Catalytic oxidation of HCl to Cl2 is very important to efficient recycling of chlorine. In this paper, temperature-programmed analysis technology (TPAT) was used to study the adsorption of HCl and release of Cl2 on 14 different metal oxides. The reaction mechanisms of metal oxides and HCl、residual chlorine after reaction and thermodynamic data were explored by using XRD、XPS and Gaussian 03 program. It is significant to the development of the reaction catalyst and process. The results showed that CoO has a better absorption of HCl(absorption rate:85.4%) and release of Cl2(release rate:85.2%). Residual chlorine after reaction was 12.8% and CoO was still better during much recycled use. Therefore CoO was the optimal catalyst in the two-step catalytic oxidative reaction of HCl to Cl2. In the temperature range studied, chlorination reaction was exothermic、spontaneous and irreversible. Oxidation reaction was the opposite.
