石油学报(石油加工) ›› 2020, Vol. 36 ›› Issue (5): 909-918.doi: 10.3969/j.issn.1001-8719.2020.05.003

• 研究报告 • 上一篇    下一篇

Ce改性CoMo/Al2O3选择性加氢脱硫催化剂的表征及其催化硫醇硫生成反应性能

于沛1,2,柯明2,王奇2,丁亚龙1,金毅2   

  1. 1. 黄淮学院 化学与制药工程学院,河南 驻马店,463000;
    2. 中国石油大学(北京) 重质油国家重点实验室, 北京 102249
  • 收稿日期:2019-08-20 修回日期:2020-04-23 出版日期:2020-09-25 发布日期:2020-11-27
  • 通讯作者: 柯明,男,教授,博士,从事清洁燃料生产技术及催化剂的研究,E-mail:keming@cup.edu.cn E-mail:keming@cup.edu.cn
  • 作者简介:第一作者:于沛,男,讲师,博士,从事清洁燃料生产技术及催化剂的研究,E-mail:yupei@huanghuai.edu.cn
  • 基金资助:
    国家自然科学基金项目(21776303)和河南省科技攻关计划项目(202102310279)

Characterization and Catalytic Performance of Ce Modified CoMo/Al2O3 Catalyst for Mercaptan Sulfur Formation During in Selective Hydrodesulfurization

YU Pei1,2, KE Ming2, WANG Qi2, DING Yalong1, JIN Yi2   

  1. 1. College of Chemistry and Pharmaceutical Engineering, Huanghuai University, Zhumadian 463000, China; 
    2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
  • Received:2019-08-20 Revised:2020-04-23 Online:2020-09-25 Published:2020-11-27

摘要: 针对Ce改性CoMo/Al2O3选择性加氢脱硫催化剂,通过XRD、H2-TPR、Py-IR、XPS、HRTEM表征分析和活性评价,考察了CeO2含量对其表面物相结构性质和生成硫醇硫反应性能的影响。结果表明:Ce改性CoMo/Al2O3催化剂载体表面的Ce以Ce3+价态存在;其与Al2O3形成CeAlO3或类似结构的物相,减弱了金属Mo和载体的相互作用,促进了Mo的硫化,使催化剂表面MoS2晶簇的堆垛层数和晶片长度均有增加,有利于II型CoMoS活性相的形成,具有较多的不饱和活性位(CUS),增大了L酸酸量;Ce的引入减少了反应过程中硫醇硫的生成;将催化剂表面酸分布和CoMoS活性相含量与生成硫醇硫反应性能进行关联,发现硫醇硫生成量与L酸的强酸酸量和弱酸酸量的比值(A(Ls)/A(Lw))以及CoMoS活性相含量相关,(A(Ls)/A(Lw))越大,CoMoS活性相含量越多,则硫醇硫生成量越少。

关键词: 选择性加氢脱硫, 硫醇硫, 催化剂, Ce改性

Abstract: To investigate the physicochemical properties and catalytic performance for mercaptan sulfur formation in selective hydrodesulfurization, Ce modified CoMo/Al2O3 catalysts were prepared. The catalysts were characterized by XRD, H2-TPR, Py-IR, XPS and HRTEM, and the catalytic performance was evaluated in a continuous flow fixedbed microreactor. Results show that Ce species are in the form of Ce3+ on the surface of supporter, as CeAlO3 or similar structures. The introduction of Ce weakens the interaction between the active component and supporter, thus improving the dispersion of Mo species on supporter. The catalyst with suitable content of CeO2 favors the sulfidation of Mo species in the pre-sulfidation process, which promotes the formation of coordinative unsaturated sites (CUSs) and then increases Lewis acid amount of sulfide catalyst. Average slab length and stacking layer number of MoS2 slabs are moderately increased, thereby promoting the formation of type II CoMoS phase. Catalysts with Ce modification exhibit poor activity for mercaptan sulfur formation. Mercaptan sulfur formation performance of catalysts is correlated to the content of CoMoS phase and the amount ratio of strong Lewis acid to weak Lewis acid (A(Ls)/A(Lw)). The mercaptan sulfur content in product is decreasing and the content of CoMoS is increasing along with the raising of (A(Ls)/A(Lw)).

Key words: selective hydrodesulfurization, mercaptan sulfur, catalyst, Ce modification