Currently, the widely used of liquid fuel hydrodesulfurization catalysts in industry are mostly supported tungsten sulfide (or molybdenum) based catalysts which adds nickel, cobalt and other aid. Such catalysts usually take ammonium tungstate or ammonium molybdate as raw material, and obtained after impregnation, pyrolysis. The particle size, degree of dispersion of the active ingredient in tungsten oxide containing desulfurization catalyst cannot achieve the desired state. In this situation, developing a higher activity catalyst with highly dispersion and nanoscale has become the main research issue of the scientists.

 

In this paper, we introduce a catalyst loading with sulfur-containing transition metal-- molybdenum or tungsten atom clusters, the steps are as follows:

1. Dissolve the tungsten oxide or molybdenum trioxide in the concentrated hydrochloric acid, and carried out electrolysis to generate the hydrochloric acid solution;

2. Inlet the hydrogen sulfide into the hydrochloric acid solution to carry out vulcanization;

3. Take out oxidation under the condition of oxygen or air at 60~120℃ for 24~56 hours;

4. The oxidized solution is distilled under reduced pressure to obtain a reaction concentrated mixture was filtered, and separate by resin column, to give the following cluster core: sulfur-containing transition metal atom clusters of [M₂O_nS_2-n]m+,[M₃O_nS₄-n]m+ or [M₄OnS_6-n]m+, where M = Mo or W, n = 0 ~ 6, m = 0 ~ 6;

5. Load or graft the sulfur-containing metal atom cluster onto the carrier by dipping or ion-exchange method under the inert atmosphere of sulfur-containing transition metal atom clusters under an inert atmosphere to give the supported type sulfur-containing transition metal atom clusters of tungsten trioxide (or molybdenum trioxide) hydrodesulfurization catalyst.

 

The tungsten trioxide hydrodesulfurization catalyst obtained in method not only has higher hydrodesulfurization activity with its high dispersion and nanoparticle; but also, the catalyst of sulfur-containing metal atom cluster has the better sulfur anti-poisoning performance.