Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Análise do desempenho de um queimador infravermelho funcionando com gás liquefeito de petróleo e glicerina

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 greater control of emissions due to the passage of exhaust gases through a macro-porous ceramic bed. This paper presents an infrared burner commercial, which was adapted an experimental ejector, capable of promoting a mixture of liquefied petroleum gas (LPG) and glycerin. By varying the percentage of dual-fuel, it was evaluated the performance of the infrared burner by performing an energy balance and atmospheric emissions. It was introduced a temperature controller with thermocouple modulating two-stage (low heat / high heat), using solenoid valves for each fuel. The infrared burner has been tested and tests by varying the amount of glycerin inserted by a gravity feed system. 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 a data acquisition system which recorded real-time measurements of the thermocouples attached. The burner had a stable combustion at levels of 15, 20 and 25% of adding glycerin in mass ratio of LPG gas, increasing the supply of heat to the plate. According to data obtained showed that there was an improvement in the efficiency of the 1st Law of infrared burner with increasing addition of glycerin. The emission levels of greenhouse gases produced by combustion (CO, NOx, SO2 and HC) met the environmental limits set by resolution No. 382/2006 of CONAMA

Desenvolvimento de sistemas de aditivos químicos para aplicação em cimentações de poços de petróleo

The primary cementing is an important step in the oilwell drilling process, ensuring the mechanical stability of the well and the hydraulic isolation between casing and formation. For slurries to meet the requirements for application in a certain well, some care in the project should be taken into account to obtain a cement paste with the proper composition. In most cases, it is necessary to add chemicals to the cement to modify its properties, according to the operation conditions and thus obtain slurries that can move inside the jacket providing a good displacement to the interest area. New technologies of preparation and use of chemicals and modernization of technological standards in the construction industry have resulted in the development of new chemical additives for optimizing the properties of building materials. Products such as polycarboxylate superplasticizers provide improved fluidity and cohesion of the cement grains, in addition to improving the dispersion with respect to slurries without additives. This study aimed at adapting chemical additives used in civil construction to be used use in oilwell cement slurries systems, using Portland cement CPP-Special Class as the hydraulic binder. The chemical additives classified as defoamer, dispersant, fluid loss controller and retarder were characterized by infrared absorption spectroscopy, thermogravimetric analyses and technological tests set by the API (American Petroleum Institute). These additives showed satisfactory results for its application in cement slurries systems for oil wells. The silicone-based defoamer promoted the reduction of air bubbles incorporated during the stirring of the slurries. The dispersant significantly reduced the rheological parameters of the systems studied. The tests performed with the fluid loss controller and the retarder also resulted in suitable properties for application as chemical additives in cement slurries

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

Síntese, caracterização e aplicação de LaSBA-15 e como catalisador para obtenção de biodiesel de soja via rota etílica

Biodiesel is an alternative fuel, renewable, biodegradable and nontoxic. The transesterification of vegetable oils or animal fat with alcohol is most common form of production of this fuel. The procedure for production of biodiesel occurs most commonly through the transesterification reaction in which catalysts are used to accelerate and increase their income and may be basic, acid or enzyme. The use of homogeneous catalysis requires specific conditions and purification steps of the reaction products (alkyl ester and glycerol) and removal of the catalyst at the end of the reaction. As an alternative to improve the yield of the transesterification reaction, minimize the cost of production is that many studies are being conducted with the application of heterogeneous catalysis. The use of nano-structured materials as catalysts in the production of biodiesel is a biofuel alternative for a similar to mineral diesel. Although slower, can esterify transesterified triglycerides and free fatty acids and suffer little influence of water, which may be present in the raw material. This study aimed at the synthesis, characterization and application of nano-structured materials as catalysts in the transesterification reaction of soybean oil to produce biodiesel by ethylic route. The type material containing SBA-15 mesoporous lanthanum embedded within rightly Si / La = 50 was used catalyst. Solid samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, nitrogen adsorption and desorption. For the transesterification process, we used a molar ratio of 20:1 alcohol and oil with 0.250 g of catalyst at 60°C and times of 6 hours of reaction. It was determined the content of ethyl esters by H-NMR analysis and gas chromatography. It was found that the variable of conversion obtained was 80%, showing a good catalytic activity LaSBA-15 in the transesterification of vegetable oils via ethylic route

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

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

Novos sistemas de liberação de fármacos à base de xilana

The aim of this work was to perform the extraction and characterization of xylan from corn cobs and prepare xylan-based microcapsules. For that purpose, an alkaline extraction of xylan was carried out followed by the polymer characterization regarding its technological properties, such as angle of repose, Hausner factor, density, compressibility and compactability. Also, a low-cost and rapid analytical procedure to identify xylan by means of infrared spectroscopy was studied. Xylan was characterized as a yellowish fine powder with low density and poor flow properties. After the extraction and characterization of the polymer, xylan-based microcapsules were prepared by means of interfacial crosslinking polymerization and their characterization was performed in order to obtain gastroresistant multiparticulate systems. This work involved the most suitable parameters of the preparation of microcapsules as well as the study of the process, scale-up methodology and biological analysis. Magnetic nanoparticles were used as a model system to be encapsulated by the xylan microcapsules. According to the results, xylan-based microcapsules were shown to be resistant to several conditions found along the gastrointestinal tract and they were able to avoid the early degradation of the magnetic nanoparticles

Micropartículas poliméricas à base de xilana e Eudragit® S-100 contendo mesalazina visando à liberação cólon-específica

Colon-specific drug delivery systems have attracted increasing attention from the pharmaceutical industry due to their ability of treating intestinal bowel diseases (IBD), which represent a public health problem in several countries. In spite of being considered a quite effective molecule for the treatment of IBD, mesalazine (5-ASA) is rapidly absorbed in the upper gastrointestinal tract and its systemic absorption leads to risks of adverse effects. The aim of this work was to develop a microparticulate system based on xylan and Eudragit® S- 100 (ES100) for colon-specific delivery of 5-ASA and evaluate the interaction between the polymers present in the systems. Additionaly, the physicochemical and rheological properties of xylan were also evaluated. Initially, xylan was extracted from corn cobs and characterized regarding the yield and rheological properties. Afterwards, 10 formulations were prepared in different xylan and ES100 weight ratios by spray-drying the polymer solutions in 0.6N NaOH and phosphate buffer pH 7.4. In addition, 3 formulations consisting of xylan microcapsules were produced by interfacial cross-linking polymerization and coated by ES100 by means of spray-drying in different polymer weight ratios of xylan and ES100. The microparticles were characterized regarding yield, morphology, homogeneity, visual aspect, crystallinity and thermal behavior. The polymer interaction was investigated by infrared spectroscopy. The extracted xylan was presented as a very fine and yellowish powder, with mean particle size smaller than 40μm. Regarding the rheological properties of xylan, they demonstrated that this polymer has a poor flow, low density and high cohesiveness. The microparticles obtained were shown to be spherical and aggregates could not be observed. They were found to present amorphous structure and have a very high thermal stability. The yield varied according to the polymer ratios. Moreover, it was confirmed that the interaction between xylan and ES100 occurs only by means of physical aggregation

Micropartículas de poli (ácido lático-co-ácido glicólico) obtidas por spray drying para a liberação prolongada de metotrexato

Methotrexate (MTX) is a drug used in the chemotherapy of some kind of cancers, autoimmune diseases and non inflammatory resistant to corticosteroids uveits. However, the rapid plasmatic elimination limits its therapeutic success, which leads to administration of high doses to maintain the therapeutic levels in the target tissues, occurring potential side effects. The aim of this study was to obtain spray dried biodegradable poly-lactic acid co-glycolic acid (PLGA) microparticles containing MTX. Thus, suitable amounts of MTX and PLGA were dissolved in appropriate solvent system to obtain solutions at different ratios drug/polymer (10, 20, 30 and 50% m/m). The physicochemical characterizing included the quantitative analysis of the drug using a validate UV-VIS spectrophotometry method, scanning electron microscopy (SEM), infrared spectrophotometry (IR), thermal analyses and X-ray diffraction analysis. The in vitro release studies were carried out in a thermostatized phosphate buffer pH 7.4 (0.05 M KH2PO4) medium at 37°C ± 0.2 °C. The in vitro release date was subjected to different kinetics release models. The MTX-loaded PLGA microparticles showed a spherical shape with smooth surface and high level of entrapped drug. The encapsulation efficiency was greater then 80%. IR spectroscopy showed that there was no chemical bond between the compounds, suggesting just the possible occurrence of hydrogen bound interactions. The thermal analyses and X-ray diffraction analysis shown that MTX is homogeneously dispersed inside polymeric matrix, with a prevalent amorphous state or in a stable molecular dispersion. The in vitro release studies confirmed the sustained release for distinct MTX-loaded PLGA microparticles. The involved drug release mechanism was non Fickian diffusion, which was confirmed by Kornmeyer-Peppas kinetic model. The experimental results demonstrated that the MTX-loaded PLGA microparticles were successfully obtained by spray drying and its potential as prolonged drug release system.

Aplicação de nanopartículas de quitosana com potencial de adjuvante na produção de soro contra o venneno do escorpião Tityus serrulatus

In Brazil, several species of scorpions are known to cause accidents which can lead to death, which are mainly belonging to the genus Tityus. The scorpion Tityus serrulatus is the main responsible for more severe cases. Anti-scorpion serums are routinely produced by various institutions, despite their effectiveness, quality and action depends on how quickly treatment is started. Studies have been developed in the search for appropriate technologies to encapsulate and release recombinant or natives proteins capable of inducing antibody production. In this context, chitosan copolymer which can be obtained from the partial deacetylation of chitin or in some microorganisms and it is biocompatible and biodegradable has been widely used for this purpose. This study aimed to search for a system release from chitosan nanoparticles for peptide / protein of the venom of the scorpion T. serrulatus, able to provide a new model of immunization in animals, in order to obtain a potential novel polyclonal serum, anti-venom T. serrulatus. The chitosan nanoparticles were prepared by ionic gelation with polyanion tripolyphosphate (TPP). After standardizing the concentrations of TPP and chitosan was evaluated the efficiency of incorporation of bovine serum albumin (BSA) and scorpion venom, showed particle size compatible with the intended purpose. The particles showed adequate size around 200nm. The crosslinking was confirmed by absorption spectroscopy in the infrared. After verified the high encapsulation efficiency (EE) for acid bicinconínico method (BCA) protein assay and the particle size distribution, the success of the technique was proven and the potential for in vivo application of nanoparticles. The experimental animals were vaccinated and the antibodies measured by ELISA

Preparação e carcterização de complexos multicomponentes contendo ciclodextrinas e benznidazol

The benznidazole (BNZ) is the only alternative for Chagas disease treatment in Brazil. This drug has low solubility, which restricts its dissolution rate. Thus, the present work aimed to study the BNZ interactions in binary systems with beta cyclodextrin (β-CD) and hydroxypropyl-beta cyclodextrin (HP-β-CD), in order to increase the apparent aqueous solubility of drug. The influence of seven hydrophilic polymers, triethanolamine (TEA) and 1-methyl-2- pyrrolidone (NMP) in benznidazole apparent aqueous solubility, as well as the formation of inclusion complexes was also investigated. The interactions in solution were predicted and investigated using phase solubility diagram methodology, nuclear magnetic resonance of protons (RMN) and molecular modeling. Complexes were obtained in solid phase by spray drying and physicochemical characterization included the UV-Vis spectrophotometric spectroscopy in the infrared region, scanning electron microscopy, X-ray diffraction and dissolution drug test from the different systems. The increment on apparent aqueous solubility of drug was achieved with a linear type (AL) in presence of both cyclodextrins at different pH values. The hydrophilic polymers and 1-methyl-2-pyrrolidone contributes to the formation of inclusion complexes, while the triethanolamine decreased the complex stability constant (Kc). The log-linear model applied for solubility diagrams revealed that both triethanolamine and 1-methyl-2-pyrrolidone showed an action cosolvent (both solvents) and complexing (1-methyl-2-pyrrolidone). The best results were obtained with complexes involving 1-methyl-2-pyrrolidone and hydroxypropylbeta- cyclodextrin, with an increased of benznidazole solubility in 27.9 and 9.4 times, respectively. The complexes effectiveness was proven by dissolution tests, in which the ternary complexes and physical mixtures involving 1-methyl- 2-pyrrolidone and both cyclodextrins investigated showed better results, showing the potential use as novel pharmaceutical ingredient, that leads to increased benznidazole bioavailability

Avaliação da argila atapulgita para potencial uso como excipiente farmacêutico em formas sólidas

Clays are natural materials that have great potential for use as excipients for solid dosage forms. Palygorskite is a type of clay that has hydrophilic properties as well as a large surface area, which could contribute to the dissolution of drugs. Thus, the present study aims to evaluate the use of palygorskite clay, from Piaui (Northeast region of Brazil), as a pharmaceutical excipient for solid dosage forms, using rifampicin and isoniazid as the model drugs. The former is a poorly soluble drug often associated with isoniazid for tuberculosis treatment. Palygorskite was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and specific surface area (BET). The rheological and technological properties of palygorskite were determined and compared to those of talc, magnesium stearate and Aersosil 200. Mixtures between drugs and palygorskite were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) combined with thermal analysis (DTA) and Fourier Transform Infrared Spectroscopy (FT-IR), where the results were compared with those of the individual compounds. In addition, dissolution studies of solid dispersions and capsules containing the drugs, mixed with either palygorskite or a mixture of talc and magnesium stearate, were performed. The results showed that palygorskite has small particles with a high surface area. Its rheological characteristics were better than those of others commonly used glidants and lubricants. There was no interaction between palygorskite and the drugs (rifampicin and isoniazid). Among the dispersions studied, the mixture with palygorskite (5%) showed the highest drug dissolution when compared to other excipients. The dissolution of the rifampicin capsules containing palygosrkite was faster in higher concentrations. However, these differences were statistically different only in the first minutes of the dissolution experiment. The dissolution profile of isoniazid was also statistically different on the initial part of the experiment. The formulations prepared with isoniazid and palygorskite showed higher drug dissolution, but it was in descending order of concentration. According to these results, the palygorskite clay used in this study has great potential for application as an excipient for solid dosage forms