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Dehydrogenative Coupling of Methanol for the Gas-Phase, One-Step Synthesis of Dimethoxymethane over Supported Copper Catalysts
journal contribution
posted on 2020-08-06, 22:22 authored by Anh The To, Trenton J. Wilke, Eric Nelson, Connor P. Nash, Andrew Bartling, Evan C. Wegener, Kinga A. Unocic, Susan E. Habas, Thomas D. Foust, Daniel A. RuddyOxymethylene
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.
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typical process limitsremarkably mild conditionspossess attractive lowmetal oxide catalystsdimethyl ether compareddimethoxy methane7 atm ).200 ° cdmm formation ratemetallic cu nanoparticlescatalyst achieved 403 sub2 sub1 – 5omes ), chphase dhc reactiondmm ),n dmm equilibriumstep synthesissingle reactorsimplest omeresults reportedoxidative approachesomes viamay addresslimited yieldkey precursorenable dehydrogenationdhc routedehydrogenative couplingcompares favorablyacid strengths1 h
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