Selective Hydrogenation of Nitriles to Primary Amines on Metal-supported Catalysts

SEGOBIA DARIO; TRASARTI ANDRES; APESTEGUIA CARLOS

Louisville, Kentucky

Congreso; 23rd North American Catalysis Society Meeting; 2013

North Amer­i­can Catal­y­sis Society

The selective liquid-phase hydrogenation of butyronitrile to n-butylamine was studied in a batch reactor on Co/SiO2, Ni/SiO2, Cu/SiO2, Pt/SiO2, Pd/SiO2, and Ru/SiO2 catalysts. At 373 K and 13 bar (H2), the initial butyronitrile conversion rate (mmol/h g) followed the order Ni > Co > Pt > Ru > Cu > Pd. Cu/SiO2 and Pd/SiO2 did not form n-butylamine and rapidly deactivated during the progress of the reaction. Pt/SiO2 produced mainly dibutylamine and only minor amounts of n-butylamine and tributylamine. In contrast, Ru/SiO2 formed preponderantly n-butylamine but also produced significant amounts of dibutylamine and butylidene-butylamine, an intermediate in the formation pathway of the secondary amine. The highest yield to n-butylamine was obtained on Ni/SiO2 (84 %). Co/SiO2 was initially highly selective to n-butylamine but with the progress of the reaction the butylamine concentration in the reaction mixture diminished because it partially reacted with the solvent (ethanol) to form N-ethylbutylamine. In an attempt to reduce the formation of byproducts, Ni/SiO2 and Co/SiO2 catalysts were tested at lower temperatures and higher H2 pressures. Butyronitrile was selectively converted to n-butylamine on Co/SiO2 at 343 K and 25 bar, yielding 97% of n-butylamine, similarly to the highest yields reported on Raney Co catalysts.