Comparative study of Ni, Co, Cu supported on γ-alumina catalysts for hydrogen production via the glycerol steam reforming reaction

• Published in: Fuel processing technology 2016-11, Vol.152, p.156-175
• Main Authors: Papageridis, Kiriakos N., Siakavelas, Giorgos, Charisiou, Nikolaos D., Avraam, Dimitrios G., Tzounis, Lazaros, Kousi, Kaliopi, Goula, Maria A.
• Format: Article
• Language: English
• Subjects: Alumina; Cobalt; Copper; Glycerol steam reforming; Hydrogen production; Nickel
• ISSN: 0378-3820; 1873-7188
• DOI: 10.1016/j.fuproc.2016.06.024

Catalysts with active phase Ni, Co or Cu supported on γ-alumina were synthesized at constant loading (8wt.%) and tested for the glycerol steam reforming reaction (GSR). The synthesized samples, at their calcined and/or their reduced form, were characterized by BET, ICP, XRD, DRS, NH3-TPD, CO2-TPD, TPR and SEM. The carbon deposited on their surface under reaction conditions was characterized by TEM, TPO, TGA and Raman. Catalytic performance for the glycerol steam reforming reaction was studied in order to investigate the effects of reaction temperature on: (i) glycerol total conversion, (ii) glycerol conversion to gaseous products, (iii) hydrogen selectivity and yield, (iv) selectivity of carbonaceous gaseous products, (v) selectivity of liquid products and (vi) molar ratios of H2/CO and CO/CO2 in the gaseous products' mixture. The stability of all catalysts was also investigated through time on stream experiments. It was concluded that catalytic performance, including liquid products' distribution, depends on the acid-base properties of the materials. Specifically, a drastic drop in the activity of the Ni/Al catalyst was observed, while Co/Al and Cu/Al catalysts deactivate in a slower rate, confirming that coke deposition, associated with dehydration, cracking and polymerization reactions, takes place on the catalyst's surface strong acid sites. Reaction pathway for the glycerol steam reforming reaction. [Display omitted] •Catalysts Ni, Co, and Cu (8wt.%) on γ-alumina tested for the glycerol steam reforming reaction•The presence of aluminate structures in calcined samples were confirmed by XRD, DRS and TPR•Liquid products distribution defined by the catalyst's acid-base properties•Coke deposition that resulted in deactivation takes place on the surface strong acid sites.•Valorization of biodiesel by-product for the production of renewable hydrogen.