Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Uso do pó da palha de carnaúba em compósitos de quitosana

In this work a biodegradable composite using the carnauba straw s powder as reinforcement on chitosan matrix polymeric were manufactured. Firstly, were carried out the chemistry characterization of the carnauba straw s powder before and after treatments with NaOH and hexane. Goering and Van Soest method (1970), flotation test, moisture absorption, FTIR, TG/DTG, DSC and SEM have also being carried out. Composites were developed with variations in granulometry and in powder concentrations. They were characterized by TG/DTG, SEM and mechanicals properties. The results of chemical composition showed that the carnauba straw s powder is composed of 41% of cellulose; 28,9% of hemicellulose and 14% of lignin.The flotation test have indicated that the chemical treatment with NaOH decreased the powder s hidrophilicity.The thermal analysis showed increased of thermal stability of material after treatments. The results of FTIR and SEM revealed the removal of soluble materials from the powder (hemicelluloses and lignin), the material became rougher and clean. The composites obtained showed that the mechanicals properties of the composites were decreased in respect at chitosan films, and the composites with the powder at 150 Mesh showed less variation in the modulus values. The speed test of 10 mm/min showed the better reproducibility of the results and is in agreement to the standard ASTM D638. The SEM analysis of fracture showed the low adhesion between the fiber/matrix. The increase of volume of powder in the composite caused a decrease in values of stress and strain for the samples with untreated powder and treated with hexane. The composite with 50% of the powder s treated in NaOH didn t have significant variation in the values of stress and strain as compared with the composites with 10% of the powder, showing that the increase in the volume of fiber didn t affect the stress and strain of the composite. Thereby, it is concluded that the manufacture of polymeric composites of chitosan using carnauba straw s powder can be done, without need for pre-treatment of reinforcement, become the couple of carnauba straw s powder-chitosan a good alternative for biodegradable composites

Micropartículas de quitosana estruturadas com aerosil®: estabilidade, adsorção, encapsulação e liberação de substâncias ativas

Biodegradable microspheres used as controlled release systems are important in pharmaceutics. Chitosan biopolymer represents an attractive biomaterial alternative because of its physicochemical and biological characteristics. Chitosan microspheres are expected to become promising carrier systems for drug and vaccine delivery, especially for non-invasive ways oral, mucosal and transdermal routes. Controlling the swelling rate and swelling capacity of the hydrogel and improving the fragile nature of microspheres under acidic conditions are the key challenges that need to be overcomed in order to enable the exploration of the full pharmaceutical potential use of these microparticles. Many studies have focused on the modification of chitosan microsphere structures with cross-linkers, various polymers blends and new organic-inorganic hybrid systems in order to obtain improved properties. In this work, microspheres made of chitosan and nanosized hydrophobic silica (Aerosil R972) were produced by a method consisting of two steps. First, a preparation of a macroscopically homogeneous chitosan-hydrophobic silica dispersion was prepared followed by spray drying. FTIR spectroscopy, X-ray powder diffraction, differential scanning calorimetry, thermal gravimetric analysis, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (TEM) were used to characterize the microspheres. Also, the were conducted acid stability, moisture sorption capacity, release properties and biological assays. The chitosan-hydrophobic silica composite microspheres showed improved thermal degradation, lower water affinity, better acid stability and ability to retard rifampicin and propranolol hydrochloride (drug models) release under simulated physiological conditions. In vitro biocompatibility studies indicated low cytotoxicity and low capacity to activate cell production of the pro-inflammatory mediator nitric oxide. The results show here encourage further studies on the use of the new chitosan-hydrophobic silica composite microspheres as drug carrier systems via oral or nasal routes.

Estudo da sinterização de eletrólito sólido de céria dopada com gadolínia

Fuel cells are electrochemical devices that convert chemical energy in electrical energy by a reaction directly. The solid oxide fuel cell (SOFC) works in temperature between 900ºC up to 1000ºC, Nowadays the most material for ceramic electrolytes is yttria stabilized zirconium. However, the high operation temperature can produce problems as instability and incompatibility of materials, thermal degradation and high cost of the surround materials. These problems can be reduced with the development of intermediate temperature solid oxide fuel cell (IT-SOFC) that works at temperature range of 600ºC to 800ºC. Ceria doped gadolinium is one of the most promising materials for electrolytes IT-SOFC due high ionic conductivity and good compatibility with electrodes. The inhibition of grain growth has been investigated during the sintering to improve properties of electrolytes. Two-step sintering (TSS) is an interesting technical to inhibit this grain growth and consist at submit the sample at two stages of temperature. The first one stage aims to achieve the critical density in the initiating the sintering process, then the sample is submitted at the second stage where the temperature sufficient to continue the sintering without accelerate grain growth until to reach total densification. The goal of this work is to produce electrolytes of ceria doped gadolinium by two-step sintering. In this context were produced samples from micrometric and nanometric powders by two routes of two-step sintering. The samples were obtained with elevate relative density, higher than 90% using low energy that some works at the same area. The average grain size are at the range 0,37 μm up to 0,51 μm. The overall ionic conductivity is 1,8x10-2 S.cm and the activation energy is 0,76 eV. Results shown that is possible to obtain ceria-doped gadolinium samples by two-step sintering technique using modified routes with characteristics and properties necessary to apply as electrolytes of solid oxide fuel cell

Adição de poliuretana em pastas de cimento para poços de petróleo como agente de correção do filtrado

Chemical admixtures, when properly selected and quantified, play an important role in obtaining adequate slurry systems for quality primary cementing operations. They assure the proper operation of a well and reduce costs attributed to corrective cementing jobs. Controlling the amount lost by filtering through the slurry to permeable areas is one of the most important requirements in an operation, commonly controlled by chemical admixtures, such as carboxymethylcellulose (CMC). However, problems related to temperature, salttolerance and the secundary retarding effect are commonly reported in the literature. According to the scenario described above, the use of an aqueous dispersion of non-ionic poliurethane was proposed to control the filter loss, given its low ionic interaction with the free ions present in the slurries in humid state. Therefore, this study aims at assessing the efficiency of poliurethane to reduce filter loss in different temperature and pressure conditions as well as the synergistic effect with other admixtures. The temperatures and pressures used in laboratory tests simulate the same conditions of oil wells with depths of 500 to 1200 m. The poliurethane showed resistance to thermal degradation and stability in the presence of salts. With the increase in the concentration of the polymer there was a considerable decrease in the volume lost by filtration, and this has been effective even with the increase in temperature

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Degradação catalítica de polietileno de alta densidade sobre a zeólita HZSM

In last years it has talked a lot about the environment and the plastic waste produced and discarded. In last decades, the increasing development of research to obtain fuel from plastic material, by catalytic degradation, it has become a very attractive looking, as these tailings are discarded to millions worldwide. These materials take a long time to degrade themselves by ways said natural and burning it has not demonstrated a viable alternative due to the toxic products produced during combustion. Such products could bring serious consequences to public health and environment. Therefore, the technique of chemical recycling is presented as a suitable alternative, especially since could be obtain fractions of liquid fuels that can be intended to the petrochemical industry. This work aims to propose alternatives to the use of plastic waste in the production of light petrochemical. Zeolites has been widely used in the study of this process due to its peculiar structural properties and its high acidity. In this work was studied the reaction of catalytic degradation of high-density polyethylene (HDPE) in the presence HZSM-12 zeolites with different acid sites concentrations by thermogravimetry and pyrolysis coupled with GC-MS. The samples of the catalysts were mixed with HDPE in the proportion of 50% in mass and submitted to thermogravimetric analyses in several heating rates. The addition of solids with different acid sites concentrations to HDPE, produced a decrease in the temperature of degradation of the polymer proportional the acidity of the catalyst. These qualitative results were complemented by the data of activation energy obtained through the non-isothermal kinetics model proposed by Vyazovkin. The values of Ea when correlated to the data of surface acidity of the catalysts indicated that there is a exponential decrease of the energy of activation in the reaction of catalytic degradation of HDPE, in function of the concentration of acid sites of the materials. These results indicate that the acidity of the catalyst added to the system is one of the most important properties in the reaction of catalytic degradation of polyethylene

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

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

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

Contribuições sobre estudos térmicos (TG/DTG, DTA, DSC e DSC-Fotovisual) da rifampicina e seus principais produtos de degradação

Since its synthesis over 48 years rifampicin has been extensively studied. The literature reports the characterization of thermal events for rifampicin in nitrogen atmosphere, however, no characterization in synthetic air atmosphere. This paper aims to contribute to the thermal study of rifampicin through thermal (TG / DTG, DTA, DSC and DSC - FOTOVISUAL ) and non-thermal (HPLC, XRPD , IR - FTIR , PCA) and its main degradation products ( rifampicin quinone , rifampicin N-oxide 3- formylrifamicin). Rifampicin study was characterized as polymorph form II from techniques DSC, IR and XRPD. TG curves for rifampicin in synthetic air atmosphere showed higher thermal stability than those in N2, when analyzed Ti and Ea. There was characterized as overlapping events melting and recrystallization under N2 with weight loss in the TG curve, suggesting concomitant decomposition. Images DSCFotovisual showed no fusion event and showed darkening of the sample during analysis. The DTA curve in synthetic air atmosphere was visually different from DTA and DSC curves under N2, suggesting the absence of recrystallization and melting or presence only decomposition. The IV - FTIR analysis along with PCA analysis and HPLC and thermal data suggest that rifampicin for their fusion is concomitant decomposition of the sample in N2 and fusion events and recrystallization do not occur in synthetic air atmosphere. Decomposition products studied in an air atmosphere showed no melting event and presented simultaneously to the decomposition initiation of heating after process loss of water and / or solvent, varying the Ti initiating events. The Coats - Redfern , Madsudhanan , Van Krevelen and Herwitz - Mertzger kinetic parameters for samples , through the methods of OZAWA , in an atmosphere of synthetic air and / or N2 rifampicin proved more stable than its degradation products . The kinetic data showed good correlation between the different models employed. In this way we contribute to obtaining information that may assist studies of pharmaceutical compatibility and stability of substances

Viabilidades térmica, econômica e de materiais de um sistema solar de aquecimento de água a baixo custo para fins residenciais

An solar alternative system for water heating is presented. Is composed for one low cost alternative collector and alternative thermal reservoir for hot water storing. The collector of the system has box confectioned in composite material and use absorption coils formed for PVC tubes. The box of hot water storage was confectioned from a plastic polyethylene drum used for storage of water and garbage, coated for a cylinder confectioned in fiber glass. The principle of functioning of the system is the same of the conventionally. Its regimen of work is the thermosiphon for a volume of 250 liters water. The main characteristic of the system in considered study is its low cost, allowing a bigger socialization of the use of solar energy. It will be demonstrated the viabilities thermal, economic and of materials of the system of considered heating, and its competitiveness in relation to the available collectors commercially. Relative aspects will be boarded also the susceptibility the thermal degradation and for UV for the PVC tubes. It will be shown that such system of alternative heating, that has as main characteristic its low cost, presents viabilities thermal, economic and of materials

Resposta térmica de um compósito PEEK+PTFE+Fibra de carbono+grafite

Composites based on PEEK + PTFE + CARBON FIBER + Graphite (G_CFRP) has increased application in the top industries, as Aerospace, Aeronautical, Petroleum, Biomedical, Mechanical and Electronics Engineering challenges. A commercially available G_CFRP was warmed up to three different levels of thermal energy to identify the main damage mechanisms and some evidences for their intrinsic transitions. An experimental test rig for systematize a heat flux was developed in this dissertation, based on the Joule Effect. It was built using an isothermal container, an internal heat source and a real-time measurement system for test a sample by time. A standard conical-cylindrical tip was inserted into a soldering iron, commercially available and identified by three different levels of nominal electrical power, 40W (manufacturer A), 40W (manufacturer B), 100W and 150W, selected after screening tests: these power levels for the heat source, after one hour of heating and one hour of cooling in situ, carried out three different zones of degradation in the composite surface. The bench was instrumented with twelve thermocouples, a wattmeter and a video camera. The twelve specimens tested suffered different degradation mechanisms, analyzed by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetry) techniques, Scanning Electron Microscopy (SEM) and Energy-Dispersive X-Rays (EDX) Analysis. Before and after each testing, it was measured the hardness of the sample by HRM (Hardness Rockwell M). Excellent correlations (R2=1) were obtained in the plots of the evaporated area after one hour of heating and one hour of cooling in situ versus (1) the respective power of heat source and (2) the central temperature of the sample. However, as resulting of the differential degradation of G_CFRP and their anisotropy, confirmed by their variable thermal properties, viscoelastic and plastic properties, there were both linear and non-linear behaviour between the temperature field and Rockwell M hardness measured in the radial and circumferential directions of the samples. Some morphological features of the damaged zones are presented and discussed, as, for example, the crazing and skeletonization mechanism of G_CFRP

Bio-óleo e biogás da degradação termoquímica de lodo de esgoto doméstico em cilindro rotativo

The objective of this study was to produce biofuels (bio-oil and gas) from the thermal treatment of sewage sludge in rotating cylinder, aiming industrial applications. The biomass was characterized by immediate and instrumental analysis (elemental analysis, scanning electron microscopy - SEM, X-ray diffraction, infrared spectroscopy and ICP-OES). A kinetic study on non-stationary regime was done to calculate the activation energy by Thermal Gravimetric Analysis evaluating thermochemical and thermocatalytic process of sludge, the latter being in the presence of USY zeolite. As expected, the activation energy evaluated by the mathematical model "Model-free kinetics" applying techniques isoconversionais was lowest for the catalytic tests (57.9 to 108.9 kJ/mol in the range of biomass conversion of 40 to 80%). The pyrolytic plant at a laboratory scale reactor consists of a rotating cylinder whose length is 100 cm with capable of processing up to 1 kg biomass/h. In the process of pyrolysis thermochemical were studied following parameters: temperature of reaction (500 to 600 ° C), flow rate of carrier gas (50 to 200 mL/min), frequency of rotation of centrifugation for condensation of bio-oil (20 to 30 Hz) and flow of biomass (4 and 22 g/min). Products obtained during the process (pyrolytic liquid, coal and gas) were characterized by classical and instrumental analytical techniques. The maximum yield of liquid pyrolytic was approximately 10.5% obtained in the conditions of temperature of 500 °C, centrifugation speed of 20 Hz, an inert gas flow of 200 mL/min and feeding of biomass 22 g/min. The highest yield obtained for the gas phase was 23.3% for the temperature of 600 °C, flow rate of 200 mL/min inert, frequency of rotation of the column of vapor condensation 30 Hz and flow of biomass of 22 g/min. The non-oxygenated aliphatic hydrocarbons were found in greater proportion in the bio-oil (55%) followed by aliphatic oxygenated (27%). The bio-oil had the following characteristics: pH 6.81, density between 1.05 and 1.09 g/mL, viscosity between 2.5 and 3.1 cSt and highest heating value between 16.91 and 17.85 MJ/ kg. The main components in the gas phase were: H2, CO, CO2 and CH4. Hydrogen was the main constituent of the gas mixture, with a yield of about 46.2% for a temperature of 600 ° C. Among the hydrocarbons formed, methane was found in higher yield (16.6%) for the temperature 520 oC. The solid phase obtained showed a high ash content (70%) due to the abundant presence of metals in coal, in particular iron, which was also present in bio-oil with a rate of 0.068% in the test performed at a temperature of 500 oC.

Síntese, caracterização e avaliação catalítica do silicoaluminofosfato SAPO-11 sulfatado

Due to environmental restrictions around the world, clean catalytic technology are of fundamental importance in the petrochemical industry and refineries. Creating the face of this a great interest in replacing the liquid acids for solid acids, so as molecular sieves have been extensively studied in reactions involving the acid catalysis to produce chemical substances with a high potential of quality. Being the activity of the catalysts involved in the reaction attributed to the acid character of them involved for the Lewis and Brönsted acid sites. Based on this context, this study aimed to prepare catalysts acids using a molecular sieve silicoalumino-phosphate (SAPO-11) synthesized in hidrotermical conditions and sulphated with sulphuric acid at different concentrations, using to it the method of controlled impregnating. The samples resulting from this process were characterized by x-ray difratometry (DRX), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TG-DTG) and determination of total acidity (by n-butilamin adsorption). The results show that the synthesis method used was efficient in the formation of AEL structure of SAPO-11 and when being incorporated the sulfate groups in this structure the acidity of the material was increased, pointing out that to very high concentrations of acid there is a trend of decrease the main peaks that form the structure. Finally they were tested catalytictly by the reaction model of conversion of m-xylene which showed favorable results of conversion for this catalyst, showing to be more selective of cracking products than isomerization, as expected, in order that for the o-xylene selectivity there was no positive change when to sulfate a sample of SAPO-11, while for light gases of C1-C4 this selectivity was remarkably observed