Solvent extraction separation of vanadium(V) from multivalent metal chloride solutions using 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester

The solvent extraction behaviour of vanadium(V) from hydrochloric acid solutions has been investigated using 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester (EHEHPA ≡ HX) in kerosene as an extractant. For comparison, extraction studies have also been carried out with vanadium(IV). The results demonstrate that the extraction of vanadium(V) follows the cation exchange mechanism: where (HX)₂ refers to the dimeric form of EHEHPA. On the other hand, two dimeric molecules of EHEHPA were found to be involved in the extracted complex of vanadium(IV): The equilibrium constants of the above extracted complexes have been calculated and found to be K_ex,V(V) = 3.14 and K_ex,V(IV) = 0.32. The effect of the nature of the diluent on the extraction of vanadium(V) with EHEHPA has been studied and correlated with the dielectric constants. IR spectral studies of the extracted complex were used to further clarify the nature of the extracted complex. The separation and recovery possibilities of vanadium(V) from other associated metal ions, viz magnesium(II), aluminium(III), titanium(IV), chromium(III), manganese(II) and iron(III), which are present in the waste chloride liquors from the processing of titanium minerals, are also discussed. © 2002 Society of Chemical Industry     

Extraction and separation of rare earths from chloride medium with mixtures of 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester and sec‐nonylphenoxy acetic acid

BACKGROUND: 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester (HEHEHP, H₂A₂) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec‐nonylphenoxy acetic acid (CA100, H₂B₂) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied. RESULTS: The synergistic enhancement coefficient decreases with increasing atomic number of the lanthanoid. A significant synergistic effect is found for the extraction of La³⁺ as the complex LaH₂ClA₂B₂ with mixtures of HEHEHP and CA100. The equilibrium constant and thermodynamic functions obtained from the experimental results are 10^?0.92 (K_AB), 13.23 kJ mol^?1 (ΔH), 5.25 kJ mol^?1 (ΔG), and 26.75 J mol^?1 K^?1 (ΔS), respectively. CONCLUSION: Graphical and numerical methods have been successfully employed to determine the stoichiometries for the extraction of La³⁺ with mixtures of HEHEHP and CA100. The mixtures have different extraction effects on different rare earths, which provides the possibility for the separation of yttrium from heavy rare earths at an appropriate ratio of HEHEHP and CA100. Copyright © 2009 Society of Chemical Industry     

非离子表面活性剂TX114浊点萃取D2EHPA的规律

引言浊点萃取[1-2]是利用表面活性剂水溶液的增溶和分相行为实现溶质富集的分离技术。由于分相后表面活性剂的富集相(亦称凝聚相)与水相的体积比非常小(0.007～0.04)[3],所以,对于被增溶的物质能够提供非常高的富集倍数和萃取效率。目前浊点萃取技术主要广泛应用于痕量有害物质     

二（2-乙基已基）磷酸萃取氨基苯甲酸的平衡特性

A series of extraction equilibrium experiments for aminobenzoic acid with di(2-ethylhexyl)phosphoric acid (D2EHPA) dissolved in n-octane or 1-octanol was carried out. The effects of aminobenzoic acid concentration,D2EHPA concentration and pH on the distribution ratio were discussed in detail. The infrared spectra of the organic phase loaded with solute illustrated that pH had little effect on the structure of the complex formed. There proceed ion association and cation-exchange.reaction in the extraction. An expression of the equilibrium distribution was proposed.     

二(2-乙基己基)磷酸萃取氨基苯甲酸的相平衡分配系数

络合萃取法分离极性有机物稀溶液具有高效性和高选择性,本文以二（２－乙基已基）磷酸（Ｄ２ＥＨＰＡ）为络合剂;正辛烷或正辛醇为稀释剂,在不同的ＰＨ值条件下实验测定了氨基苯甲酸稀溶液的萃取相分配系数,讨论了影响因素,分析了萃合物的组成。提出了平衡分配系数的关系式。     

Extraction of iron(III) from acidic sulfate solutions with bis(2‐ethylhexyl)phosphoric acid in PENRECO® 170 ES,a new friendly diluent

The extraction of iron(III) from acidic sulfate solutions by bis(2‐ethylhexyl)phosphoric acid (HDEHP) is investigated by using PENRECO® 170 ES as a diluent. PENRECO® 170 ES is new diluent which offers advantages such as improved solvency power, more complete phase disengagement and reduced losses in aqueous streams, with reductions of over 50% in diluent usage after 1 year, compared with conventional paraffinic diluents. The chemical analyses performed in the present work suggest that such properties arise, at least in part, from the presence of a series of hydrophobic branched alcohols in its composition (at least 0.6 mol dm^?3). In spite of the solvation effects due to these alcohols, HDEHP is dimeric in this diluent and, in the presence of an excess of HDEHP, the extraction of iron(III) takes place according to the classical equation: with K_ex = 10^{5.7 ± 0.2} (at I = 1 mol dm^?3). Such a value of K_ex is similar to that reported for pure hexane, which shows that the presence of long chain alcohols in PENRECO® 170 ES has no perceptible influence on the thermodynamics of iron(III) extraction by HDEHP. The extraction of iron(III) by HDEHP in PENRECO® 170 ES is slightly more rapid than in kerosene, which indicates that the molecules of alcohols constituting PENRECO® 170 ES have no negative effect on the kinetics of metal extraction although they compete with the extractant molecules for adsorption at the liquid–liquid interface. Stripping of iron(III) from loaded organic solutions by sulfuric acid is easy and rapid (95% equilibrium reached within 2 min) when HDEHP is used at moderate concentrations (typically 0.1 mol dm^?3). At higher HDEHP concentrations, stripping is difficult and incomplete, as found previously with other diluents. Thus, PENRECO® 170 ES is interesting in its ability to overcome some of the physical problems encountered in liquid–liquid operations, but its use does not modify significantly the chemistry of iron(III) extraction by HDEHP. © 2002 Society of Chemical Industry     

Equilibrium characteristics for the extraction of cobalt and nickel into di(2-ethylhexyl) phosphoric acid

The liquid-liquid extraction of cobalt and nickel from aqueous sulphate solutions into di(2-ethylhexyl) phosphoric acid, DZEHPA, has been investigated at 25°C and 60°C. The system studied was made up as follows: the aqueous phase-cobalt and nickel dphates; the organic phase-20% D2EHPA, 75% Esso solvent DX3641 and 5% tri-butyl phosphate. Analogies to vapour-liquid equilibria were made to develop three methods to correlate the binary equilibrium data, namely: 1) a delta Y method, 2) a method based on the correlation of solvent free mole fractions in both phases and 3) a “pseudo activity” coefficient or pseudo gamma method, γ_AB. The methods were evaluated as to their suitability for the prediction of binary isotherms. The delta Y and pseudo gamma methods were found to give the best results.     

Studies on the solvent extraction of rare earths from nitrate media with a combination of di‐(2‐ethylhexyl)phosphoric acid and sec‐octylphenoxyacetic acid

BACKGROUND: Di‐(2‐ethylhexyl)phosphoric acid (D2EHPA, H₂A₂) has been used extensively in hydrometallurgy for the extraction of rare earths, but it has some limitations. Synergistic extraction has attracted much attention because of its enhanced extractabilities and selectivities. In the present study, sec‐octylphenoxyacetic acid (CA12, H₂B₂) was added into D2EHPA systems for the extraction and separation of rare earths. The extraction mechanism of lanthanum with the mixtures and the separation of lanthanoids and yttrium were investigated. RESULTS: The synergistic enhancement coefficient for La³⁺ extracted with D2EHPA + CA12 was calculated as 3.63. La³⁺ was extracted as La(NO₃)₂H₂A₂B with the mixture. The logarithm of the equilibrium constant was determined as 0.80. The thermodynamic functions, ΔH, ΔG, and ΔS were calculated to be 4.03 kJ mol^?1, ? 1.96 kJ mol^?1, and 20.46 J mol^?1 K^?1, respectively. The mixtures have synergistic effects on Ce³⁺, Nd³⁺, and Y³⁺, with an especially strong synergistic effect on Y³⁺. Neither synergistic nor antagonistic effects on Dy³⁺ and weak antagonistic effects on Lu³⁺ were found. CONCLUSION: Mixtures of D2EHPA and CA12 exhibit evident synergistic effects when used to extract La³⁺ from nitric solution. The stoichiometries of the extracted complexes have been determined by graphical and numerical methods to be La(NO₃)₂H₂A₂B with the mixture. The extraction is an endothermic process. The mixture exhibits different extraction effects on rare earths, which provides possibilities for the separation of Y³⁺ from Ln³⁺ at a proper ratio of D2EHPA and CA12. Copyright © 2008 Society of Chemical Industry     

Innovative spectral investigations on the thermal-induced poly(aspartic acid)

Two-dimensional (2D) correlation FTIR spectroscopy was used to investigate the dynamic mechanism of poly(aspartic acid) during the heating process. According to the 2D asynchronous correlation spectra, the CO vibration band of Amide I was separated into three peaks at 1637, 1645 and 1677 cm⁻¹, assigned to α helical, random coil and β antiparallel conformation, respectively. And α helical structure would transform into the more ordered and stable conformation of β antiparallel in heating. In the region of 3700-2700 cm⁻¹, the H-contained groups were analyzed; the loosening of hydroxyl is found to change prior to the NH-related hydrogen bonds and the conformational reorganization of hydrocarbon chains.     

Separation of cobalt and nickel from acidic sulfate solutions using mixtures of di(2‐ethylhexyl)phosphoric acid (DP‐8R) and hydroxyoxime (ACORGA M5640)

DP‐8R and ACORGA M5640 extractants diluted in Exxsol D100 were used to co‐extract cobalt and nickel from aqueous acidic sulfate media. The influences of equilibration time, temperature, equilibrium pH and reagent concentrations on the extraction of both metals have been studied. It was observed that both cobalt and nickel extraction are slightly sensitive to temperature but are pH dependent. Metal extraction equilibria are reached within about 5 min contact time. In addition, cobalt extraction depends on the extractant concentration in the organic phase. For a solution containing 0.5 g dm^?3 each of cobalt and nickel and an initial pH of 4.1, conditions were established for the co‐extraction of both metals and selective stripping (with H₂SO₄) of cobalt and nickel. Using the appropriate reagent concentrations the yield (extraction stage) for both metals exceeded 90%, and stripping of cobalt and nickel was almost quantitative. Copyright © 2004 Society of Chemical Industry     

PVC/D2EHPA聚合物包容膜对水相中苯酚的分离

以二-(2-乙基己基) 膦酸(D2EHPA,P204)为载体,制备了聚氯乙烯(PVC)为膜基材的系列聚合物包容膜(PD-PIM),用FTIR、XRD及AFM表征了PD-PIM的化学组成、结晶行为和微观形貌.以渗透系数和渗透通量为指标,考察了PD-PIM膜中载体含量、料液相浓度和pH,以及解析相中盐酸浓度对PD-PIM分离苯酚的影响,探讨了实验条件下苯酚通过PD-PIM的传输机制.结果表明:在实验设定的范围内,PD-PIM对苯酚的传质通量随PD-PIM中载体质量分数、料液相中苯酚浓度的增加而增大,并在料液相苯酚浓度为400 mg·L^-1、pH=6,解析相盐酸浓度为0.1 mol·L^-1,载体P204含量为70%(质量)时达到最佳分离效果.PD-PIM对苯酚的传输机制为促进耦合迁移,初期传输符合一级动力学方程.重复使用实验证实PD-PIM具有较高的稳定性.     

Solvent extraction reaction of hafnium(IV) from strong sulfuric acid solutions with D2EHPA and PC 88A

Hafnium can be selectively extracted over zirconium from strong sulfuric acid solutions by D2EHPA or PC 88A. Solvent extraction experiments have been performed to identify the reaction of Hf from strong sulfuric acid solutions (1 to 7 M) by these two extractants. Hafnium extraction was gradually decreased and then increased again with the increase of sulfuric acid concentration. By applying a slope method, the extracted Hf species was proposed to be HfA₄·(HA)₂ by D2EHPA and Hf(HSO₄)₂A₂·(HA)₂ by PC 88A, respectively. This difference in the nature of the extracted species was verified by FT-IR spectra.     

Micellar Extraction of Zinc with Di(2‐ethylhexyl)phosphoric Acid and the Addition of the Cationic Surfactant Cetyltrimethylammonium Bromide

The addition of surfactants can influence extraction processes. In cases where the surfactant concentration is above the critical micelle concentration, the mass transfer rate increases due to the formation of inverse micelles and, thus, through the mechanism of micellar extraction of zinc. The influence of the added surfactant cetyltrimethylammonium bromide on zinc extraction with the cation exchanger di(2‐ethylhexyl)phosphoric acid was analyzed based on extraction equilibrium and mass transfer experiments. The observed experimental results are explained phenomenologically.     

二（2-乙基己基）磷酸/磷酸三丁酯复合萃取剂协萃对氨基苯甲酸

为强化两性官能团化合物的萃取分离性能,以对氨基苯甲酸（PABA）为被分离溶质,二（2-乙基己基）磷酸（D2EHPA）/磷酸三丁酯（TBP）/正庚烷的混合物为萃取剂进行了萃取平衡特性的研究,考察了溶液的pH值、D2EHPA浓度、TBP浓度对于萃取平衡的影响,建立了复合萃取剂协同萃取PABA的萃取平衡分配系数的表达式.结果表明,D2EHPA/TBP/正庚烷复合萃取剂萃取PABA具有明显的协萃效应,协萃机理为D2EHPA及TBP分别与PABA的Lewis碱性官能团（—NH2）和Lewis酸性官能团（—COOH）缔合形成亲油性更强的萃合物,且D2EHPA与TBP的浓度差异越小,协萃效应越明显.根据萃取平衡分配系数表达式拟合求取了表观萃取平衡常数,复合萃取剂的值远大于D2EHPA、TBP单独作为萃取剂的值,进一步证明了本文提出的协萃机理.     

Preparation and physical properties of N‐defunctionalized derivatives of poly(aspartic acid)

A number of N‐substituted poly(aspartic acid)s was prepared under mild conditions using the silylation–alkylation technique. Their physical properties were studied. Free swelling capacity (FSC) tests were performed for polymers obtained by crosslinking the parent poly(aspartic acid) as well as its defunctionalized derivatives. The hypothesis that H‐bonding is critical in superabsorbency was demonstrated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 85–90, 2001     

聚天冬氨酸的合成与表征

以L-天冬氨酸为原料,热缩合成聚天冬氨酸酐,水解得到聚天冬氨酸。采用凝胶色谱法(GPC)测定了聚天冬氨酸的分子量,并用核磁共振(NMR)对其进行了表征。     

Redox‐ and pH‐Responsive Nanogels Based on Thiolated Poly(aspartic acid)

Nanogels loaded with fluorescent dextran as a model drug are synthesized by the oxidation induced cross‐linking of water soluble redox responsive thiolated poly(amino acid) in miniemulsion without the introduction of any cross‐linker molecule. Two types of high energy methods, namely, ultrasonication and high pressure homogenization (HPH), are compared. Dynamic light scattering and transmission electron microscopy measurements confirm that spherical nanogels in 100–150 nm diameter range are prepared successfully by HPH method. Size and surface charge of the nanogels can easily be controlled by environmental pH. The release of encapsulated drug is triggered by the degradation of nanogels in reducing environment due to the cleavage of disulphide bonds.