Determinação de CD, PB, e TL em água produzida por HR-CS GF AAS após extração em ponto nuvem

Produced water is a major problem associated with the crude oil extraction activity. The monitoring of the levels of metals in the waste is constant and requires the use of sensitive analytical techniques. However, the determination of trace elements can often require a pre-concentration step. The objective of this study was to develop a simple and rapid analytical method for the extraction and pre-concentration based on extraction phenomenon cloud point for the determination of Cd, Pb and Tl in produced water samples by spectrometry of high resolution Absorption source continues and atomization graphite furnace. The Box Behnken design was used to obtain the optimal condition of extraction of analytes. The factors were evaluated: concentration of complexing agent (o,o-dietilditilfosfato ammonium, DDTP), the concentration of hydrochloric acid and concentration of surfactant (Triton X -114). The optimal condition obtained through extraction was: 0,6% m v-1 DDTP, HCl 0,3 mol L-1 and 0,2% m v-1 of Triton X - 114 for Pb; 0,7% m v-1 DDTP, HCl 0,8 mol L-1 and 0,2% m v-1 Triton X-114 for Cd. For Tl was evidenced that best extraction condition occurs with no DDTP, the extraction conditions were HCl 1,0 mol L-1 e 1,0% m v-1 de Triton X - 114. The limits of detection for the proposed method were 0,005 µg L-1 , 0,03 µg L-1 and 0,09 µg L-1 to Cd, Pb and Tl, Respectively. Enrichment factors Were greater than 10 times. The method was applied to the water produced in the Potiguar basin, and addition and recovery tests were performed, and values were between 81% and 120%. The precision was expressed with relative standard deviation (RSD) is less than 5%

Uso de água produzida na formulação de fluidos de perfuração

Drilling fluids have fundamental importance in the petroleum activities, since they are responsible for remove the cuttings, maintain pressure and well stability, preventing collapse and inflow of fluid into the rock formation and maintain lubrication and cooling the drill. There are basically three types of drilling fluids: water-based, non-aqueous and aerated based. The water-based drilling fluid is widely used because it is less aggressive to the environment and provide excellent stability and inhibition (when the water based drilling fluid is a inhibition fluid), among other qualities. Produced water is generated simultaneously with oil during production and has high concentrations of metals and contaminants, so it’s necessary to treat for disposal this water. The produced water from the fields of Urucu-AM and Riacho da forquilha-RN have high concentrations of contaminants, metals and salts such as calcium and magnesium, complicating their treatment and disposal. Thus, the objective was to analyze the use of synthetic produced water with similar characteristics of produced water from Urucu-AM and Riacho da Forquilha-RN for formulate a water-based drilling mud, noting the influence of varying the concentration of calcium and magnesium into filtered and rheology tests. We conducted a simple 32 factorial experimental design for statistical modeling of data. The results showed that the varying concentrations of calcium and magnesium did not influence the rheology of the fluid, where in the plastic viscosity, apparent viscosity and the initial and final gels does not varied significantly. For the filtrate tests, calcium concentration in a linear fashion influenced chloride concentration, where when we have a higher concentration of calcium we have a higher the concentration of chloride in the filtrate. For the Urucu’s produced water based fluids, volume of filtrate was observed that the calcium concentration influences quadratically, this means that high calcium concentrations interfere with the power of the inhibitors used in the formulation of the filtered fluid. For Riacho’s produced water based fluid, Calcium’s influences is linear for volume of filtrate. The magnesium concentration was significant only for chloride concentration in a quadratic way just for Urucu’s produced water based fluids. The mud with maximum concentration of magnesium (9,411g/L), but minimal concentration of calcium (0,733g/L) showed good results. Therefore, a maximum water produced by magnesium concentration of 9,411g/L and the maximum calcium concentration of 0,733g/L can be used for formulating water-based drilling fluids, providing appropriate properties for this kind of fluid.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Aplicação de géis de goma guar no processo de clarificação de salmouras e águas produzidas

Produced water is considered the main effluent of the oil industry, due to their increased volume in mature fields and its varied composition. The oil and grease content (TOG) is the main parameter for the final disposal of produced water. In this context, it is of great significance to develop an alternative method based on guar gum gel for the treatment of synthetic produced water, and using as the differential a polymer having high hydrophilicity for clarifying waters contaminated with oil. Thus, this study aims to evaluate the efficiency of guar gum gels in the remotion of oil from produced water. Guar gum is a natural polymer that, under specific conditions, forms three-dimensional structures, with important physical and chemical properties. By crosslinking the polymer chains by borate ions in the presence of salts, the effect salting out occurs, reducing the solubility of the polymer gel in water. As a result, there is phase separation with the oil trapped in the collapsed gel. The TOG was quantified from the spectroscopy in the ultraviolet and visible region. The system was proven to be highly efficient in the removal of dispersed oil from water produced synthetically, reaching removal percentages above 90%.

Estudo de métodos de tratamento de efluentes (troca iônica e eletroquímico) separados e sequenciais para eliminação de derivados de petróleo

The produce of waste and the amount of the water produced coming from activities of petroleum production and extraction has been a biggest challenge for oil companies with respect to environmental compliance due to toxicity. The discard or the reuse this effluent containing organic compounds as BTEX (benzene, toluene, ethylbenzene and xylene) can cause serious environmental and human health problems. Thus, the objective this paper was study the performance of two process (separately and sequential) in one synthetic effluent for the benzene, toluene and xylene removal (volatile hydrocarbons presents in the produced water) through of electrochemical treatment using Ti/Pt electrode and exchange resin ionic used in the adsorption process. The synthetic solution of BTX was prepared with concentration of 22,8 mg L-1, 9,7 mg L-1 e 9,0 mg L-1, respectively, in Na2SO4 0,1 mol L-1. The experiments was developed in batch with 0.3 L of solution at 25ºC. The electrochemical oxidation process was accomplished with a Ti/Pt electrode with different current density (J = 10, 20 e 30 mA.cm-2). In the adsorption process, we used an ionic exchange resin (Purolite MB 478), using different amounts of mass (2,5, 5 and 10 g). To verify the process of technics in the sequential treatment, was fixed the current density at 10 mA cm-2 and the resin weight was 2.5 g. Analysis of UV-VIS spectrophotometry, chemical oxygen demand (COD) and gas chromatography with selective photoionization detector (PID) and flame ionization (FID), confirmed the high efficiency in the removal of organic compounds after treatment. It was found that the electrochemical process (separate and sequential) is more efficient than absorption, reaching values of COD removal exceeding 70%, confirmed by the study of the cyclic voltammetry and polarization curves. While the adsorption (separately), the COD removal did not exceed 25,8%, due to interactions resin. However, the sequential process (electrochemical oxidation and adsorption) proved to be a suitable alternative, efficient and cost-effectiveness for the treatment of effluents petrochemical.

Uso de argilominerais e diatomita como adsorvente de fenóis em águas produzidas na indústria de petróleo

The oil production in Brazil has been increasing each year. Consequently, increasing volumes of water produced are generated with large quantities of contaminants, which brings many problems in disposing of these waters. The concern that the concentrations of contaminants in water produced meet existing laws for disposal of effluents, has been extremely important for the development of different techniques for treatment of water produced. The study of clay minerals as adsorbents of organic contaminants has grown considerably so in order to combine the low cost with the efficiency of environmental preservation and health issues. Thus, this study aims to understand the characteristics of vermiculite clay, sodium bentonite, calcium bentonite and diatomite and evaluate their performance as adsorbents for phenol in the water produced. Through adsorption isotherms it was possible to observe the behavior of these adsorptive clay and diatomite for adsorption of phenol, the main phenolic compound found in water produced. Different concentrations of synthetic solutions of phenol were put in touch with these adsorbents under same conditions of agitation and temperature. The adsorbents were composted adsorptive favorable, but the vermiculite and diatomite showed little capacity for absorption, being suggested for absorbs small concentrations of phenol in the balance isothermal

Estudo de reatores eletroquímicos para remoção de Cu2+ , Zn2+, Fenol e BTEX em água produzida

The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms

Modelagem analítica e experimental da filtração em meios porosos

Deep bed filtration occurs in several industrial and environmental processes like water filtration and soil contamination. In petroleum industry, deep bed filtration occurs near to injection wells during water injection, causing injectivity reduction. It also takes place during well drilling, sand production control, produced water disposal in aquifers, etc. The particle capture in porous media can be caused by different physical mechanisms (size exclusion, electrical forces, bridging, gravity, etc). A statistical model for filtration in porous media is proposed and analytical solutions for suspended and retained particles are derived. The model, which incorporates particle retention probability, is compared with the classical deep bed filtration model allowing a physical interpretation of the filtration coefficients. Comparison of the obtained analytical solutions for the proposed model with the classical model solutions allows concluding that the larger the particle capture probability, the larger the discrepancy between the proposed and the classical models

Rejeito de xisto como adsorvente para remoção de fenol em águas produzidas na indústria de petróleo

Produced water is the main effluent linked to the activity of extraction of oil and their caring management is necessary due to the large volume involved, to ensure to minimize the negative impacts of discharges of these waters in the environment. This study aimed to analyze the use of retorted shale, which is a reject from the pyrolysis of pirobituminous shale, as adsorbent for the removal of phenols in produced water. The material was characterized by different techniques (grain sized analysis, thermal analysis, BET, FRX, FT-IR, XRD and SEM), showing the heterogeneity in their composition, showing its potential for the removal of varied compounds, as well as the phenols and their derivatives. For the analysis of the efficiency of the oil shale for the adsorption process, assays of adsorption balance were carried through, and also kinetic studies and dynamics adsorption, in the ETE of the UTPF of Petrobras, in Guamaré-RN. The balance assays shown a bigger conformity with the model of Langmuir and the kinetic model more adjusted to describe the adsorption of phenols in retorted shale was of pseudo-second order. The retorted shale presented a low capacity of adsorption of phenols (1,3mg/g), when related to others conventional adsorbents, however it is enough to the removal of these composites in concentrations presented in the produced water of the UTPF of Guamaré. The assays of dynamics adsorption in field had shown that the concentration of phenol in the effluent was null until reaching its rupture (58 hours). The results showed the possibility of use of the reject for removal of phenols in the final operations of the treatment process, removing as well, satisfactorily, the color and turbidity of the produced water, with more than 90% of removal

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

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