| 1. |
- Aad, G., et al.
(author)
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- 2011
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swepub:Mat__t (peer-reviewed)
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| 2. |
- Bhalla, Aditya, et al.
(author)
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Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties
- 2019
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In: Biotechnology for Biofuels. - : BioMed Central (BMC). - 1754-6834. ; 12
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Journal article (peer-reviewed)abstract
- BackgroundIn 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, β-aryl ether content, and response to depolymerization by thioacidolysis.ResultsAll 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 β-aryl ether content. Key trends include a substantially higher polysaccharide content in the lignins recovered from the [Ch][Lys] pretreatment and high β-aryl ether contents and aromatic monomer yields from the Cu-AHP pretreatment. For all lignins, the 13C NMR-determined β-aryl ether content was shown to be correlated with the monomer yield with a second-order functionality.ConclusionsOverall, 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 β-aryl ether bonds, is shown to be detrimental to subsequent depolymerization.
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| 3. |
- Bär, Janosch, et al.
(author)
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Deconstruction of hybrid poplar to monomeric sugars and aromatics using ethanol organosolv fractionation
- 2018
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In: Biomass Conversion and Biorefinery. - : Springer. - 2190-6815 .- 2190-6823. ; 8:4, s. 813-824
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Journal article (peer-reviewed)abstract
- Acidic ethanol organosolv fractionation of hybrid poplar was investigated to determine the impact of pretreatment conditions on the resulting biomass and lignin properties and to assess the subsequent deconstruction of the cell wall biopolymers to monomeric sugars and aromatics. It was found that increasing reaction severity (i.e., time and temperature) during the organosolv fractionation increased the rate of delignification and xylan solubilization while the lignins recovered from the liquors were found to exhibit lower degrees of polymerization. Glucose hydrolysis yields > 75% at moderate enzyme loadings (30 mg/g glucan) could be obtained for the more severe pretreatment conditions. The lignins recovered from the pretreatment liquors were subjected to fractionation using a sequential extraction with solvents of increasing polarity. It was found that the low molar mass, low polydispersity lignins increased in pretreatment liquors with increasing time and temperature and were concentrated in the methanol fraction while a high molar mass fraction was extracted with the diethyl ether. We hypothesize that the extraction of the high molar mass fraction with diethyl ether is due to partial ethyl O-alkylation of lignin hydroxyl groups during pretreatment, rendering lignins more soluble in the non-polar solvent. Finally, depolymerization of unfractionated lignins by thioacidolysis resulted in mass yields of aromatic monomers ranging from 80 to 157 mg monomer per gram of lignin and that these yields exhibited strong positive correlations to the lignin β-O-4 content, molar mass, and strong negative correlations to the pretreatment temperature.
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| 4. |
- Crowe, Jacob D., et al.
(author)
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Identification of developmental stage and anatomical fraction contributions to cell wall recalcitrance in switchgrass
- 2017
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In: Biotechnology for Biofuels. - : BioMed Central. - 1754-6834. ; 10:1
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Journal article (peer-reviewed)abstract
- Background: Heterogeneity within herbaceous biomass can present important challenges for processing feedstocks to cellulosic biofuels. Alterations to cell wall composition and organization during plant growth represent major contributions to heterogeneity within a single species or cultivar. To address this challenge, the focus of this study was to characterize the relationship between composition and properties of the plant cell wall and cell wall response to deconstruction by NaOH pretreatment and enzymatic hydrolysis for anatomical fractions (stem internodes, leaf sheaths, and leaf blades) within switchgrass at various tissue maturities as assessed by differing internode. Results: Substantial differences in both cell wall composition and response to deconstruction were observed as a function of anatomical fraction and tissue maturity. Notably, lignin content increased with tissue maturity concurrently with decreasing ferulate content across all three anatomical fractions. Stem internodes exhibited the highest lignin content as well as the lowest hydrolysis yields, which were inversely correlated to lignin content. Confocal microscopy was used to demonstrate that removal of cell wall aromatics (i.e., lignins and hydroxycinnamates) by NaOH pretreatment was non-uniform across diverse cell types. Non-cellulosic polysaccharides were linked to differences in cell wall response to deconstruction in lower lignin fractions. Specifically, leaf sheath and leaf blade were found to have higher contents of substituted glucuronoarabinoxylans and pectic polysaccharides. Glycome profiling demonstrated that xylan and pectic polysaccharide extractability varied with stem internode maturity, with more mature internodes requiring harsher chemical extractions to remove comparable glycan abundances relative to less mature internodes. While enzymatic hydrolysis was performed on extractives-free biomass, extractible sugars (i.e., starch and sucrose) comprised a significant portion of total dry weight particularly in stem internodes, and may provide an opportunity for recovery during processing. Conclusions: Cell wall structural differences within a single plant can play a significant role in feedstock properties and have the potential to be exploited for improving biomass processability during a biorefining process. The results from this work demonstrate that cell wall lignin content, while generally exhibiting a negative correlation with enzymatic hydrolysis yields, is not the sole contributor to cell wall recalcitrance across diverse anatomical fractions within switchgrass
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| 5. |
- Phongpreecha, Thanaphong, et al.
(author)
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Predicting lignin depolymerization yields from quantifiable properties using fractionated biorefinery lignins
- 2017
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In: Green Chemistry. - : Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 19:21, s. 5131-5143
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Journal article (peer-reviewed)abstract
- Lignin depolymerization to aromatic monomers with high yields and selectivity is essential for the economic feasibility of many lignin-valorization strategies within integrated biorefining processes. Importantly, the quality and properties of the lignin source play an essential role in impacting the conversion chemistry, yet this relationship between lignin properties and lignin susceptibility to depolymerization is not well established. In this study, we quantitatively demonstrate how the detrimental effect of a pretreatment process on the properties of lignins, particularly β-O-4 content, limit high yields of aromatic monomers using three lignin depolymerization approaches: thioacidolysis, hydrogenolysis, and oxidation. Through pH-based fractionation of alkali-solubilized lignin from hybrid poplar, this study demonstrates that the properties of lignin, namely β-O-4 linkages, phenolic hydroxyl groups, molecular weight, and S/G ratios exhibit strong correlations with each other even after pretreatment. Furthermore, the differences in these properties lead to discernible trends in aromatic monomer yields using the three depolymerization techniques. Based on the interdependency of alkali lignin properties and its susceptibility to depolymerization, a model for the prediction of monomer yields was developed and validated for depolymerization by quantitative thioacidolysis. These results highlight the importance of the lignin properties for their suitability for an ether-cleaving depolymerization process, since the theoretical monomer yields grows as a second order function of the β-O-4 content. Therefore, this research encourages and provides a reference tool for future studies to identify new methods for lignin-first biomass pretreatment and lignin valorization that emphasize preservation of lignin qualities, apart from focusing on optimization of reaction conditions and catalyst selection.
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