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Design and Validation of a High-Throughput Reductive Catalytic Fractionation Method
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Number of Authors: 132024 (English)In: JACS Au, E-ISSN 2691-3704, Vol. 4, no 6, p. 2173-2187Article in journal (Refereed) Published
Abstract [en]

Reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from biomass, and bench-scale studies have enabled considerable progress in the past decade. RCF experiments are typically conducted in pressurized batch reactors with volumes ranging between 50 and 1000 mL, limiting the throughput of these experiments to one to six reactions per day for an individual researcher. Here, we report a high-throughput RCF (HTP-RCF) method in which batch RCF reactions are conducted in 1 mL wells machined directly into Hastelloy reactor plates. The plate reactors can seal high pressures produced by organic solvents by vertically stacking multiple reactor plates, leading to a compact and modular system capable of performing 240 reactions per experiment. Using this setup, we screened solvent mixtures and catalyst loadings for hydrogen-free RCF using 50 mg poplar and 0.5 mL reaction solvent. The system of 1:1 isopropanol/methanol showed optimal monomer yields and selectivity to 4-propyl substituted monomers, and validation reactions using 75 mL batch reactors produced identical monomer yields. To accommodate the low material loadings, we then developed a workup procedure for parallel filtration, washing, and drying of samples and a 1H nuclear magnetic resonance spectroscopy method to measure the RCF oil yield without performing liquid-liquid extraction. As a demonstration of this experimental pipeline, 50 unique switchgrass samples were screened in RCF reactions in the HTP-RCF system, revealing a wide range of monomer yields (21-36%), S/G ratios (0.41-0.93), and oil yields (40-75%). These results were successfully validated by repeating RCF reactions in 75 mL batch reactors for a subset of samples. We anticipate that this approach can be used to rapidly screen substrates, catalysts, and reaction conditions in high-pressure batch reactions with higher throughput than standard batch reactors.

Place, publisher, year, edition, pages
2024. Vol. 4, no 6, p. 2173-2187
Keywords [en]
high-throughput analysis, high-throughput reaction testing, lignin valorization, lignin-first biorefining, switchgrass
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-235506DOI: 10.1021/jacsau.4c00126Scopus ID: 2-s2.0-85195270885OAI: oai:DiVA.org:su-235506DiVA, id: diva2:1913604
Available from: 2024-11-15 Created: 2024-11-15 Last updated: 2024-11-15Bibliographically approved

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Kumaniaev, Ivan

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