Modelling, control and diagnosis of aftertreatment systems based on three-way catalyst in spark-ignited engines

[ES] A pesar de la tendencia actual hacia la electrificación del transporte por carretera, los motores de combustión interna alternativos han sido esenciales en este sector y se espera que sigan siendo una tecnología con notable presencia durante las próximas décadas. Los vehículos de pasajeros actuales basados en motores de combustión interna son más ecológicos que los utilizados hace años, aunque todavía queda trabajo por hacer. Los sistemas de postratamiento están enfocados a minimizar tanto como sea posible el impacto de los motores de combustión interna en términos de emisiones contaminantes. En el caso de los motores de encendido provocado, los catalizadores de tres vías representan la tecnología más extendida en las últimas décadas, debido a su compacidad y buena relación precio-prestaciones. Estos convertidores son capaces de oxidar hidrocarburos y monóxido de carbono al mismo tiempo que reducen los óxidos de nitrógeno. No obstante, para lograr su mejor eficiencia, el dosado debe controlarse con precisión en torno a condiciones estequiométricas. En este sentido, los sistemas electrónicos de gestión del motor son esenciales para aprovechar las características de estos convertidores. En particular, las estrategias de control y diagnóstico desempeñan un papel clave para lograr una reducción efectiva de las emisiones en el amplio rango de condiciones de operación que se dan en condiciones de funcionamiento reales. El desarrollo de estas estrategias es fundamental, especialmente teniendo en cuenta el bajo nivel de emisiones permitido por las normativas de emisiones actuales y la tendencia hacia cero emisiones. El propósito de esta tesis doctoral es analizar el comportamiento del sistema de postratamiento en condiciones específicas pero a la vez muy comunes en conducción real, y desarrollar estrategias que proporcionen una reducción adicional de las emisiones en sistemas basados en catalizador de tres vías. Con la popularización de pequeños motores turboalimentados de encendido provocado, ha aumentado el uso de estrategias de barrido de la cámara de combustión para mitigar los típicos problemas de falta de par a bajo régimen. Esta tesis analiza el impacto de los pulsos de cortocircuito en el catalizador y en las sondas ¿. El proceso de cortocircuito de aire fresco al escape tiene un impacto importante en la dinámica intraciclo de la composición de los gases de escape. En particular, los pulsos de monóxido de carbono e hidrógeno seguidos por los pulsos de aire fresco perturban el normal funcionamiento del sensor de oxígeno. Por lo tanto, se ha propuesto un nuevo método para estimar la tasa de cortocircuito abordo. Este método permite corregir la desviación sufrida por el sensor y, por lo tanto, ayuda a reducir la penalización en emisiones de este tipo de estrategias. Para mejorar la eficiencia del catalizador en condiciones transitorias, no solo se requiere un control preciso del dosado aguas arriba del catalizador, sino que también resulta imprescindible considerar el comportamiento dinámico del convertidor en sí mismo. Por ejemplo, el almacenamiento de oxígeno es un buen indicador del estado del catalizador, pero no se puede medir directamente mediante sensores. Por lo tanto, el desarrollo de modelos es clave en las estrategias de control actuales, para poder estimar abordo diferentes parámetros relacionados con el estado del catalizador. Varios modelos de catalizador se han desarrollado en esta tesis doctoral para lidiar con diferentes cuestiones, desde la predicción de los efectos de la condensación de agua en la evolución de la temperatura del catalizador justo después del arranque en frío, a la cuantificación del nivel de envejecimiento, pasando por el control óptimo de purga del catalizador.[CA] Malgrat la tendència actual cap a l'electrificació del transport per carretera, els motors de combustió interna alternatius han sigut essencials en aquest sector i s'espera que continuen sent una tecnologia amb notable presència durant les pròximes dècades. Els vehicles de passatgers actuals basats en motors de combustió interna són més ecològics que els utilitzats fa anys, encara que hi ha treball per fer. Els sistemes de post-tractament estan enfocats a minimitzar tant com siga possible l'impacte dels motors de combustió interna en termes d'emissions contaminants. En el cas dels motors d'encés provocat, els catalitzadors de tres vies representen la tecnologia més estesa en les últimes dècades, pel fet que són compactes i posseeixen bona relació preu-prestacions. Aquests convertidors són capaços d'oxidar hidrocarburs i monòxid de carboni al mateix temps que redueixen els òxids de nitrogen. No obstant això, per a aconseguir la seua millor eficiència, el dosatge ha de controlar-se amb precisió entorn de condicions estequiomètriques. En aquest sentit, els sistemes electrònics de gestió del motor són essencials per a aprofitar les característiques d'aquests convertidors. En particular, les estratègies de control i diagnòstic exerceixen un paper clau per aconseguir una reducció efectiva de les emissions en l'ampli rang de condicions d'operació que es donen en condicions de funcionament reals. El desenvolupament d'aquestes estratègies és fonamental, especialment tenint en compte el baix nivell d'emissions permès per les normatives actuals i la tendència cap a zero emissions. El propòsit d'aquesta tesi doctoral és analitzar el comportament del sistema de post-tractament en condicions específiques però alhora molt comunes en conducció real, i desenvolupar estratègies que proporcionen una reducció addicional de les emissions en sistemes basats en catalitzador de tres vies. Amb la popularització de xicotets motors amb sobrealimentació d'encés provocat, ha augmentat l'ús d'estratègies de curtcircuit per a mitigar els típics problemes de falta de parell a baix règim. Aquesta tesi analitza l'impacte dels polsos de curtcircuit en el catalitzador i en les sondes ¿. El procés de curtcircuit d'aire fresc té un impacte important en la dinàmica intra-cicle de la composició dels gasos. En particular, els polsos de monòxid de carboni i hidrogen seguits pels polsos d'aire fresc pertorben el normal funcionament del sensor d'oxigen. Per tant, s'ha proposat un nou mètode per a estimar la taxa de curtcircuit del motor. Aquest mètode permet corregir la desviació patida pel sensor i, per tant, ajuda a reduir la penalització en emissions d'aquest tipus d'estratègies. Per a millorar l'eficiència del catalitzador en condicions transitòries, no solament es requereix un control precís del dosatge aigües amunt del catalitzador, sinó que també resulta imprescindible considerar el comportament dinàmic del convertidor en si mateix. Per exemple, l'emmagatzematge d'oxigen és un bon indicador de l'estat del catalitzador, però no es pot mesurar directament mitjançant sensors. Per tant, el desenvolupament de models és clau en les estratègies de control actuals, per poder estimar els diferents paràmetres relacionats amb l'estat del catalitzador. Diversos models de catalitzador s'han desenvolupat en aquesta tesi doctoral per a tractar diferents qüestions, des de la predicció dels efectes de la condensació d'aigua en l'evolució de la temperatura del catalitzador just després de l'arrencada en fred, a la quantificació del nivell d'envelliment, passant pel control òptim de porga del catalitzador.[EN] In spite of the current tendency towards the electrification of the road transport, internal combustion engines have been essential in this sector and it is expected to continue being a technology with a noticeable presence during next decades. Current passenger cars based on internal combustion engines are greener than those used years ago, although it is still a developing process. Aftertreatment systems are aimed to minimize as much a possible the impact of internal combustion engines in terms of pollutant emissions. In case of spark-ignited engines, three-way catalytic converters represent the most widespread technology during last decades, due to their compactness and cost-performance. These converters are capable to oxidise hydrocarbons and carbon monoxide while simultaneously reducing nitrogen oxide. Nonetheless, to achieve their best efficiency, the air-to-fuel ratio must be accurately controlled close to stoichiometric conditions. In this sense, electronic engine management systems are essential to take advantage of the features of these converters. In particular, control and diagnosis strategies play a key role to achieve an effective emissions reduction under the wide range of operating conditions that arise in real driving conditions. The further development of this strategies is fundamental, especially taking into account the low emissions level allowed by current regulatory procedures and the trend towards zero emissions. The purpose of this dissertation is to analyse the behaviour of the aftertreatment system under very specific but at the same time very common conditions, and developing strategies that provide a further emissions reduction for systems based on three-way catalyst. With the popularization of small turbocharged spark-ignited engines, the use of scavenging strategies to solve the typical low-end torque issues has increased. This dissertation analyses the impact of the short-circuit pulses on both three-way catalyst and ¿ sensors. The short-circuit process has an important effect on the in-cycle dynamics of the exhaust gas composition. In particular, the carbon monoxide and hydrogen pulses followed by fresh air pulses cause a sensor bias. Thus a new method to on-line estimate the short-circuit rate has been proposed. This method allows to correct the sensor bias and, therefore, help to reduce the emissions penalty. To improve the TWC efficiency under transient conditions, not only an accurate air-to-fuel ratio control upstream of the converter is required, but also to consider the dynamic behaviour of the converter itself. For example, the oxygen storage is the main responsible for the converter dynamics, and thus, a good indicator of the catalyst state, but it cannot be directly measured. Hence the development of models is key in current control strategies, to on-line track different parameters related with the state of the converter. Several models have been derived in this dissertation in order to fulfil different requirements, from the prediction of water condensation effects on the temperature evolution inside the converter just after cold-start, to the quantification of the ageing level, through the optimal catalyst purge control, or the air-to-fuel ratio disturbances rejection.Real Minuesa, M. (2020). Modelling, control and diagnosis of aftertreatment systems based on three-way catalyst in spark-ignited engines [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/137040TESI

Modelling three-way catalytic converter oriented to engine cold-start conditions

This is the author¿s version of a work that was accepted for publication in International Journal of Engine Research. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published as https://doi.org/10.1177/1468087419853145[EN] This article introduces a physical model of a three-way catalytic converter oriented to engine cold-start conditions. Computational cost is an important factor, particularly when the modelling is oriented to the development of engine control strategies. That is why a one-dimensional one-channel real-time capable model is proposed. The present model accounts for two phases, gas and solid, respectively, considering not only the heat transfer by convection between both, but also the water vapour condensation and evaporation in the catalyst brick, which plays a key role during engine cold-start. Moreover, the model addresses the conductive heat flow, heat losses to the environment and exothermic reactions in the solid phase, as well as the convective heat flow in the gas phase. Regarding the chemical model, the oxidation of hydrocarbons and carbon monoxide is considered by means of the Langmuir-Hinshelwood mechanism. Three layers make up the model structure from a kinetic point of view, bulk gas, washcoat pores and noble metal in the catalyst surface. The model takes fuel-to-air ratio, exhaust gas mass flow, temperature, pressure and gas composition as inputs, providing the thermal distribution as well as the species concentration along the converter.Real, M.; Hedinger, R.; Pla Moreno, B.; Onder, C. (2021). Modelling three-way catalytic converter oriented to engine cold-start conditions. International Journal of Engine Research. 22(2):640-651. https://doi.org/10.1177/1468087419853145S64065122

Experimental and numerical study of the behavior of three-way catalytic converters under different engine operation conditions

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2005.Includes bibliographical references (p. 231-236).The thesis reports the studies on how the three-way catalytic converters behave under different operation conditions. The main focus of the work is in the oxygen storage capacity of the three-way catalyst. Rich-to-lean air/fuel ratio step-change experiments were carried out to quantify the oxygen storage capacity. Results show that the amount of oxygen stored is dependent on how much oxygen is present in the exhaust. Thus the oxygen storage capacity is not a fixed value, rather it is determined by the equilibrium between the storage sites and the feed stream. A numerical model was developed to characterize the oxygen storage capacity. The model matches well with the experiments. The effects of catalyst age and fuel sulfur content on oxygen storage were measured. The results show that the aging effects and fuel sulfur effects are decoupled. The storage capacity decreases by 10% for every 150ppm increase in fuel sulfur, and it scales with (age⁻⁰Ì⁸⁴). Different modes of air/fuel ratio modulations were tested on the catalysts, since such modulation is the practice to keep conversion efficiency high and to increase robustness of the catalyst during transients.(cont.) The results show that within a certain range, the tail-pipe NO emission is not sensitive to the variations in frequency and amplitude. When the modulation is biased towards lean, NO will eventually breakthrough when the oxygen storage capacity saturates. The observed saturation point matches well with the oxygen storage capacity observed in the air/fuel lean step experiments. A flow reactor is set up for controlled studies on catalytic actions. Results show that at typical steady state catalyst temperatures the pollutants removal rate is limited by the mass transfer speed of the slowest diffusing species in the exhaust. The experiments quantify the aging effects on conversion efficiency degradation. Results show that the front part of a catalyst loses its effectiveness exponentially with aging. The loss of effectiveness is not uniform along the catalyst; the degradation is less severe towards the back of the catalyst. A comprehensive practical model was developed based on previous works and the experiments of this project. The model takes into account oxygen storage capacity and aging effects. The comparison of the model with experiments shows good agreement.by Yuetao Zhang.Ph.D

Mathematical Methods for Design of Zone Structured Catalysts and Optimization of Inlet Trajectories in Selective Catalytic Reduction (SCR) and Three Way Catalyst (TWC)

Abgaskatalysatoren zählen zu den wichtigsten Maßnahmen, um Schadstoffemissionen von Verbrennungsmotoren zu vermindern. Mit der stetigen Verschärfung der Emissionsstandards nahm über die Jahre der Forschungsbedarf zu Abgasnachbehandlungssystemen signifikant zu. Der Fokus dieser Arbeit liegt auf der Lösung von Optimierungsproblemen im Bereich der Autoabgaskatalyse, um die Effizienz zu steigern. Dabei werden drei Problemklassen behandelt: 1) Die Light-Off-Verzögerung beim Kaltstart in Oxidationskatalysatoren, 2) Die effiziente Ammoniakdosierung bei der selektiven katalytischen Reduktion (SCR), um Ammoniakdurchbrüche zu vermeiden, 3) Die Spannungsstabilisierung der Lambda-Sonde im Drei-Wege-Katalysator (TWC) während einer Schubabschaltung. Das erste Problem wird durch eine modellbasierte mathematische Optimierung beschrieben, bei der das Beladungsprofil von gezont-strukturierten Katalysatoren auf Basis von Platingruppen-Metallen (PGM) optimiert wird. Dazu wird ein Optimierungsproblem aufgestellt, bei dem ein katalytisch aktiver Kanal in Zonen aufgeteilt wird, die mit unterschiedlichen Mengen von PGM beladen werden. Eine solche Beladung kann auch experimentell getestet werden. Die Effekte der Beladung auf Diffusionslimitierungen im Washcoat werden ebenso berücksichtigt. Ziel ist es, die axiale Verteilung der Beladung zu optimieren, wobei die Gesamtmenge an PGM konstant gehalten wird, um den Gesamtumsatz unter transienten Bedingungen zu maximieren. Dabei wird ein transientes 1D+1D-Modell mit dem impliziten Differentialgleichungslöser DASPKADJOINT numerisch gelöst und in ein nichtlineares Optimierungsproblem übersetzt, das mit einem beliebigen ableitungsbasierten nichtlinearen Optimierungslöser (NLP) behandelt werden kann. Dieses Modell wird auf zwei Beispielfälle angewandt: die CO-Oxidation auf einem Pt/Al2O3 Dieseloxidationskatalysator (DOC), um die Kaltstart-Emissionen zu minimieren, sowie die CH4-Oxidation auf Pd/Al2O3 unter Minimierung der Deaktivierungseffekte. In beiden Fällen wird beobachtet, dass bei der optimalen Lösung ein Beladungsmaximum am Kanaleingang zu einer Umsatzsteigerung führt. Die präsentierte Methode ist darüber hinaus allgemeingültig und kann auf andere Systeme mit unterschiedlicher Chemie angewandt werden, so dass auch signifikant andere Lösungen generiert werden können. Die Fähigkeit, NOx effizient durch Ammoniak zu reduzieren, ist Grundlage der SCR-Technologie für die Dieselabgasnachbehandlung. Ammoniak wird diskontinuierlich durch Zersetzung von Harnstoff-Wasser-Lösung dem SCR-Katalysator zugeführt. Bei der Anwendung im Fahrbetrieb ist es wegen hochgradig transienter Wechsel der Emissionen nicht sinnvoll, konstante Menge Ammoniak zu dosieren. Eine effiziente optimale Dosierungsstrategie ist wichtig, um einerseits hohen Umsatz zu gewährleisten und andererseits NH3-Schlupf zu vermeiden. Die Entwicklung einer optimalen Dosierungsstrategie erfordert die Anwendung einfacher, aber hinreichend akkurater mathematischer Modelle und robuster Optimierungsalgorithmen, um eine Lösung für eine große Anzahl zu optimierender Parameter zu erhalten. Mehrere Modellreduktionstechniken aus der Literatur wurden verwendet, um ein Grey-Box-Modell zu konstruieren. Die Methode der orthogonalen Kollokation über finiten Elementen (OCFE) wird genutzt, um die differential-algebraischen Gleichungen aus dem Optimierungsproblem in ein nichtlineares Programm zu überführen. Das Modell wird auf eine Simulation des WHTC-Testzyklus angewandt, um die NH3-Dosierung für jede Sekunde des Zyklus zu optimieren. Die optimale Lösung verbessert die Effizienz des Reduktion unter Einhaltung eines Schlupf-Maximums von 10 ppm zu jedem Zeitpunkt. Die präsentierte Methode lässt sich auch auf ähnliche Probleme zur Optimierung transienter Eingangsbedingungen anwenden. Im dritten Beispiel wird dieselbe Optimierungsmethode erweitert, um eine optimale Lambda-Trajektorie zu berechnen, die das Lambdasensorsignal am Katalysatorausgang stabilisiert, um Durchbrüche fetter Abgasgemische zu vermeiden. Zunächst wurde ein Beobachtermodell mit vereinfachter Kinetik entwickelt und gegen Versuchsstand-Experimente kalibriert. Direkte Kollokation auf Basis der OCFE wird genutzt, um das Optimierungsproblem in ein nichtlineares Programm zu überführen. Die optimale Lösung zeigt eine schnelle Stabilisierung der Ausgangssensor-Spannung ohne Überschwingungen. Diese Strategie verringert die Relaxationszeit der Sensorspannung signifikant, was wichtig für den Einsatz als Feedback-Controller in einem Dreiwegekatalysator wäre

Dynamic Incompressible Navier-Stokes Model of Catalytic Converter in 1-D Including Fundamental Oxidation Reaction Rate Expressions

Classical one-dimensional (1D) models of automotive catalysts are effective in designing catalyst systems that meet current emission standards. These models use various assumptions in order to simplify the mathematical formulation. Although these postulations have been effective in the past, they might not work with new versions of catalytic converters and the architectures being proposed. In particular, classical models neglect viscosity, conductivity and diffusion in the bulk gas phase. However, in low flow rate regenerative catalysts, these terms might become important. In order to account for these phenomena, an updated model is proposed for the dynamically incompressible flow in the converter. At the same time, derivation and utilization of these terms is studied for proper inclusion in the model. Furthermore, it is evident from the history of catalyst modeling that precise reaction rate expressions are needed for accurate predictions. In order to determine the correct reaction rate expression, this work includes the history of the fundamental reactions of automotive catalysts including carbon monoxide (CO), hydrogen (H2) and nitric oxide (NO) oxidation on a widely used material formulation (platinum catalyst on alumina washcoat). A detailed report of these reactions is incorporated for the reader in order to understand the reaction mechanism along with the creation of a reaction rate expression. Using this review, the CO oxidation reaction is modeled in order to validate the changes proposed in the updated flow model. Moreover, the importance of using the model for determining the characteristics of the catalyst in low flow conditions is presented. This work ends by describing the success and failures of the revised model as compared to the classical model

Modeling a NOx Storage and Reduction Catalyst

Lean burn engines are more fuel efficient than standard stoichiometric-burn engines but at the same time, the conventional three-way catalyst is not effective in reducing the NOx in oxygen-rich exhaust. One of the recent advancements in exhaust after treatment technologies for lean burn engines is the NOx storage and reduction (NSR) methodology. In this mechanism, NOx is stored on the storage component of a NSR catalyst during normal engine operation. However, before the catalyst reaches its saturation capacity, an excess of fuel is injected to the engine for a very short period resulting in reductant rich exhaust and during this period, NOx is released and subsequently reduced to N2, therefore, restoring the storage capacity of the catalyst. The operation is cyclic in nature, with the engine operating between an oxygen rich feed for long periods and a fuel rich feed for relatively shorter periods. To implement this technology in the most efficient way, a detailed understanding of the NSR chemistry under different operating conditions is required. For the past few years, several authors have studied the NSR systems using both experimental and modeling techniques. However, most of the models proposed in the literature were calibrated against the steady cyclic operation where the NOx profiles are similar for each cycle. In real life situations, the engine operation changes with different driving conditions, occurring due to sudden acceleration, roads in hilly areas, non-uniform braking, etc., which results in operation with a number of different transient cycle-to-cycle regimes depending upon the frequency with which the engine operation is altered. Due to such varying conditions, it is very important to investigate the significance of transients observed between the two different steady cycle-to-cycle operations for the optimization and control purposes. Also, the models in the literature are specific to the catalyst used in the study and therefore, their adaptation to other NSR catalysts is not straightforward. Therefore, one of the main motivations behind this research work is to develop a general approach to explain the storage dynamics. Moreover, the existing models have not studied the regeneration mechanisms, which is very important to explain the cyclic data in complete operation including both transients and steady state cycles. In this study, a pseudo one-dimensional model of a commercial NOx storage/release (NSR) catalyst is presented. The NOx storage is considered to be mass transfer limited, where as the storage proceeds, the barium carbonate particle is converted into the nitrate and for further storage, the NOx has to diffuse through this growing nitrate layer and a after certain depth, this penetration becomes nearly impossible. To explain the transient nature of the cyclic NOx profile, it is hypothesized that when incomplete regeneration occurs, only part of the nitrate is converted back to carbonate. Therefore, the nitrate layer increases in thickness with each cycle, thus making further storage increasingly more difficult. The shrinking core concept with incomplete storage in the lean phase followed by incomplete regeneration of the nitrate layer during the regeneration phase accounts for a net drop in storage capacity of the catalyst in each cycle, which continues decreasing until the amount of sites regenerated equal the amount used in NOx storage. The number of unknown parameters used for fitting were reduced by parameter sensitivity analysis and then fitted against a NOx profile at the reactor exit. The overall amount of NOx that can be stored in the lean phase of the cycle depends on the extent of regeneration that can be achieved during the previous rich phase, which in turn depends directly on the concentration of reductants in the feed. Therefore, there is a trade-off between the amount of fuel used and the NOx emissions. The proposed model can be potentially used to improve this trade-off by using model-based optimization techniques

Kinetic Intersections as a Source of Information on Rate Coefficients

C