Desenvolvimento de catalisadores bifuncionais de óxido de zircônio modificado por óxidos de tungstênio e molibdênio contendo platina para a reação de isomerização de n-parafinas

Bifunctional catalysts based on zircon oxide modified by tungsten (W = 10, 15 and 20 %) and by molybdenum oxide (Mo= 10, 15 e 20 %) containg platinum (Pt = 1%) were prepared by the polymeric precursor method. For comparison, catalysts the tungsten base was also prepared by the impregnation method. After calcinations at 600, 700 and 800 ºC, the catalysts were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, thermogravimetric and differential thermal analysis, nitrogen adsorption and scanning electron microscopy. The profile of metals reduction was determined by temperature programmed reduction. The synthesized catalysts were tested in n-heptane isomerization. X-ray diffractogram of the Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts revealed the presence of tetragonal ZrO2 and platinum metallic phases in all calcined samples. Diffraction peaks due WO3 and ZrO2 monoclinic also were observed in some samples of the Pt/WOx-ZrO2 catalysts. In the Pt/MoOx-ZrO2 catalysts also were observed diffraction peaks due ZrO2 monoclinic and Zr(MoO4)2 oxide. These phases contained on Pt/WOx-ZrO2 and Pt/MoOx-ZrO2 catalysts varied in accordance with the W or Mo loading and in accordance with the calcination temperature. The infrared spectra showed absorption bands due O-W-O and W=O bonds in the Pt/WOx-ZrO2 catalysts and due O-Mo-O, Mo=O and Mo-O bonds in the Pt/MoOx-ZrO2 catalysts. Specific surface area for Pt/WOx-ZrO2 catalysts varied from 30-160 m2 g-1 and for the Pt/MoOx-ZrO2 catalysts varied from 10-120 m2 g-1. The metals loading (W or Mo) and the calcination temperature influence directly in the specific surface area of the samples. The reduction profile of Pt/WOx-ZrO2 catalysts showed two peaks at lower temperatures, which are attributed to platinum reduction. The reduction of WOx species was evidenced by two reduction peak at high temperatures. In the case of Pt/MoOx-ZrO2 catalysts, the reduction profile showed three reduction events, which are attributed to reduction of MoOx species deposited on the support and in some samples one of the peak is related to the reduction of Zr(MoO4)2 oxide. Pt/WOx-ZrO2 catalysts were active in the n-heptane isomerization with high selectivity to 3-methyl-hexane, 2,3- dimethyl-pentane, 2-methyl-hexane among other branched hydrocarbons. The Pt/MoOx-ZrO2 catalysts practically didn't present activity for the n-heptane isomerization, generating mainly products originating from the catalytic cracking

Estudo do aproveitamento do rejeito da mineração de esmeraldas na produção de refratários conformados isolantes

Emerald mining is an important area of the economy in Brazil, country which is in second place among the exporting nations of this gem. Due to the process of extraction, a great amount of reject is generated. Since there is no appropriate destination, the reject is abandoned around the mining industries, contributing to environment degradation. Nowadays, some of the most relevant things to an industry in general are: energy conservation, cost reduction, quality and productivity enhancement. The production of isolating, transformed refractory materials achieves the sustainability dimension when protection of the environment is incorporated to such process. This work investigates the use of emerald mining rejects in the ceramic body of refractory materials, aiming at obtaining a product whose characteristics are compatible with commercial products and, at the same time, allow the use of such rejects to solve the environmental issue caused by its disposal in nature. X-ray fluorescence analysis show that the emerald reject obtained after the flotation to extract molybdenum and mica has 70% of silica and alumina (SiO2+Al2O3) and 21% of a basic oxides and alkaline metals and earthy alkaline mixture (Na2O, K2O, CaO e MgO). Because of the significant amount of silica and alumina present in the reject, four refractory ceramic bodies were prepared. Samples with a rectangular shape and dimensions 100x50x10 mm were pressed in a steel mold at 27,5 MPa and sintered at 1200ºC for 40 min. under environment atmosphere in a resistive oven. The sintered samples were characterized in relation to the chemical composition (FRX), mineralogical composition (DRX), microstructure (MEV) and physical and mechanical properties. The results indicate that the mixture with 45% of reject, 45% of alumina and 10% of kaolin presents a refractory quality of 1420ºC, dimensional linear variation below 2.00%, apparent specific mass of 1,56 g/cm3 and porosity of 46,68%, which demonstrates the potential use of the reject as raw material for the industry of isolating transformed refractory materials