Experimental study on hydrogen-carbon synergistic reduction of vanadium-titanium magnetite
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摘要: 采用钒钛磁铁矿精矿粉内配兰炭骨料与氢气进行协同还原的方式，探究了骨料量和还原温度对钒钛磁铁矿气基还原金属化率以及抗压强度的影响，并运用X射线衍射（XRD）、扫描电镜（SEM）以及X射线计算机断层扫描（XCT）方法分析了还原产物物相、微观形貌以及孔隙结构变化。结果表明，在氢气气氛下内配兰炭还原可显著提升钒钛磁铁矿的还原效果；在氮气气氛下，兰炭并未将钒钛磁铁矿还原。内配兰炭的钒钛磁铁矿还原后，金属铁的XRD衍射峰增强，而碳的衍射峰降低。在内配兰炭还原后的试样表面，兰炭颗粒保存较好且附近孔隙较多，内嵌兰炭提高了试样内部的孔隙数量并增大了孔径，促进还原气体深入试样参与还原，从而提高了钒钛磁铁矿还原效果。Abstract: The study explored the effects of aggregate quantity and reduction temperature on the gas-based reduction metallization rate and compressive strength of vanadium-titanium magnetite through a synergistic reduction method using vanadium-titanium magnetite concentrate powder internally mixed with semi-coke aggregate and hydrogen. X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray computed tomography (XCT) were employed to analyze the phase composition, micro-morphology, and pore structure changes of the reduced products. The results indicated that the reduction effect of vanadium-titanium magnetite was significantly enhanced when reduced with internally mixed semi-coke in hydrogen atmosphere. In contrast, no reduction of vanadium-titanium magnetite was observed with semi-coke in a nitrogen atmosphere. After the reduction of vanadium-titanium magnetite mixed with semi-coke, the XRD diffraction peaks of metallic iron were intensified, while the semi-coke diffraction peaks were decreased. On the surface of the samples after reduction with semi-coke, the semi-coke particles remained relatively intact, with numerous pores in their vicinity. The embedded semi-coke increased the number of pores within the samples and enlarged the pore diameters, facilitating the penetration of reducing gases into the samples for reduction, thus enhancing the reduction effect of vanadium-titanium magnetite.
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图 3 骨料量对钒钛磁铁矿金属化率的影响
Figure 3. Effect of aggregate quantity on metallization rate of vanadium-titanium magnetite
图 4 骨料量对钒钛磁铁矿抗压强度的影响
Figure 4. Effect of aggregate quantity on compressive strength of vanadium-titanium magnetite
图 5 还原温度对钒钛磁铁矿金属化率的影响
Figure 5. Effect of reduction temperature on metallization of vanadium-titanium magnetite
图 6 还原温度对钒钛磁铁矿抗压强度的影响
Figure 6. Effect of reduction temperature on compressive strength of vanadium-titanium magnetite
图 8 钒钛磁铁矿H2气氛还原的SEM图像
（a）950 ℃；（b）1 000 ℃；（c）1 050 ℃；（d）1 100 ℃；（e）1 150 ℃
Figure 8. SEM images of vanadium-titanium magnetite reduced in H2 atmosphere
图 9 钒钛磁铁矿H2气氛还原后的EDS图像
（a）点1；（b）点2；（c）点3
Figure 9. EDS images of vanadium-titanium magnetite after reduction in H2 atmosphere
图 10 钒钛磁铁矿H2还原的图谱扫描分析
Figure 10. EDS maps of vanadium-titanium magnetite reduced in H2 atmosphere
图 11 钒钛磁铁矿N2气氛还原的SEM形貌
（a）950 ℃；（b）1 000 ℃；（c）1 050 ℃；（d）1 100 ℃；（e）1 150 ℃.
Figure 11. SEM images of vanadium-titanium magnetite reduced in N2 atmosphere
图 12 钒钛磁铁矿N2气氛还原的EDS图像
Figure 12. EDS images of vanadium-titanium magnetite reduced in N2 atmosphere
(a)SEM图像; (b)点4; (c)点5; (d)点6
图 13 钒钛磁铁矿N2还原的图谱扫描分析
Figure 13. EDS maps of vanadium-titanium magnetite reduced in N2 atmosphere
图 14 还原后样品的XCT图像
（a1）～（a3）H2气氛0骨料；（b1）～（b3）H2气氛6%骨料；（c1）～（c3）N2气氛0骨料；（d1）～（d3）N2气氛6%骨料
Figure 14. XCT image of the reduced sample
图 15 内嵌骨料还原后的孔径等效直径分布频率
Figure 15. Frequency diagram of pore size equivalent diameter distribution after embedded aggregate reduction
图 16 钒钛磁铁矿氢-碳协同还原机理
Figure 16. Mechanism diagram of hydrogen-carbon synergistic reduction of vanadium-titanium magnetite
表 1 钒钛磁铁精矿化学成分
Table 1. The composition of vanadium-titanium magnetite concentrates
% TFe FeO TiO2 V2O5 SiO2 Al2O3 CaO MgO Cr2O3 55.00 32.13 9.50 0.73 4.20 4.10 0.84 3.30 0.68 
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