Sibunit-Supported Mono- and Bimetallic Catalysts Used in Aqueous-Phase Reforming of Xylitol.

Carbon-supported mono- and bimetallic catalysts prepared via incipient wetness impregnation were systematically studied in aqueous-phase reforming (APR) of xylitol aiming at hydrogen production from biomass. The catalytic performance of several VIII group metals and their combinations, such as Pt, Ni, Pt-Ni, Re, Pt-Re, Ru, Pt-Ru, and Pt-Co, was compared for xylitol APR in a fixed-bed reactor at 225 °C and 29.7 bar (N2). Ni/C, Ru/C, and Re/C catalysts displayed significantly lower activity compared to others. Activity and selectivity to H2 of bimetallic Pt-Ni/C, Pt-Co/C, and Pt-Ru/C catalysts were close to that of Pt/C. Pt-Re/C catalyst showed an outstanding performance which was accompanied by a shift of the reaction pathways to the alkane formation and thereby lower hydrogen selectivity. Addition of the second metal to Pt was not found to be beneficial for hydrogen production, thus leaving Pt/C as the optimum carbon-supported catalyst.

Kinetics of lactose and rhamnose oxidation over supported metal catalysts.

Several mono- and bimetallic Pd, Pt, Rh and Ru supported on alumina and active carbon catalysts were characterized by CO chemisorption, nitrogen adsorption, XPS and XRD and acidity titrations were performed for active carbon supported catalysts. These catalysts were tested in oxidation of two sugars, namely lactose and rhamnose, at 60 °C and at 70 °C under slightly alkaline conditions (pH 8) with molecular oxygen. The results revealed that there is an optimum metal particle size in a range of 3-10 nm giving the highest initial TOFs for both oxidations. Furthermore, the catalytic activities and conversions were related to other catalyst properties, such as the type and amount of promoters and the presence of different phases. In situ catalyst potential measurements revealed that there is an inverse correlation between the increase of catalyst potential as a function of sugar conversion and the catalyst activity after prolonged reaction times. This method is a valuable tool for in situ characterization of catalysts correlating well with their activities.

Reaction products and transformations of intermediates in the aqueous-phase reforming of sorbitol.

Aqueous phase reforming of sorbitol over Pt supported on an alumina catalyst is investigated, in order to identify the intermediates involved in the transformation of the initial feed. Parameters such as the sorbitol feed rate and temperature are studied. To identify the intermediates, an approach based on analysis of the gas and liquid phases as well as the total carbon content was developed. According to analysis by gas chromatography combined with mass spectrometry of volatile substances collected with solid-phase microextraction, over 260 compounds are involved in the transformation of sorbitol. Of these, 50 of the major products are identified with high reliability. It is shown that a great variety of compounds, bearing different functionalities, form part of the reaction network. The formation of the majority of identified compounds is explained and a reaction network for the formation of sorbitol and intermediate molecules transformation is proposed.