水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响

Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction

  • 摘要: 以硝酸盐为铈、锆原料,以柠檬酸代替碱类沉淀剂,固定n(Zr∶Ce)为2∶8,采用水热法合成Ce-Zr氧化物载体,再通过浸渍法制备Cu/Ce-Zr催化剂。通过XRD、BET、H2-TPR、XPS等手段对载体和催化剂进行表征,研究水热时间对催化剂结构、性质和水气变换反应性能的影响。结果表明,催化活性主要与Cu比表面积、CuO的还原温度以及催化剂表面氧空位含量有关。其中,Cu/Ce-Zr-12催化剂的Cu比表面积较大、CuO的还原温度较低,催化剂表面的氧空位数量较多,表现出较好的催化活性。在320 ℃、水气比(WM)为2,体积空速GHSV=6600 h−1的反应条件下,CO转化率为96.9%,与热力学平衡值97.1%接近。

     

    Abstract: Ce-Zr oxide support was hydrothermally synthesized from metal nitrates of cerium and zirconium as the raw materials using citric acid instead of alkali precipitant, and then Cu/Ce-Zr catalyst was prepared by the impregnation method. The support and catalyst samples were characterized by XRD, BET, H2-TPR, XPS techniques, and the effects of different hydrothermal time on the structure, properties and performance in water-gas shift reaction were investigated. The results show that the catalyst activity is mainly related to the Cu specific surface area, reduction temperature of CuO and the number of oxygen vacancies on the catalyst surface. Among them, the Cu/Ce-Zr catalyst with hydrothermal time of 12 h has a large Cu specific surface area, a lower reduction temperature of CuO, and a large number of oxygen vacancies, so it shows a good catalytic activity. When the reaction temperature is 320 ℃, the molar ratio of water to gas (W/M) is 2, and the gas space velocity GHSV=6600 h−1, the CO conversion rate is 96.9%, which is close to the thermodynamic equilibrium value of 97.1%.

     

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