<div> <div> <div> <p>Commercial vehicles in the United States account for a significant fraction of greenhouse gas emissions and NOx emissions. The objectives of this work are reduction in commercial vehicle NOx emissions through enhanced aftertreatment thermal management via diesel engine variable valve actuation and the reduction of commercial vehicle fuel consumption/GHG emissions by enabling more effective class 8 truck platooning. </p> <p><br></p><p>First, a novel diesel engine aftertreatment thermal management strategy is proposed which utilizes a 2-stroke breathing variable value actuation strategy to increase the mass flow rate of exhaust gas. Experiments showed that when allowed to operate with modestly higher engine-out emissions, temperatures comparable to baseline could be achieved with a 1.75x exhaust mass flow rate, which could be beneficial for heating the SCR catalyst in a cold-start scenario. </p> <p><br></p><p>Second, a methodology is presented for characterizing aerodynamic drag coefficients of platooning trucks using experimental track-test data, which allowed for the development of high-fidelity platoon simulations and thereby enabled rapid development of advanced platoon controllers. Single truck and platoon drag coefficients were calculated for late model year Peterbilt 579’s based on experimental data collected during J1321 fuel economy tests for a two-truck platoon at 65 mph with a 55’ truck gap. Results show drag coefficients of 0.53, 0.50, and 0.45 for a single truck, a platoon front truck, and a platoon rear truck, respectively. </p> <p><br></p><p>Finally, a PID-based platoon controller is presented for maximizing fuel savings and gap control on hilly terrain using a dynamically-variable platoon gap. The controller was vetted in simulation and demonstrated on a vehicle in closed-course functionality testing. Simulations show that the controller is capable of 6-9% rear truck fuel savings on a heavily-graded route compared to a production-intent platoon controller, while increasing control over the truck gap to discourage other vehicles from cutting in. </p></div></div></div>

In der vorliegenden Arbeit werden Al2O3-geträgerte Eisenoxid-Katalysatoren auf ihre Eignung in der Nachbehandlung von Dieselabgasen getestet. Hierbei werden die Oxidationsreaktionen von Kohlenmonoxid, Propen, Stickstoffmonoxid sowie Ammoniak getestet. Weiterhin wird die Katalysatoraktivität bei der Stickoxidminderung nach dem SCR-Verfahren untersucht. Basierend auf einer detaillierten Charakterisierung wird eine Struktur-Aktivitäts-Korrelation entwickelt, auf deren Basis ein Verständnis für die Art der aktiven Zentren solcher Katalysatoren generiert wird. Zudem wird ein Modell entwickelt, mit Hilfe dessen die spezifische Aktivität der verschiedenen Typen an aktiven Zentren bewertet werden kann. Darüber hinaus wird in dieser Arbeit auf die Stickoxidminderung nach dem SCR-Verfahren fokussiert, was die Untersuchungen des Reaktionsmechanismus sowie die Struktur-Aktivitäts-Korrelation an hydrothermal gealterten Katalysatoren beinhaltet.

This thesis aims at developing a method of chemical aftertreatment for reduction of free formaldehyde release of a tetrakis (hydroxymethyl) phosphonium chloride (THPC) urea precondensate, ammonia cured durable flame retardant finished cotton fabric, by preventing the formation of free formaldehyde. Formaldehyde is toxic and carcinogenic. According to the worldwide standards, acceptable limit of free formaldehyde release, for the fabrics that have skin contact, is only 75 ppm (measured by water extraction method). In this research, a cotton fabric flame retardant finished in an industrial plant in Pakistan is used. Fabric is finished by the application of THPC urea precondensate and ammonia cured, oxidized and washed. After finishing, it is not aftertreated with sodium metabisulfite that is a commonly used aftertreatment method for the reduction of free formaldehyde release. Aftertreatment with sodium metabisulfite has various problems that include large number of hot washings and there is an increase in the formaldehyde release during fabric storage. If the fabric has 75 ppm of free formaldehyde, there is often an increase in free formaldehyde release during fabric storage. There is a very limited research on the aftertreatment methods and few reports of application of these aftertreatments on flame retardant fabrics have been published. In this research, two methods of aftertreatments are developed to reduce the free formaldehyde contents to 75 ppm or less. One is the aftertreatment with a combination of resorcinol 1% and diethylene glycol 4%. The other is the combination of resorcinol 1% and boric acid 6%. For both these aftertreatments, ammonium acetate 0.5% is used as a catalyst. Fabric is padded with the solution and then dried at 130̊ C for 8 minutes. After drying, fabric is rinsed with water at 40̊ C. The aftertreatment methods developed in this research have shown a long term effect in keeping the formaldehyde release below 75 ppm during fabric storage that is not available with other conventional aftertreatment methods. These aftertreatment methods have no adverse effect on the flame retardancy of the THPC ammonia cured finished fabric and the fabric is soft as compared to the original flame retardant finished fabric and to the fabric after treated with existing methods. These new developed methods have industrial application because there is no use of any solvent and there is no use of any special equipment for the aftertreatment.

In an effort to reduce harmful pollutants emitted by medium and heavy duty diesel engines, stringent emission regulations have been imposed by the Environmental Protection Agency (EPA) and the California Air Resources Board (CARB). Effective aftertreatment thermal management is critical for controlling tail pipe outlevels of NOx and soot, while improved fuel efficiency is also necessary to meet greenhouse gas emissions standards and customer expectations. Engine manufacturers have developed and implemented several engine and non-engine based techniques for emission reduction, a few examples being: exhaust gas recirculation (EGR), use of delayed in-cylinder injections, exhaust throttling, electric heaters and hydrocarbon dosers. This work elaborates the use of variable valve actuation strategies for improved aftertreatment system (ATS) thermal management of a modern medium-duty diesel engine while presenting opportunities for simplification of engine air handling architecture.<div><br></div><div>Experimental results at curb idle demonstrate that exhaust valve profile modulation enables effective ATS warm-up without requiring exhaust manifold pressure (EMP) control. Early exhaust valve opening with internal exhaust gas recirculation (EEVO+iEGR) resulted in 8% lower fuel consumption and reduction in engine out emissions. Late exhaust valve opening with internal EGR in the absence of EMP control was able to reach exhaust temperature of 287^◦C, without a penalty in fuel consumption or emissions compared to conventional thermal management. LEVO combined with EMP control could reach turbine outlet temperature of nearly 460^◦C at curb idle.<br></div><div><br></div><div>LEVO was studied at higher speeds and loads to assess thermal management benefits of LEVO in the absence of EMP control, with an observation that LEVO can maintain desirable thermal management performance up to certain speed/load conditions, and reduction in exhaust flow rate is observed at higher loads due to the inability of LEVO to compensate for loss of boost associated with absence of EMP control.<br></div><div><br></div><div>Cylinder deactivation (CDA) combined with additional valvetrain flexibility results in low emission, fuel-efficient solutions to maintain temperatures of a warmed-up ATS. Late intake valve closing, internal EGR and early exhaust valve opening were studied with both three cylinder and two cylinder operation. Some of these strategies showed additional benefits such as ability to use earlier injections, elimination of external EGR and operation in the absence of exhaust manifold pressure control. Three cylinder operation with LIVC and iEGR is capable of reaching exhaust temperatures in excess of 230^◦C with atleast 9% lower fuel consumption than three cylinder operation without VVA. Three cylinder operation with early exhaust valve opening resulted in exhaust temperature of nearly 340^◦C, suitable for extended idling operation. Two cylinder operation with and without the use of valve train flexibility also resulted in turbine outlet temperature relevant for extended idling (and low load operation), while reducing fuel consumption by 40% compared to the conventional thermal management strategy.<br></div><div><br></div><div>A study comparing the relative merits of internal EGR via reinduction and negative valve overlap (NVO) is presented in order to assess trade-offs between fuel efficient stay-warm operation and engine out emissions. This study develops an understanding of the optimal valve profiles for achieving reinduction/NVO and presents VVA strategies that are not cylinder deactivation based for fuel efficient stay-warm operation. Internal EGR via reinduction is demonstrated to be a more fuel efficient strategy for ATS stay-warm. An analysis of in-cylinder content shows that NOx emissions are more strongly affected by in-cylinder O2 content than by method of internal EGR.<br></div>

Le secteur du transport joue un rôle majeur dans le changement climatique et la pollution atmosphérique. Parmi les secteurs d'origine anthropique, le transport routier est considéré comme le premier contributeur au réchauffement climatique, due notamment aux émissions de CO2, de précurseurs d'ozone, et d'aérosols carbonés (carbone noir). De plus, les émissions liées au transport routier telles que les oxydes d'azote (NOx), l'ammoniac (NH3), les carbonyles volatiles, les hydrocarbures gazeux, et les aérosols, contribuent à la dégradation de la qualité de l'air.Le but de cette étude était d'approfondir l'état des connaissances en termes de facteurs d'émissions associés au transport, pour les polluants en phases gazeuse et solide. Un intérêt particulier a été apporté sur l'influence des systèmes de post-traitement des gaz d'échappement, et de la qualité du carburant, sur les émissions d'espèces réglementées et non-réglementées. Des campagnes de mesure ont été menées sur différentes catégories de véhicules dans le laboratoire d'étude des émissions (VELA) du centre commun de recherche de la commission Européenne (JRC-EC) à Ispra, en Italie. La flotte de véhicules choisie comprenait des camions (moyens et poids lourds), des voitures et des deux-roues formant un ensemble représentatif des véhicules circulant en Europe. En plus des carburants classiques, essence et diesel, les véhicules ont été alimentés avec des carburants alternatifs tels que le bioéthanol, et le gaz de pétrole liquéfié. Les émissions en phase gazeuse ont été mesurées par spectroscopie infra-rouge à transformé de Fourier (FT-IR; pour les composés azotés, les carbonyles volatiles et les petits hydrocarbures), par spectrométrie de masse à temps de vol après ionisation multi-photonique résonnante (REMPI-ToF-MS; pour les hydrocarbures aromatiques mono et polycycliques), par spectromètrie de masse haute résolution à temps de vol dédié à l'analyse des aérosols atmosphériques (HR-TOF-AMS; pour les aérosols organiques), et par photométrie d'absorption multi-angle (MAAP; pour le carbone élémentaire).Parmi les véhicules étudiés, les scooters ont été les plus gros émetteurs d'aérosols organiques primaires et d'hydrocarbures mono et polycycliques. De plus, le système de post-traitement des gaz d'échappement étudié pour le scooter le plus récent (conforme à la réglementation Euro 2) pourrait être responsable d'émissions importantes d'aérosols organiques. Concernant les voitures, et en particulier celles équipées de moteurs à allumage par étincelle, la plupart de leurs émissions intervenaient en début de cycle, avant que la température d'amorçage du pot catalytique soit atteinte. Ces émissions liées au démarrage à froid du véhicule pouvaient masquer les effets bénéfiques des carburants alternatifs en terme d'émissions de précurseurs d'ozone. Finalement, les camions étaient les plus gros émetteurs de suie (carbone élémentaire) et de NOx. Malgré le fait que plusieurs systèmes de retrofit se sont montrés particulièrement efficaces pour réduire les émissions des polluants réglementés (particules et NOx) de ces véhicules, certains d'entre eux produisaient des quantités significatives de NH3. Ce projet a permis de collecter des informations précieuses pour l'élaboration de la législation relative au développement d'un transport durable en Europe. / Transport sector plays a key role in global warming and air pollution. Among the anthropogenic sectors, on-road transport is recognized as the first contributor to global warming, mainly due to its emission of carbon dioxide, ozone precursors and carbonaceous aerosols. In addition, on-road transport contributes to the deterioration of air quality by releasing nitrogen oxides, ammonia, carbonyls, hydrocarbons and aerosols. However, the current European legislation of vehicles emissions focusses on a limited number of pollutants, namely hydrocarbons, carbon monoxide, nitrogen oxides, and particulate matter.The aim of this work was to improve the knowledge about the emission factors of gas phase and particle-associated emissions from vehicle exhaust. The impacts of aftertreatment devices and fuel quality on regulated and unregulated species were studied. Several sampling campaigns with different types of vehicles were conducted in the vehicle emission laboratory (VELA) at the European Commission Joint Research Centre (EC-JRC) Ispra, Italy. The vehicles chosen were representative of some categories circulating in Europe (heavy duty vehicles, light duty vehicles, two-stroke mopeds), and either standard fuel or some alternative fuels (ethanol and liquefied petroleum gas) were used. The gas phase was monitored by a Fourier transform infrared spectrometer (carbonyls, nitrogen-containing species, small hydrocarbons), and a resonance-enhanced multiphoton ionization time-of-flight mass spectrometer (mono and polycyclic aromatic hydrocarbons). The particulate phase was analyzed by a high-resolution time-of-flight aerosol mass spectrometer (organic aerosol, chloride, nitrate), and a multiangle absorption photometer (black carbon). The mopeds were found to have the higher emission factors of primary organic aerosol and polycyclic aromatic hydrocarbons. While efficient to reduce the regulated emissions, the after-treatment used to comply with the moped Euro 2 emission standard might be responsible of large emission of unregulated organic aerosols. Most of the emission linked to the gasoline light duty vehicles were released before the light-off of the catalyst. Whereas alternative fuels studied helped to reduce ozone precursor emissions, the emissions associated to the cold start of the vehicle reduced this beneficial effect. Finally, the heavy duty diesel vehicle featured the highest NOx and black carbon emissions. Despite efficient retrofit and after-treatment systems (for particles and NOx), these vehicles could release significant amount of NH3. These results provided valuable insights for the drafting of legislation related to the achievement of sustainable transport in Europe.

<p>Diesel engines emit toxic gases like NOx and hydrocarbons. These gases need to be treated before they are released out the tailpipe. Thus, an aftertreatment system is installed which comprises of DOC, DPF and SCR. The DOC oxidizes the hydrocarbons and NO, the DPF traps the particulate matter and SCR reduces the NOx by reacting with NH3 at high temperatures. However, since NH3 is also a toxic gas, it cannot be released out the tailpipe in excess. It is important to inject an appropriate amount of NH3 so that it does not slip out the tailpipe. With increasingly stringent regulations on the emission limits of these toxic gases, control of SCR has become more necessary than before.</p> <p>In this thesis, the work done by previous members of the lab research group was improved upon. The objective remained the same, namely, keeping the NH3 slip under 50 ppm while maximizing NOx reduction. On initial inspection, it was realized that the entire controller had been designed and implemented in continuous time. Since the controller would be implemented digitally, with limited hardware sampling time, a discrete-time implementation as done via a DCU was created. The controller switched between two controllers – slip-based and storage-based. The slip-based controller was modified to include a feedforward term in the system so that the response time could be improved along with a feedback controller to eliminate any disturbances and steady-state error, using ammonia slip feedback as measured by an NH3 sensor. It aims at keeping the maximum ammonia slip under 50 ppm. The storage controller is a feedback controller which tries to limit the ammonia storage based on the values fed by a lookup table. This lookup table is a simplified table that determines the maximum ammonia storage at any given instant based on the catalyst bed temperature. The feedback controller gains for both controllers were determined based on a linearized plant model since the initial gains were ineffective with the discretized model. The initial switching mode controller that switches between slip control and storage control switched too frequently between the controllers, thereby affecting controller performance. A switching logic was implemented to limit the number of switches. A switch will be permitted only if the previous switch occurred over a certain time. By implementing all the subparts together in the controller, incremental improvements were prominent. In the end, the performance by implementing the proposed idea was distinctly better. The metrics considered for performance comparison are the number of switches and the ability to maximize slip up to 50 ppm. Parameter error was also studied as well and its effect on the controller performance was analyzed. The data when tested against sets of underestimated, overestimated and mixed estimates for the plant parameters resulted in the underestimated parameters to work within the scope of the objective. The controller was able to compensate for the underdosing. Overestimation caused overdosing in the system which led to spikes in the NH3 slip. Thus, it is better to underestimate the plant parameters than overestimate them.</p>

[ES] El carácter cada vez más estricto de las normativas de emisiones ha provocado el desarrollo de motores de combustión más respetuosos con el medioambiente. La última normativa europea aplicada al sector del transporte ha ampliado el rango de condiciones de operación en el que se realizan las pruebas de homologación. Las variables de temperatura ambiente y altitud de conducción son ahora requisitos adicionales que deben tenerse en cuenta con la intención de reducir la diferencia entre el resultado de esas pruebas y en condiciones de conducción real. La comprensión del impacto de las condiciones ambientales sobre el funcionamiento del motor es algo fundamental para superar los inconvenientes que pueden representar la respuesta del motor y teniendo un gran impacto sobre las emisiones del mismo. Como consecuencia de la variación de la altitud y de la temperatura ambiente, las condiciones de contorno de los sistemas de postratamiento de los gases de escape (EATS) se modifican, comprometiendo su funcionamiento y repercutiendo en las emisiones liberadas a la atmosfera. En el caso concreto de los motores Diesel, los dos EATS más comunes son el catalizador de oxidación diesel (DOC) y el filtro de partículas diesel (DPF). En este contexto, la presente tesis doctoral propone diferentes enfoques a fin de comprender los principales efectos que las condiciones ambientales extremas provocan en el motor y en el funcionamiento del DOC y del DPF. Una parte importante de este trabajo ha consistido en la puesta en marcha de un banco de pruebas experimental equipado con un simulador de altitud y de una herramienta de modelización termo fluidodinámica unidimensional (1D) para un amplio análisis. Tras los resultados experimentales en condiciones de estado estacionario a baja temperatura, los mapas de contorno de las emisiones de CO y HC condujeron a la evaluación como las condiciones ambientales extremas repercuten en la temperatura de activación del DOC y en la eficiencia de conversión de las emisiones contaminantes. El análisis computacinal ayudó a elaborar directrices que determinan la contribución de las propiedades del flujo causadas por dichas condiciones. Asimismo, se ha abordado el efecto de la aplicación de soluciones computacionales de aislamiento térmico del escape sobre el DOC y la respuesta del motor. Por otro lado, se ha realizado experimentalmente la actuación de la turbina de geometría variable (VGT) sobre el proceso de regeneración del DPF. El impacto que la estrategia de presión de sobrealimentación tiene sobre la tasa de consumo de hollín durante la regeneración activa en función de la altitud de conducción se considera con la orientación de las herramientas de modelado. La discusión de la reducción de la tasa de regeneración en altitud con las estrategias de sobrealimentación estándar ha conducido a la reevaluación de la actuación de la de la turbina de geometría variable (VGT) para condiciones de altitud extrema. Por último, se ha analizado experimentalmente la sensibilidad de la posición del VGT y la tasa de EGR de baja presión (LP-EGR) sobre el comportamiento del motor a cargas parciales en un amplio rango de condiciones ambientales. Los resultados han conducido a la redefinición de la calibración del motor a fin de aumentar la temperatura de entrada del EATS al tiempo que se reduce el consumo específico de combustible. / [CA] El caràcter cada vegada més estricte de les normatives d'emissions ha provocat el desenvolupament de motors de combustió més respectuosos amb el medi ambient. L'última normativa europea aplicada al sector del transport ha ampliat el rang de condicions d'operació en el qual es realitzen les proves d'homologació. Les variables de temperatura ambient i altitud de conducció són ara requisits addicionals que han de tindre's en compte amb la intenció de reduir la diferència entre el resultat d'aqueixes proves i en condicions de conducció real. La comprensió de l'impacte de les condicions ambientals en el compliment de la normativa pel motor es fonamental per a superar els inconvenients que poden representar per a la resposta del motor amb un ampli impacte en les emissions d'aquest. A conseqüència de la variació de l'altitud o de la temperatura ambient, els límits dels sistemes de posttractament dels gasos de fuita (EATS) es modifiquen, comprometent el seu funcionament i repercutint en les emissions alliberades a la atmosfera. En el cas concret dels motors Dièsel, els dos EATS més comuns són el catalitzador d'oxidació dièsel (DOC) i el filtre de partícules dièsel (DPF). En aquest context, aquesta tesi doctoral proposa diferents enfocaments per a entendre els principals factors que les condicions ambientals extremes imposen al motor i al funcionament del DOC i del DPF. Una part important d'aquest treball ha consistit en la posada en marxa d'un banc de proves experimental equipat amb un simulador d'altitud i d'una eina de modelització termo fluidodinámica unidimensional (1D) per a una ampla anàlisi. Després dels resultats experimentals en condicions d'estat estacionari a baixa temperatura, els mapes de contorn de les emissions de CO i HC ha conduí a l'avaluació de com les condicions ambientals extremes repercuteixen en la temperatura d'activació del DOC i en l'eficiència de conversió de les emissions contaminants. L'anàlisi computacinal ha ajudat a elaborar directrius que determinen la contribució de les propietats del flux causades per aquestes condicions. Així mateix, l'efecte de l'aplicació de solucions d'aïllament tèrmic del tubo d'escapament sobre el DOC i la resposta del motor. D'altra banda, s'ha realitzat experimentalment l'actuació de la turbina de geometria variable (VGT) sobre el procés de regeneració del DPF. L'impacte que l'estratègia de pressió de sobrealimentació té sobre la taxa de consum de sutge durant la regeneració activa en funció de l'altitud de conducció es considera amb l'orientació de les eines de modelatge. La discussió de la reducció de la taxa de regeneració en altitud amb les estratègies de sobrealimentació estàndard ha conduït a la reavaluació de l'actuació de la de la turbina de geometria variable (VGT) per a condicions d'altitud extrema. Finalment, s'ha analitzat experimentalment la sensibilitat de la posició del VGT i la taxa de EGR de baixa pressió (LP-EGR) sobre el comportament del motor a càrregues parcials en un ampli rang de condicions ambientals. Els resultats han conduït a la redefinició del calibratge del motor a fi d'augmentar la temperatura d'entrada del EATS al mateix temps que es redueix el consum específic de combustible. / [EN] The increasingly stringent emission standards act as a guide for the development of cleaner vehicles in a context of climate change. The latest European regulations applied to the transportation sector widened the operation range where homologation tests are carried out. The variables of ambient temperature and driving altitude are now extra requirements that must be considered in a way to shorten the gap between those tests and real driving. The understanding of the ambient conditions impact on the engine response becomes fundamental to overcome the drawbacks represented by them, being determinant for the engine response with an extended impact on engine-out emissions. As a consequence of altitude or ambient temperature variation, the exhaust aftertreatment systems (EATS) boundaries are modified, compromising their operation and impacting on tailpipe emissions. In the specific case of Diesel engines, the two most common EATS are the diesel oxidation catalyst (DOC) and the diesel particulate filter (DPF). In this context, this doctoral thesis proposes different approaches to understand the main factors that extreme ambient conditions impose to the engine and to the DOC and DPF operation. An important part of this work consisted of the set up of an experimental test bench equipped with an altitude simulator and of a one-dimensional (1D) thermo-fluid dynamic modelling tool for a wide-ranging analysis. Following low temperature steady state conditions experimental outcomes, CO and HC emission contour maps led to the evaluation of how extreme ambient conditions impact on the DOC light-off and pollutant emissions conversion efficiency. The modelling analysis helped to build guidelines that determine the contribution of the flow properties caused by such conditions. Besides, the effect of applying computational exhaust line thermal insulation solutions on the DOC and engine response is additionally addressed. On the other hand, the variable geometry turbine (VGT) actuation on the DPF regeneration process is performed experimentally. The impact that the boost pressure strategy has on the rate of soot depletion during active regeneration as a function of the driving altitude is considered with the guidance of the modelling tools. The reduction of the regeneration rate in altitude with standard boosting strategies is discussed, leading to the re-evaluation of the VGT actuation for high altitude practices. Finally, the sensitivity of the VGT position and low pressure exhaust gases recirculation (LP-EGR) rate at a vast array of ambient conditions is experimentally analysed for regular engine operation at partial loads. The results led to the engine calibration redefinition based on EATS inlet temperature increase and the reduction of the specific fuel consumption. / Diesel Costa, B. (2022). Advancement in Understanding the Extreme Altitude and Ambient Temperature Impact on Diesel Engine and Aftertreatment Performance [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/181715

The scope of this dissertation work is a description of modern methods of reducing exhaust emission in diesel engines. The fundamental part is the application of these methods for diesel engines for off-road use that means for engines that are used in tractors and road machines. The mentioned evidence for the practical utility of the results of this dissertation thesis in practice and their verification on the actual engine are given in the conclusion.

In der vorliegenden Arbeit werden Al2O3-geträgerte Eisenoxid-Katalysatoren auf ihre Eignung in der Nachbehandlung von Dieselabgasen getestet. Hierbei werden die Oxidationsreaktionen von Kohlenmonoxid, Propen, Stickstoffmonoxid sowie Ammoniak getestet. Weiterhin wird die Katalysatoraktivität bei der Stickoxidminderung nach dem SCR-Verfahren untersucht. Basierend auf einer detaillierten Charakterisierung wird eine Struktur-Aktivitäts-Korrelation entwickelt, auf deren Basis ein Verständnis für die Art der aktiven Zentren solcher Katalysatoren generiert wird. Zudem wird ein Modell entwickelt, mit Hilfe dessen die spezifische Aktivität der verschiedenen Typen an aktiven Zentren bewertet werden kann. Darüber hinaus wird in dieser Arbeit auf die Stickoxidminderung nach dem SCR-Verfahren fokussiert, was die Untersuchungen des Reaktionsmechanismus sowie die Struktur-Aktivitäts-Korrelation an hydrothermal gealterten Katalysatoren beinhaltet.:Inhalt 1. Einleitung 2. Aufgabenstellung 3. Grundlagen 3.1 Schadstoffbildung bei der Verbrennung fossiler Energieträger 3.2 Verfahren zur Schadstoffminderung bei Kraftfahrzeugen 3.3 Aktueller Stand der Entwicklung edelmetallfreier Katalysatoren für die dieselmotorische Abgasnachbehandlung 4. Verwendete Analysemethoden und Aufbau der Laborapparaturen 4.1 Untersuchungen zur Struktur der Katalysatoren 4.1.1 Stickstoff-Physisorption 4.1.2 Temperaturprogrammierte Experimente 4.1.3 Röntgendiffraktometrie 4.1.4 DRUV/VIS-Spektroskopie 4.1.5 Diffuse Reflexions-Infrarot-Fourier-Transformations-Spektroskopie 4.1.6 Transmissionselektronenmikroskopie 4.1.7 Mößbauer-Spektroskopie 4.1.8 Raman-Spektroskopie 4.2 Untersuchungen zur Analyse von Gasen 4.2.1 Fourier-Transform-Infrarotspektroskopie (FTIR) 4.2.2 Massenspektrometrie 4.3 Aufbau der Laborapparaturen 4.3.1 Laborapparatur für Aktivitätsmessungen sowie für temperaturprogrammierte Experimente 4.3.2 Laborapparatur zur Durchführung von DRIFTS-Experimenten 5 Experimentelle Ergebnisse 5.1 Katalysatorpräparation 5.2 Charakterisierung der frischen Katalysatoren 5.3 Charakterisierung der hydrothermal gealterten Katalysatoren 5.4 Aktivitätsmessungen 5.4.1 Oxidation von Kohlenmonoxid 5.4.2 Oxidation von Propen 5.4.3 Oxidation von Stickstoffmonoxid 5.4.4 Oxidation von Ammoniak 5.5 Untersuchungen zur Standard-SCR-Reaktion 5.5.1 Aktivitätsuntersuchung an frischen Katalysatoren 5.5.2 Aktivitätsuntersuchung an hydrothermal gealterten Katalysatoren 5.5.3 Untersuchungen zum Mechanismus der SCR-Reaktion 6. Diskussion der Ergebnisse 6.1 Struktur-Aktivitäts-Beziehung der FexO/Al2O3-Katalysatoren 6.1.1 Struktur der Eisenoxidspezies 6.1.2 Quantifizierung der Eisenoxidspezies 6.1.3 Modell zur Berechnung der spezifischen Aktivität der Katalysatoren 6.1.4 Sensitivitätsanalyse des entwickelten Modells 6.1.5 Anwendung des Modells bei der Oxidation von CO, C3H6, NO und NH3 6.1.6 Struktur-Aktivitäts-Beziehung der FeOx/Al2O3-Katalysatoren bei der Oxidation von CO, C3H6, NO und NH3 6.2 Evaluation der SCR-Aktivität der FeOx/Al2O3-Katalysatoren 6.2.1 Untersuchungen an frischen Katalysatoren 6.2.2 Einfluss der hydrothermalen Alterung auf die Katalysatorstruktur und -aktivität bei der Standard-SCR-Reaktion 6.3 Mechanismus der Standard-SCR-Reaktion an FeOx/Al2O3-Katalysatoren 7. Ausblick 8. Literaturverzeichnis 9. Anhang

In dieser Dissertation werden Methoden entwickelt, die die Beschreibung der Katalysatoralterung verbessern. Der Fokus liegt hierbei auf der Realalterung in Pkws und Lkws. Die ständig wechselnden Bedingungen im realen Einsatz stellen dabei eine besondere Herausforderung dar. Es wird ein physikalisches Modell entwickelt, das das Wachstum der Edelmetall-Kristallite im Washcoat beschreibt. Anhand der Kristallitgröße wird die katalytische Restaktivität des Katalysators bestimmt. Das Modell kann die Konvertierungsleistung der wesentlichen gasförmigen Schadstoffe CO, HC und sogar NOx berechnen. Es arbeitet vollumfänglich unter stationären thermischen Bedingungen einer Ofenalterung. Weitere Tests könnten es auch zur Anwendung für thermische Realalterung zulassen. Als weitere Methode wird eine empirische Korrelation entwickelt, die die Temperaturbelastung der Katalysatoren kategorisiert und diese damit hinsichtlich ihrer thermischen Realalterung zueinander einordnet. Die thermische Realalterung wird an Diesel-Oxidations-Katalysatoren (DOC) untersucht, die aus einer Edelmetall-Legierung aus Platin und Palladium bestehen. Hinsichtlich der chemischen Realalterung wird eine Diesel-AGN auf ihre Empfindlichkeit gegenüber Ablagerungen und Deaktivierung durch ungerafften Betrieb mit reinem Biodiesel untersucht. Der Biodiesel drängt sich hier in den Fokus, da in diesem, im Vergleich zu fossilem Diesel, deutlich mehr Vergiftungselemente enthalten sein können. / The combustion engine is a very important drive system. An exhaust-aftertreatment system (ATS) is widely mandatory for exhaust-gas purifcation, but the contained catalysts suffer from deactivation by aging effects. To handle the catalyst aging, its description is very significant. This PhD thesis develops two methods to improve the description of thermal real-world aging. The diesel-oxidation-catalyst (DOC) executes crucial conversion-reactions with platinum and palladium as precious metals. They are spread as small particles across the washcoat. Thermal catalyst aging is driven by temperature stress, duration and exhaust-gas atmosphere. It is irreversible and usually the dominating aging-type. Main path of the thermal aging is the precious-metal sintering, at which small precious-metal particles agglomerate to bigger ones. As result the access of the exhaust-gas to the catalyst detoriates, what leads to a deactivation. Chemical catalyst aging originates from negative effect of catalyst poisons and exhibits a very individual behaviour. The developed physical crystallite-size model calculates in its 'base version' the conversion of a catalyst after oven-aging. Input is an arbitrary oven-aging scenario to calculate the resulting crystallite-size and finally to conclude to the catalytic activity. This is possible for every species, thus CO, HC and even NO. Thereby, thermal oven-aging is described by a physical parameter. Furthermore, it is to mention, that the correlation between crystallite size and conversion is explicit for all species. The model is developed at an Pt/Pd-DOC and therefore it is expected, that general catalysts, with and without precious-metal alloys, can be described. The crystallite-size provides also the advantage, that it is independent from chemical aging. So a closed look on thermal aging is possible. The 'base version' of the model can be used in research and development as well for post-mortem analysis. The enhancement of the physical crystallite-size model could allow the description of thermal real-world aging. Input is an inconstant temperature-run for the calculation of the resulting crystallite-size to conclude again to the remaining catalytic activity. A confirmation is not possible with the available data, also the potential of the enhancement cannot be proved. But if the confirmation could get achived, for completely arbitrary thermal real-world aging scenarios the calculation of the conversion for every species would be possible. The field of application would be research and development, on-board operation as well as post-mortem analysis. The developed empirical correlation for real-world aging uses as input inconstant temperatureruns of several DOCs. They are treated by a combination and ranking system. Finally the method outputs a ranking, which represents the remaining catalytic activity. Thereby, the result for the DOCs is qualitative and relative to each other. The available seven real-world aged Pt/Pd-DOCs can get sorted completely correct by the method. The field of application is research and development, on-board operation as well as post-mortem analysis. The chemical real-world aging gets investigated by three ATS, which are driven with DIN EN 14214 biodiesel. Phosphorus and calcium indicate a B100 influence for accumulation. B100 operation clearly causes catalytic deactivation. The activity of the samples at the DOC-outlet correlates with the P+Ca accumulation. But this is not valid for the samples at the DOC-inlet.