DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions

doi:10.1016/j.radphyschem.2019.108608

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Title: DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions

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Abstract

Di-2-ethylhexylbutyramide (DEHBA) has been presented as part of a hydro-reprocessing solvent extraction system for the co-extraction of uranium and plutonium from spent nuclear fuel. Yet, there remains a lack of quantitative understanding of the impact of chemical environment on the radiation chemistry of DEHBA, especially under conditions expected in real-world solvent extraction processes. Therefore, we have undertaken a systematic investigation into the radiolytic degradation of DEHBA in n-dodecane under fully aerated and biphasic conditions. DEHBA integrity and degradation product formation were measured for both extraction (in contact with 4.0 M HNO _3(aq)) and stripping (in contact with 0.1 M HNO _3(aq)) formulations. At the lower acidity the rate of DEHBA/n-dodecane degradation was slow (G = -0.26 ± 0.02 µM J ^-1) whereas at the higher acidity this degradation was about 35% faster (G = -0.35 ± 0.02 µM J-1). Both values were much less than analogous measurements under deaerated conditions. Under continuously aerated conditions, FTIR and ESI-MS measurements identified the two major degradation products, bis-2-ethylhexylamine (b2EHA) and N-(2-ethylhexyl)butyramide (MEHBA), as well as the presence of additional oxidized product species. Solvent system performance was also investigated using uranium extraction and strip distribution ratio measurements. These reports showed that there was onlymore »« less

Authors:

^[1];

^[2];

^[1];

^[1]; Tillotson, Richard D. ^[1];

^[1];

^[3];

^[4];

^[4]; Saint-Louis, George ^[4];

^[4]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
California State Univ. (CalState), Long Beach, CA (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States); KTH Royal Inst. of Technology, Stockholm (Sweden)
Montpellier Univ., Marcoule (France)

Publication Date:: 2019-11-22

Research Org.:: Idaho National Lab. (INL), Idaho Falls, ID (United States)

Sponsoring Org.:: USDOE Office of Nuclear Energy (NE)

OSTI Identifier:: 1593903

Alternate Identifier(s):: OSTI ID: 1593181

Report Number(s):: INL/JOU-19-55911-Rev000
Journal ID: ISSN 0969-806X

Grant/Contract Number:: AC07-05ID14517; NE0008406

Resource Type:: Accepted Manuscript

Journal Name:: Radiation Physics and Chemistry (1993)

Additional Journal Information:: Journal Name: Radiation Physics and Chemistry (1993); Journal Volume: 170; Journal Issue: C; Journal ID: ISSN 0969-806X

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Di-2-ethylhexylbutyramide; Gamma Radiolysis; Air-Sparged; Uranium

Citation Formats


                    Horne, Gregory P., Mezyk, Stephen P., Mincher, Bruce J., Zarzana, Christopher A., Rae, Cathy, Tillotson, Richard D., Schmitt, Nicholas C., Ball, Richard D., Ceder, Joakim, Charbonnel, Marie-Christine, Guilbaud, Philippe, Saint-Louis, George, and Berthon, Laurence. DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions.  United States: N. p., 2019. 
        Web.  doi:10.1016/j.radphyschem.2019.108608.

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                    Horne, Gregory P., Mezyk, Stephen P., Mincher, Bruce J., Zarzana, Christopher A., Rae, Cathy, Tillotson, Richard D., Schmitt, Nicholas C., Ball, Richard D., Ceder, Joakim, Charbonnel, Marie-Christine, Guilbaud, Philippe, Saint-Louis, George, & Berthon, Laurence. DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions.  United States.  doi:10.1016/j.radphyschem.2019.108608.

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                    Horne, Gregory P., Mezyk, Stephen P., Mincher, Bruce J., Zarzana, Christopher A., Rae, Cathy, Tillotson, Richard D., Schmitt, Nicholas C., Ball, Richard D., Ceder, Joakim, Charbonnel, Marie-Christine, Guilbaud, Philippe, Saint-Louis, George, and Berthon, Laurence. Fri .  
        "DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions".  United States.  doi:10.1016/j.radphyschem.2019.108608.

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@article{osti_1593903,

  title        = {DEHBA (di-2-ethylhexylbutyramide) gamma radiolysis under spent nuclear fuel solvent extraction process conditions},

  author       = {Horne, Gregory P. and Mezyk, Stephen P. and Mincher, Bruce J. and Zarzana, Christopher A. and Rae, Cathy and Tillotson, Richard D. and Schmitt, Nicholas C. and Ball, Richard D. and Ceder, Joakim and Charbonnel, Marie-Christine and Guilbaud, Philippe and Saint-Louis, George and Berthon, Laurence},

  abstractNote = {Di-2-ethylhexylbutyramide (DEHBA) has been presented as part of a hydro-reprocessing solvent extraction system for the co-extraction of uranium and plutonium from spent nuclear fuel. Yet, there remains a lack of quantitative understanding of the impact of chemical environment on the radiation chemistry of DEHBA, especially under conditions expected in real-world solvent extraction processes. Therefore, we have undertaken a systematic investigation into the radiolytic degradation of DEHBA in n-dodecane under fully aerated and biphasic conditions. DEHBA integrity and degradation product formation were measured for both extraction (in contact with 4.0 M HNO3(aq)) and stripping (in contact with 0.1 M HNO3(aq)) formulations. At the lower acidity the rate of DEHBA/n-dodecane degradation was slow (G = -0.26 ± 0.02 µM J-1) whereas at the higher acidity this degradation was about 35% faster (G = -0.35 ± 0.02 µM J-1). Both values were much less than analogous measurements under deaerated conditions. Under continuously aerated conditions, FTIR and ESI-MS measurements identified the two major degradation products, bis-2-ethylhexylamine (b2EHA) and N-(2-ethylhexyl)butyramide (MEHBA), as well as the presence of additional oxidized product species. Solvent system performance was also investigated using uranium extraction and strip distribution ratio measurements. These reports showed that there was only minimal change in uranium extraction and stripping performance with absorbed gamma dose.},

  doi          = {10.1016/j.radphyschem.2019.108608},

  journal      = {Radiation Physics and Chemistry (1993)},

  number       = C,

  volume       = 170,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

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