M. Trombetta et al., FT-IR STUDIES ON LIGHT OLEFIN SKELETAL ISOMERIZATION CATALYSIS .2. THE INTERACTION OF C4 OLEFINS AND ALCOHOLS WITH HZSM5 ZEOLITE, Journal of catalysis, 168(2), 1997, pp. 349-363
The catalytic activity of the zeolite HZSM5 in n-butene conversion was
investigated under conditions similar to those of a commercial proces
s for skeletal isomerization. The catalyst was found to be very active
in n-butene conversion, but selectivity to isobutene was low due to a
predominance of cracking, coking, and oligomerization side reactions.
The interaction of 1-butene, cis-2-butene, trans-2-butene, isobutene,
sec-butanol, and tert-butanol was also investigated by FT-IR spectros
copy in the temperature range 150-673 K. n-Butenes were first adsorbed
on the acidic OHs of the zeolite giving rise to well-defined hydrogen
-bonded species. These species probably undergo protonation to the cor
responding carbenium ion, which could, however, not be detected, and l
ater, through skeletal isomerization/alkylation/skeletal isomerization
sequences, to polyisobutene. In the case of isobutene, a tert-butoxy
species supposed to act as the precursor for tert-butyl carbenium ions
, active as the cationic polymerization initiator, was detected and ch
aracterized spectroscopically. Starting from isobutene, the polymeriza
tion is partly hindered at low temperature because of the limited diff
usion of the olefin into the zeolite pores. The alcohols dehydrate aro
und room temperature and also give rise to polyisobutene in the same w
ay. (C) 1997 Academic Press.