Discussion on Pretreatment Method for Extracting Rare Earth Elements from Weathered Crust Elution-deposited Rare Earth Ores
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摘要:
传统观点认为，风化壳淋积型稀土矿床（即离子吸附型稀土矿床）中，稀土主要以吸附态赋存于风化壳黏土矿物表面，其他赋存形式占比较少。但近年来的同步辐射研究显示，稀土元素也同时以内层络合物形式存在，而内层络合物的存在可能会抑制稀土元素的离子交换。如何将风化壳淋积型稀土矿中各种形态的稀土元素有效地溶出，对于提高稀土资源利用率十分重要。本文选取南岭地区风化壳淋积型稀土矿石样品，选择混合酸（五酸）消解、盐酸消解、硝酸消解、硫酸铵浸提的前处理方式，采用电感耦合等离子体质谱（ICP-MS）测定，探讨样品中稀土元素的溶出情况。结果表明，采用混合酸（五酸）能够溶出样品中的全相稀土；盐酸或硝酸能够溶出以离子状态吸附于黏土矿物或铁锰氧化物中的稀土元素，以及以碳酸盐、磷酸盐等形式存在的稀土元素；硫酸铵浸提则只能将离子相的稀土元素置换出来。采用硝酸、盐酸溶出的稀土量，占混合酸（五酸）消解溶出稀土量（全相稀土）的71.7%～97.5%，硫酸铵浸提溶出的稀土量（离子相稀土）最低，仅是全相稀土量的9.1%～75.5%。Sc3+的离子半径明显小于其他稀土元素，其提取率也明显低于其他稀土元素；铈（Ce）不同于其他稀土元素的分异-富集特性，使其在硫酸铵浸提中提取率与其他稀土元素不一致。
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关键词:
- 风化壳淋积型稀土矿 /
- 样品处理 /
- 稀土元素（REEs） /
- 酸溶 /
- 硫酸铵浸提 /
- 电感耦合等离子体质谱法
Abstract:BACKGROUND Weathered crust elution-deposited rare earth ores are the dominant mineral resources in China[1-5]. The occurrence of rare earth elements (REEs) in weathering crust elution-deposited is very complicated. At present, the “ionic” rare earth extraction process can only use the “exchangeable adsorption state” rare earth elements, that is, the “ionic phase” rare earth elements, and other phase rare earth elements cannot be effectively recycled[6]. How to effectively dissolve various forms of rare earth elements in ion-adsorbed rare earth ore is very important to improve the utilization rate of rare earth resources.
OBJECTIVES To compare the extraction efficiency of REEs in weathered crust elution-deposited rare earth ores by different pretreatment methods and discuss the influencing factors.
METHODS Five pretreatment methods, being open mixed acid digestion (HCl+HNO3+HF+HClO4+H2SO4), nitric acid digestion with or without hydrogen peroxide, hydrochloric acid digestion with hydrogen peroxide and ammonium sulfate leaching, were used to extract REEs in six rare earth samples from the Nanling area. The content of REEs in samples was determined by ICP-MS. For ion-adsorbed rare earth minerals, the open digestion method of five acids can replace the complicated alkali melting method for the determination of REEs in samples under certain conditions. Nitric acid, hydrochloric acid digestion or ammonium sulfate leaching can only dissolve part of REEs in ion-adsorbed rare earth samples.
RESULTS The amount of REE extracted by different pretreatment methods is quite different. The results of mixed acid digestion (five acids) are the highest; the results of nitric acid with or without hydrogen peroxide digestion, hydrochloric acid and hydrogen peroxide digestion are similar. The amount of REEs dissolved by nitric acid or hydrochloric acid digestion is slightly lower than mixed acid digestion. The amount of REEs dissolved by ammonium sulfate leaching is the lowest. The amount of REEs dissolved by 50% nitric acid, hydrochloric acid and other digestion methods accounts for 75.3%-91.7% of the total phase REEs, and the amount of REEs dissolved by ammonium sulfate leaching (ionic phase rare earth) only accounts for 9.1%-5.5% of the total phase REEs. The extraction rate of scandium (Sc) is much lower than that of total REEs in nitric acid and hydrochloric acid digestion, and Sc can not be dissolved by ammonium sulfate leaching. There is no correlation between the extraction rate of cerium (Ce) and other REE, the total extraction rate of light REE or the total extraction rate of REEs. The difference of the results by different pretreatments is closely related to the occurrence state of REEs in the samples. Mixed acid digestion can completely destroy the structure of the sample, and all the REEs in the sample can be dissolved. The REEs are differentiated and enriched in weathering crust layers. Some REEs still exist in the form of mineral facies after weathering. The content of REEs in ionic phase is closely related to weathering degree and mineral composition of each layer of weathering crust. Proportion of REEs content in different parts of weathering crust is not the same. Hydrochloric acid or nitric acid can dissolve REEs in the ionic state adsorbed in clay minerals or iron and manganese oxides, as well as REEs in the form of carbonates, phosphates, etc. Some REEs exist stably in silicate mineral lattices that cannot be completely dissolved by nitric or hydrochloric acid. Ammonium sulfate leaching can only dissolve the ionic REEs in the sample, so the digestion result of hydrochloric acid and nitric acid is lower than that of the whole phase REEs, and higher than that of ammonium sulfate leaching.
CONCLUTIONS The differences and influencing factors of REEs extracted from ion-adsorbed rare earth samples by different pretreatment methods are discussed, which can provide reference for further research on the extraction methods of REEs from elution-deposited rare earth ores. Mixed acid digestion can extract the full phase REEs in the weathered crust eluviated rare earth ore sample, which can be used to evaluate the total amount of REEs in the weathered crust eluviated rare earth ore. Nitric acid digestion, nitric acid and hydrogen peroxide digestion, hydrochloric acid and hydrogen peroxide digestion cannot dissolve REEs in the silicate structure completely. Therefore, this method is suitable for evaluating the content of REEs in the form of ionic states, oxides, carbonates and phosphates in samples. Ammonium sulfate leaching can be used to evaluate the content of ionic phase REEs in weathering crust leaching type rare earth ores. The extraction rate of REEs is greatly affected by the chemical characteristics and occurrence state of REEs. Because the ionic radius of Sc3+ is obviously smaller than that of other REEs, Sc3+ can enter the crystal lattices of many rock-forming minerals in the form of homogeneity, which results in that ammonium sulfate leaching cannot dissolve Sc. Only a small amount of Sc can be dissolved by hydrochloric or nitric acid digestion. The different enrichment-differentiation characteristics of Ce and other REEs also make the extraction rate of Ce by ammonium sulfate leaching inconsistent with other REEs. The REEs with similar ionic radii often have similar extraction efficiency in the same pretreatment.
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表 1 电感耦合等离子体质谱仪工作条件
Table 1. Operating parameters for ICP-MS measurements.
工作参数 设定值 工作参数 设定值 ICP功率 1300W 跳峰 1点/质量 冷却气流速 13.0L/min 停留时间 10ms/点 辅助气流速 1.2L/min 扫描次数 40次 雾化气流速 0.9L/min 测量时间 31s 取样锥孔径 1.0mm 截取锥孔径 0.9mm 超锥孔径 1.1mm 
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表 2 GBW07160和GBW07161采用混合酸(五酸)消解测定结果(n=3)
Table 2. Analytical results of GBW07160 and GBW07161 determined by open mixed acid digestion (n=3).
稀土
元素GBW07160 GBW07161 五酸消解结果
（μg/g）标准值
（μg/g）五酸消解结果
（μg/g）标准值
（μg/g）Sc 6.22 5.67～6.98 8.29 7.69±0.59 Y 2383 2386±205 965 976±47 La 85.3 93.8±8.5 2271 2362±145 Ce 24.7 28.3±4.1 178 187±8.1 Pr 33.8 37.2 440 447±24.8 Nd 170 189±17 1568 1595±86 Sm 115 129±17 286 285±25.9 Eu 1.10 1.55±0.26 62.3 64.8±3.63 Gd 210 234 234 226±26 Tb 46.4 49.1±5.1 31.6 34.6±2.2 Dy 315 314±44 182 183±17 Ho 68.1 65.5±5.4 31.9 35.7±4.0 Er 207 192±26 90.1 96±9 Tm 26.8 27.7±3.1 12.3 13.2±1.1 Yb 184 193±26 78.1 87.8±11 Lu 24.9 26.7±2.6 11.24 12.0±0.88
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表 3 加标试验回收率 (n=3)
Table 3. Recovery rates of added standard tests (n=3).
样品
L04硝酸消解 硝酸+双氧水消解 盐酸+双氧水消解 硫酸铵浸提 加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）Sc 6.00 6.48 108 6.00 5.96 99.4 6.00 5.43 90.5 200 215.4 108 Y 6.00 6.50 108 6.00 5.72 95.3 6.00 6.19 103 200 183.2 91.6 La 6.00 6.84 114 6.00 6.86 114 6.00 5.99 100 200 212.9 106 Ce 6.00 6.29 105 6.00 6.53 109 6.00 6.60 110 200 208.1 104 Pr 6.00 5.75 96 6.00 6.08 101 6.00 7.12 119 200 192.0 96.0 Nd 6.00 5.66 94 6.00 5.92 98.7 6.00 6.40 107 200 177.9 89.0 Sm 6.00 6.43 107 6.00 6.57 109 6.00 6.49 108 200 203.4 102 Eu 6.00 6.14 102 6.00 6.28 105 6.00 6.18 103 200 200.6 100 Gd 1.50 1.44 96 1.50 1.70 113 1.50 1.61 107 80.0 80.4 100 Tb 1.50 1.62 108 1.50 1.68 112 1.50 1.63 109 80.0 80.2 100 Dy 1.50 1.45 96 1.50 1.67 111 1.50 1.64 109 80.0 80.1 100 Ho 1.50 1.61 108 1.50 1.61 107 1.50 1.57 105 80.0 82.8 103 Er 1.50 1.62 108 1.50 1.67 111 1.50 1.37 91.6 80.0 84.3 105 Tm 1.50 1.55 103 1.50 1.57 105 1.50 1.57 104 80.0 80.9 101 Yb 1.50 1.60 106 1.50 1.63 109 1.50 1.60 106 80.0 77.7 97.1 Lu 1.50 1.50 100 1.50 1.56 104 1.50 1.58 105 80.0 83.7 105 样品
L28硝酸消解 硝酸+双氧水消解 盐酸+双氧水消解 硫酸铵浸提 加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）加标量
（μg）回收量
（μg）回收率
（%）Sc 6.00 6.55 109 6.00 6.55 109 6.00 5.87 97.9 100 106.6 107 Y 6.00 6.10 102 6.00 6.27 104 6.00 5.92 98.6 100 105.1 105 La 6.00 6.76 113 6.00 6.88 115 6.00 4.93 82.1 100 107.6 108 Ce 6.00 6.18 103 6.00 6.56 109 6.00 6.14 102 100 106.8 107 Pr 6.00 6.16 103 6.00 6.10 102 6.00 6.68 111 100 110.9 111 Nd 6.00 6.13 102 6.00 6.19 103 6.00 5.04 84.0 100 116.6 117 Sm 6.00 6.55 109 6.00 6.45 107 6.00 5.95 99.2 100 98.9 98.9 Eu 6.00 6.35 106 6.00 6.31 105 6.00 6.17 103 100 118.4 118 Gd 1.50 1.64 109 1.50 1.79 119 1.50 1.75 116 4.00 4.09 102 Tb 1.50 1.61 108 1.50 1.54 103 1.50 1.56 104 4.00 3.88 96.9 Dy 1.50 1.44 96.0 1.50 1.70 114 1.50 1.57 104 4.00 4.31 108 Ho 1.50 1.61 107 1.50 1.57 105 1.50 1.55 103 4.00 4.17 104 Er 1.50 1.56 104 1.50 1.69 113 1.50 1.46 97.1 4.00 3.92 98.0 Tm 1.50 1.52 102 1.50 1.49 100 1.50 1.53 102 4.00 4.03 101 Yb 1.50 1.51 100 1.50 1.56 104 1.50 1.50 100 4.00 3.61 90.3 Lu 1.50 1.52 102 1.50 1.55 103 1.50 1.52 102 4.00 4.01 100
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表 4 不同前处理方法测得稀土总量与提取率 (n=3)
Table 4. Content and extraction rates of REEs by different pretreatment methods (n=3).
样品前处理方式 六个离子吸附型稀土样品稀土总量测定结果（μg/g） L20 L28 L22 L14 L05 L03 混合酸 208 344 310 511 771 152 硝酸 178 275 276 439 752 109 硝酸+过氧化氢 176 265 272 444 737 113 盐酸+过氧化氢 175 259 267 419 707 119 硫酸铵浸提 19.0 106 160 308 581 15.4 样品前处理方式 六个离子吸附型稀土样品稀土总量提取率（%） L20 L28 L22 L14 L05 L03 硝酸 85.6 79.9 89.0 85.9 97.5 71.7 硝酸+过氧化氢 84.6 77.0 87.7 86.9 95.6 74.3 盐酸+过氧化氢 84.1 75.3 86.1 82.0 91.7 78.3 硫酸铵浸提 9.1 30.8 51.7 60.3 75.5 10.2 注：提取率为各种方法提取稀土结果与混合酸（五酸）消解结果（全相稀土）相比的百分数。
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