Determination of 14 Major and Minor Elements in Dust Ash by X-ray Fluorescence Spectrometry with Powder-Pelleting-Lined Boric Acid Preparation
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摘要:
除尘灰中过高含量的钾、钠、锌、氯等元素严重影响转底炉的正常生产和稳定运行，为解决钢铁行业中除尘灰的环保和资源再利用问题，需准确测定其中各组分的含量。除尘灰种类多，钾、钠、锌和氯含量范围宽，采用X射线荧光光谱法（XRF）测定易超出工作曲线测定范围。本文基于粉末直接压片，采用硼酸衬底镶边的方法，将氯化钾、氯化钠和氧化锌基准试剂加入铁矿石标样中制备更高含量的校准样品，扩展了除尘灰日常分析中钾、钠、锌和氯的测定范围，使钾的测定范围为1.36%~12.00%，钠的测定范围为0.43%~6.85%，锌的测定范围为0.24%~35.00%，增加了氯的测定范围为0.25%~10.00%。本方法测定除尘灰中14种主次组分的精密度（RSD，n=7）均小于5.2%，实际样品的测定值与标准方法测定值基本一致，准确度和精密度良好。
Abstract:BACKGROUND The high content of potassium, sodium, zinc, and chlorine in dust ash significantly affects the stable operation of converter. To recycle the dust ash, it is necessary to accurately determine the contents of the components. Dust ash contains a broad range of potassium, sodium, zinc, and chlorine; therefore, the traditional X-ray fluorescence spectrometry (XRF) exceeds the range of the work curve.
OBJECTIVES To develop a method for the determination of 14 components in the dust ash with a broad concentration range of potassium, sodium, zinc, and chlorine.
METHODS Standard reagents of potassium chloride, sodium chloride, and zinc oxide were added to commercially available iron ore standards in a quantitative manner to provide a new series of calibration samples with wide ranges of potassium, sodium, zinc, and chlorine contents. The 14 components in the dust ash were determined by XRF spectrometry with a powder-pelleting-lined boric acid preparation.
RESULTS The measurement ranges of potassium, sodium, zinc, and chlorine were 1.36%-12.00%, 0.43%-6.85%, 0.24%-35.00%, and 0.25%-10.00%, respectively. The results of the 14 components in the dust ash were consistent with those of the traditional method, yielding a relative standard deviation of < 5.2% (n=7).
CONCLUSIONS XRF spectrometry with the powder-pelleting-lined boric acid preparation showed good accuracy and precision during the determination of 14 components in the dust ash.
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表 1 分析元素测量条件
Table 1. Measurement conditions for the elements
元素 分析线 探测器 分析晶体 峰值
2θ(°)Si Kα PC PET 109.00 Al Kα PC PET 144.650 Ca Kα PC LIF1 113.10 Mg Kα PC RX25 38.25 Mn Kα SC LIF1 62.960 Ti Kα SC LIF1 86.110 As Kα SC LIF1 33.964 Fe Kα SC LIF1 57.50 Zn Kα SC LIF1 41.780 P Kα PC Ge 141.190 Pb Lβ1 SC LIF1 28.232 Cl Kα PC Ge 92.880 Na Kα PC RX25 46.440 K Kα PC LIF1 136.680 
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表 2 分析组分的测定范围
Table 2. Measurement ranges of the components
分析组分 测定范围
(%)分析组分 测定范围
(%)SiO2 1.35~48.50 TFe 17.49~66.87 Al2O3 0.11~4.93 Zn 0.24~35.00 CaO 0.13~10.50 P 0.0048~0.37 MgO 0.16~5.98 Pb 0.0040~0.182 MnO 0.061~3.63 Cl 0.25~10.00 TiO2 0.0070~0.32 Na 0.43~6.85 As 0.0011~0.22 K 1.36~12.00
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表 3 重叠谱线及基体效应校正
Table 3. Correction of overlapping spectral lines and matrix effects
元素 分析线 基体校正元素 Si Kα P Al Kα P Ca Kα Al Mg Kα Ca, Al，P Mn Kα Fe，Al，Mg Ti Kα Mn As Kα Zn Fe Kα Ti，Mn Zn Kα Fe，Al，Mg P Kα Cl Pb Lβ1 Zn Cl Kα P，Al Na Kα P K Kα Ca，Mg，Al
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表 4 各组分标准曲线参数
Table 4. Calibration curve parameters of each component
分析组分 浓度截距 斜率 相关系数
(R2)SiO2 0.1344 -1.2920 0.9926 Al2O3 0.1370 -0.1216 0.9946 CaO 0.03978 -0.2319 0.9949 MgO 0.2320 0.1197 0.9984 MnO 0.02614 -0.0003583 0.9969 TiO2 0.1468 -0.04658 0.9908 As 0.006079 0.0002817 0.9950 TFe 0.1953 -3.4351 0.9919 Zn 0.03059 -0.1809 0.9917 P 0.03647 -0.01743 0.9967 Pb 0.01996 0.005724 0.9893 Cl 0.9710 -1.3681 0.9925 Na 2.7073 -0.0819 0.9686 K 0.8273 -0.3554 0.9591
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表 5 不同方法分析结果比对
Table 5. Comparison of analysis results by different methods
分析组分 1#转炉污泥 2#高炉污泥 3#布袋灰 4#转炉二次除尘灰 本方法测定值
(%)标准方法测定值
(%)相对偏差
(%)本方法测定值
(%)标准方法测定值
(%)相对偏差
(%)本方法测定值
(%)标准方法测定值
(%)相对偏差
(%)本方法测定值
(%)标准方法测定值
(%)相对偏差
(%)SiO2 1.41 1.46 -3.40 3.24 3.18 1.89 2.98 2.94 1.36 1.11 1.08 2.78 Al2O3 0.36 0.31 16.13 3.93 4.02 -2.24 3.11 3.07 1.30 0.26 0.27 -3.70 CaO 7.77 7.89 -1.52 3.78 3.74 1.07 2.07 2.04 1.47 9.55 9.57 -0.21 MgO 3.17 3.10 2.26 1.01 1.06 -4.72 0.58 0.61 -4.92 3.00 3.07 -2.28 MnO 0.23 0.20 9.52 0.18 0.17 5.88 0.082 0.079 3.80 0.55 0.56 -1.79 TiO2 0.041 0.045 -4.65 0.32 0.34 -5.88 0.13 0.14 -7.14 0.28 0.27 3.70 As 0.0035 0.0032 9.38 0.055 0.052 5.77 0.083 0.086 -3.49 0.17 0.18 -5.56 TFe 58.40 58.92 -0.88 32.76 32.70 0.18 21.58 21.53 0.23 52.99 52.93 0.11 Zn 0.57 0.54 5.56 25.40 25.18 0.87 12.24 12.21 0.25 5.69 5.72 -0.52 P 0.11 0.10 10.00 0.044 0.042 4.76 0.056 0.058 -3.45 0.074 0.071 4.23 Pb 0.26 0.24 8.33 0.26 0.24 8.33 0.014 0.013 7.69 0.15 0.16 -6.25 Cl 0.12 0.11 9.09 0.31 0.32 -3.13 1.49 1.51 -1.32 0.31 0.32 -3.13 Na 0.041 0.038 7.89 0.24 0.25 -4.00 0.13 0.14 -7.14 0.15 0.14 7.14 K 0.18 0.19 -5.26 0.091 0.093 -2.15 0.12 0.13 -7.69 0.074 0.072 2.78 注: ①相对偏差=(本方法分析结果-标准方法分析结果)/标准方法分析结果。
②各组分测定方法：TFe、CaO、MgO、Al2O3采用滴定法；SiO2采用重量法；Na、K采用AAS法；MnO、P、TiO2采用ICP-OES法；Zn、Pb、As采用光度法；Cl采用离子色谱法。
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