鉛冶煉分銀渣化學分析方法

鉛冶煉分銀渣化學分析方法第2部分：鉛含量的測定火焰原子吸收光譜法和Na2EDTA滴定法2編制說明任務來源根據工業(yè)和信息化部工信廳科[2017]40號)的文件精神，以及全國有色金屬標準化技術委員會“關于印發(fā)《鉛冶煉分銀渣化學分析方法》等18項標準任務落實會會議的通知”(有色標委[2017]62號)及相關會議紀要的文件精神，《鉛冶煉分銀渣化學分析方法第2部分：鉛含量的測定火焰原子吸收光譜法和Na2EDTA滴定法》由深圳市中金嶺南有色金屬股份有限公司起草，北礦檢測技術有限公司、河南豫光金鉛股份有限公司、株洲冶煉集團股份有限公司、桂林礦產地質研究院有限公司、貴研鉑業(yè)股份有限公司、山東恒邦冶煉股份有限公司、湖南桂陽銀星有色冶煉有限公司、長沙礦冶研究院有限責任公司、廣東韶關市質量計量監(jiān)督檢測所、昆明西科工貿有限公司、福建紫金礦冶測試技術有限公司、江西銅業(yè)股份有限公司等單位協(xié)助起草。項目計劃編號：(2017-0181T-YS)，完成年限2019年。工作過程2017年8月23日?27日全國有色金屬標準化技術委員會在泰安市組織召開了《鉛冶煉分銀渣化學分析方法》等18項標準任務落實會議，會議確定了標準制定的起草單位和參與驗證單位，落實了標準計劃項目的進度安排和分工。準編寫原則和編寫格式本標準是根據GB/T1.1-2009《標準化工作導則第1部分：標準的結構和編寫規(guī)則》和GB/T20001.4-2001《標準編寫規(guī)則第4部分：化學分析方法》的要求進行編寫的。標準編寫的目的和意義鉛冶煉分銀渣是鉛陽極泥在提取主要成分如鉛和貴金屬金、銀后所留下的殘渣。目前國內許多鉛冶煉行業(yè)均產出這類物料。鉛冶煉分銀渣含有鉛、銅、銻、鉍、金、銀等貴金屬，是一種品位相當高的二次資源。礦產資源日趨枯竭，以鉛冶煉分銀渣作為二次資源，最大化地提取鉛、銅、銻、鉍等有價金屬，富集回收金銀等貴金屬，實現資源循環(huán)利用及有價金屬材料生產，已成為有色金屬再生循環(huán)領域研究中的熱點，具有很高的經濟和社會價值。目前國內鉛陽極泥處理由于工藝、設備的不同或者原料中成分含量不同，產出鉛冶煉分銀渣的物理形態(tài)、各元素品位差別較大。經過充分調研，鉛冶煉分銀渣中鉛含量的范圍較寬，為0.3%~40%，因此鉛冶煉分銀渣中鉛含量測定分為：方法1火焰原子吸收光譜法(0.30%~5.00%)和方法2Na2EDTA滴定法(5.00%~40.00%)。經標準查新，目前國內尚無統(tǒng)一的鉛冶煉分銀渣化學分析方法，導致貿易時常有爭議。因此制定相應的鉛冶煉分銀渣化學分析方法，對促進生產和指導貿易具有重要的意義。國內外有關工作情況目前國內外測定低含量鉛的檢測方法主要是原子吸收法、ICP法，考慮到原子吸收儀應用比較普遍，選擇性較好，因此本法對低含量的鉛選用火焰原子吸收光譜法，就樣品消解方式及共存元素干擾情況進行了深入研究，最終確定了分析步驟。而高含量鉛的測定方法主要是EDTA滴定法，如國家標準GB/T8152-2006《鉛精礦化學分析方法》、GB/T3884-2012《銅精礦化學分析方法》，行業(yè)標準YS/T461-2013《混合鉛鋅精礦化學分析方法》、YS/T745-2010《銅陽極泥化學分析方法》等，均采用了EDTA滴定法。但鉛冶煉分銀渣與其他礦樣比，成分更加復雜，各元素含量范圍更加廣泛，分析要求更加高，如樣品消解方式、共存元素干擾情況，都不能等同采用。為此，本試驗就樣品分解方式及共存元素干擾情況進行了深入研究，最終確定了EDTA滴定法測定高含量鉛分析步驟。標準適用范圍本部分適用于鉛冶煉分銀渣中鉛含量的測定。測定范圍:0.30%?40.00%。標準制訂的主要內容與依據見《試驗報告》。協(xié)同試驗樣品的準備由中金嶺南韶關冶煉廠、山東恒邦冶煉股份有限公司、河南豫光金鉛股份有限公司等單位提供了10個水平的樣品。精密度試驗在精密度試驗方面，13個實驗室（見表1）對10個水平的樣品進行試驗，根據國家標準GB/T6379.2-2004確定標準測量方法的重復性和再現性的基本方法（ISO5725-2：1994，IDT）的規(guī)定，對收到的全部數據進行了統(tǒng)計分析。原始數據及統(tǒng)計結果見附件2。表1協(xié)同試驗的實驗室編號編號實驗室1深圳市中金嶺南有色金屬股份有限公司2北礦檢測技術有限公司3河南豫光金鉛股份有限公司4株洲冶煉集團股份有限公司5桂林礦產地質研究院有限公司6貴研鉑業(yè)股份有限公司7山東恒邦冶煉股份有限公司8湖南桂陽銀星有色冶煉有限公司9長沙礦冶研究院有限責任公司10廣東韶關市質量計量監(jiān)督檢測所11昆明西科工貿有限公司12福建紫金礦冶測試技術有限公司13江西銅業(yè)股份有限公司重復性在重復性條件下獲得的兩次獨立測試結果的測定值，在以下給出的平均值范圍內，這兩個測試結果的絕對差值不超過重復性限（r）,超過重復性限（r）的情況不超過5%，重復性限（r）按表2數據采用線性內插法求得：表2重復性限wPb/%0.3570.9972.473.875.07r/%0.0540.0750.130.170.21表3重復性限WPb/%5.9113.7522.6931.3237.61r/%0.190.250.300.340.388.4再現性在再現性條件下獲得的兩次獨立測試結果的測定值，在以下給出的平均值范圍內，這兩個測試結果的絕對差值不超過再現性限（R）,超過再現性限（R）的情況不超過5%，再現性限（R）按表4數據采用線性內插法求得：表4再現性限wpb%0.3570.9972.473.875.07r/%0.0850.130.230.320.41表5再現性限w%Db/5.9113.7522.6931.3237.61r/%0.290.320.350.400.449標準征求意見稿意見匯總與處理在協(xié)同試驗和標準預審過程中，征求的意見以及對意見的分析處理，詳見《意見匯總表》。標準水平分析本標準在技術內容、文本結構上與相應的國內標準等同，具有國內先進水平。與有關的現行法律、法規(guī)和強制性國家標準的關系本標準符合相關現行法律、法規(guī)和強制性國家標準，沒有沖突。重大分歧意見的處理經過和依據無。貫徹標準的要求和措施建議建議頒布本標準為推薦性行業(yè)標準，供相關組織參考采用。廢止現行有關標準的建議無其他應予說明的事項本標準遵守下列基礎標準：GB/T1.1標準化工作導則第1部分：標準的結構和編寫規(guī)則GB/T20001標準編寫規(guī)則第4部分：化學分析方法GB/T17433冶金產品化學分析基礎術語GB/T11792測試方法的精密度在重現性或再現性條件下所得測試結果可接受的檢查和最終測試結果的確定。深圳市中金嶺南有色金屬股份有限公司2018年12月22日附件2：鉛冶煉分銀渣化學分析方法第2部分：鉛含量的測定方法2Na2EDTA滴定法2精密度試驗數據處理1背景為了確定《鉛冶煉分銀渣化學分析方法第2部分：鉛含量的測定Na^DTA滴定法》中鉛含量測定方法的重復性與再現性，13個實驗室對5個水平的鉛冶煉分銀渣樣品進行了協(xié)同試驗。根據國家標準GB/T6379.2-2004確定標準測量方法的重復性和再現性的基本方法(ISO5725-2：1994,IDT)的規(guī)定，對收到的全部數據進行了統(tǒng)計分析。2各實驗室實驗數據2.1各實驗室提供的鉛含量實驗數據表1各實驗室提供的鉛含量實驗數據(%)實驗室水平1水平2水平3水平4水平51中金嶺南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標準偏差0.050000.096520.13800.10340.11802北礦檢測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標準偏差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標準偏差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標準偏差0.064250.064920.15290.13570.084665桂林地礦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標準偏差0?040.070.090.110.086貴研鉑業(yè)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標準偏差0.05900.07020.06980.09670.08347山東恒邦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標準偏差0.0333810.0567790.0727360.0411730.1359458桂陽銀星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標準偏差0.078250.10260.10790.12120.15939長沙礦冶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標準偏差0.0540.0980.0990.0980.07810韶關質計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標準偏差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標準偏差0.0930.0520.170.180.1512紫金礦業(yè)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標準偏差0.0920.1170.0990.1430.09513江銅集團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標準偏差0.080.130.170.210.242.2單元平均值的計算由表1的數據，計算單元平均值如表2表2單元平均值實驗室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單元離散度的計算表3單元標準差實驗室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離群值的檢查2.4.1柯克倫檢驗對n=6，p=13，柯克倫檢驗5%臨界值為0.243，1%臨界值為0.291（柯克倫檢驗沒有n=7時的臨界值可查詢，先按n=6時的臨界值進行離群值的排除。）對水平1,昆明西科的s最大，檢驗統(tǒng)計量值=0.093；對水平2，江銅集團的s最大，檢驗統(tǒng)計量值=0.13；對水平3，江銅集團的s最大，檢驗統(tǒng)計量值=0.1682；對水平4，江銅集團的s最大，檢驗統(tǒng)計量值=0.21；對水平5，江銅集團的s最大，檢驗統(tǒng)計量值=0.24；柯克倫檢驗顯示，對歧離值在表2中用“*”標出。2.4.2格拉布斯檢驗

表4格拉布斯檢驗統(tǒng)計量水平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均值的標準差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臨界值實驗室數p=13時，G臨界值：上1%點時為2.699；上5%點時為2.462。從格拉布斯檢驗結果來看，22.31為歧離值和舍棄值，其他結果均在5%范圍內，。2.5S、S、R與r的計算rR表5精密度計算實驗室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總平均值5.90613.74922.68831.32037.608r0.19000.24510.30000.33300.3356R0.29010.30990.33170.45680.4416鉛冶煉分銀渣化學分析方法第2部分：鉛量的測定方法1火焰原子吸收光譜法精密度試驗數據處理1背景為了確定《鉛冶煉分銀渣化學分析方法第2部分：鉛量的測定火焰原子吸收光譜法》中鉛含量測定方法的重復性與再現性，13個實驗室對5個水平的鉛冶煉分銀渣樣品進行了協(xié)同試驗。根據國家標準GB/T6379.2-2004確定標準測量方法的重復性和再現性的基本方法(ISO5725-2：1994,IDT)的規(guī)定，對收到的全部數據進行了統(tǒng)計分析。2各實驗室實驗數據2.1各實驗室提供的鉛含量實驗數據表1各實驗室提供的鉛含量實驗數據(%)實驗室水平1水平2水平3水平4水平51中金嶺南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標準偏差0.005450.02380.01590.05590.06362北礦檢測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標準偏差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標準偏差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標準偏差0.01070.02810.04310.04130.03385桂林地礦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標準偏差0.0060.0110.0250.0280.0226貴研鉑業(yè)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標準偏差0.01660.04670.03970.06870.06957山東恒邦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標準偏差0.005340.01110.01630.04390.04168桂陽銀星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標準偏差0.02610.02640.04690.08480.05199長沙礦冶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標準偏差0.00730.0150.0280.0340.04910韶關質計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標準偏差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標準偏差0.0180.0280.0320.0460.06412紫金礦業(yè)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標準偏差0.00500.0180.0270.0580.08913江銅集體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標準偏差0.0210.0310.0730.0650.0812.2單元平均值的計算由表1的數據，計算單元平均值如表2表2單元平均值實驗室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