Determination of Tungsten, Molybdenum and 5 Associated Elements in Tungsten-Molybdenum Ore by Inductively Coupled Plasma-Optical Emission Spectrometry with Direct Sintering
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摘要:
钨钼矿石一般由多种矿物组成，组分较为复杂，不溶于盐酸、硝酸和王水，常采用碱熔和混合酸酸溶法进行样品消解。然而，碱熔法带来的基体效应严重影响仪器测试的准确性和检出限，而酸溶法对钨钼等难溶元素溶出效率较低，并且需要使用氢氟酸和王水等多种无机强酸进行长时间且操作过程复杂的前处理流程，同时还会造成分析测试仪器损害的问题。因此，开发一种操作简单且高效定量分析钨钼矿石中钨钼及其伴生元素的方法十分必要。本文在碱熔和酸溶的基础上，探索并建立了一种由直接烧结、盐酸-磷酸-柠檬酸络合提取与电感耦合等离子体发射光谱仪（ICP-OES）联用的方法，同时准确定量分析钨钼矿石中钨钼铜铅锌钙铁7种元素。与传统碱熔法相比，通过高温直接烧结让样品中含目标元素的矿物转化为酸可溶态，随后在盐酸-磷酸-柠檬酸混合酸体系的络合作用下，将目标元素转移至溶液中，从而实现快速准确定量测定。最佳实验条件为：600℃烧结1h、5mL磷酸-盐酸（体积比1∶20）提取、5mL 10g/L柠檬酸络合，过滤后上机测定。采用钨矿标准物质（GBW07240和GBW07241）和钼矿标准物质（GBW07238和GBW07239）以及两种实际钨钼矿石样品对本方法进行验证，结果表明7种目标元素测定含量均在标准值范围内，相对误差和相对标准偏差（RSD）均在10%以内。本研究发现，高温直接烧结与盐酸-磷酸-柠檬酸混合酸体系络合提取联用的样品前处理方法，可有效地避免传统碱熔和混合酸酸溶法的缺点，具有更为环保和低能耗的优点，同时可有效地降低化学分析实验室样品分析测试过程中酸气污染物的排放，可为战略性钨钼矿床资源开发和综合利用提供基础支撑。
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关键词:
- 直接烧结 /
- 电感耦合等离子体发射光谱法 /
- 钨钼矿石 /
- 钨 /
- 钼
Abstract:BACKGROUND Tungsten-molybdenum ore is generally composed of a variety of minerals with complex composition. It is insoluble in hydrochloric acid, nitric acid and aqua regia, and the alkali melting and mixed acid dissolution method was often selected for sample digestion. However, the matrix effect cause by the alkali melting method seriously affects the accuracy and detection limit of instrument testing; the acid dissolution method has low dissolution efficiency for tungsten, molybdenum and other insoluble elements, and requires a long time and a complex pretreatment process by using a variety of inorganic strong acids such as hydrofluoric acid and aqua regia, which can also cause damage to the analytical and testing instruments.
OBJECTIVES To develop a simple and efficient method for quantitative analysis of tungsten and molybdenum and its associated elements in tungsten-molybdenum ore.
METHODS Based on alkaline melting and acid dissolution, a method was established by inductively coupled plasma-optical emission spectrometry (ICP-OES) with direct sintering and complex extraction of hydrochloric acid-phosphoric acid-citric acid. Seven elements (tungsten, molybdenum, copper, lead, zinc, calcium, and iron) were analyzed in tungsten-molybdenum ore. The tungsten ore standard substances (GBW07240 and GBW07241), molybdenum ore standard substances (GBW07238 and GBW07239) and two actual tungsten-molybdenum ore samples were used to verify the method.
RESULTS Compared with the traditional alkali melting method, the minerals containing the target elements in the samples were converted to acid soluble state by direct high-temperature sintering, and the target elements were transferred to the solution under the complexation of the mixed acid system of hydrochloric acid, phosphoric acid and citric acid, so as to achieve rapid and accurate quantitative determination. The optimal experimental conditions were: sintering at 600°C for 1h, extraction with 5mL mixed acid composed of phosphoric acid and hydrochloric acid (V/V=1:20), complexation with 5mL of citric acid with a concentration of 10g/L, and determination after filtration. The results showed that the contents of the seven target elements were within the standard value range, and the relative error and relative standard deviation (RSD) were within 10%.
CONCLUSIONS The sample pretreatment method combined with direct high-temperature sintering and complex extraction of hydrochloric acid-phosphoric acid-citric acid can be used to effectively avoid the shortcomings of traditional alkali melting and mixed acid dissolution method, and has the advantages of environmental protection and low energy consumption. At the same time, it can effectively reduce the emission of acid gas pollutants in the sample analysis and testing process and has a good application prospect. The results provide basic support for the development and comprehensive utilization of strategic tungsten-molybdenum deposit resources.
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表 1 不同酸度对GBW07238钨钼测定结果的影响
Table 1. Effect of different acidity on the determination of tungsten and molybdenum in GBW07238.
待测元素 标准值
（%）盐酸不同用量下的测定值（%） 盐酸
2.5mL盐酸
5mL盐酸
12.5mL盐酸
25mLW 0.36±0.3 0.34 0.36 0.32 0.30 Mo 1.51±0.3 1.41 1.52 1.45 1.40 
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表 2 不同柠檬酸（10g/L）添加量对GBW07238钨钼测定结果的影响
Table 2. Effect of different addition amount of citric acid on the determination of W and Mo in GBW07238.
待测元素 标准值
（%）柠檬酸不同用量下的测定值（%） 柠檬酸
1mL柠檬酸
2mL柠檬酸
5mL柠檬酸
10mLW 0.36±0.3 0.30 0.33 0.37 0.42 Mo 1.51±0.3 1.49 1.50 1.51 1.47
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表 3 柠檬酸对GBW07238钨钼测量稳定性的影响
Table 3. Effect of citric acid on the measurement stability ofW and Mo in GBW07238.
放置天数
（d）不加柠檬酸 加5mL柠檬酸 W含量
测定值
（%）Mo含量
测定值
（%）W含量
测定值
（%）Mo含量
测定值
（%）0 0.29 1.47 0.37 1.52 1 0.27 1.45 0.36 1.51 2 0.25 1.43 0.37 1.50 4 0.24 1.40 0.36 1.49 7 0.22 1.38 0.37 1.49
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表 4 元素测量波长和方法检出限
Table 4. Measured wavelengths of elements and detection limits of the method.
元素 测量波长
（nm）方法检出限
（%）元素 测量波长
（nm）方法检出限
（%）W 224.876 0.0014 Zn 213.856 0.0023 Mo 202.030 0.0017 CaO 317.933 0.0045 Cu 324.754 0.0024 TFe2O3 259.900 0.0067 Pb 220.353 0.0027
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表 5 方法准确度和精密度（n=11）
Table 5. Accuracy and precision tests of the method （n=11）.
标准物质编号 参数 W Mo Cu Pb Zn CaO TFe2O3 GBW07238 标准值（%） 0.36* 1.51* 93.6 18.7 65.5 31.44* 21.34* 测定值（%）
RSD（%）0.35*
1.211.52*
0.7592.1
2.32/
/63.4
4.5331.02*
3.4420.15*
4.09相对误差（%） 2.78 0.66 1.60 / 3.21 1.34 5.58 GBW07239 标准值（%） 0.10* 0.11* 48.6 26.1 120 23.03* 14.66* 测定值（%） 0.10* 0.11* 52.5 / 125 21.56* 14.59* RSD（%） 1.47 0.82 3.78 / 1.16 3.88 4.67 相对误差（%） 0.00 0.00 7.43 / 4.17 6.38 0.48 GBW07240 标准值（%） 150 4.2 790 0.29* 0.26* 37.33* 7.79* 测定值（%） 161 / 805 0.28* 0.27* 37.56* 7.76* RSD（%） 7.62 / 0.91 0.56 0.48 0.98 1.17 相对误差（%） 7.33 / 1.90 3.45 3.85 0.62 0.39 GBW07241 标准值（%） 2200 980 960 81.2 103 4.17* 5.6* 测定值（%） 2109 966 972 82.5 99.9 4.03* 5.4* RSD（%） 1.23 0.65 1.45 2.67 1.95 2.14 3.55 相对误差（%） 4.14 1.43 1.25 1.60 3.01 3.36 3.57 注：带“*”的数据单位为%，其余数据单位均为μg/g。
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表 6 钨钼矿石中钨钼等元素三种测定方法综合对比
Table 6. Comprehensive comparison of the three methods for determination of W and Mo in tungsten-molybdenum ore.
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表 7 实际样品不同方法分析结果对比
Table 7. Comparison of analytical results determined by different methods for actual samples.
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