Fischer-Tropsch cobalt catalyst deselectivation was studied using accelerated aging treatments dedicated to the carburization phenomenon. Cobalt carbide was successfully obtained by CO treatments, with limited simultaneously carbon deposition nor sintering. Particle sizes were found to influence the catalyst sensitivity to carburization, likely because of a possible core-shell mechanism. An important loss of both activity and selectivity to heavy products was observed after the treatments, making carburization one of the potential mechanisms responsible for deselectivation in Fischer-Tropsch synthesis. Side products were also impacted by cobalt carbide formation, with an increase of CO 2 production and a decrease of the selectivity to olefins.The extent of carburization was found to directly dictate the level of the selectivity shift.
Understanding how alumina degradation to boehmite AlOOH can be prevented under hydrothermal conditions is key to design more stable catalysts supported on alumina for Fischer–Tropsch synthesis. We compare the effect of four inorganic dopants to inhibit γ‐alumina chemical weathering under hydrothermal conditions: three metal ions: Mg2+, Zr4+, Ni2+, introduced by impregnation, and nonmetal Si, introduced by the grafting of tetraethyl orthosilicate. Boehmite is formed by a mechanism of dissolution–precipitation. A significant decrease of alumina weathering to boehmite is evidenced for all dopants. For metal ions, the thermal conversion of doped γ‐Al2O3 into an alumina‐rich mixed oxide or the coverage of the alumina surface by particles of a poorly soluble oxide such as NiO contribute to the stabilization of the solid. Alumina dissolution and degradation are only inhibited fully through Si grafting. IR spectra in the OH stretching region suggest that the most reactive alumina sites toward dissolution are basic Al−OH sites located on lateral facets that are blocked upon Si introduction. Fischer–Tropsch reactivity shows that Co catalysts prepared on Mg2+‐ and Si‐doped supports are less active or, at best, as active as a reference Co/γ‐Al2O3 catalyst, which is explained by a lower reducibility of CoO on doped supports. The Co catalyst prepared on Mg2+‐doped γ‐Al2O3 calcined at 900 °C exhibits the best combination of catalytic activity, ease of preparation, and hydrothermal stability.
The enzymatic hydrolysis of cellulose is still considered as a main limiting step of the biological production of biofuels from ligno-cellulosic biomass. Glycoside hydrolases from Trichoderma reesei are currently used to produce fermentable glucose units from degradation of cellulose packed in a complex assembly of cellulose microfibrils. The present work describes the structural evolution of two prototypical samples of cellulose (a micro-crystalline cellulose and a bleached sulfite pulp) over 5 length scale orders of magnitude. The results were obtained through wide angle, small angle and ultra-small angles synchrotron X-ray scattering, completed by Small Angle Neutron Scattering and particle size analyzers. These structural evolutions were followed as a function of enzymatic conversion. The results show that whereas there is no change at the nanometer scale, drastic changes occur at micron. The observed decrease of the size of the cellulose particles is accompanied by a smoothing of the crystalline surfaces that can be explained by a two-step mechanism of the enzymatic hydrolysis.
The emergence of high-throughput experimentation gives new opportunities for accurate and rapid data acquisition for a wide variety of chemical reactions in different fields of application such as hydrocracking, isomerization...
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