Determination of 9 Major and Minor Elements in Beryllium Ore by ICP-OES with Acid Dissolution
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摘要:
铍矿石是中国的紧缺金属矿产之一，已在多领域有广泛应用，但其组分复杂，铍含量差别较大，且常与其他金属矿物伴生，给分析测试带来诸多挑战，制约了铍矿产的勘查开发。电感耦合等离子体发射光谱法（ICP-OES）目前用于分析铍矿石仅针对单一类型样品，且存在基体干扰、分解不完全等不足，需建立适用于多种类型的铍矿石样品、仪器分析溶液基体干扰小的多元素同时测定方法。本文选用绿柱石、香花石、日光榴石样品，比较了电热板、高压密闭、微波消解、不同种类消解酸和提取酸等8种酸消解条件对铍矿石的分解效果，优化了称样量、加酸量、消解时间和仪器测定参数，建立了ICP-OES测定铍矿石中铝铍钙铁钾钠镁锂锰9种主次量元素的分析方法。结果表明，电热板消解的混合酸为硝酸-盐酸-氢氟酸-高氯酸最佳，提取酸为盐酸优于硝酸或王水，高压密闭法不能完全消解绿柱石Al、Ca、Mg元素，微波法对绿柱石Mg元素消解效果较差。通过优化现有方法的混合酸消解条件和仪器测定条件，建立的方法对精矿样品也能准确测定，仪器测定溶液的基体简单。本方法Be元素检出限0.0001%，低于铍矿石边界品位，其他元素检出限均优于现有的标准方法，主量元素精密度（RSD）均＜5%，经标准物质验证，准确度满足铍矿石测定需要。该方法适用于不同类型和不同含量铍矿石样品的多元素同时分析。
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关键词:
- 铍矿石 /
- 电感耦合等离子体发射光谱法 /
- 酸消解 /
- 仪器测定参数 /
- 多元素同时分析
Abstract:BACKGROUND Beryllium ore is one of the scarce metal minerals in China. Beryllium ore is widely used mineral resources, but it has complex components, and is always concomitant with other metallic minerals. Accurate determination of primary and secondary elements in beryllium ore is significant for its comprehensive utilization. Inductively coupled plasma-optical emission spectrometry (ICP-OES) has been used in elemental analysis of beryllium ore. However, there are some disadvantages: It is considered that beryllium concentrate is difficult to completely decompose by acid dissolution; determination of beryllium concentrate by alkali fusion has serious matrix interference; the existing research focuses on analysis of a single type of beryllium ore.
OBJECTIVES To establish a multi-element simultaneous determination method, which is suitable for various types of beryllium ore samples and has little interference with the matrix of instrumental analysis solution.
METHODS Beryl, hsianghualite and helvite samples were selected in the experiment. Digestion effect on beryllium ore under eight different acid digestion conditions were compared, such as digestion on electric heating board, high pressure sealing, microwave digestion, different kinds of acid digestion and extraction acid. The weight of the sample, the volume of the acid, the digestion time and instrument measurement were optimized. At the same time, according to beryllium ore’s mode of occurrence of elements, the best spectrum lines of each element were determined.
RESULTS (1) The results show that the best mixed digested acid on electric heating board is nitric acid-hydrochloric acid-hydrofluoric acid-perchloric acid. The best extracted acid is hydrochloric acid, which is better than nitric acid or aqua regia. The high-pressure sealing method cannot completely dissolve Al, Ca and Mg elements of beryl, and the microwave method has poor effect on the digestion of Mg elements of beryl. (2) The digestion conditions are determined. Weigh the sample of 0.1000g into polytetrafluoroethylene crucible, moisten the sample with a small amount of deionized water, and add 2mL nitric acid-3mL hydrochloric acid-5mL hydrofluoric acid-1mL perchloric acid; cover and place the crucible on electric heating plate; decomposing at 120℃ for 2h, then 150℃ for a further 2h; remove the lid and boil away perchloric acid at 190℃; extract with 4mL 50% hydrochloric acid and add deionized water to 25mL. The solution is determined by ICP-OES. The detection limit of Be is 0.0001%, which is lower than the boundary grade of beryllium ore. The detection limit of other elements is better than the existing standard method, and the precision RSD of each major element is <5%. By verification of standard materials, the accuracy of the method meets the needs of beryllium ore determination. The analysis accuracy and precision of three real beryllium ore samples from fields is satisfying. (3) By optimizing the conditions of mixed acid digestion and instrument determination of the existing method, the established method can also accurately determine concentrate sample, and the matrix of the solution is simple to be determined by the instrument.
CONCLUSIONS In this study, a mixed acid decomposition ICP-OES method for simultaneous determination of 9elements including Al, Be, Ca, Fe, K, Na, Mg, Li and Mn in beryllium ore has been established, which can be applied to different types and contents of beryllium ore. The established method provides necessary technical support for the research and exploration of beryllium ore.
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表 1 不同酸消解方式、混合酸类型、提取酸类型的条件优化
Table 1. Condition optimization of different acid digestion modes, mixed acid types and extracting acid types.
消解方式 混合酸类型 提取酸类型 电热板消解 硝酸-盐酸-氢氟酸-高氯酸 50%盐酸 50%硝酸 50%王水 硝酸-盐酸-氢氟酸-硫酸 50%盐酸 氢氟酸-高氯酸 50%盐酸 氢氟酸-硫酸 50%盐酸 高压密闭消解 硝酸-氢氟酸 50%盐酸 微波消解 硝酸-氢氟酸 50%盐酸 
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表 2 ICP-OES测定元素选择的谱线
Table 2. Spectral lines selected for elements measured by ICP-OES.
待测元素 分析谱线
（nm）曲线最高点
（mg/L）标准曲线计算公式 线性相关系数
R2Al 308.215 300 y=1206x+2272 0.9996 Be 234.861 200 y=60577x+73675 0.9994 Ca 317.933 300 y=12505x+20413 0.9996 Fe 259.939 400 y=10389x+18792 0.9999 K 766.490 200 y=2466x+1564 0.9998 Na 589.592 200 y=9528x+18859 0.9990 Mg 285.213 30.0 y=17119x+2840 0.9999 Li 670.784 100 y=63464x+124949 0.9990 Mn 257.610 300 y=44063x+116324 0.9994
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表 3 方法检出限、定量限和精密度
Table 3. Detection limit, quantitative limit and precision of the method.
待测元素 方法检出限
（%）定量限
（%）RSD
（%）YC
（%）Al 0.002 0.007 2.37 3.35 Be 0.0001 0.0004 3.87 6.57 Ca 0.003 0.01 3.36 8.56 Fe 0.001 0.003 4.70 8.94 K 0.001 0.003 3.46 4.98 Na 0.003 0.01 2.73 5.00 Mg 0.001 0.003 4.68 13.22 Li 0.0001 0.0003 4.09 17.74 Mn 0.006 0.02 6.48 16.57
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表 4 国家一级标准物质GBW07183和GBW07150测定方法准确度结果
Table 4. Accuracy of the method by determining the first class standard materials GBW07183 and GBW07150.
待测元素 GBW07183 GBW07150 标准值
（%）测定值
（%）相对误差
（%）YB
（%）标准值
（%）测定值
（%）相对误差
（%）YB
（%）Al 8.230 8.251 0.25 2.37 7.865 7.716 −1.89 2.42 Be 1.088 1.082 −0.55 4.64 0.022 0.021 −4.55 11.04 Ca 0.372 0.383 3.13 6.10 0.416 0.428 3.00 5.94 Fe 0.329 0.320 −2.75 6.28 0.359 0.355 −0.93 6.15 K 2.723 2.756 1.20 3.54 3.404 3.406 0.07 3.29 Na 2.723 2.728 0.22 3.54 3.553 3.561 0.20 3.24 Mg 0.050 0.052 3.74 9.42 0.043 0.041 −4.98 9.70 Li / 0.011 / / / 0.0006 / / Mn 0.015 0.016 6.46 11.85 0.023 0.021 −8.13 10.95 注：“/”表示没有提供标准值。
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表 5 建立的酸溶方法与碱熔结果对比
Table 5. Comparison of analytical results by acid digestion and alkali fusion.
待测元素 碱熔法测定值
（%）酸溶法测定值
（%）相对偏差
（%）YB
（%）Al 9.359 9.149 −2.24 3.18 Be 4.480 4.525 1.00 4.23 Fe 0.374 0.389 4.01 8.61 Na 0.361 0.390 8.03 8.68
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表 6 绿柱石、香花石、日光榴石实际样品测定结果
Table 6. Analytical results of beryl, balsamite and heliogarnet actual samples.
待测
元素样品BeC 样品XHS 样品RGL 测定平均值
（%）RSD
（%）YC
（%）测定平均值
（%）RSD
（%）YC
（%）测定平均值
（%）RSD
（%）YC
（%）Al 8.314 2.81 3.34 9.176 0.81 3.20 0.348 0.63 8.76 Be 0.033 2.47 14.45 0.014 2.74 16.98 4.702 2.56 4.16 Ca 0.314 2.38 8.97 15.129 1.44 2.54 1.360 0.92 6.16 Fe 0.305 3.59 9.04 7.933 2.09 3.40 18.503 1.63 2.28 K 1.711 2.11 5.77 1.076 1.12 6.58 0.069 5.06 12.48 Na 2.236 1.97 5.32 0.948 0.81 6.81 0.040 0.54 13.92 Mg 0.018 0.74 16.21 0.734 1.60 7.28 0.187 2.55 10.10 Li 0.863 2.75 6.98 1.942 1.57 5.56 0.011 9.08 17.74 Mn 0.043 11.61 13.72 1.324 4.84 6.21 12.954 1.51 2.74
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