<p>Due to continuously stricter regulations regarding emissions from power generation processes, development of existing gas turbine combustors is essential. A promising alternative to conventional flame combustion in gas turbines is catalytic combustion, which can result in ultra low emission levels of NO_x, CO and unburned hydrocarbons. The work presented in this thesis concerns the development of methane oxidation catalysts for gas turbine combustors. The application of catalytic combustion to different combustor concepts is addressed in particular.</p><p>The first part of the thesis (Paper I) reports on catalyst development for fuel-lean methane combustion. The effect on catalytic activity of diluting the reaction mixture with water and carbon dioxide was studied in order to simulate a combustion process with exhaust gas recirculation. Palladium-based catalysts were found to exhibit the highest activity for methane oxidation under fuel-lean conditions. However, the catalytic activity was significantly decreased by adding water and CO₂, resulting in unacceptably high ignition temperatures of the fuel.</p><p>In the second part of this thesis (Paper II), the development of rhodium catalysts for fuel-rich methane combustion is addressed. The effect of water addition on the methane conversion and the product gas composition was studied. A significant influence of the support material and Rh loading on the catalytic behavior was found. The addition of water influenced both the low-temperature activity and the product gas composition.</p>

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<p>Catalytic combustion is an environmentally friendlytechnique to combust fuels in e.g. gas turbines. Introducing acatalyst into the combustion chamber of a gas turbine allowscombustion outside the normal flammability limits. Hence, theadiabatic flame temperature may be lowered below the thresholdtemperature for thermal NO_Xformation while maintaining a stable combustion.However, several challenges are connected to the application ofcatalytic combustion in gas turbines. The first part of thisthesis reviews the use of catalytic combustion in gas turbines.The influence of the fuel has been studied and compared overdifferent catalyst materials.</p><p>The material section is divided into two parts. The firstconcerns bimetallic palladium catalysts. These catalysts showeda more stable activity compared to their pure palladiumcounterparts for methane combustion. This was verified both byusing an annular reactor at ambient pressure and a pilot-scalereactor at elevated pressures and flows closely resembling theones found in a gas turbine combustor.</p><p>The second part concerns high-temperature materials, whichmay be used either as active or washcoat materials. A novelgroup of materials for catalysis, i.e. garnets, has beensynthesised and tested in combustion of methane, a low-heatingvalue gas and diesel fuel. The garnets showed some interestingabilities especially for combustion of low-heating value, LHV,gas. Two other materials were also studied, i.e. spinels andhexaaluminates, both showed very promising thermal stabilityand the substituted hexaaluminates also showed a good catalyticactivity.</p><p>Finally, deactivation of the catalyst materials was studied.In this part the sulphur poisoning of palladium, platinum andthe above-mentioned complex metal oxides has been studied forcombustion of a LHV gas. Platinum and surprisingly the garnetwere least deactivated. Palladium was severely affected formethane combustion while the other washcoat materials were mostaffected for carbon monoxide and hydrogen.</p><p><b>Keywords:</b>catalytic combustion, catalyst materials,palladium, platinum, bimetallic, garnet, spinel, hexaaluminate,deactivation, sulphur, poisoning, diesel, methane,hydrocarbons</p>

<p>Due to continuously stricter regulations regarding emissions from power generation processes, further development of existing gas turbine combustors is essential. A promising alternative to conventional flame combustion in gas turbines is catalytic combustion, which can result in ultralow emission levels of NO_x, CO and unburned hydrocarbons. The work presented in this thesis concerns the development of methane oxidation catalysts for gas turbine combustors. The application of catalytic combustion to different combustor concepts is addressed in particular.</p><p>The first part of the thesis (Paper I) reports on catalyst development for fuel-lean methane combustion. Supported Pd-based catalysts were investigated at atmospheric pressure. The effect on catalytic activity of diluting the reaction mixture with water and/or carbon dioxide was studied in order to simulate a combustion process with exhaust gas recirculation. The catalytic activity was found to decrease significantly in the presence of water and CO₂. However, modifying the catalyst by changing support material can have a considerable impact on the performance.</p><p>In the second part of this thesis (Papers II-IV), the development of rhodium catalysts for fuel-rich methane combustion is addressed. The effect of catalyst composition, oxygen-to-fuel ratio and catalyst pre-treatment on the methane conversion and the product gas composition was studied. An experimental investigation at elevated pressures of partial oxidation of methane/oxygen mixtures in exhaust gas-rich environments was also conducted. The most suitable catalyst identified for fuel-rich catalytic combustion of methane, i.e. Rh/Ce-ZrO₂, showed benefits such as low light-off temperature, high activity and enhanced hydrogen selectivity.</p><p>In the final part of the thesis (Paper V), a numerical investigation of fuel-rich catalytic combustion is presented. Measurements and predictions were compared for partial oxidation of methane in exhaust gas diluted mixtures at elevated pressures. The numerical model was validated for several Rh-based catalysts. The key parameter controlling the catalytic performance was found to be the noble metal dispersion.</p>

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"Grupo de peneiras moleculares micro e mesoporosas" / Orientadores: Heloise de Oliveira Pastore, Marco Andre Fraga / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T13:56:16Z (GMT). No. of bitstreams: 1 Ruiz_JuanAlbertoChavez_D.pdf: 9318678 bytes, checksum: 0b11ace77679aab815eebe6b5abaed29 (MD5) Previous issue date: 2005 / Doutorado / Quimica Inorganica / Doutor em Quimica

Due to continuously stricter regulations regarding emissions from power generation processes, development of existing gas turbine combustors is essential. A promising alternative to conventional flame combustion in gas turbines is catalytic combustion, which can result in ultra low emission levels of NOx, CO and unburned hydrocarbons. The work presented in this thesis concerns the development of methane oxidation catalysts for gas turbine combustors. The application of catalytic combustion to different combustor concepts is addressed in particular. The first part of the thesis (Paper I) reports on catalyst development for fuel-lean methane combustion. The effect on catalytic activity of diluting the reaction mixture with water and carbon dioxide was studied in order to simulate a combustion process with exhaust gas recirculation. Palladium-based catalysts were found to exhibit the highest activity for methane oxidation under fuel-lean conditions. However, the catalytic activity was significantly decreased by adding water and CO2, resulting in unacceptably high ignition temperatures of the fuel. In the second part of this thesis (Paper II), the development of rhodium catalysts for fuel-rich methane combustion is addressed. The effect of water addition on the methane conversion and the product gas composition was studied. A significant influence of the support material and Rh loading on the catalytic behavior was found. The addition of water influenced both the low-temperature activity and the product gas composition. / QC 20101126

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Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-15T11:16:01Z No. of bitstreams: 1 2016 - Maria Clara Adum de paiva.pdf: 2279180 bytes, checksum: d1de128b3d5f5984c844a68538cd255e (MD5) / Made available in DSpace on 2017-05-15T11:16:01Z (GMT). No. of bitstreams: 1 2016 - Maria Clara Adum de paiva.pdf: 2279180 bytes, checksum: d1de128b3d5f5984c844a68538cd255e (MD5) Previous issue date: 2016-08-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The demand for electricity production, and the need for thermoelectric use as power generating units, makes it necessary to search for less polluting matrices. In this search the catalytic combustion of methane, both from natural gas and other sources (residue disposal, for example) have shown promising. It is known the use of cobalt oxides is an alternative to the use of catalysts based on noble metals which has shown high performance. In order to potentiate the activity of the cobalt based catalyst, thus reducing both the ignition temperature and the temperature of total burning of methane, this work proposes the production of cobalt-based precursors using different types of layered double hydroxides (LDHs). Cobalt based catalysts partially substituted in layered double hydroxides (LDH Mg, Al and CO32-) were prepared by co-precipitation and impregnation with a nominal content of 9% CoII in LDH, or by impregnating a commercial hydrotalcite (HT). The LDH precursors were characterized by X-ray powder diffraction (XRD) and infrared absorption spectroscopy (FTIR). The XRD patterns indicated a LDH of 3R polytype. XRD showed the presence of Gibbisite in the HT precursor. The infrared spectra of precursor LDHs presented bands related to ?1, ?2 and ?3 vibrations of the carbonate anion, and interlayer water characteristic bands, thus in line with the XRD data. Analysis by XRD of the catalysts after calcination at 800 ?C showed the presence of periclase and spinel phases. Infrared spectra showed bands ascribed to the Mg-O and Co-O stretching in tetrahedral and octahedral sites as well as bands attributed to the Mg-O-Al bond and the cobalt spinel. The catalytic activity of these materials was investigated in the catalytic combustion of methane under kinetic regime, using predetermined reaction conditions to avoid diffusional limitations, resulting in a significant decrease in the combustion temperature, with the higher activity observed for the catalyst prepared by impregnating a commercial HT. Scanning electron microscopy (SEM) and quantitative chemical analysis (EDS) of catalysts with improved performance show both the homogeneous dispersion of the components in the sample surface and the higher aluminum content of the sample supported on HT. / A demanda de produ??o de energia el?trica, e a necessidade do uso de termel?tricas como unidades geradoras de energia, fazem com que seja necess?ria a busca por matrizes menos poluentes. Nessa busca a combust?o catal?tica do metano, tanto proveniente do g?s natural como de outras fontes (res?duo do tratamento de lixo, por exemplo), tem se mostrado promissora. Sabidamente o uso de ?xidos de cobalto ? uma alternativa, que vem mostrando alto desempenho, ao uso de catalisadores a base de metais nobres. Com o intuito de potencializar a atividade do catalisador a base de cobalto, reduzindo assim tanto a temperatura de igni??o quanto a de queima total do metano, esse trabalho prop?e sua produ??o utilizando como precursor diferentes tipos de hidr?xidos duplos lamelares (HDLs). Catalisadores ? base de cobalto parcialmente substitu?dos em hidr?xidos duplos lamelares (HDL de Mg, Al e CO32-) foram preparados por co-precipita??o e impregna??o num teor nominal de 9% de CoII em HDL, ou por impregna??o em hidrotalcita comercial (HT). Os HDLs precursores foram caracterizados por difra??o de raios?X pelo m?todo de p? (DRX) e por espectroscopia de absor??o no infravermelho (FTIR). Os difratogramas indicaram a obten??o de um HDL de politipo 3R. Por meio do DRX foi identificada a presen?a de Gibbisita no suporte de HT. Os espectros de infravermelho dos HDLs precursores presentaram bandas referentes ?s vibra??es ?1, ?2 e ?3 do ?nion carbonato, al?m de bandas caracter?sticas de ?gua interlamelar, estando portanto de acordo com os dados de DRX. A an?lise por difra??o de raios-X dos catalisadores ap?s calcina??o a 800?C mostrou apenas as fases espin?lio e pericl?sio. Os espectros de infravermelho apresentaram bandas atribu?das aos estiramentos Mg?O e Co?O em s?tios tetra?dricos e octa?dricos, assim como bandas caracter?sticas de Mg?O?Al e de Co3O4. A atividade catal?tica desses materiais foi investigada na combust?o catal?tica do metano, em regime cin?tico, empregando-se condi??es reacionais preestabelecidas de forma a evitar limita??es difusionais, obtendo-se uma significativa diminui??o na temperatura de combust?o, sendo que a maior atividade foi observada para o catalisador preparado por impregna??o em HT comercial. Foi realizada microscopia eletr?nica de varredura (MEV) e an?lise qu?mica quantitativa (EDS) para os catalisadores com melhor desempenho, mostrando tanto a dispers?o homog?nea dos componentes na superf?cie das amostras como o maior teor de alum?nio presente na amostra suportada em HT.

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