The hydrogenolysis of glycerol was performed in an autoclave at temperatures between 190 and 225 • C and at a H 2 pressure of 5 MPa over a CuO/ZnO catalyst prepared by an oxalate gel (OG) method. Compared to a CuO/ZnO catalyst prepared by coprecipitation, much higher conversions of glycerol and space-time yields up to 9.8 g propylene glycol g Cu -1 h -1 are achieved with CuO/ZnO-OG, whereas both catalysts produced propylene glycol with selectivities of about 90%. Additionally, the influence of the temperature and the solvent was examined. Compared to a conversion of glycerol of only 5% in an aqueous glycerol solution, the use of 1,2-butanediol as a solvent leads to a high conversion of 55%. Moreover, experiments were carried out in pure glycerol and from transmission electron microscopy images of fresh and spent catalysts, it was obvious that the morphology of the catalyst changed during the reaction. By X-ray diffraction and N 2 O chemisorption, it was proved that a tremendous loss of copper surface area occurred during the hydrogenolysis of glycerol. Taking together the influence of the solvent on the conversion of glycerol and the results of the catalyst characterization, it can be concluded that water, as an unavoidable by-product of the reaction, is responsible for a strong deactivation of the catalyst.

The growing production of biodiesel as a renewable source-based fuel leads to an increased amount of glycerol. Thus, it is a favorable starting material to obtain highly functionalized products. From a variety of catalytic reactions three examples, namely glycerol oxidation, glycerol hydrogenolysis and aqueous-phase reforming, were chosen for detailed studies in our group. The experimental focus for the oxidation of glycerol was set on preparation and detailed examination of supported Pt-Bi catalysts in batch reactions as well as in continuous experiments using a trickle bed reactor. For aqueous-phase reforming of glycerol to hydrogen the addition of tin to supported platinum catalysts was investigated. Ruthenium and copper based catalysts could be successfully applied in the hydrogenolysis of glycerol to 1,2-propanediol.

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Copper/zinc oxide catalysts prepared by coprecipitation were proved to be highly active and selective in the hydrogenolysis of glycerol. However, they suffer from strong deactivation in the course of reaction. Modifying the CuO/ZnO catalyst with Ga 2 O 3 extremely enhances the stability of the catalyst as even after four consecutive experiments over a Cu/ZnO/Ga 2 O 3 catalyst no deactivation is observed. The catalysts were characterized by temperature-programmed reduction, powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy coupled with energy-dispersive X-ray analysis, and inductively coupled plasma optical emission spectrometry. As the Cu/ZnO/Ga 2 O 3 catalyst is stable even under harsh reaction conditions of 220°C and in the presence of water, a space-time-yield as high as 22.1 g propylene glycol /(g Cu h) can be obtained.