Isomerization of n-butane and of n-pentane in the presence of sulfated zirconia:: formation of surface deposits investigated by in situ UV-vis diffuse reflectance spectroscopy

Catalytic performance and formation of carbonaceous deposits were studied simultaneously during alkane isomerization over sulfated zirconia in a fixed-bed flow reactor with an optical window for in situ UV-vis diffuse reflectance spectroscopy. The reactions of n-butane (5 kPa) at 358 and 378 K and of n-pentane (0.25 kPa) at 298 and 308 K passed within 5 It or less through an induction period, a conversion maximum, and a period of deactivation; a steady activity of 41 and 47 mumol g(-1) h(-1) (isobutane formation) and approximate to 2.5 mumol g(-1) h(-1) (isopentane, both temperatures) remained. UV-vis spectra indicate the formation of unsaturated surface deposits; the band positions at 310 nm (n-butane reaction) and 330 nm (n-pentane) are within the range of monoenic allylic cations. More highly conjugated allylic cations (bands at 370 and 430 nm) became evident during n-butane reaction at 523 K. The chronology of events suggests that the surface deposits are (i) a result only of the bimolecular and not the monomolecular reaction mechanism, and (ii) are formed in a competitive reaction to the alkane products. (C) 2003 Elsevier Inc. All rights reserved.