Vacuum fractional distillation (VFD) is an efficient and environmentally friendly method for the separation and purification of thermally unstable and oxidizable bioactive compounds from essential oils through a virtually solvent-free process. This review highlights the importance of essential oil fractionation to meet the growing demands in the fragrance, cosmetic, food, and pharmaceutical industries. Fundamental principles and thermodynamics are summarized alongside VFD modeling, enabling prediction of phase behavior, column performance, hydrodynamics, and residence times, while reducing development time and scale-up risk. Published simulation and experimental studies are synthesized to define key influencing factors and practical operating windows for VFD performance. In addition, the review also identifies persistent data gaps, including non-standardized reporting practices, limited vacuum vapor-liquid equilibrium (VLE) data for key binary systems, and insufficient pilot-scale studies, which currently constrain reproducible research transfer and broader industrial implementation.
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