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Lignin is an abundant, renewable, and relatively cheap biobased feedstock that has potential in energy, chemicals, and materials. Kraft lignin, more specifically, has been used for more than 100 years as a self-sustaining energy feedstock for industry after which it has finally reached more widespread commercial appeal. Unfortunately, hardwood kraft lignin (HWKL) has been neglected over these years when compared to softwood kraft lignin (SWKL). Therefore, the present work summarizes and critically reviews the research and development (R&D) dealing specifically with HWKL. It will also cover methods for HWKL extraction from black liquor, as well as its structure, properties, fractionation, and modification. Finally, it will reveal several interesting opportunities for HWKL that include dispersants, adsorbents, antioxidants, aromatic compounds (chemicals), and additives in briquettes, pellets, hydrogels, carbon fibers and polymer blends and composites. HWKL shows great potential for all these applications, however more R&D is needed to make its utilization economically feasible and reach the levels in the commercial lignin market commensurate with SWKL. The motivation for this critical review is to galvanize further studies, especially increased understandings in the field of HWKL, and hence amplify much greater utilization. [ABSTRACT FROM AUTHOR]

A novel choline-based deep eutectic solvent (DES) with low halogen content—namely choline lactate-lactic acid (CLL)—was synthesized by replacing the chloride anion with lactate anion in choline chloride-lactic acid (CCL). CLL and CCL treatments were conducted at 140 °C for 12 h with hydrogen bond acceptor/hydrogen bond donor =1/10, thereafter composition analysis and characterizations of the lignin extracted by DES treatment (DES lignin) and the solid residue were carried out. The proposed low halogen content DES presented an improved lignin extraction efficiency. The CLL treatment extracted 90.13% of initial lignin from poplar, while CCL extracted 86.02%. In addition, the CLL treatment also provided DES lignin with an improved purity (91.17%), lower molecular weight (Mw/Mn=1805/971 g/mol) and more concentrated distribution (polydispersity index=1.86). The efficient lignin extraction was mainly ascribed to the cleavage of β-O-4 bonds in lignin macromolecule, especially in the guaiacyl units, thereby breaking them into smaller molecules, facilitating the lignin extraction. The replacement of chloride anion allowed CLL acting as a more efficient DES to interact with lignin macromolecules, thus providing lignin with higher uniformity and suitable molecular weight. The low halogen content DES system proposed in present work could benefit the fractionation of biomass, improve the valorization of lignin compounds and facilitate industrial process in the downstream. [ABSTRACT FROM AUTHOR]

Purity, morphology, and structural characterization of synthesized deep eutectic solvent (DES)-lignins (D6h, D9h, D12h, D18h, D24h) extracted from willow (Salix matsudana cv. Zhuliu) after treatment with a 1:10 molar ratio of choline chloride and lactic acid at 120 °C for 6, 9, 12, 18, and 24 h were carried out. The purity of DES-lignin was ~95.4%. The proportion of hydrogen (H) in DES-lignin samples increased from 4.22% to 6.90% with lignin extraction time. The DES-lignin samples had low number/weight average molecular weights (1348.1/1806.7 to 920.2/1042.5 g/mol, from D6h to D24h) and low particle sizes (702–400 nm). Atomic force microscopy (AFM) analysis demonstrated that DES-lignin nanoparticles had smooth surfaces and diameters of 200–420 nm. Syringyl (S) units were dominant, and total phenolic hydroxyl content and total hydroxyl content reached their highest values of 2.05 and 3.42 mmol·g−1 in D12h and D6h, respectively. β-Aryl ether (β-O-4) linkages were eliminated during DES treatment. [ABSTRACT FROM AUTHOR]