WO2014124428A1 - Room temperature electrodeposition of actinides from ionic solutions - Google Patents
Room temperature electrodeposition of actinides from ionic solutions Download PDFInfo
- Publication number
- WO2014124428A1 WO2014124428A1 PCT/US2014/015749 US2014015749W WO2014124428A1 WO 2014124428 A1 WO2014124428 A1 WO 2014124428A1 US 2014015749 W US2014015749 W US 2014015749W WO 2014124428 A1 WO2014124428 A1 WO 2014124428A1
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- WIPO (PCT)
- Prior art keywords
- actinide
- uranium
- room temperature
- deposited
- ionic liquid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
Definitions
- FC07-06ID 14781 awarded by the Department of Energy. The government has certain rights in the invention.
- the present invention relates to the field of deposition of metals, especially
- Typical electrochemical processes to recover uranium from spent nuclear fuel result in the accumulation of minor actinides (americium (Am) and curium (Cu)) and transuranic elements (plutonium (Pu) and neptunium (Np)). These accumulated elements usually occur as metal chlorides in the molten electrolytic salt. They must periodically be removed from the electrolyte for the fuel reprocessing to continue.
- Electrochemical reduction has two advantages over chemical reduction.
- the first advantage is that the site of reduction is localized to the cathode surface forming a cathode deposit affording easy removal from the process equipment.
- the second advantage is that the use of electrons as the reducing agent does not add to the waste volume.
- Deposition of the transuranic elements and minor actinides on a solid cathode is well-known.
- Accompanying anode reactions include the oxidation of chloride ions to chlorine gas, oxidation of a sacrificial alloy, and oxidation of metallic uranium or reduced light water reactor (LWR) feed material.
- LWR reduced light water reactor
- U.S. Patent No. 7,267,754 discloses an improved process and device for the recovery of the minor actinides and the transuranic elements (TRU's) from a molten salt electrolyte.
- the process involves placing the device, an electrically non-conducting barrier between an anode salt and a cathode salt.
- the porous barrier allows uranium to diffuse between the anode and cathode, yet slows the diffusion of uranium ions so as to cause depletion of uranium ions in the catholyte. This allows for the eventual preferential deposition of transuranics present in spent nuclear fuel such as Np, Pu, Am, Cm.
- U.S. Patent No. 6,233,298 (Bowman) describes a subcritical reactor-like apparatus for treating nuclear wastes, the apparatus comprising a vessel having a shell and an internal volume, the internal volume housing graphite.
- the apparatus has means for introducing a fluid medium comprising molten salts and plutonium and minor actinide waste and/or fission products.
- the apparatus also has means for introducing neutrons into the internal volume wherein absorption of the neutrons after thermalization forms a processed fluid medium through fission chain events averaging approximately 10 fission events to approximately 100 fission events.
- the apparatus has additional means for removing the processed fluid medium from the internal volume.
- the processed fluid medium typically has no usefulness for production of nuclear weapons.
- Uranium Separation Process US Patent 3,030,176, Apr. 1962. This work outlines the dissolution of Uranium and the separation of species from fission products. The work outlines the use of molten salts in the separation.
- the advantage of our method is that RTIL solutions are ionic providing the same properties without the need for elevated temperatures (500 - 750 C) that the molten salts require which reduces the production of unwanted gases in the recovery process.
- the method utilizes a complexing agent, tri-n-butylphosphate (TBP) and organic solvent such as kerosene or n-dodecane in the extraction and reclamation process.
- TBP tri-n-butylphosphate
- organic solvent such as kerosene or n-dodecane
- Modifications to the process have been primarily focused on developing new complexing agents or using different solvents for extraction. More recently the RTIL solutions have been examined as an alternative to more volatile organic diluents using tricaprylmethylammonium thiosalicylate as the complexing agent in the extraction of U into RTIL solution.
- Dimitrovgrad SSC--RIAR process uses high temperature (1000K) eutectic molten salt mixtures as solvents for the fuel and also as electrolyte systems.
- the solvent is typically an eutectic mixture of NaCl/KCl or CsCl/KCl.
- the process uses chemical oxidants (chlorine and oxygen gases) to react with powdered U0 2 fuel, or mixtures of U0 2 and Pu0 2 , to form higher oxidation state compounds such as U0 2 C1 2 which are soluble in the molten salt.
- the uranium and, if applicable, plutonium compounds are reduced to U0 2 or U0 2 — Pu0 2 , which form crystalline deposits.
- the molten salt becomes loaded with fission products which not only begin to affect the quality of the product, but also result in too much heat generation within the salt.
- fission products are commonly, but not exclusively, highly active lanthanide or actinide elements which may need to be isolated in a suitable form for immobilisation as a waste.
- the ANL process is, unfortunately, a batch process, since the uranium is collected in a receptacle at the bottom of the apparatus, requiring that the process is interrupted in order that the receptacle may be withdrawn and the product recovered.
- the operation of the process is
- the second method is based on the synthesis of UF 4 using HF gas.( Pushparaja; Poplit, K.; Kher, R.; Iyer, M. Radiation protection dosimetry 1992, 42, 301-305.)
- the process is expensive and dangerous process due to the health hazards and corrosive nature of hydrofluoric acid.
- reduction of the UF 4 to metal using plasma and hydrogen is complicated by
- Figure 1 shows a graphic representation of the Cyclic Voltammetric response of an Au
- Figure 3 shows a graph of an Energy dispersive spectra for U deposits on an Au electrode from
- RTIL Room temperature ionic liquids
- thermodynamic driving force for the reduction of the species can be controlled precisely minimizing side reactions and disproportionation common to plasma based reduction of actinide halide complexes.
- ionic liquid essentially refers to a salt which melts at a relatively low temperature.
- the electrochemical reactions in RTIL can be conducted at room temperature or moderately elevated temperatures in the range of 30 - 200 °C without significant degradation of the ionic solvent.
- Ionic liquids free of molecular solvents were first disclosed by Hurley and Wier in a series of U.S. Pat. Nos. (2,446,331, 2,446,349, 2,446,350).
- Common features of ionic liquids include a near zero vapor pressure at room temperature, a high solvation capacity and a large liquid range (for instance, of the order of 300°C).
- Known ionic liquids include aluminium(III) chloride in combination with an imidazolium halide, a pyridinium halide or a phosphonium halide.
- Examples include l-ethyl-3-methylimidazolium chloride, N- butylpyridinium chloride and tetrabutylphosphonium chloride.
- An example of a known ionic liquid system is a mixture of l-ethyl-3-methylimidazolium chloride and aluminium (III) chloride.
- the RTIL system of the present technology may include an asymmetric organic cation and a large anion that can both be varied to influence the solution properties including solubility, viscosity, and the overall potential window for electrochemical experiments.
- Uranium metal deposits were successfully obtained from U(III) and U(IV) complexes in molten salt systems. 16
- U(TFSI) 3 and U(TFSI) 4 were prepared in our laboratory for the electrochemical studies using RTIL. However, we will focus on the U(TFSI) 3 system. All experiments were performed in an Argon evacuated glove box to minimize the formation of oxides after reduction of the uranium TFSI complexes in RTIL. The complexes directly dissolve in the RTIL after addition.
- Uranium metal can be electrochemical deposited from room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide), [Me 3 N n Bu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Furthermore, deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. The goal was to produce TFSI complexes of uranium to ensure solubility of the species in the ionic liquid.
- the methods outlined provide a first measure of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.
- the US Argonne National Laboratory developed a new apparatus called Plannar electrode Electrorefiner (PEER) at http://www.cmt.anl.gov.
- PEER Plannar electrode Electrorefiner
- the apparatus is designed to deposit an anode including a metallic fuel in the middle and a plurality of cathodes therearound and operate an electrolytic reaction. After a certain time passes, the electrodeposites are attached on the cathode and a porous ceramic plate is moved in a vertical direction to scrap out the cathode electrodeposites.
- the density of a current applied to an electrode relates to an electrodeposition rate in a cathode and a sticking coefficient.
- the sticking coefficient is defined as the amount of the electrodeposites stuck to a cathode surface to the amount of uranium metal transmitted to the cathode. Therefore, if the current density is increased using the electrode, the electrolytic rate is increased to decrease the sticking coefficient.
- the magnitude of the current density applied to the apparatus for an electrorefining or electrodeposition according to the present invention depends on the content of an allowable electrodeposite, preferably the current density of which the sticking coefficient is 0%.
- the current density of which the sticking coefficient is 0% may be defined experimentally.
- a current density greater than of between the current used during step c) to cause electrodeposition is in the range of between K ⁇ amps and 500 ⁇ amps /cm 2 and preferably between 50 ⁇ amps and 150 or 200 ⁇ amps /cm 2 is a range that can be conveniently applied in one embodiment of the present invention using a single carbon rod as a cathode.
- the electrochemical response for U(TFSI)3 (solid line) is presented in Figure 1 with the corresponding background (dashed line) for the RTIL.
- the cyclic voltammetric response for U(TFSI)3 is for the 10 th cycle.
- Sequential cycle results in an increase in current density as the surface deposit increases increasing the overall surface area on the electrode (not shown).
- a voltammetric reduction wave is observed in the negative potential scan at— 1.25 V consistent with the deposition of U(0) on the electrode surface.
- the reverse scan shows a voltammetric wave at -0.75 which can be attributed to the combined oxidation of U(III) to U(IV) and the partial oxidation of the U deposits.
- the electrochemical deposition was achieved using multiple techniques include cyclic voltammetry and constant potential methods.
- For the constant potential methods deposition was conducted at/or more negative than -2.0 V. Dark grey deposits were obtained on the electrode surface indicative of U metal deposition. Scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) analysis was used to evaluate the deposit and provide information regarding the speciation.
- the electrode was protected from air during transportation by sealing the sample argon evacuated container immediately prior to placement in the SEM.
- the SEM image of a clean gold electrode (top) and the deposited electrode (bottom) are shown in Figure 2.
- the Au surface is clearly visible in the SEM image for the deposited electrode.
- the surface deposits were examined at eleven sights using EDS, Figure 3.
- the EDS spectrum has bands characteristic of the U deposits, with some residual S from the RTIL.
- the deposits are sufficiently thick that the contribution of Au to the EDS spectrum is not observed.
- the uranium deposits were observed with no detectable oxygen in the EDS response.
- the results confirm that the electrochemical deposition of U metal from U(TFSI) 3 complex is feasible from RTIL solutions.
- U(TFSI) 3 U(TFSI) 4
- UI 3 (THF) 2 UI 3 (THF) 2 .
- Each sample was prepared using 4 ml of RTIL solution with ⁇ 10mg of total U content.
- the complexes were dissolved directly into the ionic liquid with simple mixing.
- the gold cathode was in the form of a sheet (1 cm 2 ) that was transferred directly to do both the TEM and XRD analysis of the deposits. Similar deposition was achieved using glassy carbon disk electrodes as the cathode. Cyclic voltammetric techniques were also utilized to deposit U metal at the cathode as shown in Figure 3.
- radiopharmaceutical that is produced during U fission processes.
- the electrochemical deposition of U0 2 (s) was also achieved from the 3% solution of soluble U 3 Og on an electrode surface providing a mass density of 10 mg/cm 2 .
- the example provided highlights the dissolution and recovery of uranium oxide from ionic liquid.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14749320.9A EP2954098A4 (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
AU2014214595A AU2014214595A1 (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
CA2900932A CA2900932A1 (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
JP2015557194A JP2016507008A (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic liquids |
CN201480020469.XA CN105102688A (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/764,282 US9631290B2 (en) | 2011-10-07 | 2013-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
US13/764,282 | 2013-02-11 |
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WO2014124428A1 true WO2014124428A1 (en) | 2014-08-14 |
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PCT/US2014/015749 WO2014124428A1 (en) | 2013-02-11 | 2014-02-11 | Room temperature electrodeposition of actinides from ionic solutions |
Country Status (6)
Country | Link |
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EP (1) | EP2954098A4 (en) |
JP (1) | JP2016507008A (en) |
CN (1) | CN105102688A (en) |
AU (1) | AU2014214595A1 (en) |
CA (1) | CA2900932A1 (en) |
WO (1) | WO2014124428A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10801120B2 (en) | 2017-01-26 | 2020-10-13 | Curium Us Llc | Systems and methods for electroplating sources for alpha spectroscopy |
WO2021148318A1 (en) * | 2020-01-23 | 2021-07-29 | Mahle International Gmbh | Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition |
US11760654B2 (en) | 2019-03-29 | 2023-09-19 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Conversion of uranium hexafluoride and recovery of uranium from ionic liquids |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106702442B (en) * | 2016-11-18 | 2019-05-07 | 西北核技术研究所 | A kind of uranium target and preparation method thereof in thin beryllium on piece electro-deposition preparation |
US20190371482A1 (en) * | 2018-05-30 | 2019-12-05 | Alpha Tech Research Corp | Electrochemical Separation Mechanism in a Molten Salt Reactor |
CN116836406B (en) * | 2023-08-29 | 2023-11-17 | 北京大学 | Actinide soft iron ring material and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US6911135B1 (en) * | 1999-08-18 | 2005-06-28 | British Nuclear Fuels Plc | Process for separating metals |
US20080128284A1 (en) * | 2001-07-20 | 2008-06-05 | The Regents Of The University Of California | Methods for fabricating metal nanowires |
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US20070129568A1 (en) * | 2005-12-06 | 2007-06-07 | Ngimat, Co. | Ionic liquids |
GB0612305D0 (en) * | 2006-06-21 | 2006-08-02 | Leuven K U Res & Dev | Novel ionic liquids |
JP4631818B2 (en) * | 2006-06-27 | 2011-02-16 | 住友金属鉱山株式会社 | Method for hydrometallizing nickel oxide ore |
-
2014
- 2014-02-11 CA CA2900932A patent/CA2900932A1/en not_active Abandoned
- 2014-02-11 JP JP2015557194A patent/JP2016507008A/en active Pending
- 2014-02-11 WO PCT/US2014/015749 patent/WO2014124428A1/en active Application Filing
- 2014-02-11 EP EP14749320.9A patent/EP2954098A4/en not_active Withdrawn
- 2014-02-11 CN CN201480020469.XA patent/CN105102688A/en active Pending
- 2014-02-11 AU AU2014214595A patent/AU2014214595A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6911135B1 (en) * | 1999-08-18 | 2005-06-28 | British Nuclear Fuels Plc | Process for separating metals |
US20080128284A1 (en) * | 2001-07-20 | 2008-06-05 | The Regents Of The University Of California | Methods for fabricating metal nanowires |
Non-Patent Citations (2)
Title |
---|
BELLER ET AL., ACTINIDE FOIL PRODUCTION FOR MPACT RESEARCH, 30 October 2012 (2012-10-30), XP055278522, Retrieved from the Internet <URL:https://inlportal.inl.gov/portal/server.pt/document/113429/neup-project-no-11-3138_pdf> * |
See also references of EP2954098A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10801120B2 (en) | 2017-01-26 | 2020-10-13 | Curium Us Llc | Systems and methods for electroplating sources for alpha spectroscopy |
US11421336B2 (en) | 2017-01-26 | 2022-08-23 | Curium Us Llc | Systems and methods for electroplating sources for alpha spectroscopy |
US11760654B2 (en) | 2019-03-29 | 2023-09-19 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Conversion of uranium hexafluoride and recovery of uranium from ionic liquids |
WO2021148318A1 (en) * | 2020-01-23 | 2021-07-29 | Mahle International Gmbh | Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition |
Also Published As
Publication number | Publication date |
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EP2954098A1 (en) | 2015-12-16 |
CA2900932A1 (en) | 2014-08-14 |
AU2014214595A1 (en) | 2015-09-10 |
JP2016507008A (en) | 2016-03-07 |
CN105102688A (en) | 2015-11-25 |
EP2954098A4 (en) | 2016-09-07 |
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