This is the first of two papers on the simulation, analysis and optimization of a catalytic distillation process to produce methyl-tert-butyl-ether (MTBE) from methanol and isobutylene contained in a butylenes stream.In this paper, an MTBE catalytic distillation column was simulated using AspenPlus. The heat and material balance results compared very well with those from the literature. In addition, multiple steady states were also observed under conditions reported in the Literature. Further studies, performed to analyse the multiple steady states, revealed that the methanol-to-butylenes molar feed ratio is the main factor affecting the existence of single or multiple steady state. In addition, the molar feed ratio together with the methanol feed stage location determines if the reaction reaches equilibrium and consequently, if a high isobutylene conversion is attained. Adjusting either the methanol-to-butylenes molar feed ratio, the reflux ratio, or installing a cooler on the last reactive stage were all found to eliminate the multiple steady states and force the reaction to equilibrium.