To economically and advantageously fractionate and purify the subject mixture with a good separation efficiency under mild conditions by recycling and extracting the aromatic polyamine mixture in the multi-stage extraction in a two-phase system comprising a specific solvent phase and an aqueous phase according to the countercurrent principle and then distilling the organic phase in the multi-stage distillation.

An aromatic polyamine mixture is mixed with a two-phase system comprising a hydrophobic solvent phase consisting of (A1) a hydrophobic solvent and, as necessary, (A2) an aromatic auxiliary amine and (A3) a polyamine and an aqueous phase consisting of water, a strong acid, the component A2 and, as necessary, the component A3 to carry out a first extraction according to the countercurrent principle and provide a first aqueous phase and a first organic phase. The resultant first organic phase is then distilled in a first multi-stage distillation to afford respective fractions consisting essentially of the components A1 to A3. The first aqueous phase is extracted with a solvent phase consisting of the components A1 and A2 in a second extraction to provide a second aqueous phase and a second organic phase. The second organic phase is then distilled to provide a first distillate consisting of the components A1 and A2 and a distillation residue consisting of the fraction of the component A3. The second aqueous phase is recycled to the first aqueous phase and the first ciistillate is combined with the fraction consisting essentially recycled to the first aqueous phase and the first distillate is combined with the fraction consisting essentially of the component A3 obtained in the multi-stage distillation of the first organic phase to form the solvent phase, which is fractionated and purified.