Synthesis, Characterization, and Application of Amorphous Silica-Aluminas Support for Fischer-Tropsch Wax Hydrocracking Catalysts.

Abstract

High-performance amorphous silica-aluminas (ASAs) were prepared prior to the formation of the 10-membered ring (10-MR) ZSM-5 zeolite by regulating the hydrothermal processing time. Their structures, morphologies, acidity properties, and Si-Al coordination were well studied. Particularly, a facile FTIR method of in-situ adsorbing bulky 2,6-dimethlypyridine followed by pyridine adsorption was innovatively utilized to quantify the Brønsted acid sites in micropores. All the ASAs samples were transformed into catalysts by loading with 0.5 wt % Pt. The structure-activity relationship, especially from the strength, density, and location of Brønsted acid sites, was investigated by Fischer-Tropsch synthesis (FTS) wax hydrocracking. The evaluation results showed that the medium strong Brønsted acid sites located on the external surface played a crucial role in the activity. Contrary to the general belief that larger pores favor the production of heavy cracking fractions, the ASAs with a 10-MR microporous structure proved to be more effective for diesel production than those with a 12-membered ring (12-MR). Strong Brønsted acid sites in micropores were less conducive to diesel production mainly due to stronger adsorption at these sites and steric hindrance from the microporous system. Furthermore, the Pt/AS-20 catalyst with few intramicropore Brønsted acid sites exhibited high diesel selectivity (83.3%) at 50.5% conversion under industrially relevant reaction conditions, which provides a significant opportunity to develop FTS wax hydrocracking catalysts more rationally.