改性D201树脂从钼精矿氧压浸出液中分离回收铼(Ⅶ)的研究

傅中乔; 侯艳蕊; 黄家豪; 程德; 李光辉

doi:10.13779/j.cnki.issn1001-0076.2022.06.015

改性D201树脂从钼精矿氧压浸出液中分离回收铼(Ⅶ)的研究

中南大学资源加工与生物工程学院, 湖南长沙 410012

基金项目: 国家自然科学基金项目 (51874355）

详细信息

作者简介: 傅中乔（1995—），女，河南南阳人，硕士，主要从事复杂矿物综合利用研究，E-mail：csufzq@163.com

通讯作者: 李光辉（1972—），男，湖南益阳人，教授，主要从事矿产资源高效清洁利用，E-mail：liguanghuigroup@outlook.com。

中图分类号: TF841.8；TD98

收稿日期: 2022-06-07

刊出日期: 2022-12-26

Study on the Separation and Recovery of Re(Ⅶ) from Molybdenum Concentrate Oxygen-pressure Leaching Solution by D201 Resin

School of Minerals Processing and Bioengineering, Central South University, Changsha 410012, Hunan, China

More Information

Corresponding author: LI Guanghui, liguanghuigroup@outlook.com

Received Date: 07 June 2022

Publish Date: 26 December 2022

摘要

摘要:
为开发一种低成本、环保型离子交换工艺回收铼，基于钼铼离子在酸性体系中离子形态的差异，采用改性D201阴离子交换树脂从钼精矿氧压浸出液中分离回收铼（Ⅶ）。考察了初始pH值、转速、树脂用量、吸附温度、吸附时间对铼回收效果的影响，并利用Raman、FTIR和SEM-EDS对浸出液和改性树脂进行表征分析。结果表明：在初始pH=1.70、转速300 r/min、吸附温度20 ℃、吸附时间60 min、树脂用量0.002 g/mL的条件下，铼的吸附率达98.81%，而钼、铁、铈的吸附率分别仅为0.44%、1.04%、1.25%。铼与钼、铁、铈的最大分离系数分别为262.25、104.60、89.02。实际氧压浸出液中钼、铁、铈主要以MoO₂²⁺、Fe³⁺和Ce³⁺等阳离子形态存在，铼以ReO₄^-阴离子形态存在，改性D201阴离子交换树脂通过静电吸引和螯合作用选择性吸附铼离子，实现铼与钼、铁、铈的有效分离。
- 铼 /
- 钼 /
- 钼铼分离 /
- 吸附 /
- 阴离子交换 /
- D201树脂
Abstract:
In order to develop a low-cost and environmentally friendly ion exchange process to recover rhenium, a modified D201 anion exchange resin was used to separate and recover rhenium (Ⅶ) from the oxygen-pressure leaching solution of molybdenum concentrate based on the difference in ionic forms of molybdenum-rhenium ions in acidic systems. The effects of initial pH, rotating speed, resin relative dosage, adsorption temperature and adsorption time on the recovery of rhenium were investigated, and the leachate and modified resin were characterized and analyzed by Raman, FTIR and SEM. The results showed that under the conditions of initial pH=1.70, speed 300 r/min, adsorption temperature of 20 ℃, adsorption time of 60 min and resin dosage of 0.002 g/mL, the adsorption rate of rhenium reached 98.81%, while the adsorption rates of molybdenum, iron and cerium were only 0.44%, 1.04% and 1.25%, respectively. The maximum separation coefficients of rhenium from molybdenum, iron and cerium were 262.25, 104.60 and 89.02, respectively. In the actual oxygen pressure leaching solution, molybdenum, iron and cerium mainly exist in the form of cations such as MoO₂²⁺, Fe³⁺ and Ce³⁺, and rhenium exists in the form of ReO₄^- anion. The modified D201 anion exchange resin selectively adsorbs on rhenium ions through electrostatic attraction and chelation to achieve effective separation of rhenium from molybdenum, iron and cerium.
- rhenium /
- molybdenum /
- molybdenum-rhenium separation /
- adsorption /
- anion exchange /
- D201 resin

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图 1 D201树脂改性机理

Figure 1.

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图 2 初始pH值对铼吸附率的影响

Figure 2.

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图 3 转速和吸附时间对铼吸附率的影响

Figure 3.

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图 4 树脂用量对铼吸附率的影响

Figure 4.

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图 5 吸附温度对铼吸附率的影响

Figure 5.

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图 6 吸附时间对铼吸附率的影响

Figure 6.

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图 7 氧压浸出液的拉曼红外谱图

Figure 7.

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图 8 D201树脂改性前后以及吸附后的FTIR红外光谱图

Figure 8.

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图 9 D201树脂吸附铼的机理

Figure 9.

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图 10 吸附前（a）与吸附后（b）D201树脂的SEM图像

Figure 10.

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图 11 D201树脂的SEM图像（a）和元素图谱（b）（c）（d）（e）（f），吸附上Re(Ⅶ)的D201树脂的SEM图像(g)和Re的元素图谱(h)(i)

Figure 11.

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图 12 不同元素的吸附率

Figure 12.

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图 13 铼与有价元素的分离系数

Figure 13.

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表 1 浸出液的主要化学成分

Table 1. Main chemical compositions of the leach solution /(mg·L⁻¹)

元素	Mo	Re	Fe	Ce	SO₄^2-
浓度	771	19.11	770	38	1050

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表 2 不同pH条件下的钼酸盐种类

Table 2. Molybdate species at different pH conditions

pH	钼酸盐形式
0～1	MoO₂²⁺、H₆MoO₂⁸⁺、H₃MoO₄⁺、
1～2	MoO₂²⁺、H₃Mo₇O₂₄³⁻、H₂Mo₇O₂₄⁴⁻
2～3	H₃Mo₇O₂₄³⁻、H₂Mo₇O₂₄⁴⁻、HMo₇O₂₄⁵⁻
3～4	H₃Mo₇O₂₄³⁻、H₂Mo₇O₂₄⁴⁻、HMo₇O₂₄⁵⁻、Mo₈O₂₆⁴⁻
4～5	H₃Mo₇O₂₄³⁻、H₂Mo₇O₂₄⁴⁻、HMo₇O₂₄⁵⁻
5～6	H₂Mo₇O₂₄⁴⁻、HMo₇O₂₄⁵⁻、Mo₇O₂₄⁶⁻
>6	MoO₄²⁻

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