Grouped Actinide Extraction Process Research Articles

A comparison on the use of DEHBA or TBP as extracting agent for tetra- and hexavalent actinides in the CHALMEX Process

The Chalmers Grouped ActiNide EXtraction process is a solvent extraction process for the homogeneous recycling of spent nuclear fuel. The use of TBP for the extraction of tetra- and hexavalent actinides can be problematic for several reasons, including troublesome degradation products causing crud formation, decreased extraction yield and the possibility of explosive red oil reactions. Here, the substitution of TBP by a N,N-dialkyl monoamide, DEHBA, is investigated. The findings suggest that DEHBA can be a suitable extracting agent for use in the CHALMEX solvent, although identified drawbacks need to be further investigated.

The EURO-GANEX Process: Current Status of Flowsheet Development and Process Safety Studies

A new hydrometallurgical grouped actinide extraction process has been developed to separate the transuranic actinide ions from dissolved spent fuel solution (after an initial uranium extraction cycle). This “EURO-GANEX” process is aimed towards the homogeneous recycling of plutonium and minor actinides in a future closed fuel cycle. The separation process is based on the co-extraction of actinides and lanthanides from aqueous nitric acid into an organic phase followed by selective co-stripping of actinides. A suitable organic phase has been formulated and distribution ratios determined for lanthanides, actinides and some problematic fission products under extraction and stripping conditions. The process flowsheet has been proven on surrogate feed solutions as well as with spent fast reactor fuel; excellent recoveries of the actinides and good decontamination factors from the lanthanides and other fission products were obtained. A variation on the EURO-GANEX flowsheet (the “TRU-SANEX” process) has now been designed to produce separate Pu+Np and Am+Cm products for heterogeneous recycling. Progress on underpinning process chemistry and safety studies as well as flowsheet tests are summarized.

Development of the Chalmers Grouped Actinide Extraction Process

Abstract Several solvents for Grouped ActiNide EXtraction (GANEX) processes have been investigated at Chalmers University of Technology in recent years. Four different GANEX solvents; cyclo-GANEX (CyMe4- -BTBP, 30 vol.% tri-butyl phosphate (TBP) and cyclohexanone), DEHBA-GANEX (CyMe4-BTBP, 20 vol.% N,N-di-2(ethylhexyl) butyramide (DEHBA) and cyclohexanone), hexanol-GANEX (CyMe4-BTBP, 30 vol.% TBP and hexanol) and FS-13-GANEX (CyMe4-BTBP, 30 vol.% TBP and phenyl trifluoromethyl sulfone (FS-13)) have been studied and the results are discussed and compared in this work. The cyclohexanone based solvents show fast and high extraction of the actinides but a somewhat poor diluent stability in contact with the acidic aqueous phase. FS-13-GANEX display high separation factors between the actinides and lanthanides and a good radiolytic and hydrolytic stability. However, the distribution ratios of the actinides are lower, compared to the cyclohexanone based solvents. The hexanol-GANEX is a cheap solvent system using a rather stable diluent but the actinide extraction is, however, comparatively low.

Phenyl trifluoromethyl sulfone as diluent in a grouped actinide extraction process: extraction properties of the solvent components TBP and CyMe4-BTBP

The grouped actinide extraction (GANEX) process combines two extractants CyMe4-BTBP and TBP in a diluent, in this study phenyl trifluoromethyl sulfone (FS-13). The extraction of U-235, Np-239, Pu-238, Am-241, Cm-244 and Eu-152 has been investigated in four different systems. System 1: 70 %vol FS-13, 30 %vol TBP and 10 mM CyMe4-BTBP, system 2: 70 %vol FS-13 and 30 %vol TBP, system 3: 100 %vol FS-13 and 10 mM CyMe4-BTBP and system 4: pure FS-13. In all cases 4 M HNO3 was used as aqueous phase. In system 1 all actinides were extracted and separated from the lanthanides. In both system 2 and 3 mainly U and Pu were extracted. In system 4 none of the metals were extracted.

Single Centrifugal Contactor Test of a Proposed Group Actinide Extraction Process for Partitioning and Transmutation Purposes

In this work a solvent comprising of tri-butyl phosphate and bis-triazinyl, bi-pyridine in cyclohexanone has been used in a single centrifugal contactor test to evaluate its GANEX process potential. It was found that the density of the aqueous phase had to be increased to facilitate phase separation in the centrifuge. The kinetics of the system was also found to be relatively slow in the equipment of choice, especially regarding the stripping. However, it was still possible to recover more than 87% of all actinides in one extraction step with minor fission product contaminations using a flowrate of 30 mL/h.

Stability of phenyl trifluoromethyl sulfone as diluent in a grouped actinide extraction process

In this work, stability experiments have been performed on a phenyl trifluoromethyl sulfone based solvent containing 6,6′-bis(5,6-dialkyl-[1,2,4-]triazin-3-yl)-2,2′-bipyridine and tri-butyl phosphate. This solvent is intended to be used in a grouped actinide extraction process for partitioning and transmutation purposes. The distribution ratio for americium was determined to approximately 20 and for europium approximately 0.26 giving a separation factor of 77. The solvent maintain good distribution ratios and separation factors during both gamma irradiation of 6.6 kGy h−1 for up to 24 h and acid contact for up to 6 weeks at room temperature.

Hexanoic acid as an alternative diluent in a GANEX process: feasibility study

Used nuclear fuel is radiotoxic for mankind and its environment for a long time. However, if it can be transmuted, the radiotoxicity as well as its heat load are reduced. Before a transmutation the actinides within the used fuel need to be separated from the fission, corrosion and activation products. This separation can be achieved by using the liquid–liquid extraction technique. One extraction process that can be used for such a separation is the Group ActiNide EXtraction (GANEX) process. One GANEX process that can successfully accomplish the separation utilizes the diluent cyclohexanone in combination with the extractant tributylphosphate (TBP) (30 % vol) and a second extractant, CyMe4-BTBP (10 mM). However, there are some issues when using cyclohexanone as diluent. In this work an alternative diluent has therefore been tried in order to determine if it can replace cyclohexanone. The diluent used was hexanoic acid. In a system containing 10–12 mM CyMe4-BTBP and 30 % vol TBP in hexanoic acid with the aqueous phase 4 M HNO3, the distribution ratios for americium and curium are unfortunately low (D Am = 1.1 ± 0.27, D Cm = 1.6 ± 1.81). The concentration of CyMe4-BTBP ligand, the extractant of curium and americium, could unfortunately not be increased, because of limited solubility in hexanoic acid. The distribution ratios for fission, corrosion and activation products were low for most metals; however, cadmium, palladium and molybdenum all unfortunately have distributions ratios above 1. To conclude, low americium and curium extractions indicate that hexanoic acid is not a suitable diluent which could replace cyclohexanone in a GANEX process.

Technetium chemistry in a novel group actinide extraction process

A newly developed method for advanced reprocessing of used nuclear fuel is the Group ActiNide EXtraction (GANEX) process. It is a liquid-liquid extraction process that aims at extracting all the actinides as a group from dissolved used nuclear fuel. This extraction can either be performed after a removal of the bulk uranium or directly on the dissolution liquor. At Chalmers University of Technology in Sweden a solvent that utilizes tributyl-phosphate (TBP) and a molecule from the bis-triazine bipyridine (BTBP) class of ligands dissolved in cyclohexanone has been developed for the use in a GANEX process. Previously the system has not been tested with the presence of technetium that is one of the major fission products. Technetium is often considered a problem within reprocessing since it has a chemical behaviour that differs from most other elements in the spent fuel. Therefore, a special emphasis was put on the investigation of technetium in the selected GANEX system. It was shown that technetium is readily extracted by the GANEX solvent and that cyclohexanone is the main extractant when no other metals were present in the system. It was also found that the presence of uranium decreased the overall technetium extraction despite a slight co-extraction with TBP, while irradiation of the GANEX solvent to large doses ([>1 MGy) increased its technetium extraction capability. It was also discovered that an increased nitrate concentration in the aqueous phase and an addition of other fission products both inhibited the technetium extraction even though fission product loading most likely changed the extraction mechanism to co-extraction by BTBP.

Studies of a Solvent for GANEX Applications Containing CyMe4-BTBP and DEHBA in Cyclohexanone

Research focus within separation for transmutation in Europe today lies in the development of a solvent extraction separation process called GANEX (Group ActiNide EXtraction). In this type of process the actinides should be extracted as a group and separated from the lanthanides and the other fission and corrosion/activation products. One GANEX process has been developed combining the two extractants bis-triazine-bi-pyridine (BTBP) and tri-butyl phosphate (TBP) in cyclohexanone. In previous work the TBP has been successfully substituted with N,N-di-2-ethylhexyl-butyramide (DEHBA). In this paper, this exchange has been further studied investigating also fission product extraction as well as hydrolytic and radiolytic stability and acid extraction.

Plutonium Loading of Prospective Grouped Actinide Extraction (GANEX) Solvent Systems based on Diglycolamide Extractants

The Grouped Actinide Extraction (GANEX) process is being developed for actinide recycling within future nuclear fuel cycles. Interactions between potential solvents and macro-concentrations of plutonium are one of the most important issues in defining the GANEX process. Surprisingly, plutonium loading of diglycolamide (DGA) based solvents such as tetra-octyl DGA (TODGA) causes precipitation rather than a conventional third phase, in direct contrast to results with U(VI), Th(IV) or lanthanide ions. Various DGA based solvent systems have been screened for their plutonium loading capacity and 0.2 M TODGA with 0.5 M DMDOHEMA in a kerosene diluent is selected as the optimum solvent formulation of those tested. Plutonium can be relatively easily stripped from this solvent using aqueous acetohydroxamic acid but this is very acid dependent in the low acidity region.

A TBP/BTBP-based GANEX Separation Process—Part 2: Ageing, Hydrolytic, and Radiolytic Stability

The waste from nuclear power plants worldwide has to be isolated from man and his environment for about 100,000 years to equal the levels of natural uranium. If, however, the long-lived actinides could be separated from the spent fuel and transmuted, then the isolation time could be shortened to about 1,000 years. This does, however, require the selective separation of the actinides from the rest of the waste. Several processes exist for such a separation, of which one is the Group ActiNide Extraction (GANEX) process. A novel GANEX process has been developed at the Chalmers University of Technology utilizing the properties of already well known extractants by combining BTBP and TBP into one solvent. The stability provided by this GANEX solvent towards ageing, hydrolysis, and radiolysis has been investigated. The results show that the actinide distribution ratios are maintained after a long duration of contact with strong nitric acid. The solvent has also been found to be stable towards radiolysis up to 200 kGy in contact with 4 M nitric acid.