Methane dry reforming with and without O2 over Ni/ Ce0.5Zr0.

5O2 catalysts
Ricardo R. Soares*, Myriam S.P. Moitinho, Sabrina F. Nascimento and C. E. Hori School of Chemical Engineering Federal University of Uberlndia Uberlndia/MG Brazil CEP 38408-100 rrsoares@ufu.br (Professor)
The interest in the process of carbon dioxide reforming of methane to synthesis gas has experienced a rapid increase both for commercial and environmental reasons. Although the dry reforming is slightly more endothermic than the conventional steam reforming, it consumes the two main greenhouse gases and, produces a suitable CO/H2 ratio for the production of higher hydrocarbons and oxygenated derivatives. The major obstacle preventing commercialization of this process is that, due to the high endothermic nature of the process, high temperatures are required to reach 100% conversion. These conditions are conducive to carbon deposition via the Boudouard reaction. One potential solution to overcome this problem would be to combine the CO2 reforming and partial oxidation reactions. The presence presence of small quantities of oxygen would help to reduce carbon deposition at high temperatures allowing for much longer operating cycles, and ultimately reducing regeneration time and operating cost. The recent development of non-porous ceramic membranes that are 100% selective for oxygen separation provide an attractive solution for the costly oxygen separation problem. Although noble metals, as platinum suffer less coking than nickel, they are higher in cost and more limited in availability than the latter. Therefore, nickel-based catalysts are more appropriate for industrial practice. The main goal of this work was to evaluate the x%Ni/Ce0.5Zr0.5O2 catalysts performances during the dry and autothermal (combining with partial oxidation) reforming reaction (T=1073 K, GHSV = 36,000 h-1, CH4:CO2 ratio = 2:1). The positions of the valleys at the TPO profiles revealed the presence of carbonaceous species, probably carbon and carbonates, located at distinct points of the surface of the supports. This carbonaceous species were preferred on catalysts supported on ZrO2>CeO2> Ce0.5Zr0.5O2.