Comparison of Two Different Sample Digestion Methods for Determination of Tungsten, Molybdenum, and Bismuth in Polymetallic Ore by Inductively Coupled Plasma-Optical Emission Spectrometry
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摘要:
当前多金属伴生矿中钨钼铋元素的测定方法主要是传统的硫氰酸钾比色法和EDTA容量法，均为单元素分析，操作过程繁琐，分析效率低，检测周期长，难以满足大批量样品简便、快速的分析要求。本文改进了传统的单元素分析法，对比了盐酸-磷酸-高氯酸-硝酸四酸和盐酸-硝酸-高氯酸三酸两种消解体系，并结合电感耦合等离子体发射光谱法(ICP-OES)，建立了一种同时测定多金属伴生矿中钨、钼、铋的快速分析法。结果表明：合理引入磷酸的四酸消解法对样品的消解更为彻底，钨、钼、铋的测定结果准确度更高，各元素测定值和标准值的相对误差介于-5.36%~-1.39%，精密度较高(RSD ≤ 4.18%)，方法检出限介于0.0027%~0.0037%。本方法应用于分析湖南郴州某地区多金属伴生矿实际样品，各元素加标回收率介于95.0%~103.0%，各项技术指标均优于三酸消解法。本方法提高了分析效率，结果准确可靠，适用于多金属伴生矿样品中钨钼铋及其他主次量元素的批量检测。
Abstract:BACKGROUND Currently, tungsten, molybdenum, and bismuth contents are mainly determined by the traditional potassium thiocyanate colorimetric method and EDTA volumetric method. These methods are based on single-element analysis, which has a complicated operation process, low analysis efficiency, and long detection cycle. It is difficult to meet the requirements of accurate and rapid determination of many samples.
OBJECTIVES To improve the traditional single-element analysis method for the determination of tungsten, molybdenum, and bismuth in polymetallic ore.
METHODS A rapid method for the simultaneous determination of tungsten, molybdenum, and bismuth in the ore sample was developed by comparing the two digestion methods of HCl-H3PO4-HClO4-HNO3 and HCl-HClO4-HNO3, and was subsequently combined with inductively coupled plasma-optical emission spectrometry.
RESULTS Tungsten, molybdenum, and bismuth in the sample were digested more thoroughly using the four-acid digestion method with a reasonable addition of phosphoric acid. The relative error between the determined and certified values of each element ranged from -5.36% to -1.39%, which indicated higher accuracy. The relative standard deviation was ≤ 4.18%, and the detection limits of the method ranged from 0.0027% to 0.0037%. The method was employed for the analysis of actual samples of the polymetallic ore from a certain area in Chenzhou, Hunan Province. The recovery of each element ranged from 95.0% to 103.0%. All the technical indexes were better than those of the three-acid digestion method.
CONCLUSIONS The developed method significantly improved the analysis efficiency and gave accurate and reliable results. The method has been verified by actual samples and is suitable for batch detection of tungsten, molybdenum, bismuth, and other major and trace elements in the polymetallic ore samples.
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表 1 四酸和三酸方法处理样品后盐酸不同用量对测定结果的影响
Table 1. Analytical results of elements in samples dissoluted by four-acid digestion and three-acid digestion with different hydrochloric acid dosage
待测元素 标准值(%) 四酸消解法 盐酸(5mL) 盐酸(10mL) 盐酸(15mL) 盐酸(20mL) 盐酸(25mL) 测定值 相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)W 0.390 0.321 -18.0 0.340 -12.8 0.361 -7.69 0.380 -2.56 0.373 -5.13 Mo 0.056 0.043 -23.2 0.046 -17.9 0.048 -14.3 0.053 -5.36 0.051 -8.93 Bi 0.120 0.071 -40.8 0.080 -33.3 0.099 -17.5 0.115 -4.17 0.103 -14.2 待测元素 标准值(%) 三酸消解法 盐酸(5mL) 盐酸(10mL) 盐酸(15mL) 盐酸(20mL) 盐酸(25mL) 测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)测定值
(%)相对误差
(%)W 0.390 0.311 -20.5 0.330 -15.4 0.343 -12.1 0.360 -7.69 0.357 -8.46 Mo 0.056 0.041 -26.8 0.044 -21.4 0.048 -14.3 0.050 -9.12 0.049 -12.5 Bi 0.120 0.070 -41.7 0.076 -36.7 0.092 -23.3 0.109 -9.17 0.101 -9.50 
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表 2 四酸消解法溶样测试结果
Table 2. Analytical results of elements in samples dissoluted by four-acid digestion method
待测元素 标准值
(%)盐酸-磷酸混合酸25mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸-磷酸混合酸20mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸-磷酸混合酸15mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸-磷酸混合酸10mL，高氯酸-硝酸混合酸5mL，盐酸20mL 测定值(%) 溶液状态 测定值(%) 溶液状态 测定值(%) 溶液状态 测定值(%) 溶液状态 W 0.390 0.351 灰白色沉淀的透亮溶液 0.380 极少量灰白色沉淀的透亮溶液 0.363 极少量灰白色沉淀的透亮溶液 0.352 灰白色沉淀的透亮溶液 Mo 0.056 0.051 0.053 0.050 0.048 Bi 0.120 0.081 0.115 0.093 0.086
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表 3 三酸消解法溶样测试结果
Table 3. Analytical results of elements in samples dissoluted by three-acid digestion method
待测元素 标准值
(%)盐酸25mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸20mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸25mL，高氯酸-硝酸混合酸5mL，盐酸20mL 盐酸25mL，高氯酸-硝酸混合酸5mL，盐酸20mL 测定值(%) 溶液状态 测定值(%) 溶液状态 测定值(%) 溶液状态 测定值(%) 溶液状态 W 0.390 0.290 大量灰白色沉淀的浑浊溶液 0.342 灰白色沉淀的浑浊溶液 0.372 灰白色沉淀的浑浊溶液 0.336 灰白色沉淀的浑浊溶液 Mo 0.056 0.038 0.039 0.046 0.039 Bi 0.120 0.073 0.080 0.087 0.071
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表 4 四酸和三酸消解法的准确度和精密度测试结果
Table 4. Accuracy and precision tests of the four-acid and three-acid digestion methods
标准物质编号 待测元素 四酸消解法 三酸消解法 标准值
(%)平均测定值
(%)相对误差
(%)RSD
(%)标准值
(%)平均测定值
(%)相对误差
(%)RSD
(%)21R355 (美国研制) W 0.390 0.381 -2.31 1.66 0.390 0.359 -7.95 5.51 Mo 0.056 0.053 -5.36 4.10 0.056 0.050 -10.7 7.87 Bi 0.120 0.114 -5.00 2.85 0.120 0.107 -10.8 8.07 33M 7035-93 (美国研制) W 0.360 0.354 -1.39 1.20 0.360 0.336 -6.67 5.12 Mo 0.045 0.043 -4.44 4.18 0.045 0.039 -13.3 12.3 Bi 0.110 0.106 -4.55 2.91 0.110 0.099 -11.0 7.11
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表 5 四酸和三酸消解法处理样品回收率测试结果
Table 5. Recovery tests of the samples dissoluted with four-acid and three-acid digestion methods
原矿样品编号 待测元素 四酸消解法 三酸消解法 测定值
(%)加标量
(%)测得总量
(%)回收率
(%)测定值
(%)加标量
(%)测得总量
(%)回收率
(%)N1 W 0.340 0.390 0.734 101.0 0.340 0.390 0.755 106.0 Mo 0.045 0.056 0.102 102.0 0.045 0.056 0.098 94.6 Bi 0.100 0.120 0.218 98.3 0.100 0.120 0.212 93.3 N2 W 0.350 0.390 0.748 102.0 0.350 0.390 0.717 94.1 Mo 0.052 0.056 0.105 95.3 0.051 0.056 0.104 94.6 Bi 0.110 0.120 0.231 101.0 0.110 0.120 0.220 91.7 N3 W 0.380 0.390 0.762 97.9 0.380 0.390 0.805 109.0 Mo 0.047 0.056 0.105 103.0 0.047 0.056 0.099 92.9 Bi 0.120 0.120 0.235 95.8 0.120 0.120 0.229 90.8 N4 W 0.360 0.390 0.746 99.0 0.360 0.390 0.727 94.1 Mo 0.043 0.056 0.097 96.4 0.043 0.056 0.103 107.0 Bi 0.100 0.120 0.214 95.0 0.100 0.120 0.208 90.0 N5 W 0.400 0.390 0.798 102.0 0.400 0.390 0.813 106.0 Mo 0.046 0.056 0.104 103.0 0.046 0.056 0.098 92.9 Bi 0.110 0.120 0.224 95.0 0.110 0.120 0.243 111.0 N6 W 0.410 0.390 0.788 96.9 0.410 0.390 0.831 108.0 Mo 0.048 0.056 0.102 96.4 0.048 0.056 0.110 111.0 Bi 0.130 0.120 0.244 95.0 0.130 0.120 0.238 90.0
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