Competitive reduction mechanism of vanadium and titanium of vanadium-titanium magnetite metallized pellets smelted by electric arc furnace
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摘要: 钒钛磁铁矿是一种富含铁、钒、钛等多种金属元素的特殊铁矿资源。高炉冶炼钒钛磁铁矿技术已经非常成熟，但需要配加普通铁精矿，造成炉渣中TiO2含量低，难以进行TiO2的资源化回收。为了实现钒钛磁铁矿中铁、钒、钛的综合利用，钒钛磁铁矿气基竖炉直接还原-电炉熔分技术逐渐被认为是回收铁、钒、钛的最有效技术。该技术可以实现全钒钛磁铁矿冶炼，不需要配加熔剂，可以获得高TiO2含量的炉渣，进行炉渣中TiO2的资源化利用。钒钛磁铁矿金属化球团电炉熔分过程中，为了将钒还原进入铁水，需要配加还原剂进行深度还原，熔渣中的钒和钛会竞争还原。笔者进行了熔渣中V2O5和TiO2与碳还原反应的热力学计算，得到了TiO2与C反应生成TiC以及V2O5对TiC反应的抑制关系。计算结果表明，在熔分温度
1500 ℃以上，还原剂碳配加量足够的条件下，钒钛磁铁矿金属化球团电炉熔分过程中不可避免会还原生成TiC，V2O5虽然可以抑制TiC的生成，但由于熔渣中TiO2含量高、活度大，V2O5活度小，V2O5难以抑制TiC的生成。钒钛磁铁矿金属化球团电炉熔分仍然存在炉渣变稠，电炉排渣困难的问题。Abstract: Vanadium titano-magnetite is a special iron ore resource rich in multiple elements such as iron, vanadium, titanium. The blast furnace process for vanadium titano-magnetite is very mature, but it requires the addition of ordinary iron concentrate, resulting low TiO2 content in the slag, making it difficult to recover TiO2 from slag. To achieve comprehensive utilization of vanadium titano-magnetite, the process of direct reduction in gas-based shaft furnace and smelting in electric arc furnace is currently considered as the most effective technology to recover iron, vanadium and titanium. This technology can smelt vanadium titano-magnetite entirely without the need for flux, producing slag with high TiO2 content. During the electric arc furnace melting of vanadium titano-magnetite metalized pellets, reducing agents need be added to deeply reduce vanadium into the molten iron, and vanadium and titanium in the slag will compete for reduction. In this paper, the thermodynamics of reduction reaction of V2O5 and TiO2 with carbon in slag was calculated. The reaction process of TiO2 with C to form TiC, and the inhibition relationship of V2O5 on the TiC formation were analyzed. The results show that TiC is inevitable when the melting temperature is above1500 ℃ and the reducing agent of carbon is sufficient. It is difficult for V2O5 to inhibit the formation of TiC because of the high TiO2 activity and low V2O5 activity in slag. The problem of slag thickening and difficult slag discharge in electric arc furnace is still existed in smelting of vanadium-titanium magnetite metallized pellets. -
图 1 钒钛磁铁矿气基竖炉直接还原-电炉熔分工艺流程
Figure 1. Flow chart of vanadium-titanium magnetite gas based direct reduction-electric arc furnace smelting process
图 2 钒钛磁铁矿金属化球团XRD分析结果
Figure 2. XRD analysis of metallized pellets of vanadium titano-magnetite
图 3 不同温度条件下V的平衡活度$ {\bf{\alpha }}_{[{\rm{V}}]} $与熔渣中V2O3活度${\bf{\alpha}}_{\mathrm{\left(V_2O_3\right)}} $的关系
Figure 3. The relationship between the equilibrium activity $ {{\bf{\alpha}}}_{[{\rm{V}}]} $ and the activity ${\boldsymbol{\alpha}}_{\mathrm{\left(V_2O_3\right)}} $ in slag at different temperatures
图 4 $ \mathit{\alpha}_{\left(\mathbf{T}\mathbf{i}\mathbf{O}_2\right)} $固定条件下温度与$ \left[\mathbf{T}\mathbf{i}\right] $含量的关系
Figure 4. The relationship between temperature and $ \left[\mathrm{T}\mathrm{i}\right] $ under the condition of fixed ${\alpha}_{\left({{\bf{TiO}}_2}\right)} $
图 5 不同温度条件下$ {\alpha }_{\left(\mathrm{T}\mathrm{i}{\mathrm{O}}_{2}\right)} \cdot {{\alpha }_{\left[\mathrm{V}\right]}}^{2} $与熔渣中V2O3活度$ {\alpha }_{\left({\mathrm{V}}_{2}{\mathrm{O}}_{3}\right)} $的关系
Figure 5. The relationship between $ {{\alpha}_{\left(\mathrm{TiO_2}\right)}\cdot\mathrm{\alpha}_{\left[\mathrm{V}\right]}}^{2} $ and $ \mathrm{\alpha}_{\left(\mathrm{V_2O_3}\right)} $ in slag at different temperatures
表 1 钒钛磁铁矿金属化球团成分
Table 1. Chemical composition of vanadium titano-magnetite metallized pellets
% TFe MFe FeO CaO MgO Al2O3 SiO2 TiO2 V2O5 Cr2O3 MnO C S 67.66 57.54 12.76 0.22 1.51 4.25 4.16 15.94 2.35 0.71 0.48 0.082 0.016 
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