Catalytic destruction of oxalate in the supernatant stream generated during plutonium reconversion process
-
Arvind Prasad
and
Ananthasivan Krishnamoorty
Abstract
Plutonium oxalate supernatant requires a treatment step for further recovery of the residual Pu. As the oxalate ion present in the solution poses problems during the recovery of Pu, it needs to be destroyed. In the present work, Mn2+ based catalytic destruction of oxalate ion was studied in detail, as it could minimize the generation of secondary radioactive waste compared to the conventional process. The effect of various parameters, namely concentrations of HNO3, catalyst, oxalic acid and effect of the metal ion has been studied. Moreover, the robustness of the catalytic destruction method along with the kinetics of oxalate destruction reaction has been investigated. The process was also demonstrated with Pu supernatant generated from CORAL at 1 L scale.
Acknowledgments
Authors are sincerely thankful to Sri Bankim paul, Sri Akhilesh K. Nair, Sri R. N. Chokalingam and Sri A. John Deepak Lawrence, Reprocessing group, IGCAR for their contribution during the course of experiment.
-
Research ethics: Not applicable.
-
Author contributions: The authors have accepted responsibility for the entire content of this manuscript and approved its submission. Arvind Prasad: performed all the experiments, data analysis, written the first draft of the paper. K. S. Vijayan: data analysis, manuscript correction. R. V. Subba Rao: improvised the paper by giving constructive inputs. N. Desigan: inputs for the experiments, revised the paper. K. Ananthasivan: final revision of the manuscript.
-
Competing interests: The authors state no conflict of interest.
-
Research funding: None declared.
-
Data availability: The raw data can be obtained on request from the corresponding author.
References
1. Geist, A., Adnet, J. M., Bourg, S., Ekberg, C., Galán, H., Guilbaud, P., Miguirditchian, M., Modolo, G., Rhodes, C., Taylor, R. An Overview of Solvent Extraction Processes Developed in Europe for Advanced Nuclear Fuel Recycling, Part 1 – Heterogeneous Recycling. Sep. Sci. Technol. 2021, 56, 1866, https://doi.org/10.1080/01496395.2020.1795680.Search in Google Scholar
2. Natarajan, R. Challenges in Fast Reactor Fuel Reprocessing. IANCAS Bull. 1998, 24, 271.Search in Google Scholar
3. Natarajan, R., Dhamodharan, K., Sharma, P. K., Pugazhendi, S., Vijayakumar, V., Pandey, N. K., Rao, R. V. S. Optimization of Flowsheet for Scrubbing of Ruthenium During the Reprocessing of Fast Reactor Spent Fuels. Sep. Sci. Technol. 2013, 48, 2494, https://doi.org/10.1080/01496395.2013.807828.Search in Google Scholar
4. Manchanda, V. K. Thorium as an Abundant Source of Nuclear Energy and Challenges in Separation Science. Radiochim. Acta 2023, 111(4), 243–263; https://doi.org/10.1515/ract-2022-0006.Search in Google Scholar
5. McKibben, J. M. Chemistry of the Purex Process. Radiochim. Acta 1984, 36(1–2), 3–16; https://doi.org/10.1524/ract.1984.36.12.3.Search in Google Scholar
6. Mishra, S., Mukhopadhyaya, C., Patra, C., Panantharayil, V. A., Rajesh, P., Sivakumar, D., Desigan, N., Dhamodharan, K., Velavendan, P., Rajeev, R. P., Venkatesan, K. A., Ananthasivan, K. Comparison of the Performance of Solvent Wash Reagents Used for the Primary Cleanup of Degraded PUREX Solvent. Radiochim. Acta 2023, 111(1), 53–62; https://doi.org/10.1515/ract-2022-0079.Search in Google Scholar
7. Kumar, K. S., Tripathi, V. M., Sreekumar, G., Sugilal, G. Study on Optimization of Actinide Oxalate Precipitation Process in a Vortex Flow Reactor. Sep. Sci. Technol. 2017, 52, 930, https://doi.org/10.1080/01496395.2016.1268627.Search in Google Scholar
8. Rao, V. K., Pius, I. C., Subbarao, M., Chinnusamy, A., Natarajan, P. R. Precipitation of Plutonium Oxalate from Homogeneous Solutions. J. Radioanal. Nucl. Chem. 1986, 100, 129, https://doi.org/10.1007/bf02036506.Search in Google Scholar
9. Rout, A., Venkatesan, K. A., Srinivasan, T. G., Vasudeva Rao, P. R. Tuning the Extractive Properties of Purex Solvent Using Room Temperature Ionic Liquid. Sep. Sci. Technol. 2013, 48, 2576, https://doi.org/10.1080/01496395.2013.811423.Search in Google Scholar
10. Wick, O. J. Plutonium Handbook: V. 1: A Guide to the Technology; Gordon and Breech Science Publishers Ltd: New York, 1967; p. 372.Search in Google Scholar
11. Ji, T., Yang, B., Su, S., Ding, S., Sun, W. Leaching Characteristics and Kinetics of Iron and Manganese from Iron-Rich Pyrolusite Slag in Oxalic Acid Solution. Sep. Sci. Technol. 2021, 56, 1612, https://doi.org/10.1080/01496395.2020.1786700.Search in Google Scholar
12. Pariyan, K., Hosseini, M. R., Ahmadi, A., Zahiri, A. Optimization and Kinetics of Oxalic Acid Treatment of Feldspar for Removing the Iron Oxide Impurities. Sep. Sci. Technol. 2020, 55, 1871, https://doi.org/10.1080/01496395.2019.1612913.Search in Google Scholar
13. Poirier, M. R., Hay, M. S., Herman, D. T., Crapse, K. P., Thaxton, G. D., Fink, S. D. Removal of Sludge Heels in Savannah River Site Waste Tanks with Oxalic Acid. Sep. Sci. Technol. 2010, 45, 1858, https://doi.org/10.1080/01496395.2010.493808.Search in Google Scholar
14. Bokelund, H., Caceci, M., MÜLler, W. A Photochemical Head-End Step in Carbide. Fuel Reprocess. 1983, 33, 115, https://doi.org/10.1524/ract.1983.33.23.115.Search in Google Scholar
15. Dükkancı, M., Gündüz, G. Ultrasonic Degradation of Oxalic Acid in Aqueous Solutions. Ultrason. Sonochem. 2006, 13, 517, https://doi.org/10.1016/j.ultsonch.2005.10.005.Search in Google Scholar PubMed
16. Ketusky, E., Huff, T., Sudduth, C. Enhanced Chemical Cleaning: Effectiveness of the UV Lamp to Decompose Oxalates – 10502; Waste Management Symposia: United States, SRR-STI-2010-00015, 2010; p. 20.Search in Google Scholar
17. Nayak, S. K., Srinivasan, T. G., Vasudeva Rao, P. R., Mathews, C. K. Photochemical Destruction of Organic Compounds Formed During Dissolution of Uranium Carbide in Nitric Acid. Sep. Sci. Technol. 1988, 23, 1551, https://doi.org/10.1080/01496398808075648.Search in Google Scholar
18. Srinivasan, T. G., Nayak, S. K., Damodharan, R., Vasudeva Rao, P. R. Photochemical Destruction of Oxalate in Simulated Reconversion Supernatant (Preprint No CT-9); Department of Atomic Energy: India, 1988.Search in Google Scholar
19. Yoo, J. H., Kim, E. H. Decomposition of Oxalate Precipitates by Photochemical Reaction; Korea Atomic Energy Research Institute: Korea, 1999.Search in Google Scholar
20. Michael, K. M., Talnikar, S. G., Jambunathan, U., Kapoor, S. C., Ramanujam, A., Venkataraman, N. Electrolytic Destruction of Oxalate Ions in Plutonium Oxalate Supernatant; Fuel Reprocessing Division, Bhabha Atomic Research Centre: India, BARC/1996/E/017, 1996; p. 17.Search in Google Scholar
21. Ganesh, S., Desigan, N., Chinnusamy, A., Pandey, N. K. Electrolytic and Ozone Aided Destruction of Oxalate Ions in Plutonium Oxalate Supernatant of the PUREX Process: A Comparative Study. J. Radioanal. Nucl. Chem. 2021, 328, 857, https://doi.org/10.1007/s10967-021-07714-y.Search in Google Scholar
22. Kulik, N., Panova, Y., Trapido, M. The Fenton Chemistry and Its Combination with Coagulation for Treatment of Dye Solutions. Sep. Sci. Technol. 2007, 42, 1521, https://doi.org/10.1080/01496390701290185.Search in Google Scholar
23. Pędziwiatr, P., Mikołajczyk, F., Zawadzki, D., Mikołajczyk, K., Bedka, A. Decomposition of Hydrogen Peroxide – Kinetics and Review of Chosen Catalysts. Acta Innov. 2018, 26, 45, https://doi.org/10.32933/actainnovations.26.5.Search in Google Scholar
24. Pignatello, J. J., Oliveros, E., MacKay, A. Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry. Crit. Rev. Environ. Sci. Technol. 2006, 36, 1, https://doi.org/10.1080/10643380500326564.Search in Google Scholar
25. Sun, Y., Pignatello, J. J. Chemical Treatment of Pesticide Wastes. Evaluation of Iron(III) Chelates for Catalytic Hydrogen Peroxide Oxidation of 2,4-D at Circumneutral pH. J. Agric. Food Chem. 1992, 40, 322, https://doi.org/10.1021/jf00014a031.Search in Google Scholar
26. Tufaner, F. Evaluation of COD and Color Removals of Effluents from UASB Reactor Treating Olive Oil Mill Wastewater by Fenton Process. Sep. Sci. Technol. 2020, 55, 3455, https://doi.org/10.1080/01496395.2019.1682611.Search in Google Scholar
27. Wang, N., Zheng, T., Zhang, G., Wang, P. A Review on Fenton-like Processes for Organic Wastewater Treatment. J. Environ. Chem. Eng. 2016, 4, 762, https://doi.org/10.1016/j.jece.2015.12.016.Search in Google Scholar
28. Kovács, K. A., Gróf, P., Burai, L., Riedel, M. Revising the Mechanism of the Permanganate/Oxalate Reaction. J. Phys. Chem. A 2004, 108, 11026, https://doi.org/10.1021/jp047061u.Search in Google Scholar
29. Mailen, J. C., Tallent, O. K., Arwood, P. C. Destruction of Oxalate by Reaction with Hydrogen Peroxide; Chemical Technology Division: Oak Ridge National Laboratory, United States, ORNL/TM-7474, 1981; p. 30.10.2172/6229619Search in Google Scholar
30. Vamplew, P. A., Singer, K. 238. The Kinetics of Oxidation by Nitrous and Nitric Acid. Part III. Oxidation of Oxalic Acid by Nitrous Acid. J. Chem. Soc. 1956, 1143; https://doi.org/10.1039/jr9560001143.Search in Google Scholar
31. Mason, C., Brown, T. L., Buchanan, D., Maher, C. J., Morris, D., Taylor, R. J. The Decomposition of Oxalic Acid in Nitric Acid. J. Solut. Chem. 2016, 45, 325, https://doi.org/10.1007/s10953-016-0437-2.Search in Google Scholar
32. Kubota, M. Decomposition of Oxalic Acid with Nitric Acid. J. Radioanal. Chem. 1982, 75, 39, https://doi.org/10.1007/bf02519972.Search in Google Scholar
33. Yu-Ting, W., Xiao-Teng, Z., Xian-Jun, L., Liang-Shu, X. Kinetics and Mechanism of Oxalic Acid Oxidation by Nitric Acid Catalyzed by Mn(II). Chin. J. Appl. Chem. 2021, 38, 685.Search in Google Scholar
34. Šulka, M., Cantrel, L., Vallet, V. Theoretical Study of Plutonium(IV) Complexes Formed within the PUREX Process: A Proposal of a Plutonium Surrogate in Fire Conditions. J. Phys. Chem. A 2014, 118, 10073, https://doi.org/10.1021/jp507684f.Search in Google Scholar PubMed
35. Ghosh, K., Eroy-Reveles, A. A., Avila, B., Holman, T. R., Olmstead, M. M., Mascharak, P. K. Reactions of NO with Mn(II) and Mn(III) Centers Coordinated to Carboxamido Nitrogen: Synthesis of a Manganese Nitrosyl with Photolabile NO. Inorg. Chem. 2004, 43, 2988, https://doi.org/10.1021/ic030331n.Search in Google Scholar PubMed
36. Wayland, B. B., Olson, L. W., Siddiqui, Z. U. Nitric Oxide Complexes of Manganese and Chromium Tetraphenylporphyrin. J. Am. Chem. Soc. 1976, 98, 94, https://doi.org/10.1021/ja00417a016.Search in Google Scholar
37. Mirkin, I. A., Koltunov, V. S. Kinetics of the Oxidation of Oxalic Acid and Oxalates with Aqueous Nitric Acid. Zh. Fiz. Khim. 1955, 29, 2163.Search in Google Scholar
© 2023 Walter de Gruyter GmbH, Berlin/Boston
Articles in the same Issue
- Frontmatter
- Preface
- NUCAR-2023: Foreword
- Research Articles
- Theoretical analysis of light and heavy-ion induced reactions: production of medically relevant 97Ru
- Excitation functions of alpha-particle induced nuclear reactions on nat Sn
- Non-destructive assay of plutonium in absence of gamma-ray spectrometry
- Catalytic destruction of oxalate in the supernatant stream generated during plutonium reconversion process
- Quantification of Zr in simulated dissolver solution of U–Zr fuel by laser-induced breakdown spectroscopy
- Radiochemical and chemical characterization of fuel, salt, and deposit from the electrorefining of irradiated U-6 wt% Zr in hot cells
- Zirconium sponge production: an integrated approach for chemical characterization of process intermediates using ICP-OES
- Determination of 10B/11B in boric acid and B4C using LA-ICPMS
- Evaluating sustainability of Bhuj aquifer system, Western India using nuclear dating techniques
- Nanocrystalline Ce(OH)4-based materials: ruthenium selective adsorbent for highly alkaline radioactive liquid waste
- Production and radiochemical separation of 68Ge from irradiated Ga–Ni alloy target in 30 MeV cyclotron
- Preparation of [64Cu]Cu–NOTA complex as a potential renal PET imaging agent using 64Cu produced via the direct activation route
- Total chemical synthesis of PSMA-617: an API for prostate cancer endotherapeutic applications
- Rapid screening technique for gross α and gross β estimations in aqueous samples during radiation emergency
- Development of Dy3+ doped lithium magnesium borate glass system for thermoluminescence based neutron dosimetry applications
Articles in the same Issue
- Frontmatter
- Preface
- NUCAR-2023: Foreword
- Research Articles
- Theoretical analysis of light and heavy-ion induced reactions: production of medically relevant 97Ru
- Excitation functions of alpha-particle induced nuclear reactions on nat Sn
- Non-destructive assay of plutonium in absence of gamma-ray spectrometry
- Catalytic destruction of oxalate in the supernatant stream generated during plutonium reconversion process
- Quantification of Zr in simulated dissolver solution of U–Zr fuel by laser-induced breakdown spectroscopy
- Radiochemical and chemical characterization of fuel, salt, and deposit from the electrorefining of irradiated U-6 wt% Zr in hot cells
- Zirconium sponge production: an integrated approach for chemical characterization of process intermediates using ICP-OES
- Determination of 10B/11B in boric acid and B4C using LA-ICPMS
- Evaluating sustainability of Bhuj aquifer system, Western India using nuclear dating techniques
- Nanocrystalline Ce(OH)4-based materials: ruthenium selective adsorbent for highly alkaline radioactive liquid waste
- Production and radiochemical separation of 68Ge from irradiated Ga–Ni alloy target in 30 MeV cyclotron
- Preparation of [64Cu]Cu–NOTA complex as a potential renal PET imaging agent using 64Cu produced via the direct activation route
- Total chemical synthesis of PSMA-617: an API for prostate cancer endotherapeutic applications
- Rapid screening technique for gross α and gross β estimations in aqueous samples during radiation emergency
- Development of Dy3+ doped lithium magnesium borate glass system for thermoluminescence based neutron dosimetry applications
