Analysis and Research on Associated Elements Nb, Zr, Ga and Sc in Sedimentary Rare Earth Ores
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摘要:
通过对滇黔相邻区的不同矿点，不同品位的5个样品不同溶矿方式的对比、分析过程中仪器参数的优化以及分析方法的准确度和精密度实验，详细研究了沉积型稀土矿中共伴生元素Nb、Zr、Ga、Sc的分析方法，同时对它们在选择性浸出流程中的大致走向进行初步探讨。结果表明采用高压密闭酸溶，结合ICP-MS，沉积型稀土矿中共伴生元素Nb、Zr、Ga、Sc的相对标准偏差(RSD)均低于5%，且回收率都在96.2%～103.6%之间，方法具有良好的精密度和准确度；同时在选择性浸取试验中发现Al2O3和Ga2O3的浸出存在较为强烈的正相关关系，对沉积型稀土中镓的综合利用具有一定指导意义。
Abstract:Through comparative studies of different digestion methods for five ore samples with varying grades collected from adjacent mining areas in Yunnan and Guizhou Provinces, combined with optimization of instrumental parameters and accuracy precision tests of analytical methods, this research systematically investigated the analytical techniques for associated elements (Nb, Zr, Ga, Sc) in sedimentary rare earth ores. A preliminary exploration of their distribution patterns during selective leaching processes was also conducted. The results indicate that high-pressure sealed acid dissolution combined with ICP-MS analysis achieved excellent performance, with relative standard deviations (RSD) below 5% and recovery rates ranging from 96.2% to 103.6% for all target elements (Nb, Zr, Ga, Sc), demonstrating high precision and accuracy of the proposed method. Furthermore, selective leaching experiments revealed a strong positive correlation between the leaching behaviors of Al2O3 and Ga2O3, which provides valuable guidance for the comprehensive utilization of gallium in sedimentary rare earth ores.
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表 1 ICP-MS仪器工作参数
Table 1. The working parameters of ICP-MS
射频功率/W 雾化器流量/(L/min) 冷却气流量/(L/min) 辅助气流量/(L/min) 采样深度/步 采样锥/截取锥/mm 1400 1.0 16 1.2 88 1.1/0.7 扫描方式 测量点/峰 重复测定次数 停留时间/(ms.) 扫描次数 测量时间/s 跳峰 3 3 10 40 60 
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表 2 不同溶矿方式下稀土总量及共伴生元素的测定值 单位：g/t
Table 2. Determination values of total rare earth and associated elements by different ore dissolution methods
元素 四酸敞开体系 四酸+硫酸敞开体系 CJ-1 CJ-2 CJ-3 CJ-4 CJ-5 CJ-1 CJ-2 CJ-3 CJ-4 CJ-5 TREO 2 800 3 546 2 762 2 053 1 135 3 021 3 896 2 871 2 308 1 238 Nb 228 265 269 258 277 235 260 268 258 271 Sc 27 30 45 18 23 30 27 48 19 23 Ga 57 63 66 54 74 64 60 67 55 71 Zr 1 147 1 787 1 850 1 207 1 763 1 353 1 508 1 920 1 463 1 820 元素 四酸密闭体系 碱熔体系 CJ-1 CJ-2 CJ-3 CJ-4 CJ-5 CJ-1 CJ-2 CJ-3 CJ-4 CJ-5 TREO 3 071 4 085 3 158 2 533 1 295 2 974 3 970 2 884 2 470 1 244 Nb 242 258 271 261 279 226 240 256 240 276 Sc 35 32 52 24 25 32 30 48 24 23 Ga 62 60 72 55 78 60 57 72 54 76 Zr 1 668 1 961 2 016 1 908 2 071 1 589 1 898 1 950 1 895 2 012
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表 3 分析同位素、内标元素的选择
Table 3. Selection of measurement isotopes and internal standard
待测元素 同位素 内标元素 Ga 71 103Rh Sc 45 103Rh Nb 93 103Rh Zr 90 103Rh
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表 4 共伴生元素同位素内标及干扰校正
Table 4. Internal standards of isotopes of associated and co-occurring elements and interference correction
同位数 内标 潜在干扰 模式（*） 45Sc 103Rh BO2、CaH、SiO、C02 、AlO 标准 71Ga 103Rh ArCl、ClO2、ArP、Ce++、Nd++ 标准 90Zr 103Rh 标准 93Nb 103Rh AsO 标准
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表 5 方法的精密度和准确度试验
Table 5. Tests on the precision and accuracy of the method
样品 元素 测定值/(g/t) RSD/% 回收率/% CJ-1 Ga 62 3.86 96.4 Sc 35 2.56 97.3 Nb 242 2.89 96.2 Zr 1 668 3.12 102.5 CJ-2 Ga 60 2.33 98.3 Sc 32 2.89 101.9 Nb 258 2.42 103.6 Zr 1 961 3.22 97.8 CJ-3 Ga 72 2.12 96.3 Sc 52 1.89 98.4 Nb 271 2.68 103.2 Zr 2 016 2.98 102.3 CJ-4 Ga 55 2.87 96.3 Sc 24 3.45 98.5 Nb 261 2.73 99.1 Zr 1 908 2.47 103.3 CJ-5 Ga 78 3.11 102.7 Sc 25 2.31 97.2 Nb 279 3.33 102.9 Zr 2 071 2.98 98.5
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