Kinetic Assessment of the Dry Reforming of Methane over a Ni–La 2 O 3 Catalyst

The dry reforming of methane is a promising technology for the abatement of CH 4 and CO 2 . Ni–La 2 O 3 catalysts are characterized by their long-term stability (100 h) when tested at full conversion. The kinetics of dry reforming over these types of catalysts has been studied using both power-law and Langmuir–Hinshelwood-based approaches. However, these studies typically deal with fitting the net CH 4 rate, hence disregarding competing and parallel surface processes and the different possible configurations of the active surface. In this work, we synthesized a Ni–La 2 O 3 catalyst and tested six Langmuir–Hinshelwood mechanisms considering both single and dual active sites for assessing the kinetics of dry reforming and the competing reverse water–gas shift reaction and investigated the performance of the derived kinetic models. In doing this, it was found that: (1) all of the net rates were better fitted by a single-site model that considered that the first C–H bond cleavage in methane occurred over a metal–oxygen pair site; (2) this model predicted the existence of a nearly saturated nickel surface with chemisorbed oxygen adatoms derived from the CO 2 dissociation; (3) the CO 2 dissociation can either be an inhibitory or an irrelevant step, and it can also modify the apparent activation energy for CH 4 activation. These findings contribute to a better understanding of the dry reforming reaction’s kinetics and provide a robust kinetic model for the design and scale-up of the process.