Emulsion membrane systems for preconcentration of uranium

Various double emulsion systems with liquid membranes containing tri-n-octylphosphine oxide /TOPO/, tri-n-butylphosphate /TBP/, KELEX 100^® and di-2-ethylhexylphosphoric acid /DEHPA/, as carriers for uranium/VI/ pertraction, were studied. The conditions were found at which the systems are most efficient, comparing with solvent extraction. The use of DEHPA as a membrane carrier with solutions of H₂SO₄ and H₃PO₄ encapsulated in the membrane was substanfiated.     

Studies on emulsion liquid membrane extraction of cephalexin

An experimental study on batch extraction of cephalexin using an emulsion liquid membrane system has been reported. The effects of surfactant, carrier and solute concentrations, phase volume ratio, stirring speed, and counterion concentration on the extraction rate were examined. Surfactant, carrier and diluent used were Span-80, Aliquat-336 and n-heptane–kerosene (1:1), respectively. Under the optimised experimental conditions, emulsion swelling was found to be marginal. By maintaining an appropriate pH gradient in the feed and receiving aqueous phase, facilitated transport could be realised. Selective separation of cephalexin from a mixture of 7-aminodeacetoxy cephalosporanic acid (7-ADCA) could be demonstrated in the emulsion liquid membrane system. A mathematical model based on mass transfer across aqueous boundary layer, interfacial chemical reaction and diffusion in the emulsion globule provides a reasonable fit of the experimental solute concentration versus time profiles in the emulsion liquid membrane system.     

Feasibility of surfactant-free supported emulsion liquid membrane extraction

Supported emulsion liquid membrane (SELM) is an effective means of conducting liquid-liquid extraction. SELM extraction is particularly attractive for separation tasks in the microgravity environment where density difference between the solvent and the internal phase of the emulsion is inconsequential and a stable dispersion can be maintained without surfactant. In this research, dispersed two-phase flow in SELM extraction is modeled using the Lagrangian method. The results show that the SELM extraction process in the microgravity environment can be simulated on earth by matching the density of the solvent and the stripping phase. The feasibility of surfactant-free SELM (SFSELM) extraction is assessed by studying the coalescence behavior of the internal phase in the absence of the surfactant. Although the contacting area between the solvent and the internal phase in SFSELM extraction is significantly less than the area provided by regular emulsion due to drop coalescence, it is comparable to the area provided by a typical hollow-fiber membrane. Thus, the stripping process is highly unlikely to become the rate-limiting step in SFSELM extraction. SFSELM remains an effective way of achieving simultaneous extraction and stripping and is able to eliminate the equilibrium limitation in the typical solvent extraction processes. The SFSELM design is similar to the supported liquid membrane design in some aspects.     

乳状液膜法分离水中的铬

乳状液膜法由于其独特的物理化学性质,已广泛用于金属离子的萃取分离[1～3]。本文以span80-煤油-NaOH液膜体系分离水中铬。不加流动载体,利用内、外相中被分离物的浓度梯度实现物质迁移。当Cr2O2-7进入内相时,与内相的NaOH发生反应,在内相高浓度的NaOH存在下,可保持Cr2O2-7在液膜两侧有最大的浓度梯度,促使Cr2O2-7的迁移,实现Cr2O2-7与外相溶液的分离。1　实验部分1 1　仪器与试剂D40-1型电动搅拌器(杭州仪表电机厂),78-1型磁力加热搅拌器(江苏金坛新一佳仪器厂),721型分光光度计(上海第三分析仪器厂)。铬标准溶液(100ml/L):准…     

Separation study of cadmium through an emulsion liquid membrane

A study of the transport of Cd(2+) ions through a tri-ndashoctylamine(TOA)-sorbital monooleate (Span 80)-oxylene liquid membrane has been performed with varying concentrations of HCl, KI, TOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed at 0.01 M KI, 0.025 M HCl, 0.015 M TOA, 3% (w/v) Span 80 and 0.025 M NaOH. With this system, cadmium could be completely separated from Zn(2+), Fe(2+), Co(2+), Ni(2+), Cr(3+) and Mn(2+). The transport mechanism of this metal ions through the membrane has been discussed.     

Stability analysis of environmentally benign green emulsion liquid membrane

A new stable green emulsion liquid membrane (GELM) was formulated by selecting the environmentally benign vegetable oils. The rice bran oil (RBO) based GELM has shown better stability in comparison to that obtained from other oils. GELM was prepared using 10?mL RBO, 0.25 [M] NaOH concentration, 2 (v/v, %) surfactant concentration, 0.4 (v/v) phase ratio, 2000?rpm emulsification speed, and 20?min emulsification time. Under these optimum conditions, GELM has been found to be stable for 120?±?2?min (no significant phase change) and has shown complete phase separation after 4 hours. Therefore, RBO as a green solvent has high potential to be applied in several ELM process applications.     

铜在乳状液膜体系中的迁移行为

近年来膜分离技术在环境治理方面得到广泛应用。本文研究了铜在span80-TBP（磷酸三丁酯）-煤油-NH3液膜分离体系中的迁移行为。用TBP作为载体,在溶液中迁移时,在外相与膜相界面上形成中性络合物后穿过膜相,在膜相与内相界面上络合物再与NH3反应,生成铜氨络离子,释放出来的TBP又返回膜相。     

Extraction of strontium ions with emulsion liquid membrane technique

The aims of this study are to form a liquid membrane suitable for the extraction of strontium ions from aqueous solutions and to determine the factors influencing the stability of the membrane, the extraction efficiency and the rate of transport. The suggested membrane is composed of kerosene, Span 80 and D2EHPA. It has been observed that the extraction efficiency and the rate of transport increase with increasing ratio of emulsion to outer phase volume, stirring rate and D2EHPA concentration and decreasing pH of the inner phase. As the strontium ion concentration in the outer phase increases, the transport rate increases but the separation efficiency decreases. The maximum separation efficiency achieved in the experiments was 92%.     

Separation study of mercury through an emulsion liquid membrane

A study of the transport of Hg(II) ions through a tri-n-octylamine (TOA) - sorbital monooleate (Span 80) -toluene liquid membrane has been performed with varying concentrations of HCl, KCl, TOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed with 0.01 M KCl, 2.5 x 10(-2) M HCl, 1.5 x 10(-2) M TOA, 3% (w/v) Span 80 and 0.05 M NaOH. With this system, mercury could be completely separated from Cu, Zn, Fe, Co, Ni, Pb, Mn and Cd. The transport mechanism of this metal ion through the membrane is based on the association of metal anions (HgCl(4)(2)) with protonated TOA molecules at the feedside interface, diffusion through the membrane, decomposition of the complex at the strip-solution-side membrane interface under alkaline conditions, and backdiffusion of TOA molecules. Transport with the membrane is dependent on the concentration gradient but in the surrounding solutions it is inversely related to the concentration gradient.     

Redox-driven transport of copper ions in an emulsion liquid membrane system

A new redox-driven type of emulsion liquid membrane separation is described. Milligram amounts of copper(II) in 0.2 M hydrochloric acid were reduced to copper(I) in the presence of ascorbic acid (1 M≡1 mol l⁻¹). The copper solution was emulsified with a (1+4) mixture of toluene and n-heptane using Span-80 (sorbitan monooleate) as an emusifier. The resulting water-in-oil emulsion was dispersed in 0.2 M hydrochloric acid containing hydrogen peroxide and neocuproine (2,9-dimethyl-1,10-phenanthroline) by stirring for 10 min. The copper in the internal aqueous phase was selectively transported to the external one, leaving other heavy metals (e.g., Mn, Co, Ni, Cd and Pb) in the internal aqueous phase. After collecting the dispersed emulsion globules, they were demulsified by heating and the metals in the segregated aqueous phase were determined by graphite-furnace atomic absorption spectrometry (GFAAS). The selective transport of copper offered the multielement separation of trace heavy metals from a copper matrix, allowing the GFAAS determination of impurities at the 0.01% level in copper metal.     

Drop size prediction in liquid membrane systems

The design of separation equipment using liquid membranes requires predictive methods for the estimation of drop diameters of the dispersed liquid membrane “macrodrop”. Existing models for drop breakage in liquid-liquid systems underpredict drop diameters of liquid membrane macrodrops even after incorporating the effects of dispersed phase viscosity and hold-up. By considering that the microdroplets within a liquid membrane macrodrop cause a damping of induced drop oscillations arising from external turbulence, the recently proposed model of Calabrese et al. (1986) has been modified and the resulting model equations have been shown to predict drop diameters of both oil as well as water liquid membrane macrodrops reasonably well.     

Span80-TBP-NaOH体系破乳方法及膜内反应研究

采用Span80-TBP-NaOH体系乳状液膜法提取红土矿浸出液中的镍,对提取分离后的乳液进行破乳实验,经过加热-离心联合破乳法,破乳率可达90%.通过比较提取镍前后,乳液的红外光谱图,证明了膜内反应的发生;通过比较原始油相和破乳后油相的红外光谱图,证明了破乳后油相的重复利用性.     

Emulsion liquid membrane extraction of zinc by a hollow-fiber contactor

Emulsion liquid membranes (ELMs) can contribute to process intensification of zinc extraction, by significantly reducing the solvent and carrier requirements in comparison with conventional solvent extraction. Di(2-ethylhexyl)phosphoric acid (D2EHPA) was used as a highly selective carrier for the transport of zinc ions through the emulsified liquid membrane. The hollow-fiber extractor appears to offer significant advantages over conventional liquid–liquid contactors for this separation because emulsion leakage and swell are practically eliminated even when treating high concentration feeds. Various hydrodynamic and chemical parameters, such as variation in feed pH; zinc concentration in feed; variation in concentrations of D2EHPA; variation in feed/emulsion volume ratios and variation in feed and emulsion flow rates, were investigated. The content of sulfuric acid as an internal did not show in the studied range any significant influence on zinc extraction through the ELM, although a minimum hydrogen ion concentration is suggested in the internal aqueous solution to ensure acidity gradient between both aqueous phases to promote the permeation of zinc ions toward the internal phase. The experimental mass-transfer coefficients have shown a stronger dependence on hydrodynamic conditions in both the external feed phase and emulsion among the parameters studied. For emulsion flow rate, mass-transfer coefficient increased from 16.3 × 10⁻⁶ m/s at 200 ml/min to 31.2 × 10⁻⁶ m/s at 640 ml/min. Significant increasing in mass-transfer coefficient observed with increasing aqueous flow rate from 9.7 × 10⁻⁶ m/s at 170 ml/min to 37.2 × 10⁻⁶ m/s at 740 ml/min. The overall mass-transfer coefficient increases from 12 × 10⁻⁶ m/s at 2% D2EHPA to 28 × 10⁻⁶ m/s at 8% D2EHPA. This means that this process is chemically controlled and the interfacial resistance has a more significant role in the extraction of zinc by emulsion liquid membrane through hollow-fiber contactor. From the results obtained, it seems that the diffusion processes in aqueous feed phase and the membrane phase have the same importance as the chemical process.     

Uranium extraction enhancement form phosphoric acid by emulsion liquid membrane

This work is mainly concerned with the uranium extraction from phosphoric acid commercially produced by Abu Zaabal Fertilizers and Chemical Co., Egypt. This target would realize a dual purpose where the phosphate ore is considered as an alternative source of uranium besides eliminating its environmental contamination. The applied procedures are that of the new technology of emulsion liquid membrane. Authors have indeed pointed out that the variables explored still leave open to question the roles of stripping at the internal interface as well as the bulk transfer of uranium in the internal phase. For this purpose, two reducing agents are studied as additives to two organic solvent systems; namely the organophosphorous synergistic mixture of D2EHPA/TOPO as well as the tridodecyl amine. The relevant factors have first been optimized upon synthetic uraniferous phosphoric acid solution followed by the application upon the commercial acid after purification. These factors include the concentration of solvent system and the used emulsifier, acid concentration of the external and internal phases besides the nature and concentration of the reductant added to the internal phase. In addition, the permeation time as well as the oxidation state of the external phase was studied. All these factors have indeed been studied under different mixing speeds ranging from 300 up to 1,000 rpm. Ascorbic acid concentration, 1 % as an additive to the internal phosphoric acid phase (40 % P₂O₅) resulted in 95 % uranium extraction efficiency at the lower speed of 600 rpm.     

Mathematical modeling of silver extraction by an emulsion liquid membrane process

A general physical model of a typical batch extraction system employing an emulsion liquid membrane process for the extraction of silver has been developed. The model takes into account the extraction reaction between the silver ion and the carrier molecules at the external interface, the diffusion of the complex in the membrane phase, the stripping reaction at the internal interface and the reaction of silver ion with the reagent, HCL, in the internal phase to yield silver chloride incapable of permeating through the membrane phase. In addition, the leakage of the internal aqueous phase to the external aqueous phase due to membrane breakage has been incorporated in this model. The batch extraction of silver using D2EHPA as a carrier has been carried out under various experimental conditions. The experimental data can be well explained by the present model.     

Simplified model for extraction of rare-earth ions using emulsion liquid membrane

By considering the resistances of rare-earth ions in both the external and membrane phases, the interfacial reaction and the membrane breakage, a mathematical model for the extraction of rare-earth ions by batch emulsion liquid membrane process is established. Further, two simplified mass transfer equations are also derived from the proposed model in each of the specified cases. The validity of both the model and the resulting equations are tested by batch extraction of Sm³⁺ with emulsion liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier in kerosene. The experimental results show that both the proposed model and the resulting equations can simulate mass transfer process satisfactorily.     

Emulsion liquid membrane extraction of fission products promoted by polyvalent and organic acids

Emulsion liquid membranes (ELM) with di-2-ethylhexylphosphoric acid in n-alkane, and dipicrylamine and cobalt(III) dicarbollide in nitrobenzene stabilized in double emulsions by SPAN 80/85 surfactant were used for preconcentration of radioactive fission products (¹³⁷Cs,⁹⁰Sr,¹³⁹Ce, and¹⁵²Eu) from slightly acidic nitrate solutions. The efficiency of sulfuric, phosphotungstic and silicotungstic acids as stripping agents, and picric acid as the bulky anion additive was investigated. A group separation of the fission products is possible by the ELM technique and can be considered for their removal from waste water solutions.     

Metal ion retention by emulsion liquid membrane coupled to liquid-phase polymer-based retention

The capacity of polyelectrolytes (PELs) to enhance the metal ion retention in a double emulsion system (DES) was studied by diafiltration. Our results indicate that PELs can increase the maximum retention capacity of DES as functional groups of polymer are being saturated. Increase of retention can be explained by interaction between reverse emulsion globules and metal?Cpolymer species formed in solution. Assuming an inert membrane, if the amount of added metal ion is lower than the polymer??s maximum retention capacity, then the retention system behaves as if the polymer was the single retainer element in the filtration cell. For poly(acrylic acid), retention/adsorption and transport/regeneration processes were strongly associated to changes in hydrophilic?Clipophilic balance of polymer chains; whereas for poly(vinyl sulfonic acid) and poly(sodium 4-styrensulfonate), these processes were mainly associated to screening of surface charge density of macromolecule in solution.     

Transport of calcium and potassium ions in opposite directions in a liquid membrane system

A new type of 18-crown-6 derivative having two carboxylic acids on the side arms transported calcium and potassium ions in opposite directions across a dichloromethane membrane by pH control. Calcium and potassium ions were concentrated in the acidic and the basic phases, respectively. The presence of picrate ion in the acidic phase plays an important role in the transport of potassium ion from the acidic to the basic phase.