A range of catalysts including beta -zeolite, mordenite, ZSM-5, Y-zeolite,
mesoporous alumino silicate, and amorphous silica-alumina with varying Si:A
l ratios have been tested in the range 250-350 degreesC for the Beckmann re
arrangement of cyclohexanone oxime into caprolactam. All catalysts studied
exhibited some level of deactivation which was characterized by a loss in c
onversion of cyclohexanone oxime with time on stream. There were considerab
le differences in resistances to deactivation through coke formation. Thus,
mesoporous alumino silicate showed little decay in conversion with up to 1
6 wt % coke, whereas 6% coke on ZSM-5 caused a loss of 78% of the initial c
onversion. In general, the best catalysts were those which operated well in
the presence of coke. Selectivity to caprolactam was in the range of 30-75
% but did not change in a systematic fashion with time on stream. The numbe
r and strength of Bronsted and Lewis acid sites on each catalyst were deter
mined from FTIR analysis of pyridine adsorption. These data show that a low
ratio of strong/weak acid sites is important in achieving a high yield of
caprolactam. A low acid site strength combined with a high resistance to de
activation by coke formation are two necessary parameters for good catalyst
performance.