物理化学学报 >> 2011, Vol. 27 >> Issue (11): 2639-2645.doi: 10.3866/PKU.WHXB20111125

催化和表面科学 上一篇    下一篇

Ce添加对Cu-Fe/SiO2催化合成气制低碳醇性能的影响

毛东森, 郭强胜, 俞俊, 韩璐蓬, 卢冠忠   

  1. 上海应用技术学院化学与环境工程学院应用催化研究所, 上海 200235
  • 收稿日期:2011-07-25 修回日期:2011-09-05 发布日期:2011-10-27
  • 通讯作者: 毛东森 E-mail:dsmao@sit.edu.cn
  • 基金资助:

    上海市科委(08520513600), 上海市教委曙光跟踪计划(10GG23)及上海市教委重点学科建设(J51503)资助项目

Effect of Cerium Addition on the Catalytic Performance of Cu-Fe/SiO2 for the Synthesis of Lower Alcohols from Syngas

MAO Dong-Sen, GUO Qiang-Sheng, YU Jun, HAN Lu-Peng, LU Guan-Zhong   

  1. Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 200235, P. R. China
  • Received:2011-07-25 Revised:2011-09-05 Published:2011-10-27
  • Contact: MAO Dong-Sen E-mail:dsmao@sit.edu.cn
  • Supported by:

    The project was supported by the Science and Technology Commission of Shanghai Municipality, China (08520513600),“Shu Guang”Project of Shanghai Municipal Education Commission, China (10GG23), and Leading Academic Discipline Project of Shanghai Municipal Education Committee, China (J51503).

摘要: 采用共浸渍法制备了添加不同Ce含量(相对于SiO2的摩尔分数为0-20%)的Ce-Cu-Fe/SiO2催化剂,在连续流动微型固定床反应器中考察了其催化CO加氢合成低碳醇反应的性能, 并采用X射线衍射(XRD)、低温N2吸附、程序升温还原(H2-TPR)、CO吸附傅里叶变换红外光谱(CO-FTIR)和CO程序升温脱附(CO-TPD)技术对催化剂进行了表征. 结果表明: 添加适量的Ce, 一方面降低了Cu的晶粒大小, 提高了Cu的分散度, 进而提高了对CO的吸附能力; 另一方面掺入的Ce和Cu之间存在相互作用, 提高了CO解离和非解离吸附的能力, 从而有利于CHx的生成和CO的插入反应. 上述两方面的共同作用同时提高了Cu-Fe/SiO2催化剂的活性和醇的选择性. 当Ce含量为10%时, 在压力为3.0 MPa, 温度为250 °C, 空速为6000 mL·g-1·h-1和H2/CO摩尔比为2的反应条件下, Ce-Cu-Fe/SiO2催化剂上醇的时空产率达到121.0 g·kg-1·h-1, 比未添加Ce的Cu-Fe/SiO2催化剂的时空产率(58.0 g·kg-1·h-1)提高了一倍以上.

关键词: 铈助剂, Cu-Fe/SiO2催化剂, 合成气, 催化加氢, 低碳醇

Abstract: A series of Ce-Cu-Fe/SiO2 catalysts with different Ce contents (mole fraction relative to SiO2, 0-20%) were prepared by co-impregnation and their catalytic performances for CO hydrogenation to lower alcohols were investigated using a continuous flow fixed bed micro-reactor. These catalysts were characterized by X-ray diffraction (XRD), N2-adsorption, temperature-programmed reduction of H2 (H2-TPR), Fourier transform infrared of CO adsorption (CO-FTIR), and temperature-programmed desorption of CO (CO-TPD). The results showed that the addition of an appropriate amount of Ce decreased the Cu crystal size and promoted the dispersion of Cu, which greatly increased the amount of adsorbed CO. Additionally, the interaction of doped Ce with Cu increased the associative and dissociate adsorption capacity of CO, which is favorable for the formation of CHx and the insertion reaction of adsorbed CO to CHx. Both the activity and alcohol selectivity of the Cu-Fe/SiO2 catalyst increased under the combined effect of the above-mentioned two aspects. At a Ce content of 10%, the space time yield of lower alcohols improved from 58.0 g·kg-1·h-1 over the Cu-Fe/SiO2 catalyst to 121.0 g·kg-1·h-1 over the Ce-Cu-Fe/SiO2 catalyst at 250 °C, a pressure of 3.0 MPa, a H2/CO molar ratio of 2, and gas hourly space velocity of 6000 mL·g-1·h-1.

Key words: Cerium promoter, Cu-Fe/SiO2 catalyst, Syngas, Catalytic hydrogenation, Lower alcohols

MSC2000: 

  • O643