Evolution of the properties of PtGe/Al2O3 reforming catalysts with Ge content

Abstract

The effect of the Pt/Ge atomic ratio on the catalytic activity of PtGe/Al2O3 catalysts used in n-heptane reforming was studied. The samples were prepared by the coimpregnation method on chlorinated alumina. The platinum content was 0.5 wt.%, and Ge-loading was varied to obtain Pt/Ge atomic ratios of 0.3, 0.7, 1.4, 2.1 and 3.5. Pt/Al2O3 and Ge/Al2O3 catalysts were also prepared as references. Characterization was carried out by temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia (NH3-TPD), Fourier transform IR spectroscopy (FTIR) with CO as the probe molecule, X-ray photoelectron spectroscopy (XPS), cyclohexane (CH) dehydrogenation, and n-heptane reforming. The preparation method followed in this work revealed a decrease in the metallic activity of Pt due to the presence of Ge. The Ge2+ and Ge4+ species, after reduction at 500 °C, were detected on the surface of PtGe catalysts. The increase in the Ge content led to a decrease in hydrogenolysis activity and the formation of aromatics; an increase in the formation of isomers and cycloparaffins, and a reduction in the production of gas and in deactivation by coke, thereby improving catalyst stability. The results show that the maximum isoparaffin yield of all catalysts tested was obtained for a Ge-loading of 0.27 wt.% (Pt/Ge atomic ratio = 0.7). These changes in the performance of the PtGe catalysts may be attributed to the modifications occurring in the metallic and in the acid function of Pt/Al2O3 due to the introduction of Ge. The metallic catalytic activity of Pt is modified by the geometrical effect (dilution of Pt ensembles) and changes in the electronic properties of platinum. Ge addition produces a weakening of Pt/Al2O3 acid strength and an increase in the acid sites total density by the presence of Ge oxides.