Coke behavior with H₂O in a hydrogen-enriched blast furnace: A review

Abstract

Hydrogen-enriched blast furnace ironmaking has become an essential route to reduce CO₂ emissions in the ironmaking process. However, hydrogen-enriched reduction produces large amounts of H₂O, which places new demands on coke quality in a blast furnace. In a hydrogen-rich blast furnace, the presence of H₂O promotes the solution loss reaction. This result improves the reactivity of coke, which is 20%–30% higher in a pure H₂O atmosphere than in a pure CO₂ atmosphere. The activation energy range is 110–300 kJ/mol between coke and CO₂ and 80–170 kJ/mol between coke and H₂O. CO₂ and H₂O are shown to have different effects on coke degradation mechanisms. This review provides a comprehensive overview of the effect of H₂O on the structure and properties of coke. By exploring the interactions between H₂O and coke, several unresolved issues in the field requiring further research were identified. This review aims to provide valuable insights into coke behavior in hydrogen-rich environments and promote the further development of hydrogen-rich blast furnace ironmaking processes.

Keywords

hydrogen ironmaking / coke behavior / blast furnace / gasification / microstructure / kinetics

References

[1] Li KJ, Khanna R, Zhang JL, et al.. The evolution of structural order, microstructure and mineral matter of metallurgical coke in a blast furnace: A review. Fuel, 2014, 133: 194,

[2] Hasanbeigi A, Arens M, Price L. Alternative emerging ironmaking technologies for energy-efficiency and carbon dioxide emissions reduction: A technical review. Renewable Sustainable Energy Rev., 2014, 33: 645,

[3] Ghosh B, Sahoo BK, Niyogi OS, et al.. Coke structure evaluation for BF coke making. Int. J. Coal Prep. Util., 2017, 38(6): 321,

[4] Q. Shi, B. Zheng, Y. Zheng, et al., Co-benefits of CO₂ emission reduction from China’s clean air actions between 2013–2020, Nat. Commun., 13(2022), No. 1, art. No. 5061.

[5] Yang G, Zha D, Zhang C, Chen Q. Does environment-biased technological progress reduce CO₂ emissions in APEC economies? Evidence from fossil and clean energy consumption. Environ. Sci. Pollut. Res. Int., 2020, 27(17): 20984,

[6] L. Holappa, A general vision for reduction of energy consumption and CO₂ emissions from the steel industry, Metals, 10(2020), No. 9, art. No. 1117.

[7] Tang L, Xue XD, Bo X, et al.. Contribution of emissions from the iron and steel industry to air quality in China. Environ. Sci., 2020, 41(7): 2981

[8] Zhang XQ. The development trend of and suggestions for China’s hydrogen energy industry. Engineering, 2021, 7(6): 719,

[9] Zhao J, Zuo HB, Wang YJ, Wang JS, Xue QG. Review of green and low-carbon ironmaking technology. Ironmaking Steelmaking, 2019, 47: 296,

[10] Li JX, Wang P, Zhou LY, Cheng M. The reduction of wustite with high oxygen enrichment and high injection of hydrogenous fuel. ISIJ Int., 2007, 47(8): 1097,

[11] Lan CC, Zhang SH, Liu XJ, Liu R, Lyu Q. Kinetic behaviors of coke gasification with CO₂ and H₂O. ISIJ Int., 2021, 61(1): 167,

[12] Haapakangas J, Suopajärvi H, Iljana M, et al.. Coke reactivity in simulated blast furnace shaft conditions. Metall. Mater. Trans. B, 2016, 47(4): 2357,

[13] Fan XY, Li C, Wang MD, et al.. Effects of adding different proportions of H₂ to the simulated hydrogen-rich blast furnace. Chem. Eng. Technol., 2022, 45(12): 2284,

[14] X.B. Yu, Z.J. Hu, and Y.S. Shen, Modeling of hydrogen shaft injection in ironmaking blast furnaces, Fuel, 302(2021), art. No. 121092.

[15] J. Tang, M.S. Chu, F. Li, et al., Mathematical simulation and life cycle assessment of blast furnace operation with hydrogen injection under constant pulverized coal injection, J. Cleaner Prod., 278(2021), art. No. 123191.

[16] Zhao ZG, Yu XB, Shen YS, et al.. Model study of shaft injection of reformed coke oven gas in a blast furnace. Energy Fuels, 2020, 34(11): 15048,

[17] Qie YN, Lyu Q, Liu XJ, et al.. Effect of hydrogen addition on softening and melting reduction behaviors of ferrous burden in gas-injection blast furnace. Metall. Mater. Trans. B, 2018, 49(5): 2622,

[18] Shatokha V. Modeling of the effect of hydrogen injection on blast furnace operation and carbon dioxide emissions. Int. J. Miner. Metall. Mater., 2022, 29(10): 1851,

[19] A.M. Heikkilä, A.M. Koskela, M.O. Iljana, et al., Coke Gasification in blast furnace shaft conditions with H₂ and H₂O containing atmospheres, Steel Res. Int., 92(2021), No. 3, art. No. 2000456.

[20] Yi BJ, Zhang LQ, Yuan QX, Yan SP, Zheng CG. The evolution of coal char structure under the oxy-fuel combustion containing high H₂O. Fuel Process. Technol., 2016, 152: 294,

[21] Shin SM, Jung SM. 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, 2015, 29(10): 6849,

[22] Y. Ono, Y. Fukuda, Y. Sumitani, et al., Experimental and numerical study on degradation behavior of coke with CO₂ or H₂O gasification reaction at high temperature, Fuel, 309(2022), art. No. 122061.

[23] Numazawa Y, Hara Y, Matsukawa Y, et al.. Kinetic modeling of CO₂ and H₂O gasification reactions for metallurgical coke using a distributed activation energy model. ACS Omega, 2021, 6(17): 11436,

[24] Xu RS, Dai BW, Wang W, Schenk J, Bhattacharyya A, Xue ZL. Gasification reactivity and structure evolution of metallurgical coke under H₂O/CO₂ atmosphere. Energy Fuels, 2018, 32(2): 1188,

[25] Wang P, Zhang YQ, Long HM, et al.. Degradation behavior of coke reacting with H₂O and CO₂ at high temperature. ISIJ Int., 2017, 57(4): 643,

[26] M.W. Chapman, R.J. Nightingale, and B.J. Monaghan, Influence of coke ash on blast furnace hearth behaviour, [in] Australasian Conference on Chemical Engineering, 2011, P. 1.

[27] Grigore M, Sakurovs R, French D, Sahajwalla V. Influence of mineral matter on coke reactivity with carbon dioxide. ISIJ Int., 2006, 46(4): 503,

[28] Wang Q, Guo R, Zhao XF, Sun JF, Zhang S, Liu WZ. A new testing and evaluating method of cokes with greatly varied CRI and CSR. Fuel, 2016, 182: 879,

[29] Yan RJ, Liu ZG, Chu MS, Liu PJ. Effect of coke reactivity on softening-melting and dripping behaviors of sinter. Ironmaking Steelmaking., 2023, 50(8): 1094,

[30] Casal MD, Barriocanal C, Díez MA, Alvarez R. Influence of porosity and fissuring on coking pressure generation. Fuel, 2008, 87(12): 2437,

[31] Kubota Y, Nomura S, Arima T, Kato K. Quantitative evaluation of relationship between coke strength and pore structure. ISIJ Int., 2011, 51(11): 1800,

[32] Guo R, Wang Q. Relationship between coke properties and solution loss behavior and its influence on post-reaction strength of coke. Rev. Metall., 2012, 109(6): 443,

[33] Mochida I, Yoon SH, Qiao WM. Catalysts in syntheses of carbon and carbon precursors. J. Braz. Chem. Soc., 2006, 17(6): 1059,

[34] Tian Y, Li GY, Zhang H, Wang JP, et al.. Molecular basis for coke strength: Stacking-fault structure of wrinkled carbon layers. Carbon, 2020, 162: 56,

[35] Menéndez J A, Álvarez R, Pis J J. Determination of metallurgical coke reactivity at INCAR: NSC and ECE-INCAR reactivity tests. Ironmaking Steelmaking, 1999, 26(2): 117,

[36] Kojima K, Nishi TT, Yamaguchi T, Nakama H, Ida S. Changes in the properties of coke in blast furnace. ISIJ Int., 1977, 17(7): 401,

[37] Hatano M, Hiraoka B, Fukuda M, Masuike T. Analysis of the combustion zone in the experimental blast furnace. ISIJ Int., 1977, 17(2): 102,

[38] Ghosh B, Sahoo BK, Chakraborty B, et al.. Influence of coke structure on coke quality using image analysis method. Int. J. Coal Sci. Technol., 2018, 5(4): 473,

[39] Zhong QF, Mao QY, Zhang LY, Xiang JH, Xiao J, Mathews JP. Structural features of Qingdao petroleum coke from HRTEM lattice fringes: Distributions of length, orientation, stacking, curvature, and a large-scale image-guided 3D atomistic representation. Carbon, 2018, 129: 790,

[40] Xing X, Rogers H, Zhang GQ, et al.. Coke degradation under simulated blast furnace conditions. ISIJ Int., 2016, 56(5): 786,

[41] Xing X, Rogers H, Zhang GQ, et al.. Changes in pore structure of metallurgical cokes under blast furnace conditions. Energy Fuels, 2015, 30(1): 161,

[42] Li KJ, Zhang JL, Liu YX, et al.. Graphitization of coke and its interaction with slag in the hearth of a blast furnace. Metall. Mater. Trans. B, 2016, 47(2): 811,

[43] X.M. Zhang, S.Q. Wang, H. Chen, et al., Observation of carbon nanostructure and evolution of chemical structure from coal to graphite by high temperature treatment, using componential determination, X-ray diffraction and high-resolution transmission electron microscope, Fuel, 332(2023), No. 1, art. No. 126145.

[44] Li KJ, Zhang H, Li GY, et al.. ReaxFF molecular dynamics simulation for the graphitization of amorphous carbon: A parametric study. J. Chem. Theory Comput., 2018, 14(5): 2322,

[45] Zhang H. Relationship of coke reactivity and critical coke properties. Metall. Mater. Trans. B, 2019, 50(1): 204,

[46] Sun MM, Zhang JL, Li KJ, et al.. The interfacial behavior between coke and liquid iron: A comparative study on the influence of coke pore, carbon structure and ash. JOM, 2020, 72(6): 2174,

[47] Z.Z. Ding, Z. Sun, Q. Lu, et al., Boudouard reaction accompanied by graphitization of wrinkled carbon layers in coke gasification: A theoretical insight into the classical understanding, Fuel, 297(2021), art. No. 120747.

[48] Pusz S, Krzesi’nska M, Smkedowski Ł, Majewska J, Pilawa B, Kwieci’nska B. Changes in a coke structure due to reaction with carbon dioxide. Int. J. Coal Geol., 2010, 81(4): 287,

[49] R. Guo, C. Duan, Z. Sun, et al., Effect of pore structure and matrix reactivity on coke reactivity and post-reaction strength, Metall. Res. Technol., 114(2017), No. 5, art. No. 504.

[50] Longbottom RJ, Perkins J, O’brien G, Monaghan BJ. Effects of blast furnace representative temperatures and gas compositions on coke reactivity. ISIJ Int., 2023, 63(2): 282,

[51] Gupta S, Ye ZZ, Kanniala R, Kerkkonen O, Sahajwalla V. Coke graphitization and degradation across the tuyere regions in a blast furnace. Fuel, 2013, 113: 77,

[52] Vogt D, Weber JV, Rouzaud JN, Schneider M. Coke properties and their microstructure Part II: Coke carboxyreactivity: Relations to their texture. Fuel Process. Technol., 1988, 20: 155,

[53] Díez MA, Alvarez R, Barriocanal C. Coal for metallurgical coke production: Predictions of coke quality and future requirements for cokemaking. Int. J. Coal Geol., 2002, 50(1–4): 389,

[54] Nomura S, Naito M, Yamaguchi K. Post-reaction strength of catalyst-added highly reactive coke. ISIJ Int., 2007, 47(6): 831,

[55] Akiyama T, Sato H, Muramatsu A, Yagi JI. Feasibility study on blast furnace ironmaking system integrated with methanol synthesis for reduction of carbon dioxide emission and effective use of exergy. ISIJ Int., 1994, 33(11): 1136,

[56] Austin PR, Nogami H, Yagi JI. Prediction of blast furnace performance with top gas recycling. ISIJ Int., 1998, 38(3): 239,

[57] Chen WH, Hsu CL, Du SW. Thermodynamic analysis of the partial oxidation of coke oven gas for indirect reduction of iron oxides in a blast furnace. Energy, 2015, 86: 758,

[58] Trinkel V, Kieberger N, Bürgler T, et al.. Influence of waste plastic utilisation in blast furnace on heavy metal emissions. J. Cleaner Prod., 2015, 94: 312,

[59] Chang ZY, Wang P, Zhang JL, et al.. Effect of CO₂ and H₂O on gasification dissolution and deep reaction of coke. Int. J. Miner. Metall. Mater., 2018, 25(12): 1402,

[60] Iwanaga Y, Takatani K. Degradation behavior of coke at high-temperature zone in blast furnace. ISIJ Int., 1988, 28: 990,

[61] Li JX, Lu KC, Wang JJ, et al.. Influence of H₂O–CO₂ gas mixture on coke degradation. J. Anhui Univ. Technol. Nat. Sci., 2008, 25(3): 233

[62] W. Wang, B.W. Dai, R.S. Xu, Schenk, J. Wang, and Z.L. Xue, The Effect of H₂O on the Reactivity and Microstructure of Metallurgical Coke, Steel Res. Int., 88(2017), No. 8, art. No. 1700063.

[63] L. Liang, Z. Sun, H. Zhang, et al., Theoretical insight into the competitive effect of CO₂ and additive H₂O in coke gasification, Chem. Eng. J., 461(2023), art. No. 142003.

[64] Wang XS, Cheng YH, Li LJ. Protein function prediction based on active semi-supervised learning. Chin. J. Electron., 2016, 25(4): 595,

[65] Guo WT, Xue QG, Liu YL, et al.. Kinetic analysis of gasification reaction of coke with CO₂ or H₂O. Int. J. Hydrogen Energy, 2015, 40: 13306,

[66] Lan CC, Lyu Q, Liu XJ, Jiang MF, Qie YN, Zhang SH. Thermodynamic and kinetic behaviors of coke gasification in N₂–CO–CO₂–H₂–H₂O. Int. J. Hydrogen Energy., 2018, 43(42): 19405,

[67] Tanner J, Bhattacharya S. Kinetics of CO₂ and steam gasification of Victorian brown coal chars. Chem. Eng. J., 2016, 285: 331,

[68] Liu ZS, Wang Q. Non-isothermal kinetics of metallurgical coke gasification by carbon dioxide. Coke Chem., 2017, 60(4): 140,

[69] Fan XY, Li C, Wang MD, et al.. Gasification and kinetic study on metallurgical cokes in CO₂–N₂–H₂O and CO₂–N₂ atmosphere. Energy Sources Part A: Recovery Util. Environ. Eff., 2023, 45(1): 2144,

[70] Zhang H. Gasification of metallurgical coke in CO₂-CO-N₂ with and without H₂. Chem. Eng. J., 2018, 347: 440,

[71] Zhang LX, Huang JJ, Fang YT, Wang Y. Study on reactivity of Chinese anthracite chars gasification—Comparison of reactivity between steam and CO₂ gasification. J. Fuel Chem. Technol., 2006, 34(3): 265

[72] Guo WT, Wang JS, She XF, Xue QG, Guo ZC. Pore structure and high-temperature compressive strength of gasified coke with CO₂ and steam. J. Fuel Chem. Technol., 2015, 43(6): 8

[73] Rodríguez-Reinoso F, Molina-Sabio M, González MT. The use of steam and CO₂ as activating agents in the preparation of activated carbons. Carbon, 1995, 33(1): 15,

[74] Zhu K, Chen ZM, Ye SX, Geng SH, Zhang YW, Lu XG. Gasification of iron coke and cogasification behavior of iron coke and coke under simulated hydrogen-rich blast furnace condition. Int. J. Miner. Metall. Mater., 2022, 29(10): 1839,

[75] Li GY, Wang F, Wang JP, Li YY, Li AQ, Liang YH. ReaxFF and DFT study on the sulfur transformation mechanism during the oxidation process of lignite. Fuel, 2016, 181: 238,

[76] Li KJ, Li HT, Sun MM, et al.. Atomic-scale understanding about coke carbon structural evolution by experimental characterization and ReaxFF molecular dynamics. Energy Fuels, 2019, 33(11): 10941,

[77] Liang Z, Li KJ, Wang ZM, Bu YS, Zhang JL. Adsorption and reaction mechanisms of single and double H₂O molecules on graphene surfaces with defects: A density functional theory study. Phys. Chem. Chem. Phys., 2021, 23(34): 19071,

[78] Sumitani Y, Ono Y, Saito Y, et al.. Effect of changes in mechanical properties of coke matrix caused by CO₂ or H₂O gasification reaction on the strength of lump coke. ISIJ Int., 2021, 61(1): 119,

[79] Zou C, Zhang L, Cao SY, Zheng CG. A study of combustion characteristics of pulverized coal in O₂/H₂O atmosphere. Fuel, 2014, 115: 312,

[80] Yi BJ, Zhang LQ, Huang F, et al.. Effect of H₂O on the combustion characteristics of pulverized coal in O₂/CO₂ atmosphere. Appl. Energy, 2014, 132: 349,

[81] Guizani C, Sanz FE, Salvador S. The gasification reactivity of high-heating-rate chars in single and mixed atmospheres of H₂O and CO₂. Fuel, 2013, 108: 812,

[82] Chen C, Wang J, Liu W, et al.. Effect of pyrolysis conditions on the char gasification with mixtures of CO₂ and H₂O. Proc. Combust. Inst., 2013, 34(2): 2453,

[83] Liu TF, Fang YT, Wang Y. An experimental investigation into the gasification reactivity of chars prepared at high temperatures. Fuel, 2008, 87(4–5): 460,

[84] Donskoi E, Poliakov A, Mahoney MR, Scholes O. Novel optical image analysis coke characterisation and its application to study of the relationships between coke Structure, coke strength and parent coal composition. Fuel, 2017, 208: 281,

[85] Ouyang JC, Hong DK, Jiang LK, et al.. Effect of CO₂ and H₂O on char properties. Part 1: Pyrolysis char structure and reactivity. Energy Fuels, 2020, 34(4): 4243,

[86] Niu YQ, Liu SQ, Yan BK, et al.. Experimental and kinetics studies on separate physicochemical effects of steam on coal char combustion. Combust. Flame, 2020, 220: 168,

[87] Hong DK, Li ZH, Si T, Guo X. A study of the effect of H₂O on char oxidation during O₂/H₂O combustion using reactive dynamic simulation. Fuel, 2020, 280: 118713,

[88] Miura Y. Recent studies on the properties of blast furnace coke and their future prospect. ISIJ Int., 1982, 22(7): 483,

[89] Yamaoka H, Suyama S. Prediction model of coke strength after gasification reaction. ISIJ Int., 2003, 43(3): 338,

[90] Fan XY, Li C, Wang MD, et al.. Dissolution losses of metallurgical cokes in CO₂–H₂O mixtures. Energy Sources Part A, 2022, 44(4): 9172,

[91] M. Acik and Y.J. Chabal, Nature of Graphene Edges: A Review, Jpn. J. Appl. Phys., 50(2011), art. No. 070101.

[92] Jin H, Lu YJ, Liao B, Guo LJ, Zhang XM. Hydrogen production by coal gasification in supercritical water with a fluidized bed reactor. Int. J. Hydrogen Energy, 2010, 35(13): 7151,

[93] Huang YH, Yamashita H, Tomita A. Gasification reactivities of coal macerals. Fuel Process. Technol., 1991, 29(1–2): 75,

[94] Bai YH, Lv P, Yang XH, et al.. Gasification of coal char in H₂O/CO₂ atmospheres: Evolution of surface morphology and pore structure. Fuel, 2018, 218: 236,

[95] Xu J, Su S, Sun ZJ, et al.. Effects of steam and CO₂ on the characteristics of chars during devolatilization in oxy–steam combustion process. Appl. Energy, 2016, 182: 20,

[96] Ban S, Xie J, Wang YJ, Jing B, Liu B, Zhou HJ. Insight into the nanoscale mechanism of rapid H₂O transport within a graphene oxide membrane: Impact of oxygen functional group clustering. ACS Appl. Mater. Interfaces, 2016, 8(1): 321,

[97] Rodero JI, Sancho-Gorostiaga J, Ordiales M, et al.. Blast furnace and metallurgical coke’s reactivity and its determination by thermal gravimetric analysis. Ironmaking Steelmaking, 2015, 42(8): 618,

[98] Gao B, Zhang JL, Zuo HB, Qi CL, Rong Y, Wang Z. CO₂ gasification characteristics of high and low reactivity cokes. J. Iron Steel Res. Int., 2014, 21(8): 723,

[99] Sakurovs R, Burke L. Influence of gas composition on the reactivity of cokes. Fuel Process. Technol., 2011, 92(6): 1220,

[100] Kashiwaya Y, Ishii K. Kinetic analysis of coke gasification based on non-crystal/crystal ratio of carbon. ISIJ Int., 1991, 31(5): 440,

[101] Iwanaga Y, Takatani K. Mathematical model analysis for oxidation of coke at high temperature. ISIJ Int., 1989, 29(1): 43,

[102] B. Van Der Velden, J. Trouw, R. Chaigneau, and J. Van Den Berg, Coke reactivity under simulated blast furnace conditions. [in] The 58 th Ironmaking Conference, Chicigo, 1999, p. 275.

[103] Zhang JL, Li Y, Liu ZJ, et al.. Isothermal kinetic analysis on reduction of solid/liquid wustite by hydrogen. Int. J. Miner. Metall. Mater., 2022, 29(10): 1830,

[104] Mao XD, Garg P, Hu XJ, et al.. Kinetic analysis of iron ore powder reaction with hydrogen—carbon monoxide. Int. J. Miner. Metall. Mater., 2022, 29(10): 1882,

[105] Lan CC, Zhang SH, Liu XJ, Lyu Q, Jiang MF. Change and mechanism analysis of the softening-melting behavior of the iron-bearing burden in a hydrogen-rich blast furnace. Int. J. Hydrogen Energy, 2020, 45(28): 14255,