催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (1): 51-56.

• 研究论文 • 上一篇    下一篇

浆态相甲醇合成催化剂的失活机理

翟旭芳1,2,社本纯3,解红娟1,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 富山大学工学部应用化学系, 富山市930-8555, 日本)
  • 收稿日期:2007-01-25 出版日期:2007-01-25 发布日期:2010-08-28

Deactivation Mechanism of Cu-Based Catalyst for Methanol Synthesis in Slurry Phase

ZHAI Xufang1,2, Jun SHAMOTO3, XIE Hongjuan1, TAN Yisheng1, HAN Yizhuo1*, Noritatsu TSUBAKI3   

  1. ZHAI Xufang1,2, Jun SHAMOTO3, XIE Hongjuan1, TAN Yisheng1, HAN Yizhuo1*, Noritatsu TSUBAKI3
  • Received:2007-01-25 Online:2007-01-25 Published:2010-08-28

PDF

968

被引次数

39

摘要： 浆态床甲醇合成过程具有重要的工业应用价值,影响该过程工业化的根本原因是催化剂易失活. 以合成气为原料,医用液体石蜡为溶剂,在5 MPa, 260 ℃和 1100 ml/(g·h)的反应条件下于浆态床反应器中考察了铜基甲醇合成工业催化剂C301的稳定性,并采用程序升温还原、 X射线衍射、透射电镜、扫描电镜、 扫描电镜能谱、元素分析和N2物理吸附等表征方法对不同失活程度的催化剂的物相组成和形貌进行了表征. 结果表明,在本实验条件下,失活催化剂无中毒现象,但随着反应时间的延长,催化剂晶粒长大,比表面积减小,积炭和热烧结现象较明显,但不伴随活性组分铜的流失.

关键词: 铜基催化剂, 浆态床, 催化剂失活, 甲醇合成, 稳定性

Abstract: Compared with the traditional gas phase synthesis, slurry-phase synthesis of methanol has many advantages. The bottle neck for the commercialization of slurry-phase methanol synthesis is the catalyst deactivation. In this paper, the stability and deactivation of a commercial Cu-based C301 catalyst for methanol synthesis from syngas with paraffin in a slurry phase were studied using a stirred autoclave reactor system. Synthesis reactions were conducted under the conditions of 5 MPa, 260 ℃, and 1?100 ml/(g•h), and the reactions were lasted for different times to obtain catalyst samples with different deactivation degrees. The composition and morphology of the catalyst samples before and after reaction were characterized by means of temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, scanning electron microscopy-energy dispersive spectroscopy, elemental analysis, and N2 physical adsorption. The results showed that the deactivated catalyst was not poisoned by impurities in the reaction system. The main causes for the deactivation of the Cu-based catalyst were the sintering and carbon deposition. The Cu composition in the catalyst did not change significantly during the reaction.

Key words: Cu-based catalyst, slurry-phase reactor, catalyst deactivation, methanol synthesis, stability