A 12.9 L heavy duty compression ignition engine was tested with strategies for dual fuel optimization. The effects of varied intake manifold pressure as well as split-injection strategies at a load of 5 bar BMEP and 85 PES were observed. These results were used to allow testing of split-injection strategies at a higher load of 10 bar BMEP at 70 PES that were void of MPRR above 2000 kPa/CAD. The split-injection strategies at 5 bar BMEP showed that lower BSNOx can be achieved with minimal drop in FCE. Varying intake manifold pressure revealed that combustion occurs earlier in a cycle with increasing intake manifold pressure and indirectly increasing FCE. A load of 10 bar BMEP at 70 PES should only use split-injection strategy to maintain load without high MPRR as efficiency drops with dependency on the second injection.

Efficient propylene and propane separation is a major challenge in the modern chemical industry. With current separation methods being highly energy-intensive, there is a pressing need to find alternative green technology. Membrane separation emerged as a promising candidate for propylene and propane separation. Their small footprint, low cost, reliability, and environmental friendliness give membrane separation systems a competitive edge in the race towards sustainable development. The continuous advancements in material science created avenues for new membrane materials such as carbon molecular sieve (CMS) membranes which exhibit exceptional gas separation performances for challenging applications due to their strong size-sieving capabilities. In this work, a carbon molecular sieve (CMS) membrane derived from a polymer of intrinsic microporosity (TPE-PIM) has been investigated for propylene/propane separation made by pyrolysis at 400, 450, 500, 550, 600, 650, and 700 ºC. TPE-PIM-derived CMS films showed excellent pure and mixed-gas permeability and selectivity, exceeding the upper bound limits for propylene and propane. Observed in this work was the presence of an optimal pyrolysis temperature at 600 ºC, where the film showed the best performance with a permeability of 41.6 Barrer and a selectivity of 197 based on pure-gas measurements but dropping to 34 Barrer and selectivity of 33 under equimolar mixed-gas conditions. Such performance could be attributed to the unique internal structural changes that occurred during the pyrolysis. In addition, propane permeability though the CMS films was slow and required long times to reach steady-state values. Such slow kinetics illustrates the molecular sieving capabilities of CMS membranes for bigger and more condensable gases. Several characterization techniques have been performed on the films to confirm CMS formation and showcase deeper molecular structure insights. X-ray diffraction of all TPE-PIM films showed a broad spectrum at each peak due to the material’s amorphous nature. Diffraction patterns also revealed a gradual peak shift for the (002) plane towards smaller values closer to that of pure graphite. Raman spectra showed the characteristic D and G peaks for carbon films prepared at 500 ºC and above. FTIR analysis was also performed to investigate the potential formation of triazine crosslinks in the thermally treated samples, but no conclusive results were obtained.

No description available.

No description available.

Proteins have been known for years as the most important constituent of living matter. Their great abundance in all forms of life have made them the subject of chemical and alchemical investigations since the dawn of science. It was found during the nineteenth century, however, that these relatively complex protein polymers could be decomposed by various means to form their monomers- the amino acids. This process, in fact, takes place during the digestion and ingestion of proteins as food matter. Today, the most important use of the amino acids is as a food. With the scarcity of food so prevalent throughout the world today, it would seem desirable to devise a means of synthesizing a foodstuff from ordinarily non-edible material. Glutamic acid, one of the more common amino acids, occurs to a large extent in any agricultural products, principally core, soy-beans and beet-sugar waste. In addition to its use as a food, the sodium salt of this compound-monosodium glutamate- is very widely used as a flavoring. Moreover, the pure acid has been found recently to have brain stimulating properties and to increase the intelligence of persons taking it medicinally. There are many methods known for the synthesis of this compound. But their disadvantage is that the starting materials are themselves often uncommon and costly items. It was thought from a study of the structure of the acid, that the glutamic acid molecule could be built up from relatively simple materials, since it is only a combination of carbon, water and ammonia. One of the most practical methods devised was first, the production of glutaric acid from propane, via chlorination, followed by the amination of glutaric acid to form the amino acid - glutamic acid. The purpose of this thesis, therefore, was to develop a practical method for the synthesis of glutamic acid, starting with propane, and through the processes of chlorination, nitrilization, hydrolysis and amination, producing this acid. It was further proposed to design a pilot plant for the further carrying out of this work. / Master of Science

It was decided to determine whether or not 2,2,3-trimethylbutane could be formed by the photochemical reaction of isobutane and propane in the presence of mercury vapor energized by ultraviolet radiation from a mercury vapor lamp.

De nombreuses études sont menées pour la compréhension et l'utilisation de plasmas hors équilibre pour les procédés industriels capables d'améliorer la combustion, de stabiliser des flammes et de réduire les polluants. En effet, dans le cadre des nouvelles normes européennes, il devient indispensable de pouvoir maîtriser la qualité de la combustion et de réduire ainsi les émissions polluantes. Même si le principe de l'allumage classique par étincelle est depuis longtemps connu et utilisé dans l’industrie automobile, ce système présente néanmoins quelques limites. En effet, le caractère localisé de l’étincelle créée réduit la probabilité de rencontre entre l’étincelle et une zone de mélange inflammable ce qui conduit à des ratés d’allumages et spécialement en mélanges pauvres. Ainsi, l’utilisation de systèmes différents reposant sur des plasmas non-thermiques fournit des avantages significatifs, dont les propriétés de forte réactivité chimique et de faible coût énergétique. L’objet principal de ce travail de thèse est l’étude de l’allumage de mélanges combustibles par un certain type de décharges pulsées nanosecondes. En effet, un des intérêts du déclenchement de combustion par décharges nanosecondes est le développement d’une zone spatiale d’allumage nettement plus étendue que celle obtenue par l’étincelle de la bougie standard. Enfin, un autre avantage des décharges nanosecondes est la création de nombreux radicaux dans le milieu combustible nécessaires à l’initiation directe des cinétiques de combustion en limitant la contribution thermique, souvent impliquées dans les pertes de rendement des allumeurs. Dans notre étude, la décharge nanoseconde pulsée utilisée est caractérisée par l’application d’une surtension très élevée donnant un pulse de tension très court (12 ns), d’amplitude très élevée (50 kV) et un front de montée très raide (2 ns). Au cours de cette étude, nous avons d’abord caractérisé la décharge nanoseconde pulsée dans des mélanges air/propane et air/heptane à pression atmosphérique. Ensuite, nous avons appliqué la décharge au déclenchement de combustion dans les mélanges air/propane et air/heptane dans les proportions stœchiométriques mais aussi en mélanges pauvres et ce toujours à pression atmosphérique, ce qui a montré la réduction des délais de combustion. De plus, les résultats en mélanges stœchiométriques montrent qu’il existe trois modes d’allumage : un ponctuel, un double et un mode cylindrique et ce en fonction de la densité d’énergie. / One growing topic of interest in the field of non-thermal plasmas is the use of pulsed corona discharges for ignition purposes and more specifically the use of discharges generated under very strong overvoltages for car atmospheric engine applications. Because of strong environmental constraints on car exhaust gases, engines to be developed in the future have to run with lean air / gasoline mixtures or diluted with burnt gases. In both cases, it needs the optimization of ignition devices since classical spark gaps become inefficient in these conditions. In this context, the generation of non-equilibrium plasmas on large volumes, with high densities of active species, and the ability to induce fast gas heating is challenging. Our experimental work is dedicated to the understanding of physical mechanisms involved in the ignition of lean mixtures of air and hydrocarbons such as propane and n-heptane, at high pressure, using nanosecond range discharges. Such kind of discharges could improve the energy release in the mixtures, promoting the creation of radicals and excited species instead of direct heat through Joule effect, and thus, it could improve the ignition efficiency. A positive high voltage (50 kV) is applied between a pin electrode and a grounded plane over a short nanosecond range pulse (12 ns) with a steep rise time (2 ns). In this study, the discharge has been characterised in air/propane and air-heptane mixtures. The diffuse regime observed in pure air tends to disappear in mixtures containing few percents of propane or heptane. The experimental results show the ability of the single nanosecond pulsed discharge to ignite air-propane and air-heptane mixtures even at low equivalence ratios. It is strongly correlated to the energy density the discharge is able to release into the gas. Finally, it has been shown that for stoechiometric mixtures show that three different modes of ignition are possible, i.e. a single point, a double point or a cylindrical mode, according to the energy density. Combustion delays are strongly reduced and complete combustion of very lean mixtures can be achieved if the amount of energy is slightly increased.

L’acrylonitrile est un intermédiaire de l’industrie chimique pour la synthèse de nombreuxpolymères et revêtements. Il est produit à partir de propène qui devient de plus en plus cher et rare. Ceprojet visait à développer de nouveaux catalyseurs à base de nitrures ou d’oxynitrures permettantd’utiliser le propane moins cher et abondant, qui présente un intérêt industriel vu son potentieléconomique et sa durabilité, puisque son exploitation comme précurseur chimique permettraitd’utiliser plus efficacement les ressources naturelles. De nombreux solides ont été préparés et testéscomme catalyseurs. Certains se sont avérés instables dans les conditions de réaction comme lesoxynitrures VZrON, MoVON, et LaVON. D’autres comme MgTaVON et VZrAlON sont apparusstables mais soit faiblement actifs ou non sélectifs. L’étude s’est focalisée sur les oxynitrures VAlONet leur amélioration. Ils ont été caractérisés par de multiples techniques, telles que la DRX, XES,XANES, XPS, RMN 27Al, TPD NH3 et CO2. L’influence de paramètres tels que le rapport V/Al, lepH, la surface spécifique, le temps de contact ont été étudiés. Le catalyseur optimal possède un rapportV/Al d’environ 0,30. Les études ont permis de montrer que les sites nitrurés impliqués dansl’ammoxydation du propane sont du type OxV-NH2--AlO3 et que le degré d’oxydation moyen duvanadium en condition de catalyse est de 3,8. Une nouvelle méthode de préparation des catalyseurs aété mise au point à partir d’un complexe oxalate de vanadium et d’aluminium qui est décomposé parozonation, et nitruré en conditions réactionnelles. Ce catalyseur s’avère plus actif et sélectif que lescatalyseurs préparés par co-précipitation. / Acrylonitrile is an intermediate of the chemical industry, used for synthesis ofnumerous polymers and coating. It is produced by ammoxidation of propene, which becomes rare andexpensive. This project aimed to develop new catalysts based on nitrides and oxynitrides allowing touse abundant and cheaper propane as starting product. Propane presents an industrial interest in viewof its economical potential and durability and because its exploitation as chemical precursor wouldallow to use natural resources more efficiently. Numerous oxynitrides based catalysts have beenprepared and tested as catalysts. Some of them were shown to be unstable in reaction conditions, likeVZrON, MoVON, and LaVON, some were shown to be stable but either weakly active or notselective like MgTaVON and VZrAlON. The study has been focused on VAlON oxynitrides. Thesecatalysts have been characterized by several techniques, like XRD, XES, XANES, XPS, 27Al-NMR,NH3 and CO2-TDP and the influence of several parameters on their catalytic properties have beenstudied. The results of these studies have confirmed that these catalysts were very efficient for thereaction and shown that the optimal catalyst had a V/Al ratio around 0.30 with an average oxidationstate of vanadium in catalytic condition around 3.8. A nitridation site has been proposed correspondingto OxV-NH2--AlO3 species. Finally a new preparation method has been discovered with the synthesisof an oxalate of vanadium and aluminum complex, which is decomposed by ozonation, and nitrided inreaction conditions. This catalyst showed improved activity and selectivity compared to coprecipitatedcatalysts.

Heat transfer and pressure drop during condensation of propane flowing through minichannels is investigated in this study. Studies of condensation of hydrocarbons are important for applications in the petrochemical industry. Insights into the mechanisms of propane condensation are required for accurate design of heat transfer equipment for use in hydrocarbon processing. At present, there is very little research on vertical condensation, especially of hydrocarbons, for the tube sizes and flow conditions of interest to the present study. An experimental facility was designed and fabricated to measure the frictional pressure drop and heat transfer coefficients during condensation of propane in plain tubes with an inner diameter of 1.93 mm. Measurements were taken across the vapor-liquid dome in nominal quality increments of 0.25 for two saturation temperatures (47°C and 74°C) and four mass flux conditions (75 – 150 kg m‾² s‾¹). The data were compared to the predictions of relevant correlations in the literature. The data from this study were also used to develop models for the frictional pressure drop and heat transfer coefficient based on the measurements and the underlying condensation mechanisms. These results and the corresponding correlations contribute to the understanding of condensation of hydrocarbons in vertical minichannels.

Mélanger un oxyde de gallium avec une zéolithe H-ZSM-5 donne les mêmes résultats catalytiques en craquage du n-hexane, déshydrogénation du cyclohexane et en aromatisation du propane qu'un catalyseur préparer par échange cationique avec un sel de gallium. En fait, le véritable catalyseur est synthétisé lors du prétraitement sous hydrogène pendant lequel le suboxyde de gallium (Ga2O) issu de la réduction de Ga2O3 réagit avec les sites de Brønsted de la zéolithe pour donner des hydrures de gallium. La réaction de déshydrogénation des alcanes fait intervenir un site catalytique bifonctionnel composé d'un site de Lewis du Ga et d'un site basique généré par l'oxygène de la charpente zéolithique. L'activation du propane se produit sur un hydrure de gallium via un mécanisme de type alkyle. Les aluminosilicates dopés avec Ga sont plus performants que les gallosilicates, ce qui signifie que les espèces de gallium sont plus actives en extra-réseau que dans le réseau de la zéolithe.Le coke généré lors de l'aromatisation du propane est très polyaromatique avec plus de quinze noyaux benzéniques, localisé dans les micropores il s'avère très toxique. La création de mésopores intracristallins sans modifier les propriétés acides de la zéolithe (nombre et force des sites acides) est possible par un traitement alcalin. Leur présence permet de limiter les réactions de transfert d'hydrogène mais est peu efficace pour contrôler la croissance du coke, les mésopores sont mêmes négatifs pour la réaction de déshydrogénation rendant les catalyseurs bifonctionnels hiérarchisés inefficaces en aromatisation du propane ; l'étape cinétiquement limitante pour cette réaction étant la déshydrogénation. / The mixing Ga2O3 with the H-ZSM-5 zeolite yields to the same catalytic performance in n-hexane cracking, cyclohexane dehydrogenation and propane aromatization than a bifunctional catalyst prepared by cationic exchange. The real catalyst appears upon hydrogen pretreatment in which gallium (Ga2O) suboxide that results from Ga2O3 reduction, reacts with the zeolite Brønsted sites to yield to gallium hydrides.The dehydrogenation reaction of alkanes involves a bifunctional catalytic site constituted of a Lewis site (Ga species) and basic site (an oxygen of the zeolite framework). The aluminosilicate catalysts loaded with Ga are more efficient than the gallosilicate catalysts, therefore extraframework gallium species is more active than the framework gallium species.The coke formed during the propane aromatization is very polyaromatic with more than fifteen benzenic rings, is very toxic. The creation of intracrystalline mesopores by alkaline treatment.preserves the acidic properties of the zeolite (number and strength of acidic sites). The mesopores allow limiting the hydrogen transfer reactions but is not very effective for impeding the growth of the coke, the presence of mesopores are even negative for the dehydrogenation reaction making inefficient the hierarchical bifunctional catalysts in propane aromatization; the kinetically limiting step for this reaction being dehydrogenation.