T here are several works analysing multiple solutions in ideal, azeotropic and/or reactive distillation columns. Jacobsen and Skogestadt (1991), Cairns and Furzer (1990), Bekiaris et al., (1993Bekiaris et al., ( , 1996, Gani and Jørgensen (1994), Hauan et al. (1995), Kienle and Marquardt (1991), Scenna (1997), andMohl et al. (1999), among others, have considered their origins, the hysteresis curve behaviour or the infl uence of different variables upon them. Jacobsen and Skogestad (1995) analysed the operability and instability of binary distillation column with multiple steady state output during continuous operation. They stated that hysteresis may be experienced during the actual operation. Furthermore, Kienle et al. (1995) and Koggersbøl et al. (1996) confi rmed the existence of multiple steady states in an experimental way when separating a binary mixture.As regard to azeotropic distillation operations, Güttinger et al. (1997) found two stable steady states caused by the vapour-liquid equilibrium for the ternary homogeneous methanol-methyl butyratetoluene system in an industrial pilot column. Besides, Dorn et al. (1998) verifi ed the existence of a third unstable steady state and studied the transient behavior of that azeotropic column. Also, Lee et al. (1999) found periodic oscillations and a limit cycle (sustained oscillations) while analysing the dynamic behaviour of the open-loop column. Bossen et al. (1993) found four steady states for the dehydration of ethanol with benzene by dynamic simulation. Moreover, by means of a dynamic experiment, Müller and Marquardt (1997) verifi ed both the existence of multiple steady states in a heterogeneous azeotropic distillation (ethanol dehydration with cyclohexane as entrainer) and the hysteresis behaviour due to multiple steady states. On the other hand, Chien et al. (1999) analysed the dynamic behaviour of another heterogeneous azeotropic column (isopropyl alcohol-cyclohexane-water). They found three branches of steady states. The lowest and highest solutions were stable and the intermediate one was unstable. Besides, a bifurcation analysis showed that different operating regions could be placed in an operating variable diagram (heat duty vs. refl ux). These operating zones of the column (and different steady states) were characterised by the ratios of entrainment to other components and their potential azeotropes. Chien et al. (1999) suggested a particular desirable start-up strategy, but they did not develop it. Later, Chien et al. (2000) developed a suitable operating procedure for reaching the desirable high-purity steady state. Gani and Jorgensen (1994) proposed that the displacement of the internal composition front could be the cause of the possible connection between multiplicity and operability. Here we will show that * Author to whom correspondence may be addressed. E-mail address: sbenz@frro.utn.edu.ar The operability of azeotropic distillation columns with multiplicity is analysed during start-up by dynamic simulation. Different steady states can...