Determination of 15 Rare Earth Elements in Rare Earth Ores by Inductively Coupled Plasma-Atomic Emission Spectrometry:A Comparison of Four Different Pretreatment Methods
-
摘要: 稀土元素在矿石中有多种不同的赋存形式，主要有离子吸附型和矿物晶格型，稀土不同赋存形态对其本身准确分析测定有很大的影响。本文从稀土元素在矿石中不同赋存形态的角度出发，探讨了不同前处理方法对稀土准确测试结果的影响，采用盐酸-硝酸-氢氟酸-高氯酸(四酸)敞开酸溶、盐酸-硝酸-氢氟酸-高氯酸-硫酸(五酸)敞开酸溶、氢氟酸-硝酸封闭压力酸溶、氢氧化钠-过氧化钠碱熔四种方法对离子吸附型和矿物晶格型两类赋存类型的稀土矿石样品进行前处理，电感耦合等离子体发射光谱法测定其中的15种稀土元素。结果表明：对于离子吸附型的稀土矿石标准物质(GBW 07161、GBW 07188)，四酸敞开酸溶法测定的结果明显偏低，15种稀土元素大都偏低10%～20%，五酸敞开酸溶法、封闭压力酸溶法和碱熔法的测定值与标准值吻合；而对于稀土以离子化合物及类质同象置换的形式赋存于矿物晶格中的白云鄂博轻稀土矿石样品，三种酸溶法结果较碱熔法均偏低，其中四酸敞开酸溶法偏低最多，约偏低20%左右，五酸敞开酸溶法和封闭压力酸溶法偏低5%～15%。本文提出，对于离子吸附型稀土矿，五酸敞开酸溶法和封闭压力酸溶法可以代替传统操作复杂的碱熔法，但对于稀土以离子形式赋存于矿物晶格型的稀土矿，目前最合适的前处理法是传统的碱熔法。Abstract: Rare earth elements (REEs) in ore have many different forms, mainly ion adsorption and mineral lattice types. The occurrence state of rare earth elements has a great impact on accurate analysis. In this study, the effects of different pretreatment methods in REEs analysis are discussed from the perspective of REEs occurrence states in ore. Four pretreatment methods including HCl-HNO3-HF-HClO4 under normal pressure (the open acid digestion), HCl-HNO3-HF-HClO4-H2SO4 under normal pressure (the open acid digestion, adding sulfuric acid), HF-HNO3 in confining pressure (the pressurized acid digestion) as well as NaOH-Na2O2 alkali fusion were conducted for REEs ores. 15 rare earth elements were determined by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The results of the open HCl-HNO3-HF-HClO4 acid digestion for the two National Standard Substances (GBW 07161, GBW 07188) which are ion adsorption-type rare earth ores, are significantly lower, mostly 10%-20% lower than certified values. Meanwhile, the results from the pressurized acid digestion, the open HCl-HNO3-HF-HClO4-H2SO4 acid digestion and alkaline fusion are in agreement with certified values. For the two Baiyun Ebo REEs ore samples (SS-1 and BY-1) which are mineral lattice-type, results from all three acid digestions are lower than those from alkaline fusion. The results of the open HCl-HNO3-HF-HClO4 acid digestion are the lowest, approximately 20% lower than those from alkaline fusion, and results of the open HCl-HNO3-HF-HClO4-H2SO4 acid digestion and the pressurized acid digestion essentially are as low as approximately 5%-15%. In summary, for ion adsorption-type rare earth ores, the the open HCl-HNO3-HF-HClO4-H2SO4 acid digestion and pressurized acid digestion could replace the traditional alkaline fusion, while for mineral lattice-type rare earth ores, the most suitable pretreatment method is still alkaline fusion.
-
-
表 1 ICP-AES仪器工作条件
Table 1. Working parameters of the ICP-AES instrument
工作参数 设定条件 工作参数 设定条件 射频功率 1300 W 进样速率 1.5 mL/min 冷却气流量 15 L/min 进样时间 25 s 辅助气流量 0.2 L/min 观察高度(垂直观测) 15 mm 雾化气压力 1.15 MPa 重复测量次数 3 
下载: 导出CSV
表 2 组合标准溶液中稀土元素的浓度
Table 2. Concentration of REEs in calibration standard solution
标准溶液编号 稀土元素 稀土元素浓度ρ/(μg·mL-1) STD1 La,Ce,Sm,Eu,Ho,Tm,Yb,Lu,Y,Sc 10 STD2 Tb,Pr,Nd,Gd,Dy,Er 10 STD3 La,Ce,Y 25 STD4 La,Ce,Y 50 STD5 La,Ce,Y 100 STD6 Pr,Nd 25 STD7 Pr,Nd 50 STD8 Pr,Nd 100
下载: 导出CSV
表 3 稀土元素的分析谱线和仪器检出限
Table 3. Analytical spectral lines of REEs and detection limits of the instrument
稀土元素 分析波长
λ/nm仪器检出限
/(ng·g-1)稀土
元素分析波长
λ/nm仪器检出限
/(ng·g-1)La 408.672 3 Dy 353.170 2 Ce 418.659 16 Ho 345.600 10 Pr 422.293 15 Er 349.910 6 Nd 406.109 12 Tm 313.126 2 Sm 442.434 20 Yb 328.937 1 Eu 412.970 2 Lu 261.542 1 Gd 335.047 4 Y 360.073 9 Tb 350.917 6
下载: 导出CSV
表 4 四种溶样方法前处理GBW 07161样品的 ICP-AES分析结果
Table 4. Analytical results of REEs in GBW 07161 with four sample pretreatment methods by ICP-AES
w/(μg·g-1) 稀土
元素GBW 07161 标准值 碱熔法 氢氟酸-硝酸
封闭压力酸溶法五酸敞开
酸溶法四酸敞开
酸溶法La 2362±145 2283 2466 2375 2086 Ce 187.2±8.1 190.2 177.25 188.3 124.75 Pr 447±25 469.2 461.76 452.88 395.55 Nd 1595±86 1619 1570.5 1594 1411 Sm 284.6±25.9 270.5 295.55 290.95 309.9 Eu 64.77±3.62 62.11 66.17 68.49 57.78 Gd 225.6±26.0 225.7 233.2 231.85 164.1 Tb 34.60±2.21 31.67 38.83 41.3 31.36 Dy 183±17 173.4 182.8 196.05 158.75 Ho 35.70±4.01 - - - - Er 96.2±8.7 108.4 100.37 112 100.75 Tm 13.22±1.14 12.43 11.99 13.91 17.25 Yb 87.82±10.53 85.71 82.14 87.42 76 Lu 11.96±0.88 12.19 11.38 12.78 11.16 Y 976.38±47.24 919.9 960.4 987.4 860.05
下载: 导出CSV
表 5 四种溶样方法前处理GBW 07188样品的ICP-AES分析结果
Table 5. Analytical results of REEs in GBW 07188 with four sample pretreatment methods by ICP-AES
w/(μg·g-1) 稀土
元素GBW 07188 标准值 碱熔法 氢氟酸-硝酸
封闭压力酸溶法五酸敞开
酸溶法四酸敞开
酸溶法La 1961±170 1867 1927 1813.5 1704 Ce 431.5±32.6 405.3 371.15 340.4 309.77 Pr 736.7±33.1 804.75 784.5 736.2 629.87 Nd 3429±85 3255.5 3384.5 3349 3065 Sm 1724±86 1540 1656 1670.5 1337 Eu 18.91±1.47 18.77 20.19 20.12 18.46 Gd 2169±86 2170 2352 2244 2027 Tb 467.6±34 455.9 455.9 452.35 479.57 Dy 3223±261 3099 3150 3072 2807 Ho (558) 570.95 595.15 577.45 527.2 Er 1749±87 1780.5 1807 1756 1706 Tm 271.4±8.8 275.35 293.45 284.3 267.4 Yb 1844±176 1690.5 1799 1778 1628 Lu 263.82±17.59 230.1 240.15 231.1 217.4 Y 17007±787 17265 18230 17290 15616
下载: 导出CSV
表 6 四种溶样方法前处理样品BY-1的稀土元素ICP-AES分析结果
Table 6. Analytical results of REEs in BY-1 sample with four sample pretreatment methods by ICP-AES
w/(μg·g-1) 稀土
元素BY-1 碱熔法 氢氟酸-硝酸
封闭压力酸溶法五酸敞开
酸溶法四酸敞开
酸溶法La 9501±40 8000±168 8749±13 8057±22 Ce 15513±63 13773±642 13623±25 12943±26 Pr 1218±11 1173±46 1150±55 1116±2 Nd 3712±18 3089±155 3079±4 3224±5 Sm 485.77±3.6 488.2±22.7 459±0.9 403±0.9 Eu 57.42±0.22 53.76±1.90 50.72±0.22 48.52±0.09 Gd 63.5±4.97 79.59±1.60 76.77±0.31 69.82±0.78 Tb - - - - Dy - - - - Ho - - - - Er 15.84±2.67 14.83±3.10 19.30±0.44 13.7±0.32 Tm - - - - Yb 16.7±0.27 6.18±0.18 5.08±0.05 3.51±0.09 Lu 3.14±0.45 2.28±0.19 2.62±0.04 2.39±0.04 Y 131.2±0.71 127.4±3.49 113.8±1.42 116.1±0.93 Sc 63.06±0.40 55.33±1.61 53.18±0.51 53.13±0.19 注："-"表示未给出分析结果；分析结果以"平均值±标准偏差"的形式给出，下表同。
下载: 导出CSV
表 7 四种溶样方法前处理样品SS-1的稀土元素ICP-AES分析结果
Table 7. Analytical results of REEs in SS-1 samples with four sample pretreatment methods by ICP-AES
w/(μg·g-1) 稀土
元素样品SS-1 碱熔法 氢氟酸-硝酸
封闭压力酸溶法五酸敞开
酸溶法四酸敞开
酸溶法La 5471±45 4958±59 4589±76 4187±35 Ce 12870±118 11033±127 11817±188 9902±92 Pr 1411±17 1227.4±10 1203±12 1185±11 Nd 5639±44 4498±40 4889±79 4771±42 Sm 758±6 628.6±10.5 631±9.5 614.8±6.15 Eu 78.36±0.41 72.30±0.49 72.97±1.14 60.42±0.50 Gd 88.39±9.62 114.6±0.86 107.7±1.53 62.1±1.05 Tb - - - - Dy - - - - Ho - - - - Er 35.91±4.99 28.65±1.43 32.97±0.64 20.15±0.11 Tm - - - - Yb 8.20±0.29 8.45±0.03 7.35±0.14 5.65±0.02 Lu 7.05±2.88 7.16±0.18 6.16±0.17 4.76±0.02 Y 151.07±1.38 134.37±1.14 128.87±1.73 117.7±0.30 Sc 122.7±0.78 110.87±0.95 94.97±2.09 97.61±0.60
下载: 导出CSV
表 8 四个样品稀土元素弱酸提取态的ICP-AES分析结果
Table 8. Analytical results of the weak acid extraction of REEs in four different samples by ICP-AES
w/(μg·g-1) 稀土
元素GBW 07161 GBW 07188 提取态 标准值 提取态
所占比例
/%提取态 标准值 提取态
所占比例
/%La 2309 2361.98 97.8 1242.33 1961.21 63.3 Ce 63.67 187.24 34 82.47 431.47 19.1 Pr 407.9 446.96 91.3 359.13 736.65 48.8 Nd 1566.67 1594.58 98.2 1445.67 3429.2 42.2 Sm 278.07 284.59 97.7 588.43 1724.8 34.1 Eu 65.58 64.77 101.3 0.17 18.91 0.9 Gd 212.4 225.58 94.2 878.83 2169 40.5 Tb 34.97 34.6 101.1 215.03 467.61 46 Dy 170.73 182.97 93.3 1357.67 3223.81 42.1 Ho 35.24 35.71 98.7 308.17 558.72 55.2 Er 103.17 96.2 107.2 1035.33 1749 59.2 Tm 14.26 13.22 107.9 174.23 271.44 64.2 Tb 82.34 87.82 93.8 1171.33 1844.22 63.5 Lu 11.55 11.96 96.6 161.53 263.82 61.2 Y 952.3 976.38 97.5 10796.67 17007.84 63.5 总和 6307.85 6604.55 95.5 19817.01 35857.7 55.3 稀土
元素样品SS-1 样品BY-1 提取态 碱熔值 提取态
所占比例
/%提取态 碱熔值 提取态
所占比例
/%La 54.65 9501 0.6 11.64 5471 0.2 Ce 117.47 15513 0.8 13.04 12870 0.1 Pr 11.32 1218 0.9 5.07 1411 0.4 Nd 31.72 3712 0.9 6.36 5639 0.1 Sm 10.09 485.77 2.1 1.18 758 0.2 Eu 1.76 57.42 3.1 0.29 78.36 0.4 Gd 7.26 63.5 11.4 3.34 88.39 3.8 Tb - - - - - - Dy - - - - - - Ho - - - - - - Er 0.6 15.84 3.8 0.05 35.91 0.1 Tm - - - - - - Tb 0.61 16.7 3.6 0.16 8.2 2 Lu 0.03 3.14 0.9 0.04 7.05 0.6 Y 10.64 131.2 8.1 0.89 151.07 0.6 总和 244.82 30780.63 0.8 32.27 26640.68 0.1 注：“-”表示低于仪器检出限。
下载: 导出CSV
-
[1] 费浩,王树安,黄进初,张弘澍.电感耦合等离子体原子发射光谱法测定锡青铜中镧镍铈[J].冶金分析,2009,29(5): 56-58. http://www.cnki.com.cn/Article/CJFDTOTAL-YJFX200905015.htm
[2] 富玉,刘金霞,王彦芬,黄志荣.无滤共沉淀富集-等离子体原子发射光谱法测定痕量稀土元素[J].分析试验室,2007,26(3): 91-94. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=0&CurRec=1&recid=&FileName=FXSY200703023&DbName=CJFD2007&DbCode=CJFQ&pr=
[3] Navarro M S, Ulbrich H H, Andrade S, Janasi V A. Adaptation of ICP-OES routine determination techniques for the analysis of rare earth elements by chromatographic separation in geologic materials: Tests with reference materials and granitic rocks [J]. Journal of Alloys and Compounds, 2002, 344(3): 40-45. http://cn.bing.com/academic/profile?id=2056224092&encoded=0&v=paper_preview&mkt=zh-cn
[4] 辛仁轩.等离子体发射光谱分析[M].北京:化学工业出版社,2005: 140-144．
[5] Beata Z, Katarzyna P, Barbara F, Marzena P, Andrzej K, Rafal S. Determination of rare earth elements by spectroscopic techniques: A review [J].Journal of Analytical Atomic Spectrometry, 2011, 26(12): 2373-2390. doi: 10.1039/c1ja10140d http://cn.bing.com/academic/profile?id=1975763929&encoded=0&v=paper_preview&mkt=zh-cn
[6] Premadas A. Cation exchange chromatographic group sepa-ration and ICP-AES determination of rare earth elements and yttrium in refractory minerals zircon, ilmenite, rutile, columbite-tantalite, garnet, and silliminite [J]. Atomic Spectroscopy, 2003, 24(4): 149-158. http://www.perkinelmer.co.kr/files/AP00094.pdf#page=37
[7] Serpil Y K, Eftade O G, Aysun D, Semra G T. Deter-mination of major and rare earth elements in bastnasite ores by ICP-AES [J].Analytical Letters,2004,37(13): 2701-2709. doi: 10.1081/AL-200031966 http://www.tandfonline.com/doi/abs/10.1081/AL-200031966
[8] 刘文华,刘鹏宇.稀土元素分析[J].分析试验室,2002,21(3): 89-108. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=0&CurRec=8&recid=&FileName=FXSY200203031&DbName=CJFD2002&DbCode=CJFQ&pr=
[9] 赵庆令,李清彩.电感耦合等离子体发射光谱法同时测定土壤样品54 种组分[J].岩矿测试,2011,30(1): 75-78. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110116&flag=1
[10] 张杰,于永丽,戚淑芳,于媛君.电感耦合等离子体原子发射光谱法测定轻稀土元素[J].冶金分析,2009,29(4): 20-23. http://www.cnki.com.cn/Article/CJFDTOTAL-YJFX200904007.htm
[11] 陈道华,张欣.等离子体发射光谱法直接测定海洋沉积物中的微量稀土元素[J].岩矿测试,2003,22(1): 61-63. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20030116&flag=1
[12] Borai E H, Eid M A, Aly H F. Determination of REEs distribution in monazite and xenotime minerals by ion chromatography and ICP-AES [J].Analytical and Bioanalytical Chemistry,2002,372(7): 537-541. http://link.springer.com/article/10.1007/s00216-001-1204-8
[13] 张保科,温宏利,王蕾,马生凤,巩爱华.封闭压力酸溶-盐酸提取-电感耦合等离子体质谱法测定地质样品中的多元素[J].岩矿测试,2011,30(6): 737-744. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110615&flag=1
[14] 何红蓼,李冰,韩丽荣,孙德忠,王淑贤,李松.封闭压力酸溶-ICP-MS法分析地质样品中47个元素的评价[J].分析试验室,2002,21(5): 8-12. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=4&CurRec=1&recid=&FileName=FXSY200205003&DbName=CJFD2002&DbCode=CJFQ&pr=
[15] Marina T, Ian J, Kym E. An assessment of dissolution techniques for the analysis of geological samples by plasma spectrometry[J].Chemical Geology,1992,95(5): 35-62. http://cn.bing.com/academic/profile?id=2007976131&encoded=0&v=paper_preview&mkt=zh-cn
[16] 田晓任,张宏志.ICP-AES法同时测定岩石、矿物、土壤等样品中十五种稀土元素的方法研究[J].光谱实验室,1996,13(5): 57-63. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=8&CurRec=1&recid=&FileName=GPSS605.013&DbName=CJFD9697&DbCode=CJFQ&pr=
[17] GB/T 17417.1～17417.2—2010,稀土矿石化学分析方法；第1部分:稀土分量测定[S].
[18] Fedyunina N N, Seregina I F, Bolshov M A, Okina O I, Lyapunov S M. Investigation of the efficiency of the sample pretreatment stage for the determination of the rare earth elements in rock samples by inductively coupled plasma mass spectrometry technique [J].Analytica Chimica Acta, 2012, 713(11): 97-102. http://cn.bing.com/academic/profile?id=2083958360&encoded=0&v=paper_preview&mkt=zh-cn
[19] Frederico G P, Rainério E J, Tatiana D S. Sample preparation for determination of rare earth elements in geological samples by ICPMS: A critical review [J]. Analytical Letters, 2012, 45(12): 1537-1556. doi: 10.1080/00032719.2012.677778 http://cn.bing.com/academic/profile?id=2028820485&encoded=0&v=paper_preview&mkt=zh-cn
[20] 岩石矿物分析编委会.岩石矿物分析(第四版 第三分册)[M].北京:地质出版社,2011: 446-483.
[21] 高海洲.白云鄂博矿区稀土稀有矿产资源综合评述(一) [J].包钢科技,2009,35(5): 1-6. http://www.cnki.com.cn/Article/CJFDTOTAL-BGKJ200905003.htm
[22] 曹荣龙,朱寿华,王俊文.白云鄂博铁——稀土矿床的物质来源和成因理论问题[J].中国科学,1994,24(12): 1298-1307. doi: 10.3321/j.issn:1006-9240.1994.12.003 http://www.cnki.com.cn/Article/CJFDTOTAL-JBXK199412010.htm
[23] 罗明标,杨枝,郭国林,李伯平,刘峰,刘维.白云鄂博铁矿石中稀土的赋存状态研究[J].中国稀土学报,2007,25(11): 57-61. http://www.cnki.com.cn/Article/CJFDTOTAL-XTXB2007S1015.htm
[24] 张培善,陶克捷.中国稀土矿主要矿物学特征[J].中国稀土学报,1989,3(3): 1-6. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=16&CurRec=1&recid=&FileName=XTXB198503000&DbName=CJFD8589&DbCode=CJFQ&pr=
-
图(1)
表(8)
计量
- 文章访问数: 632
- PDF下载数: 7
- 施引文献: 0