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稀土资源在开发和提取过程中易产生低浓度稀土溶液或极低浓度的稀土废水，从而造成富集困难、环境污染和资源浪费等问题。介绍了常见低浓度稀土溶液的来源及特点，综述了近年来低浓度稀土溶液的富集回收技术的原理和研究进展，包括沉淀法、溶剂萃取法、膜分离法和吸附分离法等，分析了各类富集回收方法的优缺点，并展望了未来技术发展方向。
Abstract：Rare earth resources are easy to produce low concentration rare earth solution or very low concentration rare earth wastewater in the process of development and extraction, which causes problems such as enrichment difficulties, environmental pollution and resource waste. The sources and characteristics of common low concentration rare earth solutions are introduced, and the principles and research progress of enrichment and recovery technologies of low concentration rare earth solutions in recent years are reviewed, including precipitation, solvent extraction, membrane separation and adsorption separation. The advantages and disadvantages of various enrichment and recovery methods are analyzed, future direction for technological development are also outlined.
[1] 徐光宪.稀土(上)[M].2版.北京：冶金工业出版社，1995.
[2] 池汝安，王淀佐.稀土选矿与提取技术[M].北京：科学出版社，1996.
[3] 程建忠，车丽萍.中国稀土资源开采现状及发展趋势[J].稀土，2010,31(2):65-69.CHENG Jianzhong,CHE Liping.Current mining situation and potential development of rare earth in china[J].Chinese Rare Earths,2010,31(2):65-69.
[4] 黄小卫，李红卫，王彩凤，等.我国稀土工业发展现状及进展[J].稀有金属，2007(3):279-288.HUANG Xiaowei,LI Hongwei,WANG Caifeng,et al.Development status and research progress in rare earth industry in China[J].Chinese Journal of Rare Matals,2007(3):279-288.
[5] 肖燕飞.离子吸附型稀土矿镁盐体系绿色高效浸取技术研究[D].沈阳：东北大学，2015:80-95.
[6] 钱有军.低浓度稀土溶液碳酸氢铵沉淀及结晶过程研究[D].赣州：江西理工大学，2013:17-41.
[7] 李永绣.离子吸附型稀土资源与绿色提取[M].北京：化学工业出版社，2014.
[8] KATO Y,FUJINAGA K,NAKAMURA K,et al.Deep-sea mud in the Pacific Ocean as a potential resource for rare-earth elements[J].Nature Geoscience,2011,4(8):535-539.
[9] BI D J,SHI X F,HUANG M,et al.Geochemical and mineralogical characteristics of deep-sea sediments from the western North Pacific Ocean:constraints on the enrichment processes of rare earth elements[J].Ore Geology Reviews,2021,138.DOI:10.1016/j.oregeorev.2021.104318.
[10] LI J,SHI X F,HUANG M,et al.The transformation and accumulation mechanism of rare earth elements in deep-sea sediments from the Wharton Basin,Indian Ocean[J].Ore Geology Reviews,2023,161.DOI:10.1016/j.oregeorev.2023.105655.
[11] 刘志强，吴宇坤，张魁芳，等.太平洋中部深海黏土中稀土钇的酸浸研究[J].矿冶工程，2017,37(3):94-96.LIU Zhiqiang,WU Yukun,ZHANG Kuifang,et al.Acid leaching of rare earth yttrium in pelagic clay from Central Pacific Ocean[J].Mining and Metallurgical Engineering,2017,37(3):94-96.
[12] 张魁芳，吴宇坤，刘志强，等.从太平洋中部深海黏土盐酸浸出液中萃取回收钇的研究[J].中国稀土学报，2016,34(1):62-69.ZHANG Kuifang,WU Yukun,LIU Zhiqiang,et al.Extraction of yttrium from hydrochloric acid leaching solution of pelagic clay from Central Pacific[J].Journal of the Chinese Society of Rare Earth,2016,34(1):62-69.
[13] 潘炳，任国兴，王祥，等.印度洋海盆沉积物中稀土的赋存状态及其浸出研究[J].金属矿山，2020(11):84-89.PAN Bing,REN Guoxing,WANG Xiang,et al.Study on the occurrence state and the leaching of rare earth elements in sediments of the Indian Ocean Basin[J].Metal Mine,2020(11):84-89.
[14] AHMAD N,XINBO Y,RICK H.Parametric study and speciation analysis of rare earth precipitation using oxalic acid in a chloride solution system[J].Minerals Engineering,2022,176.DOI:10.1016/J.MINENG.2021.107352.
[15] 朱薇，刘志强，郭秋松，等.草酸沉淀稀土废水的治理现状[J].材料研究与应用，2014,8(4):219-220.ZHU Wei,LIU Zhiqiang,GUO Qiusong,et al.Treatment status of waste water from rare earth deposition with oxalic acid[J].Materials Sesearch and Application,2014,8(4):219-220.
[16] 焦芸芬，余党华，何小林，等.稀土冶炼含C2O■废水的治理与回收利用技术[J].中国资源综合利用，2016,34(7):41-44.JIAO Yunfen,YU Danghua,HE Xiaolin,et al.Treatment and recycling technolgoy on rare earth metallurgy wastewater containing C2O■[J].China Resources Comprehensive Utilization,2016,34(7):41-44.
[17] 严志安，燕利军，陈曹军，等.硫酸铵浸出-草酸沉淀稀土方法在找矿中的应用：以云南盈江县新泡山矿区为例[J].地质与勘探，2021,57(4):796-807.YAN Zhian,YAN Lijun,CHEN Caojun,et al.Application of the ammonium sulfate leaching:oxalie acid precipitating ree method to mineral exploration an example of the xinpaoshan mine in Yingjiang County,Yunnan Province[J].Geology and Exploration,2021,57(4):796-807.
[18] 吴茂法，应连芬，杨胜.碳酸氢铵沉淀富集稀土离子条件讨论[J].浙江地质，1999(2):89-92.WU Maofa,YING Lianfen,YANG Sheng.Discussion of the condition of sedimenting and enriching rare-earth ion by ammonium bydrogen carbonate[J].Geology of Zhejiang,1999(2):89-92.
[19] 喻庆华，李先柏.晶型碳酸稀土的形成及其影响因素[J].中国稀土学报，1993(2):171-173.YU Qinghua,LI Xianbo.Formation of crystalline rare earth carbonate and its influencing factors[J].Journal of the Chinese Society of Rare Earths,1993(2):171-173.
[20] 钱有军.低浓度稀土溶液碳酸氢铵沉淀及结晶过程研究[D].赣州：江西理工大学，2013.
[21] 方夕辉，尹艳芬，邱廷省，等.磁处理对碳酸氢铵沉淀稀土母液体系的影响[J].矿产综合利用，2004(3):7-10.FANG Xihui,YIN Yanfen,QIU Tingsheng,et al.The influence of magnetic treatment on rare earth lixivium during precipitation by NH4HCO3[J].Comprehensive Utilization of Mineral Resources,2004(3):7-10.
[22] 刘燕波.离子型稀土沉淀结晶工艺及机理研究[D].赣州：江西理工大学，2014.
[23] 冷美杰，尹安，符亲武，等.碳酸钠-碳酸氢钠混合沉淀剂对碳酸钇结晶过程的影响[J/OL].中国稀土学报：1-14[2024-10-12].http://kns.cnki.net/kcms/detail/11.2365.tg.20240618.1652.010.html.LENG Meijie,YIN An,FU Qinwu,et al.Effect of sodium carbonate-sodium bicarbonate mixture precipitator on the crystallization of yttrium carbonate[J/OL].Journal of the Chinese Society of Rare Earth:1-14[2024-10-12].http://kns.cnki.net/kcms/detail/11.2365.tg.20240618.1652.010.html.
[24] 胡小洣，刘书祯，袁昌望，等.离子型稀土浸出液复合钠盐高效富集稀土[J].有色金属(冶炼部分),2023(5):52-57.HU Xiaomi,LIU Shuzhen,YUAN Changwang,et al.High efficient enrichment of rare earth in lonic rare earth leachate with complex sodium salt [J].Nonferrous Metals(Extractive Metallurgy),2023(5):52-57.
[25] 孟祥龙.低浓度硫酸稀土浸液无氨沉淀富集技术及过程控制[D].北京：北京有色金属研究总院，2017.
[26] 李会婷.稀土氯化铵废水资源化利用的实验研究[D].南昌：南昌大学，2013.
[27] 余宗鹤.硫酸体系碳酸氢镁沉淀制备碳酸稀土过程研究[D].北京：北京有色金属研究总院，2019.
[28] YU Z H,WANG M,WANG L,et al.Preparation of crystalline mixed rare earth carbonates by Mg(HCO3)2 precipitation method[J].Journal of Rare Earths,2020,38(3):292-298.
[29] 张臻悦，席银龙，李丹，等.镁盐稀土浸出液稀土沉淀过程[J].有色金属(冶炼部分),2022(5):45-50.ZHANG Zhenyue,XI Yinlong,LI Dan,et al.Precipitation process of magnesium salt rare earth leaching solution[J].Nonferrous Metals(Extractive Metallurgy),2022(5):45-50.
[30] 陈久昌，姚清霞，邱建民，等.响应曲面法优化MgO沉淀离子型稀土矿浸出液工艺[J].中国稀土学报，2020,38(5):646-654.CHEN Jiuchang,YAO Qingxia,QIU Jianmin,et al.Optimization of leaching solution of magnesium oxide precipitated lonic rare earth ore by response surface methodology[J].Journal of the Chinese Society of Rare Earth,2020,38(5):646-654.
[31] LUO X P,YUAN X Q,HE K Z,et al.Precipitation process for combined impurity removal from a magnesium sulphate-based leachate of ionic rare earth ore[J].Minerals Engineering,2022,189.DOI:10.1016/J.MINENG.2022.107911.
[32] 赖安邦，贺强，邱江，等.氧化钙反加料沉淀富集稀土浸出液中稀土的研究[J].稀有金属，2021,45(7):866-878.LAI Anbang,HE Qiang,QIU Jiang,et al.Enrichment of rare earth in rare earth leaching solution by calcium oxide reverse feeding precipitation[J].Chinese Journal of Rare Metals,2021,45(7):866-878.
[33] 赖富国.镁盐体系稀土浸出液氧化钙无氨沉淀富集过程研究[D].赣州：江西理工大学，2019.
[34] 肖传绪.低浓度稀土溶液大相比萃取富集的应用基础研究[D].北京：中国科学院大学，2018.
[35] 张宏源.P507非平衡萃取富集低浓度稀土与杂质铝分离基础研究[D].北京：北京有色金属研究总院，2021.
[36] 李翠翠.稀土与铀、钍、铁、铝的萃取分离与富集性能[D].南昌：南昌大学，2018.
[37] 王悦.低浓度稀土溶液中稀土的富集与氨氮的处理[D].南昌：南昌大学，2016.
[38] 董金诗.离子吸附型稀土矿低浓度浸出液非皂化—非平衡萃取富集过程研究[D].沈阳：东北大学，2017.
[39] 董金诗，黄小卫，冯宗玉，等.离子吸附型稀土矿低浓度浸出液分步萃取富集新技术研究进展[C]//中国稀土学会稀土化学和湿法冶金专业委员会.全国稀土化学与冶金学术研讨会暨中国稀土学会稀土化学与湿法冶金、稀土火法冶金专业委员会工作会议论文摘要集.赣州：出版者不详，2014:30-31.
[40] 王湛，王志，高学理.膜分离技术基础[M].北京：化学工业出版社，2019.
[41] 陈斌，李青，祝怡斌，等.离子型稀土矿山淋洗及尾水富集[J].有色金属工程，2022,12(11):155-159.CHEN Bin,LI Qing,ZHU Yibin,et al.Leaching and tailings water enrichment of ionic rare earth mines[J].Nonferrous Metals Engineering,2022,12(11):155-159.
[42] KOSE MUTLU B,CANTONI B,TUROLLA A,et al.Application of nanofiltration for rare earth elements recovery from coal fly ash leachate:performance and cost evaluation[J].Chemical Engineering Journal,2018,349:309-317.
[43] KACZOROWSKA M A.The latest achievements of liquid membranes for rare earth elements recovery from aqueous solutions:a mini review[J].Membranes,2023,13(10).DOI:10.3390/membranes13100839.
[44] ZHANG L,CHEN Q,KANG C,et al.Rare earth extraction from wet process phosphoric acid by emulsion liquid membrane[J].Journal of Rare Earths,2016,34(7):717-723.
[45] KOCHERGINSKY N M,YANG Q,SEELAM L.Recent advances in supported liquid membrane technology[J].Separation and Purification Technology,2007,53(2):171-177.
[46] 张传成.PVDF中空纤维膜的制备及应用研究[D].武汉：湖北工业大学，2020.
[47] ASADOLLAHZADEH M,TORKAMAN R,MOSTAEDI T M.Extraction and separation of rare earth elements by adsorption approaches:current status and future trends[J].Separation and Purification Reviews,2020,50(4):1-28.
[48] 刘丽华，张顺泽.分离工程[M].北京：中国矿业大学出版社，2020:190-199.
[49] 柴诚敬，贾绍义.化工原理[M].3版.北京：高等教育出版社，2017.
[50] ZHANG T,JU P,YUAN W,et al.Adsorption of rare earth ions from highly saline media by a pyridine-modified activated carbon sorbent[J].Journal of Environmental Chemical Engineering,2024,12(6).DOI:10.1016/J.JECE.2024.114438.
[51] 钟宜航，彭陈亮，王观石，等.蒙脱石对Y3+的吸附特性及机制研究[J].中国稀土学报，2019,37(6):713-723.ZHONG Yihang,PENG Chenliang,WANG Guanshi,et al.A dsorption characteristics and mechanism of Y3+ by montmorillonite[J].Journal of the Chinese Society of Rare Earth,2019,37(6):713-723.
[52] 池汝安，王淀佐.量子化学计算粘土矿物的吸附性能和富集稀土的研究[J].中国稀土学报，1993(3):199-203.
[53] GAO Y H,FAN C Z,XU H.Experimental study on adsorption of rare earth elements on kaoliniteand halloysite[J].Acta Geologica Sinica,2017,91(Sup.1):80-82.
[54] 吴呈皓，张臻悦，池汝安，等.伊利石对钇离子的吸附行为研究[J].矿冶工程，2024,44(6):83-89.WU Chenghao,ZHANG Zhenyue,CHI Ruan,et al.Investigation on adsorption behavior of yttrium lons by illite[J].Mining and Metallurgical Engineering,2024,44(6):83-89.
[55] 陈园园.离子交换法从离子型稀土矿山尾液中回收稀土工艺及机理研究[D].赣州：江西理工大学，2014.
[56] 黄万抚，李新冬，文金磊，等.HD325树脂从低浓度稀土矿浸出液中回收稀土的研究[J].稀有金属，2015,39(8):727-734.HUANG Wanfu,LI Xindong,WEN Jinlei,et al.Recovery of rare earth from low-concentration rare earth ore leaching liquid by HD325 ion-exchange resin[J].Chinese Journal of Rare Metals,2015,39(8):727-734.
[57] 柯兆华，郭安，邱小英，等.从离子型稀土硫酸镁浸出液中制备碳酸稀土的新工艺研究[J].中国稀土学报，2023,41(6):1132-1139.KE Zhaohua,GUO An,QIU Xiaoying,et al.Magnesium sulfate leaching solution new process for preparing rare earth carbonate from lonic rare earth[J].Journal of the Chinese Society of Rare Earth,2023,41(6):1132-1139.
[58] 胡小洣，周洁英，伍莺，等.转型TP207树脂从低浓度稀土溶液中富集稀土的研究[J].中国稀土学报，2022,40(4):633-640.HU Xiaomi,ZHOU Jieying,WU Ying,et al.Study on the enrichment of rare earth from low concentration rare earth solution with transformed TP207 resin[J].Journal of the Chinese Society of Rare Earths,2022,40(4):633-640.
[59] 张胜其.离子型稀土矿浸出液的富集与除杂试验研究[D].赣州：江西理工大学，2016.
[60] 徐海波，张胜其，周洁英，等.改性树脂CB-ACT富集离子型稀土矿浸出液实验研究[J].有色金属科学与工程，2017,8(3):108-113.XU Haibo,ZHANG Qisheng,ZHOU Jieying,et al.Enrichment of ionic rare earth’s leaching solution by modified resin CB-ACT [J].Nonferrous Metals Science and Engineering,2017,8(3):108-113.
[61] LUCIANO J B,GABRIELA S C,ANA L Q C.Pre-concentration and partial fractionation of rare earth elements by ion exchange[J].Minerals Engineering,2024,205.DOI:10.1016/J.MINENG.2023.108477.
[62] MICHAEL J P,KARIN S.Comparative study of the application of chelating resins for rare earth recovery[J].Hydrometallurgy,2017,90(1):13-18.
[63] 沈秋仙，莫建军，熊春华.亚胺基二乙酸树脂对镧(Ⅲ)的吸附及其机制[J].中国稀土学报，2003,21(4):421-424.SHEN Qiuxian,MO Jianjun,XIONG Chunhua.Adsorption behavior and mechanism of diqlycolamidic acid resin for lanthanum(Ⅲ)[J].Journal of the Chinese Society of Rare Earths,2003,21(4):421-424.
[64] XIONG C H,WU X M.Study on the adsorption of iminodiacetic acid resin for yttrium(Ⅲ)[J].Chinese Journal of Inorganic Chemistry,2003,19(1):1356-1360.
[65] DRAGAN E S,DINU M V,LISA G,et al.Study on metal complexes of chelating resins bearing iminodiacetate groups[J].European Polymer Journal,2009,45(7):2119-2130.
[66] 兰俊，黎先财，杨沂凤.NaY分子筛对低浓度稀土废水的富集与回收[J].南昌大学学报(工科版),2015,37(3):224-227.LAN Jun,LI Xiancai,YANG Yifeng.NaY molecular sieve used in the enrichment and recover of rare earth from low concentration wastewater[J].Journal of Nanchang University(Engineering & Technology),2015,37(3):224-227.
[67] 兰俊.低浓度稀土废水的富集与回收技术研究[D].南昌：南昌大学，2015.
[68] 郭超逸.磷酸锆基吸附剂的制备及其吸附富集稀土La3+研究[D].赣州：江西理工大学，2022.
[69] WEI X Y,MAO X H,QIN W Q,et al.Synthesis of a green ALG@KLN adsorbent for high-efficient recovery of rare earth elements from aqueous solution[J].Separation and Purification Technology,2023,325.DOI:10.1016/J.SEPPUR.2023.124690.
基本信息:
DOI：10.13355/j.cnki.sfyj.2025.03.001
中图分类号:TF845
引用信息:
[1]胡小洣,刘书祯,李莉等.从低浓度稀土溶液中富集稀土研究进展[J].湿法冶金,2025,44(03):283-293.DOI:10.13355/j.cnki.sfyj.2025.03.001.
基金信息:
国家自然科学基金面上项目(52074094); 赣鄱俊才支持计划·青年科技人才托举项目(2025QT15); 赣鄱英才支持计划·青年类创新领军人才项目(gpyc20240040); 江西省教育厅科学技术研究项目(GJJ218517); 江西省重点研发计划项目(20202BBGL73116)