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 h or less through an induction period, a conversion maximum, and a period of deactivation; a steady activity of 41 and 47 μmol g h (isobutane formation) and ≈2.5 μmol g h (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 (npentane) 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.