Study on modification of vanadium-titanium tailings and preparation of tailings-based cementing materials
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摘要: 以攀西地区钒钛尾矿为原材料，通过物理和复合化学改性技术激发其潜在的胶凝活性，进而制备钒钛尾矿基胶凝材料。通过对所制备材料的微观性能进行分析，探讨胶凝材料体系的水化产物、微观结构的演变过程。结果表明，经机械力活化与化学复合改性处理后，钒钛尾矿养护28 d活性指数显著提升，由原始的60%提升至84%。当条件为钒钛尾矿45%、提钛渣20%、钙质材料5%、硫质材料15%和水泥熟料15%时，所制备的钒钛尾矿基胶凝材料展现出良好的力学性能，养护28 d抗压强度达到33.1 MPa，与32.5级水泥相当，表明该材料在非结构工程领域具有潜在的应用前景。Abstract: This study utilized vanadium-titanium tailings from the Panxi region as raw materials, aiming to activate their potential cementitious activity through physical and composite chemical modification techniques, thereby preparing vanadium-titanium tailings-based cementitious materials. By analyzing the micro-properties of the prepared materials, the hydration products and the evolution of microstructures within the cementitious material system were explored. The research results indicate that after treatment with mechanical activation and composite chemical modification, the 28-day activity index of the vanadium-titanium tailings significantly increases from the original 60% to 84%. When the composition is 45% vanadium-titanium tailings, 20% titanium slag, 5% calcium material, 15% sulfur material, and 15% cement clinker, the prepared vanadium-titanium tailings-based cementitious material exhibits good mechanical properties with a 28-day compressive strength of 33.1 MPa, which is comparable to that of 32.5-grade cement. This indicates that the material has potential application prospects in non-structural engineering field.
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图 3 粉磨6 min钒钛尾矿的XRD图
Figure 3. Phase composition of the ground vanadium-titanium tailings for 6 min
图 4 粉磨钒钛尾矿试样的密度与粒径中值的关系
Figure 4. Relationship diagram between the density and median particle size of the ground vanadium-titanium tailings samples
图 5 钒钛尾矿比表面积随粉磨时间的变化规律
Figure 5. Variation law of the the specific surface area of vanadium-titanium tailings with the grinding time
图 7 试样的 TG-DTG 曲线
(a) 养护 7 d的TG; (b) 养护7 d的DTG ; (c) 养护 28 d的TG; (d) 养护 28 d的DTG
Figure 7. Derivative thermo-gravimetric curves of the samples
图 8 试样在不同温度区间的水化产物质量损失的相对含量
Figure 8. Relative content of mass loss of hydration products in different temperature ranges
图 9 试样养护7、28 d的微观形貌
(a) T0-7 d; (b) T1-7 d; (c) T2-7 d; (d) T3-7 d; (e) T0-28 d; (f) T1-28 d; (g) T2-28 d; (h) T3-28 d
Figure 9. Microscopic morphology of the samples after 7 days and 28 days of curing
表 1 钒钛尾矿的主要物理性能
Table 1. Main physical properties of vanadium-titanium tailings
密度/
(g·cm−3)比表面积/
(m2·kg−1)45 μm筛
余量/%80 μm筛
余量/%需水量
比/%活性指数/% 3 d 7 d 28 d 3.09 160 80.4 64.4 92 53 55 55 
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表 2 钒钛尾矿的主要化学成分
Table 2. Main chemical components of vanadium-titanium tailings
% SiO2 Al2O3 MgO CaO Fe2O3 K2O TiO2 34.6 12.9 10.4 12.7 19.1 0.2 6.6
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表 3 粉磨后钒钛尾矿的火山灰活性技术指标
Table 3. Pozzolanic activity technical indicators of the ground vanadium-titanium tailings
粉磨时间/min 比表面积/(m2·kg−1) 需水量比/% 活性指数/% 3 d 7 d 28 d 0（原状） 160 92 53 55 55 2 618 96 59 60 60 12 730 98 60 69 69
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表 4 钒钛尾矿改性方案及活性指数测试结果
Table 4. Modification scheme and activity index test results of vanadium-titanium tailings
名称 粉磨时间/min 比表面积/(m2·kg−1) 尾矿掺量/% 提钛渣掺量/% 硫质材料掺量/% 钙质材料掺量/% 水泥熟料/% 活性指数/% 3 d 7 d 28 d MC1 2 618 30.0 70.0 59 60 60 MC2 12 730 30.0 70.0 60 69 69 CC1 2 618 25.5 4.5 70.0 53 56 73 CC2 12 730 13.5 8.25 4.5 3.75 70.0 81 87 84
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表 5 钒钛尾矿基胶凝材料配比方案及强度结果
Table 5. Ratio scheme and strength results of vanadium-titanium tailings-based cementing materials
试样
编号粉磨时间/min 钒钛尾矿 尾矿掺量/% 提钛渣
掺量/%钙质材料
掺量/%硫质材料
掺量/%水泥熟料
掺量/%抗压强度/MPa D50/μm 3 d 7 d 28 d T0 0 189 45 20 5 15 15 9.7 11.8 18.7 T1 3 14.2 45 20 5 15 15 11.5 13.2 19.6 T2 8 10.9 45 20 5 15 15 13.6 14.9 20.8 T3 12 9.7 45 20 5 15 15 15.0 19.1 33.1
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