物理化学学报 >> 2014, Vol. 30 >> Issue (11): 2127-2133.doi: 10.3866/PKU.WHXB201409121

催化和表面科学 上一篇    下一篇

Ce-Cu-Co/CNTs催化剂催化合成气制低碳醇及乙醇的研究

韩涛1, 黄伟1, 王晓东1,2, 唐钰1, 刘双强1, 游向轩1   

  1. 1. 太原理工大学煤科学与技术教育部和山西省重点实验室, 太原 030024;
    2. 中国科学院山西煤炭化学研究所煤转化国家重点实验室, 太原 030001
  • 收稿日期:2014-06-05 修回日期:2014-09-10 发布日期:2014-10-30
  • 通讯作者: 黄伟 E-mail:huangwei@tyut.edu.cn
  • 基金资助:

    国家自然科学基金重点项目(21336006), 国家自然科学基金面上项目(21176176), 高等学校博士学科点专项(优先发展领域) (20111402130002)和煤转化国家重点实验室开放课题基金项目(J14-15-603)资助

Study of Ce-Cu-Co/CNTs Catalysts for the Synthesis of Higher Alcohols and Ethanol from Syngas

HAN Tao1, HUANG Wei1, WANG Xiao-Dong1,2, TANG Yu1, LIU Shuang-Qiang1, YOU Xiang-Xuan1   

  1. 1. Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
    2. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China
  • Received:2014-06-05 Revised:2014-09-10 Published:2014-10-30
  • Contact: HUANG Wei E-mail:huangwei@tyut.edu.cn
  • Supported by:

    The project was supported by the Key Program of National Natural Science Foundation of China (21336006), General Program of National Natural Science Foundation of China (21176176), Research Fund for the Doctoral Program of Higher Education of China (20111402130002) and Foundation of State Key Laboratory of Coal Conversion, China (J14-15-603).

摘要:

采用共浸渍法制备了不同Ce含量的Ce-Cu-Co/CNTs 催化剂, 考察了其在合成气制低碳醇反应中的催化性能, 借助X射线衍射(XRD)、程序升温还原(H2-TPR)、N2吸脱附实验(BET)、透射电镜(TEM)和CO程序升温脱附(CO-TPD)对这些催化剂进行了表征. 结果表明, 当Ce的质量分数为3%时, 低碳醇的时空收率和选择性达到最高, 分别为696.4 mg·g-1·h-1和59.7%, 其中乙醇占总醇的46.8%, 适量Ce的添加能提高Cu物种在催化剂上的分散度和催化剂的还原性能, 能显著地增加催化剂吸附CO的能力, 促进合成醇活性位的形成, 进而明显提高催化剂的活性和总醇的选择性. 研究表明, 将具有高活性和高碳链增长能力的CuCo基催化剂与碳纳米管的限域效应结合, 可实现缩窄产物分布、大幅度提高乙醇选择性的目的.

关键词: Ce, CuCo/CNTs 催化剂, 合成气, 低碳醇, 乙醇

Abstract:

A series of Ce-Cu-Co/carbon nanotubes (CNTs) catalysts with different Ce contents were prepared by co-impregnation, and the catalytic performance was investigated for the synthesis of higher alcohols from syngas. The catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), N2 adsorption-desorption isotherms (BET), transmission electron microscopy (TEM), and temperature-programmed desorption of CO (CO-TPD). The results showed that at a Ce content of 3% the catalyst had the highest catalytic activity. The formation rate and selectivity of alcohol reached 696.4 mg·g-1· h-1 and 59.7%, where the mass fraction of ethanol was 46.8% of the total amount of alcohols. The addition of an appropriate amount of Ce facilitated the dispersion of Cu and promoted reduction of the catalysts. It also markedly increased the adsorption capacity for CO, and significantly improved the formation of active sites for alcohols, which is favorable for the catalytic activity and to improve the selectivity of alcohols. Research showed that combining the CuCo-based catalyst, which has high activity and a high ability of carbon chain growth, with the confinement effect of CNTs can result in a narrow distribution of alcohols and significantly improve the selectivity of ethanol.

Key words: Ce, CuCo/CNTs catalyst, Syngas, Higher alcohol, Ethanol

MSC2000: 

  • O643