Combining CMPO and HEH[EHP] for Separating Trivalent Lanthanides from the Transuranic Elements

Combining octyl(phenyl)-N,N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) into a single process solvent for separating transuranic elements from liquid high-level waste is explored. The lanthanides and americium can be co-extracted from HNO₃ into 0.2 mol/L CMPO + 1.0 mol/L HEH[EHP] in n-dodecane. The extraction is relatively insensitive to the HNO₃ concentration within 0.1–5 mol/L HNO₃. Americium can be selectively stripped from the CMPO/HEH[EHP] solvent into a citrate-buffered N-(2-hydroxyethyl)ethylenediaminetriacetic acid solution. Separation factors >14 can be achieved in the range pH 2.5–3.7, and the separation factors are relatively insensitive to pH—a major advantage of this solvent formulation.     

Advanced TALSPEAK Separations Using a Malonate Buffer System

The extraction behavior of lanthanides and americium has been evaluated under Advanced TALSPEAK (Trivalent Actinide Lanthanide Separation by Phosphorus-reagent Extraction from Aqueous Komplexes) conditions using malonic acid as the aqueous buffering agent. The extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) was used as an organic phase liquid cation exchanger in n-dodecane diluent, while N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) served as a selective aqueous holdback reagent. Extractions conducted from malonate media exhibit a pH profile that flattens as the concentration of malonate is increased up to 1.0 M malonate. This relatively flat extraction behavior from pH 2.5–4.0 is reminiscent of previous studies on Advanced TALSPEAK in lactate media. The extraction kinetics with other carboxylic acid buffers as well as the effects of varying HEDTA, HEH[EHP], and malonate concentration are compared.     

Mixed Monofunctional Extractants for Trivalent Actinide/Lanthanide Separations: TALSPEAK-MME

The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO₃ followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in a single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N’,N’’,N’’’,N’’’-hexaacetic acid (TTHA). The results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).     

Effect of HEH[EHP] impurities on the ALSEP solvent extraction process

In solvent extraction processes, organic phase impurities can negatively impact separation factors, hydrolytic performance, and overall system robustness. The resulting inconsistent performance can affect the process-level viability of a separation concept, and thus knowledge of the impurities present, their effects on the process, and how to remove them are vital. Deleterious impurities may be introduced into a system from reagent synthesis, or result from degradation via radiolysis and hydrolysis during use. In this work, the acidic extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])—proposed for application in extractive processes aimed at separating trivalent minor actinides from lanthanides and other fission products—is characterized with respect to its common impurities and their impact on Am(III) stripping in the Actinide Lanthanide SEParation (ALSEP) system. To control impurities in HEH[EHP], existing purification technologies commonly applied for the acidic organophosphorus reagent were assessed and a new chromatographic purification method specific to HEH[EHP] is presented.     

Investigation of the Impacts of Gamma Radiolysis on an Advanced TALSPEAK Separation

The advanced TALSPEAK process is a selective solvent extraction that utilizes 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) to separate lanthanide elements from trivalent actinides, which are held back in the aqueous phase by N-hydroxylethyl-N,N’,N’-ethylenediamine triacetic acid (HEDTA) buffered by citric acid. Gamma irradiation of an experiment containing Eu(III) and Am(III) as representative lanthanide and actinide elements resulted in higher distribution ratios of both and separation factors which decreased in an exponential fashion with increasing dose. Analysis of the reagents showed that the HEDTA concentration also decreased in an exponential fashion, strongly suggesting that degradation was correlated with loss of separation selectivity. In contrast, the concentration of citrate was unaffected, and while the concentration of HEH[EHP] did decrease, its dose-dependent kinetic profile indicated that it was not limiting partitioning. A second set of experiments were conducted using a citrate concentration that was 7.5 X higher, with the expectation that citrate would protect the HEDTA by scavenging radiolytically formed OH radicals. HEDTA degradation was significantly mitigated at higher gamma doses, but the Eu-Am separation was worse than in the low citrate experiments, presumably because at the high citrate concentrations, the Eu-citrate complexes formed in abundances competitive with the Am complexes, and are more effectively held back in the aqueous phase.     

Interactions between Extractant Molecules: Organic-Phase Thermodynamics of TALSPEAK–MME

To reduce the cost and complexity of separations for closed nuclear fuel cycles, solvent extraction processes based on combined solvating and cation exchange extractants are being considered. One such process, Trivalent Actinide Lanthanide Separations using Phosphorus Extractants and Aqueous Komplexes–Mixed Monofunctional Extractants (TALSPEAK–MME), that combines the neutral extractant Cyanex-923 and cation exchanging extractant 2-ethyl(hexyl)phosphonic acid mono-2-ethyl(hexyl) ester (HEH[EHP]) has shown considerable promise. However, little knowledge of the underlying chemistry of this process has been reported. In this report, ³¹P NMR and FT-IR spectroscopies have been used to investigate organic-phase extractant interactions. A 1:1 adduct between Cyanex-923 and HEH[EHP] has been identified. The equilibrium constant describing the formation of this adduct (log K) has been determined to be between 2.04 and 2.21, signifying relatively weak interactions between the extractants. In parallel, it has been determined that the presence of this adduct does not change the nitric acid extraction mechanism observed by Cyanex-923; its presence merely reduces the free concentration of Cyanex-923 available to extract nitric acid thus slightly reducing the total acid partitioned to the organic phase. These findings were used to calculate an extractant speciation diagram for TALSPEAK–MME, the results of which were used to improve understanding of the metal ion extraction behavior observed in this system.     

The Effect of Organic Diluent on the Extraction of Eu(III) by HEH[EHP]

ABSTRACT

Because there are fewer tools available to probe the interactions therein, the effect of the fundamental chemistry of the organic diluent on solvent extraction equilibria has been under-characterized relative to the aqueous. As a result, diluents for solvent extraction are often selected for an application not for their utility as a medium for reaction, but for other (often equally) important reasons (like low flammability). To begin to improve this imbalance in the science, twenty different diluents have been used in a study of the extraction of radiotracer ^152/154Eu³⁺ from dilute nitric acid solutions using the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). To increase the utility of the study and to honor the memory of Professor Jan Rydberg, this investigation was conducted by a cadre of comparatively inexperienced separation scientists (who are as a result no longer inexperienced separation scientists) as a radioanalytical chemistry and solvent extraction educational exercise. Slope analysis was used to determine the apparent stoichiometry of the extracted metal complex. The results discussed in the following indicate that, while the pH dependence exhibits the expected three H⁺ exchanged per metal ion extracted, the extractant dependence suggests that the number of protonated extractant molecules in the extracted complex changes with the organic diluent. The experimentally observed “extractant dependency” ranges from 2.5 to 3.0 dimer equivalent molecules per extracted metal ion. Ironically, in the diluents exhibiting the highest apparent M:(HA)₃ stoichiometry, HEH[EHP] extracts Eu³⁺ less efficiently. Europium luminescence spectroscopy was used to probe for changes in the first coordination sphere of the complex in different diluents. A model and conceptual framework for understanding these observations is described.     

Functionalized Dipicolinic Acid Derivatives as TALSPEAK-MME Stripping Agents

ABSTRACT

This work describes the results of an assessment of two derivatives of dipicolinic acid (DPA) as the actinide-selective stripping reagents in the combined HEH[EHP]/Cyanex-923 system, TALSPEAK-MME (mixed monofunctional extractants). One purpose of this investigation is to demonstrate probable advantages derived in phase-transfer kinetics by deploying dipicolinates as preorganized aminopolycarboxylate complexants in TALSPEAK-derived separation systems. The investigation is focused on the behavior of the lanthanides, Am, and selected transition metals (Zr, Mo, Pd, Ru, and Rh) in the extraction, solvent conditioning, and stripping steps. Solvent conditioning with glycine buffer solutions is shown to be effective for the removal of entrained HNO₃ while also managing Pd concentration prior to actinide stripping. The efficacy of the DPA derivative during the actinide-selective strip was assessed, focusing explicitly on the effects of pH and ligand concentration and evaluating the stripping kinetics. These ligands were shown to be highly selective for americium, producing in the TALSPEAK-MME platform separation factors comparable to commonly used actinide selective stripping agents for radiotracer Eu, Am, a trans-lanthanide series and selected transition metals. The stripping kinetics study revealed very rapid phase-transfer reactions, reaching equilibrium in less than 10 s on vigorous agitation. Further work will be required to address the possible contamination of the product by selected transition metals (such as Zr) during the stripping step.     

Kinetics and mechanism of Yttrium extraction with three acidic phosphorus extractants

A mechanic study is reported, which deal with the kinetic aspects of yttrium extraction from HAc-NaAc-EDTA media, using three acidic phosphorus extractants (HL), di(2-ethylhexyl)phosphoric acid (HDEHP), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and di(2,2,4-trimethylpentyl)phosphinic acid(H[DTMPP]) in n-octane solution. The initial rates of extraction for these three systems were determined under conditions of energetic stirring or mixing of the two phases. The rate data were correlated as a function of the concentration of the relevant species. From the rate equations and the interfacial characteristics, the heterogeneous chemical reaction was established as the rate-determining step of the overall reaction for the three extractants studied. A mechanism has been proposed for this reaction. The order of the extraction rate was found to be HDEHP>HEH[EHP] > H[DTMPP], and is related to the number of C? P bonds in the extractants.     

Effect of the Introduction of Amide Oxygen into 1,10-Phenanthroline on the Extraction and Complexation of Trivalent Lanthanide in Acidic Condition

The extractability and complexation properties of lanthanides with N-alkyl-N-phenyl-1,10-phenanthroline-2-carboxamide were investigated. These ligands, which contain two aza-aromatic donors and an oxygen donor in a molecule, are newly developed extractants for actinides and lanthanides. N-Octyl-N-tolyl-1,10-phenanthroline-2-carboxamide exhibited high extractability of Eu³⁺ even under acidic conditions. In addition, strong complexation in acidic media was confirmed by spectroscopic titration experiments. Investigation of the complexation equilibrium revealed that the presence of an oxygen donor promotes ligand coordination with lanthanides over the competing protonation reaction in acidic solution.     

LUMINESCENCE STUDY OF Eu( III) COMPLEXES EXTRACTED IN THE ORGANIC PHASE

Luminescence lifetimes have been measured for Eu(III) extracted into benzene solutions. The extrac-tants were HDEHP, HTTA, and mixtures of HTTA with crown ethers, TBP, and TOPO. The results were consistent with no residual hydration for Eu(DEHP)₃, and three molecules of hydration for Eu(TTA) ₃,. The Eu(TTA) ₃,-(TOPO)? _n (n = 1,2) complexes have one water molecule or less. The hydration numbers from the luminescence lifetimes compare well with the values from Karl Fischer titrations. The hydration of the crown ether complexes can be related to the degree of steric hindrance by the aliphatic or aromatic groups attached to the crown ethers.     

Permeability measurement of fresh cement paste

Fresh cement paste permeability is a key parameter to understand the hydro-mechanical behavior of cement-based materials, i.e., rhelogical properties and static stability. However, its permeability measurement is not easy to assess. The porous medium is not rigid and tends to change due to hydration kinetics. Two measurement methods, with 70 mm and 20 mm initial height specimens respectively, are presented and compared in this paper. The first uses a basic cell of soil permeability measurement and consists of simultaneous consolidation and percolation tests. The second uses a displacement-controlled oedometer cell equipped with pore water pressure transducers, and consists in inducing consolidation to a given void ratio first and, consecutively, in accurately measuring the permeability. A good correlation of results is observed. A comparison with theoretical models confirms that, from one fitted parameter relative to particle characteristics, a relationship between permeability and void ratio can be established.     

Extraction Theory and Form of the Extraction Complex for the Metals Dysprosium,Holmium, Thulium,and Curium in the Synergistic System Kerosene/HTTA/TBP/Dilute HNO3

Abstract

Data were taken for the distribution of HTTA and the metals Dy, Ho, Tm, and Cm in the system kerosene/thenoyltrifluoroacetone (HTTA)/tributylphosphate (TBP)/dilute HNO₃. The theory first proposed by Tournier (1) and Tournier and Davis (2) for the HTTA distribution was modified and new values of the equilibrium constants resulting from the theory were determined by a least squares fit of the HTTA distribution data. The new values are K ₁ = 14 and K ₂ = 3.45.

An analysis of the HTTA distribution data indicates that one molecule of TBP associates with one molecule of (HTTA·H₂O) to form a complex. Analysis of distribution data for the metals, Dy, Ho, Tm. and Cm using the modified theory indicates that the form of the metal complex is M⁺³(TTA)₃(TBP)₂ reported by most investigators.

A log-log plot of q o/a as a function of [H⁺] under conditions of constant free TBP and HTTA and constant ionic strength indicates an inverse squared effect of [H⁺] on the metal distribution ration, q o/a. This in turn supports the indications that two (TTA) molecules are associated with the metal complex. No experimental data to verify the presence of (NO₃ ^?) in the complex have as yet been obtained.     

Separation of Americium from Europium using Camphor-BisTriazinyl Pyridine: A Fundamental Study

Among the different components present in spent nuclear fuel, long-lived trivalent actinides are particularly difficult to separate from the shorter-lived lanthanide fission products due to their similar chemical properties. Selective extraction of americium from acidic solution (up to 2M HNO₃) containing tenth molar quantities of lanthanides has been achieved using neutral pyridine-based ligands dissolved in polar diluents. Nitrogen-based Bis Triazinyl Pyridine (BTP) ligands are desirable for both their excellent An/Ln selectivity and incinerability. Results pertaining to ligand solubility, kinetics, hydrolytic stability, and extraction performance in various nitric acid environments are presented.     

Modeling of early age behavior of blast furnace slag concrete based on micro-physical properties

A multi-scale system called DuCOM was enhanced to model behaviors of blast furnace slag (BFS) concrete. Tests on the strength and micro–hygro–physical properties of BFS concrete and Portland cement concrete were conducted. The current model was found to underestimate the strength of BFS concrete at later ages owing to underestimation of the water content inside C–S–H gel pores. To remedy this, enhanced modeling of porosity allowing proper simulation of the porosity of the BFS paste matrix and higher strength development at later ages is proposed. Furthermore, based on the enhanced porosity model, the moisture loss and pore size distribution of the BFS paste matrix were investigated. The pore size distribution was found to be coarser than the test at later ages in the model, resulting in overestimation of moisture loss. Hence, the pore size distribution was enhanced as well, allowing simulation of a finer pore structure of the BFS matrix. Finally, verifications showed that the enhanced model better predicts water desorption, moisture loss and drying shrinkage behaviors.     

Characterization of Extraction of Chromatographic Materials Containing Bis(2‐ethyl‐1‐hexyl)Phosphoric Acid, 2‐Ethyl‐1‐Hexyl (2‐Ethyl‐1‐Hexyl) Phosphonic Acid,and Bis(2,4,4‐Trimethyl‐1‐Pentyl)Phosphinic Acid

Abstract

This work describes the uptake of a wide range of metal ions, including alkaline earths, transition metals, post‐transition metals, lanthanides and actinides, from acidic nitrate and chloride media on extraction chromatographic resins prepared from three different acidic organophosphorus compounds: bis(2‐ethyl‐1‐hexyl) phosphoric acid (HDEHP), 2‐ethyl‐1‐hexyl(2‐ethyl‐1‐hexyl)phosphonic acid, (HEH[EHP]) and bis(2,4,4‐trimethyl‐1‐pentyl)phosphinic acid (H[DTMPP]). The data is plotted in a format allowing for the easy comparison of the uptake of all metal ions under a given condition. Additionally, examples of several novel separations using the three extraction chromatographic materials are discussed.