Highly active P-doped sulfided NiMo/alumina HDS catalysts from Mo-blue by using saccharose as reducing agents precursor

[Display omitted] •Modification of Al2O3-supported NiMo by saccharose (SA) at various contents.•Hydrolyzed SA (monosaccharides)-Mo species charge transfer complexes formation.•Highly active NiMoS Type II sites on modified formulation (SA/Ni = 1 mol ratio).•Detrimental effect of SA when at high concentration (SA/Ni = 3 mol ratio).•SA indirectly reducing Mo, forming complexing byproducts and carbonaceous remains. Saccharose (SA) was used as organic additive in simultaneously impregnated P-doped NiMo/Al2O3 hydrodesulfurization (HDS) catalysts (Mo, Ni and P at 12, 3, and 1.6 wt%, respectively). One-pot impregnating solutions were prepared by MoO3 digestion (∼353 K) in diluted aqueous H3PO4, followed by 2NiCO3·3Ni(OH)2·4H2O addition. Saccharose (SA, SA/Ni = 0.5, 1–3) was dissolved in originally emerald-green impregnating solutions which changed to cobalt blue by room-temperature aging (2–4 days, depending on SA concentration) due to Mo-blue formation by partial molybdenum species reduction. After sulfiding of samples impregnated with SA shorter MoS2 slabs of enhanced stacking were observed (by HR-TEM). Ni and Mo dispersion and nickel sulfidability (as determined by XPS) increased with the amount of organic modifier. Enhanced hydrodesulfurization activity in dibenzothiophene HDS was registered for catalyst obtained from Mo-blue precursor as to that of corresponding materials obtained from conventional emerald-green NiMoP impregnating solutions (with or without SA). However, in solids at high saccharose content (SA/Ni = 3) enhanced “NiMoS” phase amount was not reflected in improved activity. Probably, excessive amount of carbonaceous deposits from SA residua decomposition during catalyst activation provoked partially plugged porous network (as determined by N2 physisorption) in sulfided formulations. That fact seemed to limit accessibility of reactant molecules to surface active sites. Mo-blue precursor obtained through monosaccharides partial reduction seemed to play decisive role in obtaining HDS catalysts of improved properties. Saccharose results a highly soluble, cheap and non-toxic environmentally-friendly additive to produce catalysts of enhanced HDS activity.