Effect of Ca/Fe additives on solution loss reactions of cokes in H<sub>2</sub>O+CO<sub>2</sub> atmosphere

DOU Minghui; HAN Jiawei; SUN Yang; SUN Zhang; LIANG Yinghua

doi:10.13374/j.issn2095-9389.2022.09.05.001

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DOU Minghui, HAN Jiawei, SUN Yang, SUN Zhang, LIANG Yinghua. Effect of Ca/Fe additives on solution loss reactions of cokes in H2O+CO2 atmosphere[J]. Chinese Journal of Engineering. doi: 10.13374/j.issn2095-9389.2022.09.05.001

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DOU Minghui, HAN Jiawei, SUN Yang, SUN Zhang, LIANG Yinghua. Effect of Ca/Fe additives on solution loss reactions of cokes in H₂O+CO₂ atmosphere[J]. Chinese Journal of Engineering. doi: 10.13374/j.issn2095-9389.2022.09.05.001

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Effect of Ca/Fe additives on solution loss reactions of cokes in H₂O+CO₂ atmosphere

doi: 10.13374/j.issn2095-9389.2022.09.05.001

College of Chemical Engineering, North China University of Science and Technology, Tangshan 063210, China

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Corresponding author: E-mail: sunz@ncst.edu.cn
Received Date: 2022-09-05
Available Online: 2022-10-31

Abstract

Abstract

To examine the solution loss reaction properties of cokes with Ca/Fe additives in a hydrogen-rich blast furnace, the solution loss reactions of cokes were performed using a CO₂ (N₂) carrier gas with various percentages (0–30%) of H₂O vapor, and the effect of Ca/Fe additives on the Boudouard reaction (C + CO₂ = 2CO) and water–gas reaction (C + H₂O = CO + H₂) of cokes in a H₂O + CO₂ atmosphere was studied by examining the content of CO and H₂ in the off-gas. The results demonstrate that the coke reactivity has a positive linear relationship with the percentages of H₂O vapor in H₂O + CO₂ and H₂O + N₂ atmospheres, and the fitting slope k could be used to characterize the rate constant for the solution loss reaction of cokes in H₂O + CO₂ and H₂O + N₂ atmospheres. The k value for the solution loss reaction of the coke in the H₂O + CO₂ atmosphere is smaller than that of the coke in the H₂O + N₂ atmosphere, which shows that there is a competition between the reactions of H₂O and CO₂ with cokes in the H₂O + CO₂ atmosphere. Furthermore, the experimental reactivities of coke are smaller than their theoretical reactivities in the H₂O + CO₂ atmosphere, and the difference between the experimental and theoretical reactivities of the basic coke (BC) is less than those of the cokes with Ca/Fe additives (BC + Ca, BC + Fe), which shows that the Ca/Fe additives affect the competitive relationship of the reactions of CO₂ and H₂O with coke. Two inhibition factors, α_CO2/H2O and α_H2O/CO2, are proposed to measure the degree of inhibition based on the difference in the k value for the cokes in H₂O + CO₂ and H₂O + N₂ atmospheres. The inhibition factor α_CO2/H2O could quantitatively characterize the inhibition degree of CO₂ on C + H₂O reaction in the H₂O + CO₂ atmosphere, and the inhibition factor α_H2O/CO2 could quantitatively characterize the inhibition degree of H₂O on the C + CO₂ reaction in the H₂O + CO₂ atmosphere. The α_CO2/H2O factors of BC, BC + Fe, and BC + Ca cokes are 0.260, 0.251, and 0.170, respectively, and the α_H2O/CO2 factors of BC, BC + Fe, and BC + Ca are 0.121, 0.217, and 0.263, respectively. The Ca/Fe additives in cokes reduce the α_CO2/H2O factor and increase the α_H2O/CO2 factor, showing that Ca/Fe additives can attenuate the inhibition degree of CO₂ on the C + H₂O reaction and improve the activity of the C + H₂O reaction, and the Ca additive has a greater impact on the competitive relationship between the reactions of CO₂ and H₂O with coke than the Fe additive. The catalytically active substances in Ca/Fe additives in cokes could be CaFe₂O₄ and Ca₂Al₂SiO₇, and the difference in the existing states of Ca/Fe elements in cokes causes the difference in the catalytic effect of Ca/Fe additives on the solution loss reactions of cokes.
- coke,
- Ca/Fe additives,
- solution loss reaction,
- H₂O + CO₂ atmosphere,
- catalysis,
- inhibition factor

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References(46)

References

[1]	楊天鈞, 張建良, 劉征建, 等. 關于新形勢下煉鐵工業發展的認識. 煉鐵, 2020, 39(5):1 Yang T J, Zhang J L, Liu Z J, et al. Development of ironmaking industry at the new situation. Ironmaking, 2020, 39(5): 1
[2]	高建軍, 齊淵洪, 嚴定鎏, 等. 中國低碳煉鐵技術的發展路徑與關鍵技術問題. 中國冶金, 2021, 31(9):64 Gao J J, Qi Y H, Yan D L, et al. Development path and key technical problems of low carbon ironmaking in China. China Metall, 2021, 31(9): 64
[3]	張琦, 沈佳林, 許立松. 中國鋼鐵工業碳達峰及低碳轉型路徑. 鋼鐵, 2021, 56(10):152 Zhang Q, Shen J L, Xu L S. Carbon peak and low-carbon transition path of China’s iron and steel industry. Iron Steel, 2021, 56(10): 152
[4]	張龍強, 陳劍. 鋼鐵工業實現“碳達峰”探討及減碳建議. 中國冶金, 2021, 31(9):21 Zhang L Q, Chen J. Discussion on achieving “carbon peak” and suggestions for reducing carbon in iron and steel industry. China Metall, 2021, 31(9): 21
[5]	嚴珺潔. 超低二氧化碳排放煉鋼項目的進展與未來. 中國冶金, 2017, 27(2):6 Yan J J. Progress and future of ultra-low CO₂ steel making program. China Metall, 2017, 27(2): 6
[6]	王敏, 任榮霞, 董洪旺, 等. 熔融還原煉鐵最新技術及工藝路線選擇探討. 鋼鐵, 2020, 55(8):145 Wang M, Ren R X, Dong H W, et al. Latest technology of melting reduction ironmaking process and discussion of process route choice. Iron Steel, 2020, 55(8): 145
[7]	張壽榮, 張紹賢. 韓國浦項鋼鐵公司FINEX工藝. 鋼鐵, 2009, 44(5):1 Zhang S R, Zhang S X. FINEX process at POSCO steel corporation in Korea. Iron Steel, 2009, 44(5): 1
[8]	王海洋, 張建良, 王廣偉, 等. 鐵前系統的二氧化碳減排技術淺析. 中國冶金, 2018, 28(1):1 Wang H Y, Zhang J L, Wang G W, et al. Analysis of carbon dioxide emission reduction before ironmaking. China Metall, 2018, 28(1): 1
[9]	李寶忠, 董洪旺. 綠色高爐煉鐵技術發展方向. 河北冶金, 2020(增刊 1):1 Li B Z, Dong H W. Green development direction of blast furnace ironmaking technology. Hebei Metall, 2020(Suppl 1): 1
[10]	畢傳光, 唐玨, 儲滿生. 梅鋼2號高爐噴吹焦爐煤氣數值模擬. 鋼鐵, 2018, 53(4):89 Bi C G, Tang J, Chu M S. Mathematical modeling of Mei Steel No. 2 BF with coke oven gas injection. Iron Steel, 2018, 53(4): 89
[11]	Qie Y N, Lyu Q, Li J P, et al. Effect of hydrogen addition on reduction kinetics of iron oxides in gas-injection BF. ISIJ Int, 2017, 57(3): 404 doi: 10.2355/isijinternational.ISIJINT-2016-356
[12]	郭同來, 儲滿生, 柳政根, 等. 高爐噴吹天然氣風口回旋區的數學模擬 // 2012年全國煉鐵生產技術會議暨煉鐵學術年會文集(下). 無錫, 2012: 52 Guo T L, Chu M S, Liu Z G, et al. Numerical simulation of blast furnace raceway under natural gas injection // Collected Works of 2012 National Iron Making Production Technology Conference and Iron Making Academic Annual Meeting (Part II). Wuxi, 2012: 52
[13]	Xu R S, Dai B W, Wang W, et al. Gasification reactivity and structure evolution of metallurgical coke under H₂O/CO₂ atmosphere. Energy Fuels, 2018, 32(2): 1188 doi: 10.1021/acs.energyfuels.7b03023
[14]	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 doi: 10.1021/acsomega.1c00443
[15]	Wang P, Zhang Y Q, Long H M, et al. Degradation behavior of coke reacting with H₂O and CO₂ at high temperature. ISIJ Int, 2017, 57(4): 643 doi: 10.2355/isijinternational.ISIJINT-2016-488
[16]	Guo W T, Xue Q G, Liu Y L, et al. Kinetic analysis of gasification reaction of coke with CO₂ or H₂O. Int J Hydrog Energy, 2015, 40(39): 13306 doi: 10.1016/j.ijhydene.2015.07.048
[17]	趙晴晴, 薛慶國, 佘雪峰, 等. H₂O和CO₂對焦炭溶損反應動力學的研究. 過程工程學報, 12(5): 789 Zhao Q Q, Xue Q G, She X F, et al. Study on kinetics of solution loss reaction of coke with H₂O and CO₂. Chin J Process Eng, 2012, 12(5): 789
[18]	Wang W, Dai B W, Xu R S, et al. The effect of H₂O on the reactivity and microstructure of metallurgical coke. Steel Res Int, 2017, 88(8): 1700063 doi: 10.1002/srin.201700063
[19]	Lan C C, Zhang S H, Liu X J, et al. Kinetic behaviors of coke gasification with CO₂ and H₂O. ISIJ Int, 2021, 61(1): 167 doi: 10.2355/isijinternational.ISIJINT-2020-401
[20]	Chang Z Y, Wang P, Zhang J L, et al. Effect of CO₂ and H₂O on gasification dissolution and deep reaction of coke. Int J Miner Metall Mater, 2018, 25(12): 1402 doi: 10.1007/s12613-018-1694-4
[21]	Nomura S, Kitaguchi H, Yamaguchi K, et al. The characteristics of catalyst-coated highly reactive coke. ISIJ Int, 2007, 47(2): 245 doi: 10.2355/isijinternational.47.245
[22]	Nomura S, Ayukawa H, Ktaguchi H, et al. Improvement in blast furnace reaction efficiency through the use of highly reactive calcium rich coke. ISIJ Int, 2005, 45(3): 316 doi: 10.2355/isijinternational.45.316
[23]	Sharma A, Uebo K, Kubota Y. Role of Fe₂O₃ and CaCO₃ on the development of carbon structure of coke and their catalytic activity for gasification. Tetsu-to-Hagane, 2010, 96(5): 280 doi: 10.2355/tetsutohagane.96.280
[24]	Nomura S, Terashima H, Sato E, et al. Some fundamental aspects of highly reactive iron coke production. ISIJ Int, 2007, 47(6): 823 doi: 10.2355/isijinternational.47.823
[25]	Nomura S. Reaction behavior of Ca-loaded highly reactive coke. ISIJ Int, 2014, 54(11): 2533 doi: 10.2355/isijinternational.54.2533
[26]	Nomura S, Naito M, Yamaguchi K. The post-reaction strength of catalyst-doped highly reactive coke. Tetsu-to-Hagane, 2007, 93(1): 9 doi: 10.2355/tetsutohagane.93.9
[27]	Nomura S, Naito M, Yamaguchi K. Post-reaction strength of catalyst-added highly reactive coke. ISIJ Int, 2007, 47(6): 831 doi: 10.2355/isijinternational.47.831
[28]	Ueda S, Watanabe K, Inoue R, et al. Catalytic effect of Fe, CaO and molten oxide on the gasification reaction of coke and biomass char. ISIJ Int, 2011, 51(8): 1262 doi: 10.2355/isijinternational.51.1262
[29]	Kashiwaya Y, Nakaya S, Ishii K. Effect of Fe addition on coke gasification. Tetsu-to-Hagane, 1991, 77(6): 759 doi: 10.2355/tetsutohagane1955.77.6_759
[30]	左海濱, 戎妍, 張建良, 等. 氧化鈣對焦炭性能的影響. 鋼鐵, 2014, 49(1):7 Zuo H B, Rong Y, Zhang J L, et al. Effect of CaO on properties of coke. Iron Steel, 2014, 49(1): 7
[31]	張建良, 郭建, 王廣偉, 等. 配加鐵礦粉對鐵焦微觀結構及性能的影響. 鋼鐵, 2016, 51(9):22 Zhang J L, Guo J, Wang G W, et al. Effect of iron ore fines addition on microstructure and properties of iron-coke. Iron Steel, 2016, 51(9): 22
[32]	郭豪, 張建良, 馬歡, 等. 堿土金屬化合物對焦炭反應性的影響. 鋼鐵, 2009, 44(2):15 Guo H, Zhang J L, Ma H, et al. Influence of compound of alkali earth metals on coke reactivity. Iron Steel, 2009, 44(2): 15
[33]	Sun Z, Li P, Guo R, et al. Preparation of high strength and highly reactive coke by the addition of steel slag. Coke Chem, 2014, 57(10): 391 doi: 10.3103/S1068364X14100081
[34]	李鵬, 孫章, 崔文權, 等. 鋼渣對焦炭熱性能的影響. 煤炭轉化, 2014, 37(2):47 Li P, Sun Z, Cui W Q, et al. Effect of slag on thermal properties of coke. Coal Convers, 2014, 37(2): 47
[35]	梁磊, 孫章, 梁英華. 鋼渣基高反應性焦炭氣孔結構的溶損演化行為. 化工進展, 2019, 38(7):3136 Liang L, Sun Z, Liang Y H. Evolution of the porous structures for the high reactivity coke prepared by adding steel slag in blending coals during solution loss reaction. Chem Ind Eng Prog, 2019, 38(7): 3136
[36]	孫章, 劉朋飛, 李慧星, 等. 富鈣廢渣配煤對焦炭溶損反應的影響. 過程工程學報, 2015, 15(6):999 doi: 10.12034/j.issn.1009-606X.215216 Sun Z, Liu P F, Li H X, et al. Effect of blending of Ca-based slag on solution loss reaction of coke. Chin J Process Eng, 2015, 15(6): 999 doi: 10.12034/j.issn.1009-606X.215216
[37]	劉朋飛, 孫章, 王杰平, 等. 堿渣作為添加劑提高焦炭反應性的研究. 煤炭轉化, 2015, 38(3):65 Liu P F, Sun Z, Wang J P, et al. Improving coke reactivity by adding soda residue. Coal Convers, 2015, 38(3): 65
[38]	Gao M Q, Lv P, Yang Z R, et al. Effects of Ca/Na compounds on coal gasification reactivity and char characteristics in H₂O/CO₂ mixtures. Fuel, 2017, 206: 107 doi: 10.1016/j.fuel.2017.05.079
[39]	Gao M Q, Yang Z R, Wang Y L, et al. Impact of calcium on the synergistic effect for the reactivity of coal char gasification in H₂O/CO₂ mixtures. Fuel, 2017, 189: 312 doi: 10.1016/j.fuel.2016.10.100
[40]	Yu G, Yu D X, Liu F Q, et al. Different impacts of magnesium on the catalytic activity of exchangeable calcium in coal gasification with CO₂ and steam. Fuel, 2020, 266: 117050 doi: 10.1016/j.fuel.2020.117050
[41]	Yu G, Yu D X, Liu F Q, et al. Different catalytic action of ion-exchanged calcium in steam and CO₂ gasification and its effects on the evolution of char structure and reactivity. Fuel, 2019, 254: 115609 doi: 10.1016/j.fuel.2019.06.017
[42]	Ohtsuka Y, Asami K. Highly active catalysts from inexpensive raw materials for coal gasification. Catal Today, 1997, 39(1-2): 111 doi: 10.1016/S0920-5861(97)00093-X
[43]	Ohtsuka Y, Tomita A. Calcium catalysed steam gasification of Yallourn brown coal. Fuel, 1986, 65(12): 1653 doi: 10.1016/0016-2361(86)90264-4
[44]	Chen S G, Yang R T. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO₂ and H₂O. Energy &Fuels, 1997, 11: 421
[45]	Han Y, Ma T Z, Chen F, et al. Supercritical water gasification of naphthalene over iron oxide catalyst: A ReaxFF molecular dynamics study. Int J Hydrog Energy, 2019, 44(57): 30486 doi: 10.1016/j.ijhydene.2019.09.215
[46]	竇明輝, 孫洋, 韓嘉偉, 等. 焦炭在H₂O+CO₂氣氛中的溶損反應特性. 鋼鐵, 2022, 57(7):26 Dou M H, Sun Y, Han J W, et al. Solution loss characteristics of cokes in H₂O+CO₂ atmosphere. Iron Steel, 2022, 57(7): 26