Choline and lactic acid covalently incorporate into the lignin structure during deep eutectic solvent pulping

• Published in: Green chemistry : an international journal and green chemistry resource : GC 2024, Vol.26 (12), p.711-7112
• Main Authors: van Erven, Gijs, Boerkamp, Vincent J. P, van Groenestijn, Johan W, Gosselink, Richard J. A
• Format: Article
• Language: English
• Subjects: Acids; Aromatic compounds; Biomass; Biorefineries; Choline; Covalence; Environmental impact; Esterification; Ethers; Hardwoods; Lactic acid; Lignin; Miscanthus; Moisture content; NMR; Nuclear magnetic resonance; Pulping; Softwoods; Solvents; Structural analysis; Substitution reactions; Water content
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/d4gc00909f

Deep eutectic solvent (DES) pulping is a promising alternative to conventional pulping techniques, mainly owing to the favourable solvent properties and reduced environmental impact. DES lignin, however, still awaits complete structural characterisation, especially in terms of the potential incorporation of DES constituents. Here, we describe the structural modification of lignin during lactic acid : choline chloride DES pulping of Miscanthus biomass in unprecedented detail. We show that DES pulping induces β-O-4 aryl ether cleavage and extensive substitution by DES incorporation. The covalent incorporation of both lactic acid and choline was confirmed through saponification of the precipitated lignin and lignin model compound studies. Detailed multidimensional NMR analysis allowed us to validate aliphatic and benzylic lactic acid esterification as well as benzylic choline and lactic acid etherification of β-O-4 aryl ethers. We demonstrate that these reactions occur in all process phases by comprehensive analysis of the precipitated, residual and solubilised lignin fractions, together comprising 93% w/w of the initial lignin in Miscanthus . Covalent lactic acid and choline incorporation occurs independently of biomass type (grass, hardwood and softwood) and can be modulated by water content, reaction duration and temperature. Going forward, these new insights will offer ample opportunities for producing lignins with unique structural features and ultimately will open up new avenues for specific functional ingredient applications. Our work thus clearly advances the DES biorefinery concept and contributes to the valorisation of lignin in general. We demonstrate the unique substituted nature of lignin following deep eutectic solvent pulping of plant biomass. The incorporation of novel lactic acid and choline based functionalities is highlighted, now calling for targeted DES lignin application.