As an important chemical raw material, alcohols can be used as fuels, solvents and chemical feedstocks to produce a variety of downstream products. With limited fossil fuel resources, alcohol synthesis from syngas reactions can be a potential alternative to the traditional petroleum based alcohol synthesis. Among many catalysts active for syngas to alcohol processes, alkali promoted Mo2C has shown promising performance. More interestingly, the alkali promoter was found to play an important role in shifting the reaction selectivity from hydrocarbons to alcohols. However, limited understanding of the mechanism of this alkali promoter effect is available due to the complexity of syngas reaction mechanism and low content of alkali added to the catalysts. In this thesis, we performed a comprehensive investigation of the alkali promoter effect with density functional theory (DFT) calculations as our primary tool. We first examine various Mo2C surfaces to determine a representative surface structure active to alkali adsorption. On this particular surface, we develop a syngas reaction network including relevant reaction mechanisms proposed in previous literature. With energetics derived from DFT calculations and a BEP relation, we predict the syngas reaction selectivity and find it to be in excellent agreement with experimental results. The dominant reaction mechanism and selectivity determining steps are determined from sensitivity analysis. We also propose a formation mechanism of alkali promoters on Mo2C catalysts that shows consistency between experimental IR and DFT computed vibrational frequencies. Finally, the effect of alkali promoters on the selectivity determining steps for syngas reactions are investigated from DFT calculations and charge analysis. We are able to rationalize the role of alkali promoters in shifting the reaction selectivity from hydrocarbons to alcohols on Mo2C catalysts.

Syngas, a combustible gaseous mixture of hydrogen, carbon monoxide, and other species, is a promising fuel for efficient energy conversion technologies. Syngas is produced by breaking down a primary fuel into a hydrogen-rich mixture in a process called fuel reforming. The motivation for the utilization of syngas rather than the primary fuel is that syngas can be used in energy conversion technologies that offer higher conversion efficiencies, e.g. gas turbines and fuel cells. One approach for syngas production is partial oxidation, which is an oxygen starved combustion process that does not require a catalyst. Efficient conversion to syngas occurs at high levels of oxygen depletion, resulting in mixtures that are not flammable in conventional combustion applications. In non-catalytic partial oxidation, internal heat recirculation is used to increase the local reaction temperatures by transferring heat from the product stream to pre-heat the fuel/air mixture before reactions occur, thus increasing reaction rates and allowing for combustion outside the conventional flammability limits. As peak temperatures lie above the adiabatic equilibrium temperature predicted by thermodynamic calculations, the combustion regime used for non-catalytic fuel reforming is referred to as 'superadiabatic'. Counter-flow heat exchange is an effective way to transfer heat between adjacent channels and is used for a novel, heat-recirculating fuel reformer design. An analytical study predicts that combustion zone locations inside adjacent flow channels adjust to operating conditions, thus stabilizing the process for independent variations of flow velocities and mixture compositions. In experiments, a reactor prototype with four channels with alternating flow directions is developed and investigated. Tests with methane/air and propane/air mixtures validate the operating principle, and measurements of the resulting syngas compositions verify the feasibility of the concept for practical fuel-reformer applications. Results from a two-dimensional numerical study with detailed reaction chemistry are consistent with experimental observations. Details of the reaction zone reveal that reactions are initiated in the vicinity of the channel walls, resulting in "tulip"-shaped reaction layers. Overall, results confirm the viability of the non-catalytic reactor design for fuel reforming applications. / text

No description available.

This work investigates the extinction limits of laminar diffusion counterflow flames for various gaseous (methane, syngas, biogas) fuels using a high flow rate counterflow burner designed and built for this work. Equal momenta of the fuel and oxidizer streams were not maintained to provide data to check the fidelity of the numerical schemes and their chemical mechanisms at "non-standard" conditions. Strain rate values at extinction were obtained as a function of fuel mole fraction. Preliminary work with the new burner found that the methane extinction limit results were consistent with results from literature. The results provide insight into the extinction limit conditions of the aforementioned fuels. The strain rate was found to increase with increasing fuel mole fraction. Extinction limit results indicated that fuels with the highest concentration of hydrogen have the greatest extinction limit, which is believed to be attributed to the high diffusivity and reactivity of hydrogen.

This work investigates the extinction limits of laminar diffusion counterflow flames for various gaseous (methane, syngas, biogas) fuels using a high flow rate counterflow burner designed and built for this work. Equal momenta of the fuel and oxidizer streams were not maintained to provide data to check the fidelity of the numerical schemes and their chemical mechanisms at "non-standard" conditions. Strain rate values at extinction were obtained as a function of fuel mole fraction. Preliminary work with the new burner found that the methane extinction limit results were consistent with results from literature. The results provide insight into the extinction limit conditions of the aforementioned fuels. The strain rate was found to increase with increasing fuel mole fraction. Extinction limit results indicated that fuels with the highest concentration of hydrogen have the greatest extinction limit, which is believed to be attributed to the high diffusivity and reactivity of hydrogen.

Ce travail de Thèse est consacré à la caractérisation de la structure thermique des fronts de flammelaminaire de prémélange H2/CH4/Air et H2/CO/Air pauvres. L'étude a été réalisée sur un brûleur à jets opposés, permettant de stabiliser des flammes planes stationnaires, dans des conditions quasi-adiabatiques, pour différentes conditions d'étirement. Un diagnostic de Vélocimétrie par Imagerie de Particule (PIV) et un diagnostic bidimensionnel de diffusion Rayleigh induite par laser ont été utilisés successivement pour étudier l'influence de la richesse, de la concentration en hydrogène dans le combustible et de l'étirement sur le profil de température normal au front de flamme. Trois grandeurs fondamentales ont été étudiées : la température des gaz brûlés, le gradient maximum de température et l'épaisseur de flamme au sens de Spalding. Une attention particulière a été portée à l'interprétation du signal Rayleigh. Ce dernier dépendant notamment de la composition du gaz qui évolue à travers le front de flamme. Dans ce travaille de thèse, cette évolution a été évaluée numériquement (simulations 1D : CANTERA et OPPDIF) puis prise en compte pour améliorer le traitement des données expérimentales. Les résultats expérimentaux couvrent une gamme de richesses s'étalant pour H2/CH4/Air et H2/CO/Air, respectivement de 0.6 à 0.8 et de 0.4 à 0.6. Les concentrations en hydrogène dans le combustible s'étalent respectivement de 0 à 50% et de 10 à 50%. Une comparaison systématique a été faite avec les résultats de simulation numérique 1D (OPPDIF).

This thesis describes an experimental investigation of lean blowoff for H2/CO/CH4 mixtures in a swirling combustor. This investigation consisted of three thrusts. The first thrust focused on correlations of the lean blowoff limits of H2/CO/CH4 mixtures under different test conditions. It was found that a classical Damköhler number approach with a diffusion correction could correlate blowoff sensitivities to fuel composition over a range of conditions. The second part of this thesis describes the qualitative flame dynamics near blowoff by systematically characterizing the blowoff phenomenology as a function of hydrogen level in the fuel. These near blowoff dynamics are very complex, and are influenced by both fluid mechanics and chemical kinetics; in particular, the role of thermal expansion across the flame and extinction strain rate were suggested to be critical in describing these influences. The third part of this thesis quantitatively analyzed strain characteristics in the vicinity of the attachment point of stable and near blowoff flames. Surprisingly, it was found that in this shear layer stabilized flame, flow deceleration is the key contributor to flame strain, with flow shear playing a relatively negligible role. Near the premixer exit, due to strong flow deceleration, the flame is negatively strained i.e., compressed. Moving downstream, the strain rate increases towards zero and then becomes positive, where flames are stretched. As the flame moves toward blowoff, holes begin to form in the flame sheet, with a progressively higher probability of occurrence as one moves downstream. It is suggested that new holes form with a more uniform probability, but that this behavior reflects the convection of flame holes downstream by the flow. It has been shown in prior studies, and affirmed in this work, that flames approach blowoff by first passing through a transient phase manifested by local extinction events and the appearance of holes on the flame. A key conclusion of this work is that the onset of this boundary occurs at a nearly constant extinction strain rate. As such, it is suggested that Damköhler number scalings do not describe blowoff itself, but rather the occurrence of this first stage of blowoff. Given the correspondence between this first stage and the actual blowoff event, this explains the success of classical Damköhler number scalings in describing blowoff, such as shown in the first thrust of this thesis. The physics process associated with the actual blowoff event is still unclear and remains a key task for future work.

Made available in DSpace on 2014-12-17T14:07:04Z (GMT). No. of bitstreams: 1 RosaneMPBO_TESE_partes_autorizadas.pdf: 623811 bytes, checksum: 3724885447cd319f325ecaa9845943f0 (MD5) Previous issue date: 2010-10-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work, ceramic powders belonging to the system Nd2-xSrxNiO4 (x = 0, 0.4, 0.8, 1.2 and 1.6) were synthesized for their use as catalysts to syngas production partial. It was used a synthesis route, relatively new, which makes use of gelatin as organic precursor. The powders were analyzed at several temperatures in order to obtain the perovskite phase and characterized by several techniques such as thermal analysis, X-rays diffraction, Rietveld refinement method, specific surface area, scanning electron microscopy, energy dispersive spectroscopy of X-rays and temperature programmed reduction. The results obtained using these techniques confirmed the feasibility of the synthesis method employed to obtain nanosized particles. The powders were tested in differential catalytic conditions for dry reforming of methane (DRM) and partial oxidation of methane (POM), then, some systems were chosen for catalytic integrals test for (POM) indicating that the system Nd2-xSrxNiO4 for x = 0, 0.4 and 1.2 calcined at 900 ?C exhibit catalytic activity on the investigated experimental conditions in this work without showing signs of deactivation / Neste trabalho, p?s cer?micos pertencentes ao sistema Nd2-xSrxNiO4 (x = 0; 0,4; 0,8; 1,2 e 1,6) foram sintetizados visando sua utiliza??o como catalisadores para produ??o de g?s de s?ntese. Foi utilizada uma rota de s?ntese, relativamente nova, na qual faz uso de gelatina como precursor org?nico. Os p?s cer?micos sintetizados foram calcinados a v?rias temperaturas visando ? obten??o da fase perovsquita e ent?o caracterizados por v?rias t?cnicas, tais como: An?lise t?rmogravim?trica, difra??o de raios X, refinamento Rietveld, ?rea espec?fica (m?todo BET), microscopia eletr?nica de varredura, espectroscopia por dispers?o de energia de raios X e redu??o ? temperatura programada. Os resultados obtidos atrav?s destas t?cnicas confirmaram a viabilidade do m?todo de s?ntese empregado para obten??o de part?culas nanom?tricas. Os p?s foram submetidos a testes catal?ticos em condi??es diferenciais para rea??o de reforma a seco (RSM) e oxida??o parcial do metano (OPM), em seguida alguns sistemas foram escolhidos para testes catal?ticos integrais de OPM indicando que o sistema Nd2-xSrxNiO4 para x = 0, 0,4 e 1,2 calcinados a 900 ?C apresentam atividade catal?tica nas condi??es experimentais investigadas nesse trabalho sem mostrar sinais de desativa??o

abstract: Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Submitted by BENJAMIN KUNTE null (benjamin.kunte@gmail.com) on 2015-12-21T20:22:35Z No. of bitstreams: 1 Benjamin_Dissertation_Final_Version.pdf: 2440898 bytes, checksum: 129503961064a9371fbb24f9408bfbc6 (MD5) / Approved for entry into archive by Cássia Adriana de Sant ana Gatti (cgatti@marilia.unesp.br) on 2015-12-22T13:12:11Z (GMT) No. of bitstreams: 1 Benjamin_Dissertation_Final_Version.pdf: 2440898 bytes, checksum: 129503961064a9371fbb24f9408bfbc6 (MD5) / Made available in DSpace on 2015-12-22T13:12:11Z (GMT). No. of bitstreams: 1 Benjamin_Dissertation_Final_Version.pdf: 2440898 bytes, checksum: 129503961064a9371fbb24f9408bfbc6 (MD5) Previous issue date: 2015-12-18 / Os métodos mais promissores para reduzir gases de efeito estufa, bem como combater o iminente esgotamento das reservas de energia fóssil, são: a) o uso de combustíveis alternativos obtidos a partir da biomassa, como o biogás ou gás de síntese (syngas); b) o aumento da eficiência do sistema através da redução da percentagem de energia útil perdido para o ambiente. Enquanto a otimização da eficiência de uma determinada máquina da central elétrica, por exemplo, turbina a gás ou compressor, é um desenvolvimento muito demorado, a cogeração pode rápida e significativamente aumentar a eficiência global da central. Neste trabalho, análise termodinâmica, econômica e de emissões de um sistema de cogeração baseado em uma microturbina a gás de 200 kW combinado com uma caldeira de recuperação são conduzidas. Além disso, a operação de biogás e syngas é comparada com a operação de gás natural para investigar a pertinência destes dois combustíveis alternativos para o uso em micro turbinas a gás. A central de cogeração proposta mostrou-se tecnicamente viável para todos os combustíveis, porque a microturbina selecionada é disponível em várias versões, específicas para cada combustível, com sistemas de injeção de combustível otimizados. A central apresentou eficiências energéticas globais de 50,9%, 48,6% e 47,9% para operação com gás natural, biogás e syngas, respectivamente. Devido aos preços muito elevados do gás natural e do syngas, a central de cogeração apresentou viabilidade econômica apenas no caso de operação com biogás, com curtos períodos de retorno de aproximadamente 2,8 anos e alta economia anual esperada. Além disso, o biogás tem a maior eficiência ecológica e, portanto, apresentou-se como a melhor alternativa aos combustíveis fósseis. / The most promising methods to reduce greenhouse gases as well as counteract against the imminent depletion of fossil fuels are: a) the use of alternative fuels obtained from biomass, such as biogas or bio-syngas; b) enhancing the power plant efficiency by decreasing the percentage of useful energy lost to the environment. Whereas efficiency optimisation of a particular machine in a power plant, e.g. gas turbine or compressor, is a very longsome development, cogeneration can quickly and significantly increase the overall efficiency of a power plant. In this work, energetic, exergetic, emissions and economic analyses of a cogeneration system consisting of a 200 kW micro gas turbine combined with a heat recovery steam generator are introduced and conducted. Furthermore, biogas and syngas operation are compared to natural gas operation, to investigate the adequacy of these two alternative fuels for use in micro gas turbines. The proposed cogeneration plant proved to be technically feasible for all fuels, because the selected micro gas turbine Capstone C200 is available in various, fuel-specific versions with optimised fuel injection systems. The plant presented overall energetic efficiencies of 50.9%, 48.6% and 47.9% for natural gas, biogas and syngas operation, respectively. Due to very high natural gas and syngas prices, the cogeneration plant presented economic feasibility only in case of biogas operation, with short payback periods of approximately 2.8 years and high expected annual saving. Moreover, biogas has the highest ecologic efficiency and was therefore found to be the best alternative to fossil fuels.