A dynamic reactive distillation (RD) column model is developed for highly non-ideal systems with potential phase splitting. Dynamic simulations and non-linear dynamic analysis are performed for recovery of acetic acid from waste waters by esterification with n-butanol, which is an interesting alternative to non-reactive separation processes. Two alternative RD column designs were tested with respect to their open loop transient responses to process disturbances. One parameter continuation with eigenvalue calculations reveals existence of multiple steady states with stable and unstable branches. These steady states were found to have totally different phase splitting behavior of the original liquid phase inside the column. Conclusions are drawn for process operation. (C) 2008 Elsevier Ltd. All rights reserved.