微波消解-电感耦合等离子体原子发射光谱法测定华阳川多金属矿石中铌
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摘要
华阳川铀铌铅多金属矿石中的金属离子被硅晶核包裹,不易浸出,且铌元素易水解沉淀,这些均给测定样品中铌带来了难题。实验采用氢氟酸、硝酸、酒石酸混酸体系以微波消解法处理样品,以Nb 309.418nm为分析谱线,建立了电感耦合等离子体原子发射光谱法测定华阳川铀铌铅多金属矿石中铌的方法。确定微波消解的程序为:0~30min从室温达到180℃,30~60min从180℃到200℃,60~90min鼓风降温。实验表明:铌的质量浓度在0.10~2.00μg/mL范围内与其发射强度呈线性关系,线性相关系数为0.999 946,方法检出限为0.002%。因样品中主成分二氧化硅绝大部分在样品制备时已和氢氟酸反应生成四氟化硅逸出,而样品溶液中其他共存元素的质量浓度均不大于80μg/mL,故基体效应可忽略。采用实验方法测定铌质量分数为0.030 2%~0.189%的华阳川多金属矿石样品,6次平行测定结果的相对标准偏差(RSD)为3.1%~3.9%。考虑到铌钽元素通常伴生,元素性质十分相近,且矿性高度相似,所以实验采用有铌认定值的钽矿石标准物质为测定对象,按照实验方法进行测定,测得结果与认定值基本一致。采用国家标准方法 GB/T 17415.2—2010和实验方法进行方法对照,结果表明,二者对华阳川多金属矿石样品中铌的测定结果基本一致。
The metal ions in Huayangchuan uranium-niobium-lead polymetallic ore were packed by silicon crystal nucleus and hardly leached.Moreover,niobium was easily hydrolyzed and precipitated,which brought difficulty to the determination of niobium in sample.The sample was treated by microwave digestion with hydrofluoric acid-nitric acid-tartaric acid mixture system.Thus,a determination method of niobium in Huayangchuan uranium-niobium-lead polymetallic ore by inductively coupled plasma atomic emission spectrometry(ICP-AES)was established with Nb 309.418 nm as analytical line.The obtained microwave digestion procedures were listed as follows:the temperature was increased from room temperature to 180℃in range of 0-30 min,and from 180 ℃to 200 ℃in range of 30-60 min,and then cooling by blowing in range of 60-90 min.The experimental results showed that the mass concentration of niobium in range of 0.10-2.00μg/mL had good linearity to its corresponding emission intensity with correlation coefficient of 0.999 946.The detection limit was 0.002%.The major component in sample,i.e.,silicon dioxide,had been reacted with hydrofluoric acid during sample preparation and released in form of silicon tetrafluoride.Moreover,the mass concentrations of other coexisting elements in sample solution were less than 80μg/mL,so the matrix effect could be ignored.The experimental method was applied to the determination of Huayangchuan polymetallic ore samples with mass fraction of niobium in range of 0.030 2%~0.189%.The relative standard deviations(RSD,n=6)were between 3.1% and 3.9%.Since niobium and tantalum were usually associated,and their elemental properties and ore potentiality were highly similar,the certified reference material of tantalum ore with certified value of niobium was selected as the determination object.The results of experimental method were basically consistent with the certified values.The proposed method was compared with the national standard method of GB/T 17415.2-2010.The results indicated that the determination values of niobium in Huayangchuan polymetallic ore samples by the above two methods were consistent.
The metal ions in Huayangchuan uranium-niobium-lead polymetallic ore were packed by silicon crystal nucleus and hardly leached.Moreover,niobium was easily hydrolyzed and precipitated,which brought difficulty to the determination of niobium in sample.The sample was treated by microwave digestion with hydrofluoric acid-nitric acid-tartaric acid mixture system.Thus,a determination method of niobium in Huayangchuan uranium-niobium-lead polymetallic ore by inductively coupled plasma atomic emission spectrometry(ICP-AES)was established with Nb 309.418 nm as analytical line.The obtained microwave digestion procedures were listed as follows:the temperature was increased from room temperature to 180℃in range of 0-30 min,and from 180 ℃to 200 ℃in range of 30-60 min,and then cooling by blowing in range of 60-90 min.The experimental results showed that the mass concentration of niobium in range of 0.10-2.00μg/mL had good linearity to its corresponding emission intensity with correlation coefficient of 0.999 946.The detection limit was 0.002%.The major component in sample,i.e.,silicon dioxide,had been reacted with hydrofluoric acid during sample preparation and released in form of silicon tetrafluoride.Moreover,the mass concentrations of other coexisting elements in sample solution were less than 80μg/mL,so the matrix effect could be ignored.The experimental method was applied to the determination of Huayangchuan polymetallic ore samples with mass fraction of niobium in range of 0.030 2%~0.189%.The relative standard deviations(RSD,n=6)were between 3.1% and 3.9%.Since niobium and tantalum were usually associated,and their elemental properties and ore potentiality were highly similar,the certified reference material of tantalum ore with certified value of niobium was selected as the determination object.The results of experimental method were basically consistent with the certified values.The proposed method was compared with the national standard method of GB/T 17415.2-2010.The results indicated that the determination values of niobium in Huayangchuan polymetallic ore samples by the above two methods were consistent.
引文
[1]惠小朝,何升.陕西华阳川铀、铌、铅多金属矿石工艺矿物学研究[J].金属矿山,2016,51(5):85-90.HUI Xiao-chao,HE Sheng.Characteristics of process mineralogy of U-Nb-Pb polymetalltic ore in Huayangchuan Shanxi province[J].Metal Mine,2016,51(5):85-90.
[2]陈静.X射线荧光光谱法测定地质样品中铌和钽的探讨[J].冶金分析,2015,35(10):24-29.CHEN Jing.Discussion on the determination of niobium and tantalum in geological samples by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2015,35(10):24-29.
[3]于秀兰,张嘉月.安替吡啉偶氮分光光度法测定铌(V)[J].冶金分析,2013,33(12):67-69.YU Xiu-lan,ZHANG Jia-yue.Determination of niobium(V)by antipyrinylazo spectrophotometry[J].Metallurgical Analysis,2013,33(12):67-69.
[4]陶慧林,刘帅涛,黎舒怀,等.铌(V)-苯基荧光酮-亮绿SF体系共振光散射法测定痕量铌[J].冶金分析,2012,32(7):45-48.TAO Hui-lin,LIU Shuai-tao,LI Shu-huai,et al.Study on niobium(V)-phenylfluorone-brilliant green SF system determination of niobium by resonance light scattering[J].Metallurgical Analysis,2012,32(7),45-48.
[5]王芳,魏丽娜,陈鲲,等.电感耦合等离子体原子发射光谱法测定多金属矿石中的铌[J].理化检验:化学分册(Physical Testing and Chemical Analysis Part B:Chemical Analysis),2017,53(2):212-215.
[6]倪文山,张萍,姚明星,等.微波消解-电感耦合等离子体原子发射光谱法测定矿石样品中铌钽[J].冶金分析,2010,30(8):50-53.NI Wen-shan,ZHANG Ping,YAO Min-xing,et al.Inductively coupled plasma atomic emission spectrometric determination of niobium and tantalum in ore sample after microwave digestion[J].Metallurgical Analysis,2010,30(8):50-53.
[7]矿产资源综合利用手册编辑委员会.矿产资源综合利用手册[M].北京:科学出版社,2000:320-321.
[8]岩石矿物分析编委会.岩石矿物分析[M].4版.北京:地质出版社,2011:376-401.
[9]北京矿冶研究总院分析室.矿石及有色金属分析法[M].北京:科学出版社,1973:259.
[10]岩石矿物分析编写小组.岩石矿物分析[M].3版.北京:地质出版社,1991:625.
[2]陈静.X射线荧光光谱法测定地质样品中铌和钽的探讨[J].冶金分析,2015,35(10):24-29.CHEN Jing.Discussion on the determination of niobium and tantalum in geological samples by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2015,35(10):24-29.
[3]于秀兰,张嘉月.安替吡啉偶氮分光光度法测定铌(V)[J].冶金分析,2013,33(12):67-69.YU Xiu-lan,ZHANG Jia-yue.Determination of niobium(V)by antipyrinylazo spectrophotometry[J].Metallurgical Analysis,2013,33(12):67-69.
[4]陶慧林,刘帅涛,黎舒怀,等.铌(V)-苯基荧光酮-亮绿SF体系共振光散射法测定痕量铌[J].冶金分析,2012,32(7):45-48.TAO Hui-lin,LIU Shuai-tao,LI Shu-huai,et al.Study on niobium(V)-phenylfluorone-brilliant green SF system determination of niobium by resonance light scattering[J].Metallurgical Analysis,2012,32(7),45-48.
[5]王芳,魏丽娜,陈鲲,等.电感耦合等离子体原子发射光谱法测定多金属矿石中的铌[J].理化检验:化学分册(Physical Testing and Chemical Analysis Part B:Chemical Analysis),2017,53(2):212-215.
[6]倪文山,张萍,姚明星,等.微波消解-电感耦合等离子体原子发射光谱法测定矿石样品中铌钽[J].冶金分析,2010,30(8):50-53.NI Wen-shan,ZHANG Ping,YAO Min-xing,et al.Inductively coupled plasma atomic emission spectrometric determination of niobium and tantalum in ore sample after microwave digestion[J].Metallurgical Analysis,2010,30(8):50-53.
[7]矿产资源综合利用手册编辑委员会.矿产资源综合利用手册[M].北京:科学出版社,2000:320-321.
[8]岩石矿物分析编委会.岩石矿物分析[M].4版.北京:地质出版社,2011:376-401.
[9]北京矿冶研究总院分析室.矿石及有色金属分析法[M].北京:科学出版社,1973:259.
[10]岩石矿物分析编写小组.岩石矿物分析[M].3版.北京:地质出版社,1991:625.