Síntese e caracterização do carbeto de molibdênio nanoestruturado para fins catalíticos na reação de oxidação parcial do metano

The nanostructures materials are characterized to have particle size smaller than 100 nm and could reach 1 nm. Due to the extremely reduced dimensions of the grains, the properties of these materials are significantly modified relatively when compared with the conventional materials. In the present work was accomplished a study and characterization of the molybdenum carbide, seeking obtain it with particles size in the nanometers order and evaluate its potential as catalyst in the reaction of partial methane oxidation. The method used for obtaining the molybdenum carbide was starting from the precursor ammonium heptamolybdate of that was developed in split into two oven, in reactor of fixed bed, with at a heating rate of 5ºC/min, in a flow of methane and hydrogen whose flow was of 15L/h with 5% of methane for all of the samples. The studied temperatures were 350, 500, 600, 650, 660, 675 and 700ºC and were conducted for 0, 60, 120 and 180 minutes, and the percent amount and the crystallite size of the intermediate phases were determined by the Rietveld refinement method. The carbide obtained at 660ºC for 3 hours of reaction showed the best results, 24 nm. Certain the best synthesis condition, a passivating study was accomplished, in these conditions, to verify the stability of the carbide when exposed to the air. The molybdenum carbide was characterized by SEM, TEM, elemental analysis, ICP-AES, TG in atmosphere of hydrogen and TPR. Through the elemental analysis and ICP-AES the presence carbon load was verified. TG in atmosphere of hydrogen proved that is necessary the passivating of the molybdenum carbide, because occur oxidation in room temperature. The catalytic test was accomplished in the plant of Fischer-Tropsch of CTGAS, that is composed of a reactor of fixed bed. Already the catalytic test showed that the carbide presents activity for partial oxidation, but the operational conditions should be adjusted to improve the conversion

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

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

Crescimento micelial de Pleurotus ostreatus em resíduo de Simarouba amara

O objetivo deste trabalho foi avaliar o crescimento micelial do cogumelo Pleurotus ostreatus, cultivado na serragem da espécie madeireira Simarouba amara. Avaliaram-se: o efeito das temperaturas de 22, 25, 27, 30 e 35ºC sobre o crescimento micelial de P. ostreatus, nos meios malte-ágar 3% e SDA-MA (infusão da serragem de S. amara, enriquecida com farelo de soja-dextrose-ágar); e o crescimento micelial em substrato de cultivo de serragem de S. amara, com e sem suplementação de farelo de soja, a 25 e 30ºC. O melhor desenvolvimento de P. ostreatus ocorreu em meio malte-ágar 3% a 25ºC. A suplementação de farelo de soja na serragem de S. amara favorece o crescimento micelial.

Aplicação de ultrassons no deslocamento de petróleo em meio poroso

The objective of this study was to evaluate the displacement of petroleum/diesel solutions, at different concentrations, observing the effect of ultrasonic vibrations in fluids present in porous media to obtain an increase in oil production. The bubbles produced by ultrasound implode asymmetrically in the rock, generating liquid jets with high speed, displacing the oil present in porous media. The oil/diesel solutions were prepared with concentrations ranging from 20 g/L to 720 g/L in oil in relation to diesel and its viscosities were obtained in a Brookfield Rheometer RS2000, with temperature ranging from 25 to 55 °C. After, calculations were performed to obtain the activation energy data for oil/diesel solutions. For oil recovery experiments, cylindrical samples of porous rock (core samples), with resin around the perimeter and its two circular bases free to allow the passage of fluids, were first saturated with 2% KCl solution and after with oil solutions. The results of oil extraction were satisfactory for all studied solutions, being obtained up to 68% partial displacement with saline solution injection. The ultrasound system was used after saline injection, increasing oil displacement, with oil extractions ranging from 63% to 79%. During the experiments, it was observed the warming of core samples, helping to reduce the viscosity of more concentrated systems, and consequently enhancing the percentage of advanced recovery for all studied solutions

Montagem e operação de um secador pneumático tipo flash

In this work, a pneumatic dryer has been designed and assembled in laboratory scale in order to study and evaluate configurations more efficient for application in drying of important materials of Northeast region in Brazil. The equipment was tested with drying of corn and rice grains, in conditions of temperature and air velocity at 80 oC and 35 m/s, respectively. For this type of dryer, it is recommended to work at temperatures above 200 °C and air velocity with higher dynamic pressure. However, even under operating conditions below what it is recommended, the results obtained with the pneumatic dryer were satisfactory. In addition, experiments of drying were performed by using a cabinet dryer (batch dryer) under the same conditions used in the pneumatic dryer. Flash one curves for the corn were fitted satisfactorily by applying of the Lewis model, while a better agreement was found for rice by using the Page model. The data obtained with both drying processes allowed to compare the performance between pneumatic and batch dryers. In respect to drying rate, the pneumatic dryer presented a similar performance to the batch dryer during processing with corn and a superior performance to the last one during processing with rice. Therefore, it was possible to verify that the pneumatic dryer assembled in this preliminar study can be applied for different materials and under different operating conditions

Inferência do ponto de orvalho em amostras de gás natural processado

This dissertation aims to assess the representativeness of the manual chilled mirror analyzer (model II Chanscope 13-1200-CN-2) used for the determination of condensed hydrocarbons of natural gas compared to the indirect methods, based on thermodynamic models equation of state. Additionally, it has been implemented in this study a model for calculating the dew point of natural gas. The proposed model is a modification of the equation of state of Peng-Robinson admits that the groups contribution as a strategy to calculate the binary interaction parameters kij (T) temperature dependence. Experimental data of the work of Brown et al. (2007) were used to compare the responses of the dew point of natural gas with thermodynamic models contained in the UniSim process simulator and the methodology implemented in this study. Then two natural gas compositions were studied, the first being a standard gas mixture gravimetrically synthesized and, second, a mixture of processed natural gas. These experimental data were also compared with the results presented by UniSim process simulator and the thermodynamic model implemented. However, data from the manual analysis results indicated significant differences in temperature, these differences were attributed to the formation of dew point of water, as we observed the appearance of moisture on the mirror surface cooling equipment

Extração do corante reactive blue 19 utilizando tensoativo não iônico

The generation of effluent from the finishing process in textile industry is a serious environmental problem and turned into an object of study in several scientific papers. Contamination with dyes and the presences of substances that are toxic to the environment characterize this difficult treatment effluent. Several processes have already been evaluated to remove and even degrade such pollutants are examples: coagulation-flocculation, biological treatment and advanced oxidative processes, but not yet sufficient to enable the recovery of dye or at least of the recovery agent. An alternative to this problem is the cloud point extraction that involves the application of nonionic surfactants at temperatures above the cloud point, making the water a weak solvent to the surfactant, providing the agglomeration of those molecules around the dyes molecules by affinity with the organic phase. After that, the formation of two phases occurred: the diluted one, poor in dye and surfactant, and the other one, coacervate, with higher concentrations of dye and surfactants than the other one. The later use of the coacervate as a dye and surfactant recycle shows the technical and economic viability of this process. In this paper, the cloud point extraction is used to remove the dye Reactive Blue from the water, using nonionic surfactant nonyl phenol with 9,5 etoxilations. The aim is to solubilize the dye molecules in surfactant, varying the concentration and temperature to study its effects. Evaluating the dye concentration in dilute phase after extraction, it is possible to analyze thermodynamic variables, build Langmuir isotherms, determine the behavior of the coacervate volume for a surfactant concentration and temperature, the distribution coefficient and the dye removal efficiency. The concentration of surfactant proved itself to be crucial to the success of the treatment. The results of removal efficiency reached values of 91,38%, 90,69%, 89,58%, 87,22% and 84,18% to temperatures of 65,0, 67,5, 70,0, 72,5 and 75,0°C, respectively, showing that the cloud point extraction is an efficient alternative for the treatment of wastewater containing Reactive Blue

Estudo de um sistema híbrido de destilação solar para polimento de águas produzidas

The oil industry, experiencing a great economic and environmental impact, has increasingly invested in researches aiming a more satisfactory treatment of its largest effluent, i.e., produced water. These are mostly discarded at sea, without reuse and after a basic treatment. Such effluent contains a range of organic compounds with high toxicity and are difficult to remove, such as polycyclic aromatic hydrocarbons, salts, heavy metals, etc.. The main objective of this work was to study the solar distillation of produced water pre-treated to remove salts and other contaminants trough of a hybrid system with a pre-heater. This developed apparatus was called solar system, which consists of a solar heater and a conventional distillation solar still. The first device consisted of a water tank, a solar flat plate collector and a thermal reservoir. The solar distillator is of simple effect, with 1m2 of flat area and 20° of inclination. This dissertation was divided in five steps: measurements in the solar system, i.e. temperatures and distillate flow rate and weather data; modeling and simulation of the system; study of vapor-liquid equilibrium of the synthetic wastewater by the aqueous solution of p-xylene; physical and chemical analyses of samples of the feed, distillate and residue, as well as climatology pertinent variables of Natal-RN. The solar system was tested separately, with the supply water, aqueous NaCl and synthetic oil produced water. Temperature measurements were taken every minute of the thermal reservoir, water tank and distillator (liquid and vapor phases). Data of solar radiation and rainfall were obtained from INPE (National Institute for Space Research). The solar pre-heater demonstrated to be effective for the liquid systems tested. The reservoir fluid had an average temperature of 58°C, which enabled the feed to be pre-heated in the distillator. The temperature profile in the solar distillator showed a similar behavior to daily solar radiation, with temperatures near 70°C. The distillation had an average yield of 2.4 L /day, i.e., an efficiency of 27.2%. Mathematical modeling aided the identification of the most important variables and parameters in the solar system. The study of the vapor-liquid equilibrium from Total Organic Carbon (TOC) analysis indicated heteroazeotropia and the vapor phase resulted more concentrated in p-xylene. The physical-chemical analysis of pH, conductivity, Total Dissolved Solids (TDS), chlorides, cations (including heavy metals) and anions, the effluent distillate showed satisfactory results, which presents a potential for reuse. The climatological study indicates the region of Natal-RN as favorable to the operation of solar systems, but the use of auxiliary heating during periods of higher rainfall and cloud cover is also recommended

Estudo do equilíbrio líquido-vapor do sistema água+etanol+líquido iônico visando a separação do álcool anidro

Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed

Secagem de grãos de girassol em leito fixo e em leito de jorro

This work studies two methods for drying sunflower grains grown in the western region of Rio Grande do Norte, in the premises of the Instituto Federal de Educação, Ciência e Tecnologia do Rio Grande do Norte - IFRN - Campus Apodi. This initiative was made because of the harvested grain during the harvest, being stored in sheds without any control of temperature, humidity etc. Therewith, many physical, chemical and physiological characteristics are compromised and grains lose much quality for oil production as their germination power. Taking into account that most of the stored grain is used for replanting, the studied methods include drying of grains in a thin layer using an oven with air circulation (fixed bed) and drying in a spouted bed. It was studied the drying of grains in natura, i.e., newly harvested. The fixed bed drying was carried out at temperatures of 40, 50, 60 and 70°C. Experiments in spouted bed were performed based on an experimental design, 2² + 3, with three replications at the central point, where the independent variables were grains load (1500, 2000 and 2500 g) and the temperature of the inlet air (70, 80, and 90 °C), obtaining the drying and desorption equilibrium isotherms. Previously, the characteristic curves of the bed were obtained. Both in the fixed bed as in the spouted bed, drying and desorption curves were obtained by weighing the grains throughout the experiments and measurements of water activity, respectively. The grains drying in the spouted bed showed good results with significant reduction of processing time. The models of FICK and PAGE were fitted to the experimental data, models which will represent the drying of grains both in the fixed bed as in the spouted bed. The desorption curves showed no influence of the processing temperature in the hygroscopic characteristics of the grains. The models of GAB, OSWIN and LUIKOV could well represent the desorption isotherms

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

Suco desidratado de caju (Anacardium occidentale L.) por atomização: caracterização físico-química, bioativa e estudo da vida de prateleira do produto

Despite the relatively organized cashew (Anacardium occidentale L.) productive chain and the number of cashew derivatives found in the market, it is estimated that over 90% of the cashew peduncle is wasted. A possible strategy for a better commercial exploitation of this agroindustrial commodity would be the production of spray dried cashew pulp. Thus, this paper approaches the yellow cashew pulp spray drying process and the final product evaluation. Based on that, the shelf life of the spray dried cashew pulp packed in different packaging was evaluated. Drying was conducted in two drying temperatures (140 °C to 150 °C) and two concentrations of Arabic gum (AG, 15% and 25%), which summed four experimental groups. The drying performance was evaluated as well as the physicochemical characteristics (moisture, water activity, total soluble solids, pH, density, solubility, particle diameter, hygroscopicity, degree of caking, color, scanning electronic microscopy and X-ray diffraction), composition (protein, ash, fat and sugars) and bioactive and functional value (total phenolic compounds, carotenoids, ascorbic acid and antioxidant activity) of the final products. Results showed spray drying efficiency higher than 65% for all experiments, mainly for the C4 group (150 °C and 25% AG) which reached efficiency of 93.4%. It was also observed high solubility (94.7% to 97.9%) and the groups with lower hygroscopicity (5.8% and 6.5%) were those with the highest proportion of drying coadjuvant. The particle diameters ranged between 14.7 μm and 30.2 μm and increased with the proportion of AG. When comparing the product before and after spray drying, the drying impact was evident. However, despite the observed losses, dried yellow cashew showed high phenolic concentration (from 235.9 to 380.4 mg GAE eq / 100 g DM), carotenoids between 0.22 and 0.49 mg/100 g DM and remarkable ascorbic acid levels (852.4 to 1346.2 mg/100 g DM), in addition to antioxidant activity ranging from 12.9 to 16.4 μmol TE/ g DM. The shelf life study revealed decreased phenolic content over time associated to a slight water activity increase. Overall, our results unveil the technological and bioactive potential of dried yellow cashew as a functional ingredient to be used in food formulations or as a ready-to-use product. The technological approach presented here can serve as an efficient strategy for a rational use of the cashew apple, avoiding its current underutilization

Microemulsões aplicadas ao tratamento de Óleos isolantes

Naphthenic lubricating oils are used in transformers with the purpose of promoting electrical insulation and dissipating heat. The working temperature range of these oils typically lies between 60°C and 90°C and their useful life is 40 years in average. In that temperature range, the oils are decomposed during operation, whereby a small fraction of polar compounds are formed. The presence of these compounds may induce failure and loss of physical, chemical and electrical properties of the oil, thus impairing the transformer operation. By removing these contaminants, one allows the oxidized insulating oil to be reused without damaging the equipment. In view of this, an investigation on the use of surfactants and microemulsions as extracting agents, and modified diatomite as adsorbent, has been proprosed in this work aiming to remove polar substances detected in oxidized transformer oils. The extraction was carried out by a simple-contact technique at room temperature. The system under examination was stirred for about 10 minutes, after which it was allowed to settle at 25°C until complete phase separation. In another experimental approach, adsorption equilibrium data were obtained by using a batch system operating at temperatures of 60, 80 and 100°C. Analytical techniques involving determination of the Total Acidity Number (TAN) and infrared spectrophotometry have been employed when monitoring the decomposition and recovery processes of the oils. The acquired results indicated that the microemulsion extraction system comprising Triton® X114 as surfactant proved to be more effective in removing polar compounds, with a decrease in TAN index from 0.19 to 0.01 mg KOH/g, which is consistent with the limits established for new transformer oils (maximal TAN = 0.03 mg KOH/g). In the adsorption studies, the best adsorption capacity values were as high as 0.1606 meq.g/g during conventional adsoprtion procedures using natural bauxite, and as high as 0.016 meq.g/g for the system diatomite/Tensiofix® 8426. Comparatively in this case, a negative effect could be observed on the adsorption phenomenon due to microemulsion impregnation on the surface of the diatomite

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