Alexandre Carvalho

Étude de l'activité intrinsèque des catalyseurs Fischer-Tropsch à base de cobalt et de fer par des méthodes cinétiques transitoires: Les travaux exposés dans ce manuscrit portent sur l’étude de l’activité intrinsèque et de la localisation des sites actifs des catalyseurs à base de cobalt et de fer par une combinaison des méthodes cinétiques transitoires telles que le SSITKA, de la caractérisation physico-chimique étendue et des tests catalytiques. La promotion des catalyseurs à base de fer avec des métaux utilisés pour la soudure (Bi et Pb) conduit à une augmentation remarquable de la vitesse de production des oléfines légères avec la possibilité d’effectuer la synthèse Fischer-Tropsch dans des conditions très douces (basse pression) voire pression atmosphérique. Parmi tous les catalyseurs étudiés, les catalyseurs à base de zéolite de type mordenite ont présenté la valeur la plus élevée de la constante de vitesse SSITKA. La localisation des sites actifs de cobalt dans les catalyseurs bifonctionnels à base de zéolite a un impact majeur sur la vitesse de réaction et en particulier sur la sélectivité en hydrocarbures. La proximité entre les sites actifs de cobalt et les sites actifs de Bronsted a été considérée comme un paramètre clef pour obtenir une sélectivité et un rendement plus élevés en hydrocarbures ramifiés. Le SSITKA couplé à des techniques de caractérisation a révélé que le dépôt de carbone et l'agglomération des nanoparticules de cobalt étaient responsables de la désactivation du catalyseur cobalt supporté par la silice. La régénération des catalyseurs sous hydrogène diminue le nombre d'espèces de carbone déposées et libère partiellement les sites les plus actifs d’adsorption dissociative et les sites les plus forts d'adsorption réversible du monoxyde de carbone.

The efficiency of niobium oxide as catalytic support of hydrodesulfurization (HDS) catalysts (CoMo and NiW) has been investigated in the HDS of a model molecule representative of sulfur compounds present in FCC gasoline (3-methylthiophene: 3MT). The NiW catalyst presented higher catalytic activity than CoMo calcined and non-calcined catalyst, however a better ratio pentane/pentene has been achieved by CoMo catalysts, which implies a lower formation of hydrogenated products. Indeed, the activity order for the catalysts evaluated is: NiW/Nb2O5 > CoMo/Nb2O5 calcined support > CoMo/Nb2O5 non-calcined support, despite the ratio pentane/pentene which has the inverse order. Furthermore, textural and chemical characterization techniques have been performed. From NH3-TPD analysis it was observed an acidity profile with a predominance of weak/strong and weak/moderate acid for CoMo and NiW catalysts, respectively. Meanwhile, the BET analysis has shown a low specific surface area for the catalysts supported by niobium oxide. Concerning the structure characteristic, the XRD analysis has suggested an amorphous phase in all catalysts analyzed.

A larger number and a more uniform distribution of cobalt sites with almost the same intrinsic activity results in higher carbon monoxide hydrogenation rate in the mordenite compared to ZSM-5 zeolite.

A way to improve hydrotreatment processes is to enhance the intrinsic activity of Ni or Co promoted MoS₂ catalysts that are commonly used in such reactions. The aim of this work was to investigate the impact of the presence of Pluronic^® P123 as a structuring agent during the synthesis of Ni promoted MoS₂ catalysts (named NiMoS) in water at room temperature. A series of analyses, i.e., X-ray diffraction (XRD), chemical analysis, inductively coupled plasma mass spectrometry (ICP-MS), nitrogen adsorption-desorption isotherms, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), helped in characterizing the NiMoS-P123 and NiMoS catalysts, the latter being prepared in the absence of polymer. Both compounds contained MoS₂ phase (~85 atomic% considering Mo atoms), a similar amount of mixed Ni-Mo-S phase (40–50% considering Ni) and some amount of NiS and Ni-oxidized impurity phases. The main differences between the two catalysts were a much larger specific surface area (126 m²·g⁻¹ instead of 31 m²·g⁻¹) and a better dispersion of the active phase as shown by the lower slab stacking (2.7 instead of 4.8) for NiMoS-P123, and the presence of C in NiMoS-P123 (9.4 wt.% instead of 0.6 wt.%), indicating an incomplete decomposition of the polymer during thermal treatment. Thanks to its larger specific surface area and lower slab stacking and therefore modification of active Mo site properties, the compound prepared in the presence of Pluronic^® P123 exhibits a strong increase of the catalytic activity expressed per Mo atom for the transformation of 3-methylthiophene. Such improvement in catalytic activity was not observed for the transformation of benzothiophene likely due to poisonous residual carbon which results from the presence of Pluronic^® P123 during the synthesis.

A new strategy for the synthesis of metal–zeolite nanocomposite materials containing metal nanoparticles only in the zeolite pores is proposed. These materials were first prepared by zeolite impregnation with metal salts which resulted in metal species located both inside the zeolite pores and on the zeolite outer surface. Then, the metal oxide nanoparticles on the external zeolite surface were selectively extracted by larger heteropolyacid molecules which cannot enter the zeolite pores. The use of cobalt–zeolite nanocomposites with cobalt nanoparticles selectively encapsulated in the zeolite pores led to significantly higher selectivity to C₅–C₁₂ branched hydrocarbons in Fischer–Tropsch synthesis with the maximum ratio of isoparaffins to n-paraffins of 5.8.