Development of novel hybrid pre-separation/extractive reactive distillation processes for the separation of methanol/methyl acetate/ethyl acetate.

[Display omitted] • Propose three reactive distillation-based processes to separate Serafimov's class 2.0–2b mixtures containing methanol/methyl acetate. • Methyl acetate transesterification eliminates methyl acetate and coproduces high-value products. • Integrate extractive/pre-separation distillation and reactive distillation. • Two-column pre-separation-reactive distillation is preferred. • Use parallel genetic algorithms to optimize processes. The treatment of waste streams is an important research topic for the sustainable development of chemical process. Recently, reactive distillation-based (RD) processes with ethylene oxide hydrolysis have been developed to separate water-containing azeotropic mixtures. To separate Serafimov's class 2.0–2b mixtures containing methanol/methyl acetate, a methyl acetate transesterification reaction between propylene glycol monomethyl ether is introduced to convert methyl acetate to methanol and coproduce produce propylene glycol monomethyl ether acetate as advanced solvents. Three-column reactive-extractive distillation (TCRED) and extractive-reactive distillation (TCERD), and double-column pre-separation-reactive distillation (DCPSRD) processes, are proposed. Then, we use a parallel genetic algorithm to optimize processes to maximize total net revenue. The case study is methanol/methyl acetate/ethyl acetate. Though TCRED is not suitable due to the occurrence of ethyl acetate transesterification reactions, to compare economic performances of three RD-based processes, TCRED is regarded as a pseudo process. The total net revenue of three RD-based processes is relatively larger than (∼20 % increase) that of the conventional extractive distillation process. Compared with TCRED process, TCERD and DCPSRD can achieve $582336 and $1045995 increase in TNR, 27.43 % and 49.99 % TAC reduction, respectively. In summary, proposed RD-based processes are promising to separate Serafimov's class 2.0–2b mixtures containing methanol/methyl acetate, especially TCRED and DCPSRD. [ABSTRACT FROM AUTHOR]