Kinetics, Model Discrimination, and Parameters Estimation of CO2 Methanation on Highly Active Ni/CeO2 Catalyst
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Título: | Kinetics, Model Discrimination, and Parameters Estimation of CO2 Methanation on Highly Active Ni/CeO2 Catalyst |
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Autor/es: | Onrubia-Calvo, Jon A. | Quindimil, Adrián | Davó-Quiñonero, Arantxa | Bermejo-López, Alejandro | Bailón-García, Esther | Pereda-Ayo, Beñat | Lozano-Castello, Dolores | González-Marcos, José A. | Bueno López, Agustín | González-Velasco, Juan R. |
Grupo/s de investigación o GITE: | Materiales Carbonosos y Medio Ambiente |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Inorgánica |
Palabras clave: | Kinetics | Model discrimination | Parameters estimation | CO2 methanation | Ni/CeO2 catalyst |
Área/s de conocimiento: | Química Inorgánica |
Fecha de publicación: | 20-may-2022 |
Editor: | American Chemical Society |
Cita bibliográfica: | Industrial & Engineering Chemistry Research. 2022, 61(29): 10419-10435. https://doi.org/10.1021/acs.iecr.2c00164 |
Resumen: | The reaction kinetics of CO2 methanation over a highly active 8.5% Ni/CeO2 catalyst was determined in a fixed-bed reactor, in the absence of heat- and mass-transfer limitations. Once the catalyst activity was stabilized, more than 120 kinetic experiments (with varying values of reaction temperature, total pressure, space velocity (GHSV), and partial pressure of products and reactants) were performed. From initial reaction rates, an apparent activation energy of 103.9 kJ mol–1 was determined, as well as the effect of reactants (positive) and water partial pressures (negative) on CO2 methanation rate. Three mechanistic models reported in the literature, in which CO2 is adsorbed dissociatively (carbon and formyl routes) or directly (formate route), were explored for modeling the entire reaction kinetics. For that, the corresponding rate equations were developed through the Langmuir–Hinshelwood–Hougen–Watson (LHHW) approach. In agreement with DRIFTS experiments, formate route, in which the hydrogenation of bicarbonate to formate is considered to be the rate-determining step, reflects the kinetic data accurately, operating from differential conversion to thermodynamic equilibrium. In fact, this mechanism results in a mean deviation (D) of 10.38%. Based on previous own mechanistic studies, the participation of two different active sites has been also considered. Formate route on two active sites maintains a high fitting quality of experimental data, providing kinetics parameters with a higher physical significance. Thus, the LHHW mechanism, in which Ni0 sites as well as oxygen vacant near to Ni-CeO2 interface participate in CO2 methanation, is able to predict the kinetics of Ni/CeO2 catalyst accurately for a wide range of operational conditions. |
Patrocinador/es: | Support for this study was provided by the Spanish Ministry of Science and Innovation (Project Nos. PID2019-105960RB-C21 and PID2019-105960RB-C22) and the Basque Government (Project No. IT1297-19). J.A.O.-C. acknowledges the Postdoctoral research grant (No. DOCREC20/49) provided by the University of the Basque Country. A.Q. also acknowledges University of the Basque Country for his Ph.D. grant (No. PIF-15/351). |
URI: | http://hdl.handle.net/10045/123747 |
ISSN: | 0888-5885 (Print) | 1520-5045 (Online) |
DOI: | 10.1021/acs.iecr.2c00164 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2022 The Authors. Published by American Chemical Society. Creative Commons Attribution 4.0 International License (CC BY 4.0) |
Revisión científica: | si |
Versión del editor: | https://doi.org/10.1021/acs.iecr.2c00164 |
Aparece en las colecciones: | INV - MCMA - Artículos de Revistas |
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