Liquid-Liquid Equilibrium Study of Phenol Extraction with Cyanex 923

Abstract

Although phenol extraction with Cyanex 923 has widely been studied, liquid-liquid equilibrium between phenol and undiluted Cyanex 923 has not been thoroughly investigated. Many factors influence the phenol extraction with undiluted Cyanex 923. Increasing the phenol concentration causes a water molecule replacement in the extractant by phenol molecules. Increasing the pH value above 12 decreases the phenol distribution coefficient K_D by 99.9%. A temperature increase from 15°C to 65°C results in a K_D decrease of 70%. With increasing salt content K_D increases due to salting-out. Adding organic acids stabilizes phenol in the aqueous phase and obstructs the extraction.     

Extraction and Separation of Germanium Using Cyanex 301/Cyanex 923. Its Recovery from Transistor Waste

Abstract

The extraction of Ge(IV) from HCl, HNO₃ and H₂SO₄ media in toluene solution of Cyanex 301 and Cyanex 923 is investigated. It is almost quantitatively extracted (～95%) in Cyanex 301 and Cyanex 923 at 8 molL^?1 HCl but the extractions from H₂SO₄ and HNO₃ are poor in the entire investigated range of acid molarity. Detailed investigations were carried out from HCl medium. Based on the slope analysis data the extracting species is identified as GeCl₄·2R (R=Cyanex 301/Cyanex 923). The extraction of Ge(IV) is higher and comparable in diluents like toluene, n‐hexane and kerosene (160–200°C) and there is no correlation between the dielectric constant and the percent extraction. The extractants are stable towards prolonged acid contact and there is negligible loss in their extraction efficiency even after recycling them for several cycles. The extraction behavior of commonly associated metal ions namely As(V)/(III), Sn(IV), Tl(III), In(III), Ga(III), Fe(III), Al(III), Hg(II), and Cu(II) has also been investigated. Based on the partition data conditions for attaining some binary and ternary separations involving Ge(IV) have been optimized. The separation data have been fused to develop a scheme for the recovery (93%) of pure germanium (～99%) from semi conductor waste.     

Cyanex 923在金属溶剂萃取中的应用

Cyanex 923是一种有机氧化膦类萃取剂,具有萃取容量高,选择性好等特点。介绍了Cyanex923的性质,对Cyanex 923在重金属废水处理、稀土金属和贵金属萃取的应用研究现状进行了综述。     

Extraction of gold from cyanide or chloride media by Cyanex 923

A new phosphine oxide extractant, commercially known as Cyanex 923, has been studied in order to be applied in the recovery of gold from either cyanide or chloride aqueous media. Au(CN)₂⁻ is extracted by this reagent throughout the whole pH range. The presence of lithium salts in the media improves the extraction. The extraction mechanism proposed can be explained in terms of a solvating reaction, the species formed in the organic phase being the following: Li⁺Au(CN)₂⁻3(R₃PO). The stripping can be performed by low ionic strength solutions such as dilute KCN solutions, and the reaction is enhanced by an increase in temperature. In chloride media, the extractant is able to extract gold (III) in the entire range of acid concentrations. The amount of extraction agent required, to achieve the same level of extraction, in this medium is much lower than in the cyanide media. The temperature has a negative effect on the extraction. Another difference observed between the two media, is that the presence of ionic salts in chloride media has no influence on the extraction, which may be attributed to the fact that the extracted species, HAuCl₄, is a protonated instead of an ionic species. © 1998 SCI     

Studies on the Solvent Extraction of Rare Earth Metals from Fluorescent Lamp Waste Using Cyanex 923

The growing need for materials such as rare earth metals (REMs) has focused attention towards their recovery from various end-of-life products. Fluorescent lamps are considered a viable target, and can be a source of up to six REMs: lanthanum, cerium, europium, gadolinium, terbium, and yttrium. In this study a commercial mix of trialkylphosphine oxides (Cyanex 923) was investigated for the extraction of REMs from fluorescent lamp waste leachates. The kinetics of the extraction is addressed, together with the co-extraction of undesired elements (iron and mercury), the influence of temperature, nitric acid concentration in the aqueous phase and ligand concentration in the organic phase. The extraction of REMs was found to be enthalpically driven, with good separation factors between the light and heavier elements. Selective stripping of REMs was possible in a single step using 4 M hydrochloric acid solution. Further recovery of iron and mercury was carried out using nitric and oxalic acid solutions.     

Reactive Extraction of o-Aminophenol Using Trialkylphosphine Oxide

Extraction of o-aminophenol （OAP） using trialkylphosphine oxide （TRPO） was studied with different diluents The neutral OAP was extracted using TRPO under an equilibrium pH in the range of 6-7.5, and a maximum distribution coefficient occurred. It was confirmed that the pH value and the TRPO concentration are the key factors that affect distribution coefficient. Nonpolar diluents could provide better extraction distribution coefficient for the extraction of OAP and the order is： kerosene 〉n-octanol 〉chloroform.     

Kinetic study of ytterbium(III) extraction from sulfate medium with Cyanex 923

The kinetics of ytterbium(III) extraction from sulfate medium with Cyanex 923 in heptane has been investigated with a constant interfacial cell with laminar flow, which aimed to identify the extraction regime, reaction zone and rate equations. It was found that the extraction rate of ytterbium(III) increased linearly with stirring speed and specific interfacial area. The activation energy E_a (9.56 kJ mol^?1), activation enthalpy ΔH^± (7.05 kJ mol^?1), activation entropy ΔS^±₂₉₈ (?0.31 kJ mol^?1) and Gibbs free energy of activation ΔG^±₂₉₈ (98.3 kJ mol^?1) were calculated from the dependence of extraction rate on temperature. The experiential rate equations were obtained by investigating the influence of the concentration of various species on the extraction rate. A diffusion regime has been deduced from evidence of the linear dependence of extraction rate on stirring speed and the low value of the activation energy. The liquid–liquid interface is most probably the reaction zone in view of the linear dependence of extraction rate on specific interfacial area, the high interfacial activity and low water‐solubility of extractant. Thus the mass transfer rate is controlled by interfacial film diffusion of species. Copyright © 2007 Society of Chemical Industry     

Extraction separation of Ir(III) and Rh(III) with Cyanex 923 from chloride media: a possible recovery from spent autocatalysts

Liquid–liquid extraction of Ir(III) and Rh(III) with Cyanex 923 from aqueous hydrochloric acid media has been studied. Quantitative extraction of Ir(III) was observed in the range of 5.0–8.0 mol dm^?3 HCl with 0.1 mol dm^?3 Cyanex 923, while Rh(III) was extracted quantitatively in the range of 1.0–2.0 mol dm^?3 HCl with 0.05 mol dm^?3 Cyanex 923 in toluene along with 0.2 mol dm^?3 SnCl₂. The Ir(III) was back extracted with 4.0 mol dm^?3 HNO₃ quantitatively from the organic phase while Rh(III) was stripped with 3.0 mol dm^?3 HNO₃. The extraction of Rh(III) with Cyanex 923 was not quantitative without use of SnCl₂. However in the extraction of Ir(III) a negative trend was observed in the presence of SnCl₂. Varying the temperature of extraction showed that the extraction reactions of both the metal ions are exothermic in nature, and the stoichiometric ratio of Ir(III)/Rh(III) to Cyanex 923 in organic phase was found to be 1:3. The methods developed were applied to the recovery of these metal ions from a synthetic solution of similar composition to that from leaching of spent autocatalysts in 6.0 mol dm^?3 HCl. © 2002 Society of Chemical Industry     

Synergistic extraction and separation studies of Ce(III) from acidic nitrate medium using binary mixture of Cyanex 921 and Cyanex 923 in kerosene

The effect of parameters like shaking time, nitric acid, nitrate ion, extractant concentration, temperature, diluents, and phase volume ratio on the extraction of Ce(III) from acidic nitrate medium using binary mixture of Cyanex 921 and Cyanex 923 in kerosene has been investigated. Synergism was observed in the range 0.001-1.0 mol/L HNO₃. With increase in extractant concentration and O/A phase volume ratio, extraction increases while with increase in nitric acid concentration and temperature, extraction decreases. Sulphuric acid and hydrochloric acid are found to be effective in stripping. Separation factors for Nd/Ce are higher as compared to those for Ce/La and Pr/Ce.     

Comparative study of the determination of platinum by extraction with Cyanex 923 and Cyanex 471X from bromide media

The extraction equilibrium study of Pt(IV) was carried out with Cyanex 923 and Cyanex 471X in toluene from hydrobromic acid media to investigate their extraction capacity, since they have different donor atoms, ‘O’ and ‘S’. Their distribution equilibria were studied as a function of extractant concentration, diluents, hydrobromic acid concentration and the effect of temperature on extraction. Pt(IV) was quantitatively extracted with 0.1 mol dm^?3 Cyanex 923 in toluene from 5.0–8.0 mol dm^?3 HBr media and was stripped with 4.0 mol dm^?3 perchloric acid. However it was also quantitatively extracted with 0.1 mol dm^?3 Cyanex 471X (with 0.1 mol dm^?3SnCl₂) in toluene from 6.0–8.0 mol dm^?3 HBr media and was stripped with 1.0 mol dm^?3 stabilized sodium thiosulfate solution at pH 9.0. The slope analysis method indicated metal complex species of 1:1 for Pt(IV) with Cyanex 923 and Cyanex 471X in toluene from HBr media. These methods were successfully applied to the analysis of platinum in real samples. © 2001 Society of Chemical Industry     

Solvent Extraction Separation of Beryllium(ll) from Aluminum(lll) by Cyanex 921 (TOPO)

ABSTRACT

Cyanex 921, a neutral extractant, has been used for the extraction of beryllium(II)from basic media and employed for the separation of beryllium(II) in the presence of aluminum(III). Cyanex 921 diluted in cyclohexane extracted beryllium(II) in the 8–10 pH range and aluminum(III) between 4–5 pH. The selectivity of beryllium(II) over aluminum(III) was high in the 8–10 pH range. The extracted beryllium(II) was stripped with 0 M NaOH without any significant loss of the ligand while loaded aluminum(III) was stripped with 2 M HC1. The extractability of beryllium(II) and aluminum(III) was also studied separately as a function of pH, temperature, equilibration time, and stripping ability with NaOH, KOH, HCI, HNO₃, H₂SO₄, and HCIO₄. Based on these results, a sequential method was developed for the separation of beryllium(II) from aluminum(III).     

吡啶从硝酸介质中萃取铀(VI)的研究

研究了新萃取剂吡啶从硝酸介质中萃取铀的机理。考察水相硝酸浓度、萃取剂浓度、盐析剂硝酸钠以及振荡时间和温度对萃取分配比的影响 ,确定了萃合物的组成。求得萃取硝酸铀酰过程的平衡常数及反应的热力学函数。同时研究了相比的影响 ,以及稀释剂的影响。发现吡啶萃取能力在不同稀释剂中由弱到强的顺序为 :四氯化碳、氯仿、苯、甲苯、环己烷、煤油。     

Carrier-facilitated transport of Cd(II) from a high-salinity chloride medium across a supported liquid membrane containing Cyanex 923 in Solvesso 100

The transport of cadmium (II) from a high-salinity chloride medium across a flat-sheet supported liquid membrane containing Cyanex 923 in Solvesso 100 supported on a PVDF membrane into a strip solution with water was investigated. Permeability coefficients of metal increased with decreasing the pH of feed from 2.0 to 0.5. It also increases with increasing carrier concentration in the membrane phase, whereas the permeation is dependent on the organic phase diluent but independent of metal concentration in the feed phase. The performance of the present system against other carriers was also studied.     

Opposite selectivities of tri-n-butyl phosphate and Cyanex 923 in solvent extraction of lithium and magnesium

The synergic solvent extraction system of tri-n-butyl phosphate (TBP) and FeCl₃ (or ionic liquids, ILs) has been extensively studied for selective extraction of Li from Mg-containing brines. However, Cyanex 923 (C923), which extracts many metals stronger than TBP, has not yet been examined for Li/Mg separation. Here, we report on the unexpected observation that the C923/FeCl₃ system has opposite Li/Mg selectivity compared to the TBP/FeCl₃ system. Detailed investigations show that the opposite selectivity of the C923/FeCl₃ (or IL) system is due to three factors: (1) the strong extraction of Fe by C923 leads to a low concentration of [FeCl₄]⁻ in the system, which is essential for Li extraction; (2) C923 in combination with an IL extracts Mg strongly by an ion-pair mechanism; (3) most importantly, C923 extracts Mg by solvation, resulting in an insufficient concentration of C923 for Li extraction. The unexpected poor Li/Mg selectivity of C923 highlights the irreplaceable role of TBP in the selective recovery of Li.     

吡啶从硝酸介质中萃取铀(Ⅵ)的研究

研究了新萃取剂吡啶从硝酸介质中萃取铀的机理。考察水相硝酸浓度、萃取剂浓度、盐析剂硝酸钠以及振荡时间和温度对萃取分配比的影响，确定了萃合物的组成。求得萃取硝酸铀酰过程的平衡常数及反应的热力学函数。同时研究了相比的影响，以及稀释剂的影响。发现吡啶萃取能力在不同稀释剂中由弱到强的顺序为：四氯化碳、氯仿、苯、甲苯、环己烷、煤油。     

Solvent extraction of Zn(II) by Cyanex 923 and its application to a solid‐supported liquid membrane system

The extraction of zinc(II) by Cyanex 923 (phosphine oxides mixture) in Solvesso 100 from hydrochloric acid solution has been investigated. The extraction reaction is exothermic. The numerical analysis of metal distribution data suggests the formation of ZnCl₂·L₂,HZnCl₃·2L and H₂ZnCl₄·2L(L = ligand) in the organic phase with formation constants K_ext = 4.1,5.6 × 10⁹ and 6.7 × 10⁹, respectively. The results obtained for zinc(II) distribution have been implemented in a solid‐supported liquid membrane system. The influence of source phase stirring speed, membrane composition and metal concentration on zinc transport have been investigated. © 2001 Society of Chemical Industry     

皂化HA/煤油微乳液萃取赖氨酸的研究

研究了NaOH皂化HA/煤油微乳体系萃取赖氨酸的机理和工艺,考察了NaOH浓度、萃取时间、乳水比、外水相pH值、油相重复使用次数等对萃取效率的影响.结果表明,该微乳液萃取赖氨酸的最佳工艺条件为:油相中HA的浓度1.0 mol·L-1、NaOH浓度1.25 mol·L-1、萃取时间10 min、乳水比(体积比)1:4、外水相pH值3.0,此时,赖氨酸的一次性萃取率可达90.2%.该微乳液具有稳定性好、无明显溶胀和泄漏、萃取效率高、可自动破乳且油相可重复使用等优点.     

Sorption of phenol from aqueous solution by novel magnetic polysulfone microcapsules containing Cyanex 923

This paper describes the sorption of phenol from aqueous solution by using novel magnetic polysulfone (PSF) microcapsules containing Fe₃O₄ nanoparticles and mixture of trialkyl-phosphine oxides (Cyanex 923) (Cyanex 923/Fe₃O₄@PSF microcapsules). The preparation of the Cyanex 923/Fe₃O₄@PSF microcapsules was based on the phase-inversion technique. The prepared microcapsules were characterized by using Fourier Transform Infrared Spectroscopy (FT-IR), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and Vibrating Sample Magnetometer (VSM). Fe₃O₄ nanoparticles in the microcapsules provided easier separation via application of external magnetic field. The experiments indicated that phenol could be removed from aqueous solution at a pH range between 3 and 9. The Cyanex 923/Fe₃O₄@PSF microcapsules prepared with dispersed phase containing 3.35% of Cyanex 923 (by wt.) provided the highest removal. The sorption reached an equilibrium in 120 min and it obeyed the pseudo-second order kinetic model. The non-linear Chi-square (χ²) statistical test showed that Langmuir isotherm model better represented the sorption data in comparison to Freundlich and Redlich–Peterson models. The Langmuir sorption capacity (Q_o) and sorption constant (b) were 0.664 mmol/g and 0.855 L/mmol, respectively. The regenerated microcapsules could be used five times with no change in their sorption capacity and magnetic separability.