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)

Utilização do éster de soja como biolubrificante

The lubricants found in the market are of mineral or synthetic origin and harm to humans and the environment, mainly due to their improper discard. Therefore industries are seeking to develop products that cause less environmental impact, so to decrease mainly, operator aggression the Cutting Fluids became an emulsion of oil / water or water / oil. However, the emulsion was not considered the most suitable solution for environmental question, therefore the search for biodegradable lubricants and which no are toxic continues and so vegetable oils are seen, again, as a basis for the production of lubricants. The biggest problem with these oils is their oxidative instability that is intensified when working at high temperatures. The process transesterification decreases the oxidation, however changes some physical and chemical properties. Therefore soybean oil after the transesterification process was subjected to tests of density, dynamic viscosity, kinematic viscosity which is calculated from two parameters mentioned, flash point and acidity. Besides the physico-chemical test the soybean oil was subjected to a dynamic test in a tribometer adapted from a table vise, whose induced wear was the adhesive and ultimately was used as cutting fluid in a process of turning in two different materials, steel 1045 and cast iron. This latter test presented results below the mineral cutting fluid which it was compared in all tests, already in other experiments the result was satisfactory and other experiments not, so that chemical additives can be added to the oil analyzed to try equate all parameters and so formulate a biolubrificante not toxic to apply in machining processes of metalworking industry

Estudo do potencial refratário de argilas sílico-aluminosas do Rio Grande do Norte

The segment of the structural ceramics industry is one of the most important to the economy of Rio Grande do Norte. The supply chain makes a total of 206 companies that are distributed in 39 counties, concentrated in three regional centers: Seridó Apodi / Assu and great Natal. The ceramic industry in the state is around 80 million pieces per month, with 50,186 million of these tiles, which makes the Rio Grande do Norte one of the largest manufacturers of product in the Country. Different ceramic products can be manufactured by mixing two or more clays and accessory minerals. Mixtures acquire characteristics and form what is called the ceramic body. Refractory masses have a high melting point and thermal shock support. Its composition contains refractory clays with a little iron oxide and material fluxes. A line of semi-refractory ceramic products that stands out for its high added value are the bricks in ivory or red, used in building barbecues, fireplaces, wood stoves and braziers. The aim of this study was to use alumina-clay or silica- alumina-clay to the industrial RN, for the production of refractory bricks semi-refractory burning light. Clay and Kaolin were characterized for their chemical and mineralogical composition, immediately after ceramic bodies were made with different concentrations of the components, they were raised, pressed and sintered. After sintering the resulting products were characterized in terms of mechanical, thermal and dimensional than the characterization by X-ray diffraction and scanning electron microscopy. After obtaining the results, we concluded that the studied clay can be used for the production of semi-refractory bricks

Reaproveitamento e caracterização dos resíduos orgânicos provenientes do Programa MESA DA SOLIDARIEDADE da CEASA/RN

As an auxiliary tool to combat hunger by decreasing the waste of food and contributing for improvement of life quality on the population, CEASA/RN has released from August/03 to August/05 the program MESA DA SOLIDARIEDADE. Despite of the positive results of this program, that has already distributed around 226 tons of food, there is still food being thrown in the trash as the deliver of the same food in its natural form would be a health risk to those who would consume it and only the correct processing of this food can make it edible. This work has as a goal the reuse of solid residues of vegetal origin generated by the CEASA/RN, through the Program MESA DA SOLIDARIEDADE and the characterization of the product obtained so it might be used as a mineral complement in the human diet. To the collecting of samples (from September until December /2004) it was developed a methodology having as a reference the daily needs of mineral salts for infants at the age of seven to ten. The sample was packed in plastic bags and transported in an ambient temperature to the laboratory where it was selected, weighted, disinfected, fractionated and dried to 70ºC in greenhouse. The dry sample was shredded and stored in bottles previously sterilized. The sample in nature was weighted in the same proportion of the dry sample and it was obtained a uniform mass in a domestic processor. The physical-chemical analyses were carried out in triplicate in the samples in nature and in the dry product, being analyzed: pH, humidity, acidity and soluble solids according to IAL (1985), mineral salts contents (Ca, K, Na, Mg, P and Fe) determined by spectrophotometry of Atomic Absorption, caloric power through a calorimetric bomb and presence of fecal traces and E. coli through the colilert method (APHA, 1995). During this period the dry food a base of vegetables presented on average 5,06% of humidity, 4,62 of pH, acidity of 2,73 mg of citric acid /100g of sample, 51,45ºBrix of soluble solids, 2.323,50mg of K/100g, 299,06mg of Ca/100g, 293mg of Na/100g, 154,66mg of Mg/100g, 269,62mg of P/100g, 6,38mg of Fe/100g, caloric power of 3,691Kcal/g (15,502KJ/g) and is free of contamination by fecal traces and E..coli. The dry food developed in this research presented satisfactory characteristics regarding to its conservation, possessing low calories, constituting itself a good source of potassium, magnesium, sodium and iron that can be utilized as a food complement of these minerals

Efeito dos períodos de envelhecimento na lixiviação de íons e de proteínas solúveis em sementes de milho

Este trabalho foi conduzido no Laboratório de Análise de Sementes, do Departamento de Produção Vegetal, da Universidade Estadual Paulista (Botucatu/SP), com o objetivo de avaliar os efeitos causados por diferentes períodos de envelhecimento acelerado na lixiviação de íons e de proteínas solúveis em sementes de milho. Sementes de milho do híbrido BR 3123 foram colocadas sobre tela em gerbox, contendo 40mL de água destilada, e mantidas a temperatura de 42°C por períodos de 0, 24, 48, 72, 96, 120, 144 e 166 horas. Após o envelhecimento, parte das sementes foi colocada para germinar, empregando quatro repetições para cada período, obtendo-se a porcentagem de plântulas normais no quarto dia. em outra parte realizou-se, após manutenção em copos plásticos com 75mL de H2O destilada por 24 horas à 25°C, leituras de condutividade elétrica (µS.cm-1.g-1), determinação de íons (mg.L-1.g de semente-1) e de proteínas solúveis totais (µproteina.g-1.mL-1) lixiviadas na solução. Os resultados indicaram que a elevação dos valores de condutividade elétrica e de lixiviado de proteínas totais ocorreu a partir de 72 horas de envelhecimento acelerado. A lixiviação de potássio foi mais acentuada que a dos íons cálcio, zinco, manganês, cobre, ferro e magnésio.

Estudo da remoção de compostos orgânicos, benzeno e tolueno, em solução aquosa por processo oxidativo avançado do tipo Fenton

The oil and petrochemical industry is responsable to generate a large amount of waste and wastewater. Among some efluents, is possible find the benzene, toluene, ethilbenze and isomers of xilenes compounds, known as BTEX. These compounds are very volatily, toxic for environment and potencially cancerigenous in man. Oxidative advanced processes, OAP, are unconventional waste treatment, wich may be apply on treatment and remotion this compounds. Fenton is a type of OAPs, wich uses the Fenton s reactant, hydrogen peroxide and ferrous salt, to promove the organic degradation. While the Photo-Fenton type uses the Fenton s reactant plus UV radiation (ultraviolet). These two types of OAP, according to literature, may be apply on BTEX complex system. This project consists on the consideration of the utilization of technologies Fenton and Photo-Fenton in aqueous solution in concentration of 100 ppm of BTEX, each, on simulation of condition near of petrochemical effluents. Different reactors were used for each type of OAP. For the analyticals results of amount of remotion were used the SPME technique (solid phase microextraction) for extraction in gaseous phase of these analytes and the gas chromatography/mass espectrometry The arrangement mechanical of Photo-Fenton system has been shown big loss by volatilization of these compounds. The Fenton system has been shown capable of degradate benzene and toluene compounds, with massic percentage of remotion near the 99%.

Estudo comparativo da constituição nutricional da madeira e casca de espécies e clones de Eucalipto visando o cultivo de Shiitake em toras

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Degradação do fungicida tiofanato metílico pelo processo foto-Fenton em reatores anular e solar

Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of São Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor

Caracterização de Efluente Têxtil e Proposta de Tratamento

Textile industry deals with a high diversity of processes and generation of wastewaters with a high content of pollutant material. Before being disposed of in water bodies, a pre-treatment of the effluent is carried out, which is sometimes ineffective. In order to be properly treated, physical and chemical properties of the effluent must be known, as well as the pollutant agents that might be present in it. This has turned out to be a great problem in the textile industry, for there is a variety of processes and the pollutant load is very diversified. The characterization of the effluent allows the identification of most critical points and, as a consequence, the most appropriate treatment procedure to be employed, may be chosen. This study presents the results obtained after characterizing the effluent of a textile industry that comprises knitting, dyeing and apparel sections, processing mainly polyester/cotton articles. In this work, twenty samples of the effluent were collected, and related to the changes in production. From the results, a statistical evaluation was applied, determined in function of the rate of flow. The following properties and pollutants agents were quantitatively analysed: temperature; pH; sulfides; chlorine; alcalinity; chlorides; cianides; phenols; color; COD (Chemical Oxygen Demand); TOC (Total Organic Carbon); oil and grease; total, fixed and volatile solids; dissolved, fixed and volatile solids; suspended, fixed and volatile solids; setteable solids and heavy metals such as cadmium, copper, lead, chromium, tin, iron, zinc and nickel. Analyses were carried out according to ABNT NBR 13402 norm, based upon Standard Methods for the Examination of Water and Wastewater. As a consequence, a global treatment proposal is presented, involving clean production practices as contaminant load reducer, followed by conventional (biological) treatment

Biossorção utilizando alga marinha (sargassum sp.) aplicada em meio orgânico

In this work, biosorption process was used to remove heavy metals from used automotive lubricating oils by a bus fleet from Natal-RN-Brazil. This oil was characterized to determine the physical-chemistry properties. It was also characterized the used oil with the aim of determining and quantifying the heavy metal concentration. Fe and Cu were the metals existent in large concentration and these metals were choused to be studied in solubilization process. For the biosorption process was used the seaweed Sargassum sp for the study of influencing of the metals presents separately and with other metals. It was also studied the effect of the protonation treatment of alga with the objective to know the best efficiency of heavy metals removal. The study of the solubilization showed that the presence of more than a metal favors the solubilization of the metals presents in the oil and consequently, it favors the biosorption process, what becomes interesting the perspective application in the heavy metals removal in lubricating oils used, because the presence of more than a heavy metal favors the solubility of all metals present. It was observed that the iron and copper metals, which are present in large concentration, the protonated biosorbtent was more effective. In this study we used as biomass the marine alga Sargassum sp to study the influence of agitation velocity, temperature and initial biomass concentration on the removal of iron and copper from used lubricant oils. We performed an experimental design and a kinetic study. The experiments were carried out with samples of used lubricant oil and predetermined amounts of algae, allowing sufficient time for the mixture to obtain equilibrium under controlled conditions. The results showed that, under the conditions studied, the larger the amount of biomass present, the lower the adsorption capacity of the iron and of the copper, likely due to a decrease in interface contact area. The experimental design led us to conclude that a function can be obtained that shows the degree of influence of each one of the system variables

Degradação fotoquímica de efluentes industriais contendo polipropileno e isoniazida

One of the main impacts to the environment is the water pollution, where the industrial sector is one of the main sources of this problem. In order to search for a solution, the industrial sector is looking forward to new technologies to treat its wastewaters with the goal to reuse the water in the own process. In this mode, the treatment presents a reduction in its costs with the water suply. One of these technologies that are getting more and more applications is the advanced oxidative processes (AOP´s). In this work two industrial wastewaters have been studied, i.e., containing polymers and pharmacus. In the case of the wastewaters with polymers the UV/H2O2 process has been applied with a systematic series of experiments, using irradiation from a mercury lamp and also solar. The following variables of the UV/H2O2 process for the polymers wastewaters have been studied systematically with the lamp reactor: mode of addition of hydrogen peroxide, temperature, time of reaction, hydrogen peroxide concentration and power of the lamp (80, 125, 250 and 400W). The results demonstrated to be satisfactory, obtaining rates of organic charge removal of 100% in 120 minutes of reaction. The studied variables for the experiments with solar irradiation using polymers wastewaters were only the time of reaction, the mode of addition and concentration of the hydrogen peroxide. The results with the solar irradiation demonstrated to be not satisfactory, reaching maximum of 22% of TOC removal in 240 minutes of reaction. This is in accordance with the fact that the solar source has only 5% of low UV irradiation. With respect to the photodegradation of the pharmacus wastewaters, the process UV/H2O2 and photo-Fenton have been applied. As a source of photons, in this case, a mercury UV lamp of 80 W has been used. The studied variables for the experiments with artificial irradiation with the pharmacus wastewaters were: initial concentration of the pollutant, concentration of Fe2+ and time of reaction. The results demonstrated a degree of degradation fairly satisfactory, showing a maximum conversion value of 46% in 120 minutes

Alterações nos teores nutricionais foliares de bananeira 'prata-anã' adubada com composto orgânico em cinco ciclos de produção

O presente trabalho objetivou avaliar o estado nutricional da bananeira-'Prata-anã' durante cinco ciclos de cultivo com adubação orgânica, no município de Botucatu-SP. As plantas foram adubadas com composto orgânico produzido a partir de serragem de madeira e esterco bovino, em que os tratamentos foram constituídos de doses desse composto (0; 98,5; 197,0; 290,5 e 394,0 g de K2O/planta). Empregou-se delineamento experimental em blocos casualizados, com cinco tratamentos e cinco repetições. No florescimento das plantas em cada ciclo, foram retiradas amostras foliares de duas plantas por parcela para serem analisados os teores de nitrogênio, fósforo, potássio, cálcio, magnésio, enxofre, boro, cobre, ferro, manganês e zinco. A maior parte dos macronutrientes presentes nas folhas não foi influenciada pelo incremento de doses de composto orgânico. No decorrer dos ciclos avaliados, os teores foliares de nitrogênio, fósforo, potássio, enxofre, boro, ferro e manganês diminuíram, enquanto o cálcio e o magnésio se acumularam nas plantas. Os teores de potássio estavam abaixo dos padrões para a cultura no Estado de São Paulo, em todos os anos avaliados, mesmo assim as plantas não apresentaram sintomas de deficiência ou queda de produção, inferindo-se que a faixa considerada como adequada para a cultivar pode ser inferior aos padrões atualmente adotados.

Bio-óleo e biogás da degradação termoquímica de lodo de esgoto doméstico em cilindro rotativo

The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ° C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 °C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 °C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ° C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Estudo da remoção de Ba2+, Ni2+, Cd2+, Cu3+, Cr3+, Sr2+, Zn2+ por eletrocoagulação em água associada à produção de petróleo

Among the waste generated in the petrochemical industry water associated with oil production is the most important. It is considered one of the great challenges due to the presence of considered toxic chemicals present in this composition. The presence of these substances difficult to reuse the water associated with the enhanced recovery processes, so that prior to their reuse or disposal, treatment is necessary. This paper aimed to study the removal efficiency of chemical species: Ba2+, Ni2+, Cd2+, Cu2+, Cr3+, Sr2+ and Zn2+, present in the composition of the water associated with oil production by electrocoagulation. The evaluation of removal of these chemical species was performed by laboratory tests using electrochemical batch reactors and continuous flow. Initial tests were performed with electrocoagulation of synthetic wastewater in batch reactor using iron electrode. Results of removal of Zn2+ and Ni2+ were 78 % and 59 % respectively. While the percentage of removed Ba2+ was 19 % by 30 minutes of treatment and by applying current of 1.10 A. The tests were performed on effluent batch reactor applying the electrochemical technique with stainless steel electrodes 304, the objective was to remove part of the dispersed oil and also of organic compounds in the effluent. Under the experimental conditions used, the maximum result was obtained TOG was 60 % and TOC was approximately 50 % compared to the initial concentration. In the experiments carried out in continuous reactor, with effluent semisynthetic, have been used electrodes of iron and aluminum and the results were 100 % removal of Cd2+, Cu2+, Cr3+ and Zn2+ and 77 % of Sr2+. These percentages were only attainable through the use of the iron electrode. However, when the electrode was replaced by aluminum, there was a reduction in the percentage of removal to 65 %, using the same flow rate and current. Therefore according to the results obtained using the iron electrode was more effective in removing these metals and the conditions of lower current and lower flow rate was satisfactory, as observed in the experimental design adopted