Preparation of titanium dioxide from acid leaching solution of high titanium blast furnace slag by boiling hydrolysis
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摘要: 针对攀西地区高钛高炉渣有效处理不全面等问题，采用硫酸法对其钛组分进行提取，探究酸浸液沸腾水解过程中底液pH值、水解温度、加料速率、陈化时间以及二沸时间对Ti4+的水解率以及水解产物结构的影响，确定了最优水解条件。结果表明：底液pH值、水解温度、陈化时间对水解率及水解产物具有显著影响，底液pH值、加料速率以及陈化时间与水解产物的尺寸大小、分散性呈正相关，水解温度则与其呈负相关，二沸时间对其影响较小。最优水解条件为底液pH值1.7、水解温度105 ℃、加料速率6.6 mL/min、陈化时间25 min、二沸时间60 min，在此条件下Ti组分的水解率为90.71%，获得的偏钛酸经高温煅烧后为锐钛矿型二氧化钛，性能指标满足非颜料用二氧化钛的国家标准。Abstract: In order to solve the problem of incomplete treatment of high titanium blast furnace slag in Panxi area, the titanium component was extracted by sulfuric acid, and the effects of pH value of base liquid, hydrolysis temperature, feeding rate, aging time and second-boiling time on the hydrolysis rate of Ti4+ and the structure of hydrolysate were investigated. The results show that the pH value of base liquid, the hydrolysis temperature and the aging time have significant effects on the hydrolysis rate and the hydrolysate structure. pH value of base liquid, feeding rate and aging time are positively related to the size and dispersion of the hydrolysate, while the hydrolysis temperature is negatively related to them. The second-boiling time has little effect on the size and dispersion of the hydrolysate. The optimal hydrolysis conditions are pH=1.7, hydrolysis temperature of 105 ℃, feeding rate of 6.6 mL/min, aging time of 25 min and second-boiling time of 60 min. Under the optimum conditions, the hydrolysis rate of Ti component is 90.71%. After calcination at high temperature, the obtained metatitanic acid transforms into anatase titanium dioxide, meeting the national standard of non-pigment titanium dioxide.
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图 1 底液pH对Ti组分水解率及产物白度的影响
Figure 1. Effect of pH on hydrolysis rate and whiteness of Ti component
图 2 不同底液pH下水解产物的XRD图谱
Figure 2. XRD patterns of hydrolysate under different pH conditions
图 3 不同底液pH下水解产物的粒径分布
Figure 3. Size distribution of hydrolysate under different pH conditions
图 4 不同底液pH下水解产物的光学显微形貌
Figure 4. Microstructure of hydrolysates under different pH conditions
图 5 水解温度对Ti组分水解率的影响
Figure 5. Effect of hydrolysis temperature on hydrolysis rate of Ti component
图 6 不同水解温度下水解产物的粒径分布
Figure 6. Particle size distribution of hydrolysates at different hydrolysis temperatures
图 7 不同水解温度下水解产物的光学显微形貌
Figure 7. Microstructure of hydrolysates at different hydrolysis temperatures
图 8 加料速率对Ti组分水解率的影响
Figure 8. Effect of feeding rate on hydrolysis rate of Ti component
图 9 不同加料速率下水解产物的粒径分布
Figure 9. Particle size distribution of hydrolysates at different feeding rates
图 10 不同加料速率下水解产物的光学显微形貌
Figure 10. Microstructure of hydrolysates at different feeding rates
图 11 陈化时间对Ti组分水解率的影响
Figure 11. Effect of maturation time on hydrolysis rate of Ti component
图 12 不同陈化时间下水解产物的粒径分布
Figure 12. Particle size distribution of hydrolysates at different maturation time
图 13 不同陈化时间下水解产物的光学显微形貌
Figure 13. Microstructure of hydrolysate at different maturation time
图 14 二沸时间对Ti组分水解率的影响
Figure 14. Effect of second -boiling time on hydrolysis rate of Ti component
图 15 不同二沸时间下水解产物的粒径分布
Figure 15. Particle size distribution of hydrolysates under different second-boiling time
图 16 不同二沸时间下水解产物的光学显微形貌
Figure 16. Microstructure of hydrolysate under different second-boiling time
表 1 高钛高炉渣酸浸液中各金属阳离子浓度
Table 1. Concentration of metal cations in acid leaching solution of high titanium blast furnace slag
g/L Ti4+ Al3+ Mg2+ Fe3+ 33 31 19.2 3.45 
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表 2 水淬型高钛高炉渣XRF分析
Table 2. XRF analysis of water quenched high titanium blast furnace slag
% CaO SiO2 TiO2 Al2O3 MgO SO3 Fe2O3 28.08 26.74 19.65 13.86 7.64 1.05 0.79 K2O MnO Na2O F BaO SrO ZrO2 0.72 0.64 0.53 0.17 0.07 0.04 0.02
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