Operation of fixed-bed catalytic reactors undergoing catalyst deactivation has been investigated as an optimal control problem to yield optimal temperature policies. An efficient numerical scheme using a control Vector iteration method based on gradients in functional space is developed. The procedure is applied to develop optimal temperature profiles for a butadiene dimerization process. The temperature-time trajectories and dynamic activity profiles are strongly influenced by kinetics. A sensitivity analysis is done to study the effect of flow rates, conversion level and parameters that influence kinetic and deactivation processes. These results have been validated with experimentation on a lab scale reactor and a 9.14 m pilot-plant reactor.