物理化学学报 >> 2012, Vol. 28 >> Issue (08): 1943-1950.doi: 10.3866/PKU.WHXB201206051

催化和表面科学 上一篇    下一篇

纳米铁基催化剂在CO2加氢制烃中的性能

郑斌1, 张安峰1, 刘民1, 丁凡舒1, 代成义1, 宋春山1,2, 郭新闻1   

  1. 1. 大连理工大学化工学院工业催化系, 精细化工国家重点实验室, 辽宁 大连 116024;
    2. 宾夕法尼亚州立大学能源研究所, 能源与矿物工程系, 宾夕法尼亚州大学城, 16802, 美国
  • 收稿日期:2012-03-10 修回日期:2012-06-04 发布日期:2012-07-10
  • 通讯作者: 宋春山, 郭新闻 E-mail:guoxw@dlut.edu.cn; csong@psu.edu

Properties of the Nano-Particle Fe-based Catalyst for the Hydrogenation of Carbon Dioxide to Hydrocarbons

ZHENG Bin1, ZHANG An-Feng1, LIU Min1, DING Fan-Shu1, DAI Cheng-Yi1, SONG Chun-Shan1,2, GUO Xin-Wen1   

  1. 1. State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China;
    2. EMS Energy Institute and Department of Energy and Mineral Engineering, Pennsylvania State University, University Park, Pennsylvania, 16802, USA
  • Received:2012-03-10 Revised:2012-06-04 Published:2012-07-10
  • Contact: SONG Chun-Shan, GUO Xin-Wen E-mail:guoxw@dlut.edu.cn; csong@psu.edu

摘要:

使用尿素沉淀凝胶、机械混合和等体积浸渍相结合的方法, 制备了一系列的纳米尺寸FeK-M/γ-Al2O3(M=Cd, Cu)催化剂, 采用扫描电镜(SEM)、透射电镜(TEM)、N2物理吸附、X射线衍射(XRD)光谱和H2程序升温还原(H2-TPR)仪对催化剂进行表征, 并在小型固定床反应器上考察其对CO2加氢反应的催化性能. 结果表明:3 MPa, 400 °C, 3600 h-1, H2/CO2摩尔比为3 的条件下, 15%(w, 下同)Fe10%K/γ-Al2O3催化剂可稳定运行100h 以上, CO2转化率为51.3%, C2+烃类的选择性达62.6%. Fe 含量降至2.5%时, C2+烃类的选择性仍能达到60.0%. 随着K含量由0%增加至10%, 低碳烯烃选择性增加, 烯烷比增加至3.6. Cd和Cu助剂可促进Fe 物种的还原, 改善目的产物的分布, 其中Cu的加入使低碳产物烯烷比增至5.4, Cd的加入使C5+产物选择性增加了12%.

关键词: 二氧化碳, 加氢转化, 铁基催化剂, 沉淀, 低碳烃类

Abstract:

Combining co-precipitation-gelation, mechanical mixing and impregnation methods, a series of catalysts of FeK-M/γ-Al2O3(M=Cd or Cu) have been attained. The catalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 physisorption, X-ray diffraction (XRD) and temperature-programmed reduction of hydrogen (H2-TPR). The hydrogenation of carbon dioxide over these catalysts was also investigated in a fixed bed. Given a reaction time of 100 h, CO2 conversion over a 15%Fe/10%K/γ-Al2O3 catalyst reached 51.3 %, with a selectivity towards C2+ of 62.6 % at 3 MPa, 673 K, a space velocity of 3600 h-1 and at a molar ratio of H2/CO2 of 3. At the lower Fe content of 2.5%, the selectivity towards C2+ was still greater than 60.0%. Increasing the potassium content from 0% to 10%, increased the selectivity towards C2-C4= and the molar ratio of C2-C4= /C2-C40 increased to 3.6. The addition of Cd and Cu improved the reduction and catalytic activities. Specifically, Cu improved the molar ratio of C2-C4= /C2-C40 from 3.6 to 5.4, and the Cd increased the selectivity of C5+ by 12%.

Key words: Carbon dioxide, Hydrogenation, Fe-based catalyst, Precipitation, Light hydrocarbons

MSC2000: 

  • O643