Microwave roasting-assisted separation and enrichment of titanium-enriched phases from titanium-bearing electric furnace smelting slag
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摘要: 针对含钛电炉熔分渣中TiO2面临物相复杂难分离、品位偏低、杂质高富集分离难度大的问题，开展了含钛电炉熔分渣微波焙烧联合分选工艺富集钛的研究。系统研究了微波焙烧对熔分渣富钛相（主要为黑钛石）分离富集的影响，优化了微波焙烧、碱浸及浮选联合工艺参数。通过试验和XRD、SEM-EDS、Zeta电位等分析结果，结合熔分渣焙烧特性、磨矿效率及浮选回收率，明确了微波焙烧对含钛熔分渣物相、微观形貌及相边界的调控作用。研究结果表明，含钛电炉熔分渣的最优微波焙烧工艺参数为物料粒度1～5 mm、微波功率
2400 W、刚玉坩埚承装、900 ℃保温20 min，此条件下熔分渣磨矿后74 μm颗粒占比从原渣的63%提升至96%，显著提升矿相间解离效率。微波焙烧通过选择性加热产生热应力裂纹，减弱黑钛石与镁铝尖晶石、钛辉石的相界面结合力，为后续含钛相有效分离提供了条件。碱浸工艺条件为NaOH质量分数为20%、碱浸时间1 h。浮选最佳工艺条件为浮选剂pH=6、捕获剂油酸钠浓度30 mg/L。含钛熔分渣经微波焙烧-碱浸-浮选联合工艺处理，浮选产物中黑钛石含量为94.2%、回收率85.4%，较原渣相同流程处理结果分别提升38.2%和36.1%，为含钛熔分渣中钛资源有效富集提供了新路线。Abstract: Titanium dioxide (TiO2) in titanium-bearing electric furnace molten slag is characterized by complex mineral phases, low titanium grade, and high impurity content, which greatly increases the difficulty of titanium separation and enrichment. In this work, a combined process of microwave roasting and separation was proposed to realize titanium enrichment from titanium-bearing electric furnace molten slag. The effects of microwave roasting on the separation and enrichment of titanium-rich phases (mainly anosovite) were systematically investigated, and the process parameters of microwave roasting, alkaline leaching and flotation were optimized. Based on experimental results, grinding efficiency, flotation recovery, and comprehensive analyses of XRD, SEM-EDS, and Zeta potential, the regulatory mechanism of microwave roasting on the phase composition, microstructure, and phase boundary characteristics of titanium-bearing molten slag was clarified. The results show that the optimal microwave roasting parameters are as follows: particle size of 1–5 mm, microwave power of2400 W, roasting in a corundum crucible, and heat preservation at 900 ℃ for 20 min. Under these conditions, the proportion of ground particles finer than 74 μm increases from 63% for the raw slag to 96%, which significantly improves the mineral dissociation efficiency. Microwave roasting generates thermal stress cracks via selective heating, which weakens the interfacial bonding strength between anosovite, magnesia-alumina spinel and titanaugite, thereby providing favorable conditions for the subsequent efficient separation of titanium-bearing phases. The optimal alkaline leaching condition is a NaOH concentration of 20% for 1 h. The best flotation performance is achieved at a slurry pH of 6 and a sodium oleate collector concentration of 30 mg/L. After treatment by the combined microwave roasting–alkaline leaching–flotation process, the anosovite content and recovery rate of flotation concentrates reach 94.2% and 85.4%, which are 38.2% and 36.1% higher than those of the raw slag treated by the same process, respectively. This study provides an effective and feasible technical route for the efficient enrichment and utilization of titanium resources from titanium-bearing molten slag. -
图 2 含钛电炉熔分渣主要物相
Figure 2. Main phases of titanium-bearing electric furnace smelting slag
图 3 含钛电炉熔分渣SEM图及矿物表面元素分布
Figure 3. SEM images of titanium-bearing electric molten slag and elemental distribution on mineral surfaces
图 5 粒度、功率、坩埚对熔分钛渣微波焙烧特性的影响
(a)粒度对熔分渣吸波特性的影响；(b)功率对熔分渣吸波特性的影响；(c)坩埚材质对熔分渣吸波特性的影响
Figure 5. Influence of particle size, power and crucible on microwave roasting characteristics of molten-separated titanium slag
图 6 不同温度和保温时间对微波焙烧熔分渣后磨选粒径＜74 μm占比的影响
Figure 6. Effects of temperature and holding time on the proportion of ＜74 μm ground products from microwave-roasted melting-separation slag
图 7 微波焙烧不同温度保温时含钛熔分渣物相
Figure 7. Phases of titanium-bearing smelting slag under microwave roasting at different isothermal temperatures
图 8 微波焙烧不同温度保温时含钛熔分渣矿相
(a) 原渣; (b) 500 ℃; (c) 600 ℃; (d) 700 ℃; (e) 800 ℃; (f) 900 ℃
Figure 8. Mineral phases of titanium-bearing smelting slag after microwave holding sintering at different temperatures
图 9 微波加热前后含钛熔分渣表面形貌
(a)原渣；(b)焙烧渣
Figure 9. Surface morphology of titanium-bearing smelting slag pre- and post-microwave heating
图 10 熔分渣中主要物相与油酸钠吸附前后 zeta 电位与pH值的关系
Figure 10. Zeta potential-pH dependence of main phases in smelting slag pre- and post-sodium oleate adsorption
图 11 不同碱浸条件下浸出熔分渣物相变化
(a) 不同碱浸时间；(b) 不同碱浸浓度
Figure 11. Phase changes of leached smelting slag under different alkaline leaching conditions
图 12 微波焙烧含钛电炉熔分渣碱浸浮选后渣中主要物相
(a)500～800 ℃碱浸浮选主要物相；(b)900 ℃碱浸浮选与原渣主要物相
Figure 12. Main phases in slag after alkaline leaching-flotation of microwave roasted titanium-bearing electric furnace smelting slag
图 13 含钛熔分渣微波焙烧-碱浸-浮选后渣中黑钛石含量及其回收率
Figure 13. Anosovite content and recovery in slag after microwave roasting-alkaline leaching-flotation of titanium-bearing smelting slag
表 1 含钛电炉熔分渣主要成分及碱度
Table 1. Main components and basicity of titanium-bearing electric molten slag
% CaO SiO2 TiO2 MgO Al2O3 R 9.3 18.6 43.9 13.0 15.2 0.5 
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表 2 熔分渣主要物相表面元素含量分析
Table 2. Analysis of surface elements content of main phases in smelting slag
Elements MgTi2O5 Titanaugite MgAl2O4 w/% y/% w/% y/% w/% y/% O 26.89 48.57 34.34 52.53 41.84 56.93 Mg 7.42 8.80 9.06 9.12 7.20 6.45 Al 5.15 5.49 9.94 9.02 27.17 21.92 Si 1.78 1.83 12.29 10.72 9.50 7.36 Ca 0.27 0.19 10.50 6.41 9.54 5.18 Ti 58.39 35.12 23.88 12.20 4.75 2.16
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表 3 试验主要设备
Table 3. Main experimental equipment
Equipment/ device Specification and model Manufacturer Microwave high-temperature experimental furnace LY-6KW-XS Shanghai Longyu Microwave Equipment Co., Ltd. MoSi2 rod high-temperature tube furnace Self-made Flotation machine XFD-1L X-ray diffractometer D/max2500 PC Rigaku Scanning electron microscope TESCAN VEFA Ⅱ Tescan Constant temperature drying oven DHG-9245A Shanghai Yiheng Scientific Instrument Electronic balance JA2003N Shanghai Precision Scientific Instrument Planetary ball mill Retch PM100 NETZSCH X-ray fluorescence spectrometer ZSX Primus III+ Rigaku Zeta potential analyzer Zetasizer Nano ZS90 Malvern Panalytical Water bath kettle SN-HWS-2
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