Search

The chemical structure of lignin has an important effect on the lignin pyrolysis product distributions. Therefore, it is of great significance to regulate the selectivity of pyrolysis products by modifying the lignin structure. Herein, deep eutectic solvents (DESs) including choline chloride/ethylene glycol (CE), zinc chloride/ethylene glycol (ZE) and choline chloride/acetic acid, treatment of softwood kraft lignin (SKL) is demonstrated. Systematic characterization indicate that the DESs are not only highly conducive to increasing the hydrogen to carbon efficient ratio, reducing the molecular weight and β-O-4 linkage, but also contributes to the maximum degradation rate and thermal stability of SKL. Noticeably, CE and ZE treatment are significantly improved the amount of H-phenols and C-phenols derived lignin pyrolysis, respectively. In addition, DESs pretreatment are also beneficial to the increment of monomer aromatic hydrocarbons. More importantly, the CE pretreatment contributes to the improvement of bio-oil yield and decrease of char content from lignin pyrolysis.

In this work, several representative green processes were developed to extract the enzymatic lignin and deep eutectic solvents (DESs) isolated lignin from corn straw. The results revealed that enzymatic lignin and DESs isolated lignin had a relatively low and homogeneous molecular weight and DESs isolated lignin shown a higher purity. Enzymatic and DESs isolated lignin showed good representativeness and similar to original herbal lignin structures accompany few aryl ether linkage cleavages and oxidation phenomenon. Among them, the subcritical CO2-assisted autohydrolysis and ChCl/Lac DESs treatment exhibited a higher severity for lignin preparation, and sequence DESs isolated lignin had a better reactivity. The β-O-4 ether bonds and carbon-carbon bonds linkage were further broken up during the Lac and DESs sequence treatment. In short, the described processes showed practical significance for lignin extraction and potential valorization, as well as help to develop more novel strategies for the current biorefinery process.

In this work, an emerging and efficient strategy for the preparation of lignin samples with different acetylation degree by choline chloride/acetic anhydride (ChCl/Aa) treatment of pine kraft lignin (PKL) is reported, and the effects of efficient pre-acetylation of hydroxyl functional groups on subsequent lignin pyrolysis are also systematically investigated. The results show that the ChCl/Aa displays a high acetylation efficiency towards the aliphatic hydroxyl (~99.1%) and phenolic hydroxyl (~94.0%) of PKL, which enhances the hydrogen to carbon effective ratio of PKL. Noticeably, the ChCl/Aa has a slight effect on β-O-4 of PKL, and the acetylation of hydroxyl is beneficial for the improvement of the maximum degradation rate of PKL. In addition, the acetylation of hydroxyl is also significantly contributed to the increment of the pyrolysis bio-oil yield. Importantly, the relative content of the H-phenols obtained from acetylated lignins pyrolysis shows a positive correlation with the acetylation degree of hydroxyl.