熔融制样-X射线荧光光谱法测定铝矿中15种组分
|
摘要
铝矿中主、次及微量成分含量对生产工艺及产品质量具有重要影响,传统的检测方法操作过程繁琐,分析周期长,已难以满足检测需求。实验采用熔融法制样,样品经硝酸锂预氧化后,选择质量比为12∶22的Li2B4O7和LiBO2混合试剂作为熔剂,熔剂与样品比例为10∶1,以NH4I为脱模剂,在1 050℃下熔融10min制备熔片。采用有证标准物质及其与高纯Al2O3的人工合成样品为校准样品,对谱线重叠情况进行了考察,并通过变化的理论α系数法校正元素间的吸收增强效应,建立了铝矿中Al2O3、SiO2、Fe2O3、CaO、MgO、P2O5、Na2O、K2O、TiO2、MnO、Ga2O3、ZrO2、V2O5、Cr2O3及S等15种组分的X射线荧光光谱法(XRF)。精密度实验表明,各组分测定结果的相对标准偏差(RSD,n=9)在0.18%～12%之间;对标准样品进行正确度考察,测定值与认定值一致。方法可同时满足铝土矿、叶蜡石、莫来石、矾土、高岭土等多种铝矿的测定。
The contents of major,minor and micro components in aluminum ores have important influence on the production process and product quality.However,traditional analysis method cannot satisfy the detection requirements due to the tedious operation and long determination period.The sample was prepared by the fusion method.The samples were pre-oxidized by lithium nitrate for sample preparation under the following conditions:Li2 B4 O7-LiBO2 mixture[m(Li2 B4 O7)∶m(LiBO2)=12∶22]was selected as flux;the ratio between flux and sample was 10∶1;NH4 I was employed as the releasing agent;the sample was fused at 1 050℃for 10 min.The certified reference materials and their mixture with high purity aluminum oxide was used as calibrations sample.The spectral overlapping was investigated.The absorption enhancement effect among elements was corrected by variable theoreticalαinfluence coefficient method.The simultaneous determination method of fifteen elements in aluminum ores(including Al2 O3,SiO2,Fe2 O3,CaO,MgO,P2 O5,Na2 O,K2 O,TiO2,MnO,Ga2 O3,ZrO2,V2 O5,Cr2 O3 and S)by X-ray fluorescence spectrometry(XRF)was developed.The precision test showed that relative standard deviations(RSD,n=9)were between 0.18%and 12%.The accuracy test was conducted using standard samples,and the found results were consistent with the certified values.The proposed method could simultaneously meet the determination requirements of various aluminum ores such as bauxite,pyrophyllite,mullite,aluminite and kaolin.
The contents of major,minor and micro components in aluminum ores have important influence on the production process and product quality.However,traditional analysis method cannot satisfy the detection requirements due to the tedious operation and long determination period.The sample was prepared by the fusion method.The samples were pre-oxidized by lithium nitrate for sample preparation under the following conditions:Li2 B4 O7-LiBO2 mixture[m(Li2 B4 O7)∶m(LiBO2)=12∶22]was selected as flux;the ratio between flux and sample was 10∶1;NH4 I was employed as the releasing agent;the sample was fused at 1 050℃for 10 min.The certified reference materials and their mixture with high purity aluminum oxide was used as calibrations sample.The spectral overlapping was investigated.The absorption enhancement effect among elements was corrected by variable theoreticalαinfluence coefficient method.The simultaneous determination method of fifteen elements in aluminum ores(including Al2 O3,SiO2,Fe2 O3,CaO,MgO,P2 O5,Na2 O,K2 O,TiO2,MnO,Ga2 O3,ZrO2,V2 O5,Cr2 O3 and S)by X-ray fluorescence spectrometry(XRF)was developed.The precision test showed that relative standard deviations(RSD,n=9)were between 0.18%and 12%.The accuracy test was conducted using standard samples,and the found results were consistent with the certified values.The proposed method could simultaneously meet the determination requirements of various aluminum ores such as bauxite,pyrophyllite,mullite,aluminite and kaolin.
引文
[1]孟亚东,孙洛新,傅晓强,等.氟盐取代-EDTA滴定法测定铝土矿中铝量[J].岩矿测试,2008,27(6):475-476.MENG Ya-dong,SUN Luo-xin,FU Xiao-qiang,et al.Determination of aluminum in bauxites by fluorate replacement-EDTA titrimetry[J].Rock and Mineral Analysis,2008,27(6):475-476.
[2]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 14563—2008高岭土及其试验方法[S].北京:中国标准出版社,2008.
[3]王志远.刚玉粉、高岭土、莫来石中铝、硅的测定[J].中国无机分析化学,2011,1(3):35-38.WANG Zhi-yuan.Quantitative determination of alumium and silicon elements in corundum,Kaolin clay and Mullite[J].Chinese Journal of Inorganic Analytical Chemistry,2011,1(3):35-38.
[4]洪达峰.硅钼蓝分光光度法测定高岭土中二氧化硅[J].冶金分析,2017,37(10):59-64.HONG Da-feng.Determination of silicon dioxide in kaolin by silicon molybdenum blue spectrophotometry[J].Metallurgical Analysis,2017,37(10):59-64.
[5]朱鲜红,李德生,张晶华,等.乙酸丁酯萃取火焰原子吸收光谱法测定铝土矿中微量镓[J].冶金分析,2004,24(6):63-65.ZHU Xian-hong,LI De-sheng,ZHANG Jing-hua,et al.Determination of micro gallium in bauxite by butyl acetate extraction and flame atomic absorption spectrometry[J].Metallurgical Analysis,2004,24(6):63-65.
[6]文加波,李克庆,向忠宝,等.电感耦合等离子体原子发射光谱法同时测定铝土矿中40种组分[J].冶金分析,2011,31(12):43-49.WEN Jia-bo,LI Ke-qing,XIANG Zhong-bao,et al.Simultaneous determination of forty elements in bauxite by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2011,31(12):43-49.
[7]甘婷婷,赵南京,殷高方,等.水体中铬、镉和铅的X射线荧光光谱同时快速分析方法研究[J].光谱学与光谱分析,2017,37(6):1912-1918.GAN Ting-ting,ZHAO Nan-jing,YIN Gao-fang,et al.Study on simultaneous and rapid analysis method of Xray fluorescence spectrum for determination of chromium,cadmium and lead in water[J].Spectroscopy and Spectral Analysis,2017,37(6):1912-1918.
[8]仵利萍,曾英,刘卫,等.熔融制样-X射线荧光光谱法测定高钛渣主次量元素[J].矿产综合利用,2017(1):81-84.WU Li-ping,ZENG Ying,LIU Wei,et al.Determination of major and minor elements in high titanium slag by X-ray fluorescence spectrometry with samples of smelting process[J].Multipurpose Utilization of Mineral Resources,2017(1):81-84.
[9]朱俐,王瑾,尹利辉.X射线荧光光谱法快速检测化妆品中的15种重金属[J].分析试验室,2017,36(9):1084-1087.ZHU Li,WANG Jin,YIN Li-hui.Rapid screening of 15heavy metals in cosmetics by X-ray fluorescence spectrometry[J].Chinese Journal of Analysis Laboratory,2017,36(9):1084-1087.
[10]Krishna A K,Khanna T C,Mohan K R.Rapid quantitative determination of major and trace elements in silicate rocks and soils employing fused glass discs using wavelength dispersive X-ray fluorescence spectrometry[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2016,122:165-171.
[11]邓赛文,梁国立,方明渭,等.X射线荧光光谱快速分析铝土矿的方法研究[J].岩矿测试,2001,20(4):305-308.DENG Sai-wen,LIANG Guo-li,FANG Ming-wei,et al.A rapid in site method for bauxite analysis by XRF[J].Rock and Mineral Analysis,2001,20(4):305-308.
[12]中华人民共和国工业和信息化部发布.YS/T 575.23—2009铝土矿石化学分析方法第23部分:X射线荧光光谱法测定元素含量[S].北京:中国标准出版社,2010.
[13]乌静,戴学谦,刘伟,等.X射线荧光光谱法测定铁矾土中二氧化硅、氧化铝和氧化铁[J].冶金分析,2009,29(7):44-48.WU Jing,DAI Xue-qian,LIU Wei,et al.Determination of silicon dioxide,aluminum oxide and ferric oxide in laterite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2009,29(7):44-48.
[14]郭寿兴,吴玉庆.X射线荧光光谱法测定叶腊石中的铝铁钾钠[J].岩矿测试,1993,12(4):290-292.GUO Shou-xing,WU Yu-qing.Determination of Al,Fe,K and Na in pyrophyllite by XRF[J].Rock and Mineral Analysis,1993,12(4):290-292.
[15]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion samplepreparationinX-rayfluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.
[16]Fernand C,Jimmy S B.硼酸盐熔融的物理与化学[M].卓尚军,译.上海:华东理工大学出版社,2006:23.
[2]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 14563—2008高岭土及其试验方法[S].北京:中国标准出版社,2008.
[3]王志远.刚玉粉、高岭土、莫来石中铝、硅的测定[J].中国无机分析化学,2011,1(3):35-38.WANG Zhi-yuan.Quantitative determination of alumium and silicon elements in corundum,Kaolin clay and Mullite[J].Chinese Journal of Inorganic Analytical Chemistry,2011,1(3):35-38.
[4]洪达峰.硅钼蓝分光光度法测定高岭土中二氧化硅[J].冶金分析,2017,37(10):59-64.HONG Da-feng.Determination of silicon dioxide in kaolin by silicon molybdenum blue spectrophotometry[J].Metallurgical Analysis,2017,37(10):59-64.
[5]朱鲜红,李德生,张晶华,等.乙酸丁酯萃取火焰原子吸收光谱法测定铝土矿中微量镓[J].冶金分析,2004,24(6):63-65.ZHU Xian-hong,LI De-sheng,ZHANG Jing-hua,et al.Determination of micro gallium in bauxite by butyl acetate extraction and flame atomic absorption spectrometry[J].Metallurgical Analysis,2004,24(6):63-65.
[6]文加波,李克庆,向忠宝,等.电感耦合等离子体原子发射光谱法同时测定铝土矿中40种组分[J].冶金分析,2011,31(12):43-49.WEN Jia-bo,LI Ke-qing,XIANG Zhong-bao,et al.Simultaneous determination of forty elements in bauxite by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2011,31(12):43-49.
[7]甘婷婷,赵南京,殷高方,等.水体中铬、镉和铅的X射线荧光光谱同时快速分析方法研究[J].光谱学与光谱分析,2017,37(6):1912-1918.GAN Ting-ting,ZHAO Nan-jing,YIN Gao-fang,et al.Study on simultaneous and rapid analysis method of Xray fluorescence spectrum for determination of chromium,cadmium and lead in water[J].Spectroscopy and Spectral Analysis,2017,37(6):1912-1918.
[8]仵利萍,曾英,刘卫,等.熔融制样-X射线荧光光谱法测定高钛渣主次量元素[J].矿产综合利用,2017(1):81-84.WU Li-ping,ZENG Ying,LIU Wei,et al.Determination of major and minor elements in high titanium slag by X-ray fluorescence spectrometry with samples of smelting process[J].Multipurpose Utilization of Mineral Resources,2017(1):81-84.
[9]朱俐,王瑾,尹利辉.X射线荧光光谱法快速检测化妆品中的15种重金属[J].分析试验室,2017,36(9):1084-1087.ZHU Li,WANG Jin,YIN Li-hui.Rapid screening of 15heavy metals in cosmetics by X-ray fluorescence spectrometry[J].Chinese Journal of Analysis Laboratory,2017,36(9):1084-1087.
[10]Krishna A K,Khanna T C,Mohan K R.Rapid quantitative determination of major and trace elements in silicate rocks and soils employing fused glass discs using wavelength dispersive X-ray fluorescence spectrometry[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2016,122:165-171.
[11]邓赛文,梁国立,方明渭,等.X射线荧光光谱快速分析铝土矿的方法研究[J].岩矿测试,2001,20(4):305-308.DENG Sai-wen,LIANG Guo-li,FANG Ming-wei,et al.A rapid in site method for bauxite analysis by XRF[J].Rock and Mineral Analysis,2001,20(4):305-308.
[12]中华人民共和国工业和信息化部发布.YS/T 575.23—2009铝土矿石化学分析方法第23部分:X射线荧光光谱法测定元素含量[S].北京:中国标准出版社,2010.
[13]乌静,戴学谦,刘伟,等.X射线荧光光谱法测定铁矾土中二氧化硅、氧化铝和氧化铁[J].冶金分析,2009,29(7):44-48.WU Jing,DAI Xue-qian,LIU Wei,et al.Determination of silicon dioxide,aluminum oxide and ferric oxide in laterite by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2009,29(7):44-48.
[14]郭寿兴,吴玉庆.X射线荧光光谱法测定叶腊石中的铝铁钾钠[J].岩矿测试,1993,12(4):290-292.GUO Shou-xing,WU Yu-qing.Determination of Al,Fe,K and Na in pyrophyllite by XRF[J].Rock and Mineral Analysis,1993,12(4):290-292.
[15]李国会,李小莉.X射线荧光光谱分析熔融法制样的系统研究[J].冶金分析,2015,35(7):1-9.LI Guo-hui,LI Xiao-li.Systematic study on the fusion samplepreparationinX-rayfluorescence spectrometric analysis[J].Metallurgical Analysis,2015,35(7):1-9.
[16]Fernand C,Jimmy S B.硼酸盐熔融的物理与化学[M].卓尚军,译.上海:华东理工大学出版社,2006:23.