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%

Avaliação da variação sedimentológica em uma área da plataforma continental sob a atuação da indústria petrolífera

Petroleum exploration activity occurs on the offshore Potiguar Basin, from very shallow (2-3 m) until about 50 m water depth, extending from Alto de Touros (RN) to Alto de Fortaleza (CE). Take in account the biological importance and the heterogeneity of sediments on this area, it is necessary the understanding of the sedimentological dynamics, and mainly the changes generated by petroleum exploration to prevent possible damages to environment. Despite the intense activity of oil exploration in this area, research projects like these are still rare. In view to minimize this gap, this study was developed to evaluate sedimentological, mineralogical and geochemical changes in the vicinity of a exploration well, here designated as well A, located on the Middle continental shelf, near the transition to Outer shelf. The well selected for this study was the first one drilled with Riserless Mud Recovery technology (RMR) in Brazil. The main difference from this to the conventional method is the possibility of drilling phase I of the well with return of drilling material to the rig tank, minimizing fluid and gravel discharging around the vicinity, during this phase. Monitoring consisted of three surveys, first of them done before start drilling, the second one done 19 days after the end of drilling and the third one done one year after then. Comparison of the studied variables (calcium carbonate and organic matter content, sediment size, mineralogy and geochemistry) was done with their average, median and coefficient of variation values to understand the changes after drilling activity. Because operating company technical reasons, the well location was changed after the first survey (C1), resulting in a shift of the sampled area on the two last surveys (C2 e C3). Nevertheless, the acquired data presented a good correlation, with no loss to the mean goal of the study. The sedimentological, mineralogical and geochemical analyzes were done at Federal University of Rio Grande do Norte (UFRN). The results indicated a predominantly sandy environment along the three surveys. It was noticed that the first survey (C1), presented different values for all the studied variables than to the second (C2) and third (C3) surveys, which had similar values. Siliciclastic sediments are prevalent at all surveys, and quartz is the main component (more than 80%). Heavy minerals (garnet, turmaline, zircon and lmenite), rock fragments and mud aggregates also was described. Bioclastic sediments are dominated by coralline algae (more than 45%) and mollusks (more than 30%), followed by benthic foraminifera, bryozoans and worm tubes. More rarely was observed ostracoda and spike of calcareous sponge. Because the low changes of the sediments at the studied area and by the using of RMR method in the drilling, it was possible to conclude that drilling activity did not promote significant alteration on the local sediment cover. Changes in the studied variables before and after drilling activity could be influenced by the changing in the sampling area after survey 1 (C1).

Adição do resíduo de biomassa da cana-de-açúcar em pastas para cimentação de poços petrolíferos produtores de óleos pesados

The Potiguar basin has large fields of viscous oil where the used method for recovering is based on vapor injection; this operation is carried out by injecting vapor in the oilwell directly, without the protection of a revetment through thermal insulation, what causes its dilation and, consequently, cracks in the cement placed on the annular, and lost of hydraulic insulation; this crack is occasioned by the phenomenon of retrogression of the compressive resistance due to the conversion of the hydrated calcium silicate in phases calcium-rich, caused by the high temperatures in the wells, subjected to thermal recuperation. This work has evaluated the application of composite pastes with addition of residue of biomass of ground sugar-cane bagasse as anti-retrogression mineral admixture for cementation of oil-wells subjected to thermal recuperation. The addition of the mineral residue was carried out considering a relative amount of 10, 20, 30, 40 and 59% in relation to cement mass, trying to improve the microstructure of the paste, still being developed a reference paste only with cement and a paste with addition of 40% of silica flour - renowned material in the oil industry as anti-retrogression additive. Pozzolanic activity of the ash was evaluated through XRD, TG/DTG, as the resistance to compression, and it was also determined the physical and mechanical behavior of the pastes when submitted to cure at low temperatures (22 and 38º C); besides it was evaluated the behavior of the pastes when submitted to two cycles of cure at high temperature (280ºC) and pressure (7 MPa). It was verified that the ash of the sugar-cane biomass presents pozzolanic reaction and has great efficiency in decrease the permeability of the paste by filler effect, as well as that addition of ash in a relative amount of 10, 20 e 30% increases cured compressive resistance at low temperatures. It was also showed that the ash in a relative amount of 40% and 59% has very significant efficiency as anti-retrogression additive, since it prevents the decrease of compressive resistance and forms hydrated calcium silicate type xenotlita and tobermorita which have more resistance and stability in high temperatures

Injeção de vapor e solvente como um método de recuperação avançada em reservatório avançada em reservatórios de óleo pesado

Currently a resource more and more used by the petroleum industry to increase the efficiency of steam flood mechanism is the addition of solvents. The process can be understood as a combination of a thermal method (steam injection) with a miscible method (solvent injection), promoting, thus, the reduction of interfacial tensions and oil viscosity. The use of solvent alone tends to be limited because of its high cost. When co-injected with steam, the vaporized solvent condenses in the cooler regions of the reservoir and mixes with the oil, creating a zone of low viscosity between the steam and the heavy oil. The mobility of the displaced fluid is then improved, resulting in an increase of oil recovery. To better understand this improved oil recovery method, a numerical study of the process was done contemplating the effects of some operational parameters (distance between wells, injection steam rate, kind of solvent and injected solvent volume)on the accumulated production of oil, recovery factor and oil-steam rate. Semisynthetic models were used in this study but reservoir data can be extrapolated for practical applications situations on Potiguar Basin. Simulations were performed in STARS (CMG, 2007.11). It was found that injected solvent volumes increased oil recovery and oil rates. Further the majority of the injected solvent was produced and can be recycled

Otimização de vazão de poços injetores em projeto de injeção de água utilizando simulação por linhas de fluxo

Until the early 90s, the simulation of fluid flow in oil reservoir basically used the numerical technique of finite differences. Since then, there was a big development in simulation technology based on streamlines, so that nowadays it is being used in several cases and it can represent the physical mechanisms that influence the fluid flow, such as compressibility, capillarity and gravitational segregation. Streamline-based flow simulation is a tool that can help enough in waterflood project management, because it provides important information not available through traditional simulation of finite differences and shows, in a direct way, the influence between injector well and producer well. This work presents the application of a methodology published in literature for optimizing water injection projects in modeling of a Brazilian Potiguar Basin reservoir that has a large number of wells. This methodology considers changes of injection well rates over time, based on information available through streamline simulation. This methodology reduces injection rates in wells of lower efficiency and increases injection rates in more efficient wells. In the proposed model, the methodology was effective. The optimized alternatives presented higher oil recovery associated with a lower water injection volume. This shows better efficiency and, consequently, reduction in costs. Considering the wide use of the water injection in oil fields, the positive outcome of the modeling is important, because it shows a case study of increasing of oil recovery achieved simply through better distribution of water injection rates

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

Contribuição da catodoluminescência para o entendimento da diagênese da formação Jandaíra: áreas do campo de petróleo da fazenda Belém e Lajedo do Rosário

The general objective of this study was to contribute to the understanding of the chemical evolution of fluids that percolate through carbonate rocks of the Jandaíra Formation. The oxidation and reduction conditions in which grains, source and cement were formed was investigated using the cathodoluminescence technique (CL). The study area is located in the west part of the Potiguar Basin (Fazenda Belém field) and Rosário Ledge (Felipe Guerra municipality, State of Rio Grande do Norte, Brazil). The analysis of thin sections of carbonate rocks under CL revealed that grains (allochemical or not) and diagenetic products (micritization, dolomitization, neomorphism and cementation) exhibit since absence of luminescence the various luminescence colors (yellow, orange, red, brown, and blue) in a variety of intensities. As pure calcite shows dark blue luminescence, the occurrence of different luminescence colors in calcite crystals suggest one or more punctual crystal defects such as free electron, free space and impurity. The dyeing of thin sections with alizarin and potassium ferrocyanide revealed the absence of ferrous carbonate in the different lithotypes of Jandaíra Formation. Therefore, the different colors and intensities of CL observed in these rocks are probably caused by the presence of ion activators such as Mn2+ and is not an activator/inhibitor combination. In the same way, the absence of luminescence is very probably caused by the absence of activator ions and not due to the low concentration of inhibitor ions such as Fe2+. The incorporation of Mn2+ in the different members of the Jandaíra Formation must have been controlled by the redox state of the depositional environment and diagenesis. Therefore, it is possible that the luminescent members have been formed (e.g.,ooids) or have been modified (gastropod neomorphism) under reduction conditions in the depositional environments, in subsurface during the burial, or, in the case of Rosario Ledge samples , during the post-burial return to surface conditions. As regards the sudden changes from low to moderate and to strong luminescence, these features should indicate the precipitation of a fluid with chemical fluctuations, which formed the frequent zonations in the block cement of the Rosario Ledge samples. This study suggests that the different intensities and colors of CL should be correlated with the Mn2+ and Fe2+ contents, and stable isotopes of samples to determine the salinity, temperature, pH e Eh conditions during deposition

Análise de viabilidade de injeção de fluidos alternativos ao vapor em reservatórios de óleo pesado

Many of hydrocarbon reserves existing in the world are formed by heavy oils (°API between 10 and 20). Moreover, several heavy oil fields are mature and, thus, offer great challenges for oil industry. Among the thermal methods used to recover these resources, steamflooding has been the main economically viable alternative. Latent heat carried by steam heats the reservoir, reducing oil viscosity and facilitating the production. This method has many variations and has been studied both theoretically and experimentally (in pilot projects and in full field applications). In order to increase oil recovery and reduce steam injection costs, the injection of alternative fluid has been used on three main ways: alternately, co-injected with steam and after steam injection interruption. The main objective of these injection systems is to reduce the amount of heat supplied to the reservoir, using cheaper fluids and maintaining the same oil production levels. This works discusses the use of carbon dioxide, nitrogen, methane and water as an alternative fluid to the steam. The analyzed parameters were oil recoveries and net cumulative oil productions. The reservoir simulation model corresponds to an oil reservoir of 100 m x 100 m x 28 m size, on a Cartesian coordinates system (x, y and z directions). It is a semi synthetic model with some reservoir data similar to those found in Brazilian Potiguar Basin. All studied cases were done using the simulator STARS from CMG (Computer Modelling Group, version 2009.10). It was found that waterflood after steam injection interruption achieved the highest net cumulative oil compared to other fluids injection. Moreover, it was observed that steam and alternative fluids, co-injected and alternately, did not present increase on profitability project compared with steamflooding

Análise paramétrica da injeção de vapor e solvente em reservatórios de óleo pesado

A significant fraction of the hydrocarbon reserves in the world is formed by heavy oils. From the thermal methods used to recovery these resources, Steamflooding has been one of the main economically viable alternatives. In Brazil, this technology is widely used by Petrobras in Northeast fields. Latent heat carried by steam heats the oil in the reservoir, reducing its viscosity and facilitating the production. In the last years, an alternative more and more used by the oil industry to increase the efficiency of this mechanism has been the addition of solvents. When co-injected with steam, the vaporized solvent condenses in the cooler regions of the reservoir and mixes with the oil, creating a low viscosity zone between the steam and the heavy oil. The mobility of the displaced fluid is then improved, resulting in an increase of oil recovery. To better understand this improved oil recovery method and investigate its applicability in reservoirs with properties similar to those found in Potiguar Basin, a numerical study was done to analyze the influence of some operational parameters (steam injection rate, injected solvent volume and solvent type) on oil recovery. Simulations were performed in STARS ("Steam, Thermal, and Advanced Processes Reservoir Simulator"), a CMG ("Computer Modelling Group") program, version 2009.10. It was found that solvents addition to the injected steam not only anticipated the heated oil bank arrival to the producer well, but also increased the oil recovery. Lower cold water equivalent volumes were required to achieve the same oil recoveries from the models that injected only steam. Furthermore, much of the injected solvent was produced with the oil from the reservoir

Bioecologia da ictiofauna marinha descartada pelo arrasto camaroeiro em praias da Bacia Potiguar, Brasil

The composition of ichthyofauna discarded by trawling shrimping, their reproductive status and feeding ecology were studied on the beaches of Basin Rio Grande do Norte, Brazil. Fish were collected monthly in the year of 2012. During biometrics, portions of the digestive tract and of gonads were removed, fixed in formalin 10% and Bouin, respectively, for be submitted to histological processing by the techniques of hematoxylin-eosin. Stomach content analyzes were performed using the methods of Frequency of Occurrence and Volumetric and was calculated the repletion index. Throughout the study period were recorded a total of 49 species. The fish assemblages differed between sections monitoring, with the highest abundance, biomass and indices of richness and diversity in sections B, D and C. Already the excerpt A, showed higher values for dominance and equitability. In the cluster analysis according to the faunal similarity was observed the formation of three groups: group I formed by excerpts B and D, group II by excerpt C and group III formed by excerpt A. The assessment of reproductive stage revealed that the fish assemblages discarded by trawling are composed mainly of juveniles. Regarding the feeding ecology, the species Larimus breviceps, Menticirrhus littoralis and Pomadasys corvinaeformis characterized as carnivorous with tendency to carcinofagia. Already Conodon nobilis characterized as carnivorous with tendency to piscivory, but all proved generalist-opportunistic with increase of feeding activity during drought. The dendrogram of grouping of the species developed based on the food items used shows the formation of four groups: Group I consists of species that feed mainly of "gastropod" and "sediment"; group II of "teleost fish"; the group III of "crustacea" and group IV of "echinodermata" and "bivalve". The anatomical and histological characteristics of the digestive tract were consistent with the dietary habits of the analyzed species. In this context, the Costa Branca of Rio Grande do Norte can be considered a feeding site and recruitment for juveniles, which, opportunistically, utilize resources associated with the background

Aplicação e análise de metodologia de deterioração ambiental em micro-bacia do seridó potiguar

In the contemporary world to the deterioration of semi-arid areas of the planet has been the focus of media attention and the scientific community. Brazil has a semiarid, considered the most problematic of the world, either by pressure from physical factors, whether as a result of misguided public policies, has over time been suffering from the consequences of a deterioration that expands over the years. Methodologies, that amidst the problems of semi-arid, come against the deteriorating local, have a good chance to be reapplied in other contexts around the world. This research, based on methodological model for analyzing environmental deterioration, introduced and examined the applicability of the methodology in the semi-arid region of Rio Grande do Norte - Brazil. Although the results provide guidelines for the introduction of underground dams, the application of the methodology was ineffective, given the high rates of forest cover that gave low values for the physical diagnosis conservationist

Evidências da herança geotectônica pré-cambriana na geração da barcia potiguar: um estudo geofísico multdisciplinar

The 3D gravity modeling of the Potiguar rift basin consisted of a digital processing of gravity and aeromagnetic data, subsidized by the results of Euler deconvolution of gravity and magnetic data and the interpretation of seismic lines and wells descriptions. The gravity database is a compilation of independent geophysical surveys conducted by several universities, research institutions and governmental agencies. The aeromagnetic data are from the Bacia Potiguar and Plataforma Continental do Nordeste projects, obtained from the Brazilian Petroleum Agency (ANP). The solutions of the Euler Deconvolution allowed the analysis of the behavior of the rift main limits. While the integrated interpretation of seismic lines provided the delimitating horizons of the sedimentary formations and the basement top. The integration of these data allowed a 3D gravity modeling of basement topography, allowing the identification of a series of internal structures of the Potiguar rift, as well intra-basement structures without the gravity effect of the rift. The proposed inversion procedure of the gravity data allowed to identify the main structural features of the Potiguar rift, elongated in the NE-SW direction, and its southern and eastern faulted edges, where the sedimentary infill reachs thicknesses up to 5500 m. The southern boundary is marked by the Apodi and Baixa Grande faults. These faults seem to be a single NW-SE oriented fault with a strong bend to NE-SW direction. In addition, the eastern boundary of the rift is conditioned by the NE-SW trending Carnaubais fault system. It was also observed NW-SE oriented faults, which acted as transfer faults to the extensional efforts during the basin formation. In the central part of the residual anomaly map without the gravity effect of the rift stands out a NW-SE trending gravity high, corresponding to the Orós-Jaguaribe belt lithotypes. We also observe a gravity maximum parallel to the Carnaubais fault system. This anomaly is aligned to the eastern limit of the rift and reflects the contact of different crustal blocks, limited by the eastern ward counterpart of the Portalegre Shear Zone

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.

Pirometamorfismo em calcários da formação Jandaíra, bacia potiguar, nordeste do Brasil

The present study aims the characterization of thermally affected carbonate rocks from Jandaíra Formation in contact with Paleogene and Neogene basic intrusions in the region of the Pedro Avelino and Jandaíra municipalities (RN), northeastern Brazil. For this study, field, petrographic, x-ray diffraction, electron microprobe, and whole rock litogeochemistry data of carbonates were undertaken. The thermally unaffected limestones are classified like wackstones, grainstones and packstones. They may constitute carbonates grains of benthic foraminifera, echinoderm spines, ostracods, algae, corals, bivalves, gastropods, peloids and intraclasts. The porosities are classified like vug, intraparticle, interparticle, intercrystal and moldic types. The major minerals are calcite, ankerite and dolomite; the detrital are montmorillonite, pyrite, limonite, quartz and microcline. The thermally affected limestones are very coarse to very fine-grained and light to dark gray color. The fossiliferous components totally disappear, and the porosity tends to disappear. With the data obtained, it can be inferred that the carbonate protoliths would be calciferous to dolomitic limestones, both with small amount of clay minerals. Crystalline carbonates from dolomitic protolith have rhombohedral calcite and iron oxides / hydroxides, making the rocks much darker. The carbonates from calciferous protolith have a wide variation of grain size according to the recrystallization degree, increasing toward contact with the basic bodies. In this group, it was identified the minerals lizardite and spinel in weakly to moderately affected samples, and spinel and spurrite in strongly affected rocks, as well as calcite, that occur everywhere. The geological context (shallow level diabase intrusions), the crystallization of the pyrometamorphic minerals spurrite and olivine, and comparison with diagrams from the literature allow estimating temperatures and pressures around 1050-1200 °C and 0.5-1.0 kbar, respectively, for PTOTAL=PCO2. The post-intrusion cooling would have afforded the releasing of metasomatic / hydrothermal fluids, allowing the opening of the metamorphic system, with possible contribution of chemical elements from host units (sandstones, shales) and from basic intrusions. This would induce hydration of previous phases, allowing the formation of serpentine, chlorite and brucite. The results discussed here reveal the strong influence of the heat from basic intrusions within the sedimentary pile. Whereas in the offshore portion of the basin occur sills with up to 1000 m thickness, the understanding of pyrometamorphism might be useful for understanding and measuring the thermally affected rocks.