Hydration of cyclohexene to cyclohexanol in a hybrid reactive distillation with a side decanter

Abstract

Nowadays, more than 1 Mt of cyclohexanol is produced each year by the direct hydration of cyclohexene according to the patented Asahi process proposed in 1990. The Asahi process involves a reactor and a separation system to recover the reactants back to the reactor and collect the pure product. The non-reacted water is recovered in a decanter and the non-reacted cyclohexene in a distillation column. Nowadays, many processes have been successfully intensified, combining several unit operations into a single unit providing savings in units, piping and often also in energy due to the synergies generated. Examples of these synergies are: the continuous removal of products push forward the reaction to total conversion overcoming the chemical equilibrium limitations; the catalyst placed in the rectifying section of the column becomes protected from heavy compounds that could poison or deactivate the catalyst; the enthalpy of reaction is directly used in the separation; the boiling point of the mixture avoids hot spots that could damage the catalyst, etc. Although its advantages, it is not widely used in the industry and further study on intensification providing further successful examples are required. The present study shows by rigorous simulation with Aspen Plus V9.0 that the Asahi process is a good candidate to be intensified in a single unit. The rigorous simulation results show that cyclohexanol is collected with a molar fraction purity of 0.9999 at the bottoms of a hybrid reactive distillation column with 11 equilibrium stages operated at total reflux, i.e. total conversion of reactants. The water is fed at the top to stage 1 and the cyclohexene on stage 3, both in equimolar flow rate. The catalyst is only placed in these three stages at the column top. A side stream from stage 6 is fed to a side decanter, where the aqueous phase is recycled to the column top (stage 1) and the organic phase to the next bottom stage, i.e. stage 7. As in the Asahi process, a great excess of water is present to push the reaction equilibrium forward. Hence, the molar ratio of water recycled vs feed to the system is of 125. The reboiler duty is 197 kJ/mol of cyclohexene, and the condenser duty is 564 kJ/mol cyclohexene due to the exothermic reaction. Therefore, a novel intensified process scheme for cyclohexene hydration is proposed.