<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>

<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>

No description available.

Methane (CH4) plays an important role in regulating Earth’s climate. Its atmospheric concentrations are related to both biotic and abiotic processes. The biotic one can be formed either by chemoautotrophic or heterotrophic pathways by methanogens. Abiotic CH4 formation can occur from several sequential reactions starting with H2 production by serpentinization of Fe-bearing minerals followed by Fischer-Tropsch Type reactions or thermogenic reactions from hydrocarbons. In the presence of suitable electron acceptors, microbial oxidation utilizes CH4 and contributes to regulating its emission.  From the perspectives of astrobiology and Earth climate regulation, this thesis focuses on: (1) Dynamics of CH4 formation and oxidation in lake sediments (Paper I), (2) Constructing an automatic flux chamber to facilitate its emission measurements (Paper II), (3) dynamics of both abiotic and biotic CH4 formation processes related to olivine water interaction in temperature range 30 - 70°C (Paper III and IV). Paper I showed that potential CH4 oxidation strongly correlated to in situ its formation rates across a wide variety of lake sediments. This means that the oxidation rates could be enhanced in environments having the high formation rates. Thereby, the oxidation would likely be able to keep up with potentially increasing the formation rates, as a result diffusive CH4 release from freshwater sediments might not necessarily increase due to global warming. Paper II presented a new automated approach to assess temporal variability of its aquatic fluxes. Paper III and IV together revealed that H2 can be formed via olivine-water interaction. Abiotic CH4 formation was formed likely by Fischer-Tropsch Type reactions at low inorganic carbon concentration but by thermogenic processes at high inorganic carbon concentration. Paper IV showed that biotic methanogenic metabolism could harvest H2 and produce CH4. The dynamics of these processes seemed strongly affected by carbonate chemistry. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Submitted.

O principal objetivo deste trabalho foi a avaliação de estratégias que viabilizassem o uso do metano como doador de elétrons para desnitrificação em ambiente anóxico, visando à aplicação de tecnologia para pós-tratamento de efluente de reatores de manta de lodo e fluxo ascendente &#40;UASB&#41; aplicado no tratamento de esgoto sanitário. O trabalho foi dividido em cinco etapas, sendo que em todas elas o metano foi fornecido como única fonte de carbono orgânico. Na Etapa 1, foram comparados dois inóculos, em reatores em batelada sequenciais &#40;SBR&#41; com biomassa imobilizada. Como inóculo, foi utilizada mistura de sedimento marinho e sedimento de mangue &#40;SED-SBR&#41; ou lodo de reator UASB &#40;LAn-SBR&#41;. Na Etapa 2, foram avaliadas estratégias de enriquecimento da comunidade metanotrófica desnitrificante. Para tanto, foram operados dois SBRs: um com biomassa imobilizada &#40;Imob-SBR&#41; e outro com biomassa suspensa &#40;Susp-SBR&#41;. Na Etapa 3, foi operado reator contínuo de leito fixo e estruturado e fluxo ascendente &#40;Up-FSBR&#41;. Nas etapas 1 e 3, o metano suportou a ocorrência da desnitrificação e da manutenção celular. O consumo das formas nitrogenadas na Etapa 2 foi muito baixo e não foi possível concluir qual a melhor estratégia para enriquecimento da biomassa. Na Etapa 4, a biomassa retirada do Up-FSBR ao final da operação foi submetida a testes de endogenia. Foram operadas bateladas simples e, em cada uma, foi dosada apenas uma das formas nitrogenadas em condições com metano e sem metano. Os resultados mostraram que a redução das formas nitrogenadas é um processo paralelo à oxidação de metano. Na Etapa 5, foi avaliado o consumo de metano e de nitrato em SBR com biomassa suspensa em condições microaeradas e anóxicas. Foi observado que tanto a oxidação do metano quanto a redução do nitrato ocorrem em maior intensidade quando expostos a condições de microaerofilia. A análise dos resultados obtidos permite concluir que os organismos responsáveis pela redução de nitrato &#40;MD&#41; estabeleceram uma relação sintrófica com as bactérias oxidadoras de metano &#40;MM&#41;. Observou-se que, quando as bactérias oxidadoras de metano foram estimuladas, a desnitrificação ocorreu em maior intensidade. / This work aimed to develop the methane &#40;CH4&#41; application as electron donor to denitrification under anoxic conditions for post-treatment of Upflow Anaerobic Sludge Blanket &#40;UASB&#41; effluent, applied in sewage treatment systems. The study was conducted in five stages, in which methane was provided as the sole organic carbon source. In Stage 1, methanotrophic denitrification was assessed in Sequencing Batch Reactors &#40;SBR&#41; inoculated with a blend of marine and mangrove sediments &#40;SED-SBR&#41; or anaerobic sludge &#40;LAn-SBR&#41;. For both inocula. In Stage 2, strategies for the enrichment of methanotrophic-denitrifying community were evaluated. Two SBRs were operated: in one of them, biomass was immobilized &#40;Imob-SBR&#41; while the other was inoculated with suspended biomass &#40;Susp-SBR&#41;. In Stage 3, methanotrophic denitrification was addressed in an Upflow Fixed-Structured Bed Reactor &#40;Up-FSBR&#41;. In Stages 1 and 3, methane supported denitrification and cellular maintenance. In Stage 2, the consumption of oxidized nitrogen compounds was too low, and it was not possible to conclude which is the better strategy for enrichment of the methanotrophic-denitrifying community. In Stage 4, the biomass withdrawn from Up-FSBR was subjected to endogeny tests, in batch reactors. In each batch reactor, only nitrite or nitrate was provided, and both methane and methane-free conditions were tested. It was observed that nitrite and nitrate reduction occurred as a marginal process. In Stage 5, methane oxidation coupled to denitrification was assessed under both anoxic and microoxic conditions and both processes were stimulated under the latter. The obtained data suggest denitrifiers established a syntrophic relationship with methane-oxidizers, and when the latter was stimulated, the denitrification also occurred in greater extent.

Research was curried out on the perovskite systems with general formula A1-xA‘xB1-yB‘yO3± (where A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn and Cr). Perovskite oxides were sythesized by polymerisation methods and characterised by RTG analysis, BET method, SEM and EDX. TPD spectra and catalyst testing were measured in high temperature plug flow reactor and products were analysed by mass spectrometry. It was found, that metane oxidation at ratio O2/CH40,5 depended on the temperature. Total oxidation proceeded at the temperature betwen 300-700oC to the carbon dioxide and water, while the partial oxidation of metane (POM) occured at above 700oC to the hydrogen and carbon oxid (syngas). This was ascribed by equilibrium of O2 betwen gas phase and solid perovskite. There was used 12 perovskite systems, which catalysed methane oxidation by the same way. Dry reforming of methane run above temperature 700oC. Cobaltite and ferite type perovskites were found as the most active catalytic systems. On the base of obtained results the Mars van Krevelen mechanism was established for explanation of oxidation and reformation of methane by perovskite systems. It was showed, that POM was running by two steps mechanism. Products of total oxidation was occured in the first step, which were passed over to the syngas (H2+CO) in the second step.

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

No description available.

During this PhD. thesis, the importance of methane-oxidizing bacteria (methanotrophs) and their ecological demands were studied on the longitudinal transect along an important European river - the River Elbe. However, it was necessary to adjust methodologies for precise measurements of methane oxidation in such a variable aquatic environment. Based on laboratory experiments and field measurements, several key methodological recommendations for future planning of methane oxidation rate estimations in an unknown environment have been identified or specified. In line with the variability of the river habitats, considerable heterogeneity was also found in the obtained data on methane concentration and methanotrophical activity. Probably, some of the most important information gathered during many field sampling campaigns is that sites with the highest methane concentration usually showed a very low activity of methanotrophic bacteria (resulting in higher methane emissions). These sites are predominantly human modified sections of the river, such as locks, weirs, harbors and canals. On the contrary, the free-flowing parts of the river, modified only by groynes, showed low level of methane concentration. And so groynes could represent a more effective solution and "natural-close" habitats of navigability of rivers.

<p>Cu-zeolites have received renewed attention as catalytic materials that facilitate partial methane oxidation (PMO) to methanol, with a variety of mononuclear, binuclear, and multinuclear Cu active site motifs that have been proposed in prior literature. Our approach to more precisely identify and probe the Cu structures that activate O₂ and reduce in CH₄relies on the synthesis of model supports with varying composition and well-defined Cu speciation, which also facilitates connections between experimental data and theoretical models. Chabazite (CHA) zeolites are high-symmetry frameworks that contain a single lattice tetrahedral site (T-site), in which Cu²⁺ ions exchange at paired Al sites in a six-membered ring (6-MR) while CuOH⁺ species exchange at isolated 6-MR Al sites, the latter of which can react to form binuclear O/O₂-bridged Cu structures. In this work, Cu-CHA zeolites were synthesized to contain predominantly Cu²⁺ (Z₂Cu) or CuOH⁺ (ZCuOH) species of varying density, or a mixture of Z₂Cu and ZCuOH sites. Z₂Cu and ZCuOH sites were quantified by titration of residual Brønsted acid sites with NH₃, which respectively exchange with 2:1 or 1:1 H⁺:Cu²⁺ stoichiometry. Stoichiometric PMO reaction cycles on Cu-zeolites involved high-temperature (723 K) activation in O₂, and then moderate-temperature (473 K) reduction in CH₄ and treatment in H₂O (473 K) to extract CH₃OH. <i>I</i><i>n-situ</i> UV-Visible spectroscopy under oxidizing (O₂, 723 K) and reducing (CO, 523 K; CH₄, 473 K; He, 723 K) conditions detected the presence of mononuclear and binuclear Cu site types, while <i>in-situ</i> Cu K-edge X-ray absorption spectroscopy after such treatments was used to quantify Cu(I) and Cu(II) contents and <i>in situ</i> Raman spectroscopy was used to identify the Cu structures formed. ZCuOH, but not Z₂Cu sites, are precursors to binuclear O/O₂-bridged Cu sites that form upon O₂ activation and subsequently produce methanol after stoichiometric PMO cycles, at yields (per total Cu) that increased systematically with ZCuOH site density. The fraction of Cu(II) sites that undergo auto-reduction in inert at high temperatures (He, 723 K) is identical, within experimental error, to the fraction that reduces in CH₄ at temperatures relevant for PMO (473 K), providing a quantitative link between the binuclear Cu site motifs involved in both reaction pathways and motivating refinement of currently postulated PMO reaction mechanisms. These Cu-CHA zeolites were also studied for other redox chemistries including the selective catalytic reduction (SCR) of NO_x with NH₃. <i>In situ </i>UV-Visible and X-ray absorption spectroscopies were used to monitor and quantify the transient partial reduction of Cu(II) to Cu(I) during exposure to NH₃ (473 K), in concert with titration methods that use NO and NH₃ co-reductants to fully reduce all Cu(II) ions that remain after treatment in NH₃ alone to the Cu(I) state, providing quantitative evidence that both Z₂Cu and ZCuOH sites are able to reduce in NH₃ alone to similar extents as a function of time. These findings provide new insight into the reaction pathways and mechanisms in which NH₃ behaves as a reductant of mononuclear Cu(II) sites in zeolites, which are undesired side-reactions that occur during steady-state NO_x SCR and that often unintendedly result in Cu(II) reduction prior to spectroscopic or titrimetric characterization. Overall, the strategy in this dissertation employs synthetic methods to control framework Al density and arrangement in zeolite supports to emphasize extra-framework Cu site motifs of different structure and at different spatial densities, and to interrogate these model materials using a combination of <i>in situ</i> spectroscopic techniques together with theory, in order to elucidate active site structure and proximity requirements in redox catalysis. This work demonstrates how quantitative reactivity and site titration data, brought together with an arsenal of tools available in contemporary catalysis research, can provide detailed mechanistic insights into transition metal-catalyzed redox cycles on heterogeneous catalysts.</p>