高压密闭酸溶-电感耦合等离子体发射光谱法测定硼矿石中的硼

王蕾; 于汀汀; 孙红宾; 张保科

doi:10.15898/j.ykcs.202308070131

高压密闭酸溶-电感耦合等离子体发射光谱法测定硼矿石中的硼

1.
国家地质实验测试中心，北京 100037

基金项目: 国家重点研发计划项目(2021YFC2903000)课题“战略性矿产多元素同时分析技术和标准化”

详细信息

作者简介: 王蕾，高级工程师，从事地质样品分析方法研究与应用。E-mail：13311060626@189.cn

通讯作者: 张保科，高级工程师，从事地质样品分析方法研究与应用。E-mail：zhangbaoke@mail.cgs.gov.cn。

中图分类号: O657.31

收稿日期: 2023-08-07

修回日期: 2024-03-08

录用日期: 2024-03-20

刊出日期: 2024-05-31

Boron Analysis in Boron Ores by Inductively Coupled Plasma-Optical Emission Spectrometry with Sealed Acid Digestion at High Pressure

1.
National Research Center for Geoanalysis, Beijing 100037, China

More Information

Corresponding author: ZHANG Baoke, zhangbaoke@mail.cgs.gov.cn

Received Date: 07 August 2023

Revised Date: 08 March 2024

Accepted Date: 20 March 2024

Publish Date: 31 May 2024

摘要

摘要:
应用电感耦合等离子体发射光谱法(ICP-OES)分析硼矿石中的硼含量，样品分解方法多采用酸溶法和熔融法，硼酸在浓酸溶液中加热蒸发时形成易挥发的BF₃或BCl₃，造成硼的损失。熔融法可分解难溶于酸的硅硼钙石、电气石等样品，但将大量钠盐引入了样品中，基体较大，检出限高。本文建立了高压密闭酸溶、ICP-OES测定硼矿石中硼含量的方法。样品经硝酸和氢氟酸在高压密闭溶样罐中分解完全、定容稀释后，样品溶液用配备耐氢氟酸进样系统的ICP-OES测定。在ICP-OES中，硼有三条常用分析谱线，选取249.677nm为硼的分析谱线，标准曲线的线性相关系数大于0.9995。采用本方法对硼镁矿、锰方硼石和盐湖型固体硼矿三种类型5个不同含量范围的实际样品进行测定，相对标准偏差(RSD，n=11)为0.39%～2.66%，方法检出限为1.76µg/g，硼含量定量范围为5.87µg/g～10.8%。经标准物质验证，硼含量测定值与标准值一致，与容量法和微波消解法测定结果吻合。本方法试剂用量少，无需蒸干样品溶液，有效地避免了硼酸易挥发和试剂用量大的问题。
- 硼矿石 /
- 高压密闭酸溶 /
- 电感耦合等离子体发射光谱法 /
- 耐氢氟酸进样系统
Abstract:
The literature provides reference for the accurate determination of boron by inductively coupled plasma-optical emission spectrometry (ICP-OES), but most of the studies are conducted on the standard substances of soil and stream sediment. In addition, the range of boron content is low, and the methods for the determination of high boron content in boron ores are few. A method of ICP-OES with sealed acid digestion at high pressure was developed for the determination of boron content in boron ores. Using nitric acid and hydrofluoric acid as reagents, the samples of boron ores were dissolved at high temperature and high pressure without acid drive, and ICP-OES equipped with a hydrofluoric acid-resistant sampling system was used to determine boron. The samples of boromagnesite, ludwigite, chambersite and salt lake type solid boron ore were taken as the research objects. The relative standard deviation (RSD, n=11) was 0.39%−2.66%, the detection limit of the method was 1.76g/g, and the determination range was 5.87g/g−10.8%. The measured values were consistent with the certified values after the verification of the reference materials. Compared with volumetric method and microwave digestion method, the results were in good agreement. This method does not require evaporating the sample solution, which solves the boron volatile loss problem. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202308070131.
- boron ore /
- sealed acid digestion at high pressure /
- inductively coupled plasma-optical emission spectrometry /
- hydrofluoric acid-resistant sampling system

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表 1 实验用样品信息

Table 1. Information of experimental samples

样品编号	采样地点	样品类型	硼含量 (%)
NBFB-1	辽宁宽甸	硼镁矿	10.8
NBFB-2	天津蓟县	锰方硼石	1.48
NBFB-3	辽宁宽甸	硼镁矿	7.77
NBFB-4	辽宁宽甸	硼镁矿	2.95
NBFB-5	青海大柴旦盐湖	盐湖型固体硼矿	0.27

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表 2 硼标准溶液线性回归方程及线性相关系数

Table 2. Linear regression equation and linear correlation coefficient of boron standard solution

硼元素分析谱线 (nm)	线性回归方程	线性相关系数 (R²)
208.889	y=168.01x+43.037	1.0000
249.677	y=17635x+1474.1	1.0000
249.772	y=36192x+68547	0.9996

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表 3 本文方法与容量法、微波消解法测定硼含量结果对比

Table 3. Comparison of boron content determined by this method, volumetric method and microwave digestion method

标准物质和实际样品编号	硼含量标准值 (%)	硼含量测定值(%)
标准物质和实际样品编号	硼含量标准值 (%)	本文方法	容量法	微波消解法
YSB1674-05	1.75±0.047	1.74	1.73	1.74
GBW03132	2.75±0.034	2.74	2.77	2.76
NBFB-1	—	10.9	10.9	10.8
NBFB-3	—	7.75	7.82	7.80

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表 4 样品百分总和结果

Table 4. Aggregation results of samples

实际样品编号	主量元素和烧失量测定值(%)												加和 (%)
实际样品编号	Al₂O₃	CaO	TFe₂O₃	K₂O	MgO	MnO	Na₂O	P₂O₅	SiO₂	TiO₂	B₂O₃	LOI	加和 (%)
NBFB-1	0.68	3.50	6.32	0.36	37.5	0.39	0.03	0.06	2.81	0.05	34.8	13.0	99.5
NBFB-2	3.73	7.82	2.03	2.30	4.47	21.8	0.07	0.10	26.0	0.14	4.77	22.9	96.2
NBFB-3	1.51	3.40	5.06	0.90	37.2	0.29	0.08	0.63	16.4	0.05	24.8	9.81	100.2
NBFB-4	0.06	1.91	0.40	0.01	46.3	0.08	0.04	0.04	5.29	0.01	9.60	36.1	99.9
NBFB-5	2.88	15.2	1.03	0.81	18.4	0.05	3.49	0.04	16.5	0.13	0.87	37.9	97.2

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表 5 方法精密度

Table 5. Precision test of the method

实际样品编号	硼含量测定值(%)		RSD (%)
实际样品编号	11次分次测定值	平均值	RSD (%)
NBFB-1	10.80 10.72 10.80 10.84 10.79 10.80 10.76 10.80 10.86 10.86 10.77	10.80	0.39
NBFB-2	1.48 1.49 1.50 1.49 1.47 1.49 1.50 1.49 1.47 1.46 1.47	1.48	0.81
NBFB-3	7.71 7.73 7.73 7.82 7.73 7.76 7.87 7.86 7.71 7.86 7.75	7.77	0.82
NBFB-4	3.00 3.08 2.91 3.04 2.96 2.90 3.03 2.82 2.92 2.89 2.89	2.95	2.66
NBFB-5	0.26 0.27 0.26 0.27 0.26 0.27 0.28 0.27 0.26 0.27 0.27	0.27	2.23

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