Журналы →  Non-ferrous Мetals →  2022 →  №1 →  Назад

RARE METALS, SEMICONDUCTORS
Название Application of silica-based sorbents to extraction of rare earth elements from loparite processing products
DOI 10.17580/nfm.2022.01.03
Автор Muslimova A. V., Bujnovskij A. S., Karakchieva, N. I., Sachkov V. I.
Информация об авторе

Seversk Technological Institute, a branch of State Autonomous Educational Institution of Higher Education National Research Nuclear University MEPhl, Seversk, Russia:

A. V. Muslimova, Associated Professor, Department of Chemistry and Technology of Modern Energy Materials, e-mail: klameri7@gmail.com
A. S. Bujnovskij, Professor, Department of Chemistry and Technology of Modern Energy Materials

 

National Research Tomsk State University, Tomsk, Russia1 ; Siberian Research Institute of Agriculture and Peat-branch of Siberian Federal Scientific Centre of Agro-biotechnologies of The Russian Academy of Sciences, Tomsk, Russia2:

N. I. Karakchieva, Senior Researcher1, 2, e-mail: karakchieva@mail.tsu.ru

 

National Research Tomsk State University, Tomsk, Russia

V. I. Sachkov, Professor, Head of the Laboratory “Innovation and Technology Center”, e-mail: itc@spti.tsu.ru

Реферат

Apatite and loparite are the main sources of rare earth elements (REE) in Russia. Loparite is a complex titanate and niobate containing up to 30% wt. of REE oxides predominantly of the cerium group. Extraction processing methods are used at the stages of group separation and separation of REE concentrates. Tributyl phosphate (TBP) is a widely used extracting agent for these purposes. Extraction technologies have a number of disadvantages, in particular, a large number of separation stages because of low separation coefficients of individual REE combined with difficulties in separating liquid phases. The use of TBP-containing sorbents allows to eliminate the latter disadvantage. Both organic polymers and inorganic compounds may be used as sorbent carriers; among inorganic ones, silica is widely used, and it was selected for this study. The purpose of this work was to study the effect of variations of the proposed methods for synthesis of silica and modified TBP based sorbents on their ability to extract REE from the solutions of loparite concentrate processing. The article briefly describes a procedure for sorbent samples synthesis. Tetraethoxysilane, tributyl phosphate, stannic chloride and nanotubes have been used as starting reagents for the synthesis. A number of physicochemical properties have been determined for the synthesized samples (pore volume and their average diameter, surface area and morphology, acid-base properties of the surface), and thermogravimetric analysis has been performed. The sorption properties of the samples have been tested by the example of REE extraction from process solutions of loparite working up. The separation coefficients of Sm/La pairs up to 3.7, Pr/Nd up to 1.8 were obtained; therefore, the studied samples may be potentially used for samarium isolation from the REE combination, as well as for Pr – Nd pair separation.

This study was supported by the Tomsk State University Development Programme (Priority-2030).
The SEM researches and results of measuring the specific surface area (SBET) and porous structure were carried out with the equipment of Tomsk Regional Core Shared Research Facilities Center of National Research Tomsk State University. Center was supported by the Ministry of Science and Higher Education of the Russian Federation Grant no. 075-15-2021-693 (no. 13.RFC.21.0012)).

Ключевые слова Loparite, rare earth elements, thorium, separation, sorbents, tributyl phosphate, silica, stannic chloride
Библиографический список

1. Kosynkin V. D., Moiseev S. D., Peterson C. H., Nikipelov B. V. Rare Earths Industry of Today in the Commonwealth of Independent States. Journal of Alloys and Compounds. 1993. Vol. 192, Iss. 1-2. pp. 118–120.
2. Gasanov A. A., Naumov A. V., Yurasova O. V., Petrov I. M., Litvinova T. E. Certain Tendencies in the Rare-Earth-Element World Market and Prospects of Russia. Russian Journal of Non-Ferrous Metals. 2018. Vol. 59. Iss. 5. pp. 502–511.
3. Hedrick J. B., Sinha S. P., Kosynkin V. D. Loparite, a Rare-Earth Ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3. Journal of Alloys and Compounds. 1997. Vol. 250, Iss. 1-2. pp. 467–470.

4. Kudryavskii Y. P. Investigation of Physicochemical Fundamentals and Elaboration of the New, Improved Technology of Deactivation of Liquid Radioactive Waste of The Chlorination Process of Loparite Concentrates. Russian Journal of Applied Chemistry. 2011. Vol. 84, Iss. 3. pp. 515–525.
5. Tsivadze A. Y. Selective Separation of Elements of the Periodic Table with Similar Chemical Properties as a Foundation for New Technologies. Herald of the Russian Academy of Sciences. 2020. Vol. 90, Iss. 2. pp. 214–224.
6. Kosynkin V. D., Nikonov V. J. Rare Earth Production at the Sillamae Plant, 1969–1991 and the Possibility of Scandium Extraction from Loparite. In Book: Turning a Problem Into a Resource: Remediation and Waste Management at the Sillamäe Site, Estonia. Springer, Dordrecht, 2000. P. 57–61.
7. Shulin S. S., Galieva G. N., Chighevskaya S. V., Pletuhina J. V., Saveliev N. S. Extraction Separation of Rare Earth Elements of the Medium Group with Isomolar Mixtures of Aliquat®336–TBP and Cyanex®572–TBP from Nitric Solutions. Inorganic Materials. 2018. Vol. 54, Iss. 5. pp. 515– 519.
8. Ehrlich G. V., Lisichkin G. V. Sorption in the Chemistry of Rare Earth Elements. Russian Journal of General Chemistry. 2017. Vol. 87, Iss. 6. pp. 1220–1245.
9. Xue G., Yurun F., Li M., G. Dezhi, J. Jie, Y. Jincheng, S. Haibin, G. Hongyu, Z. Yujun Phosphoryl Functionalized Mesoporous Silica for Uranium Adsorption. Applied Surface Science. 2017. Vol. 402. pp. 53–60.
10. Ahmed S. H. Abdel Warith A. A., Sallman A. A., El-Gammal E. M. Studies on Uranium Recovery by Activated Carbon impregnated with Tridodecylamine and Tributyl Phosphate. Nuclear Sciences Scientific Journal. 2018. Vol. 7, Iss. 1. pp. 189–203.
11. Mokhodoeva O. B., Myasoedova G. V., Zakharchenko E. A. Solid-phase Extractants for Radionuclide Preconcentration and Separation. New Possibilities. Radiochemistry. 2011. Vol. 53, Iss. 1. pp. 35–43.
12. Nekrasova N. A., Milyutin V. V., Kaptakov V. O. Solid Extractants of Russian Manufacture for the Extraction of Rare-Earth Elements and Actinides from Nitric Acid Solutions. Transactions Kola Science Centre. Series 3: Chemistry and Materials. 2019. Vol. 10, Iss. 1. pp. 226–229.
13. Zheng R., Bao S., Zhang Y., Chen B. Synthesis of Di-(2-ethylhexyl) Phosphoric Acid (D2EHPA)-tributyl Phosphate (TBP) Impregnated Resin and Application in Adsorption of Vanadium (IV). Minerals. 2018. Vol. 8, Iss. 5. pp. 206–217.
14. Naik P., Dhami P., Misra S., Jambunathan U., Mathur J. Use of Organophosphorus Extractants Impregnated on Silica Gel for the Extraction Chromatographic Separation of Minor Actinides from High Level Waste Solutions. Journal of Radio analytical and Nuclear Chemistry. 2003. Vol. 257, Iss. 2. pp. 327–332.
15. Rozen A. M., Krupnov B. V. Dependence of the Extaction Ability of Orgaic Compounds on their Structure. Russian Chemical Reviews. 1996. Vol. 65, Iss. 11. pp. 1052–1079.
16. Grachova I. E., Karpova S. S., Moshnikov V. A., Pshchelko N. S. Netting Hierarchical Porous Structures with Electroadhesion Contacts. Proceedings of Saint Petersburg Electrotechnical University. 2010. No. 8. pp. 27–32.
17. Brown C. G., Sherrington L. G. Solvent Extraction Used in Industrial Separation of Rare Earths. Journal of Chemical Technology and Biotechnology. 1979. Vol. 29, Iss. 4. pp. 193–209.
18. Iloeje C. O. Modeling Liquid–Liquid Extraction for Critical Elements Separations: an Overview. In Book: Multidisciplinary Advances in Efficient Separation Processes. ACS Publications, 2020. pp. 335–365.
19. Liddell K. N. C., Bautista R. G. The Chemical Reactions of Tributyl Phosphate in the Solvent Extraction of Metals. In Book: Hydrometallurgical Process Fundamentals. Boston, MA: Springer, 1984. P. 429–471.
20. Mingaliov P. G., Rzhevskii D. V., Perfiliev Yu. D., Lisichkin G. V. A Mossbauer Spectroscopy Investigation of Grafted Layer of Silica Chemically Modified with Tin Compounds. Vestnik Moskovskogo Universiteta. Seriya 2. Khimiya. Vol. 41, No. 1. pp. 53–55.
21. Dyshin A. A., Eliseeva P. V., Bondarenko G. V., Kiselev M. G. Reinforcement of Polymethylmethacrylate of Various Molecular Weights by Diffusion Introduction of Single-walled Carbon Nanotubes in a Overcritical Carbon DIoxide Medium. Zhurnal Fizicheskoi Khimii. 2017. Vol. 91, No. 10. pp. 1740–1747.
22. Kamimura Y., Kurumada K. Properties and Microstructure of Silica Glass Incorporated With Tributyl Phosphate by Sol–Gel Method. Journal of Non-Crystalline Solids. 2009. Vol. 355, Iss. 34-36. pp. 1693–1697.
23. Higgins C. E., Baldwin W. H. The Thermal Decomposition of Tributyl Phosphate. The Journal of Organic Chemistry. 1961. Vol. 26, Iss. 3. pp. 846–850.
24. Horrocks A. R., Davies P. J., Kandola B. K., Alderson A. The Potential for Volatile Phosphorus-containing Flame Retardants in Textile Back-Coatings. Journal of Fire Sciences. 2007. Vol. 25, Iss. 6. pp. 523–540.
25. Barney G. S., Cooper T. D. The Chemistry of Tributyl Phosphate at Elevated Temperatures in The Plutonium Finishing Plant Process Vessels. Westinghouse Hanford Co., Richland, WA (United States). 1994. No. WHC-EP-0737. 65 p.
26. Pang L. S. K., Saxby J. D., Chatfield S. P. Thermogravimetric Analysis of Carbon Nanotubes and Nanoparticles. The Journal of Physical Chemistry. 1993. Vol. 97, Iss. 27. pp. 6941–6942.
27. McGill I., Matthey J. Rare Earth Elements. England: Technology Centre, Reading, 2000. 228 p.

Полный текст статьи Application of silica-based sorbents to extraction of rare earth elements from loparite processing products
Назад