Jack D. Law

THE UNIVERSAL SOLVENT EXTRACTION (UNEX) PROCESS. I. DEVELOPMENT OF THE UNEX PROCESS SOLVENT FOR THE SEPARATION OF CESIUM, STRONTIUM, AND THE ACTINIDES FROM ACIDIC RADIOACTIVE WASTE

A synergistic extraction mixture containing chlorinated cobalt dicarbollide (CCD), carbamoylmethyl phosphine oxide (CMPO), and polyethylene glycol (PEG) has been investigated for the simultaneous recovery of cesium, strontium, lanthanides, and actinides from highly acidic media. The extraction properties of this mixture depend on the concentration ratio of the components. For recovery of all major radionuclides, the optimal ratio of [CCD]:[PEG]: [CMPO] = 5:1:1 should be used. The use of diphenyl-N,N-dibutylcarbamoylmethyl phosphine oxide and PEG-400 provides the most efficient recovery of cesium, strontium, lanthanides, and actinides. The possibility of using polyfluorinated ethers, esters, ketones, and sulfones as diluents was examined. Phenyltrifluoromethyl sulfone was the most suitable diluent tested. The use of this diluent allows good extraction properties, chemical and radiation stability, excellent explosion/fire-safety properties, and favorable hydrodynamic characteristics. The extraction of radionuclides from HNO3 media by mixtures of CCD:PEG:CMPO in phenyltrifluoromethyl sulfone and the subsequent stripping behavior were evaluated.

THE UNIVERSAL SOLVENT EXTRACTION (UNEX) PROCESS. II. FLOWSHEET DEVELOPMENT AND DEMONSTRATION OF THE UNEX PROCESS FOR THE SEPARATION OF CESIUM, STRONTIUM, AND ACTINIDES FROM ACTUAL ACIDIC RADIOACTIVE WASTE

A novel solvent extraction process, the Universal Extraction (UNEX) process, has been developed for the simultaneous separation of cesium, strontium, and the actinides from acidic waste solutions. The UNEX process solvent consists of chlorinated cobalt dicarbollide for the extraction of 137Cs, polyethylene glycol for the extraction of 90Sr, and diphenyl-N,N-dibutylcarbamoyl phosphine oxide for the extraction of the actinides and lanthanides. A nonnitroaromatic polar diluent consisting of phenyltrifluoromethyl sulfone has been developed for this process. A UNEX flowsheet consisting of a single solvent extraction cycle has been developed as a part of a collaborative effort between the Khlopin Radium Institute (KRI) and the Idaho National Engineering and Environmental Laboratory (INEEL). This flowsheet has been demonstrated with actual acidic radioactive tank waste at the INEEL using 24 stages of 2-cm diameter centrifugal contactors installed in a shielded cell facility. The activities of 137Cs, 90Sr, and the actinides were reduced to levels at which a grout waste form would meet NRC Class A LLW requirements. The extraction of 99Tc and several nonradioactive metals by the UNEX solvent has also been evaluated.

Fission Product Extraction (FPEX): Development of a Novel Solvent for the Simultaneous Separation of Strontium and Cesium from Acidic Solutions

Abstract A synergistic extraction solvent for the simultaneous removal of cesium and strontium from acidic solutions has been investigated. The extraction solvent consists of, 4,4′,(5′)‐di‐(t‐butyldicyclo‐hexano)‐18‐crown‐6 (DtBuCH18C6), calix[4]arene‐bis‐(tert‐octylbenzo‐crown‐6) (BOBCalixC6), and 1‐(2,2,3,3‐tetrafluoropropoxy)‐3‐(4‐sec‐butylphenoxy)‐2‐propanol (Cs‐7SB modifier) in a branched aliphatic kerosene (Isopar® L). Extraction synergy for strontium was observed when DtBuCH18C6 was combined with the BOBCalixC6 cesium extractant solvent and Cs‐7SB modifier or if the Cs‐7SB modifier was substituted into the SREX (Strontium Extraction) solvent in place of TBP. The novel process extracted both cesium and strontium simultaneously from 1 M nitric acid solutions with distribution ratios of 8.8 and 7.7 for strontium and cesium, respectively, at ambient temperature. Distribution coefficients for cesium and strontium as a function of nitric acid concentration and temperature were also obtained with 0.5 M<[HNO3]<2.5 M giving favorable distribution ratios. This new process utilizing the combined solvent has been named the Fission Product Extraction Process (FPEX).

UNIVERSAL SOLVENT EXTRACTION (UNEX) FLOWSHEET TESTING FOR THE REMOVAL OF CESIUM, STRONTIUM, AND ACTINIDE ELEMENTS FROM RADIOACTIVE, ACIDIC DISSOLVED CALCINE WASTE

ABSTRACT The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the radioactive waste by minimizing waste volumes. Typically, several separate processes are required for the separation of cesium, strontium, and actinides from radioactive wastes. A novel solvent extraction process, the Universal Extraction (UNEX) process, has been developed for the simultaneous separation of cesium, strontium, and the actinides from radioactive acidic waste solutions. The UNEX process solvent consists of chlorinated cobalt dicarbollide for the extraction of 137Cs, polyethylene glycol for the extraction of 90Sr, and diphenyl-N,N-di-n-butylcarbamoylmethyl phosphine oxide for the extraction of the actinides and lanthanides. A non-nitroaromatic polar diluent, phenyltrifluoromethyl sulfone, is used for this process. A UNEX flowsheet consisting of a single solvent extraction cycle has been developed as a part of a collaborative effort between the Khlopin Radium Institute (KRI) and the Idaho National Engineering and Environmental Laboratory (INEEL). This flowsheet has been demonstrated with actual dissolved radioactive calcine waste at the INEEL using 24 stages of 2-cm diameter centrifugal contactors installed in a shielded hot cell facility. For the major radionuclides, 99.99% of the 137Cs, 99.73% of the 90Sr, and >99.9% of the actinides in the initial dissolved calcine feed were extracted and recovered in the high activity fraction. For the stable matrix elements, 12% of the Mo, 0.7% of the Zr, and 2% of the Fe were extracted and recovered in the strip product. The minor components Ba and Pb were quantitatively extracted and recovered in the strip product; 23% of the Mn was also present in this fraction. Very little Al, Ca, Cr, Na, and Ni were extracted into the UNEX solvent.

Development and demonstration of solvent extraction processes for the separation of radionuclides from acidic radioactive waste

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Immobilization of these radionuclides must be accomplished prior to long-term, permanent disposal. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the radioactive waste by minimizing waste volumes. Several solvent extraction processes have been developed and demonstrated at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90Sr, and/or 137Cs from acidic radioactive waste solutions. The Transuranic Extraction (TRUEX) and phosphine oxide (POR) processes for the separation of TRUs, the Strontium Extraction (SREX) process for the separation of 90Sr, the chlorinated cobalt dicarbollide (ChCoDiC) process for the separation of 137Cs and 90Sr, and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been demonstrated in centrifugal contactors using actual radioactive waste solutions. This article summarizes the most recent results of each of the flowsheet demonstrations and allows for comparison of the technologies. The successful demonstration of these solvent extraction processes indicates that they are all viable for the treatment of acidic radioactive waste solutions.

Extraction of uranium(VI) with diamides of dipicolinic acid from nitric acid solutions

Abstract Three structural isomers of diamides of dipicolinic acid (N,N′-diethyl-N,N′-ditolyl-dipicolinamide, EtTDPA) with varying position of the methyl group on the tolyl ring have been synthesized and investigated on extractability toward U(VI). The polar diluent FS-13 was used, and distribution ratios of U(VI) were studied as a function of nitric acid, ligand, and lithium nitrate concentrations. Extractability of uranium was shown to increase with increased concentration of nitrate and ligands. Infrared spectra of organic extraction phases indicate that nitric acid is coextracted as part of the neutral metal-ligand complex with U(VI) and EtTDPA through hydrogen bonding with the carbonyl group in the amide moiety.

Radioactive Iodine and Krypton Control for Nuclear Fuel Reprocessing Facilities

The removal of volatile radionuclides generated during used nuclear fuel reprocessing in the US is almost certain to be necessary for the licensing of a reprocessing facility in the US. Various control technologies have been developed, tested, or used over the past 50 years for control of volatile radionuclide emissions from used fuel reprocessing plants. The US DOE has sponsored, since 2009, an Off-gas Sigma Team to perform research and development focused on the most pressing volatile radionuclide control and immobilization problems. In this paper, we focus on the control requirements and methodologies for 85Kr and 129I. Numerous candidate technologies have been studied and developed at laboratory and pilot-plant scales in an effort to meet the need for high iodine control efficiency and to advance alternatives to cryogenic separations for krypton control. Several of these show promising results. Iodine decontamination factors as high as 105, iodine loading capacities, and other adsorption parameters including adsorption rates have been demonstrated under some conditions for both silver zeolite (AgZ) and Ag-functionalized aerogel. Sorbents, including an engineered form of AgZ and selected metal organic framework materials (MOFs), have been successfully demonstrated to capture Kr and Xe without the need for separations at cryogenic temperatures.

Evaluation of the SREX solvent extraction process for the removal of 90Sr and hazardous metals from acidic nuclear waste solutions containing high concentrations of interfering alkali metal ions

Abstract The SREX process, which was developed at Argonne National Laboratories, has been evaluated for its effectiveness for the decontamination of radioactive liquid waste at the Idaho Chemical Processing Plant located at the Idaho National Engineering Laboratory. The extraction solvent consists of 0.15 M 4′,4′,(5′)-di-(t-butyl-dicyclohexo)-18-crown-6 in either 1.2 M TBP/Isopar L®. Suppressed extraction due to matrix interferences limits DSr values to the range of 3-4 in batch extraction experiments. The SREX solvent has been shown to be effective in the removal of non-radioactive Pb from liquid wastes, in addition to the extraction of 90Sr. The information from this study has been used to develop a proposed flowsheet for the treatment of liquid waste in centrifugal contactors.

Radionuclide Extraction by 2,6‐Pyridinedicarboxylamide Derivatives and Chlorinated Cobalt Dicarbollide

Abstract The extraction properties of diamide derivatives of dipicolinamide (2,6‐pyridinedicarboxylamide or DPA, (R′R″NCO)2C5NH3) in mixtures containing chlorinated cobalt dicarbollide in the acid form (HCCD), with and without a substituted polyethylene glycol (PEG), have been investigated. Distribution ratios of Cs, Sr, U, Eu and Am have been measured for various concentrations of diamide, PEG, aqueous phase nitric acid, with various HCCD:diamide ratios, and using different organic diluents. In the absence of HCCD, the diamides show little affinity for the extraction of Am or Eu from nitric acid solutions (distributions typically <1). Addition of HCCD with the diamide extractants indicates a pronounced synergistic effect with regard to actinide and lanthanide extraction; the observed Am and Eu distribution ratios typically increase by several orders of magnitude. Cesium is also appreciably extracted by the HCCD in the presence of the various diamides. Addition of PEG (to simultaneously extract Sr) with HCCD and diamide has minimal impacts on the Eu and Am distribution ratios. The initial data indicate that alkyl substituted DPA derivatives weakly affect the extraction properties with regard to actinides and lanthanides, while aryl substituents decrease extraction ability of the mixture. The results of this preliminary work indicate that numerous HCCD‐PEG‐DPA systems are promising and effective for the simultaneous extraction Cs, Sr, Am, and Eu from acidic solutions.

Extraction of Lanthanides with Diamides of Dipicolinic Acid from Nitric Acid Solutions. I

Abstract Three ortho-, meta-, and para-derivates of ethyl(tolyl)diamides of dipicolinic acid were synthesized and tested on their extraction performance from nitric acids solutions. Extraction of americium and lanthanides (Ln) by these compounds as a function of nitric acid concentration was studied. Distribution ratios of studied metals were determined using ICP-OES method and radiotracer 241Am. Am/Ln separation differs among studied diamides, and the best separation was found for N,N′-diethyl-N,N′-di(ortho)tolyl-diamide.