Transport of mercury(II) ion through a supported liquid membrane containing a triisobutylphosphine sulfide (Cyanex 471X) as a mobile carrier

Carrier‐facilitated transport of mercury(II) against its concentration gradient from aqueous 0.1 mol dm^?3 hydrochloric acid solution across a flat‐sheet supported liquid membrane (SLM) containing triisobutylphosphine sulfide (Cyanex 471X) as the mobile carrier in kerosene as diluent has been investigated. Dilute sodium thiocyanate solution (0.11 mol dm^?3) was the most efficient stripping agent among several aqueous reagents tested. Various parameters such as stirring rate, concentration of HCl in the feed solution, concentration of NaSCN in the strippant, concentration of Cyanex 471X in the membrane, and contact time were investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is about 100% after 6 h. The carrier, Cyanex 471X, selectively and efficiently transported Hg(II) ions in the presence of other associated metal ions. The method has been demonstrated to recover selectively mercury from waste samples and mercurochrome solution. © 2002 Society of Chemical Industry     

The extraction of platinum from Pt(II) chloride solution by a quaternary ammonium compound

The fundamental aspects of the extraction and stripping of platinum (II) from its chloride solution by Aliquat 336 diluted with toluene have been studied. The extraction and stripping was at 99.5 and 97.6% equilibrium within 30 s and 20 min respectively. The percentage extraction increased slightly with decreasing hydrochloric acid concentration. In 0.1 mol dm^?3 hydrochloric acid, 1.0 volume percent Aliquat 336 in toluene could load 9.8 mmol dm^?3 of platinum (II). The percentage stripping of platinum (II) from Pt(II)-load organic solvent increased with increasing sodium bisulphite concentration. The enthalpy changes of extraction and of stripping were 12.8 and 114.9 kJ mol^?1 respectively. Both of the reactions were endothermic.     

Liquid membrane transport and separation of Zn2+ and Cd2+ from sulfate media using organophosphorus acids as mobile carriers

The transport and separation of Zn²⁺ and Cd²⁺ from binary sulfate solutions in a supported liquid membrane using di(2‐ethylhexyl)phosphoric acid (D2EHPA) and 2‐ethylhexylphosphonic acid mono‐2‐ethylhexyl ester (PC88A) as mobile carriers was studied. Batch solvent extraction experiments were conducted to obtain the reaction stoichiometries. Experiments were performed at different metal concentrations (1.4–14.5 mol m^?3), metal concentration ratios (0.4–9.2), pH (2–5), and carrier concentrations (0.1–0.6 mol dm^?3). A mass transfer model was proposed that considers diffusion in the aqueous feed and strip stagnant layers, and within the membrane. The interfacial reactions were assumed to approach equilibrium instantaneously. It was shown that the proposed model was applicable for binary Zn²⁺/Cd²⁺ systems (standard deviation, 5%). The larger separation factors of Zn²⁺ over Cd²⁺ with PC88A than D2EHPA under equilibrium (batch solvent extraction) and non‐equilibrium (liquid membrane) conditions were also evaluated and discussed. Copyright © 2003 Society of Chemical Industry     

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     

Solvent extraction with LIX 973N for the selective separation of copper and nickel

LIX 973N diluted with Iberfluid was used to co‐extract copper and nickel from ammoniacal/ammonium carbonate aqueous media. The influence of equilibration time, temperature, equilibrium pH and extractant concentration on the extraction of both metals has been studied. It was observed that neither copper nor nickel extraction is sensitive to temperature and equilibrium pH, however nickel extraction equilibrium is reached at a longer contact time (20 min) than that of copper (5 min), in addition nickel extraction depends greatly on the extractant concentration in the organic phase. For a solution containing 3 g dm⁻³ each of copper and nickel and 60 g dm⁻³ ammonium carbonate, conditions were established for the co‐extraction of both metals, ammonia scrubbing and selective stripping (with H₂SO₄) of nickel and copper. Using the appropriate extractant concentration the yield (extraction stage) for both metals is near 100%, whereas the percentage of nickel and copper stripping is also almost quantitative. © 1999 Society of Chemical Industry     

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.     

Effect of an electric field on the transport of Th(IV) in the presence of Eu(III) and U(VI) through supported liquid membrane containing di‐2‐ethylhexylphosphoric acid

This paper investigates the transport of Th(IV) ions in nitric acid media through a supported liquid membrane (SLM) impregnated with di‐2‐ethylhexylphosphoric acid (HDEHP) in kerosene using an electric field. The transport was carried out in a three compartment cell fitted with microporous cellulose nitrate (SLM) and cation exchange membrane (Nafion). The effect of different parameters including nitric acid concentration in the feed solution, HDEHP concentration in the membrane, and HCl concentration were studied. The optimal conditions for Th(IV) transport were 0.1 mol dm^?3 HDEHP, 10^?3 mol dm^?3 HNO₃ in the feed solution, 1 mol dm^?3 HCl in compartment 2 and 1 mol dm^?3 HCl in compartment 3 at 25 °C. Under the optimal conditions of Th(IV) transport the recovery factor after 90 min was 0.25 without applying an electrostatic field, compared with 0.9 when the electric field was applied. The effect of electric current on the flux of Th(IV) through the membrane was also studied. The flux increased as the current density increased from 10 to 30 mA cm^?2 to reach a maximum value at 30 mA cm^?2 (8 × 10^?9 g eq cm^?2 s^?1). The transport percentages of 0.3 g dm^?3 Th(IV) in the presence of 0.1 g dm^?3 Eu(III) and 1 g dm^?3 U(VI) were 66, 84 and 15%, respectively. The determined selectivities of U(VI)–Th(IV) and Th(IV)–Eu(III) were 0.12 and 0.3, respectively, after 90 min. Therefore, the order of selectivity of this system is Eu(III) > Th(IV) > U(VI). © 2001 Society of Chemical Industry     

Recycling of nickel–metal hydride batteries. II: Electrochemical deposition of cobalt and nickel

A combination of hydrometallurgical and electrochemical processes has been developed for the separation and recovery of nickel and cobalt from cylindrical nickel–metal hydride rechargeable batteries. Leaching tests revealed that a 4 mol dm^?3 hydrochloric acid solution at 95 °C was suitable to dissolve all metals from the battery after 3 h dissolution. The rare earths were separated from the leaching solution by solvent extraction with 25% bis(2‐ethylhexyl)phosphoric acid (D2EHPA) in kerosene. The nickel and cobalt present in the aqueous phase were subjected to electrowinning. Galvanostatic tests on simulated aqueous solutions investigated the effect of current density, pH, and temperature with regard to current efficiency and deposit composition and morphology. The results indicated that achieving an Ni? Co composition with desirable properties was possible by varying the applied current density. Preferential cobalt deposition was observed at low current densities. Galvanostatic tests using solutions obtained from treatment of batteries revealed that the aqueous chloride phase, obtained from the extraction, was suitable for recovery of nickel and cobalt through simultaneous electrodeposition. Scanning electron micrography and X‐ray diffraction analysis gave detailed information of the morphology and the crystallographic orientation of the obtained deposits. Copyright © 2004 Society of Chemical Industry     

Removal and recovery of gallium and indium lons in acidic solution with chelating resin containing aminomethylphosphonic acid groups

Removal and recovery of gallium and indium ions in acidic solution with the macroreticular chelating resin containing aminomethylphosphonic acid groups was investigated. The resin (RMT-P) exhibited high affinity for gallium and indium ions in sulfuric acid solution. In the column method, gallium and indium ions in sulfuric acid solution (0.05 or 0.5 mol/dm³) were favorably adsorbed on the RMT-P when the solution containing 27.6 mg/dm³ of gallium ion or 51.4 mg/dm³ of indium ion was passed through the RMT-P column at a space velocity of 15 h^?1. The gallium and indium ions adsorbed were eluted by allowing 1 mol/dm³ sodium hydroxide or 4 mol/dm³ hydrochloric acid to pass through the column. The proposed resin appears to be useful for the recovery of gallium and indium ions in sulfuric acid solution.     

Liquid Emulsion Membrane (LEM) Process for Vanadium (IV) Enrichment: Process Intensification

Abstract

A liquid emulsion membrane (LEM) system for vanadium (IV) transport has been designed using di‐2‐ethylhexyl phosphoric acid (D2EHPA), dissolved in n‐dodecane as carrier. The selection of extractant, D2EHPA, was made on the basis of conventional liquid‐liquid extraction studies. The work has been undertaken by first carrying out liquid‐liquid extraction studies for vanadium (IV) to get stoichiometric constant (n), and equilibrium constant (K_ex), which are important for process design.

Transport experiments were carried out at low vanadium (IV) concentration (ppm level). The studies on liquid emulsion membrane included i) the influence of process parameters i.e. feed phase pH, speed of agitation, treat ratio, residence time and ii) emulsion preparation study i.e., organic solvent, extractant concentration, surfactant concentration, internal strip phase concentration. When the strip phase concentration was 2 mol/dm³ (H₂SO₄) and feed phase pH 3 better extraction of vanadium was obtained. Higher V_m/V₁ gave higher extraction of vanadium (IV). A simplified, design engineer friendly model was developed.     

Distribution Behavior of Amino Acid by Extraction with Di(2-ethylhexyl) Phosphoric Acid

Abstract

The distribution equilibrium of l-tryptophan (l-Trp) by extraction with di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in n-hexane was studied. The effects of L-Trp and D2EHPA concentrations, pH, and ionic strength, particularly of L-Trp loading in the organic phase, on extraction equilibrium were examined in detail. When the amino acid loading ratio (the molar concentration ratio of the equilibrium amino acid in the organic phase to the initial dimeric D2EHPA) was less than 3 × 10^?3, one L-Trp molecule was extracted by forming a complex with four monomeric D2EHPA molecules, and the extraction equilibrium constant (K _e) was determined to be 0.045 dm³/mol. Above this loading ratio the equilibrium formula did not hold, and the apparent equilibrium constant (K _a) increased significantly with increasing loading ratio. The phenomenon was explained by taking into account two parallel reactions in which fewer D2EHPA molecules, two and one respectively, were needed to extract one l-Trp molecule.     

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.     

Synergistic interplay between D2EHPA and TBP towards the extraction of lithium using hollow fiber supported liquid membrane

Extraction of lithium (Li⁺) from synthetically prepared sea bittern using di-2-ethyl hexyl phosphoric acid (D2EHPA) and tri-n-butyl phosphate (TBP) as organic extractants has been studied. The equilibrium studies conducted show synergistic effect between D2EHPA and TBP. The equilibrium constant values for Li⁺, Na⁺ and K⁺ ions were found to be 95.4 × 10^?5 m³/kmol, 4.6 × 10^?5 m³/kmol and 3.69 × 10^?5 m³/kmol, respectively. Hollow fiber supported liquid membrane (SLM) experiments with low concentrations of Li⁺, Na⁺ and K⁺ ions in feed phase showed high flux for Li⁺ ions. However, at significantly high concentrations of Na⁺ and K⁺ in the feed phase, the flux of Li⁺ ions reduced. The model predictions were found to be in good agreement with the experimental data.     

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     

Extraction equilibria and separation of phenylalanine and aspartic acid from water with di(2‐ethylhexyl)phosphoric acid

The distribution equilibria of single and binary L ‐phenylalanine and L ‐aspartic acid between water and a kerosene solution of di(2‐ethylhexyl)phosphoric acid (D2EHPA) were studied. It was shown that the distribution ratios of phenylalanine generally increased with increasing aqueous pH (2–5) in the D2EHPA concentration range 0.1–0.5 mol dm^?3, but those of aspartic acid decreased with increasing solution pH. Different reaction stoichiometries were proposed for the extraction of phenylalanine and aspartic acid under the conditions studied. The extraction equilibrium constants were obtained. Competitive extraction in binary systems was more apparent in the pH range where the cationic form of amino acids was not predominant. The present results indicated that selective separation of phenylalanine to aspartic acid was possible with this cationic extractant when they were extracted at higher pH and stripped using higher acidity of HCl solution. Copyright © 2006 Society of Chemical Industry     

Valeric acid extraction with tri‐n‐butyl phosphate impregnated in a macroporous resin: II. Studies in fixed bed columns

Extraction and back‐extraction of valeric acid in a fixed bed packed with Amberlite XAD‐4 resin impregnated with tri‐n‐butyl phosphate were experimentally studied at 25 °C. The effects of the feed flow rate, acid concentration in the feed solution and extractant concentration in the impregnated resin on the breakthrough curves, were investigated. The bed saturation capacity was larger under the conditions of higher extractant concentration in the resin phase and higher acid concentration in the feed solution. A dynamic model that considers intraparticle diffusion and external liquid film diffusion as limiting steps in mass transfer rates was successfully applied. The intraparticle effective diffusivities (10^?9 dm² s^?1) were from one to three orders of magnitude lower than the diffusivities in the external liquid film (10^?8–10^?6 dm² s^?1). A fast and complete back‐extraction of valeric acid from the saturated bed was carried out with sodium hydroxide solutions. The operational life of the impregnated resin was also studied. Copyright © 2005 Society of Chemical Industry     

Hollow fiber supported liquid membrane process for the separation of NH3 from aqueous media containing NH3 and CO2

A hollow fiber supported liquid membrane (SLM) process was investigated experimentally and theoretically for the separation of NH₃ from aqueous solutions containing NH₃ and CO₂. DTPA and D2EHPA were used as carriers and n-decanol was used as a diluent in this process. The membrane stripping experiments, as well as the extractive equilibrium experiments, indicate that DTPA is a better carrier than D2EHPA in relation to the increase in the NH₃ stripping rate. The influence of operating conditions, such as flow rate, the ratio of NH₃ to CO₂, and carrier concentration, on the membrane stripping rate were examined. The experimental data demonstrate that the NH₃ stripping rate by an SLM process is not significantly influenced by the amount of CO₂ present, as is that by the supported gas membrane. To predict the stripping of NH₃ from solutions containing NH₃ and CO₂, a mathematical model incorporating chemical equilibria and Nernst–Planck diffusion was developed to describe the mass transport. The experimental data suggested that the SLM process can effectively strip NH₃ from aqueous solutions containing NH₃ and CO₂.     

Studies on graft copolymerization of 4‐vinylpyridine onto guar gum

Graft copolymerization of 4‐vinylpyridine (4‐VP) onto guar gum (GOH) using potassium monopersulfate (PMS)/thioacetamide (TAA) as a redox pair was studied in an aqueous medium under inert atmosphere. The concentration of potassium monopersulfate and thioacetamide should be 1.0 × 10^?2 and 5.0 × 10^?3 mol dm^?3, respectively, for highest grafting ratio and efficiency. Efficient grafting was observed at 19.25 × 10^?2 and 4.87 × 10^?2 mol dm^?3 concentration of 4‐vinylpyridine and sulfuric acid, respectively. The optimum temperature for grafting is 30°C. As the time period of reaction is increased, the grafting ratio increases, whereas efficiency decreases. The plausible mechanism of grafting has been suggested. A sample of guar gum and guar‐ g‐4‐vinylpyridine were subjected to thermogravimetric analysis with the objective of studying the effect of grafting 4‐vinylpyridine on the thermal stability of guar gum. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2380–2385, 2002     

Mn‐peroxidase production by Panus tigrinus CBS 577.79: response surface optimisation and bioreactor comparison

This study reports the statistical optimisation through response surface methodology of the growth medium for Panus tigrinus manganese‐dependent peroxidase (MnP) production in shaken culture. Three crucial variables, including carbon source, malonic acid and Mn²⁺, were optimised in a nitrogen‐limited medium. Sucrose was the best carbon source for MnP production. Mn²⁺ ions and malonic acid significantly stimulated MnP production at an optimal concentration of 53 mg dm^?3 and 8.2 mmol dm^?3, respectively, resulting in 0.83 U cm^?3. Further experiments were performed in lab‐scale stirred tank (STR) and bubble‐column (BCR) reactors using the previously optimised liquid medium. BCR proved to be more adequate than STR in supporting MnP production, leading to 3700 U dm^?3 after 144 h with a productivity of 25.7 U dm^?3 h^?1. On a comparative basis with other production data in lab‐scale reactors, these results appear to be compatible with scale transfer. Copyright © 2006 Society of Chemical Industry     

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