受阻酚对稀土萃取分离流程中Ce(Ⅳ)去除效果研究
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作者单位:

1.甘肃稀土新材料股份有限公司, 甘肃 白银 730922 ; 2.兰州大学, 甘肃 兰州 730000 ;3.中国北方稀土(集团)高科技股份有限公司, 内蒙古 包头 014030

作者简介:

胡广寿(1983—),男,甘肃白银人,硕士,高级工程师,主要从事稀土冶金与环保治理工作。

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中图分类号:

TF845;TF803.2+3

基金项目:

工信部重大科技专项项目(TC220H06A)


Removal effect of hindered phenol on Ce (Ⅳ) in rare earth extraction and separation process
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Affiliation:

1.Gansu Rare Earth New Material Limited-Liability Company,Baiyin 730922 , China ;2.Lanzhou University, Lanzhou 730000 , China ;3.China Northern Rare Earth (Group) High-Tech Co., Ltd.,Baotou 014030 , China

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    摘要:

    在稀土湿法冶炼中,采用环保型稀释剂替代传统磺化煤油后,因新型稀释剂还原性不足导致Ce(Ⅲ)氧化为易萃取的Ce(Ⅳ),使镨钕系列产品中稀土杂质Ce元素长期超标;现行H2O2还原法虽可消除Ce(Ⅳ),但存在有机相氧化降解、成本增加以及废水处理难度加大等一系列问题。本研究提出以受阻酚类抗氧化剂替代H2O2,通过抑制Ce(Ⅳ)生成并还原残留Ce(Ⅳ)来实现稀土元素的绿色、高效分离。结果表明,受阻酚通过羟基供氢与空间位阻效应,优先捕获氧自由基(HO·、ROO·),抑制Ce(Ⅲ)氧化,同时可将有机相中Ce(Ⅳ)高效还原为Ce(Ⅲ)(还原效率>99.5%),实现“氧化抑制-残留消除”协同作用;在受阻酚添加量1.0~2.0g/L、温度40~50℃时,Ce(Ⅳ)生成速率由0.021g/(L·h)降至0.0023g/(L·h),抑制时长>120h;工业化试验显示,有机相中Ce(Ⅳ)含量从0.05g/L降至<0.005g/L,镨钕产品中Ce杂质长期稳定于200~400 ppm,符合GB/T 20190—2023对镨钕产品质量要求的≤500 ppm。相较于H2O2还原,该技术降低了还原剂消耗量,同时规避了H2O2分解引发的有机相降解风险,为稀土行业绿色化、高质化发展提供了技术支撑,具备显著的行业推广价值。

    Abstract:

    In the wet metallurgy process of rare earth elements, replacing traditional sulfonated kerosene with a new environmentally friendly diluent led to insufficient reducing capacity of the new diluent, causing Ce(Ⅲ) to oxidize into easily extractable Ce(Ⅳ). This cause excessive levels of the rare earth impurity Ce for a long time in the praseodymium-neodymium series products. Although H2O2 can reduce Ce (Ⅳ), there are a series of problems such as organic phase oxidation degradation, increased cost, and increased difficulty in wastewater treatment. This study proposes to replace H2O2 with hindered phenolic antioxidants to achieve green and efficient separation of rare earth elements by inhibiting the generation of Ce (Ⅳ) and reducing residual Ce (Ⅳ). The results showed that hindered phenols preferentially capture oxygen free radicals (HO·, ROO·) through hydroxyl hydrogen supply and steric hindrance effect, inhibit Ce (Ⅲ) oxidation, and efficiently reduce Ce (Ⅳ) in the organic phase to Ce (Ⅲ) (reduction efficiency >99.5%), achieving a synergistic effect of “oxidation inhibition and residual elimination”; When the amount of hindered phenol added is 1.0~2.0g/L and the temperature is 40~50℃, the generation rate of Ce (Ⅳ) decreases from 0.021g/(L·h) to 0.0023g/(L·h), and the inhibition time is greater than 120 hours. Industrial tests have shown that the Ce (Ⅳ) of organic phase has decreased from 0.05g/L to below 0.005g/L. The Ce impurity has remained stable at 200~400 ppm for a long time in praseodymium neodymium products, which meets the quality requirements of GB/T 20190—2023. Compared to H2O2 reduction, this technology reduces the consumption of reducing agents and avoids the risk of organic phase degradation caused by H2O2 decomposition. It provides technical support for the green and high-quality development of the rare earth industry and has significant industry promotion value.

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胡广寿,唐晓亮,周晓君,等.受阻酚对稀土萃取分离流程中Ce(Ⅳ)去除效果研究[J].中国有色冶金,2025,54(5):65-74.

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  • 收稿日期:2025-04-16
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  • 在线发布日期: 2025-12-18
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