Determination of Vanadium, Iron, Aluminum and Phosphorus in Stone Coal Vanadium Ore by ICP-OES with Open Acid Dissolution
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摘要:
石煤钒矿资源的勘探、研究和利用均需对其成分进行准确的分析测试，其中钒、铁、铝、磷等主要成分的测定尚未建立标准方法，当前所用的分析测试方法各有不足。采用碱熔电感耦合等离子体发射光谱法(ICP-OES)测定石煤钒矿样品时，高浓度的可溶性盐会导致高背景，干扰测定。酸溶法可避免上述问题，但由于常规的氢氟酸-盐酸-硝酸-高氯酸四酸体系不能消除碳和有机质对样品的吸附和包裹，待测成分无法完全释放，需先将样品高温灼烧除碳，过程繁琐。本文采用少量硫酸加四酸的五酸体系处理样品，电热板加热，盐酸浸提，利用硫酸的强氧化性将样品中大量的碳氧化成二氧化碳，免却了灼烧除碳流程，消除了含碳物质对样品的吸附和包裹，显著增强了消解效果。由此建立了ICP-OES测定石煤钒中钒、铁、铝、磷的分析方法，在称样量为0.1g、浓硫酸加入量为0.30mL时，样品消解率达到99%以上。方法检出限为17~51mg/kg，相对标准偏差(RSD, n=11)在1.7%~5.1%之间；相对误差为-4.6%~2.7%。该方法背景低、测定结果准确，可满足石煤钒矿石样品的检测要求。
Abstract:BACKGROUND The exploration, research and utilization of stone coal vanadium ore resources need accurate composition determination, while there is no standard method for the determination of its main components such as vanadium, iron, aluminum and phosphorus. At the same time, every analysis method currently used has its own shortcomings. When the sample of stone coal vanadium ore is treated by alkali fusion and determined by ICP-OES, the high concentration of soluble salt will lead to high background and interference with the determination. The acid dissolution method can avoid the above problems, but when the conventional four acid system composed of HF+HCl+HNO3+HClO4 is used to digest the sample, the components to be tested in the sample cannot be completely released, so the sample needs to be burned at high temperature to remove carbon, making the process is cumbersome.
OBJECTIVES In order to establish a method for the determination of the main components in stone coal vanadium ore samples by ICP-OES using five acid systems to digest samples.
METHODS A mixed acid system of H2SO4+HF+HCl+HNO3+HClO4 with electric hot plate heating and hydrochloric acid extraction were used to digest the samples. The contents of vanadium, iron, aluminum and phosphorus in stone coal vanadium were determined by ICP-OES.
RESULTS Using the strong oxidizing property of sulfuric acid to oxidize a large amount of carbon in the sample into carbon dioxide, eliminated the process of burning carbon removal, eliminated the adsorption and wrapping of carbon-containing substances on the sample, and significantly enhanced the digestion effect. When the sample weight was 0.1g and the concentration of sulfuric acid was 0.30mL, the digestion rate of the sample reached more than 99%. The detection limit was 17-51mg/kg, relative standard deviation (n=11) was between 1.7%-5.1%, and relative error was -4.6%-2.7%.
CONCLUSIONS The method has the advantages of low background, high efficiency and accuracy, and can meet the detection requirements of stone coal and vanadium ore samples.
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表 1 标准溶液系列中钒、铁、铝、磷的质量浓度
Table 1. Mass concentrations of vanadium, iron, aluminum and phosphorus for standard solution series
分析元素 空白(μg/mL) 标准1 (μg/mL) 标准2 (μg/mL) 标准3 (μg/mL) 标准4 (μg/mL) 标准5 (μg/mL) V 0 0.50 1.00 2.00 5.00 10.00 Fe 0 2.50 5.00 10.00 25.00 50.00 Al 0 2.50 5.00 10.00 25.00 50.00 P 0 0.50 1.00 2.00 5.00 10.00 
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表 2 硫酸加入量对测定结果的影响
Table 2. Effect of sulfuric acid addition on measurement results
硫酸加入量(mL) 分析项目测定值(%) V2O5 (标准值0.62%) Fe2O3 (标准值1.31%) Al2O3 (标准值7.00%) P2O5 (标准值0.153%) 0 0.25 0.97 5.01 0.096 0.10 0.46 1.18 6.19 0.135 0.20 0.55 1.25 6.74 0.139 0.30 0.62 1.32 6.96 0.155 0.40 0.61 1.31 6.94 0.152 0.50 0.62 1.30 7.06 0.151
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表 3 工作曲线及方法检出限
Table 3. Working curves and detection limits of the method
分析元素 线性范围(μg/mL) 线性方程 相关系数 方法检出限(mg/kg) V 0.5~10 y=5109.178x-0.879 0.9999 17 Fe 2.5~50 y=875.967x+50.641 0.9999 35 Al 2.5~50 y=136.287x+2.706 0.9999 51 P 0.5~10 y=143.706x+0.978 0.9999 44
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表 4 方法准确度和精密度
Table 4. Accuracy and precision tests of the method
GBW07875分析项目 标准值(%) 测定平均值(%) 相对偏差(%) RSD (%) V2O5 0.62±0.03 0.60 -3.2 2.0 Fe2O3 1.31±0.07 1.30 -0.8 1.9 Al2O3 7.00±0.16 7.19 2.7 5.1 P2O5 0.153±0.005 0.146 -4.6 1.7
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表 5 分析方法对比
Table 5. Comparison of analytical methods
样品编号 V2O5测定值(%) Fe2O3测定值(%) Al2O3测定值(%) P2O5测定值(%) 本文方法 磷钨钒酸光度法 本文方法 重铬酸钾滴定法 本文方法 铬天青S光度法 本文方法 磷钼蓝光度法 1 0.332 0.327 7.12 7.17 8.57 8.72 1.39 1.43 2 0.686 0.689 13.2 13.1 3.51 3.39 0.606 0.604 3 0.274 0.279 8.73 8.84 13.0 12.8 1.51 1.46 4 1.36 1.35 6.49 6.40 6.31 6.34 0.763 0.767 5 1.59 1.60 7.19 7.28 5.46 5.60 0.782 0.782 6 0.623 0.628 5.45 5.54 9.19 9.06 0.419 0.415 7 0.450 0.454 8.25 8.32 7.78 7.91 0.290 0.295 8 0.853 0.839 9.64 9.55 8.60 8.83 0.353 0.350 9 0.721 0.728 5.79 5.71 10.9 10.7 0.878 0.882 10 0.875 0.866 7.96 7.94 8.61 8.50 0.546 0.551
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