铅冶炼分银渣化学分析方法

铅冶炼分银渣化学分析方法第2部分：铅含量的测定火焰原子吸收光谱法和Na2EDTA滴定法2编制说明任务来源根据工业和信息化部工信厅科[2017]40号)的文件精神，以及全国有色金属标准化技术委员会“关于印发《铅冶炼分银渣化学分析方法》等18项标准任务落实会会议的通知”(有色标委[2017]62号)及相关会议纪要的文件精神，《铅冶炼分银渣化学分析方法第2部分：铅含量的测定火焰原子吸收光谱法和Na2EDTA滴定法》由深圳市中金岭南有色金属股份有限公司起草，北矿检测技术有限公司、河南豫光金铅股份有限公司、株洲冶炼集团股份有限公司、桂林矿产地质研究院有限公司、贵研铂业股份有限公司、山东恒邦冶炼股份有限公司、湖南桂阳银星有色冶炼有限公司、长沙矿冶研究院有限责任公司、广东韶关市质量计量监督检测所、昆明西科工贸有限公司、福建紫金矿冶测试技术有限公司、江西铜业股份有限公司等单位协助起草。项目计划编号：(2017-0181T-YS)，完成年限2019年。工作过程2017年8月23日〜27日全国有色金属标准化技术委员会在泰安市组织召开了《铅冶炼分银渣化学分析方法》等18项标准任务落实会议，会议确定了标准制定的起草单位和参与验证单位，落实了标准计划项目的进度安排和分工。准编写原则和编写格式本标准是根据GB/T1.1-2009《标准化工作导则第1部分：标准的结构和编写规则》和GB/T20001.4-2001《标准编写规则第4部分：化学分析方法》的要求进行编写的。标准编写的目的和意义铅冶炼分银渣是铅阳极泥在提取主要成分如铅和贵金属金、银后所留下的残渣。目前国内许多铅冶炼行业均产出这类物料。铅冶炼分银渣含有铅、铜、锑、铋、金、银等贵金属，是一种品位相当高的二次资源。矿产资源日趋枯竭，以铅冶炼分银渣作为二次资源，最大化地提取铅、铜、锑、铋等有价金属，富集回收金银等贵金属，实现资源循环利用及有价金属材料生产，已成为有色金属再生循环领域研究中的热点，具有很高的经济和社会价值。目前国内铅阳极泥处理由于工艺、设备的不同或者原料中成分含量不同，产出铅冶炼分银渣的物理形态、各元素品位差别较大。经过充分调研，铅冶炼分银渣中铅含量的范围较宽，为0.3%~40%，因此铅冶炼分银渣中铅含量测定分为：方法1火焰原子吸收光谱法(0.30%~5.00%)和方法2Na2EDTA滴定法(5.00%~40.00%)。经标准查新，目前国内尚无统一的铅冶炼分银渣化学分析方法，导致贸易时常有争议。因此制定相应的铅冶炼分银渣化学分析方法，对促进生产和指导贸易具有重要的意义。国内外有关工作情况目前国内外测定低含量铅的检测方法主要是原子吸收法、ICP法，考虑到原子吸收仪应用比较普遍，选择性较好，因此本法对低含量的铅选用火焰原子吸收光谱法，就样品消解方式及共存元素干扰情况进行了深入研究，最终确定了分析步骤。而高含量铅的测定方法主要是EDTA滴定法，如国家标准GB/T8152-2006《铅精矿化学分析方法》、GB/T3884-2012《铜精矿化学分析方法》，行业标准YS/T461-2013《混合铅锌精矿化学分析方法》、YS/T745-2010《铜阳极泥化学分析方法》等，均采用了EDTA滴定法。但铅冶炼分银渣与其他矿样比，成分更加复杂，各元素含量范围更加广泛，分析要求更加高，如样品消解方式、共存元素干扰情况，都不能等同采用。为此，本试验就样品分解方式及共存元素干扰情况进行了深入研究，最终确定了EDTA滴定法测定高含量铅分析步骤。标准适用范围本部分适用于铅冶炼分银渣中铅含量的测定。测定范围:0.30%〜40.00%。标准制订的主要内容与依据见《试验报告》。协同试验样品的准备由中金岭南韶关冶炼厂、山东恒邦冶炼股份有限公司、河南豫光金铅股份有限公司等单位提供了10个水平的样品。精密度试验在精密度试验方面，13个实验室（见表1）对10个水平的样品进行试验，根据国家标准GB/T6379.2-2004确定标准测量方法的重复性和再现性的基本方法（ISO5725-2：1994，IDT）的规定，对收到的全部数据进行了统计分析。原始数据及统计结果见附件2。表1协同试验的实验室编号编号实验室1深圳市中金岭南有色金属股份有限公司2北矿检测技术有限公司3河南豫光金铅股份有限公司4株洲冶炼集团股份有限公司5桂林矿产地质研究院有限公司6贵研铂业股份有限公司7山东恒邦冶炼股份有限公司8湖南桂阳银星有色冶炼有限公司9长沙矿冶研究院有限责任公司10广东韶关市质量计量监督检测所11昆明西科工贸有限公司12福建紫金矿冶测试技术有限公司13江西铜业股份有限公司重复性在重复性条件下获得的两次独立测试结果的测定值，在以下给出的平均值范围内，这两个测试结果的绝对差值不超过重复性限（r）,超过重复性限（r）的情况不超过5%，重复性限（r）按表2数据采用线性内插法求得：表2重复性限wPb/%0.3570.9972.473.875.07r/%0.0540.0750.130.170.21表3重复性限WPb/%5.9113.7522.6931.3237.61r/%0.190.250.300.340.388.4再现性在再现性条件下获得的两次独立测试结果的测定值，在以下给出的平均值范围内，这两个测试结果的绝对差值不超过再现性限（R）,超过再现性限（R）的情况不超过5%，再现性限（R）按表4数据采用线性内插法求得：表4再现性限wpb%0.3570.9972.473.875.07r/%0.0850.130.230.320.41表5再现性限w%Db/5.9113.7522.6931.3237.61r/%0.290.320.350.400.449标准征求意见稿意见汇总与处理在协同试验和标准预审过程中，征求的意见以及对意见的分析处理，详见《意见汇总表》。标准水平分析本标准在技术内容、文本结构上与相应的国内标准等同，具有国内先进水平。与有关的现行法律、法规和强制性国家标准的关系本标准符合相关现行法律、法规和强制性国家标准，没有冲突。重大分歧意见的处理经过和依据无。贯彻标准的要求和措施建议建议颁布本标准为推荐性行业标准，供相关组织参考采用。废止现行有关标准的建议无其他应予说明的事项本标准遵守下列基础标准：GB/T1.1标准化工作导则第1部分：标准的结构和编写规则GB/T20001标准编写规则第4部分：化学分析方法GB/T17433冶金产品化学分析基础术语GB/T11792测试方法的精密度在重现性或再现性条件下所得测试结果可接受的检查和最终测试结果的确定。深圳市中金岭南有色金属股份有限公司2018年12月22日附件2：铅冶炼分银渣化学分析方法第2部分：铅含量的测定方法2Na2EDTA滴定法2精密度试验数据处理1背景为了确定《铅冶炼分银渣化学分析方法第2部分：铅含量的测定Na^DTA滴定法》中铅含量测定方法的重复性与再现性，13个实验室对5个水平的铅冶炼分银渣样品进行了协同试验。根据国家标准GB/T6379.2-2004确定标准测量方法的重复性和再现性的基本方法(ISO5725-2：1994,IDT)的规定，对收到的全部数据进行了统计分析。2各实验室实验数据2.1各实验室提供的铅含量实验数据表1各实验室提供的铅含量实验数据(%)实验室水平1水平2水平3水平4水平51中金岭南5.9713.8022.8931.3837.815.9213.8822.8331.0837.645.8313.7122.8831.2137.745.9013.7122.5831.3437.655.9513.6222.6031.4537.516.0213.5822.9031.4037.535.9513.8422.7831.3537.445.9013.8122.5531.3037.805.9413.8622.7131.3337.585.8913.7422.6731.2337.585.9613.7222.5731.2637.63平均值5.9313.7522.7231.3037・63标准偏差0.050000.096520.13800.10340.11802北矿检测6.0213.8622.6631.2037.436.1013.8322.5931.2037.355.9713.6422.5531.0337.285.9013.8122.5731.0037.346.1513.7222.6431.1837.705.9613.9522.7831.1137.626.1513.8822.4931.1337.716.1113.6722.6831.2537.566.0013.8822.5731.0237.796.1613.8822.7331.2237.64

6.1513.8322.5731.3437.73平均值6.0613.8122.6231.1537.56标准偏差0.089080.092470.081740.10120.17103河南豫光5.8113.5822.5731.4737・585.8313.6822.6631.4737.515.8113.7222・5631.3937・675.7013.6922.7631.4537.555.8213.5922.4831.3537.735.8313.7122.7631.4137.555.8213.4822.5231.3837.675.8013.9222.7431.2837.555.7113.7022.7031.4437.725.6913.8022.6931.4637.525.9413.5822.8531.2837.63平均值5.8013.6822.6631.4037.61标准偏差0.0720.1200.1160.0700.0804株冶5.9913.6222.1831.4437.655.8913.6622.1931.2337.446.0813.6822.3031.3837.645.9713.7022.1931.3037.565.9313.6222.2831.4537.526.0313.6622.5031.4037.535.9413.8122.5531.6637.44平均值5.9813.6822.3131.4137.54标准偏差0.064250.064920.15290.13570.084665桂林地矿5.9013.7322.8631.2737.605.9613.7222.7931.1037.685.8813.6522.8531.2937.765.8613.6222.7631.3637.695.9613.6922.7931.1137.725.8913.6122.6131.3137.525.9313.6922.7631.2637.715.9613.7722.7931.2737.735.9213.8122.6231.1937.665.8813.7922.7331.4837.835.8513.6822.8831.2837.65平均值5.9113.7122.7731.2737.69标准偏差0・040.070.090.110.086贵研铂业5.9613.9222.9531.3438.026.1013.9522.9631.6737.84

5.9613.8222.8331.4537.706.0313.8022.8631.6237.785.9813.9522.7431.5337.866.1113.8322.8331.6037.905.9813.8822.9131.5837.826.1013.9522.8831.5537.886.0813.7922.9031.4237.926.0513.7822.7831.5037.806.0013.8022.8031.5837.89平均值6.0313.8622・8631.5337.86标准偏差0.05900.07020.06980.09670.08347山东恒邦5.8813.8722.7131.2737.505.8713.7122.7331.1737.505.8813.8422.8131.2537.675.9413.8222.9131.2037.855.9313.7422.7231.2037.515.9513.7822.7331.2137.575.9313.8222.7331.2837.73平均值5.8913.7822.7831.2437.62标准偏差0.0333810.0567790.0727360.0411730.1359458桂阳银星5.6713.7522.7031.2937.325.8913.5922.5531.0037.355.7813.4822.5931.1237.355.7513.6222.6431.3737.465.7013.6622.8731.2737.695.8513.6422.7331.2337.705.8013.7922.6131.2137.48平均值5.7713.6422.6731.2137.48标准偏差0.078250.10260.10790.12120.15939长沙矿冶5.9813.6822.8531.4837.725.9613.9222.6031.3837.716.0113.6722.8131.3737.595.8313.8622.6831.2537.825.8713.8222.8131.2737.625.9413.6822.9031.2537.765.9213.8522.7931.4037.825.9113.8622.8131.3037.62

5.8613.8522.7631.4237.765.9513.8722.8131.5637.725.9413.9522.9731.3337.75平均值5.9213.8222.8031.3637.72标准偏差0.0540.0980.0990.0980.07810韶关质计5.8613.6822.6531.4537.355.9613.7522.5331.5637.465.8713.8922.7531.3537.525.9213.7622.7931.5237.415.9513.8522.6431.4437.525.8413.9122.5831.3537.465.8313.8522.7931.3437.525.9813.8722.8731.5437.445.9513.7922.8431.5737.49平均值5.906713・816722.715631.45837.463标准偏差0.0570087710.07599340.11959420.09431040.057662811昆明西科5.8713.8422.9830.9737.625.8413.8322.8731.3937.685.8113.8122.6131.1937.515.7913.8422.5931.1537.655.9413.7922.7131.4037.635.9913.7822.8531.2937.636.0213.8922.6831.0337.245.7913.8922.9931.1837.365.7213.7122.5831.0137.655.8913.8422.5430.8137.395.8013.8222.6031.1937.58平均值5.8613.8222.7331.1537.54标准偏差0.0930.0520.170.180.1512紫金矿业5.8513.8722.6131.1537.735.7113.7722.8631.3337.605.7913.8522.8331.2037・665.8613.8322.7731.4737.86

5.9913.8522.8431.3137.825.8413.8122.9431.5237.755.8213.6222.6431.1237・875.8113.8522.8131.4737.696.0313.6422.6931.4437.675.8113.6222.7531.4437.825.9213.5622.7431.2237・63平均值5.8613.7522.7731.3337.74标准偏差0.0920.1170.0990.1430.09513江铜集团5.9013.6922.8531.4037.645.7913.4822.8331.4537.235.8513.7522.5631.2337.855.9313.8422.4931.1937.515.9413.6522.7531.5637.695.7813.5422.6231.6537.785.9913.5522.8931.2537.695.8413.6322.7831.7437.855.9613.8422.4331.2137.21平均值5.8913.6622.6931.4137.61标准偏差0.080.130.170.210.242.2单元平均值的计算由表1的数据，计算单元平均值如表2表2单元平均值实验室i水平j12345Pb15.9313.7522.7231.3037.6326.0613.8122.6231.1537.5635.8013.6822.6631.4037.6145.9813.6822.31**31.4137.5455.9113.7122.7731.2737.6966.0313.8622.8631.5337.8675.8913.7822.7831.2437.6285.7713.6422.6731.2137.4895.9213.8222.8031.3637.72105.906713.816722.715631.45837.463

115.8613.8222.7331.1537.54125.8613.7522.7731.3337.74135.8913.6622.6931.4137.612.3单元离散度的计算表3单元标准差实验室i水平j水平1水平2水平3水平4水平5Pb10.050000.096520.13800.10340.118020.089080.092470.081740.10120.171030.0720.1200.1160.0700.08040.064250.064920.15290.13570.0846650.040.070.090.110.0860.05900.07020.06980.09670.083470・0333810.0567790.0727360.0411730.13594580.078250.10260.10790.12120.159390.0540.0980.0990.0980.078100.0570087710.07599340.11959420.09431040.0576628110.0930.0520.16630.180.15120.0920.1170.0990.1430.095130.080.130.16820.210.242.4一致性和离群值的检查2.4.1柯克伦检验对n=6，p=13，柯克伦检验5%临界值为0.243，1%临界值为0.291（柯克伦检验没有n=7时的临界值可查询，先按n=6时的临界值进行离群值的排除。）对水平1,昆明西科的s最大，检验统计量值=0.093；对水平2，江铜集团的s最大，检验统计量值=0.13；对水平3，江铜集团的s最大，检验统计量值=0.1682；对水平4，江铜集团的s最大，检验统计量值=0.21；对水平5，江铜集团的s最大，检验统计量值=0.24；柯克伦检验显示，对歧离值在表2中用“*”标出。2.4.2格拉布斯检验

表4格拉布斯检验统计量水平1水平2水平3水平4水平5均值的平均值5.906413.752222.698031.326537.6194均值的标准差0.091760.073860.13530.12730.1122最大均值6.0613.8622.8631.5337.86最小均值5.7713.6422.3131.1537.463Gmax1.86181.49701.19941.74552.1601Gmin1.69511.55402.91491.48161.4165G临界值实验室数p=13时，G临界值：上1%点时为2.699；上5%点时为2.462。从格拉布斯检验结果来看，22.31为歧离值和舍弃值，其他结果均在5%范围内，。2.5S、S、R与r的计算rR表5精密度计算实验室i水平j水平1水平2水平3水平4水平5S2r0.0046050.0076590.0121970.0141460.014364Sl20.0061320.0045930.0181460.0124650.010508PbSR20.0107370.0122520.0303440.0266110.024872总平均值5.90613.74922.68831.32037.608r0.19000.24510.30000.33300.3356R0.29010.30990.33170.45680.4416铅冶炼分银渣化学分析方法第2部分：铅量的测定方法1火焰原子吸收光谱法精密度试验数据处理1背景为了确定《铅冶炼分银渣化学分析方法第2部分：铅量的测定火焰原子吸收光谱法》中铅含量测定方法的重复性与再现性，13个实验室对5个水平的铅冶炼分银渣样品进行了协同试验。根据国家标准GB/T6379.2-2004确定标准测量方法的重复性和再现性的基本方法(ISO5725-2：1994,IDT)的规定，对收到的全部数据进行了统计分析。2各实验室实验数据2.1各实验室提供的铅含量实验数据表1各实验室提供的铅含量实验数据(%)实验室水平1水平2水平3水平4水平51中金岭南0.3490.9612.443.794.960.3510.9772.4413.804.980.3520.9792.4593.835.010.3550.9882.463.835.040.3560.9922.4683.855.070.3570.9962.4693.855.070.3590.9982.473.885.090.3600.9982.4733.895.100.3621.002.4813.925.110.3641.022.4843.945.140.3661.052.4893.965.16平均值0.3570.9972.473.875.07标准偏差0.005450.02380.01590.05590.06362北矿检测0.3490.9852.4053.8655.020.350.9922.4073.8885.050.3520.9952.4163.895.070.3531.0012.4223.95.080.3551.0022.4253.9025.080.3611.0112.4283.9115.090.3651.0192.4423.9395.11平均值0.3551.0012.4213.8995.070标准偏差0.00590.01150.01280.02280.02913河南豫光0.360.952.293.824.820.370.962.333.824.910.391.022.433.874.91

0.391.032.443.874.950.391.052.453.874.950.391.062.493.895.000.401.082.493.945.10.401.092.53.955.150.401.12.513.995.180.401.112.524.005.230.401.132.534.005.25平均值0.3901.0532.4533.9115.041标准偏差0.01340.05870.07810.06820.14684株冶0.350.962.333.754.990.350.962.353.804.990.350.972.363.815.020.360.972.363.835.020.360.982.383.845.030.360.992.403.855.030.371.012.413.855.050.371.022.423.855.060.371.022.443.865.070.381.032.453.895.080.381.042.473.915.10平均值0.3640.9952.43.845.04标准偏差0.01070.02810.04310.04130.03385桂林地矿0.340.972.393.855.170.350.972.413.895.180.350.992.423.915.190.350.992.423.915.200.351.002.433.925.200.351.002.433.935.200.351.002.443.935.200.361.002.453.935.210.361.002.463.945.210.361.002.463.945.230.361.012.473.955.25平均值0.350.992.433.925.20标准偏差0.0060.0110.0250.0280.0226贵研铂业0.3120.9422.3303.4504.9660.3290.9702.3463.5164.9980.3330.9962.3503.5305.0000.3371.0072.3603.5705.0400.3401.0302.3703.5805.050

0.3501.0302.3903.5865.0700.3501.0402.4003.6005.0800.3531.0502.4103.6205.1150.3601.0602.4303.6205.1400.3601.0802.4313.6705.1540.3701.1002.4503.6905.180平均值0.3451.0282.3883.5855.072标准偏差0.01660.04670.03970.06870.06957山东恒邦0.340.932.333.685.030.340.932.353.695.040.340.942.363.695.050.340.942.363.695.080.350.952.373.715.100.350.952.373.785.130.350.962.383.785.13平均值0.340.942.353.725.08标准偏差0.005340.01110.01630.04390.04168桂阳银星0.330.932.313.694.870.340.942.323.734.910.350.962.323.754.950.350.972.353.824.960.360.972.393.864.960.370.982.43.94.990.411.012.433.95.03平均值0.350.972.363・814.95标准偏差0.02610.02640.04690.08480.05199长沙矿冶0.3410.9772.3493.8125.1390.3490.9882.3863.8185.1430.3510.9902.4023.8225.1760.3520.9922.4133.8305.1800.3570.9982.4153.8425.2000.3581.0002.4193.8505.2030.3591.0012.4303.8635.2100.3601.0022.4313.8785.2160.3621.0062.4313.8925.2160.3631.0162.4333.8975.266

0.3661.0322.4503.9105.306平均值0.3561.0002.4143・8565.205标准偏差0.00730.0150.0280.0340.04910韶关质计0.3310.912.373.574.960.3340.932.463.594.980.3370.942.463.665.000.3450.972.483.675.060.3450.982.543.695.070.3461.012.543.745.070.3471.042.573.755.110.3561.062.583.755.120.3781.062.643.795.35平均值0.34660.98892.51563.6905.080标准偏差0.01400.05670.08090.07530.11611昆明西科0.330.982.463.824.810.330.992.473.834.820.330.992.483.864.830.331.012.513.874.860.341.012.513.904.870.341.012.523.904.900.351.032.523.904.910.351.042.543.914.930.371.052.543.934.970.371.052.553.934.980.381.062.553.984.98平均值0.351.022.513.894.90标准偏差0.0180.0280.0320.0460.06412紫金矿业0.340.952.393.795.030.340.962.393.815.100.340.972.403.835.120.350.982.403.865.140.350.982.413.915.150.350.992.423.925.21

0.351.002.443.935.250.351.002.453.935.270.351.002.453.945.30——2.45————2.46——平均值0.350.982.423.885.17标准偏差0.00500.0180.0270.0580.08913江铜集体0.370.872.13.534.720.380.882.193.534.750.380.892.213.564.760.390.892.213.64.840.40.912.233.644.850.410.922.243.644.860.420.932.243.654.890.420.952.313.684.920.430.962.363.714.96平均值0.400.912.233.624.84标准偏差0.0210.0310.0730.0650.0812.2单元平均值的计算由表1的数据，计算单元平均值如表2表2单元平均值实验室i水平j12345Pb10.3570.9972.473.875.0720.3551.0012.4213.8995.07030.3901.0532.4533.9115.041*40.3640.9952.43.845.0450.350.992.433.925.2060.3451.0282.3883.5855.07270.340.942.353.725.0880.35*0.972.36