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    Role of sodium sulfate in electrical conductivity and structure of lignin-derived carbons
    (Elsevier BV, 2024-08) Kane, Seth; Hodge, David B.; Saulnier, Brian; Bécsy-Jakab, Villő Enikő; Dülger, Dilara N.; Ryan, Cecily
    Lignin is a promising renewable alternative to fossil fuels for producing carbon materials such as carbon fibers, activated carbons, or carbon black. Despite extensive research, lignin-derived carbon materials show limited graphitization relative to comparable petroleum-derived carbons. Further, lignin-derived carbons show high variation in graphitization and electrical conductivity depending on the source of the lignin. Herein, nine lignins, derived from various feedstocks and isolation procedures, are pyrolyzed to produce biochar at 1100∘C. These lignins have a range of chemical compositions, carbon structures, and particle sizes. As a result, the pyrolysis behavior of these lignins varies, with powdered, clumped powder, and “foam” biochar morphologies resulting from finely powdered lignin. The produced biochars vary widely in both electrical conductivity, from 0.19 to 19 S/cm, and in-plane graphitic crystallite size, from 3.4 to 41.2Å. A significant decrease in electrical conductivity is identified when Na2SO4 is removed from lignin, accompanied by an increase in graphitic crystallite size. Based on this finding, a quadratic relationship between biochar graphitic crystallite aspect ratio and electrical conductivity is proposed that builds on established quasi-percolation models for biochar electrical conductivity.
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    Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar
    (American Chemical Society, 2024-03) Dülger, Dilara N.; Yuan, Zhaoyang; Singh, Sandip K.; Omolabake, Surajudeen; Czarnecki, Celeste R.; Nikafshar, Saeid; Li, Mingfei; Bécsy-Jakab, Villő E.; Park, Seonghyun; Park, Sunkyu; Nejad, Mojgan; Stahl, Shannon S.; Hegg, Eric L.; Hodge, David B.
    A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goal of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O2 (O2-enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pretreatment oxidation (increasing H2O2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. Lignins recovered from the second-stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than 6-fold higher than a typical hardwood kraft lignin, indicating that these lignins could serve as a biobased polyol for a range of polyurethane applications.
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