CIESC Journal ›› 2017, Vol. 68 ›› Issue (2): 670-678.DOI: 10.11949/j.issn.0438-1157.20160905

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CO2 hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al

SHAO Guangyin, ZHANG Yulong, ZHANG Zhengpai, ZHANG Jun, SU Junjie, LIU Da, HE Chongheng, XU Jing, HAN Yifan   

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2016-07-01 Revised:2016-08-13 Online:2017-02-05 Published:2017-02-05
  • Supported by:

    supported by the National Natural Science Foundation of China (21576084, 91534127) and the International Cooperation Project of Ministry of Science and Technology (2015DFG42570).

不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能

邵光印, 张玉龙, 张征湃, 张俊, 苏俊杰, 刘达, 赫崇衡, 徐晶, 韩一帆   

  1. 化学工程联合国家重点实验室, 华东理工大学, 上海 200237
  • 通讯作者: 徐晶
  • 基金资助:

    国家自然科学基金项目(21576084,91534127);科技部国际合作项目(2015DFG42570)。

Abstract:

CO2 hydrogenation directly producing value added chemicals over Fe based catalysts is an important approach to achieve its resource-oriented utilization. In this work, ZSM-5 supported iron catalysts with different ratios of Si/Al (25, 70, 150) were prepared by conventional impregnation method and the effects of supports with different Si/Al ratios on the catalytic performance were investigated. The catalyst activity increased first, then decreased with the increase of Si/Al ratio, and the optimal ratio of Si/Al was 70. With the combination of CO2-DRIFTS and CO2-TPD, it was found that ZSM-5 (Si/Al=70) zeolite supported Fe catalyst possessed more and stronger basic sites, which promoted the dissociative activation of CO2. The evolution of catalysts structure was explored using multiple techniques such as H2-TPR, XRD and Raman spectroscopy. After reduction, Fe2O3 on the catalyst surface was converted into metallic iron, which was then transferred to Fe3O4 and FeCx during the reaction. It was also found that the discrepancy in the interaction between Fe and C under different coordination environments (Si/Al) affects the formation of FeCx, thereby affecting the activity and products selectivity of CO2 hydrogenation.

Key words: CO2 hydrogenation, Fe based catalysts, ZSM-5, Si/Al ratio, catalysis, catalyst support, phase change

摘要:

CO2加氢在铁基催化剂上直接制取高附加值化学品是实现其资源化利用的重要途径。通过等体积浸渍法制备了不同硅铝比(25,70,150)的ZSM-5负载的铁基催化剂,考察硅铝比对铁基催化剂上CO2加氢性能的影响。结果表明,随着硅铝比的升高,催化剂活性先升高后降低,最优化硅铝比为70。CO2-DRIFTS和CO2-TPD结果显示,硅铝比为70的ZSM-5载体制备的催化剂具有较多且较强的表面碱性位,促进CO2分子的活化解离。通过H2-TPR、XRD、Raman等表征揭示了催化剂结构的演变过程。还原后催化剂的活性金属以单质Fe形式存在,反应过程中单质Fe向Fe3O4和FeCx物种转化。不同硅铝比配位环境影响Fe与C的相互作用,影响FeCx的生成,从而影响CO2加氢的活性和选择性。

关键词: CO2加氢, Fe基催化剂, ZSM-5, 硅铝比, 催化, 催化剂载体, 相变

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