Abstract
Ni/Al2O3 and Ni/La2O-Al2O3 catalysts were investigated for the biogas reforming reaction using CH4/CO2 mixtures with minimal dilution. Stability tests at various reaction temperatures were conducted and TGA/DTG, Raman, STEM-HAADF, HR-TEM, XPS techniques were used to characterize the spent samples. Graphitized carbon allotrope structures, carbon nanotubes (CNTs) and amorphous carbon were formed on all samples. Metallic Ni0 was recorded for all (XPS), whereas a strong peak corresponding to Ni2O3/NiAl2O4, was observed for the Ni/Al sample (650–750°C). Stability tests confirm that the Ni/LaAl catalyst deactivates at a more gradual rate and is more active and selective in comparison to the Ni/Al for all temperatures. The Ni/LaAl exhibits good durability in terms of conversion and selectivity, whereas the Ni/Al gradually loses its activity in CH4 and CO2 conversion, with a concomitant decrease of the H2 and CO yield. It can be concluded that doping Al2O3 with La2O3 stabilizes the catalyst by (a) maintaining the Ni0 phase during the reaction, due to higher dispersion and stronger active phase-support interactions, (b) leading to a less graphitic and more defective type of deposited carbon and (c) facilitating the deposited carbon gasification due to the enhanced CO2 adsorption on its increased surface basic sites.