Impregnação de metais em xisto retortado para uso como adsorventes

Concern with the environment has lead to an increase in the research for new adsorption techniques, low cost adsorvent materials and with high availability. Many works search the development of higher selectivity modified adsorvents. The Brazil has the second world reserve of oiled shale, because of it, the use of that reject is of great interest. This study has the goal of characterize and analyze the retorted shale, reject of the pirobetuminous shale pyrolysis, and the retorted shale modified through the humid impregnation method, wich the precursors were the metals nitrates ( Cobalt, Nickel and Copper), to the usage has adsorvent materials. The samples were characterized chemically, textually and structurally by the X ray fluorescence (XRF), BET, X ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The impregnated samples showed a reduction in the superficial area and in the pore volume when compared with the retorted shale. Besides that, diffractions referred to the impregnated metals where observed in the XRD analysis, wich were the same metals detected in the XRF and SEM analysis. The materials showed homogeneity in it s composition. The results shows that the materials presents adequate adsorption characteristics

Adição de subprodutos da cinza da casca de café (coffea canephora) em massa cerâmica para porcelanato

To produce porcelain tiles fluxing agents are used in order to obtain a liquid phase during firing. This liquid phase fills the pores decreasing porosity, water absorption and contributes to material densification. In the porcelain tiles industry, feldspar is the main flux material used, with quantities ranging between 35 and 50%. Studies focus on the discovery of materials with flux characteristics that can reduce the consumption of feldspar by porcelain tiles industry. In this context, the coffee husk ashes, a residue obtained when coffee husks are burned to produce heat for the dryers during the processing of the green fruit, have as main chemical constituents potassium, calcium and magnesium, giving them characteristics of fluxing material. Brazil is the largest coffee producer in the world and is responsible for over 30% of the world s production. In this work a physical treatment of coffee husk ash was carried out in order to eliminate the organic matter and, after this, two by-products were obtained: residual wastes R1 and R2. Both residues were added separately as single fluxes and also in association with feldspar in mixtures with raw materials collected in a porcelain industry located in Dias d Ávila-Ba. The addition of these residues aimed to contribute to the reduction of the consumption of feldspar in the production of porcelain tiles. Specimens were produced with dimensions of 60 mm x 20 mm x 6 mm in an uniaxial die with compacting pressure of 45 MPa. The samples were heated to a temperature of 1200 °C, for 8 minutes. Tests were performed to characterize the raw materials by XRF, XRD, particle size analysis, DTA and TGA and, additionally, the results of the physical properties of water absorption, apparent porosity, linear shrinkage, density, dilatometry, flexural strength and SEM of sintered body were analyzed. Additions of less than 8% of the residue R1 contributed to the decrease of porosity, but the mechanical strength of the samples was not satisfactory. Additions of 5% the R2 residue contributed significantly to decrease the water absorption and apparent porosity, and also to increase the mechanical strength. Samples with addition of feldspar associated with the R2 residue, in proportions of 6.7% of R2 and 6.7% of feldspar, led to results of water absorption of 0.12% and mechanical strength of 46 MPa, having parameters normalized to the manufacture of porcelain stoneware tiles

Desenvolvimento de membranas porosas de alumina para fins de tratamento de efluente industrial têxtil

Textile production has been considered as an activity of high environmental impact due to the generation of large volumes of waste water with high load of organic compounds and strongly colored effluents, toxic and difficult biodegradability. This thesis deals with obtaining porous alumina ceramic membranes for filtration of textile effluent in the removal of contaminants, mainly color and turbidity. Two types of alumina with different particle sizes as a basis for the preparation of formulation for mass production of ceramic samples and membranes. The technological properties of the samples were evaluated after using sintering conditions: 1,350ºC-2H, 1,450ºC-30M, 1,450ºC-2H, 1,475ºC-30M and 1,475ºC-2H. The sintered samples were characterized by XRD, XRF, AG, TG, DSC, DL, AA, MEA, RL, MRF-3P, SEM and Intrusion Porosimetry by Mercury. After the characterization, a standard membrane was selected with their respective sintering condition for the filterability tests. The effluent was provided by a local Textile Industry and characterized at the entry and exit of the treatment plant. A statistical analysis was used to study the effluent using the following parameters: pH, temperature, EC, SS, SD, oil and grease, turbidity, COD, DO, total phosphorus, chlorides, phenols, metals and fecal coliform. The filtered effluent was evaluated by using the same parameters. These results demonstrate that the feasibility of the use of porous alumina ceramic membranes for removing contaminants from textile effluent with improved average pore size of 0.4 micrometre (distribution range varying from 0,025 to 2.0 micrometre), with total porosity of 29.66%, and average percentages of color removal efficiency of 89.02%, 92.49% of SS, turbidity of 94.55%, metals 2.70% (manganese) to 71.52% (iron) according to each metal and COD removal of 72.80%

Efeito da Gália como aditivo de sinterização em eletrólitos cerâmicos à base de céria sintetizados pelo método de complexação de cátions

Fuel cells are considered one of the most promising ways of converting electrical energy due to its high yield and by using hydrogen (as fuel) which is considered one of the most important source of clean energy for the future. Rare earths doped ceria has been widely investigated as an alternative material for the electrolyte of solid oxide fuel cells (SOFCs) due to its high ionic conductivity at low operating temperatures compared with the traditional electrolytes based on stabilized zirconia. This work investigates the effect of gallium oxide (Gallia) as a sintering aid in Eu doped ceria ceramic electrolytes since this effect has already been investigated for Gd, Sm and Y doped ceria electrolytes. The desired goal with the use of a sintering aid is to reduce the sintering temperature aiming to produce dense ceramics. In this study we investigated the effects on densification, microstructure and ionic conduction caused by different molar fraction of the dopants europium (10, 15 and 20%) and gallium oxide (0.3, 0.6 and 0.9%) in samples sintered at 1300, 1350 and 1450 0 C. Samaria (10 and 20%) doped ceria samples sintered between 1350 and 1450 °C were used as reference. Samples were synthesized using the cation complexation method. The ceramics powders were characterized by XRF, XRD and SEM, while the sintered samples were investigated by its relative density, SEM and impedance spectroscopy. It was showed that gallia contents up to 0.6% act as excellent sintering aids in Eu doped ceria. Above this aid content, gallia addition does not promote significant increase in density of the ceramics. In Ga free samples the larger densification were accomplished with Eu 15% molar, effect expressed in the microstructure with higher grain growth although reduced and surrounded by many open pores. Relative densities greater than 95 % were obtained by sintering between 1300 and 1350 °C against the usual range 1500 - 1600 0 C. Samples containing 10% of Sm and 0.9% of Ga reached 96% of theoretical density by sintering at 1350 0 C for 3h, a gain compared to 97% achieved with 20% of Sm and 1% of Ga co-doped cerias sintered at 1450 0 C for 24 h as described in the literature. It is found that the addition of gallia in the Eu doped ceria has a positive effect on the grain conductivity and a negative one in the grain boundary conductivity resulting in a small decrease in the total conductivity which will not compromise its application as sintering aids in ceria based electrolytes. Typical total conductivity values at 600 and 700 °C, around 10 and 30 mS.cm -1 respectively were reached in this study. Samples with 15% of Eu and 0.9 % of Ga sintered at 1300 and 1350 °C showed relative densities greater than 96% and total conductivity (measured at 700 °C) between 20 and 33 mS.cm -1 . The simultaneous sintering of the electrolyte with the anode is one of the goals of research in materials for SOFCs. The results obtained in this study suggest that dense Eu and Ga co-doped ceria electrolytes with good ionic conductivity can be sintered simultaneously with the anode at temperatures below 1350 °C, the usual temperature for firing porous anode materials

Efeitos do tratamento superficial da sílica ativa com soluções de ácidos nítrico e fosfórico em propriedades do concreto

The addition of active silica potentially improves the quality of concrete due to its high reactivity and pore refinement effect. The reactivity of silica is likely related to its charge density. Variations in surface charge alter the reactivity of the material consequently affecting the properties of concrete. The present study aimed at investigating variations in the charge density of silica as a function of acid treatments using nitric or phosphoric acid and different pH values (2.0, 4.0 and 6.0). Effects on concrete properties including slump, mechanical strength, permeability and chloride corrosion were evaluated. To that end, a statistical analysis was carried out and empirical models that correlate studied parameters (pH, acid and cement) with concrete properties were established. The quality of the models was tested by variance analysis. The results revealed that the addition of silica was efficiency in improving the properties of concrete, especially the electrochemical parameters. The addition of silica treated using nitric acid at pH = 4.0 displayed the best cement performance including highest strength, reduced permeability and lowest corrosion current

Sinterização de matrizes cerâmicas à base de alumina reforçadas por carbetos a partir de precursores poliméricos

Ceramic composites produced with polymerics precursors have been studied for many years, due to the facility of obtaining a complex shape, at low temperature and reduces cost. The main objective of this work is to study the process of sintering of composites of ceramic base consisting of Al2O3 and silicates, reinforced for NbC, through the technique of processing AFCOP, as well as the influence of the addition of LZSA, ICZ and Al as materials infiltration in the physical and mechanical properties of the ceramic composite. Were produced ceramic matrix composites based SiCxOy e Al2O3 reinforced with NbC, by hidrosilylation reaction between D4Vi and D1107 mixtured with Al2O3 as inert filler, Nb and Al as reactive filler. The specimens produced were pyrolised at 1200, 1250 and 1400°C and infiltred with Al, ICZ and LZSA, respectively. Density, porosity, flexural mechanical strength and fracture surface by scanning electron microscopy were evaluated. The microstructure of the composites was investigated by X-ray diffraction to identify the presence of crystalline phases. The composites presented apparent porosity varying of 31 up to 49% and mechanical flexural strength of 14 up to 34 MPa. The infiltration process improviment of the densification and reduction of the porosity, as well as increased the values of mechanical flexural strength. The obtained phases had been identified as being Al3Nb, NbSi2, Nb5S3, Nb3Si and NbC. The samples that were submitted the infiltration process presented a layer next surface with reduced pores number in relation to the total volume

Modelagem analítica e experimental da filtração em meios porosos

Deep bed filtration occurs in several industrial and environmental processes like water filtration and soil contamination. In petroleum industry, deep bed filtration occurs near to injection wells during water injection, causing injectivity reduction. It also takes place during well drilling, sand production control, produced water disposal in aquifers, etc. The particle capture in porous media can be caused by different physical mechanisms (size exclusion, electrical forces, bridging, gravity, etc). A statistical model for filtration in porous media is proposed and analytical solutions for suspended and retained particles are derived. The model, which incorporates particle retention probability, is compared with the classical deep bed filtration model allowing a physical interpretation of the filtration coefficients. Comparison of the obtained analytical solutions for the proposed model with the classical model solutions allows concluding that the larger the particle capture probability, the larger the discrepancy between the proposed and the classical models

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, 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 arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Análise da modelagem experimental da perda de injetividade

Injectivity decline, which can be caused by particle retention, generally occurs during water injection or reinjection in oil fields. Several mechanisms, including straining, are responsible for particle retention and pore blocking causing formation damage and injectivity decline. Predicting formation damage and injectivity decline is essential in waterflooding projects. The Classic Model (CM), which incorporates filtration coefficients and formation damage functions, has been widely used to predict injectivity decline. However, various authors have reported significant discrepancies between Classical Model and experimental results, motivating the development of deep bed filtration models considering multiple particle retention mechanisms (Santos & Barros, 2010; SBM). In this dissertation, inverse problem solution was studied and a software for experimental data treatment was developed. Finally, experimental data were fitted using both the CM and SBM. The results showed that, depending on the formation damage function, the predictions for injectivity decline using CM and SBM models can be significantly different

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Simulação de fluxo de fluidos em meios porosos desordenados uma análise de efeito de escala na estimativa da permeabilidade e do coeficiente de arrasto

The present study provides a methodology that gives a predictive character the computer simulations based on detailed models of the geometry of a porous medium. We using the software FLUENT to investigate the flow of a viscous Newtonian fluid through a random fractal medium which simplifies a two-dimensional disordered porous medium representing a petroleum reservoir. This fractal model is formed by obstacles of various sizes, whose size distribution function follows a power law where exponent is defined as the fractal dimension of fractionation Dff of the model characterizing the process of fragmentation these obstacles. They are randomly disposed in a rectangular channel. The modeling process incorporates modern concepts, scaling laws, to analyze the influence of heterogeneity found in the fields of the porosity and of the permeability in such a way as to characterize the medium in terms of their fractal properties. This procedure allows numerically analyze the measurements of permeability k and the drag coefficient Cd proposed relationships, like power law, for these properties on various modeling schemes. The purpose of this research is to study the variability provided by these heterogeneities where the velocity field and other details of viscous fluid dynamics are obtained by solving numerically the continuity and Navier-Stokes equations at pore level and observe how the fractal dimension of fractionation of the model can affect their hydrodynamic properties. This study were considered two classes of models, models with constant porosity, MPC, and models with varying porosity, MPV. The results have allowed us to find numerical relationship between the permeability, drag coefficient and the fractal dimension of fractionation of the medium. Based on these numerical results we have proposed scaling relations and algebraic expressions involving the relevant parameters of the phenomenon. In this study analytical equations were determined for Dff depending on the geometrical parameters of the models. We also found a relation between the permeability and the drag coefficient which is inversely proportional to one another. As for the difference in behavior it is most striking in the classes of models MPV. That is, the fact that the porosity vary in these models is an additional factor that plays a significant role in flow analysis. Finally, the results proved satisfactory and consistent, which demonstrates the effectiveness of the referred methodology for all applications analyzed in this study.

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

Metodologia para avaliação de cinemática de partículas gasosas em fluidos de viscosidade variável com o tempo e sua aplicação na construção de poços de petróleo

Many challenges have been presented in petroleum industry. One of them is the preventing of fluids influx during drilling and cementing. Gas migration can occur as result of pressure imbalance inside the well when well pressure becomes lower than gas zone pressure and in cementing operation this occurs during cement slurry transition period (solid to fluid). In this work it was developed a methodology to evaluate gas migration during drilling and cementing operations. It was considered gel strength concept and through experimental tests determined gas migration initial time. A mechanistic model was developed to obtain equation that evaluates bubble displacement through the fluid while it gels. Being a time-dependant behavior, dynamic rheological measurements were made to evaluate viscosity along the time. For drilling fluids analyzed it was verified that it is desirable fast and non-progressive gelation in order to reduce gas migration without affect operational window (difference between pore and fracture pressure). For cement slurries analyzed, the most appropriate is that remains fluid for more time below critical gel strength, maintaining hydrostatic pressure above gas zone pressure, and after that gels quickly, reducing gas migration. The model developed simulates previously operational conditions and allow changes in operational and fluids design to obtain a safer condition for well construction

Anodização para obtenção de membranas cerâmicas

This a study on the achievement of alumina membranes by the method of anodizing. From this method got up a layer of aluminum oxide on the anodic metal, who presented the basic properties necessary for the application as a support for the production and acquisition of nanomaterials, such as porosity nano and resistance to high temperature, and other properties, as resistance to corrosion, and chemical, high ranking of the structure and pore size of the pores. The latter, ranging from 10 to 100nm depended on the electrolyte used, which in this study was the H2SO4. To remove all remaining aluminum, it is a bath of dissolution with HCl and CuCl where the residual aluminum has been withdrawn, and the deep pores were opened after chemical treatment with NaOH. After the dissolution, the membranes were calcined at temperatures of 300, 600 and 900° C, and sintered at temperatures of 1200 and 1300º C to win mechanical strength, porosity and observe the desired crystallization. Then went through analyses of composition through X-ray diffraction and morphology of the microstructure through a scanning electron microscope. The method was effective for obtaining alumine membranes applied in the processes of production of materials in nano

Caracterização de cerâmicas porosas de alumina reforçada com zircônia produzidas pelo método da réplica

Porous ceramics have many applications: thermal insulation, catalytic support, materials to fire protection, filters, and others. There are many techniques to production of ceramic filters. One technique to obtain ceramic filters is the replication method. This method consists in the impregnation of polymeric foam with ceramic slurry followed by a heating treatment that will burn out the organic elements and sintering of the material, resulting of a replication of the original foam. To perform their functions ceramic filters must satisfy mechanical requirements and permeability parameters (darcian k1 and no-darcian k2). The permeability and the strength of the ceramic material are dependent of the pore size and pore distribution. To the use at high temperatures the evaluation of mechanical properties in these temperatures is necessary. In this work the mechanical behavior of two commercial porous ceramics (10 and 40 poros per inch) was studied these materials were submitted to compression and four-point flexure test (room temperature, at 1000 °C, after thermal shock). Density and porosity measurements, permeability tests and microstructural analysis by scanning electronic microscopy (SEM) were realized. The Results showed that the decrease of mechanical strength of these materials, when submitted to thermal shock, occur for propagation of new cracks from cracks pre-existing and the permeability depends of the pore size