Mining, Metallurgy & Exploration

, Volume 36, Issue 5, pp 967–977 | Cite as

Selective Precipitation of High-Quality Rare Earth Oxalates or Carbonates from a Purified Sulfuric Liquor Containing Soluble Impurities

  • Ruberlan Gomes SilvaEmail author
  • Carlos Antonio Morais
  • Leandro Viana Teixeira
  • Éder Domingos Oliveira
Review Article


The purity of rare earth products depends on the ability of the reagents used to selectively promote the precipitation of the rare earth elements (REE) from impurities present in sulfuric liquors. The present study aims at investigating the conditions required to precipitate REE, either as rare earth oxalates or carbonates, from purified rare earth sulfuric liquor with a low Al3+ and UO22+ and a very high Ca2+, Mg2+, Mn2+, and SO42− impurity content. The rare earth sulfuric liquor was obtained in a previous study by the reaction of a rare earth ore with sulfuric acid, pyrolysis at 700 °C/2 h, cooling at 20 °C, and water leaching. The impurities such as Fe3+, Th4+, and PO43− were completely removed from the liquor in two consecutive neutralization steps. In order to recover the REE, the purified rare earth liquor was then treated with oxalic acid and sodium carbonate. Rare earth oxides (REO) precipitated with oxalic acid displayed a very high purity (99.2% w/w) and low impurity content. In contrast, the rare earth carbonates precipitated with sodium carbonate presented a comparatively lower REO content (68.5% w/w) and 94.2% of purity, but with a higher content of impurities. Better precipitating conditions were achieved at 60 °C, compared with 20 °C, and under stoichiometric reagent consumption, with REE precipitation efficiencies higher than 96%. The dosage above the stoichiometric condition caused the precipitation of calcium oxalates and co-precipitation of rare earth sulfates when oxalic acid is used, and precipitation of calcium, manganese, and uranium carbonates and also a co-precipitation of rare earth sulfate when sodium carbonate were used. An integrated flowsheet to produce a high-quality rare earth product from rare earth sulfuric liquor containing some impurities is proposed.


Sulfuric liquor Rare earth oxalates Rare earth carbonates Remove impurities Precipitation 



The authors would like to thank Vale S.A., especially Patrice Mazzoni, Cássia Souza, and Keila Gonçalves for authorizing the publication of this work. The authors are also thankful to the technicians from Mineral Development Centre’s Vale engaged in this study. We also would like to thank Daniel Saturnino, Marcus Simões, and Julius W. Martins for proofreading the paper. Éder Oliveira and Carlos Morais acknowledge the support from CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico), CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior), and FAPEMIG (Fundação de Amparo à Pesquisa de Minas Gerais).

Compliance with Ethical Standards

Conflict of Interest

The authors declare that they have no conflict of interest.


  1. 1.
    Abreu RD, Morais CA (2014) Study on separation of heavy rare earth elements by solvent extraction with organophosphorous acids and amine reagents. Miner Eng 61:82–87CrossRefGoogle Scholar
  2. 2.
    Tunsu C, Petranikova M, Ekberg C, Retegan T (2016) A hydrometallurgical process for the recovery of rare rarth elements from fluorescent lamp waste fractions. Sep Purif Technol 161:172–186CrossRefGoogle Scholar
  3. 3.
    Gupta CK, Krishnamurthy N (1992) Extractive metallurgy of rare earths. Int Mater Rev 37(5):197–210CrossRefGoogle Scholar
  4. 4.
    Borrowman SR, Rosenbaum JB (1961) Recovery of thorium from a Wyoming ore. In: BM-RI-5917, Bureau of Mines. Metallurgy Research Center, Salt Lake CityGoogle Scholar
  5. 5.
    Pilkington ES, Wylie AW (1947) Production of rare earth and thorium compounds from monazite. Part I. J Soc Chem Ind 66(11):387–394CrossRefGoogle Scholar
  6. 6.
    Shaw KG, Smutz M, Bridger GL (1954) A process for separating thorium compounds from monazite sands. Ames Laboratory, Iowa State College, Ames, IowaGoogle Scholar
  7. 7.
    Teixeira LAV, Silva RG (2015) System and process for selective rare earth extraction with sulphur recovery. Patent US 2015/0329940 A1Google Scholar
  8. 8.
    Teixeira LAV, Silva RG, Avelar A, Majuste D, Ciminelli VST (2019) Selective extraction of rare elements from monazite ores with high iron content. Min Metall Expl 36:235–244. CrossRefGoogle Scholar
  9. 9.
    Testa FG, Avelar AN, Silva RG, Souza CC (2016) Mineralogical characterization and alternative to concentrate the rare earth lithotypes from alcaline Complex of Catalão – GO. Associação Brasileira de Metalurgia. Materiais e Mineração, São Paulo. CrossRefGoogle Scholar
  10. 10.
    Yang SS, Shen J, Li ZQ, CaO YX (1995) New combined process of niobium enrichment from no.2 ore body of Baotou niobium-bearing iron ore. J Univ Sci Technol Beijing 17(3):218–223 In ChineseGoogle Scholar
  11. 11.
    Berni TV, Pereira AC, Mendes FD, Rude AL (2013) System and method for rare earth extraction. Patent US 2013/0336856 A1Google Scholar
  12. 12.
    Silva RG, Morais CA, Teixeira LV, Oliveira ED (2018a) Selective removal of impurities from rare earth sulfuric liquor using different reagents. Miner Eng 127:238–246. CrossRefGoogle Scholar
  13. 13.
    Panda R, Jha MK, Hait J, Kumar G, Singh RJ, Yoo K (2016) Extraction of lanthanum and neodymium from leach liquor containing rare earth metals (REMs). Hydrometallurgy 165:106–110CrossRefGoogle Scholar
  14. 14.
    Ru’an C, Jungming X, Peijiong H, Yongjun Z (1995) Recovering REE from leaching liquor of rare earth ore by extraction. Trans NFsoc 5(4)Google Scholar
  15. 15.
    Demol J, Ho E, Senanayake G (2018) Sulfuric acid baking and leaching of rare earth elements, thorium and phosphate from a monazite concentrate: effect of bake temperature from 200 and 800°C. Hydrometallurgy 179:254–267. CrossRefGoogle Scholar
  16. 16.
    Battsengel A, Batnasan A, Narankhuu A, Haga K (2018) Recovery of light and heavy rare earth elements from apatite ore using sulphuric acid leaching, solvent extraction and precipitation. Hydrometallurgy 179:100–109. CrossRefGoogle Scholar
  17. 17.
    Lucas J, Lucas P, Mercier TL, Rollat A, Davenport W (2015) Rare earths science, technology, production and use. ElsevierGoogle Scholar
  18. 18.
    Yun X, Liansheng X, Jiying T, Zhaoyang L, Li Z (2015) Recovery of rare earth from acid leach solution of spent nickel-metal hydride batteries using solvent extraction. J Rare Earths 33(12):1348–1354. CrossRefGoogle Scholar
  19. 19.
    Soe NN, Shwe LT, Lwin KT (2008) Study on extraction of lanthanum oxide from monazite concentrate. World Acad Sci Eng Technol 46Google Scholar
  20. 20.
    Kate and Laby (2005) Properties of inorganic compounds, 16 edn. Tables Phys Chem Constants. Version 1.0Google Scholar
  21. 21.
    Lide DR (2004) Properties of the elements and inorganic compounds, 85 edn. Handb Chem Phys. CRC Press, Boca Raton, pp 1–158Google Scholar
  22. 22.
    Dean JA (1968) Lange’s handbook of chemistry, 13rd edn. McGraw-HillGoogle Scholar
  23. 23.
    Morais CA, Abreu RD (2010) Purification of rare earth elements from monazite sulphuric acid leach liquor and the production of high-purity ceric oxide. Miner Eng 23:536–540. CrossRefGoogle Scholar
  24. 24.
    Silva RG, Morais CA, Teixeira LV, Oliveira ED (2018b) Precipitação do sulfato duplo de terras raras e sódio a partir de um licor sulfúrico de terras raras contendo impurezas. Tecnologia em Metalurgia e Mineração (TMM).
  25. 25.
    Beltrami D, Deblonde GJP, Bélair S, Weigel V (2015) Recovery of ytrium and lanthanides from sulfate solutions with high concentrations of iron and low rare earth content. Hydrometallurgy 157:356–362. CrossRefGoogle Scholar

Copyright information

© Society for Mining, Metallurgy & Exploration Inc. 2019

Authors and Affiliations

  1. 1.Centro de Desenvolvimento Mineral da VALESanta LuziaBrazil
  2. 2.Department of Chemical EngineeringUniversidade Federal de Minas Gerais (UFMG)Belo HorizonteBrazil
  3. 3.Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN)Belo HorizonteBrazil

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