The integration of reaction and separation in one single process unit proved to lead to enormous savings in capital as well as in operating costs. This paper provides a systematic framework to consider reactive separations in the early stages of process development. It highlights a process synthesis procedure guaranteeing that processes like reactive distillation, reactive crystallization, reactive extraction or reactive stripping will not be overlooked during conceptual flowsheet development. First step of this procedure is the analysis of the chemical reaction system. In case a separation of one or more products, by-products or solvents seems to be beneficial for the performance of the reactor the physical separation behavior of the components has to be checked. The chemical reaction, the physical separation and the design on the apparatus need a defined operation window. Only when an overlap of these windows can be identified a reactive separation process is feasible and might lead to advantages in the overall process performance. The paper finally demonstrates that the integration of reaction and separation in one unit does not necessarily lead to economic benefits as the overall performance of the total chemical process has to be considered. (C) 2003 Elsevier Science B.V. All rights reserved.