Liquid phase hydrogenation of cinnamaldehyde on Cu-based catalysts

• Published in: Applied catalysis. A, General General, 2003-08, Vol.249 (1), p.53-67
• Main Authors: Marchi, Alberto J, Gordo, Diego A, Trasarti, Andrés F, Apesteguı́a, Carlos R
• Format: Article
• Language: English
• Subjects: Aldehydes (α,β-unsaturated); Catalysis; Catalytic reactions; Chemistry; Cinnamaldehyde hydrogenation; Copper-based catalysts; Exact sciences and technology; General and physical chemistry; Selective hydrogenation; Spinel-like catalysts; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/S0926-860X(03)00199-6

The liquid phase hydrogenation of cinnamaldehyde was studied at 393 K and 10 bar on Cu-based catalysts containing about 12 wt.% of copper. Cu/SiO 2 was prepared by incipient wetness impregnation while Cu–Al, Cu–Zn–Al, and Cu–Ni(Co)–Zn–Al catalysts were obtained by coprecipitation at constant pH. Cinnamaldehyde was initially hydrogenated to cinnamyl alcohol and hydrocinnamaldehyde, and these products consecutively yielded hydrocinnamyl alcohol. Hydrogenation kinetic constants were determined by modeling catalytic data and using a pseudohomogeneous kinetic network. The reaction occurred via two different pathways depending on the composition and surface properties of the catalyst. On Cu/SiO 2 and binary Cu–Al samples, cinnamaldehyde hydrogenation proceeded via a monofunctional pathway on metallic copper that produced predominantly hydrocinnamaldehyde. Ternary Cu–Zn–Al and quaternary Cu–Ni(Co)–Zn catalysts were about one order of magnitude more active than Cu/SiO 2 for cinnamaldehyde conversion and produced predominantly cinnamyl alcohol. The general composition formula of reduced Cu–Zn–Al and Cu–Ni(Co)–Zn–Al catalysts was Cu 0.5 0·[MO] 0.5·ZnAl 2O 4, where M is Zn, Co, or Ni. These catalysts contained the Cu 0 particles highly dispersed in a super-stoichiometric zinc aluminate spinel and in close interaction with M 2+ cations. The presence of M 2+ cations provided a new reaction pathway for adsorbing and hydrogenating cinnamaldehyde in addition to the metal copper active sites. Cinnamaldehyde interacts linearly via the CO group with M 2+ sites and is selectively hydrogenated to unsaturated alcohol by atomic hydrogen activated in neighboring Cu 0 sites. Formation of surface Cu 0–M 2+ sites was, therefore, crucial to efficiently catalyze the cinnamyl alcohol formation from cinnamaldehyde via a dual-site reaction pathway.