Evaluation of the Interlaboratory Comparison Results of the Chemical Composition of Copper Concentrates and Analysis of the Causes of Outliers
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摘要:
铜精矿成分分析是判定其品质的重要手段，尤其是主元素铜的分析。目前，测定铜精矿中铜含量的主要分析方法有碘量法、电感耦合等离子体发射光谱法(ICP-OES)、火焰原子吸收光谱法(FAAS)、X射线荧光光谱法(XRF)、电解重量法等。为确保检测标准量值统一、准确、可靠，本文组织开展了铜精矿中铜镁铅锌的测定实验室间比对活动。通过对参加实验室的检测结果进行统计分析，评价参加实验室对铜精矿中铜镁铅锌测定的技术水平和能力。结果表明：大部分实验室的检测结果为满意，铜精矿中铜的满意率为92.9%，满意率较高；铜镁铅锌的满意率平均值为89.0%。少数实验室出现离群值主要在于样品前处理、检测人员对检测方法未能充分理解并熟练掌握、仪器状态等其他相关因素。碱浸法因样品分解不完全，不能作为铜精矿前处理方法；碱熔法因工序繁琐，易产生基体干扰，不适合作为铜精矿前处理方法。本文建议优先采用酸溶-滴定法测定铜精矿中的铜，而采用酸溶ICP-OES法测定铜精矿中的铜镁铅锌，该方法高效快捷，但其稳定性需要进一步的实验考察。
Abstract:BACKGROUND Composition analysis of copper concentrate is an important method to determine its quality, especially the analysis of the main element copper. Currently, the main analytical methods for the determination of copper content in copper concentrate include iodometry, inductively coupled plasma-optical emission spectrometry (ICP-OES), flame atomic absorption spectrometry (FAAS), X-ray fluorescence spectrometry (XRF), and electrolytic gravimetric methods.
OBJECTIVES To ensure the uniformity, accuracy, and reliability of the standard values, interlaboratory comparison activities for the determination of copper, magnesium, lead, and zinc in copper concentrate were organized.
METHODS Through the statistical analysis of the test results of the participating laboratories, the technical level and ability of the participating laboratories in the determination of copper, magnesium, lead, and zinc in copper concentrates were evaluated.
RESULTS The results showed that most laboratory results were satisfactory, the satisfaction rate of copper in the copper concentrate was 92.9%, and the average satisfaction rate of copper, magnesium, lead, and zinc was 89.0%. The outliers in a few laboratories were mainly attributed to sample pretreatment, lack of understanding and mastering of the analytical methods by the testing personnel, and other related factors, such as the instrument status.
CONCLUSIONS Because of incomplete sample decomposition, the alkali leaching method could not be used for pretreatment of copper concentrate. Additionally, the alkali fusion method is not recommended for copper concentrate pretreatment because of its complicated process and matrix interference. Acid dissolution titration is preferred as a pretreatment method for the determination of copper in the copper concentrate. The acid-dissolution ICP-OES method for simultaneous determination of Cu, Mg, Pb, and Zn in the copper concentrate is efficient and rapid with satisfactory results. However, further experiments are required to investigate their stabilities.
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Key words:
- copper concentrate /
- interlaboratory comparison /
- proficiency testing /
- outlier /
- acid dissolution /
- iodometry
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表 1 铜精矿中各元素结果的一致性检验
Table 1. Consistency check of analytical results for copper concentrate
元素 采用方法 测定平均值
(%)t值 t临界值 结论 Cu GB/T 3884.1—2012
ICP-OES法19.11
19.041.11 2.20 一致 Mg GB/T 3884.18—2014
GB/T 3884.4—20121.70
1.811.51 2.20 一致 Pb GB/T 3884.18—2014
GB/T 3884.6—20120.0191
0.01910 2.23 一致 Zn GB/T 3884.18—2014
GB/T 3884.6—20120.40
0.390.71 2.23 一致 
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表 2 铜精矿中各元素结果的统计量及相关信息
Table 2. Statistics and related information of analytical results in copper concentrate
元素 有效结果数(个) 平均值
(%)标准偏差
(%)变异系数
(%)最小值
(%)最大值
(%)极差
(%)Cu 13 19.10 0.083 0.43 18.94 19.23 0.29 Mg 13 1.73 0.12 6.94 1.48 1.87 0.39 Pb 12 0.0191 0.0014 7.33 0.0158 0.0206 0.0048 Zn 12 0.400 0.013 3.25 0.382 0.424 0.042
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表 3 各实验室评价结果统计
Table 3. Statistics of analytical results for individual laboratory
Z值评价结果 实验室完成情况 实验室代码 实验室数量 所占比例
(%)全部|Z|≤2的实验室 全项 31、35、37、38、41、48、50、51、53、56 10 71.43 缺2项 08 1 7.14 无离群值但含有2＜|Z|＜3的实验室 全项 54 1 7.14 全部|Z|中有一项离群值的实验室 全项 36 1 7.14 全部|Z|中有三项离群值的实验室 全项 65 1 7.14
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表 4 铜精矿各元素检测能力统计结果
Table 4. Statistics of analytical results for individual element of copper concentrate
Z比分数 Cu Mg Pb Zn 平均比例
(%)结果数(个) 比例(%) 结果数(个) 比例(%) 结果数(个) 比例(%) 结果数(个) 比例(%) |Z|≤2 13 92.9 12 92.3 11 78.6 12 92.3 89.0 2＜|Z|＜3 0 0 1 7.7 1 7.1 0 0 3.7 |Z|≥3 1 7.1 0 0 2 14.3 1 7.7 7.3
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表 5 参加实验室采用的检测方法及标准
Table 5. Analysis methods and standards adopted by participating laboratories
元素 技术代码 采用方法 实验室数量 标准方法编号 Cu ATC-001 ICP-OES法 3 非标 ATC-021 滴定法 11 GB/T 3884.1—2012 Mg ATC-001 ICP-OES法 10 GB/T 3884.18—2014、非标 ATC-006 FAAS法 3 GB/T 3884.4—2012 Pb ATC-001 ICP-OES法 10 GB/T 3884.18—2014、GB/T 14353.18—2014、SN/T 2047—2008、非标 ATC-006 FAAS法 4 GB/T 3884.6—2012 Zn ATC-001 ICP-OES法 9 GB/T 3884.18—2014、非标 ATC-006 FAAS法 4 GB/T 3884.6—2012
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