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

Obtenção de pós de tântalo metálico a partir da redução aluminotérmica com ignição a plasma

Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor

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

Simulador de escoamento multifásico em poços de petróleo (SEMPP)

The multiphase flow occurrence in the oil and gas industry is common throughout fluid path, production, transportation and refining. The multiphase flow is defined as flow simultaneously composed of two or more phases with different properties and immiscible. An important computational tool for the design, planning and optimization production systems is multiphase flow simulation in pipelines and porous media, usually made by multiphase flow commercial simulators. The main purpose of the multiphase flow simulators is predicting pressure and temperature at any point at the production system. This work proposes the development of a multiphase flow simulator able to predict the dynamic pressure and temperature gradient in vertical, directional and horizontal wells. The prediction of pressure and temperature profiles was made by numerical integration using marching algorithm with empirical correlations and mechanistic model to predict pressure gradient. The development of this tool involved set of routines implemented through software programming Embarcadero C++ Builder® 2010 version, which allowed the creation of executable file compatible with Microsoft Windows® operating systems. The simulator validation was conduct by computational experiments and comparison the results with the PIPESIM®. In general, the developed simulator achieved excellent results compared with those obtained by PIPESIM and can be used as a tool to assist production systems development

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Projeto, construção e análise de um prototipo vibracional em escala de bancada aplicável ao tratamento de água de produção de petróleo bruto, mediante inovadora operação híbrida de adsorção e auto-flotação

A self-flotator vibrational prototype electromechanical drive for treatment of oil and water emulsion or like emulsion is presented and evaluated. Oil production and refining to obtain derivatives is carried out under arrangements technically referred to as on-shore and off-shore, ie, on the continent and in the sea. In Brazil 80 % of the petroleum production is taken at sea and area of deployment and it cost scale are worrisome. It is associated, oily water production on a large scale, carrier 95% of the potential pollutant of activity whose final destination is the environment medium, terrestrial or maritime. Although diversified set of techniques and water treatment systems are in use or research, we propose an innovative system that operates in a sustainable way without chemical additives, for the good of the ecosystem. Labyrinth adsor-bent is used in metal spirals, and laboratory scale flow. Equipment and process patents are claimed. Treatments were performed at different flow rates and bands often monitored with control systems, some built, other bought for this purpose. Measurements of the levels of oil and grease (OGC) of efluents treaty remained within the range of legal framework under test conditions. Adsorbents were weighed before and after treatment for obtaining oil impregna-tion, the performance goal of vibratory action and treatment as a whole. Treatment technolo-gies in course are referenced, to compare performance, qualitatively and quantitatively. The vibration energy consumption is faced with and without conventional flotation and self-flotation. There are good prospects for the proposed, especially in reducing the residence time, by capillary action system. The impregnation dimensionless parameter was created and confronted with consecrated dimensionless parameters, on the vibrational version, such as Weber number and Froude number in quadratic form, referred to as vibrational criticality. Re-sults suggest limits to the vibration intensity

Análise de escalabilidade de uma implementação paralela do simulated annealing acoplado

This paper analyzes the performance of a parallel implementation of Coupled Simulated Annealing (CSA) for the unconstrained optimization of continuous variables problems. Parallel processing is an efficient form of information processing with emphasis on exploration of simultaneous events in the execution of software. It arises primarily due to high computational performance demands, and the difficulty in increasing the speed of a single processing core. Despite multicore processors being easily found nowadays, several algorithms are not yet suitable for running on parallel architectures. The algorithm is characterized by a group of Simulated Annealing (SA) optimizers working together on refining the solution. Each SA optimizer runs on a single thread executed by different processors. In the analysis of parallel performance and scalability, these metrics were investigated: the execution time; the speedup of the algorithm with respect to increasing the number of processors; and the efficient use of processing elements with respect to the increasing size of the treated problem. Furthermore, the quality of the final solution was verified. For the study, this paper proposes a parallel version of CSA and its equivalent serial version. Both algorithms were analysed on 14 benchmark functions. For each of these functions, the CSA is evaluated using 2-24 optimizers. The results obtained are shown and discussed observing the analysis of the metrics. The conclusions of the paper characterize the CSA as a good parallel algorithm, both in the quality of the solutions and the parallel scalability and parallel efficiency

Análise do efeito do tempo da moagem de alta energia no tamanho de cristalito e microdeformação da rede cristalina do WC-Co

Hard metals are the composite developed in 1923 by Karl Schröter, with wide application because high hardness, wear resistance and toughness. It is compound by a brittle phase WC and a ductile phase Co. Mechanical properties of hardmetals are strongly dependent on the microstructure of the WC Co, and additionally affected by the microstructure of WC powders before sintering. An important feature is that the toughness and the hardness increase simultaneously with the refining of WC. Therefore, development of nanostructured WC Co hardmetal has been extensively studied. There are many methods to manufacture WC-Co hard metals, including spraying conversion process, co-precipitation, displacement reaction process, mechanochemical synthesis and high energy ball milling. High energy ball milling is a simple and efficient way of manufacturing the fine powder with nanostructure. In this process, the continuous impacts on the powders promote pronounced changes and the brittle phase is refined until nanometric scale, bring into ductile matrix, and this ductile phase is deformed, re-welded and hardened. The goal of this work was investigate the effects of highenergy milling time in the micro structural changes in the WC-Co particulate composite, particularly in the refinement of the crystallite size and lattice strain. The starting powders were WC (average particle size D50 0.87 μm) supplied by Wolfram, Berglau-u. Hutten - GMBH and Co (average particle size D50 0.93 μm) supplied by H.C.Starck. Mixing 90% WC and 10% Co in planetary ball milling at 2, 10, 20, 50, 70, 100 and 150 hours, BPR 15:1, 400 rpm. The starting powders and the milled particulate composite samples were characterized by X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) to identify phases and morphology. The crystallite size and lattice strain were measured by Rietveld s method. This procedure allowed obtaining more precise information about the influence of each one in the microstructure. The results show that high energy milling is efficient manufacturing process of WC-Co composite, and the milling time have great influence in the microstructure of the final particles, crushing and dispersing the finely WC nanometric order in the Co particles

Obtenção e caracterização de um compósito de poliuretano de mamona e pó de vidro para aplicações em insolantes térmicos

Thermal insulation is used to protect the heated or cooled surfaces by the low thermal conductivity materials. The rigid ricin polyurethane foams (PURM) are used for thermal insulation and depend on the type and concentration of blowing agent. Obtaining PURM occurs by the use of polyol, silicone, catalyst and blowing agent are pre -mixed, reacting with the isocyanate. The glass is reusable, returnable and recyclable heat insulating material, whose time of heat dissipation determines the degree of relaxation of its structure; and viscosity determines the conditions for fusion, operating temperatures, annealing, etc. The production of PURM composites with waste glass powder (PV) represents economical and renewable actions of manufacturing of thermal insulating materials. Based on these aspects, the study aimed to produce and characterize the PURM composites with PV, whose the mass percentages were 5, 10, 20, 30, 40 and 50 wt%. PURM was obtained commercially, while the PV was recycled from the tailings of the stoning process of a glassmaking; when the refining process was applied to obtain micrometer particles. The PURM + PV composites were studied taking into account the standard sample of pure PURM and the influence of the percentage of PV in this PURM matrix. The results of the chemical, physical and morphological characterization were discussed taking into account the difference in the microstructural morphology of the PURM+PV composites and the pure PURM, as well the results of the physicochemical, mechanical e thermophysical tests by values obtained of density, hardness, compressive strength, specific heat, thermal conductivity and diffusivity. In general, the structure of pure PURM showed large, elongated and regular pores, while PURM+PV composites showed irregular, small and rounded pores with shapeless cells. This may have contributed to reducing their mechanical strength, especially for PURM - PV50. The hardness and density were found to have a proportional relationship with the PV content on PURM matrix. The specific heat, thermal diffusivity and thermal conductivity showed proportional relationship to each other. So, this has been realized that the increasing the PV content on PURM matrix resulted in the rise of diffusivity and thermal conductivity and the decrease of the specific heat. However, the values obtained by the PURM composites were similar the values of pure PURM, mainly the PURM-PV5 and PURM-PV10. Therefore, these composites can be applied like thermal insulator; furthermore, their use could reduce the production costs and to preserve the environment

Extração do óleo e caracterização dos resíduos da borra de petróleo para fins de reuso

The petroleum industry, in consequence of an intense activity of exploration and production, is responsible by great part of the generation of residues, which are considered toxic and pollutants to the environment. Among these, the oil sludge is found produced during the production, transportation and refine phases. This work had the purpose to develop a process to recovery the oil present in oil sludge, in order to use the recovered oil as fuel or return it to the refining plant. From the preliminary tests, were identified the most important independent variables, like: temperature, contact time, solvents and acid volumes. Initially, a series of parameters to characterize the oil sludge was determined to characterize its. A special extractor was projected to work with oily waste. Two experimental designs were applied: fractional factorial and Doehlert. The tests were carried out in batch process to the conditions of the experimental designs applied. The efficiency obtained in the oil extraction process was 70%, in average. Oil sludge is composed of 36,2% of oil, 16,8% of ash, 40% of water and 7% of volatile constituents. However, the statistical analysis showed that the quadratic model was not well fitted to the process with a relative low determination coefficient (60,6%). This occurred due to the complexity of the oil sludge. To obtain a model able to represent the experiments, the mathematical model was used, the so called artificial neural networks (RNA), which was generated, initially, with 2, 4, 5, 6, 7 and 8 neurons in the hidden layer, 64 experimental results and 10000 presentations (interactions). Lesser dispersions were verified between the experimental and calculated values using 4 neurons, regarding the proportion of experimental points and estimated parameters. The analysis of the average deviations of the test divided by the respective training showed up that 2150 presentations resulted in the best value parameters. For the new model, the determination coefficient was 87,5%, which is quite satisfactory for the studied system

Aperfeiçoamento no projeto de um protótipo de misturador-decantador à inversão de fases visando aplicação na indústria do petróleo

In the oil industry the mixture oil/water occurs in the operations of production, transportation and refining, as well as during the use of its derivatives. The amount of water produced associated with the oil varies and can reach values of 90% in volume in the case of mature phase of the production fields. The present work deals with the development of new design of the Mixer Settler based on Phase Inversion (MDIF) in a laboratory scale. We envisage this application in industrial scale so the phases of project, construction and operation are considered. The modifications most significant, in comparison with the original prototype, include the materials of construction and the substitution of the equipment used in the mixing stage of the process. It was tested the viability of substitution of the original system of mechanical mixing by a static mixer. A statistical treatment by means of an experimental design of composed central type was used in order to evaluate the behavior of the main variables of the separation process as function of the efficiency of separation for the new device. This procedure is useful to delimit an optimal region of operation with the equipment. The variables of process considered on the experimental design were: oil concentration in the feeding water (mg/L); Total volumetric flow rate (L/h); Ratio organic/water on volumetric basis (O/A). The separation efficiency is calculated by comparison of the content of oil and greases in the inlet and outlet of the equipment. For determination of TOG (Total Oil and Grease), the method used was based in the absorption of radiation in the infra-red region. The equipment used for these determinations was InfraCal® TOG/TPH Model HATR-T2 of the Wilks Enterprise, Incorporation. It´s important to stand out that this method of measure has being used by PETROBRAS S.A. Results of global efficiency of separation oil/water varied from 75.3 to 97.7% for contaminated waters containing up to 1664,1 mg/L of oil. By means of tests carried out with a real sample of contaminated water supplied by PETROBRAS we have got an effluent specified in terms of the legal standards required for discharging. Thus, the new design of equipment constitutes a real alternative for the conventional systems of treatment of produced water in the oil industry

Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented

Obtenção de Propriedades Físico-Químicas de Misturas de Hidrocarbonetos em Baixa e Alta Pressão Visando a Caracterização e a Modelagem

The composition of petroleum may change from well to well and its resulting characteristics influence significantly the refine products. Therefore, it is important to characterize the oil in order to know its properties and send it adequately for processing. Since petroleum is a multicomponent mixture, the use of synthetic mixtures that are representative of oil fractions provides a better understand of the real mixture behavior. One way for characterization is usually obtained through correlation of physico-chemical properties of easy measurement, such as density, specific gravity, viscosity, and refractive index. In this work new measurements were obtained for density, specific gravity, viscosity, and refractive index of the following binary mixtures: n-heptane + hexadecane, cyclohexane + hexadecane, and benzene + hexadecane. These measurements were accomplished at low pressure and temperatures in the range 288.15 K to 310.95 K. These data were applied in the development of a new method of oil characterization. Furthermore, a series of measurements of density at high pressure and temperature of the binary mixture cyclohexane + n-hexadecane were performed. The ranges of pressure and temperature were 6.895 to 62.053 MPa and 318.15 to 413.15 K, respectively. Based on these experimental data of compressed liquid mixtures, a thermodynamic modeling was proposed using the Peng-Robinson equation of state (EOS). The EOS was modified with scaling of volume and a relatively reduced number of parameters were employed. The results were satisfactory demonstrating accuracy not only for density data, but also for isobaric thermal expansion and isothermal compressibility coefficients. This thesis aims to contribute in a scientific manner to the technological problem of refining heavy fractions of oil. This problem was treated in two steps, i.e., characterization and search of the processes that can produce streams with economical interest, such as solvent extraction at high pressure and temperature. In order to determine phase equilibrium data in these conditions, conceptual projects of two new experimental apparatus were developed. These devices consist of cells of variable volume together with a analytical static device. Therefore, this thesis contributed with the subject of characterization of hydrocarbons mixtures and with development of equilibrium cells operating at high pressure and temperature. These contributions are focused on the technological problem of refining heavy oil fractions

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

Síntese e caracterização da peneira molecular MCM-41 contendo terras raras na dessulfurização, utilizando tiofeno como molécula sonda

Mesoporous molecular sieves of MCM-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, mesoporous molecular sieves MCM-41 were modified with different rare earth ions (La, Eu e Yb) for the obtaining nanostrutured materials with catalytic properties. The catalysts were synthesized by the hydrothermal method at 100oC for 120 h, presenting, all the samples, in the gel of synthesis molar ratio Si/Ln = 50. The obtained materials after calcination at 500oC for 2 h were characterized by XRD, surface area BET, TG/DTG, FTIR, and hydrothermal stability at 700ºC. The XRD analysis of the catalysts indicated that the materials containing rare earth presented characteristic hexagonal structure of the mesoporous materials of the type MCM-41. The TG curves showed that the decomposition of the structural template occurs in the materials at temperatures lower than 500oC. The samples presented variations as the specific superficial area, average diameter of pores and thickness of the silica wall, as a function of the nature of the rare earth impregnated in the mesoporous material. Hydrotermal stability was evaluated through the exposition of the materials to water vapour at 700°C. The thiophene adsorptions reach a maximum at 80% of conversion and incorporation of the rare earths showed influence in the process. Adsorption capacity followed the sequence: Yb-MCM-41 < La-MCM-41 < Eu-MCM-41 < MCM-41