Estudo dos ácidos naftênicos do gasóleo pesado derivado do petróleo Marlim

Pouco se conhece sobre a estrutura dos ácidos naftênicos presentes no petróleo brasileiro e derivados. Existem alguns trabalhos realizados com a fração ácida, dos óleos crus, direcionados à aplicação geológica, visto que os ácidos hopanóicos, constituintes dessa fração, podem ser indicadores de migração e maturação. Entretanto, além do interesse geológico, a fração ácida, também está relacionada à corrosão nos equipamentos de refino desses óleos, motivando pesquisas para separar e identificar os ácidos responsáveis pelo problema corrosivo nas refinarias. Os ácidos naftênicos (AN) representam um teor muito pequeno, tanto nos óleos crus, quanto nos derivados, dos quais são constituintes. A concentração bastante baixa destes ácidos, em matrizes com composição ampla e variada, dificulta sua extração. Portanto, as etapas de separação, concentração e purificação da amostra, além da análise, demandam tempo e trabalho extensivos. Os objetivos deste trabalho de pesquisa podem ser resumidos em, otimizar o método de extração e análise, para os ácidos presentes no gasóleo pesado (GOP) e verificar seu efeito corrosivo. Neste trabalho, utilizou-se extração líquido-líquido (ELL), cromatografia líquida preparativa com sílica, cromatografia de troca iônica com as resinas A-21e A-27 e extração em fase sólida (SPE) com dessorção em banho de ultra-som (US), aplicada no extrato da ELL, para extrair a fração ácida do (GOP) do petróleo Marlim (Campos, Rio de Janeiro, Brasil). A análise foi realizada, através de cromatografia em fase gasosa com detector de espectrometria de massas e ionização por impacto de elétrons, após uma etapa de derivatização com metanol/BF3 ou com N-metil-N-(terc-butildimetilsilil)trifluoracetamida. Os resultados apresentados indicam a presença de ácidos carboxílicos, pertencentes a famílias de compostos alicíclicos e cíclicos, com até quatro anéis na molécula. Também foi verificado o efeito corrosivo da amostra de GOP sobre amostras de aço ASTM 1010, associado à presença de ácidos naftênicos nesta amostra.

Estudo do desempenho de reforços de pavimentos asfálticos em via urbana sujeita à tráfego comercial pesado

O presente trabalho apresenta um estudo experimental sobre o desempenho de reforços de pavimentos asfálticos de uma via urbana com elevado volume de tráfego comercial pesado no município de São Paulo, monitorados durante quatro anos desde a mais recente restauração executada. A pesquisa envolveu o acompanhamento sistemático de seções pré-selecionadas na Avenida dos Bandeirantes, por meio de medidas de irregularidade longitudinal com um medidor tipo resposta bem como do trincamento superficial com o mapeamento e registros realizados em campo. A Avenida dos Bandeirantes é o principal corredor de interligação entre as vias localizadas no Oeste do Estado de São Paulo com o Porto de Santos, absorvendo 58% do total de veículos que passam pela Região Metropolitana, totalizando aproximadamente de 250.000 veículos/dia (em ambos os sentidos), sendo destes, cerca de 20.000 caminhões. Combase em dados levantados em campo e em projetos de restauração anteriormente realizadosforam desenvolvidos modelos empíricos de previsão de desempenho dos reforçosde pavimentos asfálticos,levando em consideração fatores relevantes para seu comportamento. Para isto, foram testados modelos lineares com diferentes estruturas de covariância e também modelos de regressão logística, que ao final mostraram-se mais conservadores que aqueles empregados na previsão de desempenho do programa HDM-4, para as condições do problema, no que tange à evolução do trincamento. No caso de previsão de irregularidade, observaram-se resultados similares entre os modelos desenvolvidos e aqueles preconizados pelo programa HDM-4. Fornecer suporte para decisões relacionadas à gerência de manutenção de pavimentos urbanos de grandes metrópoles e considerar modelos estatísticos ainda pouco utilizados para prever desempenho foram as principais contribuições buscadas durante a realização da pesquisa.

Injeção de vapor e solvente como um método de recuperação avançada em reservatório avançada em reservatórios de óleo pesado

Currently a resource more and more used by the petroleum industry to increase the efficiency of steam flood mechanism is the addition of solvents. The process can be understood as a combination of a thermal method (steam injection) with a miscible method (solvent injection), promoting, thus, the reduction of interfacial tensions and oil viscosity. The use of solvent alone tends to be limited because of its high cost. When co-injected with steam, the vaporized solvent condenses in the cooler regions of the reservoir and mixes with the oil, creating a zone of low viscosity between the steam and the heavy oil. The mobility of the displaced fluid is then improved, resulting in an increase of oil recovery. To better understand this improved oil recovery method, a numerical study of the process was done contemplating the effects of some operational parameters (distance between wells, injection steam rate, kind of solvent and injected solvent volume)on the accumulated production of oil, recovery factor and oil-steam rate. Semisynthetic models were used in this study but reservoir data can be extrapolated for practical applications situations on Potiguar Basin. Simulations were performed in STARS (CMG, 2007.11). It was found that injected solvent volumes increased oil recovery and oil rates. Further the majority of the injected solvent was produced and can be recycled

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

Análise da trajetória de poços horizontais em reservatório de óleo pesado

The application of thermal methods, to increase the recovery of heavy oil in mature fields through drainage with multilateral and horizontal wells, has been thoroughly studied, theorically, experimentally, testing new tools and methods. The continuous injection of steam, through a steam injector well and a horizontal producer well in order to improve horizontal sweep of the fluid reservoir, it is an efficient method. Starting from an heterogeneous model, geologically characterized, modeling geostatistics, set history and identification of the best path of permeability, with seismic 3D, has been dubbed a studying model. It was studied horizontal wells in various directions in relation to the steam and the channel of higher permeability, in eight different depths. Into in the same area were studied, the sensitivity of the trajectories of horizontal wells, according to the depth of navigation. With the purpose of obtaining the highest output of oil to a particular flow, quality, temperature and time for the injection of steam. The wells studied showed a significant improvement in the cumulative oil recovery in one of the paths by promoting an alternative to application in mature fields or under development fields with heavy oil

Estudo dos parâmetros operacionais do processo de combustão in situ em reservatório de petróleo pesado

The occurrence of heavy oil reservoirs have increased substantially and, due to the high viscosity characteristic of this type of oil, conventional recovery methods can not be applied. Thermal methods have been studied for the recovery of this type of oil, with a main objective to reduce its viscosity, by increasing the reservoir temperature, favoring the mobility of the oil and allowing an increasing in the productivity rate of the fields. In situ combustion (ISC) is a thermal recovery method in which heat is produced inside the reservoir by the combustion of part of the oil with injected oxygen, contrasting with the injection of fluid that is heated in the surface for subsequent injection, which leads to loss heat during the trajectory to the reservoir. The ISC is a favorable method for recovery of heavy oil, but it is still difficult to be field implemented. This work had as an objective the parametric analysis of ISC process applied to a semi-synthetic reservoir with characteristics of the Brazilian Northeast reservoirs using vertical production and vertical injection wells, as the air flow injection and the wells completions. For the analysis, was used a commercial program for simulation of oil reservoirs using thermal processes, called Steam, Thermal and Advanced Processes Reservoir Simulator (STARS) from Computer Modelling Group (CMG). From the results it was possible to analyze the efficiency of the ISC process in heavy oil reservoirs by increasing the reservoir temperature, providing a large decrease in oil viscosity, increasing its mobility inside the reservoir, as well as the improvement in the quality of this oil and therefore increasing significantly its recovered fraction. Among the analyzed parameters, the flow rate of air injection was the one which had greater influence in ISC, obtaining higher recovery factor the higher is the flow rate of injection, due to the greater amount of oxygen while ensuring the maintenance of the combustion front

Um modelo matemático baseado em wavelets para análise do método térmico de recuperação de óleo pesado aplicando irradiação eletromagnética

This work proposes a model to investigate the use of a cylindrical antenna used in the thermal method of recovering through electromagnetic radiation of high-viscosity oil. The antenna has a simple geometry, adapted dipole type, and it can be modelled by using Maxwell s equation. The wavelet transforms are used as basis functions and applied in conjunction with the method of moments to obtain the current distribution in the antenna. The electric field, power and temperature distribution are carefully calculated for the analysis of the antenna as electromagnetic heating. The energy performance is analyzed based on thermo-fluid dynamic simulations at field scale, and through the adaptation in the Steam Thermal and Advanced Processes Reservoir Simulator (STARS) by Computer Modelling Group (CMG). The model proposed and the numerical results obtained are stable and presented good agreement with the results reported in the specialized literature

Análise de viabilidade de injeção de fluidos alternativos ao vapor em reservatórios de óleo pesado

Many of hydrocarbon reserves existing in the world are formed by heavy oils (°API between 10 and 20). Moreover, several heavy oil fields are mature and, thus, offer great challenges for oil industry. Among the thermal methods used to recover these resources, steamflooding has been the main economically viable alternative. Latent heat carried by steam heats the reservoir, reducing oil viscosity and facilitating the production. This method has many variations and has been studied both theoretically and experimentally (in pilot projects and in full field applications). In order to increase oil recovery and reduce steam injection costs, the injection of alternative fluid has been used on three main ways: alternately, co-injected with steam and after steam injection interruption. The main objective of these injection systems is to reduce the amount of heat supplied to the reservoir, using cheaper fluids and maintaining the same oil production levels. This works discusses the use of carbon dioxide, nitrogen, methane and water as an alternative fluid to the steam. The analyzed parameters were oil recoveries and net cumulative oil productions. The reservoir simulation model corresponds to an oil reservoir of 100 m x 100 m x 28 m size, on a Cartesian coordinates system (x, y and z directions). It is a semi synthetic model with some reservoir data similar to those found in Brazilian Potiguar Basin. All studied cases were done using the simulator STARS from CMG (Computer Modelling Group, version 2009.10). It was found that waterflood after steam injection interruption achieved the highest net cumulative oil compared to other fluids injection. Moreover, it was observed that steam and alternative fluids, co-injected and alternately, did not present increase on profitability project compared with steamflooding

Análise paramétrica da injeção de vapor e solvente em reservatórios de óleo pesado

A significant fraction of the hydrocarbon reserves in the world is formed by heavy oils. From the thermal methods used to recovery these resources, Steamflooding has been one of the main economically viable alternatives. In Brazil, this technology is widely used by Petrobras in Northeast fields. Latent heat carried by steam heats the oil in the reservoir, reducing its viscosity and facilitating the production. In the last years, an alternative more and more used by the oil industry to increase the efficiency of this mechanism has been the addition of solvents. When co-injected with steam, the vaporized solvent condenses in the cooler regions of the reservoir and mixes with the oil, creating a low viscosity zone between the steam and the heavy oil. The mobility of the displaced fluid is then improved, resulting in an increase of oil recovery. To better understand this improved oil recovery method and investigate its applicability in reservoirs with properties similar to those found in Potiguar Basin, a numerical study was done to analyze the influence of some operational parameters (steam injection rate, injected solvent volume and solvent type) on oil recovery. Simulations were performed in STARS ("Steam, Thermal, and Advanced Processes Reservoir Simulator"), a CMG ("Computer Modelling Group") program, version 2009.10. It was found that solvents addition to the injected steam not only anticipated the heated oil bank arrival to the producer well, but also increased the oil recovery. Lower cold water equivalent volumes were required to achieve the same oil recoveries from the models that injected only steam. Furthermore, much of the injected solvent was produced with the oil from the reservoir

Produção de matéria seca em pastagem de Tifton 85 irrigada, com diferentes doses de dejeto líquido de suíno

O dejeto líquido de suíno (DLS) pode constituir-se em excelente fonte de adubação em pastagem, com aplicação por aspersão, desde que seja assegurada a proteção do meio ambiente. Apesar de seu comprovado potencial para uso em sequeiro, pouco se conhece sobre o comportamento da cultivar Tifton 85 em sistemas sob irrigação e sob aplicação de DLS. Para determinar a produção de matéria seca pré-pastejo de Tifton 85 com DLS, foi conduzido um experimento na Fazenda-Escola da Universidade de Uberaba, irrigado por aspersão em malha, com aplicação de 0; 50; 100 e 200 m³ ha-1 ano-1 de DLS. Houve efeito significativo das doses de DLS em relação à produção de matéria seca pré-pastejo, ocorrendo acréscimos de produção com o aumento das doses. O fornecimento de 200 m³ ha-1 ano-1 de DLS possibilitou produção de 5.928 kg de matéria seca (MS) da forrageira por ciclo de 28 dias.

Otimização da injeção cíclica de vapor em reservatório de óleo pesado

Thermal methods made heavy oil production possible in fields where primary recovery failed. Throughout the years steam injection became one of the most important alternatives to increase heavy oil recovery. There are many types of steam injection, and one of them is the cyclic steam injection, which has been used with success in several countries, including Brazil. The process involves three phases: firstly, steam is injected, inside of the producing well; secondly, the well is closed (soak period); and finally, the well is put back into production. These steps constitute one cycle. The cycle is repeated several times until economical production limit is reached. Usually, independent of reservoir type, as the number of cycles increases the cyclic injection turns less efficient. This work aims to analyze rock and reservoir property influence in the cyclic steam injection. The objective was to study the ideal number of cycles and, consequently, process optimization. Simulations were realized using the STARS simulator from the CMG group based in a proposed reservoir model. It was observed that the reservoir thickness was the most important parameter in the process performance, whilst soaking time influence was not significant

Remoção de frações de óleo leve e pesado de rocha calcária através de sistemas microemulsionados

In this research the removal of light and heavy oil from disintegrated limestone was investigated with use of microemulsions. These chemical systems were composed by surfactant, cosurfactant, oil phase and aqueous phase. In the studied systems, three points in the water -rich microemulsion region of the phase diagrams were used in oil removal experiments. These microemulsion systems were characterized to evaluate the influence of particle size, surface tension, density and viscosity in micellar stability and to understand how the physical properties can influence the oil recovery process. The limestone rock sample was characterized by thermogravimetry, BET area, scanning electron microscopy and X-ray fluorescence. After preparation, the rock was placed in contact with light and heavy oil solutions to allow oil adsorption. The removal tests were performed to evaluate the influence of contact time (1 minute, 30 minutes, 60 minutes and 120 minutes), the concentration of active matter (20, 30 and 40 %), different cosurfactants and different oil phases. For the heavy oil, the best result was on SME 1, with 20 % of active matter, 1 minute of contact time, with efficiency of 93,33 %. For the light oil, also the SME 1, with 20 % of active matter, 120 minutes of contact time, with 62,38 % of efficiency. From the obtained results, it was possible to conclude that microemulsions can be considered as efficient chemical systems for oil removal from limestone formations

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Análise cromossômica e molecular do javali europeu Sus scrofa scrofa e do suíno doméstico Sus scrofa domesticus

A presente investigação teve como objetivos: analisar animais presentes em diferentes criações de javalis no estado de São Paulo, com o intuito de auxiliar a identificação de javalis puros assim como javalis híbridos provenientes do cruzamento com o suíno doméstico, para tanto foram utilizadas avaliação do fenótipo dos animais, análises citogenéticas e da técnica molecular de RAPD (Random Amplified Polymorphic DNA).O estudo do número de cromossomos nas células diplóides em 104 animais destinados a análise citogenética e fenotípica, revelou polimorfismo de 2n=36, 37 e 38 cromossomos. Por meio da técnica de bandamento GTG foi possível identificação da translocação Robertsoniana entre os cromossomos 15 e 17 como responsável por esse polimorfismo. Todavia, somente com a análise citogenética isolada, não foi possível determinar se a origem desse polimorfismo é decorrente das hibridações com o suíno doméstico ou se são características inerentes ao javali. Contudo, quando associado a análise citogenética com as características fenotípicas, foi possível identificar a existência de hibridações. A análise citogenética nos animais submetidos a técnica de RAPD, revelou 2n=36 cromossomos nos 16 javalis assim como 2n=38 cromossomos nos 11 suínos e, por meio dessa técnica, foram possíveis agrupamentos, separando o suíno doméstico, javali e um possível híbrido revelando-se uma técnica com potencial no auxílio da identificação de híbridos.

Determinação da potência mecânica no limite entre os domínios pesado/severo do crawl-atado

The aim of this study was to access the P-t(Lim) model in swimming, applying the load control available in full tethered swim condition. Its physiological meaning for the determination of boundary of heavy/severe domains was assessed from the relationships with critical velocity (CV), critical power (CP) and maximal lactate steady state (MLSS). The velocity at MLSS (v(MLSS) = 1.17 +/- 0.11 m/s) and CV (1.19 +/- 0.12 m/s) were significantly different. Similarly, the power at MLSS (p(MFEL) = 89.2 +/- 15.1 W) and CP (99.4 +/- 22.9 W) were significantly different. There was no difference between lactate concentration at vMLSS (3.54 +/- 0.9 mM) and p(MLSS) (3.76 +/- 0.6 mM). Significant Pearson's coefficients (r > 0.70) were observed among v(MLSS) and P-MLSS with their respective values on time-limited model. Thus, the tethered-crawl condition seems to be valid to determine the boundary of heavy/severe domains, and to access the aerobic capacity of swimmers.