Aldol Condensation of Acetaldehyde over Titania, Hydroxyapatite, and Magnesia

The kinetics of aldol condensation of acetaldehyde were studied over anatase titania (TiO2), hydroxyapatite (HAP), and magnesia (MgO). Reactions were carried out in a fixed-bed reactor with a total system pressure of 220 kPa at temperatures between 533 and 633 K and acetaldehyde partial pressures between 0.05 and 50 kPa. Crotonaldehyde was the only product observed over all three catalysts, and severe catalyst deactivation occurred at acetaldehyde partial pressures of 5 kPa or greater. The aldol condensation reaction over all three catalysts was first order at low acetaldehyde partial pressure and approached zero order at high acetaldehyde partial pressure. No kinetic isotope effect (KIE) was observed with fully deuterated acetaldehyde reacting over TiO2 or HAP, implying that C–H bond activation is not kinetically relevant. These measurements are consistent with a mechanism in which adsorption and desorption steps are kinetically significant during the reaction. Characterization of the catalysts by adsorption microcalorimetry of acetaldehyde and ethanol and diffuse reflectance Fourier transform infrared spectroscopy of adsorbed acetaldehyde, crotonaldehyde, and acetic acid revealed a very high reactivity of these catalysts, even at low temperatures.