Interest in biodiesel has piqued with advent of stringent emissions regulations. Biodiesel is a viable substitute for petroleum diesel because biodiesel produces significantly lower particulate and soot emissions relative to petroleum diesel. Higher nitric oxide (NO) emissions for biodiesel, however, are of primary concern in biodiesel-fueled engines. Search for an in-cylinder technique to reduce NO emissions for biodiesel has motivated studies to gain an improved understanding of fundamental factors that drive increase in NO emissions with biodiesel. Potential factors include fuel-bound oxygen, fuel-bound nitrogen and post-flame gas temperature. The role of fuel-bound oxygen however is debated in the literature. The research objective of this study is to computationally determine if biodiesel and petroleum diesel yield equivalent concentrations of NO with the same oxygen equivalence ratio in a 0-D homogeneous reactor, to explain the role of fuel-bound oxygen in biodiesel on increases in NO emissions with biodiesel. The results from this study indicate that the biodiesel surrogate yields higher NO emissions than the n-heptane because of its lower oxygen consumption efficiency. The lower oxygen consumption efficiency for biodiesel is likely because of the slower decomposition of the individual components and the blending ratios of the biodiesel surrogate blend. The relative differences in combustion efficiency of individual components of the biodiesel blend suggest this conclusion. The more efficient burning of the methyl esters relative to the n-heptane in biodiesel surrogate perhaps indicates the favorable role of fuel-bound oxygen in the fuel’s combustion. The low utilization of oxygen by the biodiesel surrogate could not be explained in this study. The dominance of NO2 H ↔ NO OH and N NO ↔ N2 O mechanisms during biodiesel combustion however explain the high NO emissions for the biodiesel surrogate relative to the n-heptane. The biodiesel may yield lower NO emissions than the petroleum diesel if the blending ratios for the biodiesel are adjusted such that combustion efficiency of biodiesel and petroleum diesel is same or the NO2 H ↔ NO OH and N NO ↔ N2 O mechanisms are suppressed during biodiesel combustion.

Les industries du raffinage et du transport doivent faire face à une conjoncture marquée par une demande croissante et importante de carburant gazole et à la fois par la Directive 2003/30/EC de l’Union Européenne imposant l'incorporation progressive de sources renouvelables dans les carburants (5,75 % en 2010 à 20 % en 2020, en terme de contenu énergétique). Dans ce contexte, les schémas de raffinage ont été orientés vers la valorisation de plus de coupes lourdes en bases pour la formulation des carburants gazoles et combustibles Fuel–Oil domestique, tandis que l’aspect réglementaire est satisfait en ayant recours à des bases alternatives de type Esters Méthyliques d’Huiles Végétales (EMHV). Cependant, les gazoles moteurs ainsi formulés sont d’avantage exposés aux problématiques de cristallisation en raison de l’accroissement de composés susceptibles de s’y solidifier lors de températures hivernales (principalement les n-alcanes et les Esters Méthyliques d’Acides Gras). Il est par conséquent important de se doter d’un outil d’optimisation de la formulation permettant de prédire la température d’apparition des premiers cristaux, soit leur point de trouble. Dans cette perspective, il a été nécessaire d’acquérir les données expérimentales de transition de phase liquide – solide des Esters Méthyliques d’Acides Gras composants les EMHV, mais également celles des fluides réels (gazoles fossiles, EMHV et leurs mélanges). Les données collectées ont par la suite été comparées aux prédictions résultantes de modèles thermodynamiques se proposant de décrire l’équilibre de phase liquide – solide des gazoles et des EMHV, afin de s’en inspirer pour établir une approche prédictive de calcul des températures de transition de phase des mélanges.En définitive, nous avons reliés les résultats de la modélisation thermodynamique et les mesures du point de trouble réalisées conformément aux normes pétrolières en vigueur en Europe (ASTM D5771et D7689), afin d’établir des corrélations aptes à la prédiction de cette propriété attestant de la tenue au froid des gazoles moteurs. / The concerns about greenhouse effect have encouraged the use of biodiesels to replace petroleum-derived diesel fuel. Indeed, the European Union has issued a Directive 2003/30/EC, which mandates the use of biofuels in a percentage ranging from 5.75% in 2010 to 20.00% in 2020 (calculated on the basis of energy content) for all transportation fuels marketed within the member states. First-generation biodiesels made from vegetable oils or animals fats are blended with petroleum diesel to fuel the engines. Besides, the refining schemes were modified to produce more heavy petroleum cuts in order to satisfy the growing demand of diesel fuel. However, the resulting diesel are more exposed to operability problems as the Fatty Acid Methyl Esters and the heavy normal paraffins may solidified in the tank and filters when the temperature drops down during the winter seasons. Thus the study of the solid-liquid phase equilibria of these blends may be useful to predict the temperature of apparition of the solidified material, known as the cloud point. In this work, we collected the melting data of the pure biodiesel components (Fatty Acid Methyl Esters) and we studied the phase change temperature of real diesel samples (petroleum diesel and biodiesel blends). Then, we have developed a thermodynamic model in order to compute the solid-liquid phase equilibria of all these kind of fluids involved in the diesel fuel formulation. Comparisons were made with the experimental phase change measurements and with the cloud point normalized measurement methods (ASTM D5771 et D7689). Finally, we have correlate the phase change temperature calculated by the thermodynamic model with the normalized cloud point, so as this important data could be obtain by a predictive tool.