Revealing pyrolysis chemistry for biofuels production: Conversion of cellulose to furans and small oxygenates

Matthew S. Mettler, Samir H. Mushrif, Alex D. Paulsen, Ashay D. Javadekar, Dionisios G. Vlachos, Paul J. Dauenhauer

Research output: Contribution to journalArticle

181 Scopus citations

Abstract

Biomass pyrolysis utilizes high temperatures to produce an economically renewable intermediate (pyrolysis oil) that can be integrated with the existing petroleum infrastructure to produce biofuels. The initial chemical reactions in pyrolysis convert solid biopolymers, such as cellulose (up to 60% of biomass), to a short-lived (less than 0.1 s) liquid phase, which subsequently reacts to produce volatile products. In this work, we develop a novel thin-film pyrolysis technique to overcome typical experimental limitations in biopolymer pyrolysis and identify α-cyclodextrin as an appropriate small-molecule surrogate of cellulose. Ab initio molecular dynamics simulations are performed with this surrogate to reveal the long-debated pathways of cellulose pyrolysis and indicate homolytic cleavage of glycosidic linkages and furan formation directly from cellulose without any small-molecule (e.g., glucose) intermediates. Our strategy combines novel experiments and first-principles simulations to allow detailed chemical mechanisms to be constructed for biomass pyrolysis and enable the optimization of next-generation biorefineries.

Original languageEnglish (US)
Pages (from-to)5414-5424
Number of pages11
JournalEnergy and Environmental Science
Volume5
Issue number1
DOIs
StatePublished - Jan 1 2012

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