Development of a Portable Li-K Analyzer and Its Application in the Determination of Lithium in Spodumene
-
摘要: 我国锂钾主要矿产资源大多分布在西部偏远地区，其勘查找矿或综合利用迫切需要现场快速分析技术的支持。本文介绍了自行开发的便携式Li-K分析仪的主要性能及其在锂辉石中锂的分析应用。Li-K分析仪是一种基于大气压的液体阴极辉光放电光谱仪，以待测液体为放电阴极，实现了样品中Li、K等元素的原子化和激发。该仪器以光纤传导CCD光谱仪作为检测器，其波长范围为345～1015 nm，分辨率3 nm；以Li 670.78 nm和K 769.90 nm分析谱线，在仪器最佳工作条件下测定Li、K的精密度（RSD，n=14）均低于2%，检出限为0.03 μg/mL，检测范围0.1～10 μg/mL。研究表明，不同酸度和酸的类型对谱线强度影响较大，且存在显著的样品基体效应，标准曲线法分析锂辉石中Li的结果偏差高达267%；而标准加入法可克服基体效应的影响，获得与ICP-OES一致性较好的分析结果，为现场开展固体样品中Li的测定奠定了基础。
-
关键词:
- 便携式Li-K分析仪 /
- 液体阴极辉光放电 /
- CCD光谱仪 /
- 锂辉石 /
- 标准加入法
Abstract: Most of the mineral resources of lithium and potassium are distributed in remote western China. Fast, on-site analytical techniques are urgently needed for their exploration and comprehensive utilization. In this work, a newly developed portable Li-K analyzer was introduced for its analytical performance and the application of this equipment in determining lithium in spodumene is also discussed. The analyser is a type of atomic emission spectrometer based on solution cathode atmospheric glow discharge. Sample solution was used as a graphite cathode, which atomized and excited the elements Li and K. A charge coupled device (CCD) was used to detect the characteristic lines of Li and K, which had wavelengths ranging from 345 to 1015 nm with a 3 nm resolution. Using a Li analytical line of 670.78 nm and a K analytical line of 769.90 nm under the optimized working conditions, the measurement precisions for Li and K were greater than 2%RSD with the limit of detection of 0.03 μg/mL. Results show that different types and concentrations of acids strongly affect the intensities of Li and K, and co-existent elements produce serious matrix effect. Quantification of Li in spodumene ores by use of a calibration curve without matched matrix could not produce accurate results with relative standard deviation up to 267%. Standard addition methods can eliminate the influence of the matrix effect and obtain analytical results consistent with those by Inductively Coupled Plasma-Optical Emission Spectrometry, which thus provides a basis for on-site determination of Li in solid samples. -
-
表 1 Li-K分析仪与ICP-OES分析锂辉石中锂元素的测定结果比较
Table 1. Comparison of detection results of lithium in spodumene samples by Li-K analyser and ICP-OES
定量方法 定量方程及相关系数 F-1 F-2 F-3 F-4 标准曲线-1①测定值(mg/g) y=15057x-31.39 (R2=0.9999) 15555 11668 9174 4200 标准曲线-2②测定值(mg/g) y=14916x+50.02 (R2=1.0000) 21500 16496 12520 - F1标准加入测定值(mg/g) y=59501x+1808.56 (R2=0.9997) 5484 4047 3050 960 F2标准加入测定值(mg/g) y=50872x+260.12 (R2=0.9999) 6307 4854 3722 1275 F3标准加入测定值(mg/g) y=34777x-476.79 (R2=0.9996) 9267 7121 5334 1975 F4标准加入①测定值(mg/g) y=12413x+138.04 (R2=0.9999) 18800 14085 11060 5140 ICP-OES测定值(mg/g) - 5851 5744 5440 5444 相对偏差(%)③ - -6.27 -15.5 -1.95 -5.58 注：①表示样品稀释5000倍；②表示样品稀释3000倍；③表示各样品标准加入法定量结果与ICP-OES结果的相对偏差。 
下载: 导出CSV
-
[1] 李建康,刘喜方,王登红.中国锂矿成矿规律概要[J].地质学报,2014,88(12):2269-2283. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201412009.htm
Li J K,Liu X F,Wang D H.The Metallogenetic Regularity of Lithium Deposit in China[J].Acta Geologica Sinica,2014,88(12):2269-2283. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201412009.htm
[2] 徐修平,李波,华绍光.电感耦合等离子体发射光谱法测定锂辉石中氧化锂[J].金属矿山,2016,45(5):113-117. http://www.cnki.com.cn/Article/CJFDTOTAL-JSKS201605025.htm
Xu X P,Li B,Hua S G.Determination of Lithium Oxide in Spodumene by Inductively Coupled Plasma-Atomic Emission Spectrometry[J].Metal Mine,2016,45(5):113-117. http://www.cnki.com.cn/Article/CJFDTOTAL-JSKS201605025.htm
[3] 谢贞付,王毓华,于福顺,等.伟晶岩型锂辉石矿浮选研究综述[J].稀有金属,2013,37(4):641-649. http://www.cnki.com.cn/Article/CJFDTOTAL-ZXJS201304020.htm
Xie Z F,Wang Y H,Yu F S,et al.Reviews of Flotation Research on Pegmatite Spodumene Ores[J].Chinese Journal of Rare Metals,2013,37(4):641-649. http://www.cnki.com.cn/Article/CJFDTOTAL-ZXJS201304020.htm
[4] 刘丽君,付小方,王登红,等.甲基卡式稀有金属矿床的地质特征与成矿规律[J].矿床地质,2015,34(6):1187-1198. http://www.cnki.com.cn/Article/CJFDTOTAL-KCDZ201506008.htm
Liu L J,Fu X F,Wang D H,et al.Geological Characteristics and Metallogeny of Jiajika-style Rare Metal Deposits[J].Mineral Deposits,2015,34(6):1187-1198. http://www.cnki.com.cn/Article/CJFDTOTAL-KCDZ201506008.htm
[5] 付小方,袁蔺平,王登红,等.四川甲基卡矿田新三号稀有金属矿脉的成矿特征与勘查模型[J].矿床地质,2015,34(6):1172-1186. http://www.cnki.com.cn/Article/CJFDTOTAL-KCDZ201506007.htm
Fu X F,Yuan L P,Wang D H,et al.Mineralization Characteristics and Prospecting Model of Newly Discovered X03 Rare Metal Vein in Jiajika Orefield,Sichuan[J].Mineral Deposits,2015,34(6):1172-1186. http://www.cnki.com.cn/Article/CJFDTOTAL-KCDZ201506007.htm
[6] 郭琳,赵怀颖,温宏利,等.电感耦合等离子体发射光谱法同时测定卤水中锂钠钾钙镁硼硫氯[J].岩矿测试,2012,31(5):824-828. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201205014.htm
Guo L,Zhao H Y,Wen H L,et al.Simultaneous Determination of Li,Na,K,Ca,Mg,B,S,Cl in Brine by Inductively Coupled Plasma-Atomic Emission Spectro-metry[J].Rock and Mineral Analysis,2012,31(5):824-828. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201205014.htm
[7] 袁红战,祝云军,武丽平,等.电感耦合等离子体发射光谱法测天然饱和卤水中的高含量锂[J].岩矿测试,2011,30(1):87-89. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201101023.htm
Yuan H Z,Zhu Y J,Wu L P,et al.Determination of High-content of Lithium in Natural Saturated Brine by Inductively Coupled Plasma-Atomic Emission Spectrometry[J].Rock and Mineral Analysis,2011,30(1):87-89. http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201101023.htm
[8] 伍倩,郑绵平,乜贞,等.西藏当雄错盐湖卤水冬季日晒蒸发实验研究[J].地质学报,2013,87(3):433-440. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201303014.htm
Wu Q,Zheng M P,Nie Z,et al.Experiment Study of Solar Evaporation of Brine from the Dangxiongcuo Salt Lake in Tibet in Winter[J].Acta Geologica Sinica,2013,87(3):433-440. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201303014.htm
[9] 王洪彬,张婵,王杰.火焰原子发射光谱法测定卤水中的锂[J].理化检验(化学分册),2012,48(2):235-238. http://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201202035.htm
Wang H B,Zhang C,Wang J.Flame Atomic Emission Spectrometry for Measurement of Li Contents in Brine[J].Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2010,48(2):235-238. http://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201202035.htm
[10] Cserfalvi T,Mezei P,Apai P.Emission Studies on a Glow Discharge in Atmospheric Pressure Air Using Water as a Cathode[J].Journal of Physics D:Applied Physics,1993,26(12):2184-2188.
[11] Webb M R,Andrade F J,Hieftje G M.Compact Glow Discharge for the Elemental Analysis of Aqueous Samples[J].Analytical Chemistry,2007,79(20):7899-7905.
[12] Shekhar R,Karunasagar D,Dash K,et al.Determination of Mercury in Hepatitis-B Vaccine by Electrolyte Cathode Glow Discharge Atomic Emission Spectrometry (ELCAD-AES)[J].Journal of Analytical Atomic Spectrometry,2010,25(6):875-879.
[13] Marcus R K,Quarles Jr C D,Barinaga C J,et al.Liquid Sampling-Atmospheric Pressure Glow Discharge Ionization Source for Elemental Mass Spectrometry[J].Analytical Chemistry,2011,83(7):2425-2429.
[14] Wang Z,Schwartz A J,Ray S J,et al.Determination of Trace Sodium,Lithium,Magnesium,and Potassium Impurities in Colloidal Silica by Slurry Introduction into an Atmospheric-Pressure Solution-Cathode Glow Discharge and Atomic Emission Spectrometry[J].Journal of Analytical Atomic Spectrometry,2013,28(2):234-240.
[15] 张真,汪正,邹慧君,等.大气压电解液阴极辉光放电发射光谱技术的研究进展及应用[J].分析化学,2013,41(10):1606-1613. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201310037.htm
Zhang Z,Wang Z,Zou H J,et al.Progress and Application of Atmospheric Electrolyte Cathode Glow Discharge Emission Spectrometric Technique[J].Chinese Jounal of Analytical Chemistry,2013,41(10):1606-1613. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201310037.htm
[16] 盖荣银,汪正,贺岩峰,等.液体阴极辉光放电原子发射光谱法分析硅酸钇镥中痕量杂质元素[J].分析化学,2014,42(11):1617-1622. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201411018.htm
Gai R Y,Wang Z,He Y F,et at.Determination of Trace Metals in Lutetium-Yttrium Orthosilicate by Solution-Cathode Glow Discharge-Atomic Emission Spectrometry[J].Chinese Jounal of Analytical Chemistry,2014,42(11):1617-1622. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201411018.htm
[17] 郑培超,杨蕊,王金梅,等.内标法在电解液阴极大气压辉光放电原子发射光谱检测水体金属元素含量中的应用[J].分析试验室,2015,34(1):18-21. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201501006.htm
Zheng P C,Yang R,Wang J M,et al.Determination of Metal Elements in Aqueous Solution with Electrolyte Cathode Atmospheric Glow Discharge Atomic Emission Spectroscopy by the Internal Standard Method[J].Chinese Journal of Analysis Laboratory,2015,34(1):18-21. http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201501006.htm
[18] 郑培超,张斌,王金梅,等.大气压液体阴极辉光放电发射光谱检测水体中的铅[J].光谱学与光谱分析,2015,35(7):2012-2016. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201507056.htm
Zheng P C,Zhang B,Wang J M,et al.Detection of Lead in Water by Electrolyte Cathode Atmospheric Glow Discharge Emission Spectroscopy[J].Spectroscopy and Spectral Analysis,2015,35(7):2012-2016. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201507056.htm
[19] 汤庆峰,钱春燕,吴赞,等.ICP-AES法测定天然卤水中11种元素[J].盐业与化工,2014,43(8):15-18. http://www.cnki.com.cn/Article/CJFDTOTAL-HHYH201408004.htm
Tang Q F,Qian C Y,Wu Z,et al.Determination of 11 Elements in Natural Brine by ICP-AES[J].Journal of Salt and Chemical Industry,2014,43(8):15-18. http://www.cnki.com.cn/Article/CJFDTOTAL-HHYH201408004.htm
[20] 张保科,许俊玉,王蕾,等.锂辉石样品中稀有稀散稀土等多元素的测定方法[J].桂林理工大学学报,2016,36(1):184-190. http://www.cnki.com.cn/Article/CJFDTOTAL-GLGX201601026.htm
Zhang B K,Xu J Y,Wang L,et al.Multi-elements Simultaneous Determination Methods for Rare,Scattered and Rare Earth Elements in Spodumene Samples[J].Journal of Guilin University of Technology,2016,36(1):184-190. http://www.cnki.com.cn/Article/CJFDTOTAL-GLGX201601026.htm
[21] 王立平,冯海涛,董亚萍,等.标准加入ICP-AES法测定铬酸钠中杂质元素[J].光谱学与光谱分析,2015,35(2): 523-526. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201502054.htm
Wang L P,Feng H T,Dong Y P,et al.Standard Addition Determination of Impurities in Na2CrO4 by ICP-AES[J].Spectroscopy and Spectral Analysis,2015,35(2): 523-526. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201502054.htm
[22] 斯文,钱翠珠,林垦,等.电感耦合等离子体质谱法测定烟用接装纸中砷时内标法和标准加入法的比较[J].理化检验(化学分册),2015,51(11):1552-1556. http://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201511017.htm
Si W,Qian C Z,Lin K,et al.Comparison of Internal Standard Method and Standard Addition Method in the ICP-MS Determination of Arsenic in Tipping Paper for Cigarettes[J].Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2015,51(11):1552-1556. http://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201511017.htm
-
图(3)
表(1)
计量
- 文章访问数: 1183
- PDF下载数: 17
- 施引文献: 0