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.

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.

L’objectif de la thèse est de fabriquer des structures catalytiques washcoatées de taille centimétrique pour différentes réactions catalytiques comme le vaporeformage et le pré-reformage, le SNG (Substitute Natural Gas) et le MTP (Methanol to Propylene). L’étude de l’utilisation de ces structures alternatives aux catalyseurs extrudés conventionnels utilisés dans l’industrie est la conséquence des contraintes opératoires (gradients de pression et de température) et leur influence sur les coûts opératoires (endommagement des matériaux, désactivation des catalyseurs, perte de charge dans les réacteurs, etc.). Le dépôt des catalyseurs sur les architectures céramiques et métalliques a été possible grâce à l’étude minutieuse du comportement des solides catalytiques en suspension dans un milieu liquide. Le contrôle de paramètres comme la chimie de surface et la rhéologie a été nécessaire pour acquérir une maîtrise nécessaire afin d’obtenir des pièces catalytiques avec un dépôt homogène, stable mécaniquement et non fissuré. / L’objectif de la thèse est de fabriquer des structures catalytiques washcoatées de taille centimétrique pour différentes réactions catalytiques comme le vaporeformage et le pré-reformage, le SNG (Substitute Natural Gas) et le MTP (Methanol to Propylene). L’étude de l’utilisation de ces structures alternatives aux catalyseurs extrudés conventionnels utilisés dans l’industrie est la conséquence des contraintes opératoires (gradients de pression et de température) et leur influence sur les coûts opératoires (endommagement des matériaux, désactivation des catalyseurs, perte de charge dans les réacteurs, etc.). Le dépôt des catalyseurs sur les architectures céramiques et métalliques a été possible grâce à l’étude minutieuse du comportement des solides catalytiques en suspension dans un milieu liquide. Le contrôle de paramètres comme la chimie de surface et la rhéologie a été nécessaire pour acquérir une maîtrise nécessaire afin d’obtenir des pièces catalytiques avec un dépôt homogène, stable mécaniquement et non fissuré.

No description available.

The interest in hydrogen as a clean energy source has increased due to depletion of limited fossil resources and environmental impact related to CO2 emissions. Hydrogen production from bio-ethanol, which already contains large amount of water, by steam reforming reaction, has shown excellent potential with CO2 neutrality. However, steam reforming of ethanol reaction is a highly complex process including many side reactions which decrease hydrogen yield and have a negative effect on process economy. Also, thermodynamic limitations cause decrease in hydrogen yield. In the present study, a new reaction process called sorption enhanced steam reforming has been investigated to improve hydrogen yield in ethanol reforming over Ni and Co impregnated MCM-41 type mesoporous catalysts. In this process in-situ removal of CO2 by CaO was used to improve hydrogen yield significantly. Catalysts play a crucial role in both steam reforming of ethanol and sorption enhanced steam reforming of ethanol reactions. Discovery of mesoporous catalyst supports, like MCM-41, started a new pathway in catalysis research. In this study, Co and Ni incorporated MCM-41 type materials having metal/Si molar ratio of 0.1 were synthesized by impregnation method, characterized and tested in both steam reforming of ethanol and sorption enhanced steam reforming of ethanol reactions at 500oC, 550oC and 600oC. EDS and XRD results of the synthesized catalysts showed that Co and Ni were successfully incorporated and well dispersed in the MCM-41 support. The characteristic ordered pore structure of MCM-41 was partially conserved. Synthesized Co-MCM-41 and Ni-MCM-41 had surface area and pore diameter values of 303.6 m2/g &ndash / 1.98 nm and 449 m2/g &ndash / 2.2 nm, respectively. Catalytic test results obtained with both catalysts proved that hydrogen yield values were significantly enhanced in the presence of CaO during in situ capture of CO2. Catalytic performance of Ni-MCM-41 was much better than Co-MCM-41 in ethanol reforming reaction. The highest hydrogen yield obtained with Co-MCM-41 catalyst was achieved at 550oC as 3.1 with in situ capture of CO2. This value is not high enough for practical use of this catalyst. At the same temperature, the corresponding hydrogen yield value was only 1.62 in the absence of CaO. The catalytic test results obtained with Ni-MCM-41 at 600oC, gave a hydrogen yield value of 5.6 in the sorption enhanced reforming run, which is about 94% of the maximum possible hydrogen yield of six.

This work focuses on methane and ethanol conversion to hydrogen in the presence of a catalyst in order to increase the selectivity of the desired product (H₂) and reduce carbon monoxide emission and coke formation. Two kinds of active phase were used (copper and ruthenium) and impregnated on calcined hydrotalcites CoₓMg₆₋ₓAl₂ in order to be evaluated in the methane and ethanol steam reforming reactions. For both reactions, the influence of several factors was evaluated in order to adjust the reaction parameters. It has been shown that catalysts performances for the reforming reactions depend on the content of cobalt and magnesium. High cobalt content enhanced the catalytic activity. 1Ru/Co₆Al₂ catalyst presented the highest activity and stability in the methane steam reforming reaction among the other industrial and prepared catalysts even under a low GHSV and with no hydrogen pretreatment. Reduced ruthenium and cobalt were detected after the reaction by XRD. EPR technique was able to detect negligible amount of two kinds of carbonaceous species formed during the reaction : coke and carbon. On the other hand, 5Cu/Co₆Al₂ catalyst revealed the highest hydrogen productivity in the ethanol steam reforming reaction. However, it suffers from coke formation that deactivated the catalysts after few hours. 5Cu/Co₂Mg₄Al₂ catalyst showed a much lower quantity of carbonaceous species with no deactivating during 50 hours due to the basic character of the magnesium oxide phase present in the support.

Ce travail a porté sur la conversion du méthane et de l'éthanol en hydrogène par le procédé du vaporeformage en utilisant de nouvelles formulations de catalyseurs afin d'augmenter la sélectivité en produit désiré (hydrogène), de réduire la production du monoxyde de carbone (Co) et défavoriser la formation de coke. Deux familles de phases actives, à base de cuivre et de ruthénium supportés par les hydrotalcites calcinées CoₓMg₆₋ₓAl₂, ont été évaluées dans ces réactions. Pour les deux réactions, l'influence de plusieurs facteurs a été évaluée afin d'ajuster les paramètres de la réaction. Il a été démontré que les performances des catalyseurs pour les réactions du vaporeformage dépendent de la teneur en cobalt et en magnésium.Une grande teneur en cobalt améliore la réactivité catalytique. Le catalyseur 1Ru/Co₆Al₂ a présenté la plus forte activité et stabilité dans la réaction du vaporeformage du méthane parmi les autres catalyseurs industriels et préparés. Les espèces réduites de ruthénium et du cobalt ont été détectées après la réaction par DRX. La technique RPE était capable de détecter des quantités négligeables de deux types d'espèces carbonées formées lors de la réaction : du coke et du carbone. D'autre part, le catalyseur 5Cu/Co₆Al₂ a révélé la productivité la plus élevée en hydrogène dans la réaction du vaporeformage de l'éthanol. Cependant, il se désactive après quelques heures à cause de la formation du coke. Le catalyseur 5Cu/Co₂Mg₄Al₂ a montré une quantité beaucoup plus faible d'espèces carbonées sans désactiver pendant 50 heures en raison du caractère basique de la phase de l'oxyde du magnésium présente dans le support. / This work focuses on methane and ethanol conversion to hydrogen in the presence of a catalyst in order to increase the selectivity of the desired product (H₂) and reduce carbon monoxide emission and coke formation. Two kinds of active phase were used (copper and ruthenium) and impregnated on calcined hydrotalcites CoₓMg₆₋ₓAl₂ in order to be evaluated in the methane and ethanol steam reforming reactions. For both reactions, the influence of several factors was evaluated in order to adjust the reaction parameters. It has been shown that catalysts performances for the reforming reactions depend on the content of cobalt and magnesium. High cobalt content enhanced the catalytic activity. 1Ru/Co₆Al₂ catalyst presented the highest activity and stability in the methane steam reforming reaction among the other industrial and prepared catalysts even under a low GHSV and with no hydrogen pretreatment. Reduced ruthenium and cobalt were detected after the reaction by XRD. EPR technique was able to detect negligible amount of two kinds of carbonaceous species formed during the reaction : coke and carbon. On the other hand, 5Cu/Co₆Al₂ catalyst revealed the highest hydrogen productivity in the ethanol steam reforming reaction. However, it suffers from coke formation that deactivated the catalysts after few hours. 5Cu/Co₂Mg₄Al₂ catalyst showed a much lower quantity of carbonaceous species with no deactivating during 50 hours due to the basic character of the magnesium oxide phase present in the support.