Similarities in Recalcitrant Structures of Industrial Non-Kraft and Kraft Lignin. 2020

Andrew W Tricker, and Michael J Stellato, and Thomas T Kwok, and Nicholas S Kruyer, and Zhongzhen Wang, and Sankar Nair, and Valerie M Thomas, and Matthew J Realff, and Andreas S Bommarius, and Carsten Sievers
Renewable Bioproducts Institute, Georgia Institute of Technology, 500 10th St NW, Atlanta, GA, 30332, USA.

This work compares the structure of industrially isolated lignin samples from kraft pulping and three alternative processes: butanol organosolv, supercritical water hydrolysis, and sulfur dioxide/ethanol/water fractionation. Kraft processes are known to produce highly condensed lignin, with reduced potential for catalytic depolymerization, whereas the alternative processes have been hypothesized to impact the lignin less. The structural properties most relevant to catalytic depolymerization are characterized by elemental analysis, quantitative 13 C and 2 D HQSC NMR spectroscopy, gel permeation chromatography, and thermogravimetric analysis. Quantification of the β-O-4 ether bond content shows partial depolymerization, with all samples having less than 12 bonds per 100 aromatic units. This results in theoretical monomer yields of less than 5 %, strongly suggesting the alternative fractionation processes generate highly condensed lignin structures that are no more suitable for catalytic depolymerization than kraft lignin. However, the different thermal degradation profiles suggest there are physicochemical differences that could be leveraged in other valorization strategies.

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