Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 ValdeliceRS_TESE.pdf: 2586359 bytes, checksum: e3d9d5d8e2c97ad0990f43fd755545a2 (MD5) Previous issue date: 2010-11-26 / One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 ?C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation. / Uma das principais aplica??es do metano ? a produ??o de g?s de s?ntese, mistura de hidrog?nio e mon?xido de carbono. Os processos utilizados na produ??o de g?s de s?ntese a partir do metano s?o: reforma a vapor, reforma com CO2, oxida??o parcial e reforma autot?rmica. Neste trabalho, o comportamento de catalisadores de n?quel suportados em ?xidos mistos de c?rio e mangan?s na rea??o de oxida??o parcial do metano foi avaliado e comparado com o catalisador de n?quel suportados no ?xido misto de c?rio e zirc?nio. Os ?xidos mistos de c?rio e zirc?nio ou c?rio e mangan?s foram sintetizadas usando dois diferentes m?todos de prepara??o; o de precursores polim?ricos baseado no processo Pechini e por rea??o de combust?o usando um micro-ondas, seguido da impregna??o de n?quel com teor de 15 %. As amostras foram calcinadas a 300, 800 e 900 ?C e caracterizados por ?rea espec?fica (ASE), fluoresc?ncia de raios X (FRX), difra??o de raios X (DRX), microscopia eletr?nica de varredura (MEV), redu??o ? temperatura programada (RTP) e a rea??o de oxida??o parcial do metano. As ?reas espec?ficas das amostras diminuem com o aumento da temperatura de calcina??o e ap?s a impregna??o com n?quel. A solu??o s?lida c?rio-metal foi formada e nos composto com as maiores quantidades de ?xidos de mangan?s verificou-se a presen?a de outras esp?cies de mangan?s fora da estrutura da solu??o s?lida. Quanto ? microscopia eletr?nica de varredura os suportes a base de c?rio e zirc?nio preparados via Pechini exibem part?culas aglomeradas, sem geometria uniforme e sem a visualiza??o de poros na superf?cie, enquanto os compostos contendo mangan?s apresentaram alguns vazios na sua estrutura. Atrav?s da s?ntese por rea??o de combust?o a morfologia adquirida independente da composi??o proposta apresentou uma maior porosidade em rela??o ? s?ntese Pechini. Mesmo sendo os catalisadores preparados por diferentes m?todos de s?ntese, a inser??o de n?quel deixou seus perfis de redu??o (RTP) muito semelhantes. Para os catalisadores de n?quel suportados no ?xido misto de c?rio e zirc?nio, h? em primeiro lugar redu??o de esp?cies NiO que apresentam certa intera??o com o suporte, seguido da redu??o de Ce4+ em Ce3+ superficiais, com posterior redu??o do bulk. Para os catalisadores contendo mangan?s h? a redu??o das esp?cies de ?xido de n?quel, seguido de duas etapas de redu??o para as esp?cies Mn2O3 em Mn3O4 e Mn3O4 em MnO, com posterior redu??o do bulk. Quanto ?s rea??es de oxida??o parcial, o catalisador de n?quel suportados no ?xido misto de c?rio e zirc?nio preparado via m?todo Pechini, apresentou uma convers?o de CH4 de cerca de 80 %, sendo 81 % a convers?o quando preparado via combust?o. Esse comportamento manteve-se durante 10 horas de rea??o. Observou-se tamb?m que o teor de mangan?s influencia diretamente na atividade catal?tica dos materiais, quanto maior o teor de ?xido de mangan?s mais r?pido o catalisador apresentava desativa??o e desestabiliza??o. Para ambos os m?todos de s?ntese o catalisador de n?quel suportados no ?xido misto de c?rio e zirc?nio manteve a raz?o H2/CO bem pr?xima de 2 durante as 10 horas em que ocorre a rea??o de oxida??o parcial. As amostras contendo mangan?s apresentaram menores raz?es de H2/CO e menor desempenho na oxida??o parcial.

Made available in DSpace on 2014-12-17T14:06:55Z (GMT). No. of bitstreams: 1 AnaPP.pdf: 5176837 bytes, checksum: 9d8890c4a2dd055dfe7d581f34a7f4e8 (MD5) Previous issue date: 2011-01-07 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350?C. The samples were calcined at different temperatures (550, 750 and 950?C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750?C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750?C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750?C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process / Catalisadores a base de n?quel suportados em alumina, t?m sido amplamente empregados nas diversas rea??es para obten??o de g?s de s?ntese ou hidrog?nio. Normalmente, altos n?veis de convers?o s?o obtidos por estes catalisadores, entretanto, a desativa??o por forma??o de coque e sinteriza??o das part?culas met?licas s?o ainda problemas a serem solucionados. Diversas abordagens t?m sido empregadas com a finalidade de minimizar estes problemas, dentre as quais tem se destacado nos ?ltimos anos a utiliza??o de aditivos como ?xidos de metais alcalinos e metais terras raras. Paralelamente, o uso de metodologias de s?nteses mais r?pidas, f?ceis, aplic?veis em escala industrial e que permitam o controle das caracter?sticas microestruturais destes catalisadores, pode em conjunto, prover a solu??o para este problema. Neste trabalho, ?xidos com estrutura tipo espin?lio AB2O4, onde A representa c?tions divalentes e B representa c?tions trivalentes, s?o uma classe importante de materiais cer?micos mundialmente investigados em diferentes campos de aplica??es. As cobaltitas de n?quel (NiCo2O4) s?o ?xidos do tipo espin?lio que tem atra?do consider?vel interesse devido a sua aplicabilidade em diversas ?reas, como em sensores qu?micos, monitores de tela plana, limitadores ?pticos, materiais para eletrodos, pigmentos, eletrocat?lise, cer?micas eletr?nicas, entre outras. O precursor catal?tico NiCo2O4 foi preparado por uma nova rota de s?ntese qu?mica usando a gelatina como agente direcionador. A resina polim?rica obtida foi tratada termicamente a 350?C. As amostras foram calcinadas em diferentes temperaturas 550, 750 e 950?C e caracterizadas por difra??o de raios X, medidas de ?rea superficial espec?fica, redu??o a temperatura programada e microscopia eletr?nica de varredura. Os materiais tratados termicamente a 550 e 750?C foram testados na oxida??o parcial do metano. O conjunto de t?cnicas revelaram, nos s?lidos preparados, a presen?a da fase de estrutura espin?lio do tipo NiCo2O4 juntamente com a solu??o s?lida NixCo1-xO. Esta solu??o s?lida foi identificada atrav?s do refinamento Rietveld em todas as temperaturas de tratamento t?rmico. Os precursores catal?ticos calcinados a 550 e 750?C apresentaram n?veis de convers?o em torno de 25 e 75%, respectivamente. A raz?o H2/CO foi em torno de 2 para o precursor tratado a 750?C, raz?o proposta pela rea??o de oxida??o parcial do metano, pode-se concluir que este material pode ser indicado para produzir g?s de s?ntese adequado para ser utilizado na s?ntese de Fischer-Tropsch

Made available in DSpace on 2014-12-17T14:07:05Z (GMT). No. of bitstreams: 1 DanieleMHM_TESE.pdf: 1582500 bytes, checksum: bba4e28b78ed6df0658bf0c3609ea506 (MD5) Previous issue date: 2011-02-21 / Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 ?C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 ?C, whereas the LaFeO3 sample depicted a peak above 1000?C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion / Catalisadores a base de n?quel t?m sido empregados em diversos tipos de rea??es de reforma, inclusive na oxida??o parcial do metano para obten??o de H2 ou g?s de s?ntese (H2 + CO). Normalmente, altos n?veis de convers?o s?o obtidos por estes catalisadores, entretanto, a desativa??o por deposi??o de carbono ainda ? um problema a ser solucionado. Diversas abordagens t?m sido empregadas no intuito de minimizar este problema, dentre as quais tem se destacado nos ?ltimos anos a utiliza??o de ?xidos com estrutura perovisquita e/ou estruturas relacionadas. Paralelamente, o uso de metodologias de s?nteses mais r?pidas, f?ceis, aplic?veis em escala industrial e que permitam o controle das caracter?sticas microestruturais destes catalisadores, pode em conjunto, prover a solu??o para este problema. A n?vel de compara??o perovisquitas do tipo LaNixFe1-xO3 (x=0, x=0,3 e x=0,7) foram preparados por dois m?todos: precursores polim?ricos (pechini) e autocombust?o assistida por microondas. Todas as amostras foram calcinadas a 900 ?C/4h para obten??o das fases desejadas. Os p?s-obtidos foram caracterizados por an?lise termogravim?trica, espectroscopia na regi?o do infravermelho, difra??o de raios-X, medidas de ?rea superficial especifica, redu??o ? temperatura programada. As amostras calcinadas foram testadas na rea??o de oxida??o parcial do metano, sendo avaliados os respectivos n?veis de convers?o, seletividade e a resist?ncia ? deposi??o de carbono. Ap?s calcina??o a fase desejada foi obtida para todas as amostras independente do m?todo de s?ntese, sugerindo claramente a forma??o de p?s cristalinos. De acordo com o resultados obtidos pelo refinamento Rietveld, observou-se a forma??o de 70,0% de LaNi0,3Fe0,7O3 e 30,0 % de La2O3 para as amostras LN3F7-900-P e LN3F7-900-M e 41,6% de LaNi0.7Fe0.3O3; 30,7% de La2NiO4 e 27,7 % de La2O3 para as amostras LN7F3-900-P e LN7F3-900-M. Os perfis de redu??o ? temperatura programada da amostra LaNiO3 apresentou pico de redu??o em torno de 510 ?C, j? a amostra LaFeO 3 apresentou pico de redu??o acima de 1000?C. Dentre os catalisadores estudados o que apresentou maior n?vel de convers?o de metano foi LaNiO3 obtido pelo m?todo pechini, de uma maneira geral os catalisadores obtidos pelo m?todo pechini apresentaram melhores resultados de convers?o que os catalisadores obtidos pela autocombust?o assistida por microondas

Made available in DSpace on 2014-12-17T15:01:22Z (GMT). No. of bitstreams: 1 KalyanneKPG_ate o resumo.pdf: 69797 bytes, checksum: 49f1d53a5fe82cc0c03f9f579c34a190 (MD5) Previous issue date: 2006-09-12 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The nanostructures materials are characterized to have particle size smaller than 100 nm and could reach 1 nm. Due to the extremely reduced dimensions of the grains, the properties of these materials are significantly modified relatively when compared with the conventional materials. In the present work was accomplished a study and characterization of the molybdenum carbide, seeking obtain it with particles size in the nanometers order and evaluate its potential as catalyst in the reaction of partial methane oxidation. The method used for obtaining the molybdenum carbide was starting from the precursor ammonium heptamolybdate of that was developed in split into two oven, in reactor of fixed bed, with at a heating rate of 5?C/min, in a flow of methane and hydrogen whose flow was of 15L/h with 5% of methane for all of the samples. The studied temperatures were 350, 500, 600, 650, 660, 675 and 700?C and were conducted for 0, 60, 120 and 180 minutes, and the percent amount and the crystallite size of the intermediate phases were determined by the Rietveld refinement method. The carbide obtained at 660?C for 3 hours of reaction showed the best results, 24 nm. Certain the best synthesis condition, a passivating study was accomplished, in these conditions, to verify the stability of the carbide when exposed to the air. The molybdenum carbide was characterized by SEM, TEM, elemental analysis, ICP-AES, TG in atmosphere of hydrogen and TPR. Through the elemental analysis and ICP-AES the presence carbon load was verified. TG in atmosphere of hydrogen proved that is necessary the passivating of the molybdenum carbide, because occur oxidation in room temperature. The catalytic test was accomplished in the plant of Fischer-Tropsch of CTGAS, that is composed of a reactor of fixed bed. Already the catalytic test showed that the carbide presents activity for partial oxidation, but the operational conditions should be adjusted to improve the conversion / Os materiais nanoestruturados s?o caracterizados por terem um tamanho de cristalito inferior a 100 nm podendo atingir 1 nm. Devido ?s dimens?es extremamente reduzidas dos cristalitos, as propriedades destes materiais s?o significativamente modificadas relativamente ?s dos materiais convencionais. No presente trabalho foi realizado um estudo de s?ntese e caracteriza??o do carbeto de molibd?nio, visando obt?-lo com tamanho de part?culas na ordem de nan?metros e avaliar seu potencial como catalisador na rea??o de oxida??o parcial do metano. O m?todo utilizado para obten??o do carbeto de molibd?nio foi a partir do precursor heptamolibdato de am?nio que foi desenvolvida em forno bipartido, em reator de leito fixo, com uma taxa de aquecimento de 5?C/min, em um fluxo de metano e hidrog?nio cuja vaz?o foi de 15L/h com 5% de metano para todos os ensaios. As temperaturas estudadas foram 350, 500, 600, 650, 660, 675 e 700?C e nos tempos de isoterma de 0, 60, 120 e 180 minutos, sendo que a determina??o das fases presentes, estrutura cristalina e tamanho de cristalitos foram obtidos por refinamento de estrutura pelo m?todo de Rietveld. O carbeto obtido a 660?C e 3 horas de rea??o foi o que apresentou menor tamanho de cristalito 24 nm. Determinada a melhor condi??o de s?ntese foi realizado um estudo de passivac?o, nestas condi??es, para verificar a estabilidade do carbeto ao ser exposto ao ar. O carbeto de molibd?nio foi caracterizado por MEV, MET, an?lise elementar, ICP-AES, TG em atmosfera de hidrog?nio e RTP. Atrav?s da an?lise elementar e ICP-AES foi verificada a presen?a de carbono livre. A TG em atmosfera de hidrog?nio comprovou que ? necess?ria a passivac?o do carbeto de molibd?nio, pois ele ? oxidado em temperatura ambiente. O teste catal?tico foi realizado na planta semipiloto de Fischer-Tropsch do CTGAS, que ? composta de um reator de leito fixo. O teste catal?tico mostrou que o carbeto apresenta atividade para oxida??o parcial, mas as condi??es operacionais devem ser ajustadas para melhorar a convers?o