Ru修饰负载型Co基费托合成催化剂性能研究  

Study on performance of supported Co-based Fischer Tropsch catalysts modified by Ru

作　　者：闫敬如 娄舒洁 孟闪茹 肖海成[1] YAN Jingru;LOU Shujie;MENG Shanru;XIAO Haicheng(Petrochemical Research Insitute,PetroChina Company Limited,Beijing 102206,China;College of Chemical Engineering and Environment,China University of Petroleum(Beijing),Beijing 102249,China)

机构地区：[1]中国石油天然气股份有限公司石油化工研究院,北京102206 [2]中国石油大学(北京)化学工程与环境学院,北京102249

出　　处：《低碳化学与化工》2023年第5期46-54,共9页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(2017YFA0700100);中国石油科学研究与金属开发项目(2019A-2409-02,2019E-25,2020-CB-02-15-02)。

摘　　要：Ru助剂可以提高Co物种的分散度和还原度,抑制烧结和积炭,进而起到改善Co基催化剂的结构和费托反应催化性能的作用。采用共沉淀法分别制备了不同载体负载的Co基催化剂(Co/MgO、Co/MnO_(2)、Co/NaY、Co/SiO_(2)和Co/ZnO,Co负载量(质量分数,下同)均为30%);再以RuCl_(3)•xH_(2)O为Ru助剂修饰以上Co基催化剂,采用等体积浸渍法分别制得了Ru负载量为0.5%和1.0%的Ru修饰负载型Co基费托合成催化剂。采用N_(2)吸附、XRD和H_(2)-TPR等对催化剂的结构进行了表征,采用固定床反应器评价了催化剂的费托合成催化性能。结果表明,不同负载量的Ru助剂对不同载体负载的Co基催化剂的影响不同。浸渍Ru助剂后,所有催化剂的比表面积和孔容均下降;H_(2)-TPR表征表明Ru助剂能够促进Co物种的还原、降低还原温度,并抑制Co与载体之间难还原物种的生成。Co/MnO_(2)系列催化剂在270℃下才能体现出活性,其中0.5%Ru-Co/MnO_(2)具有最低甲烷选择性(5.45%)和最高C5+选择性(72.83%)。Ru promoter can improve the dispersion and reduction of Co species,inhibit sintering and carbon deposition,thus improve the structure of Co-based catalyst and its catalytic performance in Fischer Tropsch reaction.Co-based catalysts(Co/MgO,Co/MnO_(2),Co/NaY,Co/SiO_(2) and Co/ZnO,the loading amount(mass fraction,the same below)of Co is 30%)supported on different supports were prepared by coprecipitation method.Then RuCl_(3)•xH_(2)O was used as Ru promoter to modify the above Co-based catalysts and supported Co-based Fischer Tropsch catalysts modified by Ru were obtained by equal volume impregnation method with the loading amount of Ru is 0.5%and 1.0%,respctively.The structure of the catalysts were characterized by N_(2) adsorption,XRD and H_(2)-TPR,and the catalytic performance of the catalyst in Fischer Tropsch synthesis were evaluated in a fixed bed reactor.The results show that different loading amounts of Ru promoter have different effects on Co-based catalysts on various supports.For all the catalysts,the specific surface area and pore volume decrease after impregnation with Ru promoter.H_(2)-TPR characterization shows that Ru promoter can promote the reduction of Co species,lower the reduction temperature and inhibit the formation of refractory species between Co and the support.Co/MnO_(2) series catalysts show their activities at the temperature as high as 270℃,and 0.5%Ru-Co/MnO_(2) has the lowest methane selectivity(5.45%)and the highest C5+selectivity(72.83%).

关 键 词：费托合成 Co基催化剂 氧化物载体 Ru助剂 

分 类 号：TQ426[化学工程]