Ni/Al_(2)O_(3)与ZnO距离对含硫菲加氢性能的影响

Influence of distance between Ni/Al_(2)O_(3)and ZnO for deep hydrogenation of sulfur-containing phenanthrene

将菲深度加氢制得全氢菲(航空燃料的主要成分),是实现煤焦油清洁高效利用的有效途径之一。为解决Ni基催化剂在深度加氢过程中的硫中毒问题,将具有优异加氢性能的Ni/Al_(2)O_(3)催化剂与脱硫剂ZnO以4种不同方式耦合,系统考察了Ni/Al_(2)O_(3)与ZnO距离对含硫菲加氢性能的影响,并借助X射线衍射仪和X射线光电子能谱仪对催化剂的结构进行表征。结果表明,距离最近的装填方式Ⅳ展现出最优异的催化性能,10h后菲的转化率和二苯并噻吩的脱硫率仍能维持在100.0%,目标产物全氢菲的选择性为98.0%。表征结果显示较近的距离促进了二苯并噻吩加氢脱硫产生的中间硫物种及时与ZnO作用生成ZnS。两种位点间相互作用的调控使催化剂兼具深度加氢和加氢脱硫性能,进而提升了Ni/Al_(2)O_(3)催化剂在含硫菲加氢反应中的稳定性。

The deep hydrogenation of phenanthrene into perhydrophenanthrene,a primary component of aviation fuel,has been acknowledged as a viable strategy for the clean exploitation of coal tar.To solve the problem of sulfur poisoning in the deep hydrogenation process on Ni-based catalysts,Ni/Al_(2)O_(3)catalysts with sufficient hydrogenation centers was coupled with desulphurisation agent ZnO in four different ways.The effect of the distance between Ni/Al_(2)O_(3)and ZnO on hydrogenation performance of sulfur-containing phenanthrene was systematically investigated.X-Ray diffraction and X-ray photoelectron spectroscopy were used to characterize the structure of the catalyst.The results show that the closest filling methodⅣexhibits the best catalytic performance.After 10 h,the conversion of phenanthrene and the desulfurization of dibenzothiophene can still be maintained at 100.0%,and the selectivity of the target product perhydrophenanthrene is 98.0%.The characterization results showed that the close distance promoted the reaction of the intermediate sulfur species from dibenzothiophene with ZnO to form ZnS.This catalyst enables both deep hydrogenation and hydrodesulfurization performance by modulating the interactions between the two sites,which in turn augments the stability of Ni/Al_(2)O_(3)during the deep hydrogenation process of sulfur-containing phenanthrene.