Ni/ZnO反应吸附脱硫催化剂的界面硫转移及其利用

项目名称： Ni/ZnO反应吸附脱硫催化剂的界面硫转移及其利用

项目编号： No.21473231

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 葛晖

作者单位： 中国科学院山西煤炭化学研究所

项目金额： 80万元

中文摘要： Ni/ZnO反应吸附脱硫是近年来油品深度脱硫的新方向，中国石化将其成功应用于催化汽油的深度脱硫。但目前吸附剂的活性和硫容量仍需提高，这有赖于对反应吸附结构和反应机理的正确认识，目前普遍认为含硫物首先在Ni活性表面吸附脱硫，通过H2S介导将硫转移给ZnO吸附组分；本项目提出Ni表面的硫可以通过Ni与ZnO之间的界面直接进行转移，不通过H2S。当界面Ni与ZnO有合适的相互作用，Ni原子对硫原子吸附减弱，硫转移更易发生，活性中心可迅速再生，使得界面活性中心的催化活性更高。拟制备不同界面形式的Ni/ZnO吸附剂进行界面研究，揭示界面结构和性质对加氢脱硫反应和硫转移的影响，利用DFT计算比较界面硫转移和H2S介导的硫转移对反应中心的再生。同时利用在线表征技术跟踪Ni/ZnO吸附剂反应进程，揭示活性结构的动态变化和硫转移的动态机理。拟通过控制界面性质和界面面积，定向合成活性和硫容量更高的纳米吸附剂。

中文关键词： 界面催化；吸附脱硫；Ni/ZnO；硫转移；界面结构

英文摘要： The reactive absorption desulfurization has become a new direction for the research and development of deep desulfurization. Now the Ni/ZnO absorbent technology Z-sorb has been introduced for the deep desulfurization of FCC gasoline by Sionpec. For the enhancement of reaction properties and sulfur capacities, it needs the correct knowledge about the structures and mechanisms for the reaction and absorption. It was generally deemed that the sulfur-containing compound is firstly absorbed on the Ni surface to form NiSx species, and then the absorbed sulfur is transferred to ZnO by H2S gas. We propose that the sulfur can be directly transferred at the interface of Ni and ZnO, there is no formation of H2S gas. When the interaction between Ni and ZnO is proper, the Ni active centers around interface have weaker interaction with the absorbed sulfur atoms, so the sulfur transfer become easier, and the active sites can be regenerated quickly, leading to higher catalytic activity for desulfurization. With preparation of Ni/ZnO absorbents with different interface properties, the effects of the sturctures and properties of interface between NiSx and ZnO on the hydrodesulfurization and sulfur transfer are deeply investigated. And the DFT calculation is carried to compare the influences of sulfur transfers by interface or by H2S on the regeneration of reaction centers. The dynamic change of active sturcture and dynamic mechanism of sulfur transfers will be revealed by on-line characterizations. With controlling the interface properties and areas, we try to design and synthesize the Ni/ZnO nano absorbents with higher reaction activities and higher sulfur capacities.

英文关键词： catalysis at interface;absorption desulfurization;Ni/ZnO;sulfur transfer;interface structure