ABSTRACT Cobalt and niobium oxide solids modified with alkaline earth metals (Mg, Ca, and Sr) were synthesized and characterized to compare the second element effect on the catalyst structural and chemical properties. The materials were prepared by co-precipitation of cobalt nitrate and niobium oxalate solutions using ammonium hydroxide as precipitating agent. The samples were characterized by XRD, SEM, Ra-man, BET, TPR, ammonia TPD and cyclohexane dehydrogenation reaction (CHD). Results showed that Mg, Ca or Sr addition changed cobalt niobate crystalline structure, leading to alkaline earth metal nio-bates with lower crystallinity. It was observed that Mg, Ca or Sr increased the solids acidity and changed cobalt niobate reduction behavior so that the lowest amount of metallic cobalt was obtained when Mg was incorporated. Modifiers also decreased cobalt niobate dehydrogenation activity. This effect was higher with Mg or Sr addition.

ABSTRACT Different basic materials, such as K-L zeolite, K-Al2O3, K-Mg/Al mixed oxide and MgO, were used as supports of Pt-catalysts for the dry reforming of methane (DR) reaction. The effects of the distribution of basic strength in the support on the metal-support properties and catalyst performance were evaluated. The density of strong and the total basic sites decreased as follows: MgO>K(Mg-Al) >K-Al2O3>K-L. The total basic sites decrease from 214 to 23 µmol CO2. g-1, for MgO and KL, respectively. Pt catalysts supported on materials with high density of strong basic sites such as MgO were the most adequate for the DR reaction. An increase in the dehydrogenation velocity of 12.1 to 25.2 mol h-1 g-1 was observed between Pt/KL and Pt/MgO, which indicates a higher metallic dispersion of the latter catalyst. With respect to the DR reaction, both catalysts have a similar CO2 conversion, but the CH4 conversion and the H2/CO ratio increase from 71.1 to 83.0 % and 0.5 to 0.73, respectively. The best catalytic behaviour of Pt/MgO would be related with the good interaction between the metal and the basic support. The methane conversion and the H2/CO ratios obtained by DR reaction correlate quite well with the basicity of the different catalysts.

ABSTRACT The solid oxide fuel cells (SOFC) enable the efficient generation of clean energy, fitting the current requirements of the growing demand for electricity and for the environment preservation. When powered with biogas (from digesters of municipal wastes), the SOFCs also contribute to reduce the environmental impact of these wastes. The most suitable route to produce hydrogen inside SOFC from biogas is through dry reforming but the catalyst is easily deactivated by coke, because of the high amounts of carbon in the stream. A promising way to overcome this drawback is by adding a second metal to nickel-based catalysts. Aiming to obtain active, selective and stable catalysts for biogas dry reforming, solids based on nickel (15%) and copper (5%) supported on aluminum and magnesium oxide were studied in this work. Samples were prepared by impregnating the support with nickel and copper nitrate, followed by calcination at 500, 600 and 800 oC. It was noted that all solids were made of nickel oxide, nickel aluminate and magnesium aluminate but no copper compound was found. The specific surface areas did not changed with calcination temperature but the nickel oxide average particles size increased. The solids reducibility decreased with increasing temperature. All catalysts were active in methane dry reforming, leading to similar conversions but different selectivities to hydrogen and different activities in water gas shift reaction (WGSR). This behavior was assigned to different interactions between nickel and copper, at different calcination temperatures. All catalysts were active in WGSR, decreasing the hydrogen to carbon monoxide molar ratio and producing water. The catalyst calcined at 500 oC was the most promising one, leading to the highest hydrogen yield, besides the advantage of being produced at the lowest calcination temperature, requiring less energy in its preparation.

Abstract In this paper, a new way for γ-alumina synthesis was proposed, the raw material being aluminum powders obtained by high-energy milling of aluminum cans. This seems a good option for this metal recycling and energy saving, as well as hydrogen production. The materials were prepared by precipitation techniques, in which aluminum powders reacted with hydrochloric acid, giving aluminum chloride, which was subsequently transformed into aluminum hydroxide by reaction with ammonium hydroxide or sodium hydroxide as precipitant agents, and finally into γ-alumina by calcination. Results showed that the used preparation methods gave a γ-alumina structure, confirmed by XRD, with surface areas values (174 and 204 m2 g-1) close to those of a commercial γ-alumina Cyanamid Ketjen (180 m2 g-1) or an alumina prepared by a typical precipitation route (203 m2 g-1). Using sodium hydroxide as precipitant agent turned out to be more ecologically compatible since it did not release harmful environmental compounds.