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Issue 2, 2017
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Energetics of cellulose and cyclodextrin glycosidic bond cleavage

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Abstract

Thermochemical conversion of lignocellulosic materials for production of biofuels and renewable chemicals utilizes high temperature to thermally decompose long-chain cellulose to volatile organic compounds. Cellulose undergoes two distinct kinetic regimes of intra-chain scission: low-temperature glycosidic bond cleavage (T < 467 °C) associated with a low apparent activation energy and high-temperature glycosidic bond cleavage (T > 467 °C) associated with a high apparent activation energy. In this work, the initial breakdown kinetics of cellulose were examined from 385 °C to 505 °C using a millisecond, thin-film reactor called PHASR (pulse-heated analysis of solid/surface reactions). Using the cellulose surrogate, α-cyclodextrin, the energetics of each kinetic regime were characterized by measuring the conversion between 20 ms and 2.0 seconds. The low temperature kinetic regime exhibited glycosidic bond cleavage (Ea,1 = 23.2 ± 1.9 kcal mol−1, k0,1 = 2.0 × 107 s−1), while the high temperature kinetic regime (Ea,2 = 53.7 ± 1.1 kcal mol−1, k0,2 = 2.4 × 1016 s−1) was consistent with four reaction mechanisms including concerted transglycosylation. Apparent energetics were compared with computed literature values.

Graphical abstract: Energetics of cellulose and cyclodextrin glycosidic bond cleavage

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Publication details

The article was received on 28 Sep 2016, accepted on 06 Jan 2017 and first published on 06 Jan 2017


Article type: Paper
DOI: 10.1039/C6RE00176A
Citation: React. Chem. Eng., 2017,2, 201-214
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    Energetics of cellulose and cyclodextrin glycosidic bond cleavage

    C. Zhu, C. Krumm, G. G. Facas, M. Neurock and P. J. Dauenhauer, React. Chem. Eng., 2017, 2, 201
    DOI: 10.1039/C6RE00176A

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