不同方法合成钼基氧硫复合物催化剂及其合成气制乙醇性能研究  

Study on different synthesis methods of molybdenum-based oxide and sulfide catalyst and its performance in syngas to ethanol

作　　者：宇文晓萌 冯文爽 穆晓亮 赵璐[1] 房克功[1] YUWEN Xiaomeng;FENG Wenshuang;MU Xiaoliang;ZHAO Lu;FANG Kegong(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室,山西太原030001 [2]中国科学院大学,北京100049

出　　处：《燃料化学学报（中英文）》2024年第11期1652-1663,共12页Journal of Fuel Chemistry and Technology

基　　金：国家重点研发计划(2023YFB4103201);国家自然科学基金(21978313);中国科学院山西煤炭化学研究所创新基金(SCJC-DT-2022-05),中国科学院青年创新促进会人才项目(2020181)资助;煤转化国家重点实验室自主研究课题项目(2020BWZ002)。

摘　　要：合成气一步制乙醇是利用非石油资源生产乙醇的重要方法,如何提高乙醇选择性、创制高效催化剂是改善过程经济性的重点。本研究从硫化钼前体出发,分别采用传统热法和射频低温等离子体法制备钼基氧硫复合物催化剂并考察其催化合成气制乙醇反应性能。利用XRD、UV-visible、HR-TEM、SEM、HAADF-STEM、XPS、CO-TPD、H_(2)-TPD、CO_(2)-TPD和in-situ DRIFTS等表征手段研究不同制备方法下合成的钼基氧硫复合物催化剂的不同物化性质,进而探究特征差异引发的催化反应性能变化。其中,MOS-P催化剂表现出最佳性能,在6 MPa、320℃、空速4500 h^(-1)的反应条件下,CO转化率达到22.5%,总醇选择性可达71.4%,其中,总醇中乙醇占比为29.1%。有关研究将为合成气定向转化提供理论指导并为新型钼基材料的设计与制备提供借鉴。Ethanol is a significant chemical feedstock,which can be employed not only as a raw material for chemicals and polymers,but also as an additive to petrol.It is typically produced in industry through either fermentation or ethylene hydration.In light of the growing demand for ethanol,it is imperative to investigate the potential of multi-channel production of ethanol.One-step ethanol production from syngas represents a significant method of ethanol production from non-fossil oil energy sources,and it is also an important means of clean utilization of coal.The cost of direct ethanol production from syngas is relatively low,but the distribution of alcohols with different carbon numbers in the alcohol product is wide,which makes subsequent separation difficult and restricts its large-scale development.Consequently,in the research of direct ethanol production from syngas,the key points to improve the process economics and promote the development of this technology are to improve the selectivity of ethanol and develop the efficient catalysts.Mo-based catalysts can be employed for low-hydrogen syngas.At the same time,it is challenging to deposit carbon,exhibits robust resistance to sulfur poisoning,and demonstrates excellent stability,which also extends the reaction cycle.However,the methanol content of the alcohol product is relatively high.Although the use of Fischer-Tropsch element modification can significantly reduce the methanol selectivity,it will inevitably lead to the problem of broadening the distribution of alcohols.In recent years,there has been a growing attention in the preparation of catalysts using non-thermal plasma technology.Non-thermal plasma comprises not only electrons,ions,molecules and free radicals,but also photons and excited substances.Previous studies have demonstrated that the non-thermal plasma method can induce alterations in the nucleation of the active phase and the crystal growth mode in the preparation of catalysts.Concurrently,for thermodynamically unfavorable reactions,the utilizatio

关 键 词：合成气 CO加氢 乙醇 钼基氧硫复合物 射频低温等离子体 

分 类 号：O643.3[理学—物理化学]