Deactivation study of the Pt and/or Ni-based γ-Al2O3 catalysts used in the aqueous phase reforming of glycerol for H2 production

• Deactivation of Pt/Ni-based γ-Al2O3 catalysts in APR of glycerol was investigated.
• Properties of sol–gel catalysts were more altered by γ-Al2O3 conversion into γ-AlOOH.
• Agglomeration of Ni particles was more pronounced on the IWI catalysts.
• Superficial layer of oxidized Ni covering the sintered Ni particles was suggested.
• Leaching of Pt/Ni or coke deposition has not a significant effect on the catalysts.

A detailed and in-depth study of the deactivation of Pt and/or Ni-based γ-Al2O3 catalysts prepared by impregnation and acid and basic sol–gel methods, previously tested in glycerol aqueous phase reforming (APR) for H2 production, has been made. The aim has been to get a further and advanced understanding of the factors behind this deactivation. Accordingly, all the used catalysts were systematically characterized by appropriate techniques, such as ICP-AES, XRD, XPS and TG/DGT-O2. Some used samples were also examined by BET, TPD-NH3, TPR-H2 and TEM. The characterization results corroborate the following: (i) a significant part of γ-Al2O3 in sol–gel catalysts was structurally transformed into γ-AlOOH, changing their textural properties, such as surface area and porosity, surface acidity and metal dispersion, and (ii) the Ni metallic particles in the impregnated catalysts underwent major agglomeration, while the Ni particles in the sol–gel counterparts were more affected by re-oxidation phenomena. Data obtained by ICP-AES and thermal analysis indicate, respectively, that Pt and Ni phase leaching and the formation of highly graphitized coke were negligible. However, some adsorption of carbonaceous molecular species has been detected on some catalysts. All these observations clearly confirm that the metallic and acid active sites of Pt and/or Ni–based γ-Al2O3 catalysts experimented quantitative and qualitative modifications during the glycerol APR process that compromised their catalytic performances.

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