Estudo da influência de compostos recalcitrantes na remoção de matéria orgânica biodegradável no tratamento de efluente de refinarias de petróleo

Petroleum Refinery wastewaters (PRW) have hart-to-degrade compounds, such as: phenols, ammonia, cyanides, sulfides, oils and greases and the mono and polynuclear aromatic hydrocarbons: benzene, toluene and xylene (BTX), acenaphthene, nitrobenzene and naphtalene. It is known that the microrganisms activity can be reduced in the presence of certain substances, adversely affecting the biological process of wastewater treatment. This research was instigated due the small number of studies regarding to this specific topic in the avaiable literature. This body of work ims to evaluate the effect of toxic substances on the biodegradability of the organic material found in PRW. Glucose was chosen as the model substrate due to its biodegradable nature. This study was divided into three parts: i) a survey of recalcitants compounds and the removal of phenol by using both biological and photochemical-biological processes; ii) biomass aclimation and iii) evaluation of the inhibitory effect certain compounds have on glucose biodegradation. The phenol degradation experiments were carried out in an activity sludge system and in a photochemical reactor. The results showed the photochemical-biological process to be more effective on phenol degradation, suggesting the superioruty of a combined photochemical-biological treatment when compared with a simple biological process for phenol removal from industry wastewaters. For the acclimation step, was used an activated sludge from industrial wastewaters. A rapid biomass aclimation to a synthetic solution composed of the main inhibitory compouns fpund in a PRW was obtained using the following operation condition: (pH = 7,0; DO ≥ 2,0 mg/L; RS = 20 days e qH = 31,2 and 20,4 hours), The last part was consisted of using respirometry evaluation toxicity effects of selected compounds over oxygen uptake rate to adaptated and non adaptated biomass in the presence of inhibitory compounds. The adaptated sludge showed greater degration capacity, with lower sensibility to toxic effects. The respirometry has proved to be very practical, as the techiniques used were simple and rapid, such as: Chemical Oxygen Demand (COD), Dissolved Oxygen (DO), and Volatile Suspended Solids (VSS). Using the latter it is possible to perform sludge selection to beggingthe process; thus allowing its use for aerobic treatment system`s behacior prediction

Avaliação do comportamento de fluidos micelares na recuperação avançada de petróleo

In heavy oil fields there is a great difficulty of the oil to flow from the reservoir to the well, making its production more difficult and with high cost. Most of the original volumes of oil found in the world are considered unrecoverable by the use of the current methods. The injection of micellar solutions has a direct action in the oil interfacial properties, resulting in an enhanced oil recovery. The objective of this research was the study and selection of micellar solutions with ability to decrease the interfacial interactions between fluids and reservoir formation, increasing oil production. The selected micellar solutions were obtained using commercial surfactants and surfactants synthesized in laboratory, based on the intrinsic properties of these molecules, to use in the enhanced oil recovery. Petroleum Reservoirs were simulated using sandstone plugs from Botucatu formation. Experiments with conventional and enhanced oil recovery techniques were accomplished. The obtained results showed that all micellar solutions were able to enhance oil recovery, and the micellar solution prepared with a SB anionic surfactant, at 2% KCl solution, showed the best recovery factor. It was also accomplished an economic analysis with the SB surfactant solution. With the injection of 20% porous volume of micellar solution, followed by brine injection, the increment in petroleum recovery can reach 81% recovery factor in the 3rd porous volume injected. The increment in the total cost by the addition of surfactant to the injection water represents R$ 7.50/ton of injected fluid

Desenvolvimento de tensoativos e sistemas microemulsionados para recuperação de petróleo

The high concentration of residual oil is one of the greatest problems found in petroleum mature fields. In these reservoirs, different enhanced oil recovery methods (EOR) can be used, highlighting the microemulsion injection. The microemulsion has showed to be efficient in petroleum recovery due to its ability to promote an efficient displacement of the petroleum, acting directly in the residual oil. In this way, this research has as objective the study of microemulsion systems obtained using a commercial surfactant (TP), determining microemulsion thermal stabilities and selecting points inside the pseudoternary phases diagram, evaluating its efficiencies and choosing the best system, that has the following composition: TP as surfactant (S), isopropyl alcohol as co-surfactant (C), kerosene as oil phase, water as aqueous phase, C/S ratio = 1, and 5% sodium p-toluenesulfonate as hydrotope; being observed the following parameters for the selection of the best pseudoternary phases diagram: C/S ratio, co-surfactant nature and addition of hydrotope to the system. The efficiency in petroleum recovery was obtained using two sandstone formation systems: Assu and Botucatu. The study of thermal stabilities showed that as the concentration of active matter in the system increased, the thermal stability also increased. The best thermal stability was obtained using point F (79.56 0C). The system that presented the best recovery percentile between the three selected (3) was composed by: 70% C/S, 2% kerosene and 28% water, with 94% of total recovery efficiency and 60% with microemulsion injection, using the Botucatu formation, that in a general way presented greater efficiencies as compared with the Assu one (81.3% of total recovery efficiency and 38.3% with microemulsion injection)

Estudo da viabilidade da destilação solar para polimento de águas produzidas de petróleo

This work study of solar distillation feasibility in effluent of petroleum industry: produced water, making possible your reuse for irrigation of oleaginous cultures or fodder crops or in steam generation, as well the transport phenomena involved. The methodology for development of this project was to characterize the effluent to be treated and to accomplish physical and chemical analysis in the distilled, to build distillation equipment, concomitant operation of both equipments and implementation of data processing and economical evaluation. The methodology used for all parameters is outlined in APHA (1998) and sampling of the type compound. The feeding of distillation equipment was performed with treated effluent from UTPF of Guamaré. The temperature was monitored throughout the distillers and during the time of operation. The distillers feed occur, as a rule, for sifon. The distillers were operated by a period of 17 months between July 2007 and February 2009, in which 40 experiments were performed. The radiation and temperature datas were acquired in the INPE s site and the temperature inside of the distillers was registered by DATALOGGER Novus. The rates of condensation (mL / min) were determined by measuring of the flow in a graduate test tube of 10 mL and a chronometer. We used two simple solar effect distillers of passive type with different angles in coverage: 20 ° and 45 °. The results obtained in this study and the relevant discussions are divided into six topics: sample characterization and quality of distilled; construction of distillers; operation (data, temperature profile), climatic aspects, treatment of data and economical analysis. Results obtained can be inferred that: the energy loss by the adoption of vessel glass was not significant, however, complicates the logistics of maintenance the equipment on a large scale. In the other hand, the surface of the tub with a glass shield on the equipment deterioration, both devices showed similar performance, so there is not justified for use of equipment 450. With regard to the climatological study it was verified that the Natal city presents monthly medium radiation varying in a range between 350 and 600 W/m2, and medium of wind speed of 5 m / s. The medium humidity is around 70% and rainfall is very small. The regime of the system is transient and although it has been treated as a stationary system shows that the model accurately represents the distillers system's 20 degrees. The quality of the distilled with regard to the parameters evaluated in this study is consistent with the Class 3 waters of CONAMA (Resolution 357). Therefore we can conclude that solar distillation has viability for treat oilfield produced water when considered the technical and environmental aspects, although it is not economically viable

Avaliação de diferentes processos oxidativos avançados no tratamento de resíduos de petróleo

The petroleum industry deals with problems which are difficult to solve because of their relation to environmental issues. This is because amounts of residue are generated which vary in type and danger level. The soil contamination by non aqueous liquid phase mixtures, specifically hydrocarbon petroleum has been a reason for great concern, mainly the aromatic and polycyclic aromatic, which present risk to human health due to its carcinogenic and mutagenic character. The Advanced Oxidative Processes (AOP) are efficient technologies for destruction of organic compounds of difficult degradation and, often, they are present in low concentrations. They can be considered clean technologies, because there is no formation of solid by-products or the transfer of pollutor phases. This work focuses on the study of the degradation of petroleum industrial waste, by Advanced Oxidation Processes. Treatments tackling petroleum residues, contaminated soil, and water occurring in the production of petroleum reached the following Polycyclic Aromatic Hydrocarbons (PAH) degradation levels: solid residues 100% in 96 treatment hours; water residue - 100% in 6 treatment hours; soil contamination (COT degradation) - 50.3% in 12 treatment hours. AOP were effective in dealing with petroleum residues thus revealing themselves to be a promising treatment alternative

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

Estudo da remoção de Ba2+, Ni2+, Cd2+, Cu3+, Cr3+, Sr2+, Zn2+ por eletrocoagulação em água associada à produção de petróleo

Among the waste generated in the petrochemical industry water associated with oil production is the most important. It is considered one of the great challenges due to the presence of considered toxic chemicals present in this composition. The presence of these substances difficult to reuse the water associated with the enhanced recovery processes, so that prior to their reuse or disposal, treatment is necessary. This paper aimed to study the removal efficiency of chemical species: Ba2+, Ni2+, Cd2+, Cu2+, Cr3+, Sr2+ and Zn2+, present in the composition of the water associated with oil production by electrocoagulation. The evaluation of removal of these chemical species was performed by laboratory tests using electrochemical batch reactors and continuous flow. Initial tests were performed with electrocoagulation of synthetic wastewater in batch reactor using iron electrode. Results of removal of Zn2+ and Ni2+ were 78 % and 59 % respectively. While the percentage of removed Ba2+ was 19 % by 30 minutes of treatment and by applying current of 1.10 A. The tests were performed on effluent batch reactor applying the electrochemical technique with stainless steel electrodes 304, the objective was to remove part of the dispersed oil and also of organic compounds in the effluent. Under the experimental conditions used, the maximum result was obtained TOG was 60 % and TOC was approximately 50 % compared to the initial concentration. In the experiments carried out in continuous reactor, with effluent semisynthetic, have been used electrodes of iron and aluminum and the results were 100 % removal of Cd2+, Cu2+, Cr3+ and Zn2+ and 77 % of Sr2+. These percentages were only attainable through the use of the iron electrode. However, when the electrode was replaced by aluminum, there was a reduction in the percentage of removal to 65 %, using the same flow rate and current. Therefore according to the results obtained using the iron electrode was more effective in removing these metals and the conditions of lower current and lower flow rate was satisfactory, as observed in the experimental design adopted

Integração dos processos de flotação e foto-fenton para redução de óleos e graxas de água produzida em campos de petróleo

During production of oil and gas, there is also the production of an aqueous effluent called produced water. This byproduct has in its composition salts, organic compounds, gases and heavy metals. This research aimed to evaluate the integration of processes Induced Air Flotation (IAF) and photo-Fenton for reducing the Total Oils and Greases (TOG) present in produced water. Experiments were performed with synthetic wastewater prepared from the dispersion of crude oil in saline solution. The system was stirred for 25 min at 33,000 rpm and then allowed to stand for 50 min to allow free oil separation. The initial oil concentration in synthetic wastewater was 300 ppm and 35 ppm for the flotation and the photo-Fenton steps, respectively. These values of initial oil concentration were established based on average values of primary processing units in Potiguar Basin. The processes were studied individually and then the integration was performed considering the best experimental conditions found in each individual step. The separation by flotation showed high removal rate of oil with first-order kinetic behavior. The flotation kinetics was dependent on both the concentration and the hydrophilic-lipophilic balance (HLB) of the surfactant. The best result was obtained for the concentration of 4.06.10-3 mM (k = 0.7719 min-1) of surfactant EO 2, which represents 86% of reduction in TOG after 4 min. For series of surfactants evaluated, the separation efficiency was found to be improved by the use of surfactants with low HLB. Regarding the TOG reduction step by photo-Fenton, the largest oil removal reached was 84% after 45 min of reaction, using 0.44 mM and 10 mM of ferrous ions and hydrogen peroxide, respectively. The best experimental conditions encountered in the integrated process was 10 min of flotation followed by 45 min of photo-Fenton with overall TOG reduction of 99%, which represents 5 ppm of TOG in the treated effluent. The integration of processes flotation and photo-Fenton proved to be highly effective in reducing TOG of produced water in oilfields

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

Tratamento de água de produção de petróleo visando o aproveitamento na obtenção de barrilha

The petroleum production is associated to the produced water, which has dispersed and dissolved materials that damage not only the environment, but also the petroleum processing units. This study aims at the treatment of produced water focusing mainly on the removal of metals and oil and using this treated water as raw material for the production of sodium carbonate. Initially, it was addressed the removal of the following divalent metals: calcium, magnesium, barium, zinc, copper, iron, and cadmium. For this purpose, surfactants derived from vegetable oils, such as coconut oil, soybean oil, and sunflower oil, were used. The investigation showed that there is a stoichiometric relationship between the metals removed from the produced water and the surfactants used in the process of metals removal. It was also developed a model that correlates the hydrolysis constant of saponified coconut oil with the metal distribution between the resulting stages of the proposed process, flocs and aqueous phases, and relating the results with the pH of the medium. The correlation coefficient obtained was 0.963. Next, the process of producing washing soda (prefiro soda ahs ou sodium carbonate) started. The resulting water from the various treatment approaches from petroleum production water was used. During this stage of the research, it was observed that the surfactant assisted in the produced water treatment, by removing some metals and the dispersed oil entirety. The yield of sodium carbonate production was approximately 80%, and its purity was around 95%. It was also assessed, in the production of sodium carbonate, the influence of the type of reactor, using a continuous reactor and a batch reactor. These tests showed that the process with continuous reactor was not as efficient as the batch process. In general, it can be concluded that the production of sodium carbonate from water of oil production is a feasible process, rendering an effluent that causes a great environmental impact a raw material with large scale industrial use

Exploração de fatores de risco para lesões no atletismo de alta performance

Os fatores de risco para instalação de lesões do esporte têm sido pesquisados no sentido de facilitar o entendimento sobre o assunto. Contudo, para altos níveis de performance, nos eventos de pista e campo do atletismo, são escassos os documentos que abordam o tema. Assim, a partir da possibilidade de reunir informações sobre a condição descrita, objetivou-se com o presente estudo a exploração de fatores de risco para lesões desportivas no atletismo, a partir de inquérito aplicado a atletas da elite mundial da modalidade. A população foi composta por 60 homens e 60 mulheres alocados em grupos conforme a especificidade de sua modalidade (velocidade, resistência, arremessos e saltos). Realizou-se entrevista utilizando-se de inquérito de morbidade referida, abordando questões sobre variáveis antropométricas e de treinamento, assim como lesões. Utilizou-se a técnica da análise de variância paramétrica para as variáveis antropométricas (idade, peso, estatura) e da técnica da análise de variância não paramétrica em relação às variáveis de treinamento (anos de treinamento e horas semanais). Para associação entre momento de lesão e especialidades, utilizou-se do teste de Goodman em nível de 5% de significância. Os resultados mostraram que houve elevada freqüência de lesões na modalidade em ambos os sexos. As taxas de lesão por atleta entrevistado foram de 0,92 (velocidade), 1,08 (resistência), 1,22 (saltos) e 1,20 (arremessos). Não houve diferença estatisticamente significante para as variáveis antropométricas e de treinamento em relação às provas, com exceção dos saltadores, que apresentaram diferenças para estatura e tempo de treinamento; nesse caso, os acometidos são mais altos ou praticam atletismo há menos tempo (P < 0,05). Concluiu-se que, para população estudada, o risco de lesão é acentuado, mas sem relação entre variáveis e presença de agravos, salvo para especialistas em provas de saltos, que apresentaram estatura e tempo de treinamento como fatores predisponentes à lesão.

Análise estatística de padrões sísmicos: decomposição em multiescala

O processamento de registros sísmicos é uma tarefa muito importante dentro da Geofísica e que representa um desafio permanente na exploração de petróleo. Embora esses sinais forneçam uma imagem adequada da estrutura geológica do subsolo, eles são contaminados por ruídos e, o ground roll é a componente principal. Este fato exige um esforço grande para o desenvolvimento de metodologias para filtragem, Dentro desse contexto, este trabalho tem como objetivo apresentar um método de remoção do ruído ground roll fazendo uso de ferramentas da Física Estatística. No método, a Análise em Ondeletas é combinada com a Transformada de Karhunen-Loève para a remoção em uma região bem localizada. O processo de filtragem começa com a Decomposição em Multiescala. Essa técnica permite uma representação em tempo-escala fazendo uso das ondeletas discretas implementadas a filtros de reconstrução perfeita. O padrão sísmico original fica representado em multipadrões: um por escala. Assim, pode-se atenuar o ground roll como uma operação cirúrgica em cada escala, somente na região onde sua presença é forte, permitindo preservar o máximo de informações relevantes. A atenuação é realizada pela definição de um fator de atenuação Af. Sua escolha é feita pelo comportamento dos modos de energia da Transformada de Karhunen-Loève. O ponto correspondendo a um mínimo de energia do primeiro modo é identificado como um fator de atenuação ótimo

Aplicações da teoria da percolação à modelagem e simulação de reservatórios de petróleo

In this thesis we study some problems related to petroleum reservoirs using methods and concepts of Statistical Physics. The thesis could be divided percolation problem in random multifractal support motivated by its potential application in modelling oil reservoirs. We develped an heterogeneous and anisotropic grid that followin two parts. The first one introduce a study of the percolations a random multifractal distribution of its sites. After, we determine the percolation threshold for this grid, the fractal dimension of the percolating cluster and the critical exponents ß and v. In the second part, we propose an alternative systematic of modelling and simulating oil reservoirs. We introduce a statistical model based in a stochastic formulation do Darcy Law. In this model, the distribution of permeabilities is localy equivalent to the basic model of bond percolation

Fractais e Percolação na Recuperação de Petróleo

The complex behavior of a wide variety of phenomena that are of interest to physicists, chemists, and engineers has been quantitatively characterized by using the ideas of fractal and multifractal distributions, which correspond in a unique way to the geometrical shape and dynamical properties of the systems under study. In this thesis we present the Space of Fractals and the methods of Hausdorff-Besicovitch, box-counting and Scaling to calculate the fractal dimension of a set. In this Thesis we investigate also percolation phenomena in multifractal objects that are built in a simple way. The central object of our analysis is a multifractal object that we call Qmf . In these objects the multifractality comes directly from the geometric tiling. We identify some differences between percolation in the proposed multifractals and in a regular lattice. There are basically two sources of these differences. The first is related to the coordination number, c, which changes along the multifractal. The second comes from the way the weight of each cell in the multifractal affects the percolation cluster. We use many samples of finite size lattices and draw the histogram of percolating lattices against site occupation probability p. Depending on a parameter, ρ, characterizing the multifractal and the lattice size, L, the histogram can have two peaks. We observe that the probability of occupation at the percolation threshold, pc, for the multifractal is lower than that for the square lattice. We compute the fractal dimension of the percolating cluster and the critical exponent β. Despite the topological differences, we find that the percolation in a multifractal support is in the same universality class as standard percolation. The area and the number of neighbors of the blocks of Qmf show a non-trivial behavior. A general view of the object Qmf shows an anisotropy. The value of pc is a function of ρ which is related to its anisotropy. We investigate the relation between pc and the average number of neighbors of the blocks as well as the anisotropy of Qmf. In this Thesis we study likewise the distribution of shortest paths in percolation systems at the percolation threshold in two dimensions (2D). We study paths from one given point to multiple other points