化工学报 ›› 2022, Vol. 73 ›› Issue (6): 2677-2689.doi: 10.11949/0438-1157.20220140

• 催化、动力学与反应器 • 上一篇    下一篇

Fe5C2-MnO x 尺度调控及催化合成气制烯烃性能研究

孟博1(),刘艳萍1,蒋新科1,韩一帆1,2()   

  1. 1.郑州大学先进功能材料制造教育部工程研究中心，河南 郑州 450001
    2.华东理工大学，化学工程联合国家重点实验室，上海 200237
  • 收稿日期:2022-01-23 修回日期:2022-03-08 出版日期:2022-06-05 发布日期:2022-06-30
  • 通讯作者: 韩一帆 E-mail:mengbo8305@zzu.edu.cn;yifanhan@ecust.edu.cn
  • 作者简介:孟博（1983—），男，博士研究生，副教授，mengbo8305@zzu.edu.cn
  • 基金资助:
    国家自然科学基金项目(21606209)

The scale regulation of Fe5C2-MnO x and their catalytic performance for the preparation of olefins from syngas

Bo MENG1(),Yanping LIU1,Xinke JIANG1,Yifan HAN1,2()   

  1. 1.Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, Zhengzhou University, Zhengzhou 450001, Henan, China
    2.State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2022-01-23 Revised:2022-03-08 Published:2022-06-05 Online:2022-06-30
  • Contact: Yifan HAN E-mail:mengbo8305@zzu.edu.cn;yifanhan@ecust.edu.cn

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摘要：

催化剂结构调控及反应过程普遍面对多层次多尺度结构的复杂系统，从宏观合成条件到催化剂结构尺度调控，从催化性能到催化剂表面活性位尺度调控，均离不开对催化体系介尺度结构的认识。采用四种方式（低温共沉淀、沉积沉淀、前体混合煅烧及机械混合）制备不同结构Fe-Mn催化剂（Fe与Mn摩尔比为1∶4），探究催化剂结构对其活化历程、铁碳化合物分布以及催化合成气制烯烃性能的影响。结果表明，合成方法对催化剂结构有显著影响，体现在三个方面：活化过程、铁碳化合物尺寸及催化反应性能。发现共沉淀制备的Fe-Mn催化剂显示出较高的CO转化率（20.07%）、烯烷比（2.32）及铁时空收率（4.37×10-5 mol CO?(g Fe)-1?s-1），这主要得益于该催化剂活化后形成的较小的铁碳化合物颗粒尺寸及更多的Fe5C2活性相。

关键词: 催化剂, 铁碳化合物, 介尺度, 烯烃, 合成气

Abstract:

Complex systems with multi-level and multi-scale structures are widely encountered in the structure optimization of catalysts and catalytic reaction process, from synthesis conditions to structure regulation of catalysts, from catalytic performance to the active sites regulation, it is important to understand mesoscale structure of catalytic system. In this paper, Fe-Mn catalyst precursors (Fe/Mn mole ratio 1/4) with different structures were prepared by four methods (low-temperature co-precipitation, deposition-precipitation, calcination of mixed precursors, and mechanical mixing). The relationship between their structure and activation process, distribution of iron carbides and the catalytic performance for preparation of olefins from syngas were investigated. The results showed that the synthesis method had a significant impact on the structure of the catalysts, which mainly reflected in three aspects: activation process, iron carbides size and catalytic performance. The Fe-Mn catalysts prepared by co-precipitation had shown a higher CO conversion rate (20.07%), olefin/paraffinratio (2.32), and iron space-time yield (4.37×10-5 mol CO?(g Fe)-1?s-1), which were mainly due to the smaller particle size of iron-carbon compounds and more Fe5C2 active phases formed after the catalyst was activated.

Key words: catalyst, iron carbides, mesoscale, olefins, syngas

中图分类号: 

  • O 643.36

图1

4种合成方法制备过程示意图"

图2

不同合成方法Fe-Mn催化剂前体XRD谱图"

图3

不同合成方法Fe-Mn催化剂XRD谱图"

表1

Fe-Mn催化剂的织构性质"

催化剂比表面积/(m2?g-1)孔容/ (m3?g-1)孔径/nm平均尺寸/nm
Fe(纯铁)91.040.298.6965.91
GC158.610.336.0337.83
CC-Fe120.290.276.6249.88
CC-Mn147.980.367.1940.55
JH-hd124.470.276.4548.21
JH-dh98.760.309.1960.76
Mn(纯锰)102.310.277.6158.64

图4

不同合成方法Fe-Mn催化剂吸脱附曲线及孔径分布"

图5

不同合成方法Fe-Mn催化剂SEM图"

图6

粒径分布"

图7

不同合成方法Fe-Mn催化剂的拉曼光谱图"

图8

不同合成方法Fe-Mn催化剂的H2-TPR谱图"

图9

10% CO/Ar还原过程中Fe-Mn催化剂的原位XRD分析"

图10

不同合成方法Fe-Mn催化剂结构演变过程"

表2

不同合成方法Fe-Mn催化剂的晶相含量"

催化剂晶相含量①/%
MnFe2O4Fe5C2Fe3CFe2CMnO
GC17.955.226.9——
CC-Fe17.115.962.05.0—
CC-Mn31.720.331.7—16.3
JH-hd20.99.369.8——
JH-dh37.9—38.6—23.5

表3

不同合成方法Fe-Mn催化剂的晶粒尺寸"

催化剂晶粒尺寸①/nm
Fe5C2Fe3C
GC19.6928.44
CC-Fe20.8016.82
CC-Mn26.6827.12
JH-hd27.1421.68
JH-dh—26.79

表4

不同合成方法Fe-Mn催化剂的STO性能数据汇总"

催化剂

CO

conversion/%

FTY①

CO2

selectivity/%

Hydrocarbon distribution②/%αO/P③
CH4C2~40C2~4=C5+
GC20.074.376.3713.2817.4538.6024.290.542.32
CC-Fe15.492.7722.9717.5514.4820.1119.710.711.47
CC-Mn14.362.2333.089.4914.1927.9515.280.532.25
JH-hd8.411.5520.8426.1313.4423.6215.970.581.99
JH-dh4.630.8917.2321.5614.1426.0820.980.552.04

图11

Fe-Mn催化剂催化STO反应性能分析"

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