Dehydrogenative Coupling of Methanol for the Gas-Phase, One-Step Synthesis of Dimethoxymethane over Supported Copper Catalysts

Anh To, Trenton Wilke, Eric Nelson, Connor Nash, Andrew Bartling, Evan Wegener, Kinga Unocic, Susan Habas, Thomas Foust, Daniel Ruddy

Research output: Contribution to journalArticlepeer-review

20 Scopus Citations

Abstract

Oxymethylene dimethyl ethers (OMEs), CH3-(OCH2)n-OCH3, n = 1-5, possess attractive low-soot diesel fuel properties. Methanol is a key precursor in the production of OMEs, providing an opportunity to incorporate renewable carbon sources via gasification and methanol synthesis. The costly production of anhydrous formaldehyde in the typical process limits this option. In contrast, the direct production of OMEs via a dehydrogenative coupling (DHC) reaction, where formaldehyde is produced and consumed in a single reactor, may address this limitation. We report the gas-phase DHC reaction of methanol to dimethoxymethane (DMM), the simplest OME, with n = 1, over bifunctional metal-acid catalysts based on Cu. A Cu-zirconia-alumina (Cu/ZrAlO) catalyst achieved 40% of the DMM equilibrium-limited yield under remarkably mild conditions (200 °C, 1.7 atm). The performance of the Cu/ZrAlO catalyst was attributed to metallic Cu nanoparticles that enable dehydrogenation and a distribution of acid strengths on the ZrAlO support, which reduced the selectivity to dimethyl ether compared to a that obtained with a Cu/Al2O3 catalyst. The DMM formation rate of 6.1 h-1 compares favorably against well-studied oxidative DHC approaches over non-noble, mixed-metal oxide catalysts. The results reported here set the foundation for further development of the DHC route to OME production, rather than oxidative approaches.

Original languageAmerican English
Pages (from-to)12151-12160
Number of pages10
JournalACS Sustainable Chemistry and Engineering
Volume8
Issue number32
DOIs
StatePublished - 17 Aug 2020

Bibliographical note

Publisher Copyright:
Copyright © 2020 American Chemical Society.

NREL Publication Number

  • NREL/JA-5100-73470

Keywords

  • Dehydrogenative coupling
  • Dimethoxymethane
  • Methanol
  • OMEs
  • Oxymethylene dimethyl ethers
  • Supported copper catalysts

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