Solvent Extraction Investigations on Pu(IV) and Th(IV) Complexes with Hydrophilic SO3-Ph-BTP and SO3-Ph-BTBP Ligands

ABSTRACT

Complexation of Pu(IV) and Th(IV) cations by the title ligands – hydrophilic sulfophenyl triazinyl derivatives of bis-triazinyl-pyridine and -bipyridine – was studied in solvent extraction systems containing a TODGA extractant and one of these hydrophilic ligands. Stoichiometries and stability constants of the complexes formed in an acidic (HNO₃) aqueous phase have been determined. The Pu(IV) complexes are significantly stronger than their Th(IV) analogues. Only two complexes of each metal with SO₃-Ph-BTP (1:1 and 1:2) have been detected, and only one (1:1) with SO₃-Ph-BTBP; both numbers being less than expected based on the coordination numbers of the metal ions and on the denticities of the ligands. Possible reasons of this discrepancy are discussed.     

Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions with CMPO-Functionalized Ionic Liquid in Molecular Diluents

The extraction of microquantities of U(VI), Th(IV), and lanthanides(III) from nitric acid solutions with CMPO-functionalized ionic liquid 1-[3[[(diphenylphosphinyl)acetyl]amino]propyl]-3-tetradecyl-1H-imidazol-3-ium hexafluorophosphate, CMPO-FIL(I) in molecular organic diluents has been studied. The effect of HNO₃ concentration in the aqueous phase and that of extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined. CMPO-FIL(I) demonstrates greater extraction ability towards Ln(III) than its neutral CMPO analog, diphenylphosphorylacetic acid N-nonylamide. This inner synergistic effect increases with a decreasing organic diluent polarity. The partition of CMPO-FIL(I) between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of Ln(III) ions in the extraction system.     

Studies on the Extraction of Actinides Using a Solvent Containing D2EHiBA in Room Temperature Ionic Liquids: Unusual Extraction of the Tetravalent Ions

The extraction behavior of U(VI), Pu(IV), and Np(IV) from nitric acid medium has been studied using branched chain di(2-ethylhexyl)isobutyramide (D2EHiBA) dissolved in different room temperature ionic liquids (RTILs) [C_nmim][NTf₂] (where n = 4, 6, or 8). Uranium extraction (D_U) increased gradually with aqueous phase acidity for the three RTILs used in this study suggesting solvation mechanism. There was a reversal in the extraction behavior of Pu(IV) and Np(IV) from nitric acid medium using D2EHiBA dissolved in RTILs as solvents as compared to the behavior reported in the molecular diluent, n-dodecane, which shows negligible extraction of these metal ions. The extraction of Pu(IV) increased with aqueous phase acidity in different RTILs in the order: [C₈mim][NTf₂] > [C₆mim][NTf₂] > [C₄mim][NTf₂]. The distribution ratio values of these metal ions followed the order: D_Pu(IV) ≥ D_Np(IV) > D_U(VI) using D2EHiBA as extractant suggesting that RTILs can modify the extraction behavior of extractants.     

Extraction of Uranyl Ion Using 2-Thenoyltrifluoro Acetone (HTTA) in Room Temperature Ionic Liquids

The extraction of UO₂²⁺ ion was studied using six different solvent systems containing 2-thenoyltrifluoroacetone (HTTA) in room temperature ionic liquids such as [C_nmim][X] (where, n = 4, 6, or 8 and X^? = PF₆^? or NTf₂^?) from low to moderate pH solutions for the first time. The extraction kinetics studies indicated rather slow attainment of equilibrium which in some cases improved if the solutions were pre-equilibrated with the aqueous phase prior to the actual experiments. The D_U values were found to increase with increasing pH and leading to a plateau like profile at higher pH values. The D values were quite high as compared to that obtained with molecular diluents. The nature of the extracted species was ascertained by slope analysis method which suggested species of the type: UO₂(TTA)⁺_IL, UO₂(TTA)_2,IL, and UO₂(TTA)₂(HTTA)_IL in different ionic liquid based solvents. Temperature variation studies on UO₂²⁺ ion extraction were also carried out and the thermodynamic parameters were calculated which indicated high endothermicity of the reactions with large positive entropy values.     

Liquid Emulsion Membrane (LEM) Process for Vanadium (IV) Enrichment: Process Intensification

Abstract

A liquid emulsion membrane (LEM) system for vanadium (IV) transport has been designed using di‐2‐ethylhexyl phosphoric acid (D2EHPA), dissolved in n‐dodecane as carrier. The selection of extractant, D2EHPA, was made on the basis of conventional liquid‐liquid extraction studies. The work has been undertaken by first carrying out liquid‐liquid extraction studies for vanadium (IV) to get stoichiometric constant (n), and equilibrium constant (K_ex), which are important for process design.

Transport experiments were carried out at low vanadium (IV) concentration (ppm level). The studies on liquid emulsion membrane included i) the influence of process parameters i.e. feed phase pH, speed of agitation, treat ratio, residence time and ii) emulsion preparation study i.e., organic solvent, extractant concentration, surfactant concentration, internal strip phase concentration. When the strip phase concentration was 2 mol/dm³ (H₂SO₄) and feed phase pH 3 better extraction of vanadium was obtained. Higher V_m/V₁ gave higher extraction of vanadium (IV). A simplified, design engineer friendly model was developed.     

Selective Extraction and Separation of Ce (IV) and Th (IV) from RE(III) in Sulfate Medium using Di(2-ethylhexyl)-N-heptylaminomethylphosphonate

The extraction and separation of Ce(IV) and Th(IV) from trivalent rare earths (RE, including scandium) in sulfate medium using di(2-ethylhexyl)-N-heptylaminomethylphosphonate (DEHAMP, L) were studied. The effects of H₂SO₄ concentration, extractant concentration, and temperature on the metal extraction were investigated systematically. It was found that the extraction of metal ions by DEHAMP decreases in the following order: Ce(IV) > Th(IV) > Sc(III) > other RE(III). A possible extraction mechanism was proposed and the extracted complexes as Ce(SO₄)₂·2L and Th(HSO₄)₂SO₄·L were determined by the slope analysis method. Thermodynamic parameters (ΔH, ΔG, and ΔS) were calculated. The extraction reactions of Ce(IV) and Th(IV) were each exothermic processes. The loaded Ce(IV) and Th(IV) can be stripped efficiently by 3% H₂O₂ and 4 mol/L HCl, respectively. The extraction capacity of 0.63 mol/L DEHAMP is 30.0 g/L CeO₂ and 24.4 g/L ThO₂, respectively. Furthermore, a solvent extraction process to selectively extract and recover cerium and thorium from bastnaesite leaching was proposed, by which the purities of cerium and thorium products reached 97.2% and 96.5% with a yield of 85.4% and 98.8%, respectively.     

Ionic Liquid Extractants in Molecular Diluents: Extraction Behavior of Plutonium (IV) in 1,3-Diketonate Ionic Liquids

Abstract

Room temperature ionic liquids (RTILs) containing β-diketonate anions have been prepared and studied for the extraction of ²³⁹Pu(IV), ²³³U(VI), and ²⁴¹Am(III) from nitric acid medium. The ionic liquids such as alkylquaternaryammonium thenoyltrifluoroacetonate (R₄NTTA), and 1-alkyl-3-methylimidazolium thenoyltrifluoroacetonate (amimTTA), with methyl, butyl, hexyl, heptyl, and octyl moieties have been prepared and characterized by ¹H and ¹³C nmr and IR spectroscopy. The distribution ratio of plutonium(IV) (D _Pu(IV)) in a solution of tri-n-octylmethylammonium thenoyltrifluoroacetonate (TOMATTA) present in tri-n-octylmethylammonium bis(trifluoromethylsulfonyl)imide (TOMANTf₂) and amimTTA in amimNTf₂ was studied as a function of various parameters. The unique property of β-diketonate ionic liquids, namely, the miscibility in molecular diluents, was exploited to elucidate the mechanism of Pu(IV) extraction in these ionic liquids.     

Synergistic Extraction of U(VI), Th(IV), and Lanthanides(III) from Nitric Acid Solutions Using Mixtures of TODGA and Dinonylnaphthalene Sulfonic Acid

The extraction of U(VI), Th(IV), and lanthanides(III) from aqueous nitric acid solutions with mixtures of N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA) and dinonylnaphtalene sulfonic acid (HDNNS) in n-decane has been investigated. The extraction efficiency of U(VI), Th(IV), and Ln(III) ions is greatly enhanced by addition of HDNNS to an organic phase containing TODGA. The synergistic effect arises from the higher hydrophobicity of U(VI), Th(IV), and Ln(III) extracted species formed by TODGA and DNNS^? anions as compared to those formed by TODGA and NO₃^? ions as counter anions. The synergistic effect for U(VI), Th(IV), and Ln(III) extraction from aqueous nitric acid solutions with mixtures of TODGA and HDNNS becomes weaker when the acidity of the aqueous phase increases. A high synergistic enhancement is accompanied with a high selectivity of Ln(III) extraction from nitric acid solutions.     

Separation of rhodium(III) and iridium(IV) chlorido complexes using polymer microspheres functionalized with quaternary diammonium groups

Merrifield resin functionalized with different quaternary diammonium groups derived from ethylenediamine (EDA), tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), 1,8-diaminooctane (OMDA), 1,10-diaminodecane (DMDA) and 1,12-diaminododecane (DDMDA) were investigated for the separation of [RhCl₅(H₂O)]^2? and [IrCl₆]^2?. Selective loading of [IrCl₆]^2? in 6 M HCl medium onto the column was achieved in the presence of [RhCl₅(H₂O)]^2? by the synthesized sorbents. The iridium loading capacities were 3.80, 6.49, 13.07, 19.29, 27.09 and 4.36 mg/g for EDA, TMDA, HMDA, OMDA, DMDA and DDMDA-functionalized microspheres, respectively. The materials showed great potential for application in separating rhodium and iridium from aqueous HCl solutions.     

Synergistic Enhancement and Separation of Zirconium(IV) and Hafnium(IV) with 3-Phenyl-4-Benzoyl-5-Isoxazolone in the Presence of Crown Ethers

Abstract

3-Phenyl-4-benzoyl-5-isoxazolone (HPBI) was synthesized and examined with regard to the synergistic solvent extraction behavior of zirconium(IV) and hafnium(IV) in the presence of various crown ethers (CEs), namely, 18-crown-6 (18C6), dicylohexano-18-crown-6 (DC18C6) and benzo-15-crown-5 (B15C5) from hydrochloric acid solutions. The results demonstrated that zirconium(IV) and hafnium(IV) were synergistically extracted into chloroform with mixtures of HPBI and CEs as ZrO(PBI)₂ · CE and HfO(PBI)₂ · CE, respectively. The complexation strength follows the order DC18C6 >18C6 > B15C5. The addition of CEs not only enhances the extraction efficiency of zirconium(IV) and hafnium(IV) but also significantly, especially in the presence of B15C5, improves the selectivity (Zr/Hf = 4.73) between these metal ions as compared to HPBI alone (Zr/Hf = 2.09). On the other hand, selectivity has been moderately decreased by the addition of 18C6 or DC18C6 to the metal-chelate system.     

Extraction and separation of Pt(IV)/Rh(III) from acidic chloride solutions using Aliquat 336

Extraction and separation of Pt(IV)/Rh(III) from chloride solutions using Aliquat 336 (Quaternary ammonium salt made by the methylation of mixed tri octyl/decyl amine) diluted in kerosene as an extractant/synergist alone and mixed with organophosphorous extractants as synergists/extractants were carried out from an aqueous feed containing 0.0005 mol L⁻¹ Pt(IV)/Rh(III).Variation of hydrochloric acid concentration of aqueous phase from 0.005 to 10.0 mol L⁻¹ increased the percentage extraction of platinum up to 5.0 mol L⁻¹ there after it decreases. Whereas in the case of rhodium, from 0.005 to 1.0 mol L⁻¹ acid range the percentage extraction was decreased from 1.0 to 10.0 mol L⁻¹ acid range is favorable for extraction. Platinum(IV)/rhodium(III) separation factor of 279.2 was obtained at 1.0 mol L⁻¹ HCl concentration with 0.005 mol L⁻¹ Aliquat 336 and separation factor of 612.3 was obtained at 3.0 mol L⁻¹ HCl concentration with 0.01 mol L⁻¹ Aliquat 336. The present study optimized the various experimental parameters like phase contact time, effect of extractant, salts, temperature, loading capacity of extractant, stripping studies with various mineral acids/bases, recycling and reusing capacity of extractant up to ten cycles.     

Solvent Extraction of Au(III) by the Chloride Salt of the Amine Alamine 304 and Its Application to a Solid Supported Liquid Membrane System

Abstract

The extraction of Au(III) by the chloride salt of the amine Alamine 304 (R₃NH⁺Cl^?) in xylene from hydrochloric acid solutions has been investigated. The analysis of metal distribution data by numerical calculations suggested the formation of the species R₃NH⁺AuCl₄ ^? in the organic phase with formation constant log K _ext = 5.44. The results obtained on Au(III) distribution have been implemented in a solid‐supported liquid membrane system, where in NaSCN solutions were found to be the most effective to strip the metal from the organic solution. Influence of membrane composition, metal concentration on gold transport, and the selectivity of the system have also been studied.     

Extraction Properties of P(O)-Modified N-Aryl-Carbamoylmethylphosphine Oxides in Nitric Acid Media

Novel polyfunctional neutral organophosphorus compounds, P(O)-modified N-aryl- carbamoylmethylphosphine oxides, Ph₂P(O)CH₂C(O)NH-(o-C₆H₄)(CH₂)_n-P(O)Ph₂ and Ph₂P(O)CH₂C(O)NH-(m-C₆H₄)(CH₂)_n-P(O)Ph₂ (n = 1,2), were synthesized and studied as extractants for U(VI), Th(IV) and Ln(III) from HNO₃ solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Introduction of an additional phosphoryl group into the phenyl substitutent at the nitrogen atom of diphenyl(N-phenylcarbamoylmethyl)phosphine oxide resulted in an increase of the efficiency of U(VI), Th(IV), Ln(III), and Re(VII) extraction.     

Solvent Extraction Separation of Beryllium(ll) from Aluminum(lll) by Cyanex 921 (TOPO)

ABSTRACT

Cyanex 921, a neutral extractant, has been used for the extraction of beryllium(II)from basic media and employed for the separation of beryllium(II) in the presence of aluminum(III). Cyanex 921 diluted in cyclohexane extracted beryllium(II) in the 8–10 pH range and aluminum(III) between 4–5 pH. The selectivity of beryllium(II) over aluminum(III) was high in the 8–10 pH range. The extracted beryllium(II) was stripped with 0 M NaOH without any significant loss of the ligand while loaded aluminum(III) was stripped with 2 M HC1. The extractability of beryllium(II) and aluminum(III) was also studied separately as a function of pH, temperature, equilibration time, and stripping ability with NaOH, KOH, HCI, HNO₃, H₂SO₄, and HCIO₄. Based on these results, a sequential method was developed for the separation of beryllium(II) from aluminum(III).     

N,N′-Methylenebisacrylamide polymerization initiated by Ce(IV)—Malic acid redox system—A kinetic study

Free-radical-initiated linear cyclopolymerization of a symmetrical non-conjugated divinyl monomer, viz. N,N'-methylenebisacrylamide, was carried out using cerium sulphate as initiator and malic acid as activator, in an inert atmosphere at 25 ± 0.1°C. A gel-free polymer was formed under the experimental conditions. The order with respect to malic acid and monomer was found to be 1 and 2, respectively. The rate of polymerization was found to be inversely proportional to the concentration of Ce(IV). The overall energy of activation was found to be 25.5 kJ mol^?1. An intramolecular cyclization prior to propagation is proposed in formulating a suitable mechanism to explain the kinetic results.     

溶剂萃取法回收间氨基苯基-β-羟乙基砜

染料中间体废水所含有机物品种多、毒性大、可生化性差、环境污染严重。本文应用溶剂萃取法回收了废水中的染料中间体间氨基苯基-β-羟乙基砜。研究了萃取剂种类、溶液、pH值、稀释剂含量对萃取分配系数的影响,同时研究了萃取剂的选择性和抗疲劳性。实验结果表明,利用甲基异丁基酮做为萃取剂,盐酸做为反萃剂,相比为2:1,经两级错流萃取,可以回收91％的氨基油,且萃取剂的选择性和抗疲劳性较好。实验证明溶剂萃取法用于回收氨基油是十分可行的。     

Studies on Bi-Cyclic Aromatics Extraction using Furfural and N-Methyl Pyrrolidone (NMP) as Solvent

In this work, the separation of naphthalene, a bicyclic aromatic component, by the solvent extraction method from a model oil (p-xylene, iso-octane, and naphthalene) using furfural and n-methyl pyrrolidone (NMP) as solvent has been investigated. A four factor Box-Behnken design was used to study the individual and interactive effects of four main parameters namely paraffinic content in model oil (P/F): 0.7–0.8; solvent to feed ratio (S/F): 0.5–1.0; temperature (T): 20–40°C; time (t): 1–3 h for furfural and 1–7 h for NMP on the yield and selectivity of naphthalene. Gas chromatography was carried out to analyze the composition of raffinate and extract phases. Various polynomial models were fitted to find out the best model for the system. Pareto analysis of variance (ANOVA) and other statistical tests were performed to check the significance of the model. Furfural was found to be a better solvent as compared to NMP, both in terms of yield and selectivity. The operating conditions leading to maximum aromatic recovery have been optimized. The optimum conditions for furfural was found to be P/F = 0.7, S/F = 0.5, temperature = 24°C and time = 3 h whereas the optimum conditions for NMP were: P/F = 0.76, S/F = 0.76, temperature = 22°C, and time = 4.1 h.