Deep aerobic desulfurization of fuels over iron–сontaining zeolite based catalysts

Abstract

Herein, we present a new approach to the design of the catalysts for aerobic oxidation of sulfur-containing compounds. Iron-containing zeolite-based (ZSM-5, ZSM-12) catalysts were synthesized and successfully tested in oxidation of model mixtures as well as real petroleum fractions. The catalysts were characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), ultraviolet–visible spectroscopy (UV/Vis), temperature programmed desorption of ammonia (NH3-TPD), and low-temperature nitrogen adsorption-desorption. Among these catalysts Fe-ZSM-12 demonstrated the best activity: exhaustive oxidation of dibenzothiophene (DBT) in the presence of this catalyst was achieved in 2 h at 150°C. Influence of the reaction conditions (temperature, amount of catalyst, and time) on the conversion of the model substrate was studied. It was shown that in the presence of Fe-ZSM-12 catalyst activation of molecular oxygen proceeds via formation of superoxide radical. Fe-ZSM-12 exhibited an excellent stability and retained its activity after 10 cycles of oxidation. Under optimal reaction conditions sulfur content in straight-run gasoline fraction was reduced from 807 to 43 ppm, in diesel fraction – from 1898 to 150 ppm. Two-dimensional GC-MS analysis of diesel fraction before and after desulfurization indicates high selectivity of the process. Possibility of sulfur dioxide formation during the aerobic oxidative desulfurization process was studied for the first time. The use of zeolite-based catalysts containing transition metals for aerobic oxidation of sulfur-containing compounds is a promising approach for clean fuel production.