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A kinetic study of ethanol steam-reforming reaction on Rh catalyst supported over a spinel structure (MgAl2O4/Al2O3) was carried out. From the analysis of products distribution, the following four ...

The influence of the addition of Ni on the catalytic behaviour of a Rh/Y2O3-Al2O3 catalyst (Rh/Y-Al) was evaluated in the ethanol steam reforming reaction in the presence of methyl-2-propan-1-ol as impurity. Physical-chemical properties of modified materials were determined by H2 chemisorption, XRD, BET, TPR, IR spectroscopy and TPO. It was established that the catalytic behaviour of the Rh/Y-Al base catalyst is widely improved by the addition of Ni. Nickel incorporation leads to the formation of both dispersed nickel phase and nickel aluminate species. Basic properties of the support were not modified by the addition of Ni but it was concluded to a rearrangement of acid sites. NiAl2O4 phase leads to an increase of the Lewis acid sites (LAS) of weak strength, generating a decrease of the production of coke and higher catalyst stability. It has been shown that the incorporation of Ni on the Rh/Y-Al catalyst increases the rhodium accessibility and stabilizes the rhodium particles size. Finally, the higher performances of RhNi/Y-Al catalyst were correlated to an increase in the methane steam reforming activity.

International audience; The effect of various impurities added in a pure ethanol + water mixture was studied. The impurities chosen were acetic acid, diethylamine, butanol, butanal, ethyl acetate and diethylether. It was shown that the addition of diethylamine or butanal increases the ethanol conversion, compared to that obtained with a pure ethanol + water mixture, without changing the product selectivity. In the presence of the other impurities, butanol, ethylether and ethyl acetate, a strong deactivation of the catalyst with a decreased ethanol conversion was observed. Moreover, the selectivity in hydrogen was also strongly decreased, whereas an increase in intermediate products especially ethylene was observed. The deactivation was explained in terms of coke deposition at the catalyst surface. The poisoning effect induced by the presence of impurities can be classified in the following increasing order: diethylamine ∼ butanal < no impurity < acetic acid < butanol < diethylether ∼ ethyl acetate.

The use of noble metals in heterogeneous catalysis is limited by the scarcity of these metals, their cost and the supply difficulties due to the monopole of only two countries on the world market. The aim of this work consisted to study the association of platinum and cobalt in order to substitute partly Pt with Co while preserving the catalytic performances of the noble metal in hydrogenation. Various syntheses of 1%Pt- 5%Co supported bimetallic catalysts have been achieved and their performances have been compared with those of monometallic catalysts as well as (Pt + Co) mechanical mixtures for two hydrogenation’s reactions of industrial interest: the hydrogenation of acetonitrile and that of furfural. The physicochemical characterizations carried out (TEM, XPS …) and the model reactions (dehydrogenation of cyclohexane, hydrogenolysis of methylcyclopentane) studied have pointed out several results: - the presence of Pt increases the reducibility of Co for co-impregnated catalysts and mechanical mixtures leading to an enhancement of the catalytic performances in hydrogenation of acetonitrile or furfural; - the colloidal preparation favors the formation of PtCo alloy particles with a homogeneous composition, which are not very active for the reactions studied; - the redox route synthesis can accurately deposit Pt in contact with Co creating an improvement of the catalytic performances by a synergistic effect. Thus, in the hydrogenation of acetonitrile, the same activity was obtained by using a Pt-Co catalyst containing five times less noble metal’s content than the 1% Pt catalysts.; L’utilisation des métaux nobles en catalyse hétérogène est limitée par la rareté de ces métaux, leur coût et les difficultés d’approvisionnement, le marché mondial étant régi par deux producteurs. Le but de ce travail a consisté à étudier l’association du platine et du cobalt afin de substituer en partie Pt par Co tout en préservant les propriétés catalytiques du métal noble en hydrogénation. Différentes synthèses de catalyseurs bimétalliques 1%Pt-5%Co supportés (coimprégnation, voie redox et voie colloïdale) ont été réalisées et les performances de ces catalyseurs comparées à celles des catalyseurs monométalliques et des mélanges mécaniques (Pt + Co) pour deux réactions d’hydrogénation d’intérêt industriel : l’hydrogénation de l’acétonitrile et celle du furfural. Les caractérisations par des techniques physicochimiques (MET, XPS, …) ou par réactions modèles (déshydrogénation du cyclohexane, hydrogénolyse du méthylcyclopentane) ont permis d’obtenir les résultats suivants : - la présence de Pt augmente la réductibilité du Co pour les catalyseurs coimprégnés ou pour les mélanges mécaniques, ce qui permet d’améliorer les performances catalytiques en hydrogénation du furfural ou de l’acétonitrile ;- la préparation par voie colloïdale oriente vers la formation de particules PtCo de type alliage de composition homogène, peu actives pour les réactions étudiées ;- la synthèse par voie redox permet de déposer précisément le platine au contact du cobalt créant un effet synergétique bénéfique. Il est ainsi possible d’obtenir la même activité que le platine seul en hydrogénation de l’acétonitrile mais avec un catalyseur PtCo présentant une quantité de Pt cinq fois moins importante.