铁矿石对铁焦气化的促进作用：结构演化、影响机理及动力学分析

王杰; 王炜; 陈绪亨; 鲍俊芳; 郝秋月; 郑恒; 徐润生

doi:10.1007/s12613-024-2873-0

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文章导航 > 矿物冶金与材料学报（英文） > 2025 > 二校

Jie Wang, Wei Wang, Xuheng Chen, Junfang Bao, Qiuyue Hao, Heng Zheng, and Runsheng Xu, Role of iron ore in enhancing gasification of iron coke: Structural evolution, influence mechanism and kinetic analysis, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2873-0

Cite this article as:

Jie Wang, Wei Wang, Xuheng Chen, Junfang Bao, Qiuyue Hao, Heng Zheng, and Runsheng Xu, Role of iron ore in enhancing gasification of iron coke: Structural evolution, influence mechanism and kinetic analysis, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2873-0

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研究论文

铁矿石对铁焦气化的促进作用：结构演化、影响机理及动力学分析

1)
湖北工程学院化学与材料科学学院, 孝感 432000, 中国
2)
武汉科技大学钢铁冶金及资源利用省部共建教育部重点实验室, 武汉 430081, 中国
3)
宝钢中央研究院炼铁技术研究所, 上海 201999, 中国
4)
北京科技大学绿色低碳钢铁冶金全国重点实验室, 北京 100083, 中国

通讯作者:
陈绪亨 E-mail: chenxuheng0627@163.com

徐润生 E-mail: xurunsheng@ustb.edu.cn

文章亮点

(1) 系统研究了铁矿石含量对铁焦微观结构的影响规律。

(2) 揭示了气化反应过程中铁焦结构对动力学行为的作用机制。

(3) 确定了不同铁矿石添加量下铁焦的关键动力学模型及参数。

中文摘要

高反应性铁焦的使用为低碳炼铁提供了一条绿色途径。为了揭示铁矿石对铁焦气化行为和动力学的影响机理，本文探究了铁矿石对铁焦微观结构的影响机制，还通过非等温热重法对铁焦和焦炭的气化反应进行了对比研究。研究结果表明，与焦炭相比，铁焦的微孔和比表面积较大，且微孔会进一步扩展并相互连接，这为气化剂二氧化碳分子提供了更多的吸附位点，从而降低了铁焦的气化起始温度。结合SEM、XRD和拉曼研究发现从铁矿石中还原出来的金属铁嵌入炭基质中，降低了铁焦碳结构的有序性和石墨化程度，这是铁焦碳原子气化反应活性提高的主要原因。同时，在非等温气化过程中加快升温速度可提高铁焦的气化反应活性。动力学研究表明，由于铁焦具有丰富的孔隙结构，随机孔模型可以有效地表示铁焦的气化过程。并且随着铁矿石含量的增加，气化活化能从焦炭的 246.2 kJ/mol 逐步降低至含15wt%铁矿石铁焦的192.5 kJ/mol。本研究为铁焦气化反应行为及动力学提供了深入机制理解，对于合理设计高反应性铁焦具有重要的基础和技术意义。

关键词:

Research Article

Role of iron ore in enhancing gasification of iron coke: Structural evolution, influence mechanism and kinetic analysis

+ Author Affiliations

1)
School of Chemistry and Materials Science, Hubei Engineering University, Xiaogan 432000, China
2)
Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, China
3)
Institue of Ironmaking Technology, Baosteel Central Research Institute, Shanghai 201999, China
4)
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China

The authors have no relevant financial or non-financial interests to disclose.

Corresponding authors:
Xuheng Chen E-mail: chenxuheng0627@163.com

Runsheng Xu E-mail: xurunsheng@ustb.edu.cn
Received: 8 January 2024; Revised: 29 February 2024; Accepted: 5 March 2024; Available online: 7 March 2024

Abstract

Abstract

The utilization of iron coke provides a green pathway for low-carbon ironmaking. To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification, the effect of iron ore on the microstructure of iron coke was investigated. Furthermore, a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method. The findings indicate that compared to coke, iron coke exhibits an augmentation in micropores and specific surface area, and the micropores further extend and interconnect. This provides more adsorption sites for CO₂ molecules during the gasification process, resulting in a reduction in the initial gasification temperature of iron coke. Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke. The metallic iron reduced from iron ore is embedded in the carbon matrix, reducing the orderliness of the carbon structure, which is primarily responsible for the heightened reactivity of the carbon atoms. The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure. Moreover, as the proportion of iron ore increases, the activation energy for the carbon gasification gradually decreases, from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.
- low-carbon ironmaking;
- iron coke;
- gasification;
- structural evolution;
- kinetic model

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References

[1]	J.Y. Yu, R.S. Xu, J.L. Zhang, and A.Y. Zheng, A review on reduction technology of air pollutant in current China’s iron and steel industry, J. Clean. Prod., 414(2023), art. No. 137659. doi: 10.1016/j.jclepro.2023.137659
[2]	C.M. Tang, Z.Q. Guo, J. Pan, et al., Current situation of carbon emissions and countermeasures in China’s ironmaking industry, Int. J. Miner. Metall. Mater., 30(2023), No. 9, p. 1633. doi: 10.1007/s12613-023-2632-7
[3]	J.L. Zhang, H.Y. Fu, Y.X. Liu, et al., Review on biomass metallurgy: Pretreatment technology, metallurgical mechanism and process design, Int. J. Miner. Metall. Mater., 29(2022), No. 6, p. 1133. doi: 10.1007/s12613-022-2501-9
[4]	C. Wu, Y. Zhuo, X. Xu, et al., An integrated experimental and numerical study of iron-coke briquettes’ pyrolysis and reduction behaviour in an industrial-scale pyrolyser, Powder Technol., 409(2022), art. No. 117822. doi: 10.1016/j.powtec.2022.117822
[5]	Z.Y. Wang, D. Han, Z.G. Liu, et al., Gas release characteristics during carbonization of iron coke hot briquette and influence of heating rate, J. Iron Steel Res. Int., 30(2023), No. 11, p. 2163. doi: 10.1007/s42243-023-01046-9
[6]	J. Wang, W. Wang, J.F. Bao, X.F. Chen, L.F. Duan and R.S. Xu, Performance optimization and efficient application of highly reactive iron coke: Research progress and future trend, Steel Res. Int., 94(2023), No. 9, art. No. 2300092. doi: 10.1002/srin.202300092
[7]	F.R. Chen, W. Lv, G.W. Zhou, Z.L. Liu, M.S. Chu, and X.W. Lv, Effects of H₂, CO, and a gas mixture on the reduction process of raw and pre-oxidized ilmenite concentrate powders, Int. J. Hydrogen Energy, 55(2024), p. 502. doi: 10.1016/j.ijhydene.2023.11.217
[8]	J. Wang, W. Wang, X.H. Chen, et al., Investigation on the evolution of structure and strength of iron coke during carbonization: Carbon structure, pore structure, and carbonization mechanism, Powder Technol., 431(2024), art. No. 119059. doi: 10.1016/j.powtec.2023.119059
[9]	S. Nomura, K. Higuchi, K. Kunitomo, and M. Naito, Reaction behavior of Formed Iron Coke and Its Effect on Decreasing Thermal Reserve Zone Temperature in Blast Furnace, ISIJ Int., 50(2010), No. 10, p. 1388. doi: 10.2355/isijinternational.50.1388
[10]	S.Z. Shi, S. Lu, X.G. Bi, P. Li, and Q. Zheng, Decreasing of reaction beginning temperature of iron coke and its mechanism, Iron Steel, 50(2015), No. 7, p. 15.
[11]	S.X. Qiu, S.F. Zhang, Q.Y. Zhang, G.B. Qiu, and L.Y. Wen, Effects of iron compounds on pyrolysis behavior of coals and metallurgical properties of resultant cokes, J. Iron Steel Res. Int., 24(2017), No. 12, p. 1169. doi: 10.1016/S1006-706X(18)30014-1
[12]	J.W. Bao, M.S. Chu, Z.G. Liu, et al., Research progress on preparation and application of iron coke in blast furnace, Iron Steel, 55(2020), No. 8, p. 38. doi: 10.13228/j.boyuan.issn0449-749x.20200187
[13]	J.W. Bao, M.S. Chu, Z.G. Liu, et al., Effect of carbonization process parameters on metallurgical properties of iron coke, J. Iron Steel Res., 32(2020), No. 7, p. 532. doi: 10.13228/j.boyuan.issn1001-0963.20200059
[14]	H.T. Wang, M.S. Chu, B.Y. Guo, et al., , Investigation on gasification reaction behavior and kinetic analysis of iron coke hot briquette under isothermal conditions, Steel Res. Int., 90(2019), No. 2, art. No. 1800354. doi: 10.1002/srin.201800354
[15]	H.T. Wang, M.S. Chu, J.W. Bao, Z.G. Liu, J. Tang, and H.M. Long, Experimental study on impact of iron coke hot briquette as an alternative fuel on isothermal reduction of pellets under simulated blast furnace conditions, Fuel, 268(2020), art. No. 117339. doi: 10.1016/j.fuel.2020.117339
[16]	K. Zhu, Z.M. Chen, S.X. Ye, S.H. Geng, Y.W. Zhang, and X.G. Lu, Gasification of iron coke and cogasification behavior of iron coke and coke under simulated hydrogen-rich blast furnace condition, Int. J. Miner. Metall. Mater., 29(2022), No. 10, p. 1839. doi: 10.1007/s12613-022-2429-0
[17]	Z.J. Liu, M.H. Cao, J.L. Zhang, et al., Synergistic reaction behavior of pyrolysis and reduction of briquette prepared by weakly caking coal and metallurgical dust, J. Iron Steel Res. Int., 30(2023), No. 7, p. 1367. doi: 10.1007/s42243-023-00992-8
[18]	Z.G. Liu, L.G. Cao, M.S. Chu, et al., A new type of composite coke prepared from steel slag and mixed coal: Preparation process and microstructure, Steel Res. Int., 92(2021), No. 7, art. No. 2000697. doi: 10.1002/srin.202000697
[19]	R.S. Xu, S.L. Deng, H. Zheng, W. Wang, M.M. Song, W. Xu, and F.F. Wang, Influence of initial iron ore particle size on CO₂ gasification behavior and strength of ferro-coke, J. Iron Steel Res. Int., 27(2020), No. 8, p. 875. doi: 10.1007/s42243-020-00454-5
[20]	R.S. Xu, X.M. Huang, W. Wang, S.L. Deng, H. Zheng, M.M. Song, and F.F. Wang, Investigation on the microstructure, thermal strength and gasification mechanism of modified ferro-coke with coal tar pitch, Metall. Mater. Trans. B, 51(2020), No. 4, p. 1526. doi: 10.1007/s11663-020-01867-z
[21]	R.S. Xu, S.L. Deng, H. Zheng, et al., Gasification behaviors of ferrocoke with and without water vapor, Steel Res. Int., 93(2022), No. 11, art. No. 2200575. doi: 10.1002/srin.202200575
[22]	J. Wang, L. Qie, Y. Hu, H. Liu, and G. Zheng, Influence of zinc on nonisothermal gasification kinetics of coke in a blast furnace, ACS Omega, 6(2021), No. 43, p. 28838. doi: 10.1021/acsomega.1c03726
[23]	R.S. Xu, J.L. Zhang, G.W. Wang, et al., Isothermal kinetic analysis on fast pyrolysis of lump coal used in COREX process, J. Therm. Anal. Calorim., 123(2016), No. 1, p. 773. doi: 10.1007/s10973-015-4972-7
[24]	S.K. Bhatia and D.D. Perlmutter, A random pore model for fluid-solid reactions: I. Isothermal, kinetic control, AlChE J., 26(1980), No. 3, p. 379. doi: 10.1002/aic.690260308
[25]	J. Bai, W. Li, C.Z. Li, Z.Q. Bai, and B.Q. Li, Influences of mineral matter on high temperature gasification of coal char, J. Fuel Chem. Technol., 37(2009), No. 2, p. 134. doi: 10.1016/S1872-5813(09)60014-1
[26]	J. Szekely and J.W. Evans, A structural model for gas–solid reactions with a moving boundary, Chem. Eng. Sci., 25(1970), No. 6, p. 1091. doi: 10.1016/0009-2509(70)85053-9
[27]	J. Fermoso, M.V. Gil, C. Pevida, J.J. Pis, and F. Rubiera, Kinetic models comparison for non-isothermal steam gasification of coal–biomass blend chars, Chem. Eng. J., 161(2010), No. 1-2, p. 276. doi: https://doi.org/10.1016/j.cej.2010.04.055
[28]	S. Vyazovkin, A.K. Burnham, J.M. Criado, L.A. Pérez-Maqueda, C. Popescu, and N. Sbirrazzuoli, ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data, Thermochim. Acta, 520(2011), No. 1-2, p. 1. doi: 10.1016/j.tca.2011.03.034
[29]	Z.M. Wang, K.L. Pang, K.J. Li, et al., Positive catalytic effect and mechanism of iron on the gasification reactivity of coke using thermogravimetry and density functional theory, ISIJ Int., 61(2021), No. 3, p. 773. doi: 10.2355/isijinternational.ISIJINT-2020-348
[30]	K.J. Li, J.L. Zhang, Z.J. Liu, X.J. Ning, and T.Q. Wang, Gasification of graphite and coke in carbon–carbon dioxide–sodium or potassium carbonate systems, Ind. Eng. Chem. Res., 53(2014), No. 14, p. 5737. doi: 10.1021/ie4039955
[31]	X. Zhang, J. Zhang, R. Guo, Q. Xiao, Y.W. Feng, and H. Cheng, Highly reactive coke made from low-rank coal: Relationship between thermal properties and multilevel structure, Fuel, 337(2023), art. No. 127186. doi: 10.1016/j.fuel.2022.127186
[32]	X. Zhang, H.H. Deng, X.Y. Hou, R.L. Qiu, and Z.H. Chen, Pyrolytic behavior and kinetic of wood sawdust at isothermal and non-isothermal conditions, Renewable Energy, 142(2019), p. 284. doi: 10.1016/j.renene.2019.04.115
[33]	G.W. Wang, S. Ren, J.L. Zhang, et al., Influence mechanism of alkali metals on CO₂ gasification properties of metallurgical coke, Chem. Eng. J., 387(2020), art. No. 124093. doi: 10.1016/j.cej.2020.124093
[34]	G.W. Wang, J.L. Zhang, G.H. Zhang, et al., Experimental and kinetic studies on co-gasification of petroleum coke and biomass char blends, Energy, 131(2017), p. 27. doi: 10.1016/j.energy.2017.05.023
[35]	L. Kieush, J. Schenk, A. Pfeiffer, A. Koveria, G. Rantitsch, and H. Hopfinger, Investigation on the influence of wood pellets on the reactivity of coke with CO₂ and its microstructure properties, Fuel, 309(2022), art. No. 122151. doi: 10.1016/j.fuel.2021.122151
[36]	M.M. Sun, J.L. Zhang, K.J. Li, K. Guo, Z.M. Wang, and C.H. Jiang, Gasification kinetics of bulk coke in the CO₂/CO/H₂/H₂O/N₂ system simulating the atmosphere in the industrial blast furnace, Int. J. Miner. Metall. Mater., 26(2019), No. 10, p. 1247. doi: 10.1007/s12613-019-1846-1
[37]	H.B. Zhu, W.L. Zhan, Z.J. He, Y.C. Yu, Q.H. Pang, and J.H. Zhang, Pore structure evolution during the coke graphitization process in a blast furnace, Int. J. Miner. Metall. Mater., 27(2020), No. 9, p. 1226. doi: 10.1007/s12613-019-1927-1
[38]	K.J. Li, J.L. Zhang, M. Barati, et al., Influence of alkaline (Na, K) vapors on carbon and mineral behavior in blast furnace cokes, Fuel, 145(2015), p. 202. doi: 10.1016/j.fuel.2014.12.086
[39]	T. Murakami and E. Kasai, Utilization of ores with high combined water content for ore–carbon composite and iron coke, ISIJ Int., 51(2011), No. 8, p. 1220. doi: 10.2355/isijinternational.51.1220
[40]	L. Deng, X.L. Huang, Y. Tie, et al., Experimental study on transformation of alkali and alkaline earth metals during biomass gasification, J. Energy Inst., 103(2022), p. 117. doi: 10.1016/j.joei.2022.06.003
[41]	W. Wang, J. Wang, R.S. Xu, Y. Yu, Y. Jin, and Z.L. Xue, Influence mechanism of zinc on the solution loss reaction of coke used in blast furnace, Fuel Process. Technol., 159(2017), p. 118. doi: 10.1016/j.fuproc.2017.01.039
[42]	H. Gohar, A.H. Khoja, A.A. Ansari, et al., Investigating the characterisation, kinetic mechanism, and thermodynamic behaviour of coal–biomass blends in co-pyrolysis process, Process. Saf. Environ. Prot., 163(2022), p. 645. doi: 10.1016/j.psep.2022.05.063
[43]	R. Xu, B.W. Dai, W. Wang, J. Schenk, and Z. Xue, Effect of iron ore type on the thermal behaviour and kinetics of coal-iron ore briquettes during coking, Fuel Process. Technol., 173(2018), p. 11. doi: 10.1016/j.fuproc.2018.01.006
[44]	J.C. Maya, R. Macías, C.A. Gómez, and F. Chejne, On the evolution of pore microstructure during coal char activation with steam/CO₂ mixtures, Carbon, 158(2020), p. 121. doi: 10.1016/j.carbon.2019.11.088
[45]	W. Lv, F.R. Chen, Z.L. Liu, et al. , In situ compressive strength of iron coke in high-temperature carbonization, ISIJ Int., 62(2022), No. 9, p. 1827. doi: 10.2355/isijinternational.ISIJINT-2022-219
[46]	W.T. Guo, Q.G. Xue, C. Ling, H.B. Zuo, J.S. Wang, and Y.H. Han, Influence of pore structure features on the high temperature tensile strength of coke, Chin. J. Eng., 38(2016), No. 7, p. 930. doi: 10.13374/j.issn2095-9389.2016.07.006
[47]	J.W. Bao, M.S. Chu, H.T. Wang, et al., Evolution characteristics and influence mechanism of binder addition on metallurgical properties of iron carbon agglomerates, Metall. Mater. Trans. B, 51(2020), No. 6, p. 2785. doi: 10.1007/s11663-020-01962-1
[48]	A. Sadezky, H. Muckenhuber, H. Grothe, R. Niessner, and U. Pöschl, Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information, Carbon, 43(2005), No. 8, p. 1731. doi: 10.1016/j.carbon.2005.02.018
[49]	H. Dang, R.S. Xu, J.L. Zhang, M.Y. Wang, and J.H. Li, Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production: Physicochemical characteristics and gasification kinetics analysis, Int. J. Miner. Metall. Mater., 31(2024), No. 2, p. 268. doi: 10.1007/s12613-023-2728-0
[50]	T. Jawhari, A. Roid, and J. Casado, Raman spectroscopic characterization of some commercially available carbon black materials, Carbon, 33(1995), No. 11, p. 1561. doi: 10.1016/0008-6223(95)00117-V
[51]	M.J. Roberts, R.C. Everson, G. Domazetis, et al., Density functional theory molecular modelling and experimental particle kinetics for CO₂–char gasification, Carbon, 93(2015), p. 295. doi: 10.1016/j.carbon.2015.05.053
[52]	D. Zhao, H. Liu, C.L. Sun, L.F. Xu, and Q.X. Cao, DFT study of the catalytic effect of Na on the gasification of carbon: CO₂, Combust. Flame, 197(2018), p. 471. doi: 10.1016/j.combustflame.2018.09.002
[53]	H. Dang, R.S. Xu, J.L. Zhang, M.Y. Wang, and K. Xu, Hydrothermal carbonization of waste furniture for clean blast furnace fuel production: Physicochemical, gasification characteristics and conversion mechanism investigation, Chem. Eng. J., 469(2023), art. No. 143980. doi: 10.1016/j.cej.2023.143980
[54]	P. Wang, G.W. Wang, J.L. Zhang, J.Y. Lee, Y.J. Li, and C. Wang, Co-combustion characteristics and kinetic study of anthracite coal and palm kernel shell char, Appl. Therm. Eng., 143(2018), p. 736. doi: 10.1016/j.applthermaleng.2018.08.009
[55]	G.W. Wang, J.L. Zhang, J.G. Shao, et al., Experimental and modeling studies on CO₂ gasification of biomass chars, Energy, 114(2016), p. 143. doi: 10.1016/j.energy.2016.08.002
[56]	W. Liang, X. Ning, G.W. Wang, et al., Influence mechanism and kinetic analysis of co-gasification of biomass char and semi-coke, Renew. Energy, 163(2021), p. 331. doi: 10.1016/j.renene.2020.08.142
[57]	M. Grigore, R. Sakurovs, D. French, and V. Sahajwalla, Coke gasification: The influence and behavior of inherent catalytic mineral matter, Energy Fuels, 23(2009), No. 4, p. 2075. doi: 10.1021/ef8006728
[58]	S.M. Shin and S.M. Jung, Gasification effect of metallurgical coke with CO₂ and H₂O on the porosity and macrostrength in the temperature range of 1100 to 1500°C, Energy Fuels, 29(2015), No. 10, p. 6849. doi: 10.1021/acs.energyfuels.5b01235
[59]	Q. Wang, E. Wang, K. Li, N. Husnain, and D. Li, Synergistic effects and kinetics analysis of biochar with semi-coke during CO₂ co-gasification, Energy, 191(2020), art. No. 116528. doi: 10.1016/j.energy.2019.116528
[60]	J. Zsakó, The kinetic compensation effect, J. Therm. Anal., 9(1976), No. 1, p. 101. doi: 10.1007/BF01909271
[61]	S. Zhang, Z. Liang, K. Li, J. Zhang, and S. Ren, A density functional theory study on the adsorption reaction mechanism of double CO₂ on the surface of graphene defects, J. Mol. Model., 28(2022), No. 5, art. No. 118. doi: 10.1007/s00894-022-05105-y