Carbon-carbon composite brakes are one third the weight of typical steel brakes, and they attain strength and frictional properties at temperatures up to 1600°C. C/C composite brakes can endure high temperatures, but in the presence of oxygen they will begin to oxidize at 400°C. Anti-oxidant systems must be applied to the non-rubbing surfaces of the C/C composite stators and rotors to prevent oxidation. Currently, commercial phosphorus based coating materials are made of crystalline metal phosphates that are derived from heat treated phosphoric acid-based liquid precursors painted on the non-rubbing surface of C/C composites. These crystalline metal phosphate coatings are very porous and tend to move to the friction surface when exposed to increased levels of relative humidity. This anti-oxidant migration towards the rubbing surface causes a drop in frictional properties. Migration reduction and oxidation inhibition was improved upon with advanced anti-oxidant systems. The advanced antioxidants analyzed protected the C/C composite from thermal and catalytic oxidation six to ten times better at 650°C than commercial materials. At 871°C, the antioxidants protected the C/C composite from thermal oxidation ten times better than commercial materials. Migration of the antioxidant to the rubbing surfaces was eliminated through the use of advanced antioxidant compositions. The predicted life of the antioxidants was modeled using Avrami's equation. Characterization of the antioxidants was further analyzed through the use of SEM, EDS, and XRD systems.

As zeólitas são amplamente utilizadas pela indústria em diferentes processos. Nos processos relacionados à conversão térmica do carvão, as zeólitas encontram aplicação, por exemplo, como suporte de catalisadores para a Síntese de Fischer-Tropsch, ou mesmo como adsorventes de efluentes líquidos ou de gases poluentes. No entanto, a microporosidade da zeólita limita a difusão dos produtos e dos reagentes ocasionando um transporte de massa lento e um longo tempo de residência, aumentando a possibilidade de reações secundárias, formação de coque e desativação do catalisador. Uma das maneiras de superar essas limitações é a introdução de um sistema secundário de poros, através da reestruturação da rede cristalina com modeladores de estruturas ou ataques químicos básicos e ácidos nas zeólitas de modo a formar materiais hierárquicos ou mesoporosos. Neste trabalho, foram investigadas três rotas para promover a mesoporosidade em zeólitas do tipo Y. Primeiramente foi realizada a síntese da zeólita hierárquica através da modificação com líquidos iônicos. O segundo método empregado foi o processo de dessilicação, utilizando hidróxido de sódio como base e, por último, a desaluminação com ácido oxálico. As zeólitas mesoporosas foram caracterizadas através de análises de área específica (BET), distribuição de tamanho de poros (BJH), difração de raios X (DRX) e redução à temperatura programada (TPR-H2). Dentre os métodos adotados, os resultados para DRX e BET mostraram que o tratamento de dessilicação destruiu a cristalinidade da zeólita, acarretando no abandono dessa rota de investigação. A síntese com líquido iônico se mostrou eficiente para a formação de mesoporos e, conforme a distribuição de tamanho de poros, seu sistema apresentou-se ordenado de maneira hierarquizada. A desaluminação não danificou a estrutura da zeólita, porém foi obtido um aumento pouco expressivo em seu número de mesoporos. A reação de esterificação foi utilizada, como modelo, para avaliar o efeito dos mesoporos sobre a atividade catalítica da reação. A reação de esterificação ocorreu a 70°C por 1 h, utilizando ácido acético e álcoois com diferentes tamanhos de moléculas. Em comparação à zeólita de partida (CBV720 - Zeolyst), a criação da mesoporosidade na zeólita através dos líquidos iônicos resultou em um aumentou na conversão de ácido acético para os álcoois etílico (em 17,65%), isopropílico (em 8,42%) e isobutílico (em 2%). Para a zeólita mesoporosa sintetizada por desaluminação, houve um acréscimo de 10,93% e 2,11% na conversão para os álcoois etílico e isopropílico, respectivamente. Os resultados mostraram que a presença de mesoporosidade influenciou positivamente o desempenho das zeólitas Y na reação modelo de esterificação, mostrando-se um excelente mecanismo a ser aplicado para facilitar o transporte de massa nos poros da zeólita, especialmente para a síntese feita com o emprego de líquidos iônicos. / Zeolites are widely used by industry in different processes. In processes related to the thermal conversion of coal, the zeolites find application, for example, as catalyst support for the Fischer-Tropsch Synthesis, or even as adsorbents of liquid effluents or pollutant gases. However, the small pore diameter of the zeolite limits the diffusion of the products and the reactants causing slow mass transport and a long residence time that increase the possibility of secondary reactions, coke formation and catalyst deactivation. One of the ways to overcome these limitations is the introduction of a secondary pore system by restructuring the crystal lattice with structural modellers or basic chemical and acidic attacks on zeolites to form hierarchical or mesoporous materials. In this work, three routes were investigated to promote mesoporosity in Y type zeolites. First, the hierarchical zeolite was synthesized through the modification with ionic liquids. The second method used was the desilication process, using sodium hydroxide as the base and, finally, the desalumination method with oxalic acid. The mesoporous zeolites were characterized by specific surface area analysis (BET), pore size distribution (BJH), X-ray diffraction (XRD) and temperature programmed reduction (TPR-H2). Among the methods adopted, the results for XRD and BET showed that the desilication treatment destroyed the crystallinity of the zeolite, leading to the abandonment of this research route. The synthesis with ionic liquid was efficient for the formation of mesopores and, according to the pore size distribution, its system was hierarchically ordered. The desalumination did not damage the zeolite structure, but a small increase in its number of mesopores was noted. The esterification reaction was used to evaluate the effect of mesopores on the catalytic activityof the reaction. The esterification reaction occurred at 70°C for 1 h using acetic acid and alcohols with different sizes of molecules. Compared to the starting zeolite (CBV720 - Zeolyst), the creation of mesoporosity in the zeolite through the ionic liquids resulted in an increase in the conversion of acetic acid for the reaction conducted with ethyl (17.65%), isopropyl (8.42%) and isobutyl alcohols (2%). For the mesoporous zeolite synthesized by desalumination, there was an increase of 10.93% and 2.11% in the conversion to the ethyl and isopropyl alcohols, respectively. The results showed that the presence of mesoporosity positively influenced the performance of the zeolites Y in the esterification model reaction, showing an excellent mechanism to be applied to facilitate the mass transport in the zeolite pores, especially for the synthesis made with the use of ionic liquids.

As zeólitas são amplamente utilizadas pela indústria em diferentes processos. Nos processos relacionados à conversão térmica do carvão, as zeólitas encontram aplicação, por exemplo, como suporte de catalisadores para a Síntese de Fischer-Tropsch, ou mesmo como adsorventes de efluentes líquidos ou de gases poluentes. No entanto, a microporosidade da zeólita limita a difusão dos produtos e dos reagentes ocasionando um transporte de massa lento e um longo tempo de residência, aumentando a possibilidade de reações secundárias, formação de coque e desativação do catalisador. Uma das maneiras de superar essas limitações é a introdução de um sistema secundário de poros, através da reestruturação da rede cristalina com modeladores de estruturas ou ataques químicos básicos e ácidos nas zeólitas de modo a formar materiais hierárquicos ou mesoporosos. Neste trabalho, foram investigadas três rotas para promover a mesoporosidade em zeólitas do tipo Y. Primeiramente foi realizada a síntese da zeólita hierárquica através da modificação com líquidos iônicos. O segundo método empregado foi o processo de dessilicação, utilizando hidróxido de sódio como base e, por último, a desaluminação com ácido oxálico. As zeólitas mesoporosas foram caracterizadas através de análises de área específica (BET), distribuição de tamanho de poros (BJH), difração de raios X (DRX) e redução à temperatura programada (TPR-H2). Dentre os métodos adotados, os resultados para DRX e BET mostraram que o tratamento de dessilicação destruiu a cristalinidade da zeólita, acarretando no abandono dessa rota de investigação. A síntese com líquido iônico se mostrou eficiente para a formação de mesoporos e, conforme a distribuição de tamanho de poros, seu sistema apresentou-se ordenado de maneira hierarquizada. A desaluminação não danificou a estrutura da zeólita, porém foi obtido um aumento pouco expressivo em seu número de mesoporos. A reação de esterificação foi utilizada, como modelo, para avaliar o efeito dos mesoporos sobre a atividade catalítica da reação. A reação de esterificação ocorreu a 70°C por 1 h, utilizando ácido acético e álcoois com diferentes tamanhos de moléculas. Em comparação à zeólita de partida (CBV720 - Zeolyst), a criação da mesoporosidade na zeólita através dos líquidos iônicos resultou em um aumentou na conversão de ácido acético para os álcoois etílico (em 17,65%), isopropílico (em 8,42%) e isobutílico (em 2%). Para a zeólita mesoporosa sintetizada por desaluminação, houve um acréscimo de 10,93% e 2,11% na conversão para os álcoois etílico e isopropílico, respectivamente. Os resultados mostraram que a presença de mesoporosidade influenciou positivamente o desempenho das zeólitas Y na reação modelo de esterificação, mostrando-se um excelente mecanismo a ser aplicado para facilitar o transporte de massa nos poros da zeólita, especialmente para a síntese feita com o emprego de líquidos iônicos. / Zeolites are widely used by industry in different processes. In processes related to the thermal conversion of coal, the zeolites find application, for example, as catalyst support for the Fischer-Tropsch Synthesis, or even as adsorbents of liquid effluents or pollutant gases. However, the small pore diameter of the zeolite limits the diffusion of the products and the reactants causing slow mass transport and a long residence time that increase the possibility of secondary reactions, coke formation and catalyst deactivation. One of the ways to overcome these limitations is the introduction of a secondary pore system by restructuring the crystal lattice with structural modellers or basic chemical and acidic attacks on zeolites to form hierarchical or mesoporous materials. In this work, three routes were investigated to promote mesoporosity in Y type zeolites. First, the hierarchical zeolite was synthesized through the modification with ionic liquids. The second method used was the desilication process, using sodium hydroxide as the base and, finally, the desalumination method with oxalic acid. The mesoporous zeolites were characterized by specific surface area analysis (BET), pore size distribution (BJH), X-ray diffraction (XRD) and temperature programmed reduction (TPR-H2). Among the methods adopted, the results for XRD and BET showed that the desilication treatment destroyed the crystallinity of the zeolite, leading to the abandonment of this research route. The synthesis with ionic liquid was efficient for the formation of mesopores and, according to the pore size distribution, its system was hierarchically ordered. The desalumination did not damage the zeolite structure, but a small increase in its number of mesopores was noted. The esterification reaction was used to evaluate the effect of mesopores on the catalytic activityof the reaction. The esterification reaction occurred at 70°C for 1 h using acetic acid and alcohols with different sizes of molecules. Compared to the starting zeolite (CBV720 - Zeolyst), the creation of mesoporosity in the zeolite through the ionic liquids resulted in an increase in the conversion of acetic acid for the reaction conducted with ethyl (17.65%), isopropyl (8.42%) and isobutyl alcohols (2%). For the mesoporous zeolite synthesized by desalumination, there was an increase of 10.93% and 2.11% in the conversion to the ethyl and isopropyl alcohols, respectively. The results showed that the presence of mesoporosity positively influenced the performance of the zeolites Y in the esterification model reaction, showing an excellent mechanism to be applied to facilitate the mass transport in the zeolite pores, especially for the synthesis made with the use of ionic liquids.

We present here the hypothesis of a possible relationship between metal atom clusters and the formation of organic molecules in the interstellar medium and on small bodies as a possible pathway to the origin of such molecules. Two distinct stages are díscussed: a) the possible formation and presence of atom clusters in space and on the primitive Earth, and b) the synthesis of interstellar and terrestrial prebiotic organic molecules, a process in which metalclusters could be the active catalysts. The confirmatíon of these suggestions might be very important in arder to explain the presence of extra-terrestrial organic molecules in the interstellar medium, small bodies and planetary systems, and therefore would have great relevance in cosmochemistry and in the current theories about the origins of life.

Orientador: Antonio Carlos Luz Lisboa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T15:53:08Z (GMT). No. of bitstreams: 1 Silva_GermanGonzalez_M.pdf: 1967268 bytes, checksum: fb1da8c45ce0a2b393f58ef9ab9d72d0 (MD5) Previous issue date: 2008 / Resumo: Os reatores de leito fluidizado são uma das mais importantes tecnologias atuais para processos heterogêneos gás-sólido, tanto catalíticos como não catalíticos. As aplicações industriais mais importantes incluem o craqueamento catalítico na indústria petroquímica, a combustão e/ou gaseificação de carvão, biomassa e resíduos sólidos. Estes são importantes processos para a geração de energia, produção de combustíveis e gás de síntese. Um dos tipos de reatores de leito fluidizado mais relevante é o reator de fluxo ascendente conhecido como riser. Este reator consiste de uma coluna tubular na qual o sólido e o gás escoam co-correntes de forma ascendente. Em comparação com outras tecnologias, o reator riser tem uma importante desvantagem: uma distribuição de tempos de residência variada no reator que reduz a conversão e a seletividade. Recentemente cresceu o interesse por outro tipo de reator gás-sólido circulante que possui melhor desempenho que o reator riser. Neste tipo de reator, conhecido como downer, por oposição ao riser, o escoamento co-corrente gás-sólido ocorre de forma descendente, o que lhe outorga características fluidodinâmicas que se assemelham mais ao escoamento tipo pistão e permitem um melhor controle da conversão, da seletividade e da desativação. O objetivo deste trabalho é estudar a simulação de reatores gás-sólido tipo downer, incorporando modelos fluidodinâmicos com modelos de engenharia das reações químicas e catalíticas. Desenvolve-se, de forma geral, a modelagem dos diferentes fenômenos fluidodinâmicos, físico-químicos e catalíticos que ocorrem no reator e são propostos algoritmos de solução para diferentes situações. Posteriormente, aplica-se o modelo proposto do reator downer ao estudo de um caso industrial: o craqueamento catalítico. Os resultados mostram um enfoque geral aplicável para a modelagem e simulação de sistemas de reações gás-sólido em fluxo descendente. As simulações do processo industrial de craqueamento catalítico revelam que o reator tipo downer apresenta características de desempenho que o fazem superior ao reator tipo riser convencional. / Abstract: The fluidized bed reactor is one of the most important technologies for gas-solid heterogeneous operations, considering catalytic or non catalytic processes. The most important industrial applications include catalytic cracking, coal combustion and biomass combustion. The most relevant fluidized bed reactor is the ascendant flow reactor, which is known as riser. The riser reactor consist of a tubular column in which the solid and the gas flow cocurrently upward. The riser reactor has as main disadvantage a wide residence time distribution, which reduce the conversion and the selectivity. Recently, it has grown the interest in a new type of gas-solid circulating reactor with a better performance than the riser which is known as downer. In this reactor the gas and the solid flow cocurrently downward, creating hydrodynamic features comparable to a plug flow reactor and allowing a better control over the conversion, the selectivity and the deactivation. This work regarded it had been studied the simulation of the gas-solid downer reactor, including hydrodynamic models and models from the chemical reaction engineering. It was developed in a general way the modelling of the hydrodynamic, physical chemical and catalytic phenomena occurring in the reactor. Algorithms were proposed to solve of different simulation cases. The proposed model of the downer reactor was used in the studying of one industrial case: the catalytic cracking. The results show a general approach which is applicable for modelling and simulation of gas-solid reactive system with descendent flow. The simulations of the catalytic cracking show that the downer reactor has features that make it perform better than the conventional riser reactor. / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

O trabalho apresentado nesta tese é direcionado à preparação e caracterização de compostos aqua e diaquacomplexos polipiridínicos de rutênio(II). A partir da síntese do ligante tripiridina substituida (totpy) e dois ligantes bipiridínicos substituídos (Meo-bipy e NO2-bipy), obtiveram dois grupos de complexos, diferenciando-se em relação ao ligante bidentado fosfina: nonoaqua complexo [Ru(L)(totpy)(OH2)](PF6)2 e Ru(L)2(totpy)(OH2)](PF6)2 [totpy = 4\'-(4-toluil)-2,2\':6\',2\"-tripiridina, L = ligantes fosfínicos] (1) e diaqua complexo [Ru(L)(x-bipy)(OH2)2](PF6)2 (x-bipy = 4,4-dimetoxi-2,2-bipiridina e 4,4-dinitro-2,2-bipiridina, L = ligante bidentado) (2). As caracterizações dos compostos foram realizadas por microanálise, técnicas eletroquímicas (voltametria cíclica e pulso diferencial), EPR, RMN 31P e espectroscopia do u.v. visível. Em eletrocatálise homogênea foi estudado o comportamento eletroquímico dos complexos realizados em diferentes pHs, e suas habilidades como possíveis catalisadores foram testadas em experimentos de eletrooxidações de substratos orgânicos com diferentes funções (álcoois, aromáticos e alifáticos, alquilaromáticos, olefinas e éteres). Nos estudos de eletrocatálise heterogênea foi realizada a imobilização dos complexos em superfícies de eletrodos para a obtenção de eletrodos modificados através de eletrodos de pasta de carbono e eletrodos de carbono vítreo modificados com o monômero [4-(1H-pirrol-1-il)ácido benzóico]; e os testes de reatividade dos eletrodos foram realizados com alguns substratos utilizados em eletrocatálise homogênea. Nossos resultados mostraram que o sistema eletrocatalítico baseado na geração eletroquímica do [Ru(P-P)(totpy)(O)]2+ e [Ru(P-P)(bpy)(O2)]2+ são potencialmente capaz de procedimentos gerais e seletivos para a oxidação de uma série de moléculas orgânicas. A habilidade dos complexos de rutênio para atuar como catalisadores, apresentam dois fatores chave: (a) reatividade característica, através da acessibilidade múltipla de transferência de prótons e elétrons; (b) estabilidade coordenativa nos vários estados de oxidação. As reações de transferência de hidrogênio (reações de reduções) utilizando os aqua/diaqua complexos e seus precursores foram investigadas sob condições similares às descritas em literatura; usando como doador de hidrogênio o isopropanol. Altos valores de conversão de acetofena em 1-feniletanol e carvona em carveol, foram obtidos por alguns sistemas, entretanto, observa-se que existem diferenças acentuadas nos tempos de reações. Os rendimentos elevados (exceção aos compostos com ligantes NO2-bipy) comprovam que o uso de ligantes mistos fósforo-nitrogênio leva também a um aumento da atividade catalítica, e que possivelmente os outros ligantes coordenados ao complexo não interferem na atividade catalítica de modo significante. / In this work polypyridyl aquacomplexes of ruthenium(II) were synthesized and applied in electrooxidations or electrocatalytic oxidations of organic compounds and reduction reactions of ketones. Monoaquacomplexes of ruthenium [Ru(P-P)(totpy)(OH2)](PF6)2, [Ru(PP) 2(totpy)(OH2)](PF6)2 [totpy = 4\'-(4-tolyl)-2,2\':6\',2\"-terpyridine, P-P = phosphine ligand] and diaquacomplexes of ruthenium [Ru(P-P)(x-bipy)(OH2)2](PF6)2 (x-bipy = 4,4-dimethoxy-2,2- bipyridine; 4,4-dinitro-2,2-bipyridine; P-P = phosphine ligand) were synthesized. The complexes were characterized by voltammetric and spectroscopic methods and microanalysis. The complexes were used in electrooxidations of organic compounds with different functional groups. Benzyl alcohol was oxidized to benzaldehyde, cyclohexene to 2- cyclohexen-1-one, 1-pentanol to 1-pentanal, cyclohexanol to cyclohexanone, 1,2-butanediol to 1-hidroxi-2-butanone and 1,4-butanediol to -butyrolactone. Selectivity and good yields were obtained in the electrooxidations. Modified electrodes were obtained by incorporating the complexes to carbon paste electrode, and to poly-[4-(1H-pyrrol-1-yl)benzoic acid] which were deposited by anodic electropolimerization on glassy carbon electrode. Some complexes were used as catalysts in hydrogenation reactions of ketones, very good results were obtained in the conversion of acetophenone to 1-phenylethanol, and of carvone to carveol.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14639号 / 工博第3107号 / 新制||工||1462(附属図書館) / 26991 / UT51-2009-D351 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 榊 茂好, 教授 田中 庸裕, 教授 村上 正浩 / 学位規則第4条第1項該当

Master of Science / Department of Mechanical and Nuclear Engineering / Kirby S. Chapman / In the natural gas production industry, recent legislation has mandated new emission regulations for low horsepower reciprocating internal combustion engines. One method to achieve compliance of the new regulations is the use of non-selective catalytic reduction. Nonselective catalytic reduction utilizes a three-way catalyst and an air-to-fuel ratio controller to oxidize carbon monoxide and unburned fuel while reducing oxides of nitrogen. Testing of a non-selective catalytic reduction system was preformed on a typical exploration and production engine, a Compressco GasJack. To fully test the unit, exhaust gas samples were taken with an ECOM gas analyzer both before and after the catalyst over typical engine speeds and powers. By sampling the exhaust gas concentration before and after the catalyst, the catalyst efficiency or percent reduction in exhaust gas specific concentrations were calculated. Additionally by testing throughout the engine's typical operation range, conditions under which the non-selective catalyst reduction system fails were determined. After testing, it was found that the three-way catalyst was effective at reducing oxides of nitrogen by 98% at all speeds and power conditions. Carbon monoxide was reduced by 90% under all conditions except for maximum speed and power. At maximum speed and power, the conversion efficiency for carbon monoxide was recorded as low as 32%. One reason for the low conversion efficiency at maximum speed and power was that the oxygen concentration entering the catalyst was not sufficient to oxidize the carbon monoxide to carbon dioxide. These results indicate the three-way catalyst was effective at reducing emissions when the controller correctly maintained the pre-catalyst oxygen concentration. However, the controller was unable to maintain engine operation at the ideal airto- fuel ratio at all test conditions. The controller failed to keep the pre-catalyst oxygen concentration in the correct range because the oxygen sensor was not accurate and consistent in its output. Future work on the development of a more robust oxygen sensor is recommended.

Synthetic graphite is an important industrial material, used in nuclear reactors, electrodes and many other applications. Graphitisation of coke is the solid-state transformation of the disordered carbon atoms into a well-ordered hexagonal graphite structure, requiring temperatures as high as 2 600 ºC. Catalytic graphitisation using metals or metal compounds allows the rearrangement of atoms to occur at lower temperatures. The extent of catalytic graphitisation is markedly dependent on the structural ordering of the parent coke, the catalyst concentration and the reaction conditions. Solvent extraction of coal using dimethylformamide (DMF) as a solvent yields a refined coal solution referred to as Refcoal solution. Cokes of solvent-refined Tshikondeni coal derivatives have been found to be graphitisable. The activity of acetylacetonate and hydroxyquinolinate complexes of Al, Ca, Cu, Fe and Zr for catalysing the graphitisation of Refcoal cokes at 1 600 and 2 000 ºC was investigated. The effect of residence time on the catalytic graphitisation of Refcoal cokes was investigated by heat-treating cokes for two and six hours at 1 600 °C. For iron(III)acetylacetonate, the effect of metal concentrations was studied. Samples were analysed using thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and optical microscope techniques. The results show that calcium(II)acetylacetonate catalyses the graphitisation of Refcoal cokes. The degree of graphitisation increases with an increase in the iron concentration. However, iron promotes localised graphitisation, probably in the vicinity of the catalyst particles. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Detailed mechanistic studies on the palladium-catalyzed direct arylation of pyridine N-oxides are presented. The order of each reaction component is determined to provide a general mechanistic picture. The C-H bond cleaving step is examined in further detail through computational studies, and the calculated results are in support of an inner-sphere concerted metallation-deprotonation (CMD) pathway. Competition experiments were conducted using N-oxides of varying electronic characters, and results revealed an enhancement of rate when using a more electron-deficient species which is in support of a CMD transition state. The effect of base on reaction rate was also examined and it was found that a carboxylate base was required for the reaction to proceed. This led to the conclusion that Pd(OAc)2 plays a pivotal role in the reaction mechanism as more than merely a pre-catalyst, but as a source of acetate base required for the C-H bond cleavage step.