Rikard Malmbeck

Demonstration of a TODGA based Extraction Process for the Partitioning of Minor Actinides from a PUREX Raffinate

Abstract: Efficient recovery of minor actinides (MA) from genuine PUREX raffinate has been successfully demonstrated by the TODGA + TBP extractant mixture dissolved in an industrial aliphatic solvent TPH. The process was carried out in centrifugal contactors using an optimized flow‐sheet involving a total of 32 stages, divided into 4 stages for extraction, 12 stages for scrubbing and 16 stages for back‐extraction. Very high feed decontamination factors were obtained (Am, Cm ∼ 40 000) and the recovery of these elements was higher than 99.99%. Of the non‐lanthanide fission products only Y and a small part of Ru were co‐separated into the product fraction together with the lanthanides and the MA.

Demonstration of a SANEX Process in Centrifugal Contactors using the CyMe4‐BTBP Molecule on a Genuine Fuel Solution

Efficient recovery of minor actinides from a genuine spent fuel solution has been successfully demonstrated by the CyMe4‐BTBP/DMDOHEMA extractant mixture dissolved in octanol. The continuous countercurrent process, in which actinides(III) were separated from lanthanides(III), was carried out in laboratory centrifugal contactors using an optimized flow‐sheet involving a total of 16 stages. The process was divided into 9 stages for extraction from a 2 M nitric acid feed solution, 3 stages for lanthanide scrubbing, and 4 stages for actinide back‐extraction. Excellent feed decontamination factors for Am (7000) and Cm (1000) were obtained and the recoveries of these elements were higher than 99.9%. More than 99.9% of the lanthanides were directed to the raffinate except Gd for which 0.32% was recovered in the product.

Electrochemistry of Uranium in Molten LiCl-KCl Eutectic

The Institute for Transuranium Elements ~ITU! is building up an accurate database of actinide behavior in chloride melts in support of its nuclear fuel reprocessing development program. The electrochemical properties of uranium, dissolved in LiCl-KCl eutectic melt, were investigated by transient electrochemical techniques, such as cyclic voltammetry ~CV! and chronopotentiometry on an inert tungsten electrode. It was shown that U4+ is reduced to U0 by a two-step mechanism corresponding to U4+/U3+ and U3+/U0 transitions. In the 400-550°C s673-823 Kd range, the diffusion coefficients of U3+ and U4+ were similar and equal to: DsU3+d = 13.7 3 10−4 exph−24.2 3 103/RTsKdj and DsU4+d = 5.25 3 10−4 exph−19.8 3 103/RTsKdj cm2 s−1. The apparent standard potentials of U4+/U3+ and U3+/U0 redox systems were Eo*sU4+/U3+dsVd = −1.902 + 0.0006104T sKd vs. Cl2/Cl and Eo*sU3+/U0dsVd = −3.099 + 0.0007689T sKd vs. Cl2/Cl, respectively. Some thermochemical properties sDG*,gd of uranium solutions were also derived from the electrochemical measurements. The Gibbs free energies of dilute solution of UCl3 and UCl4 in the LiCl-KCl were determined to be: DG* = −897.09 + 0.226T sKd and −183.53 + 0.0589T sKd in kJ mol−1, respectively. In the 400-550°C s673-823 Kd range, the activity coefficients g of UCl3 and UCl4 range between 0.3 − 4.5 3 10−3 and 17.1 − 12.7 3 10−3, respectively.

Demonstration of a TODGA‐Based Continuous Counter‐Current Extraction Process for the Partitioning of Actinides from a Simulated PUREX Raffinate, Part II: Centrifugal Contactor Runs

Abstract The efficiency of the partitioning of trivalent actinides from a PUREX raffinate is demonstrated with a TODGA+TBP extractant mixture dissolved in an industrial aliphatic solvent TPH. Based on the results of cold and hot batch extraction studies and with the aid of computer code calculations, a continuous counter‐current process is developed and two flowsheets are tested using miniature centrifugal contactors. The feed solution used is a synthetic PUREX raffinate, spiked with 241Am, 244Cm, 252Cf, 152Eu, and 134Cs. More than 99.9% of the trivalent actinides and lanthanides are extracted and back‐extracted and very high decontamination factors are obtained for most fission products. The co‐extraction of zirconium, molybdenum, and palladium is prevented using oxalic acid and HEDTA. However, 10% of ruthenium is extracted and only 3% is back‐extracted using diluted nitric acid. The experimental steady‐state concentration profiles of important solutes are determined and compared with model calculations and good agreement is generally obtained.

Electroseparation of Actinides from Lanthanides on Solid Aluminum Electrode in LiCl-KCl Eutectic Melts

University of Grenoble, ENSEEG, 38402 Saint Martin d’He`res, FranceThis work presents a study on the electrochemical behavior of actinides (An 5 Am and Pu! and lanthanides (Ln 5 La and Nd!onto solid aluminum cathodes in a molten LiCl-KCl eutectic at 733 K. Cyclic voltammetry of these elements onto Al workingelectrode is carried out to estimate the reduction potentials of An and Ln and to predict the efficiency of an An/Ln separation byelectrolysis. Results show that the reduction of Am

Recovery of Minor Actinides from HLLW Using the DIAMEX Process.

Summary In this work a hot demonstration of the DIAMEX process using the new reference molecule DMDOHEMA (N,N′-DiMethyl-N,N′-DiOctylHexylEthoxyMalonAmide) and genuine high-level PUREX raffinate as feed is reported. The continuous counter-current experiment was carried out in a 16-stage centrifugal extractor battery, installed in a hot cell. In order to produce a representative High Level Liquid Waste (HLLW) a PUREX process was applied on dissolved fuel using the same equipment. It was demonstrated that 5 extraction stages were sufficient to achieve feed decontamination factors above 2200 and 320 for Am and Cm, respectively. Co-extraction of molybdenum and zirconium, as well as of palladium, were efficiently prevented using oxalic acid and HEDTA scrubbing, respectively. However, technetium, yttrium, and to some extent ruthenium, were co-extracted. The back-extraction proved to be very efficient, yielding in 4 stages more than 99.9% recovery of Am and Cm. The extraction profiles were modeled with computer code simulations and the results compared with data obtained from an experiment using the former reference molecule DMDBTDMA (DiMethylDiButylTetraDecylMalonAmide).

DIAMEX Counter‐Current Extraction Process for Recovery of Trivalent Actinides from Simulated High Active Concentrate

Abstract The partitioning of trivalent actinides was demonstrated with a new version of the French DIAMEX (DIAMide EXtraction) process. A continuous counter‐current experiment using a 16‐stage centrifugal extractor battery was tested using 1 mol/L N,N′-dimethyl‐N,N′-dioctyl‐hexylethoxy‐malonamide (DMDOHEMA) in TPH as the extractant. A high active concentrate (HAC), obtained after concentration and denitration of a high active raffinate (HAR) with a concentration factor of 10, was used as a feed. Based on results from cold and hot batch extraction experiments and computer code calculations, a flowsheet was developed and a full test was carried out using a simulated HAC solution spiked with radionuclides (241Am, 244Cm, 152Eu, and 134Cs). In the DIAMEX process, five extraction stages were sufficient to obtain Am and Cm (feed/raffinate) greater than 5000 and for the coextracted lanthanides decontamination factors between 1100 and 4500. Co‐extraction of zirconium, molybdenum, and palladium was prevented by using oxalic acid and HEDTA. The back extraction comprising 4 stages was also efficient and the recoveries of actinides were greater than 99.8%, which can be further improved by a minor process flowsheet optimisation. The experimental steady‐state concentration profiles of important solutes were determined and compared with model calculations and good agreement was generally obtained.

Partitioning of Minor Actinides from HLLW Using the DIAMEX Process. Part 1. Demonstration of Extraction Performances and Hydraulic Behaviour of the Solvent in a Continuous Process.

The French DIAMEX process shows very promising capabilities in separating minor actinides from HLLW. A counter-current centrifugal extractor experiment has been conducted to investigate the capabilities and possibilities of the DIAMEX process (hydraulic and extraction behaviour), for the separation of lanthanides from a simulated High Level Liquid Waste (HLLW), corresponding in concentration to a raffinate from the PUREX process. A ´´hot´´ batch test, using genuine HLLW, and a continuous counter-current experiment have verified the excellent extraction and hydraulic behaviour, respectively. With only four extraction stages in the cold experiment, lanthanide decontamination factors were higher than 2000, except for europium. Co-extraction of molybdenum and zirconium was efficiently prevented using oxalic acid in the feed solution. The back-extraction was very efficient, yielding in 4 stages more than 99% recovery of lanthanides. Palladium and ruthenium were more difficult to back-extract and for these elements further investigations are needed.

Partitioning of Minor Actinides from HLLW Using the DIAMEX Process. Part 2. "Hot" Continuous Counter-Current Experiment.

Among several processes proposed world-wide, the French DIAMEX (DIAMide EXtraction) process seems to be very efficient for the removal of Minor Actinides (MA) from genuine High Level Liquid Waste (HLLW). The MA are in this process directly extracted from the PUREX (Plutonium Uranium Redox EXtraction) raffinate together with fission lanthanides using the completely combustible diamide extractant. In this work a hot demonstration of the DIAMEX process using genuine high-level PUREX raffinate is reported. The continuous counter-current experiment was carried out in a 16 stage centrifugal extractor battery, installed in a hot cell. In order to produce a representative HLLW a PUREX process was applied on dissolved fuel using the same equipment. In the DIAMEX process up to 6 extraction stages were sufficient to achieve feed decontamination factors between 100 and 230 for lanthanides and above 300 for minor actinides. Co-extraction of molybdenum and zirconium were efficiently prevented using oxalic acid scrubbing. The back extraction proved to be very efficient, yielding in 4 stages more than 99.9% recovery of both the lanthanides and the actinides. Co-extracted ruthenium, technetium, palladium and neptunium are less efficiently back-extracted requiring further process development.

A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate

Abstract The selective partitioning (P) of long-lived minor actinides fromhighly active waste solutions and their transmutation (T) to short-lived or stable isotopes by nuclear reactions will reduce the long-term hazard of the high-level waste and significantly shorten the time needed to ensure their safe confinement in a repository. The present paper summarizes the on-going research activities at Forschungszentrum Jülich (FZJ), Karlsruher Institut für Technologie (KIT) and Institute for Transuranium Elements (ITU) in the field of actinide partitioning using innovative solvent extraction processes. European research over the last few decades, i.e. in the NEWPART, PARTNEW and EUROPART programmes, has resulted in the development of multi-cycle processes for minor actinide partitioning. These multi-cycle processes are based on the co-separation of trivalent actinides and lanthanides (e.g. by the DIAMEX process), followed by the subsequent actinide(III)/lanthanide(III) group separation in the SANEX process. The current direction of research for the development of innovative processes within the recent European ACSEPT project is discussed additionally. This paper is focused on the development of flow-sheets for recovery of americium and curium from highly active waste solutions. The flow-sheets are verified by demonstration processes, in centrifugal contactors, using synthetic or genuine fuel solutions. The feasibility of the processes is also discussed.