水热合成温度对CuO/CeO2催化甲醇水蒸气重整制氢性能的影响

Effects of hydrothermal reaction temperatures on the performance of CuO/CeO2 catalyst for hydrogen production from steam reforming methanol

  • 摘要: 以Ce(NO3)3·6H2O为铈源,尿素为沉淀剂,采用水热法制备纳米CeO2载体,并通过改变水热合成温度来控制CeO2载体的微观结构,再通过等体积浸渍法制得CuO/CeO2催化材料,并将其应用在甲醇水蒸气重整制氢反应(MSR)中进行性能评价。通过低温N2吸附-脱附、XRD、H2-TPR、XPS等表征,探究了不同水热合成温度对纳米CeO2载体的微观结构、CuO/CeO2催化材料结构和甲醇水蒸气重整制氢反应性能的影响。结果表明,在水热合成温度为180 ℃条件下制备的纳米CeO2载体具有立方萤石结构,且负载CuO后制备的CuO/CeO2催化材料中表相CuO的还原温度较低、Cu-Ce间的相互作用较强、催化材料表面氧空穴较多,因此,表现出较好的催化活性。当反应温度为280 ℃,水醇物质的量比(W/M)为1.2,甲醇水蒸气气体空速(GHSV)为800 h− 1时,甲醇转化率可达到91.0%,重整气中CO摩尔分数为1.29%。

     

    Abstract: Using cerium nitrate as the source material and urea as the precipitant, nanometer CeO2 carrier was prepared by hydrothermal method, and the microstructure of CeO2 carrier was controlled by changing the hydrothermal reaction temperature. Then the CuO/CeO2 catalytic material was prepared by loading CuO on the CeO2 carrier and evaluated in methanol steam reforming for hydrogen production. Based on the characterization data of low temperature nitrogen adsorption, XRD, H2-TPR and XPS, the effects of hydrothermal reaction temperature on the microstructure of CeO2, the structure of CuO/CeO2 catalytic material and the performance of methanol steam reforming were investigated. The results show that the nanometer CeO2 support prepared at 180 ℃ has a cubic fluorite structure. After loading CuO onto the CeO2, the obtained CuO/CeO2 catalyst exhibits better catalytic activity due to its stronger Cu-Ce interaction, lower reduction temperature of Cu species in the surface, and more oxygen vacancies on the surface of the catalyst. When the reaction temperature is 280 ℃, the molar ratio of water to alcohol (W/M) is 1.2, and the space velocity of methanol vapor gas (GHSV) is 800 h− 1, the methanol conversion rate can reach 91.0%, the mole fraction of CO in reforming gas is 1.29%.

     

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