SURFACE-CHEMISTRY OF V-SB-OXIDE IN RELATION TO THE MECHANISM OF ACRYLONITRILE SYNTHESIS FROM PROPANE .1. CHEMISORPTION AND TRANSFORMATION OF POSSIBLE INTERMEDIATES
G. Centi et al., SURFACE-CHEMISTRY OF V-SB-OXIDE IN RELATION TO THE MECHANISM OF ACRYLONITRILE SYNTHESIS FROM PROPANE .1. CHEMISORPTION AND TRANSFORMATION OF POSSIBLE INTERMEDIATES, Journal of the Chemical Society. Faraday transactions, 92(24), 1996, pp. 5141-5149
Citations number
34
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
The mechanism of propane ammoxidation to acrylonitrile on V-Sb-oxide i
s analysed by IR spectroscopy in three papers dealing with the study o
f (i) the reaction network in propane conversion, (ii) the relationshi
p between ammonia chemisorbed species and catalytic behaviour and (iii
) the effect of ammonia chemisorption on the surface reactivity. This
first part deals with the study of the nature of surface adspecies for
med by chemisorption of acetone, isopropyl alcohol, acrylic acid, ally
l alcohol, propene, propionic acid, acetic acid, propane and acrylonit
rile on a vanadium antimonate catalyst (V/Sb=1.0) and subsequent therm
al treatment. The results indicate that the catalyst is characterized
by multifunctional properties (II-abstraction O-insertion and oxidativ
e cleavage properties), the relevance of which for the mechanism and c
atalytic behaviour in acrylonitrile synthesis from propane is discusse
d. A surface reaction network in propane oxidation is also proposed in
volving multiple possible pathways of transformation. The main route o
f propane conversion is through the formation of propene as an interme
diate, although a side reaction of acrylate formation via a propionate
intermediate is possible. Propene may be oxidized according to two ro
utes, the first leading to acetone which undergoes quick oxidative cle
avage to an acetate species and a C-1 fragment, and the second to the
formation of an allyl alcoholate adspecies which transforms to acrolei
n which quickly further converts to an acrylate species. The acrylate
species strongly interacts with the surface and is thermally stable up
to relatively high temperatures.