Separation of Cobalt by Liquid Surfactant Membranes

Abstract

An experimental study is presented on the separation of cobalt(II) cations from an aqueous solution by means of liquid surfactant membranes containing the ion exchanger di(2-ethylhexyl)phosphoric acid. The process was studied at various emulsifier (Span 80) concentrations, membrane viscosities, pHs, and rates of stirring as well as at various KNO₃ and cobalt concentrations. Cobalt recovery over 99% was achieved with up to tenfold enrichment. A substantial difference of the process course for cobalt and copper was found which allowed for their effective separation.     

Separation of Cobalt and Nickel by Liquid Surfactant Membranes Containing a Synthesized Cationic Surfactant

ABSTRACT

Separation of cobalt(II) and nickel(II) by using a hydroxyoxime extractant has been investigated both in liquid-liquid extraction and in a liquid surfactant membrane(LSM) system. In the liquid-liquid equilibrium extraction studies, hydroxyoximes showed significant extractability for nickel ions, although LIX 84 was found to have exceptional chelating affinity for nickel ions. In the LSM system functionalized by hydroxyoxime, the cobalt ions were efficiently separated from nickel ions as a result of slower permeation of nickel chelates across the emulsion membrane. More complete cobalt recovery was achieved in the LSMs dosed with LIX 860 than when the same carrier was applied to the liquid-liquid extraction system. Furthermore, cobalt permeation rate was enhanced threefold when a quaternary ammonium type of cationic surfactant was used as an emulsifier due to carrier interaction with surfactant at the reaction interface. The permeation mechanism of ions in LSMs was elucidated by an interfacial reaction model which took into account the adsorption of the carrier and surfactant at the reaction interface.     

Separation of Cobalt and Nickel with Phenylphosphonic Acid Mono-4-tert-octylphenyl Ester by Liquid Surfactant Membranes

Abstract

The separation of cobalt and nickel with liquid surfactant membranes (LSMs) was carried out in a stirred cell using a newly synthesized extractant. The effect of a surfactant on the kinetics of cobalt and nickel extraction was investigated to elucidate the role of a surfactant used in LSMs. The extraction equilibrium of these metals was also examined. Further, the interfacial tension between the organic and aqueous phases was measured to elucidate the adsorption equilibrium of a surfactant. It was found that the interfacial activity of the extractant is as high as that of a surfactant. In the extraction equilibrium study of these metals, extraction equilibrium constants were obtained for cobalt and nickel for the following equations:

Co²⁺ + 2(HR)₂=CoR₂(HR)₂ + 2H⁺ Ni²⁺ + 3(HR)₂=NiR₂2(HR)₂ + 2H⁺ The effects of the extractant and surfactant on the extraction rate of cobalt and nickel in LSMs were studied. The results were analyzed by a proposed model with an interfacial reaction, and rate constants were obtained for each metal. It was found that the new extractant has a very strong extractability for each metal compared with a conventional commercial extractant such as 2-ethylhexylphosphonic acid mono-2-elhylhexylester (commercial name, PC-88A) or di(2-ethylhexyl)phosphoric acid (D2EHPA). Further, a surfactant strongly affected the extraction rate and the separation of these metals, and a cationic surfactant was selected.     

Separation of Liquid Solutions by Contained Liquid Membranes

Abstract

The technique of contained liquid membranes (CLM) for liquid solution separation is discussed. The CLM is obtained by confining the membrane liquid between two sets of microporous hollow fibers (MHF). The lumen of the hollow fiber carries the feed or the strip solution under proper phase pressure condition vis-a-vis the membrane phase. Various possible structural configurations of the CLM are illustrated with respect to the nature of microporous hollow fiber substrate, the feed solution and the liquid membrane. The contributions of different resistances to the solute transport rate are identified. Some basic experimental data obtained in small CLM permeators are presented for two systems with organic liquid membranes to illustrate how steady state separation is achieved after an initial unsteady period. The considerable advantages of the CLM structure over more traditional liquid membrane techniques such as supported liquid membrane (SLM) with respect to membrane stability, membrane regeneration and feed equilibration are pointed out.     

Extraction of Rare Earth Metals Using Liquid Surfactant Membranes Prepared by a Synthesized Surfactant

Abstract

Three surfactants, l-glutamic acid dioleyl ester ribitol (nonionic, 2C ₁₈Δ⁹ GE), l-glutamic acid dioleyl ester quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ GEC ₂ QA), and dioleyl dimethyl quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ QA) were synthesized for potential use in liquid membrane operations. These surfactants have strongly hydrophobic, twin oleyl chains as the hydrophobic moiety. Using the synthesized surfactants, extraction of rare earth metals was carried out by liquid surfactant membranes in a stirred tank. The extraction behavior of 12 kinds of rare earth metals was systematically studied with 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (commercial name: PC-88A) as a carrier. Different surfactants having an identical hydrophobic moiety can have significantly different behaviors in rare earth extractions by liquid surfactant membranes, where extraction efficiency appears to be governed by the nature of the interfacial microenvironment between oil and water. An interfacial reaction model which takes into account the adsorption of a surfactant at the interface has been proposed to evaluate the permeation rate of rare earth metals by liquid surfactant membranes. It was found that a cationic surfactant strongly enhances the extraction rate of rare earth metals compared with the conventional surfactant, Span 80. The cationic surfactant 2C ₁₈Δ⁹ GEC ₂ QA appears to be one of the best surfactants currently available for rare earth extraction by liquid surfactant membranes.     

Separation of Hydrogen Sulfide from Wastewater by Emulsion Liquid Membranes

Hydrogen sulfide was separated from highly saline wastewater by emulsion liquid membranes (ELMs). Such membranes consist of polyalkenyl succinimide as emulsifying agent, diethanolamine as carrier, kerosene as membrane, and sodium hydroxide as stripping solution. The effect of four surfactants on the stability of ELMs was investigated and every operational parameter was tested. The highest achievable separation efficiency was 99.73 % for a 100 mg L^–1 solution. Obviously, the salinity of the external phase has a negligible effect on the separation of H₂S using ELMs.     

Separation of Palladium(II) and Platinum(IV) by Bulk Liquid Membranes during Electrodialysis

Abstract

The process of PdCl₄ ^2? and PtCl₆ ^2? separation extracting from binary hydrochloric mixtures as well as palladium(II) extraction from individual solutions by bulk liquid membranes containing diphenylthiourea and di‐o‐tolylthiourea in 1,2‐dichloroethane is studied at galvanostatic electrodialysis. The effects of the current density, the composition of the liquid membrane and of aqueous solutions on the rate of the metal transport are determined. It is shown that an effective separation of Pt(IV) from Pd(II) is achieved in the presence of an excess of the carrier. Maximum separation factor β_Pt/Pd of 380 is obtained in 1 hour of electrodialysis under optimal conditions. The transport of platinum(IV) is supposed to occur in the form of ionic associates (PdL₄Cl)₂PtCl₆. Platinum(IV) concentration and composition of the strip solution do not exert a considerable influence on the separation factor.     

Electrostatic Splitting of the Emulsion Used in Liquid Surfactant Membranes Process for Metals Separation

Abstract

A study has been carried out to investigate the effect of different parameters on the splitting process of the emulsion used in the liquid surfactant membranes process for metals separation. The influence of electric field strength, frequency of the applied ac voltage, and membrane recycling on emulsion stability have been studied. The investigations have revealed that there exists a unique optimal frequency range in which the best separation of the emulsion phases is obtained. The effect of the membrane composition and the variation of tri-n-butyl phosphate (TBP) concentration has been shown to vary linearly with the splitting efficiency. This finding correlates quite well with Sadek and Hendrick's equation on the force causing coalescence in an electric field.     

Extraction of Copper With Liquid Surfactant Membranes

Abstract

Studies of the extraction of copper with liquid surfactant membranes containing a mobile carrier were conducted in a stirred transfer cell. It was found that: (1) the resistance of the diffusion step in liquid surfactant membranes is negligible compared with that of the diffusion step accompanied with chelating complex formation in the outer aqueous solution, (2) the initial rate of copper extraction varied inversely as the 0.5 power of hydrogen-ion concentration in the low-pH range, but in the high-pH range was not affected by hydrogen-ion concentration, (3) the initial rate of copper extraction was proportional to the concentration of benzoylacetone, which is the mobile carrier in the membranes, in the low-pH range, but the rate was scarcely affected by benzoylacetone concentration in the high pH and benzoylacetone concentration ranges. These results are consistent with a model of liquid surfactant membranes which is presented.     

Palladium Extraction from Nitric Acid Solutions by LIX 84 and LIX 860-I

ABSTRACT

The extraction of Pd(II) from weakly nitric acid solutions by LIX 84 (2-hydroxy-5-nonylacetophenone oxime) and LIX 860-I (5-dodecylsalicylaldoxime) dissolved in toluene has been studied and compared from the viewpoint of extraction equilibria. The effects of pH, nitrate ions and metal and extractant concentrations on the palladium distribution ratio have been quantified. The extraction rate of Pd(II) from this media is slow but the metal is quantitatively extracted by adding just the stoichiometric amount of the extractants. The experimental data have been treated graphically and numerically by means of the Letagrop-Distr program and can be explained by assuming the formation of the chelate PdL₂. Values of the extraction constants are also given.     

Separation of Metal Species by Supported Liquid Membranes

Abstract

The works performed in the Separation Chemistry Group of the Chemistry Division of Argonne National Laboratory on the transport and separation properties of supported liquid membranes (SLM) are reviewed. The models and equations which describe the permeation through SLMs of metal species are described. These models have been tested with various carriers absorbed on flat-sheet and hollow-fiber SLMs by measuring the permeation of several metal species of hydrometallurgical and nuclear interest. An equation for the separation factor of metal species in SLM processes and examples of separations of metal ions are reported. The possibility of bypassing the single stage character of SLM separations by using multilayer composite SLMs, arranged in series, is also analyzed. Finally, the factors which control the stability of SLMs are briefly discussed.     

Separation of Ethyl Esters of Eicosapentaenoic Acid and Docosahexaenoic Acid by Circulating Liquid Membranes Using Silver Nitrate as a Carrier. Uphill Transport by Use of Temperature and Solvent Dependencies of Distribution Ratio

Abstract

Experiments on the separation of ethyl ester of eicosapentaenoic acid (EPA-Et) and that of docosahexaenoic acid (DHA-Et) contained in ethyl ester of bonito oil (bonito oil-Et) were performed using circulating liquid membranes (CIRLMs) containing sliver nitrate as a carrier. In this liquid membrane system an aqueous silver nitrate solution was circulated between a stirred vessel containing an organic solution of bonito oil-Et and another stirred vessel containing a receiving organic solvent. Using the CIRLM, two types of uphill facilitated transport of EPA-Et and DHA-Et in bonito oil-Et were demonstrated. The first type utilizes the distribution ratio of EPA-Et and DHA-Et, defined as the ratio of the concentration in the aqueous phase to that in the organic phase at equilibrium, which is remarkably dependent on the temperature, and the second uphill transport was based on the fact that the distribution ratio is considerably dependent on the solvent of the organic phase. A model of permeation through the circulating liquid membrane was proposed to explain the experimental results.     

乳状液膜法分离富集废旧镍镉电池中的镉

该文介绍了乳状液膜法分离富集废旧镍镉电池中的镉离子。乳状液膜主要由溶剂(煤油)、表面活性剂(Span80)、载体〔二(2-乙基己基)膦酸,P204〕和内水相氨水组成。对影响镉离子渗透和分离过程的重要变量进行了考察,分析了乳状液膜的载体体积分数、外水相pH、搅拌时间、乳水比(乳液与外水相体积比)及Span80体积分数对镍镉分离效果的影响,从而选择出最佳的分离条件为:φ(P204)=4.4%,φ(Span80)=8.8%,pH=5.5,乳水比0.5,搅拌时间10min。用此乳状液膜进行100L反应釜的工业放大实验,镉的迁移率可达93.3%,而镍的迁移率仅为14.6%。     

Selective Separation of Gallium from Acidic Leach Solutions by Emulsion Liquid Membranes

Abstract

The separation and concentration of gallium from acidic leach solutions, containing various other ions such as iron, cobalt, nickel, zinc, cadmium, lead, copper, and aluminium, by an emulsion liquid membrane (ELM) technique using tributyl phosphate (TBP) as carrier has been presented. Liquid membrane consists of a diluent, a surfactant (ECA 4360J), and an extractant (TBP), and 0.1 M HCl or 0.1 M H₂SO₄ were used as the stripping solution. The important variables governing the permeation of gallium and their effect on the separation process have been studied. These variables were membrane type and composition, mixing speed, diluent type, surfactant concentration, extractant concentration, HCl concentration in the feed, acid type of stripping phase, feed concentration, and treatment ratio. The optimum conditions were determined. It was possible to selectively extract 96.0% of gallium from the acidic leach solutions, containing Fe, Co, Ni, Zn, Cd, Pb, Cu, and Al, at the optimum conditions.     

液膜分离技术

本文简要介绍了液膜分离技术的发展概况、分类和传质机理,在此基础上介绍了支撑液膜的研究现状,并对液膜分离技术的发展前景进行了展望。     

Separation of Hydrocarbons by Liquid Surfactant Membrane with a Batch Stirred Vessel

Abstract

Extraction experiments on liquid membrane permeation were conducted in a batch stirred vessel to separate aromatics from an aromatics-nonaromatics binary mixture as an inner oil phase in the emulsion. The investigations were conducted under various material systems (hydrocarbon feeds, aqueous membrane phases) and the mass transfer coefficient in the emulsion (dispersed phase) was measured. Independently of the system of hydrocarbon feed and aqueous membrane solution, the mass transfer coefficient of the dispersed phase could be correlated with the dimensionless stirring time and the solubility of the aqueous membrane phase. The batchwise results agree fairly well with previous results reported for continuous operation.     

含铜硝酸退镀液中铜的回收和硝酸的再生

用草酸铜沉淀法回收含铜硝酸退镀液中的铜并再生硝酸。研究了草酸加入系数(n_(草酸)∶n_(铜))、反应时间及反应温度等对沉淀效果的影响。确定的最佳工艺条件为:Cu~(2+) 136.52g/L,草酸加入系数0.9,搅拌速率300r/min,28℃,60min。在此工艺条件下,铜的沉淀率约为90%,草酸残留率小于1%,草酸铜产品的纯度达到98.33%。     

Membrane Aging and Related Phenomena in Liquid Surfactant Membranes Process

Abstract

The membrane aging phenomenon and its influences on the kinetics of cobalt(II) permeation by the liquid surfactant membranes (LSM) process has been studied. The experimental results showed that the emulsion formulated from the internal aqueous phase and the membrane (organic phase) of a certain age has far-reaching consequences on the kinetics of metal extraction and emulsion stability. The investigations have revealed that there exists an optimal age and composition of the membrane in which the highest extraction (synergism) and the lowest emulsion swelling are achieved. Analytical and instrumental examinations of the membrane phase during aging have shown various chemical and physical changes as a result of the surfactant decomposition, reaction products precipitation and self-association, and macroemulsion formation.