Kinetic study and deactivation phenomena for the methanation of CO2 and CO mixed syngas on a Ni/Al2O3 catalyst
Fabrizio Celoria, Fabio Salomone, Alessio Tauro, Marta Gandiglio, Domenico Ferrero, Isabelle Champon, G. Geffraye, Raffaele Pirone, Samir Bensaid
Abstract
• A three-reaction LHHW model describes successfully CO 2 and CO co-methanation. • CO adsorption promotes the dissociative carbon route, carburization and coking. • CO 2 improves significantly the catalyst stability in CO 2 and CO co-methanation. • O 2 and C 2 H 4 reduce catalyst stability, while H 2 S causes irreversible deactivation. • Power-law deactivation rates allow the activity to be predicted for scaling-up. This study presents a detailed kinetic and deactivation analysis of a 24 wt% Ni/Al 2 O 3 catalyst for the hydrogenation of CO 2 and CO to CH 4 , focusing the attention on the CO 2 and CO co-methanation. More than 300 reaction conditions were tested on a fixed-bed reactor obtaining 907 observations. Among them, 852 measurements were used to derive the kinetic parameters in an isothermal reactor model. Power-law models accurately describe CO 2 or CO methanation, but fail to predict co-methanation due to preferential adsorption of CO. On the contrary, a three-reactions Langmuir-Hinshelwood-Hougen-Watson model (model M4) successfully described it together with the different hydrogenation pathways. Experimental and literature insights suggest that CO 2 adsorption occurs via either dissociative or H-assisted associative mechanism, and then, the high H* coverage favors its conversion into CH 4 via the so-called dissociative formyl (CHO*) route. On the contrary, the exergonic CO adsorption increases the CO* coverage promoting the dissociative carbon (C*) route. In addition, C* species are responsible for the higher deactivation rates in CO methanation due to the formation of nickel carbides and coking. Long-term stability tests revealed several deactivation phenomena. CO 2 methanation induced mild sintering, while CO methanation led to a significant decrease in stability. Notably, co-methanation improved stability at low temperature by suppressing nickel carbide formation. Contaminants like O 2 and C 2 H 4 decreased the stability due to re-oxidation and coking, respectively, while poisons like H 2 S deactivated the catalyst irreversibly. Power-law deactivation models were developed to predict the activity loss, supporting the potential scale-up of CO 2 and CO methanation processes.