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

Volume 45 Issue 11

Nov. 2023

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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, 2023, 45(11): 1859-1867. 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, 2023, 45(11): 1859-1867. 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
Publish Date: 2023-11-01

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, $\alpha_{{\rm{CO}}_2/{\rm{H}}_2{\rm{O}}} $ and $\alpha_{{\rm{H}}_2{\rm{O}}/{\rm{CO}}_2} $ , 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 $\alpha_{{\rm{CO}}_2/{\rm{H}}_2{\rm{O}}} $ could quantitatively characterize the inhibition degree of CO₂ on C + H₂O reaction in the H₂O + CO₂ atmosphere, and the inhibition factor $\alpha_{{\rm{H}}_2{\rm{O}}/{\rm{CO}}_2} $ could quantitatively characterize the inhibition degree of H₂O on the C + CO₂ reaction in the H₂O + CO₂ atmosphere. The $\alpha_{{\rm{CO}}_2/{\rm{H}}_2{\rm{O}}} $ factors of BC, BC + Fe, and BC + Ca cokes are 0.260, 0.251, and 0.170, respectively, and the $\alpha_{{\rm{H}}_2{\rm{O}}/{\rm{CO}}_2} $ 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 $\alpha_{{\rm{CO}}_2/{\rm{H}}_2{\rm{O}}} $ factor and increase the $\alpha_{{\rm{H}}_2{\rm{O}}/{\rm{CO}}_2} $ 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)

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