化学学报 ›› 2017, Vol. 75 ›› Issue (4): 360-366.DOI: 10.6023/A16100549 上一篇    下一篇

研究论文

金属有机骨架材料Fe-MIL-100诱导的铁基费托催化剂的合成及催化性能研究

杨向平a, 郭晓雪a, 张成华b,c, 王小萍b, 杨勇b,c, 李永旺b,c   

  1. a 中国石油大学(华东)化学工程学院 青岛 266000;
    b 中科合成油技术有限公司煤炭间接液化国家工程实验室 北京 101407;
    c 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:2016-10-15 出版日期:2017-04-15 发布日期:2017-03-21
  • 通讯作者: 李永旺,E-mail:zhangchh@sxicc.ac.cn;Tel.:13335001342 E-mail:zhangchh@sxicc.ac.cn
  • 基金资助:

    项目受国家自然科学基金重大研究计划项目(No.91545109)和山西省国际科技合作项目(No.2014081004)资助.

Synthesis and Catalytic Properties of Iron Based Fischer-Tropsch Catalyst Mediated by MOFs Fe-MIL-100

Yang Xiangpinga, Guo Xiaoxuea, Zhang Chenghuab,c, Wang Xiaopingb, Yang Yongb,c, Li Yongwangb,c   

  1. a College of Chemical Engineering, China University of Petroleum (HD), Qingdao 266000;
    b National Engineering Laboratory of Coal Indirect Liquefaction, Synfuels CHINA Co. Ltd., Beijing 101407;
    c State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001
  • Received:2016-10-15 Online:2017-04-15 Published:2017-03-21
  • Contact: 10.6023/A16100549 E-mail:zhangchh@sxicc.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 91545109) and International Cooperation in Science and Technology of Shanxi Province (No. 2014081004).

随着石油资源的日益枯竭及环保要求的日益严苛,寻找非石油路线生产清洁燃料的方法迫在眉睫,费-托合成是一种以合成气(CO和H2)为原料生产液体燃料的高效方法.铁基费-托合成催化剂广泛应用于工业,本工作研究了多孔碳材料包裹的活性组分高度分散的铁基费托催化剂的制备、结构及费-托合成反应性能.以金属有机骨架材料Fe-MIL-100为前驱体,通过控制碳化温度调节催化剂金属负载量、催化剂粒子尺寸及铁的相态.研究发现碳化温度为500℃所得催化剂在反应温度为260℃、压力为3 MPa、空速为8000 h-1时CO转化率达到68%,展现出优良的中温费托合成反应性能.

关键词: 费-托合成, 铁基费托合成催化剂, 铁碳物相, 金属有机骨架材料, Fe-MIL-100

Depletion of crude oil resources and environmental concerns have spurred worldwide interest in finding un-oil route for liquid fuels. Fischer-Tropsch synthesis is an effective progress for a wide spectrum of hydrocarbon chains from synthesis gas. The use of iron-based catalysts would be preferred in the industry. Here we present a strategy to produce highly dispersed active component embedded in a matrix of porous carbon. Through the carbonization of iron-containing metal-organic frameworks (Fe-MIL-100) at different temperature in N2, four kinds of Fe@C catalysts were prepared. Glucose was used as additional carbon precursor for the synthesis catalyst samples to prevent particle agglomeration. Our strategy avoids the particle agglomeration in the weak metal-support interaction Fe@C catalysts during calcination, reduction and reaction. The structure and morphology of prepared catalysts were characterized by X-ray diffraction (XRD), N2 physical adsorption, transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectrometer (ICP-AES). It is demonstrated that the iron loading, the particle size, and the Fe phase structure of Fe@C catalysts can be controlled by changing the carbonization temperature of Fe-MIL-100. With increasing the temperature, the iron loading and the particle size increase gradually. Depending on the carbonization temperature, the Fe3O4 phase is dominant at 400 and 500℃. The FeO and Fe phase appear at 600℃. The Fe3C phase prevails at 700℃. The high dispersion of the metal phase and its encapsulation in a highly porous carbon matrix result in an unrivalled FTS activity. The spatial restriction created by encapsulation seems to minimize sintering and oxidation of the active Hägg carbide phase. When the reaction conditions were set at 260℃, 3 MPa, the space velocity of 8000 h-1, the conversion of CO is up to 68%. The Fe time yield (FTY) of the Fe@C-500 catalyst were as high as 164 μmolCO·gFe-1·s-1, which surpasses that of most F-T catalysts reported in the literature in middle-temperature Fischer-Tropsch synthesis.

Key words: Fischer-Tropsch synthesis, iron-based Fischer-Tropsch catalysts, iron carbide phases, metal organic frameworks, Fe-MIL-100