Abstract
The hydrogenation of ethyl butyrate, n-butyric acid, and n-butyraldehyde to their corresponding alcohol(s) has been studied over a γ-Al 2O 3-supported cobalt catalyst using a high-pressure fixed-bed reactor in the temperature range of 473–493 K. H 2–D 2–H 2 switching experiments show that ethyl butyrate and n-butyric acid follow an inverse kinetic isotope effect (KIE) (i.e. r H / r D = 0.50–0.54), whereas n-butyraldehyde did not display any KIE (i.e. r H / r D = 0.98). DRIFTS experiments were performed over the support and catalyst to monitor the surface species formed during the adsorption of ethyl butyrate and n-butyric acid at atmospheric pressure and the desired temperature. Butanoate and butanoyl species are the stable surface intermediates formed during hydrogenation of ethyl butyrate. Hydrogenation of butanoate to a partially hydrogenated intermediate is likely involved in the rate-determining step of ethyl butyrate and butyric acid hydrogenation.
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