Efficient metallurgical extraction of vanadium slag: Experimental phase diagram study and thermodynamic modeling of Na2O-K2O-V2O5 system
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摘要: 构建准确可靠的热力学数据库对提钒过程优化以及钒酸盐材料的制备具有重要的应用价值和指导意义。采用封闭铂金坩埚，结合X射线衍射(XRD)与差热分析(DTA)技术，证实了K2O-V2O5体系中K3V5O14为稳定存在的化合物，并试验测定了K2V8O21和KVO3的熔化温度分别为532.4 ℃和516.5 ℃。随后采用修正的准化学模型(MQM)，引入溶液中第二相邻阳离子短程有序对描述吉布斯自由能的变化。基于CALPHAD框架(CALculation of PHAse Diagram，相图计算)，构建了Na2O-K2O-V2O5体系的热力学模型，重现了Na2O-K2O-V2O5体系全组分范围的实验数据和热力学性质，获得了该体系中所有物相一系列自洽的热力学模型参数，最终构建了可靠的热力学数据库。进一步探讨了当前数据库在钒渣钠化焙烧提钒中的应用，明确了含钒物相的迁移规律，确定了最佳的操作温度窗口。
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关键词:
- Na2O-K2O-V2O5体系 /
- 相图 /
- 热力学优化 /
- CALPHAD
Abstract: Accurate and reliable thermodynamic databases are of significance for optimizing vanadium extraction and synthesizing vanadate materials. This study employed sealed platinum crucibles combined with X-ray diffraction (XRD) and differential thermal analysis (DTA) to confirm the presence of K3V5O14 in the K2O-V2O5 system, melting temperature of K2V8O21 and KVO3 were also determined as 532.4 ℃ and 516.5 ℃, respectively. Modified Quasichemical Model (MQM) was adopted, incorporating short-range ordering of second-neighboring cations in solution to describe changes in Gibbs free energy of solution phases. Thermodynamic model for the Na2O-K2O-V2O5 system was then developed in the framework of CALPHAD (Calculation of Phase Diagrams) methodology, reproducing experimental data across the entire composition range of the system. A self-consistent set of thermodynamic parameters for all phases in the system was obtained, ultimately establishing a reliable thermodynamic database. Furthermore, the developed database was applied to optimize sodium-roasting of vanadium slag at elevated temperatures, clarifying the phase evolution of vanadium-containing phases and identifying optimal operating temperature windows.-
Key words:
- Na2O-K2O-V2O5 system /
- phase diagram /
- thermodynamic optimization /
- CALPHAD
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图 1 K2O-V2O5体系产物及KVO3、K2V8O21的XRD与热分析
(a)K2O-V2O5体系中制备样品的X射线衍射图谱；(b)KVO3样品差热分析；(c)K2V8O21样品差热分析
Figure 1. XRD and thermal analysis of products in the K2O-V2O5 system and of KVO3, K2V8O21
图 2 Na2O-V2O5体系热力学优化和试验结果对比
(a)相平衡关系；(b)化合物标准生成焓；(c)化合物298 K熵值；(d)Na2O-V2O5体系化合物比热容
Figure 2. The optimized phase diagram of the Na2O-V2O5 system along with experimental data
图 3 K2O-V2O5体系热力学优化和试验结果对比
(a)相平衡关系；(b)化合物标准生成焓；(c)化合物298 K熵值；(d)K2O-V2O5体系化合物比热容
Figure 3. The optimized phase diagram of the K2O-V2O5 system along with experimental data
图 4 Na2O-K2O-V2O5体系热力学优化和试验结果对比
(a) Na2O-K2O优化与实验结果对比；(b) ~(c) NaVO3-KVO3垂直截面热力学优化和实验结果对比；(d) Na4V2O7-K4V2O7垂直截面预测
Figure 4. The optimized phase diagram of the Na2O-K2O-V2O5 system along with experimental data
图 5 预测得到K2O-Na2O-V2O5体系等温截面
(a)600 ℃, 100 kPa；(b)700 ℃, 100 kPa；(c)800 ℃, 100 kPa；(d)900 ℃, 100 kPa
Figure 5. The predictive isothermal section of the Na2O-K2O-V2O5 system
图 6 空气气氛下典型钒渣与15% Na2CO3混合焙烧稳定相含量随温度的变化
Figure 6. Weight of thermodynamic equilibrium phases calculated for the mixture of vanadium slag and 15% Na2CO3 at different temperatures under air conditions
表 1 优化后的体系溶液相模型参数
Table 1. The optimized model parameters for liquid phase
体 系 模型参数 Na2O-V2O5 $ \Delta g_{\rm{Na -V O}}^{0 \quad 0}$=− 401078.2 +49T; $ \Delta g_{\rm{Na -V O}}^{1 \quad 0}$=−50000 ;
$ \Delta g_{\rm{Na -V O}}^{0 \quad 1}$=−360000 −74T; $ \Delta g_{\rm{Na -V O}}^{0 \quad 2}$=410000 −132T;
$ \Delta g_{\rm{Na -V O}}^{0 \quad 3}$=100000 −400T;K2O-V2O5 $ \Delta g_{\rm{K -V O}}^{0 \quad 0}$=− 536881 +32T; $ \Delta g_{\rm{K -V O}}^{0 \quad 1}$=−330000 +50T;
$ \Delta g_{\rm{K -V O}}^{0 \quad 2}$=26000 Na2O- K2O-V2O5 
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