Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts

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. Ruddy

doi:10.1021/acssuschemeng.0c03606

Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts

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. Ruddy

Materials MicroAnalysis

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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 language	English
Pages (from-to)	12151-12160
Number of pages	10
Journal	ACS Sustainable Chemistry and Engineering
Volume	8
Issue number	32
DOIs	https://doi.org/10.1021/acssuschemeng.0c03606
State	Published - Aug 17 2020

Funding

This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, in part by Argonne National Laboratory, operated by The University of Chicago, and in part by Oak Ridge National Laboratory, operated by UT-Battelle, LLC, for the U.S. Department of Energy (DOE) under Contract Nos. DE-AC36-08GO28308, DE-AC02-06CH11357, and DEAC05- 00OR22725, respectively. A portion of this research was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies and Vehicle Technologies Offices. Co-Optima is a collaborative project of several national laboratories initiated to simultaneously accelerate the introduction of affordable, scalable, and sustainable biofuels and high-efficiency, low-emission vehicle engines. Part of this research was conducted in collaboration with the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Energy Materials Network (EMN). This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DEAC02- 06CH11357. MRCAT operations were supported by the DOE and the MRCAT member institutions. The microscopy was performed as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE Office of Science User Facility. The views expressed in this article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, in part by Argonne National Laboratory, operated by The University of Chicago, and in part by Oak Ridge National Laboratory, operated by UT-Battelle, LLC, for the U.S. Department of Energy (DOE) under Contract Nos. DE-AC36-08GO28308, DE-AC02-06CH11357, and DE-AC05-00OR22725, respectively. A portion of this research was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) project sponsored by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies and Vehicle Technologies Offices. Co-Optima is a collaborative project of several national laboratories initiated to simultaneously accelerate the introduction of affordable, scalable, and sustainable biofuels and high-efficiency, low-emission vehicle engines. Part of this research was conducted in collaboration with the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Energy Materials Network (EMN). This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. MRCAT operations were supported by the DOE and the MRCAT member institutions. The microscopy was performed as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE Office of Science User Facility. The views expressed in this article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

Funders	Funder number
Chemical Catalysis for Bioenergy
Co-Optimization of Fuels & Engines
Energy Materials Network
Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies
U.S. Government
U.S. Department of Energy	DE-AC05-00OR22725, DE-AC36-08GO28308
Office of Science	DE-AC02-06CH11357
Argonne National Laboratory
Oak Ridge National Laboratory
National Renewable Energy Laboratory
University of Chicago

Keywords

Dehydrogenative coupling
Dimethoxymethane
Methanol
OMEs
Oxymethylene dimethyl ethers
Supported copper catalysts

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10.1021/acssuschemeng.0c03606

Cite this

To, A. T., Wilke, T. J., Nelson, E., Nash, C. P., Bartling, A., Wegener, E. C., Unocic, K. A., Habas, S. E., Foust, T. D., & Ruddy, D. A. (2020). Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts. ACS Sustainable Chemistry and Engineering, 8(32), 12151-12160. https://doi.org/10.1021/acssuschemeng.0c03606

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title = "Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts",

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.",

keywords = "Dehydrogenative coupling, Dimethoxymethane, Methanol, OMEs, Oxymethylene dimethyl ethers, Supported copper catalysts",

author = "To, {Anh The} and Wilke, {Trenton J.} and Eric Nelson and Nash, {Connor P.} and Andrew Bartling and Wegener, {Evan C.} and Unocic, {Kinga A.} and Habas, {Susan E.} and Foust, {Thomas D.} and Ruddy, {Daniel A.}",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = aug,

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doi = "10.1021/acssuschemeng.0c03606",

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T1 - Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts

AU - To, Anh The

AU - Wilke, Trenton J.

AU - Nelson, Eric

AU - Nash, Connor P.

AU - Bartling, Andrew

AU - Wegener, Evan C.

AU - Unocic, Kinga A.

AU - Habas, Susan E.

AU - Foust, Thomas D.

AU - Ruddy, Daniel A.

PY - 2020/8/17

Y1 - 2020/8/17

N2 - 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.

AB - 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.

KW - Dehydrogenative coupling

KW - Dimethoxymethane

KW - Methanol

KW - OMEs

KW - Oxymethylene dimethyl ethers

KW - Supported copper catalysts

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DO - 10.1021/acssuschemeng.0c03606

M3 - Article

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SN - 2168-0485

VL - 8

SP - 12151

EP - 12160

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 32

ER -

Dehydrogenative coupling of methanol for the gas-phase, one-step synthesis of dimethoxymethane over supported copper catalysts

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