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Modélisation multiphysique de flammes turbulentes suitées avec la prise en compte des transferts radiatifs et des transferts de chaleur pariétaux. / Multi-physics modelling of turbulent sooting flames including thermal radiation and wall heat transferRodrigues, Pedro 08 June 2018 (has links)
Les simulations sont utilisées pour concevoir des chambres de combustion industrielles robustes et peu polluantes. Parmi les polluants, l’émission de particules de suies constitue une question sociétale et une priorité politico- industrielle, en raison de leurs impacts néfastes sur la santé et l'environnement. La taille des particules de suies joue un rôle important sur ces effets. Il est donc important de prévoir non seulement la masse totale ou le nombre de particules générées, mais également leur distribution en taille (PSD). De plus, les suies peuvent jouer un rôle important dans le rayonnement thermique. Dans des configurations confinées, la prédiction des transferts de chaleur est une question clé pour augmenter la robustesse des chambres de combustion. Afin de déterminer correctement ces transferts, les flux radiatifs et de conducto-convectifs aux parois doivent être pris en compte. Enfin, la température pariétale est aussi contrôlée par les transferts conjugués de chaleur entre les domaines fluides et solides. L’ensemble de ces transferts thermiques impactent la stabilisation de la flamme, la formation de polluants et la production de suies elle-même. Il existe donc un couplage complexe entre ces phénomènes et la simulation d'un tel problème multiphysique est aujourd'hui reconnu comme un important défi. Ainsi, l'objectif de cette thèse est de développer une modélisation multiphysique permettant la simulation de flammes suitées turbulentes avec le rayonnement thermique et les transferts conjugués de chaleur associés aux parois. Les méthodes retenues sont basées sur la Simulation aux Grandes Échelles (LES), une description en taille des suies, des transferts conjugués et un code Monte Carlo pour le rayonnement. La combinaison de telles approches est réalisable grâce aux ressources de calcul aujourd’hui disponibles afin d’obtenir des résultats de référence. Le manuscrit est organisé en trois parties. La première partie se concentre sur le développement d'un modèle détaillé pour la description de la production de suies dans les flammes laminaires. Pour cela, la méthode sectionnelle est retenue ici car elle permet la description de la PSD. La méthode est validée sur des flammes laminaires éthylène/air. Dans la deuxième partie, un formalisme LES spécifique à la méthode sectionnelle est développé et utilisé pour étudier deux flammes turbulentes : une flamme jet non-prémélangée et une flamme swirlée pressurisée confinée. Les champs de température et de fraction volumique de suies sont comparés aux données expérimentales. De bonnes prédictions sont obtenues et l’évolution des particules de suies dans de telles flammes est analysée à travers l'étude de l’évolution de leur PSD. Dans ces premières simulations, les pertes de chaleur aux parois reposent sur des mesures expérimentales de la température aux parois, et un modèle de rayonnement simple. Dans la troisième partie, une approche Monte Carlo permettant de résoudre l'équation de transfert radiatif avec des propriétés radiatives détaillées des phases gazeuse et solide est utilisée et couplée au solveur LES. Cette approche est appliquée à l'étude de la flamme jet turbulente. La prédiction des flux thermiques est comparée aux données expérimentales et la nature des transferts radiatifs est étudiée. Ensuite, une modélisation couplée de la combustion turbulente prenant en compte la production de suies, les transferts conjugués de chaleur et le rayonnement thermique est proposée en couplant les trois codes dédiés. Cette stratégie est appliquée pour la simulation du brûleur pressurisé confiné. L'approche proposée permet à la fois de prédire la température des parois et la bonne stabilisation de la flamme. Les processus de formation de suies se révèlent être affectés par la modélisation des transferts thermiques. Ceci souligne l’importance d’une description précise de ces transferts thermiques dans les développements futurs de modèles de production de suies et leur validation. / Numerical simulations are used by engineers to design robust and clean industrial combustors. Among pollutants, soot control is an urgent societal issue and a political-industrial priority, due to its harmful impact on health and environment. Soot particles size plays an important role in its negative effect. It is therefore important to predict not only the total mass or number of emitted particles, but also their population distribution as a function of their size. In addition, soot particles can play an important role in thermal radiation. In confined configurations, controlling heat transfer related to combustion is a key issue to increase the robustness and the life cycle of combustors by avoiding wall damages. In order to correctly determine these heat losses, radiative and wall convective heat fluxes must be accounted for. They depend on the wall temperature, which is controlled by the conjugate heat transfer between the fluid and solid domains. Heat transfer impacts the flame stabilization, pollutants formation and soot production itself. Therefore, a complex coupling exists between these phenomena and the simulation of such a multi-physics problem is today recognized as an extreme challenge in combustion, especially in a turbulent flow, which is the case of most industrial combustors. Thus, the objective of this thesis is to develop a multi-physics modeling enabling the simulation of turbulent sooting flames including thermal radiation and wall heat transfer. The retained methods based on Large-Eddy Simulation (LES), a soot sectional model, conjugate heat transfer, a Monte Carlo radiation solver are combined to achieve a stateof- the-art framework. The available computational resources make nowadays affordable such simulations that will yield present-day reference results. The manuscript is organized in three parts. The first part focuses on the definition of a detailed model for the description of soot production in laminar flames. For this, the sectional method is retained here since it allows the description of the particle size distribution (PSD). The method is validated on laminar premixed and diffusion ethylene/air flames before analyzing the dynamics of pulsed diffusion flames. In the second part, an LES formalism for the sectional method is developed and used to investigate two different turbulent flames: a non-premixed jet flame and a confined pressurized swirled flame. Predicted temperature and soot volume fraction levels and topologies are compared to experimental data. Good predictions are obtained and the different soot processes in such flames are analyzed through the study of the PSD evolution. In these first simulations, wall heat losses rely on experimental measurements of walls temperature, and a coarse optically-thin radiation model. In the third part, to increase the accuracy of thermal radiation description, a Monte Carlo approach enabling to solve the Radiative Transfer Equation with detailed radiative properties of gaseous and soot phases is used and coupled to the LES solver. This coupled approach is applied for the simulation of the turbulent jet flame. Quality of radiative fluxes prediction in this flame is quantified and the nature of radiative transfers is studied. Then, a whole coupled modeling of turbulent combustion accounting for soot, conjugate heat transfer and thermal radiation is proposed by coupling three dedicated codes. This strategy is applied for a high-fidelity simulation of the confined pressurized burner. By comparing numerical results with experimental data, the proposed approach enables to predict both the wall temperature and the flame stabilization. The different simulations show that soot formation processes are impacted by the heat transfer description: a decrease of the soot volume fraction is observed with increasing heat losses. This highlights the requirement of accurate description of heat transfer for future developments of soot models and their validation.
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Modélisation et simulation d’un étage haute température pour la purification d’un gaz chargé en goudrons et en particules carbonées par assistance plasma / Modeling and design of a high-temperature chamber fed by plasma torch for removal of tars and carbonaceous particlesDemarthon, Romain 25 January 2013 (has links)
Afin de répondre aux besoins croissants en énergie primaire, le groupe Europlasma a développé le procédé CHO-Power permettant de valoriser énergétiquement un mélange de refus de tri d’ordures ménagères et de résidus de biomasse. L’une des particularités de ce procédé est l’utilisation d’un réacteur de dégradation thermique des goudrons et des particules solides fines par assistance plasma. L’objectif de cette étude de mieux appréhender les mécanismes réactionnels mis en jeu lors de l’épuration thermique du gaz. Dans cette optique, un réacteur pilote a été dimensionné puis construit sur la plate-forme de Recherche et Développement d’Europlasma. Il a été ensuite nécessaire de modifier le schéma réactionnel permettant la modélisation numérique de la dégradation des goudrons. Ce schéma réactionnel, couplé à l’utilisation d’un logiciel de mécanique des fluides numérique, permet de représenter les processus couplés (chimie, aéraulique, transferts thermiques) se déroulant au sein du réacteur. Deux modifications importantes ont été alors apportées au modèle cinétique simplifié jusque-là utilisé : la modélisation d’une phase discrète réactive permettant de prendre en compte la gazéification des particules de résidus carbonés et l’ajout de nouvelles voies réactionnelles afin de mieux modéliser la formation des particules de suie et de ses précurseurs. À terme, la comparaison des valeurs expérimentales à celle issues de la modélisation numérique permettra de valider ou non le schéma réactionnel dans sa globalité. / In order to contest to the high world demand for primary energy, the Europlasma group developed a new process, called CHO-Power, to enhance the thermochemical potential of a mixture of urban waste and biomass residues. One of the characteristics of this process is the use of a high temperature reactor assisted by a plasma torch for tar and soots thermal cracking. The aim of this study to improve the knowledge of the global reaction mechanism involved during the thermal treatment of gas. In this context, a pilot plant reactor was designed and built on the Europlasma Research and Development Center. During this work, the reaction pathway used to represent tars cracking at high temperature has been enhanced. Coupled to a computational fluid Dynamics Software, allow simulating the complex processes occurring within the reactor (aeraulics, reaction, and heat transfer). Two major changes were made to the simplified kinetic model previously used: the modeling of a discrete and reactive phase to take into account the possible particle gasification of carbonaceous residues and the addition of new reaction pathways to enhance the modeling of the formation of soot and its precursors. The comparison between the experimental and numerical values will validate or not the global reaction scheme and will give important information about the next evolution of the tar degradation scheme.
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Numerical study of soot formation in laminar ethylene diffusion flamesZimmer, Leonardo January 2016 (has links)
O objetivo desta tese é o estudo de formação de fuligem em chamas laminares de difusão. Para o modelo de formação de fuligem é escolhido um modelo semi-empírico de duas equações para prever a fração mássica de fuligem e o número de partículas de fuligem. O modelo descreve os processos de nucleação, de crescimento superficial e de oxidação das partículas. Para o modelo de radiação, a perda de calor por radiação térmica (gás e fuligem) é modelada considerando o modelo de gás cinza no limite de chama opticamente fina (OTA - Optically Thin Approximation). São avaliados diferentes modelos de cálculo das propriedades de transporte (detalhado e simplificado). Em relação à cinética química, tanto modelos detalhados quanto reduzidos são utilizados. No presente estudo, é explorada a técnica automática de redução conhecida como Flamelet Generated Manifold (FGM), sendo que esta técnica é capaz de resolver cinética química detalhada com tempos computacionais reduzidos. Para verificar o modelo de formação de fuligem foram realizados uma variedade de experimentos numéricos, desde chamas laminares unidimensionais adiabáticas de etileno em configuração tipo jatos opostos (counterflow) até chamas laminares bidimensionais com perda de calor de etileno em configuração tipo jato (coflow). Para testar a limitação do modelo os acoplamentos de massa e energia entre a fase sólida e a fase gasosa são investigados e quantificados para as chamas contra-corrente Os resultados mostraram que os termos de radiação da fase gasosa e sólida são os termos de maior importancia para as chamas estudas. Os termos de acoplamento adicionais (massa e propriedade termodinâmicas) são geralmente termos de efeitos de segunda ordem, mas a importância destes termos aumenta conforme a quantidade de fuligem aumenta. Como uma recomendação geral o acoplamento com todos os termos deve ser levado em conta somente quando a fração mássica de fuligem, YS, for igual ou superior a 0.008. Na sequência a formação de fuligem foi estudada em chamas bi-dimensionais de etileno em configuração jato laminar usando cinética química detalhada e explorando os efeitos de diferentes modelos de cálculo de propriedades de transporte. Foi encontrado novamente que os termos de radiação da fase gasosa e sólida são os termos de maior importância e uma primeira aproximação para resolver a chama bidimensional de jato laminar de etileno pode ser feita usando o modelo de transporte simplificado. Finalmente, o modelo de fuligem é implementado com a técnica de redução FGM e diferentes formas de armazenar as informações sobre o modelo de fuligem nas tabelas termoquímicas (manifold) são testadas A melhor opção testada neste trabalho é a de resolver todos os flamelets com as fases sólida e gasosa acopladas e armazenar as taxas de reação da fuligem por área de partícula no manifold. Nas simulações bidimensionais estas taxas são então recuperadas para resolver as equações adicionais de formação de fuligem. Os resultados mostraram uma boa concordância qualitativa entre as predições do FGM e da solução detalhada, mas a grande quantidade de fuligem no sistema ainda introduz alguns desafios para a obtenção de bons resultados quantitativos. Entretanto, este trabalho demonstrou o grande potencial do método FGM em predizer a formação de fuligem em chamas multidimensionais de difusão de etileno em tempos computacionais reduzidos. / The objective of this thesis is to study soot formation in laminar diffusion flames. For soot modeling, a semi-empirical two equation model is chosen for predicting soot mass fraction and number density. The model describes particle nucleation, surface growth and oxidation. For flame radiation, the radiant heat losses (gas and soot) is modelled by using the grey-gas approximation with Optically Thin Approximation (OTA). Different transport models (detailed or simplified) are evaluated. For the chemical kinetics, detailed and reduced approaches are employed. In the present work, the automatic reduction technique known as Flamelet Generated Manifold (FGM) is being explored. This reduction technique is able to deal with detailed kinetic mechanisms with reduced computational times. To assess the soot formation a variety of numerical experiments were done, from one-dimensional ethylene counterflow adiabatic flames to two-dimensional coflow ethylene flames with heat loss. In order to assess modeling limitations the mass and energy coupling between soot solid particles and gas-phase species are investigated and quantified for counterflow flames. It is found that the gas and soot radiation terms are of primary importance for flame simulations. The additional coupling terms (mass and thermodynamic properties) are generally a second order effect, but their importance increase as the soot amount increases As a general recommendation the full coupling should be taken into account only when the soot mass fraction, YS, is equal to or larger than 0.008. Then the simulation of soot is applied to two-dimensional ethylene co-flow flames with detailed chemical kinetics and explores the effect of different transport models on soot predictions. It is found that the gas and soot radiation terms are also of primary importance for flame simulations and that a first attempt to solve the two-dimensional ethylene co-flow flame can be done using a simplified transport model. Finally an implementation of the soot model with the FGM reduction technique is done and different forms for storing soot information in the manifold is explored. The best option tested in this work is to solve all flamelets with soot and gas-phase species in a coupled manner, and to store the soot rates in terms of specific surface area in the manifold. In the two-dimensional simulations, these soot rates are then retrieved to solve the additional equations for soot modeling. The results showed a good qualitative agreement between FGM solution and the detailed solution, but the high amount of soot in the system still imposes some challenges to obtain good quantitative results. Nevertheless, it was demonstrated the great potential of the method for predicting soot formation in multidimensional ethylene diffusion flames with reduced computational time.
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Material particulado de carbono nos compartimentos de tecidos de macrófagos alveolares e de superfície pulmonar de residentes de São Paulo, Brasil / Carbonaceous particulate matter in the alveolar macrophage and lung surface tissue compartments of residents from São Paulo, BrazilMichele Galhardoni Padovan 10 March 2017 (has links)
Introdução Os fumantes inalam grandes quantidades de partículas de carbono, o que pode contribuir para efeitos adversos pulmonares e sistêmicos. É sabido que os macrófagos alveolares (MA) desempenham um papel extremamente importante no reconhecimento e processamento de qualquer material estranho inalado e são as células predominantes que processam e removem partículas inaladas. Existe também a deposição superficial a longo prazo do carbono observado nos pulmões de fumantes em autópsias. Atualmente, a distribuição e retenção de partículas de fumo derivadas de cigarros quando a pessoa também está exposta a níveis elevados de poluição do ar ainda não é clara. Portanto, procurou-se avaliar a carga de carbono nos MA e a deposição de superfície pulmonar em uma população exposta a alta poluição atmosférica (São Paulo), tanto em fumantes como não-fumantes. Métodos Uma coorte de 72 sujeitos post mortem foi obtida do Serviço de Verificação de Óbitos da Capital da Universidade de São Paulo (SVOC). As imagens das superfícies pulmonares foram obtidas sob condições padrão e pequenos fragmentos de tecido pulmonar foram coletados para análise de macrófagos usando a técnica de esfregaço. A superfície total de negro de carbono foi analisada utilizando o programa Imagem J (National Institute of Health, MD, EUA), teste cego ao fumo. A absorção interna de carbono nos MA foi medida utilizando o programa Image Pro Plus (The Proven Solution, Media Cybernetics Inc., EUA). A aprovação ética foi obtida. A média de negro de carbono de macrófagos tanto em fumantes como em não-fumantes foi analisada utilizando teste de Mann Whitney e expressa como intervalo interquartil (IQR). Resultados Os fumantes têm um nível significativamente mais elevado de negro de carbono nos macrófagos alveolares (103.4 (IQR 29.44 to 226.3) vs. 9.27 (IQR 3.1 to 85.13) um2, P < 0.001)103.4um2. Não houve diferença significativa entre a área média de deposição superficial de carbono nos pulmões de fumantes e não fumantes de 6, 74 cm2 (IQR 3, 47 a 10, 02) versus 5, 20 cm2 (IQR 2, 29 a 7, 54) P=NS. Conclusão O teor de carbono nos MA é claramente muito maior nos fumantes do que os nãofumantes. No entanto, a análise da superfície pulmonar não mostrou diferença significativa. Isso pode indicar que, em uma área de alta poluição do ar, o principal fator que contribui para a deposição de carbono no pulmão a longo prazo é a exposição à poluição com efeitos limitados da exposição à fumaça de cigarro. O preto de carbono nos MA ainda aparece significativamente influenciado pela exposição à fumaça de cigarro / Rationale Smokers inhale large amounts of carbonaceous particulate matter, which may contribute to pulmonary and systemic adverse effects. It is clear that alveolar macrophages (AM) play a critically important role in the recognition and processing of any inhaled foreign material and are the predominant cells that process and remove inhaled particulate matter from the lung. There is also long-term surface deposition of carbon seen in the lungs of smokers at post-mortem. At present the distribution and retention of cigarette smoke-derived particulate matter when the person is also exposed to high levels of background air pollution is unclear. Therefore we sought to assess both AM carbon loading and lung surface deposition in a population exposed to high background air pollution (São Paulo) in both smokers and non-smokers. Methods A cohort of 72 post-mortem subjects was obtained from São Paulo Autopsy Centre (SVOC). Images of lung surfaces were obtained under standard conditions and small fragments of lung tissue were collected for macrophage analysis using smear technique. The total surface black carbon was analysed using Image J (National Institute of Health, MD, USA), blinded to smoking status. Internal AM carbon uptake was measured using Image Pro Plus (The Proven Solution, Media Cybernetics Inc., USA). Ethical approval was obtained. Mean macrophage black carbon in both smokers and non-smokers was analysed using Mann Whitney and expressed as median (IQR). Results Smokers have a significantly higher level of mean macrophage black carbon (103.4 (IQR 29.44 to 226.3) vs. 9.27 (IQR 3.1 to 85.13) um2, P < 0.001)103.4um2. There was no significant difference between the mean area of surface deposition of carbon in the lungs of smokers and non-smokers 6.74 cm2 (IQR 3.47 to 10.02) versus 5.20cm2 (IQR 2.29 to 7.54) P=NS. Conclusion AM carbon content is clearly much higher in the smokers than the non-smokers. However the lung surface analysis showed no significant difference. This could indicate that in an area of high air pollution the main contributing factor to long term lung carbon deposition is pollution exposure with limited effects from cigarette smoke exposure. AM black carbon still appears significantly influenced by cigarette smoke exposure
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Literary Activism: James Montgomery, Joanna Baillie, and the Plight of Britain’s Chimney SweepsSlagle, Judith Bailey 01 January 2012 (has links)
Excerpt: On 6 February 1824, Joanna Baillie Notified Her Friend Walter Scott that Scottish poet James Montgomery, then living in Sherrield, England, had written to ask her for a poem on the plight on chimney sweeps, also known as climbing boys.
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Effets de la combustion du noir de carbone sur l'adsorption des NOx sur un catalyseur quatre voies / 4 way catalysts, Deactivation of the NOx storage trap function by sootKlein, Jennifer 20 October 2011 (has links)
Récemment, les constructeurs automobiles se sont intéressés au développement des catalyseurs appelés quatre voies, destinés à diminuer simultanément les émissions polluantes des moteurs diesels par l'intermédiaire d'un seul monolithe catalytique. Dans cet objectif, plusieurs études ont montré que la capacité de stockage des NOx de ces catalyseurs est inhibée par la présence de suies. Les travaux présentés dans ce manuscrit s'inscrivent dans la compréhension des phénomènes en cause. Les résultats obtenus montrent que la présence de noir de carbone entraîne une diminution de la stabilité des nitrates adsorbés par les systèmes catalytiques étudiés et, ainsi, de leur capacité de stockage des NOx. Ce phénomène a été attribué à une réduction des espèces nitrates adsorbées à la surface des matériaux par les particules de carbone adjacentes. La présence d'une particule Pt à proximité d'un site de carbone favorise la formation de complexes oxygénés de surface, limitant l'effet réducteur du carbone envers les nitrates adsorbés. La perte de capacité d'adsorption des NOx des catalyseurs étudiés, observée lors de leur mise en contact avec du noir de carbone, s'est révélée irréversible à l'issue de l'oxydation du carbone. La caractérisation des matériaux par microscopie à transmission (MET) a révélé une modification importante de la structure des matériaux. Un frittage des particules de platine et une modification de la structure des particules de Ba entraînent en effet la perte irréversible de l'activité des matériaux vis-à-vis de l'adsorption des NOx. / Recently, car manufacturers have developed "4 way" catalytic converters in order to couple hydrocarbon and CO oxidation, soot combustion and DeNOx fonctions on a single monolith. Several studies showed that the NOx storage capacity of NSR catalysts is reduced in the presence of soot. The aim of this work is to investigate the effect of carbon NSR catalyst contact on the ability of the catalyst to store NOx. The results show that the presence of carbon black in the catalytic bed involves a decrease of adsorbed nitrates stability and of the NOx storage capacity of materials. It is proposed that the proximity of the carbon particles and NOx adsorbents sites leads to a reduction of the stored nitrates species. The decrease of the NOx storage capacity is Jess important when platinum is present in the catalytic material composition. In agreement with previous studies on the catalytic combustion of soot, it is suggested that platinum increases the number of surface-oxygen complexes -C(O), which thus led to a decrease in the reducing character of carbon. Our study reveals that the deactivation of the NOx storage activity due to carbon-catalyst contact is an irreversible phenomena, and thus even when all carbon is burnt. Characterization of materials by transmission electron microscopy (TEM) showed that sintering of the platinum particles and a structural modification of the barium particles occurs after that the catalysts was in contact with carbon. The decrease in the NOx storage activity of the materials is then assigned to a lesser proximity of the oxidizing sites (Pt) and adsorption sites (Al or Ba).
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Utvärdering av lufthalts- och nedfallsmätningar gjorda vid Korsnäsverken : Samband mellan miljöförbättrande arbete i pappers- och massaindustrin och föroreningar i närområdet / Evaluation of air concentration- and deposition measurements at Korsnäs : Relationship between environmental work in the pulp and paper industry and pollution in the surrounding areaAlsmyr, Michaela January 2013 (has links)
En nedgång har setts i Sverige och Europa när det gäller luftföroreningar de senast årtiondena. Nedgången beror bland annat på minskade emissioner från industrier, övergång från uppvärmning med olje- och kolpannor till fjärrvärme och förbättrad bränslekvalitet. Denna studie utvärderar lufthalts- och nedfallsmätningar gjorda i närheten av pappers- och massaindustrin Korsnäs i Gävle. Mätserierna startar vid sent 1970-tal och går fram till årsskiftet 2009/2010. Nedfall av stoft, sulfat, natrium, kalcium och lufthalter av svaveldioxid samt sot studerades. Jämförelser gjordes med Korsnäs miljöförbättrande åtgärder och emissioner under tidsperioden och med andra mätningar gjorda i Sverige och Gävleborgs län. Studien visade en nedgång av svaveldioxidhalterna i luften. Detta stämmer bra med en kraftig reduktion av svavelemissionerna från fabriksområdet under tidigt 1990-tal då installationer av reningsanläggningar skedde på de största emissionskällorna av svaveldioxid. En minskning av svavelhalten i eldningsoljan från Karskär Energi AB, ett energikombinat ägt av Korsnäs på samma fabriksområde, bidrog under samma tidperiod även till emissionsminskningen. Sothalten visade ingen nedåtgående trend under perioden men var säsongsberoende med i genomsnitt högre halter på vinterhalvåret. Troligtvis berodde detta på förbränningsanläggningar i närområdet, så som enskild förbränning och Karskär Energi AB. Fördelning av de högsta lufthalterna visade inte högre halter av svaveldioxid och sot när medelvindriktningen var ostlig och därmed blåste från fabriksområdet mot mätstationen utan när vindriktningen var sydvästlig och blåste från inlandet. Det totala stoft- och kalciumnedfallet visade ingen nedgång men hade i genomsnitt högre uppmätta halter på sommarhalvåret. Sulfatnedfallet visade högre halter under sent 1980-tal för att därefter minska och natriumnedfallet minskade något under perioden. Inga tydliga kopplingar kunde ses mellan lufthalter respektive nedfall och emissionerna från fabriksområdet när dataserierna sorterades efter vindriktning, vindhastighet och efter sommar- respektive vinterhalvår. Nedfall och lufthalter var inte högre, förutom för svaveldioxid, när jämförelser gjordes med andra mätningar i Sverige och Gävleborgs län och samtliga mätningar låg under periodens gällande nationella gränsvärden. / A decline has been seen in Sweden and Europe when it comes to air pollution the last decades. The decline is partly due to reduced emissions from industries, switching from heating using oil and coal boilers to district heating and better fuel quality. This study evaluates deposition and air concentration measurements made in the vicinity of the pulp and paper industry Korsnäs in Gävle. The measurement series starts at the late 1970s and goes up to year-end 2009/2010. Deposition of dust, sulphate, sodium, calcium and air concentrations of sulphur dioxide and soot were studied. Comparisons were made with Korsnäs environmental measures and emissions during the same time period and with other measurements made in Sweden and Gävleborgs County. The study showed a decrease in sulphur dioxide concentrations in the air. This fits well with a major reduction of sulphur emissions from the factory area in the early 1990s when installations of treatment plants were made at the largest emission sources of sulphur dioxide. Reducing the sulphur content of fuel oil from Karskär Energi AB, an energy combine owned by Korsnäs in the same factory area, contributed to the decrease during the same time period. Air concentrations of soot showed no downward trend over the years, but were seasonal, with higher average soot concentrations in the winter. This was most likely caused by the burning of fuel oil from both the private sector and Karskär Energi AB. The largest air concentrations did not show higher levels of sulphur dioxide and soot when the mean wind direction was easterly and thus blew from factory area toward the monitoring station but when the wind direction was southwesterly and blew from inland. The total dust and calcium deposition showed no decline but had higher average measured levels in the summer. Sulphate deposition showed high levels during the late 1980s but has thereafter decreased. The sodium deposition decreased a little during the time period. No clear connection was found between deposition/air concentrations and emissions from the factory area when the data series were sorted by wind direction, wind speed and after the summer and winter months. Depositions and air concentrations were not higher except for sulphur dioxide when the comparison was made with other measurements in Sweden and Gävleborg County. All measurements were below the then current national limits.
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Context-sensitive Points-To Analysis : Comparing precision and scalability<!--[if gte mso 9]><xml> <w:data>FFFFFFFF00000000000005005400650078007400310000000B0055006E00640065007200720075006200720069006B0000000000000000000000000000000000000000000000</w:data></xml><![endif]-->Kovalov, Ievgen January 2012 (has links)
Points-to analysis is a static program analysis that tries to predict the dynamic behavior of programs without running them. It computes reference information by approximating for each pointer in the program a set of possible objects to which it could point to at runtime. In order to justify new analysis techniques, they need to be compared to the state of the art regarding their accuracy and efficiency. One of the main parameters influencing precision in points-to analysis is context-sensitivity that provides the analysis of each method separately for different contexts it was called on. The problem raised due to providing such a property to points-to analysis is decreasing of analysis scalability along with increasing memory consumption used during analysis process. The goal of this thesis is to present a comparison of precision and scalability of context-sensitive and context-insensitive analysis using three different points-to analysis techniques (Spark, Paddle, P2SSA) produced by two research groups. This comparison provides basic trade-offs regarding scalability on the one hand and efficiency and accuracy on the other. This work was intended to involve previous research work in this field consequently to investigate and implement several specific metrics covering each type of analysis regardless context-sensitivity – Spark, Paddle and P2SSA. These three approaches for points-to analysis demonstrate the intended achievements of different research groups. Common output format enables to choose the most efficient type of analysis for particular purpose.
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Magnetisch und katalytisch funktionalisierte mesoporöse MaterialienKockrick, Emanuel 17 August 2009 (has links) (PDF)
In der vorliegenden Arbeit wurden mesoporöse Materialien erfolgreich mit magnetischen bzw. katalytisch aktiven Nanopartikeln funktionalisiert, wobei zwei unterschiedliche Synthesestrategien verfolgt wurden. Zum einen erfolgte eine direkte Integration der katalytisch aktiven CeO2-Nanopartikel in poröse, thermisch stabile SiC-Matrizes mithilfe der inversen Mikroemulsionsmethode.
Die Größe dieses wässrigen, cersalzhaltigen Nanoreaktors konnte über den RW-Wert (molares Wasser-Tensid-Verhältnis) im Bereich von 2,0-9,9 nm mit einer engen Größenverteilung variiert werden. Für katalytische Untersuchungen wurden die Cerhydroxidpartikel aus dem Mikroemulsionssystem ausgefällt und bei 100-600 °C calciniert. Dabei konnte eine größenabhängige Aktivität der Nanopartikel in der Rußverbrennung nachgewiesen werden, wobei eine Herabsetzung der Rußverbrennungstemperatur um bis zu 239 K nachgewiesen werden konnte. Weiterhin konnten polymere CeO2-SiC Vorläuferverbindungen durch Zugabe einer flüssigen, präkeramischen Vorläuferverbindung (Polycarbosilan) zum Mikroemulsionssystem hergestellt werden, wobei flüssig prozessierbare, transparente Lösungen resultierten. Anschließend erfolgte nach Entfernung der flüchtigen Bestandteile die Pyrolyse zur Bildung der CeO2-SiC-Keramiken. In Abhängigkeit von den Pyrolysebedingungen konnten kristalline SiC-Strukturen mit spezifischen Oberflächen von bis zu 240 m2/g nachgewiesen werden. In weiteren Untersuchungen konnte die Modularität dieses neuartigen Synthesekonzeptes demonstriert werden, indem Platin als zusätzliche Aktivkomponente in das bestehende Mikroemulsionssystem integriert wurde. Im Gegensatz zu den platinfreien Systemen erfolgte eine Vernetzungsreaktion infolge der Pt-katalysierten Vernetzungsreaktion des allylgruppenhaltigen Polycarbosilans, mit spezifischen Oberflächen von bis zu 896 m2/g. Anhand von TEM-Untersuchungen konnte eine hohe Dispersion der CeO2-Aktivkomponente mit Partikelgrößen von 2-3 nm gezeigt werden. Durch die Zugabe von Divinylbenzol als Kreuzvernetzungskomponente konnte neben einer weiteren Erhöhung der Oberfläche auf 992 m2/g auch die Hydrophobizität des Polymerkomposits signifikant erhöht werden.
In einer zweiten Synthesestrategie wurden intermetallische MPt-Systeme (M=Fe, Co, Ni) durch Infiltration geeigneter Vorläuferverbindungen und anschließender Thermolyse in geordneten mesoporösen SiO2- bzw. Kohlenstoffmaterialien synthetisiert. Die Phasenbildung in Abhängigkeit von den Thermolysebedingungen wurde mithilfe der Röntgenpulverdiffraktometrie untersucht. Dabei wurden nach der Reduktion bei 400 °C ungeordnete fcc-MPt-Legierungen mit superparamagnetischen Eigenschaften erhalten. Dagegen resultierte für FePt-Systeme nach der Reduktion bei 750 °C bis 800 °C eine deutliche Zunahme der Raumtemperaturkoerzitivitäten auf bis zu 28,35 kOe (FePt@CMK-3) bzw. 15,60 kOe (FePt@SBA-15) infolge der Bildung der intermetallischen fct-FePt Verbindung. Weiterhin wurden die strukturellen sowie magnetischen Eigenschaften der FePt-Nanopartikel in Abhängigkeit vom Massenanteil sowie der Porengröße bzw. -geometrie der porösen Silicatemplate untersucht. Dabei konnte eine starke Abhängigkeit der Raumtemperaturkoerzitivität von der Porenstruktur sowie den jeweiligen Reduktionsbedingungen nachgewiesen werden.
Ein weiterer Aspekt dieser Arbeit war die Synthese hochporöser CDC-Kohlenstoffmaterialien (CDC: carbide derived carbon) durch die Chlorierung nichtoxidischer SiC-Keramiken. Hierbei wurde das Silicium der mesoskopisch geordneten SiC-Strukturen durch Umsetzung mit Chlor bei unterschiedlichen Thermolysebedingungen extrahiert. Die resultierenden CDC-Materialien wiesen neben sehr hohen spezifischen Oberflächen von bis zu 2865 m2/g bzw. Porenvolumina von 2,21 cm3/g auch eine von der SiC-Struktur sowie den Chlorierungsbedingungen abhängige mesoskopische Ordnung auf. Die mesoporösen CDC-Materialien eignen sich als Sorbentien mit hohen Butan- bzw. Wasserstoffspeicherkapazitäten von 0,692 gButan/gCDC (25 °C: 80 Vol% Butan) bzw. 2,58 gew% (77 K: 1 bar). Daneben resultieren überaus hohe gravimetrische Methanspeicherkapazitäten von 0,191 g Methan/gCDC im Hochdruckbereich (25 °C, 100 bar), die deutlich größer sind als die bekannter Metallorganischer Gerüstverbindungen. / Ordered mesoporous materials were successfully functionalized with magnetic and catalytic active nanoparticles. Two different synthesis strategies were employed. Cerium oxide nanoparticle containing silicon carbide composites were synthesized by direct incorporation of catalytic active CeO2 nanoparticles in preceramic polycarbosilane using inverse microemulsion technique and subsequent pyrolysis. Resulting ceramic composites offer specific surface up to 240 m2/g and a narrow pore sizes in the range of 4-6 nm. Additionally porous Pt containing CeO2-SiC composites were prepared demonstrating the versitibilty of this new synthesis strategy. Catalytic activity of ceria nanoparticles were shown in soot combustion reaction.
In a second approach intermetallic MPt nanoparticles (M= fe, Co, Ni) were synthesized inside the pores of ordered mesoporous silica and carbon materials. Crystalline structure and particles size were controlled by the porous template and the annealing conditions. Very high room temperature coercivities up to 28.4 koe were obtained for intermetallic FePt nanoparticles in mesoporus carbon matrices. Catalytic activity of FePt silica composites were demonstrated in selective acetylene hydration.
Furthermore high porous, mesostructured carbon materials (CDC: carbide derived carbon) were prepared by chlorination of ordered mesoporous silica resulting extraordinary high specific surface areas up 2865 m2/g, high pore volunina up to 2.21 cm3/g and mesoscopic ordering. These new carbon structures are appropriate as high performance energy storage materials.
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Rußbildung in der Kohlenwasserstoffpyrolyse hinter Stoßwellen / Soot Formation in Hydrocarbon Pyrolysis behind Shock WavesTanke, Dietmar 24 January 1995 (has links)
Die Rußbildung in der Pyrolyse von n-Hexan, Benzol und
Kohlenwasserstoffen im Stoßrohr wird mit hoher Zeitauflösung
absorptionsspektroskopisch beobachtet und Gasproben durch ein
besonders schnelles Ventil gesammelt.
Vom Beginn der Pyrolyse bis zum Einsetzen der Rußbildung wurde stets
eine Induktionszeit beobachtet, deren Dauer von der Temperatur, der
Kohlenstoffkonzentration und der Struktur des pyrolysierten
Kohlenwasserstoffs abhängt. Dieser Zusammenhang wird mit einem
Arrhenius-Ansatz beschrieben. Der Vorfaktor A ist für Aromaten eine
Größenordnung kleiner als für Alkane. Die scheinbare
Aktivierungsenergie beträgt (220 ± 10) kJ/mol.
Das Rußmassenwachstum, das der Induktionsperiode folgt, wird mit einem
Gesetz erster Ordnung beschrieben. Durch Normierung der
Geschwindigkeitskonstanten auf die Kohlenstoffdichte zeigt, daß das
Rußmassenwachstum in Pyrolysen und in vorgemischten Ethylenflammen
vergleichbar schnell abläuft.
Die Rußausbeute der Aromaten und Acetylen hat bei bei 1800 K ein
Maximum. Für Ethylen und Alkane liegt diese charakteristische
Temperatur um rund 100 K höher.
Neben Ruß und Wasserstoff sind Acetylen gefolgt von Methan und
Ethylen die wichtigsten Hauptprodukte. Die polycyclischen Aromaten
tragen keine Seitengruppe und enthalten maximal einen Fünfring.
Der Rußpartikeldurchmesser ist im Bereich von 30 nm.
Der Einfluß von Eisenpentacarbonyl auf die Rußbildung ist gering.
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