Omer Refa Koseoglu

The reactivity of thiophene, dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), which are the representatives of the main classes of sulfur compounds that are the constituents of diesel fractions, was studied in the course of their oxidative desulfurization with oxygen on a CuO/ZnO/Al₂O₃ catalyst modified with boron and molybdenum additives. At T ≥ 375°C, the reactivity increased in the order thiophene < DBT < 4,6-DMDBT. The degree of sulfur removal in the form of SO₂ from hydrocarbon fuel, which was simulated by a solution of 4,6-DMDBT in toluene, was 80%. Under the assumption of a first order reaction with respect to sulfur compound and oxygen, the apparent activation energies of the test processes were calculated. An attempt was made to reveal the role of the adsorption of sulfur compounds in the overall process of oxidative desulfurization with the use of X-ray diffraction analysis, X-ray photoelectron spectroscopy, and differential thermal and thermogravimetric analysis with the massspectrometric monitoring of gas phase composition.

The possibility of oxidative desulfurization of dibenzothiophene dissolved in toluene as a model organosulfur compound of diesel fuel in the presence of catalytic CuZnAl compositions was studied. It was shown that the CuZnAl catalysts at 350–450°C ensure sulfur removal from the model fuel to the extent of up to 40–45%. Part of the sulfur is removed as SO₂, and some sulfur is absorbed on the catalyst surface.

An effective gas-phase oxidative desulfurization (ODS) process was proposed. The process was studied in a laboratory reactor with a proprietary catalyst at 300-400 ºС and ambient pressure with model fuels represented by thiophene, dibenzothiophene(DBT) and 4,6-dimethyldibenzothiophene (DMDBT) dissolved in octane, isooctane or toluene. The reactivity of different sulfur containing molecules in ODS was shown to increase in the sequence: thiophene<DBT<DMDBT. The main sulfur containing product of oxidation of these compounds was SO2. During the gas-phase ODS both processes of sulfur species oxidation and processes of their adsorption were observed and studied. Based on the conducted studies, different ODS process designs comprising its integration with adsorption and regeneration processes and with conventional hydrodesulfurization (HDS) process were proposed. One scheme is based on alternating regimes of ODS and catalyst regeneration in two reactors: sulfur is removed from organic feedstock by oxidation and adsorption in one reactor while simultaneous regeneration of the catalyst that has accumulated sulfur compounds takes place in another reactor. Two other schemes are based on joint use of ODS and HDS. The conventional HDS process is most effective for removal of low-boiling sulfur containing compounds reactive with respect to hydrogen, while removal of refractory sulfur compounds, such as DMDBT is more easily achieved by gas phase ODS. Thus the combination of these processes is expected to be most efficient for deep desulfurization of diesel fuel.