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

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Estudo comparativo de diferentes sistemas de injeção de vapor aplicados à remediação de solos contaminados por diesel

Among the potentially polluting economic activities that compromise the quality of soil and groundwater stations are fuel dealers. Leakage of oil derived fuels in underground tanks or activities improperly with these pollutants can contaminate large areas, causing serious environmental and toxicological problems. The number of gas stations grew haphazardly, without any kind of control, thus the environmental impacts generated by these enterprises grew causing pollution of soil and groundwater. Surfactants using various techniques have been proposed to remedy this kind of contamination. This study presents innovation as the application of different systems containing surfactant in the vapor phase and compares their diesel removal efficiencies of soil containing this contaminant. For this, a system that contains seven injection wells the following vaporized solutions: water, surfactant solution, microemulsion and nanoemulsion, The surfactants used were saponified coconut oil (OCS), in aqueous solution and an ethoxylated alcohol UNTL-90: aqueous solution , and nanoemulsion and microemulsion systems. Among the systems investigated, the nanoemulsion showed the highest efficiency, achieving 88% removal of residual phase diesel, the most ecologically and technically feasible by a system with lower content of active matter

Construção e implementação do Balanced Scorecard em uma organização educacional: o caso do Serviço Nacional de Aprendizagem Comercial do Rio Grande do Norte SENAC RN

The changes that have taken place in the organizational environment in recent decades have led to new performance measurement systems being proposed, given the inadequacy of traditional models. The Balanced Scorecard (BSC) emerged as an instrument to translate financial and non-financial assets into real values for all interested parties in the organization, allowing the introduction of strategies to achieve the desired goals. Research shows that most errors committed with the use of this method are related to the implementation process. Thus, the aim of this dissertation is to analyze the process of building and implementing the BSC in an organization. This empirical exploratory study is based on the classic case study method, which enables the researcher to work with a set of evidence, including direct observation, interviews and document analysis. The results show that the use of BSC in the company investigated posed problems during the process of building and implementing the method. These problems were caused mainly by the lack of involvement on the part of upper management and the team s scant knowledge of Balanced Scorecard. One of the gains obtained from adopting the system was the introduction and/or consolidation of a culture of strategic planning and participative management. The continuous implementation phase was highlighted in the monitoring program, created by the organization in an attempt to reverse existing problems, using the BSC as a third generation strategic management system, which led to significant gains, better use of the system and stronger management practices

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

Determinação de dados de equilíbrio de fases para sistemas aquosos com eletrólitos

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer s ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Estudo paramétrico da segregação gravitacional na injeção contínua de vapor

Steam injection is the most used method of additional recovery for the extraction of heavy oil. In this type procedure is common to happen gravitational segregation and this phenomenon can affect the production of oil and therefore, it shoulds be considered in the projects of continuous steam injection. For many years, the gravitational segregation was not adequately considered in the calculation procedures in Reservoir Engineering. The effect of the gravity causes the segregation of fluids inside the porous media according to their densities. The results of simulation arising from reservoirs could provide the ability to deal with the gravity, and it became apparent that the effects of the gravity could significantly affect the performance of the reservoir. It know that the gravitational segregation can happen in almost every case where there is injection of light fluid, specially the steam, and occurs with greater intensity for viscous oil reservoirs. This work discusses the influence of some parameters of the rock-reservoir in segregation as viscosity, permeability, thickness, cover gas, porosity. From a model that shows the phenomenon with greater intensity, optimized some operational parameters as the rate flow rate steam, distance between the wells injector-producer, and interval of completion which contributed to the reduction in gravity override, thus increasing the oil recovery. It was shown a greater technical-economic viability for the model of distance between the wells 100 m. The analysis was performed using the simulator of CMG (Computer Modeling Group-Stars 2007.11, in which was observed by iterating between studied variables in heavy oil reservoirs with similar characteristics to Brazilian Northeast

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

Estudo de sistemas multicomponentes no processo de injeção cíclica de vapor

In Brazilian Northeast there are reservoirs with heavy oil, which use steam flooding as a recovery method. This process allows to reduce oil viscosity, increasing its mobility and consequently its oil recovery. Steam injection is a thermal method and can occurs in continues or cyclic form. Cyclic steam stimulation (CSS) can be repeated several times. Each cycle consisting of three stages: steam injection, soaking time and production phase. CSS becomes less efficient with an increase of number of cycles. Thus, this work aims to study the influence of compositional models in cyclic steam injection and the effects of some parameters, such like: flow injection, steam quality and temperature of steam injected, analyzing the influence of pseudocomponents numbers on oil rate, cumulative oil, oil recovery and simulation time. In the situations analyzed was compared the model of fluid of three phases and three components known as Blackoil . Simulations were done using commercial software (CMG), it was analyzed a homogeneous reservoir with characteristics similar to those found in Brazilian Northeast. It was observed that an increase of components number, increase the time spent in simulation. As for analyzed parameters, it appears that the steam rate, and steam quality has influence on cumulative oil and oil recovery. The number of components did not a lot influenced on oil recovery, however it has influenced on gas production

Estudo de modelos composicionais de óleo na injeção contínua de vapor

The objective of the thermal recovery is to heat the resevoir and the oil in it to increase its recovery. In the Potiguar river basin there are located several heavy oil reservoirs whose primary recovery energy provides us with a little oil flow, which makes these reservoirs great candidates for application of a method of recovery advanced of the oil, especially the thermal. The steam injection can occur on a cyclical or continuous manner. The continuous steam injection occurs through injection wells, which in its vicinity form a zone of steam that expands itself, having as a consequence the displace of the oil with viscosity and mobility improved towards the producing wells. Another possible mechanism of displacement of oil in reservoirs subjected to continuous injection of steam is the distillation of oil by steam, which at high temperatures; their lighter fractions can be vaporized by changing the composition of the oil produced, of the oil residual or to shatter in the amount of oil produced. In this context, this paper aims to study the influence of compositional models in the continuous injection of steam through in the analysis of some parameters such as flow injection steam and temperature of injection. Were made various leading comparative analysis taking the various models of fluid, varying from a good elementary, with 03 pseudocomponents to a modeling of fluids with increasing numbers of pseudocomponents. A commercial numerical simulator was used for the study from a homogeneous reservoir model with similar features to those found in northeastern Brazil. Some conclusions as the increasing of the simulation time with increasing number of pseudocomponents, the significant influence of flow injection on cumulative production of oil and little influence of the number of pseudocomponents in the flows and cumulative production of oil were found

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

Estudo da recuperação de óleo por drenagem gravitacional assistida por injeção de vapor

Steam assisted gravity drainage process (SAGD) involves two parallel horizontal wells located in a same vertical plane, where the top well is used as steam injector and the bottom well as producer. The dominant force in this process is gravitational. This improved oil recovery method has been demonstrated to be economically viable in commercial projects of oil recovery for heavy and extra heavy oil, but it is not yet implemented in Brazil. The study of this technology in reservoirs with characteristics of regional basins is necessary in order to analyze if this process can be used, minimizing the steam rate demand and improving the process profitability. In this study, a homogeneous reservoir was modeled with characteristics of Brazilian Northeast reservoirs. Simulations were accomplished with STARS , a commercial software from Computer Modelling Group, which is used to simulate improved oil recovery process in oil reservoirs. In this work, a steam optimization was accomplished in reservoirs with different physical characteristics and in different cases, through a technical-economic analysis. It was also studied a semi-continuous steam injection or with injection stops. Results showed that it is possible to use a simplified equation of the net present value, which incorporates earnings and expenses on oil production and expenses in steam requirement, in order to optimize steam rate and obtaining a higher net present value in the process. It was observed that SAGD process can be or not profitable depending on reservoirs characteristics. It was also obtained that steam demand can still be reduced injecting in a non continuous form, alternating steam injection with stops at several time intervals. The optimization of these intervals allowed to minimize heat losses and to improve oil recovery

Estudo paramétrico da segregação gravitacional na injeção contínua de vapor

Steam injection is the most used method of additional recovery for the extraction of heavy oil. In this type procedure is common to happen gravitational segregation and this phenomenon can affect the production of oil and therefore, it shoulds be considered in the projects of continuous steam injection. For many years, the gravitational segregation was not adequately considered in the calculation procedures in Reservoir Engineering. The effect of the gravity causes the segregation of fluids inside the porous media according to their densities. The results of simulation arising from reservoirs could provide the ability to deal with the gravity, and it became apparent that the effects of the gravity could significantly affect the performance of the reservoir. It know that the gravitational segregation can happen in almost every case where there is injection of light fluid, specially the steam, and occurs with greater intensity for viscous oil reservoirs. This work discusses the influence of some parameters of the rock-reservoir in segregation as viscosity, permeability, thickness, cover gas, porosity. From a model that shows the phenomenon with greater intensity, optimized some operational parameters as the rate flow rate steam, distance between the wells injector-producer, and interval of completion which contributed to the reduction in gravity override, thus increasing the oil recovery. It was shown a greater technical-economic viability for the model of distance between the wells 100 m. The analysis was performed using the simulator of CMG (Computer Modeling Group-Stars 2007.11, in which was observed by iterating between studied variables in heavy oil reservoirs with similar characteristics to Brazilian Northeast

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

Estudo de sistemas multicomponentes no processo de injeção cíclica de vapor

In Brazilian Northeast there are reservoirs with heavy oil, which use steam flooding as a recovery method. This process allows to reduce oil viscosity, increasing its mobility and consequently its oil recovery. Steam injection is a thermal method and can occurs in continues or cyclic form. Cyclic steam stimulation (CSS) can be repeated several times. Each cycle consisting of three stages: steam injection, soaking time and production phase. CSS becomes less efficient with an increase of number of cycles. Thus, this work aims to study the influence of compositional models in cyclic steam injection and the effects of some parameters, such like: flow injection, steam quality and temperature of steam injected, analyzing the influence of pseudocomponents numbers on oil rate, cumulative oil, oil recovery and simulation time. In the situations analyzed was compared the model of fluid of three phases and three components known as Blackoil . Simulations were done using commercial software (CMG), it was analyzed a homogeneous reservoir with characteristics similar to those found in Brazilian Northeast. It was observed that an increase of components number, increase the time spent in simulation. As for analyzed parameters, it appears that the steam rate, and steam quality has influence on cumulative oil and oil recovery. The number of components did not a lot influenced on oil recovery, however it has influenced on gas production