Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Um sistema para estimação da vazão de gás de poços produzindo por Plunger Lift para vaso separador de teste em plataformas de petróleo

This work intends to analyze the behavior of the gas flow of plunger lift wells producing to well testing separators in offshore production platforms to aim a technical procedure to estimate the gas flow during the slug production period. The motivation for this work appeared from the expectation of some wells equipped with plunger lift method by PETROBRAS in Ubarana sea field located at Rio Grande do Norte State coast where the produced fluids measurement is made in well testing separators at the platform. The oil artificial lift method called plunger lift is used when the available energy of the reservoir is not high enough to overcome all the necessary load losses to lift the oil from the bottom of the well to the surface continuously. This method consists, basically, in one free piston acting as a mechanical interface between the formation gas and the produced liquids, greatly increasing the well s lifting efficiency. A pneumatic control valve is mounted at the flow line to control the cycles. When this valve opens, the plunger starts to move from the bottom to the surface of the well lifting all the oil and gas that are above it until to reach the well test separator where the fluids are measured. The well test separator is used to measure all the volumes produced by the well during a certain period of time called production test. In most cases, the separators are designed to measure stabilized flow, in other words, reasonably constant flow by the use of level and pressure electronic controllers (PLC) and by assumption of a steady pressure inside the separator. With plunger lift wells the liquid and gas flow at the surface are cyclical and unstable what causes the appearance of slugs inside the separator, mainly in the gas phase, because introduce significant errors in the measurement system (e.g.: overrange error). The flow gas analysis proposed in this work is based on two mathematical models used together: i) a plunger lift well model proposed by Baruzzi [1] with later modifications made by Bolonhini [2] to built a plunger lift simulator; ii) a two-phase separator model (gas + liquid) based from a three-phase separator model (gas + oil + water) proposed by Nunes [3]. Based on the models above and with field data collected from the well test separator of PUB-02 platform (Ubarana sea field) it was possible to demonstrate that the output gas flow of the separator can be estimate, with a reasonable precision, from the control signal of the Pressure Control Valve (PCV). Several models of the System Identification Toolbox from MATLAB® were analyzed to evaluate which one better fit to the data collected from the field. For validation of the models, it was used the AIC criterion, as well as a variant of the cross validation criterion. The ARX model performance was the best one to fit to the data and, this way, we decided to evaluate a recursive algorithm (RARX) also with real time data. The results were quite promising that indicating the viability to estimate the output gas flow rate from a plunger lift well producing to a well test separator, with the built-in information of the control signal to the PCV

Redução carbotérmica de TiO2 por descarga em cátodo oco

In this study we used the plasma as a source of energy in the process of carbothermic reduction of rutile ore (TiO2). The rutile and graphite powders were milled for 15 h and placed in a hollow cathode discharge produced by in order to obtain titanium carbonitride directly from the reaction, was verified the influence of processing parameters of plasma temperature and time in the synthesis of TiCN. The reaction was carried out at 600, 700 and 800˚C for 3 to 4 hours in an atmosphere of nitrogen and argon. During all reactions was monitored by plasma technique of optical emission spectroscopy (EEO) to check the active species present in the process of carbothermal reduction of TiO2. The powder obtained after the reactions were characterized by the techniques of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The technique of EEO were detected in all reactions the spectra CO and NO, and these gas-phase resulting from the reduction of TiO2. The results of X-ray diffraction confirmed the reduction, where for all conditions studied there was evidence of early reduction of TiO2 through the emergence of intermediate oxides. In the samples reduced at 600 and 700˚C, there was only the phase Ti6O11, those reduced to 800˚C appeared Ti5O9 phases, and Ti6O11 Ti7O13, confirming that the carbothermal reduction in plasma, a reduction of the ore rutile (TiO2) in a series of intermediate titanium oxide (TinO2n-1) where n varies between 5 and 10

Avaliação da capacidade de adsorção do CO2 em zeólita 12X com gases sintéticos e originados da pirólise do lodo de esgoto

This work depicts a study of the adsorption of carbon dioxide on zeolite 13X. The activities were divided into four stages: study batch adsorption capacity of the adsorbent with synthetic CO2 (4%), fixed bed dynamic evaluation with the commercial mixture of gases (4% CO2, 1.11% CO, 1 2% H2, 0.233% CH4, 0.1% C3, 0.0233% C4 argon as inert closing balance), fixed bed dynamic modeling and evaluation of the breakthrough curve of CO2 originated from the pyrolysis of sewage sludge. The sewage sludge and the adsorbent were characterized by analysis TG / DTA, SEM, XRF and BET. Adsorption studies were carried out under the following operating conditions: temperature 40 °C (for the pyrolysis of the sludge T = 600 °C), pressures of 0.55 to 5.05 bar (batch process), flow rate of the gaseous mixture between 50 - 72 ml/min and the adsorbent masses of 10, 15 and 20 g (fixed bed process). The time for the adsorption batch was 7 h and on the fixed bed was around 180 min. The results of this study showed that in batch adsorption process step with zeolite 13X is efficient and the mass of adsorbed CO2 increases with the increases pressure, decreases with temperature increases and rises due the increase of activation temperature adsorbent. In the batch process were evaluated the breakthrough curves, which were compared with adsorption isotherms represented by the models of Langmuir, Freündlich and Toth. All models well adjusted to the experimental points, but the Langmuir model was chosen in view of its use in the dynamic model does not have implications for adsorption (indeterminacy and larger number of parameters such as occurred with others) in solving the equation. In the fixed bed dynamic study with the synthetic gas mixture, 20 g of mass adsorbent showed the maximum adsorption percentage 46.7% at 40 °C temperature and 50 mL/min of flow rate. The model was satisfactorily fitted to the three breakthrough curves and the parameters were: axial dispersion coefficient (0.0165 dm2/min), effective diffusivity inside the particle (dm2/min 0.0884) and external transfer coefficient mass (0.45 dm/min). The breakthrough curve for CO2 in the process of pyrolysis of the sludge showed a fast saturation with traces of aerosols presents in the gas phase into the fixed bed under the reaction process

Estudo da influência da temperatura na degradação termoquímica da biomassa de avelós

The bio-oil obtained from the pyrolysis of biomass has appeared as inter-esting alternative to replace fossil fuels. The aim of this work is to evaluate the influence of temperature on the yield of products originating from the pyrolysis process of the powder obtained from the dried twigs of avelós (Euphorbia tirucalli), using a rotating cylinder reactor in laboratory scale. The biomass was treated and characterized by: CHNS, moisture, volatiles, fixed carbon and ashes, as well as evaluation of lignin, cellulose and hemicellulose, besides other instrumental techniques such as: FTIR, TG/DTG, DRX, FRX and MEV. The activation energy was evaluated in non-isothemichal mode with heating rates of 5 and 10 oC/min. The obtained results showed biomass as feedstock with potential for biofuel production, because presents a high organic matter content (78,3%) and fixed-carbon (7,11%). The activation energy required for the degradation of biomass ranged between 232,92 392,84 kJ/mol, in the temperature range studied and heating rate of 5 and 10°C/min. In the pyrolysis process, the influence of the reaction temperature was studied (350-520 ° C), keeping constant the other variables, such as, the flow rate of carrier gas, the centrifugal speed for the bio-oil condensationa, the biomass flow and the rotation of the reactor. The maximum yield of bio-oil was obtained in the temperature of 450°C. In this temperature, the results achieved where: content of bio-oil 8,12%; char 32,7%; non-condensed gas 35,4%; losts 23,8%; gross calorific value 3,43MJ/kg; pH 4,93 and viscosity 1,5cP. The chromatographic analysis of the bio-oil produced under these conditions shows mainly the presence of phenol (17,71%), methylciclopentenone (10,56%) and dimethylciclopentenone (7,76%)

Estudo da influência da temperatura na degradação termoquímica da biomassa de avelós (euphorbia tirucalli Linn)

The bio-oil obtained from the pyrolysis of biomass has appeared as inter-esting alternative to replace fossil fuels. The aim of this work is to evaluate the influence of temperature on the yield of products originating from the pyrolysis process of the powder obtained from the dried twigs of avelós (Euphorbia tirucalli), using a rotating cylinder reactor in laboratory scale. The biomass was treated and characterized by: CHNS, moisture, volatiles, fixed carbon and ashes, as well as evaluation of lignin, cellulose and hemicellulose, besides other instrumental techniques such as: FTIR, TG/DTG, DRX, FRX and MEV. The activation energy was evaluated in non-isothemichal mode with heating rates of 5 and 10 oC/min. The obtained results showed biomass as feedstock with potential for biofuel production, because presents a high organic matter content (78,3%) and fixed-carbon (7,11%). The activation energy required for the degradation of biomass ranged between 232,92 392,84 kJ/mol, in the temperature range studied and heating rate of 5 and 10°C/min. In the pyrolysis process, the influence of the reaction temperature was studied (350-520 ° C), keeping constant the other variables, such as, the flow rate of carrier gas, the centrifugal speed for the bio-oil condensationa, the biomass flow and the rotation of the reactor. The maximum yield of bio-oil was obtained in the temperature of 450°C. In this temperature, the results achieved where: content of bio-oil 8,12%; char 32,7%; non-condensed gas 35,4%; losts 23,8%; gross calorific value 3,43MJ/kg; pH 4,93 and viscosity 1,5cP. The chromatographic analysis of the bio-oil produced under these conditions shows mainly the presence of phenol (17,71%), methylciclopentenone (10,56%) and dimethylciclopentenone (7,76%)

Estudo de uma coluna de absorção recheada para desidratação do gás natural utilizando microemulsão como absorvente

During natural gas processing, water removal is considered as a fundamental step in that combination of hydrocarbons and water favors the formation of hydrates. The gas produced in the Potiguar Basin (Brazil) presents high water content (approximately 15000 ppm) and its dehydration is achieved via absorption and adsorption operations. This process is carried out at the Gas Treatment Unit (GTU) in Guamaré (GMR), in the State of Rio Grande do Norte. However, it is a costly process, which does not provide satisfactory results when water contents as low as 0.5 ppm are required as the exit of the GTU. In view of this, microemulsions research is regarded as an alternative to natural gas dehydration activities. Microemulsions can be used as desiccant fluids because of their unique proprieties, namely solubilization enhancement, reduction in interfacial tensions and large interfacial area between continuous and dispersed phases. These are actually important parameters to ensure the efficiency of an absorption column. In this work, the formulation of the desiccant fluid was determined via phases diagram construction, employing there nonionic surfactants (RDG 60, UNTL L60 and AMD 60) and a nonpolar fluid provided by Petrobras GMR (Brazil) typically comprising low-molecular weight liquid hydrocarbons ( a solvent commonly know as aguarrás ). From the array of phases diagrams built, four representative formulations have been selected for providing better results: 30% RDG 60-70% aguarrás; 15% RDG 60-15% AMD 60-70% aguarrás, 30% UNTL L60-70% aguarrás, 15% UNTL L60-15% AMD 60-70% aguarrás. Since commercial natural gas is already processed, and therefore dehydrated, it was necessary to moister some sample prior to all assays. It was then allowed to cool down to 13ºC and interacted with wet 8-12 mesh 4A molecular sieve, thus enabling the generation of gas samples with water content (approximately 15000 ppm). The determination of the equilibrium curves was performed based on the dynamic method, which stagnated liquid phase and gas phase at a flow rate of 200 mL min-1. The hydrodynamic study was done with the aim of established the pressure drop and dynamic liquid hold-up. This investigation allowed are to set the working flow rates at 840 mL min-1 for the gas phase and 600 mLmin-1 for the liquid phase. The mass transfer study indicated that the system formed by UNTL L60- turpentine-natural gas the highest value of NUT

Bio-óleo e biogás da degradação termoquímica de lodo de esgoto doméstico em cilindro rotativo

The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ° C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 °C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 °C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ° C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Remoção, por flotação, de óleo em águas produzidas na indústria de petróleo: eficiência e modelagem do processo

The separation oil-water by the use of flotation process is characterized by the involvement between the liquid and gas phases. For the comprehension of this process, it s necessary to analyze the physical and chemical properties command float flotation, defining the nature and forces over the particles. The interface chemistry has an important role on the flotation technology once, by dispersion of a gas phase into a liquid mixture the particles desired get stuck into air bubbles, being conduced to a superficial layer where can be physically separated. Through the study of interface interaction involved in the system used for this work, was possible to apply the results in an mathematical model able to determine the probability of flotation using a different view related to petroleum emulsions such as oil-water. The terms of probability of flotation correlate the collision and addition between particles of oil and air bubbles, that as more collisions, better is the probability of flotation. The additional probability was analyzed by the isotherm of absorption from Freundlich, represents itself the add probability between air bubbles and oil particles. The mathematical scheme for float flotation involved the injected air flow, the size of bubbles and quantity for second, the volume of float cell, viscosity of environment and concentration of demulsifier. The results shown that the float agent developed by castor oil, pos pH variation, salt quantity, temperature, concentration and water-oil quantity, presented efficient extraction of oil from water, up to 95%, using concentrations around 11 ppm of demulsifier. The best results were compared to other commercial products, codified by ―W‖ and ―Z‖, being observed an equivalent demulsifier power between Agflot and commercial product ―W‖ and superior to commercial product ―Z‖

Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.