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中国胶磷矿中伴生稀土元素提取研究进展

Research progress on extraction of associated rare earth elements from collophane in China

  • 摘要: 中国胶磷矿资源丰富但禀赋较差,中低品位矿占比高,其中伴生稀土元素的平均质量分数约为0.046%,是重要的稀土资源。由于其“丰而不富”的特点,大量伴生稀土元素未得到有效利用,因此,实现胶磷矿中伴生稀土元素的高效回收,对提升胶磷矿综合利用率与保障中国稀土资源的供给安全具有重要战略意义。本文从预富集、浸出和分离3个核心环节综述了当前胶磷矿中稀土元素提取技术的研究现状和发展趋势。首先,选矿预富集是降低酸耗的关键,浮选法在脱除碳酸盐杂质并同步富集稀土方面表现优异,联合工艺则是处理细粒级难选胶磷矿的重要手段。在浸出阶段,详细分析了硫酸、硝酸、盐酸与磷酸等无机酸浸出工艺的优劣,指出传统硫酸法稀土浸出率偏低,仅为20%~65%,且伴生磷石膏污染严重,而硝酸、盐酸和磷酸法的稀土浸出率可达90%以上,但分别面临除杂难度大、设备腐蚀严重和浸出液浓度低等挑战。在分离与富集阶段,溶剂萃取法仍是工业化大规模应用的主流技术,而离子交换与膜分离等技术在处理低浓度稀土元素溶液和提升产品纯度方面展现出独特的优势。针对目前选、冶过程衔接不紧密、回收率低等瓶颈,未来研究应深化“浸出-分离”联合工艺,通过开发混酸/表面活性剂/外场辅助浸出技术和高容量功能化树脂、耐酸选择性萃取剂,推动胶磷矿中伴生稀土元素提取技术向更加清洁、高效、低碳的协同回收方向发展。

     

    Abstract: China is endowed with abundant collophane resources but poor ore quality, with a high proportion of medium and low-grade ores. The average mass fraction of associated rare earth elements (REEs) in collophane reaches approximately 0.046%, which forms an important rare earth resource. Due to the characteristic of abundant reserves but low grade, a large number of associated REEs are not effectively utilized. Therefore, the efficient recovery of associated REEs from collophane has important strategic significance for improving the comprehensive utilization rate of collophane and ensuring the supply security of rare earth resources in China. This paper reviews the research status and development trend of REEs extraction technologies from collophane from three core links, that is pre-concentration, leaching and separation. Beneficiation and pre-concentration is the key to reduce acid consumption. The flotation method exhibits excellent performance in removing carbonate impurities and synchronously enriching rare earths, while the combined process is an important means for treating fine-grained refractory collophane. In the leaching stage, the advantages and disadvantages of inorganic acid leaching processes such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid were analyzed in detail. The results show that the traditional sulfuric acid process has a low REEs leaching rate of only 20%-65% and causes serious phosphogypsum pollution. By contrast, nitric acid, hydrochloric acid and phosphoric acid processes achieve a REEs leaching rate of more than 90%, but they respectively face challenges including difficult impurity removal, severe equipment corrosion and low leachate concentration. In the separation and enrichment stage, solvent extraction remains the mainstream technology for large-scale industrial application, while ion exchange, membrane separation and other technologies present unique advantages in treating low-concentration REEs solutions and improving product purity. Aiming at the current bottlenecks such as poor connection between mineral processing and metallurgical processes and low recovery rate, future research should further develop the integrated leaching-separation process. The development of mixed acid/surfactant/external field-assisted leaching technologies, high-capacity functional resins and acid-resistant selective extractants promotes the collaborative development of technology for associated REEs from collophane toward cleaner, more efficient, lower carbon and collaborative recovery direction.

     

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