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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

"Desenvolvimento de agregados eletrofundidos para utilização em refratários para a zona de queima de fornos de cimento" / DEVELOPMENT OF ELECTROFUSED AGGREGATES FOR USE IN REFRACTORIES FOR THE BURNING ZONE OF CEMENT KILNS

Ferreira, Luis Leonardo Horne Curimbaba 24 August 2006 (has links)
Os agregados eletrofundidos são largamente utilizados para a produção de refratários tendo em vista a melhoria geral de propriedades propiciada pelo emprego dos mesmos. Neste trabalho projetaram-se agregados eletrofundidos adequados para aplicação em refratários para a zona de queima de fornos de cimento. Para o projeto dos mesmos foi realizada inicialmente uma avaliação a alta temperatura das reações que ocorrem entre as fases refratárias e as fases presentes no clínquer de cimento Portland, visando identificar os sistemas refratários mais promissores. Em seguida foram realizadas eletrofusões de matérias primas pertencentes a estes sistemas, visando a obtenção de diferentes composições de agregados, cujas características foram avaliadas. A última etapa do desenvolvimento envolveu a escolha de alguns agregados para a formulação de refratários para a zona de queima de fornos de cimento; medindo e comparando as propriedades dos tijolos obtidos com um tijolo refratário padrão de magnésia-espinélio. Agregados pertencentes ao sistema MgO – TiO2 – CaO, mais especificamente ao triângulo de compatibilidade formado pelas fases MgO – Mg2TiO4 – CaTiO3, mostraram características adequadas para o desenvolvimento de refratários para a zona de queima de fornos de cimento. / Electrofused aggregates are largely used in refractory production due to the better performance reached when they are employed. In this work electrofused aggregates were designed for application in refractories for the burning zone of cement kilns. Initially reaction evaluation was conducted aiming the identification of the most prone refractory systems when single refractory phases react with Portland cement phases at high temperatures. In the next step, raw materials of the best refractory systems were electrofused to generate different aggregate compositions. The electrofused aggregates properties were evaluated and the classified ones were used to produce refractory bricks for the burning zone of cement kilns. General characteristics of these bricks were measured and compared with a standard magnesia-spinel refractory. Aggregates of the system MgO – TiO2 – CaO, more specifically aggregates belonged to the compatibility triangle MgO – Mg2TiO4 – CaTiO3, showed suitable characteristics for development of refractories for the burning zone cement kilns.
22

"Desenvolvimento de agregados eletrofundidos para utilização em refratários para a zona de queima de fornos de cimento" / DEVELOPMENT OF ELECTROFUSED AGGREGATES FOR USE IN REFRACTORIES FOR THE BURNING ZONE OF CEMENT KILNS

Luis Leonardo Horne Curimbaba Ferreira 24 August 2006 (has links)
Os agregados eletrofundidos são largamente utilizados para a produção de refratários tendo em vista a melhoria geral de propriedades propiciada pelo emprego dos mesmos. Neste trabalho projetaram-se agregados eletrofundidos adequados para aplicação em refratários para a zona de queima de fornos de cimento. Para o projeto dos mesmos foi realizada inicialmente uma avaliação a alta temperatura das reações que ocorrem entre as fases refratárias e as fases presentes no clínquer de cimento Portland, visando identificar os sistemas refratários mais promissores. Em seguida foram realizadas eletrofusões de matérias primas pertencentes a estes sistemas, visando a obtenção de diferentes composições de agregados, cujas características foram avaliadas. A última etapa do desenvolvimento envolveu a escolha de alguns agregados para a formulação de refratários para a zona de queima de fornos de cimento; medindo e comparando as propriedades dos tijolos obtidos com um tijolo refratário padrão de magnésia-espinélio. Agregados pertencentes ao sistema MgO – TiO2 – CaO, mais especificamente ao triângulo de compatibilidade formado pelas fases MgO – Mg2TiO4 – CaTiO3, mostraram características adequadas para o desenvolvimento de refratários para a zona de queima de fornos de cimento. / Electrofused aggregates are largely used in refractory production due to the better performance reached when they are employed. In this work electrofused aggregates were designed for application in refractories for the burning zone of cement kilns. Initially reaction evaluation was conducted aiming the identification of the most prone refractory systems when single refractory phases react with Portland cement phases at high temperatures. In the next step, raw materials of the best refractory systems were electrofused to generate different aggregate compositions. The electrofused aggregates properties were evaluated and the classified ones were used to produce refractory bricks for the burning zone of cement kilns. General characteristics of these bricks were measured and compared with a standard magnesia-spinel refractory. Aggregates of the system MgO – TiO2 – CaO, more specifically aggregates belonged to the compatibility triangle MgO – Mg2TiO4 – CaTiO3, showed suitable characteristics for development of refractories for the burning zone cement kilns.
23

Nanotemplated High-Temperature Materials for Catalytic Combustion

Elm Svensson, Erik January 2008 (has links)
Catalytic combustion is a promising technology for heat and power applications, especially gas turbines. By using catalytic combustion ultra low emissions of nitrogen oxides (NOX), carbon monoxide (CO) and unburned hydrocarbons (UHC) can be reached simultaneously, which is very difficult with conventional combustion technologies. Besides achieving low emission levels, catalytic combustion can stabilize the combustion and thereby be used to obtain stable combustion with low heating-value gases. This thesis is focused on the high-temperature part of the catalytic combustor. The level of performance demanded on this part has proven hard to achieve. In order to make the catalytic combustor an alternative to the conventional flame combustor, more stable catalysts with higher activity have to be developed. The objective of this work was to develop catalysts with higher activity and stability, suitable for the high-temperature part of a catalytic combustor fueled by natural gas. Two template-based preparation methods were developed for this purpose. One method was based on soft templates (microemulsion) and the other on hard templates (carbon). Supports known for their stability, magnesia and hexaaluminate, were prepared using the developed methods. Catalytically active materials, perovskite (LaMnO3) and ceria (CeO2), were added to the supports in order to obtain catalysts with high activities and stabilities. The supports were impregnated with active materials by using a conventional technique as well as by using the microemulsion technique. It was shown that the microemulsion method can be used to prepare catalysts with higher activity compared to the conventional methods. Furthermore, by using a microemulsion to apply active materials onto the support a significantly higher activity was obtained than when using the conventional impregnation technique. Since the catalysts will operate in the catalytic combustor for extended periods of time under harsh conditions, an aging study was performed on selected catalysts prepared by the microemulsion technique. The stability of the catalysts was assessed by measuring the activity before and after aging at 1000 C in humid air for 100 h. One of the most stable catalysts reported in the literature, LMHA (manganese-substituted lanthanum hexaaluminate), was included in the study for comparative purposes. The results showed that LMHA deactivated much more strongly compared to several of the catalysts consisting of ceria supported on lanthanum hexaaluminate prepared by the developed microemulsion method. Carbon templating was shown be a very good technique for the preparation of high-surface-area hexaaluminates with excellent sintering resistance. It was found that the pore size distribution of the carbon used as template was a crucial parameter in the preparation of hexaaluminates. When a carbon with small pores was used as template, the formation of the hexaaluminate crystals was strongly inhibited. This resulted in a material with poor sintering resistance. On the other hand, if a carbon with larger pores was used as template, it was possible to prepare materials with hexaaluminate as the major phase. These materials were, after accelerated aging at 1400 C in humid air, shown to retain surface areas twice as high as reported for conventionally prepared materials. / QC 20100719
24

Processing And High Temperature Deformation Of Pure And Magnesia Doped Alumina

Swaroop, N R Sathya 01 1900 (has links)
Creep resistance is an important design criterion at high temperatures especially when continuous attempts are made to increase the efficiencies by increasing the operating temperatures. Alumina is an important high temperature material and in addition to that it is used in wide variety of applications such as substrates for electronic packaging, spark plugs, envelopes for sodium vapour lamps, cutting tools (when reinforced with silicon carbide) and in artificial joint prostheses. Studies on creep in alumina. have started as early as 1961. There are differing mechanisms proposed to explain the creep behaviour of alumina in the literature, but until now there is no any unanimous decision as to what the rate controlling mechanism is. Magnesia doped at ppm levels can produce significant changes in the microstructure of alumina, the most important consequence of that being the grain growth inhibition, which renders alumina superplastic. However, in a stoichiometric oxide like alumina, small impurities can create extrinsic defects which would change the diffusivities and creep rates. Therefore the background impurities in alumina should be kept to a minimum, if small dopant effects have to be studied. The present study was undertaken making use of high purity alumina powder and comparing the grain growth and creep properties of pure and magnesia doped alumina, especially since no such investigation was carried out in the recent past with high purity alumina. Pure alumina was processed by cold compaction followed by cold isostatic pressing (CIP) and pressureless sintering in air at 1773 K for 1 hour. Magnesia doped alumina was prepared by calcining a mixture of alumina and magnesium nitrate at 973 K for 2 hours followed by cold compaction, CIPing and pressureless sintering in air at 1773 K. Both pure and magnesia doped alumina were further annealed at 1873 K for various times to get grain sizes in the ranges of 1-5 μm. Grain growth kinetics of pure and magnesia doped alumina were studied at 1823 and 1873 K. The parameter Kg which quantifies the mobility of the grain boundary was got. It was found that Kg had decreased in the magnesia doped alumina (in comparison with pure alumina) by a factor of about 3 to 4 which was marginal and insignificant. The grain sizes followed a log normal distribution in both the cases, indicative of normal grain growth. Creep studies were conducted on pure and magnesia doped alumina in three modes, namely, constant stress, temperature jump and stress jump test. The temperature range used was 1673 to 1773 K and the stress range used was 10 to 100 MPa. The creep parameters were found to be n~1.6, p~3.7 and Q-545 kJ mol"1 for pure alumina and n~l .3, p~3.0 and Q~460 kJ mol-1 for magnesia doped alumina. The creep rates in the case of magnesia doped alumina were found to have increased by a factor of 2 to 3, in comparison with pure alumina. The increase in creep rates were found to be insignificant. The creep data were analyzed and the possibility of the dislocation and interface reaction controlled creep mechanisms were ruled out since they were inconsistent with the data. It was found, from creep parameters and the comparison of theoretical Coble and Nabarro-Herring creep rates with the experimental rates, that Coble creep might be rate controlling. The activation energy values suggested that aluminium ion diffusing along grain boundary might be the rate controlling species. However, when the theoretical creep rates considering various species were compared, the rate controlling species turned out to be oxygen ion diffusing along the grain boundary.
25

Diseño de catalizadores para una obtención limpia de 2-feniletanol

Bergadà Miró, Olga 12 July 2007 (has links)
El 2-feniletanol es el principal componente de la esencia de rosas y se utiliza como fragancia en la industria del perfume y la cosmética debido a su agradable olor. La hidrogenación de óxido de estireno mediante catálisis heterogénea para la obtención selectiva de 2-feniletanol se plantea como una alternativa para solucionar los graves problemas medioambientales y económicos que presentan los métodos clásicos de obtención a nivel industrial. El principal objetivo de esta tesis doctoral es la obtención de catalizadores que sean altamente activos y selectivos hacia la formación de 2-feniletanol, y resistentes a la desactivación, para que den lugar a procesos más sostenibles a nivel industrial. Se han estudiado tres grupos de catalizadores:- catalizadores de Ni y Ni-MgO- catalizadores preparados a partir de precursores hidrotalcita de Ni/Mg/Al - catalizadores de Ni-Mordenita con diferentes contenidos de Ni y obtenidos mediante diferentes métodos.Los catalizadores de Ni másicos presentan moderadas conversiones y elevadas selectividades hacia 2-feniletanol (60-95%) apreciándose una relación entre la morfología de las partículas y la formación de productos de condensación que desactivan el catalizador. Los catalizadores con MgO comercial (4NiMgO y NiMgO) presentan elevadas conversiones y selectividades hacia el alcohol de interés obteniéndose total conversión y 100% de selectividad a 2-feniletanol con el catalizador con mayor contenido en magnesia (NiMgO) después de 6 horas de reacción a temperatura ambiente. Los perfiles de TPD de CO2 para estos catalizadores no nos muestran el pico correspondiente a los centros básicos más débiles de la magnesia comercial, indicando así que las partículas metálicas de níquel están influenciadas por estos centros, lo que favorece la formación de 2-feniletanol y la minimización de reacciones secundarias. El resto de catalizadores preparados tienen una mayor cantidad de centros básicos disponibles, lo que favorece la formación de productos de condensación explicando su baja actividad.El uso de microondas durante el envejecimiento permite obtener hidrotalcitas más cristalinas en menos tiempo observándose algunas diferencias. La hidrotalcita envejecida en microondas con reactor cerrado a mayor temperatura (453 K) durante más tiempo (120 minutos) presenta un área BET y una basicidad mayor que el resto de hidrotalcitas. Estos resultados se han relacionado con una nueva mesoporosidad generada como consecuencia de la desaluminación producida por sobrecalentamientos puntuales de esta muestra por efecto de las microondas. Los catalizadores resultantes de las muestras envejecidas en el microondas tienen áreas metálicas más elevadas que el resto. Todos presentan una conversión total y una elevada selectividad hacia 2-feniletanol (95 %) después de una hora de reacción a temperatura ambiente. Después de su reutilización diez veces consecutivas, estos catalizadores siguen manteniendo elevadas conversiones y selectividades hacia 2-feniletanol.Durante la preparación de mordenitas intercambiadas con Ni2+, la realización de un tratamiento térmico intermedio con microondas entre dos procesos de intercambio en solución realizados también con microondas, aumenta el porcentaje de Ni2+ introducido hasta un 84 %. Este valor es superior a los que se encuentran referenciados en la bibliografía. También se ha observado que el uso del microondas permite obtener Ni-mordenitas con diferentes características ácidas.Los catalizadores correspondientes a las muestras preparadas por intercambio en fase líquida no presentan área metálica, explicando así, su nula actividad. Por el contrario, las muestras Ni-Mordenita preparadas en estado sólido muestran una conversión y selectividad hacia 2-feniletanol que aumenta al aumentar el contenido de Ni y su área metálica. Estos resultados permiten concluir que existe una competición entre los centros ácidos y los centros metálicos en estos sistemas catalíticos para esta reacción.Con esta tesis doctoral se ha presentado una alternativa viable para la producción de un compuesto de alto valor añadido, el 2-feniletanol, mediante un proceso mucho más limpio y sostenible. / 2-phenylethanol is the main component of rose oils. This compound is widely used in all chemical perfumes, and cosmetics due to its pleasant smell. The hydrogenation of styrene oxide to obtain selectively 2-phenylethanol by heterogeneous catalysis is an alternative to solve the environmental and economical problems which present the traditional industrial methods used for the obtention of this alcohol.The aim of this Doctoral Thesis is to obtain highly active and selective to 2-phenylethanol catalysts which should be resistant to deactivation in order to develop a sustainable process for industrial applications. The catalytic systems studied in this work are:- Ni and Ni-MgO catalysts- Catalysts based on Ni/Mg/Al Hydrotalcite-like compounds- Ni-Mordenite catalysts with different Ni contents and prepared by different methodsThe bulk Ni catalysts tested present high selectivity to 2-phenylethanol (60-95%) despite their different conversion values. There is some relation between the particles morphology, and the formation of condensation products, which block the active centres, deactivating the catalyst. Catalysts with commercial MgO (4NiMgO and NiMgO) present conversion and selectivity to 2-phenylethanol values that increase when the content of magnesia increases arriving to 100% for the catalyst NiMgO after 6 hours of reaction at room temperature. The TPD-CO2 profile for this catalyst showed the disappearance of the peak corresponding to the weaker basic sites of commercial magnesia. This means that there is some influence between the nickel particles and these basic sites that favour the formation of 2-phenylethanol and minimizes other side reactions.The rest of prepared Ni-MgO catalysts showed higher amounts of basic sites available which are responsible for the formation of condensation products explaining their lower activity.The use of microwaves during aging gives hydrotalcites with higher crystallinity in shorter times. Also, they have some different properties depend on the aging procedure. Thus, the hydrotalcite aged in an autoclave under microwaves at the highest temperature (453 K) and at longest time (120 min) presents higher BET area and higher basicity than the rest of prepared samples. These results could be related to the appearance of a new mesoporosity as a consequence of the dealumination of the hydrotalcite layers due to some local overheating during the microwaves treatment of this sample. The catalysts obtained from the hydrotalcites aged under microwaves had higher metallic areas than the rest of catalysts. All catalysts showed total conversion and 95% of selectivity to 2-phenylethanol after 1h of reaction at room temperature. After reusing them ten times, they maintain high conversion and high selectivity to 2-phenylethanol.Respect to the Ni-mordenite samples prepared by liquid exchange, we obtained 84 % of exchanged Ni2+ when we submitted the mordenite exchanged under microwaves at 333K for 15 minutes to a thermal treatment under microwaves followed by a second exchange process at the same conditions than the first exchange. This value of exchanged Ni2+ is the highest value found in the literature for this kind of samples. We also observed that the use of microwaves allows us to obtain Ni-mordenites with different acidic properties.The catalysts obtained from the samples exchanged by microwaves or by conventional method in the liquid phase did not show metallic areas, explaining their null activity. In contrast, the Ni-Mordenite catalysts prepared in solid state showed the formation of 2-phenylethanol which is detected in higher amounts for the catalysts with higher metallic area. These results allow us to conclude that there is a competition between the acidic and metallic sites in these catalytic systems for this reaction.In this Doctoral Thesis we present an alternative to obtain 2-phenylethanol, alcohol with a great industrial interest, by using a cleaner and more sustainable process.
26

Το λιγνιτικό κοίτασμα Αλμυρού (Ν. Μαγνησίας): γένεση, εξέλιξη και δυνατότητα αξιοποίησής του

Μπουζίνος, Αντώνιος 31 August 2010 (has links)
- / -
27

Αλλοίωση τοπίου από πιθανή εξόρυξη του λιγνιτικού κοιτάσματος Αλμυρού (Ν. Μαγνησίας)

Υφαντή, Ασημίνα 29 September 2010 (has links)
- / -
28

Processos de hidroxilação do óxido de magnésio (MgO): sínter e magnésia cáustica / Process of hydroxylation of magnesium oxide (MgO): sinter and caustic magnesia

Cezar Carvalho de Arruda 19 February 2014 (has links)
A principal limitação do uso de MgO em refratários é a facilidade com que reage com água formando hidróxido de magnésio (Mg(OH)2) que, devido à sua menor densidade, causa tensões destrutivas nesses materiais. Para outras aplicações, no entanto, a reação de hidroxilação do MgO é necessária, como em produção de agentes antichamas, em compósitos poliméricos e na correção de pH de solos. Observações empíricas na literatura demonstraram que diferentes fontes de MgO possuem reatividades e sensibilidades à hidroxilação distintas. Este estudo analisou o impacto de variáveis externas (por exemplo, a liberação de calor que ocorre durante a reação ou o volume das amostras) que ainda não foi completamente compreendido. O impacto auto-catalítico da temperatura reacional e da exotermia da reação foi avaliado. Por meio de medidas de temperatura in situ e de grau de hidroxilação termogravimétrico, também foram estudados os impactos do volume das amostras testadas e da concentração de sólidos nas suspensões, por meio de medidas de temperatura in situ e termogravimetria. Analisou-se também as principais diferenças estruturais entre duas principais fontes de MgO (sínter de MgO e magnésia cáustica): morfologia de partículas, densidade e área superficial específica. Em seguida, os mecanismos de hidroxilação em suspensões aquosas e seus efeitos foram avaliados por meio de testes de hidroxilação seguidos de termogravimetria, difração de raios-X, medidas de condutividade iônica, densidade, área superficial específica e microscopia eletrônica, e relacionado com as características físico-químicas e morfológicas das respectivas fontes de MgO. Pôde-se constatar que diferenças significativas entre a temperatura nominal do meio reacional e no interior da amostra podem afetar a cinética de hidroxilação do material. O volume e a concentração de sólidos variáveis também podem acentuar consideravelmente os efeitos da exotermia e gerar gradientes de hidroxilação. Também se verificou que a morfologia e a quantidade do Mg(OH)2 formado mudam significativamente dependendo do precursor e em função das condições de tempo-temperatura. / The use of MgO in refractories is restrict due to the easy reaction with water forming magnesium hydroxide (Mg(OH)2). Its lower density causes compressive stresses that can crack their structure. On the other hand, for applications such as the production of flame retardant agents for polymer composites and pH correcting of contaminated soil, this reaction is necessary. Empirical observations in the literature have shown that different sources of MgO have district levels of chemical reactiveness. The present study analyzed the main structural differences between the two main sources of MgO (magnesia sinter and caustic magnesia): particle morphology, density and specific surface area. The mechanisms of hydroxylation of these raw materials in aqueous suspensions and their effects were followed by hydroxylation tests, X-ray diffraction, ionic conductivity, density, specific surface area and scanning electron microscopy. They were associated with the physical characteristics morphological, chemical of these MgO sources. The impact of external variables (e.g., heat release during the reaction or the sample volume), that was not yet completely understood, was also evaluated through temperature measurements carried out in situ and hydroxylation degree accessed by thermogravimetry. The effects of samples volume and solid concentration in aqueous suspension were also investigated. The results showed that differences between the ambient temperature and reaction inside sample temperature can affect the kinetics of hydroxylation of the material. The samples volume and solids concentration can also enhance significantly the effects of heat release and generate gradients of hydroxylation. It was also found out that the morphology and the amount of Mg(OH)2 formed can change depending on the precursor and on the time-temperature conditions.
29

Catalisadores Ni/MgO-SiO2 aplicados na reação de reforma a vapor de glicerol / Ni/MgO-SiO2 catalysts applied on glycerol steam reforming reaction

Vivian Vazquez Thyssen 28 April 2016 (has links)
Catalisadores de Ni (10% em massa) suportado em matrizes mistas MgO-SiO2 foram aplicados na reação de reforma a vapor de glicerol. Os efeitos do teor de MgO como aditivo e do método de preparação foram avaliados frente às propriedades físico-químicas e texturais dos materiais; assim como à atividade, seletividade, estabilidade e formação de carbono na reforma a vapor do glicerol. Os catalisadores foram preparados com diferentes teores mássicos de MgO (10%, 30% e 50%) sobre SiO2 comercial, utilizando processo via seca (mistura física) e via úmida (impregnação sequencial com diferentes solventes: água, etanol e acetona). Foram utilizadas as técnicas de caracterização de espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, termogravimetria, difratometria de raios X in situ com O2, redução a temperatura programada com H2, difratometria de raios X in situ com H2, dessorção a temperatura programada com H2 e microscopia eletrônica de varredura. Foi observado que o Ni(II) interage de forma variada com os suportes com diferentes teores de MgO, e que a polaridade do solvente de impregnação utilizado no processo de preparação influencia as propriedades dos catalisadores. A fim de verificar a atividade, seletividade e deposição de carbono; os catalisadores foram testados na reação de reforma a vapor de glicerol a 600oC, por um período de 5h e razão molar água:glicerol de 12:1. Após as reações, os catalisadores foram novamente submetidos às análises de termogravimetria, difratometria de raios X e microscopia eletrônica de varredura, visando a caracterização dos depósitos de carbono obtidos durante o processo catalítico. Os catalisadores de matrizes mistas se mostraram ativos e apresentaram seletividades similares para os produtos gasosos CH4, CO e CO2, além de um alto rendimento em H2. Observou-se que a adição de MgO no suporte, aumentou a dispersão do Ni(II) no material, que por sua vez, influenciou na quantidade de carbono depositado ao longo da reação. A polaridade do solvente de impregnação também teve influência na dispersão metálica, sendo que, quanto menor a polaridade do solvente, maior foi a dispersão obtida no catalisador, e menor a deposição de carbono na reação. O material que apresentou o melhor desempenho catalítico frente ao rendimento de H2 e à deposição de carbono, foi o catalisador preparado com 30% de MgO com etanol como solvente de impregnação. / Ni catalysts (10wt%) supported on MgO-SiO2 were assessed in glycerol steam reforming reaction. The effects of MgO as additive and preparation method were evaluated on physico-chemical and textural materials properties; as their activity, selectivity, stability and carbon formation in glycerol steam reforming. The catalysts were prepared with different amounts of MgO (10wt%, 30wt% and 50wt%) on commercial SiO2 by dry process (physical mixture) and wet process (sequential impregnation with water, ethanol and acetone as solvents). Samples were characterized by energy dispersive X-ray spectroscopy, nitrogen physisorption, X-ray diffraction, thermogravimetry, in situ X-ray diffraction with O2, temperature programmed reduction with H2, in situ X-ray diffraction with H2, temperature programmed desorption with H2 and scanning electron microscopy. It was observed that the Ni(II) interacts differently with supports with different MgO content, and the polarity of impregnation solvent used in preparation process influences on catalysts properties. In order to evaluated the activity, selectivity and carbon deposition, the catalysts were tested in glycerol steam reforming reaction at 600oC for 5h and water:glycerol molar ratio of 12:1. After reaction, carbon deposits obtained during the catalytic process were characterized by thermogravimetry, X-ray diffraction and scanning electron microscopy. Mixed matrices catalysts were active in glycerol steam reforming and showed similar selectivity for the gaseous products (H2, CH4, CO and CO2), with a high H2 yield. It was observed that the addition of MgO increased Ni(II) dispersion on material, which influenced on the quantity of carbon deposited during reaction. Polarity of impregnation solvent had also influence on metallic dispersion, and smaller the solvent polarity, higher the dispersion obtained in the catalyst, and lower the carbon deposition on reaction. The material that showed the best catalytic performance in H2 yield and carbon deposition, was the catalyst prepared with 30wt% of MgO with ethanol as impregnation solvent.
30

Διερεύνηση των συνθηκών σχηματισμού των εμφανίσεων μαγνησίτη Βάβδου και Γερακινής (Κεντρική Χαλκιδική) και μελέτη αξιοποίησης του σε περιβαλλοντικές εφαρμογές

Σκληρός, Βασίλειος 30 April 2014 (has links)
Στην συγκεκριμένη διατριβή διερευνήθηκαν οι συνθήκες γένεσης του μικροκρυσταλλικού μαγνησίτη στις περιοχές Βάβδου και Γερακινής-Ορμύλιας της Χαλκιδικής. Η πετρογραφική μελέτη του μαγνησίτη και των ξενιστών του αποκάλυψαν δύο δομές δημιουργίας του μαγνησίτη: in situ εξαλλοίωση μέσα σε μανδυακά πετρώματα ξενιστές και ex situ αποθέσεις μέσα στους μανδυακούς σχηματισμούς. Επιπλέον, πιθανά υπάρχει στενή σχέση μεταξύ της κοιτασματογένεσης του μαγνησίτη και των περιβαλλόντων πυριτιωμένων πετρωμάτων (λιστβανίτες). Επίσης, οι γεωχημικές παρατηρήσεις συγχρόνως με τις ορυκτοχημικές αναλύσεις, δίνουν νέα στοιχεία όσον αφορά στην γένεση του κοιτάσματος. Παράλληλα, έγινε εργαστηριακή παραγωγή καυστικής μαγνησίας και παράχθησαν, με προσθήκη αυτής συγχρόνως με χρήση ερυθράς ιλύς και τέφρας πυθμένα, νέα κεραμικά υψηλού πορώδους. Τα αποτελέσματα υπήρξαν ιδιαίτερα ικανοποιητικά, καθώς παρατηρήθηκε ότι με προσθήκη μαγνησίας σε μικρό ποσοστό βελτιώνονται οι φυσικομηχανικές ιδιότητές τους. Κεραμικά υψηλού πορώδους είναι κατάλληλα για χρήση σε φίλτρα και σε απορροφητικά υλικά. Τέλος, προτείνεται νέος τρόπος αξιοποίησης στείρων υλικών μαγνησίτη από τις εξορυκτικές διεργασίες, καθώς αποδεικνύεται ότι ο μαγνησίτης έχει πολύ θετικά αποτελέσματα με προσθήκη του σε οξινισμένα ύδατα, δίνοντας νέες προοπτικές αξιοποίησης του σε περιβαλλοντικές εφαρμογές. Το πειραματικό σκέλος της δοκιμής σε οξινισμένα νερά, πραγματοποιήθηκε σε σύγκριση με πετρώματα που χρησιμοποιούνται για την αντιμετώπιση όξινων απορροών μεταλλείων. / In the present thesis, the microcrystalline magnesite from Central Chalkidiki (Vavdos and Gerakini areas) are investigated in order to clarify the conditions of its genesis. Petrographic study of the magnesite and its host rocks revealed two types of formation: a) in situ alteration in the mantle host rocks, due to metasomatic process, and b) ex situ deposit within mantle formations, related to hydrothermal fluids. Furthermore, petrographic observations suggest a close association between the genesis of the microcrystalline magnesite with the surrounding high silica-carbonate rocks, also termed as listwaenites. Moreover, scanning electron microscopy (S.E.M.) observations along with geochemical analysis provide new evidence for the formation of the magnesite. Caustic magnesia produced in the laboratory was mixed with red mud and bottom ash from industrial wastes, in order to make new, high porosity ceramics. It was observed that the addition of small amounts of caustic magnesia improved the physicomechanical properties of the briquettes. High porosity ceramics are suitable for their use in filters and absorbent materials for environmental applications. Finally, a new way for utilizing waste materials from magnesite mining processes in the disposal of acidified waters is proposed. Addition of magnesite improved the alkalinity of high acidic waters, offering new perspectives for environmental applications. The experimental results from magnesite were compared with similar results from other rocks used to treat acid mine drainage.

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