Dans l'objectif de combler le gap entre l'offre et la demande en propène, la réaction d'oxydation déshydrogénante du propane (ODHP) est une solution alternative à la réaction de déshydrogénation directe. Les hydroxyapatites (HAp) modifiées au vanadium sont des matériaux bi-fonctionnels aux propriétés acido-basiques et redox intéressants pour cette réaction. L'objectif de cette thèse est d'étudier le comportement catalytique de ces systèmes et d'établir des relations entre structure et réactivité. Par le contrôle des conditions de synthèse et pourvu que le pH soit maintenu élevé (~9), la solution solide Ca10(PO4)6-x(VO4)x(OH)2 est obtenue dans toute la gamme de composition (x 0→ 6), alors que pour un pH inférieur, un mélange de phases d'HAps au vanadium et de Ca2V2O7 est obtenu pour x ≥ 4. Pour la solution solide, contrairement à la sélectivité en propène, la conversion en propane n'augmente pas avec la teneur en vanadium non exposé en surface. L'activation de la liaison C-H du propane s'explique par une propriété intrinsèque à la structure HAp, en lien avec la formation thermiquement activée d'anions O2- très basiques. Leur formation in situ résulte de la déshydratation progressive des colonnes d'ions OH- via le processus de conduction ionique par les protons, exalté sous conditions réactionnelles. L'organisation du vanadium sous la forme de tétramères dans Ca2V2O7 au lieu de tétraèdres isolés dans la seule solution solide favorise les échanges redox et explique l'augmentation de la sélectivité. Le contact intime entre les deux phases et la formation d'une interface cohérente permet un optimum de rendement en propène du fait de la synergie des propriétés des deux phases. / In order to fill the gap between propene supply and demand, the oxidative dehydrogenation of propane (ODHP) is an alternative solution to the direct dehydrogenation process. Vanadium-modified hydroxyapatites (HAp) are bifunctional catalysts combining acid-base and redox properties which were shown to be of interest for the ODHP reaction. In order to optimize this system, the aim of the work was to investigate the catalytic behavior of the vanadium-modified hydroxyapatites and to establish structure reactivity relationships. By peculiar attention was devoted to the control of synthesis. Provided high pH value is maintained during the synthesis, the Ca10(PO4)6-x(VO4)x(OH)2 solid solution was successfully obtained for x 0→ 6, whereas at lower pH, a mixture of Vx-HAp solid solution and of Ca2V2O7 was obtained from x ≥ 4. For the solid solution, contrary to propene selectivity, the propane conversion does not depend on the vanadium content, unexposed on the surface. The activation of the C-H bond of propane is controlled by an intrinsic properties of the HAp structure, in relation with the thermally activated formation of strong basic O2- anions. Their in situ formation results from the progressive dehydration of OH- columns via an ionic conduction process by protons that is enhanced under catalytic conditions. Due to the tetrameric environment of vanadium in Ca2V2O7 against isolated tetrahedra in the solid solution, redox exchanges are facilitated, improving the selectivity in propene. The intimate contact between the two phases and the formation of a coherent interface leads to an optimal yield in propene, due to synergistic effects of the two phases.

Cette étude traite de la détonation et de la Transition Déflagration Détonation, TDD, en conduite dans les mélanges binaires H2/C3H8-Air. L'accent est mis sur les mécanismes d'accélération de flamme en présence d'obstacles. Les grandeurs caractéristiques de détonation autonome (célérité, pression et taille de cellule) et la distance de TDD ont été mesurées pour différentes richesses et proportions d'hydrogène dans le propane. En particulier, les effets de l'obstacle (longueur et nature) et du diamètre du tube sur la TDD ont été examinés. Les résultats montrent que les corrélations classiques Taille de cellule - Longueur d'induction chimique pour la détonation et Taille de cellule - Longueur de transition pour la TDD - bien établies pour les mélanges simples - restent valables pour ces mélanges binaires. L'addition du C3H8 à H2 diminue la détonabilité du combustible binaire. Des visualisations d'accélération de flamme par ombroscopie ont été réalisées à l'aide de caméras ultra-rapides dan le but d'identifier les mécanismes physiques contrôlant ce processus pour différentes configurations d'obstacles. Les enregistrements ont mis en évidence deux phases de propagation. Dans la première, les instabilités intrinsèques de la flamme, l'augmentation de sa surface ainsi que la combustion turbulente retardée - résultant de la zone de recirculation entre deux obstacles successifs - jouent un rôle prédominant. Dans la deuxième, l'accélération est contrôlée par l'interaction du front de flamme et des ondes de choc réfléchies sur les obstacles ou sur les parois du confinement. Il en résulte une forte accélération de la flamme avec établissement d'un régime de blocage thermique qui, dans certaines conditions, mène à l'apparition de la détonation.

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Steam reforming is the most economical and widely-used route for the conversion of light hydrocarbon (such as natural gas) to various valued-added products. This process is commonly carried out over a low-cost alumina-supported nickel catalyst, which often suffers from carbon deposition resulting in loss of active sites, flow and thermal maldistribution, as well as excessive pressure drop. A bimetallic catalyst with improved anti-coking properties was formulated by incorporating the nickel-based system (15% loading) with cobalt metal (5% loading). Two-level factorial design was employed to investigate the effect of major preparation variables, namely impregnation pH value (2-8), calcination temperature (873-973 K), heating rate (5-20 K min-1) and time (1-5 h). The catalysts prepared were subjected to various characterisation techniques to determine key physicochemical properties (i.e. BET area, H2-chemisorption and NH3- TPD acidity). X-ray diffraction revealed that NiO, Co3O4, NiCo2O4 and a proportion of Ni(Co)Al2O4 aluminates were transformed during H2-reduction to active Co and Ni crystallites. TEM images showed an egg yolk profile in the low-pH catalyst suggesting that main deposition site was located in the particle centre, while metal deposition occurred primarily around the particle exterior for the high-pH catalyst. Temperature programmed experiments were carried out to examine the extent of conversion, type of surface species and solid-state kinetics (using the Avrami-Erofeev model) involved during various stages in catalyst life-cycle (calcination, reduction, oxidation and regeneration). Steam reforming analysis suggested that enhanced catalyst activity may be due to synergism in the Co-Ni catalyst. Specifically, the low-pH catalyst exhibited better resistance towards carbon-induced deactivation than the high-pH formulation. The study also provided the first attempt to develop a quantitative relation between catalyst preparation conditions and its performance (activity, product selectivity and deactivation) for steam reforming reaction. Deactivation and reforming kinetic coefficients were simultaneously evaluated from propane reforming conversion-time data under steam-to-carbon ratios of 0.8-1.6 and reaction temperatures between 773-873 K. The time-dependent optimum operational policy derived based on these rate parameters gave better conversion stability despite the heavy carbon deposit. Thermal runs further showed that the catalysts regenerated via two-stage reductive-oxidative coke burn-off exhibited superior surface properties compared to those rejuvenated by a single-step oxidation.

The goals of this research were first to examine flame quenching in tubing smaller than the quench diameter, and then to place lower size limits on microcombustor and microreactor systems by studying a catalytic microcombustor burning propane. In the first set of experiments, flame quenching was examined as a function of wall temperature for various hydrocarbon fuels. This was accomplished by creating a wall temperature profile along a tube, allowing a flame to propagate down the tube, and measuring the temperature of the tube wall coincident with the flame front. This wall quench temperature was plotted as a function of both the equivalence ratio and tube diameter. Fuels tested included propane, hexane, kerosene and diesel. Results showed that quench diameter was reduced by elevating the wall temperature and that the quench temperature increased for increasing mixture flow velocities. Flames were produced in tubes down to 0.8 mm in diameter. In the second set of experiments, a catalyst was used in combination with fuel preheating to obtain a self-sustaining combustion reaction in a chamber approximately 0.25 mm³ in size. Propane was used in this experiment. Results demonstrated that a stable self-sustaining reaction can be obtained in the microscale regime and that reaction temperatures are on the order of 900°C. This research not only aided in the characterization of hydrocarbon combustion in small diameter channels but also showed promise for development of microcombustor systems. / Graduation date: 2002

Recent experimental and simulation studies -conducted at the Department of Petroleum Engineering at Texas A&M University - confirm oil production is accelerated when propane is used as an additive during steam injection. To better understand this phenomenon, distillation experiments were performed using seven-component synthetic oil consisting of equal weights of the following alkanes: n-C5, n-C6, n-C7, n-C8, n-C9, nC10, and n-C15. For comparison purposes, three distillation processes were investigated: dry-, steam-, and steam-propane-distillation, the latter at a propane:steam mass ratio of 0.05. The injection rate of nitrogen during dry-and steam-distillation was the same as that of propane during steam-propane distillation, 0.025 g/min, with steam injection rate kept at 0.5 g/min. The distillation temperatures ranged from 115°C to 300°C and were increased in steps of 10°C. The cell was kept at each temperature plateau (cut) for 30 minutes. Distillation pressures ranged from 0 psig for dry distillation to 998 psig for steam-and steam-propane distillation. The temperature-pressure combination used represented 15°C superheated steam conditions. Distillate samples were collected at each cut, and the volume and weight of water and hydrocarbon measured. In addition, the composition of the hydrocarbon distillate was measured using a gas chromatograph. Main results of the study may be summarized as follows. First, the hydrocarbon yield at 125°C is highest with steam-propane distillation (74 wt%) compared to steam distillation (58 wt%), and lowest with dry distillation (36 wt%). This explains in part the oil production acceleration observed in steam-propane displacement experiments. Second, the final hydrocarbon yield at 300°C however is the same for the three distillation processes. This observation is in line with the fact that oil recoveries were very similar in steam- and steam-propane displacement experiments. Third, based on the yields of individual hydrocarbon components, steam-propane distillation lowers the apparent boiling points of the hydrocarbons significantly. This phenomenon may be the most fundamental effect of propane on hydrocarbon distillation, which results in a higher yield during steam-propane distillation and oil production acceleration during steam-propane displacement. Fourth, experimental K-values are higher in distillations with steam-propane for the components n-hexane, n-heptane, n-octane, and n-nonane. Fifth, vapor fugacity coefficients for each component are higher in distillations with steam-propane than with steam. Finally, Gibbs excess energy is overall lower in distillations with steam-propane than with steam. The experimental results clearly indicate the importance of distillation on oil recovery during steam-or steam-propane injection. The experimental procedure and method of analysis developed in this study (for synthetic oil) will be beneficial to future researchers in understanding the effect of propane as steam additive on actual crude oils.

Developing environmentally sustainable processes are essential to improving the quality of life for future generations. In addition to reducing our impact on the environment, we must design processes to be both economical and safe. A large component of any chemical process is the solvents used to dissolve the reactants and extract the products. The research presented here focuses on coupling efficient homogeneous reactions with simple heterogeneous separations using propane-organic-aqueous tunable solvent systems. Our tunable solvents undergo a phase separation upon application of propane pressure to a fully miscible mixture of water and an organic solvent. The propane based tunable systems detailed here eliminate carbonic acid formation and reduce productphase contamination when compared with the equivalent CO2 based solvent systems previously studied. Additionally, we eliminate the need to use buffers and thus solids handling equipment is not needed.

Steam reforming is the most economical and widely-used route for the conversion of light hydrocarbon (such as natural gas) to various valued-added products. This process is commonly carried out over a low-cost alumina-supported nickel catalyst, which often suffers from carbon deposition resulting in loss of active sites, flow and thermal maldistribution, as well as excessive pressure drop. A bimetallic catalyst with improved anti-coking properties was formulated by incorporating the nickel-based system (15% loading) with cobalt metal (5% loading). Two-level factorial design was employed to investigate the effect of major preparation variables, namely impregnation pH value (2-8), calcination temperature (873-973 K), heating rate (5-20 K min-1) and time (1-5 h). The catalysts prepared were subjected to various characterisation techniques to determine key physicochemical properties (i.e. BET area, H2-chemisorption and NH3- TPD acidity). X-ray diffraction revealed that NiO, Co3O4, NiCo2O4 and a proportion of Ni(Co)Al2O4 aluminates were transformed during H2-reduction to active Co and Ni crystallites. TEM images showed an egg yolk profile in the low-pH catalyst suggesting that main deposition site was located in the particle centre, while metal deposition occurred primarily around the particle exterior for the high-pH catalyst. Temperature programmed experiments were carried out to examine the extent of conversion, type of surface species and solid-state kinetics (using the Avrami-Erofeev model) involved during various stages in catalyst life-cycle (calcination, reduction, oxidation and regeneration). Steam reforming analysis suggested that enhanced catalyst activity may be due to synergism in the Co-Ni catalyst. Specifically, the low-pH catalyst exhibited better resistance towards carbon-induced deactivation than the high-pH formulation. The study also provided the first attempt to develop a quantitative relation between catalyst preparation conditions and its performance (activity, product selectivity and deactivation) for steam reforming reaction. Deactivation and reforming kinetic coefficients were simultaneously evaluated from propane reforming conversion-time data under steam-to-carbon ratios of 0.8-1.6 and reaction temperatures between 773-873 K. The time-dependent optimum operational policy derived based on these rate parameters gave better conversion stability despite the heavy carbon deposit. Thermal runs further showed that the catalysts regenerated via two-stage reductive-oxidative coke burn-off exhibited superior surface properties compared to those rejuvenated by a single-step oxidation.

Isotherms of one atom thick film of adsorption for propane on purified Hipco single-walled carbon nanotube were experimentally studied at 6 different temperatures ranging from 190K up to 280K. In these isotherm measurements, two substeps were clearly present at temperatures between 190K and 220K. For propane adsorption, two different groups of binding energy sites on the nanotubes were determined by the outcome. Also, we found that those substeps were gradually smearing as the temperature increases. These features of propane adsorption were compared to the same features that were present for the case of ethane and butane adsorption on the same sample. In comparison, high binding energy sites revealed by low pressure substeps were clearly visible in all the cases. However, the high pressure substep that represents a low binding energy site, external surface site, was smearing as carbon chain length of adsorbed alkanes increase. For the case of butane adsorption, the substep was not pronounced in the alkanes' isotherms at the relative temperatures. We also determined a decrease in the values of specific surface area of the nanotubes and an increase in the values of binding energies of alkanes on the substrate were increased as the sizes and lengths of linear carbon alkanes were increased.

Metal-organic frameworks (MOFs) are porous crystalline materials built by metal clusters coordinated to organic ligands. Synthesis of MOFs has attracted considerable attention in recent decades, owing to its potential for a wide range of applications such as gas separation, dye adsorption, and catalysis, etc. The development of MOF membranes further enhances the potential of this type of material in industrial applications. Membrane fabrication methods, including in-situ growth, seeded secondary growth, interfacial growth, and vapor-phase deposition, have been widely studied. However, most of these methods either require a complicated synthesis procedure or are timeconsuming. Recently, the electrochemical synthesis has emerged as a highly promising approach to fabricate MOF membranes in a scalable manner, because it allows shorter synthesis time, milder synthesis condition, continuous reaction, and crystal self-healing. In this thesis, for the first time, an aqueously cathodic deposition (ACD) approach was developed to fabricate ZIF-8 type of MOF membranes without the addition of any supporting electrolyte or modulator. The fabrication process used 100% water as the sole solvent, and a low-defect density membrane was obtained in only 60 min under room temperature without any pre-synthesis treatment. The membrane exhibited superior performance in C3H6/C3H8 separation with C3H6 permeance of 182 GPU and selectivity of 142, making it sit at the upper bound of permeance versus selectivity graph, outperforming the majority of the published data up to 2019. Notably, this approach used an extremely low current density (0.13 mA cm-2) operated under a facile apparatus setup, enabling an attractive method for environmentally friendly, energy-efficient, and scalable MOF membrane fabrications. This work demonstrates the enormous potential of aqueously electrochemical deposition of the MOF membrane in future research.