No description available.

L'activation de la liaison Csp3-H peu réactive et sa fonctionnalisation en liaison carbone-hétéroatome constituent un défi pour les chimistes de synthèse. Un exemple d'intérêt industriel est la réaction d'oxydation du cyclohexane, dont les produits finaux (cétone et alcool) sont des intermédiaire clés pour la production de polyamides tels que les Nylon-6 et 6,6. Parmi les possibilités d'activation, la catalyse représente une méthode de choix. Dans le cadre de cette thèse des suspensions aqueuses à base de nanoparticules ont été évaluées en termes de stabilité et de performances catalytiques. Dans un premier temps, des colloïdes de ruthénium ont été synthétisés à partir de RuCl3,3H2O et caractérisés par des analyses physico-chimiques (MET, SPX, SAXS, UV-visible, etc.). Des espèces actives de Ru+3 dont la structure est de type Ru(OH)3-xClx ont été obtenues. Après optimisation des conditions de réaction, des conversions élevées, associées à des sélectivités pertinentes vis-à-vis de la cétone (jusqu'à 98%), ont été obtenues. Des études cinétiques et mécanistiques ont montré que la voie radicalaire est prépondérante. De plus, ces colloïdes de Ru aisément recyclables ont également été testés avec succès en oxydation d'autres hydrocarbures saturés et insaturés. Dans un second temps, un catalyseur à base de dioxyde de manganèse, métal moins coûteux et abondant, a été synthétisé par un procédé redox original, à partir de KMnO4 et en présence d'un ammonium quaternaire à tête polaire hydroxylée (HEA16Cl), qui joue simultanément le rôle de réducteur et d'agent stabilisant. Ce système s'est révélé être une alternative pertinente aux procédés à base de métaux nobles. Les nanobâtonnets de MnO2 se sont ainsi montrés actifs en oxydation du cyclooctane avec une sélectivité totale en cétone. / The activation of the Csp3-H bond and its transformation into a carbon-heteroatom bond remains a great challenge for the organic chemistry. An example of industrial application is the oxidation reaction of cyclohexane, leading to the production of the corresponding ketone and alcohol, key intermediates of Nylon-6 and Nylon-6,6 polyamides. Among the strategies to activate this unreactive bond, catalysis affords a relevant and sustainable tool. In this work, aqueous suspensions of metal nanoparticles were evaluated in terms of their stability and catalytic performances. Firstly, ruthenium colloids were synthesized from RuCl3.3H2O and fully characterized by various physico-chemical analyses (TEM, XPS, SAXS, UV-visible, etc.). Ru+3 active species were obtained, with a Ru(OH)3-xClx structure. After optimization of the reaction conditions, high conversions, combined with pertinent selectivities towards the ketone (up to 98%), were achieved. The presence of radical species was proved through kinetic and mechanistic studies. Furthermore, these easily recyclable Ru colloids were also evaluated in the oxidation of several saturated and unsaturated hydrocarbons. Secondly, a catalyst based on manganese dioxide, a cheap and abundant metal, was synthesized by an original redox process, starting from KMnO4 and in the presence of a hydroxylated quaternary ammonium (HEA16Cl), which plays the role of a reducing and stabilizing agent. This system proved to be a relevant alternative to methodologies based on noble metals. The MnO2 nanorods showed a good activity in the cyclooctane oxidation with a 100% selectivity towards the ketone.

No description available.

No description available.

Oil sand deposits in the Athabasca Basin in Alberta represent one of the largest global oil reserves. The bitumen contents of oil sand shallow deposits are recovered by surface mining using modified version of the Clark hot water process. Extraction of bitumen results in extremely large volumes of process water, which are contaminated with naphthenic acids. Various ex-situ treatment techniques including ozonation, advanced oxidation, adsorption, and bioremediation have been evaluated for the treatment of these waters. Previous studies conducted by Paslawski et al. (2009) investigated aerobic biodegradation of naphthenic acids in properly designed and carefully operated bioreactors. In the current work, anaerobic biodegradation of naphthenic acids under denitrifying condition was examined as a potential approach to eliminate the aeration cost in ex-situ treatment and as an alternative for application of in-situ treatment of oil sand process water in stabilization ponds was examined. Using trans-4-methyl-1-cyclohexane carboxylic acid (trans-4MCHCA), a microbial mixed culture developed in earlier works (Paslawski et al., 2009), and nitrate as an electron acceptor, anaerobic biodegradation of trans-4MCHCA were studied in batch and continuous bioreactors: continuous stirred tank reactor (CSTR) and biofilm system. Effects of naphthenic acid concentration, temperature, and loading rate on biodegradation process were investigated. The batch studies showed that initial concentration of trans-4MCHCA influenced the biodegradation rate where the increase in initial concentration of trans-4MCHCA from 100 to 250 mg L-1 led to a higher rate but further increase in concentration did not have a marked effect. Moreover, batch experiments at temperatures ranging from 10° to 35°C demonstrated that the optimum temperature was in the range of 20 - 24°C. Continuous anaerobic biodegradation in the CSTR showed that increase in loading rate of trans-4MCHCA caused an increase in removal rate of both trans-4MCHCA and nitrate. Rates were decreased as the system approached the cell washout. The maximum biodegradation rate and nitrate removal rate, achieved at trans-4MCHCA loading rate of 157.8 mg L-1 h-1, were 105.4 mg L-1 h-1 and 144.5 mg L-1 h-1, respectively. A similar dependency between the loading and removal rates was also observed in the biofilm reactor. The maximum removal rate of trans-4MCHCA and nitrate in the biofilm reactor, operated at room temperature (24 ± 2ºC) were 2,028.1 mg L-1 h-1 and 3,164.7 mg L-1 h-1, respectively and obtained at trans-4MCHCA loading rate of 2,607.9 mg L-1 h-1. Comparison of the results from aerobic batch systems obtained by Paslawski et al. (2009) and the current results showed similar profile where increase in initial concentration of naphthenic acid increased the biodegradation rate of trans-4MCHCA. As far as the effect of temperature is concerned, room temperature (20 - 24ºC) was identified as optimum temperature regardless of mode of biodegradation. Under continuous mode of operation (CSTR and biofilm reactors), anaerobic biodegradation was much faster than its aerobic counterpart. For instance the maximum anaerobic removal rate of trans-4MCHCA in the CSTR was 105.4 mg L-1 h-1, while the highest removal rate achieved in the aerobic CSTR was 9.6 mg L-1 h-1. Similarly, anaerobic biofilm reactor achieved a higher maximum removal rate of 2,028.1 mg L-1 h-1 compared to a 924.4 mg L-1 h-1 removal rate in the aerobic biofilm reactor. The overall finding indicated that biodegradation of trans-4MCHCA can be achieved effectively under anaerobic condition with the rates markedly higher than those for aerobic system.

The photo-oxygenation of 2-methylpropane and cyclohexane using visible light in aqueous acidic uranyl ion solutions at ambient temperature and pressure has been undertaken. For 2-methylpropane in the absence of oxygen, the main product (≈90%) is 2-methyl-2-propanol with a quantum yield of 0.021 ± 0.001. In the presence of molecular oxygen, both 2-methyl-2-propanol and 2-propanone (acetone) are found. Based on this, and results of gamma radiolysis of aqueous 2-methylpropane to give 'tert'-butyl radical by electronically excited uranyl ion is proposed. In the absence of oxygen, the quantum yield of 2-methyl-2-propanol shows a sigmoidal dependence on the concentration of perchloric acid. A two-species kinetic model involving an acid-base dissociation of the uranyl ion in the excited state accounts for the observed features. The addition of sodium perchlorate to the 2-methylpropane system has an inhibitory effect on the quantum yield. Excited-state ion pairing between the uranyl ion and perchlorate anion is proposed. Consequently, the two-species acid-base model is expanded upon to yield a three-species acid-base-perchlorate model that seems to account for the results from 0.01-0.4 M perchloric acid concentration. Potassium peroxydisulfate is proven effective to increase the quantum yield of 2-methyl-2-propanol from 0.021 ± 0.001 to greater than unity (1.5 ± 0.1) indicating the existence and importance of thermal chain reactions involving sulfate radical anion. The quantum yield of 2-methyl-2-propanol is found to be dependent on the concentrations of 2-methylpropane, perchloric acid and potassium peroxydisulfate, and inversely dependent on the light intensity. The net consumption of uranyl ion is zero in the presence of potassium peroxydisulfate meaning that the uranyl ion is regenerated, making this a catalytic cycle in terms of uranyl ion. The oxygenation of cyclohexane using photo-excited aqueous uranyl ion gives cyclohexanol and cyclohexanone as the two main isolated products (54%). The overall mechanism is expected to be similar to that for the 2-methylpropane system. Refluxing of this substrate with a reducing agent (CaH2 or LiAlH4) is required prior to photolysis to achieve consistent quantum yields of both products due to thermal autoxidation reactions. The presence of molecular oxygen is found to be important in determining the ratio of alcohol to ketone in the product distribution. Potassium peroxydisulfate significantly enhances the quantum yield of cyclohexanone, leaving the quantum yield of cyclohexanol relatively unchanged (as compared to without added potassium peroxydisulfate), while uranyl ion is not consumed. Possible reactions involving cyclohexyl and cyclohexyl peroxyl radicals are given to account for the experimental results.

No description available.

A modified dew point method for measuring vapor pressures of condensed phases is applied to solid mixtures of benzene and cyclohexane. From the measured vapor pressures, activity coefficients and excess Gibbs energies are derived. Much less accurate information about excess entropy and excess enthalpy is obtained. A comparison is made with the known properties of liquid mixtures of the same molecules. / Thesis / Master of Science (MSc)

Les matériaux à base de vanadium sont largement utilisés comme catalyseurs pour l'oxydation de composés organiques. Les propriétés catalytiques des catalyseurs au vanadium pour l'oxydation dépendent de l'état et de la stabilité des espèces de vanadium. Dans cette étude, nous développons des nouveaux catalyseurs hétérogènes au vanadium pour la réaction d’oxydation.Dans la première partie du travail, les matériaux mésoporeux à base de silice (MCM-41) contenant du Al (III) et du Ti (IV) sont envisagés comme supports. L'effet d'ancrage chimique de ces hétéroatomes sur les ions V (V) et leur dispersion dans la silice MCM- 41 ont été étudiés à l'aide d'une analyse quantitative des spectres UV-visible de réflectance diffuse. En complément, les matériaux ont été caractérisés par diffraction des rayons X (DRX), mesure de sorption d’azote, spectroscopie de résonance magnétique électrique (RPE) et la spectroscopie Raman. Les spectres UV-visible des échantillons hydratés et déshydratés mettent en évidence la coexistence de plusieurs espèces V (V) de différente nucléarité et différent taux d'hydratation. Le décalage vers le bleu de la bande UV des échantillons contenant comme des additifs les ions Al(III) ou Ti(IV) est cohérent avec une meilleure dispersion des ions vanadium présentant entre autres plus d’espèces mononucléaires (isolées). L'effet bénéfique du titane sur la dispersion de vanadium est compatible avec la formation directe de ponts covalents de type Ti-O-V.Dans la seconde partie, les ions V(IV) ont été déposés sur des matériaux mésoporeux à base de silice en utilisant une nouvelle stratégie dite de pochoir moléculaire ou « Molecular-Stencil Patterning ». La stratégie de pochoir moléculaire s’applique à la silice contenant des tensioactifs ioniques en utilisant ces derniers comme agent de masquage lors du greffage covalent de diverses fonctions. Cette stratégie de surface moléculaire permet de contrôler à la fois le voisinage moléculaire et la dispersion à longue distance des espèces de vanadium entre elles. La caractérisation a été effectuée en utilisant plusieurs méthodes telles l’analyse thermogravimétrique (ATG), la spectroscopie de résonance magnétique nucléaire (RMN), la spectroscopie infrarouge (IR) et la spectroscopie UV-visible. L'incorporation des ions titane (IV) joue le rôle d’ancre chimique pour les ions V(IV) comme dans le chapitre précédent. Il est montré qu’une proportion de V/Ti inférieure à un et proche de trois génère les meilleures conditions pour éviter la formation de gros agrégats d’oxyde de vanadium.Enfin, ces nouveaux matériaux au vanadium ont été testés en phase liquide pour catalyser l'oxydation partielle du cyclohexane en une huile désignée par son rapport molaire K/A de cyclohexanone (K) et de cyclohexanol (A). Ce mélange est utilisé comme telle en chimie industrielle de base, an particulier comme précurseurs de l'acide adipique et de caprolactame pour la synthèse du nylon. Les tests ont démontré que l’introduction de titane combiné à la stratégie de pochoir moléculaire a notablement amélioré les propriétés catalytiques de ce type de catalyseurs au vanadium.En conclusion, la silice MCM-41 au vanadium a été conçu par l’introduction des hétéroatomes d'ancrage et de la stratégie de pochoir moléculaire, afin d'améliorer la dispersion et la stabilité des sites actifs. Les matériaux conçus ont montré de meilleures propriétés et caractéristiques catalytiques dans divers caractérisation et la réaction d'oxydation. / Vanadium-based materials are widely used as catalysts for oxidation of organic compounds. The catalytic properties of vanadium catalysts for oxidation are related closely to the state and the stability of vanadium species. Therefore, a series of vanadium-containing MCM-41 silica were designed and developed in this study, and their catalytic application for oxidation reactions was evaluated as well.In the first part of work, the chemical anchoring effect of Al(III) or Ti(IV) heteroatoms on the dispersion of V (V) in MCM-41 type silica was investigated using a quantitative analysis of diffuse reflectance UV-visible spectra. The characteristic properties of prepared materials were determined by various characterization such as X-ray diffraction (XRD), N2 sorption measurement, Electron paramagnetic resonance (EPR) spectroscopy, UV-visible spectroscopy and Raman spectroscopy. UV-visible spectra of hydrated and dehydrated samples evidenced the coexistence of several V(V) species of different oligomerization and hydration levels. The global blue shift of the band in the presence of Al(III) or Ti(IV) additives was then assigned to a higher proportion of less clustered and isolated V(V) species. The stronger beneficial effect of Ti on the vanadium dispersion is consistent with a higher stability of the X-O-V bridges moving from X = Si to X = Al and Ti. In the second part, new mesoporous silica materials containing vanadium species were synthesized according to the molecular stencil patterning technique. Molecular stencil patterning is developed specifically for silica templated with ionic surfactants used as masking agent to sequentially immobilize via covalent bonding (grafting) different functions. This molecular surface engineering was proved to improve the vanadium species dispersion according to Thermogravimetric Analysis (TGA), Nuclear Magnetic Resonance spectroscopy (NMR), Infrared spectroscopy (IR) and UV-visible spectroscopy. The incorporation of titanium species played again the role to immobilize the vanadium species as the results in previous work. The V/Ti ratio should be less than 1 to control the formation of clusters of vanadium species.Lastly, the vanadium-containing materials were applied to the liquid phase oxidation of cyclohexane into cyclohexanol (A) and cyclohexanone (K). A mixture of these two products is often called K/A oil in the industrial chemical production. K/A oil is widely used as a raw material for adipic acid and caprolactam in the nylon industry. The catalysis results proved that the modification by adding titanium chemical anchors combined with the MSP technique improve the catalytic properties of vanadium-containing heterogeneous catalysts.In conclusion, the dispersion and stability of vanadium active sites has been improved in new syntheses of vanadium-containing MCM-41 type silica by combining both anchoring heteroatoms and molecular stencil patterning techniques. Such a novel design leads to better catalytic performance in oxidation reaction in correlation with the structural and physical characteristics of the material.

Polymeric membranes have been essential to increasing the efficiency of membrane separation processes. The viability of membrane systems for industrial gas applications lies in the tolerance of such membranes to contamination. While membrane contamination from volatile species can be addressed using purge streams and heat treatment, contamination from non-volatile hydrocarbons can cause a significant decline in membrane permselectivity. This study was focused on the characterization and remediation of cellulose acetate (CA) hollow fibre membranes contaminated by heavy hydrocarbons. CA membranes have a moderate resistance against performance decline from hydrocarbons found in natural gas. Hollow fibre CA membranes were coated with motor oil lubricant to simulate heavy hydrocarbon contamination from large-scale gas compressors and industrial feed streams, and remediation of the CA fibres was conducted using solvent extraction methods. The permeabilities of the membranes to carbon dioxide, helium, hydrogen, methane, nitrogen and oxygen were measured at pressures 300 – 1500kPa and at temperatures 25° – 50°C. It was shown that even a thin layer of oil on the membrane surface can result in substantial losses in membrane performance, with faster permeating gases (e.g. He and H₂) suffering the worst losses. Solvent exchange, in which the membrane was washed using a series of solutions of varying organic content, was unable to remediate the membrane effectively, while the removal of the heavy hydrocarbons by a direct cyclohexane rinse was found to work well to restore the membrane performance.