Industrial On-line ICP-OES Analysis of Copper, Cadmium, Cobalt and Iron in Hydrometallurgical Zinc Sulfate Solution
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摘要:
测定湿法冶炼硫酸锌溶液中的杂质元素，有助于优化电解液组成、减少能耗，精准投料，提高冶炼金属的纯度。对于杂质元素的测定，通常采用人工取样分析的方法，因杂质元素的含量较低，主元素锌和硫酸的含量较高，需要对样品进行稀释才能上机分析，难以实现自动化。为满足目前湿法冶炼的产业需求，本文建立了一种自动化工业在线过滤/稀释-电感耦合等离子体发射光谱法（ICP-OES）测定锌冶炼溶液中杂质元素铜镉钴铁的分析方法。结果表明：各元素的线性关系良好，相关系数均大于0.9998，相对标准偏差为0.72%~1.39%（n=6），加标回收率为95%~110%。该工业在线自动化分析系统可以代替传统人工取样分析的过程，在线分析结果与人工取样分析结果具有良好的一致性，实现了自动化分析，操作简单，结果准确可靠。
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关键词:
- 工业在线自动化分析系统 /
- 电感耦合等离子体发射光谱法 /
- 锌冶炼 /
- 远程传输
Abstract:BACKGROUND The determination of impurity elements in hydrometallurgical zinc sulfate solution is helpful to optimize the composition of electrolytes, reduce energy consumption, and accurately feed and improve the purity of smelting metal. Impurity elements in the wet zinc smelting process are usually determined by manual sampling. The sample needs to be diluted before the equipment analysis is performed due to high content of zinc and sulfuric acid, which is difficult to achieve automatic analysis.
OBJECTIVES In order to determine the online analysis of impurity elements in the solution of zinc smelting process and meet the current requirements of the hydrometallurgical industry.
METHODS An automatic industrial on-line filtration/dilution combined with inductively coupled plasma-optical emission spectrometry (ICP-OES) was used. By optimizing key parameters and selecting appropriate analysis lines, a method for the rapid determination of copper, cadmium, cobalt and iron in zinc smelting solution was developed.
RESULTS The experimental results showed that the linear relationship of each element was good, the correlation coefficient was greater than 0.9998, the relative standard deviation was 0.72%-1.39% (n=6), and the spiked recovery was 95%-110%.
CONCLUSIONS The factory on-line automatic analysis system can replace traditional manual sampling to achieve automatic analysis. The results of on-line analysis are compared with those of manual sampling in actual production, showing good consistency. This method can be used to fully achieve automatic analysis, simple operation, accurate and reliable results, and is suitable for the analysis of impurity elements in zinc smelting.
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表 1 方法线性范围、相关系数与检出限
Table 1. Linear range, correlation coefficient and detection limit of the method
元素 线性范围(mg/L) 相关系数r2 检出限(mg/L) Cu 0~10 0.9999 0.0132 Cd 0~10 0.9999 0.0097 Co 0~2 0.9999 0.0056 Fe 0~2 0.9998 0.0168 
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表 2 样品测定对比结果
Table 2. Comparison of results of sample determination
样品编号 元素 工业在线自动化分析系统测定值(mg/L) ICP-OES人工测定值(mg/L) 稀释倍数 一段净化前液 Cu 535.1 537.8 100 Cd 629.5 625.6 100 Co 11.5 10.9 100 Fe 8.9 8.8 100 二段净化前液 Cd 59.8 60.6 100 Co 8.6 8.5 100 Fe 8.8 8.4 100
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表 3 样品加标回收率
Table 3. Spiked recovery tests of the method
样品编号 元素 本底值(mg/L) 加入量(mg/L) 测定值(mg/L) 回收率(%) 一段净化前液 Cu 535.1 50 582.9 95.6 Cd 629.5 50 678.6 98.2 Co 11.5 10 22.1 106.0 Fe 8.9 10 18.8 99.0 二段净化前液 Cd 59.8 20 79.5 98.5 Co 8.6 10 18.7 101.0 Fe 8.8 10 19.7 109.0
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表 4 方法精密度
Table 4. Precision tests of the method
样品编号 元素 6次测定值(mg/L) RSD (%) 一段净化前液 Cu 529.6 538.2 525.7 546.4 536.3 531.5 1.37 Cd 631.3 634.6 627.8 619.3 632.1 627.4 0.85 Co 11.7 11.6 11.7 11.6 11.5 11.3 1.30 Fe 8.9 8.8 8.7 8.8 8.7 8.6 1.20 二段净化前液 Cd 58.9 59.5 59.3 59.9 60.1 59.5 0.72 Co 8.8 8.6 8.7 8.7 8.6 8.8 1.03 Fe 8.6 8.8 8.7 8.6 8.9 8.8 1.39
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