Applied Catalysis A: General, Vol.526, 37-44, 2016
Isomerization of n-pentane over La-Ni-S2O82-/ZrO2-Al2O3 solid superacid catalysts: Deactivation and regeneration
A La-Ni-S2O82-/ZrO2-Al2O3 (La-Ni-SZA) catalyst was prepared and studied in the isomerization of n-pentane. The mechanisms of deactivation and methods for regeneration of the La-Ni-SZA catalyst were explored. The results revealed that the yield of isopentane using fresh La-Ni-SZA was maintained above 65% in the first 1000 min. However, the yield fell sharply from 65% to 25% during the subsequent 2000 min. The decline in pentane isomerization activity was slow initially, but increased significantly after 1000 min. The deactivation of the La-Ni-SZA catalyst may be due to a combination of carbon deposition, loss of Bronsted acidity, removal of sulfur entities. Based on this analysis, two regeneration methods were proposed. It was found that catalytic activity of the spent catalyst could be partially recovered (58%) by calcination. Resulfating the calcined catalyst with 0.5 mol L-1 (NH4)(2)S2O8 increased the acidity significantly, especially Brensted acidity, compared with fresh catalyst. The isopentane yield using the resulfated La-Ni-SZA was maintained at about 58%, with isopentane selectivity above 90%, during the tested 3000 min. Compared with fresh catalyst, the resulfated catalyst showed sustained excellent stability, although the initial activity was slightly lower. The improved stability of the resulfated catalyst can be explained by: (1) suppression of carbon deposition to some extent; (2) formation of improved acidic nature by resulfation, favoring isomerization on acidic sites; (3) restructuring of the acid and metal sites via the calcination-resulfation procedure. (C) 2016 Elsevier B.V. All rights reserved.