Excess enthalpy combustion utilizes heat recirculation, in which heat is transferred from hot products to cold reactants to effectively preheat the reactants, in order to achieve improved combustion performance through the extension of flammability limits and increased burning rate. This research examines the effect of key parameters in excess enthalpy combustion on combustion stability, fuel conversion, and product species production through experimental and numerical investigation. Operating condition parameters that are studied include inlet reactant equivalence ratio and inlet velocity, and reactor geometry parameters that are studied include reactor channel height and length. Premixed reactants, including gaseous and liquid fuels, are investigated at rich and lean conditions. The examination of liquid fuels and the ability of a reactor to support rich and lean combustion of both gaseous and liquid fuels is a significant demonstration of a reactor’s flexibility for practical applications. This research experimentally and numerically examines excess enthalpy combustion in a counter-flow reactor. First, the counter-flow reactor, previously used for thermal partial oxidation of gaseous hydrocarbon fuels, is used in experiments to reform a liquid hydrocarbon fuel, heptane, to syngas. The effect of inlet operating conditions, including reactant equivalence ratio and inlet velocity, on combustion stability and product composition is explored. Second, lean combustion is demonstrated through experiments in the same counter-flow reactor previously used in reforming studies. The effect of inlet operating conditions, including reactant equivalence ratio and inlet velocity, on combustion stability and pollutant concentrations in combustion products is studied. An analytical model, previously developed for rich combustion, is adapted to qualitatively predict the behavior of the counter-flow reactor in response to changes in lean operating conditions. Third, lean combustion in the counter-flow reactor is further studied by examining the combustion of increasingly complex gaseous and liquid fuels. Again, the effect of inlet operating conditions, including reactant equivalence ratio and inlet velocity, on combustion stability and pollutant concentrations in combustion products is studied. Fourth and finally, a computational scaling study examines the impact of counter-flow reactor channel geometry on combustion stability, temperature increase above adiabatic values, heat recirculation, and fuel and product species conversion efficiency. / text

The Peng-Robinson equation of state (PR EOS) is incorporated with the infinite linear association model and the monomer-dimer association model as well as two different sets of mixing rules to result in four different forms of equations of state. The reformulated PR EOS have been used to represent the vapor pressures and liquid densities of pure associating compounds. The vapor pressure and liquid density values calculated by means of the reformulated PR EOS are in good agreement with the experimental data in the literature.<p>The application of the reformulated PR EOS could be extended to represent the VLE behavior of associating systems. The capabilities of different association-incorporated EOS are compared with the Hong-Hu equation, the AMH equation and the Wilson equation, respectively. The results show that, in general, the reformulated PR EOS are superior to the Wilson equation for all tested systems with the exception of alkanol-hydrocarbon systems and at least as good as the Hong-Hu equation, the AMH equation, although the number of tested systems from Hong and Hu and Nan et al. are less than the one from the present work.<p>The excess molar enthalpies of the ethanol-n-hexane and the ethanol-cyclohexane systems at 298.15 K were measured in an LKB 2107 microcalorimeter and compared with the experimental data in the literature. Additionally, new excess molar enthalpy data, measured at 298.15 K, have been reported for the ethanol-n-hexane-cyclohexane ternary system in the present work. Smooth representations of the results are described and used to construct contours of constant enthalpy on a Roozeboom diagram. The reasonable estimates of the excess enthalpies of the three constituent-binary mixtures can be obtained from both the Liebermann-Fried model and the Flory theory. <p>Finally, an attempt has been made to represent, simultaneously, both VLE and excess enthalpy behavior of the ethanol-n-hexane and ethanol-cyclohexane systems by using the Wilson equation and one of the reformulated PR EOS. Both the reformulated PR EOS and the Wilson equation could be extended to predict the ethanol-n-hexane-cyclohexane ternary system at 298.15 K with the binary interaction parameters determined from the experimental VLE data of the three constituent-binary mixtures. The calculated results show that the reformulated PR EOS is better than or as good as the Wilson equation in predicting the excess enthalpies of selected binary and ternary systems involving one associating species. However, quantitative discrepancies with the experimental data are observed.

The Peng-Robinson equation of state (PR EOS) is incorporated with the infinite linear association model and the monomer-dimer association model as well as two different sets of mixing rules to result in four different forms of equations of state. The reformulated PR EOS have been used to represent the vapor pressures and liquid densities of pure associating compounds. The vapor pressure and liquid density values calculated by means of the reformulated PR EOS are in good agreement with the experimental data in the literature.<p>The application of the reformulated PR EOS could be extended to represent the VLE behavior of associating systems. The capabilities of different association-incorporated EOS are compared with the Hong-Hu equation, the AMH equation and the Wilson equation, respectively. The results show that, in general, the reformulated PR EOS are superior to the Wilson equation for all tested systems with the exception of alkanol-hydrocarbon systems and at least as good as the Hong-Hu equation, the AMH equation, although the number of tested systems from Hong and Hu and Nan et al. are less than the one from the present work.<p>The excess molar enthalpies of the ethanol-n-hexane and the ethanol-cyclohexane systems at 298.15 K were measured in an LKB 2107 microcalorimeter and compared with the experimental data in the literature. Additionally, new excess molar enthalpy data, measured at 298.15 K, have been reported for the ethanol-n-hexane-cyclohexane ternary system in the present work. Smooth representations of the results are described and used to construct contours of constant enthalpy on a Roozeboom diagram. The reasonable estimates of the excess enthalpies of the three constituent-binary mixtures can be obtained from both the Liebermann-Fried model and the Flory theory. <p>Finally, an attempt has been made to represent, simultaneously, both VLE and excess enthalpy behavior of the ethanol-n-hexane and ethanol-cyclohexane systems by using the Wilson equation and one of the reformulated PR EOS. Both the reformulated PR EOS and the Wilson equation could be extended to predict the ethanol-n-hexane-cyclohexane ternary system at 298.15 K with the binary interaction parameters determined from the experimental VLE data of the three constituent-binary mixtures. The calculated results show that the reformulated PR EOS is better than or as good as the Wilson equation in predicting the excess enthalpies of selected binary and ternary systems involving one associating species. However, quantitative discrepancies with the experimental data are observed.

Nous avons développé un modèle prédictif, utilisant le principe de contribution de groupes, pour prédire avec précision, le comportement des fluides pétroliers. Ce modèle baptisé PPR78 utilise l’équation d’état de Peng et Robinson et des règles de mélange de type Van der Waals avec un coefficient d’interaction binaire kij, dépendant de la température. De telles règles de mélange sont équivalentes à celles obtenues en combinant à compacité constante une fonction d’excès de type Van Laar et une équation d’état cubique.La première partie de cette étude a consisté à étendre le domaine d’application du modèle PPR78 aux systèmes contenant de l’eau, des alcènes et de l’hydrogène, en définissant six nouveaux groupes élémentaires. Une bonne précision du modèle est obtenue pour décrire les équilibres de phases de systèmes binaires impliquant ces constituants, notamment pour les systèmes présentant des diagrammes de phases de Type I et de Type II. Dans la deuxième partie l’ensemble des paramètres de groupes ont été réajustés, non seulement sur des données d’équilibres de phases mais également sur des données de grandeur de mélange. L’avantage de ce nouveau modèle E-PPR78 est qu’il permet de restituer les équilibres de phases avec une précision équivalente au modèle original et qu’il conduit à une très nette amélioration de la prédiction des enthalpies d’excès et des capacités calorifiques d’excès. / We have developed a predictive model, by means of a group contribution method, in order to predict with accuracy, the behavior of petroleum fluids. The model called PPR78 uses the Peng-Robinson equation of state and Van der Waals-type mixing rules with a temperature dependent binary interaction parameter kij. Such mixing rules are identical to those obtained by combining at constant packing fraction, a Van Laar-type excess function and a cubic equation of state.The first part of this study consisted in extending the application of the model PPR78 to systems containing water, alkenes and hydrogen, by defining six new elementary groups. The phase equilibria of binary systems involving these components are accurately described by the model, especially for the phase diagrams of Type I and Type II. In the second part, all the group parameters of the original model were re-fitted by using the phase equilibrium data, as well as the mixing property data. The advantage of this new model E-PPR78 is that it is capable to correlate the phase equilibria with an accuracy which is equivalent to the original model and it produces a very clear improvement in the prediction of excess enthalpies and excess heat capacities.

Ce travail porte sur la contribution à la modélisation thermodynamique d'un atelier de purification d'acide acrylique. Après l'identification des principaux produits intervenant dans l'étape de purification et la collecte de leurs propriétés thermodynamiques disponibles dans la littérature, nous avons effectué une série de mesures expérimentales pour un ensemble de mélanges contenant des acides carboxyliques (en particulier : diagrammes d'équilibres liquide-liquide et équilibres liquide-vapeur, enthalpies d'excès et volumes d'excès). L'ensemble des données (nos mesures et les valeurs de la littérature) a été exploité selon deux approches de modélisation des équilibres liquide-vapeur : une approche symétrique (φ-φ) appliquée aux équations d'état de Peng-Robinson (P-R) et de PC-SAFT et une approche dissymétrique (γ-φ) appliquée aux modèles de coefficients d'activité en phase liquide NRTL, UNIQUAC et Van Laar associés à diverses équations d'état en phase vapeur (gaz parfait, Viriel, Hayden et O'Connell et Nothnagel). Nous avons finalement retenu le modèle UNIQUAC associé à la corrélation de Hayden et O'Connell en phase vapeur. Des nouveaux paramètres d'interaction ont été déterminés et conduisent à des résultats homogènes et satisfaisants en comparaison avec nos mesures expérimentales et aux données de la littérature. Ils permettent également de décrire convenablement les diagrammes d'équilibres liquide-vapeur et les volatilités relatives des mélanges étudiés / This work focuses on the contribution in the thermodynamic modeling of an acrylic acid purification unit. After identifying the main products involved in the purification step and collecting their thermodynamic properties available in the literature, we conducted a series of experimental measurements for a range of mixtures containing carboxylic acids(mainly liquid-liquid equilibrium and vapor-liquid equilibrium diagrams, excess enthalpies and excess volumes).The data set-our measurements and literature values-was used according to two approaches for modeling vapor-liquid equilibrium: a symmetric approach(φ-φ) applied to the equations of state Peng-Robinson (P-R) and PC-SAFT and an asymmetrical approach (γ-φ) applied to the models of activity coefficients in the liquid phase NRTL, UNIQUAC and Van Laar associated with various equations of state in the vapor phase(ideal gas, Viriel, Hayden O'Connell and Nothnagel). We have finally chosen the UNIQUAC thermodynamic model associated with the correlation of Hayden O'Connell in vapor phase. New binary parameters were determined and led to consistent and satisfactory results in comparison with our experimental measurements and literature data. These parameters can also be used to adequately describe the diagrams of vapor-liquid equilibrium and the relative volatilities of the mixtures studied