混合稠环芳烃加氢饱和催化剂设计策略及研究进展

doi:10.11949/0438-1157.20251230

摘要/Abstract

摘要：

将煤焦油中的稠环芳烃催化加氢转化为高能量密度燃料是实现煤炭资源清洁高效利用的重要路径。然而，混合稠环芳烃在催化剂表面存在竞争吸附与动态演变行为，导致其高效转化面临挑战。因此，阐明混合体系中稠环芳烃间相互作用及其对加氢饱和过程的影响机制是开发高效催化剂的关键。本文系统综述了由竞争吸附和反应路径动态演变所引发的催化加氢难题，总结了针对这些问题的催化剂设计与调控策略，主要包括优化活性中心结构以缓解竞争吸附导致的局部反应环境偏离；调控载体性质以引导因反应路径动态变化而偏离的目标反应；构建开放的分级孔道结构并进行表面功能化修饰以改善大分子传质效率并抑制积碳失活，并对混合稠环芳烃加氢饱和催化剂的未来研究方向进行了展望。

关键词: 燃料, 稠环芳烃, 多相反应, 加氢饱和, 竞争吸附, 动态演变, 催化剂

Abstract:

The catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) from coal tar into high energy density fuels represents a crucial route for the clean and efficient utilization of coal resources. However, the efficient conversion of mixed PAHs is hindered by their competitive adsorption and dynamic evolution behavior on catalyst surfaces. A fundamental understanding of the interactions among PAHs in mixtures and their impact on the hydrogenation saturation process is essential for designing high-performance catalysts. This review systematically addresses key catalytic challenges stemming from competitive adsorption and evolving reaction pathways, and summarizes advanced strategies for catalyst design and optimization. These include tailoring active sites to mitigate local environment distortions caused by competitive adsorption, modifying support properties to steer target reactions amid dynamic pathway changes, and constructing open hierarchical pore structures with surface functionalization to enhance mass transfer of large molecules and suppress coke-induced deactivation. The study also presented future research directions for catalysts aimed at the saturation hydrogenation of mixed PAHs.

Key words: fuel, polycyclic aromatic hydrocarbons, multiphase reaction, hydrogenation saturation, competitive adsorption, dynamic evolution, catalyst

中图分类号:

TQ536

齐皓烨, 田涛, 荆洁颖, 李文英. 混合稠环芳烃加氢饱和催化剂设计策略及研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20251230.

Haoye QI, Tao TIAN, Jieying JING, Wenying LI. Catalyst design strategies and research progress for hydrogenation saturation of mixed polycyclic aromatic hydrocarbons[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251230.

图/表 8

图1 煤焦油组分桑基图[15]

Fig.1 Sankey Diagram for Coal Tar Composition[15]

图2 萘分子在VMgO-[010]-fo表面上(a)平行吸附与(b)垂直吸附的示意图。图中的原子标签标示了由吸附作用形成的化学键[23]

Fig.2 A schematic representation of the (a) parallel and (b) perpendicular adsorption of naphthaleneon VMgO-[010]-fo.Atomic labels depict the bond for mation due to the adsorption[23]

图3 研究的10种稠环芳烃分别被·H、·OH与·CH3自由基夺氢的反应活化能（单位：103 J/mol）。图中亦标示了其π电子六隅体[27]

Fig.3 Activation energy values (in 103 J/mol) of the hydrogen abstractions from the 10 studied PAHs by ·H, ·OH and ·CH3 radicals, respectively. π -electron sextet notation is also depicted[27]

图4 萘加氢裂化过程的反应网络[39]

Fig.4 Reaction network of naphthalene in the hydrocracking process[39]

图5 Fe1-N4/RGO 的形态和原子结构。（a）透射电子显微镜（Transmission Electron Microscopy, TEM）图像；（b）、（c）在低电压下获得的高分辨率 TEM 图像；（d）、（e）Fe1-N4/RGO 的 HAADF-STEM 图像及放大图像（单个铁原子用红色圆圈突出显示）；（f）RGO 表面的 N4-Fe1-N4 示意图[73]

Fig.5 Morphology and atomic structure of Fe1–N4/RGO. (a) Transmission electron microscopy (TEM) image; (b,c) high-resolution TEM image obtained under low voltage; (d,e) HAADF-STEM image and enlarged image (single Fe atoms are highlighted by the red circles) of Fe1–N4/RGO; and (f) scheme of N4–Fe1–N4 on the surface of RGO[73]

图6 愈创木酚在 Ru/HBEA和 Ru/Silicalite-1上进行加氢解反应的机理[79]

Fig.6 The proposed plausible reaction mechanism for guaiacol hydrogenolysis/hydrogenation on Ru/HBEA, Ru/Silicalite-1[79]

图7 生物启发型自激活乙炔半加氢催化剂的设计理念。（a）纤毛在气道黏膜清除作用中的机理示意图。（b）复现的纤毛细胞电子显微图像。（c）PDMS锚定CrOx/Al2O3催化剂上乙炔半加氢反应的潜在机制阐释。色标说明：Al（棕色）、Cr（淡紫）、Si（米色）、O（红色）、C（灰色）、H（白色）。被PDMS分子链弹离表面的C4–C6分子代表碳质沉积物的前驱体[89]

Fig.7 Design philosophy of a bio-inspired self-activating catalyst for acetylene semihydrogenation. (a) Scheme on the role of cilia in airway mucociliary clearance. (b) Electronic micrograph of ciliated cell from Ref. (c) Delineation of the potential mechanism for semihydrogenation of acetylene over PDMS-anchored CrOx/Al2O3. Color code: Al (brown), Cr (lilac), Si (beige), O (red), C (grey), and H (white). The C4–C6 molecules, kicked away from the surface by PDMS chains, represented the precursors of carbonaceous deposits[89]

图8 Mo、C和Pd电子转移示意图[98]

Fig.8 schematic illustration of electron transfer among Mo, C, and Pd[98]

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