Abstract
Thirty liters of highly acidic spent nuclear fuel solutions need to be disposed at the “Hot Laboratory (hotlab)” facility in Paul Scherrer Institut (PSI), Switzerland. In order to significantly reduce the γ dose rate before proper disposal treatment, 137Cs must be removed. In the here presented sub-project, the ion-exchange method was evaluated. Two promising sorbents, CLEVASOL® and AMP (ammonium molybdophosphate), and two derived products AMP_PAN (AMP immobilized in polyacrylonitrile) and AMP/SiO2 (AMP immobilized on silica gel) were tested by the batch method using model solutions of important high-yield fission products (Cs, Eu, Zr, Ru, Pd and Ag), as well as U and Pu. The results showed that AMP, AMP/SiO2 and AMP_PAN have higher selectivity for Cs than CLEVASOL® in 0.1–8 M (mol/L) HNO3 solutions. 4 M HNO3 solution was identified as the most suitable condition for Cs-removal with AMP, AMP_PAN and AMP/SiO2 due to the still sufficiently high separation factor of Cs from other metal ions and an acceptable volume increase factor after dilution. The follow-up kinetic studies on AMP, AMP_PAN and AMP/SiO2 indicated that although Cs exchange on AMP and AMP/SiO2 is faster than on AMP_PAN in the first 5 min, they all nearly reach equilibrium after 30 min of contacting time. The isotherm curves of Cs adsorption on AMP, AMP_PAN and AMP/SiO2 in 4 M HNO3 showed that the maximum sorption capacity of Cs is reached asymptotically. The results from Langmuir isotherm modeling agree with results from other publications.
Acknowledgements
This study was sponsored by Swiss nuclear project “Waste treatment and Isotope Reclamation (WIR)”. CLEVASOL® was kindly provided free of charge from ADePhine GmbH. Many help on the ICP-MS measurement was provided by Pia Reichel.
References
1. IAEA nuclear data section. Available at: https://www-nds.iaea.org/sgnucdat/c3.htm. Accessed 10 July 2019.Search in Google Scholar
2. Konovalova, N. A., Rumer, I. A., Kulyukhin, S. A.: Coprecipitation of 137Cs and 85Sr microquantities with complex compound [M(18-crown-6)]BPh4 (M=Na+, Cs+) from neutral and alkaline solutions. Radiochim. Acta. 97, 559 (2011).10.1524/ract.2009.1634Search in Google Scholar
3. Dash, A., Ram, R., Pamale, Y. A., Deodhar, A. S., Venkatesh, M.: Recovery of 137Cs from laboratory waste using solvent extraction with sodium tetraphenylboron (TPB). Sep. Sci. Technol. 47, 81 (2011).10.1080/01496395.2011.614317Search in Google Scholar
4. Dozol, J. F., Dozol, M., Maclas, R. M.: Extraction of strontium and cesium by dicarbollides, crown ethers and functionalized calixarenes. J. Incl. Phenom. Macrocycl. Chem. 38, 1 (2000).10.1023/A:1008145814521Search in Google Scholar
5. Anthony, R. G., Dosch, R. G., Gu, D., Philip, C. V.: Use of silicotitanates for removing cesium and strontium from defense waste. Ind. Eng. Chem. Res. 32, 2702 (1994).10.1021/ie00035a020Search in Google Scholar
6. Todd, T. A., Brewer, K. N., Wood, D. J., Tullock, P. A., Mann, N. R., Olson, L. G.: Evaluation and testing of inorganic ion exchange sorbents for the removal of cesium-137 from actual IDAHO Nuclear Technology and Engineering Center acidic tank waste. Sep. Sci. Technol. 36, 999 (2007).10.1081/SS-100103633Search in Google Scholar
7. Mann, N. R., Todd, T. A.: Removal of cesium from acidic radioactive tank waste by using IONSIV IE-911. Sep. Sci. Technol. 39, 2351 (2005).10.1081/SS-120039321Search in Google Scholar
8. Coetzee, C. J., Rohwer, E. F. C. H.: Cation exchange studies on ammonium-12-molybdophosphate. J. Inorg. Nucl. Chem. 32, 1711 (1970).10.1016/0022-1902(70)80661-3Search in Google Scholar
9. Lin, M., Kajan, I., Schumann, D., Türler, A.: The concept for disposal of highly acidic spent nuclear fuel solutions at PSI. J. Radioanal. Nucl. Chem. 322, 1857 (2019).10.1007/s10967-019-06847-5Search in Google Scholar
10. Available at: https://www.lemerpax.com/en/products/clevasol-en/. Accessed 10 July 2019.Search in Google Scholar
11. Wells, A. F.: Structural inorganic chemistry. 2nd edition. Clarendon Press, Oxford, 351 (1950).Search in Google Scholar
12. Van, J., Smit, R.: Ammonium salts of the heteropolyacids as cation exchangers. Nature 181, 1530 (1958).10.1038/1811530a0Search in Google Scholar
13. Buchwald, H., Thistlethwaite, W. P.: Some cation exchange properties of ammonium 12-molybdophosphate. J. Inorg. Nucl. Chem. 5, 341 (1957).10.1016/0022-1902(58)80013-5Search in Google Scholar
14. Cannon, P.: A critical study of the precipitation of ammonium phospho-12-molybdate. Talanta 3, 219 (1960).10.1016/0039-9140(60)80023-9Search in Google Scholar
15. Thistlethwaite, W. P., Watson, W. T.: The formation and composition of some metal 12-12-molybdophosphates. J. Inorg. Nucl. Chem. 24, 1559 (1962).10.1016/0022-1902(62)80009-8Search in Google Scholar
16. Thistlethwaite, W. P., Watson, W. T.: The 12-molybdophosphates of Group II metals. J. Inorg. Nucl. Chem. 26, 1815 (1964).10.1016/0022-1902(64)80005-1Search in Google Scholar
17. Thistlethwaite, W. P.: The “Normal” 12-molybdophosphates of the alkali metals and ammonium. J. Inorg. Nucl. Chem. 28, 2143 (1966).10.1016/0022-1902(66)80098-2Search in Google Scholar
18. Dolezal, J., Stejskal, J., Tympl, M., Kourim, V.: Improved inorganic ion exchangers II. Ammonium molybdophosphate – silica gel system. J. Radioanal. Nucl. Chem. 21, 381 (1974).Search in Google Scholar
19. Rao, K. L. N., Mathew, C., Deshpande, R. S., Jadhav, A. V., Pande, B. M., Shukla, J. P.: Effects of electron beam irradiation on inorganic exchanger AMP. Radiat. Phys. Chem. 49, 85 (1997).10.1016/S0969-806X(96)00111-9Search in Google Scholar
20. Van, J., Smit, R.: Cation exchange properties of the ammonium heteropolyacid salts. J. Inorg. Nucl. Chem. 12, 95 (1959).10.1016/0022-1902(59)80098-1Search in Google Scholar
21. Krtil, J.: Exchange properties of ammonium salts of 12-heteropolyacids-IV: Cs exchange on ammonium phosphotungstate and phosphomolybdate. J. Inorg. Nucl. Chem. 24, 1139 (1962).10.1016/0022-1902(62)80259-0Search in Google Scholar
22. Chakravarty, R., Ram, R., Pillai, K. T., Pamale, Y., Kamat, R. V., Dash, A.: Ammonium molybdophosphate impregnated alumina microspheres as a new generation sorbent for chromatographic Cs-137/(Ba-137m) generator. J. Chromatogr. A 1220, 82 (2012).10.1016/j.chroma.2011.11.059Search in Google Scholar PubMed
23. Murthy, G. S., Sivaiah, M. V., Kumar, S. S., Reddy, V. N., Krishna, R. M., Lakshminarayana, S.: Adsorption of cesium on a composite inorganic exchanger zirconium phosphate – ammonium molybdophosphate. J. Radioanal. Nucl. Chem. 260, 109 (2004).10.1023/B:JRNC.0000027068.15669.adSearch in Google Scholar
24. Sebesta, F., John, J., Motl, A., Stamberg, K.: Evaluation of polyacrylonitrile (PAN) as a binding polymer for absorbers used to treat liquid radioactive wastes. Contractor Report. Sandia National Laboratories. SAND95-2729 (1995).10.2172/168591Search in Google Scholar
25. Sebesta, F., John, J., Motl, A.: Phase II report on the evaluation of polyacrylonitrile (PAN) as a binding polymer for absorbers used to treat liquid wastes. Contractor Report. Sandia National Laboratories. SAND96-1088 (1996).10.2172/231361Search in Google Scholar
26. Ding, D., Zhang, Z., Chen, R., Cai, T.: Selective removal of cesium by ammonium molybdophosphate-polyacrylonitrile bead and membrane. J. Hazard. Mater. 324, 753 (2017).10.1016/j.jhazmat.2016.11.054Search in Google Scholar PubMed
27. Pike, S. M., Buesseler, K. O., Breier, C. F., Dulaiova, H., Stastna, K., Sebesta, F.: Extraction of cesium in seawater off Japan using AMP-PAN resin and quantification via gamma spectrometry and inductively coupled mass spectrometry. J. Radioanal. Nucl. Chem. 296, 369 (2013).10.1007/s10967-012-2014-5Search in Google Scholar
28. Park, Y., Lee, Y., Shin, W., Choi, S.: Removal of cobalt, strontium and cesium from radioactive laundry wastewater by ammonium molybdophosphate-polyacrylonitrile (AMP-PAN). Chem. Eng. J. 162, 685 (2010).10.1016/j.cej.2010.06.026Search in Google Scholar
29. Ingale, S. V., Ram, R., Sastry, P. U., Wagh, P. B., Kumar, R., Niranjan, R., Phapate, S. B., Tewari, R., Dash, A., Gupta, S. C.: Synthesis and characterization of ammonium molybdophophate-silica nano-composite (AMP-SiO2) as a prospective sorbent for the separation of 137Cs from nuclear waste. J. Radioanal. Nucl. Chem. 301, 409 (2014).10.1007/s10967-014-3143-9Search in Google Scholar
30. Deng, H., Li, Y., Huang, Y., Ma, X., Wu, L., Cheng, T.: An efficient composite ion exchanger of silica matrix impregnated with ammonium molybdophosphate for cesium uptake from aqueous solution. Chem. Eng. J. 286, 25 (2016).10.1016/j.cej.2015.10.040Search in Google Scholar
31. Wu, Y., Zhang, X., Wie, Y., Mimura, H.: Development of adsorption and solidification process for decontamination of Cs-contaminated radioactive water in Fukushima through silica-based AMP hybrid adsorbent. Sep. Purif. Technol. 181, 76 (2017).10.1016/j.seppur.2017.03.019Search in Google Scholar
32. Samuelson, O.: Recommendation on ion exchange nomenclature. Pure Appl. Chem. 29, 618 (1972).Search in Google Scholar
33. Clifford, A. A.: Multivariate error analysis: a handbook of error propagation and calculation in many-parameter systems. John Wiley & Sons. ISBN 978-0470160558 (1973).Search in Google Scholar
34. Todd, T. A., Mann, N. R., Tranter, T. J., Sebesta, F., John, J., Motl, A.: Cesium sorption from concentrated acidic tank wastes using ammonium molybdophosphate-polyacrylonitrile composite sorbents. J. Radioanal. Nucl. Chem. 254, 47 (2002).10.1023/A:1020881212323Search in Google Scholar
35. Rieman, W., Walton, H. F.: Ion-Exchange equilibrium. In: Ion exchange in analytical chemistry. Pergamon Press, Oxford, 36 (1970).10.1016/B978-0-08-015511-1.50006-9Search in Google Scholar
36. Suss, M., Pfrepper, G.: Investigation of the sorption of cesium from acid solutions by various inorganic sorbents. Radiochim. Acta. 29, 33 (1981).10.1524/ract.1981.29.1.33Search in Google Scholar
37. Ganzerli Valentini, M. T., Maxia, V., Rollier, M. A., Barbaro Forleo, M.: Behavior of Uranyl ion in nitric acid solutions with ammonium molybdophosphate. J. Inorg. Nucl. Chem. 32, 671 (1970).10.1016/0022-1902(70)80277-9Search in Google Scholar
38. Krtil, J., Chavko, M.: Ion-exchange properties of ammonium salts of heteropolyacids. J. Chromatogr. A. 29, 460 (1967).10.1016/S0021-9673(01)85902-1Search in Google Scholar
39. Boyd, G. E., Adamson, A. W., Myers Jr, L. S.: The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics. J. Am. Chem. Soc. 69, 2849 (1947).10.1021/ja01203a067Search in Google Scholar
40. Kadous, A., Didi, M. A., Villemin, D.: A new sorbent for uranium extraction: ethylenediamino tris(methylenephosphonic) acid grafted on polystyrene resin. J. Radioanal. Nucl. Chem. 284, 431 (2010).10.1007/s10967-010-0495-7Search in Google Scholar
41. Liu, H., Cai, X., Wang, Y., Chen, J.: Adsorption mechanism-based screening of cyclodextrin polymers for adsorption and separation of pesticides from water. Water Res. 45, 3499 (2011).10.1016/j.watres.2011.04.004Search in Google Scholar
42. Tranter, T. J., Herbst, R. H., Todd, T. A., Olson, A. L., Eldredge, H. B.: Evaluation of ammonium molybdophosphate-polyacrylonitrile (AMP_PAN) as a cesium selective sorbent for the removal of 137Cs from acidic nuclear waste solutions. Adv. Environ. Res. 6, 107 (2002).10.1016/S1093-0191(00)00073-3Search in Google Scholar
43. Douglas LeVan, M., Carta, G., Yon, C. M.: Adsorption and Ion Exchange. In: Perry’s Chemical Engineer’s Handbook, 7th edition. McGraw-Hill, New York, 16-1 (1997).Search in Google Scholar
44. Hameed, B. H., Din, A. T. M., Ahmad, A. L.: Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies. J. Hazard. Mater. 141, 819 (2007).10.1016/j.jhazmat.2006.07.049Search in Google Scholar PubMed
45. Malik, P. K.: Dye removal from wastewater using activated carbon developed from sawdust: adsorption equilibrium and kinetics. J. Hazard. Mater. 113, 81 (2004).10.1016/j.jhazmat.2004.05.022Search in Google Scholar PubMed
46. Sun, C., Sun, L., Sun, X.: Graphical evaluation of the favorability of adsorption processes by using conditional Langmuir constant. Ind. Eng. Chem. Res. 52, 14251 (2013).10.1021/ie401571pSearch in Google Scholar
47. McKay, G., Blair, H. S., Gardner, J. R.: Adsorption of dyes on chitin. J. Appl. Polym. Sci. 27, 3043 (1982).10.1002/app.1982.070270827Search in Google Scholar
48. Voudrias, E., Fytianos, K., Bozani, E.: Sorption-description isotherms of dyes from aqueous solutions and waste waters with different sorbent materials. Global Nest J. 4, 75 (2002).Search in Google Scholar
49. Goldberg, S.: Equations and models describing adsorption processes in soils. in: Chemical processes in soils. Soil Science Society of America, 677 S. Segoe Road, Madison, WI 53711, USA, 489 (2005).10.2136/sssabookser8.c10Search in Google Scholar
©2020 Walter de Gruyter GmbH, Berlin/Boston
