压片制样-X射线荧光光谱法测定铝用石墨质阴极材料中14种元素
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摘要
当前铝用阴极材料无元素含量检测的规定,目前阴极材料的元素测定尚处于空白状态。采用压片制样-X射线荧光光谱法(XRF)测定铝用炭素阴极材料杂质元素目前鲜见报道。实验通过无烟煤标样、高纯石墨、铝用阳极材料标样配制成和阴极材料成分、基体类似的合成系列标准样品,研磨压片法制样,用X射线荧光光谱仪测定铝用石墨质阴极材料中硅、铝、铁、钙、镁、磷、钾、钠、钛、钒、锰、镍、铬、铅的含量。参考煤炭粘结指数测定方法,同一条件下测定对比各种粘结剂的粘结性能,选择分析纯硬脂酸作粘结剂;样品和粘结剂最合适比例为12.00g炭素试样加入2.00g硬脂酸,研磨时间为30s。通过扫描电镜(SEM)对比各类炭素微观结构,SEM图像对比以及准确度实验表明,形态差异巨大的碳元素同素异形体结构引起的基体效应对荧光测定的影响不能忽略。各元素工作曲线用经验系数法校正,未知样品的检测结果与标准值对照良好。精密度试验表明,样品中各元素多个梯度测定结果的相对标准偏差(RSD,n=11)小于5%,最高的钠和镁元素也是在7.5%左右;实验方法和电感耦合等离子体原子发射光谱法(ICP-AES)对照结果没有显著性差异。
At present,there are no regulations for the detection of elements in cathode materials for aluminum manufacturing.The determination of elements in cathode materials is still being in blank state.The determination of impurity elements in carbon cathode material for aluminum manufacturing by X-ray fluorescence spectrometry(XRF)with pressed powder pellet has been not reported.A series of standard samples with similar composition and matrix with cathode material were synthesized using certified reference materials of anthracite,high purity graphite and anode material for aluminum.The sample was prepared using grinding and tabletting method.The contents of silicon,aluminum,iron,calcium,magnesium,phosphorus,potassium,sodium,titanium,vanadium,manganese,nickel,chromium and lead in graphite cathode material for aluminum manufacturing were determined by X-ray fluorescence spectrometry.According to the measuring method of caking index of coal,the bond property of various binders was measured under same condition.Finally the analytically pure stearic acid was selected as the binder.The optimal proportion between sample and binder was 12.00 g of carbon sample and 2.00 g of stearic acid.The grinding time was 30 s.The microstructure of each carbon was compared by scanning electron microscope(SEM).SEM image contrast and accuracy tests showed that the influence of matrix effect caused by carbon allotrope structure with different morphology on the fluorescence determination could not be ignored.The working curves of elements were corrected by the empirical coefficient method.The determination results of unknown samples were in good agreement with the standard values.The precision test indicated that the relative standard deviations(RSD,n=11)of determination results of elements with several gradients were less than 5%.The RSD of sodium and magnesium was highest,i.e.,around 7.5%.There was no significant difference between the experimental method and inductively coupled plasma atomic emission spectrometry(ICP-AES).
At present,there are no regulations for the detection of elements in cathode materials for aluminum manufacturing.The determination of elements in cathode materials is still being in blank state.The determination of impurity elements in carbon cathode material for aluminum manufacturing by X-ray fluorescence spectrometry(XRF)with pressed powder pellet has been not reported.A series of standard samples with similar composition and matrix with cathode material were synthesized using certified reference materials of anthracite,high purity graphite and anode material for aluminum.The sample was prepared using grinding and tabletting method.The contents of silicon,aluminum,iron,calcium,magnesium,phosphorus,potassium,sodium,titanium,vanadium,manganese,nickel,chromium and lead in graphite cathode material for aluminum manufacturing were determined by X-ray fluorescence spectrometry.According to the measuring method of caking index of coal,the bond property of various binders was measured under same condition.Finally the analytically pure stearic acid was selected as the binder.The optimal proportion between sample and binder was 12.00 g of carbon sample and 2.00 g of stearic acid.The grinding time was 30 s.The microstructure of each carbon was compared by scanning electron microscope(SEM).SEM image contrast and accuracy tests showed that the influence of matrix effect caused by carbon allotrope structure with different morphology on the fluorescence determination could not be ignored.The working curves of elements were corrected by the empirical coefficient method.The determination results of unknown samples were in good agreement with the standard values.The precision test indicated that the relative standard deviations(RSD,n=11)of determination results of elements with several gradients were less than 5%.The RSD of sodium and magnesium was highest,i.e.,around 7.5%.There was no significant difference between the experimental method and inductively coupled plasma atomic emission spectrometry(ICP-AES).
引文
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[7]ISO 12980:2000Carbonaceous materials in the production of aluminium-Green coke and calcined coke for electrode[S].
[8]中国石油化工总公司.SH/T 0058-91石油焦中硅、钒和铁含量测定法[S].北京:中国标准出版社,1991.
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[10]ISO/TS 13605:2012Solid mineral fuels-Major and minor elements in hard coal ash and coke ash-Wavelength dispersive X-ray fluorescence spectrometric method[S].
[11]宋义,郭芬,谷松海.X射线荧光光谱法同时测定煤灰中的12种成分[J].光谱学与光谱分析,2008,28(6):1430-1434.SONG Yi,GUO Fen,GU Song-hai.Determination of 12elements in coal ash by X-ray fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2008,28(6):1430-1434.
[12]杨柳,董雪莹,孟东阳.煤中微量元素含量常用测定方法[J].中国矿业,2014,23(增刊2):293-300.YANG Liu,DONG Xue-ying,MENG Dong-yang.The common determination method of the trace elements in coal[J].China Mining Magazine,2014,23(Suppl.2):293-300.
[13]张庆建,岳春雷,孙瑞昌,等.X射线荧光光谱法测定煤灰中砷磷氯[J].冶金分析,2015,35(7):84-88.ZHANG Qing-jian,YUE Chun-lei,SUN Rui-chang,et al.Determination of arsenic,phosphorus and chlorine in coal by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2015,35(7):84-88.
[14]白万里,张爱芬,石磊,等.X射线荧光光谱法测定工业硅中11种微量元素[J].冶金分析,2016,36(10):40-46.BAI Wan-li,ZHANG Ai-fen,SHI Lei,et al.Determination of eleven trace elements in industrial silicon by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2016,36(10):40-46.
[15]中华人民共和国国家质量监督检疫总局,中国国家标准化管理委员会.GB/T 5447-2014烟煤黏结指数测定方法[S].北京:中国标准出版社,2014.
[16]高新华,宋武元,邓赛文,等.实用X射线光谱分析[M].北京:化学工业出版社,2016:223-228.
[17]ISO 14435:2005Carbonaceous materials for the production of aluminium-Petroleum-Determination of trace metals by inductively coupled plasma atomic emission spectrometry[S].
[18]中华人民共和国国家发展与改革委员会,中国国家标准化管理委员会.YS/T 587.5-2006炭阳极用煅后石油焦检测方法第5部分:微量元素的测定[S].北京:中国标准出版社,2006.
[19]王雪莹,刘和燕,王娜.电感耦合等离子体原子发射光谱法测定煤与焦炭中18种元素[J].冶金分析,2007,27(7):54-58.WANG Xue-ying,LIU He-yan,WANG Na.Determination of eighteen elements in coal and coke by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2007,27(7):54-58.
[2]牛晓东,王兆文,于旭光,等.电极材料对铝电解阴极过程研究的影响[J].轻金属,2005(6):29-33.NIU Xiao-dong,WANG Zhao-wen,YU Xu-guang,et al.Effects of electrode materials on studying cathode process in aluminum electrolysis[J].Light Metal,2005(6):29-33.
[3]罗英涛,胡振华,李旺兴,等.中国铝用炭素50年的技术创新模式分析[J].炭素技术,2007,26(2):29-33.LUO Ying-tao,HU Zhen-hua,LI Wang-xing,et al.Analysis of technology innovation modes of Chinese carbon technology for aluminum in the last fifty years[J].Carbon Techniques,2007,26(2):29-33.
[4]方宁,谢刚,俞小花,等.中国铝用阴极冷捣糊研究现状[J].中国稀土学报,2010,28(专辑):805-807.FANG Ning,XIE Gang,YU Xiao-hua,et al.Study on situation of Chinese aluminum cold ramming paste[J].Journal of the Chinese Rare Earth Society,2010,28(Spec.Issue):805-807.
[5]张志超.铝用炭素阳极企业节能[J].炭素技术,2012,31(4):29-32.ZHANG Zhi-chao.Energy saving of carbon anode enterprises[J].Carbon Techniques,2012,31(4):29-32.
[6]曹培峰,经云.阴极炭块用电煅煤标准解析[C]∥中国金属学会碳素材料分会第二十八届学术交流会论文集.涞水,2014:287-291.
[7]ISO 12980:2000Carbonaceous materials in the production of aluminium-Green coke and calcined coke for electrode[S].
[8]中国石油化工总公司.SH/T 0058-91石油焦中硅、钒和铁含量测定法[S].北京:中国标准出版社,1991.
[9]中华人民共和国国家发展与改革委员会,中国国家标准化管理委员会.YS/T 63.16-2006铝电解炭素材料检测方法第16部分:微量元素的测定X射线荧光光谱分析方法[S].北京:中国标准出版社,2006.
[10]ISO/TS 13605:2012Solid mineral fuels-Major and minor elements in hard coal ash and coke ash-Wavelength dispersive X-ray fluorescence spectrometric method[S].
[11]宋义,郭芬,谷松海.X射线荧光光谱法同时测定煤灰中的12种成分[J].光谱学与光谱分析,2008,28(6):1430-1434.SONG Yi,GUO Fen,GU Song-hai.Determination of 12elements in coal ash by X-ray fluorescence spectrometry[J].Spectroscopy and Spectral Analysis,2008,28(6):1430-1434.
[12]杨柳,董雪莹,孟东阳.煤中微量元素含量常用测定方法[J].中国矿业,2014,23(增刊2):293-300.YANG Liu,DONG Xue-ying,MENG Dong-yang.The common determination method of the trace elements in coal[J].China Mining Magazine,2014,23(Suppl.2):293-300.
[13]张庆建,岳春雷,孙瑞昌,等.X射线荧光光谱法测定煤灰中砷磷氯[J].冶金分析,2015,35(7):84-88.ZHANG Qing-jian,YUE Chun-lei,SUN Rui-chang,et al.Determination of arsenic,phosphorus and chlorine in coal by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2015,35(7):84-88.
[14]白万里,张爱芬,石磊,等.X射线荧光光谱法测定工业硅中11种微量元素[J].冶金分析,2016,36(10):40-46.BAI Wan-li,ZHANG Ai-fen,SHI Lei,et al.Determination of eleven trace elements in industrial silicon by X-ray fluorescence spectrometry[J].Metallurgical Analysis,2016,36(10):40-46.
[15]中华人民共和国国家质量监督检疫总局,中国国家标准化管理委员会.GB/T 5447-2014烟煤黏结指数测定方法[S].北京:中国标准出版社,2014.
[16]高新华,宋武元,邓赛文,等.实用X射线光谱分析[M].北京:化学工业出版社,2016:223-228.
[17]ISO 14435:2005Carbonaceous materials for the production of aluminium-Petroleum-Determination of trace metals by inductively coupled plasma atomic emission spectrometry[S].
[18]中华人民共和国国家发展与改革委员会,中国国家标准化管理委员会.YS/T 587.5-2006炭阳极用煅后石油焦检测方法第5部分:微量元素的测定[S].北京:中国标准出版社,2006.
[19]王雪莹,刘和燕,王娜.电感耦合等离子体原子发射光谱法测定煤与焦炭中18种元素[J].冶金分析,2007,27(7):54-58.WANG Xue-ying,LIU He-yan,WANG Na.Determination of eighteen elements in coal and coke by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2007,27(7):54-58.