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Effect of support and chelating ligand on the synthesis of Ni catalysts with high activity and stability for CO2 methanation

: Shanmugam, Vetrivel; Neuberg, Stefan; Zapf, Ralf; Pennemann, Helmut; Kolb, Gunther

Volltext ()

Catalysts 10 (2020), Nr.5, Art. 493, 16 S.
ISSN: 2073-4344
Zeitschriftenaufsatz, Elektronische Publikation
Fraunhofer IMM ()
Ceria; chelating ligands; Nickel; methanation; Methane; Microreactors

Carbon dioxide methanation was carried out over Ni-based catalysts on different supports and chelating ligands in microreactors. To investigate the influence of chelating ligands and supports, the Ni catalysts were prepared using different support such as CeO2, Al2O3, SiO2, and SBA-15 by a citric acid (CA)-assisted impregnation method. The properties of the developed catalysts were studied by X-ray diffraction (XRD), Transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS) measurement, and the results show that the addition of CA in the impregnation solution improved the dispersion, refines the particle size, and enhanced the interaction of nickel species. The catalytic performance of the developed Ni catalysts were evaluated by CO2 methanation in microreactors in the temperature range of 275 °C–375 °C under 12.5 bar pressure. All the catalysts exhibit high CO2 conversion and extremely high selectivity to methane. However, the catalysts prepared via CA-assisted method exhibited excellent activity and stability, compared with Ni catalysts prepared by a conventional impregnation method, which could be attributed to highly dispersed nickel particles with strong metal–support interaction. The activity of CO2 methanation followed the order of Ni/CeO2-CA > Ni/SBA-15-CA > Ni/Al2O3-CA > Ni/SiO2-CA > Ni/CeO2. The Ni/CeO2 catalysts have also been prepared using different chelating ligands such as ethylene glycol (EG), sucrose (S), oxalic acid (OA) and ethylene diamine tetra acidic acid (EDTA). Among the tested catalysts prepared with different support and chelating ligands, the Ni/CeO2 catalyst prepared via CA-assisted method gave superior catalytic performance and it could attain 98.6% of CO2 conversion and 99.7% methane selectivity at 325 °C. The partial reduction of the CeO2 support generates more surface oxygen vacancies and results in a high CO2 conversion and methane selectivity compared with other catalysts. The addition of CA as promoter favored the synergistic effect of Ni and support, which led to high dispersion, controls the size, and stabilizes the Ni nanoparticles. Furthermore, the Ni/CeO2-CA catalyst yields high CO2 conversion in a time-on-stream study due to the ability of preventing the carbon deposition and sintering of Ni particles under the applied reaction conditions. However, the Ni/Al2O3-CA and Ni/SBA-15-CA catalysts showed stable performance for 100 h of time on stream.