Change of phase composition and valuable elements in V-Ti pellet during softening-melting and dripping process
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摘要: 模拟高炉冶炼气氛，对攀钢酸性钒钛球团矿在软熔和滴落过程中的物相组成和有价元素的变化进行了定量化的研究。结果表明，在钒钛球团矿的软熔滴落过程中，Ti和V逐渐从钛赤铁矿和钛铁矿迁移至渣相中。TiO2既可生成Ti进入金属铁，也可大量生成碳氮化钛。滴落试验中V在金属铁中的收得率为36.03%，远高于Ti和Si的3.13%和17.20%。炉渣和金属铁吸收焦炭中的S与渣铁间的脱硫反应同时进行，金属铁中S所占的比例由软熔时的72.84%降低至滴落时的50%。软熔液泛渣中辉石和黑钛石超过80%，渣中超过70%的V和Ti分布于黑钛石中。软熔未滴落渣中辉石明显减少，橄榄石和尖晶石明显增加，尖晶石中的V和Ti明显增加。滴落试验过程中TiO2逐渐被还原，TiC和TiN的质量分数之和超过20%，炉渣逐渐由TiO2质量分数超过30%的高钛渣转变为TiO2质量分数低于10%的低钛渣，未滴落渣中黑钛石以及分布于其中的V和Ti明显减少，橄榄石以及分布于其中的V和Ti增加。Abstract: The change of phase composition and valuable elements in the process of softening-melting and dripping of acidic V-Ti pellet of Pangang were quantitatively studied by simulating the smelting atmosphere in blast furnace. The results show that Ti and V gradually migrated from titanohematite and ilmenite to slag phase during the softening-melting and dripping process of V-Ti pellet. TiO2 could not only be reduced to Ti into metal iron, but also generate a large amount of titanium carbonitride. In the dripping test, the yield of V in metallic iron was 36.03%, which was much higher than 3.13% of Ti and 17.20% of Si. The absorbing S from coke by slag and metallic iron and the desulfurization reaction between them were carried out simultaneously, and the ratio of S in metallic iron decreased from 72.84% after softening-melting test to 50% after dripping test. Pyroxene and anosovite were more than 80% in the flooding slag of softening-melting test, and more than 70% of V and Ti in this slag were distributed in anosovite. While in residual slag of softening-melting test, pyroxene decreased obviously, olivine and spinel increased obviously, and V and Ti increased obviously in spinel. During the dripping test, TiO2 was gradually reduced until the sum of TiC and TiN mass fraction exceeded 20%, so the slag was gradually transformed from high titanium-type slag with TiO2 mass fraction over 30% to low titanium-type slag with TiO2 mass fraction less than 10%, and anosovie and its V and Ti in the residual slag were significantly reduced, while olivine and its distribution of V and Ti were increased.
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图 2 球团矿软熔试验液泛渣SEM照片及EDS分析
Figure 2. SEM photo and EDS analysis of softening-melting flooding slag of V-Ti pellet
图 3 软熔试验未滴渣SEM照片及EDS分析
Figure 3. SEM photo and EDS analysis residual slag after softening-melting test of V-Ti pellet
图 4 滴落试验未滴渣SEM照片及EDS分析
Figure 4. SEM photo and EDS analysis of residual slag after dripping test of V-Ti pellet
图 6 TiO2、SiO2、VO还原反应的$\Delta G_{\rm{m}}^{\text{θ}}$
Figure 6. $\Delta G_{\rm{m}}^{\text{θ}}$of direct reduction reactions of TiO2, SiO2, and VO
表 1 钒钛球团矿的主要化学成分
Table 1. Main chemical composition of V-Ti pellet
% TFe FeO CaO SiO2 MgO Al2O3 TiO2 V2O5 S 53.38 3.63 0.64 5.65 3.59 3.96 9.76 0.683 0.008 
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表 2 焦炭的化学成分
Table 2. Chemical composition of coke
% Fcad Mt St Vdaf Ad K2O Na2O CaO SiO2 MgO Al2O3 Fe2O3 合计 85.88 0.23 0.63 1.09 0.08 0.10 0.49 7.24 0.13 3.73 1.03 12.80
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表 3 球团矿软熔和滴落试验的渣铁质量
Table 3. Mass of slag and metallic iron of pellet after softening-melting test and dripping test
g 类别 液泛渣 未滴落炉渣 滴落渣 滴落金属铁 未滴金属铁 合计 软熔试验 92.9 40.3 166.3 103.5 403.1 滴落试验 46.1 6.0 75.9 22.8 150.8
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表 4 软熔和滴落试验炉渣的化学成分
Table 4. Chemical compositions of slags after softening-melting and dripping test
% 样品名称 TFe MFe FeO CaO SiO2 MgO Al2O3 TiO2 V2O5 S TiC TiN 软熔试验液泛渣 8.90 4.00 6.30 2.34 21.2 9.54 12.07 30.50 2.26 0.063 <0.1 0.155 软熔试验未滴渣 16.30 12.40 5.02 1.18 19.84 9.67 10.94 25.89 1.92 0.073 0.178 <0.1 软熔试验合计 11.14 6.54 5.91 1.99 20.79 9.58 11.73 29.11 2.16 0.07 滴落试验未滴落渣 45.75 45.00 0.96 1.53 15.80 7.32 8.31 2.30 1.32 0.120 11.24 0.73 滴落试验滴落渣 12.56 11.50 1.36 2.79 32.14 11.27 15.30 19.55 0.68 0.090 0.26 <0.1 滴落试验合计 41.93 41.14 1.01 1.68 17.68 7.77 9.11 4.29 1.25 0.12 9.98
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表 5 不计MFe时造渣组份的相对质量分数
Table 5. Relative mass fraction of slagging components of different slags without MFe
% 样品名称 FeO CaO SiO2 MgO Al2O3 TiO2 V2O5 S TiC TiN 软熔试验液泛渣 6.56 2.44 22.08 9.94 12.57 31.77 2.35 0.07 <0.1 0.16 软熔试验未滴渣 5.73 1.35 22.65 11.04 12.49 29.56 2.19 0.08 0.203 <0.1 滴落试验未滴渣 1.75 2.78 28.73 13.31 15.11 4.18 2.40 0.22 20.44 1.33 滴落试验滴落渣 1.54 3.15 36.32 12.73 17.29 22.10 0.77 0.10 0.29 <0.1
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表 6 不计算MFe和FeO时造渣组分相对质量分数
Table 6. Relative mass fraction of slagging components of different slags without MFe and FeO
% 样品名称 CaO SiO2 MgO Al2O3 TiO2 V2O5 S TiC TiN 软熔试验液泛渣 2.61 23.63 10.64 13.46 34.00 2.52 0.07 0.11 0.17 软熔试验未滴渣 1.43 24.03 11.71 13.25 31.67 2.33 0.09 0.22 0.12 软熔试验炉渣合计 2.27 23.75 10.94 13.40 33.65 2.46 0.08 0.14 0.16 滴落试验未滴渣 2.83 29.24 13.55 15.38 7.74 2.44 0.22 20.80 1.35 滴落试验滴落渣 3.20 36.88 12.93 17.56 22.74 0.78 0.10 0.30 0.11 滴落试验炉渣合计 2.90 30.56 13.44 15.76 10.35 2.15 0.20 17.24 1.14
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表 7 软熔和滴落试验金属铁的化学成分
Table 7. Chemical compositions of metallic iron after softening-melting and dripping test
% 样品名称 C S V Ti Si 软熔试验未滴铁 5.29 0.088 0.112 0.170 0.133 软熔试验滴落铁 5.31 0.087 0.104 0.087 0.066 滴落试验未滴铁 4.72 0.100 0.242 0.528 1.77 重熔试验滴落铁 5.13 0.050 0.130 0.130 0.240 生产铁样 4.42 0.087 0.333
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表 8 Ti的相互作用系数、活度及反应(1)的吉布斯自由能
Table 8. Interaction coefficient and activity of Ti and $ \Delta G $ of reaction (1)
温度/K $ e_{{\text{Ti}}}^{\text{C}} $ $ e_{{\text{Ti}}}^{\text{S}} $ $ e_{{\text{Ti}}}^{{\text{Si}}} $ $ e_{{\text{Ti}}}^{{\text{Ti}}} $ ${ {{a} }_{\left[ { {\text{Ti} } } \right]} }$ $ \Delta G $/(kJ·mol−1) 1273 −0.44 −0.12 0.074 0.071 0.0035 −85.05 1373 −0.41 −0.11 0.068 0.066 0.0038 −90.92 1473 −0.38 −0.10 0.064 0.061 0.0041 −96.79 1573 −0.36 −0.10 0.060 0.058 0.0043 −102.66 1673 −0.34 −0.09 0.056 0.054 0.0045 −108.53 1773 −0.32 −0.08 0.053 0.051 0.0047 −114.40 1873 −0.3 −0.08 0.05 0.0483 0.0049 −120.27
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表 9 软熔和滴落试验中S的质量
Table 9. Mass of S during softening-melting and dripping test
g 阶段 原料质量 S质量 合计 炉渣 金属铁 炉渣S 金属铁S 软熔 133.2 269.8 0.088 0.236 0.324 重熔 52.1 98.7 0.061 0.061 0.122 球团矿 500 0.040
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表 10 不同炉渣的物相组成和元素分布
Table 10. Phase and element distribution of different slag
% 物相名称 软熔试验液泛渣 软熔试验未滴落渣 滴落试验未滴落渣 w Fe V Ti w Fe V Ti w Fe V Ti 金属铁 9.63 52.9 2.67 1.07 30.18 80.91 10.08 5.84 56.58 90.14 31.18 6 黑钛石 30.51 6.3 71.11 75.39 22.13 2.15 41.29 63.22 1.92 0.28 10.19 9.19 辉石 47.44 33.59 19.53 19.15 15.07 5.27 10.54 12.5 17.11 3.54 24.44 37.81 橄榄石 0.65 0.87 0.73 0.17 5.48 1.5 3.23 1.29 6.64 0.9 5.94 9.2 玻璃质 9.21 2.03 0.06 2.06 9.06 0.96 0.26 2.54 1.57 0.08 0.47 0.91 尖晶石 1.18 0.84 3.36 0.98 13.71 4.57 28.27 10.92 6.69 0.37 7.86 7.02 碳氮氧化钛 0.1 0.01 0.19 0.25 0.41 0.02 0.41 1.07 3.75 0.12 6.88 18.56 氮化钛 0.03 0 0.14 0.09 0.02 0 0.07 0.06 0.52 0.02 3.48 4.06 氧化铁 0.11 0.4 0.06 0.06 0.28 0.55 0.13 0.17 1.22 1.23 1.68 0.79 铁板钛矿 1.1 3.02 2.13 0.79 2.78 3.96 4.56 2.29 3.42 2.92 7.42 5.53 绿泥石 0.01 0 0.03 0 0.56 0.08 1.15 0.08 0.08 0.01 0.26 0.02 其它 0.04 0.03 0.01 0.01 0.33 0.02 0.02 0.02 0.51 0.41 0.21 0.9
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