Denna fallstudie undersöker hur två marina system för rening av kväveoxider från rökgaser, EGR samt SCR, presterar med avseende på emissioner och ekonomi. En vanligt förekommande tvåtakt dieselmotor valdes att teoretiskt utrustas med respektive system där ett beräkningsprogram, CEAS, kunde användas för att genomföra beräkningar efter valda driftsförhållanden och därmed få ut relevant data. Med förbrukning av de för systemen erforderliga kemikalierna samt förbrukning av bränsle kunde kostnader beräknas efter inhämtande av priser. Med IMO:s Tier III-krav som mål kunde förhindrad mängd utsläppt NOX beräknas och med hjälp av bildad rökgasmängd vid användande med och utan system kunde en uppfattning fås om hur systemen påverkar fartygets emissioner. Beräkningar valdes att göras över en uppskattad livslängd för ett fartyg, 20 år. Vidare valdes de ekonomiska kostnaderna för systemen att slås samman med inköpspriset för systemen. Slutsatser som kunde tas från studien var bland annat att SCR är det system vars sammanräknade kostnad är lägst vid drift. EGR är en teknik som utöver att klara Tier III-kraven även medför en minskning av en del andra miljöförorenande ämnen. Studien antyder att EGR är det bättre systemet ur emission synpunkt och SCR är det bättre systemet sett till ekonomi. / This case study examines how two marine systems used for reduction of nitrogen oxides from exhaust gases, EGR and SCR, performs in terms of emissions and economic impact. A commonly used two-stroke diesel engine was chosen to be, in theory, equipped with each system. By using a calculation program, CEAS, calculations based on different running conditions were possible and thereby obtain relevant data. With the given consumption of chemicals for each system and the consumption of fuel, costs were able to be calculated after price data was retrieved. With IMO’s tier III regulation as the limit, the inhibited amount of released NOX could be calculated. By using data of produced amounts of exhaust gases, with and without the systems, an estimate could be made on how the systems affect the ship emissions. Calculations were based on an approximation of a vessels lifespan, 20 years. Furthermore, the economic cost for each system was added with the purchase price of each system. Conclusions that could be drawn from the study were, amongst other things, that SCR was the system with the lowest operational cost. EGR does, besides being able to manage the Tier III-requirement, also manage to reduce some other environmental hazardous substances. The study implies that EGR is the better system when viewed in terms of emissions and SCR is the better system when viewed in terms of economy.

La SCR (Selective Catalytic Reduction) permet de réduire les oxydes d'azote (NOx) à l'intérieur d'une ligne d'échappement d'un véhicule Diesel à l’aide d’une solution réductrice à base d’urée injectée en amont d’un catalyseur. L'urée est convertie en NH3 par pyrolyse et hydrolyse, et NH3 réduit les NOx enN2 sur le catalyseur. Cependant, comme cette technique met en jeu un ensemble de réactions très complexes, beaucoup de réactions parasites peuvent entraîner la formation de produits secondaires contenant de l'azote et perturber le bon déroulement du procédé. Par conséquent, l’élaboration d’une étude sur la mesure de ces produits secondaires et de leurs conditions de formation est donc essentielle pour la bonne calibration de la SCR. Si pour certains composés, les techniques de mesures sont encore à développer, dans tous les cas, on se trouve confronté à des problèmes liés au prélèvement des espèces. L'objectif de la thèse est d'identifier, de comprendre et de quantifier les phénomènes qui entrent en jeu et qui perturbent l'analyse des composés azotés dans la ligne d'échappement et dans la ligne de prélèvement. Le travail a été mené selon différents axes de recherche : la comparaison des méthodes de mesure de composés azotés en situation réelles dans les gaz d‘échappement d'un moteur Diesel muni d’un catalyseur SCR, l'étude du prélèvement des composés azotés et notamment NH3 dans une ligne de prélèvement standard et la modélisation des pertes dans une ligne de prélèvement. A la fin de ce travail, nous avons évalué l’impact des conditions de prélèvements : température des gaz, composition et/ou longueur des lignes de prélèvement, sur les résultats de la mesure. Ce travail nous permet d'apporter des suggestions pour améliorer le prélèvement et les mesures des composés azotés présents à l'échappement d'un véhicule Diesel équipé d'une SCR. / SCR (Selective Catalytic Reduction) reduces nitrous oxides (NOx) in the exhaust line of a Diesel vehicle using a reducing solution containing urea injected upstream of a catalyst. Urea is converted by pyrolysis and hydrolysis in NH3, NH3 reduces NOx in N2 on the catalyst. However, as this technique involves a very complex set of reactions, many side reactions can lead to the formation of secondary products containing nitrogen and disturb the process. Therefore, the study of the measurement of these secondary products and the conditions of their formation is essential for the proper calibration of the SCR technology. If for some compounds, the measurement techniques are already on the market, for other devices they are still developing, but in all cases, we are faced with problems related to the collection of species that disturb measurement. The objective of this thesis is to identify, understandand quantify the phenomena that disturb the analysis of nitrogen compounds in the exhaust and the sampling line. The work was carried out in different areas of research: comparison of methods for measuring nitrogen compounds in real situations in the exhaust gas of a Diesel engine equipped with an SCR catalyst, study of the sampling of nitrogen compounds and particularly NH3 in a standard sampling line and modelling of losses in the sampling line. At the end of this work, we evaluated the impact of sampling conditions: temperature, gas composition and / or length of the sample lines on the measurement results. This work allows us to make suggestions to improve the sampling and the measurement of nitrogen compounds present in the exhaust of a Diesel vehicle equipped with an SCR.

La Réduction Catalytique Sélective (SCR) par l'ammoniac, ou l'urée, est un procédé connu de post-traitement permettant de réduire efficacement les oxydes d'azote émis par les motorisations Diesel, en azote et en eau. Les zéolithes échangées au cuivre sont parmi les meilleures formulations pour une application sur véhicules légers, puisque efficaces sur une large zone de température. Le but de cette thèse était d'étudier la stabilité hydrothermale de ce type de catalyseur. L'approche utilisée au cours de ce travail repose sur l'étude des différentes fonctionnalités d'un catalyseur commercial de NH3-SCR présent sous forme de monolithe, à l'état frais et pour différentes conditions de vieillissement, au Banc Gaz Synthétique couplée à une analyse physico-chimique précise de la phase active du catalyseur. Ceci nous a permis de comprendre les phénomènes de désactivation intervenant au cours d'un vieillissement hydrothermal et de mesurer leur impact sur l'activité et la sélectivité de ce type de catalyseur. Après traitement hydrothermal, on assiste à une désalumination plus ou moins importante de la zéolithe, pouvant conduire à l'effondrement de sa structure, ainsi que d'importantes modifications au niveau du cuivre dès les plus faibles températures de vieillissements. Les résultats ont montré l'importance de maintenir une teneur minimal de cuivre en position d'échange, afin de conserver une capacité de stockage en ammoniac suffisante, mais surtout pour garantir une bonne efficacité à basse température en SCR du NO. Le maintien de la structure de la zéolithe semble essentiel pour que le catalyseur conserve une bonne efficacité et sélectivité au cours du temps. / The Selective Catalytic Reduction (SCR) by ammonia, or urea, is a well-known after-treatment process used for converting efficiently the nitrogen oxides, emitted by Diesel engines, into nitrogen and water. Copper-exchanged zeolites are among the most efficient formulations for light-duty applications, since effective over a wide temperature-range. The aim of this thesis is to study the hydrothermal stability of this type of catalyst. The approach used is this work is based on the study of the catalytic properties of a fresh commercial monolith catalyst for NH3-SCR in fresh and after different ageing conditions, at synthetic gas test bench, coupled with a comprehensive physicochemical analysis of the catalyst active phase. This allowed us to understand the deactivation phenomena occurring during a hydrothermal ageing and the impact on the catalyst activity and selectivity. A hydrothermal treatment induces a dealumination of the zeolite, into a more or less significant extent, which can lead to its collapse, as well as important modifications of the copper sites, even at low ageing. The results showed the importance to maintain a minimal copper content into exchanged sites, in order to retain a sufficient ammonia storage capacity, and especially to provide a good efficiency for the SCR of NO at low temperature. The preservation of the zeolite structure seems to be essential in order to maintain the catalyst efficiency and selectivity over time.

La présente étude a pour objectif l'obtention d'une équation donnant la vitesse globale de la réaction (activité catalytique) de la réaction NH3-SCR sur des catalyseurs du type V2O5/WO3/TiO2 (a) utilisable pour des conditions expérimentales (pressions partielles des réactifs et des constituants du mélange gazeux et températures) réalistes des conditions des rejets gazeux des centrales à charbon et (b) capable de rendre compte des effets d'empoisonnements chimiques du catalyseur. Cette équation sera implantée dans un logiciel de modélisation de l'évolution des performances des catalyseurs industriels développé par EDF. Pour remplir ces objectifs, les outils et les procédures pour l'approche microcinétique expérimentale ont été appliqués. La caractérisation de la première étape clé qui consiste à adsorbé le réactif NH3 à la surface du catalyseur (type d'adsorption, chaleurs d'adsorption de chaque espèce) a nécessité le développement de la méthode AEIR (initialement adaptée à la caractérisation de CO adsorbé sur des particules métalliques). La réactivité des espèces NH3 adsorbées vis-à-vis des différents réactifs (H2O, NOx, O2) a ensuite été étudiée, conduisant à l'élaboration d'un mécanisme cinétique plausible. A partir de ce mécanisme, un modèle cinétique de la réaction NH3-SCR a été développé et comparé aux données expérimentales obtenues sur catalyseurs modèles et commerciaux. Dans la suite de l'étude, les impacts de plusieurs poisons sur les paramètres contrôlant la cinétique de la réaction ont été déterminés expérimentalement. Dans une dernière partie, un modèle permettant de modéliser les performances catalytique de monolithes a été développé (en intégrant le modèle cinétique mis en place au cours de cette étude) et comparé à des données expérimentales / The aim of the study is to obtain an equation for the overall reaction rate of the NH3-SCR reaction over V2O5/WO3/TiO2 catalysts (a) used for the experimental conditions (partial pressure of components of the gas mixture and temperature) realistic conditions of discharges from coal power plant and (b) able to take into account the chemical poisoning effects of the catalyst. This equation will be implemented in software developed by EDF for modeling the evolution of the performance of industrial catalysts. To fulfill these objectives, tools and procedures for the experimental microkinetic approach were applied. The characterization of the first key step of the reagent adsorbed NH3 on the surface of catalyst (type adsorption, heats of adsorption of each species) has necessitated the development of the AEIR method (initially adapted to the characterization of CO adsorbed on metal particles). The reactivity of the NH3 adsorbed species to the various reagents (H2O, NOx, and O2) was then studied, leading to the development of plausible kinetic mechanism. From this mechanism, a kinetic model of the NH3-SCR reaction has been developed and compared to experimental data obtained on model and commercial catalysts. In the remainder of the study, the impacts of several poisons to parameters that control the kinetics of the reaction were determined experimentally. In the last part, a model of catalytic monoliths performances was developed (by integrating the kinetic model developed in this study) and compared to experimental data

Le but de cette étude est de trouver un matériau catalytique pour la réduction catalytique sélective des NOx par les hydrocarbures (HC-SCR) dans l’échappement Diesel par une approche haut débit (HTE : high throughput experiments). Ce matériau doit être actif à basse température et stable hydrothermiquement à hautes températures. Une bibliothèque de 150 catalyseurs a été synthétisée. Les catalyseurs sont constituées d’Ag, Au, Cu supportés sur Al2O3, TiO2, ZrO2, CeO2 qui peuvent être dopés (Ga, Mo…). Ceux-ci sont testés en parallèle dans un dispositif constitué de 16 réacteurs (SWITCH-16) au cours réaction à température programmée (TPR) avec un flux modèle (100ppm NO / 350ppm C3H6 / 15% O2 /11% H2O). Le meilleur catalyseur 5%Ag/1%P/Al2O3, testé plus avant, montre une température de light-off de 50°C en dessous de celle d’un catalyseur commercial de référence et celui-ci est stable après un vieillissement de 16h à 750°C en présence d’eau. Ce catalyseur est ensuite enduit par voie sol-gel sur un monolithe (1*2 pouces et 300 cpsi) et testé sur un mini-pilote. Les tendances obtenues en réacteur à lit fixe montés en parallèle sont confirmées sur mini-pilote. En parallèle une approche microcinétique expérimentale des étapes élémentaires de surface impliquées dans la HC-SCR du NO sur un catalyseur Ag/Al2O3 a été utilisée pour déterminer les étapes élémentaires contrôlant la conversion du NO en prenant en compte l’adsorption compétitive entre NO et CO présent dans le gaz d’échappement Diesel. Nous avons identifié l’élimination des espèces Oads adsorbées sur des sites Ag° comme étape limitante pour la production de N2 et suggéré une nouvelle orientation possible pour l’étude HTE. / The aim of this study was to discover a catalytic material for NOx reduction by HC-SCR in Diesel exhaust which is active at the lowest temperatures and hydro thermally stable at high temperatures by using High Throughtput experiments (HTE). A library of 150 catalysts was synthesized. Catalysts are supported Ag, Au, Cu on Al2O3, TiO2, ZrO2, CeO2 and further doped with different dopants (Ga, Mo, …). They were tested in a 16-parallel reactor (SWITCH-16) using a Temperature Program Reaction (TPR) protocol with a model feed (100ppm NO / 350ppm C3H6 / 15% O2 /11% H2O). The best catalyst formulation 5%Ag/1%P/Al2O3, which was further improved, exhibits a light off temperature of 50°C lower than a reference commercial catalyst and is stable after ageing at 750°C in presence of water for 16 hrs. For pilot testing, the best catalyst was deposited by sol-gel method on a 1x2 inch monolith (300 cpsi). We showed the consistency of catalytic results obtained in the parallel fixed beds match with monolith bench testing. In parallel a experimental microkinetic approach of surface elementary steps involved in the HC-SCR of NO on Ag/Al2O3 catalyst has been performed to reveal the elementary steps controlling the conversion of the NO reactant taking into account the competitive chemisorption between NO and CO that is present in an exhaust gas. We identified the elimination of Oads species adsorbed on Ag° sites as the limiting step for the N2 production and suggested a new orientation of a HTE study.

This thesis investigates the impact of Solvency II on the asset side of Swedish mutual life insurers. With the help of a quantitative analysis and a qualitative examination of our results we find that there will be a significant change in demand for certain products. A substantial increase in demand for government bonds and interest rate swaps with long maturities should be expected. Furthermore, both corporate and covered bonds will be more attractive investments under the new regulatory framework. Another big impact is the lower risk-adjusted return for equity, which over time will lead to a reduction in Swedish life insurers’ relatively high exposure to equity and equity based products. Furthermore, we conclude that there are large gains to be made by incorporating an optimization with regard to the solvency capital requirements dictated by the legislative texts. / Denna uppsats har undersökt vilken inverkan Solvens II kommer ha på svenska ömsesidiga livbolags tillgångssidor. Med hjälp av en kvantitativ analys och en kvalitativ undersökning av våra resultat har vi funnit att det kommer ske en betydande förändring i efterfrågan av vissa instrument. En stor ökning på efterfrågan av statsobligationer och ränteswappar med långa löptider är att vänta. Dessutom kommer både företags- och säkerställda obligationer vara betydligt mer attraktiva investeringsalternativ under det nya regelverket. En annan stor inverkan är den lägre riskjusterade avkastningen för aktier och aktierelaterade produkter. Över tid kommer detta sannolikt leda till en reduktion av svenska livbolags relativt höga exponering har gentemot aktier. Därutöver finner vi att bolagen har mycket att vinna på att införliva en optimering med avseende på de av regelverket angivna kapitalkraven.

<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>

Stringent pollutant regulations on diesel-powered vehicles have resulted in the development of new technologies to reduce emission of nitrogen oxides (NOx). The urea Selective Catalyst Reduction (SCR) system and Lean NOx Trap (LNT) have become the two promising solutions to this problem. Whilst the LNT results in a fuel penalty due to periodic regeneration, the SCR system with aqueous urea solution or ammonia gas reductants could provide a better solution with higher NOx reduction efficiency. This thesis describes an experimental investigation which has been designed for comparing the effect NOx abatement of a SCR system with AdBlue urea spray and ammonia gas at 5% and 4% concentration. For this study, a SCR exhaust system comprising of a diesel particulate filter (DPF), a diesel oxidation catalyst (DOC) and SCR catalysts was tested on a steady state, direct injection 1998 cc diesel engine. It featured an expansion can, nozzle and diffuser arrangement for a controlled flow profile for CFD model validation. Four different lengths of SCR catalyst were tested for a space velocity study. Chemiluminescence (CLD) based ammonia analysers have been used to provide high resolution NO, NO2 and NH3 measurements across the SCR exhaust system. By measuring at the exit of the SCR bricks, the NO and NO2 profiles within the bricks were found. Comparison of the measurements between spray and gas lead to insights of the behaviour of the droplets upstream and within the SCR bricks. From the analysis, it was deduced that around half to three quarters of the droplets from the urea spray remain unconverted at the entry of the first SCR brick. Approximately 200 ppm of potential ammonia was released from the urea spray in the first SCR brick to react with NOx. The analysis also shows between 10 to 100 ppm of potential ammonia survived through the first brick in droplet form for cases from NOx-matched spray input to excess spray. Measurements show NOx reduction was complete after the second SCR bricks. Experimental and CFD prediction showed breakthrough of all species for the short brick with gas injection due to the high space velocity. The long brick gas cases predictions gave reasonable agreement with experimental results. NO2 conversion efficiency was found higher than NO which contradicts with the fast SCR reaction kinetics. Transient response was observed in both cases during the NOx reduction, ammonia absorption and desorption process. From the transient analysis an estimate of the ammonia storage capacity of the bricks was derived. The amount of ammonia slippage was obtained through numerical integration of the ammonia slippage curve using an excel spreadsheet. Comparing the time constant for the spray and gas cases, showed a slightly faster time response from the gas for both NOx reduction and ammonia slippage.

<p>Samples of SCR catalysts were impregnated with the following alkali salts; KCl, K2SO4 and ZnCl2 at two different concentrations in a wet impregnation method. The activities of the six samples were measured in a test reactor and at different temperatures between 250-350 ºC. Compared to fresh catalyst, the impregnated samples all had lower activity. It seems like KCl is the most poisoning salt, depending on the lowest value of the activity. The experimental results are expected as compared to earlier articles, which reports that all alkali salts has deactivating effects on a catalyst and that KCl is among the most poisoning ones. By making a cross-section SEM analysis, the penetration of the metals at different depths in to the catalyst material wall was evaluated. An ICP-AES analysis was carried out in order to see the concentration of K and Zn of the test samples. Finally, the pore diameter and active surface was measured by BET method. Since the values of the active surface didn’t change compared to a fresh catalyst and the pore diameter was only slightly decreased we can suppose that the alkali salts deactivates the catalyst by coating of the catalyst pore structure and not as a pore blocking.</p>

The depletion of fossil fuels together with growing environmental concerns have created incitement for developing a more energy-efficient and environmentally-friendly vehicle fleet. The development towards cleaner heavy-duty vehicles started already in the 80’s with the introduction of emission legislations. Initially, engine optimization was enough for reaching the legislated levels of emissions. However, at present engine optimization is not enough but exhaust aftertreatment has become an essential part of heavy-duty vehicles, in order to meet the emission standards. Today, the total emissions are targeted which means that there is an interest in decreasing the idling emissions as well as the emissions during operation. To reduce the overall emissions several states in the USA have introduced idling legislations. Due to the limitations in idling time alternative solutions for power generation during rests are requested. A possible alternative is a fuel cell auxiliary power unit, combining a fuel cell with a fuel reformer (FC-APU).  The focus of this thesis is the development of the fuel reformer for an FC-APU, in which the hydrogen to the fuel cell is generated from diesel in a high-temperature catalytic process. The produced hydrogen can also be used in other heavy-duty vehicle applications i.e. selective catalytic reduction of NOx (HC-SCR), where addition of hydrogen is essential for reaching high conversion at low temperatures. The effect of using hydrogen from a fuel reformer in HC-SCR is included in this work. The catalytic material development is focused on developing promoted materials with lower rhodium content but with catalytic activity comparable to that of materials with higher rhodium content. This includes evaluation and extensive characterization of both fresh and aged promoted materials. The work also includes reactor design where a micro reactor with multiple air inlets is evaluated. This work has contributed to increased knowledge of catalytic materials suitable for reforming of diesel. By changing the support material from the traditionally used alumina to ceria-zirconia, increased H2 yield was achieved. In addition, the ceria-zirconia supported material was less prone to coke. By promoting the material with cobalt or lanthanum it was possible to decrease the rhodium content by 2/3 with enhanced catalytic performance. It was also discovered that promotion with lanthanum decreased the tendency for coking even further. Additionally, the lanthanum-promoted material had higher thermal stability as well as a stable highly dispersed rhodium phase. Furthermore, the work has contributed to an increased knowledge concerning the fuel reformer’s effect on HC-SCR. The work displays clear evidence of benefits with using hydrogen-rich gas from a fuel reformer instead of pure hydrogen. The benefits are derived from the content of low molecular weight hydrocarbons present in the hydrogen-rich gas, which are strong reducing agents increasing the NOx reduction. This finding proves that fuel reforming in combination with HC-SCR is a viable option for NOx abatement. / <p>QC 20150202</p>