Effect of method of preparation of Ni and/or Cu supported on ZSM-5 catalysts for the aqueous phase hydrogenation of levulinic acid to γ-valerolactone

A series of Cu and Ni supported on ZSM-5 catalysts were synthesized by ion exchange (IE) and impregnation (IMP) techniques and examined for the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) at atmospheric pressure. Hydrogenation of LA to GVL proceeds through LA dehydration to AL (angelica lactone) and subsequent hydrogenation of it to GVL, emphasizing the combined role of an acid and a metal site present on the catalyst surface. The interaction of Cu and/or Ni with ZSM-5 was elucidated using various characterization techniques such as powder XRD, XPS, H2-TPR, NH3-TPD, CO and/or H2 pulse chemisorption and SS NMR techniques. The CO chemisorption results indicated a lower uptake on Cu-ZSM-5(IMP) than on Cu-ZSM-5(IE). The H2 uptake was lower on Ni-ZSM-5(IE) than on Ni-ZSM-5(IMP). In the comparative analysis, the Ni-ZSM-5(IMP) catalyst exhibited a high rate of GVL formation, while the Cu-ZSM-5(IE) catalyst displayed a larger proportion of AL formation than the other catalysts prepared under similar protocols. The influence of the surface active sites on the product distribution was rationalized based on the physico-chemical characteristics of the fresh and reduced catalysts.