Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Efeito da força iônica nas propriedades de fluidos de perfuração aquosos à base de polímeros carboxilados e sulfatados

In the well drilling operations problems caused by contamination of the drilling fluid are common. The dissolution of ions from the geological formations affects the rheological and filtration properties of the fluids. These ions shield the charges of ionic polymers, leading to its precipitation. In this work was performed a detailed study on the stability of the properties of aqueous solutions and aqueous drilling fluids in the presence of sulphated and carboxylated polymers, using carboxymethylcellulose and kappa-carrageenan as polymer compounds carboxylated and sulfated model, respectively. The effects of ionic strength of the aqueous medium containing Na+, Mg2+ and Ca2+ on rheological properties of the polymer and drilling fluids solutions were evaluated by varying the concentration of salts, pH and temperature. It was observed that the fluids with κ-carrageenan suffered less influence against the contamination by the ions at pH 9 to 10, even at higher concentrations, but higher influence on pH> 11. The fluids containing carboxymethylcellulose were more sensitive to contamination, with rapid reduction in viscosity and significant increase of the filtrate volume, while the fluid based polymer sulfated kappa-carrageenan showed evidence of interaction with cations and preserve the rheological properties and improved stability the volume of filtrate.

Efeito da força iônica nas propriedades de fluidos de perfuração aquosos à base de polímeros carboxilados e sulfatados

In the well drilling operations problems caused by contamination of the drilling fluid are common. The dissolution of ions from the geological formations affects the rheological and filtration properties of the fluids. These ions shield the charges of ionic polymers, leading to its precipitation. In this work was performed a detailed study on the stability of the properties of aqueous solutions and aqueous drilling fluids in the presence of sulphated and carboxylated polymers, using carboxymethylcellulose and kappa-carrageenan as polymer compounds carboxylated and sulfated model, respectively. The effects of ionic strength of the aqueous medium containing Na+, Mg2+ and Ca2+ on rheological properties of the polymer and drilling fluids solutions were evaluated by varying the concentration of salts, pH and temperature. It was observed that the fluids with κ-carrageenan suffered less influence against the contamination by the ions at pH 9 to 10, even at higher concentrations, but higher influence on pH> 11. The fluids containing carboxymethylcellulose were more sensitive to contamination, with rapid reduction in viscosity and significant increase of the filtrate volume, while the fluid based polymer sulfated kappa-carrageenan showed evidence of interaction with cations and preserve the rheological properties and improved stability the volume of filtrate.

Criação de zonas de alta permeabilidade em fraturas: modelagem numérica do Lajedo de Soledade, Formação Jandaíra, Bacia Potiguar

The fracturing in carbonate rocks has been attracting increasingly attention due to new oil discoveries in carbonate reservoirs. This study investigates how the fractures (faults and joints) behave when subjected to different stress fields and how their behavior may be associated with the generation of karst and consequently to increased secondary porosity in these rocks. In this study I used satellite imagery and unmanned aerial vehicle UAV images and field data to identify and map faults and joints in a carbonate outcrop, which I consider a good analogue of carbonate reservoir. The outcrop comprises rocks of the Jandaíra Formation, Potiguar Basin. Field data were modeled using the TECTOS software, which uses finite element analysis for 2D fracture modeling. I identified three sets of fractures were identified: NS, EW and NW-SE. They correspond to faults that reactivate joint sets. The Ratio of Failure by Stress (RFS) represents stress concentration and how close the rock is to failure and reach the Mohr-Coulomb envelopment. The results indicate that the tectonic stresses are concentrated in preferred structural zones, which are ideal places for carbonate dissolution. Dissolution was observed along sedimentary bedding and fractures throughout the outcrop. However, I observed that the highest values of RFS occur in fracture intersections and terminations. These are site of karst concentration. I finally suggest that there is a relationship between stress concentration and location of karst dissolution in carbonate rocks.

Criação de zonas de alta permeabilidade em fraturas: modelagem numérica do Lajedo de Soledade, Formação Jandaíra, Bacia Potiguar

The fracturing in carbonate rocks has been attracting increasingly attention due to new oil discoveries in carbonate reservoirs. This study investigates how the fractures (faults and joints) behave when subjected to different stress fields and how their behavior may be associated with the generation of karst and consequently to increased secondary porosity in these rocks. In this study I used satellite imagery and unmanned aerial vehicle UAV images and field data to identify and map faults and joints in a carbonate outcrop, which I consider a good analogue of carbonate reservoir. The outcrop comprises rocks of the Jandaíra Formation, Potiguar Basin. Field data were modeled using the TECTOS software, which uses finite element analysis for 2D fracture modeling. I identified three sets of fractures were identified: NS, EW and NW-SE. They correspond to faults that reactivate joint sets. The Ratio of Failure by Stress (RFS) represents stress concentration and how close the rock is to failure and reach the Mohr-Coulomb envelopment. The results indicate that the tectonic stresses are concentrated in preferred structural zones, which are ideal places for carbonate dissolution. Dissolution was observed along sedimentary bedding and fractures throughout the outcrop. However, I observed that the highest values of RFS occur in fracture intersections and terminations. These are site of karst concentration. I finally suggest that there is a relationship between stress concentration and location of karst dissolution in carbonate rocks.

Resolução em tomografia de tempo de trânsito poço-a-poço: a dependência da iluminação

The key aspect limiting resolution in crosswell traveltime tomography is illumination, a well known result but not as well exemplified. Resolution in the 2D case is revisited using a simple geometric approach based on the angular aperture distribution and the Radon Transform properties. Analitically it is shown that if an interface has dips contained in the angular aperture limits in all points, it is correctly imaged in the tomogram. By inversion of synthetic data this result is confirmed and it is also evidenced that isolated artifacts might be present when the dip is near the illumination limit. In the inverse sense, however, if an interface is interpretable from a tomogram, even an aproximately horizontal interface, there is no guarantee that it corresponds to a true interface. Similarly, if a body is present in the interwell region it is diffusely imaged in the tomogram, but its interfaces - particularly vertical edges - can not be resolved and additional artifacts might be present. Again, in the inverse sense, there is no guarantee that an isolated anomaly corresponds to a true anomalous body because this anomaly can also be an artifact. Jointly, these results state the dilemma of ill-posed inverse problems: absence of guarantee of correspondence to the true distribution. The limitations due to illumination may not be solved by the use of mathematical constraints. It is shown that crosswell tomograms derived by the use of sparsity constraints, using both Discrete Cosine Transform and Daubechies bases, basically reproduces the same features seen in tomograms obtained with the classic smoothness constraint. Interpretation must be done always taking in consideration the a priori information and the particular limitations due to illumination. An example of interpreting a real data survey in this context is also presented.

Resolução em tomografia de tempo de trânsito poço-a-poço: a dependência da iluminação

The key aspect limiting resolution in crosswell traveltime tomography is illumination, a well known result but not as well exemplified. Resolution in the 2D case is revisited using a simple geometric approach based on the angular aperture distribution and the Radon Transform properties. Analitically it is shown that if an interface has dips contained in the angular aperture limits in all points, it is correctly imaged in the tomogram. By inversion of synthetic data this result is confirmed and it is also evidenced that isolated artifacts might be present when the dip is near the illumination limit. In the inverse sense, however, if an interface is interpretable from a tomogram, even an aproximately horizontal interface, there is no guarantee that it corresponds to a true interface. Similarly, if a body is present in the interwell region it is diffusely imaged in the tomogram, but its interfaces - particularly vertical edges - can not be resolved and additional artifacts might be present. Again, in the inverse sense, there is no guarantee that an isolated anomaly corresponds to a true anomalous body because this anomaly can also be an artifact. Jointly, these results state the dilemma of ill-posed inverse problems: absence of guarantee of correspondence to the true distribution. The limitations due to illumination may not be solved by the use of mathematical constraints. It is shown that crosswell tomograms derived by the use of sparsity constraints, using both Discrete Cosine Transform and Daubechies bases, basically reproduces the same features seen in tomograms obtained with the classic smoothness constraint. Interpretation must be done always taking in consideration the a priori information and the particular limitations due to illumination. An example of interpreting a real data survey in this context is also presented.

Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Estimação e previsão no processo INARCH(2)

In the last decades the study of integer-valued time series has gained notoriety due to its broad applicability (modeling the number of car accidents in a given highway, or the number of people infected by a virus are two examples). One of the main interests of this area of study is to make forecasts, and for this reason it is very important to propose methods to make such forecasts, which consist of nonnegative integer values, due to the discrete nature of the data. In this work, we focus on the study and proposal of forecasts one, two and h steps ahead for integer-valued second-order autoregressive conditional heteroskedasticity processes [INARCH (2)], and in determining some theoretical properties of this model, such as the ordinary moments of its marginal distribution and the asymptotic distribution of its conditional least squares estimators. In addition, we study, via Monte Carlo simulation, the behavior of the estimators for the parameters of INARCH(2) processes obtained using three di erent methods (Yule- Walker, conditional least squares, and conditional maximum likelihood), in terms of mean squared error, mean absolute error and bias. We present some forecast proposals for INARCH(2) processes, which are compared again via Monte Carlo simulation. As an application of this proposed theory, we model a dataset related to the number of live male births of mothers living at Riachuelo city, in the state of Rio Grande do Norte, Brazil.

Estimação e previsão no processo INARCH(2)

In the last decades the study of integer-valued time series has gained notoriety due to its broad applicability (modeling the number of car accidents in a given highway, or the number of people infected by a virus are two examples). One of the main interests of this area of study is to make forecasts, and for this reason it is very important to propose methods to make such forecasts, which consist of nonnegative integer values, due to the discrete nature of the data. In this work, we focus on the study and proposal of forecasts one, two and h steps ahead for integer-valued second-order autoregressive conditional heteroskedasticity processes [INARCH (2)], and in determining some theoretical properties of this model, such as the ordinary moments of its marginal distribution and the asymptotic distribution of its conditional least squares estimators. In addition, we study, via Monte Carlo simulation, the behavior of the estimators for the parameters of INARCH(2) processes obtained using three di erent methods (Yule- Walker, conditional least squares, and conditional maximum likelihood), in terms of mean squared error, mean absolute error and bias. We present some forecast proposals for INARCH(2) processes, which are compared again via Monte Carlo simulation. As an application of this proposed theory, we model a dataset related to the number of live male births of mothers living at Riachuelo city, in the state of Rio Grande do Norte, Brazil.

Classificador máquina de suporte vetorial com análise de Fourier aplicada em dados de EEG e EMG

The classifier support vector machine is used in several problems in various areas of knowledge. Basically the method used in this classier is to end the hyperplane that maximizes the distance between the groups, to increase the generalization of the classifier. In this work, we treated some problems of binary classification of data obtained by electroencephalography (EEG) and electromyography (EMG) using Support Vector Machine with some complementary techniques, such as: Principal Component Analysis to identify the active regions of the brain, the periodogram method which is obtained by Fourier analysis to help discriminate between groups and Simple Moving Average to eliminate some of the existing noise in the data. It was developed two functions in the software R, for the realization of training tasks and classification. Also, it was proposed two weights systems and a summarized measure to help on deciding in classification of groups. The application of these techniques, weights and the summarized measure in the classier, showed quite satisfactory results, where the best results were an average rate of 95.31% to visual stimuli data, 100% of correct classification for epilepsy data and rates of 91.22% and 96.89% to object motion data for two subjects.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Modelagem multiescala de fenômenos eletrocinéticos em meios porosos carregados eletricamente: aplicação a meios porosos argilosos

In this master thesis, we propose a multiscale mathematical and computational model for electrokinetic phenomena in porous media electrically charged. We consider a porous medium rigid and incompressible saturated by an electrolyte solution containing four monovalent ionic solutes completely diluted in the aqueous solvent. Initially we developed the modeling electrical double layer how objective to compute the electrical potential, surface density of electrical charges and considering two chemical reactions, we propose a 2-pK model for calculating the chemical adsorption occurring in the domain of electrical double layer. Having the nanoscopic model, we deduce a model in the microscale, where the electrochemical adsorption of ions, protonation/ deprotonation reactions and zeta potential obtained in the nanoscale, are incorporated through the conditions of interface uid/solid of the Stokes problem and transportation of ions, modeled by equations of Nernst-Planck. Using the homogenization technique of periodic structures, we develop a model in macroscopic scale with respective cells problems for the e ective macroscopic parameters of equations. Finally, we propose several numerical simulations of the multiscale model for uid ow and transport of reactive ionic solute in a saturated aqueous solution of kaolinite. Using nanoscopic model we propose some numerical simulations of electrochemical adsorption phenomena in the electrical double layer. Making use of the nite element method discretize the macroscopic model and propose some numerical simulations in basic and acid system aiming to quantify the transport of ionic solutes in porous media electrically charged.

Análise comparativa de diferentes configurações de poços no processo de combustão in-situ

With an increasing number of mature fields, heavy oil recovery has performed one of the great challenges of the oil industry. The Brazilian Northeast, for example, has numerous heavy oil reservoirs are explored with the use of thermal methods. Among the types of methods used for heavy oil, there is the method of in-situ combustion, a technique in which heat is produced within the container, unlike the injection of heated fluid when the heat is generated at the surface and transported to the reservoir. In this type of process, it is common to use vertical wells as injectors and producers. However, methods which use horizontal wells like oil producers are increasingly studied because of greater contact area between the formation and combustion front. Thus, the main objective of this work was to study the different configurations of wells (CIS THAITM and CAGD) in the process of in-situ combustion in oil recovery using a semi-synthetic tank with Brazilian Northeast features. The method "toe-to-heel air injection" (THAITM) is a process of enhanced oil recovery, which is the integration of in-situ combustion with technological advances in drilling horizontal wells. This method uses horizontal wells such as oil producers, keeping vertical injection wells for injecting air. The oil drain process by differential gravitational assisted with combustion (CAGD) is an integrated, in this configuration the horizontal injector well is drilled at the top formation with a horizontal production well in the lower section. The simulations were performed in a commercial program of thermal processes, called "STARS" (Steam, Thermal, and Advanced Processes Reservoir Simulator), the company CMG (Computer Modelling Group). An analysis of the air flow injection was performed and it was found that each method had a maximum injection to the base model, a show that through this air injection limit was reduced cumulative production of oil. Analyses of operating parameters were used: injection flow, configuration and completion of wells. In the sensitivity analysis we found that the air injection flow showed greater influence on THAI method, since the CIS method the completion of the wells was the most influential parameter and CAGD configuration wells showed the greatest influence in the recovered fraction. The economic results have shown that the best case obtained in CAGD method because, despite having higher initial cost showed the best financial return compared to the best cases the CIS and THAI.