Abstract

The selection of feasible solvent is of great significance for separating azeotropes via extractive distillation since various solvents can cause different product orders, flowsheet structures, and eco-efficiencies of extractive distillation processes. Limited efforts are focused on the effect of various solvents on the separation of ternary mixtures embedding two azeotropes, especially for the design of the extractive dividing-wall column separation configurations. To fill the research gap, the separation of azeotropic mixtures embedding two azeotropes is investigated using extractive distillation method with various solvents through taking the methyl acetate/ethyl acetate/methanol mixture as an example. First, the theoretical thermodynamic feasibility of four solvents including ethylene glycol, dimethyl sulfoxide, chlorobenzene, and aniline is explored. The individual light-heavy component orders are determined through the thermodynamic insights including the construction of the pseudo binary vapor–liquid phase equilibrium diagrams and overall phase diagrams with residue curves and iso-volatility curves after adding solvents, while are further verified using σ-profiles from microscopic mechanism. Second, the conceptual design of the extractive distillation flowsheets including conventional extractive distillation and extractive dividing-wall column separation configurations with individual solvents is performed. The effects of various solvents on the flowsheet structures and product orders are analyzed. Afterwards, the extractive distillation flowsheets are simulated and optimized economically to minimize the total annual costs through the genetic algorithm, except for the solvent ethylene glycol due to the unfeasibility of realistic simulation. The eco-efficiency analysis is performed via quantifying the Eco-Indicator 99 and thermodynamic performances as well as economic costs. The results indicate that the extractive distillation processes with dimethyl sulfoxide or chlorobenzene as solvent can show a certain degree of advantage compared with that using aniline as solvent in terms of eco-efficiency. The optimal separation configuration is the extractive dividing-wall column containing two dividing-walls with CB as solvent, and its Eco-efficiency Comparison Index increased to 80.54% compared to the worst scheme that is the extractive dividing-wall column containing one dividing-wall with AN as solvent.

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