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

Otimização do processo de flotação de emulsão óleo/água através do planejamento fatorial completo

In recent decades, the generation of solid and liquid waste has increased substantially due to increased industrial activity that is directly linked to economic growth. For that is the most efficient process, it is inevitable generation of such wastes. In the oil industry, a major waste generated in oil exploration is produced water, which due to its complex composition and the large amount generated, has become a challenge, given the restrictions imposed by environmental laws regarding their disposal, making if necessary create alternatives for reuse or treatment in order to reduce the content of contaminants and reduce the harmful effects to the environment. This water can be present in free form or emulsified with the oil, when in the form of an emulsion of oil-water type, it is necessary to use chemicals to promote the separation and flotation is the treatment method which has proved to be more efficient, for it can remove much of the emulsified oil when compared to other methods. In this context, the object of this work was to study the individual effects and interactions of some physicochemical parameters of operations, based on previous work to a flotation cell used in the separation of synthetic emulsion oil / water in order to optimize the efficiency of the separation process through of the 24 full factorial design with center point. The response variables to evaluate the separation efficiency was the percentage of color and turbidity removal. The independent variables were: concentration of de-emulsifying, oil content in water, salinity and pH, these being fixed, minimum and maximum limits. The analysis of variance for the equation of the empirical model, was statistically significant and useful for predictive purposes the separation efficiency of the floater with R2 > 90%. The results showed that the oil content in water and the interaction between the oil content in water and salinity, showed the highest values of the estimated effects among all the factors investigated, having great and positive influence on the separation efficiency. By analyzing the response surface was determined maximum removal efficiency above 90% for both measured for turbidity as a measure of color when in a saline medium (30 g/L), the high oil concentrations (306 ppm) using low concentrations of de-emulsifying (1,1 ppm) and at pH close to neutral

Projeto e Operação em Escala Semi-Industrial de um Equipamento para Tratamento de Águas Produzidas na Indústria do Petróleo Utilizando Nova Tecnologia: misturador-decantador à inversão de fases - MDIF

The aim of this work is to use a new technology in the treatment of produced wastewaters from oil industry. An unit for treat produced waters called UTMDIF, was designed, installed and operated in an industrial plant for treatment of effluents from oil industry. This unit operates by means of the method of separation of phase inversion and can become a promising alternative to solve the problem of oil/water separation. This method constitutes the basis of the working of a new design of mixersettler of vertical configuration which occupies small surface area. The last characteristic becomes specially important when there is limitation on the lay-out of the plant, for example, over maritime platforms to explore oil. This equipment in a semi-industrial scale treats produced wastewaters contaminated with oil at low concentrations (ranging from 30 to 150 mg/L) and throughputs of 320 m3/d (47,4 m3 m-2 h-1). Good results were obtained in oil/water separation which leads to the necessary specification to discharge those wastewaters. Besides, the non dependence of the efficiency of separation in spite of the salinity of the medium becomes the equipment an attractive new technology to treat wastewaters containing oil at low concentrations

Extração de metais pesados de efluentes da indústria do petróleo utilizando derivados de óleos vegetais como extratantes

The study of a promising alternative for the treatment of produced water from the oil industry envisaging its reuse was the focus of this work. Millions of liters of water are generated per day, containing heavy metals in low concentrations (< 0,15 mg/L for Pb, <0,04 mg/L for Cd, <0,04 mg/L for Ni). The technology applied to extract these metals from aqueous phase was the solvent extraction and the extratants used were vegetable oils originated from coconut oil. They can be used in natural form or as derivatives, known as MAC - Mixture of Carboxílics Acids. The determination of the heavy metal con¬centrations in a complex matrix was made by using the atomic absorption spectrometry technique (AAS). On the bench tests using synthetics aqueous solutions containing metals, vegetable oils showed no power to extract the metals studied. The extractant MAC was selective for the Pb> Cd> Ni, in the concentration of 8% in the same organic phase. In this condition, the lower efficiency of extraction obtained was 92% for the Pb, 69% for the Cd, in the range of pH ranging from 6 to 8. An experimental planning was conducted for continuous tests. The device used was called MDIF Misturador-Decantador à Inversão de Fases and the aqueous phase was produced water from Pólo Indutrial de Guamaré/RN . No correlation between the studied variables (concentration of metal, concentration of extratant and agitation in the mixing chamer) could be obtained, because of possible factors which occurred as: variation in the composition of the studied sample, phenomena of precipitation and complexation of metals in the reservoir of feed, solubility of extratant

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find altenatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo¬Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. it's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find alternatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo- Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. It's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal

Efeitos da dieta suplementada com ômega-3 no músculo sóleo de ratos submetidos à natação: análise histológica e morfométrica

As lesões musculares têm sido observadas como as mais frequentes nos esportes. Considerando a produção de espécies reativas de oxigênio como um fator de risco para instalação de lesões e características antioxidantes e anti-inflamatórias do ômega-3, o objetivo deste trabalho foi verificar as alterações histológicas e morfométricas do músculo sóleo de ratos que realizaram natação, associado a uma dieta suplementada com ômega-3. Para sua realização foram utilizados 31 ratos Wistar divididos em quatro grupos, sendo os grupos A e C suplementados com azeite de oliva e B e D com 3g/dia de ômega-3 por quatro semanas. Os grupos C e D foram submetidos à natação cinco dias/semana por 28 dias, com acréscimo de 5% do peso corporal a partir da segunda semana, enquanto que os grupos A e B não realizaram treinamento. Após este período os animais foram sacrificados, o músculo sóleo retirado e corado com Hematoxilina-eosina para avaliação morfológica. Análise de variância bifatorial, com nível de significância de 5%, foi utilizada para análise dos valores do menor diâmetro das fibras musculares. Os grupos A e B (sedentários) apresentaram padrões histológicos de normalidade. O grupo C apresentou aumento do tecido endomisial e do número de núcleos, presença de fibras fagocitadas e de contornos poligonais não mantidos, enquanto que o grupo D apresentou poucas fibras fagocitadas e de contornos poligonais preservados. Com relação à medida do menor diâmetro das fibras musculares, as análises mostraram diferenças para o fator treinamento, mas não para o fator suplementação e a interação entre eles. As alterações histológicas induzidas pelo exercício foram atenuadas no grupo suplementado com ômega-3, sugerindo um efeito protetor da suplementação, contudo, o aumento do diâmetro das fibras para os grupos expostos ao exercício está relacionado ao efeito do treinamento e não à suplementação.

Migration of Tinuvin P, a UV stabilizer, from PET bottles into fatty-food simulants

Tinuvin P migration from Polyethyleneterephthalate (PET) bottles was investigated using several fatty-food simulants such as olive oil, soybean oil, n-heptane and iso-octane, at exposure conditions of 2-10 days at 40 degrees C (total immersion). The stability of several UV stabilizers (BHT, Cyasorb UV 5411, Tinuvin P, Tinuvin 326 and Tinuvin 327) in n-heptane and iso-octane was also studied. After 10 days at 40 degrees C, losses of 6% and 20% in iso-octane and n-heptane respectively, were verified for Tinuvin P. Other UV stabilizers at the same experimental conditions showed higher losses (up to 30% for Tinuvin 327). These results confirm that, when carrying out specific migration studies, the stability of the substance of interest should be established in the food simulant to avoid underestimating the real migration behaviour. In order to quantify UV stabilizer migration, n-heptane and iso-octane solutions were concentrated and directly analysed by SIM mode GC-MS. For olive and soybean oils, Tinuvin P was isolated using size-exclusion chromatography and quantified by SIM mode GC-MS. Iso-octane proved to be a move suitable fatty-food simulant than n-heptane for the migration study of Tinuvin P from PET. Higher levels of Tinuvin P migrated to olive and soybean oils rather than to n-heptane. These results suggest that the MERCOSUL recommended official methods for specific migration studies should be revised since the migration levels using n-heptane as a fatty-food simulant could be underestimated when compared to edible oils. Copyright (C) 1999 John Wiley & Sons, Ltd.

Effect of Gamma Irradiation on Caprolactam Migration from Multi layer Polyamide 6 Films into Food Simulants: Development and Validation of a Gas Chromatographic Method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise sísmica usando transformada de Curvelet

Oil prospecting is one of most complex and important features of oil industry Direct prospecting methods like drilling well logs are very expensive, in consequence indirect methods are preferred. Among the indirect prospecting techniques the seismic imaging is a relevant method. Seismic method is based on artificial seismic waves that are generated, go through the geologic medium suffering diffraction and reflexion and return to the surface where they are recorded and analyzed to construct seismograms. However, the seismogram contains not only actual geologic information, but also noise, and one of the main components of the noise is the ground roll. Noise attenuation is essential for a good geologic interpretation of the seismogram. It is common to study seismograms by using time-frequency transformations that map the seismic signal into a frequency space where it is easier to remove or attenuate noise. After that, data is reconstructed in the original space in such a way that geologic structures are shown in more detail. In addition, the curvelet transform is a new and effective spectral transformation that have been used in the analysis of complex data. In this work, we employ the curvelet transform to represent geologic data using basis functions that are directional in space. This particular basis can represent more effectively two dimensional objects with contours and lines. The curvelet analysis maps real space into frequencies scales and angular sectors in such way that we can distinguish in detail the sub-spaces where is the noise and remove the coefficients corresponding to the undesired data. In this work we develop and apply the denoising analysis to remove the ground roll of seismograms. We apply this technique to a artificial seismogram and to a real one. In both cases we obtain a good noise attenuation

Comportamento e ecologia acústica da baleia jubarte (Megaptera novaeangliae) na região Nordeste do Brasil

The acoustic ecology concept involve the relation between the live organisms and their sound environment and is applied in the present work to study the context in which the humpback whale (Megaptera novaeangliae) singing behavior, known as the most complex display in the nature, occurred in the northeastern Brazilian coast, outside the core area of Abrolhos Bank, between 2005 and 2010.I analyze the singer male occurrence , their spatial distribution and probable relations with oceanographic features, such as depth, tide regimen and moon phases. I also describe the acoustic structure and temporal variation of the singing behavior, based on song frequency and time measurements outside the Abrolhos Bank, and further compare the song complexity, registered in the same period, between Abrolhos Bank (16°- 19° S, 37°- 39° W) and the adjacent North Coast, herein considered from Itacaré (14° S, 38° W) to Aracaju (11° S, 37° W). Additionally, I look for describe and analyze anthropogenic noise sources in the marine environment of the study area, produced by the oil industry as well as by the whale watching operation, relating their frequencies to the acoustic niche utilized by the humpbacks. The results indicated a great plasticity in the singing behavior, evidenced by the occurrence of singer males in diverse social structures, from solitary individuals to other groups, even containing females and calves, as well as by the diversity which compound the song, when compared between two regions inside the same breeding area, which present distinct oceanographic characteristics. The singer male distribution may be related with the continental shelf extent along the study area. The anthropogenic noise presented frequency range, amplitude and sound intensity in potential to interfere acoustically in the singing behavior of the species, may resulting in disturbance during the breeding season in the Brazilian coast. Implications about the obtained results in the humpback whale mating system are discussed. In this way, I pretend to contribute with the acoustic ecology subject and provide information to subsidize humpback whale conservation

Viscosity measurement of Newtonian liquids using the complex reflection coefficient

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterização e aplicação de sistemas micelares e microemulsionados como inibidores de corrosão

Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers

Tratamento eletroquímico de água produzida sintética para remoção de hidrocarbonetos policíclicos aromáticos

The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive