To provide a method for co-producing cyclohexanol and cyclohexane by hydrogenating benzene, separating the products and hydrating cyclohexene, capable of profitably giving the by-produced cyclohexane in high purity without requiring a complicated separation treatment process and capable of reducing the load of a separation process such as an extractive distillation process without accumulating impurities in a large amount in the reaction system.

This method for co-producing cyclohexanol and cyclohexane comprises a process for partially hydrolyzing benzene, the first separation process, a hydration process, the second separation process, a circulation process and a hydrogenating purification process. The cyclohexene, the cyclohexane and the unreacted benzene obtained by the hydrogenation of the benzene are separated in the first separation process comprising an extractive distillation process. The separated cyclohexene is fed into the hydration process as a hydration raw material, and the separated unreacted benzene is recycled to the hydrogenation process. The cyclohexanol is produced in the hydration process and subsequently separated from the unreacted cyclohexene in a hydrogenating purification process. The unreacted cyclohexene is recycled to the hydrogenation process. In order to prevent the accumulation of impurities comprising methylcyclopentene compounds in the recycling system, a part of the impurities are extracted, concentrated in a distillation calumn and subsequently purged. The cyclohexane separated in the first separation process is hydrogenatingly purified in the presence of a hydrogenation catalyst to give the highly pure cyclohexane.