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A series of Ce1-xCuxO2-δ mixed oxides were synthesized using a co-precipitation method and tested as catalysts for the steam reforming of methanol. XRD patterns of the Ce1-xCuxO2-δ mixed oxides indicated that Cu2+ ions were dissolved in CeO2 lattices to form a solid solution by calcination at 773K when x < 0.2. A TPR (temperature-programmed reduction) investigation showed that the CeO2 promotes the reduction of the Cu2+ species. Two reduction peaks were observed in the TPR profiles, which suggested that there were two different Cu2+ species in the Ce1-xCuxO2-δ mixed oxides. The TPR peak at low temperature is attributed to the bulk Cu2+ species which dissolved into the CeO2 lattices, and the peak at high temperature is due to the CuO species dispersed on the surface of CeO2. The Ce1-xCuxO2-δ mixed oxides were reduced to form Cu/CeO2 catalysts for steam reforming of methanol, and were compared with Cu/ZnO, Cu/Zn(Al)O and Cu/AL2O3 catalysts. All the Cu-containing catalysts tested in this study showed high selectivities to CO2 (over 97%) and H2. A 3.8wt% Cu/CeO2 catalyst showed a conversion of 53.9% for the steam reforming of methanol at 513K (W/F = 4.9 g h mol-1), which was higher than that over Cu/ZnO (37.9%), Cu/Zn(Al)O (32.3%) and Cu/AL2O3 (11.2%) with the same Cu loading under the same reaction conditions. It is likely that the high activity of the Cu/CeO2 catalysts may be due to the highly dispersed Cu metal particles and the strong metalsupport interaction between the Cu metal and CeO2 support. Slow deactivations were observed over the 3.8wt% Cu/CeO2 catalyst at 493 and 513K. The activity of the deactivated catalysts can be regenerated by calcination in air at 773K followed by reduction in H2 at 673K, which indicated that a carbonaceous deposit on the catalyst surface caused the catalyst deactivation. Using the TPO (temperature-programmed oxidation) method, the amounts of coke on the 3.8wt% Cu/CeO2 catalyst were 0.8wt% at 493K and 1.7wt% at 513K after 24h on stream. [ABSTRACT FROM AUTHOR]

Isomerization of n-hexane and n-heptane was carried out over Cs2.5H0.5PW12O40 (denoted by Cs2.5) promoted by Pt which was introduced by either impregnation of H2PtCl6 or mechanical mixing of Pt/Al2O3 and over non-promoted Cs2.5H0.5PW12O40 in the presence of hydrogen at atmospheric pressure. The reaction temperature studied was relatively low (typically 453 and 423 K for n-hexane and n-heptane, respectively) and the hydrogen pressure was also rather low (standard conditions: feed = n-alkane 0.05 atm, H2 0.20 atm, N2 balance; W/F = 40 g h mol−1). Results were compared with those obtained under the same conditions for other Pt-promoted solid acids, where particular attention was paid to the time courses of the reaction (initial vs. stationary performance). Both the activity and selectivity of Cs2.5 at the initial stage (after 5 min) increased by the addition of the Pt component. Pressure dependencies of the rate at the initial stage were approximately first and −0.5th orders in alkane and hydrogen, respectively. Most remarkable was the suppression of the deactivation during the reaction in the presence of both Pt and hydrogen. For example, the mechanical mixture of Pt/Al2O3 and Cs2.5 (abbreviated as Pt+Cs2.5) showed little deactivation and much improved selectivity; resulting in high stationary conversion and selectivity; e.g., 98.4 and 92.1% selectivities for n-hexane and n-heptane at the conversions of 58.6 and 39.4%, respectively. Most of the results were well explained by a classical bifunctional mechanism, although other mechanisms are not all excluded. As for the other solid acids, the initial activity of Pt-promoted SO4/ZrO2 was high, but decreased rapidly. The deactivation was small with Pt-promoted H-ZSM-5, but the activity was low. The stationary yields of isomerized products were higher for Pt-promoted beta zeolite and Al-pillared saponite (tested only for n-heptane), although higher reaction temperatures were necessary. [ABSTRACT FROM AUTHOR]