Plutonium Loading of Prospective Grouped Actinide Extraction (GANEX) Solvent Systems based on Diglycolamide Extractants

The Grouped Actinide Extraction (GANEX) process is being developed for actinide recycling within future nuclear fuel cycles. Interactions between potential solvents and macro-concentrations of plutonium are one of the most important issues in defining the GANEX process. Surprisingly, plutonium loading of diglycolamide (DGA) based solvents such as tetra-octyl DGA (TODGA) causes precipitation rather than a conventional third phase, in direct contrast to results with U(VI), Th(IV) or lanthanide ions. Various DGA based solvent systems have been screened for their plutonium loading capacity and 0.2 M TODGA with 0.5 M DMDOHEMA in a kerosene diluent is selected as the optimum solvent formulation of those tested. Plutonium can be relatively easily stripped from this solvent using aqueous acetohydroxamic acid but this is very acid dependent in the low acidity region.     

Solvent Extraction and Spectrophotometric Studies on Synergistic Extraction of Plutonium(IV) by Mixtures of Thenoyltrifluoroacetone (HTTA) and Tri-n-butylphosphate (TBP) in Benzene

Abstract

The synergistic extraction of Pu(IV) from perchloric acid solutions into mixtures of thenoyltrifluoroacetone (HTTA) and tri-n-butylphosphate (TBP) in benzene was investigated by solvent extraction methods. The adduct responsible for synergism was found to be Pu(TTA)₄·TBP. The adduct formation between Pu(TTA)₄ and TBP in the benzene phase was also investigated by spectrophotometry. The equilibrium constants for the equilibria involved were obtained both by solvent extraction and by spectrophotometric methods.     

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.     

TRPO Impregnated Levextrel Resin: Synthesis and Extraction Behavior of Zr (IV) and Nd (III) Ions

A novel kind of Levextrel resin with trialkylphosphine oxide (TRPO) extractant impregnated in the styrene-divinylbenzene copolymerization was synthesized. The extraction behavior of the resin toward Zr (IV) and Nd (III) ions was investigated by batch and column operations. The influence factors such as suspension system, porogen content, stirring rate, and temperature were systematically examined. The TRPO impregnated Levextrel resin showed excellent extraction ability toward the metal ions. The adsorption capacity of 47 mg/g for Zr (IV) ion and 48 mg/g for Nd (III) ion could be obtained in 1.0 g/L solutions. The fast kinetics in the extraction process was another noteworthy feature of the resin. The numerous micro- and macro-pores in the internal resin facilitated the mass transfer, and the equilibrium could be reached in only tens of minutes. Besides, the cyclic operations showed that the resin had a reliable performance and could be conveniently recovered. The TRPO impregnated Levextrel resin possesses the potential for the removal of the lanthanides and actinides ions in radioactive liquid waste.     

N8161 萃取铼(Ⅶ)的热力学

以萃取剂N8161、稀释剂正庚烷研究了萃取铼的热力学. 在N8161 (NH4)ReO4 n C7H16 HCl H2O体系中,在温度278.15~298.15 K和离子强度0.1~2.0 mol/kg范围内,以NH4Cl为支持电解质,在HCl体系中测定了萃取平衡水相中的ReO4 浓度和pH值. 计算了萃取反应的标准平衡常数K0,并得到经验公式logK0 23.0353 4330.282T 1 0.04831T, 同时计算了萃取反应的其它热力学量,指出焓和熵是该萃取过程的推动力.     

Studies on the Separation and Recovery of Plutonium from Nitric Acid Medium using Di-nonyl Phenyl Phosphoric Acid (DNPPA) / n-Dodecane as Extractant System

This paper deals with the studies on the separation and recovery of plutonium from nitric acid medium using Di-nonyl phenyl phosphoric acid (DNPPA) in n-paraffin as an extractant system. The different extraction parameters were investigated. The percentage extraction of plutonium decreased with increase in nitric acid concentration. The optimum solvent concentration for quantitative separation of plutonium from aqueous feed solution was 0.15 M of DNPPA whereas n-paraffin/n-dodecane was the most suitable of diluents with an organic to aqueous phase ratio of 1:1. Among the various strippants used, 0.5 M solution of (NH₄)₂CO₃ was found to be the most suitable for back extraction of plutonium from the loaded organic phase. The developed method was used to separate and recover plutonium from actual wash solution of ion exchange column used for plutonium purification. More than 73% of plutonium was separated from 7 M HNO₃ wash solution using 0.15M of DNPPA in n-dodecane.     

天然氨基酸作用下丙交酯的开环聚合反应

研究了天然氨基酸作用下丙交酯的开环聚合反应,探讨了氨基酸的酸碱性、浓度、反应条件等对聚合物相对分子质量的影响。结果表明,碱性氨基酸作用下丙交酯的开环聚合可以进行;在D, L-丙交酯的开环聚合反应中,随着氨基酸碱性的增强,聚合物的相对分子质量增大;在反应时间为48 h、反应温度为150 ℃、D,L-丙交酯/L-赖氨酸=50/1（物质的量比,下同）的条件下,可得到重均相对分子质量为12800 g/mol、相对分子质量分布为2.11的聚丙交酯;在D,D-丙交酯和L,L-丙交酯的开环聚合反应中,氨基酸的碱性越强,得到的聚合物的消旋作用越明显。     

Extraction Behavior of Ln(III) Ions by T2EHDGA/n-Dodecane from Nitric Acid and Sodium Nitrate Solutions

The diglycolamide extractant T2EHDGA has proven to be promising for the separation of lanthanides and minor actinides in high-level nuclear waste reprocessing. This neutral extractant has shown significant extraction capacity for HNO₃ into the nonpolar organic phase, along with hyper-stoichiometric nitrate dependence on extraction of trivalent f-elements. The transport behavior of T2EHDGA/n-dodecane toward trivalent lanthanides is not well understood. This work found a significant increase in distribution ratios for Eu(III) extracted from aqueous HNO₃ media compared with that from NaNO₃. The extraction of Eu(III) from HNO₃ results in a different thermodynamic product than predicted by classic solvent extraction of 3:1 ligand–metal complex as observed with NaNO₃ in FTIR and UV-vis spectroscopy. Experimental distribution measurements in conjunction with mass-action modeling using the solvent extraction modeling program SXLSQI suggest participation of 1 to 2 HNO₃ molecules in the Eu(III)/T2EHDGA complex upon extraction from HNO₃ media, indicative of a mechanism change responsible for the enhanced extraction behavior toward lanthanides in the presence of HNO₃.     

Synergic Extraction of Folic Acid with Di(2-ethylhexyl) Phosphoric Acid and Amberlite LA-2

The influences of extractants concentrations and solvent polarity on the efficiency of folic acid separation by synergic extraction with Amberlite LA-2 and di(2-ethylhexyl) phosphoric acid (D2EHPA) mixture have been analyzed. The results indicated the formation of an interfacial compound which includes one molecule of folic acid and one of D2EHPA, the hydrophobicity of this compound being increased by solvation with Amberlite LA-2 molecules. The number of aminic molecules participating in the interfacial complex formation is controlled by solvent polarity and D2EHPA concentration, decreasing from 3 to 1 with the increase of these two parameters. The results indicated that the most important synergic effect corresponds to the extractants mixture dissolved n-heptane, at low D2EHPA concentration in the organic phase (5 g/l).     

A Kinetic and Mechanistic Study on the Oxidation of Hydroxy Acids by <Emphasis Type="Italic">N</Emphasis>-Bromophthalimide in the Presence of a Micellar System

The kinetics of oxidation of some α-hydroxy acids viz. Tartaric acid (TA) and Malic acid (MA) by N-bromophthalimide (NBP) were studied in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), in perchloric acid medium at 313 K. The oxidation of TA and MA by N-bromophthalimide in the presence of CTAB is faster than in the absence of surfactant. The rate of oxidation of hydroxy acids was found to be in the order: TA > MA. First order kinetics with respect to NBP was observed in the oxidation of both hydroxy acids. The kinetics results indicate that the first order kinetics in hydroxy acids at lower concentrations tends towards a zero order at its higher concentrations. Inverse fractional order in [H⁺] and [phthalimide] were noted throughout its tenfold variation. With a progressive increase in [CTAB], the rate of reaction increased, reaches a maximum value and then constancy in k _Ψ was observed. Variation of [Hg(OAc)₂] and ionic strength (μ) of the medium did not bring about any significant change in the rate of reaction. The applicability of different kinetic models viz. the Piszkiewicz cooperative model, the Raghvan and Srinivasan model, and the Menger–Portnoy model were tested to explain the observed micellar effects. The effect of [CTAB] on the activation parameters was explored to rationalize the micellar effect. The values of rate constants observed at four different temperatures were utilized to calculate the activation parameters. A suitable mechanism consistent with the experimental findings has been proposed. The index of cooperativity and the micelle binding constant have been calculated.

Extraction behavior of Am(III) and Eu(III) by tri-n-octylmethylammonium diglycolamate ionic liquid impregnated XAD-7

Aliquat-336-based strongly hydrophobic ionic liquid, tri-n-octylmethylammonium diglycolamate ([A336]⁺[DGA]^?), was prepared and impregnated in Amberlite XAD-7 (abbreviated as [A336]⁺[DGA]^?/XAD-7) for studying the extraction behavior of Am(III) and Eu(III) from nitric acid medium. The distribution ratio of Am(III) and Eu(III) in [A336]⁺[DGA]^?/XAD-7 decreased with an increase in the concentration of nitric acid and the mechanism of trivalent metal ion extraction in the resin phase was elucidated. The uptake of Am(III) and Eu(III) in [A336]⁺[DGA]^?/XAD-7 followed a second order and from the Langmuir adsorption model the apparent europium extraction capacity was determined. The conditions needed for efficient separation of Am(III) from Eu(III) was optimized.     

氢化可的松母液错流萃取行为研究

将氢化可的松母液解析为氢化可的松、表氢化可的松和６α－羟基ＲＳ三种组分，模拟了母液的表观分配系数。拟合结果与实验值符合较好，平均相对误差＜５．５％。     

Separation of U(VI) and Th(IV) from Nd(III) by Cross-Current Solvent Extraction Mode Using Tri-iso-amyl Phosphate as the Extractant

Separation of U(VI) and Th(IV) from Nd(III) in nitric acid media with solutions of tri-iso-amyl phosphate (TiAP) in n-dodecane has been studied by batch extraction in cross-current mode to evaluate the feasibility of employing TiAP as an alternate extractant to tri-n-butyl phosphate (TBP) for monazite ore processing. The interference of U(VI), Th(IV), and Nd(III) in the presence of each other during their analyses by titrations has also been validated in the present study. The extraction studies substantiate that the high solvent loading conditions can be achieved without organic phase splitting in the extraction from concentrated feed solutions with TiAP based solvents, whereas TBP forms third phase under such conditions. The separation factor for Th(IV) with respect to Nd(III) can be improved with TiAP as the extractant and by carrying out the extraction with feed solution in 8 M HNO₃. Solvent extraction studies conducted with solutions of U(VI), Th(IV), and Nd(III) in nitric acid media by TBP and TiAP revealed the identical extraction, scrubbing, and stripping behavior of both the extractants with respect to U(VI), Th(IV), and Nd(III). The results insinuate that TiAP can be used as an alternate extractant to TBP for the separation of U(VI) and Th(IV) from monazite ores. The data generated in the present study can be exploited for the development of flow sheets using TiAP based solvents to separate U(VI) and Th(IV) from rare earths for the processing of monazite leach solutions.     

The Influence of Extractant Structure on the Solvent Extraction of Uranium(VI) and Thorium(IV) from Nitrate Media by Dialkyl Sulphoxides

The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate solutions (0·20–6·00 M ) by a series of dialkyl sulphoxides with different structures was studied. For sulphoxides with n-alkyl groups (R₂SO, where R = n-hexyl, n-octyl and n-decyl) using 0·20 M solutions in xylene, the extractions of both uranium and thorium are relatively high, and the values of the separation factor β_Th^U are correspondingly low (≈20). Replacement of an n-hexyl group by a cyclohexyl group has little effect on metal extraction, whilst the introduction of a second cyclohexyl group causes a slight decrease in extraction. Similarly, there is little variation in the extraction of uranium and thorium through the series of asymmetrical compounds RR′SO, where R = n-octyl and R′ = cyclopentyl, cyclohexyl or cyclooctyl. When two aromatic (phenyl) rings are introduced into the sulphoxide, however, the extraction of both metals falls to zero. For the series of isomeric compounds R₂SO with C₈ alkyl groups, the separation factors increase in the order: R = n-octyl, 2-ethylhexyl, 2-octyl, 3-octyl, which is also the order of increasing steric bulk of the alkyl group. For these compounds, slope analysis studies are consistent with the formulation of the extracted metal complexes as UO₂(NO₃)₂(R₂SO)₂ and Th(NO₃)₄(R₂SO)₃. © 1997 SCI.     

Equilibrium Analysis of Aggregation Behavior in the Solvent Extraction of Cu(II) from Sulfuric Acid by Didodecylnaphthalene Sulfonic Acid

Abstract

By use of the principles of equilibrium analysis, the liquid-liquid cation exchange of Cu(II) from aqueous sulfuric acid at 25°C by didodecylnaphthalenesulfonic acid (HDDNS) in toluene may be understood in terms of small hydrated aggregated species in the organic phase. Extraction data have been measured as a function of organic-phase HDDNS molarity (1.0 × 10^?4 to 1.0 × 10^?1), aqueous copper(II) sulfate molarity (1.2 × 10^?8 to 1.3 × 10^?2), and aqueous sulfuric acid molarity (0.03 to 6.0). Graphical analysis of linear regions of the data support a model in which organic-phase aggregates of HDDNS function by cation exchange to incorporate Cu(II) ions with no apparent change in aggregation number at low loading. Supporting FTIR spectra and water-content measurements of HDDNS solutions in toluene show that the HDDNS aggregates are highly hydrated. By use of the computer program SXLSQA, a comprehensive equilibrium model was developed with inclusion of activity effects. Aqueous-phase activity coefficients and degree of aqueous bisulfate formation were estimated by use of the Pitzer treatment. Organic-phase nonideality was estimated by the Hildebrand-Scott treatment and was shown to be a negligible effect under the conditions tested. Excluding aqueous sulfuric acid molarities greater than 1, it was possible to model the data to within experimental error by assuming only the equilibrium extraction of Cu²⁺ ion by the aggregate (HDDNS)₄(H₂O)₂₂ and the equilibrium dissociation of (HDDNS)₄(H₂O)₂₂ to the monomer. The dependence of Cu(II) distribution on aqueous sulfuric acid molarity was shown to be quantitatively consistent with a cation-exchange process. In comparison with the graphical approach, the computer analysis allows comprehensive model testing over large, nonlinear data sets and eliminates the need to make limiting assumptions. Overall, the results provide useful insight toward the development of selective synergistic extraction systems in which HDDNS provides a nonselective cation-exchange vehicle in combination with a selective second extractant.     

Influence of Poly(L-lactic acid) Molecular Weight on the Encapsulation Efficiency of Urea in Microcapsule Using a Simple Solvent Evaporation Technique

Poly(L-lactic acid) microencapsulated urea was prepared in water-in-oil-in-water (W₁/O/W₂) system by the solvent evaporation technique. The influence of poly(L-lactic acid) molecular weight on the percent loading, encapsulation efficiency, and the microcapsule morphology was studied using poly(L-lactic acid) having different number average molecular weights (M_n). Using the higher M_n, the smoother shell with complete encapsulation microcapsules was formed. Moreover, the percent loading and encapsulation efficiency of urea also increased with the poly(L-lactic acid) molecular weight. At 80,000 g/mol of poly(L-lactic acid), the obtained microcapsule gave the highest both percent loading (32%) and encapsulation efficiency (56%). The urea control release study of the prepared microcapsules was implemented by in vitro testing. The encapsulated urea was gradually released from the microcapsules, approximately 53, 29, and 22% of poly(L-lactic acid) at 3,000, 30,000, and 80,000 g/mol, respectively, for a month. These results presented the possibility of the prepared poly(L-lactic acid) microcapsules-encapsulated urea for urea control release that could be utilized in agricultural applications.     

细雕刻肋海胆性腺脂肪酸的超声波提取与化学成分分析

采用Folch液超声提取细雕刻肋海胆性腺中脂肪酸类脂,经氢氧化钾皂化、甲醇-三氟化硼法甲酯化后,以毛细管气相色谱法、气相色谱-质谱联机技术进行了成分分离分析,配合以线性程序升温等当碳长度值结合标准品对照的方法,对样品中的脂肪酸甲酯定性,用峰面积归一化法定量,并且将脂肪酸甲酯的相对质量分数近似认定为脂肪酸的相对质量分数。鉴定了34种脂肪酸,占峰面积的92.5%。样品中不饱和脂肪酸质量分数超过60%,脂肪酸主要成分(质量分数)为:十六碳酸(13.72%),(Z,Z,Z,Z,Z)-5,8,11,14,17-二十碳五烯酸(12.77%)、(Z,Z,Z,Z,Z,Z)-4,7,10,13,16,19-二十二碳六烯酸(10.63%)、E-6-十八碳烯酸(9.45%)、硬脂酸(7.98%)、Z-11-十八碳烯酸(6.43%)。