Síntese e caracterização do carbeto de molibdênio nanoestruturado para fins catalíticos na reação de oxidação parcial do metano

The nanostructures materials are characterized to have particle size smaller than 100 nm and could reach 1 nm. Due to the extremely reduced dimensions of the grains, the properties of these materials are significantly modified relatively when compared with the conventional materials. In the present work was accomplished a study and characterization of the molybdenum carbide, seeking obtain it with particles size in the nanometers order and evaluate its potential as catalyst in the reaction of partial methane oxidation. The method used for obtaining the molybdenum carbide was starting from the precursor ammonium heptamolybdate of that was developed in split into two oven, in reactor of fixed bed, with at a heating rate of 5ºC/min, in a flow of methane and hydrogen whose flow was of 15L/h with 5% of methane for all of the samples. The studied temperatures were 350, 500, 600, 650, 660, 675 and 700ºC and were conducted for 0, 60, 120 and 180 minutes, and the percent amount and the crystallite size of the intermediate phases were determined by the Rietveld refinement method. The carbide obtained at 660ºC for 3 hours of reaction showed the best results, 24 nm. Certain the best synthesis condition, a passivating study was accomplished, in these conditions, to verify the stability of the carbide when exposed to the air. The molybdenum carbide was characterized by SEM, TEM, elemental analysis, ICP-AES, TG in atmosphere of hydrogen and TPR. Through the elemental analysis and ICP-AES the presence carbon load was verified. TG in atmosphere of hydrogen proved that is necessary the passivating of the molybdenum carbide, because occur oxidation in room temperature. The catalytic test was accomplished in the plant of Fischer-Tropsch of CTGAS, that is composed of a reactor of fixed bed. Already the catalytic test showed that the carbide presents activity for partial oxidation, but the operational conditions should be adjusted to improve the conversion

Preparação e caracterização de um material híbrido, à base de vermiculita modificada com quitosana, para a remoção de íons de chumbo presentes em efluentes sintéticos

Actually, surveys have been developed for obtaining new materials and methodologies that aim to minimize environmental problems due to discharges of industrial effluents contaminated with heavy metals. The adsorption has been used as an alternative technology effectively, economically viable and potentially important for the reduction of metals, especially when using natural adsorbents such as certain types of clay. Chitosan, a polymer of natural origin, present in the shells of crustaceans and insects, has also been used for this purpose. Among the clays, vermiculite is distinguished by its good ion exchange capacity and in its expanded form enhances its properties by greatly increasing its specific surface. This study aimed to evaluate the functionality of the hybrid material obtained through the modification of expanded vermiculite with chitosan in the removal of lead ions (II) in aqueous solution. The material was characterized by infrared spectroscopy (IR) in order to evaluate the efficiency of modification of matrix, the vermiculite, the organic material, chitosan. The thermal stability of the material and the ratio clay / polymer was evaluated by thermogravimetry. To evaluate the surface of the material was used in scanning electron microscopy (SEM) and (BET). The BET analysis revealed a significant increase in surface area of vermiculite that after interaction with chitosan, was obtained a value of 21, 6156 m2 / g. Adsorption tests were performed according to the particle size, concentration and time. The results show that the capacity of removal of ions through the vermiculite was on average 88.4% for lead in concentrations ranging from 20-200 mg / L and 64.2% in the concentration range of 1000 mg / L. Regarding the particle size, there was an increase in adsorption with decreasing particle size. In fuction to the time of contact, was observed adsorption equilibrium in 60 minutes with adsorption capacity. The data of the isotherms were fitted to equation Freundlich. The kinetic study of adsorption showed that the pseudo second- order model best describes the adsorption adsorption, having been found following values K2=0,024 g. mg-1 min-1and Qmax=25,75 mg/g, value very close to the calculated Qe = 26.31 mg / g. From the results we can conclude that the material can be used in wastewater treatment systems as a source of metal ions adsorbent due to its high adsorption capacity

Caracterização morfológica e microestrutural da perovskita BaCexPr1-xO3 sintetizada a partir do método de complexação combinando EDTA/Citrato

In this study, binary perovskite (BaCexO3) were doped with praseodymium (Pr) to obtainment of the ternary material BaCexPr1-xO3. This material was synthesized by the complexation method combining EDTA/Citrate with the stoichiometric ratio of the element Praseodymium ranging from x = 0.1 to x = 0.9 in order to determine the influence of this rare earth element on the morphology and microstructure of the final powder. At first the material was synthesized based on the route proposed by literature (Santos, 2010), and then characterized by SEM and XRD, besides being refined by the Rietveld method. In the material that had lowest residual parameter, S, and lowest average size of crystal, pH variation of synthesis solution was made in order to identify the influence of this parameter on the morphology and microscopy of the final powder. The results show that addition of praseodymium did not directly influence the crystallographic and lattice parameters, keeping even the same orthorhombic structure of the binary material BaCexO3, according to Yamanaka et al (2003). Material type BaCe0,2Pr0,8O3 had lowest residual parameter (S=1.4) and lowest average size of crystallite (26.4 nm), being used as reference in the pH variation of synthesis solution for 9, 7, 5 and 3, respectively. Variation of this parameter showed that when the synthesis solution pH was decreased to below 11, there was an increase in the average size of crystals, for pH 9, about 58.3%, for pH 7 (30.3 %), for pH 2 (2.3%) and for pH 3 (42%), indicating that the value initially used and quoted by Santos (2010) was the most coherent

Caracterização de água produzida na indústria de petróleo para fins de descarte e otimização do processo de separação óleo/água

The oil industry has several segments that can impact the environment. Among these, produced water which has been highlight in the environmental problem because of the great volume generated and its toxic composition. Those waters are the major source of waste in the oil industry. The composition of the produced water is strongly dependent on the production field. A good example is the wastewater produced on a Petrobras operating unit of Rio Grande do Norte and Ceará (UO-RNCE). A single effluent treatment station (ETS) of this unit receives effluent from 48 wells (onshore and offshore), which leads a large fluctuations in the water quality that can become a complicating factor for future treatment processes. The present work aims to realize a diagnosis of a sample of produced water from the OU - RNCE in compliance to certain physical and physico-chemical parameters (chloride concentration, conductivity, dissolved oxygen, pH, TOG (oil & grease), nitrate concentration, turbidity, salinity and temperature). The analysis of the effluent is accomplished by means of a MP TROLL 9500 Multiparameter probe, a TOG/TPH Infracal from Wilks Enterprise Corp. - Model HATR - T (TOG) and a MD-31 condutivimeter of Digimed. Results were analyzed by univariated and multivariated analysis (principal component analysis) associated statistical control charts. The multivariate analysis showed a negative correlation between dissolved oxygen and turbidity (-0.55) and positive correlations between salinity and chloride (1), conductivity, chloride and salinity (0.70). Multivariated analysis showed there are seven principal components which can explain the variability of the parameters. The variables, salinity, conductivity and chloride were the most important variables, with, higher sampling variance. Statistical control charts have helped to establish a general trend between the physical and chemical evaluated parameters

Síntese e caracterização de tungstatos de cério e estrôncio para fins catalíticos

The main goal of this work was to produce nanosized ceramic materials of the family of the tungstates (tungstates of cerium and strontium), and test them for their catalytic activity in processes involving the transformation of methane (CH4). The methodology used for the synthesis of the ceramic powders involved the complexation combining EDTA-citrate. The materials characterization was performed using simple and differential thermogravimetry, x-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy (EDS). The microstructure analysis was performed using the refinement by the Rietveld method, and the crystallite size and distribution of the materials was elucidate by the Scherrer and Williamson-Hall methods. The conditions of the synthesis process for the three envisaged materials (SrWO4, SrWO4 using tungsten oxide concentrate as raw material, and Ce2(WO4)3) were adjusted to obtain a single phase crystalline material. The catalytic tests were carried out in the presence of methane and synthetic air, which is composed of 21% O2 and 79% N2. The analysis of the conversion of the reaction was done with the aid of an fourier transform infrared device (FTIR). The analysis showed that, structurally, the SrWO4 produced using raw materials of high and poor purity (99% and 92%, respectively) are similar. The ideal parameters of calcination, in the tested range, are temperature of 1000 °C and time of calcination 5 hours. For the Ce2(WO4)3, the ideal calcination time and are temperature 15 hours and 1000°C, respectively. The Williamson-Hall method provided two different distributions for the crystallite size of each material, whose values ranged between the nanometer and micrometer scales. According to method of Scherrer, all materials produced were composed of nanometric crystallites. The analyses of transmission electron microscopy confirmed the results obtained from the Williamson- Hall method for the crystallite size. The EDS showed an atomic composition for the metals in the SrWO4 that was different of the theoretical composition. With respect to the catalytic tests, all materials were found to be catalytically active, but the reaction process should be further studied and optimized.

Caracterização de um isolado de Bidens mosaic virus proveniente de alface

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Extração enzimática de óleo e produção in situ de biodiesel a partir da Moringa oleífera Lam

With the growth and development of modern society, arises the need to search for new raw materials and new technologies which present the "clean" characteristic, and do not harm the environment, but can join the energy needs of industry and transportation. The Moringa oleifera Lam, plant originating from India, and currently present in the Brazilian Northeast, presents itself as a multi-purpose plant, can be used as a coagulant in water treatment, as a natural remedy and as a feedstock for biodiesel production. In this work, Moringa has been used as a raw material for studies on the extraction and subsequently in the synthesis of biodiesel. Studies have been conducted on various techniques of Moringa oil extraction (solvents, mechanical pressing and enzymatic), being specially developed an experimental design for the aqueous extraction with the aid of the enzyme Neutrase© 0.8 L, with the aim of analyzing the influence variable pH (5.5-7.5), temperature (45-55°C), time (16-24 hours) and amount of catalyst (2-5%) on the extraction yield. In relation to study of the synthesis of biodiesel was initially carried out a conventional transesterification (50°C, KOH as a catalyst, methanol and 60 minutes reaction). Next, a study was conducted using the technique of in situ transesterification by using an experimental design variables as temperature (30-60°C), catalyst amount (2-5%), and molar ratio oil / ethanol (1:420-1:600). The extraction technique that achieved the highest extraction yield (35%) was the one that used hexane as a solvent. The extraction using 32% ethanol obtained by mechanical pressing and extraction reached 25% yield. For the enzymatic extraction, the experimental design indicated that the extraction yield was most affected by the effect of the combination of temperature and time. The maximum yield obtained in this extraction was 16%. After the step of obtaining the oil was accomplished the synthesis of biodiesel by the conventional method and the in situ technique. The method of conventional transesterification was obtained a content of 100% and esters by in situ technique was also obtained in 100% in the experimental point 7, with a molar ratio oil / alcohol 1:420, Temperature 60°C in 5% weight KOH with the reaction time of 1.5 h. By the experimental design, it was found that the variable that most influenced the ester content was late the percentage of catalyst. By physico-chemical analysis it was observed that the biodiesel produced by the in situ method fell within the rules of the ANP, therefore this technique feasible, because does not require the preliminary stage of oil extraction and achieves high levels of esters

Extração, caracterização e avaliação bioativa do extrato de Rumex acetosa

Studies show the great influence of free radicals and other oxidants as responsible for aging and degenerative diseases. On the other hand, the natural phenolic compounds has shown great as antioxidants to inhibit lipid peroxidation and lipoxygenase in vitro. Among these, is highlighted trans-resveratrol ( 3,5,4 `- trihydroxystilbene ) phenolic compound , characterized as a polyphenol stilbene class. The vegetables popularly known as "Azedinha" (Rumex Acetosa) has trans-resveratrol in its composition and from this, the present work aimed to study on the supercritical extraction and conventional extraction (Soxhlet and sequential) in roots of Rumex Acetosa, evaluating the efficiency of extractive processes, antioxidant activity, total phenolic content and quantification of trans-resveratrol contained in the extracts. Extractions using supercritical CO2 as solvent, addition of co-solvent (ethanol) and were conducted by the dynamic method in a fixed bed extractor. The trial met a 23 factorial design with three replications at the central point, with the variable reply process yield and concentration of trans-resveratrol and pressure as independent variables, temperature and concentration of co-solvent (% v/v). Yields ( mass of dry extract / mass of raw material used ) obtained from the supercritical extraction ranged from 0,8 to 7,63 % , and the best result was obtained at 250 bar and 90 °C using the co-solvent 15% ethanol (% v/v). The value was calculated for YCER a flow rate of 1,0 ± 0,17 g/min resulting in 0,0469 CO2 ( g solute / g solvent ). The results of the mass yield varied between conventional extractions 0,78 % ( hexane) and 9,97 % (ethanol). The statistical model generated from the data of the concentration of trans-resveratrol performed as meaningful and predictive for a 95% confidence. GC analysis on HPLC (High Performance Liquid Chromatography), transresveratrol was quantified in all extracts and concentration values ranged between 0,0033 and 0,42 ( mg / g extract) for supercritical extracts and between 0,449 and 17,046 (mg / g extract) to conventional extractions and therefore, the Soxhlet extraction with ethanol for more selective trans-resveratrol than the supercritical fluid. Evaluation of antioxidant (radical method to sequester 2,2- diphenyl-1- picryl - hydrazyl - DPPH) the supercritical extracts resulted in EC50 values (concentration effective to neutralize 50% of free radicals) of between 7,89 and 18,43 mg/mL , while resulting in a Soxhlet extraction with EC50 values in the range of 6,05 and 7,39 mg/mL. As for quantification of the phenolic compounds (Method Spectrophotometer Folin-Ciocalteau) the supercritical extracts resulted in values between 85,3 and 194,79 mg GAE / g extract, whereas values derived from the Soxhlet extract resulted in values between 178,5 and 237,8 mg GAE / g extract. The high antioxidant activity can not be attributed solely to the presence of phenolic compounds, but the presence of other antioxidants in the existing Rumex acetosa

Palma forrageira (Opuntia ficus indica e Nopalea cochenillifera) como matéria-prima para produção de etanol celulósico e enzimas celulolíticas

The need for new sources of energy and the concern about the environment have pushed the search for renewable energy sources such as ethanol. The use of lignocellulosic biomass as substrate appears as an important alternative because of the abundance of this raw material and for it does not compete with food production. However, the process still meets difficulties of implementation, including the cost for production of enzymes that degrade cellulose to fermentable sugars. The aim of this study was to evaluate the behavior of the species of cactus pear Opuntia ficus indica and Nopalea cochenillifera, commonly found in northeastern Brazil, as raw materials for the production of: 1) cellulosic ethanol by simultaneous saccharification and fermentation (SSF) process, using two different strains of Saccharomyces cerevisiae (PE-2 and LNF CA-11), and 2) cellulolytic enzymes by semi-solid state fermentation (SSSF) using the filamentous fungus Penicillium chrysogenum. Before alcoholic fermentation process, the material was conditioned and pretreated by three different strategies: alkaline hydrogen peroxide, alkaline using NaOH and acid using H2SO4 followed by alkaline delignification with NaOH. Analysis of composition, crystallinity and enzymatic digestibility were carried out with the material before and after pretreatment. In addition, scanning electron microscopy images were used to compare qualitatively the material and observe the effects of pretreatments. An experimental design 2² with triplicate at the central point was used to evaluate the influence of temperature (30, 40 and 45 °C) and the initial charge of substrate (3, 4 and 5% cellulose) in the SSF process using the material obtained through the best condition and testing both strains of S. cerevisiae, one of them flocculent (LNF CA-11). For cellulase production, the filamentous fungus P. chrysogenum was tested with N. cochenillifera in the raw condition (without pretreatment) and pretrated hydrothermically, varying the pH of the fermentative medium (3, 5 and 7). The characterization of cactus pear resulted in 31.55% cellulose, 17.12% hemicellulose and 10.25% lignin for N. cochenillifera and 34.86% cellulose, 19.97% hemicellulose and 15.72% lignin for O. ficus indica. It has also been determined, to N. cochenillifera and O. ficus indica, the content of pectin (5.44% and 5.55% of calcium pectate, respectively), extractives (26.90% and 9.69%, respectively) and ashes (5.40% and 5.95%). Pretreatment using alkaline hydrogen peroxide resulted in the best cellulose recovery results (86.16% for N. cochenillifera and 93.59% for O. ficus indica) and delignification (48.79% and 23.84% for N. cochenillifera and O. ficus indica, respectively). This pretreatment was also the only one which did not increase the crystallinity index of the samples, in the case of O. ficus indica. However, when analyzing the enzymatic digestibility of cellulose, alkali pretreatment was the one which showed the best yields and therefore it was chosen for the tests in SSF. The experiments showed higher yield of conversion of cellulose to ethanol by PE-2 strain using the pretreated N. cochenillifera (93.81%) at 40 °C using 4% initial charge of cellulose. N. cochenillifera gave better yields than O. ficus indica and PE-2 strain showed better performance than CA-11. N. cochenillifera proved to be a substrate that can be used in the SSSF for enzymes production, reaching values of 1.00 U/g of CMCase and 0.85 FPU/g. The pretreatment was not effective to increase the enzymatic activity values

Jambolão (Syzygium cumini) desidratado por liofilização e secagem em leito de jorro: avaliação do impacto do processo de secagem e caracterização do potencial funcional do produto final

Tropical fruits have been extensively studied due to their functional potential attributed to the presence of natural bioactive compounds. The exotic fruit jambolan (Syzygium cumini) has been reported for its appreciable amount of phenolic compounds, especially anthocyanins and antioxidant capacity. Nevertheless, there are hardly any derived jambolan products in the Brazilian market. In addition to that, considerable volumes of fruit are lost due to their high perishability. Dried fruits have become an important fruit market segment due to its weight and volume reduction and decreased transportation and storage costs. Thus, this study evaluated the jambolan pulp submitted to spouted bed drying (JLJ) and lyophilization (JLI), besides assessing the drying impact on the final product. In order to achieve this, the process performance was calculated and compared, as well the physicochemical and bioactive characteristics (moisture, water activity (aw), solubility, hygroscopicity, density, color, structure through images obtained by scanning electron microscopy (SEM), concentration of bioactive (total phenolic compounds (TPC), anthocyanins, proanthocyanidins and ascorbic acid) and antioxidant activity. The results showed drying efficiency higher than 60% for both products and that JLJ group showed higher moisture and water activity when compared to the JLI group (p<0.05). The two types of drying were able to produce stable final product in the microbiological point of view, given that both showed aw < 0.6. The final products exhibited high solubility (73.7 to 81.6%) and low hygroscopicity (9.8 to 11.6%), desirable characteristics for dehydrated foods. Despite the losses caused by drying, the dried jambolan pulp by both methods showed high TPC (468.6 to 534.0 mg GAE/100g dm), anthocyanins (from 491.9 to 673.4 mg. eq. cyanidin-3-glicoside/100g dm), proanthocyanidins (66.9 to 76.6 mg QTE/g dm) and ascorbic acid (156.4 to 186.8 mg/100 g dm). Taken together, the results of this study reveal spouted dried and freeze dried jambolan pulp as bioactive-rich natural products with suitable physicochemical and functional characteristics to be used as food ingredients. The data also demonstrate the drying techniques as rational strategies for the exploitation of the exotic fruit jambolan

Suco desidratado de caju (Anacardium occidentale L.) por atomização: caracterização físico-química, bioativa e estudo da vida de prateleira do produto

Despite the relatively organized cashew (Anacardium occidentale L.) productive chain and the number of cashew derivatives found in the market, it is estimated that over 90% of the cashew peduncle is wasted. A possible strategy for a better commercial exploitation of this agroindustrial commodity would be the production of spray dried cashew pulp. Thus, this paper approaches the yellow cashew pulp spray drying process and the final product evaluation. Based on that, the shelf life of the spray dried cashew pulp packed in different packaging was evaluated. Drying was conducted in two drying temperatures (140 °C to 150 °C) and two concentrations of Arabic gum (AG, 15% and 25%), which summed four experimental groups. The drying performance was evaluated as well as the physicochemical characteristics (moisture, water activity, total soluble solids, pH, density, solubility, particle diameter, hygroscopicity, degree of caking, color, scanning electronic microscopy and X-ray diffraction), composition (protein, ash, fat and sugars) and bioactive and functional value (total phenolic compounds, carotenoids, ascorbic acid and antioxidant activity) of the final products. Results showed spray drying efficiency higher than 65% for all experiments, mainly for the C4 group (150 °C and 25% AG) which reached efficiency of 93.4%. It was also observed high solubility (94.7% to 97.9%) and the groups with lower hygroscopicity (5.8% and 6.5%) were those with the highest proportion of drying coadjuvant. The particle diameters ranged between 14.7 μm and 30.2 μm and increased with the proportion of AG. When comparing the product before and after spray drying, the drying impact was evident. However, despite the observed losses, dried yellow cashew showed high phenolic concentration (from 235.9 to 380.4 mg GAE eq / 100 g DM), carotenoids between 0.22 and 0.49 mg/100 g DM and remarkable ascorbic acid levels (852.4 to 1346.2 mg/100 g DM), in addition to antioxidant activity ranging from 12.9 to 16.4 μmol TE/ g DM. The shelf life study revealed decreased phenolic content over time associated to a slight water activity increase. Overall, our results unveil the technological and bioactive potential of dried yellow cashew as a functional ingredient to be used in food formulations or as a ready-to-use product. The technological approach presented here can serve as an efficient strategy for a rational use of the cashew apple, avoiding its current underutilization

Extração, caracterização e aplicação do corante de urucum (Bixa orellana L.) no tingimento de fibras naturais

The increasing demand for natural dyes in place of synthetic ones is justified by the non-toxicity or low toxicity of the former. The synthetic dyes are associated with diseases like cancer as well as when released in the environment takes longer to degrade and the intermediates could be still more toxic. The Annatto (Bixa Orellana L.) is a carotenoid and one of the more important natural dyes used in the food industry. In the form of dye, it represents nearly 70% of the world natural dye production and 90% in Brazil. In the present work, annatto seeds were used of the species peruana paulista, which had nearly 2.1% of bixin. The process of dye extraction with ethyl alcohol showed 4% of dye in the form of powder with particle diameter of 28mm. The extraction process did not alter the chemical composition of the dye, which was confirmed by the electronic spectrum of absorption. Dyeings were carried out with different mordents to study the total colour difference as well as the wash fastness properties and friction fastness properties under wet and dry conditions. The samples treated with copper sulphate showed colour difference but at the same time showed better fastness results. The samples treated with resin (no formaldehyde) did not alter the colour significantly still better the fastness properties. From the results, it could be stated that the resin could be an alternative for heavy metallic mordents

Caracterização de Efluente Têxtil e Proposta de Tratamento

Textile industry deals with a high diversity of processes and generation of wastewaters with a high content of pollutant material. Before being disposed of in water bodies, a pre-treatment of the effluent is carried out, which is sometimes ineffective. In order to be properly treated, physical and chemical properties of the effluent must be known, as well as the pollutant agents that might be present in it. This has turned out to be a great problem in the textile industry, for there is a variety of processes and the pollutant load is very diversified. The characterization of the effluent allows the identification of most critical points and, as a consequence, the most appropriate treatment procedure to be employed, may be chosen. This study presents the results obtained after characterizing the effluent of a textile industry that comprises knitting, dyeing and apparel sections, processing mainly polyester/cotton articles. In this work, twenty samples of the effluent were collected, and related to the changes in production. From the results, a statistical evaluation was applied, determined in function of the rate of flow. The following properties and pollutants agents were quantitatively analysed: temperature; pH; sulfides; chlorine; alcalinity; chlorides; cianides; phenols; color; COD (Chemical Oxygen Demand); TOC (Total Organic Carbon); oil and grease; total, fixed and volatile solids; dissolved, fixed and volatile solids; suspended, fixed and volatile solids; setteable solids and heavy metals such as cadmium, copper, lead, chromium, tin, iron, zinc and nickel. Analyses were carried out according to ABNT NBR 13402 norm, based upon Standard Methods for the Examination of Water and Wastewater. As a consequence, a global treatment proposal is presented, involving clean production practices as contaminant load reducer, followed by conventional (biological) treatment

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

Estudo do mecanismo de produção de oligossacarídeos com atividades nutracêuticas a partir da quitosana por hidrólise enzimática com processo fermentativo simultâneo

The obtaining of the oligosaccharides from chitosanase, has showed interest of the pharmaceutical area in the last years due their countless functional properties. Although, the great challenge founded out is how to keep a constant and efficient production. The alternative proposed by this present work was to study the viability to develop an integrated technology, with reduced costs. The strategy used was the obtaining of the oligomers through enzymatic hydrolysis using chitosanolitic enzymes obtained straight from the fermented broth, eliminating this way the phases involved in the enzymes purification. The two chitosanases producing strains chosen for the work, Paenibacillus chitinolyticus and Paenibacillus ehimensis, were evaluated according to the behavior in the culture medium with simple sugar and in relation to the pH medium variations. The culture medium for the chitosanases induction and production was developed through addition of soluble chitosan as carbon source. The soluble chitosan was obtained using hydrochloric acid solution 0.1 M and afterwards neutralization with NaOH 10 M. The enzymatic complexes were obtained from induction process in culture medium with 0.2% of soluble chitosan. The enzymes production was verified soon after the consumption of the simple sugars by the microorganisms and the maximum chitosanolitic activity obtained in the fermented broth by Paenibacillus chitinolyticus was 249 U.L-1 and by Paenibacillus ehimensis was 495U.L-1. These two enzymatic complexes showed stability when stored at 20°C for about 91 days. The enzymes in the fermented broth by Paenibacillus chitinolyticus, when exposed at temperature of 55°C and pH 6.0, where the activity is maximum, showed 50% lost of activity after 3 hours Meanwhile, for the complex produced by Paenibacillus ehimensis, after 6 days of exposure, it was detected 100% of the activity. The chito-oligosaccharides obtained by the hydrolysis of a 1% chitosan solution, using the enzymatic complex produced by Paenibacillus chitinolyticus showed larger quantity after 9 hours hydrolysis and using the complex produced by Paenibacillus ehimensis after 20 minutes was observed the chito-ligosacharides with polymerization degree between 3 and 6 units. Evaluating these results, it was verified that the production of chitosan-oligosaccharides is possible, using a simultaneous process