Determination of Rhenium in Tungsten and Molybdenum Ore by ICP-MS with Lefort Aqua Regia Microwave Digestion and 8-hydroxyquinoline Precipitation
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摘要:
铼在地壳中的丰度低且分散，多伴生于钨钼矿中，现有方法常采用碱熔富集，流程长且繁琐，亟需开发一种简便快捷的检测方法。本文建立了逆王水微波消解钨钼矿石样品，8-羟基喹啉沉淀分离钨钼元素，与电感耦合等离子体质谱联用的检测方法。结果表明：0.0500g样品，2.80mL逆王水即可实现铼元素的全部溶出，0.20mL有机沉淀剂8-羟基喹啉（3%）在乙酸-乙酸铵缓冲体系（pH 4.5）中可选择性沉淀钼、钨元素，有效消除基体元素钼、钨（沉淀率>95%）对Re定量干扰，同时不引入新干扰元素。相比现有分离富集前处理流程更加简便快捷，前处理时间缩短为现有方法的1/4；该方法对Re的检出限为6.9ng/g，采用国家一级标准物质钼矿石（GBW07238）、钼矿石（GBW07285）、铼钼矿石（GBW07373）和钨锡铋矿石（GBW07369）对方法的准确度进行了验证，测定值与推荐值吻合，相对误差为0.71%～6.07%，RSD＜5%。本方法建立的“消解-分离富集”处理流程所需时间从常规的8～12h缩短至2h左右，在准确定量矿石样品中Re的同时简化了样品前处理流程，快速的样品处理及低廉的测试成本有助于关键稀有金属矿产的开发利用。
Abstract:BACKGROUND Rhenium (Re) is a key mineral resource widely used in the aerospace field. As one of the rarest elements in the earth, Re rarely exists as an independent mineral but is dispersed in various sulfide ores. Due to its low content and dispersed distribution, the highly sensitive and accurate quantification of Re (ng/g) in complex ore is one of the challenges of modern geological analysis. In order to solve the problem of incomplete decomposition and the great interference caused by co-dissolution of high abundance matrix elements, the existing “digestion-separation” method using 8-12h for one sample is complicated, time-consuming and labor-intensive. Therefore, the development of a simple, fast and low-cost method is urgently required.
OBJECTIVES To establish an analytical method based on Lefort aqua regia microwave digestion, molybdenum and tungsten precipitation, ICP-mass spectrometry for the determination of rhenium in ore.
METHODS Lefort aqua regia microwave digestion was used to fully decompose ore, and then the organic precipitator 8-hydroxyquinoline (8-HQ) was used to selectively precipitate high-abundance matrix interference elements molybdenum (Mo) and tungsten (W) in the acid-ammonium acetate buffer system (pH 4.5). The organic precipitator 8-HQ was used to precipitate Mo and W to produce stable hydroxyquinoline molybdenum [MoO2(C9H6ON)2] and tungsten [WO2(C9H6ON)2], thereby removing the high-abundance Mo and W in the digestion solution and reducing the interference of matrix on the quantitative analysis of Re. The relevant parameters of Lefort aqua regia microwave digestion and 8-HQ precipitation were systematically studied, and the digestion and precipitation properties were deeply studied by using national certified reference materials.
RESULTS The key parameters that influence ore digestion including volume of Lefort aqua regia and temperature of microwave digestion, were determined as 2.8mL and 130℃ for step 1 and 150℃ for step 2 separately. The addition amount of 8-HQ was also determined as 0.2mL (3%, w%) by comparing precipitation rates of W, Mo and W-Mo solution (25g/mL) under different amounts, and results showed that the precipitation rate was greater than 95% in different ore digestion solutions. In the established method, the detection limit of Re was 6.9ng/g, the relative error was 0.71%-6.07%, and the RSD was less than 5%.
CONCLUTIONS The method established in this study can effectively eliminate the interference of matrix elements molybdenum and tungsten on Re quantification without introducing new interference elements. Compared with the existing “digestion-separation” process, the method is simpler and faster (shortened from 8-12h for one sample to approximately 1h) and the method has been successfully applied in molybdenum ore, rhenium molybdenum ore and tungsten-tin bismuth ore. This study proves that interfering instead of target element precipitation is feasible and provides a simple, fast and low-cost method for accurate quantification of Re in complex ore.
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表 1 微波消解两段式程序升温中温度的优化
Table 1. Optimization of temperature in two-step microwave digestion program (50mg sample in 1000W microwave).
第一段温度
（℃）铼测定值
（µg/g）第二段温度
（℃）铼测定值
（µg/g）铼推荐值
（µg/g）110 10.5 140 10.5 10.9±0.7
10.9±0.7
10.9±0.7120 10.4 150 10.8 130 10.8 160 10.6 
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表 2 逆王水微波消解过程中W、Mo的溶出
Table 2. Dissolution of W and Mo in Lefort aqua regia microwave digestion (130℃ for 8min and 150℃ for 38 min in 1000W microwave).
标准样品编号 钨标准值
（µg/g）钨测定值
（µg/g）钨溶出率
（%）钼标准值
（%）钼测定值
（%）钼溶出率
（%）GBW07285 54.7 52.0 95.1 5.17 5.27 102.0 GBW07373 370 344 93.0 9.09 8.99 98.9 GBW07238 3600 1312 25.0 1.51 1.50 99.3 GBW07369 79600 1652 0.8 0.361 0.360 99.7
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表 3 W、Mo单元素及双元素溶液在不同8-HQ添加量下的沉淀率
Table 3. Precipitation rate of W, Mo and W-Mo solution (25µg/mL) under different 8-HQ addition amount.
沉淀剂及
相应浓度沉淀剂用量
（mL）单元素沉淀率
（%）双元素沉淀率
（%）Mo W Mo W 8-HQ
（0.3%，w%）0.20 99.21 28.72 53.19 22.41 0.50 99.66 31.36 99.77 70.72 0.75 99.81 53.37 99.86 90.95 1.00 99.94 79.32 99.86 97.27 1.50 99.96 92.73 99.84 99.16 2.00 99.97 93.08 99.81 99.39 8-HQ
（3%，w%）0.20 99.99 99.54 99.83 99.32 0.50 99.97 99.80 99.85 99.56 0.75 99.99 99.96 99.85 99.57 1.00 99.96 99.96 99.86 99.76 1.50 99.97 99.97 99.77 99.73 2.00 99.99 99.97 99.81 99.79
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表 4 8-HQ对实际样品中W、Mo元素的沉淀率
Table 4. Precipitation rate of W, Mo elements in real samples under 8-HQ.
标准物质
编号待测
元素沉淀前元素含量
（µg/mL）沉淀后元素含量
（µg/mL）沉淀率
（%）GBW07238 Mo 3.020 0.0224 99.26 W 0.2625 0.0035 98.67 GBW07373 Mo 18.20 0.0511 99.72 W 0.6880 0.0013 99.81 GBW07369 Mo 0.7251 0.0326 95.50 W 0.3304 0.0054 98.37
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表 5 方法的精密度和准确度
Table 5. Accuracy and precision tests of the method.
标准物质
编号铼含量测定值
（μg/g）铼含量标准值
（μg/g）相对误差
（%）RSD
（%）GBW07238 0.37±0.01 （0.35） 6.07 2.6 GBW07285 32.50±0.49 31.20±3.70 4.09 1.5 GBW07373 10.80±0.20 10.90±0.70 0.85 2.0 GBW07369 0.35±0.01 0.35±0.03 0.71 4.6 注：测定值以“平均值±标准偏差”的形式表示（平行实验次数n=8）。
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