Sonia A. Bocanegra

MgAl2O4 spinel prepared by mechanochemical synthesis used as a support of multimetallic catalysts for paraffin dehydrogenation

The catalytic performance in n-butane dehydrogenation of bimetallic PtSn, PtGa and PtIn, and trimetallic PtSnIn and PtSnGa catalysts (with low metal contents) supported on a MgAl2O4 prepared by a novel mechanochemical synthesis was evaluated both in flow and pulse equipment. The influence of the addition of different promoters (Sn, Ga and In) to Pt on the activity, selectivity and deactivation in the n-butane dehydrogenation reaction was studied. Stability experiments through successive reaction-regeneration cycles were carried out for selected catalysts. In order to correlate the properties of the metallic phase of the catalysts with the catalytic behavior, several characterization techniques were used, such as test reactions of the metallic phase (cyclohexane dehydrogenation and cyclopentane hydrogenolysis), TPR, XPS, H2 chemisorption and TEM. Bimetallic PtSn catalyst has a better catalytic behavior than PtIn and PtGa ones. For PtSnM (M: In or Ga) catalysts, whereas Ga addition to the bimetallic catalyst does not practically modify the dehydrogenation performance, the addition of In produces an increase of the activity and the selectivity to butenes. Characterization results indicate the presence of geometric effects for the PtSn catalyst, and geometric and electronic effects for PtIn and PtGa ones. For trimetallic catalysts, the presence of a close contact between Pt, Sn and In or Ga in both trimetallic catalysts was found, mainly due to geometric effects like blocking and dilution of the active sites by the promoters. In stability experiments, the trimetallic PtSnIn/MgAl2O4 catalyst clearly displays the best catalytic performance along reaction-regeneration cycles, though PtSnGa and PtSn catalysts also showed a very good behavior through the successive cycles. The characterization of these catalysts after cycles shows that their metallic phases are slightly modified along the cycles.

Innovative Coating Method of MgAl2O4 or ZnAl2O4 on α-Al2O3 Spheric Nuclei

Structured materials composed of α-Al2O3 spheres covered with a porous and thin layer of MgAl2O4 or ZnAl2O4 were obtained. The innovative coating method developed consists in the formation of a precursor gel of MgAl2O4 or ZnAl2O4 by citrate-nitrate combustion method. The alumina spheres are submerged in this gel and then submitted to a drying process in vacuum and to calcinations with N2 and N2/O2. SEM results showed that a very rough and porous layer uniformly covers the spheres. The thickness of the layer reaches the maximum value of 16 µm in the sample coated with two layers of ZnAl2O4. XRD results confirmed the MgAl2O4 or ZnAl2O4 spinel formation in the layered material. The structured materials were used as Pt catalysts supports, showing a good catalytic activity in the n-butane dehydrogenation reaction.