Ultra-deep adsorptive desulfurization of a model diesel fuel on regenerable Ni-Cu/γ-Al₂O₃ at low temperatures in absence of hydrogen

Abstract

A model diesel fuel containing 250 ppmw sulfur (as dibenzothiophene) in n-hexadecane was desulfurized at low temperatures in absence of hydrogen, down to about zero ppmwS on a novel adsorbent of well dispersed 3-12 nm Nix-Cu10-x (x=Ni wt%) nanoparticles formed by impregnation on γ-Al2O3 and reduced in H2 at 275 or 450°C. The sorbents were characterized by XRD, TEM-EDX, FESEM-EDS, H2-TPR, TPO, BJH and BET surface area measurement techniques. Effects of various parameters comprising Cu content, reduction and desulfurization temperatures, inhibition by naphthalene, and regeneration of spent sorbents were investigated. As copper is added to nickel: (a) the sorbent reduction temperature shifts to dramatically lower values, (b) sulfur adsorption capacity of the sorbents at lower reduction and desulfurization temperatures is significantly improved, and when 14 wt% Ni5Cu5 sorbent is added to the fuel, the sulfur content reduces from 250 ppmwS to about zero in less than 1 min, (c) loss of adsorption capacity after the regeneration of the spent sorbent reduced at 275°C is significantly diminished, and (d) the selectivity of the sorbents to dibenzothiophene in the presence of naphthalene is improved. A higher reduction temperature tends to agglomerate nickel nanoparticles and reduce the sulfur adsorption capacity.

Keywords: Adsorptive desulfurization; Copper; Dibenzothiophene; Diesel fuel; Nickel.