Effect of Aluminum Impurity on Extraction of Rare Earth From Ammonium Salt Leaching Solution with Phosphate Ester Mixed Extractant
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摘要:
风化壳淋积型稀土矿是我国重要的战略性资源，使用原地浸出开采工艺得到的稀土浸出液中铝含量较高，是主要的杂质离子。为了从该浸出液中一步法分离富集稀土，探讨了一种磷酸酯混合——萃取剂P0261(2-乙基己基磷酸酯，单酯和二酯1 GA6FA 1混合)在NH4Cl、(NH4)2SO4、NH4NO3三种模拟浸出液中对稀土La3+、Nd3+的萃取行为，并分析杂质铝离子对稀土萃取行为的影响。试验结果表明：在三种铵盐溶液中，萃取剂均能够有效萃取分离稀土离子La3+、Nd3+；加入Al3+后，稀土萃取率E会随Al3+浓度增大而减小。但当Al3+浓度在300 mg·dm-3以内时，E降幅缓慢，最大下降值为14.68%。通过分析负载有机相，Al3+比RE3+更易与P=O形成配位键，且铵根离子浓度变化会影响P=O→RE配位键的形成，从而影响萃取行为。因此，将浸出液中的杂质铝离子浓度控制在300 mg·dm-3以内，则可以使用萃取剂P0261一步法萃取分离稀土。
Abstract:The weathered shell leaching type rare earth ore is an important strategic resource in China. The rare earth leaching solution obtained by in situ leaching process has high content of Al3+ and is the main impurity ion. In order to separation rare earth ions from leaching solution by one-step way, the extraction behavior of a phosphate ester extractant, P0261 (2-ethylhexyl phosphate, 1 GA6FA 1 mixture of mono ester and diester), was investigated for rare earth ions La3+、Nd3+ in three simulated leaching solutions of NH4Cl, (NH4)2SO4 and NH4NO3, and the effect of impurity Al3+ on the extraction behavior of rare earth was also analyzed. The results show that the extractant P0261 has good extraction affinity towards rare earth ions La3+ and Nd3+ in the three kinds of ammonium salts solution. With the addition of Al3+, the extraction rate E of rare earth ions decreases with the increase of Al3+ concentration. E declines slowly when C(Al3+) at 0~300 mg·dm-3, while the maximum reduction of E is 14.68%. By analyzed the load organic phase, Al3+ was easier to coordination bonds with P=O than RE3+, and the change of NH4+ concentration has novel effect on the formation of P=O→RE coordination bonds, which was one of the reasons caused the change of rare earth extraction behavior. From experimental results, control the C(Al3+) below 300 mg·dm-3 in in-situ leaching solution, the effect of impurity ion on selective extraction and separation rare earths by one-step way using extractant P0261 is accepted.
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Key words:
- rare earth /
- Al3+ /
- acidic phosphorus extractor /
- extraction /
- ammonium salt
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表 1 NH4Cl中含P基团峰吸收频率变化
Table 1. Peak absorption frequency changes of phosphorus-containing groups in NH4Cl
体系 编号 C(NH4+)/mol·dm-3 P-O-RE P=O P-O-C 皂后萃取剂 0 2 730.43 2 323.42 1 648.30 1 201.58 1 030.25 Nd3+-NH4Cl 1 0 2 727.84 2 309.77 1 640.60 1 194.40 1 031.74 2 0.5 2 727.74 2 308.64 1 636.49 1 194.12 1 032.23 3 1.0 2 727.49 2 310.30 1 632.76 1 196.83 1 031.64 4 1.5 2 728.06 2 309.43 1 641.21 1 196.96 1 031.99 5 2.0 2 727.58 2 309.47 1 646.94 1 197.82 1 033.9 6 2.5 2 728.19 2 309.68 1 647.75 1 198.34 1 034.81 7 3.0 2 727.53 2 309.18 1 643.07 1 198.73 1 036.07 La3+-NH4Cl 22 0 2 723.16 2 311.75 1 640.02 1 198.76 1 031.54 23 0.5 2 729.38 2 309.82 1 646.68 1 199.67 1 037.88 24 1.0 2 724.73 2 316.57 1 642.20 1 199.73 1 031.59 25 1.5 2 724.92 2 312.23 1 647.24 1 199.94 1 034.38 26 2.0 2 723.59 2 312.71 1 641.64 1 201.10 1 036.48 27 2.5 2 723.66 2 308.86 1 640.91 1 201.67 1 036.82 28 3.0 2 726.22 2 310.79 1 642.51 1 201.16 1 036.80 
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表 2 (NH4)2SO4中含磷基团峰吸收频率变化
Table 2. Peak absorption frequency changes of phosphorus-containing groups in (NH4)2SO4 solution
体系 编号 C(NH4+)/mol·dm-3 P-O-RE P=O P-O-C 皂后萃取剂 0 2 730.43 2 323.42 1 648.30 1 201.58 1 030.25 Nd3+-(NH4)2SO4 8 0 2 726.13 2 311.63 1 641.74 1 198.00 1 035.48 9 0.5 2 728.06 2 309.61 1 646.95 1 198.12 1 036.82 10 1.0 2 728.83 2 309.68 1 646.75 1 198.61 1 036.23 11 1.5 2 728.70 2 309.87 1 646.88 1 198.67 1 036.11 12 2.0 2 727.38 2 310.02 1 646.69 1 198.68 1 036.31 13 2.5 2 729.52 2 316.56 1 646.69 1 200.46 1 036.04 14 3.0 2 728.34 2 309.85 1 646.66 1 200.91 1 036.59 La3+-(NH4)2SO4 29 0 2 730.30 2 309.58 1 642.83 1 198.86 1 031.19 30 0.5 2 730.01 2 309.43 1 641.34 1 199.39 1 031.37 31 1.0 2 730.21 2 309.92 1 647.04 1 201.86 1 030.82 32 1.5 2 730.76 2 309.92 1 646.17 1 200.22 1 031.15 33 2.0 2 729.49 2 309.88 1 646.50 1 200.98 1 033.06 34 2.5 2 729.77 2 311.20 1 646.84 1 201.08 1 030.20 35 3.0 2 729.52 2 310.33 1 646.52 1 201.95 1 030.35
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表 3 NH4NO3中含磷基团峰吸收频率变化
Table 3. Peak absorption frequency changes of phosphorus-containing groups in NH4NO3 solution
体系 编号 C(NH4+)/mol·dm-3 P-O-RE P=O P-O-C 皂后萃取剂 0 2 730.43 2 323.42 1 648.30 1 201.58 1 030.25 Nd3+-NH4NO3 15 0 2 730.86 2 306.93 1 636.49 1 196.66 1 034.55 16 0.5 2 729.71 2 306.93 1 636.09 1 197.58 1 036.39 17 1.0 2 730.62 2 305.91 1 636.34 1 200.01 1 037.18 18 1.5 2 730.59 2 307.41 1 636.28 1 201.14 1 037.12 19 2.0 2 730.27 2 306.45 1 636.54 1 201.67 1 038.13 20 2.5 2 731.28 2 307.41 1 636.88 1 204.79 1 038.34 21 3.0 2 731.18 2 308.38 1 636.50 1 209.20 1 038.52 La3+-NH4NO3 36 0 2 729.10 2 309.61 1 646.55 1 200.01 1 037.14 37 0.5 2 728.10 2 309.82 1 646.51 1 200.78 1 036.86 38 1.0 2 729.09 2 309.86 1 646.61 1 203.30 1 036.87 39 1.5 2 728.77 2 309.65 1 646.52 1 200.05 1 036.57 40 2.0 2 728.02 2 309.93 1 646.54 1 200.47 1 036.67 41 2.5 2 728.53 2 309.54 1 646.58 1 199.94 1 036.66 42 3.0 2 728.64 2 309.89 1 646.51 1 199.30 1 037.38
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