A comprehensive technical feasibility study was conducted of a bioethanol demonstration plant with the aim of converting parts of an existing fuel-grade bioethanol production into a more valuable solvent-grade ethanol. The study focuses on the separation unit, which consists of three consecutive distillation columns and a dehydration step using molecular sieves. This separation unit did not permit sufficient removal of crotonaldehyde and methanol for obtaining solvent-grade ethanol. Therefore, an additional distillation column after the dehydration step was investigated by simulation. It is operated at subatmospheric pressure and enables simultaneous removal of methanol, crotonaldehyde, and water in the distillate. The distillate meets the fuel-grade ethanol specifications, while the bottom product meets the solvent-grade specifications. It enables around 70% solvent-grade ethanol production and employs a vacuum pump that is already used in the considered plant. A stationary operating point is characterized by online operational data and experimental results of liquid samples. Particular emphasis during the characterization is put on trace compounds. Ethanol and the following 13 trace compounds were analyzed experimentally: Acetaldehyde, 1-propanal, 1-butanal, crotonaldehyde, benzaldehyde, ethyl acetate, methanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-l-propanol, 2-methyl-l-butanol, and 3-methyl-1-butanol. A simulation platform was established and evaluated with excellent agreement compared to the operational data. The beer composition (separation unit feed) and a complete stream summary for the separation unit is provided.