Aplicação da espectroscopia de absorção de raios X no estudo do comportamento do íon Cu2+ em micelas inversas

This work deals with the application of X-Ray Absorption Spectroscopy on the study of the behavior of Cu2+ ions in inverse micelles. The formation of copper nanoparticles in water-in-oil microemulsions in pseudo-ternary systems of cetyl trimethylammonium Bromide (CTAB) surfactant, butanol co-surfactant, heptane as oil phase and aqueous solutions of CuSO4.5H2O, and NaBH4. The microemulsions were prepared with a fixed percentage (60 %) of oil phase and a variable water to tensoative proportion. It was observed an increase on Cu2+ reduction by the sodium borohydride in microemulsions with 13 % of aqueous phase, independent of the reaction time. For the microemulsions in which the aqueous phase is composed only by the CuSO4 solution, it was observed that the color of the solution depends on the water to surfactant ratio. These changes in color were attributed to a competition for the hidratation water between the polar head of the tensoative and Cu2+ ions with the eventual substitution of oxygen by bromine atoms in the first coordination shell of Cu2+ ions

Nanotechnological delivery systems for the oral administration of active molecules: Polymeric microparticles and microemulsions applied to anti-inflammatory and anti-infectious drugs

This thesis was devoted to the development of innovative oral delivery systems for two different molecules. In the first part, microparticles (MPs) based on xylan and Eudragit® S- 100 were produced and used to encapsulate 5-aminosalicylic acid for colon delivery. Xylan was extracted from corn cobs and characterized in terms of its physicochemical, rheological and toxicological properties. The polymeric MPs were prepared by interfacial cross-linking polymerization and spray-drying and characterized for their morphology, mean size and distribution, thermal stability, crystallinity, entrapment efficiency and in vitro drug release. MPs with suitable physical characteristics and satisfactory yields were prepared by both methods, although the spray-dried systems showed higher thermal stability. In general, spraydried MPs would be preferable systems due to their thermal stability and absence of toxic agents used in their preparation. However, drug loading and release need to be optimized. In the second part of this thesis, oil-in-water microemulsions (O/W MEs) based on mediumchain triglycerides were formulated as drug carriers and solubility enhancers for amphotericin B (AmB). Phase diagrams were constructed using surfactant blends with hydrophiliclipophilic balance values between 9.7 and 14.4. The drug-free and drug-loaded MEs presented spherical non-aggregated droplets around 80 and 120 nm, respectively, and a low polydispersity index. The incorporation of AmB was high and depended on the volume fraction of the disperse phase. These MEs did not reduce the viability of J774.A1 macrophage-like cells for concentrations up to 25 μg/mL of AmB. Therefore, O/W MEs based on propylene glycol esters of caprylic acid may be considered as suitable delivery systems for AmB

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

Aplicação de microemulsão na recuperação de petróleo de reservatórios carbonáticos

The large investment in exploration activities offshore Brazil has generated new findings, generally in carbonate reservoirs, with different wettability conditions usually considered in the sandstone, strongly water-wet. In general, the carbonates reservoirs tend to be oil-wet, it difficult to mobilize of oil these reservoirs. These oils can be mobilized by different methods, or it may reverse the wettability of the surface of the reservoir and facilitate the flow of oil, improving production rates. Thus, the objective of this work was to study the influence of inversion on the wettability of the rock in the production and recovery of petroleum from carbonate reservoirs, using microemulsions. Three systems were chosen with different classes of surfactants: a cationic (C16TAB), an anionic (SDS) and nonionic (Unitol L90). Studies of the influence of salinity on the formation of the microemulsion as well as the characterization of fluids using density and viscosity measurements were also performed. To verify the potential of microemulsion systems in changing the wettability state of the chalk oil-wet to water-wet, contact angle measurements were performed using chalk of neutral-wet as surface material. Overall, with respect to the ionic character of the surfactants tested, the cationic surfactant (C16TAB) had a greater potential for reversal in wettability able to transform the rock wettability neutral to strongly water-wet, when compared with the anionic surfactant (SDS) and nonionic (Unitol L90), which showed similar behavior, improving the wettability of the rock to water. The microemulsions of all surfactants studied were effective in oil recovery, resulting in 76.92% for the system with C16TAB, 67.42% for the SDS and 66.30% for Unitol L90 of residual oil

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

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.

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.

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

Adição de superplastificante e anti-segregante à base de CMC em pastas de cimento para Poços de Petróleo

Oil well cementing materials consist of slurries of Special class Portland cement dispersed in water. Admixtures can be used to provide the necessary fluidity, so the material can be efficiently pumped down as well as penetrate porous rocks with controlled filter loss. Construction admixtures can be used to modify the properties of oil well cements provided they can withstand and hold their properties at the higher than ambient temperatures usually encountered in oil fields. In civil construction, superplasticizer play the role of dispersants that reduce the facto r of water cement improve mechanical properties and fluidity of the cement, whereas anti-segregation agents improve the workability of the slurry. In the present study, oil well cement slurries were produced adding both a dispersant and an anti-segregation agent conventionally used in Portland CPII-Z-32 RS cement aiming at materials for primary cementing and squeeze operations. Three basic aspects were evaluated: fluidity, filter loss and the synergetic effect of the admixtures at two temperatures, i.e., 27°C and 56°C, following API RP 10B practical recommendations. The slurries were prepared using admixture concentrations varying from 2.60 Kgf/m3 (0.02 gallft3) to 5.82 Kgf/m3 (0.045 galJft3) BWOC. The density of the slurries was set to 1.89 g/cm3 (15.8 Ib/gal). 0.30 to 0.60% BWOC of a CMC-based anti-segregation agent was added to the cement to control the filter loss. The results showed that the addition of anti-segregation at concentrations above 0.55% by weight of cement resulted in the increased viscosity of the folders in temperatures evaluated. The increasing the temperature of the tests led to a reduction in the performance of anti-segregation. At concentrations of 5.20 kgf/m3 (0,040 gallft3) and 5.82 Kgf/m3 (0,045 gal/ft 3) observed a better performance of the properties evaluated in the proposed system. At low temperature was observed instability in the readings of rheology for all concentrations of anti-segregation. Contents that increasing the concentration of anti¬-segregation is limited concentrations greater than 0.55 % BWOC of the CMC in temperature analyzed. The use of the system with CMC promoted a good performance against the properties evaluated. The principal function of anti¬-segregation was optimized with increasing concentration of superplasticizer, at temperatures above the 2rC. The study of the behaviour of systemic additives, resulting in slurries of cement, which can be optimized face studies of other intrinsic properties in oil fields

Análise do comportamento reológico de pastas de cimento contendo resíduos de pneu para poços de petróleo

The low tenacity presented by the Portland cement pastes used in the oil wells cementation has been motivating several researches with attention focused on alternative materials. Additives have been developed to generate flexible pastes with mechanical resistance capable to support the expansions and retractions of the metallic covering of the wells that submit to the steam injection, technique very used to increase the recovery factor in oil reservoirs with high viscosity. A fresh paste with inadequate rheological behavior may commit the cementation process seriously, involving flaws that affect the performance of the paste substantially in the hardened state. This work proposes the elaboration and the rheological analysis of Portland cement pastes with addition of residues of rubber tire in several proportions, with the aim of minimizing the damages provoked in the hem cementing of these wells. By thermogravimetric analysis, the particles of eraser that go by the sieve of 0,5mm (35 mesh) opening and treated superficially with NaOH solution of 1 mol/L presented appropriate thermal resistance for wells that submit to thermal cyclic. The evaluation of the study based on the results of the rheological analysis of the pastes, complemented by the mechanical analysis, thickening, stability, tenor of free water and filtrate loss, being used as parameter a paste reference, without rubber addition. The results showed satisfactory rheology, passive of few corrections; considerable loss of mechanical resistance (traction and compression), compensated by earnings of tenacity, however with established limits for its application in oil wells; satisfactory stability, free water and thickening time

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

Desenvolvimento de pastas de cimento flexíveis para poços de petróleo submetidos à injeção de vapor utilizando látex do tipo SBR

Novel cementing materials formulations containing flexible polymeric admixtures have been studied aiming at improving the mechanical behavior of oil well cement slurries submitted to steam injection. However, research activities in this sector are still under development. The steam injected directly into the well causes casing dilation, which after a reduction in temperature, tends to return to its original dimensions, resulting in crack formation and hydraulic isolation loss of the well, which will result in shortening of well life. In this scenario, the objective of the present study was to evaluate the mechanical behavior of Portland-based slurries containing SBR latex, applied in oil well cementing of wells submitted to steam injection. Were formulated slurries with densities of 1.797 g/cm3 (15.0 lb/Gal) and 1.869 g/cm3 (15.6 lb/Gal), containing admixtures with a latex concentration of 0; 66.88; 133.76; 200.64 and 267.52 L/m3 (0, 0.5, 1.0, 1.5 and 2.0 gpc). Tests including rheology, fluid loss control, thickening time, API compressive strength and splitting tensile strength, beyond steam injection simulation. Microstrutural characteristics of the slurries were also performed (XRD, TG, FTIR and SEM). The results showed that increasing the polymer concentration increased in the rheological properties and fluid loss, and a decrease in the elasticity modulus of the cement slurries. The results obtained showed that the slurries can be applied in cementing operations of oil wells submitted to steam injection.

Síntese e impregnação de peneiras moleculares Fe MCM-41 derivada de sílica da casca do arroz

The mesoporous molecular sieves of the MCM-41 and FeMCM-41 type are considered promissory as support for metals used as catalysts in oil-based materials refine processes and as adsorbents for environmental protection proposes. In this work MCM-41 and FeMCM41 were synthesized using rice husk ash - RHA as alternative to the conventional silica source. Hydrothermal synthesis was the method chosen to prepare the materials. Pre-defined synthesis parameters were 100°C for 168 hours, later the precursor was calcinated at 550°C for 2 hours under nitrogen and air flow. The sieves containing different proportions of iron were produced by two routes: introduction of iron salt direct synthesis; and a modification post synthesis consisting in iron salt 1 % and 5% impregnation in the material followed by thermal decomposition. The molecular sieves were characterized by X ray diffraction XRD, Fourier transform infrared spectroscopy FT-IR, X ray fluorescence spectroscopy XFR, scanning electronic microscopy SEM, specific surface area using the BET method, Termogravimetry TG. The kinetic model of Flynn Wall was used with the aim of determining the apparent activation energy of the surfactant remove (CTMABr) in the MCM- 41 porous. The analysis made possible the morphology characterization, identifying the presence of hexagonal structure typical for mesoporous materials, as well as observation of the MCM41 and iron of characteristic bands.

Influência da adição de cálcio nas propriedades de pastas geopoliméricas destinadas a cimentação de poços de petróleo

Nowadays, the search for new technologies that are able to follow the upcoming challenges in oil industry is a constant. Always trying properties improvements of the used materials, looking for the best performance and greater life time. Besides the search for technologies that show an improvement of performance, the search for materials environmentally correct along the whole production process. In Oil well cementing, this search for new technologies passes through the development of slurry systems that support these requests and that are also environmentally friendly. In this context, the use of geopolymer slurries is a great alternative route to cementing oil wells. Besides having good properties, comparable to Portland cement slurries, this alternative material releases much less CO2 gas in the production of their root materials when compared the production of Portland cement, which releases tons of CO2. In order to improve the properties of geopolymer slurries has been added Calcium Oxide, as observed in other studies that slurries where the Calcium is present the values of compressive strength is greater. The addition has been realized based in the CaO/SiO2 molar ratio of 0.05, 0.10 and 0.15. Have been performed compressive strength tests, thickening time, rheology and fliud loss control test of the slurries, following NBR 9831, as well as the physical chemical characterization of XRD, SEM and TG. Has been observed in most of the tests the slurries follow a tendency until the ratio of 0.10, which inverses in the ratio 0.15. This behavior can be explained by two phenomena that occur simultaneously, the first one is the break of the polymer chains and a consequent increase in molucules mobility, which prevails until the ratio of 0.1, and the second is possible approach of the chains due to the capacity of the calcium ions stabilize the charges of two different aluminum. There is only one linearity in the mechanical behavior that can be attributed to the appereance of the C-S-H phase. Based on this, it is concluded that the phenomenon of breaking the polymer chains predominates until the ratio of 0.1, causing an increase of the filtrate volume, lower rheological parameters and increasing thickening time. From the ratio of 0.15 the approach of the chains predominates, and the behavior is reversed

Utilização de nanosílica como aditivo estendedor para pastas cimentantes de baixa densidade destinadas à cimentação de poços petrolíferos

Cementing operations are conducted at different times of the well s life and they have high importance, because the functions are fundamental to keep good properties during a long life of the well, such as, maintain the mechanical stability of the well, to promote the isolation hydraulic and support the tubing. In some situations, the rocky zones have low fractures pressures and require the use of lightweight slurries to prevent the hydrostatic pressure in the formation is greater than the pressure of fracture. There are three ways to reduce the density of cement slurries: exterders water additives, microspheres and foamed slurries. The most used extender water additive is sodium bentonite, which is a clay with a good capacity of water absorption and expansion of its volume, the main disadvantage of this additive is the reduction of the strength. Currently, the use of nanoscale particles has received special attention, mainly because they get new functionalities. Following this trend, this paper aims to use a colloidal solution of nano-silica as an exterders water additives for use in oil wells. Slurries were designed with fixed 13lb/gal density and concentration of nano silica 0.1 gpc; 0.4 gpc; 0.7 and 1gpc, the influence of nano-silica was studied at these levels in isolation and combined varying concentrations of CaCl2,. Tests including rheology, stability, strength, thickening time, porosity and permeability. Besides the API tests, microstructural characterizations were performed after 28 days of the slurries, X-ray diffraction (XRD) and scanning electron microscopy (SEM)