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Hexachlorobenzene (HCB) was co-heated with SiO2/CaO in ampoules at temperature of 340℃ – 400℃.Influence of temperature,heating time and ratio of HCB/CaO on thermal-degradation pathways of HCB were investigated.Inorder to enhance gas-solid interface reaction,ultrafine CaO particles with large surface areas has also been employed.