Síntese e caracterização de materiais nanoporosos para pirólise catalítica de óleos pesados

The present work reports the study of nanoporous structures, aiming at their use in research directed to the current demand of the petroleum industry to value heavy oil. Initially, two ways were chosen for the synthesis of porous structures from the molecular sieves of type Si-MCM-41. In the first way, the structure MCM-41 is precursory for heteroatom substitutes of silicon, generating catalyst of the type Al-MCM-41 from two different methods of incorporation of the metal. This variation of the incorporation method of Aluminum in the structure of Si-MCM-41 was carried out through the conventional procedure, where the aluminum source was incorporated to the gel of synthesis, and the procedure post-synthesis, where the Aluminum source was incorporated in catalyst after the synthesis of Si-MCM-41. In the second way, the MCM-41 acts as a support for growth of nanocrystals of zeolite embedded in their mesoporous, resulting in hybrid MCM-41/ZSM-5 catalyst. A comparative analysis was carried through characterizations by XRD, FTIR, measures of acidity through n-butylamine adsorption for TGA, SEM-XRF and N2 adsorption. Also crystalline aluminosilicate with zeolitic structure MFI of type ZSM-5 was synthesized without using organic templates. Methodologies to the preparation of these materials are related by literature using conventionally reactants that supply oxides of necessary silicon and aluminum, as well as a template agent, and in some cases co-template. The search for new routes of preparation for the ZSM-5 aimed at, above all, the optimization of the same as for the time and the temperature of synthesis, and mainly the elimination of the use of organic templates, that are material of high cost and generally very toxic. The current study is based on the use of the H2O and Na+ cations playing the role of structural template and charge compensation in the structure. Characterizations by XRD, FTIR, SEM-XRF and N2 adsorption were also conducted for this material in order to compare the samples of ZSM-5 synthesized in the absence of template and those used industrially and synthesized using structuring

Avaliação da poatencialidade da perlita natural e expandida na adsorção de metais

The contamination by metal ions has been occurring for decades through the introduction of liquid effluent not treated, mainly from industrial activities, rivers and lakes, affecting water quality. For that the effluent can be disposed in water bodies, environmental standards require that they be adequately addressed, so that the concentration of metals does not exceed the limits of standard conditions of release in the receptor. Several methods for wastewater treatment have been reported in the literature, but many of them are high cost and low efficiency. The adsorption process has been used as effective for removal of metal ions. This paper presents studies to evaluate the potential of perlite as an adsorbent for removing metals in model solution. Perlite, in its natural form (NP) and expanded (EP), was characterized by X-ray fluorescence, X-ray diffraction, surface area analysis using nitrogen adsorption (BET method), scanning electron microscopy and Fourier transform infrared spectroscopy. The physical characteristic and chemical composition of the material presented were appropriate for the study of adsorption. Adsorption experiments by the method of finite bath for model solutions of metal ions Cr3+, Cu2+, Mn2+ and Ni2+ were carried out in order to study the effect of pH, mass of the adsorbent and the contact time on removal of ions in solution. The results showed that perlite has good adsorption capacity. The NP has higher adsorption capacity (mg g-1) than the EP. According to the values of the constant of Langmuir qm (mg g-1), the maximum capacity of the monolayer was obtained and in terms of proportion of mass, we found the following order experimental adsorption: Cr3+ (2.194 mg g- 1) > Ni2+ (0.585 mg g-1) > Mn2+ (0.515 mg g-1) > Cu2+ (0.513 mg g-1) and Cr3+ (1.934 mg g-1)> Ni2+ (0.514 mg g-1) > Cu2+ (0.421 mg g-1) > Mn2+ (0.364 mg g-1) on the NP and EP, respectively. The experimental data were best fitted the Langmuir model compared to Freundlich for Cu2+, Mn2+ and Ni2+. However, for the Cr3+, both models fit the experimental data

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Avaliação do potencial de toxicidade de florações de cianobactérias como subsídio para ações de gestão ambiental em açudes do semiárido potiguar

Blooms negatively compromise the aquatic environment, plants, animals and human health.Some species are toxin-producing, such as the neurotoxin saxitoxin and the hepatotoxin microcystin, which may contaminate water reservoirs, as those existing in the semiarid region of Rio Grande do Norte (Brazil) which are used to supply the population, fishing, aquiculture and recreational activities, thereby providing the risk of human exposure through water intake, dermal contact and respiratory tract. Thus, it is recommended a constant monitoring of the density of cyanobacteria with the quantification of cyanotoxins. One goal with this work was the monitoring of water in four reservoirs in semiarid of RN through the identification and enumeration of cyanobacteria and through the identification and quantification of cyanotoxins by ELISA. Furthermore, we intended to assess the environmental perception of farmers and artisanal fishers in reservoirs of semiarid of RN through semi-structured interviews with questions mostly related to water and eutrophication. Through these objectives the aim was the development of management strategies for aquaculture and prevention of risks to public health. The results showed that the highest values of microcystins were found in the rainy season. Standards for drinking water, according to the guidelines of Ministry of Health 2914/2011 and CONAMA 357/05, setting the maximum values for raw water density of cyanobacteria: 50,000 cel.mL-1; microcystin: 1 μg. L-1 and saxitoxin: 3 μg. L-1. The values found for microcystin ranged between 0.00227 μg. L-1 and 24.1954 μg. L-1. From 128 samples analyzed, 27% were above the limit. There was no clear seasonal pattern for saxitoxins and their values ranged between 0.003 μg. L-1 and 0.766 μg. L-1 with none of the values above the limit. Furthermore, 76% of the densities of cyanobacteria values were above the limit. About environmental perception, 52 interviews were conducted and the results show that the respondents recognize the main uses of water of the rervoirs, recognize the importance and have a positive view about the reservoirs. They also realize that the water has a poor quality and can cause health problems. The results provide data showing the persistence of cyanobacteria and cyanotoxins, many times over the limit, reinforcing the importance of constant monitoring. The assessment of environmental perception gives foundation for later proposed environmental education linked to public health management into the context of this particular population, making it more effective

Uso do GPR na geração de modelos estáticos 3D para o planejamento de lavra de minerais pesados depositados em dunas eólicas

This project was developed as a partnership between the Laboratory of Stratigraphical Analyses of the Geology Department of UFRN and the company Millennium Inorganic Chemicals Mineração Ltda. This company is located in the north end of the paraiban coast, in the municipal district of Mataraca. Millennium has as main prospected product, heavy minerals as ilmenita, rutilo and zircon presents in the sands of the dunes. These dunes are predominantly inactive, and overlap the superior portion of Barreiras Formation rocks. The mining happens with the use of a dredge that is emerged at an artificial lake on the dunes. This dredge removes sand dunes of the bottom lake (after it disassembles of the lake borders with water jets) and directs for the concentration plant, through piping where the minerals are then separate. The present work consisted in the acquisition external geometries of the dunes, where in the end a 3D Static Model could be set up of these sedimentary deposits with emphasis in the behavior of the structural top of Barreiras Formation rocks (inferior limit of the deposit). The knowledge of this surface is important in the phase of the plowing planning for the company, because a calculation mistake can do with that the dredge works too close of this limit, taking the risk that fragments can cause obstruction in the dredge generating a financial damage so much in the equipment repair as for the stopped days production. During the field stages (accomplished in 2006 and 2007) topographical techniques risings were used with Total Station and Geodesic GPS as well as shallow geophysical acquisitions with GPR (Ground Penetrating Radar). It was acquired almost 10,4km of topography and 10km of profiles GPR. The Geodesic GPS was used for the data geopositioning and topographical rising of a traverse line with 630m of extension in the stage of 2007. The GPR was shown a reliable method, ecologically clean, fast acquisition and with a low cost in relation to traditional methods as surveys. The main advantage of this equipment is obtain a continuous information to superior surface Barreiras Formation rocks. The static models 3D were elaborated starting from the obtained data being used two specific softwares for visualization 3D: GoCAD 2.0.8 and Datamine. The visualization 3D allows a better understanding of the Barreiras surface behavior as well as it makes possible the execution of several types of measurements, favoring like calculations and allowing that procedures used for mineral extraction is used with larger safety

Caracterização de minerais pesados ao longo do Rio Piranhas-Açu/RN distribuição e proveniência

This dissertation deals with the characterization, distribution and provenience of heavy minerals along the Piranhas-Açu River, from the City of Parelhas (Seridó River) to your mouth at the City of Macau-RN. Many heavy minerals species were recorded in this study: clinoamphibole, epidote (including zoisite), garnet, sillimanite, tourmaline, staurolite, andalusite, zircon, rutile, augite, ilmenite, hematite and magnetite. Major transparent minerals, those forming more than 5% of some assemblages, are hornblende, epidote, tourmaline, staurolite and zircon. Predominant opaque mineral is ilmenite. Six assemblages were identified along the river: (i) Garnet-hornblende-tourmaline with sillimanite, when cutting rocks of the Seridó Formation; (ii) Hornblende-garnet-zircon, when crossing rocks of the Caicó gnaisse-migmatitic Complex; (iii) Hornblende-zircon-epidote-staurolite, when draining rocks of the Jucurutu Formation; (iv) Hornblende-zircon-epidote, when cutting rocks of the Açu Formation; (v) Hornblende-zircon-staurolite, on the lowermost Açu River, when crossing limestones of the Jandaíra Formation and (vi) Zircon-tourmaline-staurolite in the Açu River mouth (Cenozoic rocks) where coastal process dominate. Mineral ratios that reflect differences in grain shape, density, and selective chemical decomposition were used in an attempt to isolate the effects of source and process as controls of mineral variability. Reworking of the sediments was regionally effective in selective sorting; the more equant minerals (e.g. epidote) and heavier minerals (e.g. opaques) had a higher probability of being selected for permanent deposition during reworking. The processes of selective decomposition stand out at the river mouth. A priori knowledge of provenance, associated with the assemblage distribution and effects of process were utilized to the interpretations, that points to the follow provenances: hornblende comes from micashists of the Seridó Formation, orthognaisses and amphibolites of the Caico Complex, paragnaisses and paranphibolites of the Jucurutu Formation and granites intrusions; epidote comes from paragnaisses and calciosilicatics of the Jucurutu Formation, granites intrusions (-Npy3al/ca and -Npy3mz, gravels deposits and Açu Formation; Andalusite and staurolite come from the Seridó Formation; Sillimanite, tourmaline and garnet come from micashists of the Seridó Formation, as well as from quartzites of the Equador Formation; Zircon comes from Precambrian rocks (pink and prismatic zircon) and from sediments of several cycles (round zircon); Opaques come from all rocks cutted for the Piranhas-Açu River; Rutile comes from metamorphic rocks, in general; Augite comes from the Ceará-Mirim, Serra do Cuó and Macau volcanisms. The texture of gravels deposits reveals a sediment transport mechanisms by traction-current processes, together with a diagenetic clay matrix suggests a hot-humid environments for deposition. The presence of unstable heavy minerals assemblages, as well as pebbles of different composition and degrees of rounding and esfericity, indicate more than one source. The occurrence of calcio/alkaline granites suites, in areas closed to the gravel deposits, suggests that these intrusions are the main source of sediments. This could explain for instance, the significant amounts of epidote and presence of unstable heavy minerals (e.g. hornblende). The analyses of heavy minerals also show significante variability between the modern (Piranhas-Açu) and ancestral (Açu Formation) river sediments. In general, these variations reflect relatively higher unstable and lower stable heavy minerals contents of the modern Piranhas-Açu sediments. The absence of significant compositional differences probably reflects uniform weathering conditions

Determinação da concentração de metais no material particulado (PM10 e PM2,5) do ar atmosférico em uma área urbana da cidade do Natal – RN

This study aimed to assess ambient air quality in a urban area of Natal, capital of Rio Grande do Norte (latitude 5º49'29 '' S and longitude 35º13'34'' W), aiming to determine the metals concentration in particulate matter (PM10 and PM2,5) of atmospheric air in the urban area o the Natal city. The sampling period for the study consisted of data acquisition from January to December 2012. Samples were collected on glass fiber filters by means of two large volumes samplers, one for PM2,5 (AGV PM 2,5) and another for PM10 (PM10 AGV). Monthly averages ranged from 8.92 to 19.80 g.m-3 , where the annual average was 16,21 g.m-3 for PM10 and PM2,5 monthly averages ranged from 2,84 to 7,89 g.m -3 , with an annual average of 5,61 g.m-3 . The results of PM2,5 and PM10 concentrations were related meteorological variables and for information on the effects of these variables on the concentration of PM, an exploratory analysis of the data using Principal Component Analysis (PCA) was performed. The results of the PCA showed that with increasing barometric pressure, the direction of the winds, the rainfall and relative humidity decreases the concentration of PM and the variable weekday little influence compared the meteorological variables. Filters containing particulate matter were selected in six days and subjected to microwave digestion. After digestion samples were analyzed by with Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The concentrations for heavy metals Vanadium, Chromium, Manganese, Nickel, Copper, Arsenic and lead were determined. The highest concentrations of metals were for Pb and Cu, whose average PM10 values were, respectively, 5,34 and 2,34 ng.m-3 and PM2,5 4,68 and 2,95 ng.m-3 . Concentrations for metals V, Cr, Mn, Ni, and Cd were respectively 0,13, 0,39, 0,48, 0,45 and 0,03 ng.m-3 for PM10 fraction and PM2,5 fraction, 0,05, 0,10, 0,10, 0,34 and 0,01 ng.m-3. The concentration for As was null for the two fractions

Metagenoma de comunidades microbianas expostas à radiação natural e a metais

Many species have specialized to live in the most varied existing environments showing the remarkable adaptability of the microbial world the most diverse physicochemical conditions. Environments exposed to natural radiation and metals are scarce around the world, presenting a microbiota still unknown. With a total number estimated between 4 and 6 x 1030 microrganisms on earth, they constitute an enormous biological and genetic pool to be explored. Metagenomic approach independent of cultivation, provides a new form to access to the potential genomic environmental samples becoming a powerful tool for the elucidation of ecological functions, metabolic profiles, as well as to identify new biomolecules. In this context, the genetic material of environmental soil and water samples from Açude Boqueirao Parelhas-RN, under the influence of natural radiation and the presence of metals, was extracted, pirosequencing and the generated sequences were analyzed by bioinformatics programs (MG-RAST and STAMP). Taxonomic comparative profiles of both samples showed high abundance of Domain Bacteria, followed by a small portion attributable to Eucaryota Domains, Archaea and Viruses. Proteobacteria, Actinobacteria and Bacterioidetes phyla showed the greater dominance in both samples. Important genera and species associated with resistance to various stressors found in region were observed. Sequences related to oxidative and heat stress, DNA replication and repair, and resistance to toxic compounds were observed, suggesting a significant relationship between the microbiota and their metabolic profile, influenced by regional environmental variables. The results of this study add valuable and unpublished data on the composition of microbial communities in these regions

Síntese e caracterização de complexo tetranuclear de cobre com o ligante resorcinareno

The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxoplásmico character.

Recuperação avançada de óleos pesados em poços fraturados utilizando aquecimento eletromagnético indutivo

The success achieved by thermal methods of recovery, in heavy oils, prompted the emergence of studies on the use of electromagnetic waves as heat generating sources in oil reservoirs. Thus, this generation is achieved by three types of different processes according to the frequency range used. They are: the electromagnetic induction heating, the resistive and the dielectric, also known as radiation. This study was based on computer simulations in oil reservoirs with characteristics similar to those found in the sedimentary basins of the Brazilian Northeast. All cases studied were simulated using the software STARS, CMG (Computer Group, version 2012.10 Modeling). Some simulations took into account the inclusion of electrically sensitive particles in certain sectors of the reservoir model studied by fracturing. The purpose of this work is the use of the electromagnetic induction heating as a recovery method of heavy oil, to check the influence of these aforementioned particles on the reservoir model used. Comparative analyses were made involving electromagnetic induction heating, the operation of hydraulic fracturing and the injection of water to the different situations of the reservoir model studied. It was found that fracturing the injection well in order that the electromagnetic heating occurs in the same well where there is water injection, there was a considerable increase in the recovery factor and in the cumulative oil production in relation to the models in which hydraulic fracturing occurred in the production well and water injection in the injection well. This is due to the generation of steam in situ in the reservoir.

Avaliação da toxicidade subcrônica e reprodutiva do extrato seco de pericarpo de passiflora edulis variedade flavicarpa degener em ratos

The pericarp of Passiflora edulis var. flavicarpa Degener is now being investigated for medicine purposes. There are no reports about it toxicity. The aim of the present study was investigate the sub chronic toxicity in male rats and reproductive toxicity in pregnant rats and exposed fetuses of an extract obtained by infusion of the pericarp in water (1:3 m/v;100o C, 10 min). The extract composition was evaluated by tube reactions and thin lawyer chromatography (TLC). Adult male rats (n=8) were treated with 300 mg/kg of the extract, by gavage, during 30 days and pregnant rats (n=7) from gestation day 0 to day 20. Control received tap water (1 mL). Water and food intakes and body weight gain were recorded. At day 29 of treatment the sexual behavior of the males was analyzed and then half of males from each group received cyclophosphamide (50 mg/kg, i.p.) to (anti)genotoxic assessment in bone marrow. At day 30, males were anesthesized for parameters collection. At day 20 of gestation, the dams were anesthesized for reproductive performance evaluation. The fetal analysis was conducted by visceral and skeletal. Phytochemical analysis revealed the presence of flavonoids, unspecific alkaloids, phenols and triterpenic compounds. Statistical analysis revealed absence of significant differences between experimental and control. This study suggest that the aqueous extract obtained from pericarp of P. edulis var. flavicarpa Degener was not able to promote toxic effects in rats. Cytotoxicity was evaluated with the PCE/NCE ratio (NCE=normochromatic erythrocytes). Statistical analysis (mean ± SEM) revealed absence of changes in the frequency of MNPCE (negative control: 3.26±0.42; positive control: 11.72±1.02; negative experimental: 4.02±0.13; positive experimental: 10.47±0.87) or cytotoxicity (negative control: 0.37±0.08; positive control: 0.23±0.05; negative experimental: 0.37±0.07; positive experimental: 0.23±0.02). This study suggests that the extracts showed no (anti)genotoxic and no cytotoxic activities under the experimental conditions.