Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions: Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

David Robichaud, Tabitha Evans, Mark Nimlos, Calvin Mukarakate, Cong Liu, Lei Cheng, Rajeev Assary, Larry Curtiss

Research output: Contribution to journalArticlepeer-review

19 Scopus Citations

Abstract

Catalytic C-C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. The computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C-C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

Original languageAmerican English
Pages (from-to)24025-24035
Number of pages11
JournalJournal of Physical Chemistry C
Volume119
Issue number42
DOIs
StatePublished - 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

NREL Publication Number

  • NREL/JA-5100-65162

Keywords

  • biomass pyrolysis
  • computational modeling
  • zeolite

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