Preparation of Tertiary Amyl Alcohol in a Reactive Distillation Column. 1. Reaction Kinetics, Chemical Equilibrium, and Mass-Transfer Issues

The hydration of isoamylenes to produce 2-methyl-2-butanol (tert-amyl alcohol, or TAA) is strongly limited by chemical equilibrium to olefin conversions of less than 50%. The general goal of this work was to determine whether reactive distillation would be a valid method to enhance the yield of TAA. The first step was to study the reaction kinetics and chemical equilibrium, using a polymeric acid catalyst (Amberlyst-15). Acetone was identified as a suitable medium to enable single liquid phase operation and also to enhance the reaction rate. It was found that the intraparticle mass-transfer resistance is negligible at temperatures below 70 °C. A kinetic expression, based on Langmuir−Hinshelwood formalism, is proposed. The forward and reverse reactions show first-order dependence on isoamylenes and TAA, respectively, while water is essentially an inhibitor of the reaction in both directions. The temperature effect on the forward reaction is quantified with an activation energy of 69.5 kJ/mol.