Affiliation:
1. Catalytica Advanced Technologies Inc., 430 Ferguson Drive, Mountain View, CA 94043, USA.
Abstract
Platinum catalysts are reported for the direct, low-temperature, oxidative conversion of methane to a methanol derivative at greater than 70 percent one-pass yield based on methane. The catalysts are platinum complexes derived from the bidiazine ligand family that are stable, active, and selective for the oxidation of a carbon-hydrogen bond of methane to produce methyl esters. Mechanistic studies show that platinum(II) is the most active oxidation state of platinum for reaction with methane, and are consistent with reaction proceeding through carbon-hydrogen bond activation of methane to generate a platinum-methyl intermediate that is oxidized to generate the methyl ester product.
Publisher
American Association for the Advancement of Science (AAAS)
Reference22 articles.
1. For developments in this area see Oil Gas J. 95 (no. 16) 16 (1997); U.S. Patents 4 833 170; 4 973 453; 4 686 238; 5 628 931; 5 658 497; 5 653 916; 5 639 401; 5 645 613; 5 621 155; 5 620 670; 5 543 437; 5 506 272; 5 504 118; 5 500 449; and 5 324 335.
2. The Mechanism of a C-H Bond Activation Reaction in Room-Temperature Alkane Solution
3. A. E. Shilov Activation of Saturated Hydrocarbons by Transition Metal Complexes (Reidel Dordrecht Netherlands 1984).
4. The oxidation of butane to maleic anhydride or acetic acid propane to acrylonitrile or isobutane to t -butyl hydroperoxide are atypical free-radical–based alkane autooxidation reactions that proceed in reasonable selectivities and yields (>10% per pass) because either the products are uniquely stable as in the case of maleic anhydride acetic acid and acrylonitrile or in the case of isobutane the reactivity of the tertiary C–H bond is significantly higher than those in the products.
5. The phrase “one-pass yield” is used to describe the yield of product generated without separation and recycle of the starting materials. This is analogous to the yield from a batch process. Conversion, selectivity, and yield are defined as %conversion≡ [CH4]initial−[CH4]final[CH4]initial×100 %selectivity to CH3OH≡ [CH3OH][CH4]initial–[CH4]final×100 %yield≡(%conversion)×(%selectivity) Periana R. A., et al., Science 259, 340 (1993); U.S. Patents 5,233,113 and 5,306,855.
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