Remoção de hidrocarbonetos do gás natural visando o ajuste do índice de metano

The use of the natural gas is growing year after year in the whole world and also in Brazil. It is verified that in the last five years the profile of natural gas consumption reached a great advance and investments had been carried through in this area. In the oil industry, the use of the natural gas for fuel in the drive of engines is usual for a long date. It is also used to put into motion equipment, or still, to generate electric power. Such engines are based on the motor cycle of combustion Otto, who requires a natural gas with well definite specification, conferring characteristic anti-detonating necessary to the equipment performance for projects based on this cycle. In this work, process routes and thermodynamic conditions had been selected and evaluated. Based on simulation assays carried out in commercial simulators the content of the methane index of the effluent gas were evaluated at various ranges of pressure, temperature, flowrate, molecular weight and chemical nature and composition of the absorbent. As final result, it was established a route based on process efficiency, optimized consumption of energy and absorbent. Thereby, it serves as base for the compact equipment conception to be used in locu into the industry for the removal of hydrocarbon from the natural gas produced

Degradação fotoquímica de hidrocarbonetos da gasolina em efluentes aquosos

Photo-oxidation processes of toxic organic compounds have been widely studied. This work seeks the application of the photo-Fenton process for the degradation of hydrocarbons in water. The gasoline found in the refinery, without additives and alcohol, was used as the model pollutant. The effects of the concentration of the following substances have been properly evaluated: hydrogen peroxide (100-200 mM), iron ions (0.5-1 mM) and sodium chloride (200 2000 ppm). The experiments were accomplished in reactor with UV lamp and in a falling film solar reactor. The photo-oxidation process was monitored by measurements of the absorption spectra, total organic carbon (TOC) and chemical oxygen demand (COD). Experimental results demonstrated that the photo-Fenton process is feasible for the treatment of wastewaters containing aliphatic hydrocarbons, inclusive in the presence of salts. These conditions are similar to the water produced by the petroleum fields, generated in the extraction and production of petroleum. A neural network model of process correlated well the observed data for the photooxidation process of hydrocarbons

Planejamento experimental aplicada a um novo separador líquido-líquido utilizado no tratamento de águas residuais contaminadas com petróleo

The present work had as objective to apply an experimental planning aiming at to improve the efficiency of separation of a new type of mixer-settler applied to treat waste water contaminated with oil. An unity in scale of laboratory, was installed in the Post-graduation Program of Chemical Engineering of UFRN. It was constructed in partnership with Petrobras S.A. This called device Misturador-Decantador a Inversão de Fases (MDIF) , possess features of conventional mixer-settler and spray column type. The equipment is composed of three main parts: mixing chamber; chamber of decantation and chamber of separation. The efficiency of separation is evaluated analyzing the oil concentrations in water in the feed and the output of the device. For the analysis one used the gravimetric method of oil and greases analysis (TOG). The system in study is a water of formation emulsified with oil. The used extractant is a mixture of Turpentine spirit hydro-carbons, supplied for Petrobras. It was applied, for otimization of the efficiency of separation of the equipment, an experimental planning of the composite central type, having as factorial portion fractionary factorial planning 2 5-2, with the magnifying of the type star and five replications in the central point. In this work, the following independents variables were studied: contents of oil in the feed of the device; volumetric ratio (O/A); total flowrate ; agitation in the mixing chamber and height of the organic bed. Minimum and maximum limits for the studied variables had been fixed according previous works. The analysis of variance for the equation of the empirical model, revealed statistically significant and useful results for predictions ends. The variance analysis also presented the distribution of the error as a normal distribution and was observed that as the dispersions do not depend on the levels of the factors, the independence assumption can be verified. The variation around the average is explained by 98.98%, or either, equal to the maximum value, being the smoothing of the model in relation to the experimental points of 0,98981. The results present a strong interaction between the variable oil contents in the feed and agitation in the mixing chamber, having great and positive influence in the separation efficiency. Another variable that presented a great positive influence was the height of the organic bed. The best results of separation efficiency had been obtained for high flowrates when associates the high oil concentrations and high agitation. The results of the present work had shown excellent agreement with the results carried out through previous works with the mixer-settler of phase inversion

Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented

Obtenção de Propriedades Físico-Químicas de Misturas de Hidrocarbonetos em Baixa e Alta Pressão Visando a Caracterização e a Modelagem

The composition of petroleum may change from well to well and its resulting characteristics influence significantly the refine products. Therefore, it is important to characterize the oil in order to know its properties and send it adequately for processing. Since petroleum is a multicomponent mixture, the use of synthetic mixtures that are representative of oil fractions provides a better understand of the real mixture behavior. One way for characterization is usually obtained through correlation of physico-chemical properties of easy measurement, such as density, specific gravity, viscosity, and refractive index. In this work new measurements were obtained for density, specific gravity, viscosity, and refractive index of the following binary mixtures: n-heptane + hexadecane, cyclohexane + hexadecane, and benzene + hexadecane. These measurements were accomplished at low pressure and temperatures in the range 288.15 K to 310.95 K. These data were applied in the development of a new method of oil characterization. Furthermore, a series of measurements of density at high pressure and temperature of the binary mixture cyclohexane + n-hexadecane were performed. The ranges of pressure and temperature were 6.895 to 62.053 MPa and 318.15 to 413.15 K, respectively. Based on these experimental data of compressed liquid mixtures, a thermodynamic modeling was proposed using the Peng-Robinson equation of state (EOS). The EOS was modified with scaling of volume and a relatively reduced number of parameters were employed. The results were satisfactory demonstrating accuracy not only for density data, but also for isobaric thermal expansion and isothermal compressibility coefficients. This thesis aims to contribute in a scientific manner to the technological problem of refining heavy fractions of oil. This problem was treated in two steps, i.e., characterization and search of the processes that can produce streams with economical interest, such as solvent extraction at high pressure and temperature. In order to determine phase equilibrium data in these conditions, conceptual projects of two new experimental apparatus were developed. These devices consist of cells of variable volume together with a analytical static device. Therefore, this thesis contributed with the subject of characterization of hydrocarbons mixtures and with development of equilibrium cells operating at high pressure and temperature. These contributions are focused on the technological problem of refining heavy oil fractions

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find altenatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo¬Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. it's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Desenvolvimento de um sistema foto-oxidativo visando aplicação no tratamento de águas produzidas em campos de petróleo

Increasing concern with the environment, in addition to strict laws, has induced the industries to find alternatives to the treatment of their wastes. Actually, the oil industry has sought solutions to overcome a big environmental problem, i.e., oil field produced water being discharged to the sea. These effluents have organic compounds dissolved, such as polycyclic aromatic hydrocarbons, phenols, benzene, toluene, ethylbenzene and xylenes (BTEX). These compounds are difficult to be removed and have high toxicity. The advanced oxidation processes - AOP are effective to degradation of these organic compounds, because they generate hydroxyl radicals with high potential of oxidation. This work includes the reactor photochemical development applied in the photodegradation treatment (by photo-Fenton process) of wastewaters containing organic compounds dissolved, aiming at treatment and recovery the oil field produced water. The studied reactor allowed the evaluation of two ultraviolet radiation sources that is the main factor to describe the feasibility of the photo- Fenton treatment, i.e., sun and black light fluorescent lamps, and other relevant variables the process: concentration of reagents, irradiated area and also various reactor configurations to maximize the use of radiation. The organic matter degradation was verified with samples collected during the experimental and analyzed with a total organic carbon analyzer (TOC), which expressed the results in terms of mgC/L. The solar radiation was more effective than radiation from the lamps. It's an important factor for the operation costs cutting. Preliminary experiments applied to oil field produced water treatment have showed satisfactory results, reducing up to 76 % of organic matter

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products

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

Otimização de metodologias para determinação de hidrocarbonetos policíclicos aromáticos:aplicação em água do Rio Potengi

This work aims to detect polycyclic aromatic hydrocarbons (PAHs) through optimized analytical techniques, such as gas chromatography with flame-ionisation detector (CGFID), gas chromatography coupled to mass spectrometry (CGMS), Fluorescence Spectroscopy of Molecular and Purpot of oils and greases (POG). Apply to chemometrics, Factorial Planning 23, in the preparation of samples by liquid-liquid extraction. The sample preparation was used for liquid-liquid extraction and factors in this sample was used for the application of factorial planning 23, such as the use of ultrasound, solvents (dichloromethane, hexane and chloroform) and ratio of solvent / synthetic sample. These factors were assigned two types of levels: positive and negative. It was used to form the cube to better analyze the answers. The responses of the eight combinations were obtained in reading the spectrofluorimetric. The optimization of equipment were used, and they served in the HPA's identification of the samples collected in Rio Potengi. The optimization of the equipment was observed every 16's and PAH in the samples was found that the HPA's came from contamination of the Rio Potengi. The contamination comes through organic household waste, hospital waste, and among other contamination that comes from industries that are installed around the River The factorial design of high validity, it was observed a more effective sample preparation. The factorial design of liquid-liquid extraction showed a way to spend less solvent in less time using an ideal solvent, but also a way to extract more analyte from the matrix itself is water. In planning a smaller form factor extraction was the use of ultrasound, the ratio 1:3 corresponding to a solvent and sample 3 and the best solvent was dichloromethane who presented a viable extraction, not discarding the possibility of using also the hexane. The chloroform and may be toxic not had a good extraction

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Hidrocarbonetos policíclicos aromáticos no meio ambiente: diferenciação de fontes em sedimentos e metabólitos em bile de peixes

Many studies on environmental ecosystems quality related to polycyclic aromatic hydrocarbons (PAH) have been carried out routinely due to their ubiquotus presence worldwide and to their potential toxicity after its biotransformation. PAH may be introduced into the environmet by natural and anthropogenic processes from direct runoff and discharges and indirect atmospheric deposition. Sources of naturally occurring PAHs include natural fires, natural oil seepage and recent biological or diagenetic processes. Anthropogenic sources of PAHs, acute or chronic, are combustion of organic matter (petroleum, coal, wood), waste and releases/spills of petroleum and derivatives (river runoff, sewage outfalls, maritime transport, pipelines). Besides the co-existence of multiples sources of PAH in the environmental samples, these compounds are subject to many processes that lead to geochemical fates (physical-chemical transformation, biodegradation and photo-oxidation), which leads to an alteration of their composition. All these facts make the identification of the hydrocarbons sources, if petrogenic, pyrolytic or natural, a challenge. One of the objectives of this study is to establish tools to identify the origin of hydrocarbons in environmental samples. PAH diagnostic ratios and PAH principal component analysis were tested on a critical area: Guanabara Bay sediments. Guanabara Bay is located in a complex urban area of Rio de Janeiro with a high anthropogenic influence, being an endpoint of chronic pollution from the Greater Rio and it was the scenario of an acute event of oil release in January 2000. It were quantified 38 compounds, parental and alkylated PAH, in 21 sediment samples collected in two surveys: 2000 and 2003. The PAH levels varied from 400 to 58439 ng g-1. Both tested techniques for origin identification of hydrocarbons have shown their applicability, being able to discriminate the PAH sources for the majority of the samples analysed. The bay sediments were separated into two big clusters: sediments with a clear pattern of petrogenic introduction of hydrocarbons (from intertidal area) and sediments with combustion characteristics (from subtidal region). Only a minority of the samples could not display a clear contribution of petrogenic or pyrolytic input. The diagnostic ratios that have exhibited high ability to distinguish combustion- and petroleum-derived PAH inputs for Guanabara Bay sediments were Phenanthrene+Anthracene/(Phenanthrene+Anthracene+C1Phenanthrene); Fluorantene/(Fluorantene+Pyrene); Σ (other 3-6 ring PAHs)/ Σ (5 alkylated PAH series). The PCA results prooved to be a useful tool for PAH source identification in the environment, corroborating the diagnostic indexes. In relation to the temporal evaluation carried out in this study, it was not verified significant changes on the class of predominant source of the samples. This result indicates that the hydrocarbons present in the Guanabara Bay sediments are mainly related to the long-term anthropogenic input and not directly related to acute events such as the oil spill of January 2000. This findings were similar to various international estuarine sites. Finally, this work had a complementary objective of evaluating the level of hydrocarbons exposure of the aquatic organisms of Guanabara Bay. It was a preliminary study in which a quantification of 12 individual biliar metabolites of PAH was performed in four demersal fish representing three different families. The analysed metabolites were 1-hydroxynaphtalene, 2-hidroxinaphtalene, 1hydroxyphenanthrene, 9-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1hydroxypyrene, 3-hidroxibiphenil, 3- hydroxyphenanthrene, 1-hydroxychrysene, 9hydroxyfluorene, 4-hydroxyphenanthrene, 3-hydroxybenz(a)pyrene. The metabolites concentrations were found to be high, ranging from 13 to 177 µg g-1, however they were similar to worldwide regions under high anthropogenic input. Besides the metabolites established by the used protocol, it was possible to verified high concentrations of three other compounds not yet reported in the literature. They were related to pyrolytic PAH contribution to Guanabara Bay aquatic biota: 1-hydroxypyrine and 3-hydroxybenz(a)pyrine isomers

Litoestratigrafia e deformação cenzóica na região de Icapuí, Ceará, e implicações para a estruturação de campos de petróleo na borda ocidental da bacia Potiguar(NE do Brasil)

This thesis deals with the sedimentological/stratigraphic and structural evolution of the sedimentary rocks that occur in the NW continental border of the Potiguar Basin. These rocks are well exposed along coastal cliffs between the localities of Lagoa do Mato and Icapuí, Ceará State (NE Brazil). The sedimentological/stratigraphic study involved, at the outcrop scale, detailed facies descriptions, profile mapping of the vertical succession of different beds, and columnar sections displaying inferred lateral relationships. The approach was complemented by granulometric and petrographic analyses, including the characterization of heavy mineral assemblages. The data set allowed to recognize two kinds of lithological units, a carbonate one of very restricted occurrence at the base of the cliffs, and three younger, distinct siliciclastic units, that predominate along the cliffs, in vertical and lateral extent. The carbonate rocks were correlated to the late Cretaceous Jandaíra Formation, which is covered by the siliciclastic Barreiras Formation. The Barreiras Formation occurs in two distinct structural settings, the usual one with nondeformed, subhorizontal strata, or as tilted beds, affected by strong deformation. Two lithofacies were recognized, vertically arranged or in fault contacts. The lower facies is characterized by silty-argillaceous sandstones with low-angle cross bedding; the upper facies comprises medium to coarse grained sandstones, with conglomeratic layers. The Tibau Formation (medium to coarse-grained sandstones with argillite intercalations) occurs at the NW side of the studied area, laterally interlayered with the Barreiras Formation. Eolic sediments correlated to the Potengi Formation overly the former units, either displaying an angular unconformity, or simply an erosional contact (stratigraphic unconformity). Outstanding structural features, identified in the Barreiras Formation, led to characterize a neocenozoic stress field, which generated faults and folds and/or reactivated older structures in the subjacent late cretaceous (to paleogene, in the offshore basin) section. The structures recognized in the Barreiras Formation comprise two distinct assemblages, namely a main extensional deformation between the localities of Ponta Grossa and Redonda, and a contractional style (succeeded by oblique extensional structures) at Vila Nova. In the first case, the structural assemblage is dominated by N-S (N±20°Az) steep to gently-dipping extensional faults, displaying a domino-style or listric geometry with associated roll-over structures. This deformation pattern is explained by an E-W/WNW extension, contemporaneous with deposition of the upper facies of the Barreiras Formation, during the time interval Miocene to Pleistocene. Strong rotation of blocks and faults generated low-angle distensional faults and, locally, subvertical bedding, allowing to estimate very high strain states, with extension estimates varying between 40% up to 200%. Numerous detachment zones, parallel to bedding, help to acommodate this intense deformation. The detachment surfaces and a large number of faults display mesoscopic features analoguous to the ones of ductile shear zones, with development of S-C fabrics, shear bands, sigmoidal clasts and others, pointing to a hydroplastic deformation regime in these cases. Local occurrences of the Jandaíra limestone are controled by extensional faults that exhume the pre-Barreiras section, including an earlier event with N-S extension. Finally, WNWtrending extensional shear zones and faults are compatible with the Holocene stress field along the present continental margin. In the Vila Nova region, close to Icapuí, gentle normal folds with fold hinges shallowly pluging to SSW affect the lower facies of the Barreiras Formation, displaying an incipient dissolution cleavage associated with an extension lineation at high rake (a S>L fabric). Deposition of the upper facies siliciclastics is controlled by pull-apart graben structures, bordered by N-NE-trending sinistral-normal shear zones and faults, characterizing an structural inversion. Microstructures are compatible with tectonic deformation of the sedimentary pile, burried at shallow depths. The observed features point to high pore fluid pressures during deformation of the sediments, producing hydroplastic structures through mechanisms of granular flow. Such structures are overprinted by microfractures and microfaults (an essentially brittle regime), tracking the change to microfracturing and frictional shear mechanisms accompanying progressive dewatering and sediment lithification. Correlation of the structures observed at the surface with those present at depth was tested through geophysical data (Ground Penetrating Radar, seismics and a magnetic map). EW and NE-trending lineaments are observed in the magnetic map. The seismic sections display several examples of positive flower structures which affect the base of the cretaceous sediments; at higher stratigraphic levels, normal components/slips are compatible with the negative structural inversion characterized at the surface. Such correlations assisted in proposing a structural model compatible with the regional tectonic framework. The strong neogenepleistocene deformation is necessarily propagated in the subsurface, affecting the late cretaceous section (Açu and Jandaíra formations), wich host the hydrocarbon reservoirs in this portion of the Potiguar Basin. The proposed structural model is related to the dextral transcurrent/transform deformation along the Equatorial Margin, associated with transpressive terminations of E-W fault zones, or at their intersections with NE-trending lineaments, such as the Ponta Grossa-Fazenda Belém one (the LPGFB, itself controlled by a Brasiliano-age strike-slip shear zone). In a first step (and possibly during the late Cretaceous to Paleogene), this lineament was activated under a sinistral transpressional regime (antithetic to the main dextral deformation in the E-W zones), giving way to the folds in the lower facies of the Barreiras Formation, as well as the positive flower structures mapped through the seismic sections, at depth. This stage was succeeded (or was penecontemporaneous) by the extensional structures related to a (also sinistral) transtensional movement stage, associated to volcanism (Macau, Messejana) and thermal doming processes during the Neogene-Pleistocene time interval. This structural model has direct implications to hydrocarbon exploration and exploitation activities at this sector of the Potiguar Basin and its offshore continuation. The structure of the reservoirs at depth (Açu Formation sandstones of the post-rift section) may be controlled (or at least, strongly influenced) by the deformation geometry and kinematics characterized at the surface. In addition, the deformation event recognized in the Barreiras Formation has an age close to the one postulated for the oil maturation and migration in the basin, between the Oligocene to the Miocene. In this way, the described structural cenario represents a valid model to understand the conditions of hydrocarbon transport and acummulation through space openings, trap formation and destruction. This model is potentially applicable to the NW region of the Potiguar Basin and other sectors with a similar structural setting, along the brazilian Equatorial Atlantic Margin

Influência de tensoativos não iônicos na destilação molecular de petróleo

The molecular distillation is show as an alternative for separation and purification of various kinds of materials. The process is a special case of evaporation at high vacuum, in the order from 0.001 to 0.0001 mmHg and therefore occurs at relatively lower temperatures, preserves the material to be purified. In Brazil, molecular distillation is very applied in the separation of petroleum fractions. However, most studies evaluated the temperature of the evaporator, condenser temperature and flow such variables of the molecular distillation oil. Then, to increase the degree of recovery of the fraction of the distillate obtained in the process of the molecular distillation was evaluated the use nonionic surfactants of the class of nonylphenol ethoxylate, molecules able to interact in the liquid-liquid and liquid-vapor interface various systems. In this context, the aim of this work was to verify the influence of commercial surfactant (Ultranex-18 an Ultranex-18-50) in the molecular distillation of a crude oil. The physicochemical characterization of the oil was realized and the petroleum shown an API gravity of 42°, a light oil. Initially, studied the molecular distillation without surfactant using star design experimental (2H ± ) evaluated two variables (evaporator temperature and condenser temperature) and answer variable was the percentage in distillate obtained in the process (D%). The best experimental condition to molecular distillation oil (38% distillate) was obtained at evaporator and condenser temperatures of 120 °C and 10 ° C, respectively. Subsequently, to determine the range of surfactant concentration to be applied in the process, was determined the critical micellar concentration by the technique of scattering X-ray small angle (SAXS). The surfactants Ultranex-18 an Ultranex-18-50 shown the critical micelle concentration in the range of 10-2 mol/L in the hydrocarbons studied. Then, was applied in the study of distillation a concentration range from 0.01 to 0.15 mol/L of the surfactants (Ultranex- 18 and 50). The use of the nonionic surfactant increased the percentage of hydrocarbons in the range from 5 to 9 carbons in comparison to the process carried out without surfactant, and in some experimental conditions the fraction of light compounds in the distilled was over 700% compared to the conventional process. The study showed that increasing the degree of ethoxylation of Ultranex18 to Ultranex-50, the compounds in the range of C5 to C9 reduced the percentage in the distilled, since the increase of the hydrophilic part of the surfactant reduces its solubility in the oil. Finally, was obtained an increase in the degree of recovery of light hydrocarbons, comparing processes with and without surfactant, obtained an increase of 10% and 4% with Ultranex-18 and Ultranex-50, respectively. Thus, it is concluded that the Ultranex- 18 surfactant showed a higher capacity to distillation compared with Ultranex-50 and the application of surfactant on the molecular distillation from petroleum allowed for a greater recovery of light compounds in distillate