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The selective catalytic reduction by ammonia (NH3-SCR) of nitrogen oxides (NOx) is a promising technology that is applied to eliminate NOx pollutants from combustion sources like diesel engines. Mn-based oxides are considered a promising catalyst for this process and many efforts were exerted by scholars to make improvements, including addition of other elements to the catalyst framework. The present study investigates the reaction mechanism and pathways using in-situ DRIFTS FTIR analysis for three Mn-based catalysts: a) mixed metal oxide MnCeTiOx, b) Mn impregnated on mesoporous titanium silicate-1 Mn/MesoTS1, and c) Mn/MesoTS1 after protection by secondary growth of silicalite-1 abbreviated as SG-Mn/MesoTS1. Various experiments were carried out on all the catalysts involving pre adsorbing NH3 then introducing NO+O2 to react with the pre adsorbed species and vice versa. It was found that the mixed metal oxide, MnCeTiOx, exhibited higher activity due to variation of different metals and higher metal content compared to the Mn-zeolite catalysts, approximately 29 Wt% Mn vs 4 Wt %, respectively. However, from comparing the two Mn-zeolite catalysts, each containing roughly 5 Wt% Mn, the catalyst after protection by secondary growth, SG-Mn/MesoTS1, showed improvement in the adsorption capability enhancing the overall performance due to the higher amount of acid sites than Mn/MesoTS1, explained by the presence of additional Brønsted and Lewis acid sites. From DRIFTS experiments, both E-R and L-H mechanism could be coexisting and taking place at 150C for all three catalysts. However, it was concluded that although both mechanisms could take place during the reaction, the acid sites on the catalyst surface for all three samples mostly favor the adsorption of NH3 species over NOx species making the E-R mechanism more assertive at 150C.

A contourite drift complex on the J-Anomaly Ridge (JAR) and Southeast Newfoundland Ridge (SENR), offshore eastern Canada, records an extensive archive of North Atlantic circulatory and sedimentary dynamics formed under the influence of the Deep Western Boundary Current (DWBC). Seismic-reflection profiles constrained by drill sites from IODP Expedition 342 are used to map the spatial and temporal distribution of contourite sedimentation and to evaluate the Cenozoic history of the DWBC within a preexisting climatic framework. This study indicates three phases of sedimentation termed here Pre-Contourite-Drift Phase (~115-50 Ma), Active-Contourite-Drift Phase (~50-2.6 Ma), and Post-Contourite-Drift Phase (~2.6-0 Ma). Bottom current controlled sedimentation began at the boundary between Pre-Contourite-Drift Phase and Active-Contourite-Drift Phase (~50 Ma), and correlates to a long-term global cooling trend that initiated at the end of the Early Eocene Climatic Optimum. Within the Active-Contourite-Drift Phase at ~30 Ma depocenters shifted deeper and current energy and focus is interpreted to have increased in association with global oceanographic change at the Eocene-Oligocene transition. The beginning of Post-Contourite-Drift Phase sedimentation (~2.6 Ma) marks a shift in bottom current path towards shallower water depths, and corresponds with the onset of Northern Hemisphere ice sheets. These events of circulatory reorganization correlate with other North Atlantic seismic stratigraphic studies, suggesting that these events occurred throughout the North Atlantic. An improved understanding of long-term (>1000000 yr) dynamics of North Atlantic circulation in response to significant reorganization of Cenozoic climate provides important context towards refining models and prediction of oceanic response to contemporary climate change. / Master of Science

Yes / We provide a generalized analytical methodology for evaluating a real sequential investment opportunity, which does not rely on a multivariate distribution function, but which allows for stage-specific risks and drifts. This model may be a useful capital budgeting and valuation tool for exploration and development projects, where risks change over the stages. We construct a stage threshold pattern whereby the final stage threshold exceeds the early stage threshold due to drift differentials between the project values at the various stages, value volatility differences, and correlation differentials, implying a rich menu of parameter values that may be suitable for a variety of projects. Governments seeking to motivate early final stage investments might lower final stage project volatility or specify project value decline over time, unless prospective owners are willing to pay the real option value (ROV) for concessions. In contrast, concession owners, more interested in ROV than thresholds that motivate early investments, may welcome final stage value escalation, or guarantees that reduce the correlation between project value and construction cost.

Les normes plus restrictives visent à réduire les émissions de polluants, en particulier le CO2, favorisant l'usage des biocarburants. Cependant, le biodiesel contient des éléments inorganiques (Na, K, Ca et P) qui réduisent la durabilité des systèmes de post-traitement. Dans ce travail sont évalués les performances des catalyseurs d'oxydation diesel (DOCs, catalyseur de référence PtPd/CeZrO2/La-Al2O3). Les résultats de caractérisation ont montré l’influence de ces impuretés sur les propriétés physico-chimiques et catalytiques. Bien que la structure cristalline du catalyseur de référence ne change pas après l'incorporation des impuretés, la surface spécifique diminue. La capacité redox a diminué lorsque les impuretés Na, K et Ca sont présents du à leur faible électronégativité, ce qui augmente l'interaction avec l'oxygène. Cette interaction semble être responsable de l’augmentation de la vitesse de réaction de C3H6. Les résultats NO-TPD ont montré que la forte basicité ces impuretés entraînait une plus forte adsorption du NO. Par DRIFT il a été aussi montré que l’adsorption des intermédiaires du NO, associée au champ électrostatique créé par ces cations, empêche l'oxydation de NO. L'adsorption de CO a été favorisée, améliorant la conversion du CO. La formation de phosphate de cérium observée pourrait stabiliser l'état d'oxydation de Ce3+ (vérifié par XPS), en diminuant l'oxydation de NO due au blocage des sites catalytiques. Néanmoins, les co-oxydations de CO et de C3H6 ont été améliorées en évitant l'auto-empoisonnement. Après vieillissement hydrothermal, l'effet des impuretés a été masqué par le frittage de Pt/Pd, ce qui diminue les performances catalytiques / The more restrictive regulations to reduce pollutants emissions, especially CO2, promote the use of biofuels. However, biodiesel contains inorganic elements (Na, K, Ca and P) that reduce the durability of the after-treatment catalysts. This work aims to evaluate the performance of Diesel Oxidation Catalysts (DOCs, PtPd/CeZrO2/La-Al2O3 reference catalyst). The characterization results have shown that the above-mentioned impurities affect the physico-chemical, redox, surface and catalytic properties. Although the catalyst crystalline structure of reference catalyst did not change after impurities incorporation, the specific surface area decreased. The redox ability was also decreased when Na, K and Ca impurities are present due to their low electronegativity, which increased the oxygen interaction. This high interaction seems to be responsible of the enhanced C3H6 reaction rate. NO-TPD results evidenced that the high basicity of Na, K and Ca impurities resulted in an increase of NO adsorption strength. Accordingly, DRIFT results showed the presence of NO intermediates adsorption associated to the electrostatic field created by these cations, hindering NO oxidation. CO adsorption was also promoted, enhancing CO reaction rate. The formation of cerium phosphate was also observed, which could stabilize the Ce3+ oxidation state (checked by XPS), decreasing NO oxidation due to the blockage of catalytic sites. Nevertheless, CO and C3H6 co-oxidations were enhanced by avoiding self-poisoning. After catalyst hydrothermal aging, the effect of impurities was masked by the sintering of Pt/Pd active sites, which decreases the DOC catalytic performances

La réaction d’oxydation sélective du CO par O2 en présence d’un excès d’hydrogène (PROX) est considérée comme une étape de purification essentielle de l’H2 à utiliser dans des piles à combustible. L’objectif de cette thèse est de mieux comprendre le mécanisme de cette réaction sur des catalyseurs bimétallique s à base de Pt et Sn. Des catalyseurs modèles Pt et Pt-Sn ont été synthétisés en deux étapes : (i) formation de nanoparticules (NP) métalliques colloïdales en suspension suivi par ( ii) l’imprégnation de ces particules sur des supports. L’adsorption du CO suivit par spectroscopie FT-IR en réflexion diffuse (DRIFTS) a été utilisée pour caractériser ces solides après une réduction permettant de reformer des phases d’alliage PtSn. L’analyse DRIFTS permet de caractériser la nature des sites de Pt présents, soit dans l’alliage, soit dans des phases pures de Pt. La chaleur d’adsorption du CO sur la phase d’alliage a été mesurée par DRIFTS, pour la première fois, et apparait bien plus faible que celle sur le Pt seul. De manière surprenante, la ségrégation de l’alliage en présence de CO/H 2 à des températures inférieur es à 175°C a été mise en évidence. Des mesures in situ DRIFTS de la réaction d’oxydation préférentielle du CO (PROX) indiquent que l’alliage se transforme rapidement en Pt et SnOx de par la présence de l’O2. Aucune indication de la présence d’alliage n’a jamais pu être obtenue sous PROX, indiquant que les meilleures propriétés catalytiques associés aux phases Pt-Sn sont dues à leur habilité à générer une nouvelle phase active Pt+SnOx lors de leur ségrégation. Un modèle microcinétique du PROX sur Pt+SnOx a été développé sur la base de ceux pertinents à l’oxydation du CO et PROX sur Pt seul, permettant une modélisation satisfaisante des données. Ce travail montre l’intérêt du couplage des méthodes spectroscopiques et cinétiques pour la compréhension de la structure des catalyseurs « au travail » et des mécanismes de réactions complexes / The selective oxidation of CO in the presence of a large excess of H2 (PROX) is considered as a crucial step in the purification of H 2 to be used in low-temperature fuel cells, which are clean sources of energy. The objective of this thesis was to better understand the reaction mechanisms taking place over promising catalysts based on Pt and Sn. Model Pt-Sn catalysts were prepared by a two-step method: (i) synthesis of metallic nanoparticules (NP) in a colloidal suspension followed by (ii) the deposition of these NPs onto a support. The first step of the method enabled to produce well-controlled Pt-Sn NPs in terms of size and composition. However, the NPs were partly destroyed during the deposition step followed by calcination, due to the reoxidation of Sn. The adsorption of CO followed by diffuse reflectance spectroscopy (DRIFTS) was used to characterize the nature of these solids following a reduction, which was able to regenerate an alloyed phase. The DRIFTS analysis enabled to discriminate between Pt in an alloyed phase and Pt on monometallic surfaces. The heat of CO adsorption measured by DRIFTS appeared to be much lower than that associated with the pure Pt phase. Surprinsingly, a segregation of Pt and Sn was observed under a CO/H2 mixture below 175°C. In situ analysis by DRIFTS of the PROX reaction indicated that the Pt-Sn alloy rapidly decomposed in the presence of O2, forming an intimate mixture of Pt and SnOx. No evidence of the presence of Pt -Sn alloyed phases could be obtained under PROX conditions, suggesting that the superior catalytic activity of the Pt –Sn materials were related to the Pt+SnOx mixture. A detailed PROX microkinetic model was developed over Pt+SnOx, based on those relevant to CO oxidation and PROX over pure Pt. This work epitomises the benefits in combining in situ spectroscopic study with kinetic modelling to better understand the structure of catalysts “at work” and reaction mechanisms

Model ceria catalysts were evaluated for NOx storage and desorption performance under lean conditions. Three different storage temperatures (80 °C, 120 °C, and 160 °C) were utilized to evaluate NOx storage. Higher temperatures resulted in higher NOx storage. It was observed that storage of platinum promoted ceria resulted in higher NOx storage compared to promotion with palladium. NOx desorption behavior of platinum promoted ceria indicated that the majority of NOx is released at high temperatures (> 350 °C), comparatively palladium promotion released more of the stored NOx at lower temperatures. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) indicated that platinum promotion results in NOx storage as thermally stabile nitrates, while palladium promotion results in NOx storage as thermally labile nitrites. Doping ceria with trivalent rare earth oxides has been shown to improve NOx storage by generating lattice oxygen vacancies. Ceria doped with Pr, Y, La, Sm, and Nd at two different concentrations (5 and 20 mol%) and promoted with Pt were evaluated. Doping ceria with 5% Sm, Nd, and Pr improved the amount of NOx stored while the addition of Sm and La did not improve storage. Upon increasing dopant concentration, NOx storage decreased in all cases but Pr. However, increasing Pr concentration was found to increase NOx storage as well as low temperature NOx release. Ceria doped with Pr promoted with Pd increased the amount of NOx released at lower temperatures compared to Pt promotion, although palladium promotion resulted in lower storage. Similar DRIFTS spectra were obtained with Ce-Pr when promoted with Pt or Pd compared to model catalysts. Platinum promotion results in the storage of NOx at nitrates, which require high temperatures for removal. Comparatively, Pd promotion results in NOx stored at nitrites requiring lower temperatures for removal. Ceria doped with Pr proved to be promising, although not thermally stable when exposed to high temperatures as may be seen during a DPF clean up. Therefor, stabilizing Ce-Pr catalysts with Zr were evaluated. It was found that stabilizing Ce-Pr with Zr was not found to be beneficial to the catalyst performance.

ABSTRACT KINETIC STUDIES FOR THE PRODUCTION OF TERTIARY ETHERS USED AS GASOLINE ADDITIVES Boz, Nezahat Ph. D., Department of Chemical Engineering Supervisor: Prof. Dr. Timur Dogu Co-supervisor: Prof. Dr. G&uuml / lSen Dogu June 2004, 174 pages In the present study, the kinetics studies for etherification reactions were investigated in detail. In the first phase of present study, different acidic resin catalysts were prepared by the heat treatment of Amberlyst-15 catalysts at 220&deg / C at different durations of time and also by the synthesis of sulfonated styrene divinylbenzene cross-linked resins at different conditions. A linear dependence of reaction rate on hydrogen ion-exchange capacity was in 2M2B+ethanol reaction. However, in the case of 2M1B+ethanol reaction hydrogen ion-exchange capacities over 2.8 meq.H+/g did not cause further increase in reaction rate, which was concluded to be majorly due to significance of diffusional resistances. DRIFTS experiments carried out with alcohols, isobutylene, isoamylenes and TAME (tert-amyl-methyl-ether) in a temperature range of 333-353 K supported a Langmuir-Hinshelwood type reaction mechanism involving adsorbed isoolefins molecules forming a bridged structure between &ndash / SO3H sites of the catalyst and adsorbed alcohol molecules. A rate expression derived basing on the mechanism proposed from the DRIFTS results gave good agreement with the published data. Reaction rate was found to give a sharp maximum at ethanol activity of around 0.1. The third phase of this work included evaluation of effective diffusivities and adsorption equilibrium constants of methanol, ethanol and 2M2B, in Amberlyst-15 from moment analysis of batch adsorber dynamic results. Models proposed for monodisperse and bidisperse pore structures were used for the evaluation of effective diffusivities. It was shown that surface diffusion contribution was quite significant. In the last phase of the work, a batch Reflux-Recycle-Reactor (RRR) was proposed, modeled and constructed to achieve high yields and selectivities in equilibrium limited reactions. The batch reflux recycle reactor was modeled by assuming plug flow in the reactor section, perfect mixing in the reboiler and vapor-liquid equilibria between the liquid in the reboiler and reactor inlet stream. In this system conversion values of isoamylenes reaching to 0.91 were achieved at 82&deg / C with almost 100% selectivity. Such conversion values were shown to be much higher than the corresponding equilibrium values that could be obtained in vapor phase fixed bed reactors. The activation energies evaluated in this system were found to be much less than the activation energies evaluated in the fixed bed reactor studies. This was concluded to be majorly due to the significance of transport resistant in the batch Reflux-Recycle-Reactor in which catalyst particles are partially wet. As a result of catalyst development, characterization, kinetic and reactor development studies carried out in this study, it was concluded that tert-amyl-ethyl-ether (TAEE) could be effectively produced and used as a gasoline blending oxygenate.

Dissertação apresentada como requisito parcial para à obtenção do grau de Mestre em Química no Curso de Pós-Graduação em Química, Setor de Ciências Exatas, Universidade Federal do Paraná. Orientador: Prof. Dr. Patricio G. Peralta-Zamora. 2006 / Submitted by Nilson Junior (nilson.junior@unila.edu.br) on 2016-05-25T20:59:32Z No. of bitstreams: 2 Dissertação Gilcélia Cordeiro.pdf: 1411855 bytes, checksum: 33927381684c7c85ff44e446611d8891 (MD5) Recibo Deposito Legal_TESE_Gilcéia Aparecida Cordeiro.pdf: 229315 bytes, checksum: 6555acb6430c7e757d89b1cb6e13b523 (MD5) / Made available in DSpace on 2016-05-25T20:59:47Z (GMT). No. of bitstreams: 2 Dissertação Gilcélia Cordeiro.pdf: 1411855 bytes, checksum: 33927381684c7c85ff44e446611d8891 (MD5) Recibo Deposito Legal_TESE_Gilcéia Aparecida Cordeiro.pdf: 229315 bytes, checksum: 6555acb6430c7e757d89b1cb6e13b523 (MD5) Previous issue date: 2006 / Este trabalho é um exemplo do uso de ferramentas de calibraçăo multivariada(regressăo dos mínimos quadrados parciais, PLSR) na quantificaçăo desulfametoxazol (SMZ) e o trimetoprim (TMP) em formas farmacęuticas, utilizando-se espectroscopia de absorçăo no ultravioleta-visível (UV-Vis) e espectroscopia no infravermelho por refletância difusa (DRIFTS). Estudos preliminares permitiram constatar a inconvenięncia dos processos decalibraçăo univariados, em razăo da interferęncia espectral observada naespectroscopia UV-Vis e da extrema complexidade dos sinais de DRIFT. Modelos multivariados foram desenvolvidos a partir de espectros originais(UV-Vis), registrados entre 190 e 330 nm, e pré-processados por derivaçăoalisamentoe autoescalonamento. Os melhores resultados foram conseguidos commodelos desenvolvidos a partir de espectros originais, envolvendo o uso de oitovariáveis latentes (VLs). Nestas condiçőes, os parâmetros avaliados na validaçăoforam realizados a partir de cinco misturas sintéticas, evidenciando erros de previsăoinferiores a 3%, para ambas espécies em estudo. Na análise de medicamentos,algumas inconsistęncias foram observadas, principalmente devido á modificaçăo dosinal espectral em funçăo de variaçőes de pH, estas últimas originadas,provavelmente, pela presença de excipientes diferenciados. Nos estudos envolvendo DRIFT, modelos multivariados foram desenvolvidosem diversas regiőes espectrais e utilizando-se diversos sistemas de préprocessamentode sinais. Na fase de validaçăo, os melhores resultados foramconseguidos com modelos elaborados entre 7001 e 399 cm-1, empregando-se 8variáveis latentes e o sistema de correçăo multiplicativa de sinal (MSC). Nestas condiçőes, erros de previsăo inferiores a 5% foram obtidos para ambas espécies emestudo. Na análise de medicamentos, resultados insatisfatórios foram obtidos,principalmente devido á modificaçőes espectrais introduzidas pela presença deexcipientes. O efeito da presença destas espécies foi demonstrado por análise decomponentes principais (PCA).De maneira geral, os resultados demonstram uma boa capacidade preditivados modelos multivariados fundamentados em ambos tipos de espectroscopia. Paraa análise de medicamentos, entretanto, há necessidade de se considerar a presençade excipientes, os quais deverăo ser modelados junto com os fármacos de interesse.

Catalytic combustion is a promising combustion technology for gas turbines, which results in ultra low emission levels of nitrogen oxides (NOx), carbon monoxide (CO) and unburned hydrocarbons (UHC). Due to the low temperature achieved in catalytic combustion almost no thermal NOx is formed. This thesis is concentrated on the first stage in a catalytic combustion chamber, i.e. the ignition catalyst. The catalyst used for this application is often a supported palladium based catalyst due to its excellent activity for methane combustion. However, this type of catalyst has a serious drawback; the methane conversion decreases severely with time during operation. The unstable activity will result in increasing difficulties to ignite the fuel. The parameters that govern the poor stability and other features of the palladium catalysts are discussed in the thesis. The objective of the work is to improve the catalytic performance of supported palladium catalysts, with focus on stabilising the methane conversion. A large number of different bimetallic palladium catalysts have been evaluated, where the influence of co-metals, molar ratio and support material is addressed. Results from the activity tests of methane combustion showed that it is possible to stabilise the activity by adding certain co-metals into the palladium catalyst. An extensive characterisation study has been carried out on the various bimetallic catalysts in order to gain a better understanding of how their morphology and physicochemical properties determine the various patterns of combustion behaviour. The environment inside a gas turbine combustor is very harsh for a catalyst. Since the stability of the catalyst is of great importance for ignition catalysts, it is essential to evaluate the risk of deactivation. In this work special emphasis has been given to thermal deactivation, water inhibition and sulphur poisoning. It was found that a bimetallic Pd Pt catalyst is significantly more tolerant to the various deactivation processes investigated than the monometallic palladium catalyst. Finally, the influence of pressure on the catalytic performance has been investigated. The catalysts were assessed at more realistic conditions for gas turbines, in a high-pressure test facility with 100 kW fuel power. / QC 20100916