<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>U ovom radu izvr&scaron;ena su ispitivanja deaktivacije katalizatora za hidrodesulfurizaciju (HDS), uz simulaciju starenja u laboratorijskim uslovima i paralelna ispitivanja katalizatora iz realnog industrijskog postrojenja. &Scaron;irok interval uslova u laboratorijskoj simulaciji (temperatura, vreme tretmana, oksidacione i inertne atmosfere) pružio je osnov za ocenu uticaja različitih parametara na brzinu starenja katalizatora i definisanje kritičnih uslova, posebno pri regeneraciji katalizatora. Ispitivanja dva tipa HDS katalizatora, NiO-MoO₃/y-Al₂O₃ i CoO- MoO₃/y-Al₂O₃ i binarnih modelnih sistema NiO/ Al₂O₃, uz primenu komplementamih metoda za ispitivanje stukture i teksture čvrstih poroznih materijala, omogućila su uvid u mehanizme starenja u ovim složenim katalitičkim sistemima. Utvrđeno je da je oksidaciona atmosfera, posebno vodena para, kritičan faktor u kinetici stukturnih i teksturalnih promena u katalitičkom sistemu. Segregacija aktivne faze, interakcija sa nosačem, sinterovanje i gubitak aktivne faze iz sistema simultani su procesi koji dovode do trajne deaktivacije katalizatora. Visina radne temperature i moguća lokalna pregrevanja u sloju katalizatora, podstaknuta promenama difuzionih karakteristika kataličkog zrna, ključni su za destrukciju aktivne faze katalizatora, uz segregaciju prekursora oksidne faze molibdena, čiji je uticaj izrazit u fazi regeneracije. Intermedijarno prisustvo tečne faze oksida molidena, koja obliva povr&scaron;inu nosača, uslovljavajući intenzivno sinterovanje i ubrzanu interakciju izmedju ostalih faza u sistemu, predstavlja osnovni mehanizam u starenju katalizatora za HDS.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>Deactivation studies of hydrodesulphurization catalysts were performed, based on both aging simulation in laboratory conditions and investigation of catalysts from an industrial HDS plant. Broad interval of conditions applied in laboratory simulation (temperature, treatment duration, oxidation and inert atmospheres) was the basis for evaluating the effect of different parameters on catalyst aging kinetics and defining critical conditions, with emphasis on regeneration procedure. The investigations of two catalyst types, NiO-MoO3/y-Al2O3 and C0O-MoO3/y-Al2O3, and NiO/Al2O3 binary model systems, using complementary methods for structural and textural investigations of porous solid systems, enabled the insight in aging mechanisms of these complex catalytic systems. The oxidation atmosphere, especially water vapor, is critical for the rate of structural and textural changes in the catalysts. Segregation in active phase, interaction with the support, sintering and loss of active component from the catalyst are the simultaneous processes bringing about the irreversible deactivation of the catalyst. The temperature gradient in working conditions and possible formation of hot spots in catalyst reactor bed, affected also by changes of diffusion characteristics of catalyst grain, are crucial factors for segregation of molybdenum oxide precursor, which effect is pronounced during regeneration. The mechanism of HDS catalyst aging is based on intermediary presence of moIybdenum oxide liquid phase on the support surface, facilitating intensive sintering and interactions of other phases of catalytic system.</p>

Dans le cadre d’une Convention CIFRE, la thèse est financée par la société Renault, ce travail vise à développer un supercondensateur carbone-carbone dont le coût de fabrication est compatible avec le marché automobile ; c’est en effet leur coût élevé qui constitue encore à l’heure actuelle un frein à leur développement. Dans une première partie de ce travail, il a été montré que l’essentiel du coût repose en grande partie sur la purification de l’électrolyte utilisé mais surtout du carbone activé, qui est le matériau actif d’électrode. Notre travail s’est donc focalisé sur l’étude du vieillissement électrochimique de cellules de supercondensateurs de laboratoire assemblées avec différents carbones, afin d’essayer d’identifier les phénomènes responsables du vieillissement. Un autre objectif a été d’identifier les caractéristiques que doivent présenter les carbones alternatifs candidats au remplacement des carbones commerciaux. L’étude réalisée dans ce travail de thèse a permis de définir deux modes de vieillissement différents suivants les carbones utilisés. Un premier type de vieillissement entraîne l’augmentation conjointe de la résistance série équivalente et de la capacité, dû à une dégradation/oxydation du carbone à l’électrode positive. Un second mode de vieilissement mène à l’augmentation seule de la résistance série équivalente par la formation d’une couche d’interface solide conductrice ionique. Quelque soit le mode vieillissement, aucune corrélation directe n’a pu être établie avec les fonctions de surface des carbones activés. La piste la plus probable repose sur le taux et la nature des impuretés présentes dans le carbone activé, certaines étant électroactives, voire pouvant jouer un rôle catalytique. / In the context of a CIFRE Convention, the thesis is financed by Renault s.a.s., this work aims at developing a carbon-carbon supercapacitor whose manufacturing cost is compatible with the automotive market, which still hinders their development. In a first part of this work, it has been shown that the cost mainly depends on the purity of the materials used: electrolyte but also activated carbon, the electrode active material. Our work has therefore been focused on the study of the electrochemical aging of laboratory supercapacitor cells assembled with different carbons, to identify their ageing mechanisms and to define the key features alternative carbons must achieve to replace commercial carbons. This work has evidenced two different modes of aging, depending on the carbon used. A first ageing mode results in the joint increase of the equivalent series resistance as well as the capacity, due to a degradation / oxidation of the carbon at the positive electrode. A second mode leads to the sole increase in equivalent series resistance by the formation of an ionic conductive solid interface layer. Whatever the aging mode, no clear influence of the surface functions of activated carbons could be evidenced. The most likely assumption is based on the content and the nature of the impurities present in the activated carbon, some of which are electroactive and can even play a catalytic role.