Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Mutagênese induzida por flavonóides presentes do decocto das cascas da aroeira (Schinus terebinthifolius, Raddi)

The decoction of Brazilian pepper tree barks (Schinus terebinthifolius, Raddi), is used in medicine as wound healing and antiinflamatory. Once extracts from this plant are used for acceleration of scar s process, it is important to study their mutagenic and genotoxic potential. In previous works in our laboratory, it was observed mutagenicity caused by the decoction when in high concentrations. Among the chemical compounds of this plant that could be able to induce mutation, the flavonoids were the only group that was referred to have either an oxidant or antioxidant potential. The flavonoids were isolated, purified and quantified by adsorptive column chromatography under silica gel, bacterial and in vitro genotoxic tests were realized to determine if the flavonoids were the responsible agents for this mutagenicity found. The tests realized with plasmidial DNA were indicative that the flavonoids are probably genotoxic, due to the presence of correlation between increase of the flavonoid concentration and in plasmidial DNA double strand breakage visualized in agarose gel, as well as they were capable to generated abasic sites shown by the in vitro treatment with exonuclease III. The same tests with plasmidial DNA in the presence of copper [10 µM] and of a Tris-HCl pH 7.5 [10 µM] buffer were realized with the isolated flavonoids to determine if there would be or not participation of reactive oxygen species (ROS). The transformation of plasmidial DNA in different bacterial strains proficient and deficient in DNA repair enzymes in the presence or not of a Tris-HCl buffer, suggests that the enzymes that repair oxidative lesions are necessary to repair the lesions generated by the flavonoids and that ROS are generated and are necessary to promote the lesions. Bacterial tests with Escherichia coli strains of the CC collection (deficient or not for DNA repair enzymes), showed that the flavonoids are able to increase the frequency of mutations, mainly in strains mutated in repair enzymes (MutM, MutY-glicosylases and double mutant), suggesting that these agents are responsible for the enhancement in the mutation rate. In order to determine the mutation spectrum caused by the flavonoids of the Brazilian pepper tree stem bark, plasmidial DNA previously treated with the flavonoids were transformed in bacterial strains deficient and proficient in the DNA repair enzymes, followed by a blue-white selection with X-gal, DNA amplification by PCR and sequencing the positive mutant clones. Analysis of the mutants obtained from strains CC104, CC104mutM, CC104mutY, CC104mutMmutY, BW9101, BW9109 indicated a predominance of some mutations like G:C to C:G that can be correlated with the origin of 8-oxoG, due to oxidative lesions caused by the flavonoids. So it can concluded that the flavonoid isolated or in fractions enriched on them are genotoxic and mutagenic, and their mutations are predominantly oxidative, mediated by ROS, and the lesions are recognized by the BER system. In this way it is proposed that the flavonoids can act in two different ways to generate the DNA lesion: 1. in a Fenton-like reaction, when the flavonoid are in the presence of metal ions and that together with the water generate ROS that promotes the DNA lesions; 2. in another way the lesions can be generated by the formation of ROS due to the internal chemical structure of the flavonoid molecule due to the quantity and location of hydroxyl groups, and so producing the DNA lesions, those lesions can be directly (suggested by the in vitro experiments) or indirectly done (supported by the experiments using the CC bacterial strains)

Condicionadores químicos do solo e seus efeitos sobre os Índices físicos

Dois condicionadores químicos, a carboximetilcelulose, nas dosagens de 0,1% e 0,25% em relação ao peso do solo seco, e o silicato de sódio, de relação sílica-álcali igual a 3,2, a 0,6% e 1,2% em peso, foram pesquisados quanto aos seus efeitos sobre os índices físicos dos solos argiloso e barro arenoso empregados neste trabalho. Os dados obtidos foram estatisticamente analisados e os resultados permitiram que se chegassem a algumas conclusões. O tratamento 0,25% de carboximetilcelulose diminuiu o peso específico aparente seco e aumentou, consequentemente, o índice de vazios e porosidade dos solos estudados. O efeito dos tratamentos 1,2% de silicato de sódio e 0,1% de carboximetilcelulose sobre o peso específico aparente seco dos solos argilosos e barro arenoso, respectivamente, foi semelhante ao do tratamento 0,25% de carboximetilcelulose.

Medição da densidade óssea através de ondas eletromagnéticas e classificação por MVS

This work holds the purpose of presenting an auxiliary way of bone density measurement through the attenuation of electromagnetic waves. In order to do so, an arrangement of two microstrip antennas with rectangular configuration has been used, operating in a frequency of 2,49 GHz, and fed by a microstrip line on a substrate of fiberglass with permissiveness of 4.4 and height of 0,9 cm. Simulations were done with silica, bone meal, silica and gypsum blocks samples to prove the variation on the attenuation level of different combinations. Because of their good reproduction of the human beings anomaly aspects, samples of bovine bone were used. They were subjected to weighing, measurement and microwave radiation. The samples had their masses altered after mischaracterization and the process was repeated. The obtained data were inserted in a neural network and its training was proceeded with the best results gathered by correct classification on 100% of the samples. It comes to the conclusion that through only one non-ionizing wave in the 2,49 GHz zone it is possible to evaluate the attenuation level in the bone tissue, and that with the appliance of neural network fed with obtained characteristics in the experiment it is possible to classify a sample as having low or high bone density

Estudo do efeito do óxido de bário no comportamento de massas para porcelanato

In this work, it is proposed the study of the effect of barium oxide acting as synthetic flow in the behavior of masses for stoneware from the use of raw materials found in the deposits of minerals of the Rio Grande do Norte that it makes use of a great natural potential for the industrialization of the product. The porcelanato is a sophisticated product with excellent final properties being applied as ceramic coating in buildings of high standard of engineering. The raw materials selected for the development of the study had been two types of argilas, two types of feldspatos, dolomita, talco, barium carbonate and silica, being characterized by X-ray fluorescence, X-ray diffraction, granulometric analysis, dilatometric analysis and thermal analysis. Thus, it is intended to define four formulations using the cited raw materials that will be processed, conformed and sintered in the temperatures of 1150 °C, 1175 °C, 1200 °C, 1225 °C e 1250 °C. From the physical characterizations, chemical and morphologic of the formed formulations, the effect of barium oxide is determined in the physical and mechanical properties of the studied system carrying water absorption tests, linear retraction, apparent porosity, apparent specific mass, compacting curve, flexural strength and microstructural analysis by XRD and SEM. After analyzing the results, indicated that barium oxide acts as a flux of high temperature and as the ordering of structure, where the embedded glass phase has the nucleating effect phase potassium silico-aluminum reacting with free silica which together with the high content of potassium concentrated form a new crystalline phase called microcline. The masses studied with the addition of barium oxide present physical-mechanical properties highly satisfactory in reduced firing temperatures, which implies a saving in energy given off in the production and increased productivity

Estudo do aproveitamento do rejeito da mineração de esmeraldas na produção de refratários conformados isolantes

Emerald mining is an important area of the economy in Brazil, country which is in second place among the exporting nations of this gem. Due to the process of extraction, a great amount of reject is generated. Since there is no appropriate destination, the reject is abandoned around the mining industries, contributing to environment degradation. Nowadays, some of the most relevant things to an industry in general are: energy conservation, cost reduction, quality and productivity enhancement. The production of isolating, transformed refractory materials achieves the sustainability dimension when protection of the environment is incorporated to such process. This work investigates the use of emerald mining rejects in the ceramic body of refractory materials, aiming at obtaining a product whose characteristics are compatible with commercial products and, at the same time, allow the use of such rejects to solve the environmental issue caused by its disposal in nature. X-ray fluorescence analysis show that the emerald reject obtained after the flotation to extract molybdenum and mica has 70% of silica and alumina (SiO2+Al2O3) and 21% of a basic oxides and alkaline metals and earthy alkaline mixture (Na2O, K2O, CaO e MgO). Because of the significant amount of silica and alumina present in the reject, four refractory ceramic bodies were prepared. Samples with a rectangular shape and dimensions 100x50x10 mm were pressed in a steel mold at 27,5 MPa and sintered at 1200ºC for 40 min. under environment atmosphere in a resistive oven. The sintered samples were characterized in relation to the chemical composition (FRX), mineralogical composition (DRX), microstructure (MEV) and physical and mechanical properties. The results indicate that the mixture with 45% of reject, 45% of alumina and 10% of kaolin presents a refractory quality of 1420ºC, dimensional linear variation below 2.00%, apparent specific mass of 1,56 g/cm3 and porosity of 46,68%, which demonstrates the potential use of the reject as raw material for the industry of isolating transformed refractory materials

Desenvolvimento de iniciadores para detecção e identificação de Diaporthe phaseolorum var. meridionalis em sementes de soja

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Conversão do metano via oxicloração em reator de leito fixo utilizando catalisador do tipo CuCl2/SiO2

Supported catalysts of CuCl2 on sílica were used in the methane oxychlorination reaction. The materials were synthesized by the ion exchange technique in a basic solution, using a copper-ammonia complex with 3 and 6 % of nominal copper loading. The materials where characterized by thermogravimetry (TG), X-ray Fluorescence Spectroscopy (XRF), Temperature Programmed Reduction (TPR), Scanning Electron Microscopy with X-ray microanalysis (SEM/EDS), BET specific area and pore distribution. The characterization confirms the presence of copper on the support surface, concluding that the ion exchange technique was adequate in the catalyst synthesis. For the reaction test, an oxychlorination bench scale unit was employed. The tests were carried at 673 and 773 K. The results showed the influence of temperature and catalyst copper content on the oxychlorination of methane reaction

Desenvolvimento de sistemas de pastas leves para aplicação em cimentação de poços petrolíferos com baixo gradiente de fratura

All around the world, naturally occurring hydrocarbon deposits, consisting of oil and gas contained within rocks called reservoir rocks , generally sandstone or carbonate exists. These deposits are in varying conditions of pressure and depth from a few hundred to several thousand meters. In general, shallow reservoirs have greater tendency to fracture, since they have low fracture gradient, ie fractures are formed even with relatively low hydrostatic columns of fluid. These low fracture gradient areas are particularly common in onshore areas, like the Rio Grande do Norte basin. During a well drilling, one of the most favorable phases for the occurrence of fractures is during cementing, since the cement slurry used can have greater densities than the maximum allowed by the rock structure. Furthermore, in areas which are already naturally fractured, the use of regular cement slurries causes fluid loss into the formation, which may give rise to failures cementations and formation damages. Commercially, there are alternatives to the development of lightweight cement slurries, but these fail either because of their enormous cost, or because the cement properties were not good enough for most general applications, being restricted to each transaction for which the cement paste was made, or both reasons. In this work a statistical design was made to determine the influence of three variables, defined as the calcium chloride concentration, vermiculite concentration and nanosilica concentration in the various properties of the cement. The use of vermiculite, a low density ore present in large amounts in northeastern Brazil, as extensor for cementing slurries, enabled the production of stable cements, with high water/cement ratio, excellent rheological properties and low densities, which were set at 12.5 lb / gal, despite the fact that lower densities could be achieved. It is also seen that the calcium chloride is very useful as gelling and thickening agent, and their use in combination with nanosilica has a great effect on gel strength of the cement. Hydrothermal Stability studies showed that the pastes were stable in these conditions, and mechanical resistance tests showed values of the order of up to 10 MPa

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

Análise fitoquímica e atividade antimicobacteriana de extratos metanólicos de Jacaranda cuspidifolia Mart. (Bignoniaceae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Confinamento de fónons ópticos em estruturas piezoelétricas periódicas e quasiperiódicas

We study the optical-phonon spectra in periodic and quasiperiodic (Fibonacci type) superlattices made up from III-V nitride materials (GaN and AlN) intercalated by a dielectric material (silica - SiO2). Due to the misalignments between the silica and the GaN, AlN layers that can lead to threading dislocation of densities as high as 1010 cm−1, and a significant lattice mismatch (_ 14%), the phonon dynamics is described by a coupled elastic and electromagnetic equations beyond the continuum dielectric model, stressing the importance of the piezoelectric polarization field in a strained condition. We use a transfer-matrix treatment to simplify the algebra, which would be otherwise quite complicated, allowing a neat analytical expressions for the phonon dispersion relation. Furthermore, a quantitative analysis of the localization and magnitude of the allowed band widths in the optical phonon s spectra, as well as their scale law are presented and discussed

Cinza de casca de arroz (CCA) altamente reativa: método de produção e atividade pozolânica

Este trabalho apresenta um método de produção para a obtenção de cinza de casca de arroz (CCA) de elevada reatividade a partir de um processo de combustão não controlado. São detalhados os processos de obtenção da CCA, assim como sua atividade pozolânica. Pela Análise Termogravimétrica (TGA), foi possível quantificar o consumo de portlandita por parte da CCA, ou seja, a reação pozolânica. Adicionalmente, foram preparadas argamassas com diferentes porcentagens de CCA (5%, 10% e 15%) com o objetivo de comprovar sua influência nas propriedades mecânicas. Os resultados obtidos mostram que a CCA em estudo apresenta elevada reatividade, podendo ser utilizada como uma fonte alternativa da sílica ativa (SA).

Estudo da regeneração de aditivos para catalisadores de craqueamento aluminofosfatos (ALPO s)e silicoaluminofosfatos (SAPO s)

Heterogeneous catalysts such as aluminophosphate and silicoaluminophosphate, molecular sieves with AEL of ALPO-11 and SAPO-11, were synthesized by the hydrothermal method with the following molar composition: 2.9 Al +3.2 P + 3.5 DIPA +32.5 H20 (ALPO-11); 2.9 Al +3.2 P + 0.5 Si + 3.5 DIPA +32.5 H20 (SAPO-11) starting from silica (only in the SAPO-11), pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 170ºC for a period of 48 hours under autogeneous pressure. The obtained materials were washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), thermo gravimetric differential thermal analysis (TG/DTA) and nitrogen adsorption (BET). The acidic properties were determined using adsorption of n-butylamine followed by programmed thermodessorption. This method revealed that ALPO-11 has weaker acid sites due to structural defects, while SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by the cracking of the n-hexane in a fixed bed continuous flow microrreator 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 regeneration and removal of the organic template

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products