Enhancing the CO2 methanation activity of γ-Al2O3 supported mono- and bi-metallic catalysts prepared by glycerol assisted impregnation

• Published in: Applied catalysis. B, Environmental Vol. 296; p. 120322
• Main Authors: Quindimil, Adrián, Bacariza, M. Carmen, González-Marcos, José A., Henriques, Carlos, González-Velasco, Juan R.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 05-11-2021; Elsevier BV
• Subjects: Aluminum oxide; Ammonia; Bimetals; Carbon dioxide; Carbonyl compounds; Carbonyls; Catalysts; CO2 methanation; Fixed bed reactors; Fixed beds; Formates; Glycerol; Glycerol assisted impregnation; Impregnation; Intermediates; Low temperature; Metal particles; Metal surfaces; Methanation; Ni-Ru bimetallic catalyst; Nickel; Operando FTIR; Reaction mechanism; Transitional aluminas; Reaction mechanism; Operando FTIR; CO2 methanation; Glycerol assisted impregnation; Ni-Ru bimetallic catalyst
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2021.120322

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•γ-Al2O3 supported Ni and Ru catalysts are applied in CO2 methanation.•Glycerol-assisted impregnation increases the number of available active sites.•Ni-Ru catalysts with Ru < 1.5 wt% achieves enhanced catalytic performance.•Ru promotes CO adsorption and boosts Ni capacity to adsorb H atoms.•Reaction mechanism with formates and carbonyls as intermediates is identified.
Conventional Ni/Al2O3 catalyst, currently used for COx removal in ammonia production, admits room for improvement as catalysts for application in low temperature CO2 methanation, which is the aim of this work. The Incipient Wetness Impregnation (IWI) has been replaced by Glycerol Assisted Impregnation (GAI) method and, afterwards, a secondary metal (Ru) has been co-impregnated forming a bimetallic system. The monometallic as well as bimetallic systems have been characterized by several techniques (TGA, XRD, N2-physisorption, TEM, H2-TPR, H2-TPD, STEM-EDX and operando FTIR) and tested for CO2 methanation reaction in a downflow fixed bed reactor (conditions: P =1 bar, H2: CO2 ratio = 4 and WHSV = 30,000 mL h−1 g−1). GAI method together with a reducing calcination atmosphere (20 %H2/N2) results effective to avoid the formation of large metal particles during the synthesis, especially for Ru/Al2O3 formulation. In fact, the Ru dispersion of the catalyst prepared by GAI (RuAlGAI) is around 5 times higher than that of RuAlIWI catalyst. On the other hand, NiAlGAI presents larger population of reduced particles but bigger in size than NiAlIWI catalyst, which finally provides the former with slightly higher metal surface and superior catalytic performance. By co-impregnating small amounts of Ru (0.5, 1.0 or 1.5 wt%) the Ni surface is considerably increased which, together with Ru synergistic collaboration, results in a methane yield rise from 20 to 44 % at 300 °C. The operando FTIR results show no differences in the reaction pathway with GAI preparation method and incorporation of Ru, but different evolution of reaction intermediates concentration with temperature. The bimetallic Ni-RuAl system presents much higher capacity to adsorb CO and hydrogenate the reaction intermediates (adsorbed formates and carbonyls) by dissociated H2 than its monometallic counterparts.