陈羽, 李泽, 荆洁颖, 李文英. Co掺杂对Ni/NiAlOx催化剂结构和菲加氢饱和性能的影响[J]. 煤炭学报, 2023, 48(3): 1413-1424.
引用本文: 陈羽, 李泽, 荆洁颖, 李文英. Co掺杂对Ni/NiAlOx催化剂结构和菲加氢饱和性能的影响[J]. 煤炭学报, 2023, 48(3): 1413-1424.
CHEN Yu, LI Ze, JING Jieying, LI Wenying. Effect of Co doping on structure and phenanthrene hydrogenation saturation of Ni/NiAlOx catalyst[J]. Journal of China Coal Society, 2023, 48(3): 1413-1424.
Citation: CHEN Yu, LI Ze, JING Jieying, LI Wenying. Effect of Co doping on structure and phenanthrene hydrogenation saturation of Ni/NiAlOx catalyst[J]. Journal of China Coal Society, 2023, 48(3): 1413-1424.

Co掺杂对Ni/NiAlOx催化剂结构和菲加氢饱和性能的影响

Effect of Co doping on structure and phenanthrene hydrogenation saturation of Ni/NiAlOx catalyst

  • 摘要: 煤焦油中富含稠环芳烃菲,菲加氢饱和后的产物全氢菲因具有高能量、高密度、高稳定性等优势是高能量密度燃料的理想组分。高效加氢催化剂是菲加氢至全氢菲的关键因素之一。贵金属催化剂加氢能力强,但价格昂贵,传统镍钼硫催化剂加氢能力较弱,镍基催化剂成本较低且加氢能力强被广泛应用于稠环芳烃加氢饱和领域。课题组前期利用活性金属镍与载体镍铝尖晶石之间强相互作用合成了Ni/NiAlOx催化剂,活性组分镍处于“缺电子”状态,有利于芳烃的吸附与活化,使得该催化剂具有较高的初始全氢菲选择性,但随着反应进行全氢菲选择性逐渐下降,主要是在反应过程中活性组分镍电子结构发生变化导致。考虑到钴与镍具有相似结构,容易溶到镍晶格中直接调控镍电子结构这一性质,采用先溶胶凝胶法再浸渍法制备出不同钴掺杂量的催化剂,考察了钴掺杂量对Ni/NiAlOx催化剂结构以及菲加氢饱和性能的影响。当反应温度300℃、压力为5.0 MPa、反应原料1%菲/十氢萘溶剂、进料速率为6 mL/h、氢气流量为60 mL/min、重时空速为52 h-1时,钴掺杂量为2%的催化剂在反应第6小时全氢菲选择性为53.6%,高出Ni/NiAlOx催化剂第6小时全氢菲选择性43%。对催化剂结构进行表征分析,发现适量钴掺杂可以促进活性金属的还原,减小催化剂粒径,稳定活性组分镍“缺电子”程度,促进芳烃吸附,最终提升催化剂稳定性。

     

    Abstract: Coal tar is rich in dense cyclic aromatic hydrocarbons phenanthrene, and perhydrophenanthrene is an ideal component for high energy density fuels used in aerospace because of its high energy, high density and high stability. The key is to design efficient hydrogenation catalysts. Noble metal catalysts have the characteristics of high hydrogenation capacity, but have the disadvantage of high cost. Traditional nickel-molybdenum-sulfur catalysts have weak hydrogenation capacity, and nickel based catalysts are widely used in the aromatics hydrogenation saturation field due to their low price and high hydrogenation saturation capacity. The Ni/NiAlOx catalysts are used by the strong interaction between the active nickel metal and the support nickel aluminum spinel, which makes the active component nickel show the “electron deficient” state and promote the adsorption and activation of aromatics. This catalyst has high perhydrophenanthrene selectivity, but perhydrophenanthrene selectivity decreases gradually as the reaction proceeding, mainly due to the change of nickel's electron density during the reaction. Considering that cobalt has a similar structure to nickel, it is easy to dissolve into the nickel lattice and directly modulate nickel's electronic structure. The catalysts with different cobalt contents were prepared by the sol-gel method followed by impregnation method, and then the effect of cobalt doping on the structure and the performance of Ni/NiAlOx catalysts with phenanthrene hydrosaturation was investigated. The catalysts were evaluated at a reaction temperature of 300 ℃, pressure of 5.0 MPa, reaction feed: 1% phenanthrene/decahydronaphthalene solvent, feed rate: 6 mL/h, hydrogen flow rate: 60 mL/min, and weight hourly space velocity: 52 h-1. The catalyst with cobalt doping of 2% had a perhydrophenanthrene selectivity of 53.6% at the 6th of the reaction, which was higher than that of the Ni/NiAlOx catalyst. This is due to the fact that the appropriate content of cobalt doping promotes the reduction of active metal, reduces the catalyst particle size, stabilizes the “electron deficiency” of the active component Ni, promotes the adsorption of aromatics, and finally improves the catalyst stability.

     

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