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Homogeneous catalytic oxidation of coconut shells to high-yield aromatic monomers and holocellulose in mild
Chenjun He1, Ruoruo Jiang1, Yunxuan Wang2
1Guangdong Laboratory for Lingnan Modern Agriculture, Institute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural University, Guangzhou 510642, PR China.
Abstract:
An efficient homogeneous catalytic oxidation (HCO) process based on tetramethylammonium hydroxide derived deep eutectic solvent (TMAH-DES) was designed to enable "lignin-first" biorefining. Compared to the other TMAH-DES, the TMAH-imidazole exhibited superior HCO performance. An aromatic monomer yield of 19.5% (71% of the theoretical value based on nitrobenzene oxidation) with a considerable cellulose (86.3%) and hemicellulose recovery (54.4%) was achieved under oxidation at a mild condition of 100℃ for 2 h using the TMAH-imidazole DES with a molar ratio of 3:7. The kinetic simulation of results indicated that both diffusion and surface chemical reactions played a crucial role in lignin dissolution, with surface chemical reactions being the dominant mechanism. An in-depth investigation of lignin structural change and the model compound study revealed that multiple LCC bonds was cleaved to separate lignin from biomass in TMAH-imidazole, contributing to good carbohydrate retention. Meanwhile, a high aromatic monomer yield can be obtained through the efficient cleavage of the β-O-4 bond. Therefore, an enhanced catalytic oxidation process enabling efficient recovery of carbohydrates was obtained in a low-energy homogeneous system, further advancing lignin-first biorefinery operations.
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