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.

The scope of this thesis investigates value added by a turbocharger with an associated motor-generator unit to a diesel engine used by a commercial vehicle. A thermodynamic model of the engine was prepared in GT-SUITE software. Case studies were primary focused on a reduction of specific fuel consumption as well as a nitrogen oxides production using an energy recuperation of exhaust gas. Furthermore, there are described potential benefits of using an electric assistance in order to increase an exhaust gas temperature during a steady state engine operation. Additionally, there is an investigation of potential benefits of a turbocharger assistance in a transition engine mode operating during rapid acceleration of the vehicle. The results of individual analysis will be taken into account for a selection of turbocharger regarding specific engine implementation. The results of simulation suggest that it is possible to lower specific fuel consumption, production of nitrogen oxides, as well as accelerate turbocharger response.

The objective of the presented diploma thesis is reduction of nitrogen oxides from the flue gas stream on catalyst under non-standart conditions. Emphasis is places on the description of selected pollutants in flue gas (especially nitrogen oxides), legislative requirements for air protection and technologies for removal of nitrogen oxides, expecially methods of selective catalytic and non-catalytic reduction. The practical part is devoted to the reduction of nitrogen oxides by selective catalytic reduction on a pilot plant INTEQ II in the laboratory NETME Center. The subject of interest is the determination of the NOx reduction efficiency depend on the temperature for selected catalyst. The end of the practical part pursues with comparison of measurement results and their evaluation.

No description available.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24253号 / エネ博第451号 / 新制||エネ||84(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー変換科学専攻 / (主査)教授 川那辺 洋, 教授 林 潤, 教授 澄川 貴志 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Comparative studies over micro-/mesoporous Cu-containing zeolites ZSM-5 prepared by top-down treatment involving NaOH, TPAOH or mixture of NaOH/TPAOH (tetrapropylammonium hydroxide) were conducted. The results of the catalytic data revealed the highest activity of the Cu-ZSM-5 catalyst both in the absence and presence of water vapor. The physico-chemical characterization (diffuse reflectance UV-Vis (DR UV-Vis), Fourier transform infrared (FT-IR) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, temperature-programmed desorption of NOx (TPD-NOx), and microkinetic modeling) results indicated that the microporous structure of ZSM-5 effectively stabilized isolated Cu ion monomers. Besides the attempts targeted to the modification of the textural properties of the parent ZSM-5, in the next approach, we studied the effect of the co-presence of sodium and copper cations in the microporous H-ZSM-5. The presence of co-cation promoted the evolution of [Cu–O–Cu]2+ dimers that bind NOx strongly with the desorption energy barrier of least 80 kJ mol−1. Water presence in the gas phase significantly decreases the rate of ammonia oxidation, while the reaction rates and activation energies of NH3-SCR remain unaffected.

Nanosized SSZ-13 was synthesized hydrothermally by applying N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as a structure-directing agent. In the next step, the quantity of TMAdaOH in the initial synthesis mixture of SSZ-13 was reduced by half. Furthermore, we varied the sodium hydroxide concentration. After ion-exchange with copper ions (Cu2+ and Cu+), the Cu-SSZ-13 catalysts were characterized to explore their framework composition (XRD, solid-state NMR, ICP-OES), texture (N2-sorption, SEM) and acid/redox properties (FT-IR, TPR-H2, DR UV-Vis, EPR). Finally, the materials were tested in the selective catalytic reduction of NOx with ammonia (NH3-SCR). The main difference between the Cu-SSZ-13 catalysts was the number of Cu2+ in the double six-membered ring (6MRs). Such copper species contribute to a high NH3-SCR activity. Nevertheless, all materials show comparable activity in NH3-SCR up to 350 °C. Above 350 °C, NO conversion decreased for Cu-SSZ-13(2–4) due to side reaction of NH3 oxidation.

[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. / [CA] 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]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52601

Les travaux développés dans cette thèse portent sur la "co-conception diagnostic / ordonnancement des mesures dans un système contrôlé en réseau" qui est un sujet multidisciplinaire nécessitant des compétences en théorie du contrôle et en théorie des réseaux. La thèse a pour but de développer, dans le contexte des systèmes contrôlés en réseau, une approche de co-conception qui intègre de façon coordonnée les caractéristiques qui expriment la performance du diagnostic des défauts et les paramètres de l'ordonnancement temps-réel des messages. L'intérêt de cette approche coordonnée réside essentiellement dans la minimisation des ressources nécessaires pour atteindre la performance du diagnostic requise, minimisation qui prend tout son sens dans le contexte des systèmes embarqués. Nous nous sommes intéressés plus particulièrement à l'étude des problèmes liés à l'élaboration d'algorithmes de diagnostic efficaces et adaptés aux caractéristiques de l'application de façon tout en prenant en compte différents types de contraintes liées au réseau. En conjonction avec ces algorithmes, deux ensembles de techniques d'ordonnancement des mesures ont été développés : - ordonnancement hors ligne - ordonnancement évènementiel en ligne Pour l'ordonnancement hors ligne, les séquences de communication sont conçues en amont, préalablement à la mise en oeuvre de l'algorithme de diagnostic (implémentation). D'autre part, nous proposons aussi des techniques d'ordonnancement en ligne basées sur l'échantillonnage évènementiel développé au cours de la dernière décennie. Au contraire de la plupart des recherches en automatique classique, considérant que l'échantillonnage des signaux continus est réalisé d'une manière périodique, les mesures dans cette approche sont transmises si et seulement si la condition de transmission (évènement) est vérifiée / The works developed in this thesis deal with 'fault diagnosis and sensor scheduling co-design' in networked control system. This multidisciplinary subject requires theoretical knowledge in both fault diagnosis and communication networks. Our contribution consists in developing a co-design approach that integrates in the same framework the characteristics of fault diagnosis performance and real time sensor scheduling. The main benefit of this approach is minimizing the required network resources for attending acceptable fault diagnosis performances. We are interested in the development of more efficient and more adapted for real time implementation fault diagnosis algorithms while taking into account different types of communication constraints. In conjunction with these algorithms, two sets of sensor scheduling techniques are used : - Off-line scheduling - On-line scheduling (event triggered sampling) For off-line scheduling, the communication sequences are designed before the implementation of the diagnostic algorithm. In this context, we proposed several techniques for scheduling with different spatial and temporal complexity and adapted to different operating condition for the detection and the isolation of faults based on the information provided by the selected communication sequences. Moreover, we deal also with on-line scheduling techniques based on the event triggered sampling developed during the last decade. In This approach measurement packets are transmitted if and only if the transmission condition (event) is verified. This saves resources provided by the network while maintaining acceptable performance of fault diagnosis. The objective of these algorithms is to minimize the number of transmitted information which means less energy consumption and has a major importance in wireless networked control systems

In appetitive conditioning, a neutral stimulus (CS) is conditioned to elicit a positive emotional response by pairing it with a positive/appetitive unconditioned stimulus (US). This method is useful for studying emotional disorders and emotion in general. Studying appetitive conditioning in humans has been hampered by the lack of adequate positive unconditioned stimuli. This study investigated multimodal social stimuli as potential unconditioned stimuli in an appetitive conditioning paradigm. Neutral faces (CS+’giggle’ and CS+’woohoo’) were paired with two multimodal unconditioned stimuli consisting of the same smiling face and two different sound stimuli (US‘giggle’ and US‘woohoo’). The dependent variable was participant skin conductance response (SCR) alongside participant emotional ratings of the stimuli, that together indexes the conditioned response. CS+’giggle’ was hypothesized to be rated as happier, and less fearful than CS+’woohoo’. Successful conditioning was evidenced by higher happiness ratings for both stimuli after acquisition compared to habituation. However, no effect of acquisition was found on SCR.  US’woohoo’ was also rated as more fearful and arousing and less happy and pleasant than the US’giggle’. In sum, this thesis presents a paradigm that can be used in future studies on appetitive conditioning.