乙醇增敏-电感耦合等离子体发射光谱法测定矿石及选冶样品中的铌钽

姚玉玲; 吴丽琨; 刘卫; 李刚

doi:10.15898/j.cnki.11-2131/td.2015.02.012

乙醇增敏-电感耦合等离子体发射光谱法测定矿石及选冶样品中的铌钽

中国地质科学院矿产综合利用研究所, 四川成都 610041

基金项目: 中国地质调查局地质调查项目(12120113014300)

详细信息

作者简介: 姚玉玲, 工程师, 主要从事岩石矿物分析测试技术研究.E-mail: yaoyling@163.com

中图分类号: O657.31

收稿日期: 2014-09-18

修回日期: 2015-03-05

录用日期: 2015-03-08

刊出日期: 2015-02-25

Determination of Nb and Ta in Ores and Metallurgical Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry with Ethanol as a Sensitizer

Institute of Multipurpose Utilization of Mineral Resources, Chinese Academy of Geological Sciences, Chengdu 610041, China

Received Date: 18 September 2014

Revised Date: 05 March 2015

Accepted Date: 08 March 2015

Publish Date: 25 February 2015

摘要

摘要:
电感耦合等离子体发射光谱法(ICP-AES)在铌钽测定方面获得广泛应用, 但灵敏度较低、检出限较高, 不能满足矿石和选冶样品中的低含量铌钽的检测要求。本文优化了ICP-AES测试过程中多种有机试剂的增敏效果, 结果表明:样品采用氢氟酸-硝酸-硫酸敞开酸溶, 选择乙醇作增敏剂, 雾化效率最佳, 当乙醇浓度为6%时, 原子线Nb 292.781 nm、Ta 240.063 nm的灵敏度分别增强了180.5%和265.5%;铌的检出限由不加乙醇的5.85 μg/g降低到3.22 μg/g, 钽的检出限由不加乙醇的10.65 μg/g降低到5.03 μg/g; Nb₂O₅回收率为97.7%~101.9%, Ta₂O₅回收率为96.8%~97.2%;方法精密度(RSD) < 6%。本方法适用于低含量和高含量铌钽的同时测定, 尤其有利于选冶流程样品中同一批次的精矿、中矿和尾矿的同时测定, 克服了以往分别采用光谱法和质谱法测定所产生的仪器间误差导致回收率吻合程度不好的缺陷。
- 矿石 /
- 选冶样品 /
- 铌 /
- 钽 /
- 敞开酸溶 /
- 乙醇 /
- 电感耦合等离子体发射光谱法
Abstract:
Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) has been widely used in the determination of Nb and Ta, but its low sensitivity and high detection limits cannot meet the analysis requirement of low content Nb and Ta in ores and metallurgical samples. The sensitizing effect of many organic reagents was optimized in the ICP-AES determination. The results show that ethanol is the best sensitizer for determination of Nb and Ta after the samples were decomposed by open acid-solution with HF-HNO₃-H₂SO₄ mixture. When the concentration of ethanol reaches 6%, the sensitivities of Nb (292.781 nm) and Ta (240.063 nm) have increases of 180.5% and 265.5%, respectively. Moreover, the detection limits of Nb and Ta were reduced from 5.85 to 3.22 μg/g and from 10.65 to 5.03 μg/g, respectively. The recoveries of Nb₂O₅ and Ta₂O₅ were 97.7%-101.9% and 96.8%-97.2%, respectively. The precision of this method was less than 6%. The method is suitable for the simultaneous determination of low and high contents of Nb and Ta, and is particularly suitable for determining Nb and Ta in ore concentrates, medium ores and the tailings of metallurgical samples from the same batch, which overcomes the bad agreement of recovery between ICP-AES and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS).
- ores /
- metallurgical samples /
- niobium /
- tantalum /
- open acid-solution /
- ethanol /
- Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES)

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表 1 谱线选择与增敏效果

Table 1. The selection of spectral line and sensitization effect

元素	谱线长度 (nm)	响应值	增敏倍数 (%)	灵敏度改善情况
Nb	309.418	-757.5	-	标准不成线性，不采用
	313.079	45467.4	150.1	干扰较多，不采用
	269.706	6267.8	155.2	灵敏度较低，不采用
	292.781	13563.8	155.5	增敏效果较好，干扰小，采用
Ta	226.230	1767.9	162.5	灵敏度低，不采用
	233.198	541.2	173.4	灵敏度低，不采用
	248.87	2666.1	183.2	灵敏度低，不采用
	267.59	5725.6	-	-
	240.063	6213.2	170.3	灵敏度相对较高，谱线简单，采用

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表 2 ICP-AES工作条件

Table 2. Working parameters of the ICP-AES instrument

工作参数	设定条件	工作参数	设定条件
入射功率	1300 W	积分时间	6 s
雾化气(Ar)流速	0.80 L/min	观测高度	12 mm
冷却气(Ar)流速	14.0 L/min	Nb分析线	292.781 nm
辅助气(Ar)流速	1.0 L/min	Ta分析线	240.063 nm
进样速度	1.48 L/min
清洗时间	30 s

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表 3 加入乙醇前后的方法检出限对比

Table 3. A comparison of the detection limits of Nb and Ta with or without ethanol

元素	加入乙醇情况	元素测定值 (ng/mL)	标准偏差 (ng/mL)	检出限 (μg/g)
Nb₂O₅	不加乙醇	0.0050.0170.0230.014 0.0060.0270.0110.009 0.0150.0020.006	0.008	5.85
Nb₂O₅	加6%乙醇	0.0080.0060.0110.004 0.0090.0140.0170.005 0.01 0.0030.007	0.004	3.22
Ta₂O₅	不加乙醇	0.012 0.002-0.015 0.004 0.020.0310.004-0.004 -0.017 0.0090.013	0.014	10.65
Ta₂O₅	加6%乙醇	0.005 0.011 0.0090.004 0.0120.0210.007 0.003 0.0180.018 0.004	0.007	5.03

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表 4 方法精密度和准确度

Table 4. The precision and accuracy tests of the method

标准物质编号	Nb₂O₅测定值(μg/g)	平均值 (μg/g)	标准值 (μg/g)	相对误差 (%)	RSD(%)
GBW 07184	59.25 62.34 60.65 57.82 55.2 64.5 53.85 55.10 60.25 58.74 64.23	59.27	56.62	4.68	6.1
GBW 07185	5264.9 5233.5 5058.1 5201.4 5376.6 5250.4 5369.2 5420.3 5237.8 5201.0 5117.0	5248.2	5200	0.93	2.1
标准物质编号	Ta₂O₅测定值(μg/g)	平均值 (μg/g)	标准值 (μg/g)	相对误差 (%)	RSD(%)
GBW 07184	113.52 112.25 108.25 111.56 107.21 103.89 101.25 104.52 104.12 101.36 118.24	107.83	108.11	-0.26	4.7
GBW 07185	9888.5 10680.0 10348.8 10322.4 10284.5 10635.6 10203.8 10381.9 9901.9 10203.6 10295.3	10286.0	10200	0.84	2.4

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表 5 实际样品分析

Table 5. Analytical results of Nb and Ta in the actual samples

样品类型	Nb₂O₅			Ta₂O₅
样品类型	ICP-AES (本法)	国家标准方法	相对误差 (%)	ICP-AES (本法)	国家标准方法	相对误差 (%)
精矿	12.36%	12.09%	2.23	4.09%	4.02%	1.74
尾矿	11.81 μg/g	12.56 μg/g	-5.97	5.65 μg/g	5.27 μg/g	-7.21

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乙醇增敏-电感耦合等离子体发射光谱法测定矿石及选冶样品中的铌钽

中国地质科学院矿产综合利用研究所, 四川 成都 610041

作者简介: 姚玉玲, 工程师, 主要从事岩石矿物分析测试技术研究.E-mail: yaoyling@163.com

Determination of Nb and Ta in Ores and Metallurgical Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry with Ethanol as a Sensitizer

Institute of Multipurpose Utilization of Mineral Resources, Chinese Academy of Geological Sciences, Chengdu 610041, China

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中国地质科学院矿产综合利用研究所, 四川成都 610041