The effect of microwave radiation on the prepared 0.5Fe/ZSM-5 catalysts as a post-synthesis modification step was studied in the methanol-to-hydrocarbons process using the temperature-programmed surface reaction (TPSR) technique. This was achieved by preparing a series of 0.5Fe/ZSM-5 based catalysts under varying microwave power levels (0–700 W) and over a 10 s period, after iron impregnating the HZSM-5 zeolite (Si/Al = 30 and 80). Physicochemical properties were determined by XRD, SEM, BET, FT-IR, C3H9N-TPSR, and TGA techniques. It was found that microwave radiation induced few changes in the bulk properties of the 0.5Fe/ZSM-5 catalysts, but their surface and catalytic behavior were distinctly changed. Microwave radiation enhanced crystallinity and mesoporous growth, decreased coke and methane formation, decreased the concentration of Brønsted acidic sites, and decreased surface area and micropore volume as the microwave power level was increased from 0 to 700 W. From the TPSR profiles, it was observed that microwave radiation affects the peak intensities of the produced hydrocarbons. Application of microwave radiation shifted the desorption temperatures of the MTH process products over the HZSM-5(30) and HZSM-5(80) based catalysts to lower and higher values respectively. The MeOH-TPSR profiles showed that methanol was converted to DME and subsequently converted to aliphatic and aromatic hydrocarbons. It is reasonable to suggest that microwave radiation would be an essential post-synthesis modification step to mitigate coke formation and methane formation and increase catalyst activity and selectivity. / Chemical Engineering / M. Tech. (Chemical Engineering)

Dans cette thèse, des particules de polymère fonctionnalisées en surface avec des groupes poly (éthylène glycol) (PEG) ont été synthétisées pour favoriser leur interaction avec les dérivés cellulosique via liaisons hydrogène intermoléculaires. Deux voies de synthèse ont été proposées pour obtenir ses composites cellulose/latex.La première voie est basée sur l'auto-assemblage induit par polymérisation (PISA) pour former des nanoparticules fonctionnalisées avant leur adsorption sur un substrat cellulosique. La PISA tire profit de la formation de copolymères blocs amphiphiles dans l'eau en combinant la polymérisation en émulsion avec les techniques de polymérisation radicalaire contrôlées (RDRP). Ces dernières sont utilisées pour synthétiser des polymères hydrophiles agissant à la fois comme précurseur pour la polymerization en émulsion d'un monomère hydrophobe, et comme stabilisant des particules de latex obtenues. Deux techniques de RDRP ont été étudiées : les polymérisations RAFT et SET-LRP. Des polymères hydrophiles à base de PEG de faible masse molaire ont été synthétisés en utilisant ses deux techniques qui sont ensuite utilisés pour la polymérisation d'un bloc hydrophobe dans l'eau. Le transfert de l'agent de contrôle au site de la polymérisation était difficile en utilisant la SET-LRP en émulsion, conduisant à la formation de larges particules. En utilisant la RAFT en émulsion, des particules nanométriques ont été obtenues, avec un changement morphologique observé en fonction de la taille du segment hydrophobe, puis adsorbées sur des nanofibrilles de cellulose (CNF).La seconde voie utilise la polymérisation en émulsion classique réalisée en présence de nanocristaux de cellulose (CNC) conduisant à une stabilisation Pickering des particules de polymère. L'interaction cellulose/particule est assurée grâce à l'ajout d’un comonomère à type PEG. Une organisation a été visualisé dans laquelle plusieurs particules de polymère recouvrent chaque CNC / In this thesis, polymer particles surface-functionalized with poly(ethylene glycol) (PEG) groups were synthesized to promote their interaction with cellulose derivatives via intermolecular hydrogen bond. Two synthetic routes were proposed to obtain such cellulose/latex composites.The first route was based on the polymerization-induced self-assembly (PISA) to form functionalized polymer nanoparticles prior to adsorption onto cellulosic substrate. PISA takes advantage of the formation of amphiphilic block copolymers in water by combining emulsion polymerization with reversible-deactivation radical polymerization (RDRP) techniques. The latter were used to synthesize well-controlled hydrophilic polymer chains, acting as both precursor for the emulsion polymerization of a hydrophobic monomer, and stabilizer of the final latex particles. Two RDRP techniques were investigated: reversible addition-fragmentation chain transfer (RAFT), and single electron transfer-living radical polymerization (SET-LRP). Low molar mass PEG-based hydrophilic polymers have been synthesized using both techniques, used for the polymerization of a hydrophobic block in water. The transfer of controlling agent at the locus of the polymerization was challenging for SET-LRP in emulsion conditions leading to surfactant-free large particles. Nanometric latex particles were obtained via RAFT-mediated emulsion polymerization, with morphology change from sphere to fibers observed depending on the size of the hydrophobic segment, which were then able to be adsorbed onto cellulose nanofibrils (CNFs).The second route used conventional emulsion polymerization performed directly in presence of cellulose nanocrystals (CNCs) leading to Pickering-type stabilization of the polymer particles. Cellulose/particle interaction was provided thanks to the addition of PEG-based comonomer. Original organization emerged where CNCs were covered by several polymer particles