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Title: Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

Abstract

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways,more » which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.« less

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1426220
Grant/Contract Number:  
AC02-06CH11357; AR0000433
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 551; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; Catalysis; Methane; Materials for energy and catalysis

Citation Formats

Shan, Junjun, Li, Mengwei, Allard, Lawrence F., Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts. United States: N. p., 2017. Web. doi:10.1038/nature24640.
Shan, Junjun, Li, Mengwei, Allard, Lawrence F., Lee, Sungsik, & Flytzani-Stephanopoulos, Maria. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts. United States. doi:10.1038/nature24640.
Shan, Junjun, Li, Mengwei, Allard, Lawrence F., Lee, Sungsik, and Flytzani-Stephanopoulos, Maria. Thu . "Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts". United States. doi:10.1038/nature24640. https://www.osti.gov/servlets/purl/1426220.
@article{osti_1426220,
title = {Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts},
author = {Shan, Junjun and Li, Mengwei and Allard, Lawrence F. and Lee, Sungsik and Flytzani-Stephanopoulos, Maria},
abstractNote = {An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.},
doi = {10.1038/nature24640},
journal = {Nature (London)},
number = ,
volume = 551,
place = {United States},
year = {2017},
month = {11}
}

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