High-yield production of levulinic acid from cellulose and its upgrading to γ-valerolactone

Abstract

Direct catalytic conversion of cellulose to levulinic acid (LA) by niobium-based solid acids and further upgrading to γ-valerolactone (GVL) on a Ru/C catalyst were realized through sequential reactions in a reactor. Firstly, using aluminium-modified mesoporous niobium phosphate as a catalyst, cellulose can be directly converted to LA with as high as 52.9% yield in aqueous solution, even in the presence of the Ru/C catalyst. To the best of our knowledge, this is the best result over a heterogeneous catalyst so far. It was found that the type of acid (Lewis and Brønsted acids) and acid strength had an influence on the yield of LA; the doping of aluminium can enhance the strong Lewis and Brønsted acids, especially the strong Lewis acid, thus resulting in the increase of LA yield from cellulose as well as from glucose and HMF. Such an enhancement by a Lewis acid on LA yield from HMF was further confirmed by adding lanthanum trifluoroacetate [(TfO)₃La], a strong Lewis acid, in the catalytic system (HCl, (TfO)₃H, niobium phosphate), indicating that a suitable ratio of Lewis/Brønsted acid is important for higher selectivity to LA from HMF, as well as from cellulose. Then, after replacing N₂ with H₂, the generated LA in the reaction mixture can be directly converted to γ-valerolactone through hydrogenation over the Ru/C catalyst without further separation of LA.