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Background Here we analysed the possibility of improving the sustainability performance for the recovery of dichloromethane and methanol from a binary azeotropic mixture using different energy‐intensified extractive distillation‐based processes: side‐stream extractive distillation (SSED), thermally coupled extractive distillation (TCED), and extractive dividing wall column (EDWC). The sustainability performance of the different processes was analysed based on three main factors: total annual cost (TAC), CO2 emissions, and condition number. Results The EDWC was found to give the best improvement in terms of TAC and CO2 emissions by about 18% and 21%, relative to conventional extractive distillation (CED). These however were traded‐off by the increase in conditional number (CN) by 186 times, signifying a complex dynamic characteristic for the EDWC. Thus, the SSED was suggested as an alternative sustainable option as it also provides significant improvement in TAC and CO2 emissions by about 11%, and 18% with respect to the CED, whilst providing the least reduction in operational controllability, as evidenced by the marginal increase in the CN of about 1.5 times. We also investigated the dynamic performance of the SSED and found that the SSED provides identical dynamic performance in handling both ±10% throughput and ±5% feed composition disturbances as those of the CED. Conclusion Among the different processes, SSED is the best sustainable alternative that provides compromised steady‐state (i.e. TAC and CO2 emissions) and dynamic (i.e. control) performance for the recovery of dichloromethane and methanol. © 2022 Society of Chemical Industry (SCI).

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The reactive-extractive distillation (RED) has the advantages of combining the beneficial features of both reaction and separation processes. Relative to the conventional reactive or extractive distillation-based processes, the RED is also less energy intensive as it relies on the reaction heat produced for the subsequent separation process. Therefore, the application of RED for ternary azeotropic separation has become the subject of popular interest, as evident by the increasing number of publications since 2020. This review paper is the first that puts together, in a chronological manner, all the existing studies on the RED to date, starting from the initial three column reactive-extractive distillation (TCRED) to the most recent dividing wall reactive-extractive distillation (DW-RED), for ternary azeotropic separation, so that the rapid progress in this area is summarised and any existing gaps in these studies become easier to identify for future work. The last part of this review provides three potential areas for future work, i.e. analysis of the sustainability of RED, combination of different process intensification strategies to improve the energy efficiency and separation performance, and further exploration on the control studies for the RED.