磷酸三丁酯萃取硝酸的动力学

在改进的恒界面池内研究了磷酸三丁酯（ＴＢＰ）－正庚烷（ｎＣ７Ｈ１６）萃取硝酸的宏观动力学。采用热力学方法处理实验数据，计算了两相内组份的传质系数及传质阻力。研究结果表明，萃取过程的传质阻力主要在有机相内。根据动力学研究实验结果，进而分析了磷酸三丁酯萃取硝酸过程的机理，并以被萃组份的活度差为传质推动力作为计算基准建立了萃取速率的数学模型：模型计算结果与实验结果的平均相对偏差为２．５％。实验结果和理论分析表明，此萃取过程为有机相内的扩散控制机制，扩散阻力主要来自有机相内ＴＢＰ和萃合物ＨＮＯ３·ＴＢＰ分子的扩散。     

Solvent Extraction of Selenium(IV) with 2-Thenoyltrifluoroacetone

Abstract

Selenium (IV) can be quantitatively extracted at trace concentrations with 2-thenoyltrifluoroacetone-xylene (0.03 M) at pH 1.0–4.5. It is determined in the organic phase photometrically by complexation with 3,3′-diaminobenzidine. The system conforms to Beer's law in the concentration range of 22–132 μg/ml of selenium. The complex is stable. Salting-out agents have no effect on extraction. Selenium can be extracted and determined in one operation in the presence of several elements.     

Solvent and Emulsion Extractions of Gallic Acid by Tributylphosphate: Mechanisms and Parametric Study

The aim of this paper was to study solvent extraction or liquid-liquid extraction (LLE) and extraction by emulsion (ELM) of gallic acid, a biomolecule present in many plants. A mechanism involving three tributylphosphate molecules for one molecule of undissociated gallic acid with co-extraction of water was found in LLE. ELM process is as fast as LLE and more efficient; in addition, it is more environmentally-friendly because lower extractant concentrations and smaller organic phase volumes were needed.     

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.     

Separation of Electrochemically Generated Ce(IV) from Rare Earths(III) in Nitric Acid Media by TBP Impregnated Resin

Abstract

Electro‐oxidation of Ce(III) to Ce(IV) in nitric acid media at different anode materials with high oxygen evolution overpotential was carried out. Ce(IV) nitrato complexes were adsorbed on a novel resin, based on porous silica beads with immobilized polystyrene/DVB copolymer, that was impregnated with tri‐n‐butyl phosphate (TBP). Under the studied conditions, Ce(IV) sorption increased with increasing nitric acid concentration (0.5–6 mol · dm^?3). Oxidation of sorbent by adsorbed Ce(IV) species resulting in Ce(III) release to the solution was observed and thoroughly evaluated. In spite of problems with TBP leakage (12%), column separation of pure Ce(IV) from Y(III) and La(III) was achieved in 6 mol · dm^?3 HNO₃ at 288 K. Ce(IV) breakthrough capacity was 0.48 mol · kg^?1‐TBP. Column regeneration with 0.1 mol · dm^?3 nitric acid yielded Ce solution with purity higher than 99.99 wt.% with respect to La and Y impurities.     

Solvent Extraction of Pu(IV) Using TBP: A Comparative Study of n-dodecane and a Room Temperature Ionic Liquid

The extraction of Pu(IV) from nitric acid medium using TBP has been compared with two diluents using n-dodecane and a RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethanesulphonyl)imide (C₄mimTf₂N). Kinetics of extraction was slower in RTIL compared to n-dodecane. The mechanism of extraction was found to be cation exchange at lower acidity which changes to the formation of a neutral complex at higher acidity greater than 1M HNO₃ for RTIL. Back extraction of Pu from the loaded organic phase was equally effected using 0.1M oxalic acid and a mixture of guanidine carbonate and EDTA as strippant from both the extraction systems under study. Radiation stability and reusability studies showed promise for future application.     

Comprehensive Studies on Third Phase Formation: Application to U(VI)/Th(IV) Mixtures Extracted by TBP in N-dodecane

ABSTRACT

Phase splitting of tributylphosphate (TBP)/n-dodecane organic phases resulting from the extraction of UO₂(NO₃)₂, Th(NO₃)₄ and mixtures of both actinides from aqueous nitrate solutions has been investigated. Limiting organic concentrations (LOC) and metals distribution beyond third phase formation have been determined, with comparison between the cases of single metal-systems and metals mixtures. Simultaneous quantification of TBP and both metals was achieved through X-ray fluorescence (XRF) analyses. LOC studies reveal that thorium (IV) drives the third phase formation as it is the most destabilizing element in the solvent. After organic phase splitting, studies of the distributions of metals between the heavy organic phase (HOP) and the diluted organic phase (DOP) in the case of U^(VI)/Th^(IV) mixtures revealed that they are similar to those observed when both metals are alone in the solvent: Thorium (IV) has a strong affinity for the HOP, whereas uranium (VI) distributes both in HOP and in DOP. A supersaturation coefficient (N_LOC) is proposed as a new tool to account for the data obtained in the present study. Furthermore, the approach was successfully applied to analyse available data in the literature regarding thorium (IV) distribution studies after phase splitting in various TBP-alkane solvents. Such a study beyond third phase formation paves the way for studying the mechanism involved in third phase formation, as the metal is clearly identified as the key parameter.     

Extraction and Stripping Behavior of Iron (III) from Phosphoric Acid Medium by D2EHPA Alone and Its Mixtures with TBP/TOPO

In the present study an attempt has been made to understand the extraction and stripping behavior of iron (III) with D2EHPA alone and its mixture with TBP or TOPO in phosphoric acid medium. Effect of variables such as concentrations of iron (III), phosphoric acid, and phosphate in the aqueous phase, D2EHPA, TBP, and TOPO concentrations in the organic phase and temperature on the extraction process has been studied. The extraction of iron (III) decreased with increase in phosphoric acid concentration. The increase in D2EHPA concentration increased the extraction of iron (III). The presence of TOPO or TBP with D2EHPA showed antagonism. The increase in temperature decreased the extraction of iron (III) with D2EHPA alone and its mixture with either TOPO or TBP showing the exothermic nature of the extraction reaction. The stripping of iron (III) by various reagents followed the order: oxalic acid > phosphoric acid > hydrochloric acid > sulphuric acid > mixture of sulphuric and hydrofluoric acids > ascorbic acid > citric acid irrespective of extraction systems. Higher temperature favors the stripping. The effect of diluents on iron (III) extraction has also been studied. The mechanism of extraction has been explained in the light of the results obtained.     

Synergistic Extraction of Np(IV) by Mixtures of HTTA and TBP in Chloroform

Abstract

Extraction of Np(IV) from perchloric acid medium by chloroform solutions of HTTA and TBP was studied. The species Np(TTA)₄TBP was found to be mainly responsible for the observed synergism. Equilibrium constants for the extraction equilibria involved were obtained.     

Synergistic Extraction of Th(IV) by Mixtures of HTTA and TBP in Benzene

Abstract

Extraction of Th(IV) from dilute perchloric acid medium by mixtures of HTTA and TBP in benzene medium was studied. The species Th(TTA)₄ TBP was found responsible for the observed synergism. Equilibrium constants for the extraction equilibria involved are log K_A = 2.25, log K_AB = 6.88, and log β_AB = 4.63.     

Chemical Reactivity of Tributyl Phosphate with Selected Solvent Extraction Reagents

It has recently been shown that Cyanex 272 can react with tributyl phosphate (TBP) to form the corresponding butyl ester species under both commercial and anhydrous operating conditions. The present work found that acidic organic extractants MEHPA, DEHPA, Ionquest 801, Cyanex 302, Cyanex 301, and decanoic acid also react with TBP to form the corresponding butyl ester species and dibutyl phosphate under anhydrous conditions at 65°C, whereas non-acidic reagents Alamine 308, LIX 84, LIX 63, and Acorga M5640 do not. Excluding MEHPA, the rate of ester formation appears inversely correlated with the pKa of the organic acid used.     

Solvent extraction of zirconium(IV) from acidic chloride solutions using the thiosubstituted organophosphorus acids Cyanex 301 and 302

Solvent extraction of zirconium(IV) from acidic chloride solutions has been carried out with the thiosubstituted organophosphorus acids Cyanex 301 and Cyanex 302. The extraction follows an ion exchange mechanism: MO²⁺_(aq) + 2 HA_(org) ? MOA_2(org) + 2 H⁺_(aq), where, M = Zr(IV); HA = Cyanex 301 or Cyanex 302. The plots of log D (distribution ratio) vs log [HA], are linear with slopes of 2, indicating the association of two moles of extractant with the extracted metal species. The plots of log D vs log [H⁺] gave straight lines with a negative slope of 1.7 for Cyanex 301 and 1.8 for Cyanex 302, indicating the exchange of two moles of hydrogen ions for every mole of Zr(IV). Addition of sodium salts enhanced the extraction of metal. The stripping behavior of metal from the loaded organic (LO) with HCl and H₂SO₄ was studied. Increase of temperature during the extraction and the stripping stage increases the metal transfer, showing the process is exothermic. Mixed extractants, the extraction behavior of associated elements such as Hf(IV), Ti(IV), Al(III), Fe(III) and the IR spectra of the metal complexes were studied. Copyright © 2004 Society of Chemical Industry     

Speciation of Molybdenum (VI) In Aqueous and Organic Phases of Selected Extraction Systems

Abstract

The extraction study of molybdenum (VI) by 30% tri-n-butyl phosphate in n-dodecane and 0.2 M octyl (phenyl)-N,N-di-isobutylcarbamoylmethylphosphine oxide in 30% tri-n-butyl phosphate extraction systems was performed from aqueous solution containing HCl, HNO₃ and acetohydroxamic acid. Depending on extraction conditions, acetohydroxamic acid can significantly affect the speciation of molybdenum and can increase or decrease its distribution ratio. Our investigation confirmed the strong ability of the acetohydroxamic acid to form complexes with Mo even in highly acidic solutions. UV absorption spectra confirmed that a fraction of the Mo(VI)-AHA species can be present in the organic phase after extraction.     

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.     

Synergistic Extraction of Dysprosium and Aggregate Formation in Solvent Extraction Systems Combining TBP and HDBP

During treatment of nuclear fuel in the Plutonium/URanium EXtraction (PUREX) process, the extractant tri-n-butyl phosphate (TBP) is known to degrade to dibutylphosphoric acid (HDBP), which increases the extraction of metal ions, thereby inhibiting their stripping from the organic phase. To better understand this phenomenon, we investigated how mixtures of TBP and HDBP influenced the extraction of metal, nitric acid, and water, and correlated the results to aggregated structures in the organic phase. The mole ratios of TBP-HDBP mixtures had a non-linear effect on the extraction of Dy³⁺ and water from 0.2 M HNO₃, indicating synergism. In 2 M HNO₃, the TBP:HDBP mole ratio had a more linear relation to Dy³⁺ and water extraction, so the synergistic effect was less pronounced than in the low acid system. The extraction of nitric acid showed no synergistic effect and follows closely what would be expected in a system using TBP only. The small-angle X-ray scattering (SAXS) data of the 0.2 M acid system showed maximum contrast at a TBP:HDBP mole ratio of 0.25, so that the synergistic mixture is also the most aggregated at 0.2 M acid. The 2 M acid system also showed that the mixed system is more aggregated than the end members, although this does not result in peak extraction. Previous studies of synergistic extraction of metal cations explain the enhanced extraction by increased dehydration of the metal ion. Although our data do not rule out the formation of mixed complexes according to the classical mechanism of synergism, our evidence of increased water extraction and aggregate formation in systems combining TBP and HDBP are complementary to the metal-centric dehydration aspects of the process. The findings in this study give insights into the complex chemistry of solvent extraction, providing a possible link between formation of aggregates in the organic phase and synergistic extraction.     

炼油碱渣废水处理——萃取脱酚实验研究

碱渣废水是炼油厂油品精制过程产生的高浓含酚废水。本文选用磷酸三丁酯 (TBP)煤油溶液 ,研究了不同 p H值、温度、溶剂比条件下体系的萃取性能。实验表明 ,经三级萃取后废水酚含量由 10 76 7mg/ L降至 5 0 mg/ L以下 ,脱酚率高于 99.5 %。     

Decomposition of Solvent Extraction Media during Nuclear Reprocessing: Literature Review

Abstract

Reprocessing spent nuclear fuel is indispensable for the economical use of uranium in nuclear energy production, and has been used industrially for more than 40 years. These processes involve the use of an extractant/diluent (solvent) for separation of the reusable actinides from unwanted fission products. The most widely used processes employ tributyl phosphate (TBP) diluted with normal-paraffin hydrocarbon. However, on repeated use, the solvent becomes degraded due to thermal, radiolytic, and chemical attacks, resulting in chemical as well as physical damage. In view of the considerable expansion in the knowledge and understanding regarding the chemical and radiolytical decomposition of both TBP and the hydrocarbon diluent, an up-to-date review seemed appropriate. This review is concerned mainly with the mechanisms of the degradation of the solvent system. Schemes of TBP and diluent radiation-chemical transformations occurring on decomposition of the solvent system are presented.     

炼油碱渣废水处理萃取剂反萃再生实验研究

研究了磷酸三丁酯 (TBP) 煤油络合萃取剂的再生问题。萃取剂采用碱洗反萃的方式再生 ,系统地研究了反萃再生条件对萃取剂再生效果的影响。实验表明 ,经三级错流萃取后萃取剂含酚量可由约 6 0 0 0 0mg/L降至10 0 0mg/L以下 ,满足了萃取剂循环使用的要求     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.