Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Membrana de alumina anódica: comportamento da microestrutura e estudo das propriedades ópticas após tratamento térmico

Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300° C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700° C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700° C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study

Estudos comparativos do ciclo de regeneração de diferentes tipos de silicoaluminofosfatos

Different types of heterogeneous catalysts of the silicoaluminophosphate type, (SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-41), molecular sieves with a: AFI, AEL, ATO, CHA and AFO structure, respectively, were synthesized through the hydrothermal method. Using sources such as hydrated alumina (pseudobohemita), phosphoric acid, silica gel, water, as well as, different types of organic structural templates, such as: cetyltrimethylammonium bromide (CTMABr), di-isopropylamine (DIPA), di-n- propylamine (DNPA) and tetraethylammonium hydroxide (TEOS), for the respective samples. During the preparation of the silicoaluminophosphates, the crystallization process of the samples occurred at a temperature of approximately 200 ° C, ranging through periods of 18-72 h, when it was possible to obtain pure phases for the SAPOs. The materials were furthermore washed with deionized water, dried and calcined to remove the molecules of the templates. Subsequently the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared region (FT-IR), specific surface area and thermal analysis via TG/DTG. The acidic properties were determined using adsorption of n-butylamine followed by programmed termodessorption. These methods revealed that the SAPO samples showed a typically weak to moderate acidity. However, a small amount of strong acid sites was also detected. The deactivation of the catalysts was conducted by artificially coking the samples, followed by n-hexane cracking reactions in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the catalysts regeneration and removal of the coke

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates

Síntese e caracterização de CuNb2O6 e CuNbC através de reação sólido- sólido e gás- sólido a baixa temperatura

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Novos monômeros obtidos a partir do metacrilato de glicidila, bisfenol A e 4, 4 isopropilidenodicicloexanol : síntese, caracterização estrutural e propriedades de compósitos para utilização em resinas de restauração dental

Nowadays, composite resins are the direct restorative materials more important in dental clinical performance, due to their versatility and aesthetic excellence. Bis-GMA (2,2-bis[4(2-hydroxy-3-metacryloxypropoxy)phenil]propane) is the base monomer more frequently used in restorative composite resins. However, this monomer presents some disadvantages, such as high viscosity and two aromatic rings in its structure that can promote allergic reactions to the humans. In this work, the main purpose was to synthesize new monomers from glycidyl methacrylate to use in dental restorative materials. Structural characterization of the monomers was carried out through FTIR and NMR 1H, and eight composites were produced from the new monomers, by addition of silane-treated alumino silicate particles (inorganic filler) and a photocuring system (camphorquinone and ethyl 4-dimethylaminebenzoate). The composites were analyzed by environmental scanning electronic microscopy and the water sorption and solubility, compressive strength and elastic modulus were determined. A commercial composite resin [Z100 (3M)] was used to comparison effect. The new composites presented general characteristics similar to the commercial ones; however, they didn t present the properties expected. This behavior was attributed to the lower degree of monomer reaction and to the granulometry and size distribution of the mineral filler in the polymeric matrix

Influência das tensões tectônicas na permeabilidade da formação Açu - Bacia Potiguar

The behavior of the fluid flux in oil fields is influenced by different factors and it has a big impact on the recovery of hydrocarbons. There is a need of evaluating and adapting the actual technology to the worldwide reservoirs reality, not only on the exploration (reservoir discovers) but also on the development of those that were already discovered, however not yet produced. The in situ combustion (ISC) is a suitable technique for these recovery of hydrocarbons, although it remains complex to be implemented. The main objective of this research was to study the application of the ISC as an advanced oil recovery technique through a parametric analysis of the process using vertical wells within a semi synthetic reservoir that had the characteristics from the brazilian northwest, in order to determine which of those parameters could influence the process, verifying the technical and economical viability of the method on the oil industry. For that analysis, a commercial reservoir simulation program for thermal processes was used, called steam thermal and advanced processes reservoir simulator (STARS) from the computer modeling group (CMG). This study aims, through the numerical analysis, find results that help improve mainly the interpretation and comprehension of the main problems related to the ISC method, which are not yet dominated. From the results obtained, it was proved that the mediation promoted by the thermal process ISC over the oil recovery is very important, with rates and cumulated production positively influenced by the method application. It was seen that the application of the method improves the oil mobility as a function of the heating when the combustion front forms inside the reservoir. Among all the analyzed parameters, the activation energy presented the bigger influence, it means, the lower the activation energy the bigger the fraction of recovered oil, as a function of the chemical reactions speed rise. It was also verified that the higher the enthalpy of the reaction, the bigger the fraction of recovered oil, due to a bigger amount of released energy inside the system, helping the ISC. The reservoir parameters: porosity and permeability showed to have lower influence on the ISC. Among the operational parameters that were analyzed, the injection rate was the one that showed a stronger influence on the ISC method, because, the higher the value of the injection rate, the higher was the result obtained, mainly due to maintaining the combustion front. In connection with the oxygen concentration, an increase of the percentage of this parameter translates into a higher fraction of recovered oil, because the quantity of fuel, helping the advance and the maintenance of the combustion front for a longer period of time. About the economic analysis, the ISC method showed to be economically feasible when evaluated through the net present value (NPV), considering the injection rates: the higher the injection rate, the higher the financial incomes of the final project

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Incorporação de resíduo cerâmico para prevenção da retrogressão da resistência de cimentos de poços de petróleo submetidos à injeção de vapor

Steam injection is the most used thermal recovery method of oil nowadays because of the high degree of development of the technique that allows high recovery factors. However, injection of superheated steam into the reservoir affects the entire structure of the well, including the cemented layer that presents a retrogression of compressive strength and increases the permeability due to formation of more crystalline and denser phases at temperatures above 110 °C. These changes result in failures in the cement that favor the entrance of formation fluids into the annulus space resulting in unsafe operations and restrictions in the economic life of the well. But the strength retrogression can be prevented by partial replacement of cement by silica-based materials that reduce the CaO/SiO2 ratio of cement slurries changing the trajectory of the reactions, converting those deleterious phases in phases with satisfactory mechanical strength and permeability. The aim of this study was to evaluate the behavior of a ceramic waste material rich in silica in partial and total substitution of a mineral additive used to fight the strength retrogression of cement slurries subjected to high temperatures. The evaluation was made by compression, X-ray diffraction (XRD) and thermogravimetry (TG/DTG). The samples were submitted to a cycle of low temperature (38 °C) for 28 days and a cycle of low temperature followed by exposure to 280 ºC and 1000 psi by 3 days. The results showed that slurries with additions of up to 30% of the waste material are not enough to prevent the strength retrogression, while slurries with additions of the waste material combined with silica flour in various proportions produced hydrated products of low Ca/Si ratios that maintained the compressive strength at satisfactory levels

Estudo do processo de combustão in-situ em reservatórios maduros de óleos médios e leves (high pressure air injection)

Nearly 3 x 1011 m3 of medium and light oils will remain in reservoirs worldwide after conventional recovery methods have been exhausted and much of this volume would be recovered by Enhanced Oil Recovery (EOR) methods. The in-situ combustion (ISC) is an EOR method in which an oxygen-containing gas is injected into a reservoir where it reacts with the crude oil to create a high-temperature combustion front that is propagated through the reservoir. The High Pressure Air Injection (HPAI) method is a particular denomination of the air injection process applied in light oil reservoirs, for which the combustion reactions are dominant between 150 and 300°C and the generation of flue gas is the main factor to the oil displacement. A simulation model of a homogeneous reservoir was built to study, which was initially undergone to primary production, for 3 years, next by a waterflooding process for 21 more years. At this point, with the mature condition established into the reservoir, three variations of this model were selected, according to the recovery factors (RF) reached, for study the in-situ combustion (HPAI) technique. Next to this, a sensitivity analysis on the RF of characteristic operational parameters of the method was carried out: air injection rate per well, oxygen concentration into the injected gas, patterns of air injection and wells perforations configuration. This analysis, for 10 more years of production time, was performed with assistance of the central composite design. The reservoir behavior and the impacts of chemical reactions parameters and of reservoir particularities on the RF were also evaluated. An economic analysis and a study to maximize the RF of the process were also carried out. The simulation runs were performed in the simulator of thermal processes in reservoirs STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator) from CMG (Computer Modelling Group). The results showed the incremental RF were small and the net present value (NPV) is affected by high initial investments to compress the air. It was noticed that the adoption of high oxygen concentration into the injected gas and of the five spot pattern tends to improve the RF, and the wells perforations configuration has more influence with the increase of the oil thickness. Simulated cases relating to the reservoir particularities showed that smaller residual oil saturations to gas lead to greater RF and the presence of heterogeneities results in important variations on the RF and on the production curves

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Aplicação de técnicas eletroquímicas na determinação do potencial de corrosividade de ligas de alumínio em água produzida

The resistance of aluminum and their alloys, to the corrosion phenomenon, in aqueous solutions, is a result of the oxide layer formed. However, the corrosion process in the aluminum alloy is associated with the presence a second phase of particles or the presence of chloride ions which promote the disruption of the oxide layer located producing the corrosion process. On the other hand, the term water produced is used to describe the water after the separation of the oil and gas in API separators. The volumes of produced water arrive around 5 more times to the volume of oil produced. The greatest feature of the water is the presence of numerous pollutants. Due to the increased volume of waste around the world in the current decade, the outcome and the effect of the discharge of produced water on the environment has recently become an important issue of environmental concern where numerous treatments are aimed at reducing these contaminants before disposal. Then, this study aims to investigate the electrochemical corrosion behavior of aluminum alloy 6060 in presence of water produced and the influence of organic components as well as chloride ions, by using the electrochemical techniques of linear polarization. The modification of the passive layer and the likely breakpoints were observed by atomic force microscopy (AFM). In the pit formation potential around -0.4 to -0.8 V/EAg/AgCl was observed that the diffusion of chloride ions occurs via the layer formed with the probable formation of pits. Whereas, at temperatures above 65 °C, it was observed that the range of potential for thepit formation was -0.4 to -0.5 V/EAg/AgCl. In all reactions, the concentration of Al(OH)3 in the form of a gel was observed

Efeitos da temperatura do ar, linhagem e período do dia nas freqüências de ocorrências e tempos de expressão comportamental de matrizes pesadas

Ajustes de comportamento podem ocorrer rapidamente e a custo menor do que os ajustes fisiológicos. Considerando o comportamento social, é sugestivo que a freqüência e a intensidade de interações agressivas, o total de coesão social e a extensão de vícios sociais possam ser utilizados para avaliação de bem-estar. Esta pesquisa apresenta uma análise das interações entre os fatores experimentais, como temperatura, linhagem e período do dia, nos comportamentos de matrizes pesadas alojadas em câmara climática, buscando evidenciar as diferentes reações das aves submetidas a distintas condições ambientais. Os resultados encontrados mostraram diferenças significativas entre os comportamentos expressos pelas diferentes linhagens, reforçando a necessidade do monitoramento em tempo real do bem-estar de matrizes pesadas em alojamentos comerciais, dada a complexidade com que as variáveis ambientais interferem no bem-estar. A pesquisa permitiu concluir também que a avaliação do bem-estar de matrizes pesadas deve considerar o período do dia na observação dos comportamentos.

Desenvolvimento e caracterização de um sistema microemulsionado contendo anfotericina b para uso oftalmológico

Universidade Federal do Rio Grande do Norte