1. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
基金项目：
the National Key R&D Program of China(2018YFB1501602);National Natural Science Foundation of China(22132006);the China Postdoctoral Science Foundation(2021M690149)
1. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
Abstract:
Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y3+, Sc3+, and Al3+) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y3+ > Al3+ > Sc3+. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y3+ > Al3+, Y3+ > Sc3+), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc3+ > Y3+ > Al3+), and the conversion of DHA or GLY to the final product lactic acid (Al3+ > Y3+ > Sc3+). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.
