A rigorous structural design procedure for fully thermally coupled distillation columns (FTCDC) is applied to the example system of butanol isomers in order to show the design performance. The procedure gives structural information of the column, and therefore iterative computation encountered in the design using conventional procedure and commercial packages can be eliminated. Using the outcome of the structural design, other topics, such as thermodynamic efficiency, dividing wall column structure and the arrangement of interlinking streams, are investigated. Finally, a 3 x 3 operation scheme, which has favorable indices of multivariable controllability, is examined by checking the control performances of set-point tracking and regulation with a model predictive control.