Gamma Radiolysis. Tributyl Phosphate and Its Diluent Systems

Burger, L.L.; McClanahan, E.D.

doi:10.1021/ie50578a025

Cited by 40 publications

(22 citation statements)

References 1 publication

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“…[67] Many early studies of the radiation chemistry of TBP involved irradiation of the neat compound. [82,86,88] However, it was quickly realized that diluents and aqueous phases altered radiolysis product yields. [81,88] Unfortunately, few studies have been done under conditions that allow direct comparison.…”

Section: Degradation Mechanismmentioning

confidence: 99%

“…[82,86,88] However, it was quickly realized that diluents and aqueous phases altered radiolysis product yields. [81,88] Unfortunately, few studies have been done under conditions that allow direct comparison. During solvent extraction, TBP is irradiated as a complex with water, acid, and/or metals, and these complexes react at different rates with the produced radiolytic reactive species, altering competition kinetics and thus product yields.…”

Section: Degradation Mechanismmentioning

confidence: 99%

See 1 more Smart Citation

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

Mincher

Modolo

Mezyk

2009

Solvent Extraction and Ion Exchange

191

100

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Section: Degradation Mechanismmentioning

confidence: 99%

Section: Degradation Mechanismmentioning

confidence: 99%

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

Mincher

Modolo

Mezyk

2009

Solvent Extraction and Ion Exchange

191

100

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“…Therefore, the uranyl complex and NaDBP concentrations should not exceed O.01 M and O.02 M, respectively, in the Na2C03 solution, which requires a carbonate scrub volume of 2500 liters/MTHM. Third, the concentration of Na2MBP is approximately one-third that of NaDBP, assuming no losses of H 2 MBP during HN0 3 scrubbing (17). In addition to the above constituents, the Na2C03 scrub waste will also contain a certain amount of NaHC03 and NaN03 from the neutralization of HNO3 present in the TBP.…”

Section: Resultsmentioning

confidence: 99%

The Extraction of DBP and MBP from Actinides: Application to the Recovery of Actinides from TBP-Sodium Carbonate Scrub Solution

Horwitz

Mason

Bloomquist

et al. 1980

ACS Symposium Series

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Significantamounts of actinides are present in nuclear wastes other than high-level liquid waste produced in spent nuclear fuel reprocessing(1). One such waste stream is produced by scrubbing the radiolytic and hydrolytic degradation products from extractant solutions with Na 2 CO 3 . Actinide concentrations in the range of 0.5 to 5 Kg of actinides may be present in the Na 2 CO 3 scrub solutions used to "clean-up" TBP-nDD solutions from the reprocessing of one metric ton of spent nuclear fuel (1,2). In addition, Na 2 CO 3 scrub waste will be generated in the clean-up of the dihexyl-N,N-diethyl carbamoylmethylene phosphonate (DHDECMP) extractant which is to be used to extract all of the actinides from high-level liquid waste (HLLW) in the proposed waste treatment facility described by Tedder, Finney, and Blomeke(3). Na 2 CO 3 scrub solutions from TBP-nDD consist essentially of a NaHCO 3 -NaNO 3 solution containing varying amounts of the sodium salts of dibutylphosphoric and monobutyl phosphoric acids (HDBP and H 2 MBP, respectively) and carbonato-and hydroxo-complexes of the tetra-and hexavalent actinides and zirconium. The actual quantities of DBP, MBP, and actinides depend on the extent of hydrolysis and radiolysis. Analogous waste from DHDECMP-DIPB processing would be similar in composition but would contain mono-and diacidic salts of phosphonic acids and degradation products of DHDECMP (4).The efficient removal of actinides from the Na2CU3 scrub waste solution presents several problems.Acidification of the carbonate solution with excess HNO3 followed by extraction with TBP (or, preferably, DHDECMP) (3) results in the rapid build-up of acidic degradation products (HDBP and H2MBP in the case of TBP) which prevent efficient back extraction.In addition, acidification of Na2C03 scrub waste results in the precipitation of actinide-DBP and -MBP complexes which are difficult to dissolve 1 Work performed under the auspices of the Office of Basic Energy Sciences and the Office of Nuclear Waste Management of the U.S.

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“…For example, Kulikov et al [24] and Nowak et al [25] have reported an increase in the yield of HDBP in the presence of uranium. However, Williams and Wilkinson [15], Becker et al [20] and Burger and McClanahan [37] held the view of a protective effect of uranium on the 30 % TBP/CCl 4 system against radiolysis. Unfortunately, our present experimental results only indicate that there is a competitive relationship between UO 2 2?…”

Section: Plutonium Retention Testmentioning

confidence: 99%

Studies on Pu238 induced alpha radiolysis of the solvent TBP

Gao

Zheng

Cao

et al. 2014

J Radioanal Nucl Chem

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Radiolysis and degradation of a 30 % volume mixture of TBP in n-dodecane has been studied by means of alpha radiation from Pu 238 . Radiolysis effects are quantitatively estimated by the percent of Pu 238 retained in the irradiated organic phase after the washing procedure. The effects of radiation dose, nitric acid concentration, and the presence of UO 2 2? and Zr 4? , have been investigated. The results indicate that Zr 4? accelerates the alpha-particle degradation of the organic phase, and that both UO 2 2? and Pu 4? complex with the degradation products formed by the absorbed radiation.

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Gamma Radiolysis. Tributyl Phosphate and Its Diluent Systems

Cited by 40 publications

References 1 publication

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

The Extraction of DBP and MBP from Actinides: Application to the Recovery of Actinides from TBP-Sodium Carbonate Scrub Solution

Studies on Pu238 induced alpha radiolysis of the solvent TBP

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