Fe5C2-MnO x 尺度调控及催化合成气制烯烃性能研究

doi:10.11949/0438-1157.20220140

摘要/Abstract

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

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.

图/表 15

图1 4种合成方法制备过程示意图

Fig.1 Schematic diagram of four synthesis methods

图2 不同合成方法Fe-Mn催化剂前体XRD谱图

Fig.2 XRD patterns of Fe-Mn precursors prepared by different methods

图3 不同合成方法Fe-Mn催化剂XRD谱图

Fig.3 XRD patterns of Fe-Mn catalysts prepared by different methods

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

图4 不同合成方法Fe-Mn催化剂吸脱附曲线及孔径分布

Fig.4 Adsorption and desorption curves and pore size distribution of Fe-Mn catalysts prepared by different methods

图5 不同合成方法Fe-Mn催化剂SEM图

Fig.5 SEM images of Fe-Mn catalysts prepared by different methods

图6 粒径分布

Fig.6 Particle size distribution

图7 不同合成方法Fe-Mn催化剂的拉曼光谱图

Fig.7 Raman spectra of Fe-Mn catalysts prepared by different methods

图8 不同合成方法Fe-Mn催化剂的H2-TPR谱图

Fig.8 H2-TPR spectra of Fe-Mn catalysts prepared by different methods

图9 10% CO/Ar还原过程中Fe-Mn催化剂的原位XRD分析

Fig.9 In situ XRD patterns of Fe-Mn catalyst during reduction at 10% CO/Ar

图10 不同合成方法Fe-Mn催化剂结构演变过程

Fig.10 Structural evolution of Fe-Mn catalysts prepared by different methods

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/%
催化剂	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
催化剂	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/%	FTY^①	CO₂ selectivity/%	Hydrocarbon distribution^②/%				α	O/P^③
催化剂	CO conversion/%	FTY^①	CO₂ selectivity/%	CH₄	$C 2 ~ 4 0$	$C 2 ~ 4 =$	C₅₊	α	O/P^③
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/%	FTY^①	CO₂ selectivity/%	Hydrocarbon distribution^②/%				α	O/P^③
催化剂	CO conversion/%	FTY^①	CO₂ selectivity/%	CH₄	$C 2 ~ 4 0$	$C 2 ~ 4 =$	C₅₊	α	O/P^③
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

图11 Fe-Mn催化剂催化STO反应性能分析

Fig.11 Catalytic performance of the Fe-Mn catalysts for STO reaction

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Fe₅C₂-MnO _x 尺度调控及催化合成气制烯烃性能研究

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

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