The conversion of the biomass-derived lipid, lignocellulosic and carbohydrate resources into renewable platform intermediates, chemicals and biofuels has been lately increasing in interest. The mechanistic reaction pathways, like hydro-deoxygenation, decarboxylation and hydrocracking, of the selected palmitic acid, as a model fatty acid, over Ni/ZSM-5 zeolite catalysts were studied. The ZSM-5 material with different Al/Si molar ratios was synthesized via a green template-free hydrothermal synthesis procedure, treated and subsequent functionalised with various Ni metal loadings. However, Ni/Al molar ratio was kept stoichiometric (Ni/Al = 0.5). The characteristic physicochemical properties of composite catalysts were studied by numerous characterization techniques, such as X-ray powder diffraction (XRD), scanning-, as well as high-resolution transmission electron microscopy (SEM/HRTEM), and X-ray photoelectron spectroscopy (XPS). NiO with an average particle size of 10–20 nm was found on ZSM-5 support. The relative Ni/Al atom fraction in Ni/ZSM-5 systems influenced their Lewis/Brønsted acidic sites, as well as the external exposed area of prepared heterogeneous structures. Furthermore, the mentioned morphological parameters affected predominant catalytic routes. Species’ production mechanism, as a consequence of Lewis/Brønsted centre weak/strong acidity, as well as their integral concentration, was proposed, mirroring the observed process kinetics, selectivity and turnover. It was demonstrated that the main obtained products were esters, aldehydes, alcohols, hydrocarbons and gases (CO2, CO…), produced by deoxygenation (e.g. decarbonylation), hydrogenation and cracking, less, though, through isomerisation.
Bifunctional Ni/ZSM-5 catalyst Stoichiometric Ni/Al molar ratio Palmitic acid model compound Waste edible oil Reaction pathway mechanism Cracking with deoxygenation
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The authors gratefully acknowledge the financial support of the Slovenian Research Agency (ARRS) (Programs P1-0021, P2-0152, P2-0393), EU COST Action TD1203 and EU COST Action FP1306. Dr. Matjaž Mazaj and Mojca Opresnik from National Institute of Chemistry performed preliminary TEM characterization and nitrogen physisorption measurements, respectively. XPS and acidity characterization were performed at University of Cordoba in Spain. Catalytic tests were performed by James J Leachy at University of Limerick in Ireland.
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Conflict of interest
The authors declare no conflict of interest.
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