Aplicação de termogravimetria acoplada à espectrometria de massas para caracterização de petróleo e determinação da curva de evolução de gás sulfídrico

With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

Sistemas microemulsionados como carreador lipídico para fármacos insolúveis

Several pharmaceutical products have been developed in recent years aiming to enhance the treatment of diseases by increasing the effectiveness of drugs. Many of these new products are based on new drug delivery systems. Among these, microemulsions, which were first studied in 1943 by Hoar and Schulman, is of great interest. Microemulsion can be defined as a thermodynamically stable, isotropic, translucent and transparent system of two immiscible liquids stabilized by a surfactant film located in the oil / water interface. The aim os this work was the incorporation of Amphotericin B and Simvasatin to a microemulsion system and analyzes its physicochemical properties and their therapeutical activity when incorporated into this system. Some very promising results were achieved as the reduction of the toxicity and maintenance of the efficacy of the Amphotericin B incorpored into a microemulsion, which was demonstrated in the in vitro pharmacotoxicological study. As for the incorporation of Simvastatin in microemulsion, it was observed a significant improvement in the potential antiinflammatory and anti-infective properties when the system was use to treat infected wounds (simvastatin pleiotropic effects). Therefore, it can be concluded that the incorporation of these drugs into microemulsion system reveal the potential of microemulsions as a promising and novel dosage form, qualifying them for future trials in order to make them available in the pharmaceutical market

Nanotechnological delivery systems for the oral administration of active molecules: Polymeric microparticles and microemulsions applied to anti-inflammatory and anti-infectious drugs

This thesis was devoted to the development of innovative oral delivery systems for two different molecules. In the first part, microparticles (MPs) based on xylan and Eudragit® S- 100 were produced and used to encapsulate 5-aminosalicylic acid for colon delivery. Xylan was extracted from corn cobs and characterized in terms of its physicochemical, rheological and toxicological properties. The polymeric MPs were prepared by interfacial cross-linking polymerization and spray-drying and characterized for their morphology, mean size and distribution, thermal stability, crystallinity, entrapment efficiency and in vitro drug release. MPs with suitable physical characteristics and satisfactory yields were prepared by both methods, although the spray-dried systems showed higher thermal stability. In general, spraydried MPs would be preferable systems due to their thermal stability and absence of toxic agents used in their preparation. However, drug loading and release need to be optimized. In the second part of this thesis, oil-in-water microemulsions (O/W MEs) based on mediumchain triglycerides were formulated as drug carriers and solubility enhancers for amphotericin B (AmB). Phase diagrams were constructed using surfactant blends with hydrophiliclipophilic balance values between 9.7 and 14.4. The drug-free and drug-loaded MEs presented spherical non-aggregated droplets around 80 and 120 nm, respectively, and a low polydispersity index. The incorporation of AmB was high and depended on the volume fraction of the disperse phase. These MEs did not reduce the viability of J774.A1 macrophage-like cells for concentrations up to 25 μg/mL of AmB. Therefore, O/W MEs based on propylene glycol esters of caprylic acid may be considered as suitable delivery systems for AmB

Elaboration of sausage using minced fish of Nile tilapia filleting waste

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização térmica (TG/DTG, DTA, DSC, DSC-fotovisual) de Hormônios bioidênticos (estriol estradiol)

Bioidentical hormones are defined as compounds that have exactly the same chemical and molecular structure as hormones that are produced in the human body. It is believed that the use of hormones may be safer and more effective than the non-bioidentical hormones, because binding to receptors in the organism would be similar to the endogenous hormone. Bioidentical estrogens have been used in menopausal women, as an alternative to traditional hormone replacement therapy. Thermal data of these hormones are scarce in literature. Thermal analysis comprises a group of techniques that allows evaluating the physical-chemistry properties of a drug, while the drug is subjected to a controlled temperature programming. The thermal techniques are used in pharmaceutical studies for characterization of drugs, purity determination, polymorphism identification, compatibility and evaluation of stability. This study aims to characterize the bioidentical hormones estradiol and estriol through thermal techniques TG/DTG, DTA, DSC, DSC-photovisual. By the TG curves analysis was possible to calculated kinetic parameters for the samples. The kinetic data showed that there is good correlation in the different models used. For both estradiol and estriol, was found zero order reaction, which enabled the construction of the vapor pressure curves. Data from DTA and DSC curves of melting point and purity are the same of literature, showed relation with DSC-photovisual results. The analysis DTA curves showed the fusion event had the best linearity for both hormones. In the evaluation of possible degradation products, the analysis of the infrared shows no degradation products in the solid state

Manejo da irrigação na cultura do feijoeiro em sistemas plantio direto e convencional

O manejo inadequado do solo e da água é limitante à produtividade do feijoeiro irrigado. O objetivo deste trabalho foi avaliar dois métodos de manejo da irrigação, um via solo (tensiometria) e outro via clima (tanque Classe A), conjugados com os sistemas plantio direto e convencional de manejo do solo com a cultura do feijoeiro de inverno, no segundo ano de plantio direto, em Jaboticabal - SP. Foi medido o potencial mátrico do solo e estimada a variação diária do armazenamento de água no solo, na camada de 0 a 0,40 m de profundidade, e avaliados os componentes de produtividade, além de determinadas a evapotranspiração real média e a eficiência média de uso de água pela cultura. O sistema de preparo convencional do solo com manejo de irrigação pelo tanque Classe A proporcionou maior produtividade de grãos, evapotranspiração média e eficiência de uso de água pela cultura, seguido pelo plantio direto com manejo de irrigação por tensiometria e por tanque Classe A. O sistema plantio direto foi menos suscetível às variações hídricas no solo decorrentes dos manejos de irrigação empregados do que o sistema de preparo convencional, resultando em menor variação na produtividade de grãos.

Número mínimo de tensões para determinação da curva característica de retenção de água de um latossolo vermelho eutrófico sob sistema de semeadura direta

Para o conhecimento do comportamento físico-hídrico do solo, é fundamental a determinação da curva de retenção de água (CRA). A aquisição de dados para obtenção da CRA envolve processos demorados e custos elevados. A hipótese deste estudo foi a de que é possível determinar a CRA com menor número de tensões, reduzindo seu tempo de obtenção, sem, contudo, comprometer a acurácia dos resultados. Assim, o objetivo deste trabalho foi determinar quais tensões podem ser utilizadas para determinação da CRA de Latossolo Vermelho eutrófico de maneira acurada e em menor tempo. Foram determinados os conteúdos de água retidos em amostras de um Latossolo Vermelho eutrófico sob sistema de semeadura direta (SSD). As tensões utilizadas na determinação dos conteúdos de água foram: 0, 10, 20, 40, 60, 80, 100, 200, 300, 500, 700, 1.000, 3.000, 5.000 e 15.000 hPa. Os dados foram combinados e determinaram-se 450 CRAs ajustadas pelo modelo de van Genuchten. Os parâmetros α, m, n e Ug res, gerados pelo modelo, foram submetidos à análise de variância (teste F) e as médias comparadas pelo teste de Scott-Knott (p = 0,05). A hipótese deste estudo foi confirmada, ou seja, é possível determinar a CRA com menor número de tensões, reduzindo seu tempo de obtenção em até cinco vezes, sem, contudo, comprometer a acurácia dos resultados. A tensão de 15.000 hPa deve estar contida na combinação de tensões a serem utilizadas para determinação da curva característica de retenção de água, quando se emprega o modelo matemático de van Genuchten para ajuste dos dados. As curvas características de retenção de água do solo, definidas com as combinações de tensões (0, 60, 700 e 15.000 hPa), (0, 80, 700 e 15.000 hPa), (0, 100, 1.000 e 15.000 hPa), (0, 20, 60, 100, 700 e 15.000 hPa), (0, 80, 300, 700 e 15.000 hPa) e (0, 100, 300, 1.000 e 15.000 hPa), sendo os dados ajustados ao modelo de van Genuchten, proporcionaram estimativas dos conteúdos de água, retidos no Latossolo Vermelho eutrófico sob sistema de semeadura direta, com a mesma acurácia, quando comparada à curva de referência partindo-se de um conjunto de 15 valores de tensões.

Spatial variability of soil penetration resistance influenced by season of sampling

O objetivo deste trabalho foi analizar a distribuição espacial da compactação do solo e a influência da umidade do solo na resistência à penetração. Esta última variável foi descrita pelo índice de cone. O solo estudado foi Nitossolo e os dados de índice de cone foram obtidos usando um penetrômetro. A resistência do solo foi avaliada a 5 profundidades diferentes, 0-10 cm, 10-20 cm, 20-30 cm, 30-40 cm e mais de 40 cm, porém o conteúdo de umidade do solo foi medido a 0-20 cm e 20-40 cm. As condições hídricas do solo variaram nas diferentes amostragems. Os coeficientes de variação para o índice de cone foram 16,5% a 45,8% e os do conteúdo de umidade do solo variaram entre 8,96% e 21,38%. Os resultados sugeriram elevada correlação entre a resistência do solo, estimada pelo índice de cone e a profundidade do solo. Sem embargo, a relação esperada com a umidade do solo não foi apreciada. Observou-se dependência espacial em 31 de 35 séries de dados de índice de cone e umidade do solo. Esta dependência foi ajustada por modelos exponenciais com efeito pepita variável de 0 a 90% o valor do patamar. em séries de dados o comportamento foi aleatório. Portanto, a técnica das distâncias inversas foi utilizada para cartografar a distribuição das variáveis que não tiveram estrutura espacial. Na krigagem constatou-se uma suavização dos mapas comparados com esses das distâncias inversas. A krigagem indicadora foi utilizada para cartografar a variabilidade espacial do índice de cone e recomendar melhor manejo do solo.

Estudo do efeito do óxido de bário no comportamento de massas para porcelanato

In this work, it is proposed the study of the effect of barium oxide acting as synthetic flow in the behavior of masses for stoneware from the use of raw materials found in the deposits of minerals of the Rio Grande do Norte that it makes use of a great natural potential for the industrialization of the product. The porcelanato is a sophisticated product with excellent final properties being applied as ceramic coating in buildings of high standard of engineering. The raw materials selected for the development of the study had been two types of argilas, two types of feldspatos, dolomita, talco, barium carbonate and silica, being characterized by X-ray fluorescence, X-ray diffraction, granulometric analysis, dilatometric analysis and thermal analysis. Thus, it is intended to define four formulations using the cited raw materials that will be processed, conformed and sintered in the temperatures of 1150 °C, 1175 °C, 1200 °C, 1225 °C e 1250 °C. From the physical characterizations, chemical and morphologic of the formed formulations, the effect of barium oxide is determined in the physical and mechanical properties of the studied system carrying water absorption tests, linear retraction, apparent porosity, apparent specific mass, compacting curve, flexural strength and microstructural analysis by XRD and SEM. After analyzing the results, indicated that barium oxide acts as a flux of high temperature and as the ordering of structure, where the embedded glass phase has the nucleating effect phase potassium silico-aluminum reacting with free silica which together with the high content of potassium concentrated form a new crystalline phase called microcline. The masses studied with the addition of barium oxide present physical-mechanical properties highly satisfactory in reduced firing temperatures, which implies a saving in energy given off in the production and increased productivity

Utilização do éster de soja como biolubrificante

The lubricants found in the market are of mineral or synthetic origin and harm to humans and the environment, mainly due to their improper discard. Therefore industries are seeking to develop products that cause less environmental impact, so to decrease mainly, operator aggression the Cutting Fluids became an emulsion of oil / water or water / oil. However, the emulsion was not considered the most suitable solution for environmental question, therefore the search for biodegradable lubricants and which no are toxic continues and so vegetable oils are seen, again, as a basis for the production of lubricants. The biggest problem with these oils is their oxidative instability that is intensified when working at high temperatures. The process transesterification decreases the oxidation, however changes some physical and chemical properties. Therefore soybean oil after the transesterification process was subjected to tests of density, dynamic viscosity, kinematic viscosity which is calculated from two parameters mentioned, flash point and acidity. Besides the physico-chemical test the soybean oil was subjected to a dynamic test in a tribometer adapted from a table vise, whose induced wear was the adhesive and ultimately was used as cutting fluid in a process of turning in two different materials, steel 1045 and cast iron. This latter test presented results below the mineral cutting fluid which it was compared in all tests, already in other experiments the result was satisfactory and other experiments not, so that chemical additives can be added to the oil analyzed to try equate all parameters and so formulate a biolubrificante not toxic to apply in machining processes of metalworking industry

Desenho e Construção de um protótipo gerador de jato de plasma frio a pressão atmosférica para aplicações biomédicas

Research for better performance materials in biomedical applications are constants. Thus recent studies aimed at the development of new techniques for modification of surfaces. The low pressure plasma has been highlighted for its versatility and for being environmentally friendly, achieving good results in the modification of physic chemical properties of materials. However, it is requires an expensive vacuum system and cannot able to generate superficial changes in specific regions. Furthermore, it is limits their use in polymeric materials and sensitive terms due to high process temperatures. Therefore, new techniques capable of generating cold plasma at atmospheric pressure (APPJ) were created. In order to perform surface treatments on biomaterials in specific regions was built a prototype capable of generating a cold plasma jet. The prototype plasma generator consists of a high voltage source, a support arm, sample port and a nozzle through which the ionized argon. The device was formed to a dielectric tube and two electrodes. This work was varied some parameters such as position between electrodes, voltage and electrical frequency to verify the behavior of glow discharges. The disc of titanium was polished and there was a surface modification. The power consumed, length, intensity and surface modifications of titanium were analyzed. The energy consumed during the discharges was observed by the Lissajous figure method. To check the length of the jets was realized with Image Pro Plus software. The modifications of the titanium surfaces were observed by optical microscopy (OM ) and atomic force microscopy (AFM ). The study showed that variations of the parameters such as voltage, frequency and geometric position between the electrodes influence the formation of the plasma jet. It was concluded that the plasma jet near room temperature and atmospheric pressure was able to cause modifications in titanium surface

Produção de biodiesel a partir de óleo de coco (Cocos nucifera L

The production of biodiesel has become an important and attractive process for the production of alternative fuels. This work presents a study of the biodiesel production from coconut oil (Cocos nucifera L.), by two routes: direct transesterification using NaOH as catalyst and esterification (with H2SO4) followed by basic transesterification. The reactor was built in pirex with 1L of capacity and was equipped with a jacket coupled with a thermostatic bath to temperature control, a mecanical stirring is also present in the reactor. The analysis of oil composition was carried out by gas chromatography and esters compounds were identified. The parameters of molar ratio oil/alcohol, reaction time and temperature were studied and their influence on the conversion products was evaluated using experimental planning (23). The molar ratio was the most significant variable by the statistical planning analysis. Conversions up to 85.3% where achived in the esterification/transesterification, with molar ratio 1:6 at 60ºC and 90 minutes of reaction. For the direct transesterification, route conversions up 87.4% eas obtained using 1:6.5 molar ratio at 80ºC and 60 minutes of reaction. The Coconut oil was characterized by their physic chemical properties and key constituents of the oil. The lauric acid was the main constituint and the oil showed high acidity. The biodiesel produced was characterized by its main physicochemical properties, indicating satisfactory results when compared to standard values of National Petroleum Agency. The work was supplemented with a preliminary assessment of the reaction kinetic

Tensão superficial dinâmica e ângulo de contato de soluções aquosas com surfatantes em superfícies artificiais e naturais

O trabalho objetivou avaliar o efeito de surfatantes em soluções aquosas sobre a tensão superficial dinâmica e ângulo de contato das gotas em diferentes superfícies: artificiais (lâmina de vidro e de óxido de alumínio) e naturais (superfícies adaxiais de folhas de Euphorbia heterophylla, Ipomoea grandifolia e Brachiaria plantaginea). Seis formulações de surfatantes (Antideriva®; Uno®; Pronto 3®; Li-700®; Supersil® e Silwet L-77®), respectivamente nas doses recomendadas do produto comercial (0,050; 0,025; 0,100; 0,250; 0,100 e 0,100 % v v-1) e o dobro delas, foram avaliadas em soluções aquosas. A tensão superficial dinâmica e o ângulo de contato formado sobre as superfícies naturais foram medidos por tensiômetro. Os ângulos de contato formados pelas gotas nas superfícies artificiais foram obtidos por análise de imagens capturadas por uma câmera digital. Os surfatantes influenciam nas propriedades físico-químicas de soluções aquosas. As soluções contendo os surfatantes Silwet L-77® e Supersil®; nas doses de 0,100 e 0,200% v v-1; proporcionaram maiores reduções na tensão superficial dinâmica e menores ângulos de contato das gotas sobre as superfícies artificiais e naturais. Os surfatantes organossiliconados em solução aquosa foram mais eficientes na redução da tensão superficial e proporcionaram maior molhamento de superfícies natural e artificial. em alvos naturais, essas propriedades obtidas com organossiliconados são dependentes das características de superfície das espécies vegetais.

Purificação da glicerina bruta obtida a partir da transesterificação do óleo de algodão

The crude glycerine is a raw material that can be used in a wide variety of products. Even with all the impurities inherent in the process of being obtained, the crude glycerin is already in a marketable product. However, the market is much more favorable to the commercialization of purified glycerine. The glycerin is a byproduct gotten from the process of transesterification of waste oils and fats in the production of biodiesel. More recently, the deployment of the new Federal Law of Brazil, related to the implementation of energy resources, forces, from 2008, the increase of 2% biodiesel in diesel common with prospects for 5% (B5). Therefore, it is indispensable that new routes of purification as well as new markets are developed. The objective of this work was to purify, through ion exchange, the crude glycerin, obtained from the reaction of transesterification of cottonseed oil. The cottonseed oil was characterized as the fatty acid composition and physical-chemical properties. The process of ion exchange was conducted in batch. In this process were used strong cation, low anion resins and a mixed resin used to de-ionize water. The purified glycerin was characterized as the content of metals. Tests were performed with activated charcoal adsorption, and for this, it was made tests of time contact with coal as well as quantity of coal used. The time of activation, the amount of the activation solution, the contact time of the glycerol solution in resins, the amount and type of resin applied were evaluated. Considering the analysis made with activated charcoal, when the glycerin solution was treated using the resins individually it was observed that in the conditions for treatment with 10 g of resin, 5 hours of contact with each resin and 50 mL of glycerin solution, its conductivity decreased to a cationic resin, increased to the anionic resin and had a variable value with respect to resin mixed. In the treatment in series, there was a constant decrease in the conductivity of the solution of glycerin. Considering two types of treatment, in series and individually, the content of glycerol in glycerin pre-purified solution with the different resins varied from 12,46 to 29.51% (diluted solution). In analysis performed without the use of activated charcoal, the behavior of the conductivity of the solution of glycerin were similar to results for treatment with activated charcoal, both in series as individually. The solution of glycerin pre-purified had a glycerol content varying from 8.3 to 25.7% (diluted solution). In relation to pH, it had a behavior in accordance with the expected: acid for the glycerin solution treated with cationic resin, basic when the glycerin solution was treated with the anionic resin and neutral when treated with the mixed resin, independent of the kind of procedure used (with or without coal, resins individually or in series). In relation to the color of the glycerin pre-purified solution, the resin that showed the best result was the anionic (colorless), however this does not mean that the solution is more in pure glycerol. The chromatographic analysis of the solutions obtained after the passage through the resins indicated that the treatment was effective by the presence of only one component (glycerol), not considering the solvent of the analysis

Nano emulsões aplicadas a recuperação avançada de petróleo

A exploração de petróleo está a cada dia em circunstâncias mais adversas, no que diz respeito à profundidade dos poços como também, em relação à fluidez do óleo. Os reservatórios de descobertas recentes não possuem energia própria para produzir ou os métodos convencionais não são eficientes para fazer com que esses reservatórios tenham uma vida útil elevada, devido a alterações das propriedades físico-químicas, como por exemplo a viscosidade, que torna o deslocamento do óleo pelos poros do reservatório até a superfície cada vez mais complexo. O presente trabalho tem como objetivo estudar a preparação, caracterização e a utilização de nanoemulsões obtidas a partir de sistemas microemulsionados, com e sem a presença de polímero. Esses sistemas foram aplicados como método químico de recuperação de petróleo, com o intuito de obter maior eficiência de volume de óleo deslocado. O interesse por esse tipo de sistema existe devido a sua baixa tensão superficial, o pequeno tamanho de gotícula e, principalmente, pelo baixo percentual de matéria ativa presente em sua composição. Os ensaios realizados para caracterizar esses sistemas foram: aspecto físico, medidas de tamanho de gotícula, índice de polidispersão, tensão superficial, pH e condutividade. Ensaios de reologia e de adsorção dos sistemas foram realizados com o objetivo de avaliar sua influencia na recuperação de petróleo. Os ensaios de recuperação foram realizados em um equipamento que simula as condições de um reservatório de petróleo, utilizando plugs de rocha arenito Botucatu. Esses plugs foram saturados com salmoura (KCl 2%) e com petróleo proveniente da Bacia Potiguar do campo de Ubarana. Após essas etapas foi realizada a recuperação convencional utilizando a salmoura e, por último, foi injetada, a nanoemulsão, como método de recuperação avançada. Os sistemas obtidos variaram de 0% à 0,4% de polímero. Os ensaios de tamanhos de partícula obtiveram como resultado uma variação de 9,22 a 14,8 nm, caracterizando que as nanoemulsões estão dentro da faixa de tamanho inerente a esse tipo de sistema. Para ensaios de tensão superficial os valores foram na faixa de 33,6 a 39,7 dynas/cm, valores semelhantes à microemulsões e bem abaixo da tensão superficial da água. Os resultados obtidos para os valores de pH e condutividade se mantiveram estáveis ao longo do tempo de armazenamento, essa avaliação indica estabilidade das nanoemulsões estudadas. O teste de recuperação avançada utilizando nanoemulsão com baixo percentual de matéria ativa obteve como resultado de eficiência de deslocamento 39,4%. Porém esse valor foi crescente, de acordo com o aumento do percentual de polímero na nanomeulsão. Os resultados de eficiência de deslocamento de petróleo estão diretamente relacionados com o aumento da viscosidade das nanoemulsões. A nanoemulsão V (0,4% polímero) é o sistema mais viscoso dentre os analisados, e obteve o maior percentual de óleo deslocado (76,7%), resultando na maior eficiência de deslocamento total (90%). Esse estudo mostrou o potencial de sistemas nanoemulsionados, com e sem polímeros, na recuperação avançada de petróleo. Eles apresentam algumas vantagens com relação a outros métodos de recuperação avançada, como: o baixo percentual de matéria ativa, baixo índice de adsorção do polímero, dissolvido em nanoemulsão, na rocha e alta eficiência de recuperação