Below about 300◦C the Ni2P catalysts were active in the direct hydrogenolysis of the C N bond of PA, however, the main reaction was the PA dispro-portionation to dipropylamine (DPA) and ammonia. Above about 300◦C the hydrogenolysis of the DPAC N bond became the main reaction. Near to full HDN of PA could be attained without hydrogenolysisof C C bond. In contrast, Ni/silica gel catalyst was hardly active in the direct C–N hydrogenolysis of PAbut was active in the PA disproportionation to DPA. Above about 300◦C reaction temperature ammonia,less propane, and significant amount of methane and ethane were formed.