Trade-off between NOx storage capacity and sulfur tolerance on Al2O3/ZrO2/TiO2–based DeNOx catalysts

Abstract

Al2O3/ZrO2/TiO2 (AZT) ternary mixed oxides functionalized with Pt and BaO were synthesized in powder and monolithic forms and were utilized in NOx Storage Reduction/Lean NOx Trap (NSR/LNT) catalysis as novel catalytic materials. Adsorption of NOx and SOx species and their interactions with the catalyst surfaces were systematically investigated via in-situ FTIR technique revealing different NOx coordination geometries governed by the presence and the loading of BaO in the powder catalyst formulation. While BaO-free Pt/AZT stored NOx as surface nitrates, BaO incorporation also led to the formation of bulk-like ionic nitrate species. NOx adsorption results obtained from the current Temperature Programmed Desorption (TPD) data indicated that NOx Storage Capacity (NSC) was enhanced due to BaO incorporation into the powder catalyst and NSC was found to increase in the following order: Pt/AZT < Pt/8BaO/AZT < Pt/20BaO/Al2O3 < Pt/20BaO/AZT. Increase in the NSC with increasing BaO loading was found to be at the expense of the formation of bulk-like sulfates after SOx exposures. These bulk-like sulfates were observed to require higher temperatures for complete regeneration with H2(g). Catalytic activity results at 473 K and 573 K obtained via flow reactor tests with monolithic catalysts suggested that Pt/AZT and Pt/8BaO/AZT catalysts with stronger surface acidity also revealed higher resistance against sulfur poisoning and superior SOx regeneration in spite of their relatively lower NSC. Monolithic Pt/20BaO/AZT catalyst revealed superior NSC with respect to the conventional Pt/20BaO/Al2O3 benchmark catalyst at 573 K after sulfur regeneration. On the other hand, this trend was reversed at high-temperatures (i.e. 673 K). Preliminary results were presented demonstrating the enhancement of the high-temperature NSC of AZT-based materials by exploiting multiple NOx-storage components where BaO functioned as the low/mid-temperature NOx-storage domain and K2O served as the high-temperature NOx storage domain. Enhancement in the high-temperature NOx-storage in the BaO-K2O multiple storage domain systems was attributed to the formation of additional thermally stable bulk-like nitrates upon K2O incorporation.