Abstract: With the development of world economy,demand for clean energy,especially high purity hydrogen,is increasing rapidly.In chlor-alkali industry there are much byproduct hydrogen.A new process for the preparation of high purity hydrogen has been developed by separating and purifying byproduct hydrogen from chlor-alkali plants.Adsorbents with different properties were filled in classification to ensure that various impurity gases could be got rid of in one vessel at one time.Combination of temperature swing adsorption (TSA) and pressure swing adsorption (PSA) was adopted in regeneration process to optimize the regeneration effect of adsorbents.During the process of adsorbents regeneration,adsorbents were heated step by step,which not only guaranteed a good regeneration effect,but also reduced the consumption amount of regenerated gas.Experiment results showed a higher separation efficiency for bypdroduct hydrogen has been obtained by applying this new process and the purity of product hydrogen could reach more than 99.999% (volume fraction).