Study on the influence of highly oxygen enrichment and H2-rich oxygen blast furnace atmospheres on softening-melting behaviors of vanadium titanomagnetite mixed burden
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摘要: 探讨了高炉富氧、全氧及全氧富氢气氛对钒钛磁铁矿混合炉料软熔性能、透气性及气体利用率的影响规律。结果表明，高炉富氧气氛下，炉料软化开始温度下降，软化结束温度、熔化开始温度、滴落温度升高，软化区间、熔化区间变宽，但透气性指数下降，气体利用率降低；全氧富氢气氛条件下，通过引入H2，炉料软化开始温度、软化结束温度、熔化开始温度升高，软化区间变宽，熔化区间变窄，透气性能进一步得到改善，H2利用率增加。进一步研究表明，还原气体成分的变化对炉渣和铁水的化学成分产生了重要影响，富氧气氛下炉渣中Ti(C,N)含量显著降低，全氧富氢气氛下炉渣中TiC含量及铁水中[Si]、[Ti]、[V]含量均显著提高。研究为钒钛矿高炉冶炼过程中的绿色低碳技术提供了理论依据，为提高钒钛磁铁矿高炉冶炼效率并减少碳排放提供了重要的基础试验支持。Abstract: This study investigates the effects of oxygen-enriched, oxygen blast furnace, and H2-rich oxygen blast furnace atmospheres on the softening-melting behaviors, permeabilities, and gas utilization efficiency of vanadium titanomagnetite mixed burden. The results indicate that under oxygen-rich blast furnace atmosphere, the softening start temperature of furnace burden decreases, while the softening end temperature, melting start temperature, and dripping temperature increase. Consequently, both the softening and melting intervals become widened. However, the permeabilities and total reduction gas utilization efficiency decline. Under the H2-rich oxygen blast furnace atmosphere, the introduction of H2 leads to an increase in the softening start temperature, softening end temperature, and melting start temperature. Additionally, the softening interval expands, while the melting interval narrows, resulting in the improved gas permeability and enhanced H2 utilization efficiency. Further investigation reveals that variations in the reducing gas compositions significantly influence the chemical compositions of both slags and hot metals. Under the oxygen-enriched atmosphere, the Ti(C,N) content in slag decreases markedly, whereas under fully oxygen-enriched, H2-rich conditions, the TiC content in the slag, as well as [Si], [V] and [Ti] concentrations in hot metal, increase substantially. This study provides a theoretical basis for green low-carbon technologies in vanadium titanomagnetite smelting, and offers important experimental support for improving smelting efficiency and reducing carbon emissions.
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图 1 钒钛炉料XRD图谱
(a) 钒钛烧结矿；(b) 钒钛球团矿
Figure 1. XRD patterns of vanadium titanomagnetite feeds
图 2 软熔性能试验设备示意 (单位：mm)
Figure 2. Schematic diagram of the softening and melting apparatus (unit: mm)
图 3 不同气氛下钒钛混合炉料收缩率和压差与温度的关系
（a）收缩率；（b）压差
Figure 3. The relationships between shrinkage rates and pressure losses of vanadium titanomagnetite mixed burden with temperatures under different atmospheres
图 4 不同气氛下钒钛混合炉料软熔试验特征参数随气氛的变化
Figure 4. Characteristic parameters of the softening and melting experiments of vanadium titanomagnetite mixed burden under different atmospheres
图 5 不同气氛条件下钒钛混合炉料的最大压差ΔPmax和透气性特征指数SD
Figure 5. Maximum loss of pressures (ΔPmax) and permeability characteristic indexes (SD) of vanadium titanomagnetite mixed burden under different atmospheres
图 6 不同气氛条件下熔滴试验后样品形貌
Figure 6. Morphologies of the samples after softening-melting experiments under different atmospheres
图 7 不同气氛下滴落渣的背散射电镜照片
（a）气氛5；（b）气氛3
Figure 7. Backscattered SEM images of dripping slags under different atmospheres
图 8 软熔试验尾气成分随温度的变化及CO利用率、H2利用率和总利用率的对比
（a）气氛1（去除N2含量）；（b）气氛3；（c）气氛4；（d）气氛1~5利用率的对比
Figure 8. The variation of tail gas compositions with temperatures and the comparison of CO, H2 and total utilization efficiencies
表 1 钒钛炉料主要化学成分
Table 1. Main chemical compositions of the vanadium titanomagnetite feeds
% TFe FeO CaO SiO2 Al2O3 MgO TiO2 V2O5 S P R2 烧结矿 49.50 8.88 13.86 7.06 2.84 2.10 3.02 0.21 0.07 0.04 1.96 球团矿 54.88 <0.50 0.57 3.86 3.53 3.03 9.75 0.72 <0.01 <0.01 0.15 
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表 2 焦炭化学成分
Table 2. Chemical composition of the coke
% FCad Mt St Vdaf Ad K2O Na2O CaO SiO2 MgO Al2O3 Fe2O3 Total 85.88 0.23 0.63 1.09 0.08 0.10 0.49 7.24 0.13 3.73 1.03 12.80 注：M为水分；V为挥发分；FC为固定碳；A为灰分。
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表 3 软熔试验还原气组分(体积分数)
Table 3. Compositions of the reducing gases used during the softening and melting tests
% 编号 N2 CO H2 普通高炉气氛 1 70 30 0 富氧高炉气氛 2 35 65 0 全氧高炉气氛 3 0 100 0 全氧高炉富氢气氛 4 0 90 10 5 0 80 20
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表 4 不同气氛下钒钛混合炉料软熔试验特征参数
Table 4. Characteristic parameters of the softening and melting experiments for vanadium titanomagnetite mixed burden under different atmospheres
气氛编号 T10/℃ T40/℃ ΔT1/℃ TS/℃ TD/℃ ΔT2/℃ ΔPmax/kPa SD 1 1218 1290 72 1299 1407 108 19.05 1179.45 2 1209 1308 99 1317 1428 111 10.24 689.96 3 1197 1320 123 1338 1476 138 4.93 430.97 4 1223 1346 123 1364 1508 144 3.18 299.31 5 1222 1354 132 1387 1504 117 2.47 208.03
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表 5 不同气氛条件下熔滴试验后炉渣化学成分
Table 5. Chemical compositions of slags after softening-melting experiments under different atmospheres
气氛序号 样品部位 MFe/% 渣成分/% FeO Al2O3 CaO MgO SiO2 TiO2 V2O5 Ti(C,N) R2 1 压头上渣 4.20 5.43 11.75 29.26 6.15 22.26 22.24 1.09 1.82 1.31 2 压头上渣 2.50 3.77 12.23 29.57 6.79 22.72 22.60 1.08 1.24 1.30 4 压头上渣 3.40 4.86 12.70 28.42 7.23 21.86 21.52 0.95 2.46* 1.30 5 压头上渣 2.30 3.30 13.14 28.11 7.70 21.46 21.41 0.85 4.04* 1.31 1 压头下渣 26.40 7.60 11.04 27.34 6.92 20.89 21.88 1.09 3.24 1.31 2 压头下渣 21.50 6.07 11.51 27.52 8.51 20.87 22.52 1.03 1.98 1.32 3 滴落渣 1.90 3.94 12.88 27.92 9.41 21.37 23.59 0.76 0.12* 1.31 4 滴落渣 4.30 2.56 12.67 27.72 9.58 21.52 23.56 0.64 1.73* 1.29 5 滴落渣 6.30 2.13 13.06 28.14 9.13 21.32 23.53 0.62 2.07* 1.32 注：*样品仅存在TiC，无TiN存在。
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表 6 不同气氛条件下熔滴试验后滴落铁化学成分
Table 6. Chemical compositions of the dripping iron samples after softening-melting experiments under different atmospheres
% 气氛编号 C S Si Ti V 1 4.500 0.098 0.009 0.023 0.011 2 4.300 0.092 0.012 0.028 0.019 3 3.440 0.081 0.040 0.033 0.038 4 2.840 0.078 0.265 0.215 0.150 5 2.600 0.050 0.495 0.561 0.187
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