高炉碱金属富集区域钾、钠加剧焦炭劣化新认识及其量化控制模型
New cognition on coke degradation regions and quantificational control by potassium and sodium in alkali enriched model for BF
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摘要: 碱金属对高炉内焦炭的破坏大多通过研究碱金属碳酸盐对焦炭气化反应的影响,从而得出钾、钠破坏性相近,在控制碱金属入炉时也基本不对二者进行区分;但高炉调研表明在碱金属富集明显加剧的区域碱金属碳酸盐已分解且焦炭中钾含量均大于钠.本文通过热力学计算得知在碱富集区域碱金属主要以单质蒸气而非碳酸盐或氧化物形式存在,据此设计了模拟此区域有无CO2时钾、钠单质蒸气在焦炭上的自主吸附和破坏实验,结合原子吸收光谱法、X射线衍射法和扫描电镜-能谱分析发现钾蒸气和焦炭中灰分大量结合形成钾霞石后体积膨胀、裂纹扩展导致碱金属富集区域钾在焦炭上的吸附和破坏能力均远大于钠,因此建议尽量采用低灰分焦炭并严格控制入炉钾负荷.进一步研究体系中不同钾蒸气含量对气化反应的影响规律,得出当钾蒸气与焦炭的气固质量比率超过3%后焦炭反应性陡升.依据碱金属富集区域钾、钠在焦炭上的不同吸附和破坏性,建立了钾、钠各自入炉上限及总量上限的量化控制模型.Abstract: The effects of potassium and sodium on coke degradation are commonly thought to be similar by studying the influence of alkali carbonates on coke gasification, and the amounts of potassium and sodium into the blast furnace (BF) are controlled without considering the differences. But BF investigations indicate that alkali carbonates have decomposed and in coke the potassium content is always larger than the sodium content, where the enrichment of alkali metals is obviously aggravated. In this article it is found by thermodynamic calculations that alkali metals exist as simple substance vapors instead of carbonates or oxides in the alkali enriched regions. Based on that, experiments for testing the autonomic absorption and damage of potassium and sodium vapors on coke with or without carbon dioxide were designed to simulate the alkali enriched regions. Atomic absorption spectrometry (AAS), X-ray diffraction (XRD) and scanning electron microscope-energy dispersive spectrometry (SEM-EDS) analysis reveal that the absorbance and damage of potassium vapor on coke are much larger than those of sodium vapor because of easy combination with ash in coke to form kaliophilite, which induces volume expansion and crack propagation. So it is proposed that the ash content in coke should be low and potassium into BF should be strictly controlled. Coke gasification tests with different contents of potassium vapor show a steep ascent in coke reaction index (CRI) when the mass ratio of potassium vapor to coke in the gas-solid system is above 3%. According to the different absorption and damage effects of potassium and sodium on coke, quantificational control models are constructed for determining the upper limits of potassium and sodium as well as the total amount into BF.