Error analysis and correction of vapor-liquid equilibrium of WF6-MoF6 systems by static method

doi:10.11949/0438-1157.20241258

Abstract

Abstract:

The lack of vapor-liquid equilibrium data for nuclear-pure grade uranium fluoride and related fluoride impurities has become a bottleneck in the development of China's dry-process uranium purification and conversion technology. However, the complexity and particularity of the physical properties of the system have brought great difficulties to the accurate determination of the data. Therefore, a high-pressure corrosion-resistant static vapor-liquid equilibrium measurement device was designed and developed. The saturated vapor pressure data of pure components VF₅ and MoF₆, as well as the isothermal vapor-liquid equilibrium data of the WF₆-MoF₆ binary system at different temperatures, were measured. Emphasis was placed on conducting a comprehensive error analysis and data correction from three perspectives: device design, operation process, and analysis and detection. The results show that the impact of gas-phase sampling on the liquid-phase composition is less than five ten-thousandths; there is an error of approximately 0.5% when considering the raw material composition as the liquid-phase composition; reducing the purge gas velocity of gas-phase sampling and decreasing the heating rate can reduce errors, etc. After correcting the experimental data based on the results of error analysis and estimation, the thermodynamic consistency test was passed. This provides a supporting means for accurately obtaining the thermodynamic data of vapor-liquid equilibrium of metal fluorides.

Key words: vapor-liquid balance, binary mixture, fluoride, static method, error analysis

摘要：

核纯级氟化铀及相关氟化物杂质的汽液相平衡数据缺乏，已成为我国干法铀纯化转化工艺开发的瓶颈。然而，该体系物性的复杂性与特殊性给数据的准确测定带来了极大困难。为此设计并研制了一种高压耐腐蚀静态法汽液相平衡测量装置，测定了纯组分VF₅和MoF₆的饱和蒸气压数据以及WF₆和MoF₆二元体系在不同温度下的恒温汽液相平衡数据。重点从装置设计、操作过程和分析检测三个角度进行了全面的误差分析与数据校正，结果表明气相取样对液相组成的影响不足万分之五；原料组成视为液相组成存在约0.5%的误差；降低气相取样吹扫气速和减小升温速率会减少误差等。基于误差分析与估算结果对实验数据进行修正后，通过了热力学一致性检验，为准确获取金属氟化物汽液相平衡热力学数据提供了支撑。

关键词: 汽液平衡, 二元混合物, 氟化物, 静态法, 误差分析

CLC Number:

TQ 028.8

Zhenguang TUO, Rongliang LI, Shaohui KANG, Yuqing NIU, Zhiquan ZHOU, Kaikai YE, Haitao MA, Shun LIU, Hong LI, Xin GAO. Error analysis and correction of vapor-liquid equilibrium of WF₆-MoF₆ systems by static method[J]. CIESC Journal, 2025, 76(5): 2270-2278.

拓振光, 李荣亮, 康绍辉, 牛玉清, 周志全, 叶开凯, 马海桃, 刘顺, 李洪, 高鑫. 静态法测定WF₆-MoF₆体系汽液相平衡数据的误差分析与修正[J]. 化工学报, 2025, 76(5): 2270-2278.

Figures/Tables 9

Table 1 Experimental reagent information

试剂名称	化学式	供应商	质量分数/%
六氟化钼	MoF₆	山东重山光电材料股份有限公司	≥99.9
六氟化钨	WF₆	山东重山光电材料股份有限公司	≥99.9
五氟化钒	VF₅	山东重山光电材料股份有限公司	≥99.9
氮气	N₂	山东重山光电材料股份有限公司	≥99.999
液氮	N₂	山东重山光电材料股份有限公司	≥98
纯净水	H₂O	山东重山光电材料股份有限公司	100

Fig.1 Schematic diagram of the experimental device

Fig.2 Saturated vapor pressure of VF5

Fig.3 Saturated vapor pressure of MoF6

Fig.4 P-xy diagram of MoF6(1)-WF6 (2) system at 58.4, 72.9 and 87.1℃

Table 2 Feed parameters of MoF6-WF6 binary mixture vapor-liquid equilibrium experiment

F/mol	L/mol	G/mol	x_F	x_L	x_G	（x_L-x_F）×100%
1.0105	0.9913	0.0192	0.1677	0.1701	0.0466	0.24%
1.0052	0.9861	0.0192	0.3347	0.3373	0.2000	0.26%
0.9942	0.9750	0.0192	0.5057	0.5107	0.2518	0.50%
1.0033	0.9841	0.0192	0.6678	0.6733	0.3873	0.55%
0.8976	0.8784	0.0192	0.8341	0.8379	0.6623	0.38%

Table 3 Analysis of common faults in ICP-OES detection

异常现象	异常原因	解决措施
检测信号强度过低	样品溶解不完全；雾化器效率降低；检测器老化；等离子体功率不足	优化样品溶解方法（如碱溶），确保样品完全溶解；检查并清洗或更换雾化器；考虑更换检测器；适当提高等离子体功率
检测信号强度过高	样品污染；标准溶液配制错误；检测器响应异常	排查样品污染来源并重新制备样品；重新配制标准溶液并校准；检查检测器，调整其工作参数或进行维修
波长不准确	光学系统元件故障或磨损；温度变化影响光栅性能	检查光学系统，维修或更换故障元件；控制仪器环境温度，确保温度稳定
背景信号过高	样品基体干扰严重；连续光谱干扰；散射光干扰	采用基体匹配法或内标法降低基体干扰；优化背景校正方法；减少散射光影响，如改善光路设计
重复性差	进样系统不稳定；等离子体参数波动；仪器未充分预热；雾化器残留杂质	检查进样系统，确保稳定进样；稳定等离子体参数，如气体流量、功率等；充分预热仪器后再进行测量；清洗或更换雾化器

Fig.5 Modified P-xy diagram of MoF6(1)-WF6 (2) system at 58.4, 72.9 and 87.1℃

Table 4 Binary interaction parameters of NRTL model

参数

数值

$a i j$

$a j i$

$b i j$

$b j i$

$c i j$

88.213

88.352

986.13

2200.2

0.5

Table 4 Binary interaction parameters of NRTL model

参数

数值

$a i j$

$a j i$

$b i j$

$b j i$

$c i j$

88.213

88.352

986.13

2200.2

0.5

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Error analysis and correction of vapor-liquid equilibrium of WF₆-MoF₆ systems by static method

静态法测定WF₆-MoF₆体系汽液相平衡数据的误差分析与修正

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