Tetraoctyl Diglycolamide Research Articles

Elucidation of the Decomplexation and Reverse Migration Mechanism of Uranyl Ions from the Oil Phase to the Aqueous Phase Using Microsecond (0.2 μs) Molecular Dynamics Simulations.

Interphase ion transfer is ubiquitous in chemistry, physics, biology, and various engineering sciences. Ion transfer from the aqueous phase to the oil phase or vice versa is a complex chemical phenomenon, and its fundamental understanding is crucial for efficient and economical mass transfer. This ion transfer is much more complex for radionuclide metal ions. Therefore, an attempt has been made to elucidate the decomplexation and mechanism of reverse migration of uranyl ions from the loaded oil phase to the aqueous phase using large time-scale molecular dynamics simulations (microseconds) and density functional theory (DFT). The strength of the metal-ligand complex is the key factor for stripping among other mass transfer parameters. Stronger the metal-ligand complex, the lower the tendency for reverse migration into the aqueous phase, which was demonstrated by three different ligands for reverse migration using water as the stripping agent. The interaction energy of the metal-ligand complex has been calculated using DFT. The reverse migration is validated by the distance between the centers of mass. Higher interface thickness and lower interfacial tension belong to N,N,N',N'-tetra-octyldiglycolamide (TODGA), which are favorable for mass transfer across the liquid-liquid interface. The computed distribution coefficient (KD) is favorable for tributyl phosphate (TBP) and tri-iso-amyl phosphate (TiAP), whereas TODGA shows a higher KD, indicating a less favorable value for reverse migration. The distance between the uranyl ion and the TODGA molecule confirms that the entrapment of uranyl ions in the TODGA phase might be attributed to aggregation. Further, the aggregation tendency of TODGA molecules reduces the back extraction and the recovery of uranyl ions into the aqueous phase. The present MD results might be important for predicting an efficient back-extracting agent for the recovery of the metal ions from the oil phase.

Selective separation and recovery of rare-earth elements (REEs) from acidic solutions and coal fly ash leachate by novel TODGA-Impregnated organosilica media

Rare-earth elements (REEs) are essential in a wide range of applications including magnets and satellite technology, with demand driven by geopolitical factors. While multiple techniques exist for REE recovery including solvent extraction and selective precipitation, solid–liquid extraction offers key advantages in selectivity, scalability, and recyclability. N, N, N′, N′-tetraoctyl diglycolamide (TODGA) is a tridentate ligand widely used in solvent extraction, but the incorporation in a solid support to separate individual lanthanides from acid solutions remains largely unexplored. A novel TODGA-organosilica sorbent material was developed and tested to evaluate recovery of 17 elements (REEs and thorium) in terms of selectivity, kinetics, and equilibrium isotherms in 0.01 to 15.9 M nitric acid. Characterization of the new sorbent was performed before and after sorption using FTIR, XPS, and SSA techniques to help elucidate sorption mechanisms and limiting variables. REE adsorption increased from 1.26 mg g−1 to 10 mg g−1 with nitric acid concentrations of 0.01 M and 15.9 M, respectively. TODGA-organosilica exhibits high selectivity towards heavy REEs (Dy to Lu), with minimal sorption of lighter REEs (Ce to Gd). Batch adsorption experiments confirm pseudo-second-order kinetics and a Langmuir adsorption isotherm with TODGA binding to REEs in a 3:1 complex. A packed bed column study confirmed the high selectivity of TODGA-impregnated organosilica towards heavy REEs and a proof-of concept experiment with coal fly ash leachate shows high selectivity for REEs over Al, Fe, and Ca present in several orders of magnitude higher concentrations. Fractionation was observed where loading cycle effluent contained 84 % light REEs while strip cycle effluent contained 80 % heavy REEs. More than 90 % of loaded REEs were successfully stripped with water as the stripping agent.

Experimental and theoretical insights into the influence of gamma irradiation degradation products of N,N,N′,N′-tetraoctyl diglycolamide on extraction efficiency toward trivalent f-elements

Understanding the effect of radiation rays on N,N,N′,N′-tetraoctyl diglycolamide (TODGA) based solvent extraction systems is an essential task for establishing and optimizing related extraction processes in nuclear industries. However, the influence of various radiolysis degradation products on extraction efficiency and the mechanism involved still remain elusive. In this work, the radiolysis degradation products of TODGA were analyzed with the aid of high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) technique and documented results, followed by the successful synthesis of ten radiolysis degradation products P1–P10. The extraction ability of each main degradation product towards Eu(III) and their effects on the extraction performance of TODGA system were systematically studied. These radiolysis degradation products with diverse chemical structures were found to reveal different roles in extraction such as serving as co-extractant and synergist, in which P2 resemblance in structure to TODGA offers the highest extraction ability among others, thus mitigating the decrease of extraction efficiency. Mechanism investigations including slope analysis and density functional theory (DFT) calculations reveal that P2 is involved as one of the extracted species in the complexation with Eu(III) in its first coordination sphere. These findings provide in-depth experimental and theoretical guidance on the molecular scale for designing TODGA-based metal separation processes.

Using Diglycolamide Extractants in an Imidazolium-Based Ionic Liquid for Rare Earth Element Extraction and Recovery.

Growing demands for rare earth elements (REEs) have prompted sustainability concerns worldwide. Given the need for sustainable extraction methods amidst REEs, ionic liquids (ILs) have been investigated as tunable extraction substitutes for conventional organic solvents, offering negligible volatility and diverse physical and chemical properties. Recent reports have shown that the introduction of extractants, like N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N-dioctyldiglycolamic acid (DODGAA), into ILs can provide high selectivity and affinity for REE capture. Precipitate formation has been observed in IL-extractant systems across several studies; however, the molecular interactions that drive this phenomenon have yet to be explored. This study investigates the coordination environment in the precipitate formed between [Yb3+], DODGAA, and the 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM+][PF6 -]) IL. The composition of the precipitate was confirmed using several spectroscopic techniques and revealed an underlying hydrogen bonding interaction between the fluorine atom of [PF6 -] anion and -OH of the Yb-DODGAA complex. Computational studies were also conducted to examine the coordination environment of the Yb-TODGA and Yb-DODGAA complexes. The binding affinity of the extractants toward [Yb3+] is analyzed by calculating the associated binding energy values. The results clearly show a stronger binding affinity of the extractants toward [Yb3+], supporting the observed high extraction efficiencies of DODGAA and TODGA.

Influence of Aqueous Phase Acidity on Ln(III) Coordination by N,N,N',N'-Tetraoctyldiglycolamide.

This study highlights the importance of combining distribution ratio measurements with multiple spectroscopic techniques to provide a more comprehensive understanding of organic phase Ln coordination chemistry. Solvent extraction investigations with N,N,N',N'-tetraoctyldiglycolamide (TODGA) in n-heptane reveal the sensitivity of Ln complexation to the HNO3 concentration. Distribution ratio measurements in tandem with UV-Vis demonstrated that increasing the concentration of HNO3 above 0.5 M with a constant NO3- of 1 M increases the number of coordinating TODGA molecules, from a 1:2 to a 1:3 Ln:TODGA complex. At each concentration of HNO3 considered herein (from 0.01 to 1 M), Eu lifetime analysis demonstrated no evidence of H2O coordination. Results from Fourier transform infrared investigations suggest the presence of inner-sphere NO3- under low concentrations of HNO3 when the 1:2 Ln:TODGA complex is present. Increasing the HNO3 concentration above 0.5 M increases the propensity for outer-sphere interactions by removing the coordinated NO3- and saturating the Ln coordination sphere with three TODGA molecules, resulting in the well-established cationic, trischelate homoleptic [Ln(TODGA)3]3+ complex. This work demonstrates the importance in considering the NO3- source for solvent extraction systems. In particular, for systems with an affinity for outer-sphere interactions with molar concentrations of HNO3, changing the NO3- source can change the inner-sphere coordination of the Ln complex, which, in turn, affects the separation efficacy.

Quantification of enthalpy of extraction of Eu(III)-glycolamide solvent systems using isothermal solution calorimetry-Influence of extraction parameters and solvent aggregation

The present work highlights the utility of isothermal solution calorimetry as a reliable and convenient tool for the determination of enthalpy of extraction (ΔHextr) of metal ions under biphasic solvent extraction conditions. In comparison to the conventional indirect method based on Van't Hoff isotherm analysis, calorimetric method offers the flexibility of direct enthalpy measurements under a variety of operating conditions. The ΔHextr of Eu(III) at different HNO3 concentrations was measured for N,N,N’,N’-tetraoctyldiglycolamide (TODGA) and N,N-di-octyl-2-hydroxyacetamide (DOHyA) solvents for the first time using this method. A strong dependence of ΔHextr with changes in aqueous phase acidity as well as the concentration of solvent phase was discerned during the measurements. Parallel measurements using DLS spectroscopy divulged that the observed decrease in ΔHextr is a consequence of the aggregation of extractants. The pivotal role of aggregation of solvents on the extraction enthalpy of solvent extraction systems was demonstrated by a comparison of the results in two solvent systems with different aggregation properties.

Radiolytic stability and effects on metal extraction of N,N,N′-trioctyldiglycolamide, an important TODGA degradation product

N,N,N′-Trioctyldiglycolamide (TrODGA) is an important degradation compound of N,N,N′,N′-tetraoctyl diglycolamide (TODGA), one of the most successful extractants under study for minor actinide recovery.

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction.

Adding hydrophilic ligands into aqueous solutions for the selective binding of actinides(III) is acknowledged as an advanced strategy in Ln(III)/An(III) separation. In view of the recycling and radioactive waste disposal of the minor actinide, there remains an urgent need to design and develop the appropriate ligand for selective separation of An(III) from Ln(III). Herein, four novel hydrophilic ligands with hard-soft hybrid donors, derived from the pyridine and phenanthroline skeletons, were designed and synthesized as masking agents for selective complexation of An(III) in the aqueous phase. The known N,N,N',N'-tetraoctyl diglycolamide (TODGA) was used as lipophilic extractant in the organic phase for extraction of Ln(III), and a new strategy for the competitive extraction of An(III) and Ln(III) was developed based on TODGA and the above hydrophilic ligands. The optimal hydrophilic ligand of N,N'-bis(2-hydroxyethyl)-2,9-dicarboxamide-1,10-phenanthroline (2OH-DAPhen) displayed exceptional selectivity toward Am(III) over Ln(III), with the concentrations of HNO3 ranging from 0.05 to 3.0 M. The maximum separation factors were up to 1365 for Eu/Am, 417.66 for Eu/Cm, and 42.38 for La/Am. The coordination mode and bonding property of 2OH-DAPhen with Ln(III) were investigated by 1H NMR titration, UV-vis spectrophotometric titration, luminescence titration, FT-IR, ESI-HRMS analysis, and DFT calculations. The results revealed that the predominant species formed in the aqueous phase was a 1:1 ligand/metal complex. DFT calculations also confirmed that the affinity of 2OH-DAPhen for Am(III) was better than that for Eu(III). The present work using a competitive extraction strategy developed a feasible alternative method for the selective separation of trivalent actinides from lanthanides.

Salting out of americium-241 in the sorption process using a solid-phase extractant based on TODGA

Today, the «Proryv» project is developing effective methods of reprocessing irradiated nuclear fuel (SNF) to return long-lived radionuclides to the fuel cycle to close it. One of the challenges of closed fuel cycle development is the reprocessing of highly active nitric acid raffinates from the PUREX-process. To achieve this task, it is necessary to separate americium-241 from liquid radioactive waste. When processing and fractionating liquid radioactive waste, extraction and sorption technologies for the extraction, purification and concentration of radionuclides are widely used. The highest efficiency and selectivity in the extraction processes of actinoids (III) and lanthanides (III) with rare earth elements (REE) and transplutonium elements (TPE) from nitric acid solutions of spent nuclear materials reprocessing were shown by extractants based on N, N, N', N'-tetraoctyldiglycolamide (TODGA). Before using a solid-phase extractant based on TOGDA, the ions of the substance in solution must be converted to neutral complexes or other non-dissociated compounds. This can be achieved by adding neutral salts to the solution, which reduce the solubility of the elements to be separated, shift the extraction distribution and significantly increase the extraction efficiency. The extracted substance is extracted in the form of a new phase - solid precipitate, liquid or gas phase, and in the case of liquid extraction there is an increase in the capacity of the extractant for the target component. Therefore, the addition of salts-salting agents to the aqueous phase to increase the ionic strength of the solution increases the distribution coefficients of extracted substances, which in turn increases the capacity of sorbents. The purpose of this work is to study the process of salting out of americium-241 during sorption using an experimental modified sample of solid-phase extractant based on TODGA in the studied model solutions of liquid radioactive waste with a uranium macrocomponent for different NaNO3 contents. The study revealed that the highest distribution coefficients for the sorption of americium-241 and uranium were obtained in a solution containing 100 g/l NaNO3, but for uranium this effect is much less pronounced than for americium-241. During the study of the sorption kinetics of americium-241 and uranium, the salting effect was revealed, which is confirmed by the values of the equilibrium concentrations of americium-241 and uranium in solution at the same time point but with different NaNO3 concentrations. The difference in the equilibrium concentrations for americium-241 was an order of magnitude towards its decrease when NaNO3 concentration was increased up to 100 g/litre. The use of this effect makes it possible to obtain the maximum capacity for americium-241 in the system with uranium macrocomponents

Process flowsheet test of the i-SANEX process with CHON-compliant ligands in aqueous and organic phases

We report the results of a “CHON-compliant” i-SANEX flowsheet test using a surrogate feed with process concentrations of 241Am (>1 g/L) and major lanthanide and fission product species in a 32-stage counter-current centrifugal contactor (CC) rig. By combining flowsheet modelling with experience from the European GENIORS project, a flowsheet was designed that included the lanthanide/actinide extraction, fission product scrubbing, actinide stripping and finally, lanthanide stripping; therefore, covering the entire flowsheet except solvent treatment. The extraction system was 0.2 M N,N,N′,N′-tetraoctyldiglycolamide (TODGA) in Isane-185 with 5 v/v.% 1-octanol as a phase modifier. Actinide stripping was afforded by the aqueous soluble pyridine-2,6-bis(1H-1,2,3-triazol-4-yl) (PTD), whilst the lanthanide stripping was performed by N,N,N′,N′-tetraethyldiglycolamide (TEDGA). This represents the first test of PTD and TEDGA across the full flowsheet using counter-current CC and with process concentrations of americium. This CHON-compliant i-SANEX flowsheet offers clear improvements to the reference process. The use of a full PUREX raffinate simulant as the feed for the process has also permitted the measurement of concentration profiles of many species that are not normally followed in such detail. This has highlighted that under the conditions used – 8 stages of extraction, 8 stages of scrubbing (0.7 M HNO3) – some of the lanthanides recycle and do not reach steady-state in the timeframe of the experiment. Overall, the flowsheet demonstrated good control of 241Am with 98.6 % being routed to the actinide product although further work is needed to fully control some lanthanides and fission products, including; La, Ce, Pr, Gd, Tc, Ru and Sr.

Gamma radiolysis studies of N,N-dioctyl-2-hydroxyacetamide: Complexation effect on the stability and implications on the hydrometallurgical extraction performance

N,N-dioctyl-2-hydroxyacetamide (DOHyA) is one of the most important degradation compounds (DCs) of the well-known extractant N,N,N′,N′-tetraoctyldiglycolamide (TODGA), employed for the minor actinide (MA) recovery processes development from spent nuclear fuel. Due to its lipophobicity, DOHyA would not be easily removed from the solvent through simple washing steps. Therefore, it is expected that DOHyA will be accumulated in the recycled TODGA solvent along the operation, but it also may be degraded itself by radiation. In this work, the radiolytic stability of DOHyA and its possible implications on the extraction process performance were studied under different experimental conditions. For that, DOHyA samples in OK (odourless kerosene) and pre-equilibrated with a) nitric acid and b) the expected europium(III) concentration in a real process dissolved in nitric acid, were subjected to gamma radiation (up to 500 kGy) and analyzed. The extraction properties and changes in the composition of the solvent were checked upon irradiation by different techniques: gamma spectroscopy and ICP-MS for the evaluation of the extraction performance; and HPLC-MS to quantify the degradation of the DOHyA samples, but also to identify and quantify its own degradation compounds. The results indicate that the Eu-complexes formed in the organic phase protect DOHyA from degradation by radiation and induce a change in the degradation pathway, highlighting the importance to perform the irradiation of the resulting solutions of the stability studies in the presence of the corresponding metal ions. Moreover, DOHyA, as well as its degradation compounds (DCs), showed a high affinity for different undesirable fission products in these kinds of extraction processes. In consequence, DOHyA and its DCs must be taken into account in the long-term performance of the extraction process, as well as in the development of the cleaning strategies to recycle the TODGA solvent.

Gamma Radiolysis of Phenyl-Substituted TODGAs: Part II

ABSTRACT The radiolytic degradation chemistry of three phenylated analogs of N,N,N’,N’-tetraoctyl diglycolamide (TODGA) was investigated: 2-(2-(di-n-octylamino)-2-oxoethoxy)-N,N-di-n-octyl-2-phenylacetamide (PhTODGA), which has a phenyl substituent bound to a central methylene, 2-(2-(di-n-octylamino)-2-oxo-1-phenylethoxy)-N,N-di-n-octylpropanamide (PhMeTODGA), which also contains a methyl substituent bound to the methylene on the other side of the ether moiety, and, 2-(2-N-n-hexyl-N-phenylamino)-2-oxoethoxy)-N-n-hexyl-N-phenylacetamide (DHDPDGA), which has phenyl substituents located on the amide groups instead of the central methylenes. In Part II of this series of papers radiolytic degradation products were identified after separation with liquid chromatography by High Resolution, Accurate-Mass mass spectrometry and collision-induced dissociation. At least twenty-two radiolytic degradation products were identified for PhTODGA, twenty-nine for PhMeTODGA, and over three dozen for DHDPDGA. The suite of radiolytic degradation products of these three investigated ligands was significantly larger than has been reported for previously studied diglycolamides, owing to their asymmetric nature, and to the identification of several new degradation mechanisms, including addition of methyl, hydroxyl, and nitrogen oxide radicals, that have not been previously reported for diglycolamides. Degradation products that contained addition of a NO2 or NO3 group were particularly prevalent for DHDPDGA, likely due to the phenyl side-groups. Several of these newly observed mechanisms do not appear to depend on the presence of the phenyl groups, suggesting these novel mechanisms may apply to other diglycolamides

Cyclohexyl substituted diglycolamide ligands for highly efficient separation of strontium: Synthesis, extraction and crystallography studies

A series of novel diglycolamide (DGA) ligands containing cyclohexyl substituent on the amidic N atom were investigated for their solvent extraction and complexation ability toward Sr2+ in HNO3 solution. Compared with the most commonly used N,N,N′,N′-tetraoctyldiglycolamide (TODGA), the introduction of cyclohexyl substituent into the DGA skeleton can significantly enhance the extractability toward Sr2+ in the case of toluene as the diluent. And the more cyclohexyl substituents there are, the more significant the effect is. About 8−80 fold increase of the Sr2+ distribution value for LI−LVI ligands can be achieved than that for TODGA at 2.0 mol/L HNO3. The extractability of these cyclohexyl substituted DGA ligands follows the order of LI ≈ LIII > LII > LIV > LV > LVI > > TODGA. Meanwhile, for the DGA ligands with the same number of cyclohexyl substituents, LIII with moderate alkyl chain length (n-butyl) has higher extractability than LII with short chain (n-ethyl) and LIV with long chain (n-octyl). Slope analysis reveals the formation of 1:3 metal-ligand extracted species during the extraction process, which is also confirmed by the results obtained from ESI-MS, FT-IR and single-crystal X-ray diffraction analyses. Furthermore, the single crystal of DGA ligand with Sr(NO3)2 was obtained for the first time, and the analysis of its structure indicates that each DGA molecule participates in the complexation with the 9-fold coordinated Sr2+ through two amide carbonyl O atoms and one ether O atom, accompanied by two free NO3− in the outer coordination sphere. The extraction of Sr2+ by the novel DGA ligand is a spontaneous and exothermic process of increasing entropy, and follows neutral complexing extraction model. In addition, an extraction test of Sr2+ from simulated high level liquid waste was also carried out and demonstrates a highly efficient and selective separation of Sr2+ over the other co-existing ions.

Improvement in the elution performance of an N,N,N’,N-tetraoctyl diglycolamide impregnated extraction chromatography adsorbent using neodymium via micro-particle-induced X-ray emission analysis

An adsorbent used for the recovery of trivalent minor actinides (MA(III); Am and Cm) from high level liquid waste generated from reprocessing of spent nuclear fuel was subjected to micro-particle induced X-ray emission (micro-PIXE) analysis to improve its elution performance. The experimental adsorbent comprised SiO2 particles, a polymer coating, and an N,N,N′,N′-tetraoctyl diglycolamide (TODGA). The particles to be analyzed were subjected to Nd adsorption and an elution operation, but Nd in the adsorbent was found to be uniformly distributed. This might have been caused by individual differences in the amount of impregnated TODGA. The remaining Nd species were not localized to a specific part of the adsorbent after the adsorption operation. Some Nd elements were retained in the adsorbent after elution, probably because of the poor diffusion of the mobile phase inside the adsorbent. An adsorbent having a different microstructure from the first was then evaluated, and rapid elution was observed on new adsorbent along micro-PIXE analysis.

The complexation of lanthanides by glycolamide extractants: Evidences from electronic spectroscopy and DFT calculations

The extraction of trivalent metal ions (Nd and Eu) in N,N,N’,N’-tetraoctyldiglycolamide (TODGA) was compared with N,N-di-octyl-2-hydroxyacetamide (DOHyA), a monoglycolamide derivative of TODGA. The studies based on UV–visible spectroscopy showed the differences in Nd(III) ion complexation for the extractants in both polar and non-polar diluents. n-Dodecane modified with 5 vol% 1-octanol was employed as diluent for extraction studies with TODGA, while DOHyA was studied with no modifiers in n-Dodecane. Time resolved luminescence spectroscopy studies of the Eu(III) extracted organic phases showed strong complexation of metal ion with both the extractants. The co-extraction of water in DOHyA solvent phase during Eu(III) extraction from nitric acid medium was found to be more as compared to TODGA. The better solubilization of water in DOHyA solvent was substantiated by DFT analysis of the optimized electronic structures of Eu-DMHyA (dimethyl hydroxyacetamide) and Eu-TMDGA (tetramethyldiglycolamide) complexes.

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation.

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙+ from 10-40 °C, giving the activation energy (Ea = 17.43 ± 1.64 kJ mol-1) and pre-exponential factor (A = (2.36 ± 0.05) × 1013 M-1 s-1). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙+, relative to the non-complexed ligand: k([LnIII(TODGA)3(NO3)3] + RH˙+) = (8.99 ± 0.93) × 1010, (2.88 ± 0.40) × 1010, and (1.53 ± 0.34) × 1010 M-1 s-1, for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations-based on a model [LnIII(TOGDA)]3+ complex system-indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [LnIII(TEGDA)3(NO3)3], toward electrophilic attack is for the coordinated nitrate (NO3-) counter anions. Therefore, it is possible that radical reactions with the complexed NO3- counter anions dominate the differences in rates seen for the [LnIII(TODGA)3(NO3)3] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

A multi-faceted approach to probe organic phase composition in TODGA systems with 1-alcohol phase modifiers.

The effect of varying 1-alcohol alkyl chain length on extraction of lanthanides (Lns), H2O, and H+ was studied with tetraoctyl diglycolamide (TODGA) via solvent extraction coupled with FT-IR investigations. This multi-faceted approach provided understanding regarding the relationship between extracted Lns, H2O and H+, 1-alcohol volume fraction, and 1-alcohol alkyl chain length. Under acidic conditions there is competition with 1-alcohols and their ability to solubilize aggregates and incidentally induce third phase formation by increasing the extraction of H2O. At low 1-alcohol concentrations (5 vol%), the trend for 1-alcohol alkyl lengths in solubilizing the aggregates is 1-hexanol > 1-octanol > 1-decanol. Shorter alkyl chains suppress aggregation, ultimately resulting in lower H2O concentrations and less available TODGA to hydrogen bond with H+. Increasing the 1-alcohol concentration to 30 vol% results in the opposite trend, with longer alkyl chains suppressing aggregation. These results suggest this approach is effective at probing trends in the organic phase micro-structure, and indicates trends across the Ln period with various 1-alcohol alkyl chain lengths are a function of outer-sphere coordination.

Modulating Aggregation in Microemulsions: The Dispersion by Competitive Intermolecular Interaction Model.

A phenomenological model has been developed for the mechanism of action of phase modifiers as additives that control aggregation phenomena within water-in-oil emulsions. The "Dispersion by Competitive Intermolecular Interaction" model (DCI) explicitly considers the strength and prevalence of different intermolecular interactions that influence the molecular association of amphiphiles, the resulting distribution of aggregate size, and interaggregate interactions that influence phase phenomena. The existing "cosolvent" and "cosurfactant" association models, which describe the distribution of these amphiphiles within the solution, are re-examined in the context of intermolecular interactions. The different contributions of intermolecular interactions to the potential energy landscape of molecular association create distinct regimes within the DCI model that explain prior observations of cosolvent and cosurfactant behavior. The specific system under consideration, the N,N,N',N'-tetraoctyl diglycolamide amphiphile extractant with tributyl phosphate or dihexyl octanamide phase modifier additives, represents a new regime-labeled the polar disruption regime-where strong hydrogen bonding of the phase modifier with the polar-solutes disrupts the internal hydrogen bonding network of the polar micellar core, thereby decreasing aggregate size and narrowing the polydispersity in solution.

Molecular Dynamics Study of the Aggregation Behavior of N,N,N',N'-Tetraoctyl Diglycolamide.

Liquid–liquid extraction is a commonly used technique to separate metals and is a process that has particular relevance to the nuclear industry. There has been a drive to use environmentally friendly ligands composed only of carbon, hydrogen, nitrogen, and oxygen. One example is the i-SANEX process that has been developed to separate minor actinides from spent nuclear fuel. The underlying science of such processes, is, however, both complex and intriguing. Recent research indicates that the liquid phases involved are frequently structured fluids with a hierarchical organization of aggregates. Effective flow-sheet modeling of such processes is likely to benefit from the knowledge of the fundamental properties of these phases. As a stepping stone toward this, we have performed molecular dynamics simulations on a metal free i-SANEX system composed of the ligand N,N,N′,N′-tetraoctyl diglycolamide (TODGA), diluent hydrogenated tetrapropylene (TPH), and polar species water and nitric acid. We have also studied the effects of adding n-octanol and swapping TPH for n-dodecane. It would seem sensible to understand this simpler system before introducing metal complexes. Such an understanding would ideally arise from studying the system’s properties over a wide range of compositions. The large number of components, however, precludes a comprehensive scan of compositions, so we have chosen to study a fixed concentration of TODGA while varying the concentrations of water and nitric acid over a substantial range. Reverse aggregates are observed, with polar species in the interior in contact with the polar portions of the TODGA molecules and the organic diluent on the exterior in contact with the TODGA alkyl chains. These aggregates are irregular in shape and grow in size as the amount of water and nitric acid increases. At a sufficiently high polar content, a single extended cluster forms corresponding to the third phase formation. No well-defined bonding motifs were observed between the polar species and TODGA. The cluster size distribution fits an isodesmic model, where the Gibbs energy change of adding a TODGA molecule to a cluster ranges between 4.5 and 7.0 kJ mol–1, depending on the system composition. The addition of n-octanol was found to reduce the degree of aggregation, with n-octanol acting as a co-surfactant. Exchanging the diluent TPH for n-dodecane also decreased the aggregation. We present evidence that this is due to the greater penetration of n-dodecane into the reverse aggregates. It is known, however, that the propensity for the third phase formation is greater with n-dodecane as the diluent than is the case with TPH, but we argue that these two results are not contradictory. This research casts light on the driving forces for aggregation, informs process engineers as to what species are present, and indicates that flow-sheet liquid–liquid extraction modeling might benefit by incorporating an isodesmic aggregation approach.

Process Scale‐Up of an Energy‐Efficient Membrane Solvent Extraction Process for Rare Earth Recycling from Electronic Wastes

This study reports the process scale‐up and long‐term performance of an energy‐efficient and cost‐effective membrane solvent extraction (MSX) process for separation and recovery of high purity rare earth oxides (REOs) from scrap permanent magnets (SPMs). The rare earth elements (REEs), including dysprosium, neodymium, and praseodymium, are recovered from SPMs using a neutral extractant, tetraoctyl diglycolamide (TODGA) embedded in a microporous polypropylene hollow fiber membrane module. The MSX process performance is demonstrated with bench scale module with membrane surface area of 1.4 m2 to industrial scale modules with membrane surface area of up to 20 m2 to enable the processing of up to 1 ton month−1 of SPMs. The purity and the yield of the recovered REOs are >99.5 wt% and >95%, respectively. The average extraction rate of REOs is >10 g m−2 hr−1. A skid of MSX system is assembled with a membrane area of 40 m2. The MSX skid successfully recovers REOs with a capacity of 300 kg REOs/month. Finally, it is determined that the organic phase containing the extractant maintains its performance up to 250 h. The results suggest that the MSX process is an economically viable and environmentally friendly process for separation and recovery of REOs from electronic wastes.