Síntese e caracterização de peneiras moleculares mesoporosas do tipo MCM-41 e AlMCM-41 a partir de fontes alternativas de sílica e de alumínio

The mesoporous molecular sieves of MCM-41 and AlMCM-41 type are considered as promising support for metal in the refining processes of petroleum-based materials as catalysts and adsorbents for environmental protection. In this work the molecular sieves MCM-41 and AlMCM-41 were synthesized by replacing the source of silica conventionally used, for quartz, an alternative and abundant, and the use of waste from the production of diatomaceous earth, an aluminum-silicate, as a source aluminum, due to abundant reserves of diatomaceous earth in the state of Rio Grande do Norte in the city of Ceará-Mirim, with the objective of producing high-value materials that have similar characteristics to traditional commercial catalysts in the market. These materials were synthesized by the method of hydrothermal synthesis at 100 º C for 7 days and subjected to calcination at 500 º C for 2 hours under flow of nitrogen and air. The molecular sieves were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG), adsorption of N2 (BET and BJH methods), spectroscopy in the infra red (FTIR), microscopy scanning electron (SEM) and transmission electron microscopy (TEM). The analysis indicated that the synthesized materials showed characteristic hexagonal structure of mesopores materials with high specific surface area and sort and narrow distribution of size of pores

Estudo da viabilidade do sistema LZAS para uso como selante de PaCOS

Cells the solid oxide fuel are systems capable to directly convert energy of a chemical reaction into electric energy in clean, quiet way and if its components in the solid state differentiate of excessively the techniques for having all. Its more common geometric configurations are: the tubular one and to glide. Geometry to glide beyond the usual components (anode, cathode and electrolyte) needs interconnect and sealant. E the search for materials adjusted for these components is currently the biggest challenge found for the production of the cells. The sealants need to present chemical stability in high temperatures, to provoke electric isolation, to have coefficient of compatible thermal expansion with the excessively component ones. For presenting these characteristics the glass-ceramics materials are recommended for the application. In this work the study of the partial substitution of the ZrO2 for the Al2O3 in system LZS became it aiming at the formation of system LZAS, this with the addition of natural spodumene with 10, 20 and 30% in mass. The compositions had been casting to a temperature of 1500°C and later quickly cooled with the objective to continue amorphous. Each composition was worn out for attainment of a dust with average diameter of approximately 3μm and characterized by the techniques of DRX, FRX, MEV, dilatometric analysis and particle size analysis. Later the samples had been conformed and treated thermally with temperatures in the interval between 700-1000 °C, with platform of 10 minutes and 1 hour. The analyses for the treated samples had been: dilatometric analysis, DRX, FRX, electrical conductivity and tack. The results point with respect to the viability of the use of system LZAS for use as sealant a time that had presented good results as isolating electric, they had adhered to a material with similar α of the components of a SOFC and had presented steady crystalline phases

Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Influência da substituição de areia natural por pó de pedra no comportamento mecânico, microestrutural e eletroquímico de concretos

The construction industry is one of the largest consumers of natural raw materials, and concrete is considered today the most used material wide. This accentuated consumption of natural resources has generated concern with the preservation of the environment, and has motivated various studies related to the use of resid ues, which can partially or entirely substitute, with satisfactory performance, some materials such as the aggregate, and in so doing, decrease the impact on the environment caused by the produced residues. Research has been done to better understand and improve the microstructure of concrete, as well as to understand the mechanism of corrosion in reinforced steel. In this context, this work was developed aiming at discovering the influence of the substitution of natural sand by artificial sand, with rega rd to mechanical resistance, microstructure, and durability. To obtain the electrochemical parameters, an adaptation was made to the galvanostatic electrochemical method to study the corrosion in reinforced steel. Concretes of categories 20 MPa and 40 MPa were produced, containing natural sand, and concretes of the same categories were produced with artificial sand substituting the natural sand, and with the addition of sodium nitrate and sodium chloride. Due to the use of rock dust reject (artificial sand), an evaluation was made of its environmental risk. The results indicate that the concretes of category 20 MPa present a better performance than the concrete made with natural sand, thus making it a viable substitute. For the category 40 MPa, the better performance is from the concrete containing natural sand. The adaptation of the galvanostatic electrochemical technique to the study of the corrosion of reinforced steel within concrete proved to be valid for obtaining electrochemical parameters with a high degree of reliability, considering the number of degrees of freedom

Aproveitamento de resíduo de beneficiamento do caulim na produção de porcelanato cerâmico

Nowadays, industries from all sectors have great concerns over the disposition of the residues generated along the productive process. This is not different in the mineral sector, as this generates great volumes of residues. It was verified that the kaolin improvement industry generates great volumes of residue basically constituted of kaolinite, muscovite mica and quartz, which are basic constitution elements to formularisations of ceramics masses to the production of covering of stoneware tiles type. This happens because the methodology applied to the improvement process is still very rudimentary, what causes a very low yield, only ¼ from all the material volume that enters the improvement process, in the end, is marketable. The disposal of this residue, in a general way, causes a very big negative environmental impact, what has justified the researches efforts aiming to find a rational solution to this problem. In this way, the intention of this present work is the utilization of this residue in the manufacture of products to high quality ceramics covering, stoneware tiles in an industrial scale. For this purpose, the influence of the addition of the residue to a standard ceramics mass used by a ceramics sector company, already established in the market, with the intention of verifying the possibility of use of this residue as the mass complementary raw material and even the possible partial or total substitution of one of the components of the mass for the raw material in evidence will be studied. To the accomplishment of this work, the kaolin improvement residue generated by an industry of exploitation and improvement of kaolin, located in the region of Equador-RN, in the levels 1,2,4,8, 16 and 32% will be added to the standard mass already used for the production of stoneware tiles. The raw materials used, kaolin residue and the standard mass, were characterized through DRX, FRX, DTA, TGA and dilatometry. After the sintering of the bodies of test, tests of water absorption, apparent porosity, post burning linear retraction, apparent specific mass and flexural strength (3 point bending) were realized to determinate the technological properties of these materials. The results show the studied residue can be considered raw material of great potential to the industry of floor and ceramics covering of the stoneware tiles type

Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Análise de modelos geológicos utilizando percolação dinâmica

In the present study we elaborated algorithms by using concepts from percolation theory which analyze the connectivity conditions in geological models of petroleum reservoirs. From the petrophysical parameters such as permeability, porosity, transmittivity and others, which may be generated by any statistical process, it is possible to determine the portion of the model with more connected cells, what the interconnected wells are, and the critical path between injector and source wells. This allows to classify the reservoir according to the modeled petrophysical parameters. This also make it possible to determine the percentage of the reservoir to which each well is connected. Generally, the connected regions and the respective minima and/or maxima in the occurrence of the petrophysical parameters studied constitute a good manner to characterize a reservoir volumetrically. Therefore, the algorithms allow to optimize the positioning of wells, offering a preview of the general conditions of the given model s connectivity. The intent is not to evaluate geological models, but to show how to interpret the deposits, how their petrophysical characteristics are spatially distributed, and how the connections between the several parts of the system are resolved, showing their critical paths and backbones. The execution of these algorithms allows us to know the properties of the model s connectivity before the work on reservoir flux simulation is started

Ambiente computacional paradesenvolvimento de aplicações de controladores lógicos programáveis baseado em linguagens SFC e ST

This work proposes an environment for programming programmable logic controllers applied to oil wells with BCP type method of artificially lifting. The environment will have an editor based in the diagram of sequential functions for programming of PLCs. This language was chosen due to the fact of being high-level and accepted by the international standard IEC 61131-3. The use of these control programs in real PLC will be possible with the use of an intermediate level of language based on XML specification PLCopen T6 XML. For the testing and validation of the control programs, an area should be available for viewing variables obtained through communication with a real PLC. Thus, the main contribution of this work is to develop a computational environment that allows: modeling, testing and validating the controls represented in SFC and applied in oil wells with BCP type method of artificially lifting

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

Avaliação da biodegradabilidade de petróleo utilizando microrganismos isolados do estuário do Rio Potengi (RN)

The oil activity in the Rio Grande do Norte State (RN) is a permanent threat to coastal ecosystems, particularly mangroves, with the possibility of oil spills. In this context, the objective of this study was to evaluate the potential resistance of the mangrove environment of a possible spill. Were selected and isolated microorganisms degrading oil by the technique of enrichment cultures and formation of a bacterial consortium. The kinetic study of the consortium was held in rotary incubator shaken at 150 rpm and 30° C. Samples were taken at intervals of 4 hours for analysis of cell concentration and surface tension. The biodegradation was monitored using two methods of respirometry: manometric (OxiTop-C ®) and conductivimetry, where the biodegradation of oil was estimated indirectly by oxygen consumption and CO2 production, respectively. Furthermore, it was used a full 2² factorial design with triplicate at central point to the runs that used the conductivimetric methodology.. The technique of enrichment cultures allowed to obtain thirteen bacterial strains. Kinetic study of the consortium, we can showed the absence of the lag phase, reaching a maximum cell concentration of 2.55 g / L at 16 h of cultivation and a reduction on surface tension. When we adopted the methodology of OxiTop-C was detected a band indicating biodegradability (1% oil v/v), however when we used the conductivimetry methodology did not observe any band that would indicate effective biodegradation. By monitoring a process of biodegradation is necessary to observe the methodology will be adopted to evaluate the biodegradation process, since for the same conditions adopted different methodologies can produce different results. The oil-degrading isolates from soils of the mangrove estuary Potengi / RN are largely to be used in bioremediation strategies of these places, in the case of a possible oil spill, or it can be used in the treatment of waste oil generated in saline environments, since they are optimized the conditions of the tests so that the efficiency of biodegradation reach the minimum level suggested by the standarts

Avaliação de metodologia de preparo de amostra de petróleo por digestão ácida auxiliada por microondas para determinação de metais por ICP-OES

This project describes a methodology optimization that would allow for a more efficient microwave assisted digestion process for petroleum samples. With the possible chance to vary various factors at once to see if any one factor was significant enough in the answers, experimental planning was used. Microwave assisted digestion allows, through the application of potency, an increasing number of collisions between the HNO3 and H2O2 molecules, favoring sample opening for complex matrixes. For this, a 24 factorial experimental planning was used, varying potency, time and the volumes for HNO3 65% and H2O2 30%. To achieve the desired answers, several elements were monitored (C, Cu, Cr, Fe, Ni, Zn and V) through Inductively coupled plasma atomic emission spectroscopy (ICP-OES). With this initial study it was noticed that the HNO3 was not a significant factor for any of the statistical studies for any of the analytes and the other 3 factors and their interactions showed statistical significance. A Box Behnken experimental planning was used taking in consideration 3 factors: H2O2 volume, time (min) and Potency (W), Nitric Acid kept at 4mL for a mass of 0,1g of petroleum. The results were extremely satisfying showing higher efficiency in the digestion process and taking in a responsibility between the answers for each analyte and the carbon monitoring was achieved in the following conditions: 7mL of H2O2, 700 Watts of potency and a reaction time of 7 minutes with 4mL de HNO3 for a mass of 0,1g of petroleum. The optimized digestion process was applied to four different petroleum samples and the analytes determined by ICP-OES

Extração de metais (K, Mg, Ba, Ca, Cr, Mn, Li, Fe) de água produzida utilizando sistema microemulsionado

The produced water is a byproduct formed due to production of petroleum and carries with it a high amount of contaminants such as oil particles in suspension, organic compounds and metals. Thus, these latter pollutants are very difficult to treat because of its high solubility in water. The objective of this work is to use and evaluate a microemulsioned system to remove metals ( K , Mg , Ba , Ca , Cr , Mn , Li , Fe ) of synthetic produced water. For the extraction of metals, it was used a pseudoternary diagram containing the following phases: synthetic produced water as the aqueous phase (AP), hexane as organic phase (OP), and a cosurfactant/surfactant ratio equal to four (C/S = 4) as the third phase, where the OCS (saponified coconut oil) was used as surfactant and n-butanol as cosurfactant. The synthetic produced water was prepared in a bench scale and the region of interest in the diagram for the removal of metals was determined by experimental design called. Ten points located in the phase Winsor II were selected in an area with a large amount of water and small amounts of reagents. The samples were analyzed in atomic absorption spectrometer, and the results were evaluated through a statistical assesment, allowing the efficiency analysis of the effects and their interactions. The results showed percentages of extraction above 90% for the metals manganese, iron, chromium, calcium, barium and magnesium, and around 45% for metals lithium and potassium. The optimal point for the simultaneous removal of metals was calculated using statistical artifact multiple response function (MR). This calculation showed that the point of greatest extraction of metals occurs was the J point, with the composition [72% AP, 9% OP, 19% C/S], obtaining a global extraction percentage about 80%. Considering the aspects analyzed, the microemulsioned system has shown itself to be an effective alternative in the extraction of metals on synthetic produced water remediation

Desenvolvimento ponderal de bubalinos da raça Murrah criados em pastagem de Brachiaria brizantha no Centro-Oeste do Estado de São Paulo, Brasil

Foram analisados os dados de desempenho ponderal de bubalinos Murrah do Sistema de Produção de Leite da Universidade Estadual Paulista, Faculdade de Medicina Veterinária e Zootecnia, campus de Botucatu. Os pesos foram corrigidos às diversas idades-padrão e o modelo incluiu os efeitos de sexo (S), mês (M) e ano (A) de nascimento, classe de idade da búfala ao parto (C) e as interações S x M, S x A, S x C e M x A. As médias ajustadas e respectivos erros-padrão estimados para as características estudadas foram: Peso ao Nascer (PN): 37,71 ± 8,25kg; Peso aos 120 dias (P120): 102,08 ± 16,27kg; Peso aos 240 dias (P240): 169,84 ± 22,83kg; Peso aos 365 dias (P365): 250,59 ± 25,12kg; Peso aos 550 dias (P550): 326,13 ± 39,27kg e Peso aos 730 dias (P730): 389,80 ± 31,26kg. O efeito de sexo (S) foi significativo somente para PN e P365, sendo que machos tenderam a nascer mais pesados que fêmeas. O mês de nascimento (M) exerceu efeito sobre o PN, P120 e P730 sendo que animais nascidos em maio foram os mais pesados ao nascer, enquanto os nascidos em janeiro e maio, foram os mais pesados aos 120 e 730 dias, respectivamente. O efeito de ano de foi significativo sobre o PN, P120, P240 e P730. Os filhos de búfalas das classes de idade 1 (3 anos ou menos) e da classe 6 (10,11 e 12 anos) foram os mais leves e mais pesados ao nascer, respectivamente. O fato de a classe de idade da búfala não exercer efeito sobre os P365, P550 e P730 sugere que, em rebanhos comerciais possa ser feita a substituição de búfalas não gestantes por novilhas prenhes, apesar de esta prática reduzir a média de idade do rebanho de cria. Bubalinos da raça Murrah oriundos de rebanhos leiteiros podem ser utilizados para a produção de carne.

Papel da localização da carga em determinação dos parâmetros do canal iônico

To aureus α-HL channel, we used the cysteine-scanning mutagenesis technique. Twenty-four mutants were produced from the substitution of a single aminoacid of the primary structure of the α-HL pro this yzed after the incorporation of a mutant channel in planar lipid bilayer membranes. The modified proteins were studied in the absence and presence of watersoluble specific sulphydryl-specific reagents, in order to introduce a strong positive or negative harge at positions of substitution. The introduction of a negative charge in the stem region onverted the selectivity of the channel from weak anionic to more cationic. However, the troduction of a positive charge increased its selectivity to the anion. The degree of these alterations was inversely dependent on the channel radius at the position of the introduced harge (selectivity). As to the asymmetry of the conductance-voltage, the influence of the harge was more complex. The introduction of the negative charge in the stem region (the trans art of the pore) provoked a decrease. The intensity of these alterations depended on the radius, and on the type of free charge at the pore entrance. These results suggest that the free charge at surrounds the pore wall is responsible for the cation-anion selectivity of the channel. The istribution of the charges between the entrances is crucial for determining the asymmetry of e conductance-voltage curves. We hope that these results serve as a model for studies with other nanometric channels, in biological or planar lipid bilayer membranes or in iotechnological applications