Metal regulating the highly selective synthesis of gamma-valerolactone and valeric biofuels from biomass-derived levulinic acid. (1st January 2020)

• Record Type: Journal Article
• Authors: Yi, Zixiao; Hu, Di; Xu, Hong; Wu, Zuotong; Zhang, Man; Yan, Kai
• Is Part Of: Fuel. Volume 259(2020)
• Publication Date: 2020-01-01
• Subjects: Levulinic acid -- Ni/HZSM-5 -- Ru/HZSM-5 -- Gamma-valerolactone -- Valeric biofuels -- Metal effect; Fuel -- Periodicals; Coal -- Periodicals; Coal; Fuel; Periodicals; 662.6
• DOI: 10.1016/j.fuel.2019.116208
• Languages: English
• ISSNs: 0016-2361

Abstract

Highlights: Ru/HZSM-5 has strong acidic sites and the ring-opening of GVL intermediate. High yield (93.1%) of GVL was achieved employing 3 wt% Ni/HZSM-5. 3 wt% Ru/HZSM-5 catalyst exhibits 85.7% yield of vaeric biofuels. Cyclic test of 3 wt% Ru/HZSM-5 displayed perfect conversion even after 5 runs. Abstract: Highly selective upgrade of biomass-derived source to biofuels is crucial for the utilization of biomass. Herein, we report a strategy for the highly selective conversion of biomass-derived levulinic acid (LA) to gamma-valerolactone (GVL) or valeric biofuels simply by tuning the used metal Ni or Ru on HZSM-5 support. The catalytic experimental results show that 3 wt% Ni/HZSM-5 catalyst achieves high yield (93.1%) of GVL with negligible formation of pentanoic acid (<1% yield) or pentanoic esters (<1% yield), while 3 wt% Ru/HZSM-5 catalyst exhibits a high yield (85.7%) of pentanoic esters (PE) and pentanoic acid (PA) under the identical conditions. It is found that the introduction of Ru into HZSM-5 would increase the strong acidic sites and enhance the ring-opening of GVL intermediate, promoting the formation of PE and PA. In comparison, 3 wt% Ni/HZSM-5 catalyst shows relative lower acidic sites and negligible ring-opening ability of GVL. The metal effect is further confirmed using GVL and 1, 4-dioxane as substrate, respectively. After that, reaction kinetics are investigated in details and a rational pathway is proposed for the metal effect in deciding the product distribution of LA hydrogenation. This work provides a useful guideline to design proper catalyst for the valorization of biomass resources.