Avfallsförbränning kan användas för att minska volymen hos avfallet, destruera farligt avfall och utvinna energi för el- och värmeproduktion. Umeå Energis kraftvärmeverk Dåva 1 förbränner hushålls- och verksamhetsavfall. Vid förbränningen bildas bland annat kväveoxider (NOx) vars utsläpp regleras dels av Förordning SFS 2013:253 om förbränning av avfall och dels av Lagen (1990:613) om miljöavgift på utsläpp av kväveoxider (NOx) vid energiproduktion (kväveoxidavgiften). Dåva 1 använder selektiv icke-katalytisk rening (SNCR) med ammoniakinsprutning för att rena rökgaserna från NOx. En del av ammoniaken förblir oreagerad (ammoniakslip) och bidrar troligen till korrosion på den kallare lågtrycksekonomisern nedströms rökgaskanalen. Umeå Energi vill minska sina utsläpp av NOx utan att öka risken för ammoniakrelaterad korrosion av lågtrycksekonomisern. I det här arbetet undersöktes om och hur NOx-bildningen kunde minskas och om det befintliga SNCR-systemet kunde optimeras. Vidare gjordes en utredning om användningen av selektiv katalytisk rening (SCR) på svenska avfallsförbränningsanläggningar samt om och var i Dåva 1 SCR skulle vara fördelaktig att installera. Effektiviteten hos SNCR-systemet testades genom att i perioder stänga av ammoniakdoseringen och logga rökgasinnehållet. Det visade sig vara mycket effektivt (80 %) om det kördes vid rätt temperaturintervall. Men det framkom också att temperaturgränserna för vilken tdoseringsnivå som används troligen kan behöva korrigeras för förbättringar i effektiviteten vid andra temperaturer. Det skulle kunna minska både NOx-utsläpp och ammoniakanvändningen. Användningen av SCR vid svenska avfallsanläggningar undersöktes genom intervjuer. Det visade sig vara bara fem anläggningar och där alla hade placerat katalysatorn i rengasposition, alltså efter elfilter och våt rening. Rökgasinnehållet vid tre olika positioner i Dåva 1 undersöktes för att se om det fanns höga halter av SO2, HCl och stoft, vilka i kombination med ammoniak kan skapa beläggningar som minskar effektiviteten hos en katalysator. Alla positioner låg efter slangfiltren och hade därmed låg stofthalt. Position A låg mellan slangfilter och högtryckseko1 hade den varmaste positionen (205℃) och position B efter ekopaketen (145℃). Position C var efter alla reningssteg i rengaspostion och svalaste positionen (65℃). Variationen hos temperaturerna för de olika positionerna medför en stor skillnad i behovet av att återvärma rökgaserna. Den säkraste positionen, med lägst innehåll av stoft, HCl och SO2 var rengaspositionen, men den krävde istället mest uppvärmning av rökgaserna. Med tanke på att SNCR-systemet visade sig ha förbättringspotential, borde det effektiviseras innan man överväger att installera ett SCR system. / Waste incineration is used to reduce the volume of waste, destruction of hazardous waste and to extract energy in combined heat and power plants (CHP). Umeå Energi’s CHP Dåva 1 incinerates municipal solid waste (MSW) and other hazardous waste. Nitrogen oxides (NOx) are formed in the combustion process. The emission of NOx is regulated in Sweden’s regulation SFS 2013:253 and law 1990:613. Dåva 1 uses selective non-catalytic reduction (SNCR) with ammonia as flue gas treatment, to reduce NOx in the flue gas. Some of the ammonia in the process remains unreacted (ammonia slip) and it probably contributes to corrosion in the colder economizer. Umeå Energi wants to reduce the NOx emissions without increasing the ammonia related corrosion of the economizer. In the present study, the possibility to reduce NOx formation by SNCR optimization was evaluated. Furthermore an investigation on the use of selective catalytic reduction (SCR) in waste incineration plants in Sweden, and whether it is beneficent to install in Dåva 1, was included. The current efficiency of the SNCR system was tested by switching of the ammonia in short periods of time and measuring and logging the flue gas composition. The efficiency (80 %) proved to be very high if operated at the optimal temperature. ButHowever, the test also showed that the temperature limits for the injection levels could be optimized for improved efficiency. Improved efficiency at all temperatures could reduce both NOx emission and ammonia use. The use of SCR in Swedish waste incineration plants was investigated through interviews. It was found that only five plants are equipped with SCR and they were placed in the clean gas position – after electrostatic precipitatorelectric filter and wet scrubber treatment. The contents of the flue gas was examined monitored at three positions at Dåva 1. The content of SO2, HCl and dust were measured, which in combination with ammonia can cause coating with reduces the efficiency of the catalyst. All three positions were located after the textile filters and had low contents of dust. Position A was located between the textile fabric filters and the economizers and was the hottest position with 205℃. Position B was located after the economizers and had the temperature of 145℃. Position C had the cleanest and thereby the safest position for a catalyst, due to its location after all the flue gas treatments, but the temperature was only 65℃ and requires most re-heating of the flue gas. Since the SNCR system proved to have potential to be more efficient, it should be optimized before considering an investment in a SCR system.

O trabalho procura sistematizar de forma metodológica a análise da inserção de uma usina termoelétrica no contexto do planejamento, no âmbito regional, sob o ponto de vista de impacto ambiental atmosférico. O método de previsão indica a primeira estimativa da condição regional, alternativo ao método convencional de medição, sobretudo em regiões carentes de informações. Baseado em informações disponíveis em banco de dados e uma análise preliminar da região de influência do empreendimento, é estimada a carga de poluentes atmosféricos existentes (poluição de fundo). As taxas de emissão por fonte são obtidas através de fatores de emissão, enquanto que a qualidade do ar é obtida por modelo de dispersão. O impacto da nova usina é incluído no modelo para avaliar o acréscimo. O modelo foi aplicado na análise de emissão e dispersão de NOx, sendo desenvolvido um estudo de caso para a região de Paulínia em São Paulo. / This paper intends to introduce a methodology to analyze the insertion of a Thermal Power Plant (TPP ) within a planning environmental phase from the viewpoint of air pollution impact, focusing the regional ambiance. The prediction methodology indicates the first regional condition estimative, as an alternative to the monitoring conventional one, mainly in region without information. Based on available data basis information and preliminary analysis of the region affected by the TPP, the local pollutants are estimated (background pollution). The source emission rates are calculated through emission factors while the air quality is obtained by using a dispersion model. The impact of the new TPP is added to the model to evaluate the emission growth. The predictive and dispersion model for NOx is synthesized and applied in a case study that considers Paulínia region in State of São Paulo.

Electricity generating units (EGUs) are major emitters of both nitrogen oxides (NOx) and CO₂, and cap-and-trade programs are either currently used or proposed as management strategies for both pollutants. Emission cap and trade programs for these two pollutants have generally been considered independently, but since each EGU will have a characteristic NOx to CO₂ emission ratio, these programs are inherently connected. This thesis examines the extent to which CO₂ emission pricing and NOx emission markets are likely to influence each other, using Texas as a case study. The relationship is first demonstrated with a simple scenario of four power plants, followed by a second scenario accounting for the largest 34 plants in Texas. The analysis demonstrates that future CO₂ pricing will cause NOx emissions markets to be inefficient at reducing emissions through changes in the dispatching order. There will also exist a greater potential for NOx price spikes. Two plausible alternatives to this problem are suggested: a temporally- and spatially-variable NOx program, or increased emphasis on retrofitting the existing fleet of power plants for NOx reduction. / text

A comprehensive model, previously developed and tested for prediction of behavior of continuous fluidized bed combustors is extended to incorporate NOx formation and reduction reactions and applied to the simulation of METU 0.3 MWt Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) burning lignites with high volatile matter in their own ashes. The predictive accuracy of the model was assessed by comparing its predictions with measurements taken previously on the same rig. Favorable comparisons are obtained between the predicted and measured temperatures and concentrations of gaseous species along the combustor. Results show that determination of partitioning of coal nitrogen into char nitrogen and volatile nitrogen, and release of volatile nitrogen along the combustor are found to be the most important parameters that affect NOx formation and reduction in bubbling fluidized bed combustors. The system model proposed in this study proves to be a useful tool in qualitatively and quantitatively simulating the processes taking place in an atmospheric fluidized bed combustor.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T13:25:50Z No. of bitstreams: 1 Rodrigo Albuquerque.pdf: 737432 bytes, checksum: 3351ed8449f3bb0f3c8410fe64500d25 (MD5) / Made available in DSpace on 2013-04-23T13:25:50Z (GMT). No. of bitstreams: 1 Rodrigo Albuquerque.pdf: 737432 bytes, checksum: 3351ed8449f3bb0f3c8410fe64500d25 (MD5) Previous issue date: 2006 / Recentemente, o desenvolvimento de tecnologias eficientes visando à redução dos óxidos de nitrogênio, em regeneradores de unidades de craqueamento catalítico em leito fluidizado, tem se tornado uma grande preocupação, devido aos rigorosos limites de emissão impostos pela legislação ambiental. Como a maioria das refinarias utiliza promotores de combustão, os catalisadores de redução devem operar em presença de monóxido de carbono e devem ser capazes de remover ambos os poluentes. Os óxidos metálicos suportados têm sido considerados como substituintes apropriados para os catalisadores à base de metais nobres. Entre eles, o cobre tem sido apontado como uma espécie ativa muito atrativa para a reação. Além disso, observou-se que a adição de um segundo metal melhora o desempenho catalítico dos materiais e que o suporte desempenha um papel importante na reação. Considerando estes aspectos, neste trabalho foi estudada a influência de diferentes suportes (ZrO2, CeO2 e ZrO2 -CeO2), no desempenho de catalisadores à base de cobre e ferro na redução catalítica de óxidos de nitrogênio usando monóxido de carbono como agente redutor. Os suportes foram preparados por técnicas de precipitação e os metais foram impregnados a partir de soluções de acetato de cobre e nitrato de ferro, seguido de calcinação a 450ºC. As amostras foram caracterizadas por análise química, análise térmica diferencial, termogravimetria, difração de raios X, medida de área superficial específica, espectroscopia por reflectância difusa na região do ultravioleta e visível, espectroscopia no infravermelho por transformadas de Fourier de monóxido de carbono quimissorvido, redução por hidrogênio à temperatura programada e espectroscopia fotoeletrônica de raios X. Os catalisadores foram avaliados, na faixa de 150 a 500ºC, na redução do óxido nítrico com monóxido de carbono. Observou-se que o suporte à base de zircônio era constituído das fases tetragonal e monoclínica e o óxido de cério da fase cúbica. Foi observado que o cério estabilizava a fase tetragonal do óxido de zircônio no suporte misto. Em todas as amostras, as áreas superficiais específicas foram próximas a 100 m2.g-1. Os resultados de XPS mostraram que o estado de oxidação do cobre era função do suporte usado. Entretanto, independente do suporte utilizado, a adição de ferro modificou as propriedades químicas do cobre favorecendo a formação de espécies mais redutíveis na superfície do catalisador. Os catalisadores contendo os dois metais mostraram-se mais ativos, seguidos por aqueles contendo ferro e cobre. O desempenho superior do catalisador bimetálico suportado em óxido de cério foi atribuído à capacidade dos metais em facilitar o ciclo redox, que ocorre durante a reação de redução do óxido nítrico com monóxido de carbono. / Salvador

Made available in DSpace on 2015-05-14T13:21:16Z (GMT). No. of bitstreams: 1 Arquivototal.pdf: 2075679 bytes, checksum: 6487008fc918692d361b88ccaa75fbd5 (MD5) Previous issue date: 2012-08-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Vegetable oils can be used as alternative for diesel fuel, due to their combustion characteristics and low environmental impact. However, due to their fluid dynamic properties its usage "in nature" is limited. But they may be used as a component for microemulsion fuels. In such context, the present work aims to obtain, characterize and evaluate the combustion properties of three different babassu microemulsions. Therefore, pseudo-ternary phase diagrams were constructed for each system. According to the phase diagrams, the following homogeneous regions were selected: MAIb consisting of 54:3:43 %(m/m.) (refined babassu oil: distilled alcohol: isobutyl alcohol); MAIa consisting of 51:1:48 %(m/m.) (refined babassu oil: distilled alcohol: isoamyl alcohol); MEF consisting of 49:5:46 %( m/m) (refined babassu oil: hydrated ethanol fuel: fusel alcohol). Then, all samples were evaluated using light scattering test (LST), being observed microemulsion characteristic droplet sizes: 3.80 (MAIb), 1.55 (MAIa) and 26.0 (MEF) nm. Later, new pseudoquaternary systems were obtained by blending the pseudo-ternary microemulsions with diesel [10, 20 and 30% (wt./wt.)]. All samples were characterized by kinematic viscosity at 40 ° C, density at 20 ° C, flash point, turbidity and acidity index. The emission levels and cetane number were determined for each systems. It was observed a decrease of CO and an increase of NOx emissions for the system MEF and for system which contain 30% and 100% of the MAIa. All other mixing systems emitted less NOx than diesel. All systems tested have lower cetane number than diesel. It follows that microemulsions can be used as fuel in partial or total replacement of diesel, in a wide variety of compositions, most available in remote locations. / Os óleos vegetais constituem uma alternativa renovável para substituir o diesel por causarem um menor impacto ambiental. Entretanto, devido suas propriedades fluidodinâmicas, o seu uso in natura em motores é limitado. Ainda assim, os mesmos podem ser utilizados como componentes de microemulsões combustíveis. O objetivo deste trabalho é obter três diferentes sistemas microemulsionados de óleo de babaçu e avaliar se os mesmos apresentam características de combustíveis. Inicialmente, foi se construindo um diagrama de fases pseudoternário para cada sistema. Na região homogênea de cada diagrama foram selecionadas proporções, em massa, de cada componente. Os sistemas microemulsionados estudados receberam a seguinte denominação: MAIb,formado por 54:3:43 % (m/m) (óleo de babaçu refinado: aguardente:álcool isobutílico). MAIa, formado por 51:1:48 % (m/m) (óleo de babaçu refinado: aguardente: álcool isoamílico) e MEF, formado por 49:5:46 % (m/m) (óleo de babaçu refinado: etanol hidratado: óleo fúsel). Os três sistemas foram submetidos à análise por espalhamento de luz, onde se observou que os mesmos apresentam tamanho de gotículas, característico de microemulsões, ou seja, 3,80; 1,55 e 26,0 nm para MAIb, MAIa e MEF, respectivamente. Logo após, foram preparadas misturas desses sistemas com o diesel, na proporção de [10, 20 e 30 % (m/m)]. Em seguida, cada microemulsão pura ou misturada ao diesel foi submetida a análises de caracterização (viscosidade cinemática a 40 °C, massa específica a 20 °C, ponto de fulgor, turbidez e índice de acidez), obtendo-se resultados satisfatórios. Também foram determinados os níveis de emissão e o número de cetano para os combustíveis. Os resultados mostraram uma diminuição das emissões de CO e uma elevação das emissões de NOx para o sistema MEF, para a microemulsão pura do sistema MAIa e para a sua mistura 30 % com o diesel. Os demais combustíveis emitiram menos NOx que o diesel. Quanto ao número de cetano, este foi menor que o determinado para o diesel em todas as misturas combustíveis. Dessa forma, acredita-se que é possível utilizar as microemulsões como combustíveis em substituição parcial ou total ao diesel, podendo utilizar uma ampla variedade de composições, a maioria disponível em localidades remotas.

Ce travail traite de la réduction catalytique sélective des oxydes d’azote en utilisant du méthane comme agent réducteur sur catalyseurs bimétalliques Pd/Ce/zéolithes. Dans un premier temps, la méthode d’introduction du palladium, la teneur en palladium et cérium ainsi que l’ordre d’introduction des métaux ont été optimisés pour une formulation considérant une zéolithe MOR comme support catalytique. Puis, l'effet des différentes conditions opératoires ont été évalués. L’effet du support catalytique a été également étudié en comparant un catalyseur PdCe-BEA au catalyseur PdCe-MOR résultant de l’optimisation effectuée. Il a été montré que les deux catalyseurs possèdent différentes espèces métalliques conduisant ainsi à différentes performances catalytiques. Des Relations structure/réactivité ont été établies par différentes techniques de caractérisation et des résultats des tests catalytiques. Il a été mis en évidence un effet synergique résultant de la combinaison de ces deux catalyseurs dans le même pot catalytique (configurations lit mélangé et lit double). Un traitement thermique innovant appliqué au catalyseur PdCe-MOR, pendant sa préparation a été développé et optimisé. Dans certaines conditions, ce traitement conduit à l’amélioration de la performance catalytique, notamment, à une conversion de NOx à N2 et à une sélectivité de CH4 pour la réaction NOx RCS plus élevée. Enfin, des catalyseurs structurés ont été préparés par "washcoating" de PdCe-MOR sur des monolithes de cordiérite possédant des géométries différentes. Les paramètres de préparation ont été ainsi évalués par des techniques de caractérisations et par des tests en banc de gaz. / The selective catalytic reduction of nitrogen oxides, in lean-conditions, using methane as reductant (NOx CH4-SCR) over PdCe/zeolite-based catalysts was considered in this work. Preparation method for palladium introduction, palladium/cerium loadings and metal introduction order were optimised for a formulation considering MOR zeolite as the catalytic support. The effect of different test conditions, namely [CH4]/[NO] ratio and water presence in the reaction mixture was assessed. The effect of the zeolite support in the stabilisation of Pd/Ce species was also evaluated by preparing a similar PdCe-BEA catalyst to the optimised PdCe-MOR catalyst, considering the same metal loadings and preparation methods. Both catalysts exhibited different metal species and different catalytic performances. Structure-reactivity relationships were drawn from the comparison of several characterisation techniques and catalytic test results for both catalysts. A synergic effect resulting from the use of both catalysts in a single bed application (mixed-bed and dual-bed configuration) is reported. An innovative thermal treatment applied to PdCe-MOR catalyst during its preparation is reported. Under certain conditions, this treatment results in the enhancement of the catalytic performance, namely, in higher NOx conversion into N2 and CH4 selectivity towards NOx SCR. Structured catalysts were prepared by washcoating of PdCe-MOR onto cordierite monoliths with different geometry (cpsi). Preparation parameters were evaluated through characterisation techniques and the catalytic performance was assessed in a synthetic gas bench plant.

La réduction des émissions polluantes des foyers aéronautiques est un enjeu majeur pour les motoristes. Afin de les accompagner dans cette tâche, il est nécessaire de développer des outils de simulation numérique permettant de prédire avec précision les émissions d'espèces chimiques en sortie du foyer. Pour cela, une description détaillée des réactions chimiques est nécessaire. Celle-ci est néanmoins incompatible avec la simulation des foyers industriels, compte tenu des puissances de calcul actuelles. C'est pourquoi il est nécessaire de recourir à des méthodes de réduction de la chimie qui préservent la capacité de prédire la concentration des polluants. La démarche consistant à tabuler la chimie nous a semblé appropriée pour aborder ces problèmes et son développement a fait l'objet de cette thèse. Un premier travail a été effectué afin de sélectionner dans la littérature les modèles permettant de traiter des écoulements réactifs turbulents diphasiques avec une approche de chimie tabulée. Par rapport à l’existant, des améliorations ont été apportées à la génération des tables chimiques, afin de prendre en compte l'effet du temps de résidence des gaz brûlés dans le foyer sur la formation des oxydes d'azote. Le couplage de la méthode avec un modèle de formation des suies a également été réalisé. La chimie tabulée permet d’avoir accès à la concentration des précurseurs de suie et des espèces oxydantes, quantités sur lesquelles s’appuie le modèle de formation des suies. Le modèle de chimie tabulée développé dans le cadre de cette thèse a été appliqué à la simulation d'une configuration représentative des foyers aéronautiques. Les concentrations d'oxydes d'azote, de particules de suie, mais aussi de monoxyde de carbone et d'hydrocarbures imbrûlés prédites par les calculs ont été comparées aux résultats expérimentaux. Un bon accord avec l'expérience est observé concernant la topologie du champ de suie et l'allure des profils de concentration de polluants en sortie. Néanmoins, les niveaux de concentration obtenus par les simulations diffèrent des résultats expérimentaux. Cela est imputable notamment à une erreur de prédiction du champ de température qui n'est pas due à l'approche de chimie-tabulée puisque une erreur similaire a été observée avec un autre modèle de combustion. / The reduction of pollutant emissions of aeronautical combustion chambers is a major issue for engine manufacturers. In order to support them in this task, it is necessary to develop numerical simulation tools able to predict accurately chemical species emissions at the chamber outlet. To achieve this, a detailed description of the chemical reactions is necessary. Nevertheless, considering the current computer capabilities, this description is not presently affordable. This is why the use of chemistry reduction methods preserving the capability to predict pollutants species is necessary. The method of tabulated chemistry is a good candidate to tackle these problems and therefore is used as the basis of model developments achieved in the framework of this PhD thesis. A preliminary work has been made to select in the literature tabulated chemistry methods applying to turbulent reactive two-phase flows. The technique to create the chemical tables has been improved in order to take into account the effect of the residence time of the burnt gases on nitrogen oxides formation. The coupling of the method with a soot model has also been achieved. The tabulated chemistry gives access to the concentration of soot precursors and oxidizers, quantities which are required by the model used for the soot prediction. The developed tabulated chemistry model has been applied to the simulation of a configuration representative of aeronautical combustors. The concentration of nitrogen oxides, soot particles, carbon monoxide and unburnt hydrocarbons predicted by the numerical simulations have been compared to experimental results. The topology of the soot volume fraction field and the shape of pollutant concentrations profiles at the outlet agree quite well with the experiments. Nevertheless, concentration levels obtained from the simulations differ from the experimental results. This can be imputed to the error in the prediction of the temperature field that is independent of the combustion model, since a similar error was observed with another combustion model.

En esta tesis doctoral se ha optimizado el desarrollo de catalizadores basados en cobre y óxidos mixtos BaTiO3 con estructura perovskita para ser utilizados en la eliminación de los NOx, emitidos por los vehículos diésel, mediante el proceso de almacenamiento y reducción de NOx (NSR). La actividad de los catalizadores para el almacenamiento de NOx ha sido analizada en distintas atmósferas, en condiciones de temperatura programada y mediante ciclos de adsorción y reducción de NOx a distintas temperaturas. Además, se ha llevado a cabo un estudio mecanístico del proceso de almacenamiento de NOx y se ha probado el efecto de la incorporación en la estructura de otros cationes alcalinotérreos, en la resistencia al envenenamiento por SO2 del óxido mixto.

No description available.