). We study paths from one given point to multiple other points. In oil recovery terminology, the given single point can be mapped to an injection well (injector) and the multiple other points to production wells (producers). In the previously standard case of one injection well and one production well separated by Euclidean distance r, the distribution of shortest paths l, P(l|r), shows a power-law behavior with exponent gl = 2.14 in 2D. Here we analyze the situation of one injector and an array A of producers. Symmetric arrays of producers lead to one peak in the distribution P(l|A), the probability that the shortest path between the injector and any of the producers is l, while the asymmetric configurations lead to several peaks in the distribution. We analyze configurations in which the injector is outside and inside the set of producers. The peak in P(l|A) for the symmetric arrays decays faster than for the standard case. For very long paths all the studied arrays exhibit a power-law behavior with exponent g ∼= gl.

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Estudo teórico aplicado ao petróleo: estabilidade dos alcenos e recuperação terciária

The present work aims to study the theoretical level of some processes employed in the refining of petroleum fractions and tertiary recovery of this fluid. In the third chapter, we investigate a method of hydrogenation of oil fractions by QTAIM (Quantum Theory of Atoms in Molecules) and thermodynamic parameters. The study of hydrogenation reactions, and the stability of the products formed, is directly related to product improvement in the petrochemical refining. In the fourth chapter, we study the theoretical level of intermolecular interactions that occur in the process of tertiary oil recovery, or competitive interactions involving molecules of non-ionic surfactants, oil and quartz rock where oil is accumulated. Calculations were developed using the semiempirical PM3 method (Parametric Model 3). We studied a set of ten non-ionic surfactants, natural and synthetic origin. The study of rock-surfactant interactions was performed on the surface of the quartz (001) completely hydroxylated. Results were obtained energetic and geometric orientations of various surfactants on quartz. QTAIM was obtained through the analysis of the electron density of interactions, and thus, providing details about the formation of hydrogen bonds and hydrogen-hydrogen systems studied. The results show that the adsorption of ethoxylated surfactants in the rock surface occurs through the hydrogen bonding of the type CH---O, and surfactants derivatives of polyols occurs by OH---O bonds. For structures adsorption studied, the large distance of the surfactant to the surface together with the low values of charge density, indicate that there is a very low interaction, characterizing physical adsorption in all surfactants studied. We demonstrated that surfactants with polar group comprising oxyethylene units, showed the lowest adsorption onto the surface of quartz, unlike the derivatives of polyols

Estudo paramétrico da recuperação de petróleo pesado por aquecimento eletromagnético resistivo

Electrical resistive heating (ERH) is a thermal method used to improve oil recovery. It can increase oil rate and oil recovery due to temperature increase caused by electrical current passage through oil zone. ERH has some advantage compared with well-known thermal methods such as continuous steam flood, presenting low-water production. This method can be applied to reservoirs with different characteristics and initial reservoir conditions. Commercial software was used to test several cases using a semi-synthetic homogeneous reservoir with some characteristics as found in northeast Brazilian basins. It was realized a sensitivity analysis of some reservoir parameters, such as: oil zone, aquifer presence, gas cap presence and oil saturation on oil recovery and energy consumption. Then it was tested several cases studying the electrical variables considered more important in the process, such as: voltage, electrical configurations and electrodes positions. Energy optimization by electrodes voltage levels changes and electrical settings modify the intensity and the electrical current distribution in oil zone and, consequently, their influences in reservoir temperature reached at some regions. Results show which reservoir parameters were significant in order to improve oil recovery and energy requirement in for each reservoir. Most significant parameters on oil recovery and electrical energy delivered were oil thickness, presence of aquifer, presence of gas cap, voltage, electrical configuration and electrodes positions. Factors such as: connate water, water salinity and relative permeability to water at irreducible oil saturation had low influence on oil recovery but had some influence in energy requirements. It was possible to optimize energy consumption and oil recovery by electrical variables. Energy requirements can decrease by changing electrodes voltages during the process. This application can be extended to heavy oil reservoirs of high depth, such as offshore fields, where nowadays it is not applicable any conventional thermal process such as steam flooding

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

Análise da recuperação em reservatório de gás com baixa permeabilidade (TIGHT GAS) através do fraturamento hidráulico

With the increasing of energetic consumption in the worldwile, conventional reservoirs, known by their easy exploration and exploitation, are not being enough to satisfy this demand, what has made necessary exploring unconventional reservoirs. This kind of exploration demands developing more advanced technologies to make possible to exploit those hydrocarbons. Tight gas is an example of this kind of unconventional reservoir. It refers to sandstone fields with low porosity, around 8%, and permeabilities between 0.1 and 0.0001 mD, which accumulates considerable amounts of natural gas. That natural gas can only be extracted by applying hydraulic fracturing, aiming at stimulating the reservoir, by creating a preferential way through the reservoir to the well, changing and making easier the flow of fluids, thus increasing the productivity of those reservoirs. Therefore, the objective of this thesis is analyzing the recovery factor of a reservoir by applying hydraulic fracturing. All the studies were performed through simulations using the IMEX software, by CMG (Computer Modelling Group), in it 2012.10 version

Desenvolvimento de metodologia para determinação de Co, Cr, Fe, Mn, Ni, Se e V em amostras de água produzida da indústria do petróleo através da técnica ICP OES utilizando digestão por micro-ondas

O descarte ou reutilização da água produzida da indústria do petróleo é difícil por causa dos impactos ambientais causados devido à presença de alta salinidade e componentes tóxicos, ou pelo risco de obstrução nas colunas de produção devido à formação de incrustações que causam redução na produção de petróleo e enormes perdas no processo de extração. Assim, o conhecimento da composição química da água produzida é muito importante. O método proposto por este trabalho visa a determinação de elementos traço (Co, Cr, Fe, Mn, Ni, Se e V) em amostras de água produzida de petróleo por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) utilizando a digestão ácida assistida por micro-ondas para o preparo das amostras (15 g de amostra e 2 mL de HNO3 concentrado). A curva analítica construída em HNO3 2% v v-1 foi adotada para o método após verificar que não é necessário o uso de salinidade para equiparação de matriz. Para o elemento Ni, não há necessidade do uso de padrão interno, para os elementos Co, Cr, Fe, Mn e V os melhores resultados foram obtidos usando Sc como padrão interno. Para o elemento Se é recomendado o uso de Y como padrão interno. Os limites de detecção obtidos foram Co 0,67, Cr 1,2, Fe 2,3, Mn 0,49, Ni 1,9, Se 3,7 e V 5,5 μg L-1; e os limites de quantificação foram Co 2,2, Cr 4,0, Fe 7,7, Mn 1,6, Ni 6,5, Se 12,4 e V 18,3 μg L-1. A exatidão do procedimento foi verificada através de testes de recuperação em dois níveis de concentração (40 e 80 μg L-1) e análise dos materiais certificados de referência de água estuarina SLEW-2 e de água do mar NASS-5. Bons valores de recuperação foram obtidos e não houve diferença significativa (95% de confiança) entre os resultados obtidos e os valores certificados dos materiais de referência.

Degradação fotocatalítica de petróleo e seus derivados através da utilização de nanopartículas de dióxido de titânio puro e misturado com óxido de grafeno reduzido

Dissertação de mestrado integrado em Engenharia de Materiais

Resultados obtidos em mulheres portadoras de endometriose pélvica avançada e mulheres com ligadura tubária, submetidas a ICSI: análise comparativa

OBJETIVO: análise comparativa dos resultados obtidos em mulheres portadoras de endometriose pélvica avançada e mulheres com ligadura tubária, submetidas a injeção intracitoplasmática de espermatozóide (ICSI). MÉTODOS: noventa e três mulheres com diagnóstico de infertilidade, com ciclo menstrual normal, não submetidas a qualquer tratamento hormonal e cirúrgico durante o último ano, índice de massa corporal igual a 20-25, portadoras de ovários sem a presença de cistos ou tumores participaram deste estudo e foram divididas em dois grupos: tubário (TUB), 39 mulheres com ligadura tubária, e endometriose (EDT), 54 mulheres com EDT-III e EDT-IV, submetidas a indução ovulatória com FSH-r e ICSI. Os dados clínicos e laboratoriais foram comparados. Testes chi2, Fisher, t pareado, t de Student e Mann-Whitney foram empregados. RESULTADOS: níveis mais baixos de estradiol (2243,1 vs 1666,3; p=0,001) e número menor de folículos por paciente (16,9 vs 13,9; p=0,001) foram recuperados no grupo EDT, apesar da utilização de maior número de unidades de FSH-r (1775,6 vs 1998,6; p=0,007, para TUB e EDT, respectivamente). Não houve diferença quanto à taxa de recuperação ovocitária (69 vs 73,5%; p=0,071) assim como nas taxas de fertilização normal (83,7 vs 81,7%; p=0,563 respectivamente para TUB e EDT. No entanto, menor número de pré-embriões ótimos foi obtido no grupo EDT (36,4 vs 24,8%, respectivamente para TUB e EDT; p=0,005). As taxas de gestação total (41,0 vs 42,6%; p=0,950) e de implantação (13,9% x 14,5%; p=0,905) não foram significativamente diferentes quando TUB e EDT foram comparados. CONCLUSÕES: os ovários das mulheres do grupo EDT parecem ser menos responsivos à indução da ovulação com FSH-r. A endometriose parece comprometer o número médio de folículos e de pré-embriões ótimos sem prejudicar as taxas de recuperação ovocitária e fertilização. No entanto, uma vez formados, os pré-embriões do grupo EDT exibem chances de implantação e gestação semelhantes àquelas do grupo TUB.

O Mecanismo de transmissão de preços do petróleo para a gasolina e para o diesel nos EUA nos anos 2000

Através de um Modelo de Correção de Erros este estudo explora possíveis assimetrias no passthrough dos preços de petróleos para os preços do diesel e da gasolina no mercado dos Estados Unidos, analisando, principalmente, se as inversões das tendências das demandas destes derivados afetaram o mecanismo de transmissão de preços. A partir de dados mensais de janeiro de 2001 a dezembro de 2012, para a gasolina foram encontrados indícios de que houve alterações do passthrough em decorrência da quebra da demanda. Porém, é válido destacar que tal resultado ocorreu concomitantemente ao período de recuperação de preços presenciada após a crise de 2008. Em relação ao diesel, não há indícios de que houve alterações no passthrough. Por fim, há evidências da redução do WTI como petróleo de referência em decorrência da sua desvalorização a partir de 2010.