熔融制样X射线荧光光谱法测定锑矿石中的锑和14种微量元素

刘江斌; 余宇; 段九存; 赵伟华; 李瑞仙; 黄兴华; 和振云; 党亮

熔融制样X射线荧光光谱法测定锑矿石中的锑和14种微量元素

国土资源部兰州矿产资源监督检验中心, 甘肃兰州 730050

基金项目: 甘肃省科技计划资助项目(1306FTGA011)

详细信息

作者简介: 刘江斌, 工程师, 长期从事X射线荧光光谱分析.E-mail: liu-jiangbin@163.com

中图分类号: P578.14;O657.34

收稿日期: 2013-12-02

修回日期: 2014-10-23

录用日期: 2014-11-15

刊出日期: 2014-06-25

Determination of Antimony and 14 Trace Elements in Antimony Ores by X-ray Fluorescence Spectrometry with Fusion Sample Preparation

Lanzhou Testing and Quality Supervision Center, Ministry of Land and Resources, Lanzhou 730050, China

Received Date: 02 December 2013

Revised Date: 23 October 2014

Accepted Date: 15 November 2014

Publish Date: 25 June 2014

摘要

摘要:
锑矿石分析通常分别采用酸分解系统和碱熔系统, 萃取分离后应用容量法、原子吸收光谱法、原子荧光光谱法等分析手段进行单项测定, 样品处理繁琐、操作复杂, 分析过程常因熔矿不完全而导致结果偏低或失真, 难以满足地质测试的需要。本文建立了玻璃熔融制样, 波长色散X射线荧光光谱测定锑矿石中的锑及14种次量元素与伴生元素(Cu、Pb、Zn、As、Co、Ni、W、Ba、S、SiO₂、Al₂O₃、TFe、CaO、MgO)的快速分析方法。用国家标准物质和人工合成标准参考物质拟合校准曲线, 对熔融条件进行了研究。确定样品与四硼酸锂-偏硼酸锂-氟化锂复合熔剂的熔融稀释比例为1:20, 以硝酸铵为氧化剂, 碳酸锂为保护剂, 700℃预氧化, 在1050℃温度下熔融完全, 有效地防止了As、S的挥发损失, 解决了化学法测试样品处理复杂、不能同时测定多元素、测试元素偏少的问题。一些元素的检出限为Sb 0.14%, Cu 0.0027%, Pb 0.0025%, Zn 0.0046%, As 0.0028%, S 0.021%;方法精密度(RSD, n=12) 小于5%;选用合成标准物质和实际生产锑矿试样进行验证, 测定结果与参考值或化学值一致性良好。本法大部分元素检出限都要稍高于粉末压片法, 但操作简单, 测试范围更宽, 适用于实验室对不同锑矿矿种批量样品中多元素快速、准确检测的需要。
- 锑矿石 /
- 锑 /
- 微量元素 /
- 伴生元素 /
- 四硼酸锂-偏硼酸锂-氟化锂复合熔剂 /
- X射线荧光光谱法
Abstract:
The analysis of antimony ores usually uses acid decomposition and an alkali fusion system, followed by the volumetric method after solvent extraction. Each component employs various analytical methods such as capacity, Atomic Absorption Spectrometry and Atomic Fluorescence Spectrometry. These methods not only have complicated operations with long time consuming, but also obtain low or become distorted due to incomplete digestion or serious interferences, which subsequently make it difficult to meet the needs of geological analysis. The glass fusion preparation technique and establishing the rapid analysis method by using wavelength dispersion X-ray Fluorescence Spectrometry (XRF) are discussed and presented in this paper to determine antimony and 14 kinds of trace and associated elements (Cu, Pb, Zn, As, Co, Ni, W, Ba, S, SiO₂, Al₂O₃, TFe, CaO and MgO) in antimony ores. The calibration cure was calibrated by using the national standard material and synthetic standard reference material, in order to study melting conditions. The sample and lithium teraborate-lithium metaborate-lithium fluoride were melted with dilution ratio of 1:20 with ammonium nitrate as oxidant and lithium carbonate as protective agent. The sample was preoxidated at 700℃, and was melted completely at 1050℃, which effectively prevented the volatilization of arsenic and sulfur to solve the problems of complex procedure, the inability to simultaneous determine elements and insufficient test elements by chemical methods. The method detection limits are lower than previous methods (Sb: 0.14%, Cu: 0.0027%, Pb: 0.0025%, Zn: 0.0046%, As: 0.0028% and S: 0.021%) and the method precision degree (RSD, n=12) is lower than 5.0%. Verified by synthetic standard material and the actual production of an antimony ore sample, the results show good consistency with the reference value obtained by the chemical method. Although the detection limits are higher than those for the powder pellet method, the operation if this method was simple, rapid and accurate making it applicable to lab analysis requirements of varied and batch antimony ores samples.
- antimony ore /
- antimony /
- trace elements /
- associated elements /
- lithium teraborate-lithium metaborate-lithium mixed flux /
- X-ray Fluorescence Spectrometry

HTML全文

表 1 元素测量条件

Table 1. Measurement conditions of the elements

分析线	分光晶体	准直器	探测器	衰减器	PHA	电压 (kV)	电流 (mA)	2θ(°)		t(s)
分析线	分光晶体	准直器	探测器	衰减器	PHA	电压 (kV)	电流 (mA)	峰值	背景	峰值	背景
Sb Kα	LiF1	S2	SC	1/10	100~300	60	60	13.440	14.780	20	10
Cu Kα	LiF1	S8	SC	1/1	100~330	60	60	45.014	46.500	20	10
Pb Lα	LiF1	S8	SC	1/1	100~300	60	60	33.918	34.880	30	15
Zn Kα	LiF1	S8	SC	1/1	100~300	60	60	41.784	42.500	20	10
As Kα	LiF1	S8	SC	1/1	100~310	60	60	33.985	34.880	20	10
Co Kα	LiF1	S8	SC	1/1	100~300	60	60	52.782	54.020	30	15
Ni Kα	LiF1	S8	SC	1/1	100~300	60	60	48.656	50.420	20	10
W Lα	LiF1	S8	SC	1/1	100~320	60	60	43.020	44.340	30	15
Ba Lα	LiF1	S8	SC	1/1	100~350	60	60	87.164	88.560	20	10
S Kα	Ge	S8	F-PC	1/1	120~300	60	60	110.818	113.800	40	10
Si Kα	PET	S4	F-PC	1/1	100~310	40	90	109.184	110.700	20	10
Al Kα	PET	S4	F-PC	1/1	100~300	40	90	144.894	147.050	20	10
Fe Kα	LiF1	S2	SC	1/1	100~290	60	60	57.514	56.220	20	10
Ca Kα	LiF1	S4	F-PC	1/1	100~300	40	90	113.154	114.800	30	15
Mg Kα	RX25	S4	F-PC	1/1	100~310	40	90	38.010	39.400	30	15
Rh Kαc	LiF1	S2	SC	1/1	100~300	50	50	18.360	-	10	-
注：PHA为脉冲高度分析器。

下载: 导出CSV

表 2 校准样品中分析元素的含量范围

Table 2. Concentration ranges for elements in calibration samples

元素	含量 (%)	元素	含量 (%)
Sb	0.25~83.52	Ba	0.010~17.90
Cu	0.0010~2.00	S	0.28~19.87
Pb	0.010~1.86	SiO₂	1.03~75.26
Zn	0.016~1.74	Al₂O₃	0.30~19.62
As	0.0080~3.55	TFe₂O₃	0.15~6.36
Co	0.0005~1.50	CaO	0.12~12.50
Ni	0.0010~1.42	MgO	0.070~4.77
W	0.0050~1.59

下载: 导出CSV

表 3 重叠谱线和影响元素

Table 3. Concentration ranges for elements in calibration samples

元素	内标线	干扰重叠线	基体影响元素
Sb	Rh Kαc	-	Si, Al, Fe
Cu	Rh Kαc	Zn Kα	Sb, Si, Fe, Ca
Pb	Rh Kαc	As Kα	Fe, Ca
Zn	Rh Kαc	Cu Kβ	Sb, Si, Fe, Ca
As	Rh Kαc	Cu Kα, Pb Lα	Si
Co	Rh Kαc	Fe Kα, Ni Kα	Sb, Si
Ni	Rh Kαc	Co Kβ	Sb, Fe, Ca
W	Rh Kαc	NiKα, Zn Kα	Si, Fe
Ba	-	-	Sb, Fe
S	-	-	Sb, Si, Al, Fe
Si	-	-	Sb, Fe, Ca, Mg
Al	-	-	Sb, Si, Fe
Fe	-	-	Sb, Si, Ca, Mg
Ca	-	Ni Kβ₁	Si, Fe, Mg
Mg	-	As Lα	Si, Fe, Ca

下载: 导出CSV

表 4 硝酸铵-碳酸锂加入量试验

Table 4. The experiment on dosage of NH₄NO₃-Li₂CO₃

试样	元素及含量	0.2 g碳酸锂保持不变时，硝酸铵加入量(g)			2.0 g硝酸铵保持不变时，碳酸锂加入量(g)
试样	元素及含量	1.0	2.0	3.0	0.1	0.2	0.3	0.4
Sb-1	As(1.51%)	403.253	442.762	442.584	410.613	442.762	442.507	436.988
Sb-1	S(5.02%)	35.241	38.727	38.725	38.244	38.727	38.726	38.519
Sb-5	As(0.076%)	49.996	50.073	50.075	50.081	50.073	50.047	50.002
Sb-5	S(0.29%)	3.373	3.384	3.382	3.386	3.381	3.379	3.326

下载: 导出CSV

表 5 熔融温度试验

Table 5. Melting temperature tests of the method

元素	荧光强度(kcps)
元素	1000℃	1050℃	1100℃
As	100.135	103.454	100.381
S	13.282	15.324	12.697

下载: 导出CSV

表 6 方法检出限与测定范围

Table 6. Detection limits and measurement range of the method

元素	检出限 (%)	测定范围 (%)	元素	检出限 (%)	测定范围 (%)
Sb	0.14	0.50~83.50	Ba	0.089	0.10~15.00
Cu	0.0027	0.0040~2.00	S	0.021	0.30~19.00
Pb	0.0025	0.012~1.50	SiO₂	0.15	1.05~75.00
Zn	0.0046	0.030~1.70	Al₂O₃	0.077	0.50~15.00
As	0.0028	0.020~3.50	TFe₂O₃	0.013	0.30~5.00
Co	0.0011	0.0020~1.50	CaO	0.015	0.15~12.50
Ni	0.0036	0.0070~1.42	MgO	0.093	0.30~4.50
W	0.0070	0.0070~1.50

下载: 导出CSV

表 7 方法精密度

Table 7. Precision tests of the method

元素	含量(%)		RSD (%)	元素	含量(%)		RSD (%)
元素	参考值	测量平均值	RSD (%)	元素	参考值	测量平均值	RSD (%)
Sb	19.21	19.28	0.38	Ba	8.97	8.94	1.69
Cu	0.80	0.78	2.45	S	2.59	2.56	4.87
Pb	0.93	0.96	3.02	SiO₂	36.42	36.61	0.76
Zn	0.81	0.80	0.98	Al₂O₃	6.70	6.67	1.73
As	0.76	0.78	4.14	TFe₂O₃	1.07	1.10	0.65
Co	0.71	0.70	3.52	CaO	0.78	0.78	0.50
Ni	0.71	0.69	3.66	MgO	0.65	0.62	0.82
W	0.80	0.79	4.97

下载: 导出CSV

表 8 分析结果对照

Table 8. Comparison of analytical results

元素	SY-1		SY-2		SY-3		2013KY637
元素	参考值 (%)	本法 (%)	参考值 (%)	本法 (%)	参考值 (%)	本法 (%)	其他方法 (%)	本法 (%)
Sb	30.96	31.02	1.92	1.79	68.49	68.57	68.54	68.57
Cu	1.28	1.34	0.080	0.078	0.53	0.54	0.026	0.027
Pb	1.48	1.52	0.096	0.091	0.66	0.63	0.12	0.13
Zn	1.29	1.31	0.083	0.084	0.54	0.55	0.027	0.030
As	1.21	1.24	0.076	0.075	0.50	0.52	0.25	0.27
Co	1.14	1.17	0.071	0.074	0.47	0.47	0.0030	0.0026
Ni	1.11	1.09	0.072	0.073	0.38	0.40	0.0007	0.0002
W	1.27	1.31	0.081	0.086	0.53	0.56	0.0001	0.0000
Ba	14.33	14.46	0.93	0.95	5.96	5.99	-	0.012
S	4.02	4.07	0.69	0.62	1.68	1.70	12.68	12.57
SiO₂	14.57	14.33	65.55	65.70	5.30	5.23	-	3.49
Al₂O₃	2.68	2.63	12.06	11.98	0.78	0.75	-	0.83
TFe₂O₃	0.33	0.34	2.03	2.06	0.50	0.49	0.80	0.77
CaO	0.25	0.23	1.47	1.51	10.09	10.27	0.35	0.35
MgO	0.44	0.41	1.59	1.63	3.17	3.20	0.20	0.19
注：其他测定方法说明:Sb采用容量法，Cu、Pb、Zn、Co、Ni、W采用电感耦合等离子体发射光谱/质谱法，As采用原子荧光光谱法，S采用燃烧法，TFe、CaO、MgO采用原子吸收光谱法

下载: 导出CSV

参考文献(19)

[1]
[2]	GB/T 15925—2010, 锑矿石分析方法; 硫酸铈容量法测定锑量[S].
[3]	GB/T 14353—2010, 铜矿石、铅矿石、锌矿石化学分析方法[S].
[4]	GB/T 6730. 67—2009, 砷含量的测定; 氢化物发生原子光谱法[S].
[5]	http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN200608046.htm
[6]	GB/T 24224—2009, 含硫量的测定; 燃烧-中和滴定法[S].
[7]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS198702011.htm
[8]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201206010.htm
[9]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201102018.htm
[10]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201305009.htm
[11]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS198903011.htm
[12]	http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN401.019.htm
[13]	http://www.cnki.com.cn/Article/CJFDTOTAL-FXKX603.003.htm
[14]	http://www.cnki.com.cn/Article/CJFDTOTAL-YJFX201309010.htm
[15]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS200702023.htm
[16]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS200703015.htm
[17]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201306014.htm
[18]	http://www.cnki.com.cn/Article/CJFDTOTAL-YJFX201401008.htm
[19]

施引文献

资源附件(0)

访问统计

表(8)

计量

文章访问数: 463
PDF下载数: 1
施引文献: 0

熔融制样X射线荧光光谱法测定锑矿石中的锑和14种微量元素

国土资源部兰州矿产资源监督检验中心, 甘肃 兰州 730050

作者简介: 刘江斌, 工程师, 长期从事X射线荧光光谱分析.E-mail: liu-jiangbin@163.com

Determination of Antimony and 14 Trace Elements in Antimony Ores by X-ray Fluorescence Spectrometry with Fusion Sample Preparation

Lanzhou Testing and Quality Supervision Center, Ministry of Land and Resources, Lanzhou 730050, China

计量

出版历程

目录

国土资源部兰州矿产资源监督检验中心, 甘肃兰州 730050