Towards sustained product formation in the liquid phase hydrogenation of mandelonitrile over a Pd/C catalyst

McAllister, M., Boulho, C., Brennan, C., Parker, S. F. and Lennon, D. (2020) Towards sustained product formation in the liquid phase hydrogenation of mandelonitrile over a Pd/C catalyst. Organic Process Research and Development, 24(6), pp. 1112-1123. (doi: 10.1021/acs.oprd.0c00111) (PMID:32587453) (PMCID:PMC7309435)

Abstract

The liquid phase hydrogenation of the aromatic cyanohydrin mandelonitrile (C6H5CH(OH)CH2CN) over a carbon supported Pd catalyst to produce the primary amine phenethylamine (C6H5CH2CH2NH2) is investigated with respect to the transition from operation in single batch mode to repeat batch mode. Whilst a single batch reaction returns a complete mass balance, product analysis alongside mass balance measurements for a 6 addition repeat batch procedure shows an attenuation in the rate of product formation and an incomplete mass balance from the 4th addition onwards. 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 for hydrogen solubility in the process solvent (methanol). Deviations from optimised product selectivity are attributed to mass transport constraints, specifically the transition of H2(solv) → 2H(ads), 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 post-reaction. This overlayer is thought to be formed via oligomerisation of hydroxyimine or imine species via specific pathways that are identified within a postulated global reaction scheme.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: McAllister, Miss Mairi and Boulho, Dr Cedric and Lennon, Professor David
• Authors: McAllister, M., Boulho, C., Brennan, C., Parker, S. F., and Lennon, D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Organic Process Research and Development
• Publisher: American Chemical Society
• ISSN: 1083-6160
• ISSN (Online): 1520-586X
• Published Online: 04 May 2020
• Copyright Holders: Copyright © 2020 American Chemical Society
• First Published: First published in Organic Process Research and Development 24(6): 1112-1123
• Publisher Policy: Reproduced under an Open Government Licence

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
190906		EPSRC 2015 DTP	Mary Beth Kneafsey	Engineering and Physical Sciences Research Council (EPSRC)	EP/M508056/1	Research and Innovation Services