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潘越1(), 刘相洋1, 黄奕晨1, 李江涛1, 邱丽1, 李瑞丰1,3, 李莎2, 闫晓亮1,3()
收稿日期:
2024-04-28
修回日期:
2024-07-15
出版日期:
2024-07-16
通讯作者:
闫晓亮
作者简介:
潘越(2001—),女,硕士研究生,3477816839@qq.com
基金资助:
Yue PAN1(), Xiangyang LIU1, Yichen HUANG1, Jiangtao LI1, Li QIU1, Ruifeng LI1,3, Sha LI2, Xiaoliang YAN1,3()
Received:
2024-04-28
Revised:
2024-07-15
Online:
2024-07-16
Contact:
Xiaoliang YAN
摘要:
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/Al2O3催化剂与脱硫剂ZnO以四种不同方式耦合,系统考察了Ni/Al2O3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,10 h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/Al2O3催化剂在含硫菲加氢反应中的稳定性。
中图分类号:
潘越, 刘相洋, 黄奕晨, 李江涛, 邱丽, 李瑞丰, 李莎, 闫晓亮. Ni/Al2O3与ZnO距离对含硫菲加氢性能的影响[J]. 化工学报, DOI: 10.11949/0438-1157.20240466.
Yue PAN, Xiangyang LIU, Yichen HUANG, Jiangtao LI, Li QIU, Ruifeng LI, Sha LI, Xiaoliang YAN. Influence of distance between Ni/Al2O3 and ZnO for deep hydrogenation of sulfur-containing phenanthrene[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240466.
装填方式名称 | 装填方法 |
---|---|
Ⅰ | 由石英砂将Ni/Al2O3与ZnO分隔 |
Ⅱ | Ni/Al2O3和ZnO分别混合石英砂再分层装填 |
Ⅲ | 石英砂、Ni/Al2O3和ZnO颗粒直接混合 |
Ⅳ | ZnO和Ni/Al2O3研磨均匀后与石英砂混合 |
表1 Ni/Al2O3催化剂与ZnO装填方式
Table 1 Ni/Al2O3 catalyst and ZnO filling methods
装填方式名称 | 装填方法 |
---|---|
Ⅰ | 由石英砂将Ni/Al2O3与ZnO分隔 |
Ⅱ | Ni/Al2O3和ZnO分别混合石英砂再分层装填 |
Ⅲ | 石英砂、Ni/Al2O3和ZnO颗粒直接混合 |
Ⅳ | ZnO和Ni/Al2O3研磨均匀后与石英砂混合 |
图3 四种装填方式的PHE加氢性能(代表DHP的选择性,代表THP的选择性,代表s-OHP的选择性,代表as-OHP的选择性,代表PHP的选择性)
Fig.3 PHE hydrogenation performance on four filling methods ( represents DHP selectivity, represents THP selectivity, represents s-OHP selectivity, represents as-OHP selectivity, represents PHP selectivity)
装填方式 | DBT脱硫产物选择性(%) | ||
---|---|---|---|
BCH | CHB | BP | |
Ⅰ | 21.1 | 15.7 | 63.2 |
Ⅱ | 10.5 | 20.6 | 68.9 |
Ⅲ | 93.0 | 7.0 | 0 |
Ⅳ | 98.2 | 1.8 | 0 |
表2 四种装填方式第10 h DBT脱硫产物选择性
Table 2 Selectivity of DBT desulfurization products on four filling methods
装填方式 | DBT脱硫产物选择性(%) | ||
---|---|---|---|
BCH | CHB | BP | |
Ⅰ | 21.1 | 15.7 | 63.2 |
Ⅱ | 10.5 | 20.6 | 68.9 |
Ⅲ | 93.0 | 7.0 | 0 |
Ⅳ | 98.2 | 1.8 | 0 |
图7 反应后ZnO的XRD图谱(右图为左侧虚线范围内的局部放大图)
Fig.7 XRD patterns of the spent ZnO (the figure on the right shows a partial enlargement within the dotted line on the left)
催化剂名称 | 表面Ni物种峰位置(eV) | |
---|---|---|
Ni0 | Ni2+ | |
Ni/Al2O3-I | 852.9 | 856.0 |
Ni/Al2O3-Ⅱ | 852.8 | 855.9 |
Ni/Al2O3-Ⅲ | 852.6 | 855.6 |
Ni/Al2O3-Ⅳ | 852.2 | 855.5 |
表3 由XPS得到的四种装填方式反应后Ni/Al2O3的表面Ni物种峰位置
Table 3 Peak position of surface Ni species on four filling methods from XPS
催化剂名称 | 表面Ni物种峰位置(eV) | |
---|---|---|
Ni0 | Ni2+ | |
Ni/Al2O3-I | 852.9 | 856.0 |
Ni/Al2O3-Ⅱ | 852.8 | 855.9 |
Ni/Al2O3-Ⅲ | 852.6 | 855.6 |
Ni/Al2O3-Ⅳ | 852.2 | 855.5 |
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