高温水解-离子色谱法测定有色金属矿中氟和氯
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摘要
采用自动化高温水解装置处理样品,建立了高温水解离子色谱法测定有色金属矿中氟和氯含量的方法。对比了水蒸气蒸馏法和高温水解法的样品前处理效果,确定了高温水解法为样品前处理方法。考察了高温水解过程催化剂的使用情况,并采用高温灼烧的方法驱除了催化剂中的氟和氯,消除其对测定结果的影响。实验方法在测定范围内氟和氯的含量与峰面积呈良好的线性关系,相关系数R2均为0.999 9;方法检出限为0.11ng/mL(氟)和0.24ng/mL(氯)。按照实验方法对有氟含量认定值的铜精矿及没有氟和氯认定值的多金属矿有证标准物质进行测定,统计测定结果的相对标准偏差(RSD)均小于5%(n=11);铜精矿中氟的测定值与认定值一致,多金属矿中氟和氯的加标回收率为97.0%~100.0%。对来自不同国家的铅精矿、铜精矿和锌精矿进行检测,氟、氯的测定结果分别与离子选择电极法和电位滴定法的测定结果基本一致。实验方法与离子选择电极法相比,检出限由g/mL降低至ng/mL;采用的高温水解法与现有的水蒸气蒸馏法相比,待测组分提取率更高,解决了水蒸气蒸馏法不能有效提取硫含量较高的铜精矿、铅精矿和锌精矿等样品中氟和氯的问题。
The sample was treated in automatic pyrohydrolysis device.The determination method of fluoride and chloride contents in nonferrous metal ore by pyrohydrolysis-ion chromatography was established.The pretreatment effect of sample by steam distillation and pyrohydrolysis was compared.The sample pretreatment method of pyrohydrolysis was selected in this study.The use condition of catalyst in pyrohydrolysis process was investigated.The fluoride and chloride in catalyst was removed by pyrohydrolysis to eliminate their influence on determination results.The content of fluoride and chloride in determination range had good linear relationship to the peak area.The correlation coefficients were both 0.999 9.The detection limit of fluoride and chloride in this method was 0.11 ng/mL and 0.24 ng/mL,respectively.The copper concentrate with certified value of fluoride as well as certified reference materials of polymetallic ore without certified values of fluoride and chloride were determined according to the experimental method.The relative standard deviations(RSD,n=11)were all less than 5%.The found result of fluoride in copper concentrate was consistent with the certified value.The spiked recoveries of fluoride and chloride in polymetallic ore were between 97.0%and 100.0%.The lead concentrate,copper concentrate and zinc concentrate samples from different countries were determined,and the found results of fluoride and chloride were basically consistent with those obtained by ion selective electrode method and potentiometric titration method,respectively.The experimental method was compared with the ion selective electrode method,and the detection limit was reduced from g/mLto ng/mL.Compared to the existing steam distillation method,the pyrohydrolysis process improved the extraction rate of testing components.It solved the problem that the fluoride and chloride in copper concentrate,lead concentrate and zinc concentrate samples with high sulfur content could not be extracted by steam distillation method.
The sample was treated in automatic pyrohydrolysis device.The determination method of fluoride and chloride contents in nonferrous metal ore by pyrohydrolysis-ion chromatography was established.The pretreatment effect of sample by steam distillation and pyrohydrolysis was compared.The sample pretreatment method of pyrohydrolysis was selected in this study.The use condition of catalyst in pyrohydrolysis process was investigated.The fluoride and chloride in catalyst was removed by pyrohydrolysis to eliminate their influence on determination results.The content of fluoride and chloride in determination range had good linear relationship to the peak area.The correlation coefficients were both 0.999 9.The detection limit of fluoride and chloride in this method was 0.11 ng/mL and 0.24 ng/mL,respectively.The copper concentrate with certified value of fluoride as well as certified reference materials of polymetallic ore without certified values of fluoride and chloride were determined according to the experimental method.The relative standard deviations(RSD,n=11)were all less than 5%.The found result of fluoride in copper concentrate was consistent with the certified value.The spiked recoveries of fluoride and chloride in polymetallic ore were between 97.0%and 100.0%.The lead concentrate,copper concentrate and zinc concentrate samples from different countries were determined,and the found results of fluoride and chloride were basically consistent with those obtained by ion selective electrode method and potentiometric titration method,respectively.The experimental method was compared with the ion selective electrode method,and the detection limit was reduced from g/mLto ng/mL.Compared to the existing steam distillation method,the pyrohydrolysis process improved the extraction rate of testing components.It solved the problem that the fluoride and chloride in copper concentrate,lead concentrate and zinc concentrate samples with high sulfur content could not be extracted by steam distillation method.
引文
[1]中华人民共和国国家质量监督检验检疫总局.SN/T2261—2009铁矿中水溶性氯化物的测定电位滴定法[S].北京:中国标准出版社,2009.
[2]史静,孟萌萌,路遥,等.电位滴定法测定铜精矿中氯[J].冶金分析,2016,36(10):52-56.SHI Jing,MENG Meng-meng,LU Yao,et al.Determination of chloride in copper concentrate by potentiometric titration[J].Metallurgical Analysis,2016,36(10):52-56.
[3]胡晓静,卢琪,姜莉,等.基体分离-电位滴定法测定高硫金属矿中的微量氯[J].岩矿测试,2010,29(1):80-82.HU Xiao-jing,LU Qi,JIANG Li,et al.Determination of micro-amount of chloride in high sulfur-metallic ores by matrix separation-potentiometric titration[J].Rock and Mineral Analysis,2010,29(1):80-82.
[4]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 6730.64—2007铁矿石水溶性氯化物含量的测定离子选择电极法[S].北京:中国标准出版社,2007.
[5]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 1819.15—2006锡精矿化学分析方法氟量的测定离子选择电极法[S].北京:中国标准出版社,2006.
[6]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 3884.5—2012铜精矿化学分析方法第5部分:氟量的测定离子选择电极法[S].北京:中国标准出版社,2012.
[7]崔海容,陈建华,谢建峰,等.水蒸气蒸馏-离子色谱法测定磷矿石中氟化物和氯化物[J].分析测试学报,2005,24(6):92-95.CUI Hai-rong,CHEN Jian-hua,XIE Jian-feng,et al.Simultaneous determination of fluoride and chloride in phosphorus rock by steam distillation-ion chromatography[J].Journal of Instrumental Analysis,2005,24(6):92-95.
[8]阳兆鸿,李华昌,于力,等.水蒸气蒸馏-离子色谱法测定硫化矿石中氟和氯[J].冶金分析,2015,35(4):34-38.YANG Zhao-hong,LI Hua-chang,YU Li,et al.Determination of fluoride and chloride in sulfide ores by steam distillation ion chromatography[J].Metallurgical Analysis,2015,35(4):34-38.
[9]李颖娜,徐志彬,张志伟.高温水解-离子色谱法测定铁矿石中氟和氯[J].冶金分析,2016,36(6):23-28.LI Ying-na,XU Zhi-bin,ZHANG Zhi-wei.Determination of fluorine and chlorine in iron ores by pyrohydrolysis-ion chromatography[J].Metallurgical Analysis,2016,36(6):23-28.
[10]胡德新,侯书建,孟凯,等.水蒸气蒸馏-离子色谱法测定锰矿石中氟和氯[J].冶金分析,2012,32(9):64-67.HU De-xin,HOU Shu-jian,MENG Kai,et al.Determination of fluorine and chlorine in manganese ore by steam distillation-ion chromatography[J].Metallurgica1Analysis,2012,32(9):64-67.
[11]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 6730.69—2010铁矿石氟和氯含量的测定离子色谱法[S].北京:中国标准出版社,2010.
[12]窦怀智,陆彩霞,侯晋.离子色谱法测定镍矿中氟和氯[J].冶金分析,2012,32(8):59-62.DOU Huai-zhi,LU Cai-xia,HOU Jin.Determination of fluoride and chloride in nickel ore by ion chromatography[J].Metallurgical Analysis,2012,32(8):59-62.
[13]刘建权,赵峰华,刘璟,等.氧弹燃烧-离子色谱法测定煤中氯含量[J].分析化学,2009,37(8):1152-1156.LIU Jian-quan,ZHAO Feng-hua,LIU Jing,et al.Determination of chlorine in coal by oxygen bomb-ion chromatography[J].Chinese Journal of Analytical Chemistry,2009,37(8):1152-1156.
[14]彭炳先,吴代赦.高温热水解离子色谱法快速同时测定粘土中的卤素[J].分析化学,2013,41(10):1499-1504.PENG Bing-xian,WU Dai-he.Simultaneous determination of halogens in clay using pyrohydrolysis combined with ion chromatography[J].Chinese Journal of Analytical Chemistry,2013,41(10):1499-1504.
[15]Warf J C,Cline W D,Tevebaugh R D.Pyrohydrolysis in determination of fluoride and other halides[J].Anal.Chem.,1954,26(2):342-346.
[2]史静,孟萌萌,路遥,等.电位滴定法测定铜精矿中氯[J].冶金分析,2016,36(10):52-56.SHI Jing,MENG Meng-meng,LU Yao,et al.Determination of chloride in copper concentrate by potentiometric titration[J].Metallurgical Analysis,2016,36(10):52-56.
[3]胡晓静,卢琪,姜莉,等.基体分离-电位滴定法测定高硫金属矿中的微量氯[J].岩矿测试,2010,29(1):80-82.HU Xiao-jing,LU Qi,JIANG Li,et al.Determination of micro-amount of chloride in high sulfur-metallic ores by matrix separation-potentiometric titration[J].Rock and Mineral Analysis,2010,29(1):80-82.
[4]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 6730.64—2007铁矿石水溶性氯化物含量的测定离子选择电极法[S].北京:中国标准出版社,2007.
[5]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 1819.15—2006锡精矿化学分析方法氟量的测定离子选择电极法[S].北京:中国标准出版社,2006.
[6]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 3884.5—2012铜精矿化学分析方法第5部分:氟量的测定离子选择电极法[S].北京:中国标准出版社,2012.
[7]崔海容,陈建华,谢建峰,等.水蒸气蒸馏-离子色谱法测定磷矿石中氟化物和氯化物[J].分析测试学报,2005,24(6):92-95.CUI Hai-rong,CHEN Jian-hua,XIE Jian-feng,et al.Simultaneous determination of fluoride and chloride in phosphorus rock by steam distillation-ion chromatography[J].Journal of Instrumental Analysis,2005,24(6):92-95.
[8]阳兆鸿,李华昌,于力,等.水蒸气蒸馏-离子色谱法测定硫化矿石中氟和氯[J].冶金分析,2015,35(4):34-38.YANG Zhao-hong,LI Hua-chang,YU Li,et al.Determination of fluoride and chloride in sulfide ores by steam distillation ion chromatography[J].Metallurgical Analysis,2015,35(4):34-38.
[9]李颖娜,徐志彬,张志伟.高温水解-离子色谱法测定铁矿石中氟和氯[J].冶金分析,2016,36(6):23-28.LI Ying-na,XU Zhi-bin,ZHANG Zhi-wei.Determination of fluorine and chlorine in iron ores by pyrohydrolysis-ion chromatography[J].Metallurgical Analysis,2016,36(6):23-28.
[10]胡德新,侯书建,孟凯,等.水蒸气蒸馏-离子色谱法测定锰矿石中氟和氯[J].冶金分析,2012,32(9):64-67.HU De-xin,HOU Shu-jian,MENG Kai,et al.Determination of fluorine and chlorine in manganese ore by steam distillation-ion chromatography[J].Metallurgica1Analysis,2012,32(9):64-67.
[11]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 6730.69—2010铁矿石氟和氯含量的测定离子色谱法[S].北京:中国标准出版社,2010.
[12]窦怀智,陆彩霞,侯晋.离子色谱法测定镍矿中氟和氯[J].冶金分析,2012,32(8):59-62.DOU Huai-zhi,LU Cai-xia,HOU Jin.Determination of fluoride and chloride in nickel ore by ion chromatography[J].Metallurgical Analysis,2012,32(8):59-62.
[13]刘建权,赵峰华,刘璟,等.氧弹燃烧-离子色谱法测定煤中氯含量[J].分析化学,2009,37(8):1152-1156.LIU Jian-quan,ZHAO Feng-hua,LIU Jing,et al.Determination of chlorine in coal by oxygen bomb-ion chromatography[J].Chinese Journal of Analytical Chemistry,2009,37(8):1152-1156.
[14]彭炳先,吴代赦.高温热水解离子色谱法快速同时测定粘土中的卤素[J].分析化学,2013,41(10):1499-1504.PENG Bing-xian,WU Dai-he.Simultaneous determination of halogens in clay using pyrohydrolysis combined with ion chromatography[J].Chinese Journal of Analytical Chemistry,2013,41(10):1499-1504.
[15]Warf J C,Cline W D,Tevebaugh R D.Pyrohydrolysis in determination of fluoride and other halides[J].Anal.Chem.,1954,26(2):342-346.