Este trabalho propõe um método com base no planejamento estatístico de testes de confiabilidade para proporcionar um tratamento quantitativo aos dois primeiros níveis da abordagem de padrões baseados em metas (Goal-Based Standards). O uso do método é demonstrado em dois exemplos práticos, através da sua aplicação na meta de confiabilidade dos componentes do sistema de pós-tratamento de gases de exaustão, em motores a diesel de veículos automotivos e marítimos. Os fundamentos do trabalho incluem a teoria do planejamento estatístico de testes de confiabilidade, os princípios do GBS, tipos e características de metas de confiabilidade, a ferramenta de avaliação de segurança formal (FSA), e da análise do modo e efeito da falha (FMEA). A originalidade da contribuição do trabalho está na combinação das técnicas de planejamento de testes de confiabilidade com os princípios do GBS para quantificar o nível de atendimento das metas de confiabilidade. Dessa forma, é possível ajustar o programa de testes na verificação das metas de segurança, aumentando o conhecimento sobre o desempenho do sistema. O método é de simples aplicação permitindo a sua aplicação expedita e integrada aos processos de desenvolvimento de sistemas. / This research proposes a probabilistic method based on reliability test planning in order to provide a quantitative approach to the Tier I and II of the Goal-Based Standards (GBS). The use of the method is exhibited through its application in the reliability goal of the components of the exhaust gases post-treatment system in diesel engines for automotive and marine vehicles. The fundamentals of this work includes the theory of statistical design of reliability tests, the GBS principles, a brief description of the types and characteristics of reliability goals, the tool of Formal Safety Assessment (FSA) recommended for marítima projects, and the risk qualitative methodology based on Failure Mode Effect Analysis (FMEA). This theoretical framework was applied to two practical examples, one in the automotive industry and the other in the shipbuilding sector. The originality of this research lies in the combination of the reliability test planning techniques with the principles of GBS, in order to verify, from the whole project tests planning, the reliability goals of the basic components as a fundamental step in the assessment of system safety. The testing program can be adjusted to focus on verifying the safety goals, so that the level of knowledge about the product performance before it is delivered to the client. This work also offers the benefit of providing an easy method of system safety assessment, which allows a large number of companies to use it and to integrate it into their product development process.

Deactivation of catalysts were investigated focusing on three industrial processes: 1) Selective Catalytic Reduction (SCR) for abatement of NOx from biomass combustion using V2O5-WO3 /TiO2 catalysts; 2) Catalytic oxidation of volatile organic compounds (VOC) from printing industries using a Pt/γ-Al2O3 catalyst; and 3) Ni and Pt/Rh catalysts used in steam reforming reaction of bio-syngas obtained from biomass gasification. The aim has been to simulate industrial conditions in laboratory experiments in order to comprehend influence of compounds affecting catalysts performance. Typical catalyst lifetimes in industrial processes are several years, which are a challenge when accelerating deactivation in laboratory scale experiments where possible exposure times are few hours or days. Catalysts can be introduced to deactivating compounds through different routes. The first method examined was gaseous exposure, which was applied to deactivate VOC oxidation catalyst through exposure of gaseous hexamethyldisiloxane. The second method involved wet impregnation and was used for impregnation of SCR catalyst with salt solutions. The third method was based on exposure and deposition of size selected particles of deactivating substances on the catalyst. The latter device was developed during this work. It was applied to monolithic SCR catalysts as well as to pellet catalysts intended for steam reforming of biomass gasification syngas. Deactivated SCR catalyst samples by size selected exposure method were verified and compared with SCR catalysts used in a commercial biomass boiler for 6 500 h. Evaluations of fresh and deactivated samples were investigated using BET surface area; chemisorption and temperature programmed desorption (TPD); surface morphology using Scanning Electron Microscopy (SEM) and poison penetration profile through SEM with an Electron Micro Probe Analyser (EMPA) also equipped with a energy dispersive spectrometer (EDS); chemical analysis of accumulation of exposed compounds by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES); and influence on catalyst performance. The size selected generated particles of deactivating substances were characterized with respect to mean diameter and number size distribution through Scanning Mobility Particle Sizer (SMPS) and mass size distribution applying an Electric Low Pressure Impactor (ELPI). Results from catalyst characterization methods were useful tools in evaluation of catalyst deactivation routes. Understanding deactivation processes and impact on catalyst performance is vital for further optimization of catalysts with respect to performance and lifetime. Further research in this field can provide more resistant catalysts for application in industry leading to higher commercial benefits and further application of environmental catalysts in thermo-chemical conversion of biomass.

No description available.

This thesis describes a new concept, applicable to high-power current-sourced conversion (CSC), where a controllable firing-angle shift is introduced between series and parallel converters to enable independent active and reactive power control. The firing-shift concept solves a difficult problem, by giving thyristor based CSCs the control flexibility of pulse-width modulated (PWM) converters, but without a loss in efficiency or rating. Several configurations are developed, based on the firing-shift concept, and provide flexible, efficient solutions for both very high power HVDC transmission, and very high current industrial processes. HVDC transmission configurations are first developed for 4-quadrant high-pulse operation, based on the series connected multi-level current reinjection (MLCR) topology. Independent reactive power control between two ends of an HVDC link are proven under firing-shift control, with high-pulse operation, and without on-load tap changing (OLTC) transformers. This is followed by application of firing-shift control to a bi-directional back-to-back HVDC link connecting two weak systems to highlight the added dc voltage control flexibility of the concept. The fault recovery capability of an MLCR based ultra-HVDC (UHVDC) long distance transmis-sion scheme is also proven under firing-shift control. The scheme responds favourably to both ac disturbances and hard dc faults, without the risk of commutation failures and instability experienced during fault recovery of line-commutated conversion. The two-quadrant capability of very high current rectification is also proven with configurations based on phase-shifted 12-pulse and MLCR parallel CSCs. The elimination of the electro-mechanical OLTC/satruable reactor voltage control, the high-current CSC’s biggest shortcoming, greatly improves controllability and with firing-shift control, ensures high power-factor for all load conditions. This reduces the reactive power demands on the transmission system, which results in more efficient power delivery

La SCR (Selective Catalytic Reduction) permet de réduire les oxydes d'azote (NOx) à l'intérieur d'une ligne d'échappement d'un véhicule Diesel à l'aide d'une solution réductrice à base d'urée injectée en amont d'un catalyseur. L'urée est convertie en NH3 par pyrolyse et hydrolyse, et NH3 réduit les NOx enN2 sur le catalyseur. Cependant, comme cette technique met en jeu un ensemble de réactions très complexes, beaucoup de réactions parasites peuvent entraîner la formation de produits secondaires contenant de l'azote et perturber le bon déroulement du procédé. Par conséquent, l'élaboration d'une étude sur la mesure de ces produits secondaires et de leurs conditions de formation est donc essentielle pour la bonne calibration de la SCR. Si pour certains composés, les techniques de mesures sont encore à développer, dans tous les cas, on se trouve confronté à des problèmes liés au prélèvement des espèces. L'objectif de la thèse est d'identifier, de comprendre et de quantifier les phénomènes qui entrent en jeu et qui perturbent l'analyse des composés azotés dans la ligne d'échappement et dans la ligne de prélèvement. Le travail a été mené selon différents axes de recherche : la comparaison des méthodes de mesure de composés azotés en situation réelles dans les gaz d'échappement d'un moteur Diesel muni d'un catalyseur SCR, l'étude du prélèvement des composés azotés et notamment NH3 dans une ligne de prélèvement standard et la modélisation des pertes dans une ligne de prélèvement. A la fin de ce travail, nous avons évalué l'impact des conditions de prélèvements : température des gaz, composition et/ou longueur des lignes de prélèvement, sur les résultats de la mesure. Ce travail nous permet d'apporter des suggestions pour améliorer le prélèvement et les mesures des composés azotés présents à l'échappement d'un véhicule Diesel équipé d'une SCR.

Dans le cadre du projet FNRAE COTECH, nos travaux avaient pour objectifs d'améliorer le fonctionnement des structures électroniques à haute température d'une technologie SOI (200°C). La technologie choisie pour ce travail est une technologie de puissance intelligente comprenant une bibliothèque CMOS basse tension (5V), des transistors de puissance LDMOS (25V, 45V et 80V) et des transistors bipolaires NPN et PNP. Afin de caractériser cette technologie en température, dans un premier temps, nous avons conçu un véhicule de test en introduisant certaines règles de dessin bénéfiques pour le comportement en température, à la fois pour les composants basse et haute puissance. Nous avons également étudié une nouvelle architecture de composants combinant au sein d'un même composant un composant MOS et un composant IGBT, dans un objectif d'auto-compensation des effets négatifs de la température. Afin d'optimiser la conception de ces composants mixtes MOS-IGBT, la méthodologie que nous avons adoptée s'est appuyée sur des simulations 2D et 3D sur Sentaurus. Dans le cadre de ce travail, deux véhicules de test ont été réalisés et caractérisés. Ces structures mixtes MOS-IGBT ont été proposées en tant que structures de protection contre les décharges électrostatiques (ESD) pour remplacer une structure de protection de type "power clamp". En s'appuyant sur la simulation 3D, nous avons proposé plusieurs solutions, à la fois topologiques et d'architecture, permettant d'augmenter significativement le niveau de ce courant. Ces diverses solutions ont été validées expérimentalement. Enfin, les bonnes performances de ces structures mixtes ont motivé leur étude en tant que structures de puissance.

Dissertation (Ph.D.)--University of South Florida, 2007. / Includes vita. Includes bibliographical references. Also available online.

The master thesis deals with possibilities of utilization of conventional power plant fly ash after introduction of SNCR (Selective non-catalytic reduction) as a method of flue gas denitrification. Behaviour of fly ash containing products of denitrification, ash with water and stabilizate prepared from contaminated ash was studied. Experiments were focused on the study of various factors affecting the release of ammonia from prepared mixtures. Samples were exposed to the weather conditions to simulate deposition in addition to the laboratory experiment. Influence of the fly ash containing denitrification to mechanical properties and volume stability of pastes and mortars were also studied. The interaction of denitrification products with superplasticizers was studied on pastes. Achieved results were verified on concretes.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-05-24T12:54:55Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tese mar 1.pdf: 2548372 bytes, checksum: e5acdc58a26dcd7f9102954cb7d402dc (MD5) / Made available in DSpace on 2017-05-24T12:54:55Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Tese mar 1.pdf: 2548372 bytes, checksum: e5acdc58a26dcd7f9102954cb7d402dc (MD5) Previous issue date: 2016-06-06 / Um dos principais problemas ambientais nos países industrializados está relacionado a liberação no meio ambiente de gases formadores de chuva ácida. A quantidade desses gases lançada para atmosfera é controlada pela legislação ambiental que vem se tornando cada vez mais restritiva. Vários são os processos aplicados a indústria capazes de remover esses contaminantes de correntes advindas de processos industriais. Dentre esses, destaca-se o processo SNOX® da Haldor Topsoe®, o qual é capaz de remover NOX e SOX de efluentes gasosos industriais, visando enquadrar a concentração desses gases dentro dos parâmetros exigidos pela legislação ambiental. A remoção desses gases é realizada por um reator constituído por dois leitos catalíticos, distintos, em série. O primeiro leito catalítico é constituído por um catalisador de estrutura monolítica, nesse ocorre a reação de redução do NOX. Enquanto que, o segundo leito é constituído por um catalisador em formato de anéis de Rashig, e nesse ocorre a oxidação do SO2. Neste trabalho foi modelado e simulado o comportamento dinâmico de um reator de abatimento de emissões atmosféricas nas condições operacionais similares a um reator de uma unidade SNOX®. Cada um dos leitos catalíticos que compõem o reator foi modelado e validado separadamente. No primeiro leito além da reação de redução do NO também considerou-se a reação de oxidação do SO2, esse modelo matemático foi simulado e avaliado nas condições operacionais apresentadas em Tronconni et al. (1998). No segundo leito catalítico do reator considerou-se apenas que a reação de oxidação do SO2 acontecia no leito, o modelo matemático do leito de oxidação foi simulado e avaliado nas condições operacionais apresentadas em Almqvist et al. (2008). Ambos os modelos apresentaram bom ajuste aos dados experimentais com erros entre 2 e 11%. Com isso, os dois modelos foram acoplados num código computacional e simulados nas condições operacionais do reator SNOX® mostrado em Schoubye e Jensen (2007). O primeiro leito catalítico teve um incremento na temperatura ao longo do reator de 9°C e a conversão de NO foi de 92%, a região de entrada do primeiro leito foi a região com maior quantidade de sítios catalíticos ocupados pela amônia. Já no segundo leito catalítico a conversão do SO2 foi de 96%. Como parte do estudo de modelagem e simulação do reator, técnicas de análise de sensibilidade global foram aplicadas, determinando-se o grau de dependência de parâmetros específicos sobre: as concentrações de NO, NH3 e SO3, no primeiro leito do reator, e as concentrações de SO2 e SO3 no segundo leito. Determinou-se que dentre os parâmetros avaliados o que teve maior influência sobre as concentrações de saída de ambos os leitos foi o comprimento do leito. A partir do modelo matemático desenvolvido neste trabalho também foram gerados dados para inferir as concentrações de NO e SO3 na saída do reator, que foi realizada através de redes neurais e máquinas de vetor de suporte. Verificou-se que a performance da estimação realizada pelas redes neurais se assemelha a das máquinas de vetor de suporte. / One of the main environmental problems in industrialized countries is related to release into the forming gas environment of acid rain. The amount of greenhouse gases released into the atmosphere is controlled by the environmental legislation, that is becoming increasingly restrictive. Several processes are applied to industry to remove these contaminants from currents resulting from industrial processes. Among these, there is the SNOX® Haldor Topsoe process, which is capable of removing NOx and SOx from industrial emissions, aiming to frame the concentration of these gases within the parameters required by environmental legislation. The removal of these gases is conducted by the process reactor consisting of two catalytic beds distinct in series. The first catalyst bed has a monolithic catalyst structure, in it occurs the reduction reaction of NOx. The second bed has a catalyst with shape of cylindrical rings, in this bed occurs the oxidation of SO2. In this work was modeled and simulated the dynamic behavior of atmospheric emissions abatement reactor in similar operating conditions to a reactor of a SNOX® unit. Each of the catalyst beds, that it make up the reactor, was modeled and validated separately. In the first bed was considered the reactions of reduction of NO and oxidation of SO2, this mathematical model was simulated and evaluated in the operating conditions presented in Tronconni et al. (1998). In the second catalytic bed was considered that only the reaction of oxidation SO2 occurred in the bed, the mathematical model of the oxidation bed was simulated and evaluated in operating conditions presented in Almqvist et al. (2008). Both models showed good fit to the experimental data with error between 2-11%. Thus, the two models had been written in computer code and simulated in reactor operating conditions SNOX® shown on Schoubye and Jensen (2007). The first catalyst bed had an increase in temperature along it of 9 ° C and the conversion of NO was 92%. In the first bed, the inlet region was the region with larger amount of catalytic sites occupied by ammonia. On the second catalytic bed, the SO2 conversion was 96,6%. As part of the modeling and simulation study for reactor the global sensitivity analysis techniques were applied aiming to determine the influence of some parameters over the concentrations of NO, NH3 and SO3 in the bed of catalytic reduction of NO and the concentration SO2 and SO3 in SO2 oxidation bed. From this study it was determined that among the evaluated parameters which it had the greatest influence on the output levels of the first reactor bed was the length of this bed. From the mathematical model developed in this paper we were also generated data to infer the concentrations of NO and SO3 in the reactor outlet, which was performed by neural networks and support vector machines. It was found that the performance of infer carried out by the neural network resembles to the performance of support vector machines.

[EN] The Selective Catalytic Reduction of nitrogen oxides (SCR-NOx) is nowadays a very relevant process for reducing NOx emissions in diesel vehicles, which must comply with increasingly restrictive European regulations. In this thesis the reaction mechanism and active centers in Cu-zeolite catalysts with different structures has been investigated. For his purpose two in situ spectroscopic techniques were mainly used, being Nuclear Magnetic Resonance NMR and Electron Paramagnetic Resonance EPR, which allowed the detection of reaction intermediates and identification of Cu active species. In particular we have studied the SCR-NOx reaction using NH3 as the reducing agent and Cu-zeolites catalysts with the chabazite structure. The preliminary study of the interaction of the catalysts with NH3 has shown the formation of several Cu-NH3 complexes with different stability. At SCR typical reaction temperatures (250 ° C), ammonia forms NH4+ ions in Brønsted acids centers of the zeolite and stable Cu+-(NH3) complexes, while Cu2+ remains isolated at the 6R plane, which is precisely the active site. However, when studying species formed on Cu-zeolites in the presence of the reaction mixture NH3/NO/O2, it appears that NH4+ ions are consumed during reaction and the formation of various intermediates including nitrite/nitrate species that decompose at T > 250 ° C to the reaction products (N2 and H2O). We also investigated the mechanism of the SCR-NOx reaction using C3H8 as the reducing agent and Cu-zeolites of different topology with medium and large pore systems. The results show the formation of a hydrocarbon activated species in the Cu2+ which is related to the catalytic activity. Furthermore, isolated Cu2+ is an active site that is reduced to Cu+ during reaction, and then re-oxidized to Cu2+ in the presence of O2. Finally, the hydrothermal stability of Cu-zeolites has been studied, since it is a prerequisite for its application as SCR catalysts, comparing the very hydrothermally stable Cu-SSZ-13 zeolite and the Cu-ZSM-5 which is completely disabled after hydrothermal treatment. The findings suggest the origin of the deactivation to be a change in the coordination of isolated Cu2+ in the Cu-ZSM-5 type to form CuAlOx species which are inactive in the SCR-NOx reaction. / [ES] La Reducción Catalítica Selectiva de óxidos de nitrógeno, SCR-NOx (acrónimo del inglés Selective Catalytic Reduction of NOx) es un proceso muy importante actualmente para la reducción de las emisiones de NOx en vehículos diésel, que deben ajustarse a nuevas normativas europeas más restrictivas. En la presente tesis doctoral se ha investigado el mecanismo de reacción y los centros activos en catalizadores de Cu en zeolitas (Cu-zeolitas) con distintas estructuras. Para ello se han utilizado fundamentalmente dos técnicas espectroscópicas in situ, la resonancia magnética nuclear RMN y la resonancia paramagnética electrónica EPR, que han permitido la detección de intermedios de reacción y la identificación de especies de Cu activas. En concreto se ha estudiado la reacción SCR-NOx utilizando NH3 como reductor y catalizadores Cu-zeolitas con estructura chabazita. Los resultados obtenidos en el estudio preliminar de la interacción del catalizador con el NH3 muestran la formación de distintos complejos de Cu-NH3 con diferente estabilidad. A la temperatura de reacción (250 °C), el amoniaco forma iones NH4+ en centros ácidos Brønsted de la zeolita y complejos Cu+(NH3) estables, y el Cu2+ permanece aislado en el plano de los anillos 6R, que es precisamente el centro activo. Sin embargo, cuando se estudian las especies formadas con la mezcla de reacción NH3/NO/O2 en las Cu-zeolitas, se observa que los iones NH4+ se consumen en el transcurso de la reacción y la formación de varios intermedios incluyendo nitritos/nitratos que descomponen a T > 250 °C a los productos de reacción (N2 y H2O). También se ha investigado el mecanismo de la reacción SCR-NOx utilizando C3H8 como reductor y Cu-zeolitas de distinta topología con tamaños de poros medio y grande. Los resultados obtenidos evidencian la formación de una especie activada del hidrocarburo en el Cu2+ que está relacionada con la actividad catalítica. Además el Cu2+ aislado es un centro activo que se reduce a Cu+ en el transcurso de la reacción, y se re-oxida posteriormente a Cu2+ en presencia de O2. Finalmente, se ha estudiado la estabilidad hidrotermal de las zeolitas con cobre, puesto que es una condición indispensable para su aplicación como catalizadores SCR, comparando la zeolita Cu-SSZ-13 muy estable hidrotermalmente, y la Cu-ZSM-5 que se desactiva por completo tras el tratamiento hidrotermal. Los resultados obtenidos apuntan que el origen de la desactivación es el cambio en la coordinación del Cu2+ en la Cu-ZSM-5 para formar especies tipo CuAlOx inactivas en la reacción. / [CAT] La reducció catalítica selectiva d'òxids de nitrogen, SCR-NOx (acrònim del anglès Selective Catalytic Reduction of NOx) és un procés molt important actualment per a la disminució de les emissions de NOx en vehicles dièsel, que deuen ajustar-se a les normatives europees més restrictives. En la present tesi doctoral s'ha investigat el mecanisme de reacció i els centres actius en catalitzadors de Cu en zeolites (Cu-zeolites) amb diferents estructures. Per a dur a terme aquesta tasca s'han utilitzat fonamentalment dos tècniques espectroscòpiques in situ, la ressonància magnètica nuclear RMN i la ressonància paramagnètica electrònica EPR, les quals han permès la detecció d'intermedis de reacció i la identificació d'espècies de Cu actives. Concretament s'ha estudiat la reacció SCR-NOx emprant NH3 com a reductor i catalitzadors Cu-zeolita amb estructura chabacita. Els resultats obtinguts en l'estudi preliminar de la interacció del catalitzador amb NH3 mostren la formació de diversos complexes de Cu-NH3 amb diferent estabilitat. A la temperatura de reacció (250 °C), l'amoníac forma ions NH4+ en centres àcids Brønsted de la zeolita i complexes Cu+(NH3) estables, a més, el Cu2+ roman aïllat en el plànol dels anells 6R, que és precisament el centre actiu. No obstant, quan s'estudien les espècies formades amb la mescla de reacció, NH3/NO/O2 en les Cu-zeolites, s'observa que els ions NH4+ es consumeixen durant la reacció i la formació de diversos intermedis incloent nitrits/nitrats que descomponen, a T > 250 °C, als productes de la reacció (N2 y H2O). També s'ha estudiat el mecanisme de la reacció SCR-NOx utilitzant C3H8 com a reductor i Cu-zeolites amb diferent topologia amb mides de porus mitges i grans. Els resultats obtinguts evidencien la formació d'una espècie en forma activa del hidrocarbur al Cu2+ que està relacionada amb l'activitat catalítica. A més a més, el Cu2+ aïllat és un centre actiu que és redueix amb el transcurs de la reacció, i es re-oxida posteriorment a Cu2+ en presència de O2. Finalment, s'estudia l'estabilitat hidrotermal de les zeolites amb coure, puix que és una condició indispensable per a la seua aplicació com a catalitzadors SCR, comparant la zeolita Cu-SSZ-13 que és molt estable hidrotermalment, i Cu-ZSM-5 que es desactiva completament després del tractament hidrotermal. Els resultats obtinguts indiquen que la causa de la desactivació és el canvi en la coordinació del Cu2+ en Cu-ZSM-5 per a formar espècies tipus CuAlOx que són inactives a la reacció. / Moreno González, M. (2015). APLICACIÓN DE TÉCNICAS ESPECTROSCÓPICAS IN SITU AL ESTUDIO DE REACCIONES DE INTERÉS MEDIOAMBIENTAL: ELIMINACIÓN DE ÓXIDOS DE NITRÓGENO [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52601 / TESIS