The Extraction of Am(III) and Fe(III) by Selected Dihexyl N,N-Dialkylcarbamoylmethyl-phosphonates, -Phosphinates and -Phosphine Oxides from Nitrate Media

Abstract

A series of neutral bifunctional extractants related to dihexyl N,N,-diethylcarbamoylmethylphosphonate (DHDECMP) have been prepared and studied for the liquid-liquid extraction of Am(III) and Fe(III) from nitrate solutions. Changes in the steric bulk of the substitutent alkyl chains and in the electro-negativity of the groups attached to the phosphoryl center in these compounds have brought about large changes in distribution ratios and selectivities for the extraction of these metals. Comparisons of these extractants to related monofunctional phosphorus-based compounds have revealed that these bifunctional species behave as monodentate, rather than chelating, extractants. The presence of the carbamoyl portion of the extractant molecules is important not for coordination to the metal, but for the ability to buffer the extractant against the effects of HNO₃.     

THE EXTRACTION OF Am(III) FROM NITRIC ACID BY OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE - TRI-n-BUTYL PHOSPHATE MIXTURES

Abstract

The extraction behavior of Am(III) from nitric acid by octy1(phenyl)-N,N-diisobutylcarbamoyl methyphosphine oxides, OØD[IB]CMPO, in the presence of tributylphosphate, TBP, has been studied using diethylbenzene, decalin, and normal aliphatic hydrocarbon diluents. Relative to ØD[IB]CMPO alone, mixtures of TBP and OØD[IB]CMPO show a slight enhancement in the extraction of Am(III) from nitric acid solution above 2 M and a moderate decrease in extraction for lower acid concentrations. The net effect of TBP addition to OØD[IB]CMPO (as well as other selected carbamoyl methylphosphoryl extractants) is a relative insensitivity of the distribution ratio of Am(III) to HNO₃ concentration in the range of 0.5 M to 6 M and facilitated stripping of Am(III) with dilute acid. Since a continuous variation study of Am(III) extraction using mixtures of ØOD[IB]CMPO and TBP at a fixed total concentration revealed no evidence of a mixed complex, the TBP appears to be behaving primarily as a phase modifier

The most significant benefit gained from addition of TBP to ØD[IB]CMPO is the increased metal ion loading capacity and extractant compatibility with alicyclic and aliphatic diluents. The use of TBP to overcome phase compatibility with other bifunctional extractants of the carbamoylmethylphosphoryl type and the use of other phase modifiers with ØD[IB]CMPO have also been investigated.     

THE INFLUENCE OP THE DILUENT ON THE DISTRIBUTION BEHAVIOR OF OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPH0SPHINE OXIDE*

The degree of Interaction or compatibility of the neutral bifunctional extractant 0фD(lB)CMP0 with a diluent was determined by measuring the distribution ratio of the extractant between two phases. The distribution ratio, D_CMPO, was highest in chloro-carbon and aromatic diluents with small molar volumes and lowest in normal paraffinic hydrocarbon diluents with large molar volumes. An approximate correlation between D_CMPO in a variety of diluents and the solubility parameter (𝛅) of the diluent was obtained using equations for regular solutions and b.delta;H₂o =34.8. A much better correlation was obtained between DCMP0 find an empirical solution parameter. It was found that the distribution ratio of diisobutylcarbamoylmethylphosphine oxides increased by 3 orders of magnitude as the basicity of the phosphoryl group on the extractant was increased by the replacement of two phenyl substi-tutents on the phosphorus atom with two octyl groups

The influence of TBP as a phase modifier in 0фD (iB)CMPO -diluent systems was also studied. No evidence was found for complex formation between CMPO extractants and TBP. Changes in D_CMPO on addition of TBP appear to be essentially solvent effects. The interaction between 0фD(1B)CMP0 and diluents also explains, to some extent, variations of D_AM using different diluents.     

Reactive extraction of propionic acid using tri‐n‐octylamine,tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as diluent

BACKGROUND : Propionic acid is widely used in chemical and allied industries and can be produced by biocultivation in a clean and environmentally friendly route. Recovery of the acid from the dilute stream from the bioreactor is an economic problem. Reactive extraction is a promising method of recovering the acid but suffers from toxicity problems of the solvent employed. There is thus a need for a non‐toxic solvent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. RESULTS: The effect of different extractants (tri‐n‐butylphosphate (TBP), tri‐n‐octylamine (TOA) and Aliquat 336) and their mixed binary solutions in sunflower oil diluent was studied to find the best extractant‐sunflower oil combination. Equilibrium complexation constant, K_E, values of 4.02, 3.13 and 1.87 m³ kmol^?1 were obtained for propionic acid extraction using Aliquat 336, TOA and TBP, respectively, in sunflower oil. The effect of different modifiers (1‐decanol, methylisobutyl ketone, butyl acetate and dodecanol) on the extraction was also studied and it was found that modifiers enhance extraction, with 1‐decanol found to be the best. CONCLUSION: The problem of toxicity in reactive extraction can be reduced by using a non‐toxic diluent (sunflower oil) or a modifier in a non‐toxic solvent, with the extractant. The addition of modifiers was found to improve the extraction. Copyright © 2008 Society of Chemical Industry     

A Review of New Developments in Amine Solvent Extraction Systems for Hydrometallurgy

Abstract

Amine extractants, regardless of structure, have been of limited utility for the extraction of complex metallic anions from alkaline solution due to an inability to increase the amine's basicity. This situation is contrasted to acid extractants in which case such control of extractant strength is possible. Recent studies with amine extractants have shown that the use of specific modifiers allows for the control of amine basicity over an appreciable pH range for certain anions. Particularly significant is the potential for the extraction of gold from alkaline cyanide solutions.     

Nitric Acid Extraction into the TODGA/TBP Solvent

The tridentate diglycolamide ligand N,N,N′,N′-tetraoctyl diglycolamide (TODGA) shows many interesting properties and is a very good extractant for the minor actinides (MAs) and lanthanides but, due to its low loading capacity, requires a phase modifier when used in a solvent extraction process. Consequently, applications of TODGA in conjunction with tri-butyl phosphate (TBP) in novel DIAMEX and SANEX processes for recovering MAs have been reported. However, TODGA and TBP also extract nitric acid and this has a significant influence on process performance. Here new distribution data for the extraction of nitric acid into solvent phases containing TODGA and TBP have been collected and modeled using an equilibrium-based approach accounting for nitric acid activities in the aqueous phase. Models for the extraction of nitric acid using the individual extractants were obtained using a variety of complexes and these were then combined to give the extraction of the mixed TODGA and TBP solvent. Using this approach, the nitric acid extraction of the mixed TODGA/TBP system can be reliably reproduced indicating that no significant synergistic or antagonistic complexes are formed in solution.     

Synergistic Effects in the Extraction of Uranium(VI) by Di-4-octylphenyl Phosphoric Acid

Abstract

The extraction of uranium(VI) from sulfuric acid solutions by di-4-octylphenyl phosphoric acid (DOPPA) is enhanced by the addition of neutral organophosphorus compounds due to synergistic action. The effect of tri-n-butyl phosphate (TBP), dibutylbutyl phosphonate (DBBP), and tri-n-octyl phosphine oxide (TOPO) was studied. The synergistic effect increased in this order. In the case of TBP and DBBP the extraction coefficient for U(VI) decreased with increasing concentration of synergistic agent after reaching a maximum. With TOPO, on the other hand, there was an increase even after this limit. This was because of the extraction of uranium by TOPO itself. The effect of uranium loading in the organic phase on the synergistic behavior was studied and the results were compared with those obtained with di-2-ethylhexyl phosphoric acid (DEHPA) in the presence of the same synergistic agents. The results with these two extractants indicate that with TOPO the synergism is mainly due to the formation of substitution products of the type UO₂A₂B₂ and with TBP addition products of the type UO₂(HA₂)₂B.     

Selected Alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine Oxides as Extractants for Am(III) from Nitric Acid Media

Abstract

A new series of neutral bifunctional extractants, alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides, has been prepared and studied as extractants for Am(III) from nitric acid media. Two types of alkyl(phenyl)-N,N-dialkyl CMPO compounds were prepared, one containing N,N-diethyl groups and the other containing N,N-diisobutyl groups. The N,N-diethyl series contained hexyl(phenyl) and 6-methylheptyl(phenyl) derivatives, abbreviated HφDECMPO, and 6-MHφDECMPO, respectively. The N,N-diisobutyl series contained the n-octyl(phenyl), 6-methylheptyl(phenyl), and the 2-ethylhexyl(phenyl) derivatives, abbreviated OφD[IB]CMPO, 6-MHφD[IB]CMPO, and 2-EHφD[IB]CMPO, respectively. Third power extractant dependencies for the extraction of Am(III) from 0.5 and 3 M HNO₃ were obtained at low (<0.25 M) concentrations of extractant, but higher power dependencies were obtained above 0.25 M extractant from 3 M HNO₃. The HφDECMPO, 6-MHφDECMPO, 6-MHφD[IB]CMPO, and OφD[IB]CMPO [all 0.5 M in diethylbenzene (DEB)] are significantly better extractants than DHDECMPO for Am(III) from 1 to 6 M HNO₃. These same extractants have lower D _Am values than DHDECMPO at low acidities. HφDECMPO and OφD[IB]CMPO also have better selectivity for Am(III) over Fe(III) than DHDECMPO. HφDECMPO in DEB has a strong tendency toward the formation of a second liquid organic phase on extracting macroconcentrations of Nd(III) and U(VI) from 3 M HNO₃; however, this behavior is substantially diminished with the OφD[IB]CMPO and 6-MHφD[IB]CMPO compounds.     

Reactive extraction of itaconic acid using tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as a non‐toxic diluent

Itaconic acid finds a place in various industrial applications. It can be produced by biocultivation in a clean and environment friendly route but recovery of the acid from the dilute stream of the bioreactor is an economic problem. Reactive extraction is a promising method to recover carboxylic acid but suffers from toxicity problems of the diluent and extractant employed. So there is need for a non‐toxic extractant and diluent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. Effect of different extractants: tri‐n‐butylphosphate (TBP) (an organophosporous compound) and Aliquat 336 (a quaternary amine) in sunflower oil was studied to find the best extractant–sunflower oil combination. Equilibrium complexation constant, K_E, values of 1.789 and 2.385 m³ kmol^?1, respectively, were obtained for itaconic acid extraction using TBP and Aliquat 336 in sunflower oil. The problem of toxicity in reactive extraction can be reduced by using a natural non‐toxic diluent (sunflower oil) with the extractant. Copyright © 2010 Society of Chemical Industry     

NON-DISPERSIVE LIQUID EXTRACTION OF Cr(VI) BY TBP/ALIQUAT 336 USING CHITOSAN-MADE HOLLOW FIBER

ABSTRACT

TBP and alkylammonium extractants were investigated for chromate removal from dilute solutions using chitosan-made hollow fibers. Chromate is adsorbed by the chitosan fiber and simultaneously desorbed by the extractant. The influence of chromate concentration, extractant concentration, extractant volume on relative concentration deccrease were investigated as a function of time. These experimental parameters barely influenced the decrease in the relative concentration. Fiber length is more significant in the control of the extraction kinetics. In recirculation flow mode, the relative concentration can be well described as an exponential function of time. The kinetic constant varies as a linear function of fiber length. Amine extractants (Aliquat 336, Alamine 336, Amberlite LA-2) are better extractants than TBP both from the kinetics and equilibrium standpoints. With Aliquat 336 the final Cr(VI) concentration tends to zero, while with TBP, the equilibrium is controlled by the volume of the extractant.     

THE EXTRACTION OF SOME BASE METAL IONS BY CYANEX 30L CYANEX 302 AND THEIR BINARY EXTRACTANT MIXTURES WITH ALIQUAT 336

ABSTRACT

The extraction behaviour of Cyanex 301, Cyanex 302 and their binary extractant mixtures with Aliquat 33b towards copper(II), zinc(II), iron(III), iron(II), cobalt(II), nickel(II) and manganese(Il) is indicated. The extraction data were collected from sulphate solutions with acidities ranging from pH 10 to 8 mol/dm³ sulphuric acid. Cyanex 301 is a more efficient extractant than Cyanex 302 and is able to effect extraction at greater acidities. In combination with the organic base Aliquat 336 the extraction power of these extractants is lowered and in some cases the extraction is suppressed appreciably. However, the suppression of extraction can be useful in metal separation and affords greater control over the back-extraction. The suppression is ascribed to the high stability of the acid-base couple which must dissociate in order to effect extraction.     

INFRARED STUDIES OF BIFUNCTIONAL EXTRACTANTS*

The infrared spectra of a series of neutral bifunctional extractants were examined. The carbonyl and phosphoryl stretching regions were monitored for changes as nitric or hydrocloric acid was extracted and as Nd(III) or Sm(III) was extracted. It was found that the phosphoryl group is the primary site of extraction as was predicted from solvent extraction measurements. Upon heavy loading of the metal ion in the organic phase, the extractant OφD(iB)CMP0 (octyl(phenyl)-diisobutylcarbamoylmethylphosphine oxide) can behave as a bidentate ligand as does the analogous di-hexyl-N,N-diethylcarbamoylmethylphosphonate solid state complex. The tendency for the carbonyl oxygen to form a bond directly to the metal ion is enhanced in chloride media at low acidity. The spectra of mixtures of 0φD(iB)CMP0 with the phase modifier TBP indicate no interaction between the two extractants and TBP does not appear to be part of the primary metal-extractant complex.     

Development of a TODGA based Process for Partitioning of Actinides from a PUREX Raffinate Part I: Batch Extraction Optimization Studies and Stability Tests

Abstract

The extractant, N,N,N′,N′‐tetraoctyl diglycolamide (TODGA) has been evaluated for the separation of actinides(III) and lanthanides(III) from a high active raffinate (HAR). The effect of oxalic acid and HEDTA complexant on the extraction of actinides(III), lanthanides(III), and important fission products (e.g. Mo, Pd, Sr, Zr, Ru etc.) from synthetic HAR has been studied with 0.2 mol/L TODGA in TPH. With an extractant mixture of TODGA and tributyl phosphate (TBP) the amount of oxalic acid can be reduced to less than 0.3 mol/L for the effective complexation of zirconium, whereas the distribution ratios of actinides(III) and lanthanides(III) are still high for the separation from HAR. Furthermore the maximum loading of lanthanides (e.g. Nd) can be significantly increased by adding TBP to the extractant. However, the extraction of oxalic acid and nitric acid also increased by the addition of TBP, which can lead to problems during back extraction of the loaded extractant. Extraction studies after radiolysis and hydrolysis reveal that the TODGA+TBP mixture is a sufficient stable extraction system suited for further process development studies.     

Intensification of Nicotinic Acid Separation using Organophosphorous Solvating Extractants by Reactive Extraction

Nicotinic acid (3‐pyridine carboxylic acid) is widely used in food, pharmaceutical, and biochemical industries. Compared to chemical methods, enzymatic conversion of 3‐cyanopyridine is an advantageous alternative for the production of nicotinic acid. This study is aimed to intensify the recovery of nicotinic acid using reactive extraction with organophosphorus solvating extractants such as tri‐n‐octyl phosphine oxide (TOPO) and tri‐n‐butyl phosphate (TBP). The distribution of nicotinic acid between water and phosphorus‐based solvents dissolved in various diluents and the comparison of extraction efficiency with pure diluents are studied at isothermal conditions. Pure diluents are not found to be good extracting agents and the maximum distribution coefficient (K_D) obtained with 1‐octanol is 0.31. Experimental studies are carried out to investigate the effect of diluent, initial acid concentration, extractant type, and extractant composition on the degree of extraction. The maximum recovery of nicotinic acid is obtained by dissolving TOPO in MIBK at an initial nicotinic acid concentration of 0.10 kmol/m³. Solvation numbers and extraction equilibrium are also estimated with both TBP and TOPO.     

Solvent Extraction and Emulsion Separation in Magnetic Fields

Abstract

In two-phase emulsion separations, it is customary to employ large settling volumes (for mixer-settling apparatus) or large centrifugal forces (for centrifugal contactors). Improvement can sometimes be achieved by using an extractant with magnetic properties in the presence of a variable field. In the work reported in this paper, two different extractants (D-2EHPA and TBP) were employed in magnetic field experiments. These compounds are both stable and resistant to acid (15% H₂SO₄) and basic (NaOH, pH = 10) media. The test results for extraction of Cu²⁺ (with D-2EHPA) and UO₂ ²⁺ (with TBP) from aqueous media were positive. The emulsion separation for these two systems in the presence of a magnetic field was 160 times faster than in the gravitational field alone.     

Role of Acetohydroxamic Acid in Selective Extraction of Technetium and Uranium Employing N,N-Dihexyloctanamide as Extractant

Straight chain N,N-dihexyloctanamide (DHOA) has been identified as a promising alternate extractant to tributyl phosphate (TBP) for the reprocessing of uranium based spent fuels. The present work compares extraction behavior of technetium using DHOA and TBP solutions in n-dodecane, under varying experimental conditions such as acidity (0.5–6 M HNO₃); extractant concentration (1.1 and 1.5 M), and uranium loading (50 g/L, relevant for Pu rich spent fuel feed solutions). The effect of acetohydroxamic acid concentration on U, Pu, Np, and Tc extraction behavior has also been investigated. Pu(IV)-AHA interaction and its influence on extraction using TBP and DHOA extractants has been studied spectrophotometrically. The experimental data suggest that 1.1 M DHOA is better than 1.1 M TBP with respect to co-extraction of Tc and U, and U decontamination with respect to Np/Pu.     

Efficacy of tri-n-octylamine,tri-n-butyl phosphate and di-(2-ethylhexyl) phosphoric acid for reactive separation of protocatechuic acid

ABSTRACT

Owing to its chemical and pharmacological significances, the efficacy of reactive separation of protocatechuic acid (0.001–0.01 kmol m^?3) from aqueous stream by means of tri-n-octylamine (TOA), di-2-ethylhexyl phosphoric acid (D2EHPA) as well as tri-n-butyl phosphate (TBP) in octanol has been investigated, in terms of extraction efficiency, loading ratio, equilibrium complexation constants, and distribution coefficients. Extraction ability was obtained in the order TOA (91.2%) > TBP (88.64%) > D2EHPA (86.43%). In all cases, 1:1 protocatechuic acid:extractant complex is obtained. Further, diffusion coefficients, number of stages for extraction systems, and relative basicity model were used for relating the efficacy.     

ACTIVITY COEFFICIENTS OF CARBAMOYLMETHYLPHOSPHORYL EXTRACTANTS IN TOLUENE*

The activity coefficients of four extractants belonging to the carbamoylmethylphosphoryl class were measured by vapor-phase osmometry. All of the activity coefficients were within 15% of unity for concentrations up to 0.5 M in toluene. As the basicity of the extractant's phosphoryl-group increases, its activity coefficient decreases. Octylphenyl-N,N-diisobutylcarbamoylmethyl-phosphine oxide [OφD(iB)CMPO] in toluene exhibited a marked decrease in activity coefficient upon equilibration with water or nitric acid. This helps explain a negative deviation from a third-power extractant dependency exhibited by americium distribution ratios, D_AM, from 0.500 M HNO₃. A positive deviation from a third-power extractant dependency, of D_AM for Am extracted from 5.00 M HNO₃, is explained by the alteration of the diluent's physico-chemical properties as its nitric acid content Increases. The extraction of nitric acid and water by toluene solutions of 0φD(iB)CMPO was also measured.     

乙醇酸与乙醛酸的萃取分离

以乙醇酸和乙醛酸的稀溶液为分离对象,采用三烷基氧磷 (TRPO)为萃取剂、甲基异丁基酮 (MiBK)为稀释剂,研究了单、双溶质有机酸的萃取分离特性,测定了TRPO、有机酸的浓度等因素对单、双溶质有机酸萃取平衡的影响,在适当假定的基础上,建立了描述TRPO萃取乙醇酸、乙醛酸单、双溶质特性的数学模型.结果表明,随TRPO浓度的增大,分离系数β_{（glycolic /glyoxylic）}由小于1逐渐增大至大于1,乙醇酸与TRPO的萃合物有1∶1和1∶2两种形式,采用单溶质萃取反应平衡常数预测双溶质萃取的结果,预测值与实验值相当接近.同时,还对三烷基胺、磷酸三丁酯等萃取剂分离乙醇酸和乙醛酸的特性进行了讨论.     

Extraction Behavior of Am(III) and Eu(III) from Nitric Acid Medium in Tetraoctyldiglycolamide-Bis(2-Ethylhexyl)Phosphoric Acid Solution

The extraction behavior of Am(III) and Eu(III) in a solution of tetra-octyldiglycolamide (TODGA), bis(2-ethylhexyl)phosphoric acid (HDEHP), and n-dodecane (n-DD) was studied to understand the role of TODGA and HDEHP in the combined solvent system. The extraction behavior of these metal ions was compared with those observed in TODGA/n-DD and HDEHP/n-DD. The effect of various parameters such as concentrations of HNO₃, TODGA, and HDEHP on the distribution ratio of Am(III) and Eu(III) was studied. Synergistic extraction of both the metal ions observed at lower acidities (<2.0 M) was attributed to the involvement of TODGA and HDEHP for extraction. However, the extraction of Am(III) and Eu(III) in the combined solvent was comparable with that observed in TODGA at higher acidities. The slope analysis of the extraction data confirmed the involvement of both the extractants at all acidities investigated in the present study.