Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Estudo paramétrico da injeção de vapor em reservatórios delgados

Exploration of heavy oil reservoirs is increasing every year in worldwide, because the discovery of light oil reservoirs is becoming increasingly rare. This fact has stimulated the research with the purpose of becoming viable, technically and economically, the exploration of such oil reserves. In Brazil, in special in the Northeast region, there is a large amount of heavy oil reservoir, where the recovery by the so called secondary methods Water injection or gas injection is inefficient or even impracticable in some reservoirs with high viscosity oils (heavy oils). In this scenario, steam injection appears as an interesting alternative for recover of these kinds of oil reservoirs. Its main mechanism consists of oil viscosity reduction through steam injection, increasing reservoir temperature. This work presents a parametric simulation study of some operational and reservoir variables that had influence on oil recovery in thin reservoirs typically found in Brazilian Northeast Basins, that use the steam injection as improved oil recovery method. To carry out simulations, it was used the commercial software STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator) from CMG (Computer Modeling Group) version 2007.11. Reservoirs variables studied were horizontal permeability, vertical and horizontal permeability ratio, water zone and pay zone thickness ratio, pay zone thickness and thermal conductivity of the rock. Whereas, operational parameters studied were distance between wells and steam injection rate. Results showed that reservoir variables that had more influence on oil recovery were horizontal permeability and water zone and pay zone thickness ratio. In relation to operational variables, results showed that short distances between wells and low steam injection rates improved oil recovery

Estudo da segregação gravitacional do processo de injeção de vapor em reservátórios heterogêneos

Due to reservoirs complexity and significantly large reserves, heavy oil recovery has become one of the major oil industry challenges. Thus, thermal methods have been widely used as a strategic method to improve heavy oil recovery. These methods improve oil displacement through viscosity reduction, enabling oil production in fields which are not considered commercial by conventional recovery methods. Among the thermal processes, steam flooding is the most used today. One consequence in this process is gravity segregation, given by difference between reservoir and injected fluids density. This phenomenon may be influenced by the presence of reservoir heterogeneities. Since most of the studies are carried out in homogeneous reservoirs, more detailed studies of heterogeneities effects in the reservoirs during steam flooding are necessary, since most oil reservoirs are heterogeneous. This paper presents a study of reservoir heterogeneities and their influence in gravity segregation during steam flooding process. In this study some heterogeneous reservoirs with physical characteristics similar those found in the Brazilian Northeast Basin were analyzed. To carry out the simulations, it was used the commercial simulator STARS by CMG (Computer Modeling Group) - version 2007.11. Heterogeneities were modeled with lower permeability layers. Results showed that the presence of low permeability barriers can improve the oil recovery, and reduce the effects of gravity segregation, depending on the location of heterogeneities. The presence of these barriers have also increased the recovered fraction even with the reduction of injected steam rate

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

Pastas compósitas cimento/sílica/polímero para cimentação de poços de baixa profundidade sujeitas à injeção de vapor

The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection

Estudo do comportamento de pastas compósitas cimento/sílica/poliuretana para poços de petróleo HPHT

Os poços HPHT atravessam zonas anormalmente pressurizadas e com altos gradientes de temperatura. Esses poços apresentam elevadas concentrações de tensões produzidas pelas operações de perfuração e fraturamento hidráulico, flutuações da pressão e temperatura, forças dinâmicas geradas durante a perfuração, formações inconsolidadas, entre outros aspectos, podendo resultar em falhas mecânicas na bainha de cimento. Tais falhas comprometem a estabilidade mecânica do poço e o isolamento das zonas produtoras de óleos e/ou gás. Para que operações corretivas não se façam necessárias, é preciso adequar as pastas às condições de cada poço. Sistemas de pastas de cimento para poços HPHT requerem um bom controle de suas propriedades termo-mecânicas. Visto que a temperaturas superiores a 110 oC (230 oF) o cimento, após alcançar um valor máximo de resistência, inicia um processo de perda de resistência (retrogressão). Para prevenir esse efeito substitui-se parcialmente o cimento Portland por sílica com objetivo de incrementar a reação pozolânica. Esta reação modifica a trajetória do processo natural de hidratação do cimento, o gel de silicato de cálcio hidratado (C-S-H) se converte em várias outras fases com maior resistência. Polímeros também são adicionados para proporcionar maior flexibilidade e agir como barreira à propagação de trincas desenvolvidas sob tensão. O presente trabalho teve como objetivo estudar o comportamento do sistema cimento/sílica/polímero quando submetido às condições de alta temperatura e alta pressão. Foram formuladas pastas de cimento puro, pastas contendo 40 % BWOC de sílica flour e pastas com diferentes concentrações de poliuretana (5 % a 25 %) e 40 % BWOC de sílica flour. O peso específico das pastas foi fixado em 1,87 g/cm3 (15,6 lb/gal). Os resultados demonstram que as resistências da pasta contendo 40% de sílica e das com adição de polímero foram muito superiores a da pasta de cimento puro, não ocorrendo o efeito da retrogressão. As pastas com polímero apresentaram um crescente aumento da tenacidade com o aumento da concentração da mesma, sendo assim capaz de suportar as tensões. Além de se manterem estáveis termicamente acima de 180 ºC. O sistema também apresentou excelentes resultados de filtrado, reologia, água livre, estabilidade e permeabilidade. Sendo assim, o mesmo mostrou ser aplicável a poços HPHT

Estudo de sistemas multicomponentes no processo de injeção cíclica de vapor

In Brazilian Northeast there are reservoirs with heavy oil, which use steam flooding as a recovery method. This process allows to reduce oil viscosity, increasing its mobility and consequently its oil recovery. Steam injection is a thermal method and can occurs in continues or cyclic form. Cyclic steam stimulation (CSS) can be repeated several times. Each cycle consisting of three stages: steam injection, soaking time and production phase. CSS becomes less efficient with an increase of number of cycles. Thus, this work aims to study the influence of compositional models in cyclic steam injection and the effects of some parameters, such like: flow injection, steam quality and temperature of steam injected, analyzing the influence of pseudocomponents numbers on oil rate, cumulative oil, oil recovery and simulation time. In the situations analyzed was compared the model of fluid of three phases and three components known as Blackoil . Simulations were done using commercial software (CMG), it was analyzed a homogeneous reservoir with characteristics similar to those found in Brazilian Northeast. It was observed that an increase of components number, increase the time spent in simulation. As for analyzed parameters, it appears that the steam rate, and steam quality has influence on cumulative oil and oil recovery. The number of components did not a lot influenced on oil recovery, however it has influenced on gas production

Comportamento agronômico de girassol no período de safrinha em Jaguariúna-SP.

2009

Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

Análise comparativa entre simuladores de linha de fluxo e diferenças finitas para um reservatório de petróleo submetido a injeção de água

Water injection is the most widely used method for supplementary recovery in many oil fields due to various reasons, like the fact that water is an effective displacing agent of low viscosity oils, the water injection projects are relatively simple to establish and the water availability at a relatively low cost. For design of water injection projects is necessary to do reservoir studies in order to define the various parameters needed to increase the effectiveness of the method. For this kind of study can be used several mathematical models classified into two general categories: analytical or numerical. The present work aims to do a comparative analysis between the results presented by flow lines simulator and conventional finite differences simulator; both types of simulators are based on numerical methods designed to model light oil reservoirs subjected to water injection. Therefore, it was defined two reservoir models: the first one was a heterogeneous model whose petrophysical properties vary along the reservoir and the other one was created using average petrophysical properties obtained from the first model. Comparisons were done considering that the results of these two models were always in the same operational conditions. Then some rock and fluid parameters have been changed in both models and again the results were compared. From the factorial design, that was done to study the sensitivity analysis of reservoir parameters, a few cases were chosen to study the role of water injection rate and the vertical position of wells perforations in production forecast. It was observed that the results from the two simulators are quite similar in most of the cases; differences were found only in those cases where there was an increase in gas solubility ratio of the model. Thus, it was concluded that in flow simulation of reservoirs analogous of those now studied, mainly when the gas solubility ratio is low, the conventional finite differences simulator may be replaced by flow lines simulator the production forecast is compatible but the computational processing time is lower.

Estudo comparativo da injeção de água usando poços verticais e horizontais

Oil recovery using waterflooding has been until now the worldwide most applied method, specially for light oil recovery, its success is mainly because of the low costs involved and the facilities of the injection process. The Toe- To-Heel Waterflooding TTHWTM method uses a well pattern of vertical injector wells completed at the bottom of the reservoir and horizontal producer wells completed at the top of it. The main producing mechanism is gravitational segregation in short distance. This method has been studied since the early 90´s and it had been applied in Canada with positive results for light heavy oils, nevertheless it hasn´t been used in Brazil yet. In order to verify the applicability of the process in Brazil, a simulation study for light oil was performed using Brazilian northwest reservoirs characteristics. The simulations were fulfilled using the STARS module of the Computer Modelling Group Software, used to perform improved oil recovery studies. The results obtained in this research showed that the TTHWTM well pattern presented a light improvement in terms of recovery factor when compared to the conventional 5- Spot pattern, however, it showed lower results in the economic evaluation

Avaliação da biodessulfurização de 4-metildibenzotiofeno por Rhodococus rhodochrous (NRRL B-2149)

Crude oil has between 0.04 up to 5% of sulphur, the higher the oil the higher the sulphur levels. Sulphur usually gives problems such as corrosion in refinery, and once burnt produces SO2 that goes to atmosphere. This work aim to investigate the capacity of Rhodococcus rhodochrous (NRRL B-2149) to metabolize the model compound 4-methyldibenzotiophene (4-MDBT), to remove the sulphur and transform it in 2-hydroxybiphenyl (2-HBF) and sulphite using the 4S pathway. Kynetic runs were carried out in shaker at 120 rpm and 32°C. Samples were taken every 12h to assay substrate consume as well as cells production using HPLC. Results showed that R. rhodochrous NRRL B-2149 can use the 4S pathway in order to remove sulphur without change the carbon chain of the molecule as well as that cells and 4-MDBT affects the product formation. The production of 2-hydroxybiphenyl has interest for industry once it is a potent biocide. However, evaluation is necessary in order to obtain better results compatible with industry needs

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Estudo de modelos composicionais de óleo na injeção contínua de vapor

The objective of the thermal recovery is to heat the resevoir and the oil in it to increase its recovery. In the Potiguar river basin there are located several heavy oil reservoirs whose primary recovery energy provides us with a little oil flow, which makes these reservoirs great candidates for application of a method of recovery advanced of the oil, especially the thermal. The steam injection can occur on a cyclical or continuous manner. The continuous steam injection occurs through injection wells, which in its vicinity form a zone of steam that expands itself, having as a consequence the displace of the oil with viscosity and mobility improved towards the producing wells. Another possible mechanism of displacement of oil in reservoirs subjected to continuous injection of steam is the distillation of oil by steam, which at high temperatures; their lighter fractions can be vaporized by changing the composition of the oil produced, of the oil residual or to shatter in the amount of oil produced. In this context, this paper aims to study the influence of compositional models in the continuous injection of steam through in the analysis of some parameters such as flow injection steam and temperature of injection. Were made various leading comparative analysis taking the various models of fluid, varying from a good elementary, with 03 pseudocomponents to a modeling of fluids with increasing numbers of pseudocomponents. A commercial numerical simulator was used for the study from a homogeneous reservoir model with similar features to those found in northeastern Brazil. Some conclusions as the increasing of the simulation time with increasing number of pseudocomponents, the significant influence of flow injection on cumulative production of oil and little influence of the number of pseudocomponents in the flows and cumulative production of oil were found