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  1. Storage-Induced Collapse of Lignin Macromolecular Structure and Its Impacts on the Biorefinery

    Lignin plays a vital role in the economics of biorefineries, serving as a source of process energy and a feedstock for sustainable fuels and chemical production. While understanding lignin’s chemical composition is crucial, emerging evidence suggests that a more comprehensive understanding of its macromolecular structure is critical to explaining its complex behavior in the biorefinery. This study investigated the collapse of the lignin network in corn stover feedstock after harvest and storage as a result of the microbial digestion of hemicellulose. Fluorescence microscopy was used to detect the collapse of lignin by the changes in lignin’s fluorescence lifetime, anisotropy, andmore » the number of effective emitters. Our in situ microscopic results revealed lignin’s coil–globule transition phenomena, which was only previously predicted by molecular dynamics modeling of extracted lignin in solvent. This collapse of lignin macromolecular structure was supported by results from NMR, IR, Raman, and powder X-ray diffraction. Our study revealed that the two major approaches for lignin valorization in the lignin-first biorefinery model, namely, monomer extraction and milled wood lignin extraction, were negatively impacted by the lignin collapse. As changes during storage are a source of feedstock variability, our study highlights the importance of understanding the effect of feedstock handling on biorefinery operations and economics.« less
  2. Integrated thermal and biological conversion of microalgal proteins to lipids

    Microalgal composition varies with cultivation strategy, and low-cost approaches often produce high-protein biomass. This presents challenges for biorefineries designed around static, lipid-rich feedstocks. In particular, hydrolysates from high-protein algae are nitrogen-rich and sugar-poor, limiting microbial conversion and reducing product yields. This study develops a sequential thermal conditioning and biological upgrading strategy to integrate high-protein hydrolysate processing within conventional lipid extraction and upgrading designs. Oxidative deconstruction was used to break down proteins into ammonium and short-chain carboxylates. Ammonium was subsequently removed to yield a nitrogen-depleted, carboxylate-rich medium suitable for microbial lipid production. Bioconversion trials with Cutaneotrichosporon oleaginosum showed lipid accumulation onlymore » from hydrolysates treated with both oxidative deconstruction and nitrogen removal, reaching 1.2 g/L lipids at 30 % intracellular content. This integrated approach enables protein-to-lipid conversion and improves flexibility to process variable algal feedstocks, advancing fuel-oriented microalgal biorefineries.« less
  3. Nutrient Recovery from Algae Using Mild Oxidative Treatment and Ion Exchange

  4. De-risking Pretreatment of Microalgae To Produce Fuels and Chemical Co-products

  5. Lignin alkaline oxidation using reversibly-soluble bases

    When excess base is required to drive desired reactions, such as in lignin alkaline oxidation, Sr(OH) 2 can offer a reversibly-soluble alternative to NaOH that allows simple recycle of the excess base with concomitant cost and environmental benefits.
  6. Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation

    Analysis of a promising lignin-first biorefining technique, reductive catalytic fractionation, provides useful metrics for cost and sustainability to guide researchers toward critical areas for improvement.
  7. Flow-through solvolysis enables production of native-like lignin from biomass

    Flow-through solvolysis offers an opportunity to limit lignin condensation reactions that prevent isolation of native lignin in biomass processing, thus allowing for the study of intrinsic lignin properties and steady-state lignin depolymerization.
  8. Integrated diesel production from lignocellulosic sugars via oleaginous yeast

    Oleaginous microbes are promising platform strains for the production of renewable diesel and fatty-acid derived chemicals given their capacity to produce high lipid yields.
  9. Revisiting alkaline aerobic lignin oxidation

    Lignin conversion to renewable chemicals is a promising means to improve the economic viability of lignocellulosic biorefineries. Alkaline aerobic oxidation of lignin has long been employed for production of aromatic compounds such as vanillin and syringaldehyde, but this approach primarily focuses on condensed substrates such as Kraft lignin and lignosulfonates. Conversely, emerging lignocellulosic biorefinery schemes enable the production of more native-like, reactive lignin. Here, we revisit alkaline aerobic oxidation of highly reactive lignin substrates to understand the impact of reaction conditions and catalyst choice on product yield and distribution. The oxidation of native poplar lignin was studied as a functionmore » of temperature, NaOH loading, reaction time, and oxygen partial pressure. Besides vanillin and syringaldehyde, other oxidation products include acetosyringone and vanillic, syringic, and p-hydroxybenzoic acids. Reactions with vanillin and syringaldehyde indicated that these compounds are further oxidized to non-aromatic carboxylic acids during alkaline aerobic oxidation, with syringaldehyde being substantially more reactive than vanillin. The production of phenolic compounds from lignin is favored by high NaOH loadings and temperatures, but short reaction times, as the products degrade rapidly, which is further exacerbated by the presence of oxygen. Under optimal conditions, a phenolic monomer yield of 30 wt% was obtained from poplar lignin. Testing a range of catalysts showed that Cu-containing catalysts, such as CuSO4 and LaMn0.8Cu0.2O3, accelerate product formation; specifically, the catalyst does not increase the maximum yield, but expands the operating window in which high product yields are obtainable. We also demonstrate that other native and isolated lignin substrates that are significantly chemically modified are effectively converted to phenolic compounds. Finally, alkaline aerobic oxidation of native lignins was compared to nitrobenzene oxidation and reductive catalytic fractionation, as these methods constitute suitable benchmarks for lignin depolymerization. While nitrobenzene oxidation achieved a somewhat higher yield, similar monomer yields were obtained through RCF and alkaline aerobic oxidation, especially for lignins with a high guaiacyl- and/or p-hydroxyphenyl-content, as syringyl units are more unstable during oxidation. Overall, this study highlights the potential for aerobic lignin oxidation revisited on native-like lignin substrates.« less
  10. Integrated conversion of 1-butanol to 1,3-butadiene

    1-Butanol is dehydrated to linear butenes in high yield, and the butenes are converted to 1,3-butadiene in high selectivity in a one-tube process.
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