The depletion of fossil fuels has heightened research and utilization of renewable energy such as biodiesel. However, this has thrown up another challenge of significant increase in its byproduct, glycerol. In view of the characteristics and potentials of glycerol, efforts are on the increase to convert it to higher-value products, which will in turn improve the overall economics of biodiesel production. These high-value products include biofuels, oxygenated fuel additives, polymer precursors and other industrial bio-based chemicals. This review gives up-to-date research findings in the conversion of glycerol to the above high-value products, with a special focus on the performance of the catalysts used and their challenges. The specific products reviewed in this paper include hydrogen, ethanol, methanol, acetin, glycerol ethers, solketal, acetal, acrolein, glycerol carbonate, 1,3-propanediol, polyglycerol and olefins.
A randomly mixed monodispersed nanosized Pt-Ru catalyst, an ultimate catalyst for CO oxidation reaction, was prepared by the rapid quenching method. The mechanism of CO oxidation reaction on the Pt-Ru anode catalyst was elucidated by investigating the relation between the rate of CO oxidation reaction and the current density. The rate of CO oxidation reaction increased with an increase in unoccupied sites kinetically formed by hydrogen oxidation reaction, and the rate was independent of anode potential. Results of extended X-ray absorption fine structure spectroscopy showed the combination of N(Pt-Ru)/(N(Pt-Ru) + N(Pt-Pt)) ≑ M(Ru)/(M(Pt) + M(Ru)) and N(Ru-Pt)/(N(Ru-Pt) + N(Ru-Ru)) ≑ M(Pt)/(M(Ru) + M(Pt)), where N(Pt-Ru)(N(Ru-Pt)), N(Pt-Pt)(N(Ru-Ru)), M(Pt), and M(Ru) are the coordination numbers from Pt(Ru) to Ru(Pt) and Pt (Ru) to Pt (Ru) and the molar ratios of Pt and Ru, respectively. This indicates that Pt and Ru were mixed with a completely random distribution. A high-entropy state of dispersion of Pt and Ru could be maintained by rapid quenching from a high temperature. It is concluded that a nonelectrochemical shift reaction on a randomly mixed Pt-Ru catalyst is important to enhance the efficiency of residential fuel cell systems under operation conditions.
Structural modifications of Cu/ZnO catalysts for methanol steam reforming (MSR) as a function of precipitate aging in catalysts preparation process has been investigated comparatively. Freshly precipitated Cu,Zn-hydroxycarbonate (HC) and Cu,Zn-hydroxynitrate (HN) were aged in their mother liquor for a period of 120 min followed by washing, drying, calcination and reduction. Pronounced effect of aging was found for aged HC precipitates while no significant effect of aging was observed for aged HN solids. The bulk structure of the Cu/ZnO catalysts was investigated by means of TG/MS, in situ XRD and 63Cu NMR. The increase in the activity of the catalysts prepared by HC aging did not correlate linearly with the specific Cu surface area but coincides with an increase in the microstrain in the copper clusters presumably because of the improved interface between Cu and ZnO. Meanwhile, aging of HN precipitates results in large, separated and less strained Cu and ZnO particles with an inferior catalytic activity. Finally, both aged Cu/ZnO catalysts revealed smaller copper crystallite size compared to unaged samples
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