Determination of Sn, W, Ti and Other Elements in Polymetallic Ore by Inductively Coupled Plasma-Optical Emission Spectrometry with Sodium Peroxide Fusion
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摘要: 准确、快速测定多金属矿中的主次量成分，对矿产资源的综合利用具有十分重要的意义，但针对锡、钨、钛三种元素等难以被酸溶解的元素，选择适宜的样品前处理方法和电感耦合等离子体发射光谱（ICP-OES）技术结合起来，有利于提高准确度和测试效率。本文以过氧化钠为熔剂，样品经高温熔融，盐酸+酒石酸+过氧化氢混合酸提取，结合内标法建立了测定多金属矿中铜铅锌以及锡钨钛等15个主次量成分的分析方法。实验优化了各元素的分析谱线和背景校正模式，系统研究了坩埚、熔剂的选择、铝元素和内标元素的影响，获得方法检出限为7~995 μg/g，加标回收率为90.3%~105.0%，精密度（RSD，n=12）为0.8%~6.6%。本方法针对5种不同类型的典型多金属矿，具有不分矿种、前处理步骤相同、多成分同时测定和测试范围宽（40 μg/g~25%）的技术特点，尤其对于矿种类型不确定、测定范围在百分含量以上的多金属矿具有优势。
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关键词:
- 多金属矿 /
- 锡钨钛 /
- 过氧化钠碱熔 /
- 电感耦合等离子体发射光谱法 /
- 内标法
Abstract: For tin, tungsten, titanium and other elements not easily digested by acid, a suitable sample preparation method combined with Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) can help to improve the accuracy and efficiency. Polymetallic ore samples were melted with Na2O2 and then extracted by mixed leaching solution (hydrochloric acid-tartaric acid-hydrogen peroxide).15 major and minor elements including Cu, Pb, Zn, Sn, W and Ti were determined by ICP-OES using an internal standard method. The analytical lines of analyzed elements and the correction mode of the background were optimized. The effect of crucible contamination, solvent, Al and internal standard element on the results were systematically studied. The method has detection limits of 7-995 μg/g, recoveries of 90.3%-105.0% (in Table 4), and relative standard deviations (RSD, n=12) of 0.8%-6.6% (in Table 3) by the standard addition method. For five different types of polymetallic ores, the method has a wide test range (40 μg/g to 25%). -
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表 1 各元素分析谱线及扣背景模式
Table 1. Analytical spectral line and background deduction model for each element
元素 分析谱线
(nm)扣背景
模式Eu 381.967 左、右 Ca 422.673 - Mg 279.553 - Fe 259.940 - Mn 257.610 左、右 Ti 336.121 左、右 P 178.284 左、右 Cu 324.754 右 Pb 220.353 左、右 Zn 213.856 左、右 W 239.709 左 Mo 202.030 左、右 Sn 189.989 左、右 V 310.231 左、右 Cr 267.716 左、右 Sr 407.771 左、右 
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表 2 熔剂对分析结果的影响
Table 2. Effect of the flux on the determination of elements
元素 GBW07281 GBW07284 标准值
(%)测定值 (%) 标准值
(%)测定值 (%) 过氧化钠
(4 g)氢氧化钠
+过氧化钠
(3 g+1 g)碳酸钠
+硝酸钾
(5 g+2 g)硼砂
+碳酸钠
(2 g+5 g)过氧化钠
(4 g)氢氧化钠
+过氧化钠
(3 g+1 g)碳酸钠
+硝酸钾
(5 g+2 g)硼砂
+碳酸钠
(2 g+5 g)Cu 0.26 0.26 0.26 0.27 0.26 0.13 0.13 0.13 0.13 0.12 MnO 1.17 1.16 1.18 1.20 1.22 - 0.61 0.63 0.62 0.62 Mo 0.027 0.029 0.030 0.029 0.034 0.0085 0.0086 0.0081 0.0079 0.0082 Pb 2.72 2.72 2.74 2.74 2.96 0.081 0.083 0.087 0.083 0.078 Sn 4.47 4.49 1.76 1.81 0.18 0.017 0.019 0.020 0.019 0.020 TiO2 0.85 0.83 0.82 0.75 0.69 - 0.84 0.85 0.85 0.83 V2O5 - 0.088 0.091 0.095 0.10 - 0.034 0.036 0.035 0.034 WO3 0.086 0.089 0.087 0.087 0.096 4.62 4.58 4.16 3.51 3.39 Zn 0.74 0.73 0.73 0.74 0.80 0.032 0.032 0.034 0.035 0.034 CaO 7.73 7.75 7.74 7.75 7.74 - 1.77 1.75 1.72 1.74 MgO 0.99 1.00 0.98 1.01 1.01 - 1.75 1.76 1.69 1.69 Fe2O3 36.19 34.15 32.32 31.68 25.26 - 8.44 8.47 8.39 8.32 P2O5 0.25 0.24 0.24 0.26 0.24 - 0.52 0.51 0.51 0.49 Cr2O3 - 0.016 0.016 0.015 0.016 - 0.015 0.015 0.014 0.014 SrO - 9.65 9.59 9.61 9.61 - 4.08 4.09 4.05 4.04
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表 3 准确度和精密度试验
Table 3. Accuracy and precision tests of the method
元素 GBW07240 GBW07281 标准值
(%)测定平均值
(%)相对误差
(%)RSD
(%)标准值
(%)测定平均值
(%)相对误差
(%)RSD
(%)Cu 0.079 0.084 6.33 2.9 0.26 0.26 0.00 0.8 MnO 0.97 1.01 4.12 3.0 1.17 1.19 1.71 0.8 Mo 0.0004 0.0006 - 2.6 0.027 0.028 3.70 5.7 Pb 0.26 0.27 3.85 3.0 2.72 2.73 0.37 1.0 Sn 0.14 0.14 0.00 3.1 4.47 4.47 0.00 1.2 TiO2 0.079 0.080 1.27 5.1 0.85 0.83 -2.35 2.6 V2O5 - 0.006 - 4.9 - 0.088 - 3.6 WO3 0.019 0.020 5.26 2.4 0.086 0.088 2.33 4.0 Zn 0.29 0.30 3.45 3.3 0.74 0.73 -1.35 0.8 CaO 37.30 37.41 0.29 3.6 7.73 7.75 0.26 3.1 MgO 1.45 1.43 -1.38 5.0 0.99 1.00 1.01 2.3 Fe2O3 7.79 7.82 0.39 4.7 36.19 34.15 - 6.6 P2O5 - 0.034 - 2.6 0.25 0.24 -4.00 1.2 Cr2O3 0.00095 - - - - 0.016 - 1.4 SrO - 16.50 - 3.7 - 9.65 - 1.8
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表 4 加标回收试验
Table 4. Recovery tests of the method
元素 GBW07225 GBW07282 原始量
(μg/mL)加入量
(μg/mL)测定值
(μg/mL)回收率
(%)原始量
(μg/mL)加入量
(μg/mL)测定值
(μg/mL)回收率
(%)Cu 0.16 0.15 0.307 98.0 3.22 3.00 6.19 99.0 MnO 2.62 3.00 5.64 100.7 4.71 5.00 9.50 95.8 Mo 0.00 0.10 0.097 97.0 0.33 0.20 0.527 98.5 Pb 0.00 0.10 0.099 99.0 28.31 20.00 47.50 96.0 Sn 0.01 0.01 0.020 100.0 12.72 10.00 22.62 99.0 TiO2 97.5 100 197 99.5 3.76 3.00 6.78 100.7 V2O5 2.63 3.00 5.65 100.7 0.55 0.50 1.04 98.0 WO3 0.02 0.02 0.041 105.0 0.18 0.20 0.383 101.5 Zn 0.03 0.04 0.069 97.5 9.07 10.00 18.87 98.0 CaO 74.8 75 152 102.9 182 180 360 98.9 MgO 61.8 65 126 98.8 16.09 15.00 31.80 104.7 Fe2O3 365 300 636 90.3 342 300 615 91.0 P2O5 1.21 1.00 2.22 101.0 1.56 1.50 3.10 102.7 Cr2O3 0.15 0.15 0.30 100.0 0.10 0.10 0.20 100.0 SrO 286 250 513 90.8 89.3 100 182 92.7
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表 5 不同样品分析方法测定结果比较
Table 5. Comparison of the analytical results with different methods
样品
编号方法 含量 (%) Cu MnO Mo Pb Sn TiO2 V2O5 WO3 Zn CaO MgO Fe2O3 P2O5 Cr2O3 SrO A-10 化学法 0.005 0.19 0.038 0.076 0.012 0.54 0.032 0.015 0.029 6.32 1.86 5.81 0.18 0.025 1.49 本法 0.005 0.18 0.039 0.075 0.010 0.54 0.033 0.018 0.028 6.35 1.87 5.79 0.17 0.026 1.47 A-16 化学法 0.005 0.21 0.11 0.38 0.008 0.38 0.048 0.011 0.055 7.93 2.38 6.31 0.11 0.063 1.23 本法 0.006 0.22 0.10 0.38 0.005 0.37 0.049 0.014 0.056 7.95 2.41 6.33 0.10 0.064 1.22 L-31 化学法 0.052 0.98 0.003 0.022 0.31 0.78 0.12 0.023 0.31 9.64 1.01 11.73 0.28 0.075 0.037 本法 0.052 0.98 0.001 0.023 0.30 0.77 0.12 0.023 0.32 9.60 1.02 11.69 0.28 0.074 0.033 L-40 化学法 0.060 0.54 0.006 0.008 0.12 0.66 0.067 0.17 0.069 7.72 3.63 13.87 0.26 0.096 0.005 本法 0.059 0.54 0.007 0.010 0.12 0.65 0.068 0.16 0.068 7.77 3.59 13.99 0.25 0.094 0.007 M-10 化学法 0.016 0.081 0.045 0.003 0.050 0.53 0.019 0.011 0.061 1.28 1.74 6.21 0.11 0.13 0.005 本法 0.016 0.080 0.044 0.002 0.051 0.55 0.020 0.013 0.061 1.30 1.77 6.18 0.10 0.12 0.006 M-12 化学法 0.013 0.069 0.061 0.003 0.046 0.59 0.022 0.012 0.063 1.76 2.05 5.75 0.10 0.037 0.007 本法 0.014 0.070 0.059 0.002 0.046 0.58 0.023 0.015 0.060 1.74 2.08 5.72 0.10 0.036 0.005 N-01 化学法 0.055 1.13 0.003 0.79 0.010 0.20 0.018 0.001 0.39 3.97 2.39 8.67 0.059 0.081 0.015 本法 0.054 1.10 0.001 0.81 0.008 0.19 0.015 0.005 0.38 4.01 2.41 8.72 0.060 0.078 0.012 N-02 化学法 0.32 0.81 0.003 8.47 0.008 0.14 0.015 0.015 1.44 1.41 1.34 6.51 0.025 0.12 0.003 本法 0.32 0.91 0.001 8.50 0.010 0.13 0.011 0.013 1.42 1.39 1.36 6.48 0.020 0.12 0.006 X-03 化学法 0.007 0.019 0.001 0.003 0.008 0.57 0.11 0.004 0.024 3.01 1.64 4.82 0.25 0.53 0.021 本法 0.006 0.020 0.002 0.006 0.005 0.58 0.12 0.006 0.025 2.97 1.67 4.88 0.24 0.55 0.028 X-08 化学法 0.025 0.021 0.004 0.003 0.003 0.29 1.03 0.009 0.043 0.82 0.36 5.52 0.39 1.02 0.082 本法 0.026 0.020 0.004 0.002 0.007 0.30 1.01 0.006 0.042 0.82 0.37 5.56 0.40 0.99 0.080
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