Kinetic and Thermodynamic Evidence of the Paal-Knorr and Debus-Radziszewski Reactions Underlying Formation of Pyrroles and Imidazoles in Hydrothermal Liquefaction of Glucose-Glycine Mixtures

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dc.contributor.authorSudibyo, Hanifrahmawan
dc.contributor.authorBudhijanto, Budhijanto
dc.contributor.authorCabrera, Daniela V.
dc.contributor.authorMahannada, Aqiela
dc.contributor.authorMarbelia, Lisendra
dc.contributor.authorPrasetyo, Dwi Joko
dc.contributor.authorAnwar, Muslih
dc.date.accessioned2025-01-20T17:09:03Z
dc.date.available2025-01-20T17:09:03Z
dc.date.issued2024
dc.description.abstractWe evaluated Paal-Knorr and Debus-Radziszewski reactions as the mechanisms underlying formation of pyrroles and imidazoles, respectively, in hydrothermal liquefaction (HTL) via semicontinuous HTL experiments on a glucose-glycine mixture. We developed cheminformatic-based HTL reaction pathways for a range of feedstock pH (2-12), reaction temperatures (280-370 degrees C), and reaction times (2-60 min). The developed pathways were validated using transient concentration of the reacting compounds and assessed using reversible power-law kinetics, Arrhenius equation, and Maxwell relation for Gibbs free energy. The assessment informed the exothermicity of both proposed mechanisms and their activation under acidic conditions with (1) succinaldehyde and amino acid/ammonia and (2) alpha-dicarbonyls, formaldehyde, and amino acid/ammonia as precursors, respectively. Endothermic amidation and exothermic decarboxylation followed both reactions, producing amide- and alkyl-substituted pyrroles and imidazoles in biocrude and an aqueous-phase coproduct. Moreover, exothermic C-C coupling of pyrroles and a series of exothermic Wittig olefination and Hoesch reactions involving dicarboxylic acid of imidazole, fumaronitrile, and ylide precipitated polypyrrole and azepine- and azocine-embedded imidazole in hydrochar. Meanwhile, the HTL of neutral and alkaline feedstocks presented a transition from alkali-catalyzed (e.g., the endothermic Maillard reaction between pyruvaldehyde and amino acid/ammonia producing pyrazines and oxazoles) to acid-catalyzed (e.g., the Debus-Radziszewski reaction) mechanisms at reaction times longer than 10 min due to significant acetic acid formation from the decomposition of carbohydrate and protein monomers. This study proved that the HTL mechanism of formation of N-heterocycles varied with feedstock pH.
dc.description.funderInstrumental Analysis Lab in Chemical Engineering Department of Universitas Gadjah Mada for the analytical support through the department research grant
dc.fuente.origenWOS
dc.identifier.doi10.1021/acs.energyfuels.3c05051
dc.identifier.eissn1520-5029
dc.identifier.issn0887-0624
dc.identifier.urihttps://doi.org/10.1021/acs.energyfuels.3c05051
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/91008
dc.identifier.wosidWOS:001160856100001
dc.issue.numero4
dc.language.isoen
dc.pagina.final3356
dc.pagina.inicio3343
dc.revistaEnergy & fuels
dc.rightsacceso restringido
dc.titleKinetic and Thermodynamic Evidence of the Paal-Knorr and Debus-Radziszewski Reactions Underlying Formation of Pyrroles and Imidazoles in Hydrothermal Liquefaction of Glucose-Glycine Mixtures
dc.typeartículo
dc.volumen38
sipa.indexWOS
sipa.trazabilidadWOS;2025-01-12
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