Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Xian, Liang; Tian, Guoxin; Beavers, Christine M.; Teat, Simon J.; Shuh, David K.

doi:10.1002/anie.201510712

Title: Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Abstract

Abstract Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt‐free complexing and reducing reagent, glutarimidedioxime (H ₂ A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1 m HNO ₃ with H ₂ A. The complexation‐reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu ^IV complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu ^IV , through the complexation‐reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.

Authors:

Xian, Liang ^[1]; Tian, Guoxin ^[2]; Beavers, Christine M. ^[3]; Teat, Simon J. ^[3]; Shuh, David K. ^[4]

Radiochemistry Department China Institute of Atomic Energy P. O. Box 275-26 Beijing 102413 China
Radiochemistry Department China Institute of Atomic Energy P. O. Box 275-26 Beijing 102413 China, Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Publication Date:: Fri Mar 11 00:00:00 EST 2016

Sponsoring Org.:: USDOE

OSTI Identifier:: 1401193

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition) Journal Volume: 55 Journal Issue: 15; Journal ID: ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Xian, Liang, Tian, Guoxin, Beavers, Christine M., Teat, Simon J., and Shuh, David K. Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing.  Germany: N. p., 2016. 
Web.  doi:10.1002/anie.201510712.

Copy to clipboard


                    Xian, Liang, Tian, Guoxin, Beavers, Christine M., Teat, Simon J., & Shuh, David K. Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing.  Germany.  https://doi.org/10.1002/anie.201510712

Copy to clipboard


                    Xian, Liang, Tian, Guoxin, Beavers, Christine M., Teat, Simon J., and Shuh, David K. Fri .  
"Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing".  Germany.  https://doi.org/10.1002/anie.201510712.

Copy to clipboard


                    
@article{osti_1401193,

  title        = {Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing},

  author       = {Xian, Liang and Tian, Guoxin and Beavers, Christine M. and Teat, Simon J. and Shuh, David K.},

  abstractNote = {Abstract Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt‐free complexing and reducing reagent, glutarimidedioxime (H 2 A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1  m HNO 3 with H 2 A. The complexation‐reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu IV complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu IV , through the complexation‐reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.},

  doi          = {10.1002/anie.201510712},

  journal      = {Angewandte Chemie (International Edition)},

  number       = 15,

  volume       = 55,

  place        = {Germany},

  year         = {Fri Mar 11 00:00:00 EST 2016},

  month        = {Fri Mar 11 00:00:00 EST 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Publisher's Version of Record
https://doi.org/10.1002/anie.201510712

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 15 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

The Reduction of Plutonium (IV) and Neptunium (VI) Ions by Ν,Ν-ethyl (hydroxyethyl) Hydroxylamine in Nitric Acid
journal, January 1999

Koltunov, V. S.; Taylor, R. J.; Baranov, S. M.
Radiochimica Acta, Vol. 86, Issue 3-4
DOI: 10.1524/ract.1999.86.34.115

Purification of uranium product from plutonium contamination using acetohydroxamic acid (AHA) based process
journal, June 2012

Sukumar, S.; Sharma, Pradeep Kumar; Govindan, P.
Journal of Radioanalytical and Nuclear Chemistry, Vol. 295, Issue 1
DOI: 10.1007/s10967-012-1855-2

An empirical correction for absorption anisotropy
journal, January 1995

Blessing, R. H.
Acta Crystallographica Section A Foundations of Crystallography, Vol. 51, Issue 1
DOI: 10.1107/S0108767394005726

Advances in Actinide and Technetium Kinetics for Applications in Process Flowsheet Modeling
journal, June 2001

Taylor, Robin J.; May, Iain
Separation Science and Technology, Vol. 36, Issue 5-6
DOI: 10.1081/SS-100103647

Kinetic and Solvent Extraction Studies of the Selective Reduction of Np(VI) by New Salt-Free Reducing Agents
journal, July 1998

Taylor, R. J.; May, I.; Koltunov, V. S.
ract, Vol. 81, Issue 3
DOI: 10.1524/ract.1998.81.3.149

A short history of SHELX
journal, December 2007

Sheldrick, George M.
Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
DOI: 10.1107/S0108767307043930

Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane
journal, March 2013

Prabhu, D. R.; Kumari, Neelam; Kanekar, A. S.
Journal of Radioanalytical and Nuclear Chemistry, Vol. 298, Issue 1
DOI: 10.1007/s10967-013-2456-4

Corrections to tabulated anomalous-scattering factors
journal, March 1990

Kissel, L.; Pratt, R. H.
Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 3
DOI: 10.1107/S0108767389010718

Kinetics and mechanism of Np and Pu reactions with organic derivatives of hydrazine
journal, December 1987

Koltunov, V. S.; Baranov, S. M.
Inorganica Chimica Acta, Vol. 140
DOI: 10.1016/S0020-1693(00)81042-7

Kinetics of reductive stripping of Pu(IV) in the tributylphosphate-kerosene/nitric acid-water system using dihydroxyurea
journal, April 2009

Yan, Taihong; Zuo, Chen; Zheng, Weifang
Journal of Radioanalytical and Nuclear Chemistry, Vol. 280, Issue 3
DOI: 10.1007/s10967-009-7482-x

Similar Records in DOE PAGES and OSTI.GOV collections:

Zurückgezogen: Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Journal Article Xian, Liang ; Tian, Guoxin ; Beavers, Christine M. ; ... - Angewandte Chemie

Abstract Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt‐free complexing and reducing reagent, glutarimidedioxime (H ₂ A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1 m HNO ₃ with H ₂ A. The complexation‐reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu ^IVmore »« less
https://doi.org/10.1002/ange.201510712
Chinese experience in the removal of actinides from highly active waste by trialkylphosphine-oxide extraction

Journal Article Zhu, Y ; Jiao, R - Nuclear Technology; (United States)

Mixed trialkylphosphine oxide (TRPO) (alkyl is C[sub 6]-C[sub 8]) was chosen as the extractant for the removal of uranium, neptunium, plutonium, and americium from highly active waste (HAW) in China. Composition and properties of the extractant and process chemistry are based on 30 vol% TRPO-kerosene as solvent. Hexa- and tetravalent actinides are highly extractable in 30 vol% TRPO extraction from acidic HAW, and trivalent americium (curium) can be extracted effectively from HAW with a nitric acid concentration of [approximately]1 mol/[ell]. Actinides extracted can be stripped successively by 5.5 mol/[ell] HNO[sub 3], 0.6 mol/[ell] H[sub 2]C[sub 2]O[sub 4], and 5% Na[submore »« less
CoDCon Project (Final Report)

Technical Report Lumetta, Gregg J. ; Allred, Jarrod R. ; Asmussen, Susan E. ; ...

The co-decontamination (CoDCon) project was established in FY 2016 with the objectives of (a) evaluating the uncertainty in the uranium (U)/plutonium (Pu) ratio in a mixed U/Pu product from a tributyl phosphate (TBP)–based solvent extraction flowsheet, and (b) developing and demonstrating on-line optical spectroscopy for real-time monitoring of key components (e.g., Pu, U, and HNO₃ concentrations) in the process solutions. We were interested in assessing the accuracy and precision to which a specific uranium-to-plutonium (U/Pu) ratio can be achieved, which for the purposes of this project was set at a U/Pu mass ratio of 7/3. The uncertainty associated with achievingmore »« less
https://doi.org/10.2172/1845703

Full Text Available
Overview of reductants utilized in nuclear fuel reprocessing/recycling

Conference Paviet-Hartmann, Patricia ; Riddle, Catherine ; Campbell, Keri ; ...

Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but itmore »« less
Full Text Available
Electrochemistry of PUREX: R is for reduction and ion transfer

Journal Article Bertelsen, Erin R. ; Antonio, Mark R. ; Jensen, Mark P. ; ... - Solvent Extraction and Ion Exchange

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 themore »« less
https://doi.org/10.1080/07366299.2021.1920674

Full Text Available

Similar Records

Title: Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Abstract

Citation Formats

The Reduction of Plutonium (IV) and Neptunium (VI) Ions by Ν,Ν-ethyl (hydroxyethyl) Hydroxylamine in Nitric Acid journal, January 1999

Purification of uranium product from plutonium contamination using acetohydroxamic acid (AHA) based process journal, June 2012

An empirical correction for absorption anisotropy journal, January 1995

Advances in Actinide and Technetium Kinetics for Applications in Process Flowsheet Modeling journal, June 2001

Kinetic and Solvent Extraction Studies of the Selective Reduction of Np(VI) by New Salt-Free Reducing Agents journal, July 1998

A short history of SHELX journal, December 2007

Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane journal, March 2013

Corrections to tabulated anomalous-scattering factors journal, March 1990

Kinetics and mechanism of Np and Pu reactions with organic derivatives of hydrazine journal, December 1987

Kinetics of reductive stripping of Pu(IV) in the tributylphosphate-kerosene/nitric acid-water system using dihydroxyurea journal, April 2009

The Reduction of Plutonium (IV) and Neptunium (VI) Ions by Ν,Ν-ethyl (hydroxyethyl) Hydroxylamine in Nitric Acid
journal, January 1999

Purification of uranium product from plutonium contamination using acetohydroxamic acid (AHA) based process
journal, June 2012

An empirical correction for absorption anisotropy
journal, January 1995

Advances in Actinide and Technetium Kinetics for Applications in Process Flowsheet Modeling
journal, June 2001

Kinetic and Solvent Extraction Studies of the Selective Reduction of Np(VI) by New Salt-Free Reducing Agents
journal, July 1998

A short history of SHELX
journal, December 2007

Biphasic kinetic investigations on the evaluation of non-salt forming reductants for Pu(IV) stripping from tributyl phosphate and N,N-dihexyl octanamide solutions in n-dodecane
journal, March 2013

Corrections to tabulated anomalous-scattering factors
journal, March 1990

Kinetics and mechanism of Np and Pu reactions with organic derivatives of hydrazine
journal, December 1987

Kinetics of reductive stripping of Pu(IV) in the tributylphosphate-kerosene/nitric acid-water system using dihydroxyurea
journal, April 2009