Extração supercrítica do óleo de linhaça: construção do extrator, estudo de parâmetros de processo, avaliação química e antioxidante do produto

The aim of the present study was to extract vegetable oil from brown linseed (Linum usitatissimum L.), determine fatty acid levels, the antioxidant capacity of the extracted oil and perform a rapid economic assessment of the SFE process in the manufacture of oil. The experiments were conducted in a test bench extractor capable of operating with carbon dioxide and co-solvents, obeying 23 factorial planning with central point in triplicate, and having process yield as response variable and pressure, temperature and percentage of cosolvent as independent variables. The yield (mass of extracted oil/mass of raw material used) ranged from 2.2% to 28.8%, with the best results obtained at 250 bar and 50ºC, using 5% (v/v) ethanol co-solvent. The influence of the variables on extraction kinetics and on the composition of the linseed oil obtained was investigated. The extraction kinetic curves obtained were based on different mathematical models available in the literature. The Martínez et al. (2003) model and the Simple Single Plate (SSP) model discussed by Gaspar et al. (2003) represented the experimental data with the lowest mean square errors (MSE). A manufacturing cost of US$17.85/kgoil was estimated for the production of linseed oil using TECANALYSIS software and the Rosa and Meireles method (2005). To establish comparisons with SFE, conventional extraction tests were conducted with a Soxhlet device using petroleum ether. These tests obtained mean yields of 35.2% for an extraction time of 5h. All the oil samples were sterilized and characterized in terms of their composition in fatty acids (FA) using gas chromatography. The main fatty acids detected were: palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2n-6) and α-linolenic (C18:3n-3). The FA contents obtained with Soxhlet dif ered from those obtained with SFE, with higher percentages of saturated and monounsaturated FA with the Soxhlet technique using petroleum ether. With respect to α-linolenic content (main component of linseed oil) in the samples, SFE performed better than Soxhlet extraction, obtaining percentages between 51.18% and 52.71%, whereas with Soxhlet extraction it was 47.84%. The antioxidant activity of the oil was assessed in the β-carotene/linoleic acid system. The percentages of inhibition of the oxidative process reached 22.11% for the SFE oil, but only 6.09% for commercial oil (cold pressing), suggesting that the SFE technique better preserves the phenolic compounds present in the seed, which are likely responsible for the antioxidant nature of the oil. In vitro tests with the sample displaying the best antioxidant response were conducted in rat liver homogenate to investigate the inhibition of spontaneous lipid peroxidation or autooxidation of biological tissue. Linseed oil proved to be more efficient than fish oil (used as standard) in decreasing lipid peroxidation in the liver tissue of Wistar rats, yielding similar results to those obtained with the use of BHT (synthetic antioxidant). Inhibitory capacity may be explained by the presence of phenolic compounds with antioxidant activity in the linseed oil. The results obtained indicate the need for more detailed studies, given the importance of linseed oil as one of the greatest sources of ω3 among vegetable oils

Arquitetura, litofácies e evolução tectonoestratigráfica da bacia do rio do peixe, nordeste do Brasil

The Rio do Peixe Basin is located in the border of Paraíba and Ceará states, immediately to the north of the Patos shear zone, encompassing an area of 1,315 km2. This is one of the main basins of eocretaceous age in Northeast Brazil, associated to the rifting event that shaped the present continental margin. The basin can be divided into four sub-basins, corresponding to Pombal, Sousa, Brejo das Freiras and Icozinho half-grabens. This dissertation was based on the analysis and interpretation of remote sensing products, field stratigraphic and structural data, and seismic sections and gravity data. Field work detailed the lithofacies characterization of the three formations previously recognised in the basin, Antenor Navarro, Sousa and Rio Piranhas. Unlike the classical vertical stacking, field relations and seismostratigraphic analysis highlighted the interdigitation and lateral equivalency between these units. On bio/chrono-stratigraphic and tectonic grounds, they correlate with the Rift Tectonosequence of neocomian age. The Antenor Navarro Formation rests overlies the crystalline basement in non conformity. It comprises lithofacies originated by a braided fluvial system system, dominated by immature, coarse and conglomeratic sandstones, and polymict conglomerates at the base. Its exposures occur in the different halfgrabens, along its flexural margins. Paleocurrent data indicate source areas in the basement to the north/NW, or input along strike ramps. The Sousa Formation is composed by fine-grained sandstones, siltites and reddish, locally grey-greenish to reddish laminated shales presenting wavy marks, mudcracks and, sometimes, carbonate beds. This formation shows major influence of a fluvial, floodplain system, with seismostratigraphic evidence of lacustrine facies at subsurface. Its distribution occupies the central part of the Sousa and Brejo das Freiras half-grabens, which constitute the main depocenters of the basin. Paleocurrent analysis shows that sediment transport was also from north/NW to south/SE

Atividade antibacteriana e cicatrizante do óleo de buriti Mauritia flexuosa L

O objetivo deste estudo foi avaliar a atividade antibacteriana in vitro e cicatrizante do óleo de buriti (M. flexuosa) em feridas realizadas em ratos (Rattus norvegicus albinus). Para a avaliação antibacteriana in vitro, foram utilizados cinco patógenos bacterianos incluindo espécies gram-positivas e espécies gram-negativas mediante o uso do método de difusão em ágar. Para a avaliação da atividade cicatrizante, foram utilizados 40 ratos da linhagem Wistar, divididos em dois grupos: o grupo I, composto por 20 ratos com feridas cutâneas, tratados com aplicação tópica do creme base com 10% de óleo de buriti, e o grupo II, controle, com o mesmo número de animais que receberam a aplicação tópica do creme base. A aplicação do produto foi realizada em feridas padronizadas, circulares de 1cm de diâmetro na região dorsolombar. As avaliações clínica, morfométrica e histopatológica das feridas foram realizadas no 3°, 7°, 14° e 21° dias. Em relação à avaliação da atividade antibacteriana, os resultados mostraram que houve inibição do crescimento bacteriano em quatro dos cinco patógenos testados. Em relação à área da ferida, foi observada redução significativa da área no 14o dia e maior percentual de contração das feridas do grupo tratado em relação ao controle. No décimo quarto dia, as feridas tratadas com o óleo do buriti apresentavam aumento significativo na contagem de fibroblastos e fibras colágenas, além de completo processo de reepitelização, enquanto o grupo controle necessitava de mais tempo para resolução do processo cicatricial

Investigação e avaliação da toxicidade aguda dos agrotóxicos mais utilizados no cinturão verde da Grande Natal (RN, Brasil) para o peixe-zebra (Danio rerio Hamilton Buchanan, 1822, Teleostei, Cyprinidae

The objectives of this research were to investigate the agrotoxic most used in the Gramorezinho region in the green belt of Natal, and to evaluate the acute toxicity of these, based on the LC50-48h values estimated in tests for Danio rerio, internationally used as test organism. The acute toxicity tests were performed under laboratory conditions, according to standardized methods (ABNT/NBR/15088/04) for this species. The LC50-48h estimated to Tamaron BR was 352.89 mg.L-1, which characterizes that as practically non-toxic, according to toxicological classes cited by Zucker. For Decis 25EC, the LC50-48h estimated was 0.0004156 mg.L-1 (4.156 X 10-4 mg.L-1), which classifies it as highly toxic to this species

Avaliação da toxicidade aguda do inseticida metomil e o seu efeito sobre a atividade da acetilcolinesterase do peixe Danio rerio

Methomyl (Lannate®) is an insecticide from the carbamate group, frequently used in pest control in various types of crops. This compound works inhibiting the activity of the enzyme acetylcholinesterase. The use of physicochemical and ecotoxicological analysis is the most efficient strategy for the correct characterization and control of residues of metomil. The main objectives of this study were to evaluate the acute toxicity of methomyl in 96 hours of exposure and, through a sublethal assay of 5 hours, to assess its effect on the activity of acetylcholinesterase present in brain and squeletic dorsal muscle of the Danio rerio fish. The results showed that the LC50-96 found to D. rerio was 3.4 mg/L and it was found through the average of four definitive tests. In vitro assays were used to test the inhibitory action of methomyl directly over soluble AChE, extracted from the squeletic dorsal muscle, with maximum inhibition of 68.57% to the insecticide concentrations of 0.2 mg/L. In sublethal tests with D. rerio, inhibitory effect of methomyl was found over the soluble form of AChE in the squeletic dorsal muscle, both in one and five hours of fish exposure to the insecticide. In both period, the average values of inhibition were around 61%. In the same condition, no significant inhibitory effect of methomyl soluble and membrane AChE of the D. rerio was observed in the 0.42, 0.85, 1.70 and 2.50 mg/L concentrations and in both times of fish exposure

Diversidade Ictiofaunística e Ecologia reprodutiva de uma espécie nativa de peixe da Bacia Piranhas-Assu, RN

The Caatinga biome is rich in endemic fish species fauna. The present study the results of fish faunal surveys conducted in the hydrographic basin of Piranhas-Assu of the Brazilian Caatinga biome. The fish samples collected were distributed in four orders (Characiformes, Perciformes, Siluriformes and Synbranchiformes), 11 families (Characidae, Curimatidae, Auchenipteridae, Anostomidae, Prochilodontidae, Erythrinidae, Cichlidae, Sciaenidae, Heptapteridae, Loricariidae, Synbranchidae) and 22 species, of which 17 are endemic and five have been introduced from other basins. The order Characiformes was the most representative in number of species (46,35% ) followed by Perciformes (35,38%), Siluriformes (17,44%) and Synbranchiformes (0,5%). The Nile tilapia, Oreochomis niloticus, the only exotic species, was most expressive in number of individuals (24.92%) followed by the native species piau preto, Leporinus piau (18,77 %). Considering the relative frequency of occurrence of the 22 species, 13 were constant, five were accessory and four were occasional. This study investigated the reproductive ecology of an endemic fish black piau, Leporinus piau from the Marechal Dutra reservoir, Acari, Rio Grande do Norte. Samplings were done on a monthly basis from January to December 2009, and a total of 211 specimens were captured. The environmental parameters such as rainfall, temperature, pH, electrical conductivity and dissolved oxygen of water were recorded. The sampled population showed a slight predominance of males (55%), however females were larger and heavier. Both sexes of L. piau showed positive allometric growth, indicating a higher increase of weight than length. The first sexual maturation of males occurred at smaller size, with 16.5 cm in total length than females (20.5 cm). During the reproductive period, the condition factor and gonadosomatic index (GSI) of L. piau were negatively correlated. This species has large oocytes with a high mean fecundity of 54.966 with synchronous oocyte development and total spawning

Ecologia reprodutiva do peixe-donzela, Stegastes fuscus cuvier, 1830 (osteichthyes: pomacentridae) em arrecifes rochosos da praia de Búzios, Rio Grande do Norte, Brasil

The reproductive ecology of fish plays a key role both for rational exploitation methods and for protective measures of natural stocks. The purpose of this study was to analyze the reproductive aspects of the damsel-fish, Stegastes fuscus, during October 2004 to September 2005, in the coastal rocky reefs of Búzios Beach, Nísia Floresta, RN. Fish were captured using hooks and hand nets, during low tide. Reproduction was determined using sexual ratio, mean length of first maturation (L50), absolute fecundity and macroscopic characteristics of gonads. The following parameters were related to gonadosomatic index (GSI): condition factor (CF), hepatosomatic index (HSI), rain fall and temperature. In relation to sex distribution, it was observed that 78% were females and 22% were males. The L50 was 6.2 cm for females and 7.0 for males. Average fecundity was 6832 oocytes. Results showed that S. fuscus had better body condition in the months prior to spawning, particularly during initial and intermediate stages of maturation. Five stages of gonadal maturation were identified through macroscopic analysis: immature, in maturation, mature, spent and resting. The HSI was inversely related to the GSI. This was possibly due to the reproductive cycle of this species which was associated to the dry period of this region. During this period, low rain fall and high temperatures provide an propitious reproductive condition for the study species

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

Estudo paramétrico da recuperação de óleo no processo de drenagem gravitacional com injeção de CO2

The gas injection has become the most important IOR process in the United States. Furthermore, the year 2006 marks the first time the gas injection IOR production has surpassed that of steam injection. In Brazil, the installation of a petrochemical complex in the Northeast of Brazil (Bahia State) offers opportunities for the injection of gases in the fields located in the Recôncavo Basin. Field-scale gas injection applications have almost always been associated with design and operational difficulties. The mobility ratio, which controls the volumetric sweep, between the injected gas and displaced oil bank in gas processes, is typically unfavorable due to the relatively low viscosity of the injected gas. Furthermore, the difference between their densities results in severe gravity segregation of fluids in the reservoirs, consequently leading to poor control in the volumetric sweep. Nowadays, from the above applications of gas injection, the WAG process is most popular. However, in attempting to solve the mobility problems, the WAG process gives rise to other problems associated with increased water saturation in the reservoir including diminished gas injectivity and increased competition to the flow of oil. The low field performance of WAG floods with oil recoveries in the range of 5-10% is a clear indication of these problems. In order to find na effective alternative to WAG, the Gas Assisted Gravity Drainage (GAGD) was developed. This process is designed to take advantage of gravity force to allow vertical segregation between the injected CO2 and reservoir crude oil due to their density difference. This process consists of placing horizontal producers near the bottom of the pay zone and injecting gás through existing vertical wells in field. Homogeneous models were used in this work which can be extrapolated to commercial application for fields located in the Northeast of Brazil. The simulations were performed in a CMG simulator, the STARS 2007.11, where some parameters and their interactions were analyzed. The results have shown that the CO2 injection in GAGD process increased significantly the rate and the final recovery of oil

Análise da trajetória de poços horizontais em reservatório de óleo pesado

The application of thermal methods, to increase the recovery of heavy oil in mature fields through drainage with multilateral and horizontal wells, has been thoroughly studied, theorically, experimentally, testing new tools and methods. The continuous injection of steam, through a steam injector well and a horizontal producer well in order to improve horizontal sweep of the fluid reservoir, it is an efficient method. Starting from an heterogeneous model, geologically characterized, modeling geostatistics, set history and identification of the best path of permeability, with seismic 3D, has been dubbed a studying model. It was studied horizontal wells in various directions in relation to the steam and the channel of higher permeability, in eight different depths. Into in the same area were studied, the sensitivity of the trajectories of horizontal wells, according to the depth of navigation. With the purpose of obtaining the highest output of oil to a particular flow, quality, temperature and time for the injection of steam. The wells studied showed a significant improvement in the cumulative oil recovery in one of the paths by promoting an alternative to application in mature fields or under development fields with heavy oil

Análise de um queimador infravermelho funcionando com combustível híbrido : GLP/Bio-óleo

Biomass is considered the largest renewable energy source that can be used in an environmentally sustainable. From the pyrolysis of biomass is possible to obtain products with higher energy density and better use properties. The liquid resultant of this process is traditionally called bio-oil. The use of infrared burners in industrial applications has many advantages in terms of technical-operational, for example, uniformity in the heat supply in the form of radiation and convection, with a greater control of emissions due to the passage of exhaust gases through a macroporous ceramic bed. This paper presents a commercial infrared burner adapted with an ejector proposed able to burn a hybrid configuration of liquefied petroleum gas (LPG) and bio-oil diluted. The dilution of bio-oil with absolute ethanol aimed to decrease the viscosity of the fluid, and improving the stability and atomization. It was introduced a temperature controller with thermocouple modulating two stages (low heat / high heat), and solenoid valves for fuels supply. The infrared burner has been tested, being the diluted bio-oil atomized, and evaluated its performance by conducting energy balance. The method of thermodynamic analysis to estimate the load was used an aluminum plate located at the exit of combustion gases and the distribution of temperatures measured by thermocouples. The dilution reduced the viscosity of the bio-oil in 75.4% and increased by 11% the lower heating value (LHV) of the same, providing a stable combustion to the burner through the atomizing with compressed air and burns combined with LPG. Injecting the hybrid fuel there was increase in the heat transfer from the plate to the environment in 21.6% and gain useful benefit of 26.7%, due to the improved in the efficiency of the 1st Law of Thermodynamics of infrared burner

Caracterização batimétrica e fisicooceanográfica do canal de acesso ao porto de Cabedelo/PB: uma análise ambiental ao derrame de óleo

The State of Paraíba is one of the most dynamic states of Brazil, strategically located in the northeast, is notable for the excellent potential for integration of different transportation modes forming the states of Rio Grande do Norte, Pernambuco and Alagoas. The dynamic that occurs with port activity causes changes in the space where it is installed. And the elements of this space are always more than suffering direct or indirect influences as the flow in the port is expanded. Therefore, this region became subject to the accidental spillage of oil, because it presents a heavy traffic of ships of various sizes that can run aground or collide with oil causing accidental events. The study of geomorphological and sedimentological compositions of seafloor becomes important as more is known about the relationships between these parameters and associated fauna, and can identify their preferred habitats. The database background, acoustically collected along the proposed study area, is a wealth of information, which were duly examined, cataloged and made available. Such information can serve as an important tool, providing a geomorphological survey of the sedimentary area studied, and come to subsidize, in a flexible, future decision making. With the study area Port of Cabedelo, Paraíba - Brazil, this research aimed to evaluate the influence of the tidal surface and background in modeling the seabed, including the acquisition of information about the location of submerged rocky bodies and the depth of these bodies may turn out to be natural traps for the trapping of oil in case of leaks, and obtain the relationship between types of bed and the hydrodynamic conditions present in the region. In this context, for this study were collected bathymetric data (depth) and physical oceanographic (height of water column, water temperature, intensity and direction of currents, waves and turbidity), meteorological (rainfall, air temperature, humidity, winds and barometric pressure) of the access channel to the Port of Cabedelo / PB and its basin evolution (where the cruise ships dock), and includes tools of remote sensing (Landsat 7 ETM +, 2001), so that images and the results are integrated into Geographic Information Systems and used in the elaboration of measures aimed at environmental protection areas under the influence of this scale facilities, serving as a grant to prepare a contingency plan in case of oil spills in the region. The main findings highlight the techniques of using hydroacoustic data acquisition together bathymetric surveys of high and low frequency. From there, five were prepared in bathymetric pattern of Directorate of Hydrography and Navigation - DHN, with the depth in meters, on a scale of 1:2500 (Channel and Basin Evolution of Access to Port of Cabedelo), where there is a large extent possible beachrocks that hinder the movement of vessels in the port area, which can cause collisions, running aground and leaking oil. From the scatter diagram of the vectors of currents, it can be seen as the tidal stream and undergoes a channeling effect caused by the bidirectional effect of the tide (ebb and flood) in the basin of the Port of Cabedelo evolution in NW-direction SE and the highest speed of the currents occurs at low tide. The characterization weather for the period from 28/02 to 04/07/2010 values was within the expected average for the region of study. The multidisciplinary integration of products (digital maps and remote sensing images), proved to be efficient for the characterization of underwater geomorphological study area, reaching the aim to discriminate and enhance submerged structures, previously not visible in the images

Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Estudo do processo de combustão in-situ usando poços horizontais como produtores de óleo (Toe-to-Hell Air Injection)

The method "toe-to-heel air injection" (THAITM) is a process of enhanced oil recovery, which is the integration of in-situ combustion with technological advances in drilling horizontal wells. This method uses horizontal wells as producers of oil, keeping vertical injection wells to inject air. This process has not yet been applied in Brazil, making it necessary, evaluation of these new technologies applied to local realities, therefore, this study aimed to perform a parametric study of the combustion process with in-situ oil production in horizontal wells, using a semi synthetic reservoir, with characteristics of the Brazilian Northeast basin. The simulations were performed in a commercial software "STARS" (Steam, Thermal, and Advanced Processes Reservoir Simulator), from CMG (Computer Modelling Group). The following operating parameters were analyzed: air rate, configuration of producer wells and oxygen concentration. A sensitivity study on cumulative oil (Np) was performed with the technique of experimental design, with a mixed model of two and three levels (32x22), a total of 36 runs. Also, it was done a technical economic estimative for each model of fluid. The results showed that injection rate was the most influence parameter on oil recovery, for both studied models, well arrangement depends on fluid model, and oxygen concentration favors recovery oil. The process can be profitable depends on air rate