负载型MoS_(2)基加氢催化剂活性相的限域构建及其加氢脱硫活性  

Active-phase construction and hydrodesulfurization activity evaluation of supported MoS_(2)-based hydrogenation catalysts designed with spatial confinement strategy

作　　者：李彦鹏[1,2] 孙于林 杨兆胜 刘大鹏[1] 柴永明[1] 刘晨光[1] LI Yanpeng;SUN Yulin;YANG Zhaosheng;LIU Dapeng;CHAI Yongming;LIU Chenguang(State Key Laboratory of Heavy Oil Processing in China University of Petroleum(East China),Qingdao 266580,China;Advanced Chemical Engineering and Energy Materials Research Center in China University of Petroleum(East China),Qingdao 266580,China)

机构地区：[1]中国石油大学(华东)重质油国家重点实验室,山东青岛266580 [2]中国石油大学(华东)高端化工与能源材料研究中心,山东青岛266580

出　　处：《中国石油大学学报（自然科学版）》2024年第3期207-214,共8页Journal of China University of Petroleum(Edition of Natural Science)

基　　金：中央高校基本科研业务费专项(22CX01002A)。

摘　　要：基于对负载型NiMo加氢脱硫催化剂活性相的结构设计,以具有内径10~30 nm直通孔道的天然埃洛石纳米管(HNT)为载体,利用其“孔道空间限域效应”作为MoS_(2)活性相结构的控制基础,以硫代钼酸铵和硝酸镍为金属前驱物,采用等体积浸渍法一次浸渍工艺,通过改变金属负载量、Ni/Mo(原子比)等工艺条件制备系列双金属NiMo/HNT催化剂。通过X射线衍射(XRD)、比表面积(BET)、高分辨透射电子显微镜(HRTEM-EDS mapping)、X射线光电子能谱仪(XPS)等手段对所得催化剂的结构进行表征,以二苯并噻吩(DBT)为模型化合物对催化剂的脱硫活性进行评价。结果表明:HNT载体的使用可有效控制MoS_(2)活性相尺寸,催化剂中的Mo、Ni金属组分几乎全部集中于载体的孔道内部并呈原生的亲密接触状态,同时Ni、Mo组分具有更高的硫化程度,协同效果更好;NiMo/HNT催化剂的加氢脱硫活性和加氢选择性均显著优于使用氧化铝载体的参比催化剂,其中DBT转化率最高增幅41.6%,反应速率R最大可以提升92%,加氢选择性最大可提升60%。Based on the structural design of the active phase of the supported NiMo hydrodesulfurization catalyst,a “spatial confinement strategy” was adopted in order to achieve the structure design of the active MoS_(2) phase with a natural tubular halloysite nanotube(HNT) with 10~30 nm inner diameter as support,ammonium thiomolybdate and nickel nitrate were selected as metal precursors,and incipient-wetness impregnation method was applied to prepare a series of bimetallic NiMo/HNT catalysts.The structure of the as-prepared catalysts has been characterized with XRD,BET,HRTEM-EDS mapping and XPS.The desulfurization activity of the catalyst was evaluated with dibenzothiophene( DBT) as a model compound.It is found that the dimensions of the active MoS_(2) phase can be effectively controlled with the HNT support.Almost all the Mo and Ni metal components in the catalysts are located inside the pores of the support and present a native intimate contact state.Meanwhile,Ni and Mo components show a higher sulfidation degree and the synergy effect is better.The hydrodesulfurization activity and hydrogenation selectivity of the NiMo/HNT catalysts are significantly higher than those of the reference catalyst using typical alumina support.The highest DBT conversion,reaction rate and hydrogenation selectivity can be be increased up to 41.6 %,92 % and 60%,respectively.

关 键 词：加氢脱硫 活性相 埃洛石纳米管 孔道限域 

分 类 号：TE624.43[石油与天然气工程—油气加工工程]