Avaliação da síntese e caracterização de zeólita ZSM-5 ausente de direcionador orgânico estrutural

The catalytic processes play a vital role in the worldwide economy, a business that handles about US$ 13 billion per year because the value of products depends on the catalytic processes, including petroleum products, chemicals, pharmaceuticals, synthetic rubbers and plastics, among others. The zeolite ZSM-5 is used as catalyst for various reactions in the area petrochemical, petroleum refining and fine chemicals, especially the reactions of cracking, isomerization, alkylation, aromatization of olefins, among others. Many researchers have studied the hydrothermal synthesis of zeolite ZSM-5 free template and they obtained satisfactory results, so this study aims to evaluate the hydrothermal synthesis and the physicochemical properties of ZSM-5 with the presence and absence of template compared with commercial ZSM-5. The methods for hydrothermal synthesis of zeolite ZSM-5 are of scientific knowledge, providing the chemical composition required for the formation of zeolitic structure in the presence and absence of template. Samples of both zeolites ZSM-5 in protonic form were obtained by heat treatment and ion exchange, according to procedures reported in the literature. The sample of commercial ZSM-5 was acquired by the company Sentex Industrial Ltda. All samples were characterized by XRD, SEM, FTIR, TG / DTG / DSC, N2 adsorption and desorption and study of acidity by thermo-desorption of probe molecule (n-butylamine), in order to understand their physicochemical properties. The efficiency of the methods applied in this work and reported in the literature has been proved by well-defined structure of ZSM-5. According as the evaluation of physicochemical properties, zeolite ZSM-5 free template becomes promising for application in the refining processes or use as catalytic support, since its synthesis reduces environmental impacts and production costs

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Horticultura no baixo curso do Rio Doce, zona norte do Natal/RN: avaliação da qualidade da água por meio de ensaios ecotoxicológicos

The research is developed in areas of horticulture in the city of Natal, in the neighborhoods of Lagoa Azul, Pajuçara and Redinha, along the Doce River, border area with Extremoz city, Rio Grande do Norte State. The region of the fluvial plain of Doce River is located in an Environmental Protection Zone (ZPA-9). This is one of the ZPA which is not under the regulatory marks and there are several environmental problems caused by use and land occupation, featuring an evident disregard of environmental laws and whose protection is hindered by the lack of specific legal mechanisms. This study aims to provide an overview of the use of pesticides in the lower course of the Doce River, in Natal, Rio Grande do Norte, and to assess environmental degradation in the area through chronic toxicity tests using the microcrustaceous Ceriodaphnia dubia Richard 1894 (Cladocera, Crustacea) as test organism. Visits were made to the area in 2009 and 2010. To obtain information a diagnosis of the local situation was accomplished based on personal observation and non-participatory photographic record, with the aim of assessing the environmental characteristics, population diversity and work processes of horticulturists. During the visits four different points of the Doce River were chosen to collect water for ecotoxicological tests and survey of physico-chemical parameters (dissolved oxygen, pH, chloride, turbidity, conductivity and temperature), which were measured in the field using Multiparameter Probe (TROLL 9500). The adverse effects of pesticide use in the lower course of the Doce River is a major problem for both the environmental and human health, since many of the substances and active principles that enter in the composition of the products are synthesized molecules whose effects can only be evaluated through different studies on their actions and behavior at short, medium or long term

Metais pesados no caranguejo Ucides cordatus (Linnaeus, 1763) e ecotoxicologia de sedimentos do estuario dos Rios Jundiai e Potengi - RN

This study is conducted in the estuary of the rivers Jundiaí and Potengi, one of the most important estuaries of Rio Grande do Norte, which suffers a strong anthropogenic influence from neighboring cities. According to Resolution 344/2005 environments that have high concentrations of metals such as arsenic, cadmium, lead and mercury need ecotoxicological tests. This study aims to evaluate the heavy metals contamination in the estuary through analysis of sediment collected at four points distributed from Macaíba to Natal city, and in the crab Uçá, Ucides cordatus. The study aims also to evaluate the effects of sediment toxicity in the tests organisms Leptocheirus plumulosus. To obtain data about the concentrations of heavy metals in the environment, sediments were collected in January and May 2011 and crab Uçá was collected in June 2011. On the other hand the monitoring was carried out through toxicological tests with sediment collected from July to October 2011. During the collection of sediment samples the physico-chemical parameters of water (dissolved oxygen, pH, chloride, turbidity, conductivity and temperature) were measured by using multi-parametric probe (TROLL 9500). It was possible to identify contamination by metals such as lead, cadmium, arsenic and copper both in the sediment and in the Uçá crab, which characterizes that the consumption of this crustacean may be a risk to human health. Once the concentrations of metals were identified, toxicology tests were performed and revealed toxic effect to organisms in at least one of the four months studied. Point 2 was classified as toxic in three of the four months studied . The heavy metal contamination is a risk to the environment, to aquatic organisms and to the community which survives of resources taken from the environment

Obtenção e conservação de espermatozoides de cutia (Dasyprocta leporina Linneaus, 1753) do semiárido brasileiro

The general objective of this thesis was to stablish protocols to obtain and conserve agouti (Dasyprocta leporina) sperm bred in captivity in the Brazilian semi-arid, aiming its sustainable production. The thesis was divided in three experiments. In the first one, we studied the influence of the interaction between two probes (quadratics and sine waves) and two stimulation protocols (continuous and in series) on the agouti sperm collection by electroejaculation efficiency. The most efficient interaction on this obtainment was the one with probes with rings associated with stimuli in series (4/7; 57%, P<0.05). In the second experiment we compared the cryoprotectant effects of different substances (glycerol, ethyleneglycol, dimethylsulfoxide, dimethylformamide) on epididymis sperm cryopreservation. The highest values on motility (39.5±4.6%), vigor (2.9±0.2) and membrane integrity (30.6±4.5%) were observed on the samples cryopreserved using glycerol when compared to those with ethyleneglycol and dimethylformamide, but there was no difference (P>0.05) when compared to the samples cryopreserved with dimethylsulfoxide. At last, we studied the effects of the methods to obtain sperm (electroejaculation vs epididymal collection) on post thawing sperm quality. The samples obtained by epididymal retrograde flushing showed values for motility of 25.0±10.9% and vigor 2.4±0.8, and those obtained by electroejaculation had 31.2±14.2% of motility and vigor of 2.2±0.7, however, without statistical difference (P>0.05), which shows the possibility to successfully use the epididymal sperm cryopreservation protocol on agouti ejaculated sperm. In conclusion, significant advances on obtainment and processing of agouti sperm were made, allowing the establishment of germplasm banks from sperm samples obtained from the epididymis or by electroejaculation.

Avaliação da variação sedimentológica em uma área da plataforma continental sob a atuação da indústria petrolífera

Petroleum exploration activity occurs on the offshore Potiguar Basin, from very shallow (2-3 m) until about 50 m water depth, extending from Alto de Touros (RN) to Alto de Fortaleza (CE). Take in account the biological importance and the heterogeneity of sediments on this area, it is necessary the understanding of the sedimentological dynamics, and mainly the changes generated by petroleum exploration to prevent possible damages to environment. Despite the intense activity of oil exploration in this area, research projects like these are still rare. In view to minimize this gap, this study was developed to evaluate sedimentological, mineralogical and geochemical changes in the vicinity of a exploration well, here designated as well A, located on the Middle continental shelf, near the transition to Outer shelf. The well selected for this study was the first one drilled with Riserless Mud Recovery technology (RMR) in Brazil. The main difference from this to the conventional method is the possibility of drilling phase I of the well with return of drilling material to the rig tank, minimizing fluid and gravel discharging around the vicinity, during this phase. Monitoring consisted of three surveys, first of them done before start drilling, the second one done 19 days after the end of drilling and the third one done one year after then. Comparison of the studied variables (calcium carbonate and organic matter content, sediment size, mineralogy and geochemistry) was done with their average, median and coefficient of variation values to understand the changes after drilling activity. Because operating company technical reasons, the well location was changed after the first survey (C1), resulting in a shift of the sampled area on the two last surveys (C2 e C3). Nevertheless, the acquired data presented a good correlation, with no loss to the mean goal of the study. The sedimentological, mineralogical and geochemical analyzes were done at Federal University of Rio Grande do Norte (UFRN). The results indicated a predominantly sandy environment along the three surveys. It was noticed that the first survey (C1), presented different values for all the studied variables than to the second (C2) and third (C3) surveys, which had similar values. Siliciclastic sediments are prevalent at all surveys, and quartz is the main component (more than 80%). Heavy minerals (garnet, turmaline, zircon and lmenite), rock fragments and mud aggregates also was described. Bioclastic sediments are dominated by coralline algae (more than 45%) and mollusks (more than 30%), followed by benthic foraminifera, bryozoans and worm tubes. More rarely was observed ostracoda and spike of calcareous sponge. Because the low changes of the sediments at the studied area and by the using of RMR method in the drilling, it was possible to conclude that drilling activity did not promote significant alteration on the local sediment cover. Changes in the studied variables before and after drilling activity could be influenced by the changing in the sampling area after survey 1 (C1).

Influência da desordem estrutural nas propriedades magnéticas de filmes finos de Co2FeAl

Thin films of Co2FeAl (CFA) and trilayers with CFA/M/CFA, where M is Au or Ag, produced by magnetron sputtering onto glass and oriented (MgO (100)) substrates were investigated. The structural, magnetic static and magnetic dynamics properties were analyzed by distinct experimental techniques. Through X-ray diffraction was observed an A2 phase for the samples (completely disordered), where the atoms are randomly located in the lattice. The static magnetic behavior, in some samples, reveal a plateau behavior generated by a biphasic system. The magnetoimpedance measurements were performed by varying the angle between the external magnetic field and current with respect of anisotropy direction. For this reason, the MI results show a asymmetric magnetoimpedance (AMI) behavior. For the single and trilayers samples with 500 nm-thick, the AMI effect is more evident in comparison with samples with 1000 nm-thick. Therefore, in this work was stablished a route to produce Heusler alloy samples with A2 phase in thin film geometry onto amorphous and oriented substrates, and due to structural disorder was possible to study the hysteretic and MI asymmetric effects.

Análise da eficiência de contratos de serviços de elevada especificidade terceirizados pela petrobras

The definition of the boundaries of the firms is subject that has occupied the organizational theorists long ago, being the seminal work of Coase (1937) indicated as the trigger for one theoretical evolution, with emphasis on governance structures, which led to a modern theory of incomplete contracts. The Transaction Cost Economics (TCE) and Agency Theory arise within this evolution, being widely used in studies related to the theme. Empirically, data envelopment analysis (DEA) has established itself as a suitable tool for analysis of efficiency. Although TCE argues that specific assets must be internalized, recent studies outside the mainstream of theory show that, often, firms may decide, for various reasons, hire them on the market. Researches on transaction costs face with the unavailability of information and methodological difficulties in measuring their critical variables. There`s still the need for further methodological deepening. The theoretical framework includes classic works of TCE and Agency Theory, but also more recent works, outside the mainstream of TCE, which warn about the existence of strategies in use of specific assets that aren`t necessarily aligned with the classical ideas of TCE. The Brazilian oil industry is the focus of this thesis, that aimed to evaluate the efficiency of contracts involving high specificity service outsourced by Petrobras. In order to this, we made the categorization of outsourced services in terms of specificity, as well the description of services with higher specificity. Then, we verified the existence of relationship between the specificity of services and a number of variables, being found divergent results than those that are preached by the mainstream of TCE. Then, we designed a DEA model to analyze the efficiency in the use of onshore drilling rigs, identified among the services of highest specificity. The next step was the application of the model to evaluate the performance of drilling rigs contracts. Finally, we verified the existence of relationship between the efficiency of contracts and a number of variables, being found, again, results not consistent with the theory mainstream. Regarding to analyze of efficiency of drilling rigs contracts, the model developed is compatible with what is found in academic productions in efficiency of drilling rigs. The results on efficiency show a wide range of scores, with efficiencies ranging from 31.79% to 100%, being low the sample efficiency average. There is consonance between the model results and the practices adopted by Petrobras. The results strengthen the DEA as an important tool in studies of efficiency with possibility to use for analysis other types of contracts. In terms of theoretical findings, the results reinforce the arguments that there are situations in which the strategies of the organizations, in terms of use of assets and services of high specificity, do not necessarily follow what is recommended by the mainstream of TCE

Influência da adição do NaCl e KCl em sistemas de pastas contendo sílica para poços de petróleo em zonas evaporíticas e carbonáticas

One of the major challenges faced nowadays by oil companies is the exploration of pre-salt basins. Thick salt layers were formed in remote ages as a consequence of the evaporation of sea water containing high concentrations of NaCl and KCl. Deep reservoirs can be found below salt formations that prevent the outflow of oil, thus improving the success in oil prospection. The slurries used in the cement operations of salt layers must be adequate to the properties of those specific formations. At the same time, their resulting properties are highly affected by the contamination of salt in the fresh state. It is t herefore important to address the effects of the presence of salt in the cement slurries in order to assure that the well sheath is able to fulfill its main role to provide zonal isolation and mechanical stability. In this scenario, the objective of the present thesis work was to evaluate the effect of the presence of NaCl and KCl premixed with cement and 40% silica flour on the behavior of cement slurries. Their effect in the presence of CO2 was also investigated. The rheological behavior of slurries containing NaCl and KCl was evaluated along with their mechanical strength. Thermal and microstructural tests were also carried out. The results revealed that the presence of NaCl and KCl affected the pozzolanic activity of silica flour, reducing the strength of the hardened slurries containing salt. Friedel´s salt was formed as a result of the bonding between free Cl- and tricalcium aluminate. The presence of CO2 also contributed to the degradation of the slurries as a result of a process of carbonation/bicarbonataion

Análise das emissões gasosas de um veículo flex funcionando com diferentes combustíveis

Efforts in research and development of new technologies to reduce emission levels of pollutant gases in the atmosphere has intensified in the last decades. In this context, it can be highlighted the modern systems of electronic engine management, new automotive catalysts and the use of renewable fuels which contributes to reduce the environmental impact. The purpose of this study was a comparative analysis of gas emissions from a automotive vehicle, operating with different fuels: natural gas, AEHC or gasoline. To execute the experimental tests, a flex vehicle was installed on a chassis dynamometer equipped with a gas analyzer and other complementary accessories according to the standard guidelines of emission and security procedures. Tests were performed according to NBR 6601 and NBR 7024, which define the urban and road driving cycle, respectively. Besides the analysis of exhaust gases in the discharge tube, before and after the catalyst, using the suction probe of the gas analyzer to simulate the vehicle in urban and road traffic, were performed tests of fuel characterization. Final results were conclusive in indicating leaded gasoline as the fuel which most contributed with pollutant emissions in atmosphere and the usual gasoline being the fuel which less contributed with pollutant emissions in atmosphere

Avaliação da corrosão em dutos por técnica gravimétrica e de resistência elétrica

With the increasing of demand for natural gas and the consequent growth of the pipeline networks, besides the importance of transport and transfer of oil products by pipeline, and when it comes to product quality and integrity of the pipeline there is an important role regarding to the monitoring internal corrosion of the pipe. This study aims to assess corrosion in three pipeline that operate with different products, using gravimetric techniques and electrical resistance. Chemical analysis of residues originated in the pipeline helps to identify the mechanism corrosive process. The internal monitoring of the corrosion in the pipelines was carried out between 2009 and 2010 using coupon weight loss and electrical resistance probe. Physico-chemical techniques of diffraction and fluorescence X-rays were used to characterize the products of corrosion of the pipelines. The corrosion rate by weight loss was analyzed for every pipeline, only those ones that has revealed corrosive attack were analyzed located corrosion rate. The corrosion potential was classified as low to pipeline gas and ranged from low to severe for oil pipelines and the pipeline derivatives. Corrosion products were identified as iron carbonate, iron oxide and iron sulfide