Síntese citrato-hidrotermal e caracterização eletroquímica de LSCF para aplicação como catodo em célula a combustível de temperatura intermediária

The lanthanum strontium cobalt iron oxide (La1-xSrxCo1-yFeyO3 LSCF) is the most commonly used material for application as cathode in Solid Oxide Fuel Cells (SOFCs), mainly due to their high mixed ionic electronic conductivity between 600 and 800ºC. In this study, LSCF powders with different compositions were synthesized via a combination between citrate and hydrothermal methods. As-prepared powders were calcined from 700 to 900°C and then characterized by X-ray fluorescence, X-ray diffraction, thermal analyses, particle size analyses, nitrogen adsorption (BET) and scanning electronic microscopy. Films of composition La0,6Sr0,4Co0,2Fe0,8O3 (LSCF6428), powders calcined at 900°C, were screen-printed on gadolinium doped ceria (CGO) substrates and sintered between 1150 and 1200°C. The effects of level of sintering on the microstructure and electrochemical performance of electrodes were evaluated by scanning electronic microscopy and impedance spectroscopy. Area specific resistance (ASR) exhibited strong relation with the microstructure of the electrodes. The best electrochemical performance (0.18 ohm.cm2 at 800°C) was obtained for the cathode sintered at 1200°C for 2 h. The electrochemical activity can be further improved through surface activation by impregnation with PrOx, in this case the electrode area specific resistance decreases to values as low as 0.12 ohm.cm2 (800°C), 0.17 ohm.cm2 (750°C) and 0.31 ohm.cm2 (700°C). The results indicate that the citrate-hydrothermal method is suitable for the attainment of LSCF particulates with potential application as cathode component in intermediate temperature solid oxide fuel cells (IT-SOFCs)

Estudo do equilíbrio líquido-vapor do sistema água+etanol+líquido iônico visando a separação do álcool anidro

Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed

Palma forrageira (Opuntia ficus indica e Nopalea cochenillifera) como matéria-prima para produção de etanol celulósico e enzimas celulolíticas

The need for new sources of energy and the concern about the environment have pushed the search for renewable energy sources such as ethanol. The use of lignocellulosic biomass as substrate appears as an important alternative because of the abundance of this raw material and for it does not compete with food production. However, the process still meets difficulties of implementation, including the cost for production of enzymes that degrade cellulose to fermentable sugars. The aim of this study was to evaluate the behavior of the species of cactus pear Opuntia ficus indica and Nopalea cochenillifera, commonly found in northeastern Brazil, as raw materials for the production of: 1) cellulosic ethanol by simultaneous saccharification and fermentation (SSF) process, using two different strains of Saccharomyces cerevisiae (PE-2 and LNF CA-11), and 2) cellulolytic enzymes by semi-solid state fermentation (SSSF) using the filamentous fungus Penicillium chrysogenum. Before alcoholic fermentation process, the material was conditioned and pretreated by three different strategies: alkaline hydrogen peroxide, alkaline using NaOH and acid using H2SO4 followed by alkaline delignification with NaOH. Analysis of composition, crystallinity and enzymatic digestibility were carried out with the material before and after pretreatment. In addition, scanning electron microscopy images were used to compare qualitatively the material and observe the effects of pretreatments. An experimental design 2² with triplicate at the central point was used to evaluate the influence of temperature (30, 40 and 45 °C) and the initial charge of substrate (3, 4 and 5% cellulose) in the SSF process using the material obtained through the best condition and testing both strains of S. cerevisiae, one of them flocculent (LNF CA-11). For cellulase production, the filamentous fungus P. chrysogenum was tested with N. cochenillifera in the raw condition (without pretreatment) and pretrated hydrothermically, varying the pH of the fermentative medium (3, 5 and 7). The characterization of cactus pear resulted in 31.55% cellulose, 17.12% hemicellulose and 10.25% lignin for N. cochenillifera and 34.86% cellulose, 19.97% hemicellulose and 15.72% lignin for O. ficus indica. It has also been determined, to N. cochenillifera and O. ficus indica, the content of pectin (5.44% and 5.55% of calcium pectate, respectively), extractives (26.90% and 9.69%, respectively) and ashes (5.40% and 5.95%). Pretreatment using alkaline hydrogen peroxide resulted in the best cellulose recovery results (86.16% for N. cochenillifera and 93.59% for O. ficus indica) and delignification (48.79% and 23.84% for N. cochenillifera and O. ficus indica, respectively). This pretreatment was also the only one which did not increase the crystallinity index of the samples, in the case of O. ficus indica. However, when analyzing the enzymatic digestibility of cellulose, alkali pretreatment was the one which showed the best yields and therefore it was chosen for the tests in SSF. The experiments showed higher yield of conversion of cellulose to ethanol by PE-2 strain using the pretreated N. cochenillifera (93.81%) at 40 °C using 4% initial charge of cellulose. N. cochenillifera gave better yields than O. ficus indica and PE-2 strain showed better performance than CA-11. N. cochenillifera proved to be a substrate that can be used in the SSSF for enzymes production, reaching values of 1.00 U/g of CMCase and 0.85 FPU/g. The pretreatment was not effective to increase the enzymatic activity values

Formulação de novos combustíveis base diesel: avaliação de desempenho e emissões

The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides

Síntese e caracterização de componentes nanoestruturados de células a combustível de óxidos sólidos

Perovskite-like ceramic materials present the general formula ABO3, where A is a rare earth element or an alkaline metal element, and B is a transition metal. These materials are strong candidates to assume the position of cathode in Solid Oxide Fuel Cells (SOFC), because they present thermal stability at elevated temperatures and interesting chemical and physical properties, such as superconductivity, dieletricity, magnetic resistivity, piezoelectricity, catalytic activity and electrocatalytic and optical properties. In this work the cathodes of Solid Oxide Fuel Cells with the perovskite structure of La1-xSrxMnO3 (x = 0.15, 0.22, 0.30) and the electrolyte composed of zirconia-stabilized-yttria were synthesized by the Pechini method. The obtained resins were thermal treatment at 300 ºC for 2h and the obtained precursors were characterized by thermal analysis by DTA and TG / DTG. The powder precursors were calcined at temperatures from 450 to 1350ºC and were analyzed using XRD, FTIR, laser granulometry, XRF, surface area measurement by BET and SEM methods. The pellets were sintered from the powder to the study of bulk density and thermal expansion

Desenvolvimento de componentes nanométricos para aplicação em células a combustível à base de sólidos estruturados e filmes finos

The present work aims the preparation of filmes of strontium-doped lanthanum manganite (perovskita) yttria-stabilized zirconia (LSM-SDC) films deposited on substrate of YSZ by means of spin coating technique having as principal objective their application to solid oxide fuel cells of intermediate temperature. La0,8Sr0,2MnO3 and Ce0,8Sm0,2O1,9 were obtained by modified Pechini method by use of gelatin which act as polymerization agent. The powders obtained were characterized by Xray fluorescence, X ray diffraction, electronic scanning microscopy and the superficial area by BET method. The results obtained by X-ray fluorescence showed that the route adopted for obtention of powders was effective in the obtention of the compositions with close values to the stoichiometrics. Ethyl cellulose was used as pore-forming agent and mixed with the LSM-SDC powders in weight proportions of 1:24, 2:23 and 1:9. The films were sintered at 1150 °C for 4 h and characterized by X-ray diffraction and scanning electron microscopy technique (SEM) and atomic force. The phases quantification of the precursory powders and of the obtained films was carried through Rietveld method. According with the analysis of SEM, as the content of ethyl cellulose was increased, the pore distribution in films become more uniform and the pore size reduced. The methodology used for the obtention of the films was very efficient, considering a material was obtained with characteristics that were proper to the application as electrolyte/cathode system to solid oxide fuel cells

Caracterização dos eletrocatalisadores LaMnO3, LaFeO3, LaFe0,2Mn0,8O3 E La0,5Fe0,5MnO3 preparados por autocombustão assistida por microondas para cátodos de células a combustível do tipo SOFC

Materials consisting of perovskite-type oxides (ABO3) have been developed in this work for applications in fuel cell cathodes of solid oxide type (SOFC). These ceramic materials are widely studied for this type of application because they have excellent electrical properties, conductivity and electrocatalytic. The oxides LaMnO3, LaFeO3, LaFe0.2Mn0.8O3 e La0.5Fe0.5MnO3 were synthesized by the method of microwave assisted combustion and after sintering at 800°C in order to obtain the desired phases. The powders were characterized by thermogravimetry (TG), X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and voltammetric analysis (cyclic voltammetry and polarization curves). The results obtained by XRF technique showed that the microwave synthesis method was effective in obtaining doping oxides with values near stoichiometric. In general, powders were obtained with particle size less than 0.5 μm, having a porous structure and uniform particle size distribution. The particles showed spherical form, irregular and crowded of varying sizes, according to the analysis of SEM. The behavior of the oxides opposite the thermal stability was monitored by thermogravimetric curves (TG), which showed low weight loss values for all samples, especially those of manganese had its structure. By means of Xray diffraction of the samples sintered at 800°C was possible to observe the formation of powders having high levels of crystallinity. Furthermore, undesirable phases such as La2O3 and MnOx were not identified in the diffractograms. These phases block the transport of oxygen ions in the electrode/electrolyte interface, affecting the electrochemical activity of the system. The voltammetric analysis of the electrocatalysts LF-800, LM-800, LF2M8-800 e L5F5M-800 revealed that these materials are excellent electrical conductors, because it increased the passage of electrical current of the working electrode significantly. Best performance for the oxygen reduction reaction was observed with iron-rich structures, considering that the materials obtained have characteristics suitable for use in fuel cell cathodes of solid oxide type

Uso do gpr na caracterização da pluma de contaminação gerada por hidrocarbonetos a partir de um posto de combustível na praia de Búzios/RN

This work is the application of geophysical methods, using the Ground Penetrating Radar (GPR), with the objective of survey in a subsurface plume of contamination caused by a disabled gas station. The gas station is located on the Búzios beach in southern coast of the state to Rio Grande do Norte in an Area of Environmental Protection called Bonfim-Guaraíra. The interest to develop this work was the presence of contaminants (hydrocarbons) in a well located on the desktop, previously used for the abstraction of groundwater for residents living near the site. Were raised 15 geophysical survey lines totaling 775,48 lifting and installed 4 piezometer, to confirm the contamination and prepare a pluviometric map that helped in indicating the direction of local groundwater flow, thus showing the direction of movement of the probably plume of contamination. From the processing of the GPR lines was possible to identify two likely phases of contamination according to the classification proposed by Azambuja et al 2000, which are called phase absorbed and dissolved phase

O Circuito espacial de produção do biodiesel: configuração no território brasileiro e uso do território Norte-Rio-Grandense

This research aims to understand the use of the territory from the Rio Grande do Norte to the circuit spatial of production from the Biodiesel understanding it as part of the national context. The introduction of biodiesel into the Brazilian energy matrix begins to take shape in the year 2005 with the implementation of the National Program for Production and Use of Biodiesel (NPPB). This is anchored on three pillars: social inclusion (through family agriculture), environmental sustainability and economic viability. The NPPB consists of a set of standards, which turned into shares and distributed by almost all the national territory. Our reflection assumes that the places accommodating different forms of productive activities and, thus, the performance of the circuit space of biodiesel production depends on several factors, including the configuration of the territory they receive this new nexus economic. Understanding that the places by their technical content determine the realization of productive activities, it was found that the inclusion of this circuit space production in Rio Grande do Norte, reveals the reality expressed in the national territory, where some places are endowed with a privileged technical content and other extremely poor infrastructure. As our research could confirm the circuit space of biodiesel production that is expressed in the way plants are distributed within the country (mostly in South-Central), in more significant participation of small farmers in the South in the supply of raw material for the production of biodiesel and the main raw material used for the production of agrofuels (soybeans, whose production sector is highly consolidated and technified). Already the project materialization of NPPB regarding the settlements and communities of the Rio Grande do Norte State, we observed that the "event" or advent of realization encountered a technical means lacking in infrastructure that need to be molded to the needs of production, or is to cultivate castor beans or sunflower would be needed inputs and implements that farmers don´t have. Given the above, the research concludes that, as proposed previously, the use of the territory of Rio Grande do Norte to this circuit has summarized the performance of experiments, either with regard to the participation of family farmers as suppliers of raw materials, including the development of related research in the stage of production fuel oil by Petrobras. This finding came from research done from the concept of "spatial circuits of production," which allowed the verification of the circuit that steps outlined in Potiguar territory. Regarding the inclusion of family farmers in the productive circuit in RN, research reveals that, in the manner as has been done, it is doomed to failure. Furthermore, we dare say that this persistence in trying to put these family farmers, the way is being made, and the resulting successive failures, indicating that social inclusion advocated by NPPB not take place, and that this production circuit relies on the same logic circuit concentrated and exclusive space for ethanol production