We report an investigation of the continuous oxidative dehydrogenation of 4-vinylcyclohexene (VCH) in high pressure steam. Oxidative dehydrogenation reactions such as this are often limited by unselective or total oxidation. We find that these side-reactions not only occur in this case, but can also have a major influence on the selectivity; a small increase in flow rate results in a complete switch in selectivity of the reaction. Our results suggest that styrene (ST) is formed as the initial product but that unless the H2 is sequestered, ST may then be hydrogenated to yield ethylbenzene (EB).
The observation of periodic temperature spikes near the surface of the catalyst bed indicate cycles of propagating flames occur in a relatively small volume of the reactor, leading to total oxidation of some VCH and removal of O2, which would otherwise sequester the H2. These flames give rise to the large variations in the observed product selectivity. We suggest that these observations may not be restricted to this reaction system and reactor configuration, and may occur in other situations where small-scale continuous flow oxidation reactors are used.
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