催化学报

催化学报 ›› 2008, Vol. 29 ›› Issue (1): 63-68.

• 研究论文 • 上一篇    下一篇

CO2对浆态床一步法合成二甲醚铜基催化剂稳定性的影响

王东升1,2,谭猗生1,韩怡卓1,椿范立3   

  1. 1 中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001; 2 中国科学院研究生院, 北京 100049; 3 日本富山大学工学部应用化学系, 富山 930-8555, 日本
  • 收稿日期:2008-01-25 出版日期:2008-01-25 发布日期:2011-12-25

Effect of CO2 on Stability of Cu-Based Catalyst for Dimethyl Ether Synthesis in Slurry Phase

WANG Dongsheng1,2, TAN Yisheng1*, HAN Yizhuo1, Noritatsu TSUBAKI3   

  1. 1 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, The Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China; 2 Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 3 Department of Applied Chemistry, School of Engineering, Toyama University, Toyama 930-8555, Japan
  • Received:2008-01-25 Online:2008-01-25 Published:2011-12-25

PDF

764

被引次数

53

摘要： 研究了260 ℃, 5.0 MPa和原料气空速4000h-1条件下,不同浓度的CO2对甲醇合成Cu基催化剂稳定性的影响. 结果表明,原料气中较高浓度的CO2可导致Cu基甲醇合成催化剂快速失活. 原料气中CO2浓度的增大可促进逆水煤气变换反应,导致反应体系中H2O的量增加,不能被及时导出反应体系的H2O使Cu基催化剂的晶体结构和表面特性发生了变化. 采用程序升温还原、N2吸附、元素分析、透射电镜和X射线光电子能谱分别对较低浓度和较高浓度CO2反应条件下的催化剂进行了表征. 结果表明,原料气中较高浓度的CO2可导致催化剂颗粒变大,孔径减小,比表面积降低,催化剂中元素Zn和Al有明显的流失, Cu与ZnO之间的协同作用有所减弱,这些都是导致催化剂失活的重要原因. 原料气中较高浓度的CO2在一定程度上抑制了催化剂上积炭的生成.

关键词: 二氧化碳, 浆态床反应器, 二甲醚合成, 甲醇合成, 铜基催化剂, 稳定性

Abstract: The effect of CO2 concentration on the stability of the Cu-based catalyst was studied under the reaction conditions of 260 ℃, 5.0 MPa, and4000h-1. High concentration CO2 caused rapid deactivation of the Cu-based catalyst. Temperature-programmed reduction, N2 adsorption, elemental analysis, transmission electron microscopy, andX-rayphotoelectron spectroscopy were used to characterize the reduction behavior, surface physical properties, components, and surface morphologies of the Cu-based catalyst. Under the reaction condition of high CO2 concentration, the catalyst particle size increased and the total pore volume and BET surface area decreased greatly. There was significant metal loss of Zn and Al, and the synergistic effect between Cu and ZnO became weaker under the one-step slurry phase dimethyl ether synthesis conditions. High concentration CO2 restrained carbon deposition to some extent.

Key words: carbon dioxide, slurry reactor, dimethyl ether synthesis, methanol synthesis, Cu-based catalyst, stability