Recovery of caprolactam from waste water of caprolactam production factory was investigated using benzene as solvent in a small-scale pulsed-sieve-plate column. First, liquid-liquid equilibrium (LLE) data were measured, including water-caprolactam-benzene system at low caprolactam concentrations, and waste water-benzene system. Then, the operating regions and mass transfer of the pulsed-sieve-plate column were measured. Finally, the overall apparent heights of a transfer unit based on continuous phase are correlated in terms of the column operation variables.