化工学报 ›› 2022, Vol. 73 ›› Issue (6): 2677-2689.DOI: 10.11949/0438-1157.20220140
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
作者简介:
孟博(1983—),男,博士研究生,副教授,基金资助:
Bo MENG1(),Yanping LIU1,Xinke JIANG1,Yifan HAN1,2()
Received:
2022-01-23
Revised:
2022-03-08
Online:
2022-06-05
Published:
2022-06-30
Contact:
Yifan HAN
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。
中图分类号:
孟博, 刘艳萍, 蒋新科, 韩一帆. Fe5C2-MnO x 尺度调控及催化合成气制烯烃性能研究[J]. 化工学报, 2022, 73(6): 2677-2689.
Bo MENG, Yanping LIU, Xinke JIANG, Yifan HAN. The scale regulation of Fe5C2-MnO x and their catalytic performance for the preparation of olefins from syngas[J]. CIESC Journal, 2022, 73(6): 2677-2689.
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) | 91.04 | 0.29 | 8.69 | 65.91 |
GC | 158.61 | 0.33 | 6.03 | 37.83 |
CC-Fe | 120.29 | 0.27 | 6.62 | 49.88 |
CC-Mn | 147.98 | 0.36 | 7.19 | 40.55 |
JH-hd | 124.47 | 0.27 | 6.45 | 48.21 |
JH-dh | 98.76 | 0.30 | 9.19 | 60.76 |
Mn(纯锰) | 102.31 | 0.27 | 7.61 | 58.64 |
表1 Fe-Mn催化剂的织构性质
Table 1 Texture properties of the Fe-Mn catalysts
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) | 91.04 | 0.29 | 8.69 | 65.91 |
GC | 158.61 | 0.33 | 6.03 | 37.83 |
CC-Fe | 120.29 | 0.27 | 6.62 | 49.88 |
CC-Mn | 147.98 | 0.36 | 7.19 | 40.55 |
JH-hd | 124.47 | 0.27 | 6.45 | 48.21 |
JH-dh | 98.76 | 0.30 | 9.19 | 60.76 |
Mn(纯锰) | 102.31 | 0.27 | 7.61 | 58.64 |
催化剂 | 晶相含量①/% | ||||
---|---|---|---|---|---|
MnFe2O4 | Fe5C2 | Fe3C | Fe2C | MnO | |
GC | 17.9 | 55.2 | 26.9 | — | — |
CC-Fe | 17.1 | 15.9 | 62.0 | 5.0 | — |
CC-Mn | 31.7 | 20.3 | 31.7 | — | 16.3 |
JH-hd | 20.9 | 9.3 | 69.8 | — | — |
JH-dh | 37.9 | — | 38.6 | — | 23.5 |
表2 不同合成方法Fe-Mn催化剂的晶相含量
Table 2 Crystal phase content of Fe-Mn catalysts prepared by different methods
催化剂 | 晶相含量①/% | ||||
---|---|---|---|---|---|
MnFe2O4 | Fe5C2 | Fe3C | Fe2C | MnO | |
GC | 17.9 | 55.2 | 26.9 | — | — |
CC-Fe | 17.1 | 15.9 | 62.0 | 5.0 | — |
CC-Mn | 31.7 | 20.3 | 31.7 | — | 16.3 |
JH-hd | 20.9 | 9.3 | 69.8 | — | — |
JH-dh | 37.9 | — | 38.6 | — | 23.5 |
催化剂 | 晶粒尺寸①/nm | |
---|---|---|
Fe5C2 | Fe3C | |
GC | 19.69 | 28.44 |
CC-Fe | 20.80 | 16.82 |
CC-Mn | 26.68 | 27.12 |
JH-hd | 27.14 | 21.68 |
JH-dh | — | 26.79 |
表3 不同合成方法Fe-Mn催化剂的晶粒尺寸
Table 3 Grain sizes of Fe-Mn catalysts prepared by different methods
催化剂 | 晶粒尺寸①/nm | |
---|---|---|
Fe5C2 | Fe3C | |
GC | 19.69 | 28.44 |
CC-Fe | 20.80 | 16.82 |
CC-Mn | 26.68 | 27.12 |
JH-hd | 27.14 | 21.68 |
JH-dh | — | 26.79 |
催化剂 | CO conversion/% | FTY① | CO2 selectivity/% | Hydrocarbon distribution②/% | α | O/P③ | |||
---|---|---|---|---|---|---|---|---|---|
CH4 | C5+ | ||||||||
GC | 20.07 | 4.37 | 6.37 | 13.28 | 17.45 | 38.60 | 24.29 | 0.54 | 2.32 |
CC-Fe | 15.49 | 2.77 | 22.97 | 17.55 | 14.48 | 20.11 | 19.71 | 0.71 | 1.47 |
CC-Mn | 14.36 | 2.23 | 33.08 | 9.49 | 14.19 | 27.95 | 15.28 | 0.53 | 2.25 |
JH-hd | 8.41 | 1.55 | 20.84 | 26.13 | 13.44 | 23.62 | 15.97 | 0.58 | 1.99 |
JH-dh | 4.63 | 0.89 | 17.23 | 21.56 | 14.14 | 26.08 | 20.98 | 0.55 | 2.04 |
表4 不同合成方法Fe-Mn催化剂的STO性能数据汇总
Table 4 Summary of STO performance for Fe-Mn catalysts prepared by different methods
催化剂 | CO conversion/% | FTY① | CO2 selectivity/% | Hydrocarbon distribution②/% | α | O/P③ | |||
---|---|---|---|---|---|---|---|---|---|
CH4 | C5+ | ||||||||
GC | 20.07 | 4.37 | 6.37 | 13.28 | 17.45 | 38.60 | 24.29 | 0.54 | 2.32 |
CC-Fe | 15.49 | 2.77 | 22.97 | 17.55 | 14.48 | 20.11 | 19.71 | 0.71 | 1.47 |
CC-Mn | 14.36 | 2.23 | 33.08 | 9.49 | 14.19 | 27.95 | 15.28 | 0.53 | 2.25 |
JH-hd | 8.41 | 1.55 | 20.84 | 26.13 | 13.44 | 23.62 | 15.97 | 0.58 | 1.99 |
JH-dh | 4.63 | 0.89 | 17.23 | 21.56 | 14.14 | 26.08 | 20.98 | 0.55 | 2.04 |
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