Electrochemistry of PUREX: R is for reduction and ion transfer
Abstract
The PUREX (Plutonium, Uranium, Reduction, EXtraction) process is the foundation of all industrial activities that involve the recycling of plutonium and uranium from used nuclear fuel. With over 70 years of research, engineering, and operations, it can be argued that little opportunity is left for further discovery and new fundamental understandings regarding PUREX, in general, and tri-n-butyl phosphate (TBP), in particular. Through use of an advanced electroanalytical approach, molecular-level insights regarding the back-extraction of Pu(IV) by reductive separation is reported. Studies of model PUREX systems, with lanthanide ions extracted into 20 % TBP in n-dodecane, are used to demonstrate the approach. These studies reveal knowledge pertinent to mass transfer aspects of the biphasic reductive stripping reaction central to the separation of U and Pu in PUREX. Two lanthanide ions—Ce(IV) and Yb(III)—were extracted from their concentrated solutions in aqueous 3 M HNO3 to expressly provide electrically conducting third phases to facilitate electrochemical data acquisition. To simplify the diabolically-complicated reductive separation aspects of PUREX, the controlled polarization of electrode surfaces was used to reduce Ce(IV) and Yb(III) in place of chemical reductants. Electroanalyses of the biphasic systems with Ce(IV) and Yb(III) using three-phase electrode differential pulse voltammetry demonstrate the effects of massmore »
- Authors:
-
[1];
[2];
[1];
[1]
- Colorado School of Mines, Golden, CO (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Colorado School of Mines, Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Graduate Student Research (SCGSR) Program; USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1839948
- Alternate Identifier(s):
- OSTI ID: 1657530
- Grant/Contract Number:
- AC02-06CH11357; SC0020189
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solvent Extraction and Ion Exchange
- Additional Journal Information:
- Journal Volume: 40; Journal Issue: 1-2; Journal ID: ISSN 0736-6299
- Publisher:
- Taylor and Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrochemistry; PUREX; voltammetry; third phase; reduction; ion-transfer
Citation Formats
Bertelsen, Erin R., Antonio, Mark R., Jensen, Mark P., and Shafer, Jenifer C. Electrochemistry of PUREX: R is for reduction and ion transfer. United States: N. p., 2021.
Web. doi:10.1080/07366299.2021.1920674.
Bertelsen, Erin R., Antonio, Mark R., Jensen, Mark P., & Shafer, Jenifer C. Electrochemistry of PUREX: R is for reduction and ion transfer. United States. https://doi.org/10.1080/07366299.2021.1920674
Bertelsen, Erin R., Antonio, Mark R., Jensen, Mark P., and Shafer, Jenifer C. Fri .
"Electrochemistry of PUREX: R is for reduction and ion transfer". United States. https://doi.org/10.1080/07366299.2021.1920674. https://www.osti.gov/servlets/purl/1839948.
@article{osti_1839948,
title = {Electrochemistry of PUREX: R is for reduction and ion transfer},
author = {Bertelsen, Erin R. and Antonio, Mark R. and Jensen, Mark P. and Shafer, Jenifer C.},
abstractNote = {The PUREX (Plutonium, Uranium, Reduction, EXtraction) process is the foundation of all industrial activities that involve the recycling of plutonium and uranium from used nuclear fuel. With over 70 years of research, engineering, and operations, it can be argued that little opportunity is left for further discovery and new fundamental understandings regarding PUREX, in general, and tri-n-butyl phosphate (TBP), in particular. Through use of an advanced electroanalytical approach, molecular-level insights regarding the back-extraction of Pu(IV) by reductive separation is reported. Studies of model PUREX systems, with lanthanide ions extracted into 20 % TBP in n-dodecane, are used to demonstrate the approach. These studies reveal knowledge pertinent to mass transfer aspects of the biphasic reductive stripping reaction central to the separation of U and Pu in PUREX. Two lanthanide ions—Ce(IV) and Yb(III)—were extracted from their concentrated solutions in aqueous 3 M HNO3 to expressly provide electrically conducting third phases to facilitate electrochemical data acquisition. To simplify the diabolically-complicated reductive separation aspects of PUREX, the controlled polarization of electrode surfaces was used to reduce Ce(IV) and Yb(III) in place of chemical reductants. Electroanalyses of the biphasic systems with Ce(IV) and Yb(III) using three-phase electrode differential pulse voltammetry demonstrate the effects of mass transfer across water-oil interfaces on the electrode potentials for the reduction to Ce(III) and Yb(II). These reductions trigger nitrate transfer out of the oil phase for Ce and proton transfer into the organic phase for Yb. This is in correlation with the transfer of the charge-neutral ion pairs Ce·3NO3 and Yb·2NO3 out of the oil phases. Here, the differences in ion transfer steps reflect significant variations in the equilibrium speciation of multinuclear Ce(IV) and mononuclear Yb(III) solvates of TBP in the oil phases and the loading of the organic phase.},
doi = {10.1080/07366299.2021.1920674},
journal = {Solvent Extraction and Ion Exchange},
number = 1-2,
volume = 40,
place = {United States},
year = {Fri May 07 00:00:00 EDT 2021},
month = {Fri May 07 00:00:00 EDT 2021}
}
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