Desenvolvimento de sistemas micro e nanoestruturados de quitosana/MDI para aplicações cosméticas

Currently, studies in the area of polymeric microcapsules and nanocapsules and controlled release are considerably advanced. This work aims the study and development of microcapsules and nanocapsules from Chitosan/MDI, using a new technique of interfacial polycondensation combined to spontaneous emulsification, for encapsulation of BZ-3. It was firstly elaborated an experimental design of 23 of the particle in white without the presence of BZ-3 and Miglyol, where the variables were the concentrations of MDI, chitosan and solvent. Starting from the data supplied by the experimental design was chosen the experiment with smaller particle diameter and only added like this BZ-3 and Miglyol. The suspension containing concentrations of 6.25 mg/mL, 12.5 mg/mL, 18.75 mg/mL, 25 mg/mL of BZ-3 were prepared, nevertheless, during the storage time, these formulations presented drug precipitates in the suspensions of 18.75 mg/mL and 25 mg/mL of BZ-3. This apparition of precipitate was attributed to the diffusion of BZ-3 for the aqueous phase without any encapsulation, suggesting so the use of the smaller concentrations of the BZ-3. The suspension containing 6.25mg/mL of BZ3 presented average size of 1.47μm, zeta potential of 61 mV, pH 5.64 and this sample showed an amount of BZ-3 and drug entrapment of 100 %. The suspension containing 12.5mg/mL of BZ-3 presented average size of 1.76μm, zeta potential of 47.4 mV, pH 5.71 and this sample showed an amount of BZ-3 and drug entrapment of 100 %. Then, showing such important characteristics, these two formulations were chosen for futher continuity to the study. These formulations were also characterized by the morphology, FTIR, stability for Turbiscan, DSC and a study of controlled release of the BZ-3 was elaborated in different receiving means

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.

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.

Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

Estudo dos óxidos A2B2O7 e ABO3 a base de terras raras, para aplicações térmicas e catalíticas a altas temperaturas

Rare earth elements have recently been involved in a range of advanced technologies like microelectronics, membranes for catalytic conversion and applications in gas sensors. In the family of rare earth elements like cerium can play a key role in such industrial applications. However, the high cost of these materials and the control and efficiencies associated processes required for its use in advanced technologies, are a permanent obstacle to its industrial development. In present study was proposed the creation of phases based on rare earth elements that can be used because of its thermal behavior, ionic conduction and catalytic properties. This way were studied two types of structure (ABO3 and A2B2O7), the basis of rare earths, observing their transport properties of ionic and electronic, as well as their catalytic applications in the treatment of methane. For the process of obtaining the first structure, a new synthesis method based on the use of EDTA citrate mixture was used to develop a precursor, which undergone heat treatment at 950 ° C resulted in the development of submicron phase BaCeO3 powders. The catalytic activity of perovskite begins at 450 ° C to achieve complete conversion at 675 ° C, where at this temperature, the catalytic efficiency of the phase is maximum. The evolution of conductivity with temperature for the perovskite phase revealed a series of electrical changes strongly correlated with structural transitions known in the literature. Finally, we can establish a real correlation between the high catalytic activity observed around the temperature of 650 ° C and increasing the oxygen ionic conductivity. For the second structure, showed clearly that it is possible, through chemical processes optimized to separate the rare earth elements and synthesize a pyrochlore phase TR2Ce2O7 particular formula. This "extracted phase" can be obtained directly at low cost, based on complex systems made of natural minerals and tailings, such as monazite. Moreover, this method is applied to matters of "no cost", which is the case of waste, making a preparation method of phases useful for high technology applications

Estudo do desempenho de resinas poliméricas para remoção de H2S do gás natural

The natural gas (NG) is a clean energy source and found in the underground of porous rocks, associated or not to oil. Its basic composition includes methane, ethane, propane and other components, like carbon dioxide, nitrogen, hydrogen sulphide and water. H2S is one of the natural pollutants of the natural gas. It is considered critical concerning corrosion. Its presence depends on origin, as well as of the process used in the gas treatment. It can cause problems in the tubing materials and final applications of the NG. The Agência Nacional do Petróleo sets out that the maximum concentration of H2S in the natural gas, originally national or imported, commercialized in Brazil must contain 10 -15 mg/cm3. In the Processing Units of Natural Gas, there are used different methods in the removal of H2S, for instance, adsorption towers filled with activated coal, zeolites and sulfatreat (solid, dry, granular and based on iron oxide). In this work, ion exchange resins were used as adsorbing materials. The resins were characterized by thermo gravimetric analysis, infrared spectroscopy and sweeping electronic microscopy. The adsorption tests were performed in a system linked to a gas-powered chromatograph. The present H2S in the exit of this system was monitored by a photometrical detector of pulsing flame. The electronic microscopy analyzes showed that the topography and morphology of the resins favor the adsorption process. Some characteristics were found such as, macro behavior, particles of variable sizes, spherical geometries, without the visualization of any pores in the surface. The infrared specters presented the main frequencies of vibration associated to the functional group of the amines and polymeric matrixes. When the resins are compared with sulfatreat, under the same experimental conditions, they showed a similar performance in retention times and adsorption capacities, making them competitive ones for the desulphurization process of the natural gas

Estudo do desempenho de resinas poliméricas para remoção de H2S do gás natural

The natural gas (NG) is a clean energy source and found in the underground of porous rocks, associated or not to oil. Its basic composition includes methane, ethane, propane and other components, like carbon dioxide, nitrogen, hydrogen sulphide and water. H2S is one of the natural pollutants of the natural gas. It is considered critical concerning corrosion. Its presence depends on origin, as well as of the process used in the gas treatment. It can cause problems in the tubing materials and final applications of the NG. The Agência Nacional do Petróleo sets out that the maximum concentration of H2S in the natural gas, originally national or imported, commercialized in Brazil must contain 10 -15 mg/cm3. In the Processing Units of Natural Gas, there are used different methods in the removal of H2S, for instance, adsorption towers filled with activated coal, zeolites and sulfatreat (solid, dry, granular and based on iron oxide). In this work, ion exchange resins were used as adsorbing materials. The resins were characterized by thermo gravimetric analysis, infrared spectroscopy and sweeping electronic microscopy. The adsorption tests were performed in a system linked to a gas-powered chromatograph. The present H2S in the exit of this system was monitored by a photometrical detector of pulsing flame. The electronic microscopy analyzes showed that the topography and morphology of the resins favor the adsorption process. Some characteristics were found such as, macro behavior, particles of variable sizes, spherical geometries, without the visualization of any pores in the surface. The infrared specters presented the main frequencies of vibration associated to the functional group of the amines and polymeric matrixes. When the resins are compared with sulfatreat, under the same experimental conditions, they showed a similar performance in retention times and adsorption capacities, making them competitive ones for the desulphurization process of the natural gas

Electrochemical and spectroscopic studies of tungstencarbonyl complexes containing nitrogen and phosphorous ligands

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

Balanço de massa de reatores anaeróbicos de fluxo ascendente com manta de lodo (UASB) tratando águas residuárias de suinocultura

Foi obtido o balanço de massa, a partir dos valores médios das determinações de demanda química de oxigênio (DQO) e produção de metano (CH4), em dois reatores UASB de bancada com volume de 10,5 L tratando águas residuárias de suinocultura, submetidos a condições operacionais distintas no que diz respeito às concentrações de sólidos suspensos totais do afluente (SST de 500; 1.000; 1.500 e 2.000 mg L-1), tempo de detenção hidráulica (TDH de 30; 20; 12 e 8 h), taxas de carregamento orgânico volumétrico (TCOV de 0,8 a 8,0 kg DQO total (m³ d)-1) e temperatura (ambiente e controlada a 25º e 30ºC). Verificou-se que a DQO total removida convertida em CH4 variou de 28 a 51% e a relação DQO-CH4 por DQO dissolvida removida de 0,94 a 2,07; indicando alta participação da remoção física dos sólidos do afluente, de 49 a 72%, na remoção de DQO total nos reatores, a qual variou de 75 a 92%. A concentração de SST do afluente, a temperatura, o TDH e a TCOV influenciaram nesse desempenho dos reatores UASB.

Desempenho de reatores anaeróbios de fluxo ascendente com manta de lodo em dois estágios tratando águas residuárias de suinocultura

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

Desempenho de processo anaeróbio em dois estágios (reator compartimentado seguido de reator UASB) para tratamento de águas residuárias de suinocultura

Avaliou-se o efeito das águas residuárias de suinocultura com concentrações de sólidos suspensos totais em torno de 6.000 mg L-1 (DQOtotal variando de 7.557 a 11.640 mg L-1) no desempenho de processo anaeróbio em dois estágios compostos por reator compartimentado (ABR) e reator de fluxo ascendente com manta de lodo (UASB), instalados em série, em escala-piloto (volumes de 530 e 120 L, respectivamente), submetidos a tempos de detenção hidráulica (TDH) de 56 a 18 h no primeiro reator e de 13 a 4 h no segundo reator. As eficiências médias de remoção de DQOtotal variaram de 71,1 a 87,5% no reator ABR e de 41,5 a 50,1% no reator UASB, resultando em valores médios de 86,8 a 94,9% para o sistema de tratamento anaeróbio em dois estágios com carga orgânica volumétrica (COV), na faixa de 5,05 a 10,12 kg DQOtotal (m³ d)-1, no reator ABR, e de 2,83 a 9,63 kg DQOtotal (m³ d)-1, no reator UASB. As eficiências de remoção de SST e SSV foram da ordem de 95,6%. O teor de metano no biogás manteve-se acima de 70% para os dois reatores. A produção volumétrica de metano máxima de 0,755 m³ CH4 (m³ d)-1 ocorreu no reator 1, com COV de 10,12 kg DQOtotal (m³ d)-1 e TDH de 18 h. Os valores médios de pH variaram na faixa de 7,2 a 8,0 para os efluentes dos reatores 1 e 2. Os ácidos voláteis totais mantiveram-se estáveis com concentrações abaixo de 200 mg L-1. Com variações abruptas e acentuadas de concentrações de SST e DQOtotal do afluente, os reatores mantiveram as eficiências de remoção de DQO e sólidos suspensos, em torno de 70%, e a qualidade do biogás, com 80% de CH4.

Tratamento anaeróbio de águas residuárias do beneficiamento de café por via úmida em reatores UASB em dois estágios

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Biodigestão anaeróbia de dejetos de suínos com e sem separação da fração sólida em diferentes tempos de retenção hidráulica

O objetivo deste trabalho foi avaliar o processo de biodigestão anaeróbia utilizando dejetos de suínos, com e sem separação da fração sólida, considerando-se diferentes tempos de retenção hidráulica. Para tanto, foram utilizados biodigestores tubulares semicontínuos abastecidos com água residuária de suinocultura, com e sem separação da fração sólida (CSFS e SSFS, respectivamente), manejados com tempos de retenção hidráulica (TRH) iguais a 36; 29; 22 e 15 dias. A eficiência dos tratamentos foi avaliada pela redução dos números mais prováveis de coliformes totais e fecais, teores de fibra em detergentes neutro e ácido, demandas química e bioquímica de oxigênio e dos potenciais de produção de biogás e metano. A qualidade do biofertilizante foi avaliada quanto aos teores de macro e micronutrientes. A separação da fração sólida acarretou decréscimo nos teores de fibra dos afluentes, o que contribuiu para o aumento da eficiência da produção de metano. Foram observados valores de 0,47 e 0,75 m³ CH4 kg-1 SV adicionado para os afluentes SSFS e CSFS, respectivamente, no TRH de 15 dias. Com o aumento do TRH, houve acréscimo médio de 50% no potencial de produção de metano kg-1 de SV adicionado. Não foram observadas diferenças significativas nas reduções de coliformes fecais e totais, sendo a maior redução de 3,6 10(9) para 3,6 10² NMP 100 mL-1 para o TRH de 36 dias CSFS.

Potencial de produção de biogás remanescente nos efluentes de biodigestores abastecidos com dejetos de suínos, com e sem separação da fração sólida, e conduzidos sob diferentes tempos de retenção hidráulica

O objetivo foi avaliar o potencial poluidor remanescente dos efluentes de biodigestores abastecidos com dejetos de suínos com separação da fração sólida (CSFS) e sem separação da fração sólida (SSFS), e conduzidos sob diferentes tempos de retenção hidráulica (TRH). Os efluentes utilizados eram de biodigestores semicontínuos manejados com TRH de 15; 22; 29 e 36 dias, com e sem separação da fração sólida. Foram utilizados biodigestores batelada, que permaneceram em operação por todo o tempo em que houve produção de biogás (60 dias). Foram avaliadas a produção e a qualidade do biogás, bem como os potenciais de produção por kg de sólidos totais e sólidos voláteis, e as demandas química e bioquímica de oxigênio. Utilizou-se do delineamento inteiramente casualisado, em esquema fatorial 2x4, com três repetições por tratamento. Foram encontrados potenciais de produção de 385 e 117 litros de CH4kg-1 de SV adicionados no material SSFS e CSFS, respectivamente, no menor TRH (15 dias), e potenciais de produção de 74 e 18 litros de CH4kg-1 de SV adicionados no material SSFS e CSFS, respectivamente, no maior TRH (36 dias).

Influência da relação volumoso: concentrado e do tempo de retenção hidráulica sob a biodigestão anaeróbia de dejetos de bovinos

O objetivo deste trabalho foi avaliar as possíveis alterações existentes na composição e no processo de biodigestão anaeróbia dos dejetos de bovinos em fase de terminação alimentados com diferentes proporções de volumoso: concentrado e com diferentes tempos de retenção hidráulica (TRH). Foram utilizados 24 biodigestores batelada de bancada com 12 litros de capacidade, dos quais 12 foram abastecidos com dejetos de bovinos alimentados com a dieta 1 (60% volumoso:40% concentrado) e dieta 2 (40% volumoso:60% concentrado) e submetidos a 30, 60, 90 e 120 dias de TRH. A eficiência do processo de biodigestão anaeróbia foi avaliada pelas reduções de sólidos totais, sólidos voláteis, fibra em detergente neutro, fibra em detergente ácido, celulose e número mais provável (NMP) de coliformes totais e termotolerantes, além dos potenciais de produção de biogás e metano. Os resultados mostraram que o aumento da proporção de volumoso na dieta levou a menor eficiência do processo, principalmente nos potenciais de produção de biogás e metano que foram em média 13% menor. Com relação ao NMP de coliformes totais e termotolerantes, foram observadas reduções significativas conforme aumentou TRH.