Chemocatalytic Conversion of Cellulosic Biomass to Methyl Glycolate, Ethylene Glycol, and Ethanol

Abstract

Production of chemicals and fuels from renewable cellulosic biomass is important for the creation of a sustainable society, and it critically relies on the development of new and efficient transformation routes starting from cellulose. Here, a chemocatalytic conversion route from cellulosic biomass to methyl glycolate (MG), ethylene glycol (EG), and ethanol (EtOH) is reported. By using a tungsten-based catalyst, cellulose is converted into MG with a yield as high as 57.7 C % in a one-pot reaction in methanol at 240 °C and 1 MPa O , and the obtained MG can be easily separated by distillation. Afterwards, it can be nearly quantitatively converted to EG at 200 °C and to EtOH at 280 °C with a selectivity of 50 % through hydrogenation over a Cu/SiO catalyst. By this approach, the fine chemical MG, the bulk chemical EG, and the fuel additive EtOH can all be efficiently produced from renewable cellulosic materials, thus providing a new pathway towards mitigating the dependence on fossil resources.

A Durable Nickel Single‐Atom Catalyst for Hydrogenation Reactions and Cellulose Valorization under Harsh Conditions

“…In fact, the high temperature pyrolysis as well as the subsequent acid‐etching processing during the synthesis of Ni‐N‐C SACs has already indicated that the Ni‐N x sites are highly resistant against sintering and acid‐leaching. To study the stability of the Ni‐N x during hydrogenation reactions, here we apply the catalyst to the one‐pot conversion of cellulose to ethylene glycol, which is a key reaction in the valorization of renewable lignocellulose . To degrade the recalcitrant cellulose, a binary catalyst composed of tungstic acid and Ni‐N‐C‐600 was used, in which the tungstic acid promotes C−C cleavage of the cellulose‐derived sugars via a retro‐aldol pathway while the Ni‐N‐C‐600 catalyzes the hydrogenation of aldehyde intermediates (Supporting Information, Figure S18) …”

“…Based on our earlier studies, cellulose hydrolysis as well as the C−C cleavage reaction had a high activation energy and thus required a very harsh reaction condition (245 °C, 60 bar H 2 , stongly acidic hydrothermal conditions). Cogently, most of the base metal catalysts could not survive under such severe conditions.…”

Selective Cellulose Hydrogenolysis to Ethanol Using Ni@C Combined with Phosphoric Acid Catalysts

“…ethanol over aC u/SiO 2 catalyst. [12] The two-step approach could give an ethanol yield of 29 %b ased on cellulose. However,t he use of methanol and O 2 may cause environmental problems in large-scale production.…”

Low‐Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis

“…Since no CO 2 is produced during C−C cleavage, the bio‐based C2‐amines are formed with a “greener” carbon efficiency than that of the bioethanol route . R‐A‐like reactions are well‐studied in carbohydrate chemistry for the synthesis of glycolaldehyde, glyceraldehyde, lactic acid, and novel chemicals such as methyl and vinyl glycolate, but they are also involved in the formation of ethylene glycol and propylene glycol . The C−C scission of the R‐A reaction usually requires a high reaction temperature (>430 K).…”