Low-carbon olefins from CO2 hydrogenation over Zn-modulated Fe-based catalysts

doi:10.16085/j.issn.1000-6613.2024-0471

Abstract

Abstract:

The current excessive emission of carbon dioxide (CO₂) has led to global problems such as the greenhouse effect, glacier melting and climate anomalies. In order to solve this problem, CO₂ hydrogenation is proposed to prepare various high value-added chemicals. This solution can not only effectively reduce the problem of excessive CO₂ concentration, but also achieve the resourceful use of CO₂ to alleviate the energy crisis. In this study, Zn-modulated K-nFe/Zn catalysts were prepared by co-precipitation and isocratic impregnation for the hydrogenation of CO₂ to low-carbon olefins (C₂⁼—C₄⁼), with emphasis on the effect of Zn content on the catalytic activity. The results of catalyst evaluation showed that at 320℃, 3MPa, and H₂/CO₂=3, the catalyst exhibited the highest CO₂ conversion of 29.3% and low carbon olefin selectivity of 33.8% with Fe/Zn=1. The results of charging showed that the modulating effect of Zn could effectively increase the dispersion degree of Fe nanoparticles and reduce the reduction temperature of Fe-based catalysts, while Zn was also able to promote the formation of iron carbide, which enhanced the performance of CO₂ hydrogenation to low-carbon olefins.

Key words: carbon dioxide, low-carbon olefins, catalyst, Zn modulation, activity, iron carbide

摘要：

目前，二氧化碳（CO₂）的过度排放导致温室效应、冰川融化和气候异常等问题，为了解决这一问题，提出了CO₂加氢制备各种高附加值的化学品，不仅可以有效降低CO₂浓度过高的问题，同时也可以实现CO₂的资源化利用缓解能源危机。本研究采用共沉淀和等量浸渍的方法制备了Zn调控的K-nFe/Zn催化剂用于CO₂加氢制低碳烯烃（C₂⁼~C₄⁼），重点考察了Zn含量对于Fe基催化剂反应活性和目标产物选择性的影响。催化剂评价结果表明，在320℃、3MPa和H₂/CO₂=3的条件下，当Fe/Zn=1时催化剂表现出最高29.3%的CO₂转化率和33.8%的低碳烯烃选择性。表征结果显示，Zn的调控作用可以有效提高Fe纳米粒子的分散程度，降低Fe基催化剂的还原温度，同时Zn也能够促进催化活性相碳化铁的形成，从而提升CO₂加氢制低碳烯烃的性能。

关键词: 二氧化碳, 低碳烯烃, 催化剂, Zn调控, 活性, 碳化铁

CLC Number:

TQ426

LIU Jiangtao, PENG Chong, ZHANG Yongchun. Low-carbon olefins from CO₂ hydrogenation over Zn-modulated Fe-based catalysts[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1396-1405.

刘江涛, 彭冲, 张永春. Zn调控Fe基催化剂催化CO₂加氢制低碳烯烃[J]. 化工进展, 2025, 44(3): 1396-1405.

Figures/Tables 16

References 40

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催化剂	氧化铁晶相	晶粒尺寸/nm
K-Fe	Fe₂O₃	33.56
K-6Fe/Zn	Fe₂O₃	28.36
K-3Fe/Zn	Fe₂O₃	25.88
K-1Fe/Zn	Fe₂O₃	24.36

催化剂	氧化铁晶相	晶粒尺寸/nm
K-Fe	Fe₂O₃	33.56
K-6Fe/Zn	Fe₂O₃	28.36
K-3Fe/Zn	Fe₂O₃	25.88
K-1Fe/Zn	Fe₂O₃	24.36

催化剂	比表面积/m²∙g^-1	孔径/nm	孔体积/cm³∙g^-1
K-Fe	30.39	11.87	0.18
K-6Fe/Zn	37.72	11.48	0.21
K-3Fe/Zn	39.12	8.84	0.23
K-1Fe/Zn	44.30	6.36	0.27

催化剂	比表面积/m²∙g^-1	孔径/nm	孔体积/cm³∙g^-1
K-Fe	30.39	11.87	0.18
K-6Fe/Zn	37.72	11.48	0.21
K-3Fe/Zn	39.12	8.84	0.23
K-1Fe/Zn	44.30	6.36	0.27

元素	质量分数/%	原子分数/%
Fe	38.74	34.86
Zn	41.38	27.76
O	18.71	36.15
K	1.17	1.23
总量	100	100

Low-carbon olefins from CO₂ hydrogenation over Zn-modulated Fe-based catalysts

Zn调控Fe基催化剂催化CO₂加氢制低碳烯烃

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Figures/Tables 16

References 40

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催化剂	CO₂转化率/%	CO选择性%	烃类选择性/%				参考文献
催化剂	CO₂转化率/%	CO选择性%	CH₄	C₂~C₄^p	C₂~C₄⁼	C₅⁺	参考文献
Fe₃O₄	27.0	35.9	43.2	33.9	5.7	17.2	[37]
5Fe-1Zr-Ce-1K	28.1	10.5	46.8	22.5	25.2	5.5	[38]
0.1Mn-Na/Fe	35.7	10.9	7.3	2.5	24.1	54.7	[39]
K-Fe-Co	23.8	31.4	17.0	4.0	11.5	36.1	[40]
K-1Fe/Zn	29.3	18.1	13.9	12.4	33.8	39.8	本研究

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元素	质量分数/%	原子分数%
C Fe	39.7 18.3	56.0 16.5
Zn	30.4	20.4
O	11.1	5.5
K	0.5	1.6
总量	100	100

元素	质量分数/%	原子分数%
C Fe	39.7 18.3	56.0 16.5
Zn	30.4	20.4
O	11.1	5.5
K	0.5	1.6
总量	100	100