Remoção conjugada de metais e óleo de água produzida

Petroleum can be associated or not with natural gas, but in both cases water is always present in its formation. The presence of water causes several problems, such as the difficulty of removing the petroleum from the reservoir rock and the formation of waterin-oil and oil-in-water emulsions. The produced water causes environmental problems, which should be solved to reduce the effect of petroleum industry in the environment. The main objective of this work is to remove simultaneously from the produced water the dispersed petroleum and dissolved metals. The process is made possible through the use of anionic surfactants that with its hydrophilic heads interacts with ionized metals and with its lipophilic tails interacts with the oil. The studied metals were: calcium, magnesium, barium, and cadmium. The surfactants used in this research were derived from: soy oil, sunflower oil, coconut oil, and a soap obtained from a mixture of 5wt.% coconut oil and 95wt.% animal fat. It was used a sample of produced water from Terminal de São Sebastião, São Paulo. As the concentration of the studied metals in produced water presented values close to 300 mg/L, it was decided to use this concentration as reference for the development of this research. Molecular absorption and atomic absorption spectroscopy were used to determine petroleum and metals concentrations in the water sample, respectively. A constant pressure filtration system was used to promote the separation of solid and liquid phases. To represent the behavior of the studied systems it was developed an equilibrium model and a mathematical one. The obtained results showed that all used surfactants presented similar behavior with relation to metals extraction, being selected the surfactant derived from soy oil for this purpose. The values of the partition coefficients between the solid and liquid phases " D " for the studied metals varied from 0.2 to 1.1, while the coefficients for equilibrium model " K " varied from 0.0002 and 0.0009. The removal percentile for oil with all metals associated was near 100%, showing the efficiency of the process

Extração e pirólise do óleo de girassol (Helianthus annus l.) visando a produção de biocombustíveis

Nowadays, the growing environmental worry leads research the focus the application of alternative materials from renewable resources on the industrial process. The most common vegetable oil extractant using around the world is the hexane, a petroleum derived, toxic and flammable. Based on this fact, the goal of this work was to test vegetable oil extractions from sunflower seeds cultivated on the Rio Grande do Norte State using two extraction process, the mechanical expelling and solvent extraction, this one using hexane and ethanol as a alternative solvent. The solvent extractions were carried out in the Soxhlet extractor in three different extraction times (4, 6, and 8 hours). The effect of solvent and extraction time was evaluated. The mechanical extraction was carried out in a expeller and the sunflower oil obtained was characterized by its physical-chemical properties and compared with sunflower refinery oil. Furthermore this work also explored the pyrolysis reaction carried out by thermogravimetry measurement as alternative route to obtain biofuel. For this purpose the oil samples were heated to ambient temperature until 900°C in heating rate of 5, 10, 20ºC min-1 with the objective evaluated the kinetics parameters such activation energy and isoconversion. The TG/DTG curves show the thermal profile decomposition of triglycerides. The curves also showed that antioxidant presents on the refinery oil not influence on the thermal stability of sunflower oil. The total yield of the extraction s process with hexane and ethanol solvent were compared, and the results indicated that the extraction with ethanol were more efficient. The pyrolysis reaction results indicated that the use of unpurified oil required less energy to obtain the bio-oil

Otimização da injeção cíclica de vapor em reservatório de óleo pesado

Thermal methods made heavy oil production possible in fields where primary recovery failed. Throughout the years steam injection became one of the most important alternatives to increase heavy oil recovery. There are many types of steam injection, and one of them is the cyclic steam injection, which has been used with success in several countries, including Brazil. The process involves three phases: firstly, steam is injected, inside of the producing well; secondly, the well is closed (soak period); and finally, the well is put back into production. These steps constitute one cycle. The cycle is repeated several times until economical production limit is reached. Usually, independent of reservoir type, as the number of cycles increases the cyclic injection turns less efficient. This work aims to analyze rock and reservoir property influence in the cyclic steam injection. The objective was to study the ideal number of cycles and, consequently, process optimization. Simulations were realized using the STARS simulator from the CMG group based in a proposed reservoir model. It was observed that the reservoir thickness was the most important parameter in the process performance, whilst soaking time influence was not significant

Caracterização de água produzida na indústria de petróleo para fins de descarte e otimização do processo de separação óleo/água

The oil industry has several segments that can impact the environment. Among these, produced water which has been highlight in the environmental problem because of the great volume generated and its toxic composition. Those waters are the major source of waste in the oil industry. The composition of the produced water is strongly dependent on the production field. A good example is the wastewater produced on a Petrobras operating unit of Rio Grande do Norte and Ceará (UO-RNCE). A single effluent treatment station (ETS) of this unit receives effluent from 48 wells (onshore and offshore), which leads a large fluctuations in the water quality that can become a complicating factor for future treatment processes. The present work aims to realize a diagnosis of a sample of produced water from the OU - RNCE in compliance to certain physical and physico-chemical parameters (chloride concentration, conductivity, dissolved oxygen, pH, TOG (oil & grease), nitrate concentration, turbidity, salinity and temperature). The analysis of the effluent is accomplished by means of a MP TROLL 9500 Multiparameter probe, a TOG/TPH Infracal from Wilks Enterprise Corp. - Model HATR - T (TOG) and a MD-31 condutivimeter of Digimed. Results were analyzed by univariated and multivariated analysis (principal component analysis) associated statistical control charts. The multivariate analysis showed a negative correlation between dissolved oxygen and turbidity (-0.55) and positive correlations between salinity and chloride (1), conductivity, chloride and salinity (0.70). Multivariated analysis showed there are seven principal components which can explain the variability of the parameters. The variables, salinity, conductivity and chloride were the most important variables, with, higher sampling variance. Statistical control charts have helped to establish a general trend between the physical and chemical evaluated parameters

Remediação de solos contaminados com óleo diesel utilizando um sistema de lavagem com microemulsão

The underground reservoirs of fuel retailing system represent an environmental threat, because once in bad conservation, these tanks allow fuel leakage and infiltration. For soil contaminated with fuel, such as diesel oil, the present study introduces the microemulsion systems used by the method of washing. In tests carried out in column with a sample of sandy soil artificially contaminated and previously characterized as to its void level to porosity, to permeability which is an important parameter concerning the study of the method of washing. While microemulsions were characterized for their viscosity and wettability, a variation of active matter was also done departing from the original formulation. The hydraulic diffusivity of the microemulsion was studied so as the injection of such fluid in a soil with sandy characteristics. The results of the extractions revealed the excellent performance of these systems which get to remove around 95% of diesel fuel. This proves the efficiency of the microemulsion in the process of removal of diesel fuel from the soil with the advantage of being a system easily obtainable and less aggressive to the environment when compared to organic solvents.

Modelagem da transferência de massa na remoção do óleo da água produzida por flotação em coluna com uso de tensoativos de origem vegetal

The treatment of oil produced water and its implications are continually under investigation and several questions are related to this subject. In the Northeast Region Brazil, the onshore reservoirs are, in its majority, mature oil fields with high production of water. As this oil produced water has high levels of oil, it cannot be directly discarded into the environment because it represents a risk for contamination of soil, water, and groundwater, or even may cause harm to living bodies. Currently, polyelectrolytes that promote the coalescence of the oil droplets are used to remove the dispersed oil phase, enhancing the effectiveness of the flotation process. The non-biodegradability and high cost of polyelectrolytes are limiting factors for its application. On this context, it is necessary to develop studies for the search of more environmentally friendly products to apply in the flotation process. In this work it is proposed the modeling of the flotation process, in a glass column, using surfactants derived from vegetal oils to replace the polyelectrolytes, as well as to obtain a model that represents the experimental data. In addition, it was made a comparative study between the models described in the literature and the one developed in this research. The obtained results showed that the developed model presented high correlation coefficients when fitting the experimental data (R2 > 0.98), thus proving its efficiency in modeling the experimental data.

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

Extração enzimática de óleo e produção in situ de biodiesel a partir da Moringa oleífera Lam

With the growth and development of modern society, arises the need to search for new raw materials and new technologies which present the "clean" characteristic, and do not harm the environment, but can join the energy needs of industry and transportation. The Moringa oleifera Lam, plant originating from India, and currently present in the Brazilian Northeast, presents itself as a multi-purpose plant, can be used as a coagulant in water treatment, as a natural remedy and as a feedstock for biodiesel production. In this work, Moringa has been used as a raw material for studies on the extraction and subsequently in the synthesis of biodiesel. Studies have been conducted on various techniques of Moringa oil extraction (solvents, mechanical pressing and enzymatic), being specially developed an experimental design for the aqueous extraction with the aid of the enzyme Neutrase© 0.8 L, with the aim of analyzing the influence variable pH (5.5-7.5), temperature (45-55°C), time (16-24 hours) and amount of catalyst (2-5%) on the extraction yield. In relation to study of the synthesis of biodiesel was initially carried out a conventional transesterification (50°C, KOH as a catalyst, methanol and 60 minutes reaction). Next, a study was conducted using the technique of in situ transesterification by using an experimental design variables as temperature (30-60°C), catalyst amount (2-5%), and molar ratio oil / ethanol (1:420-1:600). The extraction technique that achieved the highest extraction yield (35%) was the one that used hexane as a solvent. The extraction using 32% ethanol obtained by mechanical pressing and extraction reached 25% yield. For the enzymatic extraction, the experimental design indicated that the extraction yield was most affected by the effect of the combination of temperature and time. The maximum yield obtained in this extraction was 16%. After the step of obtaining the oil was accomplished the synthesis of biodiesel by the conventional method and the in situ technique. The method of conventional transesterification was obtained a content of 100% and esters by in situ technique was also obtained in 100% in the experimental point 7, with a molar ratio oil / alcohol 1:420, Temperature 60°C in 5% weight KOH with the reaction time of 1.5 h. By the experimental design, it was found that the variable that most influenced the ester content was late the percentage of catalyst. By physico-chemical analysis it was observed that the biodiesel produced by the in situ method fell within the rules of the ANP, therefore this technique feasible, because does not require the preliminary stage of oil extraction and achieves high levels of esters

Preparo de amostras e métodos para a determinação do teor de óleo essencial de frutos de limoeiro

Objetivou-se avaliar alternativas de preparo da amostra e os métodos quantitativos para a determinação do teor de óleo em frutos de limão. Os tratamentos foram avaliados por meio do delineamento estatístico inteiramente casualizado, em esquema fatorial 2x2x6, com quatro repetições, sendo duas variedades-copa de limoeiro verdadeiro ('Siciliano' e 'Eureka'), dois métodos analíticos para a determinação do teor de óleo (Scott e Clevenger) e seis formas de preparo dos frutos para análise (análise do fruto inteiro; frutos cortados na longitudinal e análise de ¼; frutos cortados na longitudinal e análise de ¹/2; frutos cortados ao meio e análise da parte superior; frutos cortados ao meio e análise da parte inferior; e análise de ²/8 do fruto). O método denominado de Clevenger foi o mais eficiente na determinação do teor de óleo essencial, e as formas de preparo de amostras ½ inferior, ½ superior, ¼ longitudinal e ½ longitudinal dos frutos proporcionaram valores superiores de óleo essencial.

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

Preparação de poliuretana à base de óleo de mamona

Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction

Comparação entre planejamento estatístico experimental e análise dimensional em operações de mistura e separação para sistema óleo-água

This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador à Inversão de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design® (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU

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.

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Estudo da circulação hidrodinâmica e da dispersão de óleo na zona costeira entre Macau e Galinhos RN

This paper presents a study on coastal hydrodynamics and the spread of an oil spill in waters off Macau and Galinhos, on the east coast of the state of Rio Grande do Norte in Northeast Brazil. This area has a very marked coastal dynamic owing to the complexity of its geomorphological features, developed in a regime of semidiurnal mesotides involving reefs, spits, estuaries, mangroves, lakes and dunes. The region also plays an important role in the socioeconomic development of the state, given that the production of oil, natural gas, salt and shrimp is concentrated there. The series of oil platforms is interconnected by a pipeline system that carries oil to the local terminal. This pipeline could leak at any moment, causing immense ecological damage. To gauge the risks of an oil leak and resulting contamination of the coastal region, two hydrodynamic scenarios were simulated. The results obtained were used to implement a contaminant transport model with the creation of various oil leak scenarios modeled at different volumes (from small to large) and intensities (sporadic and continuous), at points considered critical for the model (on two platforms and at two pipeline intersections), under different wind (summer and winter) and tidal (high and low at new, full and quarter moon phases) conditions. The use of hydrodynamic circulation computer models as a tool for representing a real project design has been increasingly frequent in recent years, given that they enable the realistic simulation of the hydrodynamic circulation pattern in bodies of water and an analysis of the impacts caused by contaminants released into the water. This study used the computer models contained in SisBAHIA®, in continuous development in the area of Coastal Engineering and Oceanography at COPPE/UFRJ