Natural clay nanotube supported Mo and W catalysts for exhaustive oxidative desulfurization of model fuels

Abstract

Oxidative desulfurization is a promising way to produce, under mild conditions, clean ecological fuels with ultra-low sulfur content. Herein, we present for the first time heterogeneous catalysts based on natural aluminosilicate nanotubes (halloysite) loaded with transition metal oxides for oxidative sulfur removal using hydrogen peroxide as environmentally safe oxidant. The halloysite nanotubes (HNTs) provide acid sites for C–S bond scission, while the Mo and W oxides act as hydrogen peroxide activators. The structure and acidity of both the clay support and catalysts were investigated by low-temperature nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray fluorescence analysis, and transmission electron microscopy techniques. These clay-based catalysts revealed the high activity in the oxidation of various classes of sulfur-containing compounds (sulfides, heteroatomic sulfur compounds) under mild reaction conditions. The conversion of various substrates decreases in the following trend: MeSPh > Bn2S > DBT > 4-MeDBT > BT, which deals with substrate electron density and steric hindrance. The influence of the temperature, oxidant to sulfur molar ratio, and reaction time on catalytic behavior was evaluated for Mo- and W-containing systems with various metal content. The complete oxidation of the most intractable dibenzothiophene to the corresponding sulfone was achieved at 80 °C and H 2 O 2 :S = 6:1 (molar) for 2 h both for Mo- and W-containing systems. These transition metal oxides HNTs supported catalysts are stable for 10 cycles of dibenzothiophene oxidation, which makes them promising systems for clean fuel production.