Abstract: The invention provides a process for separating saturated and unsaturated carboxylic acids is described. The process includes providing a stream comprising same carbon number saturated and unsaturated carboxylic acids; contacting said stream with an extractive solvent in an extractive distillation unit, to produce a first stream comprising extractive solvent and unsaturated carboxylic acids and a second stream comprising saturated carboxylic acids, and feeding said first stream to a solvent recovery unit, to produce a third stream comprising unsaturated carboxylic acids and a fourth stream comprising extractive solvent. In some embodiments, the extractive solvent has a boiling point at atmospheric pressure that is at least 5° C. higher than the boiling point of the unsaturated carboxylic acid.