Theoretical Insights on the Fragmentation of Cellulosic Oligomers to Form Hydroxyacetone and Hydroxyacetaldehyde

Denson, Melba Domes; Terell, Evan; Kostetskyy, Pavlo; Broadbelt, Linda; Olarte, Mariefel; Garcia-Perez, Manuel

doi:10.1021/acs.energyfuels.3c01924

Title: Theoretical Insights on the Fragmentation of Cellulosic Oligomers to Form Hydroxyacetone and Hydroxyacetaldehyde

Journal Article · 01 September 2023 · Energy and Fuels

DOI: https://doi.org/10.1021/acs.energyfuels.3c01924 · OSTI ID:2332944

Denson, Melba Domes ^[1];

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Washington State Univ., Pullman, WA (United States); Central Luzon State Univ., Munoz (Philippines)
US Dept. of Agriculture (USDA), New Orleans, LA (United States). Agricultural Research Service (ARS), Southern Regional Research Center
Northwestern Univ., Evanston, IL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Washington State Univ., Pullman, WA (United States)

The presence of heavy unknown oligomeric sugar products in bio-oil is evidenced in experimental results reported in the literature. In this paper, we study the fragmentation reactions yielding acetol and glycolaldehyde from oligomeric sugars following previous work on dehydration reactions to propose structures of these oligomers. Acetol and glycolaldehyde are primary products of cellulose fast pyrolysis but the fragmentation reaction mechanism of these compounds from oligomers merits further study. The density functional theory (DFT) approach was employed to study this reaction. Results revealed that acetol and glycolaldehyde fragments are favorably removed from the non-reducing end based on their thermodynamic stabilities. Theoretical FTIR and NMR spectra were calculated to aid in understanding the structures of the oligomeric sugars. Also, the thermodynamics and physical properties of these compounds were estimated using the Group Contribution Method (GCM). In conclusion, these properties are essential in the design of processing technologies and the upgrading of products.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Dept. of Agriculture (USDA); USDOE

Grant/Contract Number:: AC05-76RL01830; EE0008505

OSTI ID:: 2332944

Report Number(s):: PNNL-SA--181688

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 18 Vol. 37; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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