Cyclic distillation uses a periodic operation mode that leads to key benefits, such as increased column throughput, lower energy requirements and much higher separation performance. By integrating chemical reactions with cyclic distillation, a novel process intensification approach is possible - catalytic cyclic distillation - which outperforms classic reactive distillation. This paper is the first to describe the catalytic cyclic distillation process and to develop a rigorous mathematical model. By means of a case study involving a simple reaction system, the model is used to demonstrate the key benefits of this operation mode. In addition, the synthesis of dimethyl ether by catalytic cyclic distillation is considered, for which a design algorithm is suggested. Investigation of the column behavior reveals the coexistence of two periodic states, one of them being unstable. (C) 2014 Elsevier B.V. All rights reserved.