Pollutant control and efficiency improvement propel the need for clean combustion research on internal combustion engines. To design cleaner fuels for advanced combustion engines, gasoline combustion chemistry must be both understood and developed. A comprehensive examination of gasoline combustion chemistry in a jet stirred reactor is introduced in this dissertation. Real gasoline fuels have thousands of hydrocarbon components, which complicate numerical simulation. To mimic the behavior of real gasoline fuels, surrogates, composed of a few hydrocarbon components, are offered as a viable approach. In this dissertation, combustion chemistry of n-heptane, a key surrogate component, is investigated first, followed by an evaluation of a surrogate kinetic model. Finally, real gasoline fuels are assessed with the surrogate kinetic model. Mass spectrometry was employed to measure intermediates in n-heptane low temperature chemistry. Reaction pathways of the observed intermediates were proposed and clarified. n-Heptane low temperature oxidation reaction scheme was expanded by the proposed reactions. After surrogate proposal and formation, a surrogate kinetic model was examined. Low temperature and high temperature chemistry were observed and predicted. The octane number and composition effect on low temperature oxidation reactivity were revealed. High temperature combustion chemistry was found to be similar among the different surrogates, and the surrogate kinetic model reproduced surrogate behavior well in both low and high temperatures. Finally, the proposed surrogate model was examined using real gasoline fuels. Five real FACE (fuel for advanced combustion engines) gasolines were selected as target fuels to cover a wide range of octane number, sensitivity and hydrocarbon compositions. Low temperature oxidation chemistry was investigated for two intermediate octane number gasolines, FACE A and C. For a high octane number gasoline, FACE F, key pollutant production pathways were the focus of high temperature combustion chemistry. Two low octane number gasolines, FACE I and J, were compared with three other FACE gasolines to clarify gasoline combustion chemistry over a wide range. The gasoline surrogate chemical kinetic model proved to be a comprehensive, viable, accurate and powerful approach for numerical simulations. The proposed gasoline surrogate chemical kinetic model can aid in the numerical design of advanced combustion engines.

No description available.

Mixtures of ammonia and hydrogen have received significant interest recently as a possible replacement for hydrocarbon fuels. A toroidal jet-stirred reactor (TJSR) was designed and constructed to combust these mixtures in the well-stirred limit for validating chemical kinetic mechanisms and improving the current understanding of the combustion properties of this fuel. The TJSR was designed to achieve low residence times – on the order of 5 ms – to approximate the conditions in an aircraft gas turbine combustor. Simulations were conducted to determine mass flow rates, expected emissions output, and expected lean blow out. Based on these results, material studies were conducted to determine the best materials for each of the TJSR's components. Thermomechanical were conducted to determine the expected temperature distribution and thermal expansion during operation. Casing components were designed to seal the gases in the reactor as well as provide means to connect it to a pressure vessel or other piping. This work will allow for chemical mechanism validation of lean blowout in ammonia-hydrogen mixtures while laying the foundation for future high-pressure testing of such mixtures up to 60 bar.

Novel combustion technologies ensuring low emissions, high efficiency and fuel flexibility are essential to meet the future challenges associated to air pollution, climate change and energy source shortage, as well as to cope with the increasingly stricter environmental regulation. Among them, Moderate or Intense Low oxygen Dilution (MILD) combustion has recently drawn increasing attention. MILD combustion is achieved through the recirculation of flue gases within the reaction region, with the effect of diluting the reactant streams. As a result, the reactivity of the system is reduced, a more uniform reaction zone is obtained, thus leading to decreased NOx and soot emissions. As a consequence of the dilution and enhanced mixing, the ratio between the mixing and chemical time scale is strongly reduced in MILD combustion, indicating the existence of very strong interactions between chemistry and fluid dynamics. In such a context, the use of combustion models that can accurately account for turbulent mixing and detailed chemical kinetics becomes mandatory.Combustion models for conventional flames usually rely on the assumption of time-scale separation (i.e. flamelets and related models), which constrain the thermochemical space accessible in the numerical simulation. Whilst the use of transported PDF methods appears still computationally prohibitive, especially for practical combustion systems, there are a number of closures showing promise for the inclusion of detailed kinetic mechanisms with affordable computational cost. They include the Partially Stirred Reactor (PaSR) approach and the Eddy Dissipation Concept (EDC) model.In order to assess these models under non-conventional MILD combustion conditions, several prototype burners were selected. They include the Adelaide and Delft jet-in-hot coflow (JHC) burners, and the Cabra lifted flames in vitiated coflow. Both Reynolds Averaged Navier Stokes (RANS) and Large Eddy Simulations (LES) were carried out on these burners under various operating conditions and with different fuels. The results indicate the need to explicitly account for both the mixing and chemical time scales in the combustion model formulation. The generalised models developed currently show excellent predictive capabilities when compared with the available, high-fidelity experimental data, especially in their LES formulations. The advanced approaches for the evaluation of the mixing and chemical time scale were compared to several conventional estimation methods, showing their superior performances and wider range of applications. Moreover, the PaSR approach was compared with the steady Flamelet Progress Variable (FPV) model on predicting the lifted Cabra flame, proving that the unsteady behaviours associated to flame extinction and re-ignition should be appropriately considered for such kind of flame.Because of the distributed reaction area, the reacting structures in MILD combustion can be potentially resolved on a Large Eddy Simulation (LES) grid. To investigate that, a comparative study benchmarking the LES predictions for the JHC burner obtained with the PaSR closure and two implicit combustion models was carried out, with the implicit models having filtered source terms coming directly from the Arrhenius expression. Theresults showed that the implicit models are very similar with the conventional PaSR model on predicting the flame properties, for what concerns the mean and root-mean-square of the temperature and species mass fraction fields.To alleviate the cost associated to the use of large kinetic mechanisms, chemistry reduction and tabulation methods to dynamically reduce their size were tested and benchmarked, allowing to allocate the computational resources only where needed. Finally, advanced post-processing tools based on the theory of Computational Singular Perturbation (CSP) were employed to improve the current understanding of flame-turbulence interactions under MILD conditions, confirming the important role of both autoignition and self propagation in these flames. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Depuis ces dernières années, le monde doit faire face à une problématique énergétique importante due à la demande croissante en énergie primaire, sans mentionner les émissions de polluants nocives pour notre environnement. Pour cela les chercheurs étudient des voies alternatives à l’utilisation massive de carburants fossiles, telles que l’incorporation de biocarburants dans les essences conventionnelles, ou le développement de technologies modernes. De nouveaux types de moteur utilisant une combustion à plus basse température sont actuellement à l’étude. Ces derniers auraient l’avantage d’allier à la fois un bon rendement ainsi qu’une diminution des émissions de polluants (NOx et particules de suies). De fortes incertitudes existent pourtant encore, tant sur la caractérisation de la réactivité et des émissions des biocarburants, que sur la chimie d’oxydation en phase gazeuse à basse température. Les principaux objectifs de cette thèse sont donc : - d’établir une base de données expérimentales en identifiant les produits et intermédiaires réactionnels, et plus particulièrement à basse température d’oxydation (de 500 à 1100K), - de développer et valider de nouveaux modèles cinétiques détaillés afin de reproduire les résultats expérimentaux ainsi que la combustion du carburant étudié sur une large gamme de conditions. Les expériences d’oxydation ont été réalisées à partir d’un réacteur auto-agité par jets gazeux. Grâce à son homogénéité à la fois en température et en concentration, il est considéré comme un réacteur idéal, parfaitement adapté aux études cinétiques. Les produits formés en sortie du réacteur, sont analysés via trois méthodes complémentaires : la chromatographie en phase gazeuse (GC), la cavity ring-down spectroscopy (CRDS) et la spectrométrie de masse (SM). La GC est une technique efficace dans la séparation des composés (incluant les isomères) et nous permet d’identifier une large gamme de composés. La CRDS est une technique d’absorption spectroscopique qui a l’avantage d’analyser des espèces plus spécifiques telles que HCHO, H2O et H2O2. Enfin la spectrométrie de masse couplée à une source d’ionisation douce permet l’analyse de composés de type hydroperoxyde et de formule R-OOH. Que ce soit H2O2 ou les hydroperoxydes, ces derniers constituent d’importants intermédiaires réactionnels en combustion et il existe malheureusement très peu de données expérimentales les concernant. Due à la fragilité de la liaison O-O, ces espèces sont thermolabiles et difficiles à analyser de manière quantitative (indétectables via la GC). Cette thèse a permis l'étude de l'oxydation de différents carburants, en passant par les hydrocarbures (n-pentane, n-hexane, n-hexènes, n-heptane, iso-octane, n-décane), jusqu'aux molécules oxygénées (diméthyl-éther, 1-hexanol, hexanal, méthyl-esters lourds) / In recent years, the world is facing a major energetic issue due to the growing primary energy demand and not to mention the emissions of harmful pollutants for the environment. Researchers have been studying alternative pathways to the massive use of fossil fuels, such as the incorporation of biofuels into conventional gasoline or the development of modern technology. New types of engines using a low-temperature combustion are currently under study. They have the advantage of combining both a good performance and a reduction in pollutant emissions (like NOx and soot particles). Significant gaps of knowledge are still remaining, both on the characterization of the reactivity, the emissions and on the low-temperature gas phase oxidation chemistry of biofuels. Main objectives of this thesis are to: ? - Establish an experimental database by identifying reaction products and intermediates and more particularly during the low-temperature oxidation (from 500 to 1100K), ? - Develop and validate detailed kinetic models in order to reproduce the combustion of the fuel. Oxidation experiments were performed using a jet-stirred reactor. Thanks to its homogeneity in both temperature and concentration, it can be considered as an ideal reactor for kinetic studies. The products obtained at the outlet of the reactor have been analyzed using three complementary methods: gas chromatography (GC) and cavity ring-down spectroscopy (CRDS) and mass spectrometry (MS). The GC method is efficient in separating compounds (including isomers) and allows us to analyze a wide range of products. The CRDS method is an absorption spectroscopic technique which allows us to analyze specific species such as HCHO, H2O and H2O2. Finally MS coupled with a soft ionization technique allows us to analyze hydroperoxides products of formula R-OOH. Both H2O2 and hydroperoxides are important reaction intermediates in combustion, but there is very little experimental data available on those species. Due to their weak O-O bond, those compounds are thermolabile and difficult to analyze (undectable using GC). This thesis allowed the study of different fuels oxidation, from hydrocarbons (n-pentane, n-hexane, n-hexenes, n-heptane, iso-octane, n?decane) to oxygenated compounds (dimethyl-ether, 1-hexanol, hexanal, large methyl-esters)

Les mélanges GtL/EMHC/éthanol ont un potentiel important comme carburant alternatif pour moteur Diesel.Néanmoins, l’utilisation de ce type de biocarburant en moteur Diesel nécessite une connaissance précise de la cinétiqued’oxydation de ses différents constituants.Une étude bibliographique approfondie a permis de sélectionner quatre espèces modèles représentatives des mélangesGtL/EMHC/éthanol : le n-décane, l’iso-octane, l’octanoate de méthyle et l’éthanol. L’oxydation de mélanges de cesespèces modèles a ensuite été étudiée en réacteur auto-agité à haute pression (10 atm), pour trois richesses (0,5 ; 1 et 2) etsur un large domaine de température (550-1150 K). L’analyse des échantillons par chromatographie en phase gazeuse apermis de quantifier les principaux produits issus de l’oxydation des mélanges étudiés. Un mécanisme cinétique détaillécapable de reproduire l’oxydation des mélanges n-décane/iso-octane/octanoate de méthyle/éthanol a ensuite été mis aupoint. Les prédictions du modèle reproduisent de manière satisfaisante les résultats expérimentaux sur toute la gamme derichesse et de température testée en réacteur auto-agité. L’analyse du modèle a également permis de déterminer les voiesréactionnelles prépondérantes en fonction de la composition des mélanges.Enfin, la combustion de mélanges GtL/EMAG/éthanol a été étudiée en moteur monocylindre Diesel. Cette phased’essais, incluant une analyse approfondie des émissions non réglementées, a permis d’observer l’influence de laformulation des carburants sur l’initiation de la combustion et sur la composition des gaz d’échappements. / As concern about global warming and dependences on fossil fuel grows, there is an increasing interest to shift fromtraditional fuel to renewable energy sources. Blends of Fischer-Tropsch (F-T) fuels, biodiesel and ethanol seem to be apromising fuel for compression ignition (CI) engine application. The aim of this work is to study and model the impact ofthese fuels on combustion and pollutant emissions.In the present study, mixtures of 4 species are proposed to represent the oxidation of F-T/biodiesel/ethanol blends: ndecane,iso-octane, methyl octanoate and ethanol. The kinetic of oxidation of n-decane/iso-octane/methyloctanoate/ethanol blends was studied experimentally in a jet stirred reactor at 10 atm and a constant residence time of 1 s,over the temperature range of 560-1160 K and for three equivalence ratio (0.5, 1 and 2). A kinetic reaction mechanismwas developed and used to simulate the oxidation of n-decane/iso-octane/methyl octanoate/ethanol mixtures. Theproposed kinetic reaction mechanism yields a good representation of the kinetic of oxidation of the tested biofuel blends.The kinetic analyses allowed identifying the most influencing reactions for the oxidation rate of the fuels.Finally, four F-T/biodiesel/ethanol blends have been tested on a single cylinder, direct injection, four-stroke Dieselengine. This study, including an analysis of unregulated emissions allowed observing the influence of fuel formulationon combustion and on pollutant emissions. These main engine results tendencies have been compared to the results of thekinetic model.

The chemical complexity of the interstellar medium and combustion environments pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel and interstellar species. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing polar molecules. However, rotational spectra usually contain transitions from multiple components with multiple conformations as well as other dynamical properties interleaved with one another, making the assignment of the spectra very challenging. This thesis describes experimental work using broadband microwave spectroscopy and vacuum ultraviolet time-of-flight mass spectrometry to address a number of challenging problems in the spectroscopy of gas complex mixtures.<div><br></div><div>In the first part of my work, we report details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave spectroscopy (CP-FTMW) with VUV photoionization Time-of-Flight Mass Spectrometry (VUV TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are illustrated through results on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with <i>o-</i>guaiacol as precursor. <br></div><div><br></div><div>The broadband spectrum of 3-phenylpropionitrile was recorded under jet-cooled conditions over the 8-18 GHz region. A novel multi-resonance technique called strong field coherence breaking (SFCB) was implemented to record conformer-specific microwave spectra. This technique involves sweeping the broadband chirp followed by selectively choosing a set of single frequencies pulses to yield a set of rotational transitions that belong to a single entity in the gas-phase mixture, aiding assignment greatly. Transitions belonging to anti and gauche conformers were identified and assigned and accurate experimental rotational constants were determined to provide insight on the molecular structure. Experimental rotational transitions provided relative abundances in the supersonic expansion. A modified line picking scheme was developed in the process to modulate more transitions and improve the overall efficiency of the SFCB multiple selective excitation technique.<br></div><div><br></div><div>The rotational spectrum of 2-hexanone was recorded over the 8-18 GHz region using a CPFTMW spectrometer. SFCB was utilized to selectively modulate the intensities of rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to selectively identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a₁ and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. The difference spectra, final fit and structural parameters are discussed for the three assigned conformers of 2-hexanone.<br></div><div><br></div><div>Developing new experimental techniques that allow for species identification and quantification in the high-temperature environment of reacting flows is a continuing challenge in combustion research. Here, we combine broadband chirped-pulse microwave (rotational) spectroscopy with an atmospheric-pressure jet-stirred reactor as a novel method to identify key reactive intermediates in low-temperature and ozone-assisted oxidation processes. In these experiments, the gas sample, after being withdrawn from reactive dimethyl ether/O₂/Ar, dimethoxy methane/O₂/Ar, and ethylene/O₂/O₃/Ar mixtures, expands via a supersonic expansion into the high vacuum of a microwave spectrometer, where the rotationally cold ensemble of polar molecules is excited with short MW radiation frequency ramps (chirps). The response of the molecular ensemble is detected in the time domain and after a Fourier transformation, the spectral composition of the transient emission is obtained in the frequency domain. The observed rotational frequencies are uniquely correlated to molecular structures and allow for an unambiguous identification of the sampled species. Detection and identification of intermediates such as formaldehyde, methyl formate, formic acid, formic acid anhydride, and the primary ethylene ozonide via literature-known rotational frequencies are evidence for the superb identification capabilities of broadband chirped-pulse microwave spectroscopy. Strong-field coherence breaking is employed to identify and assign transitions due to a specific component. The observation of van der Waals complexes provides an opportunity to detect combustion intermediates and products that are impossible to detect by rotational spectroscopy as isolated molecules. <br></div><div><br></div><div>Lastly, preliminary data on important combustion precursors is studied including pentanal, <i>trans-</i>2-pentenal and <i>o-,m- </i>and <i>p</i>-vinylanisole. The rotational spectrum of these five molecules is recorded from the 8-18 GHz region under jet-cooled conditions. For pentanal and <i>trans-</i>2-pentenal, SFCB was utilized to dissect the broadband spectrum, identifying the four and two lowest energy structures, respectively. The structural parameters and finals fits are provided. <br></div>

La réduction des apports phosphorés des eaux usées régie par la Directive Européenne de 1991 (91/271/EEC) est considérée comme le facteur clé de la lutte contre la pollution des rivières et des lacs. Ces travaux concernent exclusivement l'étude de la formation maîtrisée de struvite (MgNH4PO4.6H2O) par précipitation comme alternative originale de récupération du phosphore et, par voie de conséquence, de l'ammonium à partir d'eaux usées. Un atout de ce procédé concerne la valorisation du précipité en tant que fertilisant. Dans ce contexte général, l'objectif consiste à développer une démarche combinant des aspects expérimentaux et de modélisation de la précipitation de la struvite. Un effluent synthétique contenant du phosphore, du magnésium et de l'ammonium a servi de solution modèle pour étudier le rôle de la température, de la concentration en réactifs, et du pH sur l'efficacité de la précipitation de la struvite ainsi que sur la distribution de la taille des cristaux obtenus. Les essais expérimentaux ont été réalisés par précipitation en cuve agitée. Diverses méthodes d'analyse des phases solide et liquide (spectrophotométrie, absorption atomique, granulométrie laser, MEB et Morphométrie) ont été utilisées. Le dosage du magnésium, ainsi que celui d'ammonium et du phosphore permet de déterminer le taux de conversion de ces composés et d'étudier une éventuelle formation d'un sous-produit. L'approche développée dans ce mémoire permet de déterminer les conditions de pH et de température favorisant l'efficacité maximale pour la récupération de la struvite. Deux voies complémentaires ont été proposées. La première étape concerne la modélisation des équilibres chimiques, d'une part, pour calculer le taux de conversion du phosphate final en fonction du pH à l'équilibre pour plusieurs températures et, d'autre part, pour évaluer l'impact de la température sur la constante de solubilité de la struvite. La stratégie numérique implique un algorithme génétique (NSGA II) pour initialiser efficacement un algorithme de résolution classique (Newton Raphson) et garantir la robustesse de la procédure. Dans la seconde étape, un modèle numérique basé sur un bilan de population couplé avec le modèle thermodynamique prédit la distribution de taille des particules,. Cette approche s'est avérée particulièrement stable d'un point de vue numérique lors du calcul des paramètres des vitesses de nucléation et de croissance, utilisés ensuite pour prédire la distribution de taille à l'aide d'une méthode de reconstruction. La forme de la distribution de taille des cristaux obtenue est typique d'un modèle nucléation – croissance. La méthodologie proposée trouve tout son intérêt pour traiter des effluents de qualité variable et prédire l'efficacité du procédé dans lequel le contrôle du pH et de la sursaturation constituent des paramètres clés. / The reduction of phosphorus contribution in wastewater, governed by the European directive of 1991 (91/271/EEC) is regarded as the key factor of the fight against pollution of rivers and lakes. This work concerns exclusively the study of the controlled struvite formation (MgNH4PO4.6H2O) by precipitation as an alternative removal of phosphorus and, consequently, of ammonium from waste-water discharges. The valorization of the precipitate as a fertilizer constitutes an asset of the process. In this general context, the objective consists in developing a methodology combining an experimental approach with struvite precipitation modelling. A synthetic effluent containing phosphorus, magnesium and ammonium was used as a model solution to study the role of temperature, concentration in reagents and pH on struvite precipitation efficiency as well as on particle size distribution in a stirred tank reactor. Various analysis methods of both solid and liquid phases (spectrophotometry, atomic absorption, laser granulometry, MEB and Morphology) were used. The residual concentration of magnesium, ammonium and phosphorus allows to determine the conversion rate of these compounds and to study a likely formation of a co-product. The proposed framework is based on a two-level modelling approach. The former level, based on an equilibrium prediction of the study system Mg-PO4-NH4, involves, on the one hand, the computation of the final conversion rate of phosphate as a function of equilibrium pH at different temperatures and, on the other hand, the temperature impact assessment on struvite solubility product. The numerical strategy implies a genetic algorithm (NSGA II) to initialize a traditional algorithm of resolution (Raphson Newton) and to guarantee the robustness of the process. In the second stage, a population balance-based model coupled with the thermodynamic one predicts the particle size distribution. This approach turns out to be particularly numerically stable for the identification of nucleation and particle growth kinetics parameters that are then used to predict the size distribution, typical of a nucleation - growth model, using a method of reconstruction. The proposed methodology is particularly interesting for the treatment of industrial waste-water discharges that may be of variable quality as well as for the prediction of the process efficiency for which pH control and supersaturation constitute key parameters.

[pt] O presente trabalho tem como finalidade avaliar os diferentes modelos de mistura para o cálculo da combustão de reagentes pré- misturados utilizando a abordagem de Reator Parcialmente Misturado (PaSR). Os modelos de mistura considerados neste trabalho foram os modelos IEM estendido, Langevin e Langevin estendido. Investiga-se aqui o grau de mistura previsto por tais modelos e sua influência sobre as propriedades termoquímicas em um processo de combustão. A primeira parte deste trabalho consiste na apresentação e avaliação destes modelos de mistura, considerando-se um campo escalar inerte em presença de um campo turbulento homogêneo e isotrópico. Uma vez que estes modelos de mistura envolvem formulações do tipo estocástico, sua implementação foi realizada utilizando o método de Monte Carlo, mediante a utilização de esquemas numéricos adequados à resolução de equações diferenciais estocásticas. Assim, estuda-se a evolução da Função Densidade de Probabilidade (PDF) e das principais propriedades do campo escalar para cada modelo implementado. Os resultados obtidos também são comparados com simulação numérica direta e com resultados analáticos disponsáveis. Um ótimo acordo em termos qualitativos e quantitativos é obtido. A segunda parte deste trabalho utiliza estes modelos para o estudo numérico de um PaSR no qual são modelados os processos difusivos e reativos presentes durante a combustão. O PaSR é usado para avaliar a influência dos modelos de mistura nas propriedades termoquímicas da mistura em uma situação de combustão de tipo pré-misturada, que é modelada utilizando-se uma variável de progresso de uma reação. Os resultados obtidos com os diferentes modelos de mistura são comparados para diferentes regimes de funcionamento do PaSR, mostrando que, em situações de mistura rápida e reação intensa, os diferentes modelos apresentam resultados similares. Porém, nos casos de mistura lenta e reação moderada, discrepancias importantes são observadas entre os resultados dos modelos; as quais atingem até 65% para o valor médio da variável de progresso da reação. / [en] The present work evaluates several mixing models for the prediction of premixed combustion in a Partially Stirred Reactor (PaSR). The models considered in this work were the extended IEM, Langevin and extended Langevin models. The degree of mixing and its influence on the termochemical properties in a combustion process are investigated here. The first part of this work consists on the presentation and the assesment of these mixing models in which a single scalar field was considered in presence of a homogeneous and isotropic turbulent field. Since these mixing models involve stochastic terms, their implementation is performed by the Monte Carlo method using numerical schemes which solve the corresponding Stochastic Differential Equations (SDE). The evolution of the Probability Density Function (PDF) and the main properties for a single scalar field are studied for each mixing model. The numerical results are compared with Direct Numerical Simulation and available analytical results. Excellent qualitative and quantitative agreements are obtained. In the second part of this work, mixing models are used for numerical simulation of a PaSR where the diffusive and reactive processes occur. The PaSR is used to assess the mixing model influence on the termochemical properties of the mixture in a premixed combustion process, which is modeled using a reaction progress variable. The results obtained with the different mixing models are compared in several operating regimes of the PaSR, showing that when mixing is fast and reaction is intense, the different models lead to similar results. However, when mixing is slow and reaction is weak, important discrepancies are observed between the model results, which reach 65%, as far as the averaged reaction progress variable is concerned

Les carburants synthétisés à partir de la biomasse représentent une alternative crédible aux carburants conventionnels. La biomasse lignocellulosique présente en effet une importante disponibilité et son traitement physico-chimique permet d’obtenir une grande variété de composés aux propriétés intéressantes. La structure de ces biocarburants fait cependant intervenir des fonctions oxygénées, qui rendent la compréhension des phénomènes d’oxydation complexes. Le projet 2G-CSAFE, dans lequel s’inscrit le travail présenté ici, a pour objectif d’explorer la cinétique d’oxydation de certains de ces carburants. Les fonctions chimiques étudiées lors de ce travail sont les fonctions cétone, éther et ester. La combinaison de deux de ces fonctions (comme dans le cas des lévulinates) est également étudiée. Après une étude bibliographique qui vise à identifier les informations apportées par les études passées sur les composés les plus simples de chaque famille (acétone, diméthyl-éther et formiate de méthyle), l’accent est mis sur les rares travaux disponibles liés à la butanone, la cyclopentanone, la cyclohexanone, le dibutyl-éther, le formiate de butyle et le lévulinate de méthyle. La cinétique d’oxydation de ces composés est ensuite étudiée par des approches numériques et expérimentales. Des calculs de chimie théorique sont menés dans un premier temps pour étudier l’impact des fonctions oxygénées sur la structure du carburant et pour obtenir les constantes de vitesse relatives aux principales réactions mises en jeu. Des expériences en réacteur auto-agité par jets gazeux sont ensuite réalisées sur une gamme de température pouvant aller de 450 à 1250 K, à des pressions de 1 ou 10 atm et pour des richesses allant de 0,5 à 2. Les données ainsi collectées sont enfin utilisées pour développer des mécanismes cinétiques. L’accord entre les simulations et les données expérimentales est globalement satisfaisant pour des composés aussi complexes et les résultats présentés ici pourront être source d’analogies pour la modélisation d’autres carburants oxygénés. / Fuels produced from biomass are an interesting alternative to conventional fuels. Lignocellulosic biomass is indeed highly available and a wide variety of compounds can be obtained through its physico-chemical conversion. However, the structure of the fuels obtained from such processes involves oxygenated groups that make complicated the understanding of the oxidation chemistry. The work presented here is part of the 2G-CSAFE project, which aims at exploring the oxidation kinetics of these fuels. Chemical functions studied in this work include ketones, ethers and esters. The combination of two functions (as for levulinates) is also investigated. After a literature review aiming at collecting the information reported on the simplest compound of each group (acetone, dimethylether and methylformate), available studies on butanone, cyclopentanone, cyclohexanone, dibutyl-ether, butyl-formate and methyl levulinate are considered. The oxidation of these compounds is thereafter studied by numerical and experimental approaches. Ab initio calculations are performed to study the impact of the oxygenated groups on the structure and to derive rate constants for the major chemical pathways. Experiments are then carried out in a jet-stirred reactor for temperatures ranging from 450 to 1250 K, pressures of 1 or 10 atm and equivalence ratios from 0.5 to 2. The data obtained through these two approaches are finally used to develop and validate kinetic mechanisms. The overall agreement between experiments and simulations is satisfactory and results presented here can be used as a source of analogy for the future modeling of other similar oxygenated fuels.