The impact of start-up procedures on the behaviour of simple distillation columns with multiple steady states is analyzed. A well-known system with hysteresis is studied in this paper and transient responses for a binary distillation column yielding, different steady states during the start-up operation are shown. Several dynamic simulation results showing an interesting behaviour are presented. Through the examination of the profile evolutions corresponding to given start-up policies, it can be seen how the column arrives to different steady, states. It is shown that it is possible to identify a set of critical values for the start-up supervision. Also, guidelines of general validity are achieved with the aim of finding the appropriate start-up policy to obtain the desired solution.