Butene skeletal isomerization over H-ferrierite: a TEOM and in situ IR study on the role of carbonaceous deposits and the location of Brønsted acid sites Original Research Article

Butene skeletal isomerization over H-ferrierite (H-FER) is monitored in a catalysis set-up including a tapered element oscillating microbalance (TEOM) and using in situ infrared (IR) spectroscopy. For the first time the location and number of vacant Brønsted acid groups sited in the 10, 8, 6, and 5 membered rings (MRs) of the H-ferrierite framework are established as a function of time-on-stream (TOS). By deconvolution of the acid site-band, it is determined that with proceeding reaction the 8 MR channels are blocked and the available micropore volume and Brønsted acidity on the aged H-ferrierite will be primarily located inside the 10 MR channels. When a maximum amount of hydrocarbons is deposited on the catalyst, vacant Brønsted acid sites are still present. Additionally, IR spectroscopy shows that with TOS carbonaceous deposits are slowly converted from hydrogen-rich alkyl-aromatics into hydrogen-poor cyclopenta-fused-alkyl-aromatics, reducing by-product formation and therefore enhancing isobutene selectivity.