Toward Sustained Product Formation in the Liquid-Phase Hydrogenation of Mandelonitrile over a Pd/C Catalyst

Abstract

The liquid-phase hydrogenation of the aromatic cyanohydrin mandelonitrile (MN, C6H5CH(OH)CN) over a carbon-supported Pd catalyst to produce the primary amine phenethylamine (PEA, C6H5CH2CH2NH2) is investigated with respect to the transition from operation in single-batch mode to repeat-batch mode. While a single-batch reaction returns a complete mass balance, product analysis alongside mass balance measurements for a six-addition repeat-batch procedure shows an attenuation in the rate of product formation and an incomplete mass balance from the fourth addition onward. This scenario potentially hinders possible commercial operation of the phenethylamine synthesis process, so it is investigated further. With reference to a previously reported reaction scheme, the prospects of sustained catalytic performance are examined in terms of acid concentration, stirrer agitation rate, catalyst mass, and hydrogen availability. Gas-liquid mass transfer coefficient measurements indicate efficient gas → liquid transfer kinetics within the experimental constraints of the Henry's law limitation on hydrogen solubility in the process solvent (methanol). Deviations from the optimized product selectivity are attributed to mass transport constraints, specifically the H2(solv) → 2H(ads) transition, which is ultimately restrained by the availability of H2(solv). Finally, in an attempt to better understand the deactivation pathways, inelastic neutron scattering measurements on a comparable industrial-grade catalyst operated in an analogous reaction in fed-batch mode indicate the presence of an oligomeric overlayer postreaction. This overlayer is thought to be formed via oligomerization of hydroxyimine or imine species via specific pathways that are identified within a postulated global reaction scheme.