Catalytic Oxidative Dehydration of Butanol Isomers: 1-Butanol, 2-Butanol, and Isobutanol

Report No. ARL-TR-5721
Authors: Ivan C. Lee, Jeffrey G. St. Clair, and Adam S. Gamson
Date/Pages: September 2011; 34 pages
Abstract: The catalytic production of economically important four-carbon olefins was achieved through catalytic oxidative dehydration of 1-butanol, 2-butanol, and isobutanol using a millisecond contact time reactor. Both alumina foam and rhodium-alumina foam catalysts convert these four-carbon alcohols into four-carbon olefins, with contact time equal to 25 ms over a wide range of equivalence ratios (Φ) from 0.176 to 6.338 (or C/Oair ratio from 0.0659 to 2.11). The cracking of the carbon backbone was found to be minimal. A mixture of butene isomers was obtained due to the isomerization of the carbocation intermediates. The degree of this isomerization was determined by analyzing the ratios of butenes/(total olefins), 1-butene/2-butene, cis-2-butene/trans-2-butene, and isobutene/(linear butenes). In addition, a reaction mechanism of the catalytic oxidative dehydration of butanol in short contact times was proposed. In this mechanism, the C-O bond of the majority of butanol was broken to form olefinic species on the alumina surface. These surface olefinic species would undergo successive oxidation to form CO and/or CO2, depending on the availability of oxygen.
Distribution: Approved for public release
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Last Update / Reviewed: September 1, 2011