Rare Earth Metal Extraction by Liquid Surfactant Membranes Containing a Calixarene Carboxylate Derivative: Permeation Acceleration Effect of Sodium Ions

ABSTRACT

Calixarene carboxylate derivatives were used as a mobile carrier for rare earth permeation in a liquid surfactant membrane (LSM) system. The effect of alkali metal ions on the extraction behavior of rare earth metals in both liquid-liquid extraction and LSM systems has been studied. The addition of sodium ions considerably enhanced the extraction ability of rare earth metals in the extraction equilibrium. Furthermore, the presence of alkali metal ions in the material solution affected the rate of rare earth permeation in LSMs. The most accelerative transport of rare earth metals by LSMs was achieved by the addition of sodium ions. This acceleration effect of sodium ions was predominant in a tetracarboxylate calixarene whose cavity size just fits the ionic diameter of sodium ions. The sodium-loaded calix[4]arene derivative showed good performance as an effective mobile carrier for rare earth metals in the presence of sodium ions.     

Precipitate Foam Flotation of Copper,Nickel, Cobalt,and Manganese with LIX Reagents

Abstract

The precipitate flotation of copper, nickel, cobalt, manganese, zinc, and cadmium with LIX65 and LIX63 (hydroxyoxime compounds) and carrier surfactants hexadecyltrimethylammonium bromide and TX100 was investigated. The effects of pH and possibly interfering ions (sulfate, phosphate, EDTA) were studied. LIX65 was found to give good results with copper, nickel, cobalt, and manganese; LIX63 was less satisfactory.     

Separation of Palladium and Silver from a Nitric Acid Solution by Liquid Surfactant Membranes

Abstract

The recovery of palladium from a nitric acid solution containing silver has been conducted by application of liquid surfactant membranes (LSMs) containing LIX 860, a β-hydroxyoxime, as a mobile carrier in a stirred tank. The extraction equilibria of palladium and silver using several different extractants were also studied. Palladium was selectively extracted from a silver-containing liquor with LIX 860 while it was also observed that both palladium and silver were extractable with a sulfur-containing extractant. The recovery of palladium with LIX 860 was selectively achieved by using perchloric acid solution as the LSM internal phase dosed with thiourea. In the LSM operation, the effects of several chemical parameters on the selective recovery of palladium were studied. The use of hydrochloric acid as an internal receiving phase prevented the transport of silver into the emulsion due to the formation of silver chloride in the external feed solution. Commercially available Span 80 was found suitable for the selective extraction of palladium as a surfactant in LSM operation. Under optimum conditions, palladium was successfully separated from silver and concentrated into a receiving phase in W/O emulsions.     

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.     

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.

     

Reagent Degradation in the Synergistic Solvent Extraction System LIX®63/Versatic™10/Nonyl-4PC

Direct solvent extraction of nickel and cobalt from nitrate-based leach liquors has become of interest due to the successful piloting of nitric acid processes for treating nickel laterite ores. The current study investigated the stability of both hydroxyoxime and nonyl-4PC (nonyl-4-pyridine carboxylate) in LIX 63/Versatic 10/nonyl-4PC under conditions relevant to the recovery of nickel and cobalt from a nitrate-based leach liquor with stripping into sulfuric acid. Nonyl-4PC increased both the rate of hydroxyoxime degradation under the pH 1.5 extract conditions required for a potential nickel–cobalt separation process and the rate of cobalt poisoning of LIX 63. Under strip conditions and the pH 4 extract conditions required for co-extraction of nickel and cobalt, nonyl-4PC did not otherwise affect the rate of hydroxyoxime loss. Additionally, the presence of nitrate anions did not increase the loss of either hydroxyoxime or nonyl-4PC. The combination LIX 63/Versatic 10/nonyl-4PC therefore appears prospective for the co-extraction of nickel and cobalt at pH 4 from nitrate-based leach liquors.     

Structure of the Extracted Complex in the Ni(II)‐LIX84I System and the Effect of D2EHPA Addition

Abstract

The structure of the Ni(II) complex extracted with the commercial hydroxyoxime, LIX84I, and the effect of adding bis(2‐ethylhexyl) phosphoric acid (D2EHPA) to LIX84I on the extraction rate and the coordination of Ni(II) were investigated by solvent extraction and XAFS methods. The XANES spectrum and the curve fits of the EXAFS spectrum of the Ni‐LIX84I complex showed that the complex is four‐coordinate square‐planar with a 1:2 stoichiometry. In the Ni(II)–D2EHPA–LIX84I system, the coordination geometry changes from square‐planar to six‐coordinate octahedral with an increase in the D2EHPA concentration. Although the rate of Ni(II) extraction from the model spent electroless nickel plating bath with LIX84I is significantly accelerated by adding a small amount of D2EHPA ([LIX84I]: 0.5 M, [D2EHPA]: 0.05 M), most of the Ni(II) complexes extracted with this organic solution remain square‐planar. This indicates that the increase in the extraction rate does not depend on the change in the coordination structure of the extracted complex.     

Development of Spiral-Type Supported Liquid Membrane Module for Separation and Concentration of Metal Ions

Abstract

Experiments on the single permeation of cobalt, nickel, and zinc, and the simultaneous permeation of cobalt and nickel were performed using newly developed spiral-type supported liquid membrane modules. These metal ions were successfully separated and concentrated. EHPNA (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) was used as the carrier of cobalt and nickel, and D2EHPA (di-(2-ethylhexyl)phosphoric acid) for the recovery of zinc. In these modules the flow pattern of both feed and stripping solutions is plug flow, which led to very high recovery of metal ions. For example, 99.97% of cobalt in the feed was recovered in a once-through operation, and cobalt could be pumped against its concentration gradient even if the ratio of the metal concentration in the strip phase to that in the feed phase was as high as 70,000. It was confirmed by a life test of the module that the membrane was stable for more than one month without appreciable decrease in metal flux, and that the degraded membrane could be easily and rapidly regenerated without interrupting the permeation of metal ions by re-impregnating the module with the organic membrane solution. The degree of removal for both single and simultaneous permeation of cobalt and nickel was satisfactorily simulated by design equations of the module and the flux equations in which the formation of aggregates of metal-carrier complexes was taken into account.     

Selective transport of cobalt (II) from ammoniacal solutions containing cobalt (II) and nickel (II) by emulsion liquid membranes using 8-hydroxyquinoline

The selective transport of cobalt (II) from ammoniacal solutions containing nickel (II) and cobalt (II) by emulsion liquid membranes (ELMs) using 8-hydroxyquinoline (8-HQ) as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (ECA 4360J), and an extractant (8-HQ). Very dilute sulphuric solution buffered at pH 5.0 has been used as a stripping solution. The ammoniacal feed solution pH was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt (II) have been studied. These variables are membrane composition, pH of the feed solution, cobalt (II) and nickel (II) concentrations of the feed solution, stirring speed, surfactant concentration, extractant concentration, complexing agent concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively transport 95.0% of cobalt (II) from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt (II) with respect to nickel (II), based on initial feed concentration, have experimentally found to be of as high as 31 for equimolar Co(II)–Ni(II) feed solution.     

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.     

A Reaction Flux Model for Extraction of Cu(II) with LIX84I in HFSLM

Hollow fiber supported liquid membrane (HFSLM) is a favorable method to extract both valuable compounds and heavy metal pollutants such as chromium, copper, and nickel at a very low concentration. In this work, the extraction of Cu(II) by LIX84I dissolved in kerosene was theoretically and experimentally investigated. A model to estimate the percentage of extraction of copper ions from synthetic water considering the effect of reaction flux in membrane phase of the HFSLM system was studied. H₂SO₄ solution was used as the stripping solution. The facilitated transport mechanism of the chemical reaction at the feed-membrane interface was taken into account in the model equations. The percentage of copper ion extraction was plotted against its initial concentration in feed and also feed flow rate. Subsequently, the separation time and separation cycle were determined in accordance with the simulated values of copper ion concentration and the feed flow rate from the model. The modeled results were in good agreement with the experimental data at the average percentage of deviation about 2%.     

Interfacial Mass Transfer in Ligand Accelerated Metal Extraction by Liquid Surfactant Membranes

Abstract

Interfacial mass transfer rates were determined for the extraction of Co(II), Ni(II), and Cu(II) by di-(2-ethyl hexyl) phosphoric acid by using a modified Lewis cell. This allowed us to elucidate the effect of ligands on liquid surfactant membrane extraction of heavy metal ions by ligand addition to the external aqueous phase. The effects of different ligands on the kinetics of extraction and the influence of surfactant on interfacial resistance to mass transfer were then examined.     

Mechanistic study of cobalt,nickel and copper transfer across a supported liquid membrane

The mechanism of cobalt, copper and nickel transport through supported liquid membranes containing di(2-ethylhexyl)phosphoric acid as a mobile carrier has been studied. An equation describing the permeation rate has been derived, taking into account stagnant layer aqueous diffusion, interfacial resistance due to solvatation reaction and liquid membrane diffusion as simultaneous controlling factors. The validity of this model is evaluated with experimental data of mass transfer coefficient measured employing a permeation cell. For these ions it was found that at low stirring conditions the stagnant layer resistance mainly controlled the processes, but it is controlled by diffusion of the ion complex through the supported liquid membrane when the stagnant layer resistance is negligible.     

The Effect of Hydroxyoxime Isomer Conformation on Metal Extraction in the LIX 63/Versatic 10 Synergistic System

LIX 63 contains an aliphatic α-hydroxyoxime as its active component, with two isomeric forms (anti and syn) being present in a 3:2 ratio in “as supplied” reagent. In the present work, > 90% pure syn hydroxyoxime was isolated from LIX 63. Examination of metal extraction properties in systems containing Versatic 10 with anti and/or syn hydroxyoxime established unequivocally that the syn isomer plays no beneficial role in metal extraction in this synergistic solvent extraction system, thereby excluding the possibility of monodentate coordination of hydroxyoxime. Economic consequences arising from this outcome and the opportunity to maximize reagent utilisation are briefly discussed.     

Selective and Synergistic Extraction of Nickel from Simulated Cr-Ni Electroplating Bath Solutions using LIX 63 and D2EHPA as Carriers

The main goal of the present study is to explain synergistic extraction of nickel from simulated Cr-Ni electroplating bath solutions (SEBS) using 5,8-diethyl-7-hydroxydodecane-6-one oxime (LIX 63) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) as extractants by emulsion liquid membrane (ELM) technique. The importance of membrane composition and aqueous phase properties on nickel extraction percentage has been highlighted for the selective extraction of nickel. Some important parameters like acid concentration, stripping solution type and concentration, mixing speed, extractant concentrations, phase ratio, and surfactant concentration was studied to improve the extraction and stripping efficiencies. Higher than > 99% of nickel was recovered at optimum conditions within 6 min. The higher separation factors (β_Ni/Cr) were obtained as 580. As a result, the nickel extraction kinetic with D2EHPA has been defined as faster than LIX63. So, the kinetic transport of nickel mainly depends on LIX63 than D2EHPA. According to these results, D2EHPA behaves as a synergistic extractant in the present extraction mechanism.     

Solvent Extraction of Europium with Diisostearylphosphoric Acid and Its Application to an Emulsion Liquid Membrane Technique

Abstract

The extraction equilibrium of europium (Eu) with diisostearylphosphoric acid (DISPA, HR) was measured in various solvents at 303 K. The stoichiometry of the complex extracted and the extraction equilibrium constants were determined. The extraction rate of Eu with DISPA was measured using a stirred transfer cell. The extraction rate was found to be limited by the diffusion process. The permeation of Eu through an emulsion liquid membrane containing DISPA as a carrier and Span 80 as a surfactant was carried out. Under the experimental conditions, the reaction resistance contributed to the overall permeation process. An interfacial reaction model was proposed to explain the experimental results.     

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.     

Coupled transport of copper through different commercial supports containing LIX 984 as carrier

The coupled transport of copper(II) ions through a supported liquid membrane containing LIX 984 as the mobile carrier dissolved in kerosene has been studied. Many commercial membrane supports were investigated at different stirrer speeds in a permeation cell. An equation describing the permeation rate has been derived, taking into account stagnant layer aqueous diffusion and liquid membrane diffusion. By means of this treatment the copper overall transfer resistance and the experimental determination of the effective porosity factor (ε/τ), for each support have been performed. The Accurel^® 2E-PP membrane showed a relatively high value of ε/τ (0·91), which makes this membrane an adequate support when the transport properties of the supported liquid membrane are concerned. © 1998 SCI     

Mass Transfer Rate through Liquid Membranes: Interfacial Chemical Reactions and Diffusion as Simultaneous Permeability Controlling Factors

Abstract

Equations describing the permeability of a liquid membrane to metal cations have been derived taking into account aqueous diffusion, membrane diffusion, and interfacial chemical reactions as simultaneous permeability controlling factors. Diffusion and chemical reactions have been coupled by a simple model analogous to the one previously described by us to represent liquid-liquid extraction kinetics. The derived equations, which make use of experimentally determined interfacial reaction mechanisms, qualitatively fit unexplained literature data regarding Cu²⁺ transfer through liquid membranes. Their use to predict and optimize membrane permeability in practical separation processes by setting the appropriate concentration of the membrane carrier [LIX 64 (General Mills), a commercial β-hydroxy-oxime] and the pH of the aqueous copper feed solution is briefly discussed.     

THE COMPETITIVE PERMEATION OF COBALT AND NICKEL WITH SUPPORTED LIQUID MEMBRANES

In this paper, the competitive permeation of cobalt and nickel from nitrate solutions through supported liquid membranes was studied, in which contained 2-ethylhexyIphosphonic acid mono-2-cthylhexyl ester (HEHEHP) dissolved in kerosene as a mobile carrier. The permeation rate equations were derived taking into account the aqueous film diffusion of metal ions towards and out of the membrane and the membrane diffusion of HEHEHP and its metal complexes. The mass transfer coefficients of metal ions and metal-HEHEHP complexes were also determined using the permeation cell. It was found that the calculated permeation rates were in good agreement with the measured ones.