Aqueous-phase reforming of n-BuOH over Ni/Al 2O 3 and Ni/CeO 2 catalysts

Abstract

The aqueous-phase reforming (APR) of n-butanol (n-BuOH) over Ni(20 wt%) loaded Al 2O 3 and CeO 2 catalysts has been studied in this paper. Over 100 h of run time, the Ni/Al 2O 3 catalyst showed significant deactivation compared to the Ni/CeO 2 catalyst, both in terms of production rates and the selectivity to H 2 and CO 2. The Ni/CeO 2 catalyst demonstrated higher selectivity for H 2 and CO 2, lower selectivity to alkanes, and a lower amount of C in the liquid phase compared to the Ni/Al 2O 3 sample. For the Ni/Al 2O 3 catalyst, the selectivity to CO increased with temperature, while the Ni/CeO 2 catalyst produced no CO. For the Ni/CeO 2 catalyst, the activation energies for H 2 and CO 2 production were 146 and 169 kJ mol −1, while for the Ni/Al 2O 3 catalyst these activation energies were 158 and 175 kJ mol −1, respectively. The difference of the active metal dispersion on Al 2O 3 and CeO 2 supports, as measured from H 2-pulse chemisorption was not significant. This indicates deposition of carbon on the catalyst as a likely cause of lower activity of the Ni/Al 2O 3 catalyst. It is unlikely that carbon would build up on the Ni/CeO 2 catalyst due to higher oxygen mobility in the Ni doped non-stoichiometric CeO 2 lattice. Based on the products formed, the proposed primary reaction pathway is the dehydrogenation of n-BuOH to butaldehyde followed by decarbonylation to propane. The propane then partially breaks down to hydrogen and carbon monoxide through steam reforming, while CO converts to CO 2 mostly through water gas shift. Ethane and methane are formed via Fischer–Tropsch reactions of CO/CO 2 with H 2.