Clean, high efficiency and green utilization of vanadium tailings extracted by calcium process
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摘要: 以钙法提钒尾渣为研究对象,通过对尾渣成分、物相和主要元素赋存状态的分析,在结合前人研究的基础上,提出了钙法提钒尾渣通过物理法和火法冶金分离技术制取含钒铁合金及含钛炉渣的综合利用途径。研究表明:提钒尾渣经摇床脱硫处理后,分离出石膏渣和含钒富铁料,石膏渣供水泥厂使用,含钒富铁料配加一定比例的还原剂、粘接剂成球后,在矿热炉进行熔分还原冶炼,可获得钒含量3%左右的含钒铁合金及TiO2含量36%左右的还原渣,含钒铁合金可用于含钒钢水合金化;还原渣可用于高钛渣冶炼。能实现钙法提钒尾渣中的有价元素铁、钒、钛等有效提取与回收以及减轻环保压力。Abstract: Calcium extraction of vanadium tailings was taken as research object, the composition, phase and occurrence state of main elements of the tailings were analyzed. On the basis of combining previous studies, the comprehensive utilization of vanadium-bearing alloy and titanium-bearing furnace slag from calcium-based vanadium extraction tailings by physical method and pyrometallurgical separation technology is put forward. Studies have shown that after the removal of vanadium tailings by shaking desulfurization treatment, gypsum residue and iron-rich vanadium material were separated, gypsum residue is used in cement plants. V/Fe-rich material with a certain proportion of reducing agent and adhesive mixed press into pellets, smelting by ore-thermal furnace smelting reduction, ferroalloys with a vanadium content of about 3% and reduction slag containing about 36% TiO2 were obtained, V-containing ferroalloys can be used for alloying V-containing molten steel, and reduced slag can be used for smelting high titanium slag. It can be exploited for effective extraction and recovery of valuable elements such as Fe, V and Ti from calcium-based extraction of vanadium tailings and can reduce the environmental pollution.
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表 1 提钒尾渣主要化学成分
Table 1. Main chemical composition of vanadium extraction tailings
% TV TFe SiO2 CaO MnO S P TiO2 H2O 0.8~1.4 20~35 10~15 4~10 3~7 1.0~2.5 0.04~0.06 7~11.0 20~35 表 2 钙法提钒尾渣中主要元素的赋存状态
Table 2. Occurrence state of main elements in vanadium tailings extracted by calcium method
% 矿物质 Al Ca Cr Fe K Mg Mn Mo Na P S Si Ti V 铁(镁)氧化物 26.07 11.41 5.01 41.53 0.00 32.74 4.83 100.00 83.46 0.00 4.92 9.05 58.47 30.57 钛(铁)氧化物 0.15 0.03 0.00 0.10 0.00 0.24 0.00 0.00 0.00 0.00 0.00 0.03 0.56 0.07 铝(铁)氧化物 1.84 0.06 0.00 0.04 0.00 0.53 0.14 0.00 0.00 0.00 0.00 0.06 0.01 0.01 铁 0.00 0.00 0.00 0.86 0.00 0.00 0.44 0.00 0.00 0.00 0.00 0.00 0.06 0.12 硅酸钙(钒-镁) 11.65 31.66 0.00 1.61 3.21 22.27 18.91 0.00 0.00 70.38 12.21 16.70 4.45 36.06 铁(钛)硅酸盐 55.18 25.46 94.97 54.84 79.73 18.19 73.05 0.00 12.18 0.00 28.46 53.17 34.42 29.19 铝硅酸盐 3.83 0.72 0.02 0.21 7.05 1.35 0.41 0.00 0.87 0.00 0.00 1.91 0.07 0.20 镁硅酸盐 0.99 2.01 0.00 0.13 0.00 24.35 0.41 0.00 0.00 0.00 0.00 8.55 1.69 2.77 硫酸钙(铁) 0.00 27.48 0.00 0.58 10.02 0.00 1.42 0.00 3.49 0.00 54.31 0.51 0.20 0.00 钒酸铁 0.24 0.09 0.00 0.10 0.00 0.24 0.10 0.00 0.00 29.62 0.00 0.06 0.00 0.94 石英 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.92 0.00 0.00 氧化钙 0.05 1.08 0.00 0.00 0.00 0.10 0.29 0.00 0.00 0.00 0.09 0.02 0.07 0.07 总计 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 表 3 提钒尾渣粒度及硫含量分布
Table 3. Particle size and sulfur content distribution of tailings
粒级/mm 重量/g 产率/% 硫含量/% 分布率/% ≥0.3 40 0.75 0.323 0.21 −0.3~+0.15 570 10.71 0.234 2.15 −0.15~+0.074 945 17.75 0.082 1.25 −0.074~+0.052 350.4 6.58 0.145 0.82 −0.052~+0.037 654.5 12.30 0.088 0.93 −0.037~+0.019 1355.3 25.46 0.087 1.90 −0.019~+0.01 762.6 14.33 0.117 1.44 <0.01 645.3 12.12 8.78 91.31 合 计 5323.1 100 1.17 100 表 4 刻槽摇床脱硫效果
Table 4. Desulfurization effect of slotting and shaking table
编 号 产 率/ % 硫品位/ % 硫回收率/ % 给 矿 100 1.17 100 刻槽-1 19.93 0.038 2.92 刻槽-2 23.53 0.045 3.43 刻槽-3 26.17 0.102 9.16 刻槽-4 20.02 1.054 47.16 刻槽-5 10.35 1.519 37.32 表 5 含钒富铁料主要化学成分
Table 5. Main chemical compositions of vanadium-rich iron material
% TV TFe SiO2 CaO MnO Al2O3 TiO2 S P 范围 1.39~1.61 37~41.8 13.34~14.6 2.2~2.9 1.52~1.62 2.1~2.38 11.98~
13.060.2~
0.30.047~
0.053平均值 1.43 40.8 13.76 2.45 1.58 2.2 12.35 0.28 0.049 表 6 含钒富铁料球团主要化学成分
Table 6. Main chemical composition of vanadium-rich iron pellet
% TFe MFe V2O5 TiO2 CaO SiO2 MnO Al2O3 S P 范围 32.36~
38.65<0.5 2.08~
2.679.87~
11.343.62~
6.1410.22~
13.281.04~
1.732.08~
3.120.22~
0.310.038~
0.052平均 35.62 <0.5 2.22 10.23 4.15 11.07 1.16 2.78 0.26 0.047 表 7 含钒铁合金主要成分
Table 7. Main components of alloy
% C V Si Mn Ti S P 范围 3.09~
5.392.15~3.54 0.56~1.24 1.52~1.89 0.63~2.51 0.037~
0.0560.052~0.084 平均值 4.31 3.05 0.84 1.73 1.32 0.048 0.072 表 8 高钛还原渣主要成分
Table 8. Main components of reducing slag
% 组元 V2O5 CaO FeO MgO MnO TFe SiO2 TiO2 Al2O3 范围 0.13~0.50 19.19~35.21 0.60~5.11 2.16~3.68 0.12~0.47 1.09~2.60 9.96~15.64 32.61~38.16 4.33~10.14 平均值 0.21 28.02 2.48 2.94 0.24 2.02 14.07 36.16 6.42 表 9 HRB400E化学成分统计
Table 9. Main components of HRB400E
名称 w/% 统计
炉数C Si Mn P S V 试验 0.21~0.25 0.32~0.45 1.26~1.40 0.018~0.038 0.011~0.040 0.018~0.032 27 0.235 0.38 1.32 0.029 0.028 0.025 原生产 0.21~0.25 0.30~0.47 1.22~1.37 0.012~0.037 0.007~0.035 0.021~0.035 34 0.227 0.38 1.31 0.021 0.025 0.027 表 10 HRB400E力学性能统计
Table 10. Main mechanical properties of HRB400E
品种 规格组距/mm ReL/MPa Rm
/MPaA
/%Agt
/%强屈比 反弯 统计
炉数线材 Ø8、Ø10 (430~485)/460 (620~685)/658 (23.0~44.0)/35.0 (12.5~20.8)/16.2 (1.39~1.54)/1.47 合格 12 Ø12 (440~500)/473 (625~695)/649 (28.0~41.0)/34.0 (11.3~20.5)/15.9 (1.40~1.56)/1.49 合格 15 标准要求 ≥400 ≥540 ≥16 ≥9.0 ≥1.25 无裂纹 -
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