稠环芳烃加氢饱和催化剂活性调控策略研究进展

Research progress on activity regulation strategy of catalysts for hydrogenation saturation of polycyclic aromatic hydrocarbons

  • 摘要: 作为煤焦油主要成分,稠环芳烃保留了煤中特有的多环结构,其加氢饱和产物环烷烃是高能量密度燃料的优质组分。然而,稠环芳烃自身结构的高稳定性、中间产物的空间位阻及竞争吸附阻碍了其吸附活化导致加氢饱和困难。系统分析了稠环芳烃加氢饱和反应特征,作为可逆放热反应,低温高压的反应条件有助于稠环芳烃加氢饱和,全氢产物具有较高的热力学选择性,但反应速率随着加氢程度的加深而降低。综述了催化剂中活性金属和载体的调控策略,活性金属与稠环芳烃间的吸附机制表明,适宜的缺电子结构有利于反应物的吸附活化,而活性金属的电子结构可通过金属载体间相互作用、掺杂其他原子促进电子迁移或晶格畸变及利用金属集团效应等方式调控。除了借助多孔结构充当活性金属的分散平台外,载体还能通过表面酸性、官能团功能化或缺陷工程等方式调控表面性质,实现反应物在载体表面富集与转化。总结发现,具有分散良好的缺电子活性金属和辅助反应物扩散吸附的载体的催化剂是稠环芳烃加氢饱和的关键。未来催化剂的设计研究应着重考虑以下3方面:煤焦油原料的复杂,反应中多组分稠环芳烃间的影响规律及针对影响规律的多功能催化剂的设计;溢流氢与载体表面上稠环芳烃的反应拓展了反应场所,L-H(Langmuir-Hinshelwood)机理无法直接应用导致催化加氢饱和途径和催化剂设计需重新审视;以及不同体系加氢饱和催化剂的失活机制与抗失活研究。

     

    Abstract: As the main constituent of coal tar, polycyclic aromatic hydrocarbons (PAHs) retain the unique polycyclic structure of coal, and its hydrogenation saturated product cycloalkanes are high-quality components of high energy density fuels. However, the high structure stability of the reactants, as well as the steric factors and competitive adsorption of the intermediates, hinder their adsorption activation, which make hydrogen saturation challenging. In this work, the characteristics of hydrogenation saturation reaction of PAHs were systematically analyzed, as a reversible exothermic reaction, the reaction conditions of low temperature and high pressure contribute to the hydrogenation saturation of polycyclic aromatic hydrocarbons. The total hydrogen product has high thermodynamic selectivity, but the reaction rate decreases with the deepening of hydrogenation. The regulation strategies of active metals and supports of catalysts were reviewed. For active metals, the adsorption mechanism between them and PAHs indicates that the suitable electron-deficient structure is conducive to the adsorption and activation of reactants, and the electronic structure of active metals can be regulated by the interaction between metal supports, doping other atoms to promote electron migration or lattice distortion, and using metal ensemble effect. In addition to acting as a dispersion platform for the active metal by means of porous structure, the supports can also regulate the surface properties by means of surface acidity, functionalization of functional groups or defect engineering, so as to realize the enrichment and transformation of reactants on the surface of the supports. In summary, catalysts with well dispersed electron-deficient active metals and supports that assist the diffusion adsorption of reactants are the key to the hydrogenation saturation of PAHs. Finally, the design of catalysts in the future should focus on the following three aspects: catalysts research ignoring the application limitations caused by multi-component competition of coal tar, the reaction of spilled hydrogen with PAHs on the surface of the support expands the reaction site, and the L-H (Langmuir-Hinshelwood) mechanism cannot be directly applied, which leads to the need to re-examine the catalytic hydrogenation saturation pathway and catalyst design, and the deactivation mechanism and anti-deactivation of hydrogenation saturated catalysts in different systems were studied.

     

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