THE EFFECT OF PHOSPHORUS ON THE HDN REACTION OF PIPERIDINE, DECAHYDROQUINOLINE AND ORTHO-PROPYLANILINE OVER NI-MOS2/AL2O3 CATALYSTS

The hydrodenitrogenation (HDN) of piperidine, decahydroquinoline (DHQ) and ortho-propylaniline (OPA) has been studied over NiMo(P)/Al2O3 catalysts at 593 K and 3.0 MPa in order to understand the effect of phosphorus on the elementary HDN reaction steps. Phosphorus exhibited a negative effect on the HDN of piperidine and DHQ, both on the C-N bond cleavage reaction and on the subsequent hydrogenation reaction of alkene to alkane. A P/Al2O3 catalyst showed no HDN activity at all, neither with piperidine, nor with DHQ. A positive effect of phosphorus was observed in the HDN of OPA, where hydrogenation of the aromatic ring is needed and is rate limiting. It is suggested that introduction of phosphorus to NiMo/Al2O3 catalysts on the one hand decreases the available support surface area, and as a consequence the dispersion of the Ni-Mo-S phase and thus the capacity for C-N bond breaking and olefin hydrogenation. On the other hand, phosphorus induces either new or more active sites for the hydrogenation of aromatics.