Syngas production from dry reforming of methane over ni/perlite catalysts: Effect of zirconia and ceria impregnation

Ni catalysts with nominal loadings ranging between 2.5 and 20 wt% were synthesized over perlite by wet impregnation, then filtered, washed and calcined at 500 °C. Chemical analyses performed by MP-AES revealed that the maximum Ni content loaded over perlite corresponded to ~15 wt%. Therefore, for comparison reasons, a Ni(20 wt%)/perlite catalyst was prepared by wetness impregnation without performing any washing treatment. The so prepared catalysts were tested in methane dry reforming without performing any pre-treatment reduction. The catalytic performances were compared by increasing the temperature from 500 up to 800 °C under the reaction mixture composed of 15 vol% CH4 + 15 vol% CO2/N2. Ni(15 wt%)/perlite was the most active catalyst among the series of monometallic samples. The effect of co-impregnating perlite with Ni and Zr or Ni and Ce precursors in order to obtain catalysts with final composition, Ni(15 wt%), 10 and 20 wt% as Zr or Ce, perlite (75 or 65 wt%) was, then, investigated. Characterizations performed by XRD, BET, DRS and H2-TPR evidenced that the physico-chemical and reduction properties are influenced by the Ni content and by the presence of zirconia and ceria oxides. It is worth of noting the increased reducibility of NiO species promoted by zirconia and ceria addition. The catalytic activity in the dry reforming of methane was also affected by the presence of doping oxides, in terms of enhanced CH4 and CO2 conversions and higher H2/CO atomic ratios. Runs tests at 700 °C for 12 h were carried out and the spent catalysts were analysed by TGA and TEM. Over Ni(15 wt%)/perlite large amount of amorphous carbon grows on the surface blocking the active centres, while zirconia and ceria doping improved the resistance to carbon poisoning favouring growing of filamentous carbon residues in small amount.