Degradação eletroquímica de benzeno, tolueno e xileno via oxidação eletroquímica utilizando eletrodo Ti/Pt

This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves

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

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

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

Adsorção de cobre e cromo utilizando fibra de sisal visando o tratamento da água produzida pela indústria petrolífera

Currently, the oil industry is the biggest cause of environmental pollution. The objective was to reduce the concentration of copper and chromium in the water produced by the oil industry. It was used as adsorbent natural sisal fiber Agave sp treated with nitric acid and sodium hydroxide. All vegetable fibers have physical and morphological properties that enablies the adsorption of pollutants. The basic composition of sisal is cellulose, hemicellulose and lignin. The features are typically found in the characterization of vegetable fibers, except the surface area that was practically zero. In the first stage of adsorption, it was evaluated the effect of temperature and time skeeking to optimize the execution of the factorial design. The results showed that the most feasible fiber was the one treated with acid in five hours (30°C). The second phase was a factorial design, using acid and five hours, this time was it determined in the first phase. The tests were conducted following the experimental design and the results were analyzed by statistical methods in order to optimize the main parameters that influence the process: pH, concentration (mol / L) and fiber mass/ metal solution volume. The volume / mass ratio factor showed significant interference in the adsorption process of chromium and copper. The results obtained after optimization showed that the highest percentages of extraction (98%) were obtained on the following operating conditions: pH: 5-6, Concentration: 100 ppm and mass/ volume: 1 gram of fiber/50mL solution. The results showed that the adsorption process was efficient to remove chromium and copper using sisal fibers, however, requiring further studies to optimize the process.

Avaliação de floculante natural à base de Moringa oleifera no tratamento de água produzida na indústria do petróleo: aplicação da técnica combinada floculação/flotação

The principal effluent in the oil industry is the produced water, which is commonly associated to the produced oil. It presents a pronounced volume of production and it can be reflected on the environment and society, if its discharge is unappropriated. Therefore, it is indispensable a valuable careful to establish and maintain its management. The traditional treatment of produced water, usualy includes both tecniques, flocculation and flotation. At flocculation processes, there are traditional floculant agents that aren’t well specified by tecnichal information tables and still expensive. As for the flotation process, it’s the step in which is possible to separate the suspended particles in the effluent. The dissolved air flotation (DAF) is a technique that has been consolidating economically and environmentally, presenting great reliability when compared with other processes. The DAF is presented as a process widely used in various fields of water and wastewater treatment around the globe. In this regard, this study was aimed to evaluate the potential of an alternative natural flocculant agent based on Moringa oleifera to reduce the amount of oil and grease (TOG) in produced water from the oil industry by the method of flocculation/DAF. the natural flocculant agent was evaluated by its efficacy, as well as its efficiency when compared with two commercial flocculant agents normally used by the petroleum industry. The experiments were conducted following an experimental design and the overall efficiencies for all flocculants were treated through statistical calculation based on the use of STATISTICA software version 10.0. Therefore, contour surfaces were obtained from the experimental design and were interpreted in terms of the response variable removal efficiency TOG (total oil and greases). The plan still allowed to obtain mathematical models for calculating the response variable in the studied conditions. Commercial flocculants showed similar behavior, with an average overall efficiency of 90% for oil removal, however it is the economical analysis the decisive factor to choose one of these flocculant agents to the process. The natural alternative flocculant agent based on Moringa oleifera showed lower separation efficiency than those of commercials one (average 70%), on the other hand this flocculant causes less environmental impacts and it´s less expensive

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

Adsorção de cobre e cromo utilizando fibra de sisal visando o tratamento da água produzida pela indústria petrolífera

Currently, the oil industry is the biggest cause of environmental pollution. The objective was to reduce the concentration of copper and chromium in the water produced by the oil industry. It was used as adsorbent natural sisal fiber Agave sp treated with nitric acid and sodium hydroxide. All vegetable fibers have physical and morphological properties that enablies the adsorption of pollutants. The basic composition of sisal is cellulose, hemicellulose and lignin. The features are typically found in the characterization of vegetable fibers, except the surface area that was practically zero. In the first stage of adsorption, it was evaluated the effect of temperature and time skeeking to optimize the execution of the factorial design. The results showed that the most feasible fiber was the one treated with acid in five hours (30°C). The second phase was a factorial design, using acid and five hours, this time was it determined in the first phase. The tests were conducted following the experimental design and the results were analyzed by statistical methods in order to optimize the main parameters that influence the process: pH, concentration (mol / L) and fiber mass/ metal solution volume. The volume / mass ratio factor showed significant interference in the adsorption process of chromium and copper. The results obtained after optimization showed that the highest percentages of extraction (98%) were obtained on the following operating conditions: pH: 5-6, Concentration: 100 ppm and mass/ volume: 1 gram of fiber/50mL solution. The results showed that the adsorption process was efficient to remove chromium and copper using sisal fibers, however, requiring further studies to optimize the process.

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.

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

Tratamento eletroquímico de efluente proveniente de caixas separadoras de água e óleo de postos revendedores de combustíveis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Tratamento eletroquímico de efluente proveniente de caixas separadoras de água e óleo de postos revendedores de combustíveis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

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

Estudo da hidrodinâmica de um novo separador líquido-líquido: aplicação ao sistema óleo-bruto/água produzida

This work aims to use a different hydrodynamic condition applied 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 use of this different hydrodynamic behaviour is possible due to vertical disposition of the device and the principle of Phase Inversion that controls the MDIF, providing the generation (creation) of a cascade of drops, into an organic layer, that works as micro-decanters, thus making possible the formation of a bed of non-coalesced drops, called Bed Formation . The use of this new hydrodynamics condition allows to increase the residence time of the oil carrier drops, into an organic layer, and the device can treat a greater volume of wastewater. In view of to get this condition it is necessary to operate at high throughput (58,6 m3.m-2.h-1). By results, the condition of Bed Formation is the best one to be used when MSPI operates with throughput up to 58,6 m3.m-2.h-1. The results using the condition of Bed Formation show that increasing the height of the bed of non-coalesced drops and/or decreasing the volumetric ratio (O/A) an increase of the separation efficiency is detected

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