Ni-Cu/Al2O3 from Layered Double Hydroxides Hydrogenates Furfural to Alcohols

Abstract

The hydrogenation of furfural is an important process in the synthesis of bio-based chemicals. Copper-based catalysts favor the hydrogenation of furfural to alcohols. Catalytic activity and stability were higher at a Ni-to-Cu atomic ratio of 1:1 and 1.5:0.5 compared to 0.5:1.5. Here, we prepared Ni-Cu/Al2O3 hydrogenation catalysts derived from layered double hydroxides (LDHs). Catalysts calcined at 673 K and reduced at 773 K with nominal Ni/Cu atomic ratios y/x = 1.5/0.5, 1/1 and 0.5/1.5 were characterized by XRD, FESEM-EDX, H2-TPR, XPS, FAA and BET. Their activity was tested at 463 K and in a 0.05 g g−1 furfural solution in ethanol, and the space velocity in a packed-bed reactor (PBR) was 2.85 gFF gcat−1 h−1. In a slurry reactor (SSR) at 5 MPa H2 and a contact time of 4 h, conversion was complete, while it varied from 91 to 99% in the PBR. Tetrahydrofurfuryl alcohol (TFA) was the main product in the SSR, with a selectivity of 32%, 63% and 56% for Ni0.5Cu1.5Al1, Ni1Cu1Al1 and Ni1.5Cu0.5Al1, respectively. The main product in the atmospheric PBR was furfuryl alcohol (FA), with a selectivity of 57% (Ni0.5Cu1.5Al1), 61% (Ni1Cu1Al1) and 58% (Ni1.5Cu0.5Al1). Other products included furan, methylfuran, 1-butanol and 1,2-pentanediol. Ethyl tetrahydrofurfuryl ether and difurfuryl ether were also formed via the nucleophilic addition of furfural with ethanol and furfuryl alcohol.