二（2—乙基已基）磷酸从含氟稀土硫酸溶液中萃取铈的机制

研究了二（２－乙基已基）磷酸（ＤＥＨＰＡ）－磺化煤油体系从氟碳铈矿氧化焙烧－硫酸浸出液中萃取Ｃｅ＾４＋的机制,发现水相中Ｆ＾－和Ｃｅ＾４＋同时被萃入有机相,通过斜率法和研究平衡有机相中ｃＦ－／ｃＣｄ＾４＋和初始水相酸度、初始水相氟离子浓度、有机相浓度之间的关系,推测出Ｆ＾－和Ｃｅ＾４＋以ＣｅＦ２Ａ２形式被ＤＥＨＰＡ萃入有机相。     

从含氟硫酸稀土溶液中萃取铈过程产生第三相的原因

研究了二（2－乙基己基）磷酸（DEHPA）从含氟硫酸稀土溶液中萃取Ce4 过程中生成第三相的组成。运用X荧光光谱法和化学法测定了有机相中析出沉淀物的成分。并分析其原因,发现产生第三相主要是由于有机相对Ce^4 的还原作用造成的。研究了有机相的还原性,进而找出抑制其还原作用,避免第三相生成的方法。     

十四烷基二甲基苄基氯化铵萃取Au(CN)-2的微观机理

通过萃取平衡、傅里叶变换红外光谱及分峰技术研究了季铵盐十四烷基二甲基苄基氯化铵 ( TDM-BAC) -磷酸三丁酯 ( TBP) -正庚烷体系萃取 Au( CN) - 2 的机理及过程 .提出了萃合物的结构模型是基于氢键的超分子体系 ,组成为 [R4N+]· [Au( CN) - 2 ]· 4 H2 O· 4 TBP.当有机相金浓度大于 3g·L- 1 时 ,有机相中存在聚集现象 .通过激光光散射技术测定了有机相中反向胶团的大小 ,表明萃取过程是分散在水相中的胶团在协萃剂 (或助表面活性剂 )作用下溶入有机相 ,转型为反向胶团或微乳液 ( W/O型 )聚集状态 .     

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与钍及稀土元素的作用(Ⅲ)——对稀土元素的萃取及固态络合物组成与性质的研究

本文研究了PMBP-CHCl_2与Ln(NO_3)_3-H_2O(Ln=La、Ce、Eu、Yb和Lu)的作用。发现,当PMBP浓度≥0.2M时,分配比与氢离子浓度的三次方成反比,与PMBP浓度的四次方成正比,全部稀土离子以LnA_3·HA;形式被萃入有机相,其萃取平衡常数(lgK)分别为La(-6.20)、Ce(-4.30)Eu(-3.62)、Yb(-2.90)及 Lu(-3.20)。 在萃取条件下,除Pm未经研究外,其余三价稀土元素经萃取后,从有机相都获得了与PMBP形成的固态络合物,其组成除Lu外均为LnA_3·HA,并对它们的晶形、红外光谱和热谱进行了研究。     

2-乙基己基膦酸单2-乙基己基酯和二(2-乙基己基)磷酸从硫酸介质中协同萃取Ce(Ⅳ)的研究

研究了用2-乙基己基膦酸单-2-乙基己基酯(HEH/EHP,P507)和二(2-乙基己基)磷酸(HDEHP,P204)从硫酸介质中协同萃取Ce(Ⅳ)的机制.结果表明:在HEH/EHP的摩尔分散在0.6时,体系的协萃系数最大.Ce(Ⅳ)以Ce(SO4)0.5HL2A2的形式被萃人有机相,协萃反应为阳离子交换机制.同时还得到了HEH/EHP和HDEHP从硫酸介质中协同萃取Ce(Ⅳ)时,体系的平衡常数及热力学函数如△G,△H和△S等.     

伯胺N_(1923)从离子吸附型稀土浸出液中萃取分离稀土与铝

离子吸附型稀土浸出液中共存杂质铝的含量随矿床产地和浸取条件而变化,其浓度有时与稀土属于同一数量级,而铝对稀土的分离纯化过程影响严重。因此,稀土与铝的分离具有重要意义。本文研究了伯胺N_(1923)萃取分离稀土与铝的性能,结果表明:N_(1923)-煤油-异辛醇有机相可以从离子吸附型稀土浸出液中直接萃取稀土,而铝及其他低价金属离子留在水相;其分离系数可以达到10~5。少量进入有机相的铝继续用(NH_4)_2SO_4溶液反洗(O/A=1∶1),使负载有机相中稀土与铝的比值大大增加,其分离系数随(NH_4)_2SO_4浓度的升高和溶液pH的下降而增大。确定的最佳浓度和pH分别为2%和1。有机相中的稀土经3 mol·L~(-1) NH_4Cl溶液反萃(O/A=2∶1),可以得到浓度大纯度高的稀土溶液;采用c_(Al)/c_(RE)=8.443的含铝稀土浸出液,经萃取、洗涤和反萃,可以得到浓度为4.3～13.34 g·L~(-1)的c_(Al)/c_(RE)=0.0023～0.0027的稀土溶液,稀土回收率大于96%。     

萃取有机相的微结构和性质的研究

本文用FTIR, 荧光, ICP/AES等方法研究了含稀土的HDEHP[二(2-乙基己基)磷酸, HA]-正庚烷的萃取有机相的结构和聚集态。结果表明: (1)不同稀土离子与萃取剂的配位能力不一样, La相似文献   

氰化金浸取液萃取机理研究

本文利用Fourier变换红外光谱 (FTIR)、放射性同位素示踪、激光光散射的实验等方法研究了有机相的溶液结构 ,初步提出季胺盐萃取金有机相中氰化金阴离子参与形成超分子结构 ,并且随着有机相中金浓度的增加 ,萃合物形成聚集体     

N1923从碱性氰化液中萃取金(Ⅰ)的研究

采用放射性同位素198Au示踪法研究了伯胺N1923和TBP从碱性氰化液中萃取金(Ⅰ),考察了酸化率、水相pH值、萃取剂浓度等对萃取率的影响,以及NaOH对载金有机相的反萃作用。结果表明,TBP含量大于20％,酸化的N1923与KAu(CN)2摩尔比值在11时,金能够完全被萃取。载金有机相可采用0.1mol·L-1的NaOH溶液定量反萃。机理研究表明,伯胺和TBP萃取Au(CN)2-,符合BC类协同萃取机理。当金浓度大于10g·L-1时,在萃取有机相中形成纳米级的聚集体。     

磷酸三丁酯/正辛醇络合萃取对氯苯酚

以对氯苯酚稀溶液为研究对象,以正辛醇为稀释剂,研究了萃取剂种类及其浓度、水相平衡pH、对氯苯酚初始浓度等因素对萃取分配比的影响,并用NaOH对其负载溶质的有机相进行反萃.结果表明,络合萃取对处理高浓度对氯苯酚废水具有优势;磷酸三丁酯(TBP)的浓度和体系的pH是影响络合萃取的关键因素;采用NaOH对有机相进行反萃,当NaOH浓度为0.5mol/L时反萃率达到98.55%.红外光谱分析表明,TBP萃取对氯苯酚基于氢键作用机理.     

含氟硫酸介质中伯胺N1923对Ce（Ⅳ）的萃取

铈（Ce）在轻稀土矿物中常与诸如F等多种其它元素伴生,针对矿物处理过程中得到的同时含有Ce（Ⅳ）和F^－等多组分复杂体系硫酸浸出液,从铈氟综合回收并丰富理论依据的角度出发,对伯胺N1923在含氟硫酸介质中Ce（Ⅳ）的萃取及反萃过程进行了研究。考察了酸度、萃取剂浓度、盐析剂浓度及温度对萃取过程的影响,采用斜率法初步讨论了反应机理。研究表明,预先质子化处理后的伯胺N1923在硫酸介质中可同时萃取Ce（Ⅳ）和F^－,H₂SO₄浓度对Ce（Ⅳ）和F^－的萃取过程无显著影响。Ce（Ⅳ）的萃取率随水相中F^－浓度的增加而增大,萃取过程符合加合机理,其萃合物可表示为CeF（SO₄）_1.5（RNH₃·HSO₄）_1.5。通过考察不同温度下N1923对Ce（Ⅳ）的萃取分配比并计算相应的反应平衡常数及热力学参数,表明萃取过程为自发进行的、熵焓双驱动的放热反应。在含氟体系中,体积分数15%的N1923对Ce（Ⅳ）的饱和负载量为18.85 g／L,同时F^－的负载量为2.00 g／L。通过红外和核磁对萃合物结构分析可知部分萃合物间有多聚作用,硫酸根在萃合物中为双齿配位。此外,萃合物中的Ce（Ⅳ）可被含H₂O₂的硝酸反萃剂有效反萃,反萃率最高为90%,同时F^－几乎可以被完全反萃。     

Extraction of lutetium(III) from aqueous solutions by employing a single fibre‐supported liquid membrane

Transport behaviour of Lu(III) across a polypropylene hollow fibre‐supported liquid membrane containing di(2‐ethylhexyl)phosphoric acid (DEHPA) in dihexyl ether as a carrier has been studied. The donor phase was LuCl₃ in the buffer solution consisting of 0.2 M sodium acetate at pH 2.5–5.0. A miniaturised system with a single hollow fibre has been operated in a batch mode. The concentration of Lu(III) was determined by indirect voltammetric method using Zn–EDTA complex. The effect of pH and volume of the donor phase, DEHPA concentration in the organic (liquid membrane) phase, the time of extraction and the content of the acceptor phase on the Lu(III) extraction and stripping behaviour was investigated. The results were discussed in terms of the pertraction and removal efficiency, the memory effect and the mean flux of Lu(III). The optimal conditions for the removal of ¹⁷⁷Lu(III) from labelled ¹⁷⁷Lu‐radiopharmaceuticals were discussed and identified. The removal efficiency of Lu(III) greater than 99% was achieved at pH of the donor phase between 3.5 and 5.0 using DEHPA concentration in the organic phase of 0.47 M and the ratio of the donor to the acceptor phase of 182.     

Radiation effects on the extraction of americium(III) with di(2-ethylhexyl) phosphoric acid

Radiation effects on the extraction of Am(III) with di (2-ethylhexyl) phosphoric acid (DEHPA) was studied by exposing DEHPA to gamma rays under various conditions. Gamma irradiation of undiluted DEHPA causes an enhancement of extraction of Am(III) due to the formation of mono (2-ethylhexyl) phosphoric acid (MEHPA) similarly to that of Nd(III). The presence of diluent during irradiation brought about a slight difference from the results in the absence of a diluent. The marked change occurred in Df when the organic solvent was exposed to γ-ray while being mixed with nitric acid solution. An initial slight increase of Df for Am(III) and Nd(III) was followed by a subsequent decrease beyond an absorbed dose of approximately 200 Wh·1⁻¹. This phenomenon was explained by the enhanced decomposition of DEHPA and the subsequent strong hydrolytic and radiolytic decomposition of MEHPA to H₃PO₄ in the aqueous phase, and the complex forming nature of H₃PO₄ with Am(III) and Nd(III).     

Radiochemical separation of cerium from natural uranium irradiated with thermal neutrons

The extraction of cerium from uranium fission products using different concentrations of di(2-ethylhexyl)-phosphoric acid (DEHPA) and varying concentrations of nitric acid solutions was studied. Cerium was quantitatively stripped from the organic phase with 6N HNO₃ after washing with 0.01N HCl. The gamma-ray spectra were obtained with a Ge(Li) detector and recorded in a 4096-channel pulse-height analyzer.     

In situ electro-oxidation and liquid-liquid extraction of cerium(IV) from nitric acid medium using tributyl phosphate and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate

The process of in situ electro-oxidation of Ce(III) to Ce(IV) followed by its extraction into the organic phase has been investigated for its applicability in the separation of Ce from nitrate medium. Solvent extraction of cerium from nitric acid after its electro-oxidation to fourth valency state was carried out using tributyl phosphate (TBP) and 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17, equivalent to PC-88A). The efficiency of the extractants at different aqueous phase nitric acid concentrations and different electrode potentials were determined. Various reducing agents such as hydroxylamine hydrochloride, sodium nitrite, ferrous sulphate as well as complexing agents like EDTA, oxalic acid etc, were studied as strippants for the back extraction of cerium from the loaded organic phase. The method developed for the extraction of cerium was further extended to the partitioning of cerium from Ce-Am mixture obtained during the KSM-17 based extraction chromatographic elemental fractionation of PUREX High Activity Waste (HAW) solutions. Recovery of Ce obtained in the extraction experiments by batch as well as by continuous flow organic phase was >95% with good radiochemical purity.     

Self-assembled aggregates originated from the balance of hydrogen-bonding, electrostatic, and hydrophobic interactions

Rich phase behavior was observed in salt-free cationic and anionic (catanionic) mixtures of a double-tailed surfactant, di(2-ethylhexyl)phosphoric acid (abbreviated as DEHPA), and tetradecyldimethylamine oxide (C(14)DMAO) in water. At a fixed C(14)DMAO concentration, phase transition from L(1) phase to L(α) phase occurs with increasing amounts of DEHPA. Moreover, in the L(α) phase, with the increase in DEHPA concentration, a gradual transition process from vesicle phase (L(αv)) to stacked lamellar phase (L(αl)) was determined by cryo- and FF-TEM observations combining with (2)H NMR measurements. The rheological data show that the viscosity increases with DEHPA amounts for L(αv) phase samples because of the increase in vesicle density. At a certain molar ratio of DEHPA to C(14)DMAO, i.e., 80:250, the samples are with the highest viscoelasticity, indicating the existence of densely packed vesicles. While for L(αl) phase samples, with increasing DEHPA amount, a decrease of bilayer curvature was induced, leading to a decrease of viscosity obviously. Compared with general catanionic surfactant mxitures, in addition to the electrostatic interaction of ion pairs, the transition of the microstructures is also ascribed to the formation of the hydrogen bonding (-N(+)-O-H···O-N-) between C(14)DMAO molecules and protonated C(14)DMAOH(+), which induces the growth of aggregates and the decrease of aggregate curvatures.     

Extraction of cadmium(II) by organophosphorus compounds

The extraction of cadmium(II) by di-(2-ethylhexyl) phosphoric acid dissolved in tetradecane from aqueous chloride and perchlorate solutions has been studied at 25°C. The distribution of the metal has been determined as a function of metal and DEHPA concentrations. Distribution data have been treated both graphically and numerically using the program LETAGROP-DISTR (Acta Chem. Scand. 1971, 25, 1521) and the composition of the extracted species into the organic phase has been determined. The extraction constants for these species are given in Table 1.     

Phenomena Affecting the Equilibrium of Al(III) and Zn(II) Extraction with Winsor II Microemulsions

The extraction of Al(III) and Zn(II) from an aqueous solution with two water-in-oil microemulsions, one containing di(2-ethylhexyl)phosphoric acid (DEHPA), was investigated to aid the understanding of the role of the extractant and the metal specific characteristics in the mechanism of microemulsion extraction. The extraction of Al with the DEHPA microemulsion increased by a factor of about 10 with respect to that in the conventional DEHPA system, whereas the extraction of Zn was lower than that in the single DEHPA system. Extraction with the DEHPA-free microemulsion was very low, showing that metal ion solubilization was not important in the mechanism of microemulsion extraction. It is proposed that the effect of the mixed microemulsion on the metal distribution coefficient is the result of the balance between a decrease in the complexation reaction yield due to the interaction between butanol and DEHPA, and the adsorption of the metal complex at the macro- and microinterfaces. The former leads to a decrease in Zn(II) extraction and the latter to Al(III) extraction synergism. Copyright 2000 Academic Press.     

Quantitative separation of carrier-free cerium from fission products

The extraction of Ce (IV) by di-(2-ethylhexyl)-phosphoric acid (HDEHP) has been studied as a function of nitric acid concentration. Using the distribution coefficient data, the optimum conditions for recovery of Ce (IV) from nitric acid medium were arrived at. Under the conditions employed for Ce(IV), a small percentage of Ru was also found to be extracted. Cerium could be selectively stripped from the organic phase with 8M HNO₃/30% H₂O₂ solution. This procedure led to the recovery of¹⁴⁴Ce free of¹⁰⁶Ru. Based on the solvent extraction data, an extraction-chromatographic procedure employing HDEHP (40% w/w) loaded on Amberlite XAD-7 as the stationary phase was developed for the isolation of pure, carrier-free¹⁴⁴Ce from the spent fuel solution.