Hydroisomerization of <i>n</i>-Pentane over Zn-Fe-S<sub>2</sub>O<sub>8</sub><sup style="margin-left:-6px;">-2</sup>/ZrO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> Superacid Catalyst: Activity, Surface Analysis and the Investigation of Deactivation and Regeneration

Abstract

The Zn and Fe modified S2O8-2/ZrO2-Al2O3 catalyst (Zn-Fe-SZA) was prepared and mechanisms of deactivation and methods for regeneration of as-prepared catalyst were explored with n-pentane isomerization as a probe reaction. The results indicated that the isopentane yield of the fresh Zn-Fe-SZA-F catalyst was about 57% at the beginning of the run, and declined gradually to 50% within 1500 min, then fell rapidly from 50% to 40% between 1500 and 2500 minutes. The deactivation of Zn-Fe-SZA catalyst may be caused by carbon formation on surface of the catalyst, sulfate group attenuation owing to reduction by hydrogen, removal of sulfur species and the loss of strong acid sites. It was found that the initial catalytic activity over Zn-Fe-SZA-T catalyst was 48%, which recovered by 84.3% as compared to that of fresh catalyst (57%). However, it showed a sharp decrease in isopentane yield from 48% to 29% within 1500 minutes, showing poor stability. This is associated to the loss of acidity caused by removal of sulfur species cannot be basically restored by thermal treatment. Resulfating the calcined catalyst could improve the acidity of catalyst significantly, especially strong acid sites, as compared with the calcined sample. The improved stability of the resulfated catalyst can be explained by: 1) eliminaton of carbon deposition to some extent by calcination process, 2) formation of improved acidic nature by re-sulfation, favoring isomerization on acidic sites, 3) restructuring of the acid and metal sites via the calcination-re-sulfation procedure.