Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Ativos intangíveis (modelo RBV) como recurso estratégico e competitivo: um estudo em hotéis de pequeno porte (zona sul, Natal/RN)

The study aims to analyze the perception of managers on intangible assets as strategic and competitive resources in small hotels in Natal/RN, through the theory of the Resource Based View (RBV). This is a qualitative study of exploratory and descriptive, conducted with managers of the means of hosting small the capital of Rio Grande do Norte through semi-structured interviews, which was applied later, the technique content analysis based on the results of the information obtained in the interviews. Thus, research has shown that managers of small hotels visited (A, B, C) are not sufficient and satisfactory knowledge to set as their unique intangible assets of the company and makes use of them, on an occasional basis, without understanding or in essence understand its true value as a resource that can be used strategically for sustainable competitive advantage in the hotel market in Natal/RN. This means that managers do not know how to create new attributes and use them strategically. And they need to expand their partnerships with stakeholders. Given the importance of the subject of the present research, the information achieved by this analysis may contribute to the provision of information to establish a current situation with regard to the attributed to the knowledge and use of resources (intangible assets) importance as a strategic source and competitive for the internal management of the company by managers and thus, enabling a differential and greater economic profit over time in this segment

Litoestratigrafia e deformação cenzóica na região de Icapuí, Ceará, e implicações para a estruturação de campos de petróleo na borda ocidental da bacia Potiguar(NE do Brasil)

This thesis deals with the sedimentological/stratigraphic and structural evolution of the sedimentary rocks that occur in the NW continental border of the Potiguar Basin. These rocks are well exposed along coastal cliffs between the localities of Lagoa do Mato and Icapuí, Ceará State (NE Brazil). The sedimentological/stratigraphic study involved, at the outcrop scale, detailed facies descriptions, profile mapping of the vertical succession of different beds, and columnar sections displaying inferred lateral relationships. The approach was complemented by granulometric and petrographic analyses, including the characterization of heavy mineral assemblages. The data set allowed to recognize two kinds of lithological units, a carbonate one of very restricted occurrence at the base of the cliffs, and three younger, distinct siliciclastic units, that predominate along the cliffs, in vertical and lateral extent. The carbonate rocks were correlated to the late Cretaceous Jandaíra Formation, which is covered by the siliciclastic Barreiras Formation. The Barreiras Formation occurs in two distinct structural settings, the usual one with nondeformed, subhorizontal strata, or as tilted beds, affected by strong deformation. Two lithofacies were recognized, vertically arranged or in fault contacts. The lower facies is characterized by silty-argillaceous sandstones with low-angle cross bedding; the upper facies comprises medium to coarse grained sandstones, with conglomeratic layers. The Tibau Formation (medium to coarse-grained sandstones with argillite intercalations) occurs at the NW side of the studied area, laterally interlayered with the Barreiras Formation. Eolic sediments correlated to the Potengi Formation overly the former units, either displaying an angular unconformity, or simply an erosional contact (stratigraphic unconformity). Outstanding structural features, identified in the Barreiras Formation, led to characterize a neocenozoic stress field, which generated faults and folds and/or reactivated older structures in the subjacent late cretaceous (to paleogene, in the offshore basin) section. The structures recognized in the Barreiras Formation comprise two distinct assemblages, namely a main extensional deformation between the localities of Ponta Grossa and Redonda, and a contractional style (succeeded by oblique extensional structures) at Vila Nova. In the first case, the structural assemblage is dominated by N-S (N±20°Az) steep to gently-dipping extensional faults, displaying a domino-style or listric geometry with associated roll-over structures. This deformation pattern is explained by an E-W/WNW extension, contemporaneous with deposition of the upper facies of the Barreiras Formation, during the time interval Miocene to Pleistocene. Strong rotation of blocks and faults generated low-angle distensional faults and, locally, subvertical bedding, allowing to estimate very high strain states, with extension estimates varying between 40% up to 200%. Numerous detachment zones, parallel to bedding, help to acommodate this intense deformation. The detachment surfaces and a large number of faults display mesoscopic features analoguous to the ones of ductile shear zones, with development of S-C fabrics, shear bands, sigmoidal clasts and others, pointing to a hydroplastic deformation regime in these cases. Local occurrences of the Jandaíra limestone are controled by extensional faults that exhume the pre-Barreiras section, including an earlier event with N-S extension. Finally, WNWtrending extensional shear zones and faults are compatible with the Holocene stress field along the present continental margin. In the Vila Nova region, close to Icapuí, gentle normal folds with fold hinges shallowly pluging to SSW affect the lower facies of the Barreiras Formation, displaying an incipient dissolution cleavage associated with an extension lineation at high rake (a S>L fabric). Deposition of the upper facies siliciclastics is controlled by pull-apart graben structures, bordered by N-NE-trending sinistral-normal shear zones and faults, characterizing an structural inversion. Microstructures are compatible with tectonic deformation of the sedimentary pile, burried at shallow depths. The observed features point to high pore fluid pressures during deformation of the sediments, producing hydroplastic structures through mechanisms of granular flow. Such structures are overprinted by microfractures and microfaults (an essentially brittle regime), tracking the change to microfracturing and frictional shear mechanisms accompanying progressive dewatering and sediment lithification. Correlation of the structures observed at the surface with those present at depth was tested through geophysical data (Ground Penetrating Radar, seismics and a magnetic map). EW and NE-trending lineaments are observed in the magnetic map. The seismic sections display several examples of positive flower structures which affect the base of the cretaceous sediments; at higher stratigraphic levels, normal components/slips are compatible with the negative structural inversion characterized at the surface. Such correlations assisted in proposing a structural model compatible with the regional tectonic framework. The strong neogenepleistocene deformation is necessarily propagated in the subsurface, affecting the late cretaceous section (Açu and Jandaíra formations), wich host the hydrocarbon reservoirs in this portion of the Potiguar Basin. The proposed structural model is related to the dextral transcurrent/transform deformation along the Equatorial Margin, associated with transpressive terminations of E-W fault zones, or at their intersections with NE-trending lineaments, such as the Ponta Grossa-Fazenda Belém one (the LPGFB, itself controlled by a Brasiliano-age strike-slip shear zone). In a first step (and possibly during the late Cretaceous to Paleogene), this lineament was activated under a sinistral transpressional regime (antithetic to the main dextral deformation in the E-W zones), giving way to the folds in the lower facies of the Barreiras Formation, as well as the positive flower structures mapped through the seismic sections, at depth. This stage was succeeded (or was penecontemporaneous) by the extensional structures related to a (also sinistral) transtensional movement stage, associated to volcanism (Macau, Messejana) and thermal doming processes during the Neogene-Pleistocene time interval. This structural model has direct implications to hydrocarbon exploration and exploitation activities at this sector of the Potiguar Basin and its offshore continuation. The structure of the reservoirs at depth (Açu Formation sandstones of the post-rift section) may be controlled (or at least, strongly influenced) by the deformation geometry and kinematics characterized at the surface. In addition, the deformation event recognized in the Barreiras Formation has an age close to the one postulated for the oil maturation and migration in the basin, between the Oligocene to the Miocene. In this way, the described structural cenario represents a valid model to understand the conditions of hydrocarbon transport and acummulation through space openings, trap formation and destruction. This model is potentially applicable to the NW region of the Potiguar Basin and other sectors with a similar structural setting, along the brazilian Equatorial Atlantic Margin

Condutividade térmica de rochas: uma aplicação para granitos ornamentais

This dissertation focuses on rock thermal conductivity and its correlations with petrographic, textural, and geochemical aspects, especially in granite rocks. It aims at demonstrating the relations of these variables in an attempt to enlighten the behavior of thermal effect on rocks. Results can be useful for several applications, such as understanding and conferring regional thermal flow results, predicting the behavior of thermal effect on rocks based upon macroscopic evaluation (texture and mineralogy), in the building construction field in order to provide more precise information on data refinement on thermal properties emphasizing a rocky material thermal conductivity, and especially in the dimension stone industry in order to open a discussion on the use of these variables as a new technological parameter directly related to thermal comfort. Thermal conductivity data were obtained by using Anter Corporation s QuicklineTM -30 a thermal property measuring equipment. Measurements were conducted at temperatures ranging between 25 to 38 OC in samples with 2cm in length and an area of at least 6cm of diameter. As to petrography data, results demonstrated good correlations with quartz and mafics. Linear correlation between mineralogy and thermal conductivity revealed a positive relation of a quartz percentage increase in relation to a thermal conductivity increase and its decrease with mafic minerals increase. As to feldspates (K-feldspate and plagioclase) they show dispersion. Quartz relation gets more evident when compared to sample sets with >20% and <20%. Sets with more than 20% quartz (sienogranites, monzogranites, granodiorites, etc.), exhibit to a great extent conductivity values which vary from 2,5 W/mK and the set with less than 20% (sienites, monzonites, gabbros, diorites, etc.) have an average thermal conductivity below 2,5 W/mK. As to textures it has been verified that rocks considered thick/porphyry demonstrated in general better correlations when compared to rocks considered thin/medium. In the case of quartz, thick rocks/porphyry showed greater correlation factors when compared to the thin/medium ones. As to feldspates (K-feldspate and plagioclase) again there was dispersion. As to mafics, both thick/porphyry and thin/medium showed negative correlations with correlation factor smaller than those obtained in relation to the quartz. As to rocks related to the Streckeisen s QAP diagram (1976), they tend to fall from alcali-feldspates granites to tonalites, and from sienites to gabbros, diorites, etc. Thermal conductivity data correlation with geochemistry confirmed to a great extent mineralogy results. It has been seen that correlation is linear if there is any. Such behavior could be seen especially with the SiO2. In this case similar correlation can be observed with the quartz, that is, thermal conductivity increases as SiO2 is incremented. Another aspect observed is that basic to intermediate rocks presented values always below 2,5 W/mK, a similar behavior to that observed in rocks with quartz <20%. Acid rocks presented values above 2,5 W/mK, a similar behavior to that observed in rocks with quartz >20% (granites). For all the other cases, correlation factors are always low and present opposite behavior to Fe2O3, CaO, MgO, and TiO2. As to Al2O3, K2O, and Na2O results are not conclusive and are statistically disperse. Thermal property knowledge especially thermal conductivity and its application in the building construction field appeared to be very satisfactory for it involves both technological and thermal comfort aspects, which favored in all cases fast, cheap, and precise results. The relation between thermal conductivity and linear thermal dilatation have also shown satisfactory results especially when it comes to the quartz role as a common, determining phase between the two variables. Thermal conductivity studies together with rocky material density can function as an additional tool for choosing materials when considering structural calculation aspects and thermal comfort, for in the dimension stone case there is a small density variation in relation to a thermal conductivity considerable variation

Caracterização hidrodinâmica e morfo-sedimentar do estuário Potengi e áreas adjascentes: subsídios para controle e recuperação ambiental no caso de derrames de hidrocarboneto

This study presents the Environmental Sensibility Mapping to oil spillings on the Potengi estuary - RN and neighboring coastline through remote sensing data, collecting, treatment and integration of the geomorphologic, oceanographic (temperature, salinity, density, direction and intensity), meteorological (wind speed and direction) and high resolution seismic (bathymetry and sonography) data. The Potengi river estuary is located on the eastern coastline of the Rio Grande do Norte State, being inserted in the geological context for the coastal Pernambuco-Paraíba basin and spreading over 18 km; it shelters the Natal harbor zone and an oil terminal, centralizing, therefore, important oil transport operations that can cause accidental spillings. Under the oceanographic point of view, the Potengi estuary is characterized by the absence of any expressive thermic stratification, being classified as partially mixed, B type according to Pritchard (1955), and 2 type in conformity to the stratification-circulation diagram by Hansen & Rattray (1966). Two main wind systems are responsable for the formation of wave sets that occur in the area. The dynamic tide presents, in the Natal Harbor, mean amplitude in spring and quadrature tides, with around 2.8 and 2m, respectively. The mechanism of saline tide mixing was defined through the salinity which is the main parameter for the identification of this mechanism. Important variations of the salinity mean values (36.32 psu), temperature (28.11ºC) and density (22.96 kg/m3) in the estuarine waters presented features belonging to low latitude regions. The water temperature follows the air temperature variations, in the region, with expressive daily amplitudes. In this study, the identification of the estuarine bed morphology through bathymetric and sonographic analysis, had the purpose to evaluate the influence of the superficial and bottom currents for the bottom shaping. In this way, the use of the side scan sonar showed, to be very useful in the identification of the bottom morphology and its relationship with the predominant action of the tidal currents in the Potengi estuary. Besides, it showed how the sonograms can be a support to the comparison of the several patterns derived from the local hydrodynamic variations. The holocene sediments, which fill the estuarine channel, are predominantly sandy, varying from selected, sometimes silty. The sedimentation is controlled by the environmental hydrodynamic conditions, being recognized two important textural facies: Muddy Facies and Sandy Facies. The distribution of these textural facies apparently oscillates owing to the tidal cycle and flow intensity. Each one of the above mentioned data was integrated in a Geographic Information System (GIS), from which was produced the Environmental Sensibility Map to oil spillings with Coastal Sensibility Index (CSI) to the Potengi estuary. The integrated analysis of these data is essential to oil spilling contingency plans, in order to reduce the spilling environmental consequences and to make efficient the endeavours of contention and cleaning up/removal on the Natal Harbor. This study has the aim to collaborate for the increase of informations about the estuarine environment and contribute to a better management of the question: environment/polluting loads