Preparation of homogeneous lignin nanoparticles by efficient extraction of lignin and modification of its molecular structure using a functional deep eutectic solvent containing -valerolactone

GREEN CHEMISTRY(2024)

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Abstract
Deep eutectic solvents (DESs) are widely used as recyclable green solvents for the separation of lignin from lignocellulosic biomass. However, the poor permeability of DES solution limits the green advancement of separation systems. In addition, lignin fragment molecules are susceptible to repolymerization reactions during separation, resulting in reduced lignin reactivity. In this study, a DES consisting of choline chloride (ChCl) as a hydrogen acceptor, 5-sulfosalicylic acid (5Saa) as a hydrogen donor, and a certain amount of gamma-valerolactone (GVL) as an additive was designed. The system not only efficiently fractionated lignin from poplar (71.35%), but also selectively retained almost complete cellulose (retention 92.87%) under the optimal fractionation (ChCl/5Saa/GVL molar ratio 1/4/15, temperature 120 degrees C, time 3.0 h). Pre-crushing processing of raw materials was avoided as the new DES solution has stronger permeability compared to the previous DES solution. Selective deconstruction of lignocellulose was achieved due to a strong hydrogen network structure. The lignin fragments were effectively dissolved. The results showed that the stability of the carbo-positive active intermediates was enhanced by ChCl-5Saa/GVL. Lignin with a low molecular weight (2305 g mol-1), high purity (98.77%) and high total phenolic hydroxyl content (6.92 mmol g-1) was obtained. Homogeneous lignin nanoparticles (LNPs) were prepared with an average particle size of 23 nm. LNPs had high dispersion stability and excellent UV shielding properties. The green advancement of the new DES has been significantly improved and the efficient fractionation of high-value lignin was realized. A lignin-extractive green reaction medium consisting of choline chloride, 5-sulfosalicylic acid, and gamma-valerolactone was designed. Polyphenolic lignin was obtained. The green advancement of DES processing has been enhanced.
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