Orientador: Célio Pasquini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T15:29:23Z (GMT). No. of bitstreams: 1 Vieira_FranciscoSenna_M.pdf: 2577567 bytes, checksum: 88e8b413d192407a39a0f0d341572223 (MD5) Previous issue date: 2012 / Resumo: A autoxidação de lipídeos é uma das principais causas de degradação de óleos e gorduras. Este processo gera uma série de compostos indesejáveis, tais como, peróxidos, hidroperóxidos e ácidos carboxílicos de cadeia curta. A determinação da estabilidade oxidativa de um óleo, é, portanto, essencial para estimar o tempo de prateleira - um parâmetro importante para a indústria alimentícia. Para quantificar o grau de oxidação de um óleo, uma série de parâmetros pode ser utilizada, como os índices de peróxido e de anisidina, o teor de dienos conjugados, dentre outros. Métodos acelerados foram desenvolvidos para a estabilidade oxidativa - uma medida da variação do grau de oxidação ao longo do tempo -, em particular o método Rancimat. Nele, uma amostra de cerca de 3 g de óleo e aquecida em temperaturas na faixa de 100-130 °C, e um fluxo de ar constante e passado através da amostra e carreado para um recipiente contendo água deionizada. O monitoramento da condutividade elétrica desta solução permite identificar o período de tempo necessário para que a taxa de formação de ácidos carboxílicos de cadeia curta se torne significativa. Este tempo é denominado tempo de indução (TI), e corresponde ao índice de estabilidade oxidativa (OSI - Oxidative Stability Index) do óleo. A espectroscopia de emissão no infravermelho próximo (NIRES), por outro lado, permite o monitoramento de hidroperóxidos, devido ao aumento e alargamento de uma banda em 2900 nm que ocorre ao longo do processo oxidativo. Neste trabalho foi desenvolvido e avaliado um fotômetro NIRES, dedicado para a determinação de estabilidade oxidativa. No método NIRES, uma amostra de 10 mL e aquecida a uma temperatura fixa (140 - 180 °C), sendo mantido um fluxo constante de ar purificado ao redor da amostra. A emissividade do óleo em 2850 e 2675 nm e continuamente monitorada com um detector de PbS, sendo a seleção dos comprimentos de onda realizada por dois filtros de interferência. A formação de hidroperóxidos ocasiona um aumento significativo da emissividade a 2850 nm, permitindo a determinação de TI de forma análoga ao método Rancimat.. O equipamento construído apresenta uma série de vantagens com relação ao método Rancimat, tais como: rapidez na análise, simplicidade operacional, menor consumo de amostra e a possibilidade de determinar a estabilidade oxidativa em temperaturas de fritura (140-180 °C). A precisão do método NIRES encontrada é equivalente à precisão do método Rancimat, e existe uma correlação entre eles (R = 0,90). / Abstract: Lipid autoxidation is the main cause of fats and oils deterioration. This process generates a series of undesirable compounds, such as hydroperoxides and low chain carboxylic acids. Thus, determination of oil fs oxidative stability is essential for estimation of the shelf life - an important parameter for the food industry. Several parameters are used for quantifying the degree of oxidation of an oil sample, such as the peroxide value, anisidine value, and conjugated dienes. Accelerated methods have been developed for measuring oxidative stability - the variation of the degree of oxidation with time -, particularly the Rancimat method. In this method, a constant air flow passes through a 3 g oil sample, heated at 110 - 130°C, and then is collected in a vessel containing deionized water. By monitoring the deionized water fs conductance, an induction time (IT) - which corresponds to the Oil Stability Index (OSI) - can be determined. On the other hand, near infrared emission spectroscopy (NIRES) allows the determination of IT by monitoring the formation of hydroperoxides. As the oil undergoes autoxidation, a band at 2900 nm becomes broader and more intense. In this work, a near infrared emission spectroscopy photometer, dedicated to determination of oxidative stability, has been developed and evaluated. In the NIRES method, a 10 mL oil sample is heated at a constant temperature (140 - 180 °C), and a purified air flow is maintained around the sample. The oil fs emissivity at 2675 and 2850 nm is continually monitored with a PbS detector, and the wavelengths are selected with two interference filters. Formation of hydroperoxides increases significantly the emissivity at 2900 nm, allowing the determination of IT in a way analogous to the Rancimat method. The developed equipment presents several advantages towards the Rancimat, including: faster analysis, lower sample consumption, operational simplicity, and the possibility of measuring oxidative stability at frying temperatures. Also, the method fs precision is equivalent to the Rancimat fs precision, and a correlation between them has been found (R = 0,90). / Mestrado / Quimica Analitica / Mestre em Química

A novel technique for measuring gas temperature and spectral particle emissivity in high-temperature gas-particle streams is presented. The main application of this optical sensor is to improve the process control of batch unit operations, such as steelmaking furnaces. The spectral emission profile of CO and CO2 and the continuous particle emission in the 3.5 to 5 μm wavelength region was recorded and analyzed in real time with a low-resolution passive sensor. The sensor consisted of light collecting optics, a dispersion element (grating spectrometer) and a 64-pixel pyroelectric array. Wavelength and radiance calibrations were performed. The temperature of the gas-particle medium (Tg+p) followed from the least-squares minimization of the difference between the measured radiance in the 4.56-4.7 μm region –which saturates due to the large CO2 concentrations and path lengths in industrial furnaces– and the corresponding blackbody radiance. Particle emissivity (εp) was calculated at 3.95 μm from an asymptotic approximation of the Radiative Transfer Equation that yields the emerging radiance from a semi-infinite particle cloud. The major source of error in the magnitude of Tg+p and εp could come from particle scattering. Through the method of embedded invariance an expression was developed to estimate the lowering effect of particle size and volume fraction on the saturation of the 4.56-4.7 μm CO2 emission region. An iterative procedure for correcting the values of the gas-particle temperature and particle emissivity was applied to the datasets from the two industrial tests. Results from the measurement campaigns with the infrared sensor prototype at two full-scale furnaces are presented. A proof-of-concept test at a coal-fired boiler for electricity production was followed by more extensive measurements at a Basic Oxygen Furnace (BOF) for steelmaking. The second test provided temperature and particle emissivity profiles for eight heats, which highlighted the simplicity of the technique in obtaining in-situ measurements for modeling studies. Through the analysis of the particle emissivity profile in the BOF and the definition of a new variable –the minimum carbon time– a novel end-point strategy to stop the injection of high-purity oxygen during low-carbon heats in BOF converters was proposed.

A novel technique for measuring gas temperature and spectral particle emissivity in high-temperature gas-particle streams is presented. The main application of this optical sensor is to improve the process control of batch unit operations, such as steelmaking furnaces. The spectral emission profile of CO and CO2 and the continuous particle emission in the 3.5 to 5 μm wavelength region was recorded and analyzed in real time with a low-resolution passive sensor. The sensor consisted of light collecting optics, a dispersion element (grating spectrometer) and a 64-pixel pyroelectric array. Wavelength and radiance calibrations were performed. The temperature of the gas-particle medium (Tg+p) followed from the least-squares minimization of the difference between the measured radiance in the 4.56-4.7 μm region –which saturates due to the large CO2 concentrations and path lengths in industrial furnaces– and the corresponding blackbody radiance. Particle emissivity (εp) was calculated at 3.95 μm from an asymptotic approximation of the Radiative Transfer Equation that yields the emerging radiance from a semi-infinite particle cloud. The major source of error in the magnitude of Tg+p and εp could come from particle scattering. Through the method of embedded invariance an expression was developed to estimate the lowering effect of particle size and volume fraction on the saturation of the 4.56-4.7 μm CO2 emission region. An iterative procedure for correcting the values of the gas-particle temperature and particle emissivity was applied to the datasets from the two industrial tests. Results from the measurement campaigns with the infrared sensor prototype at two full-scale furnaces are presented. A proof-of-concept test at a coal-fired boiler for electricity production was followed by more extensive measurements at a Basic Oxygen Furnace (BOF) for steelmaking. The second test provided temperature and particle emissivity profiles for eight heats, which highlighted the simplicity of the technique in obtaining in-situ measurements for modeling studies. Through the analysis of the particle emissivity profile in the BOF and the definition of a new variable –the minimum carbon time– a novel end-point strategy to stop the injection of high-purity oxygen during low-carbon heats in BOF converters was proposed.

This thesis describes the synthesis and characterisation of titania photocatalysts for incorporation into a polyethylene film. Monodisperse, anatase-phase titania nanoparticles are prepared and the synthesis conditions necessary for attraction to a laponite clay support are determined. Methods of preventing agglomeration of the laponite system such as the use of a polyethylene oxide surfactant or chemical modification of the laponite plate edges with a dimethyloctyl methoxysilane are also explored. Finally, photocatalytic studies on the laponite-supported titania nanoparticles are performed, and the compatibility and photoactivity of these materials in the polyethylene film are examined.