New Sorbents for Processing Radioactive Waste

  • Aslan Yu TsivadzeEmail author
  • Vladimir Baulin
  • Dmitry Baulin
Living reference work entry


A great volume of higher activity waste (HAW) has been accumulated in the nuclear industry. The radionuclides contained in them are elements of nuclear fuel (233,235,238U, 239Pu, 241,243Am), uranium fission products (134Cs, 137Cs, 90Sr, 95Zr, 95Nb, 129I, 131I, 144Се, 103,106Ru, 147Pm, 152,154Eu, 140Ba, etc.), and products of induced neutron activation of construction materials (58,60Co, 54Mn, 51Cr, 59Fe). The key principle of HAW processing is maximally efficient and feasibly selective recovery of both highly active and industrial and nuclear medicine radionuclides. At present only uranium and plutonium are recycled during the waste processing, while fission products and residues of uranium and plutonium are immobilized into solid matrices and sent for burial. The technology reduces the risk of radionuclides entering the environment. However it cannot be considered rational since the irreversibly lost elements are isotopes 90Sr and 147Pm used in fuel cells; 137Cs used as a source of ionizing radiation; 99Мо needed for nuclear pharmaceuticals; and nonferrous and precious metals Ag, Ru, Pd, Au, Rh, etc. which account for almost 30% of the whole mass of all radioactive wastes.

The many years of development of routines of selective extraction of valuable components from radioactive solutions show that sorption technologies are highly promising. Therefore efficient sorption materials (sorbents) are required. Unfortunately, most selective sorbents used currently for the purification of radioactive wastes are quite costly and dependent on the chemical compositions of the solutions being purified. This is not always adequate for tackling the current technological challenges successfully, and this stimulates development of new high-level sorption materials.

Among the known sorbents, the most interesting are synthetically feasible impregnated sorbents in which the stationary phase is complexation organic compounds, extractants non-covalently bound to the surface of a macroporous or nonorganic carrier. Metal ion sorption by impregnated sorbents is based on guest-host bonding between an organic extractant and a metal ion. Therefore the sorption properties of sorbents rely mainly on the extraction ability of the organic extractant. Its choice and structural optimization are determined. Quite common extractants are neutral organophosphorous compounds, i.e., phosphine oxides, carbamoyl phosphine oxides, as well as substituted calixarenes, which carry phosphor-containing moieties in the lower rim. Application of organophosphorous acids and zirconium salts of dialkyl phosphoric acids as extractants has been described. Macrocyclic compounds, i.e., crown ethers and crown-containing calixarenes, have also been studied quite well. High extraction properties are present in diamides of malonic, diglycolic, and heterocyclic acids, polynitrogen heterocyclic compounds, and synergistic mixtures of various extractants.

This review represents the results of the development of physicochemical principles for the obtainment and practical application of new impregnated sorbents in which the extractants are synthetically feasible acidic phosphoryl podands, in particular, the results of the studies of influence of structure of phosphoryl podands on the efficiency of partitioning, extraction, and purification of U(VI), Th(IV), Np(IV), and и Pu(IV) and rare earths La(III), Nd(III), 147Pm, Sm(III), and 99Мо.


Radioactive waste Sorption Impregnated sorbents Phosphoryl podands Extraction chromatography Separation of actinides Lanthanides Extraction of molybdenum 


  1. 1.
    Weber E (2004) In: Atwood JL, Steed JW (eds) Podands encyclopedia of Supramolecular chemistry. CRC Press, Boca Raton, pp 1106–1119CrossRefGoogle Scholar
  2. 2.
    Stead J, Etwood JL (2007) Supramolecular chemistry. IKTs Akademkniga, Moscow, 895 pagesGoogle Scholar
  3. 3.
    Varnek A, Fourches D, Solov'ev VP, Baulin VE, Turanov AN, Karandashev VK, Fara D, Katritzky R (2004) “In silico” design of new uranyl extractants based on phosphoryl-containing podands: QSPR studies, generation and screening of virtual combinatorial library and experimental tests. J Chem inf Comp Sci 44:1365–1382CrossRefGoogle Scholar
  4. 4.
    Baulin VE (2012) Doctoral Thesis. Institute of Physiologically Active Compounds of RAS. Chernogolovka, p. 352. (in Russian)Google Scholar
  5. 5.
    Baulin VE, Syundyukova VK, Tsvetkov EN (1989) Phosphor containing Podands. Acidic mono-podands with Phosphonyl phenyl terminal groups. J Gen Chem USSR 59(1):62–67. (in Russian)Google Scholar
  6. 6.
    Tsivadze AY, Baulin VE, Baulin DV, Tananaev IG, Safiulina AM (2010) Certificate of authorship no. 2391349 RF. Byulleten Izobretatelya (Bulletin of Inventor), no. 16. (In Russian)Google Scholar
  7. 7.
    Baulin DV, Baulin VE, Safiulina AM, Tsivadze GA (2009) Certificate of authorship no. 2352576 RF. Byulleten Izobretatelya (Bulletin of Inventor), no. 11. (In Russian)Google Scholar
  8. 8.
    Safiulina AM, Matveeva AG, Ivanets DV, Kudryavtsev EM, Grigoriev MS, Baulin VE, Tsivadze AY (2015) Phosphoryl containing acidic Podands as Extractants for recovery of f-elements 1. Synthesis and comparison of Podands different in polyether chain length and structure. Russ Chem Bull, Int Ed 64(1):161–168CrossRefGoogle Scholar
  9. 9.
    Safiulina AM, Matveeva AG, Ivanets DV, Kudryavtsev EM, Baulin VE, Tsivadze AY (2015) Phosphoryl containing acidic Podands as Extractants for recovery of f-elements 2. Synthesis and comparison of Podands different in terminal group structure. Russ Chem Bull, Int Ed 64(1):169–175., Published in Russian in Izvestiya Akademii Nauk. Seriya KhimicheskayaCrossRefGoogle Scholar
  10. 10.
    Timofeeva GI, Matveeva AG, Safiulina AM, Ivanets DV, Kudryavtsev EM, Baulin VE, Tsivadze AY (2015) Phosphoryl containing acidic Podands as Extractants for recovery of f-elements. 3. Dependence of the degree of Association of Podands on the nature of substituent and concentration in water-methanol solutions. Russ Chem Bull, Int Ed 64(1):224–227CrossRefGoogle Scholar
  11. 11.
    Turanov AN, Karandashev VK, Baulin VE, Tsivadze AY (2014) Extraction of REEs(III), U(VI) and Th(IV) with Phosphoryl containing acidic Podands from nitric acid solutions. J. Radiokhimia 56(1):21–24Google Scholar
  12. 12.
    Gujar RB, Ansari SA, Mohapatra PK (2015) Spectacular enhancements in actinide ion uptake using novel extraction chromatography resins containing TODGA and ionic liquid. Sep Purif Technol 141:229–234CrossRefGoogle Scholar
  13. 13.
    Brown T, Gersini G (1978) Extraction chromatography. Mir Publishers, Moscow, 628 pGoogle Scholar
  14. 14.
    Dietz ML, Dzielawa JA (2001) Ion-exchange as a mode of Cation transfer into room-temperature ionic liquids containing crown ethers: implications for the “greenness” of ionic liquids as diluents in liquid-liquid extraction. Chem Commun 20:24–2125Google Scholar
  15. 15.
    Visser AE, Swatloski RP, Reichert WM, Griffin ST, Rogers RD (2000) Traditional Extractants in nontraditional solvents: groups 1 and 2 extraction by crown ethers in room-temperature ionic liquids. Ind Eng Chem Res 39:3596–3604CrossRefGoogle Scholar
  16. 16.
    Sangki C, Dzyuba SV, Bartsch RA (2001) Influence of structural variation in room-temperature ionic liquids on the selectivity and efficiency of competitive alkali metal salt extraction by a crown ether. Anal Chem 73:3737–3741CrossRefGoogle Scholar
  17. 17.
    Visser AE, Rogers RD (2003) Room-temperature ionic liquids: new solvents for f-element separations and associated solution chemistry. J Solid State Chem 171:109–113CrossRefGoogle Scholar
  18. 18.
    Luo H, Sheng D, Bonnesen PV (2004) Solvent extraction of Sr2+ and Cs+ based on room-temperature ionic liquids containing Monoaza-substituted crown ethers. Anal Chem 76:2773–2779CrossRefGoogle Scholar
  19. 19.
    Luo H, Dai S, Bonnesen PV, Haverlock TJ, Moyer BA, Buchanan AC III et al (2006) Solv Extr Ion Exch 24:19–31CrossRefGoogle Scholar
  20. 20.
    Heitzman H, Blake YA, Rausch DJ, Dominique PR, Stepinski C, Dietz ML (2006) Fluorous ionic liquids as solvents for the liquid–liquid extraction of metal ions by macrocyclic Polyethers. Talanta 69:527–531CrossRefGoogle Scholar
  21. 21.
    Turanov AN, Karandashev VK, Baulin VE (2010) Extraction of alkaline earth metal ion with TODGA in presence of ionic liquids. Solv Extr Ion Exch 28(3):367–387CrossRefGoogle Scholar
  22. 22.
    Horwitz EP, Dietz ML, Chiarizia R, Diamond H, Maxwell SL III, Nelson M (1995) Separation and Preconcentration of actinides by extraction chromatography using a supported liquid anion exchanger: application to the characterization of high-level nuclear waste solutions. Anal Chim Acta 310:63–78CrossRefGoogle Scholar
  23. 23.
    Hawkins CA, Momen MA, Dietz ML (2017) Application of ionic liquids in the preparation of extraction chromatographic materials for metal ion separations: progress and prospects. Sep Sci Technol.
  24. 24.
    Chiarizia R, Chiarizia DR, McAlister AWH (2005) Trivalent actinide and lanthanide separations by Dialkyl-substituted Diphosphonic acids. Sep Sci Technol 40(1–3):69–90CrossRefGoogle Scholar
  25. 25.
    Kolaric Z (1982) Critical evaluation of some equilibrium constants involving Organophosphorus Extractants. Pure Appl Chem 54:2593–2674Google Scholar
  26. 26.
    Baulin VE, Minacheva LK, Ivanova IS, Pyatova EN, Churakov AV, Baulin DV, Sergienko VS, Tsivadze AY (2011) Synthesis, oscillation spectra, crystal and molecular structure of dehydrate 1,5-bis[2-(dioxyphosphinyl)phenoxy]-3-oxapenthane [(OH)2(O)P(C6H4)(OCH2CH2)2O(C6H4)P(O)(OH)2(H)2].H2. J Inorg Chem 56(8):1293–1302Google Scholar
  27. 27.
    Serebryannikov VV (1959) Chemistry of rare earth elements, vol I. Tech State Univ, Tomsk, 531 pGoogle Scholar
  28. 28.
    Zaytsev ID, Aseev GG (eds) (1988) Physicochemical properties of Binar and multicomponent solutions of inorganic substances. Reference book. Khimia Publisher, Moscow, 372 pGoogle Scholar
  29. 29.
    Turanov AN, Karandashev VK, Yarkevich AN, Safronova ZV (2004) Extraction of rare-earth elements from nitric acid solutions by selected bifunctional acidic organophosphorus compounds. Solv Extr Ion Exch 22(4):573–598CrossRefGoogle Scholar
  30. 30.
    Turanov AN, Karandashev VK, Bondarenko NA (2008) Extraction of perchlorates of rare earth elements and scandium by Podands with Diphenylphosphoryl Acetamide terminal groups. J Inorg Chem 53(11):1923–1931Google Scholar
  31. 31.
    Lee GS, Uchikoshi M, Minura K, Isshiki M (2010) Separation of major impurities Ce, Pr, Nd, Sm, al, ca, Fe and Zn from la using Bis(2-ethylhexyl)phosphoric acid (D2EHPA) – impregnated resin in a hydrochloric medium. Sep Purif Technol 71(2):186–191CrossRefGoogle Scholar
  32. 32.
    Horwitz EP, McAlister DR, Bond AH, Barrans RE Jr (2005) Novel extraction of chromatographic resins based on tetraalkyl diglycolamides: characterization and potential applications. Solv Extr Ion Exch 23(3):319–344CrossRefGoogle Scholar
  33. 33.
    Shikata E, Iguchi A (1986) Production of Mo99 and its application in nuclear medicine. Radioanal Nucl Chem 102(2):530–550CrossRefGoogle Scholar
  34. 34.
    Gusev NG, Rubtsov PM, Kovalenko VV, Kolobashkin VM (1974) Radiation characteristics of fission products. Atomizdat Publisher, Moscow, 367 pGoogle Scholar
  35. 35.
    Horwitz EP, McAlister DR, Dietz ML (2006) Extraction chromatography versus solvent extraction: how similar are they? Sep Sci Technol 41(10):2163–2182CrossRefGoogle Scholar
  36. 36.
    Turanov AN, Evseeva NK, Baulin VE, Tsvetkov EN (1995) Extraction of scandium from chloride solutions by Phosphoryl containing Podands. J Inorg Chem 40(5):861–865Google Scholar
  37. 37.
    Turanov AN, Karandashev VK, Baulin VE, Tsvetkov EN (1995) Extraction of trade amounts of gold by Phosphoryl containing Podands. J Inorg Chem 40(11):1926–1930Google Scholar
  38. 38.
    Turanov AN, Karandashev VK, Baulin VE (2006) Extraction of rhenium(VII) by Phosphoryl containing Podands. J Inorg Chem 51(4):735–742Google Scholar
  39. 39.
    Rovny SI, Logunov MV, Voroshilov YA, Betenekov ND, Denisov EI, Sharygin LM, Bugrov KV, Nikipelov VB (2006) Method of Obtainment of Concentrate of Radionuclide Mo-99: Patent 2288516 RF. Bulletin no. 33Google Scholar
  40. 40.
    Korobochkin VV, Nesterov EA, Skrudin SV, Stasyuk ES, Chibisov EV (2004) A study of adsorption of Мо on γ-Al2O3 with various structures. J Radiokhimia 46(2):144–148Google Scholar
  41. 41.
    Mushtaq A (2012) Future of low specific activity molybdenum-99/technetium-99m generator. Curr Radiopharm 5(4):325–328CrossRefGoogle Scholar
  42. 42.
    Pillai MR, Knapp FF Jr (2012) Molybdenum-99 production from reactor irradiation of molybdenum targets: a viable strategy for enhanced availability of technetium-99m. Q J Nucl Med Mol Imaging 56(4):385–399Google Scholar

Copyright information

© Springer International Publishing AG 2018

Authors and Affiliations

  • Aslan Yu Tsivadze
    • 1
    Email author
  • Vladimir Baulin
    • 1
    • 2
  • Dmitry Baulin
    • 1
  1. 1.Russian academy of sciences A.N. Frumkin Institute of Physical chemistry and Electrochemistry RAS (IPCE RAS)MoscowRussia
  2. 2.Russian academy of sciences Institute of Physiologically Active Compounds (IPAC RAS)ChernogolovkaRussia

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