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.

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis.

Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet-Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by 31 P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC.

Hydrogen-free catalytic fractionation of woody biomass.

The pulping industry could become a biorefinery if the lignin and hemicellulose components of the lignocellulose are valorized. Conversion of lignin into well-defined aromatic chemicals is still a major challenge. Lignin depolymerization reactions often occur in parallel with irreversible condensation reactions of the formed fragments. Here, we describe a strategy that markedly suppresses the undesired condensation pathways and allows to selectively transform lignin into a few aromatic compounds. Notably, applying this strategy to woody biomass at organosolv pulping conditions, the hemicellulose, cellulose, and lignin were separated and in parallel the lignin was transformed into aromatic monomers. In addition, we were able to utilize a part of the lignocellulose as an internal source of hydrogen for the reductive lignin transformations. We hope that the presented methodology will inspire researchers in the field of lignin valorization as well as pulp producers to develop more efficient biomass fractionation processes in the future.

Ethanol-based organosolv fractionation of wheat straw for the production of lignin and enzymatically digestible cellulose.

Wheat straw fractionation by ethanol organosolv was studied as pretreatment for enzymatic cellulose hydrolysis. A parametric study focusing on temperature, reaction time, acid catalyst dose, solvent concentration, and particle size was performed to determine their influence on delignification, xylan hydrolysis, and enzymatic cellulose digestibility. Major process parameters were found to be temperature, ethanol concentration, and acid dose. Optimisation of the process towards enzymatic digestibility resulted in a maximum glucose yield of 86% without the use of a catalyst (lignin yield 84%, organosolv at 210 °C, 50% w/w aqueous EtOH). Using 30 mM H2SO4 as catalyst resulted in similar glucose and lignin yields at a lower temperature (190 °C, 60% w/w aqueous EtOH). Lowering the pretreatment temperature by using an acid catalyst substantially improved the yield of the hemicellulose derivatives xylose and furfural. A systematic approach in pretreatment optimisation is vital for development of efficient lignocellulosic biorefineries.

Solid acid-catalyzed cellulose hydrolysis monitored by in situ ATR-IR spectroscopy.

The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and other compounds, were measured in water under ambient and elevated temperatures. A combination of spectroscopic and HPLC analysis revealed that the cellulose hydrolysis proceeds first through the disruption of the glycosidic linkages of cellulose to form smaller cellulose molecules, which are readily observed by their distinctive C-O vibrational stretches. The continued disruption of the linkages in these oligomers eventually results in the formation and accumulation of monomeric glucose. The solid-acid catalyst accelerated the isomerization of glucose to fructose, which then rapidly reacted under hydrothermal conditions to form degradation products, which included HMF, LA, formic acid, and acetic acid. The formation of these species could be suppressed by decreasing the residence time of glucose in the reactor, reaction temperature, and contact with the metal reactor. The hydrolysis of regenerated cellulose proceeded faster and under milder conditions than microcrystalline cellulose, which resulted in increased glucose yield and selectivity.