TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Process: The azeotrope agent comprises toluene, xylene, naphthalene, and/or benzene (preferably toluene). In the process (M1): the azeotropic distillation is carried out at a top column pressure below atmospheric pressure (preferably 10-750 mmHg), and at a bottom column temperature below 140 (preferably 30-130) degrees C. The azeotrope agent is derived from the water-depleted bio-oil stream. The process (M1) further involves, subsequent to step (B), recovering at least a portion of the azeotrope agent from an overhead phase separator of the azeotropic distillation column and recycling at least a portion of the recovered azeotrope agent for use in step (A). The water-rich overhead stream comprises at least 90 wt.% of the bound water, where the amount of the azeotrope agent combined in step (A) with the bio-oil comprising bound water is 1-60 wt.% of the bio-oil comprising bound water. The process further involves, subsequent to step (B), adding an amine to the water-depleted bio-oil stream. The process (M1) further involves prior to step (A), removing free water from the bio-oil comprising bound water. The viscosity of the water-depleted bio-oil stream is less than or equal to 400 centistokes greater than the viscosity of the bio-oil comprising bound water. The combining of step (A) takes place within the azeotropic distillation column (preferably upstream of the azeotropic distillation column). The azeotropic distillation column includes an overhead phase separator through which the recovered azeotrope agent is separated and withdrawn during the step of recovering at least a portion of the azeotrope agent. Preferred System: In the system (S1) the azeotropic distillation column comprises an overhead phase separator for recovering at least a portion of the azeotrope agent from the azeotropic distillation column and providing the recovered azeotropic agent to the azeotrope agent transport mechanism. EXAMPLE - A bio-oil was produced using fast pyrolysis in a riser reactor in the presence of a kaolin catalyst. Subsequent to condensing, the bio-oil had a bound water content of 9.99 wt.% after removal of the free water phase and had a total acid number (TAN) value of 110.14 mg KOH/g. The bio-oil (166 g) was subjected to azeotropic distillation in the presence of toluene (40.6 g) at a pressure of 210 mmHg and a maximum temperature of 105.3 degrees C. After azeotropic distillation, the bio-oil had a bound water content of 0.22 wt.%, a TAN value of 55.14 mg KOH/g, and was miscible with about 10 wt.% of toluene.