电感耦合等离子体质谱法测定钒钛磁铁矿中的稀土元素

刘淑君; 雷勇; 赵朝辉; 易建春; 王洪彬

doi:10.7513/j.issn.1004-7638.2024.03.028

电感耦合等离子体质谱法测定钒钛磁铁矿中的稀土元素

doi: 10.7513/j.issn.1004-7638.2024.03.028

1.
中国地质科学院矿产综合利用研究所, 中国地质调查局稀土资源应用技术创新中心, 四川省稀土技术创新中心, 自然资源部战略性矿产综合利用工程技术创新中心, 四川成都 610041
2.
攀钢集团矿业有限公司, 四川攀枝花 617000

基金项目: 国家自然科学基金战略性矿产资源开发利用专项（典型战略金属氧化矿强化浮选分离过程的多尺度化学原理与调控，编号：2021YFC2900800）；中国地质调查项目（金属矿产资源节约与综合利用调查，编号：DD20230039）。

详细信息

作者简介:
刘淑君，1984年出生，女，湖南永州人，硕士，工程师，主要从事岩矿分析测试方法研究，E-mail:382120656@qq.com

中图分类号: O657.31,TF041
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出版历程
- 收稿日期: 2023-10-10
- 刊出日期: 2024-07-02

Determination of rare earth elements in vanadium-titanium magnetite by ICP-MS

1.
Institute of Comprehensive Utilization of Mineral Resources, Chinese Academy of Geological Sciences, Rare Earth Resources Application Technology Innovation Center of China Geological Survey, Sichuan Rare Earth Technology Innovation Center, Technology Innovation Center for Comprehensive Utilization of Strategic Mineral Resources, Chengdu 610041, Sichuan, China;
2.
Pangang Group Mining Co., Ltd., Panzhihua 617000, Sichuan, China

摘要

摘要: 准确、快速地测定钒钛磁铁矿中的稀土元素，对钒钛磁铁矿的高效利用有着重要的作用。针对目前国内外缺乏钒钛磁铁矿中稀土元素分析方法的问题，试验选取不同矿区具有代表性的5件钒钛磁铁矿作为试验样品，采用盐酸、氢氟酸、硝酸外加硫酸混合酸溶分解的方式，并结合电感耦合等离子体质谱仪检出限低、灵敏度高、干扰小的特点，对钒钛磁铁矿中稀土元素测定过程中的仪器条件、测定模式、内标元素、同位素选择及质谱干扰进行研究。结果表明，在最佳的仪器工作参数的条件下，采用STD模式，选择干扰小且丰度大的同位素，选择合适的内标元素Rh和Re，能够有效地降低基体效应引起的信号强度漂移。此外，通过精密度试验及加标回收试验发现，采用电感耦合等离子体质谱法测定钒钛磁铁矿中的稀土元素能获得良好的精密度与准确度，此方法准确有效。
- 钒钛磁铁矿 /
- 稀土元素 /
- 电感耦合等离子体质谱法 /
- 准确度 /
- 精密度
Abstract: Accurate and rapid determination of rare earth elements in vanadium titanium magnetite plays an important role in the efficient utilization of vanadium titanium magnetite. In view of the lack of analysis methods for rare earth elements in vanadium titanium magnetite at home and abroad, 5 representative vanadium titanium magnetite crystals from different mining areas were selected as test samples, and hydrofluoric acid, nitric acid and sulfuric acid mixed acid solution decomposition method were adopted. Combined with the characteristics of inductively coupled plasma mass spectrometer with low detection limit, high sensitivity and low interference, the instrument conditions, internal standard elements, isotope selection and mass spectrum interference during the determination of rare earth elements in vanadium titanium magnetite were studied. The results show that the signal intensity drift caused by matrix effect can be effectively reduced by using STD mode, selecting the isotopes with small interference and large abundance, and selecting the appropriate internal standard elements Rh and Re under the conditions of the optimal instrument parameters. In addition, it is found by the precision tests and standard recovery tests that the inductively coupled plasma mass spectrometry method can obtain good precision and accuracy for the determination of rare earth elements in vanadium titanium magnetite.
- vanadium titanium magnetite /
- rare earth elements /
- inductively coupled plasma mass spectrometry(ICP-MS) /
- accuracy /
- precision

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表 1 电感耦合等离子体质谱仪工作条件

Table 1. Inductively coupled plasma mass spectrometer operating conditions

射频功率/W	雾化器流量/ (L·min⁻¹)	冷却气流量/ (L·min⁻¹)	辅助气流量/ (L·min⁻¹)	采样深度/步	（采样锥/截取锥）/mm	扫描方式	测量点/峰	重复测定次数	停留时间/ (ms·点⁻¹)	扫描次数	测量时间/s
1400	1.0	16	1.2	88	1.1/0.7	跳峰	3	3	10	40	60

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表 2 分析同位素、内标及干扰校正

Table 2. Analysis of isotopes, internal standards and interference correction

分析元素	内标	潜在干扰
⁸⁹Y	¹⁰³Rh
¹³⁹La	¹⁸⁵Re
¹⁴⁰Ce	¹⁸⁵Re
¹⁴¹Pr	¹⁸⁵Re
¹⁴³Nd	¹⁸⁵Re
¹⁴⁷Sm	¹⁸⁵Re	Gd,CeO, BaO
¹⁵³Eu	¹⁸⁵Re	BaO
¹⁵⁸Gd	¹⁸⁵Re	PrO,NdO,CeO
¹⁵⁹Tb	¹⁸⁵Re	PrO,NdO,
¹⁶³Dy	¹⁸⁵Re	SmO,NdO
¹⁶⁵Ho	¹⁸⁵Re	SmO
¹⁶⁶Er	¹⁸⁵Re	SmO,NdO
¹⁶⁹Tm	¹⁸⁵Re	EuO
¹⁷²Yb	¹⁸⁵Re	Dy,SmO,NdO
¹⁷⁵Lu	¹⁸⁵Re

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表 3 方法精密度（RSD）

Table 3. Method precision (RSD)

元素	RSD/%
元素	A1	A2	A3	A4	A5
La₂O₃	3.33	2.51	3.07	3.63	3.03
CeO₂	1.62	1.80	1.69	1.68	1.64
Pr₆O₁₁	6.84	5.95	6.19	7.44	5.86
Nd₂O₃	2.87	2.43	3.20	3.19	2.78
Sm₂O₃	6.55	6.30	6.22	6.71	5.59
Eu₂O₃	5.50	7.73	5.86	4.56	6.55
Gd₂O₃	5.10	6.45	4.54	4.28	5.08
Tb₄O₇	6.48	5.23	6.31	6.84	5.83
Dy₂O₃	6.44	5.95	6.64	6.97	6.42
Ho₂O₃	3.19	3.11	3.08	2.70	3.48
Er₂O₃	3.46	3.67	3.79	3.30	3.55
Tm₂O₃	3.47	3.60	3.50	3.34	3.61
Yb₂O₃	3.15	3.26	2.82	2.92	3.11
Lu₂O₃	3.45	5.39	4.14	3.87	4.53
Y₂O₃	2.28	2.00	2.30	2.14	2.24

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表 4 加标回收率

Table 4. Recovery rate of spikes

元素	回收率/%
元素	A1	A2	A3	A4	A5
La₂O₃	98.35	101.2	97.25	104.56	96.25
CeO₂	102.14	98.15	97.36	103.87	94.57
Pr₆O₁₁	97.38	96.57	102.36	96.74	103.56
Nd₂O₃	104.20	103.74	97.58	105.20	95.41
Sm₂O₃	102.56	98.97	94.34	104.57	97.37
Eu₂O₃	98.51	95.68	96.87	105.67	103.26
Gd₂O₃	97.32	94.57	103.25	96.35	105.46
Tb₄O₇	104.56	102.69	106.89	97.56	95.48
Dy₂O₃	103.86	105.86	98.87	95.42	106.54
Ho₂O₃	106.57	107.25	103.25	95.62	104.35
Er₂O₃	96.54	98.56	102.87	104.85	103.57
Tm₂O₃	104.58	106.25	93.57	96.12	107.25
Yb₂O₃	105.65	102.11	97.22	96.15	95.37
Lu₂O₃	106.78	104.37	95.87	94.53	103.57
Y₂O₃	98.25	95.61	103.58	105.41	97.45

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