Robson S. Monteiro

Characterization of PdCeO2 interaction on alumina support and hydrogenation of 1,3-butadiene

Abstract The influence of the preparation method and loading of CeO 2 on the interaction of Pd/CeO 2 /Al 2 O 3 catalysts was studied. The materials were characterized by temperature-programmed reduction, hydrogen chemisorption and X-ray photoelectron spectroscopy measurements. The 1,3-butadiene hydrogenation was used as a model reaction. The Pd Ce interaction affected the reduction behavior of the catalysts. Temperature-programmed reduction (TPR) results showed that the presence of CeO 2 shifts the reduction temperature of PdO to lower values, while palladium similarly facilitates the reduction of the cerium surface species. The hydrogen uptake decreased when increasing the ceria content. XPS results showed that the Pd/Al ratio decreased with CeO 2 addition being affected by the preparation method and content. The formation of catalytic sites at the interface of Pd Ce was postulated from turnover frequency (TOF) results of the 1,3-butadiene hydrogenation. The number of these new sites increases with the addition of ceria. The nature of these sites is discussed in terms of the influence on the selectivity in butadiene hydrogenation.

The nature of metal oxide on adsorptive and catalytic properties of Pd/MeOx/Al2O3 catalysts

Abstract The role of ceria, niobium and molybdenum oxides on the promotion of the NO reduction by CO was studied. A bifunctional mechanism was discussed as a function of both the nature of interaction between metal oxide and palladium and the redox properties of each metal oxide. The NO dissociation was better on the Pd/MoO 3 /Al 2 O 3 catalyst than on the Pd/CeO 2 /Al 2 O 3 and Pd/Nb 2 O 5 /Al 2 O 3 catalysts. The explanation for the very high N 2 production on Pd–Mo catalyst during the TPD analysis may be attributed to the NO+Me δ + stoichiometric reaction. The promoting effect of a reducible oxide for the NO+CO reaction at low temperature can be ascribed mainly to its easiness for a redox interchange and its interaction with the noble metal particles. This would increase the surface redox ability and favor the dynamic equilibrium needed for high N 2 selectivity.

Oxidation and reduction effects of propane-oxygen on Pd-chlorine/alumina catalysts

Pd–chloride precursor salt was used to prepare Pd/Al2O3 catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd2+ sites observed on Pd/Al2O3 through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H2, the IR spectra showed the linear and bridge adsorbed CO species on the Pd0 surface. After propane reaction, a new band at 2130 cm-1 related to CO adsorption on Pd2+ species was noted. Carbon monoxide species adsorbed on Pd0 were also observed in all samples after reaction. Our results suggest surface ratios of Pd0/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature.

Química e sustentabilidade: novas fronteiras em biocombustíveis

This contribution discusses the state of the art and the challenges in producing biofuels, as well as the need to develop chemical conversion processes of CO2 in Brazil. Biofuels are sustainable alternatives to fossil fuels for providing energy, whilst minimizing the effects of CO2 emissions into the atmosphere. Ethanol from fermentation of simple sugars and biodiesel produced from oils and fats are the first-generation of biofuels available in the country. However, they are preferentially produced from edible feedstocks (sugar cane and vegetable oils), which limits the expansion of national production. In addition, environmental issues, as well as political and societal pressures, have promoted the development of 2nd and 3rd generation biofuels. These biofuels are based on lignocellulosic biomass from agricultural waste and wood processing, and on algae, respectively. Cellulosic ethanol, from fermentation of cellulose-derived sugars, and hydrocarbons in the range of liquid fuels (gasoline, jet, and diesel fuels) produced through thermochemical conversion processes are considered biofuels of the new generation. Nevertheless, the available 2nd and 3rd generation biofuels, and those under development, have to be subsidized for inclusion in the consumer market. Therefore, one of the greatest challenges in the biofuels area is their competitive large-scale production in relation to fossil fuels. Owing to this, fossil fuels, based on petroleum, coal and natural gas, will be around for many years to come. Thus, it is necessary to utilize the inevitable CO2 released by the combustion processes in a rational and economical way. Chemical transformation processes of CO2 into methanol, hydrocarbons and organic carbonates are attractive and relatively easy to implement in the short-to-medium terms. However, the low reactivity of CO2 and the thermodynamic limitations in terms of conversion and yield of products remain challenges to be overcome in the development of sustainable CO2 conversion processes.

Carbon Dioxide as a Feedstock for the Chemical Industry. Production of Green Methanol

Carbon dioxide (CO2) has a restricted use as a feedstock in the chemical industry. Its emission and accumulation in the atmosphere in great quantities have been largely associated to the greenhouse effect. Thus, the conversion of CO2 into value-added chemical products will bring on not only economical benefits but also far greater importance for the environmental stewardship. The hydrogenation of CO2 into methanol (CH3OH) is a promising route to fix CO2 in the chemical industry. The reaction can be carried out by Cu and Zn-based catalysts, which are highly selective to CH3OH formation. However, the reaction is severely affected by the thermodynamic equilibrium. Therefore, the effect of reaction temperature and pressure needs to be known in order to achieve high conversion rates of CO2 into CH3OH, thus allowing the development of feasible and highly efficient conversion processes.