Extração de boro de água produzida sintética por sistema microemulsionado

Boron is a semi-metal present in certain types of soils and natural waters. It is essential to the healthy development of plants and non-toxic to humans, depending on its concentration. It is used in various industries and it s present in water production coming from oil production. More specifically in Rio Grande do Norte, one of the largest oil producers on shore of Brazil, the relationship water/oil in some fields becomes more than 90%. The most common destination of this produced water is disposal in open sea after processing to meet the legal specification. In this context, this research proposes to study the extraction of boron in water produced by microemulsion systems for industrial utilization. It was taken into account the efficiency of extraction of boron related to surfactant (DDA and OCS, both characterized by FT-IR), cosurfactant (butanol and isoamyl alcohol), organic phase (kerosene and heptanes) and aqueous phase (solution of boron 3.6 ppm in alkaline pH). The ratio cosurfactant/ surfactant used was four and the percentage of organic phases for all points of study was set at 5%. It was chosen points with the highest percentage of aqueous phase. Each system was designed for three points of different compositions in relation to the constituents of a pseudoternary diagram. These points were chosen according to studies of phase behavior in pseudoternary diagrams made in previous studies. For this research, points were chosen in the Winsor II region. The excess aqueous solution obtained in these systems was separated and analyzed by ICP OES. For the data set obtained, the better efficiency in the extraction of boron was obtained using the system with DAC, isoamyl alcohol and heptanes, which extracted 49% in a single step. OCS was not viable to the extraction of boron by microemulsion system in the conditions defined in this study

Estudos hidroquímicos da água produzida de um determinado campo de petróleo da bacia potiguar

Waste generated during the exploration and production of oil, water stands out due to various factors including the volume generated, the salt content, the presence of oil and chemicals and the water associated with oil is called produced water. The chemical composition of water is complex and depends strongly on the field generator, because it was in contact with the geological formation for thousands of years. This work aims to characterize the hydrochemical water produced in different areas of a field located in the Potiguar Basin. We collected 27 samples from 06 zones (400, 600, 400/600, 400/450/500, 350/400, A) the producing field called S and measured 50 required parameter divided between physical and chemical parameters, cations and anions. In hydrochemical characterization was used as tools of reasons ionic calculations, diagrams and they hydrochemical classification diagram Piper and Stiff diagram and also the statistic that helped in the identification of signature patterns for each production area including the area that supplies water injected this field for secondary oil recovery. The ionic balance error was calculated to assess the quality of the results of the analysis that was considered good, because 89% of the samples were below 5% error. Hydrochemical diagrams classified the waters as sodium chloride, with the exception of samples from Area A, from the injection well, which were classified as sodium bicarbonate. Through descriptive analysis and discriminant analysis was possible to obtain a function that differs chemically production areas, this function had a good hit rate of classification was 85%

Metodologias estatísticas aplicadas a dados de análises químicas da água produzida em um campo maduro de petróleo

Produced water is characterized as one of the most common wastes generated during exploration and production of oil. This work aims to develop methodologies based on comparative statistical processes of hydrogeochemical analysis of production zones in order to minimize types of high-cost interventions to perform identification test fluids - TIF. For the study, 27 samples were collected from five different production zones were measured a total of 50 chemical species. After the chemical analysis was applied the statistical data, using the R Statistical Software, version 2.11.1. Statistical analysis was performed in three steps. In the first stage, the objective was to investigate the behavior of chemical species under study in each area of production through the descriptive graphical analysis. The second step was to identify a function that classify production zones from each sample, using discriminant analysis. In the training stage, the rate of correct classification function of discriminant analysis was 85.19%. The next stage of processing of the data used for Principal Component Analysis, by reducing the number of variables obtained from the linear combination of chemical species, try to improve the discriminant function obtained in the second stage and increase the discrimination power of the data, but the result was not satisfactory. In Profile Analysis curves were obtained for each production area, based on the characteristics of the chemical species present in each zone. With this study it was possible to develop a method using hydrochemistry and statistical analysis that can be used to distinguish the water produced in mature fields of oil, so that it is possible to identify the zone of production that is contributing to the excessive elevation of the water volume.

Extração de metais (K, Mg, Ba, Ca, Cr, Mn, Li, Fe) de água produzida utilizando sistema microemulsionado

The produced water is a byproduct formed due to production of petroleum and carries with it a high amount of contaminants such as oil particles in suspension, organic compounds and metals. Thus, these latter pollutants are very difficult to treat because of its high solubility in water. The objective of this work is to use and evaluate a microemulsioned system to remove metals ( K , Mg , Ba , Ca , Cr , Mn , Li , Fe ) of synthetic produced water. For the extraction of metals, it was used a pseudoternary diagram containing the following phases: synthetic produced water as the aqueous phase (AP), hexane as organic phase (OP), and a cosurfactant/surfactant ratio equal to four (C/S = 4) as the third phase, where the OCS (saponified coconut oil) was used as surfactant and n-butanol as cosurfactant. The synthetic produced water was prepared in a bench scale and the region of interest in the diagram for the removal of metals was determined by experimental design called. Ten points located in the phase Winsor II were selected in an area with a large amount of water and small amounts of reagents. The samples were analyzed in atomic absorption spectrometer, and the results were evaluated through a statistical assesment, allowing the efficiency analysis of the effects and their interactions. The results showed percentages of extraction above 90% for the metals manganese, iron, chromium, calcium, barium and magnesium, and around 45% for metals lithium and potassium. The optimal point for the simultaneous removal of metals was calculated using statistical artifact multiple response function (MR). This calculation showed that the point of greatest extraction of metals occurs was the J point, with the composition [72% AP, 9% OP, 19% C/S], obtaining a global extraction percentage about 80%. Considering the aspects analyzed, the microemulsioned system has shown itself to be an effective alternative in the extraction of metals on synthetic produced water remediation

Aplicação de técnicas eletroquímicas na determinação do potencial de corrosividade de ligas de alumínio em água produzida

The resistance of aluminum and their alloys, to the corrosion phenomenon, in aqueous solutions, is a result of the oxide layer formed. However, the corrosion process in the aluminum alloy is associated with the presence a second phase of particles or the presence of chloride ions which promote the disruption of the oxide layer located producing the corrosion process. On the other hand, the term water produced is used to describe the water after the separation of the oil and gas in API separators. The volumes of produced water arrive around 5 more times to the volume of oil produced. The greatest feature of the water is the presence of numerous pollutants. Due to the increased volume of waste around the world in the current decade, the outcome and the effect of the discharge of produced water on the environment has recently become an important issue of environmental concern where numerous treatments are aimed at reducing these contaminants before disposal. Then, this study aims to investigate the electrochemical corrosion behavior of aluminum alloy 6060 in presence of water produced and the influence of organic components as well as chloride ions, by using the electrochemical techniques of linear polarization. The modification of the passive layer and the likely breakpoints were observed by atomic force microscopy (AFM). In the pit formation potential around -0.4 to -0.8 V/EAg/AgCl was observed that the diffusion of chloride ions occurs via the layer formed with the probable formation of pits. Whereas, at temperatures above 65 °C, it was observed that the range of potential for thepit formation was -0.4 to -0.5 V/EAg/AgCl. In all reactions, the concentration of Al(OH)3 in the form of a gel was observed

O princípio constitucional da eficiência aplicado à outorga e à cobrança da água produzida na exploração petrolífera

Water production is unavoidable during a petrol well s lifetime. The amount of produced water associated with oil varies a lot. It can reach values which account to 50% in volume up to nearly 100%, at the end of the well s economic life. It could be verified that, once the water reaches the productive wells, there must be a management of this produced water. Its destiny is defined after a precise study, after which the best option is chosen between relieving it into the environment, re-injecting it into the producing container or disposing it into non-producing formations. Whichever option is made by the involved professionals, after the necessary analysis, it shall consider, besides the technical and economical aspects, also the alternatives which entail less environmental impact. The purpose of the present research is to conduct a study about the application of the constitutional principle of efficiency on the instruments worked out by the public administration on water management, specifically the water use licence and charging for the use in the management of water resources applicable to water production at the petrol wells. In this attempt, before entering the proper approach of the efficiency of the mentioned instruments, it was necessary not only bring to light the doctrinal perception about the constitutional principle of administrative efficiency, but also make some considerations concerning to the structure of the national water resources management, set by the Federal Constitution (1988) and the federal legislation (9433/97)

Remoção de óleo da água de produção por flotação em coluna utilizando tensoativos de origem vegetal

In the petroleum industry, water is always present in the reservoir formation together with petroleum and natural gas and this fact provokes the production of water with petroleum, resulting in a great environmental impact. Several methods can be applied for treatment of oily waters, such as: gravitational vases, granulated media filtration systems, flotation process, centrifugation process and the use of hydrocyclones, which can also be used in a combined way. However, the flotation process has showed a great efficiency as compared with other methods, because these methods do not remove great part of the emulsified oil. In this work was investigated the use of surfactants derived from vegetable oils, OSS and OGS, as collectors, using the flotation process in a glass column with a porous plate filter in its base for the input of the gaseous steam. For this purpose, oil/water emulsions were prepared using mechanical stirring, with concentrations around 300 ppm. The air flow rate was set at 700 cm3/min and the porous plate filter used for the generation of the air bubbles has pore size varying from 16 to 40 Pm. The column operated at constant volume (1500mL). A new methodology has been developed to collect the samples, where, instead of collecting the water phase, it was collected the oil phase removed by the process in the top of the flotation column. It has been observed that it is necessary to find an optimum surfactant concentration to achieve enhanced removal efficiency. Being for OSS 1.275 mmol/L and for OGS 0.840 mmol/L, with removal efficiencies of 93% and 99%, respectively, using synthetic solutions. For the produced water, the removal in these concentrations was 75% for OSS and 65% for OGS. It is possible to remove oil from water in a flotation process using surfactants of high HLB, fact that is against the own definition of HLB (Hydrophile-Lipophile Balance). The interfacial tension is an important factor in the oil removal process using a flotation process, because it has direct interference in the coalescence of the oil drops. The spreading of the oil of the air bubble should be considered in the process, and for the optimum surfactant concentrations it reached a maximum value. The removal kinetics for the flotation process using surfactants in the optimum concentration has been adjusted according to a first order model, for synthetic water as for the produced water.

Aperfeiçoamento no projeto de um protótipo de misturador-decantador à inversão de fases visando aplicação na indústria do petróleo

In the oil industry the mixture oil/water occurs in the operations of production, transportation and refining, as well as during the use of its derivatives. The amount of water produced associated with the oil varies and can reach values of 90% in volume in the case of mature phase of the production fields. The present work deals with the development of new design of the Mixer Settler based on Phase Inversion (MDIF) in a laboratory scale. We envisage this application in industrial scale so the phases of project, construction and operation are considered. The modifications most significant, in comparison with the original prototype, include the materials of construction and the substitution of the equipment used in the mixing stage of the process. It was tested the viability of substitution of the original system of mechanical mixing by a static mixer. A statistical treatment by means of an experimental design of composed central type was used in order to evaluate the behavior of the main variables of the separation process as function of the efficiency of separation for the new device. This procedure is useful to delimit an optimal region of operation with the equipment. The variables of process considered on the experimental design were: oil concentration in the feeding water (mg/L); Total volumetric flow rate (L/h); Ratio organic/water on volumetric basis (O/A). The separation efficiency is calculated by comparison of the content of oil and greases in the inlet and outlet of the equipment. For determination of TOG (Total Oil and Grease), the method used was based in the absorption of radiation in the infra-red region. The equipment used for these determinations was InfraCal® TOG/TPH Model HATR-T2 of the Wilks Enterprise, Incorporation. It´s important to stand out that this method of measure has being used by PETROBRAS S.A. Results of global efficiency of separation oil/water varied from 75.3 to 97.7% for contaminated waters containing up to 1664,1 mg/L of oil. By means of tests carried out with a real sample of contaminated water supplied by PETROBRAS we have got an effluent specified in terms of the legal standards required for discharging. Thus, the new design of equipment constitutes a real alternative for the conventional systems of treatment of produced water in the oil industry

Desenvolvimento de um destilador solar para tratamento de águas de produção de petróleo com vistas a sua utilização na agricultura e geração de vapor

The production of petroleum is frequently accomplished with great volumes of water, that it is carried of the underground with the oil. It is a challenge of the present century the development of technologies that allow the use of waste water for purposes that consume great amounts of water and don't demand as rigid as the one of the drinking water requirements. The solar distillation has been configuring as an alternative of clean technology for desalination of brine and saline. Besides causing the minimum possible damage to the environment, it takes advantage of an abundant and free energy source: the solar energy. That study aims to develop a Solar Distillator for treatment of the produced water of the oil wells, to obtain an efluent to use in agriculture and vapor generation. The methodology for collection, conservation and analysis of the physical-chemical parameters obeyed the norms in APHA (1995). The sampling was of the composed type. Experiments were accomplished in the solar distillation pilot and simulation in thermostatic bathing. The operation was in batch system and for periods of 4, 6 and 12 h. The developed Distillator is of the type simple effect of two waters. It was still tested two inclination angles for covering; 20º and 45º. The Distillator presented minimum of 2,85 L/m2d revenues and maximum of 7,14 L/m2d. The removals of salts were great than 98%. The removal of TOC in the simulation was great than 90%. In agreement with the data of energy and mass balance, it was verified that the developed solar Distillator presented compatible revenues with those found in literature for similar types. It can be inferred that the obtained distilled water assists to the requirements CONAMA in almost all the points and could be used for irrigation of cultures such as cotton and mamona. As the distilled water has characteristics of fresh water it can be used in the generation of vapor

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

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

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

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.

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