The aluminum electrolytic capacitor is used extensively in the electric utility industry. A factor limiting the storage of spare capacitors is the integrity of the aluminum oxide dielectric, which over time breaks down contributing to a shelf life currently estimated at one nuclear power electric generating station to be approximately five years. This project examined the electrical characteristics of naturally aged capacitors of several different styles to determine if design parameters were still within limits. Additionally, the effectiveness of a technique known as “Reforming” was examined to determine its impact on those characteristics.

The aim of this study is to analyze the current readiness of Russia to become a member of WTO and to analyze how this membership will impact the russian economy generally.That is why this work set out the following tasks: In the first chapter - to explore the specific activities of the World Trade Organization, to determine its objectives and functions. In the second chapter - to explore the various stages of the Russia's accession to WTO and define the emerging results and complications. In the third chapter, I consider it necessary to examine the current status of Russia in international trade. Some attention will be paid to attitude of Russia's largest trading partners to accession. In the fourth chapter - to explore how Russian accession to the WTO will impact its main sectors and analyze the impact of economic liberalization on the overall economic situation in the country. In the final chapter - to explore possible ways of reforming the economy

No presente trabalho foi estudado o efeito da adição de cálcio, bário e estrôncio (0%-5% em massa) em catalisadores Ni/Al2O3, contendo 5% de níquel em massa, frente à reação de reforma a vapor do etanol com o objetivo de inibir a reação de desidratação do etanol, precursor do carbono. Os catalisadores foram preparados por dois métodos: impregnação (I) e co-precipitação (C). Inicialmente todos os catalisadores obtidos foram submetidos a analise de espectroscopia dispersiva em emissão de raios X (EDX), para confirmação de suas composições químicas, em seguida foram aplicados na reação de reforma a vapor do etanol, dentre os catalisadores estudados os que apresentaram a menor formação de eteno foram, 5%Ca-5%Ni/Al (I) e 5%Ca-5%Ni/Al (C) dentre os que continham cálcio; 0,5%Ba-5%Ni/Al (I) e 5%Ba-5%Ni/Al (C) dentre os que continham bário e 5%Sr-5%Ni/Al (I) e 5%Sr-5%Ni/Al (C) dentre os que continham estrôncio, sendo então submetidos as etapas de caracterização, difração de raios X (DRX), redução a temperatura programada (RTP), área superficial específica pelo método BET e reação de decomposição do isopropanol. O desempenho destes catalisadores foi comparado com o obtido para os catalisadores sem aditivos 5Ni/Al(I) e 5Ni/Al(C). O método da impregnação demonstrou ser mais eficiente do que o método da co-precipitação para o alcance dos objetivos do trabalho e o catalisador 5Ca-5Ni/Al (I) foi o mais efetivo na redução da acidez da alumina e consequentemente mostrou menor deposição de carbono. / Catalysts of Ni/Al2O3 containing 5wt% of nickel and modified by calcium, barium and strontium addition (0wt% - 5wt%) were tested in the ethanol steam reforming with the goal of reduce the reaction of dehydratation of ethanol, a carbon precursor. The catalysts were prepared by two methods: impregnation (I) and co-precipitation (C). Initially, all catalysts were subjected to analysis by Energy-dispersive X-ray spectroscopy (EDX), to confirm their chemical compositions, then they were applied in the steam reforming of ethanol, Among the catalysts studied those with lower ethene production were: 5%Ca-5%Ni/Al (I), 5%Ca-5%Ni/Al (C) among those containing calcium; 0,5%Ba-5%Ni/Al (I), 5%Ba-5%Ni/Al (C) among those containing barium and 5%Sr-5%Ni/Al (I), 5%Sr-5%Ni/Al (C) among those containing strontium, being submitted to the characterization by X-ray diffraction (XRD), temperature programmed reduction (TPR), specific surface area by BET method and reaction of isopropanol decomposition. The performance of these catalysts was compared to with the catalysts without additives 5(wt%)Ni/Al(I) and 5(wt%)Ni/Al(C). The impregnation method was more effective than the method co-precipitation for achieving the objectives of this work and the catalyst 5Ni-5Ca/Al (I) was the more effective in the reduction of alumina acidity and also showed the lower carbon deposition.

Catalisadores de Ni suportado em La2O3, SiO2 e La2O3-SiO2 (com teores mássicos de La2O30 de 10%, 30% e 50%) tiveram seu desempenho avaliado frente a reação de reforma a vapor de glicerol. O efeito do suporte sobre a atividade, estabilidade e seletividade do catalisador foi avaliado, assim como diferentes métodos de preparo, teores de Ni e temperaturas de reação. Os catalisadores foram preparados pelos métodos da impregnação úmida seqüencial, impregnação úmida simultânea, impregnação sobre o suporte precipitado e co-precipitação, utilizando teores mássicos de 5%, 10% e 15% de Ni. Foram utilizadas as seguintes técnicas de caracterização: espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, redução a temperatura programada e difração de raios X in situ. Os catalisadores foram testados por um período de 5h, a fim de verificar a atividade e seletividade para a reação de reforma a vapor de glicerol a 500°C, 600°C e 700°C, e as propriedades dos catalisadores foram correlacionadas com os resultados obtidos dos ensaios catalíticos. Após as reações, os catalisadores foram submetidos as seguintes análises: análise elementar, difratometria de raios X e microscopia eletrônica de varredura. Foi observado que o Ni interage de forma variada com os diferentes suportes, que o método de preparação utilizado influencia propriedades dos catalisadores e que, dependendo do teor mássico de Ni suportado, o catalisador pode ser mais ou menos ativo para a reação de reforma a vapor de glicerol. Observou-se também que a temperatura influencia no desempenho da reação, sendo que os melhores resultados foram obtidos a 600°C com o catalisador 15Ni30LaSi preparado por impregnação úmida simultânea, que foi testado também por 20h para que fosse analisada sua estabilidade em um maior intervalo de tempo. / Ni catalysts supported on La2O3, SiO2 and La2O3-SiO2 (with 10%, 30% and 50%wt.La2O3) were evaluated in the glycerol steam reforming reaction. The effect of the supports was analyzed on the catalysts activity; stability and selectivity as well as different methods of preparation, Ni contents and reaction temperatures. Catalysts were prepared by the sequential wet impregnation, simultaneous wet impregnation, impregnation of Ni on support precipitate and co-precipitation methods using 5%, 10% and 15%wt.Ni. The catalysts were characterized by energy dispersive X-ray spectroscopy, nitrogen physisorption, X-ray diffraction, temperature programmed reduction and X-ray diffraction in situ. The catalytic tests were performed during 5 hours in order to verify the activity and selectivity for the glycerol steam reforming at 500°C, 600°C and 700°C, and identify the relationship between the catalysts properties and the results obtained with the catalytic tests. After the reactions, the catalysts were characterized by elemental analysis, X-ray diffraction and scanning electron microscopy. It was observed that the Ni interacted variously with different supports; the preparation method used influenced on the catalysts properties and, depending on the Ni content, the catalyst was more or less active for the glycerol steam reforming. It was also observed that the temperature of reaction influenced on the reaction performance, and the best results were obtained at 600°C with the 15Ni30LaSi catalyst, prepared by simultaneous wet impregnation, which was also tested for 20 hours to analyze its stability in a longer period.

Fixed bed reactors are an essential part of the chemical industry as they are used in a wide variety of chemical processes. To better model these systems a more fundamental understanding of the processes taking place in a fixed bed is required. Fixed bed models are traditionally based on high tube-to particle diameter ratio (N) beds, where temperature and flow profile gradients are mild and can be averaged. Low-N beds are used in extremely exo- and endothermic processes on the tube side of tube and shell type reactors. In these beds, heat transfer is one of the most important aspects. The importance of accurate modeling of heat transfer and its dependence on accurate modeling of the flow features leads to the need for studying the phenomena in these low-N beds in detail. In this work a comparative study is made of the influence of spherical and cylindrical packing particle shapes, positions and orientations on the rates of heat transfer in the near-wall region in a steam reforming application. Computational Fluid Dynamics (CFD) is used as a tool for obtaining the detailed flow and temperature information in a low-N fixed bed. CFD simulation geometries of discrete particle packed beds are designed and methods for data extraction and analysis are developed. After conceptual and quantitative analysis of the simulation data it is found that few clear relations between the complex phenomena of flow and heat transfer can be easily identified. Investigated features are the orientations of the particle in the flow, and many design parameters, such as the number and size of longitudinal holes in the particle and external features on the particle. We find that many of the investigated features are related and their individual influences could not be isolated in this study. Some of the related features are, for example, the number of holes in the particle design and the particle orientation in the flow. Some general conclusions could be drawn. External features on the particles enhance the overall heat transfer properties by better mixing of the flow field. When holes are present in the cylindrical particle design, heat transfer effectiveness can be improved with fewer larger holes. After identifying the packing-related features influencing the near-wall heat transfer under steam reforming conditions, an attempt was made to incorporate the steam reforming reaction in the simulation. In the initial attempts the reaction was modeled as an energy flux at the catalyst particle surfaces. This approach was based on the abilities of the CFD code, but turned out not accurate enough. Elimination of the effects of local reactant depletion and the lack of solid energy conduction in the catalyst particles resulted in an unphysical temperature field. Several suggestions, based on the results of this study, are made for additional aspects of particle design to be investigated. Additionally, suggestions are made on how to incorporate the modeling of a reaction in fixed bed heat transfer simulations.

Visando a produção de hidrogênio, como uma fonte renovável de energia, estudaram-se as reações de reforma a vapor e oxidativa do etanol sobre catalisadores de Ru/CeO2-Al2O3. Foi verificado o efeito do suporte e das interações metal/suporte sobre a atividade e seletividade para as reações. Os suportes e catalisadores foram caracterizados por fisissorção de nitrogênio pelo método B.E.T., para avaliar as áreas superficiais específicas, espectroscopia dispersiva de raios-X (EDX), para determinar a distribuição qualitativa da fase metálica sobre os suportes, difração de raios-X (DRX), para identificação das fases óxidas, espectroscopia na região do ultra-violeta e do visível (UV-vis NIR), para avaliar as transições eletrônicas presentes no material, e redução a temperatura programada (RTP), para avaliação do comportamento de redução e das fases redutíveis. Através dos ensaios catalíticos, pode-se verificar que todos os catalisadores foram ativos para ambas as reações de reforma, sob as temperaturas de 400, 600 e 700ºC, onde a conversão do etanol aumentou com o aumento da temperatura e com o aumento da adição de CeO2 ao suporte catalítico. O catalisador 3%Ru/CeO2 foi o mais ativo frente a reação de reforma a vapor e o 3%Ru/25%CeO2-Al2O3 o catalisador mais ativo para a reação de reforma oxidativa do etanol. A maior seletividade para H2 foi obtida a 600ºC para ambas as reações de reforma, com exceção dos catalisadores 3%Ru/20%CeO2-Al2O3, que foi mais seletivo a 700ºC para a reforma a vapor, e 3%Ru/CeO2, que foi mais seletivo a 400ºC para a reforma oxidativa. / Aiming at hydrogen production, as a source of renewable energy, Ru/CeO2-Al2O3 catalysts were studied in ethanol steam reform and ethanol oxidative reforming. The effect of the support and metal/support interaction was verified on the activity and selectivity of the reactions. The supports and catalysts were characterized by x-rays dispersive spectroscopy (XDS), to verify the qualitative distribution of the metallic phase on the supports, x-rays diffraction (XRD), for identification of the crystalline oxide phases, spectroscopy in the region of the ultraviolet and the visible (UV-vis NIR), to evaluate the electronic transitions present in the material, and temperature programmed reduction (TPR), for evaluation of the reductive phases. According to the catalytic tests, all catalysts were active for both reactions under the temperatures of 400, 600 and 700ºC, where the ethanol conversion increased together with the increase of the temperature and, with the addition of CeO2 to the catalytic support. The 3%Ru/CeO2 catalyst was the most active for ethanol steam reforming and the 3%Ru/25%CeO2-Al2O3 catalyst was the most active for ethanol oxidative reforming. The higher selectivity for H2 occurred at 600ºC for both reactions, excluding the 3%Ru/20%CeO2-Al2O3 catalyst, which was more selective at 700ºC for steam reforming, and the 3%Ru/CeO2 catalyst, which was more selective for the oxidative reforming at 400ºC.

Neste trabalho foram avaliadas as atividades de catalisadores do tipo perovskita LaNi1-xCoxO3 frente à reação de reforma a vapor de etanol. Devido à baixa área superficial, característica de óxidos do tipo perovskita, esses foram suportados em SiO2, Al2O3 e ZrO2, a fim de verificar o efeito do suporte na atividade catalítica.<br /> Os catalisadores foram preparados pelo método da co-precipitação e caracterizados por espectrometria de emissão atômica por plasma induzido, difração de raios X pelo método do pó, adsorção de nitrogênio pelo método B.E.T, redução a temperatura programada e espectroscopia de absorção de raios X.<br /> Para estudar o processo de redução e a possibilidade de oxidação durante a reação catalítica, foram realizados estudos in situ da reação de reforma a vapor, através da espectroscopia de absorção de raios X. Estes dados foram comparados com os resultados de aplicação das técnicas de RTP e DRX às amostras parcial e totalmente reduzidas e foi proposto um mecanismo de redução do óxido do tipo perovskita durante o processo de ativação do catalisador.<br /> Todos os catalisadores mostraram-se ativos nas reações de reforma a vapor de etanol e a seletividade dos produtos foi dependente do tipo do catalisador avaliado. De acordo com os resultados obtidos, destaca-se o catalisador não suportado LaNiO3, com conversão de etanol de 99% e seletividade para H2, CO e CO2 de 4,8; 1,1 e 1,3, respectivamente. Além disso, o ensaio com dois catalisadores simultâneos (LaNiO3 + LaCoO3) foi o que apresentou melhor estabilidade na reação, com 100% de conversão de etanol e seletividade semelhante à obtida pelo catalisador LaNiO3. / In this work, the catalytic activity of perovskite oxides, LaNi1-xCoxO3, was evaluated in the ethanol steam reforming. Due to the low surface area, characteristic of perovskite oxides, these catalysts were supported on SiO2, AI2O3 and ZrO2 and the effect of the support was evaluated. The catalysts were prepared by the co-precipitation method and characterized by Atomic Induced Plasma Spectroscopy, X-Ray Powder Diffraction (XRD), Nitrogen adsorption by B.E.T. method, Temperature Programmed Reduction (TPR) and X-ray Absorption Near Edge Structure (XANES).<br /> The catalytic process was accompanied by XANES in situ to verify changes in the oxidation state of the active phase during the activation process with H2 and also during the process of steam reforming of ethanol. By relation of these results with TPR and XRD, for samples partially and fully reduced, it was proposed a mechanism for the reduction of the perovskite oxides during the conditions of activation.<br /> All catalysts showed activity for the ethanol steam reforming with the selectivity dependent of the catalyst evaluated. Summarizing, the results showed that the unsupported catalyst LaNiO3 presented the better performance, with the ethanol conversion of 99% and selectivity for H2, CO and CO2 of 4.8; 1.1 and 1.3, respectively. Moreover, the test using two simultaneous catalysts (LaNiO3 + LaCoO3), showed better stability in the reaction, presenting ethanol conversion of 100% and selectivity to H2, CO and CO2 similar to the LaNiO3 catalyst.

Steam reforming is the most economical and widely-used route for the conversion of light hydrocarbon (such as natural gas) to various valued-added products. This process is commonly carried out over a low-cost alumina-supported nickel catalyst, which often suffers from carbon deposition resulting in loss of active sites, flow and thermal maldistribution, as well as excessive pressure drop. A bimetallic catalyst with improved anti-coking properties was formulated by incorporating the nickel-based system (15% loading) with cobalt metal (5% loading). Two-level factorial design was employed to investigate the effect of major preparation variables, namely impregnation pH value (2-8), calcination temperature (873-973 K), heating rate (5-20 K min-1) and time (1-5 h). The catalysts prepared were subjected to various characterisation techniques to determine key physicochemical properties (i.e. BET area, H2-chemisorption and NH3- TPD acidity). X-ray diffraction revealed that NiO, Co3O4, NiCo2O4 and a proportion of Ni(Co)Al2O4 aluminates were transformed during H2-reduction to active Co and Ni crystallites. TEM images showed an egg yolk profile in the low-pH catalyst suggesting that main deposition site was located in the particle centre, while metal deposition occurred primarily around the particle exterior for the high-pH catalyst. Temperature programmed experiments were carried out to examine the extent of conversion, type of surface species and solid-state kinetics (using the Avrami-Erofeev model) involved during various stages in catalyst life-cycle (calcination, reduction, oxidation and regeneration). Steam reforming analysis suggested that enhanced catalyst activity may be due to synergism in the Co-Ni catalyst. Specifically, the low-pH catalyst exhibited better resistance towards carbon-induced deactivation than the high-pH formulation. The study also provided the first attempt to develop a quantitative relation between catalyst preparation conditions and its performance (activity, product selectivity and deactivation) for steam reforming reaction. Deactivation and reforming kinetic coefficients were simultaneously evaluated from propane reforming conversion-time data under steam-to-carbon ratios of 0.8-1.6 and reaction temperatures between 773-873 K. The time-dependent optimum operational policy derived based on these rate parameters gave better conversion stability despite the heavy carbon deposit. Thermal runs further showed that the catalysts regenerated via two-stage reductive-oxidative coke burn-off exhibited superior surface properties compared to those rejuvenated by a single-step oxidation.

Hydrogen production from reforming bio-fuels is considered as one of the major ways of utilizing renewable energy sources. Conventionally, most reforming catalysts are noble metal catalysts with high operation temperature above 1000 °C, which result in low thermal efficiency, long start-up time and use of high grade materials. These reasons hinder the development of hydrogen production technology. Novel self-sustained electrochemical promotion (SSEP) catalysts were developed and evaluated for heavy hydrocarbon reforming at relatively low temperatures, 450 to 650 °C. Typically, the SSEP catalysts contain NiO/Ni/CuO/Cu/CeO2 as a selective anodic phase, La0.9Sr0.1MnO3 (LSM) as a selective cathodic phase, yttria stabilized zirconia (YSZ) as an oxygen ion conduction phase, and Ni/Cu also as an electronic conduction phase. The reforming performance of the SSEP catalysts was evaluated using a fixed bed reforming reactor for n-pentadecane. A commercially available noble metal containing catalyst, 2.4 %Pt on CeO2 support, was evaluated using exactly the same method. The following conclusions can be drawn as a consequence of this study: 1) The fuel conversion for the SSEP catalyst was 10 folds of that for the noble metal catalyst and the yield of hydrogen and carbon monoxide for the SSEP catalysts was 100 folds of that for the noble metal catalyst at 450°C. 2) The mechanism of the SSEP catalysts was proved by the experimental results. 3) The study of the effect of each component and the effect of the concentration clearly reveals that the performance of the SSEP catalysts can be further improved to a higher level by many ways. In addition, all the catalysts were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Transmission Electron Microscopy (TEM) and Accelerated Surface Area and Porosimetry Analyzer 2020 (ASAP 2020).

Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.