大孔型Ni基催化剂用于乙醇水蒸气重整制氢反应的研究-工业催化专业论文.docx

摘 要 镍基催化剂对乙醇水蒸气重整（ESR）反应具有高活性和高 H2 选择性，而 且与贵金属相比价格低廉，是很有潜力的 ESR 制氢催化剂。但镍基催化剂的抗 积碳和高温烧结性能仍有待进一步提高。从催化剂设计角度分析，优良的有序结 构可以使催化剂的活性组分更高效地发挥作用，得到更好的催化性能，从而有效 抑制积碳失活问题。大孔材料具有分布均一的大孔、排列有序的孔道、高的比表 面积、良好的传质传热性能等特点，在催化领域有良好的应用前景。 本文以聚苯乙烯（PS）胶晶为模板，通过柠檬酸络合法制得的三维有序大孔 （3DOM）Ni/Mg-Al 催化剂，具有十分大的比表面积和孔体积，能有效地促进活 性组分高度分散在 MgAl2O4 尖晶石载体上。与非大孔催化剂进行对比，发现 3DOM Ni/Mg-Al 催化剂具有更高的 H2 选择性，能稳定运行 100 小时以上，而常 规颗粒催化剂运行 60 小时即出现明显失活。 此外采用向大孔整体式 PS 泡沫模板中填充水溶胶的方法制备大孔整体式 Al2O3，并负载 MgO 和 NiO 制得大孔-介孔整体式 Ni/Mg-Al 催化剂。研究发现， 该催化剂具有高比表面积（高达 230 m2/g）、大平均孔径、大孔体积等优点。ESR 性能测试表明，反应 100 小时后催化剂仍有很高活性和 H2 选择性，且有效抑制 了催化剂表面积碳，这主要归因于催化剂的优良的质量扩散及热量传导特性，以 及 Ni 颗粒的高分散度。 总结：大介孔催化剂中的 Ni 颗粒负载于分级的大孔-介孔载体上，增加了反 应的活性位，利于提高 ESR 反应的催化性能，并且进一步提高了催化剂的稳定 性。 关键词： 大孔 整体式 制氢 乙醇水蒸汽重整 Ni-基催化剂 聚苯乙烯模板 ABSTRACT Ni has been used as one of the most preferred active component for ethanol steam reforming (ESR) reaction due to its low cost, excellent activity and high hydrogen selectivity. The major concern for the Ni-based catalyst is the deactivation due to coking, metal sintering and phase transformation. Generally, the active component of a catalyst works more efficiently only in combination with a well-organized structure. Recently, a macroporous monolithic material is proposed to be beneficial to heterogeneous catalysis, especially from the viewpoint of their low resistance of heat and mass diffusion, regular macroporous structure and high surface area as well as excellent thermal and chemical stability. In this work, a three-diamensional ordered macroporouus (3DOM) Ni/Mg-Al catalyst is prepared using colloidal PS as the template via a citric acid route.Characterization results show that the 3DOM catalyst has a very high surface area and pore volume, and the active component is highly dispersed on spinel support of MgAl2O4. Compared to the catalyst prepared without template, the 3DOM catalyst exhibits better reactivity at both 700 and 800 oC in terms of higher H2 but lower CH4 yields. Moreover, the 3DOM catalyst maintains its excellent