Desenvolvimento de uma unidade laboratorial para quantificação de BTX como poluentes atmosféricos, usando microextração em fase sólida

This dissertation aims the development of an experimental device to determine quantitatively the content of benzene, toluene and xylenes (BTX) in the atmosphere. BTX are extremely volatile solvents, and therefore play an important role in atmospheric chemistry, being precursors in the tropospheric ozone formation. In this work a BTX new standard gas was produced in nitrogen for stagnant systems. The aim of this dissertation is to develop a new method, simple and cheaper, to quantify and monitor BTX in air using solid phase microextraction/ gas chromatography/mass spectrometry (SPME/CG/MS). The features of the calibration method proposed are presented in this dissertation. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fiber exposed for 10 min standard gas mixtures. It is observed that the main parameters that affect the extraction process are sampling time and concentration. The results of the BTX multicomponent system studied have shown a linear and a nonlinear range. In the non-linear range, it is remarkable the effect of competition by selective adsorption with the following affinity order p-xylene > toluene > benzene. This behavior represents a limitation of the method, however being in accordance with the literature. Furthermore, this behavior does not prevent the application of the technique out of the non-linear region to quantify the BTX contents in the atmosphere.

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

O problema biobjetivo da árvore geradora quadrática em adjacência de arestas

The Quadratic Minimum Spanning Tree Problem (QMST) is a version of the Minimum Spanning Tree Problem in which, besides the traditional linear costs, there is a quadratic structure of costs. This quadratic structure models interaction effects between pairs of edges. Linear and quadratic costs are added up to constitute the total cost of the spanning tree, which must be minimized. When these interactions are restricted to adjacent edges, the problem is named Adjacent Only Quadratic Minimum Spanning Tree (AQMST). AQMST and QMST are NP-hard problems that model several problems of transport and distribution networks design. In general, AQMST arises as a more suitable model for real problems. Although, in literature, linear and quadratic costs are added, in real applications, they may be conflicting. In this case, it may be interesting to consider these costs separately. In this sense, Multiobjective Optimization provides a more realistic model for QMST and AQMST. A review of the state-of-the-art, so far, was not able to find papers regarding these problems under a biobjective point of view. Thus, the objective of this Thesis is the development of exact and heuristic algorithms for the Biobjective Adjacent Only Quadratic Spanning Tree Problem (bi-AQST). In order to do so, as theoretical foundation, other NP-hard problems directly related to bi-AQST are discussed: the QMST and AQMST problems. Bracktracking and branch-and-bound exact algorithms are proposed to the target problem of this investigation. The heuristic algorithms developed are: Pareto Local Search, Tabu Search with ejection chain, Transgenetic Algorithm, NSGA-II and a hybridization of the two last-mentioned proposals called NSTA. The proposed algorithms are compared to each other through performance analysis regarding computational experiments with instances adapted from the QMST literature. With regard to exact algorithms, the analysis considers, in particular, the execution time. In case of the heuristic algorithms, besides execution time, the quality of the generated approximation sets is evaluated. Quality indicators are used to assess such information. Appropriate statistical tools are used to measure the performance of exact and heuristic algorithms. Considering the set of instances adopted as well as the criteria of execution time and quality of the generated approximation set, the experiments showed that the Tabu Search with ejection chain approach obtained the best results and the transgenetic algorithm ranked second. The PLS algorithm obtained good quality solutions, but at a very high computational time compared to the other (meta)heuristics, getting the third place. NSTA and NSGA-II algorithms got the last positions

Condicionamento estrutural das zonasa de cisalhamento da região de Forquilha, domínio Ceará Central: uma abordagem integrada de sensoriamento remoto e geologia estrutural

The studied region, named Forquilha and localized in northwestern Central Ceará domain (northern portion of Borborema Province), presents a lithostratigraphic framework constituted by paleoproterozoic metaplutonics, metasedimentary sequences and neoproterozoic granitoids. The metasedimentary rocks of Ceará group occupy most part of the area. This group is subdivided in two distinct units: Canindé and Independência. Canindé unit is represented basically by biotite paragneisses and muscovite paragneisses, with minor metabasic rocks (amphibolite lens). Independência sequence is composed by garnetiferous paragneisses, sillimanite-garnet-quartz-muscovite schists and quartz-muscovite schists, pure or muscovite quartzites and rare marbles. At least three ductile deformation events were recognized in both units of Ceará group, named D1, D2 and D3. The former one is interpreted as related to a low angle tangential tectonics which mass transport is southward. D2 event is marked by the development of close/isoclinal folds with a N-S oriented axis. Refolding patterns generated by F1 and F2 superposition are found in several places. The latest event (D3) corresponds to a transcurrent tectonics, which led to development of mega-folds and several shear zones, under a transpressional regime. The mapped shear zones are Humberto Monte (ZCHM), Poço Cercado (ZCPC) and Forquilha (ZCF). Digital image processing of enhanced Landsat 7-ETM+ satellite images, combined with field data, demonstrate that these penetrative structures are associated with positive and negative geomorphologic patterns, distributed in linear and curvilinear arrangements with tonal banding, corresponding to the ductile fabric and to crests. Diverse color composites were tested and RGB-531 and RGB-752 provided the best results for lineament analysis of the most prominent shear zones. Spatial filtering techniques (3x3 and 5x5 filters) were also used and the application of Prewitt filters generated the best products. The integrated analysis of morphological and textural aspects from filtered images, variation of tonalities related to the distribution of geologic units in color composites and the superposition over a digital elevation model, contributed to a characterization of the structural framework of the study area. Kinematic compatibility of ZCHM, ZCPC, ZCF shear zones, as well as Sobral-Pedro II (ZCSPII) shear zone, situated to the west of the study area, was one of the goal of this work. Two of these shear zones (ZCHM, ZCPC) display sinistral movements, while the others (ZCSPII, ZCF) exhibit dextral kinematics. 40Ar/39Ar ages obtained in this thesis for ZCSPII and ZCPC, associated with other 40Ar/39Ar data of adjacent areas, indicate that all these shear zones are related to Brasiliano orogeny. The trend of the structures, the opposite shear senses and the similar metamorphic conditions are fitted in a model based on the development of conjugate shear zones in an unconfined transpression area. A WNW-ESE bulk shortening direction is infered. The geometry and kinematic of the studied structures suggest that shortening was largely accommodated by lateral extrusion, with only minor amounts of vertical stretch

Controlador adaptativo backstepping a estrutura variavel com Observadores de estado

This research aims at developing a variable structure adaptive backstepping controller (VS-ABC) by using state observers for SISO (Single Input Single Output), linear and time invariant systems with relative degree one. Therefore, the lters were replaced by a Luenberger Adaptive Observer and the control algorithm uses switching laws. The presented simulations compare the controller performance, considering when the state variables are estimated by an observer, with the case that the variables are available for measurement. Even with numerous performance advantages, adaptive backstepping controllers still have very complex algorithms, especially when the system state variables are not measured, since the use of lters on the plant input and output is not something trivial. As an attempt to make the controller design more intuitive, an adaptive observer as an alternative to commonly used K lters can be used. Furthermore, since the states variables are considered known, the controller has a reduction on the dependence of the unknown plant parameters on the design. Also, switching laws could be used in the controller instead of the traditional integral adaptive laws because they improve the system transient performance and increase the robustness against external disturbances in the plant input