Sulfur poisoning of platinum/BaK-LTL catalyst: a catalytic and structural study using hydrogen chemisorption and x-ray absorption spectroscopy

The sulfur poisoning of a Pt/BaK-LTL catalyst has been studied with X-ray absorption spectroscopy and hydrogen chemisorption. The fresh catalyst contained highly dispersed platinum inside the zeolite pores. EXAFS analysis determined a Pt-Pt coordination number of 3.7, suggesting an average platinum cluster size of 5 or 6 atoms, consistent with the TEM and chemisorption data (H/Pt = 1.4). The catalyst was poisoned with H2S until the dehydrocyclization activity of n-hexane decreased to 30% of fresh activity. The first-shell Pt---Pt coordination number increased to 5.5, indicating a growth of the average platinum cluster size to 13 atoms. Hydrogen chemisorption measurements of the poisoned catalyst show a decrease in the H/Pt value to 1.0. The EXAFS data also provide evidence for the presence of sulfur adsorbed on the surface of the platinum particles with a Pt---S bond distance of 2.27 Å. The high sensitivity of the Pt/LTL catalyst to poisoning by very low levels of sulfur is attributed to the loss of active platinum surface by adsorption of sulfur and the growth of the platinum clusters. Much of the available platinum surface was found to be capable of chemisorbing hydrogen, but with no activity for dehydrocyclization. Growth of the platinum particle was sufficient to block the pore. In the sulfur-poisoned catalyst, only the sulfur-free platinum atoms exposed through the pore windows remain active. The evidence suggests the location of the sulfur was at or near the metal-zeolite interface. Since both high activity and selectivity require extremely small platinum particles, regeneration of sulfur-poisoned catalysts will require removal of the adsorpted sulfur and restoration of the original particle size.