Vapor phase Beckmann rearrangement using high silica zeolite catalyst

Vapor phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam has been studied using high silica zeolite catalysts. Catalysts with different crystal sizes and gel-ageing times have been activated by ionic exchange in different conditions by means of a highly basic solution and a nearly neutral solution both containing ammonium salts. Samples have been calcined at different temperatures in order modify the number of defective sites. We observed that samples exchanged by means of a highly basic solution (pH > 10)1,2 and calcined at a relatively lower temperature (450 C) show the most interesting catalytic results. X-ray powder diffraction patterns of these samples show2 retention of the unit cell symmetry (orthorhombic cell) if compared to the dried sample. NH3-TPD confirms the low acidity of high silica zeolites, however a higher amount of desorbed ammonia is observed for the samples exchanged at higher pH and calcined at 450 C. Due to silanol nests the IR spectra of the same samples show the formation of Si\u2013NH2 bonds which are absent in the same material exchanged by other methods. Such sites seem to promote the high stability of the high silica zeolite catalysts also to the regeneration which is needed to remove the heavy carbonaceous compounds from the catalyst surface

The control of catalytic performance of rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

This paper describes the effect of the composition of rutile-type Sn/V/Nb/Sb mixed oxides catalysts on the catalytic performance in the gas-phase ammoxidation of propane to acrylonitrile. The variation in the atomic ratio between components in catalysts is the key for the control of activity and selectivity. In samples with atomic composition Sn/V/Nb/Sb 1/0.2/1/x (0 x 5) and 1/0.2/y/3 (0 y 3) several compounds formed, i.e., SnO2, Sb/Nbmixed oxide, Sb6O13 and non-stoichiometric rutile-type V/Nb/Sb/O; the latter segregated preferentially at the surface of the catalyst. Tin oxide provided the rutile matrix for the dispersion of the mixed oxides. The main role of Sb was shown to generate mixed oxides containing specific sites for the allylic ammoxidation of propylene intermediately formed. The presence of Nb enhanced the activity and selectivity of these sites