金属助剂对合成气制高碳醇Co/AC催化剂性能影响  

Effect of metal promoters on catalytic performance of Co/AC for higher alcohols synthesis from syngas

作　　者：郭磊 刘培功 龚坤 齐行振[2,3] 林铁军 GUO Lei;LIU Pei-gong;GONG Kun;QI Xing-zhen;LIN Tie-jun(School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210,China;CAS Key Laboratory of Low-Carbon Conversion Science and Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201210,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]上海科技大学物质科学与技术学院,上海201210 [2]中国科学院上海高等研究院中国科学院低碳转化科学与工程重点实验室,上海201210 [3]中国科学院大学,北京100049

出　　处：《燃料化学学报（中英文）》2023年第11期1663-1672,共10页Journal of Fuel Chemistry and Technology

基　　金：The project was supported by Natural Science Foundation of China(22072177);Natural Science Foundation of Shanghai(21ZR1471700);Shanghai Youth Science and Technology Talents Sailing Program(21YF1453600)。

摘　　要：本实验考察了不同金属助剂(Mn、Zn、La和Zr)对活性炭负载的Co基催化剂(Co/AC)在合成气转化中的活性和产物选择性调控的影响。结果表明,这些金属助剂对CO解离速率,Co_(2)C生成以及醇类产物选择性都有明显的促进作用。所构筑的Co_(2)C/Co^(0)构成了高碳醇合成所需的双活性位结构。其中,Zn修饰的Co/AC催化剂表现出最强的CO解离速率、最高的活性和醇类产物的时空收率。Mn助剂最有利于Co_(2)C的生成,但过高的Co_(2)C/Co^(0)比例导致活性略有下降。Zr和La助剂修饰的催化剂具有相似的CO解离速率和催化活性,但CoZr/AC催化剂适宜的Co_(2)C/Co^(0)比及界面环境更有利于实现CO解离和CO非解离功能的协同,从而表现出最高的醇产物选择性。Shifting products of Fischer-Tropsch Synthesis(FTS)from paraffins to value-added higher alcohols receives great attention but remains great challenge.Herein,metal oxides of Mn,Zn,La and Zr are investigated as promoters to tune the activity and product distributions of Co/AC catalyst for syngas conversion.It is found that these promoters show different 0 promotion effect on CO dissociation rate,the formation of Co_(2)C phase and the alcohols selectivity.The formed Co_(2)C/Co^(0) constitutes the dual active site for higher alcohols synthesis.The strongest CO dissociation rate is observed for Zn-promoted Co/AC catalyst,resulting in the highest activity and space-time yield(STY)of alcohols.The Mn promoter is most conducive to the formation of Co2C,but slightly decreases the activity.The similar CO dissociation rate and CO conversion are obtained over both Zr-and La-promoted Co/AC catalysts,but the Zr-promoted Co/AC catalyst exhibits the highest alcohols selectivity due to the function balance between CO non-dissociative insertion and CO dissociation.

关 键 词：合成气 高碳醇合成 CO加氢 助剂 碳化钴 

分 类 号：TQ546[化学工程—煤化学工程]