Study on phase and chemical composition of V-Ti sinter during softening, melting and dripping process
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摘要: 钒钛磁铁精矿的入炉方式是攀钢优化高炉炉料结构的重要内容，对V和Ti在软熔滴落过程中的迁移以及Ti(C,N)的生成有重要影响。目前钒钛烧结矿是攀钢高炉的主要炉料，约一半的钒钛磁铁精矿通过烧结矿进入高炉。通过对钒钛烧结矿在软熔滴落过程中的物相组成和化学成分的变化规律进行研究发现，在烧结矿的软熔滴落过程中，Ti、V、Si、Mg、Al等元素逐渐从钛赤铁矿、钛磁铁矿、铁酸钙等物相迁移到渣相中，同时炉渣吸收焦炭的硫分和灰分。金属铁中Ti、Si、S和C的质量分数已达到甚至超过正常生产时的水平，V的质量分数虽远低于正常生产时的水平，但在金属铁中的收得率远高于Ti、Si、S。烧结矿炉渣冷却后形成的主要物相是黄长石，其次是钙钛矿和辉石。Ti和V主要赋存于钙钛矿中，其次是黄长石和辉石中。在软熔过程中，生成的碳氮化钛很少；在重熔滴落过程中，渣中碳氮化钛显著增加。Abstract: The charging mode of vanadium-bearing titanomagnetite concentrate is an important matter for optimizing the burden structure of blast furnace in Pangang, which also has an important influence on the migration of V and Ti in the process of softening and melting process and the formation of Ti(C,N). At present, vanadium-titanium sinter is the main burden of blast furnace in Pangang, and about half of vanadium-bearing titanomagnetite concentrate enters the blast furnace through sinter. Therefore, the change of phase and chemical composition of vanadium-titanium sinter in the process of softening and melting process was studied. In the softening and dripping process of sinter, Ti, V, Si, Mg, and Al gradually migrate from the phases of titanohematite, titanomagnetite, calcium ferrite to the slag phase, and the slag absorbs the sulfur and ash of coke. The mass fraction of Ti, Si, S and C in hot metal has reached or even exceeded that of normal production. Although the mass fraction of V is much lower than that in normal production, the yield in metallic iron is much higher than that of Ti, Si and S. The main phase of slag after cooling is melilite, followed by perovskite and pyroxene. Ti and V mainly exist in perovskite, followed by melilite and pyroxene. In the process of softening, little titanium carbonitride is produced. However, in the process of melting, the content of titanium carbonitride in slag increases significantly.
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图 1 铁矿石软熔性能试验设备示意
Figure 1. Schematic diagram of experimental apparatus for iron ore softening-melting property
图 2 钒钛烧结矿软熔性能测定后的试样
Figure 2. Different samples of vanadium-titanium sinter after softening-melting property testing
图 3 烧结矿软熔液泛渣的SEM照片
Figure 3. SEM photo of flooding slag on graphite pusher during softening
图 4 烧结矿软熔未滴渣的SEM照片及EDS分析
Figure 4. SEM image and EDS analysis of the sinter softening-melting undripped slag
图 5 烧结矿软熔滴落渣的SEM照片及EDS分析
Figure 5. SEM image and EDS analysis of the sinter softening-melting dripped slag
图 6 烧结矿重熔滴落渣的SEM照片及EDS分析
Figure 6. SEM image and EDS analysis of the sinter remelting dripped slag
表 1 钒钛烧结矿的主要化学成分
Table 1. Chemical composition of vanadium-titanium sinter
化学成分/% RO TFe FeO CaO SiO2 MgO Al2O3 TiO2 V2O5 S 50.77 7.99 10.97 5.58 2.72 3.00 5.59 0.388 0.025 1.97 
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表 2 焦炭的化学成分
Table 2. Chemical compositions 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 烧结矿重熔后的渣铁质量
Table 3. Weight of slag and metallic iron after sinter remelting
g 未滴落炉渣 未滴落金属铁 滴落炉渣 滴落金属铁 合计 41.0 70.0 13.1 25.8 149.9
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表 4 不同炉渣的化学成分
Table 4. Chemical compositions of different slags
样品名称 化学成分/% TFe FeO CaO SiO2 MgO Al2O3 TiO2 V2O5 S TiC TiN 软熔液泛渣 6.00 2.25 38.47 22.42 5.14 10.14 14.64 0.695 0.18 <0.1 <0.1 软熔未滴渣 4.25 3.09 29.72 15.83 8.56 8.14 15.31 0.701 0.14 <0.1 <0.1 软熔滴落渣 14.00 3.92 37.34 21.23 7.74 10.41 16.56 0.720 0.16 <0.1 <0.1 重熔未滴渣 11.75 3.41 30.52 21.23 7.91 8.79 13.45 0.232 0.53 1.13 0.34 重熔滴落渣 19.88 2.08 29.95 18.68 7.77 8.25 12.77 0.145 0.41 <0.1 0.247
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表 5 主要造渣组份的相对质量分数
Table 5. Relative content of main slagging components in different slags
样品名称 相对质量分数/% R2 CaO SiO2 MgO Al2O3 TiO2 V2O5 S 软熔液泛渣 41.96 24.45 5.61 11.06 15.97 0.76 0.20 1.72 软熔未滴渣 37.91 20.19 10.92 10.38 19.53 0.89 0.18 1.88 软熔滴落渣 39.66 22.55 8.22 11.06 17.59 0.76 0.17 1.76 重熔未滴渣 36.92 25.68 9.57 10.63 16.27 0.28 0.64 1.44 重熔滴落渣 38.41 23.96 9.96 10.58 16.38 0.19 0.53 1.60 烧结矿渣相 38.80 19.74 9.62 10.61 19.77 1.37 0.09 1.97
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表 6 不同金属铁的化学成分
Table 6. Chemical compositions of different metallic irons
样品名称 化学成分/% C S V Ti Si 软熔未滴铁 4.83 0.055 0.102 0.114 0.135 软熔滴落铁 3.40 0.080 0.029 0.207 0.193 重熔未滴铁 4.53 0.125 0.076 0.259 1.100 重熔滴落铁 4.76 0.088 0.080 0.070 0.431 生产铁样 4.42 0.087 0.333
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表 7 烧结矿软熔液泛渣的物相组成和元素分布
Table 7. Phase and element distribution of flooding slag on graphite pusher during softening
矿物名称 w/% 化学成分/% Fe O Ti V Si Ca Mg Al 黄长石 68.54 3.71 74.00 23.39 39.00 90.19 72.93 84.19 88.65 钙钛矿 21.84 2.21 21.40 73.70 56.03 4.34 23.16 5.86 7.15 金属铁 4.71 81.52 0.09 0.28 1.55 0.24 0.17 0.59 0.32 辉石 1.21 0.04 1.33 1.01 0.10 1.30 0.91 3.45 1.72 透辉石 0.80 0.23 0.91 0.20 0.54 1.12 0.63 2.58 0.38 铁酸钙 1.15 8.70 0.62 0.94 1.33 0.67 0.59 1.54 0.64 玻璃质 0.04 0.00 0.05 0.01 0.05 0.07 0.01 0.11 0.06 其它 1.71 3.61 1.60 0.47 1.42 2.07 1.58 1.69 1.08
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表 8 烧结矿软熔未滴落渣的物相组成和元素分布
Table 8. Phase and element distribution of residual slag in graphite crucible during softening
矿物名称 w/% 化学成分/% Fe O N Ti V Si Ca Mg Al 黄长石 35.73 0.26 47.26 0 7.40 13.83 69.45 51.82 35.88 56.82 钙钛矿 22.76 0.49 27.03 0 84.13 58.82 3.91 31.48 3.68 8.61 金属铁 22.15 93.21 0.50 0 1.10 7.28 1.24 0.82 1.89 1.59 辉石 7.03 0.07 9.91 0 2.89 4.78 9.66 7.22 16.04 16.93 透辉石 6.03 0.19 8.36 0 1.45 4.89 12.01 6.46 17.50 2.60 镁铝尖晶石 1.90 0.05 2.90 0 0.99 4.47 0.55 0.38 6.21 11.28 MgO 1.26 0.03 1.76 0 0.14 2.68 0.04 0.07 14.57 0 铁酸钙 2.09 4.67 1.14 0 1.46 2.00 1.41 1.19 1.85 1.28 玻璃质 0.03 0 0.05 0 0.01 0.03 0.09 0.01 0.05 0.07 碳氧化钛 0.01 0 0.01 0 0.03 0.02 0 0 0 0 碳氮化钛 0 0 0 100.00 0.05 0.01 0 0 0 0 其它 1.00 1.03 1.09 0 0.37 1.20 1.64 0.55 2.33 0.82 *注：碳氮化钛为0.005225%，碳氮化钛物相0.006066%。
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表 9 烧结矿软熔滴落渣的物相组成和元素分布
Table 9. Phase and element distribution of dripping slag during softening
矿物名称 w/% 化学成分/% Fe O N Ti V Si Ca Mg Al 黄长石 57.84 8.98 59.91 0 41.28 62.71 71.22 63.54 53.06 61.51 钙钛矿 16.33 2.12 15.87 0 45.05 32.97 3.45 18.32 3.22 5.47 金属铁 3.50 79.48 0.04 0 0.10 0.34 0.11 0.08 0.18 0.15 辉石 20.94 0.01 23.04 0 12.93 2.88 23.96 17.24 41.61 31.88 透辉石 0.28 0.06 0.35 0 0.08 0.16 0.40 0.24 0.57 0.21 镁铝尖晶石 0.01 0 0.01 0 0 0.01 0 0 0.02 0.04 铁酸钙 0.57 5.37 0.32 0 0.39 0.56 0.36 0.32 0.55 0.35 碳氮化钛 0.454* 0 0 100.00 0 0 0 0 0 0 其它 0.54 3.98 0.46 0 0.17 0.38 0.51 0.27 0.79 0.41 *注：碳氮化钛为0.000454%。
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表 10 烧结矿重熔未滴落渣的物相组成和元素分布
Table 10. Phase and element distribution of residual slag in graphite crucible during remelting
矿物 w/% 化学成分/% Fe O N Ti V Si Ca Mg Al 黄长石 53.16 1.78 59.29 0.00 17.99 29.30 72.54 64.68 50.79 69.71 钙钛矿 16.92 0.57 17.38 0.00 65.59 47.47 1.91 19.99 2.54 5.18 金属铁 9.61 90.43 0.31 0.00 1.02 3.58 0.83 0.63 1.39 1.16 辉石 5.32 0.24 6.15 0.00 5.37 2.50 5.73 3.87 11.27 9.26 透辉石 8.87 0.44 10.51 0.00 2.06 6.96 12.93 8.31 23.37 2.96 钙铁辉石 2.48 5.66 2.24 0.00 0.84 2.80 2.91 1.72 3.20 2.57 镁铝尖晶石 1.61 0.14 2.05 0.00 1.51 3.62 0.20 0.20 5.31 7.64 碳氮化钛 0.31 0.01 0.01 100.00 2.43 0.43 0.05 0.05 0.06 0.00 碳氧化钛 0.39 0.00 0.34 0.00 1.97 1.34 0.21 0.19 0.34 0.27 其它 1.32 0.74 1.72 0.00 1.22 2.01 2.69 0.36 1.74 1.25
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表 11 不同炉渣主要物相组成对比
Table 11. Main phase composition of different slags
% 样品名称 黄长石 钙钛矿 辉石 其它 软熔液泛渣 71.93 22.92 2.11 3.04 软熔未滴落渣 45.90 29.24 16.78 8.08 软熔滴落渣 59.93 16.92 21.99 1.16 重熔未滴落渣 58.82 18.72 18.44 4.02
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表 12 生产高炉渣的化学成分
Table 12. Chemical composition of blast furnace slag during production
% CaO SiO2 MgO Al2O3 TiO2 V2O5 S R2 27.03 24.72 8.11 13.09 21.85 0.24 0.50 1.09
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