Cyclodextrins (CD) are cyclic oligosaccharides composed of six to more than sixty glucose units. Large-ring cyclodextrins (LR-CD) are novel CD comprised of more than eight glucose units with cavity structures and sizes different from that of commercially available CD₆ – CD₈. LR-CD may offer unique molecular recognition properties and can be produced biocatalytically from starch using cyclodextrin glucanotransferase (CGTase, E.C. 2.4.1.19) in a short reaction time. LR-CD were isolated from glucose, CD₆ – CD₈ and other compounds by complexation of CD₆ – CD₈ as well as precipitation techniques. The yield of LR-CD (degree of polymerization from 9 to 21) was optimized using central composite design. Addition of polar organic solvents to the synthesis resulted in higher yields of LR-CD. LR-CD composed of 9 to 21 glucose units were successfully separated using reversed-phase of ODS-AQ chromatography and normal-phase of polyamine II chromatography. Maintaining optimized reaction conditions aided in a high yield of CD₉; it could be separated with reasonable yield using a single step of polyamine II chromatography. A co-grinding method helped to obtain higher solubilization levels of glibenclamide, vitamin A acetate and vitamin D₃ in CD₁₃, CD₁₀ and CD₁₁, respectively when compared to other CD. Vitamin K₁ was solubilized in distilled water with CD₆ – CD₁₃ using a co-precipitation method. When compared with other CD, CD₉ was seen to be the best solubilizer. The analysis of complexes using ESI MS showed spironolactone and glibenclamide complexed with CD₉ and CD₁₃, respectively.

The present thesis is concerned with methods for determination and modeling of characteristic parameters of combustion of gaseous fuels. The focus is stressed on formation of nitrogen oxides and heat transfer from hot flue gases into combustion chamber’s walls. Experimental work, which is focused on testing of two burners with suppressed formation of nitrogen oxides, is an important part of the thesis. Its aim is to obtain data that is necessary for further processing and modeling. The work presents two methods that may be used in modeling of characteristic combustion parameters, namely the method based on statistical processing of data and the method based on computational fluid dynamics. The approaches are applied to two devices (burner with two-staged fuel supply, burner with two-staged air supply) with the objective to analyze their parameters. First approach covers detailed planning of burner test prior to its own carrying out (definition of the goal of experiment, choice of input factors and response, experimental plan) and subsequent statistical processing of experimental data. On the contrary, CFD approach offers simulations as an alternative option to traditional experimental methods. The simulation of combustion includes building of computational grid, setup of boundary conditions, turbulence model, heat transfer model and chemical kinetics. Results of simulations are compared with experimental measured data.

[pt] Nos últimos anos, a indústria automotiva se reinventou para atender às demandas do mercado, que tem se mostrado competitivo em um contexto com legislações ambientais severas. Uma alternativa para reduzir as emissões de gases de efeito estufa prejudiciais ao longo da vida do veículo são os carros elétricos. No entanto, a produção e o descarte de baterias elétricas ainda é um problema a ser resolvido. Por isso, as empresas também buscam alternativas para aumentar a eficiência do motor de combustão interna e desenvolver tecnologias verdes, como a Ignição por Compressão de Carga Homogênea ou a Ignição por Compressão Assistida por Centelha (SACI). Uma rotina MATLAB foi criada para prever o desempenho da combustão SACI de gás natural usando um modelo termodinâmico de duas zonas. Este trabalho realiza análise de sensibilidade para cinco parâmetros de desempenho: eficiência térmica (Nth), pressão efetiva média indicada (IMEP), emissões de NOx, temperatura média no cilindro (Tavg) e tempo de autoignição (AIT), com várias variáveis como a velocidade do motor (RPM), a razão de equivalência combustível-ar (0s), o tempo da centelha (0s), a razão de compressão (rc) e a pressão de admissão (Pint), usando planejamento de experimentos para avaliar o impacto dos fatores. O Planejamento de Composto Central indica que o RPM e o 0 foram os fatores mais importantes no SACI, uma vez que influenciam todos os parâmetros de desempenho. A Pint foi significativa em três parâmetros de desempenho (Nth, IMEP e Tavg), assim como o 0s (NOx, Tavg e AIT). A rc foi relevante em apenas um deles (AIT). Além disso, uma Análise Univariada foi feita para comparar as técnicas de ignição por centelha (SI) e SACI. Os resultados indicam que os motores SACI tendem a ser cerca de 9% mais eficientes e as emissões de NOx caem mais de 90%. / [en] In the last few years, the automotive industry has reinvented itself to meet the demands of the international market, which has been increasingly competitive in a context with environmental laws each year more severe. One alternative to lower harmful greenhouse gases emissions over the life of the vehicle is electric cars. However, the production and disposal of electric batteries is still a major problem to be solved. Therefore, companies are also searching for other potentialities to increase the internal combustion engine s efficiency and develop green technology, such as Homogeneous Charge Compression Ignition (HCCI) or Spark-Assisted Compression Ignition (SACI). A MATLAB routine was created to predict the performance of SACI multimode combustion of natural gas using a two-zone thermodynamic model. This work performs sensitivity analysis for five performance parameters: thermal efficiency (Nth), indicated mean effective pressure (IMEP), NOx emissions, mean in-cylinder temperature (Tavg), and auto-ignition timing (AIT), with several variables such as engine speed (RPM), fuel-air equivalence ratio (0s), spark timing (0s), compression ratio (rc), and intake pressure (Pint), using the design of experiments tools to assess the factors impact. The Central Composite Design indicates that RPM and 0 were the most important SACI factors since they influence all engine performance parameters. The Pint was significant in three performance parameters (Nth, IMEP and Tavg), as was 0s (NOx, Tavg and AIT). The rc, however, was relevant in only one of them (AIT). Furthermore, a Univariate Analysis (UA) was done to compare Spark-Ignition (SI) and SACI engines. The results show that SACI engines tend to be around 9% more efficient, NOx emissions drop notably, more than 90%, IMEP presents an increase of 76%, and Tavg decreases 200-300 K.

D. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / A novel low-cost ternary Mn-Fe-Cu (MFC) metal oxide nanocomposite adsorbent was fabricated using facile co-precipitation method and successfully applied for the sequestration of Cr(VI) and As(III) from simulated aqueous efflent. The central composite design (CCD) of the response surface methodology (RSM) optimization technique determined the optimal working parameters for the preparation of the ternary MFC metal oxide nanocomposite. The spectroscopic microstructural analysis of the ternary MFC metal oxide nanocomposite was performed using fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) spectroscopy. The spectroscopic analyses revealed a rough surface with hydroxyl groups and the presence of mixed metal oxides in different valence states. The BET surface area, pore volume and pore size of the nanostructured MFC ternary metal oxide composite were found to be 77.2427 m2/g, 0.2409 cm3/g and 14.7560 nm, respectively. The pH drift method determined that the pHpzc of the adsorbent was 6.75. The batch technique was employed to investigate the adsorption dynamics (effects of ionic strength, co-existing anions, adsorbent regeneration and reuse) and optimum parameters (solution pH, adsorbent dosage concentration, desorption) of Cr(VI) and As(III) adsorption onto the MFC nanocomposite. The fitting of non-linear kinetic (pseudo-first-order, pseudo-second-order and Elovich), diffusion (intraparticle and Boyd) and isotherm (Langmuir, Freundlich and Dubinin-Radushkevich) models to the Cr(VI) and As(III) experimental adsorption data gave an insight into the adsorption mechanisms. The Langmuir adsorption capacities, qm (mg/g), were 168.71 at solution pH 3 and 35.07 at solution pH 9 for Cr(VI) and As(III) adsorption, respectively. The adsorption of Cr(VI) onto the ternary MFC metal oxide nanocomposite was physical and formed outer-sphere surface complexes through electrostatic interactions, while the removal of As(III) was specific due to inner-sphere surface complexation and ligand/ion exchange reactions. The results from XPS and FTIR analysis after the adsorption of Cr(VI) and As(III) showed that the surface hydroxyl groups on the MFC nanocomposite interacted with the Cr(VI) and As(III) species during the formation of the surface complexes. To facilitate ease of adsorbent removal from the treated simulated aqueous effluent, the ternary MFC metal oxide system was co-precipitated onto biochar support.

Made available in DSpace on 2017-07-10T18:08:17Z (GMT). No. of bitstreams: 1 Jamal Abd Awadallak.pdf: 7067148 bytes, checksum: 8e321c5aa3d2b9b3eeaafb2fd17b9d47 (MD5) Previous issue date: 2012-02-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Diacylglycerol rich oils have its organoleptic characteristics very similar to those of conventional edible oils, but these oils do not tend to accumulate in the body, even when consumed in high quantities, making them a great resource in the fight against obesity. Palm oil ranks first the world production of edible oils mainly due to its low cost. This work aimed to propose a new technology for enzyme production using diacylglycerol lipase Lipozyme RM IM and ultrasound to promote water in oil emulsions, which increases the interfacial area of the system leading to higher reaction rates compared to conventional enzymatic processes. . The reactions were carried out at 55 °C with two different methods. First, the reaction system was exposed to ultrasonic waves for the whole reaction time, which led to enzymatic inactivation and water evaporation. Ultrasound was then used to promote emulsification of the water/oil system before the hydrolysis reaction, avoiding contact between the probe and the enzymes. Achieved conversions were superior to the conventional method further hydrolysis rate when the ultrasound is employed for emulsion formation was significantly greater. For 12 hours of reaction the conversion was 85% higher than the conventional method and 15% higher for a period of 24 hours of reaction. . An experimental design was used to optimize the ultrasound-related parameters and maximize the hydrolysis rate, and in these conditions, with a change in equilibrium, DAG production was evaluated.Better reaction conditions were achieved for the second method: 11.20 wt% (water+oil mass) water content, 1.36 wt% (water+oil mass) enzyme load, 12 h of reaction time, 1.2 min and 200 W of exposure to ultrasound. In these conditions diacylglycerol yield was 37.69 wt%. / Óleos enriquecidos com diacilglicerol possuem características organolépticas muito semelhantes às dos óleos comestíveis convencionais, porém, estes óleos não tendem a se acumular no organismo, mesmo quando consumidos em altas quantidades, tornando-os um grande recurso no combate à obesidade. O óleo de palma está no topo da produção mundial de óleos comestíveis principalmente devido ao seu baixo custo. Este trabalho teve como objetivo propor uma nova tecnologia para a produção enzimática de diacilglicerol empregando a lipase Lipozyme RM IM e utilizando ultrassom como gerador de emulsões de água em óleo, o que aumenta a área interfacial do sistema conduzindo a maiores taxas de reação em relação aos processos enzimáticos convencionais. A hidrólise parcial do óleo de palma foi realizada em meio livre de solventes a 55 °C em duas etapas distintas e comparadas com reações em condições semelhantes sem o uso do ultrassom. Primeiramente o sistema reacional foi exposto às ondas ultrassônicas, o que levou a taxas iniciais de reação elevadas, porém, as conversões obtidas foram baixas, em função da desativação enzimática e da evaporação de água, pelo longo período de exposição ao ultrassom. Posteriormente, utilizou-se o ultrassom para gerar emulsões antes a etapa reacional, não permitindo seu contato com o sistema contendo a enzima. As conversões obtidas foram superiores ao método convencional, além disso, taxa de hidrólise quando se empregou o ultrassom para a formação de emulsões foi significativamente maior. Para 12 horas de reação a conversão foi 85% superior ao método convencional e de 15% superior para um período de 24 horas de reação. Foi desenvolvido um planejamento fatorial, o delineamento central composto rotacional para avaliar os efeitos das variáveis tempo de exposição ao ultrassom, potência do ultrassom e razão água/óleo na conversão em ácidos graxos livres da reação, sendo que a razão água/óleo e o produto tempo x potência apresentaram os maiores efeitos. Nas melhores condições, foi produzido um óleo concentrado com 37,69% de DAG em de 12h de reação, exposto ao ultrassom por 1,2min à 200W.