Determination of Iridium and Rhodium in Copper Anode Slime by Inductively Coupled Plasma-Mass Spectrometry with Nickel Sulphide Fire Assay
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摘要:
铜阳极泥富集了矿石、精矿或熔剂中绝大部分贵金属(如铱和铑)，具有很高的综合回收价值。目前尚无铜阳极泥中铱和铑检测标准，而对其中铱和铑检测方法的开发是铱铑回收提取工作的重要前提。本文建立了锍镍试金富集结合电感耦合等离子体质谱法(ICP-MS)测定铜阳极泥中铱铑的检测技术。实验中通过锍镍试金捕集试样中的贵金属铱和铑，用50%盐酸溶解锍镍扣，使得含铱和铑的沉淀物与银及其他杂质元素有效分离，趁热过滤，铱铑沉淀物和滤膜转入封闭消解罐中以50%王水为介质溶解。试液采用ICP-MS直接测定铱和铑含量。实验优化了样品预处理条件，镍硫比为4∶1，时，熔渣为酸性，熔渣流动性和渣扣分离效果好且能有效捕集试样中铱和铑；锍镍扣溶解酸度为50%盐酸时，锍镍扣溶解反应合适且溶解完全，趁热过滤，其中银、镍、铜等杂质元素大部分被盐酸除去，达到了分离含铱和铑沉淀物与银及其他杂质元素的效果; 密封消解温度和时间分别为160℃、2~3h时，铱和铑消解完全；选择合适的测定同位素可以消除可能存在的质谱干扰，以193Ir和103Rh为测定同位素、203Tl和185Re分别为铱和铑的内标时消除了信号漂移基体效应的影响。在优化的实验条件下测定铑和铱混合标准溶液系列，结果表明，铑和铱在10~100μg/L质量浓度范围内和铑及铱质谱强度与内标质谱强度之比呈线性关系，铱和铑的线性回归方程分别为y=36674.6x+8264.7和y=45686.7x+288.6，线性相关系数均大于0.999，方法检出限分别为0.007μg/L和0.011μg/L，定量下限分别为0.024μg/L和0.038μg/L。按照实验方法测定8个实际铜阳极泥试样中铱和铑，测定结果的相对标准偏差(RSD，n=7)为1.40%~4.57%，加标回收率为95.00%~103.65%。该方法能够满足铜阳极泥样品的检测要求。
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关键词:
- 铱 /
- 铑 /
- 铜阳极泥 /
- 锍镍试金 /
- 电感耦合等离子体质谱法
Abstract:BACKGROUND With the wide application of iridium and rhodium in aerospace, electronics, energy and other fields, it has become a very attractive metal in the world. In China, iridium and rhodium ore resources are relatively scarce with low grade, so it is essential to recover iridium and rhodium from secondary mineral resources. Copper anode slime enriches most of the precious metals such as iridium and rhodium in ores, which has high comprehensive recovery value. At present, there is no detection standard for iridium and rhodium in copper anode slime. The migration behavior of iridium and rhodium was not clear, so it was difficult to achieve directional enrichment and efficient extraction of iridium and rhodium metals. Therefore, the development of detection methods for iridium and rhodium in copper anode slime is an important prerequisite for the recovery and extraction of iridium and rhodium.
OBJECTIVES An analytical method for accurate determination of iridium and rhodium in copper anode slime was established to maximize the utilization of mineral resources and the recycling rate of iridium, rhodium and other precious metals. At the same time, it could provide data support for the purification of iridium and rhodium in copper anode slime.
METHODS In this paper, a method for determination of iridium and rhodium in copper anode slime by inductively coupled plasma-mass spectrometry (ICP-MS) with nickel sulphide fire assay was established. In the experiment, the precious metals iridium and rhodium in the sample were captured by nickel sulphide fire assay. The NiS beads were dissolved with 50% hydrochloric acid so that the precipitation of rhodium and iridium was separated from silver and other impurity elements through filtration when it was hot. The precipitates containing iridium and rhodium were effectively separated from silver and other impurity elements. The precipitate of iridium and rhodium with filter film were transferred into a closed digestion tank and dissolved in 50% aqua regia. The contents of iridium and rhodium in the solution were directly determined by ICP-MS.
RESULTS The conditions such as the ingredient of nickel sulphide fire assay, the concentration of hydrochloric acid, tellurium coprecipitation, the sealing digestion time and temperature were studied. The experimental results showed that the molten slag was acidic when the ratio of nickel to sulfur was 4∶1, and it could effectively capture the iridium and rhodium in the sample with good fluidity of molten slag and the separation effect of slag buckle. When the NiS beads were dissolved by 50% hydrochloric acid, the dissolution reaction of NiS beads was suitable and complete. The precipitation containing rhodium and iridium was separated from impurity elements and filtered when hot. The precipitation was sealed and digested by dilute aqua regia (1∶1) at 160℃ for 2-3h. The possible MS interference was eliminated by selecting a suitable determination isotope. The 185Re was selected as the internal standard of 103Rh and 203Tl as the internal standard of 193Ir to eliminate the effect of signal drift, the results of iridium and rhodium had high precision and accuracy. The standard solution series of iridium and rhodium were determined under the optimized experimental conditions. The results indicated that the mass concentration of iridium and rhodium in the range of 10-100μg/L were linear to the ratio of the intensity of iridium and rhodium to the internal standard mass spectrometry. The calibration curves of iridium and rhodium were y=36674.6x+8264.7 and y=45686.7x+288.6, respectively, and the linear correlation coefficient (r) of calibration curves of iridium and rhodium were more than 0.999. The detection limits for iridium and rhodium were 0.007μg/L and 0.011μg/L, respectively, and the lower limits of detection were 0.024μg/L and 0.038μg/L, respectively. The content results of rhodium and iridium in 8 actual samples with the method showed that, the relative standard deviation (RSD, n=7) was between 1.40% and 4.57%, and the recovery was in the range of 95.00% to 103.65%.
CONCLUSIONS The method has high efficiency and accuracy and can meet the detection requirements of copper anode slime samples.
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表 1 3#试样采用不同锍镍试金配方(即不同镍硫比)的实验现象并于镍：硫为4∶1时获得良好锍镍扣
Table 1. Experimental phenomena in 3# sample with different ratios of nickel to sulfur. The ratio of nickel to sulfur was 4∶1, it could effectively capture the iridium and rhodium in the sample to obtain good NiS beads with good fluidity of molten slag and the separation effect of slag buckle
方案编号 配料各成分的质量(g) 实验现象 锍镍扣质量(g) 碳酸钠 碱式碳酸镍 二氧化硅 硼砂 淀粉 硫 方案1 20 1 8 10 1 1 扣偏小, 渣与扣未完全分离 0.72 方案2 20 2 8 10 1 1 扣溶解时存在大量硫漂浮物 1.42 方案3 20 2 8 10 1 0.5 流动性好，与扣易分离 1.37 方案4 10 2 3 20 0 0.5 粘渣，扣不光滑 0.48 
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表 2 样品3#采用不同温度不同时间消解的实验现象并于密封消解温度和时间分别为160℃和2~3h时消解完全
Table 2. Experimental phenomena in 3# sample with different temperatures and digestion time. The precipitation containing rhodium and iridium could completely digestion at 160℃ for 2-3h
消解温度(℃) 不同消解时间下实验现象 1h 2h 3h 4h 5h 120 有不溶物 有不溶物 有不溶物 有不溶物 有不溶物 140 有不溶物 有不溶物 有不溶物 溶液澄清，消解完全 溶液澄清，消解完全 160 有不溶物 溶液澄清，消解完全 溶液澄清，消解完全 溶液澄清，消解完全 溶液澄清，消解完全 180 有不溶物 溶液澄清，消解完全 溶液澄清，消解完全 溶液澄清，消解完全 溶液澄清，消解完全
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表 3 方法准确度和精密度能满足铜阳极泥中铱、铑元素的分析要求
Table 3. Accuracy and precision tests of the method. The proposed method could satisfy the detection requirements of copper anode slime samples with high efficiency and accuracy
样品编号 元素 测定值(μg/g) RSD(%) 实验1 实验2 加标量(μg/g) 测得总量(μg/g) 回收率(%) 加标量(μg/g) 测得总量(μg/g) 回收率(%) 1# Ir 10.16 3.83 10.00 19.66 95.00 20.00 29.51 96.75 Rh 84.24 3.22 80.00 161.42 96.48 160.00 241.24 98.12 2# Ir 50.35 3.91 50.00 100.89 101.08 100.00 149.77 99.42 Rh 128.71 4.50 100.00 227.35 98.64 200.00 330.11 100.70 3# Ir 86.80 1.40 80.00 163.69 96.11 160.00 247.00 100.12 Rh 192.81 1.99 100.00 293.84 101.03 200.00 397.15 102.17 4# Ir 136.32 2.45 100.00 233.57 97.25 200.00 335.86 99.77 Rh 214.14 3.06 100.00 310.64 96.50 200.00 416.82 101.34 5# Ir 192.64 2.97 100.00 293.00 100.36 200.00 395.17 101.26 Rh 285.81 3.12 150.00 433.94 98.75 300.00 583.88 99.36 6# Ir 253.78 4.29 100.00 355.48 101.70 200.00 451, 73 98.98 Rh 423.67 3.10 100.00 520.19 96.52 200.00 619.83 98.08 7# Ir 281.99 2.02 100.00 383.41 101.42 200.00 479.52 98.76 Rh 501.01 2.32 100.00 600.00 98.99 200.00 708.31 103.65 8# Rh 21.41 4.57 20.00 41.04 98.15 40.00 60.07 96.65
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