Extraction, recovery, and characterization of lignin from industrial corn stover lignin cake.

Lignin utilization in value-added co-products is an important component of enabling cellulosic biorefinery economics. However, aqueous dilute acid pretreatments yield lignins with limited applications due to significant modification during pretreatment, low solubility in many solvents, and high content of impurities (ash, insoluble polysaccharides). This work addresses these challenges and investigates the extraction and recovery of lignins from lignin-rich insoluble residue following dilute acid pretreatment and enzymatic hydrolysis of corn stover using three extraction approaches: ethanol organosolv, NaOH, and an ionic liquid. The recovered lignins exhibited recovery yields ranging from 30% for the ionic liquid, 44% for the most severe acid ethanol organosolv condition tested, and up to 86% for the most severe NaOH extraction condition. Finally, the fractional solubilities of different recovered lignins were assessed in a range of solvents and these solubilities were used to estimate distributions of Hildebrand and Hansen solubility parameters using a novel approach.

Effect of Dilute Acid Pretreatment and Lignin Extraction Conditions on Lignin Properties and Suitability as a Phenol Replacement in Phenol-Formaldehyde Wood Adhesives.

Corn stover was subjected to dilute sulfuric acid pretreatment to assess the impact of pretreatment conditions on lignin extractability, properties, and utility as a phenol replacement in wood phenol-formaldehyde (PF) adhesives. It was identified that both formic acid and NaOH could extract and recover 60-70% of the lignin remaining after pretreatment and enzymatic hydrolysis under the mildest pretreatment conditions while simultaneously achieving reasonable enzymatic hydrolysis yields (>60%). The availability of reaction sites for the incorporation of lignins into the PF polymer matrix (i.e., unsubstituted phenolic hydroxyl groups) was shown to be strongly impacted by the pretreatment time and the recovery. Finally, a lignin-based wood adhesive was formulated by replacing 100% of the phenol with formic-acid-extracted lignin, which exhibited a dry shear strength exceeding a conventional PF adhesive. These findings suggest that both pretreatment and lignin extraction conditions can be tailored to yield lignins with properties targeted for this co-product application.

Effect of catalyst and reaction conditions on aromatic monomer yields, product distribution, and sugar yields during lignin hydrogenolysis of silver birch wood.

The impact of catalyst choice and reaction conditions during catalytic hydrogenolysis of silver birch biomass are assessed for their effect on aromatic monomer yields and selectivities, lignin removal, and sugar yields from enzymatic hydrolysis. At a reaction temperature of 220 °C with no supplemental H2, it was demonstrated that both Co/C and Ni/C exhibited aromatic monomer yields of >50%, which were close to the theoretical maximum expected for the lignin based on total ß-O-4 content and exhibited high selectivities for 4-propylguaiacol and 4-propylsyringol. Pd/C exhibited a significantly different set of products, and using a model lignin dimer, showed a product profile that shifted upon inclusion of supplemental H2, suggesting that the generation of surface hydrogen is critical for this catalyst system. Lignin removal during hydrogenolysis could be correlated to glucose yields and inclusion of lignin depolymerizing catalysts significantly improves lignin removal and subsequent enzymatic hydrolysis yields.

Impact of dilute acid pretreatment conditions on p-coumarate removal in diverse maize lines.

Prior work has identified that lignins recovered from dilute acid-pretreated corn stover exhibit superior performance in phenol-formaldehyde resins used in wood adhesive applications when compared to diverse process-modified lignins derived from other sources. This improved performance is hypothesized to be due to the higher content of unsubstituted phenolic groups specifically p-coumarate lignin esters. In this work, a diverse set of corn stover samples are employed that exhibit diversity in p-coumarate content and total lignin content to explore the relationship between dilute acid pretreatment conditions, p-coumarate ester hydrolysis, xylan solubilization, and the resulting glucose enzymatic hydrolysis yields. The goal of this study is to identify pretreatment conditions that preserve a significant fraction of the p-coumarate esters while simultaneously achieving high enzymatic hydrolysis yields. Kinetic parameters for p-coumarate ester hydrolysis were quantified and pretreatment-biomass combinations were identified that result in glucose hydrolysis yields of more than 90% while retaining nearly 50 mg p-coumarate/g lignin.

Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties.

BACKGROUND: In this work, three pretreatments under investigation at the DOE Bioenergy Research Centers (BRCs) were subjected to a side-by-side comparison to assess their performance on model bioenergy hardwoods (a eucalyptus and a hybrid poplar). These include co-solvent-enhanced lignocellulosic fractionation (CELF), pretreatment with an ionic liquid using potentially biomass-derived components (cholinium lysinate or [Ch][Lys]), and two-stage Cu-catalyzed alkaline hydrogen peroxide pretreatment (Cu-AHP). For each of the feedstocks, the pretreatments were assessed for their impact on lignin and xylan solubilization and enzymatic hydrolysis yields as a function of enzyme loading. Lignins recovered from the pretreatments were characterized for polysaccharide content, molar mass distributions, ß-aryl ether content, and response to depolymerization by thioacidolysis. RESULTS: All three pretreatments resulted in significant solubilization of lignin and xylan, with the CELF pretreatment solubilizing the majority of both biopolymer categories. Enzymatic hydrolysis yields were shown to exhibit a strong, positive correlation with the lignin solubilized for the low enzyme loadings. The pretreatment-derived solubles in the [Ch][Lys]-pretreated biomass were presumed to contribute to inhibition of enzymatic hydrolysis in the eucalyptus as a substantial fraction of the pretreatment liquor was carried forward into hydrolysis for this pretreatment. The pretreatment-solubilized lignins exhibited significant differences in polysaccharide content, molar mass distributions, aromatic monomer yield by thioacidolysis, and ß-aryl ether content. Key trends include a substantially higher polysaccharide content in the lignins recovered from the [Ch][Lys] pretreatment and high ß-aryl ether contents and aromatic monomer yields from the Cu-AHP pretreatment. For all lignins, the 13C NMR-determined ß-aryl ether content was shown to be correlated with the monomer yield with a second-order functionality. CONCLUSIONS: Overall, it was demonstrated that the three pretreatments highlighted in this study demonstrated uniquely different functionalities in reducing biomass recalcitrance and achieving higher enzymatic hydrolysis yields for the hybrid poplar while yielding a lignin-rich stream that may be suitable for valorization. Furthermore, modification of lignin during pretreatment, particularly cleavage of ß-aryl ether bonds, is shown to be detrimental to subsequent depolymerization.

Lignin-Based Polyurethanes: Opportunities for Bio-Based Foams, Elastomers, Coatings and Adhesives.

Polyurethane chemistry can yield diverse sets of polymeric materials exhibiting a wide range of properties for various applications and market segments. Utilizing lignin as a polyol presents an opportunity to incorporate a currently underutilized renewable aromatic polymer into these products. In this work, we will review the current state of technology for utilizing lignin as a polyol replacement in different polyurethane products. This will include a discussion of lignin structure, diversity, and modification during chemical pulping and cellulosic biofuels processes, approaches for lignin extraction, recovery, fractionation, and modification/functionalization. We will discuss the potential of incorporation of lignins into polyurethane products that include rigid and flexible foams, adhesives, coatings, and elastomers. Finally, we will discuss challenges in incorporating lignin in polyurethane formulations, potential solutions and approaches that have been taken to resolve those issues.

Solubility of lignin and chitin in ionic liquids and their biomedical applications.

Ionic liquids (ILs), are considered as eco-friendly solvents due to their low vapor pressure and non-volatile properties compared to organic solvents and can be employed during processes for the extraction and/or conversion of lignin and chitin to value-added products which can improve the overall economics of the integrated biorefinery concept. However, relatively few studies have investigated their ability to solubilize and modify during solvation of lignin and chitin in terms of crystallinity, molecular weight, etc., with a significant focus on polysaccharides like cellulose and hemicellulose. Similarly, the biomedical applications of lignin and chitin are not recognised so much as compared to polysaccharides. The aim of this review is survey the current literature based on the cutting-edge-knowledge regarding the solubilization of chitin and lignin in various classes of ILs and furthermore, the upgradation of these biopolymers and/or their derivatives for the biomedical applications. Moreover, this review provides a comprehensive summary of the latest progress on the solubilization of integrated biorefinery lignin and chitin with a wide range of ILs using experimental and theoretical studies.

Bioinspired carbon dots: from rose petals to tunable emissive nanodots.

Engineering biomass into functional nanomaterials is captivating. The limitation of versatility in green precursors is pursued by exploring the formation of carbon dots with respect to the contents of the green precursor, i.e. Rosa indica. The intermediates formed at different intervals are analyzed. Moreover, the mechanism of heteroatom-doped Rosa indica derived carbon-dot is proposed.

Isolation of lignin by organosolv process from different varieties of rice husk: Understanding their physical and chemical properties.

The aim of this work was to study the difference in properties of lignins, those (organosolv lignins (ORGLs, 12±3% yield and 93±5% mass balance) were isolated from diverse rice husk (RH) substrates using organosolv procedure (water:ethanol, H2SO4) carried out at 180°C for 1h. To identify the possible alterations in lignin structures several bulk and molecular level advanced characterization tools were employed. Even though lignins were extracted using common isolation procedure from three varieties of similar species of RH; from XRD, GPC, and elemental analysis it was found that those have comparable properties on bulk level. But molecular level analysis conducted using UV-vis, ATR, 1D/2D HSQC NMR techniques could help disclose that isolated lignins have varying concentrations of G, H, S and T substructures. Additionally, the double bond equivalence of 4.4-4.7 reveals that few of the aromatic rings are devoid of substituent.