CoMoS_x/γ-Al_2O_3催化剂在还原脱硫中的吸附性能和催化活性  

Adsorption Properties and Catalytic Activity of CoMoS_x/γ-Al_2O_3 Catalysts in Reduction Desulfurization

作　　者：刘哲男 耿云峰 石泉 黎汉生 史大昕 吴芹 赵芸 冯彩虹 矫庆泽 LIU Zhe-Nan;GENG Yun -Feng;SHI Quan;LI Han-Sheng;SHI Da-Xin;WU Qin;ZHAO Yun;FENG Cai-Hong;JIAO Qing-Ze(School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China;Beijing Peking University Pioneer Technology Co., Ltd, Beijing 100080, China;School of Chemical Engineering and Materials Science, Beijing Institute of Technology, Zhuhai, Guangdong 519085, China)

机构地区：[1]北京理工大学化学与化工学院,北京100081 [2]北京北大先锋科技有限公司,北京100080 [3]北京理工大学珠海学院化工与材料学院,珠海519085

出　　处：《无机化学学报》2019年第1期34-42,共9页Chinese Journal of Inorganic Chemistry

摘　　要：以等体积浸渍法与原位还原硫化法相结合制备了CoMoS_x/γ-Al_2O_3催化剂。采用X射线衍射(XRD)、扫面电子显微镜/能谱(SEM/EDS)、X射线光电子能谱(XPS)、程序升温脱附/程序升温还原/程序升温表面反应-质谱分析(TPD/TPR/TPSR-MS)对催化剂进行了表征,系统地研究了CoMoS_x/γ-Al_2O_3催化剂的结构、表面CO和SO_2的吸附-脱附行为及其表面反应特性。采用微型固定床反应器评价了CoMoS_x/γ-Al_2O_3催化剂的催化特性。研究表明,CoMoS_x/γ-Al_2O_3催化剂由γ-Al_2O_3和高分散的Co-Mo-S组成,预硫化过程中不会出现CoS_2和Co_9S_8等硫化物。γ-Al_2O_3几乎不会吸附CO,CoMoS_x对CO具有强吸附作用;而γ-Al_2O_3和CoMoS_x都可以吸附SO_2,但γ-Al_2O_3的吸附作用较弱,CoMoS_x的吸附作用较强。在γ-Al_2O_3上会吸附微量的COS,而CoMoS_x不会吸附COS。在SO_2与CO的表面反应中,吸附在CoMoS_x上的SO_2会与CO发生反应,而吸附在γ-Al_2O_3上的SO_2不会发生反应。在400℃时,SO_2的转化率和硫单质的选择性都接近100%。CoMoSx/γ-Al2O3 catalyst was prepared by using an impregnation method combining with in-situ reduction method. In order to systematically obtain the structure of the CoMoSx /γ-Al2O3 catalyst and study the adsorption-desorption performance and the surface reactions of CO and SO2, the catalyst was characterized using X-ray diffraction (XRD), scanning electron microscope/energy dispersive spectrdmeter (SEM/EDS), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption/programmed temperature reduction/temperature progra-mmed surface reaction-mass spectrometry (TPD/TPR/TPSR-MS). The catalytic performances of the CoMoSx/γ-Al2O3 catalyst were tested in a packed-bed microreactor. The results show that the CoMoSx/γ-Al2O3 catalyst was composed of γ-Al2O3 and highly dispersed Co-Mo-S. During the pre-vulcanization, no sulfides such as CoS2 and Co9S8 were formed. CO was adsorbed on CoMoSx instead of γ-Al2O3. SO2 was weakly adsorbed on γ-Al2O3 but strongly adsorbed on CoMoSx. COS was adsorbed on γ-Al2O3 with a small amount, but not adsorbed on CoMoSxFurthermore, SO2 adsorbed on CoMoSx was active and reacted with CO adsorbed on CoMoSx, while SO2 adsorbed on γ-Al2O3 did not react. Finally, the conversion of SO2 and the selectivity of sulfur were obtained up to 100% at 400 ℃.

关 键 词：还原脱硫 一氧化碳 二氧化硫 钴 钼 氧化铝 吸附 

分 类 号：O647[理学—物理化学]