Predicting Molecular Weight Characteristics of Reductively Depolymerized Lignins by ATR-FTIR and Chemometrics.

Recent scientific advances in the valorization of lignin, through e.g., (partial-)catalytic depolymerization, require equally state-of-the-art approaches for the analysis of the obtained depolymerized lignins (DLs) or lignin bio-oils. The use of chemometrics in combination with infrared (IR) spectroscopy is one avenue to provide rapid access to pertinent lignin parameters, such as molecular weight (MW) characteristics, which typically require analysis via time-consuming size-exclusion methods, or diffusion-ordered NMR spectroscopy. Importantly, MW serves as a marker for the degree of depolymerization (or recondensation) that the lignin has undergone, and thus probing this parameter is essential for the optimization of depolymerization conditions to achieve DLs with desired properties. Here, we show that our ATR-IR-based chemometrics approach used previously for technical lignin analysis can be extended to analyze these more processed, lignin-derived samples as well. Remarkably, also at this lower end of the MW scale, the use of partial least-squares (PLS) regression models well-predicted the MW parameters for a sample set of 57 depolymerized lignins, with relative errors of 9.9-11.2%. Furthermore, principal component analysis (PCA) showed good correspondence with features in the regression vectors for each of the biomass classes (hardwood, herbaceous/grass, and softwood) obtained from PLS-discriminant analysis (PLS-DA). Overall, we show that the IR spectra of DLs are still amenable to chemometric analysis and specifically to rapid, predictive characterization of their MW, circumventing the time-consuming, tedious, and not generally accessible methods typically employed.

Rapid Lignin Thermal Property Prediction through Attenuated Total Reflectance-Infrared Spectroscopy and Chemometrics.

To expedite the valorisation of lignin as a sustainable component in materials applications, rapid and generally available analytical methods are essential to overcome the bottleneck of lignin characterisation. Where features of a lignin's chemical structure have previously been found to be predicted by Partial Least Squares (PLS) regression models built on Infrared (IR) data, we now show for the first time that this approach can be extended to prediction of the glass transition temperature (Tg), a key physicochemical property. This methodology is shown to be convenient and more robust for prediction of Tg than prediction through empirically derived relationships (e. g., Flory-Fox). The chemometric analysis provided root mean squared errors of prediction (RMSEP) as low as 10.0 °C for a botanically, and a process-diverse set of lignins, and 6.2 °C for kraft-only samples. The PLS models could separately predict both the Tg as well as the degree of allylation (%allyl) for allylated lignin fractions, which were all derived from a single lignin source. The models performed exceptionally well, delivering RMSEP of 6.1 °C, and 5.4 %, respectively, despite the conflicting influences of increasing molecular weight and %allyl on Tg. Finally, the method provided accurate determinations of %allyl with RMSEP of 5.2 %.

Expanding lignin thermal property space by fractionation and covalent modification.

To fully exploit kraft lignin's potential in material applications, we need to achieve tight control over those key physicochemical lignin parameters that ultimately determine, and serve as proxy for, the properties of lignin-derived materials. Here, we show that fractionation combined with systematic (incremental) modification provides a powerful strategy to expand and controllably tailor lignin property space. In particular, the glass transition temperature (Tg) of a typical kraft lignin could be tuned over a remarkable and unprecedented 213 °C. Remarkably, for all fractions the Tg proved to be highly linearly correlated with the degree of derivatisation by allylation, offering such tight control over the Tg of the lignin and ultimately the ability to 'dial-in' this key property. Importantly, such control over this proxy parameter indeed translated well to lignin-based thiol-ene thermosetting films, whose Tgs thus covered a range from 2-124 °C. This proof of concept suggests this approach to be a powerful and generalisable one, allowing a biorefinery or downstream operation to consciously and reliably tailor lignins to predictable specifications which fit their desired application.

Tuning the Properties of Biobased PU Coatings via Selective Lignin Fractionation and Partial Depolymerization.

Polyurethane (PU) coatings with high lignin content and tunable properties were made using a combination of fractionation and partial catalytic depolymerization as a novel strategy to tailor lignin molar mass and hydroxyl group reactivity, the key parameters for use in PU coatings. Acetone organosolv lignin obtained from pilot-scale fractionation of beech wood chips was processed at the kilogram scale to produce lignin fractions with specific molar mass ranges (Mw 1000-6000 g/mol) and reduced polydispersity. Aliphatic hydroxyl groups were distributed relatively evenly over the lignin fractions, allowing detailed study of the correlation between lignin molar mass and hydroxyl group reactivity using an aliphatic polyisocyanate linker. As expected, the high molar mass fractions exhibited low cross-linking reactivity, yielding rigid coatings with a high glass transition temperature (Tg). The lower Mw fractions showed increased lignin reactivity, extent of cross-linking, and gave coatings with enhanced flexibility and lower Tg. Lignin properties could be further tailored by lignin partial depolymerization by reduction (PDR) of the beech wood lignin and its high molar mass fractions; excellent translation of the PDR process was observed from laboratory to the pilot scale necessary for coating applications in prospective industrial scenarios. Lignin depolymerization significantly improved lignin reactivity, and coatings produced from PDR lignin showed the lowest Tg values and highest coating flexibility. Overall, this study provides a powerful strategy for the production of PU coatings with tailored properties and high (>90%) biomass content, paving the path to the development of fully green and circular PU materials.

Biomass Pre-Extraction as a Versatile Strategy to Improve Biorefinery Feedstock Flexibility, Sugar Yields, and Lignin Purity.

Feedstock flexibility is highly advantageous for the viability of (solvent-based) biorefineries but comes with the considerable challenge of having to cope with the varying nature and typically high abundance of nonlignocellulose compounds in the most readily available residual biomass streams. Here, we demonstrate that mild aqueous acetone organosolv fractionation of various complex lignocellulosic raw materials (roadside grass, wheat straw, birch branches, almond shells, and a mixed stream thereof) is indeed negatively affected by these compounds and present a versatile strategy to mitigate this bottleneck in biorefining. A biomass pre-extraction approach has been developed to remove the detrimental extractives with (aqueous) acetone prior to fractionation. Pre-extraction removed organic extractives as well as minerals, primarily reducing acid dose requirements for fractionation and loss of hemicellulose sugars by degradation and improved the purity of the isolated lignin. We show how pre-extraction affects the effectiveness of the biorefinery process, including detailed mass balances for pretreatment, downstream processing, and product characteristics, and how it affects solvent and energy use with a first conceptual process design. The integrated biorefining approach allows for the improved compatibility of biorefineries with sustainable feedstock supply chains, enhanced biomass valorization (i.e., isolation of bioactive compounds from the extract), and more effective biomass processing with limited variation in product quality.