In order to separate and purify the chlorinated cyclohexane in the multi-component mixture, a two-step rectification method is adopted. First carry out atmospheric pressure batch distillation of the mixed liquid, distill most of the cyclohexane, cyclohexene and a small amount of impurities, complete the rectification, and filter the column kettle liquid, and obtain the product, according to the purity of the product, and then vacuum rectification column liquid, directly distill the chlorocyclohexane. The influencing factors in the distillation process were investigated: pressure, reflux ratio, heating amount, and full reflux start time. Using the variable reflux ratio operation, the best experimental conditions obtained at the top of the tower are: heating voltage 160V, full reflux 30 min, variable reflux ratio 4.5~3~1.5.Operating conditions for purification of chlorocyclohexane: vacuum degree is 0.068~0.072 MPa, purity reaches 99.06%.