Zn调控Fe基催化剂催化CO2加氢制低碳烯烃

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

摘要/Abstract

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

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

中图分类号:

TQ426

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.

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.

图/表 16

参考文献 40

1	BARRIOS Alan J, PERON Deizi V, CHAKKINGAL Anoop, et al. Efficient promoters and reaction paths in the CO₂ hydrogenation to light olefins over zirconia-supported iron catalysts[J]. ACS Catalysis, 2022, 12(5): 3211-3225.
2	YUAN Fei, ZHANG Guanghui, WANG Mingrui, et al. Boosting the production of light olefins from CO₂ hydrogenation over Fe-Co bimetallic catalysts derived from layered double hydroxide[J]. Industrial & Engineering Chemistry Research, 2023, 62(21): 8210-8221.
3	WANG Shunwu, WU Tijun, LIN Jun, et al. Iron-potassium on single-walled carbon nanotubes as efficient catalyst for CO₂ hydrogenation to heavy olefins[J]. ACS Catalysis, 2020, 10(11): 6389-6401.
4	姜霞, 李雯, 郭云龙, 等. 生物模板法制备金属氧化物及其催化应用研究进展[J]. 化工进展, 2019, 38(1): 485-494.
	JIANG Xia, LI Wen, GUO Yunlong, et al. Progress on bio-templated synthesis of metal oxides and their catalytic applications[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 485-494.
5	周红军, 周颖, 徐春明. 中国碳中和目标下CO₂转化的思考与实践[J]. 化工进展, 2022, 41(6): 3381-3385.
	ZHOU Hongjun, ZHOU Ying, XU Chunming. Exploration of the CO₂ conversion under China’s carbon neutrality goal[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3381-3385.
6	WEBER Daniel, HE Tina, WONG Matthew, et al. Recent advances in the mitigation of the catalyst deactivation of CO₂ hydrogenation to light olefins[J]. Catalysts, 2021, 11(12): 1447.
7	XU Qiangqiang, XU Xingqin, FAN Guoli, et al. Unveiling the roles of Fe-Co interactions over ternary spinel-type ZnCo _x Fe_2- _x O₄ catalysts for highly efficient CO₂ hydrogenation to produce light olefins[J]. Journal of Catalysis, 2021, 400: 355-366.
8	贾晨喜, 邵敬爱, 白小薇, 等. 二氧化碳加氢制甲醇铜基催化剂性能的研究进展[J]. 化工进展, 2020, 39(9): 3658-3668.
	JIA Chenxi, SHAO Jing’ai, BAI Xiaowei, et al. Review on Cu-based catalysts for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3658-3668.
9	XU Yao, ZHAI Peng, DENG Yuchen, et al. Highly selective olefin production from CO₂ hydrogenation on iron catalysts: A subtle synergy between manganese and sodium additives[J]. Angewandte Chemie International Edition, 2020, 59(48): 21736-21744.
10	KIM Kwang Young, LEE Hojeong, Woo Yeong NOH, et al. Cobalt ferrite nanoparticles to form a catalytic Co-Fe alloy carbide phase for selective CO₂ hydrogenation to light olefins[J]. ACS Catalysis, 2020, 10(15): 8660-8671.
11	WANG Shunwu, JI Yushan, LIU Xuancheng, et al. Potassium as a versatile promoter to tailor the distribution of the olefins in CO₂ hydrogenation over iron-based catalyst[J]. ChemCatChem, 2022, 14(6): e202101535.
12	JIANG Jiandong, WEN Chengyan, TIAN Zhipeng, et al. Manganese-promoted Fe₃O₄ microsphere for efficient conversion of CO₂ to light olefins[J]. Industrial & Engineering Chemistry Research, 2020, 59(5): 2155-2162.
13	ELISHAV Oren, SHENER Yuval, BEILIN Vadim, et al. Electrospun Fe-Al-O nanobelts for selective CO₂ hydrogenation to light olefins[J]. ACS Applied Materials & Interfaces, 2020, 12(22): 24855-24867.
14	YANG Miao, FAN Dong, WEI Yingxu, et al. Recent progress in methanol-to-olefins (MTO) catalysts[J]. Advanced Materials, 2019, 31(50): 1902181.
15	BARGER Paul. Methanol to olefins (MTO) and beyond[M]//Zeolites for cleaner technologies. London: Imperial College Press, 2002: 239-260.
16	TIAN Peng, WEI Yingxu, YE Mao, et al. Methanol to olefins (MTO): From fundamentals to commercialization[J]. ACS Catalysis, 2015, 5(3): 1922-1938.
17	JIANG Mingyang, LIU Siyi, DENG Huachu, et al. The efficacy and safety of fast track surgery (FTS) in patients after hip fracture surgery: A meta-analysis[J]. Journal of Orthopaedic Surgery and Research, 2021, 16(1): 162.
18	ZHU Yi fen, XIE Bingqiao, AMAL Rose, et al. Light-enhanced conversion of CO₂ to light olefins: Basis in thermal catalysis, current progress, and future prospects[J]. Small Structures, 2023, 4(6): 2200285.
19	WANG Kai, LIU Na, WEI Jian, et al. Bifunctional CoFe/HZSM-5 catalysts orient CO₂ hydrogenation towards liquid hydrocarbons[J]. Chemical Communications, 2023, 59(92): 13767-13770.
20	HAN Xiao, QING Ming, WANG Hong, et al. Effect of Fe₃O₄ content on the CO₂ selectivity of iron-based catalyst for Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology, 2023, 51(2): 155-164.
21	CHENG Yang, CHEN Yong, ZHANG Shuxian, et al. High-yield production of aromatics over CuFeO₂/hierarchical HZSM-5 via CO₂ Fischer-Tropsch synthesis[J]. Green Chemistry, 2023, 25(9): 3570-3584.
22	LIU Renjie, BERCH John N EL, HOUSE Stephen, et al. Reactive separations of CO/CO₂ mixtures over Ru-Co single atom alloys[J]. ACS Catalysis, 2023, 13(4): 2449-2461.
23	TORRES GALVIS Hirsa M, DE JONG Krijn P. Catalysts for production of lower olefins from synthesis gas: A review[J]. ACS Catalysis, 2013, 3(9): 2130-2149.
24	HAN Seung Ju, HWANG Sun-Mi, PARK Hae-Gu, et al. Identification of active sites for CO₂ hydrogenation in Fe catalysts by first-principles microkinetic modelling[J]. Journal of Materials Chemistry A, 2020, 8(26): 13014-13023.
25	SHAFER Wilson D, JACOBS Gary, GRAHAM Uschi M, et al. Increased CO₂ hydrogenation to liquid products using promoted iron catalysts[J]. Journal of Catalysis, 2019, 369: 239-248.
26	MALHI Haripal Singh, SUN Chao, ZHANG Zhengzhou, et al. Catalytic consequences of the decoration of sodium and zinc atoms during CO₂ hydrogenation to olefins over iron-based catalyst[J]. Catalysis Today, 2022, 387: 28-37.
27	YANG Qingxin, KONDRATENKO Vita A, PETROV Sergey A, et al. Identifying performance descriptors in CO₂ hydrogenation over iron-based catalysts promoted with alkali metals[J]. Angewandte Chemie International Edition, 2022, 61(22): e202116517.
28	ZHAO Yunxia, MA Jiajun, YIN Juli, et al. Alkali metal promotion on Fe-Co-Ni trimetallic catalysts for CO₂ hydrogenation to light olefins[J]. Applied Surface Science, 2024, 657: 159783.
29	WANG Dong, XIE Zhenhua, POROSOFF Marc D, et al. Recent advances in carbon dioxide hydrogenation to produce olefins and aromatics[J]. Chem, 2021, 7(9): 2277-2311.
30	CHOI Yo Han, JANG Youn Jeong, PARK Hunmin, et al. Carbon dioxide Fischer-Tropsch synthesis: A new path to carbon-neutral fuels[J]. Applied Catalysis B: Environmental, 2017, 202: 605-610.
31	ZHANG Zhenzhou, WEI Chongyang, JIA Lingyu, et al. Insights into the regulation of FeNa catalysts modified by Mn promoter and their tuning effect on the hydrogenation of CO₂ to light olefins[J]. Journal of Catalysis, 2020, 390: 12-22.
32	ZHANG Jianli, LU Shipeng, SU Xiaojuan, et al. Selective formation of light olefins from CO₂ hydrogenation over Fe-Zn-K catalysts[J]. Journal of CO₂ Utilization, 2015, 12: 95-100.
33	GAO Xinhua, ZHANG Jianli, CHEN Ning, et al. Effects of zinc on Fe-based catalysts during the synthesis of light olefins from the Fischer-Tropsch process[J]. Chinese Journal of Catalysis, 2016, 37(4): 510-516.
34	ZHANG Chao, XU Minjie, YANG Zixu, et al. Uncovering the electronic effects of zinc on the structure of Fe₅C₂-ZnO catalysts for CO₂ hydrogenation to linear α‍-olefins[J]. Applied Catalysis B: Environmental, 2021, 295: 120287.
35	SHINAGAWA Tsutomu, IZAKI Masanobu, INUI Haruyuki, et al. Microstructure and electronic structure of transparent ferromagnetic ZnO-spinel iron oxide composite films[J]. Chemistry of Materials, 2006, 18(3): 763-770.
36	ZHANG Zhiqiang, HUANG Gongxun, TANG Xinglei, et al. Zn and Na promoted Fe catalysts for sustainable production of high-valued olefins by CO₂ hydrogenation[J]. Fuel, 2022, 309: 122105.
37	XU Yuebing, SHI Chengming, LIU Bing, et al. Selective production of aromatics from CO₂ [J]. Catalysis Science & Technology, 2019, 9(3): 593-610.
38	ZHANG Jianli, SU Xiaojuan, WANG Xu, et al. Promotion effects of Ce added Fe–Zr–K on CO₂ hydrogenation to light olefins[J]. Reaction Kinetics, Mechanisms and Catalysis, 2018, 124(2): 575-585.
39	LIANG Binglian, SUN Ting, MA Junguo, et al. Mn decorated Na/Fe catalysts for CO₂ hydrogenation to light olefins[J]. Catalysis Science & Technology, 2019, 9(2): 456-464.
40	JIANG Feng, LIU Bing, GENG Shunshun, et al. Hydrogenation of CO₂ into hydrocarbons: Enhanced catalytic activity over Fe-based Fischer-Tropsch catalysts[J]. Catalysis Science & Technology, 2018, 8(16): 4097-4107.

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

Zn调控Fe基催化剂催化CO₂加氢制低碳烯烃

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 40

相关文章 15

编辑推荐

Metrics

本文评价

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

[1]	陶金泉, 贾亦静, 白天瑜, 姚荣鹏, 黄文斌, 崔岩, 周亚松, 魏强. Silicalite-1分子筛的低成本合成及其MTP催化性能[J]. 化工进展, 2025, 44(3): 1550-1558.
[2]	王文, 金央, 李军, 陈建钧, 陈明, 孟昕. 基于FeOOH原位生长制备用于CO₂吸收的超疏水PVDF膜[J]. 化工进展, 2025, 44(3): 1570-1577.
[3]	陈宇航, 李巧艳, 梁美生, 宋天远, 汪玥, 李思萌, 周宇璇. Sn掺杂Cu/CeZrO₂/γ-Al₂O₃对三效催化（TWC）反应的作用：提高低温活性和抗硫性[J]. 化工进展, 2025, 44(3): 1368-1377.
[4]	张馨儿, 裴刘军, 周雨蝶, 靳凯丽, 王际平. 基于TiO₂的光催化剂利用太阳能裂解水制氢研究进展[J]. 化工进展, 2025, 44(3): 1298-1308.
[5]	刘俊杰, 吴建民, 孙启文, 王建成, 孙燕. 茂金属催化线性α-烯烃聚合获取高分子量产物研究进展[J]. 化工进展, 2025, 44(3): 1309-1322.
[6]	朱国瑜, 葛棋, 付名利. 甲醇重整制氢催化剂耐久性评价和寿命预测方法[J]. 化工进展, 2025, 44(3): 1338-1346.
[7]	谢鑫瑶, 万芬, 伏炫羽, 范雨婷, 陈令修, 李鹏. Cu-Ag纳米团簇CO₂电催化还原性能和机理[J]. 化工进展, 2025, 44(3): 1387-1395.
[8]	左骥, 罗莉, 谢永锴, 陈文尧, 钱刚, 周兴贵, 段学志. 甲醇无氧脱氢制甲醛Cu催化剂的粒径效应[J]. 化工进展, 2025, 44(3): 1347-1354.
[9]	毕文涛, 王学林, 曲炜, 王从新, 田志坚. Mg改性对低铂载量Pt/ZSM-22烷烃加氢异构性能的影响[J]. 化工进展, 2025, 44(3): 1355-1367.
[10]	张茂润, 孙伟如, 马天麟, 辛志玲. Mo改性MnCe/SiC低温SCR脱硝催化剂抗SO₂中毒性能[J]. 化工进展, 2025, 44(3): 1378-1386.
[11]	张琪, 王涛, 张雪冰, 李为真, 程萌, 张魁, 吕毅军, 门卓武. 合成气/CO₂转化制高级醇Fe基催化剂研究进展[J]. 化工进展, 2025, 44(3): 1323-1337.
[12]	张琪, 王涛, 张雪冰, 李为真, 冯波, 蒋智慧, 吕毅军, 门卓武. 合成气制高级醇Co基催化剂研究进展[J]. 化工进展, 2025, 44(2): 773-787.
[13]	贾亦静, 陶金泉, 黄文斌, 刘昊然, 李蓉蓉, 姚荣鹏, 白天瑜, 魏强, 周亚松. CO₂加氢制低碳烯烃Fe基催化剂研究进展[J]. 化工进展, 2025, 44(2): 820-833.
[14]	廖旭, 王玮, 黄文婷, 熊文涛, 王泽宇, 覃佐东, 林金清. 生物质基催化剂在二氧化碳转化为环状碳酸酯中的研究进展[J]. 化工进展, 2025, 44(2): 834-846.
[15]	李章良, 杨月珠, 伍传田, 吕源财. 活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂固定化漆酶降解双酚A[J]. 化工进展, 2025, 44(2): 887-898.

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