Study on the influences of melt components on the physical properties of molten salt chlorination system
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摘要: 氯化物熔盐物性对于熔盐氯化法制备四氯化钛效率至关重要。为了考察氯化用熔盐组分含量变化对熔盐体系物性的影响规律，以工业生产中的熔盐为对象，对正常原盐、泡沫盐和过滤熔盐的电导率和粘度物性进行了测试以及XRD物相分析、化学成分分析。根据实际生产中的组分配比以及化学分析结果，设置了三因素为FeCl2、FeCl3以及MgCl2 : NaCl的正交试验，研究不同组分配比下熔盐体系的物性变化。结果表明：FeCl2含量对熔盐体系电导率影响最为显著，每5%的FeCl2增加量会使熔盐整体电导率提高0.33 S/cm；FeCl3含量对熔盐体系粘度影响最大，其组分占比在10 %～ 15%区间内的影响最为明显。最后，利用综合评分法评估出最佳的熔盐氯化组分方案为：CaCl2 4%、FeCl2 20%、FeCl3 5%、MgCl2 : NaCl = 1 : 1。Abstract: The physical properties of chloride molten salt are very important for the preparation efficiency of titanium tetrachloride produced by molten salt chlorination. To investigate the influence of changes in chloride-containing molten salt composition on the physical properties of molten salt systems, this study conducted the physical property tests including conductivity and viscosity on normal raw salt, foam salt and filtered molten salt. Furthermore, XRD analysis and chemical composition analysis were also performed. Based on the component ratios in actual production and chemical analysis results, an orthogonal experiment with three factors including FeCl2, FeCl3, and MgCl2 : NaCl was designed to study the changes of physical properties of molten salt systems under different component ratios. The results indicate that the FeCl2 content has the most significant effect on the conductivity of the molten salt system, with an increase of 5% FeCl2 resulting in a 0.33 S/cm increase in overall molten salt conductivity. The FeCl3 content has the greatest impact on the viscosity of the molten salt system, with the effect being most pronounced within the 10% to 15% range of its composition. Finally, utilizing a comprehensive scoring method, the optimal chlorinated component scheme for molten salt was determined to be CaCl2 4%, FeCl2 20%, FeCl3 5% and MgCl2 : NaCl = 1 : 1.
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Key words:
- TiCl4 /
- molten salt chlorination /
- melt components /
- normal raw salt /
- foam salt /
- filtered molten salt /
- electrical conductivity /
- viscosity
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图 2 正常原盐、泡沫盐和过滤熔盐的XRD谱
Figure 2. XRD patterns of normal raw salt, foam salt and filtered molten salt
图 3 24 ℃的1 mol/L KCl溶液电导率测试标定结果
Figure 3. Conductivity test result for 1 mol/L KCl solution at 24 ℃
图 8 氯化熔盐体系在700 、750、800 ℃条件下的电导率测试
Figure 8. Conductivity test of chlorinated molten salt system at 700, 750 ℃ and 800 ℃
图 9 氯化熔盐体系在700、750、800 ℃条件下的粘度测试
Figure 9. Viscosity test of chlorinated molten salt system at 700, 750 ℃ and 800 ℃
表 1 试剂样品信息
Table 1. Reagent sample information
试剂名称 纯度(AR)/% 品牌 氯化钠 ≥99.5 Greagent 无水氯化镁 99.5 益之辰 氯化钙 99.0 阿拉丁 无水氯化亚铁 99.5 麦克林 无水氯化铁 99.5 麦克林 
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表 2 正交试验因素及水平
Table 2. Orthogonal experimental factors and horizontal parameters
水平 因素 A
FeCl2含量/%B
FeCl3含量/%C
L = MgCl2 : NaCl1 5 0 3 : 2 2 10 5 1 : 1 3 15 10 2 : 3 4 20 15 1 : 2 注：CaCl2含量占比固定为4%，基础盐系即MgCl2+NaCl的含量占比由1 - FeCl2% - FeCl3% - CaCl2%得出
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表 3 氯化熔盐在750 ℃条件下的电导率分析结果
Table 3. Conductivity analysis results of chlorinated molten salt at 750 ℃
试验号 w(FeCl2)/% w(FeCl3)/% 基础盐系L κ/(S·cm−1) 1 5 0 3:2 1.30 2 5 5 1:1 1.45 3 5 10 2:3 1.42 4 5 15 1:2 1.18 5 10 0 1:1 1.58 6 10 5 3:2 1.17 7 10 10 1:2 2.35 8 10 15 2:3 1.30 9 15 0 2:3 1.29 10 15 5 1:2 2.24 11 15 10 3:2 1.22 12 15 15 1:1 2.84 13 20 0 1:2 1.45 14 20 5 2:3 2.99 15 20 10 1:1 1.63 16 20 15 3:2 3.23 k1 1.337 1.405 1.730 k2 1.600 1.963 1.875 k3 1.897 1.655 1.750 k4 2.325 2.138 1.805 极差R 0.988 0.733 0.145
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表 4 氯化熔盐在750 ℃条件下的粘度分析结果
Table 4. Viscosity analysis results of chlorinated molten salt at 750 ℃
试验号 w(FeCl2)/% w(FeCl3)/% 基础盐系L η/(mPa·s) 1 5 0 3:2 4.69 2 5 5 1:1 4.89 3 5 10 2:3 5.28 4 5 15 1:2 6.36 5 10 0 1:1 5.24 6 10 5 3:2 5.49 7 10 10 1:2 5.10 8 10 15 2:3 6.38 9 15 0 2:3 5.77 10 15 5 1:2 4.97 11 15 10 3:2 5.77 12 15 15 1:1 5.49 13 20 0 1:2 5.01 14 20 5 2:3 5.21 15 20 10 1:1 5.40 16 20 15 3:2 5.78 k1 5.305 5.178 5.433 k2 5.553 5.140 5.255 k3 5.500 5.387 5.660 k4 5.350 6.003 5.360 极差R 0.248 0.863 0.405
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表 5 氯化熔盐在750 ℃条件下的多指标综合评分结果
Table 5. Results of multi-index comprehensive score of chlorinated molten salt at 750 ℃
试验号 w(FeCl2)/% w(FeCl3)/% 基础盐系L 电导率
隶属度粘度
隶属度综合分 1 5 0 3:2 0.06 1.00 0.53 2 5 5 1:1 0.14 0.88 0.51 3 5 10 2:3 0.12 0.65 0.39 4 5 15 1:2 0.00 0.01 0.01 5 10 0 1:1 0.20 0.67 0.44 6 10 5 3:2 0.00 0.53 0.26 7 10 10 1:2 0.57 0.76 0.67 8 10 15 2:3 0.06 0.00 0.03 9 15 0 2:3 0.06 0.36 0.21 10 15 5 1:2 0.52 0.83 0.68 11 15 10 3:2 0.02 0.36 0.19 12 15 15 1:1 0.81 0.53 0.67 13 20 0 1:2 0.14 0.81 0.47 14 20 5 2:3 0.88 0.69 0.79 15 20 10 1:1 0.22 0.58 0.40 16 20 15 3:2 1.00 0.36 0.68 k1 1.44 1.65 1.66 k2 1.40 2.24 2.02 k3 1.75 1.65 1.42 k4 2.34 1.39 1.83 极差R 0.94 0.85 0.60
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