Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory

[ES] En este trabajo estudiamos dos reacciones catalíticas relevantes para la industria y la localización del anión fluoruro en la zeolita RTH, sintetizada en medio fluoruro. El capítulo 3 es el primer capítulo de resultados, donde se estudia la reducción quimioselectiva del nitroestireno en las superficies Ni(111), Co(111), Cu(111) y Pd(111). El mecanismo generalmente aceptado de esta reacción está basado en el esquema propuesto por Haber en 1898, en el que la reacción puede transcurrir por dos rutas, la directa y la de condensación. En este capítulo exploramos ambas rutas, y observamos que la ruptura de los enlaces N-O y la consecuente formación de enlaces metal-O está más favorecida que la formación de enlaces N-H en las superficies Ni(111) y Co(111), debido al carácter oxofílico de ambos metales. Las etapas más lentas involucran la formación de enlaces N-H. En las superficies de metales nobles como Pt(111) y Pd(111) se observa el comportamiento contrario. La superficie Cu(111) es un caso intermedio comparado con los metales nobles y no nobles. Además, el nitroestireno interactúa con los átomos de Cu de la superficie solo a través de grupo nitro, con lo cual es un candidato ideal para alcanzar selectividades cerca del 100%. Sin embargo, la superficie Cu(111) no es capaz de activar la molécula de H2. En este sentido, proponemos un catalizador bimetálico basado en Cu, dopado con otro metal capaz de activar al H2, tales como el Pd o el Ni. En los capítulos 4 y 5 se ha estudiado la reducción catalítica selectiva de los óxidos de nitrógeno (SCR, en inglés) con amoníaco. Usando métodos de DFT, hemos encontrado rutas para la oxidación de NO a NO2, nitritos y nitratos con energías de activación relativamente bajas. También, hemos encontrado que la reducción de Cu2+ a Cu+ requiere la participación simultánea de NO y NH3. Posteriormente, hemos estudiado la influencia del NH3 en este sistema con métodos de dinámica molecular. El NH3 interacciona fuertemente con el Cu+ de forma que dos moléculas de este gas son suficientes para romper la coordinación del catión Cu+ con los oxígenos del anillo 6r, y formar el complejo lineal [Cu(NH3)2]+. Además, los cationes Cu2+ pueden ser estabilizados fuera de la red mediante la formación del complejo tetraamincobre(II). Debido a la presencia de los cationes Cu+ y Cu2+ coordinados a la red de la zeolita, aparecen bandas en la región entre 800-1000 cm-1 del espectro infrarrojo. El análisis de las frecuencias IR de varios modelos con Cu+ y Cu2+ coordinados al anillo 6r, o formando complejos con amoniaco indica que cuando los cationes Cu+ y Cu2+ están coordinados a los oxígenos del anillo 6r aparecen vibraciones entre 830 y 960 cm-1. Frecuencias en esta zona también se obtienen en los casos en que NO, NO2, O2 y combinaciones de dos de ellos están adsorbidos en Cu+ y Cu2+. Sin embargo, cuando los cationes Cu+ y Cu2+ están fuera del anillo (no hay enlaces entre los cationes de cobre y los oxígenos del anillo 6r) no se obtienen vibraciones de IR en esta región del espectro. Estos resultados indican que con el seguimiento del espectro IR durante la reacción SCR es posible determinar si los cationes Cu+ y Cu2+ están coordinados o no al anillo de 6r en las etapas de oxidación y reducción. Por último, hemos simulado el desplazamiento químico de 19F, δiso,, en la zeolita sintetizada RTH. El análisis del δiso de los distintos modelos utilizados nos ha permitido reconocer la simetría del material sintetizado, el cual pertenece al grupo espacial P1 y la nueva celda unidad ha sido confirmada experimentalmente por difracción de rayos X. Finalmente, hemos asignado la señal experimental que aparece en el espectro de 19F a -67.2_ppm, al F- localizado en un sitio T2, el cual es a su vez la posición más estable. Además, la señal a -71.8 ppm se ha asignado al anión F- localizado en un sitio T4.[CA] En aquest treball estudiem dues reaccions catalítiques rellevants per a la indústria i la localització de l'anió fluorur en la zeolita RTH, sintetitzada al mig fluorur. El capítol 3 és el primer capítol de resultats, on s'estudia la reducció quimioselectiva del nitroestireno en les superfícies Ni(111), Co(111), Cu(111) i Pd(111). El mecanisme generalment acceptat d'aquesta reacció està basat en l'esquema proposat per Haver-hi en 1898, en el qual la reacció pot transcórrer per dues rutes, la directa i la de condensació. En aquest capítol explorem totes dues rutes, i observem que la ruptura dels enllaços N-O i la conseqüent formació d'enllaços metall-O està més afavorida que la formació d'enllaços N-H en les superfícies Ni(111) i Co(111), a causa del caràcter oxofílico de tots dos metalls. Les etapes més lentes involucren la formació d'enllaços N-H. En les superfícies de metalls nobles com Pt(111) i Pd(111) s'observa el comportament contrari. La superfície Cu(111) és un cas intermedi comparat amb els metalls nobles i no nobles. A més, el nitroestireno interactua amb els àtoms de Cu de la superfície sol a través de grup nitre, amb la qual cosa és un candidat ideal per a aconseguir selectivitats prop del 100%. No obstant això, la superfície Cu(111) no és capaç d'activar la molècula d'H2. En aquest sentit, proposem un catalitzador bimetàl·lic basat en Cu, dopat amb un altre metall capaç d'activar a l'H2, com ara el Pd o el Ni. En els capítols 4 i 5 hem estudiat la reducció catalítica selectiva dels òxids de nitrogen (SCR, en anglés) amb amoníac. Usant mètodes de DFT, hem trobat rutes per a l'oxidació de NO a NO2, nitrits i nitrats amb energies d'activació relativament baixes. També, hem trobat que la reducció de Cu2+ a Cu+ requereix la participació simultània de NO i NH3. Posteriorment, hem estudiat la influència del NH3 en aquest sistema amb mètodes de dinàmica molecular. El NH3 interacciona fortament amb el Cu+ de manera que dues molècules d'aquest gas són suficients per a trencar la coordinació del catió Cu+ amb els oxígens de l'anell 6r, i formar el complex lineal [Cu(NH3)2]+. A més, els cations Cu2+ poden ser estabilitzats fora de la xarxa mitjançant la formació del complex tetraamincobre(II). A causa de la presència dels cations Cu+ i Cu2+ coordinats a la xarxa de la zeolita, apareixen bandes a la regió entre 800-1000 cm-1 de l'espectre infraroig. L'anàlisi de les freqüències IR de diversos models amb Cu+ i Cu2+ coordinats a l'anell 6r, o formant complexos amb amoníac indica que quan els cations Cu+ i Cu2+ estan coordinats als oxígens de l'anell 6r apareixen vibracions entre 830 i 960 cm-1. Freqüències en aquesta zona també s'obtenen en els casos en què NO, NO2, O2 i combinacions de dues d'ells estan adsorbidos en Cu+ i Cu2+. No obstant això, quan els cations Cu+ i Cu2+ estan fora de l'anell (no hi ha enllaços entre els cations de coure i els oxígens de l'anell 6r) no s'obtenen vibracions d'IR en aquesta regió de l'espectre. Aquests resultats indiquen que amb el seguiment de l'espectre IR durant la reacció SCR és possible determinar si els cations Cu+ i Cu2+ estan coordinats o no a l'anell de 6r en les etapes d'oxidació i reducció. Finalment, hem simulat el desplaçament químic de 19F, δiso, en la zeolita sintetitzada RTH. L'anàlisi del δiso dels diferents models utilitzats ens ha permés reconéixer la simetria del material sintetitzat, el qual pertany al grup espacial P1 i la nova cel·la unitat ha sigut confirmada experimentalment per difracció de raigs X. Finalment, hem assignat el senyal experimental que apareix en l'espectre de 19F a -67.2 ppm, al F- localitzat en un lloc T2, el qual és al seu torn la posició més estable. A més, el senyal a -71.8 ppm s'ha assignat a l'anió F- localitzat en un lloc T4.[EN] In this work, we have studied two heterogeneous catalytic reactions and the localization of the fluoride anion in the as-made RTH framework, synthesized in fluoride medium. The first results, included in chapter 3, correspond to the chemoselective reduction of nitrostyrene on different metal surfaces, i.e, Ni(111), Co(111), Cu(111) and Pd(111). Until very recently, the reduction of the nitro group was explained on the basis of the general mechanism proposed by Haber in 1898 where the reaction can follow two routes, the direct and condensation route. We have explored the relevant elementary steps of both routes and found that because of the oxophilic nature of Ni and Co, the steps involving the dissociation of N-O bonds and formation of metal-O bonds are significantly favored compared with the other steps on both metal surfaces. In addition, the most demanding steps in terms of energy involve the formation of N-H bonds. These findings are in contrast to those of noble metals such as Pt and Pd, where the opposite behavior is observed. The behavior of Cu(111) lies in between the aforementioned cases, and also no chemical bonds between the carbon atoms of the aromatic ring of nitrostyrene and the Cu(111) surface is formed. For this reason, it might be an ideal candidate to achieve nearly 100 % selectivity. However, the Cu(111) surface does not seem to activate the H2 molecule. In this regard, we propose a bimetallic Cu-based catalyst whose surface is doped with atoms of a H2-activating metal, such as Ni or Pd. On another matter, we have also investigated the selective catalytic reduction of nitrogen oxides (SCR-NOx) and the main results are presented in the following two chapters, 4 and 5. By using static DFT methods, we found pathways for the oxidation of NO to NO2, nitrites and nitrates with relatively low activation energies. We also found, in agreement with experimental reports, that the reduction of Cu2+ to Cu+ requires the simultaneous participation of NO and NH3. Later, molecular dynamics simulations allowed us to assess the influence of NH3. The strong interaction of NH3 with the Cu+ cation is evidenced by its ability to detach Cu+ from the zeolite framework and form the mobile linear complex [Cu(NH3)2]+. Cu+ is no longer coordinated to the zeolite framework in the presence of two NH3 molecules. This observation and the fact that the T-O-T vibrations of the framework produce bands in the 800-1000 cm-1 region of the IR spectrum when perturbed by the coordination of Cu+ and Cu2+ cations, indicate that bands in the 800-1000 cm-1 regions should be observed when both copper cations are bonded to the framework oxygens. Finally, we have also studied NMR properties of the as-made pure silica RTH framework, aiming at locating the compensating fluoride anion. The calculation of the 19F chemical shift in different T sites and comparison with the experimental NMR spectra shows that the as-made RTH belongs to the P-1 space group with 16 Si, 32 O atoms, one fluoride anion and one OSDA cation. These results have been confirmed experimentally by XRD. In addition, we have assigned the experimental signal of 19F at -67.2 ppm to the fluoride anion in a T2 site, which in turn is the most stable location found, and the signal of -71.8 ppm to a fluoride anion sitting in a T4 site.My acknowledgements to “La Caixa foundation” for the financial support through “La Caixa−Severo Ochoa” International PhD Fellowships (call 2015), to the Spanish Supercomputing Network (RES), to the Centre de Càlcul de la Universitat de València, to the Flemish Supercomputer Center (VSC) of Ghent University for the computational resources and technical support, and to the Spanish Government through the MAT2017-82288-C2-1-P programmeMillan Cabrera, R. (2021). Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/161934TESI

The state of the art in selective catalytic reduction control

Selective Catalytic Reduction (SCR) is a leading after treatment technology for the removal of nitrogen oxide (NOx) from exhaust gases (DeNOx). It presents an interesting control challenge, especially at high conversion, because both reagents (NOx and ammonia) are toxic, and therefore an excess of either is highly undesirable. Numerous system layouts and control methods have been developed for SCR systems, driven by the need to meet future emission standards. This paper summarizes the current state-of-the-art control methods for the SCR aftertreatment systems, and provides a structured and comprehensive overview of the research on SCR control. The existing control techniques fall into three main categories: traditional SCR control methods, model-based SCR control methods, and advanced SCR control methods. For each category, the basic control technique is defined. Further techniques in the same category are then explained and appreciated for their relative advantages and disadvantages. Thus this paper presents a snapshot of the current state of the art for the research area of SCR control. This is a very active field, and it is hoped that by providing a better understanding of the different control strategies already developed for SCR control, future areas of interest will be identified and developed with the ultimate aim of satisfying the increasingly stringent emissions legislation. Copyright © 2014 SAE International

Meta-heuristic algorithms in car engine design: a literature survey

Meta-heuristic algorithms are often inspired by natural phenomena, including the evolution of species in Darwinian natural selection theory, ant behaviors in biology, flock behaviors of some birds, and annealing in metallurgy. Due to their great potential in solving difficult optimization problems, meta-heuristic algorithms have found their way into automobile engine design. There are different optimization problems arising in different areas of car engine management including calibration, control system, fault diagnosis, and modeling. In this paper we review the state-of-the-art applications of different meta-heuristic algorithms in engine management systems. The review covers a wide range of research, including the application of meta-heuristic algorithms in engine calibration, optimizing engine control systems, engine fault diagnosis, and optimizing different parts of engines and modeling. The meta-heuristic algorithms reviewed in this paper include evolutionary algorithms, evolution strategy, evolutionary programming, genetic programming, differential evolution, estimation of distribution algorithm, ant colony optimization, particle swarm optimization, memetic algorithms, and artificial immune system

Nitric oxide reduction by non-thermal plasma and catalysis

Combustion of fossil fuels produces millions of tons of air pollutants such as NOx and SO2. The high cost and operating difficulties of prevailing selective catalytic reduction (SCR) process are driving R&D efforts towards alternative technologies and modifications to the SCR technology. Non-thermal plasma technique has been found to be one of the most promising technologies for NOx removal. In the present study, a non-thermal plasma technique in the form of dielectric barrier discharge (DBD) has been extensively investigated for the removal of NOx. The main variables including electrical parameters, chemical compounds and flow conditions are identified and studied in terms of their effects on NO/NOx conversions. Significant increases in NO/NO x conversions of 90% and 40% are observed in the presence of both O 2 and H2O than in the presence of either O2 or H2O alone. Addition of 1000 ppm ethylene to the NO/O2/CO 2/N2 mixture almost promotes 100% NO oxidation to NO 2. The chemistry of plasma reactions is discussed. The DBD system is found to be effective for NO oxidization into NO2 and HNO 3. Kinetics studies have also been made for NO-O2 reaction under plasma conditions. A rate equation has been proposed, -d[NO]/dt = kp [NO]1/2[O2] 1/2 with kp = 0.0143exp(-1865/E d) showing that a reaction can be initiated at much lower activation energy under plasma conditions. A hybrid plasma-catalyst (P-C) system has been developed to achieve the synergy. gamma-Al2O3 and laboratory-prepared tungsten catalysts have been used in the hybrid P-C experiments. The improvement in NOx removal by the P-C system is about 15% compared to by the SCR alone when 1000--3000 ppm of methane or ethylene is added to the inlet gas stream. There is no formation of N2O (greenhouse gas) in the P-C system when inlet gas contains moisture or ethylene. DBD reactor design parameters have also been investigated in terms of SO2 oxidation to SO3 with respect to reactor geometry, dielectric material and thickness. The DBD technique has the great potential to replace the prevailing combined SCR and flue gas disulfurization (FGD) processes both technically and economically. The P-C system has the potential to be used for the removal of NOx from diesel engine exhausts

Chemical gradients in automotive Cu-SSZ-13 catalysts for NOx_{x} removal revealed by operando X-ray spectrotomography

NOx emissions are a major source of pollution, demanding ever improving performance from catalytic aftertreatment systems. However, catalyst development is often hindered by limited understanding of the catalyst at work, exacerbated by widespread use of model rather than technical catalysts, and global rather than spatially-resolved characterisation tools. Here we combine operando X-ray absorption spectroscopy with microtomography to perform 3D chemical imaging of the chemical state of copper species in a Cu-SSZ-13 washcoated monolith catalyst during NO$_{x}$ reduction. Gradients in copper oxidation state and coordination environment, resulting from an interplay of NOx reduction with adsorption-desorption of NH$_{3}$ and mass transport phenomena, were revealed with micrometre spatial resolution while simultaneously determining catalytic performance. Crucially, direct 3D visualisation of complex reactions on nonmodel catalysts is only feasible using operando X-ray spectrotomography, which can improve our understanding of structure-activity relationships including the observation of mass and heat transport effects

Reaction kinetics of NH3-SCR over Cu-CHA from first principles

Ammonia assisted selective catalytic reduction (NH3-SCR) is a leading technology that is used for NOx reduction to N2 and H2O in oxygen excess. Thanks to its high activity, high selectivity, and durability, Cu-CHA is commercialized as an NH3-SCR catalyst. Despite the superior catalytic performance, small amounts of nitrous oxide (N2O) are formed during the NH3-SCR as an unwanted by-product. N2O has a strong greenhouse potential and should be avoided. To further enhance the performance of NH3-SCR catalysts to handle the increasingly stringent emission standards, understanding the mechanism for NH3-SCR and, in particular, N2O formation over Cu-CHA is essential.In this thesis, density functional theory (DFT) calculations and first principles microkinetic simulations are used to investigate the reaction path and the reaction kinetics for low temperature-NH3-SCR. Based on a previously proposed catalytic cycle for NH3-SCR over Cu-CHA, an N2O formation path is put forward. It is proposed that N2O can form over linear [Cu(NH3)2]+ complexes, which are present during low temperature operation. N2O is formed from H2NNO, which is generated via NH2-NO coupling over a Cu-OOH-Cu site. The reaction proceeds with a low barrier and rationalizes the low-temperatureN2O emission peak observed experimentally at high Cu-loadings. N2O formation at high temperatures is instead proposed to occur through the decomposition of NH4NO3.With a catalytic cycle including N2O formation, a first principles microkinetic model is developed to investigate the reaction kinetic of NH3-SCR over Cu-CHA. When developing the model, special attention is paid assessing the change in entropy for each reaction step. The results from the kinetic model show good agreement with the experimental data of apparent activation energies, reaction orders and N2O selectivity. The model links the catalytic performance with structure and forms the basis for further developments of the NH3-SCR technology

Advances and challenges of ammonia delivery by urea-water sprays in SCR systems

Over the past decades, selective catalytic reduction (SCR) using aqueous urea sprays as ammonia precursor has become the prevalent technique for NO$_{X}$ emission control in mobile applications. Preparation of ammonia from urea water sprays still represents a challenge in aftertreatment engineering as complex interactions of multi-phase physics and chemical reactions have to be handled. Increasingly stringent emission legislations and the ongoing development of fuel-efficient engines and close-coupled aftertreatment systems raise high demands to SCR systems. Due to highly transient conditions and short mixing lengths, incomplete spray evaporation can result in liquid/wall contact and formation of solid urea deposits lowering ammonia selectivity and homogeneity. This article reviews the ongoing development of SCR systems with focus on the efficient evaporation and decomposition of the injected spray for a homogeneous ammonia distribution in front of the SCR catalyst. Critical aspects of spray evaporation and impingement, liquid film and deposit formation are pointed out and potentials for system optimization are discussed

Control-oriented modelling and diagnostics of diesel after-treatment catalysts

[ES] Esta tesis doctoral abarca el desarrollo de algoritmos orientados a mejorar el sistema de control de emisiones en motores Diesel. Para este propósito, la inclusión en el vehículo de sensores embarcados como los de temperatura, los de NOx o el de NH3 permite realizar diagnóstico a bordo de los sistemas de post-tratamiento foco de este trabajo, los cuales son el DOC y el SCR. Así pues, el objetivo es el de satisfacer las normativas de diagnóstico a bordo para mantener las emisiones por debajo del umbral permitido por la normativa a lo largo del tiempo. Los tests experimentales, incluyendo las medidas con analizador de gases, permiten tener una visión más amplia de las especies en la línea de escape. Complementariamente, se utilizan unidades nuevas y envejecidas para tener el efecto experimental del envejecimiento en los catalizadores. De esta manera, se analiza el efecto de la temperatura, el gasto de escape, las concentraciones de las especies y el envejecimiento en el DOC y en el SCR, así como la evaluación de algunas de las medidas relevantes realizadas por los sensores. Las temperaturas tienen una influencia destacada en el funcionamiento de los catalizadores, por lo que se requiere la evaluación de las medidas de los sensores de temperatura, junto con el desarrollo de modelos de transmisión de calor, para alimentar las funciones a continuación desarrolladas. En este sentido, la medida lenta del sensor aguas arriba del DOC se mejora en condiciones transitorias mediante una técnica de fusión de la información basada en un filtro de Kalman. Luego, se presenta un modelo de transmisión de calor 1D y un modelo agrupado 0D, en los cuales se evalúan las entradas aguas arriba según el uso del modelo. Por otra parte, se presenta una técnica para estimar el incremento de temperatura debido a la oxidación de los pulsos de post-inyección en el DOC. Se proponen modelos para ambos DOC y SCR para estimar el efecto del envejecimiento en las emisiones, en los cuales el factor de envejecimiento es modelado como un parámetro sintonizable que permite variar desde estados nuevos a envejecidos. Por una parte, un modelo agrupado 0D es desarrollado para el DOC con el propósito de estimar el desliz de HC y CO, el cual es validado en un WLTC para después ser usado en simulación. Por otra parte, un modelo 1D y un modelo 0D se desarrollan para el SCR, los cuales se usan a continuación para alimentar la estrategia de diagnóstico y para simulación. Finalmente, las estrategias de diagnóstico se presentan para fallo total o retirada de DOC, así como para la estimación de la eficiencia en DOC y SCR. Por una parte, la primera estrategia se divide en pasiva y activa, en la que se usan post-inyecciones en la activa para excitar el sistema y confirmar el fallo total si es el caso. A continuación, la eficiencia del DOC se estima a través de una técnica indirecta en la que la temperatura de activación se detecta y se relaciona con el incremento de emisiones a través del modelo. Por otra parte, se desarrolla un observador para estimar el estado de envejecimiento del SCR, el cual está basado en un filtro de Kalman extendido. Sin embargo, para evitar asociar baja eficiencia del catalizador debido a pobre calidad de la urea inyectada, a envejecimiento del SCR, un indicador de la calidad de la urea se ejecuta en paralelo.[CA] Esta tesi doctoral abasta el desenvolupament d'algoritmes orientats a millor el sistema de control d'emissions en motors Diesel. Per a este propòsit, la inclusió en el vehicle de sensor embarcats com els de temperatura, els de NOx o el d'NH3 permet realitzar el diagnòstic a bord dels sistemes de post-tractament focus d'este treball, els quals són el DOC i el SCR. Així doncs, l'objectiu és el de satisfer les normatives de diagnòstic a bord per a mantindre les emissions per baix de l'umbral permés per la normativa al llarg del temps. Els tests experimentals, incloent les mesures amb analitzador de gasos, permeten obtindre una visió més àmplia de les espècies en la línia d'escapament. Complementàriament, s'utilitzen unitats noves i envellides per tal de tindre l'efecte experimental de l'envelliment en els catalitzadors. D'aquesta manera, s'analitza l'efecte de la temperatura, la despesa d'escapament, les concentracions de les espècies i l'envelliment en el DOC i en el SCR, així com l'avaluació d'algunes mesures rellevants realitzades pels sensors. Les temperatures tenen una influència destacada en el funcionament dels catalitzadors, pel que es requerix l'avaluació de les mesures dels sensors de temperatura, junt amb el desenvolupament de models de transmissió de calor, per a alimentar les funcions a continuació desenvolupades. En este sentit, la mesura lenta del sensor a l'entrada del DOC es millora en condicions transitòries mitjançant una tècnica de fusió de la informació basada en un filtre de Kalman. Després, es presenta un model de transmissió de calor 1D i un model agrupat 0D, en els quals s'avaluen les entrades a l'entrada segons l'ús del model. Per altra banda, es presenta una tècnica per a estimar l'increment de temperatura degut a l'oxidació dels polsos de post-injecció en el DOC. Es proposen models per a DOC i SCR per a estimar l'efecte de l'envelliment en les emissions, en els quals es modela el factor d'envelliment com un paràmetre sintonitzable, que permet variar des d'estats nous a envellits. Per altra banda, un model agrupat 0D _es desenvolupat per al DOC amb el propòsit d'estimar la relliscada de HC i CO, el qual és validat en un WLTC per a després ser usat en simulació. Per altra banda, un model 1D i un model 0D es desenvolupen per al SCR, els quals s'usen a continuació per a alimentar l'estratègia de diagnòstic i per a simulació. Finalment, les estratègies de diagnòstic es presenten per a la fallada total o retirada del DOC, així com per a l'estimació de l'eficiència en DOC i SCR. Per altra banda, la primera estratègia es divideix en passiva i activa, en la que s'utilitzen post-injeccions en la activa per a excitar el sistema i confirmar la fallada total si es dona el cas. A continuació, l'eficiència del DOC s'estima a través d'una tècnica indirecta en la que la temperatura d'activació es detecta i es relaciona amb l'increment d'emissions a través del model. Per altra banda, es desenvolupa un observador per a estimar l'estat d'envelliment del SCR, el qual està basat en un filtre de Kalman extés. No obstant això, per a evitar associar baixa eficiència degut a pobre qualitat de l'urea injectada a l'envelliment del SCR, un indicador de la qualitat de l'urea s'executa en paral·lel.[EN] This dissertation covers the development of algorithms oriented to improve the emission control system of Diesel engines. For this purpose, the inclusion of on-board sensors like temperature, NOx and NH3 sensors allows performing on-board diagnostics to the after-treatment systems focus of this work, which are the DOC and the SCR system. Then, the target is to meet on-board diagnostics regulations in order to keep emissions below a regulation threshold over time. Experimental tests, including gas analyzer measurements, allow having a wider view of the species in the exhaust line. Complementary, new and aged units are used in order to have the experimental effect of ageing on the catalysts. Then, the effect of temperature, exhaust mass flow, species concentrations and ageing is analyzed for DOC and SCR, in combination with the assessment of some relevant sensors measurements. As a result, the characteristics, opportunities and limitations extracted from experimental data are used as the basis for the development of models and diagnostics techniques. The assessment of temperature sensors measurements, along with the development of heat transfer models is required to feed temperature dependent functions. In this sense, the slow measurement of the DOC upstream temperature sensor is improved in transient conditions by means of a data fusion technique, based on a fast model and a Kalman filter. Then, a 1D and a 0D lumped heat transfer models are presented, in which the upstream inputs are assessed in relation to its use. On the other hand, a technique to estimate the temperature increase due to post-injection pulses oxidation is also presented. Both DOC and SCR models are proposed in order to estimate the effect of ageing on emissions, in which an ageing factor is modelled as a tunable parameter that allows varying from new to aged states. On the one hand, a 0D lumped model is developed for DOC in order to estimate the HC and CO species slip, which is validated in a WLTC and is then used for simulation. On the other hand, a 1D and a 0D models are developed for SCR, which are then used to feed the diagnostics strategy and for simulation. Finally, diagnostics strategies are presented for total failure or removal of DOC, as well as for efficiency estimation of DOC and SCR. On the one hand, the former strategy is separated into passive and active diagnostics, in which post-injections are used in active diagnostics in order to excite the system and confirm a total failure, in case. Then, the DOC efficiency estimation is done by means of an indirect technique in which the light-off temperature is detected and an emissions increase is related by means of the DOC ageing model. On the other hand, an observer to estimate the SCR ageing state is developed, which is based on an extended Kalman filter. However, in order to avoid associating low SCR efficiency to ageing, an indicator of the injected urea quality is developed to run in parallel.Mora Pérez, J. (2018). Control-oriented modelling and diagnostics of diesel after-treatment catalysts [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/115937TESI

On the reaction mechanism for selective catalytic reduction of NOx by NH3 over Cu-zeolites

Nitrogen oxides (NOx) are major pollutants from combustion processes, being corrosive and hazardous to human health. The main technology for exhaust aftertreatment of NOx emitted from diesel engines is selective catalytic reduction with ammonia as reducing agent (NH3-SCR). Among a range of catalysts for NH3-SCR, copper-exchanged zeolites are efficient with high activity and selectivity combined with good hydrothermal stability. Zeolites are crystalline microporous aluminosilicates constructed by corner-sharing SiO4 and AlO4 tetrahedra. Replacement of a four-valent Si by a three-valent Al gives the framework a negative charge, which is compensated by a cation. The cation in the case of copper exchanged zeolites is Cu(I) or Cu(II).In this thesis, the reaction mechanism for NH3-SCR over copper-exchanged zeolites with CHA framework (Cu-CHA) has been studied through density functional theory in combination with ab initio thermodynamics and molecular dynamics. Firstly, the character of the active site for NH3-SCR over Cu-CHA under typical reaction conditions has been investigated. It is found that the Cu(I)-ion is preferably solvated by two NH3 ligands forming a linear Cu(NH3)2+ complex under low-temperature operating conditions. The storage of NH3 in the Cu(NH3)2+ complex is consistent with measured features from NH$_3$ temperature-programmed desorption. Moreover, the linear Cu(NH3)2+ complex is found to be important for solid-state ion exchange of Cu(I) into zeolites, which is one strategy for zeolite functionalization.Secondly, a complete reaction mechanism for low-temperature NH3-SCR over Cu-CHA has been explored. The reaction is found to proceed in a redox manner via alternating Cu(I) and Cu(II) oxidation states. A pair of Cu(NH3)2+ complexes is found to be required for O2 activation in similarity to O2 activation in homogeneous catalysis. The potential energy surface for O2 dissociation is found to depend strongly on the choice of the exchange-correlation functional. The PBE+U approach together with van der Waals corrections is found to provide a reasonable, simultaneous accuracy of the different bonds in the system. Based on the fact that Cu(I) is solvated and the need of complex pairs for O2 activation, two possible reaction cycles for low-temperature NH3-SCR are proposed. The reaction is suggested to proceed in a multi-site fashion over both copper-sites and Bronsted acid sites.\ua0The proposed mechanism highlights the similarities between low-temperature NH3-SCR over Cu-CHA and homogeneous liquid-phase catalytic reactions and provides a solid basis for future improvements of Cu-exchanged zeolites for NH3-SCR