Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

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

Diagênese e proveniência dos arenitos da tectonossequência Rifte na bacias do Rio do Peixe Araripe, NE do Brasil

This thesis presents diagenetic and provenance studies of sandstones belonging to the Rift Tectonosequence of the Rio do Peixe and Araripe basins. These basins are located in the interior of Northeast Brazil aligned along the Trend-Cariri Potiguar. Their origin is related to the Early Cretaceous rifting event. In terms of lithostratigraphy, the studied section corresponds to the Antenor Navarro, Sousa and Rio Piranhas formations of the Rio do Peixe Basin, and the Missão Velha and Abaiara formations of the Araripe Basin, outcropping in the central-west Cariri Valley. A facies analysis was performed and identified nine distinct sedimentary facies for the Rio de Peixe Basin and ten sedimentary facies for the Araripe Basin, individualized according to the different rock types and their sedimentary structures. These facies associations to led paleoenvironments interpretations and their vertical succession allowed understanding the evolution of the depositional setting during the cronostratigraphic interval studied in these basins. Based on petrographic and diagenetic studies it was possible to characterize the texture and mineralogy of these sandstones, identifying their diagenetic stage and the grain framework provenance. The petrographic study allowed to classify the lithotypes studied in both basins as quartzarenites. Such quartzarenites, in general, are rich in quartz, feldspar and lithic fragment grains, and at accessory levels tourmaline, sphene, zircon, epidote and other mineralogy. The diagenetic history of the studied rocks proved to be very complex, being characterized by a variety mineral of phases that succeeded each other during the eo, meso and telodiagenetic stages. According to the studied formation and the textural and compositional aspects of the rocks, some processes were more or less active, while others were even absent. The eodiagenetic stage is marked by mechanical infiltration of clays and early mechanical compactional processes. The mesodiagenetic phase is characterized by continuity of the mechanical compaction and the beggining of chemical compaction, with quartz and feldspar overgrowths, precipitation of kaolinite, alteration of framework grains to chlorite and illite, and finally, precipitation of opaque minerals. The telodiagenetic stage is represented by the oxidation of some grains, matrix and cements. For the provenance analysis of the studied sandstones were used ternary diagrams whose vertices correspond to the percentage of quartz, feldspar and lithic fragments. This study allowed identifies the source area of these rocks as continental blocks. It was also possible, based on the chemical stability and mineralogical maturity of the rocks, recognize that the Antenor Navarro Formation of the Rio do Peixe Basin, and the upper section of the Missão Velha Formation of Araripe Basin have less maturity and stability when compared with the other studied formations