Ion-exchanged pillared clays for selective catalytic reduction of NO by ethylene in the presence of oxygen

Abstract

Ion-exchanged pillared clays (PILCs) were studied as catalysts for selective catalytic reduction (SCR) of NO by ethylene. Three most important pillared clays, Al 2O 3-PILC (or Al-PILC), ZrO 2-PILC (or Zr-PILC) and TiO 2-PILC (or Ti-PILC), were synthesized. Cation exchanges were performed to prepare the following catalysts: Cu–Ti-PILC, Cu–Al-PILC, Cu–Zr-PILC, Cu–Al–Laponite, Fe–Ti-PILC, Ce–Ti-PILC, Ce–Ti-PILC, Co–Ti-PILC, Ag–Ti-PILC and Ga–Ti-PILC. Cu–Ti-PILC showed the highest activities at temperatures below 370°C, while Cu–Al-PILC was most active at above 370°C, and both catalysts were substantially more active than Cu-ZSM-5. No detectable N 2O was formed by all of these catalysts. H 2O and SO 2 only slightly deactivated the SCR activity of Cu–Ti-PILC, whereas severe deactivation was observed for Cu-ZSM-5. The catalytic activity of Cu–Ti-PILC was found to depend on the method and amount of copper loading. The catalytic activity increased with copper content until it reached 245% ion-exchange. The doping of 0.5 wt% Ce 2O 3 on Cu–Ti-PILC increased the activities from 10% to 30% while 1.0 wt% of Ce 2O 3 decreased the activity of Cu–Ti-PILC due to pore plugging. Cu–Ti-PILC was found to be an excellent catalyst for NO SCR by NH 3, but inactive when CH 4 was used as the reducing agent. Subjecting the Cu–Ti-PILC catalyst to 5% H 20 and 50 ppm SO 2 at 700°C for 2 h only slightly decreased its activity. TPR results showed that the overexchanged (245%) PILC sample contained Cu 2+, Cu + and CuO. The TPR temperatures for the Cu–Ti-PILC were substantially lower than that for Cu-ZSM-5, indicating easier redox on the PILC catalyst and hence higher SCR activity.