催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (9): 1132-1138.DOI: 10.3724/SP.J.1088.2010.00142

• 研究论文 • 上一篇    下一篇

Mo 和 Cu 助剂对 FeK/SiO2 催化剂费托合成性能的影响

秦绍东1,2, 张成华1, 许健1, 吴宝山1, 相宏伟1, 李永旺1   

  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
  • 收稿日期:2010-09-30 出版日期:2010-09-30 发布日期:2014-01-25

Mo and Cu Modified FeK/SiO2 Catalysts for Fischer-Tropsch Synthesis

QIN Shaodong1,2, ZHANG Chenghua1,*, XU Jian1, WU Baoshan1, XIANG Hongwei1, LI Yongwang1   

  1. 1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2010-09-30 Online:2010-09-30 Published:2014-01-25

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摘要： 研究了 Mo 和 Cu 助剂对 FeK/SiO2 催化剂的性质及费托 (F-T) 合成性能的影响. 采用 N2 物理吸附、H2 程序升温还原、X 射线衍射、穆斯堡尔谱和 X 射线光电子能谱技术对催化剂进行了表征. 结果表明, Mo 加入后与 Fe 产生了较强的相互作用, 抑制了催化剂的还原和碳化; Cu 助剂的加入促进了催化剂的还原和碳化; 当 Mo 和 Cu 共同加入后, 催化剂的还原和碳化行为与单独加入 Cu 助剂时相似. 催化剂 F-T 合成性能在固定床上于 280 oC, 1.5 MPa, 2 000 h-1, H2/CO = 2.0 的合成气中测试. 结果表明, Mo 的加入降低了催化剂活性, 但提高了重质烃 (C5+) 的选择性; Cu 的添加提高了催化剂的活性, 但对稳定 C5+选择性作用不明显. Mo 和 Cu 共同加入后, 催化剂既表现出较为稳定的 C5+选择性, 同时其活性也没有降低.

关键词: 费托合成, 铁基催化剂, 钼助剂, 铜助剂, 重质烃选择性

Abstract: The effects of Mo and Cu promoters on the properties of FeK/SiO2 catalysts and their Fischer-Tropsch synthesis (FTS) performance were studied. The catalysts were characterized by N2 adsorption, H2 temperature-programmed reduction, X-ray diffraction, Mössbauer effect spectroscopy and X-ray photoelectron spectroscopy. The characterization results indicate that Mo addition inhibits the reduction and carburization of the catalysts, which is opposite to Cu promoter. When Mo and Cu are co-added, similar reduction and carburization behavior is observed as that of Cu promoter alone. FTS performance was tested at 280 oC, 1.5 MPa, 2 000 h-1, and syngas H2/CO = 2.0 in a fixed-bed reactor. The reaction results show that Mo addition decreases the FTS activity and improves the stability of heavy hydrocarbon (C5+) selec-tivity over the catalysts; Cu addition increases the activity but has no contribution to the stability of C5+ selectivity. For the co-promoted catalyst, stable selectivity to C5+ is obtained without sacrificing activity.

Key words: Fischer-Tropsch synthesis, iron-based catalyst, molybdenum promoter, copper promoter, heavy hydrocarbon selectivity