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为了探究富氢高炉内高反应性焦炭的溶损反应特性，考察了基础焦炭(BC)和Ca基高反应性焦炭(BC+Ca)在1 000、1 100、1 200℃和CO_2+20%H_2O(体积分数，下同)、N_2+20%H_2O、CO2气氛下的溶损反应过程，通过检测反应尾气中CO和H2的摩尔分数，分析碳溶反应■和水煤气反应■的动力学过程，研究CaO对焦炭在CO_2+20%H_2O气氛下溶损动力学的影响.研究结果表明：焦炭在CO_2+20%H_2O气氛下碳溶反应的溶损速率小于CO2气氛下碳溶反应的溶损速率，水煤气反应的溶损速率小于N_2+20%H_2O气氛下水煤气反应的溶损速率，这说明H_2O和CO2与焦炭反应有竞争作用；CaO能够显著提高碳溶反应和水煤气反应的焦炭溶损速率，对碳溶反应和水煤气反应均有催化作用，能使碳溶反应的活化能(Ea)减小22.1～24.5 kJ/mol,水煤气反应的活化能减小37.8～38.9 kJ/mol.同时，进一步提出水煤气反应速率常数kH与碳溶反应速率常数kC的比值C(即kH/kC),用该参数表征H_2O对CO2的竞争力.结果表明：CaO对水煤气反应的催化作用强于对碳溶反应的催化作用，在1 000～1 200℃下可提高焦炭C值6.1%～20.0%(与基础焦炭C值相比);Ca以硅铝酸盐形式赋存在焦炭中，可有效提高H_2O对CO2的竞争力.
Abstract：To investigate the solution-loss properties of high-reactivity cokes in a hydrogen-rich blast furnace, the solution-loss processes of basic coke(BC) and high-reactivity coke with CaO(BC+Ca) at 1 000, 1 100, 1 200 ℃ under CO_2+20%H_2O(volume fraction, the same below), N_2+20%H_2O, and CO2 atmosphere were studied. The kinetics of Boudouard reaction ■ and water-gas reaction ■ were analyzed by detecting the mole percent of CO and H2 in the off-gas, to study the effect of CaO on the solution-loss kinetics of cokes in a CO_2+20%H_2O atmosphere. The results show that the Boudouard reaction rates of BC and BC+Ca cokes in CO_2+20%H_2O atmosphere are lower than those in CO2 atmosphere, and the water-gas reaction rates of BC and BC+Ca cokes are also lower than those in N_2+20%H_2O atmosphere, which indicates that there is a competition between the reactions of H_2O and CO2 with cokes. The Boudouard reaction rate and the water-gas reaction rate of BC+Ca coke are larger than those of BC coke, which shows that CaO has a catalytic effect on both reactions. CaO addition can decline Ea for the Boudouard reaction about 22.1～24.5 kJ/mol and Ea for the water-gas reaction about 37.8～38.9 kJ/mol. Furthermore, the ratio C(kH/kC) of the water-gas reaction rate constant to the Boudouard reaction rate constant is proposed to characterize the competitiveness of H_2O to CO2. The results show that the catalytic effect of CaO on the water-gas reaction is stronger than that of the Boudouard reaction, which increases from 6.1% to 20.0% compared with the C value of coke at 1 000～1 200 ℃. The silica-aluminate existing states of Ca in cokes are calcium aluminosilicates, which effectively improve the competitiveness of H_2O to CO2.
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基本信息:
DOI：10.14186/j.cnki.1671-6620.2026.01.003
中图分类号:TF526.1
引用信息:
[1]张帅宇,窦明辉,韩嘉伟,等.CaO对焦炭在CO_2+20%H_2O气氛下溶损动力学的影响[J].材料与冶金学报,2026,25(01):20-29.DOI:10.14186/j.cnki.1671-6620.2026.01.003.
基金信息:
国家自然科学基金资助项目(51874136)
2025-05-29
2025-05-29
2025-05-29