Browsing by Author "Ribeiro, Fernando Ramôa"
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- Activity–acidity relationship in zeolite ZSM-5. Application of Brönsted-type equationsPublication . Costa, Carla; Dzikh, I. P.; Lopes, Jose M.; Lemos, Francisco; Ribeiro, Fernando RamôaIn this paper the relation between activity and acidity in a variety of ZSM-5 zeolite catalysts, with different Si/Al ratios and different protonic content, is analysed and a quantitative correlation is obtained. The acid site strength distribution was estimated using temperature-programmed desorption (TPD) of ammonia by applying a digital deconvolution method to the curves. These data were then correlated with experimental catalytic activity data for the same catalysts towards n-heptane cracking reaction, by means of a Brönsted-type equation similar to the ones used for homogeneous acid catalysis and already used for other zeolites. It can be noticed that the same types of equation that are used for homogeneous acid catalysis also hold for heterogeneous acid catalysis and that the activation energy for ammonia desorption can be used as acid-strength scale for the purpose of correlation with catalytic activity.
- Study of Pt/MCM-22 based catalysts in the transformation of n-hexane: effect of rare earth elements and mode of platinum introductionPublication . Martins, Angela; Silva, João; Ribeiro, Fernando Ramôa; Filipa Ribeiro, M.The bifunctional transformation of n-hexane was carried out over Pt/MCM-22 based catalysts. MCM-22 was synthesized and submitted to ion exchange with rare earth nitrate solutions of La, Nd and Yb, followed by Pt introduction. Three different methods were used to introduce about 1 wt% of Pt in the zeolite: ion exchange, incipient wetness impregnation and mechanical mixture with Pt/Al(2)O(3). The bifunctional catalysts were characterized by transmission electron microscopy and by the model reaction of toluene hydrogenation. These experiments showed that, in the ion exchanged sample, Pt is located both within the inner micropores and on the outer surface, whereas in the impregnated one, the metal is essentially located on the outer surface under the form of large particles. The presence of RE elements increases the hydrogenating activity of Pt/MCM-22 since the location of these species at the vicinity of metal particles causes modification on its electronic properties. Whatever the mode of Pt introduction, a fast initial decrease in conversion is observed for n-hexane transformation, followed by a plateau related to the occurrence of the catalytic transformations at the hemicages located at the outer surface of the crystals. The effect of rare earth elements on the hydrogenating function leads to a lower selectivity in dibranched isomers and increased amounts of light products.