An approach, based purely on steady-state analyses, for synthesizing effective control structures for reactive distillation (RD) columns is presented. The main idea is to analyze the steady-state relationships between the manipulated (input) variables and the potential controlled (output) variables to identify input-output (IO) pairings that are sensitive and avoid steady-state multiplicities providing a large range of nearly linear operating region around the base case design. Traditional SISO control loops are then implemented using these IO pairings to obtain control structures that maintain the column near the design product purity and conversion for the anticipated primary disturbances. The Niederlinski Index is used to eliminate dynamically unstable pairings in control structures with multiple loops. The approach is demonstrated on an example MTBE RD column. The impact of steady-state multiplicities on control structure design is highlighted. (c) 2005 Elsevier Ltd. All rights reserved.