Azeotropic and Extractive Distillation for Bio-Ethanol Dehydration: Process Design, Simulation, and Cost Analysis

The global demand for sustainable fuels has intensified interest in bioethanol production. Conventional distillation is limited by the ethanol–water azeotrope at ~95.8 wt.% ethanol, necessitating alternative separation methods. This study presents a technical and economic comparison of bioethanol dehydration via azeotropic distillation using cyclopentane as a novel entrainer and extractive distillation with ethylene glycol. Steady-state simulations were conducted in AVEVA PRO/II v.2024 under identical feed conditions, targeting a final ethanol purity of 99.94 wt.%. Cyclopentane proved effective, producing high-purity ethanol and water streams free of entrainer, while ethylene glycol also achieved comparable purity. Economically, the azeotropic process required ~36.5% higher capital investment due to taller columns, larger condensers, and the entrainer cost, resulting in a total annual cost (TAC) ~25.6% higher than the extractive process. Nevertheless, the azeotropic configuration offers lower operating costs, relying solely on low-pressure steam, and residual cyclopentane in ethanol does not compromise fuel quality, unlike ethylene glycol. The study demonstrates that cyclopentane-based azeotropic distillation is technically viable for fuel-grade ethanol production and provides a quantitative framework for evaluating entrainer selection and process economics, particularly in regions where cyclopentane is available or cost-effective.