Mo-Co系加氢精制催化剂中TiO~2-Al~2O~3载体效应的PASCA研究

本文采用PASCA(化学分析正电子湮没谱)技术, 系统地研究了MoO~3/γ-Al~2O~3,CoO/γ-Al~2O~3, MoO~3/TiO~2-Al~2O~3, CoO/TiO~2-Al~2O~3等体系中活性组分的表面分散状态和化学状态及其变化规律, 揭示了用TiO~2改性Al~2O~3对Mo-Co系加氢精制催化剂所产生的载体效应的作用机理。Al~2O~3中引入TiO~2使得载体与MoO~3间的相互作用大大减弱, 导致分散态MoO~3易于还原和硫化。助剂CoO与TiO~2-Al~2O~3载体间存在极为显著的电子相互作用, 对于改善Co在活性相中的化学状态, 提高活性中心的内在活性具有重要的作用。PASCA研究的另一个重要结果是, 由于载体表面的不均匀性,使得上述负载型催化剂中氧化物活性组分的表面状态十分复杂, 存在与载体相互作用强弱程度不同的多类特征区, 这些特征区与内在活性不同的催化中心相关联. 通过TiO~2改性Al~2O~3载体, 有效地调节载体表面性质, 改变活性组分表面物种的分布及化学状态。

Application of PASCA in studying the carrier effect of Mo-Co type hydrotreating catalysts

A novel type of TiO2-modified Al2O3 carrier was prepared to investigate the carrier effect of Mo-Co type hydrotreating catalysts as compared with Al2O3 using positron annihilation spectroscopic chem. anal. Three different molybdena surface species were located at three different sites on either the alumina carrier or the TiO2-modified alumina. However, the fraction and characteristics for each sort of surface site on the alumina carrier are quite different from those on TiO2-modified alumina. The interaction between MoO3 and the surface of the carrier was weakened remarkably by addition of TiO2, which leads to an increase of polymolybdate-like surface species (active phase). The synergism of Co-Ti was verified and the nature of it might be the electron interaction.