Separation of Zinc Ions from an Acidic Mine Drainage using a Stirred Transfer Cell–Type Emulsion Liquid Membrane Contactor

Abstract

This is a report on the separation and recovery of zinc ions from an acidic mine drainage using a stirred transfer cell‐type emulsion liquid membrane contactor. Di(2‐ethylhexyl) phosphoric acid was used as a highly selective carrier for the transport of zinc ions through the emulsified liquid membrane. A study was made of the effect on the extraction extent and initial extraction rate of the following variables: pH and initial metal concentration of the feed phase, carrier content in the organic solution, a stripping agent concentration in the receiving phase, and stirring speed in the transfer cell. The content of sulfuric acid as a stripping agent did not show in the studied range any significant influence on metal permeation through the SLM, although a minimum hydrogen ion concentration of 100 g/L is suggested in the internal aqueous solution to ensure an acidity gradient between both aqueous phases to promote the permeation of metal ions toward the strip liquor. Results show that using a pH of 4.0 in the feed acid solution, a concentration of 3% w/w_o of phosphoric carrier in the organic phase and a H₂SO₄ content of 100 g/L in the strip liquor, the extent and rate of extraction through the liquid membrane can be highly favored, pointing to the potential of this method for extracting heavy metals from many kinds of dilute aqueous solutions.     

Selective Transport of a Peptide from Its Mixture with an Amino Acid Using a Supported Liquid Membrane Process

Abstract

Some experimental results on the separation of a peptide from a mixture of peptide and amino acid through a continuous supported liquid membrane process are described. As a model system a mixture of tryptophan (Trp, an amino acid) and tryptophan-leucine (Trp-Leu, a dipeptide) was chosen. The liquid membrane contained an anionic surfactant, sodium di-2-ethylhexyl sulfosuccinate (Aerosol OT/AOT), as a carrier dissolved in oleyl alcohol, as an organic solvent, supported on a commercial grade support (Celgard 2500). The liquid-liquid extraction experiments were carried out to study the influence of feed pH, feed and strip flow rates, and feed and carrier concentrations on the selective transport of Trp-Leu from its mixture with Trp. At pH 4–5 the transport rate of Trp-Leu was significantly higher than that of Trp. The increase in flow rate up to a value of 40 mL/h did not effect the selective removal of Trp-Leu. The flux rate increased with an increase of the carrier concentration up to 20% AOT, but the selectivity for Trp-Leu was highest at 10% AOT. An increase of Trp concentration up to 10-fold had little effect on the flux rate of Trp-Leu. The stability of SLM system in continuous removal of Trp-Leu from a single component system and from a binary mixture with Trp was studied. The effect of a competitive component did not alter significantly the flux rate and long-time performance in continuous operation. A procedure for regenerating SLM was examined, and the regenerated SLM performed as good as the freshly prepared one.     

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     

A Double Liquid Membrane System for the Removal of Actinides and Lanthanides from Acidic Nuclear Wastes

Abstract

Supported liquid membranes (SLM), consisting of an organic solution of n-octyl(phenyl)-N, N-diisobutylcar-bamoylmethylphosphine oxide (CMPO) and tributyl-phos-phate (TBP) in decalin are able to perform selective separation and concentration of actinide and lantha-nide ions from aqueous nitrate feed solutions and synthetic nuclear wastes.

In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of HNOs which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO₃ from the strip solution.

In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/ primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HN0₃ concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion.     

SOLVENT EXTRACTION OF ANTIMONY (III), BISMUTH (HI), LEAD (II) AND TIN (IV) WITH BIS(2,4,4-TRIMETHYLPENTYL)PHOSPHINODITHIOIC ACID (CYANEX 301®)

The solvent extraction of antimony (in), bismuth (111), lead (II) and tin (IV) from aqueous hydrochloric acid solutions by bis(2,4,4-trimethylpentyl) phosphinodithioic acid (Cyanex 301® denoted HL) in kerosene + 10 % v/v n-decanol was investigated. Lead (II), tin (IV), bismuth (III) and antimony (III) are efficiently extracted by Cyanex 301® up to about 5, 6, 9 and 11 mol.L^1? HCl, respectively. The corresponding extracted species were identified as PbL₂, SnCl₂L₂, BiL₃ and SMvj. However, it was observed that Sn (IV) can be moderately extracted from the aqueous phase by the mere mixture of kerosene and n-decanol above 9 mol.L^1?HCl. In all cases, extraction equilibrium was reached within a few minutes. Finally, a thermodynamic modelling of the extraction system was developed in the particular case of lead (II).     

Transport of Au(CN)2 − by Mixtures of Amine Primene JMT and Phosphine Oxide Cyanex 923 Using the Pseudo-Emulsion Based Hollow-Fiber Strip Dispersion Technology

The transport of Au(CN)₂ ^? between alkaline aqueous solutions and organic phases consisting of a mixture of the amine Primene JMT and the phosphine oxide Cyanex 923 in xylene was studied using the pseudo-emulsion based hollow-fiber strip dispersion (PEHFSD) technology. The feed phase was passed through the lumen side, and the pseudo-emulsions of the extractant mixtures and NaOH were passed through the shell side in a countercurrent mode using a single hollow-fiber contactor for extraction and stripping. In this membrane technology, the strippant (NaOH solution) is dispersed in the organic (Primene JMT + Cyanex 923 in xylene) membrane solution in a tank with an impeller stirrer adequate to form strip dispersion. The pseudo-emulsion phase is circulated from the reservoir tank to the membrane contactor to provide a constant supply of the organic solution to the membrane fibers. Furthermore, this technology allows a direct contact between the organic and strip solutions, providing a greater area for stripping and facilitating the metal recovery from the strip solution once both phases are separated. Various hydrodynamic and chemical parameters, such as flow of feed phase, extractant mixtures and gold concentrations, organic diluents, variation in feed pH, and the selectivity of the system with respect to the transport of different metal-cyano complexes, were investigated. Aqueous and membrane mass transfer coefficients were estimated for the present system.     

Transport of chromium(VI) through a Cyanex 921‐supported liquid membrane from HCl solutions

The transport of chromium(VI) through a flat‐sheet supported liquid membrane containing Cyanex 921 as a carrier has been investigated. The permeation of the metal is investigated as a function of various experimental variables: hydrodynamic conditions, concentration of chromium(VI) and HCl in the feed phase, carrier concentration and diluent in the membrane and strippant concentration in the stripping phase. The mass transfer coefficient and the thickness of the aqueous boundary layer were calculated from the experimental data. Furthermore, the selectivity of Cyanex 921‐based flat‐sheet supported liquid membrane towards different metal ions and the behaviour of the system against other carriers are presented. Copyright © 2003 Society of Chemical Industry     

Non-dispersive selective extraction of germanium from fly ash leachates using membrane-based processes

ABSTRACT

Non-dispersive selective extraction of Ge(IV) tartrates was carried out from simulated fly ash solutions containing heavy metals through supported liquid membranes (SLM). The optimum transport was obtained using a PTFE membrane containing Alamine 336 5%v/v in the condition of tartaric acid 2.76 mmol/L and HCl 1 mol/L in feed and strip phases, respectively. Under this condition, a hollow fiber (HF) SLM experiment was conducted. The results showed that this system could transport germanium from the feed to the strip phase so much faster than the flat sheet (FS) SLM system. The rate of transport through HFSLMs is comparable to dispersive extractions.

Abbreviation: A: Effective area of the membrane (cm²); BDL: Below detection limit; C_f,: Feed concentration (mg/L); C_t,: Initial concentration (mg/L); D: Distribution coefficient; ELM: Emulasion liquid membranes; FSSLM: Flat sheet supported liquid membrane; HF: Hollow fiber; LLX: Liquid-liquid extraction; P: Permeation coefficient (m/h); PTFE: Poly tetra fluoro ethylene; PVDF: Polyvinylidene difluoride; T: Tartrate species (C₄H₄O₆); T: Temperature (K); %T:Germanium transport effeciency; V: Volume of feed solution (cm³); t: time (h); η: Viscosity (P.s (c.P)); κ: Boltzmann constant; r: Ionic radius of species; τ: Tortuosity of the membrane; ρ: Porosity; α: Separation factor.     

Separation of As(III) and As(V) by hollow fiber supported liquid membrane based on the mass transfer theory

Separation of As(III) and As(V) ions from sulphate media by hollow fiber supported liquid membrane has been examined. Cyanex 923 was diluted in toluene and used as an extractant. Water was used as a stripping solution. The extractability of As(V) was higher than As(III). When the concentration of sulphuric acid in feed solution and Cyanex 923 in liquid membrane increased, more arsenic ions were extracted into liquid membrane and recovered into the stripping solution. The mathematical model was focused on the extraction side of the liquid membrane system. The mass transfer coefficients of the aqueous phase (k _i ) and organic phase (k _m ) are 7.15×10⁻³ and 3.45×10⁻² cm/s for As(III), and 1.07×10⁻² and 1.79×10⁻² cm/s for As(V). Therefore, the rate-controlling step for As(III) and As(V) in liquid membrane process is the mass transfer in the aqueous film between the feed solution and liquid membrane. The calculated mass transfer coefficients agree with the experimental results.     

Separation of Silver(I) and Copper(II) from Aqueous Solutions by Transport through Polymer Inclusion Membranes with Cyanex 471X

In this work the selective transport of silver(I) and copper(II) ions from aqueous nitrate(V) solutions by transport through polymer inclusion membrane (PIM) has been studied. The membrane consisted of cellulose triacatate (CTA) as the polymeric support, o-nitrophenyl pentyl ether (ONPPE) as the plasticizer and Cyanex 471X (triisobutylphosphine sulphide) as the ion carrier. Ag(I) ions were effectively removed from the source phase by transport through PIM into 0.01 M Na₂S₂O₃ as the receiving phase. The influence of membrane composition on the transport of silver(I) ions has been evaluated.     

Coupled transport of Pb2+ through tri‐n‐octylamine‐xylene‐polypropylene supported liquid membranes

Transport of Pb²⁺ was carried from acidic solution into alkaline stripping phase through tri‐n‐octylamine‐xylene‐polypropylene supported liquid membrane. The transport of Pb²⁺ through the membrane was studied by varying the concentration of Pb²⁺ and HNO₃ in feed solution, NaOH concentration in strip solution and TOA concentration in membrane phase. The flux data obtained has been used to study the stoichiometry of complex Pb(NO₃)_n+2(HNR₃)_n. The supported liquid membrane (SLM) has been found stable for 10 runs with 24 h between each run. This SLM has been used effectively to extract lead ions along with chromium, copper and zinc ions from aqueous acidic leached solution of paint and industrial effluents. © 2012 Canadian Society for Chemical Engineering     

Studies on permeation of uranium (VI) from phosphoric acid medium through supported liquid membrane comprising a binary mixture of PC88A and Cyanex 923 in n-dodecane as carrier

Present studies deal with the application of supported liquid membrane (SLM) technique for the separation of uranium (VI) from phosphoric acid medium using a binary mixture of 2-ethyl hexyl phosphoric acid-mono-2-ethyl hexyl ester (PC88A) and neutral donor which is a mixture of four tri-alkyl phosphine oxide better known as Cyanex 923 in n-dodecane as a carrier and (NH₄)₂CO₃ as a receiving phase. Various parameters like feed acidity, nature of strippant, carrier concentration, membrane pore size, membrane thickness etc. which affect the transport of U(VI) have been studied in detail. Experiments have also been carried out to see the transport behaviour of different fission products from a diluted High Level Waste (HLW) solution. Stability of the membrane against the leaching of the extractant and stability of the membrane support have also been investigated. We have tried to model the physicochemical transport of U(VI) in SLM as well as establishing the mechanism (Diffusion controlled) of transport. More than 95% uranium (VI) is recovered in 360 min using a binary mixture of 0.60 M PC88A and 0.15 M Cyanex 923 in n-dodecane as carrier and 0.5 M (NH₄)₂CO₃ as stripping phase from the 0.5 M H₃PO₄ feed. Lower concentration of H₃PO₄ (0.5 M) and optimum carrier concentration (0.60 M PC88A + 0.15 M Cyanex 923) in the mole ratio of 4:1 is found to be the most suitable condition for maximum transport of uranium (VI). The optimum conditions obtained from this study was also applied to recover uranium from analytical waste in phosphoric acid medium generated in the laboratory.     

Transport of Chromium(VI) through a Supported Liquid Membrane Containing Tri-n-octylphosphine Oxide

ABSTRACT

In this study the transport of chromium(VI) from aqueous solutions of pH 2–4 through a supported liquid membrane (SLM) with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene as a mobile carrier was investigated. The transport flux of Cr(VI) increased with an increase in the concentrations of Cr(VI) in the feed phase and of TOPO in the membrane phase, but with a decrease in pH of the feed phase. Considering the equilibria of various Cr(VI) species in the aqueous phase and of the Cr(VI)—TOPO complexes formed in the membrane phase, a permeation model including the aqueous film diffusion of HCrO₄ ^? and Cr₂O₇ ^2? toward the membrane, the interfacial chemical reaction between them and TOPO, and the membrane diffusion of the Cr(VI)—TOPO complexes (H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃) was proposed to describe the transport of Cr(VI) through the SLM. By best fitting the transport flux equations of Cr(VI) with the experimental data using the Rosenbrock method, the apparent mass-transfer coefficients of HCrO₄ ^? and Cr₂O_7^. across the aqueous film, and those of H₂CrO₄(TOPO) and H₂Cr₂O₇(TOPO)₃ across the membrane phase, were obtained. This work helps to clarify the transport mechanism of Cr(VI) through an SLM.     

Supported Liquid (SLM) and Polymer Inclusion (PIM) Membranes Pertraction of Copper(II) from Aqueous Nitrate Solutions by 1-Hexyl-2-Methylimidazole

The facilitated transport of Cu(II) ions from different aqueous nitrate source phases (c _Me = 0.001 M, pH = 6.0) across supported (SLMs) and polymer inclusion membranes (PIMs) doped with 1-hexyl-2-methylimidazole as ion carrier was reported. The membrane is characterized by means of atomic force microscopy (AFM). The results show that Cu²⁺ can be separated very effectively from other transition metal cations as Zn²⁺, Co²⁺, and Ni²⁺ from different equimolar mixtures of these ions. The highest initial fluxes of Cu(II) were found for PIM, while lower values were observed for SLM. However, after taking into account the morphology of the membranes (porosity, tortuosity), the values of the initial flux of Cu(II) transport across PIM is less than that across SLM. The recovery factor of Cu²⁺ ions during transport across PIM from different mixtures of cations is above 91% after 24 hrs and above 76% during transport across SLM. Also, the stability of PIM and SLM doped with 1-hexyl-2-methylimidazole was confirmed in replicate experiments.     

Iridium(IV) Transport across Trioctylamine Supported Liquid Membrane

Abstract

Transport behavior of iridium through a supported liquid membrane (SLM) was investigated using trioctylamine (TOA) as a mobile carrier. Iridium(IV) was almost quantitatively extracted with TOA in kerosene from a low HCl solution, and extracted Ir(IV) was stripped with an HClO₄ or HNO₃ solution. Based on the extraction and stripping data, transport of Ir(IV) through a TOA-SLM was performed. Iridium(IV) in the feed solution with low HCl concentration was effectively transported into the HClO₄ or the HNO₃ product solution. Iridium(IV) was recovered and concentrated in the 1 M HClO₄ product solution by reducing the volume of strip solution relative to the volume of feed solution, yielding a sufficient enrichment factor.     

Comparison of separation behavior of Ir(IV) and Rh(III) between tin(II) chloride and ascorbic acid as a reducing agent in the extraction with Cyanex 921 and Cyanex 301

In order to compare the separation of Ir(IV) and Rh(III) between SnCl₂ and ascorbic acid as a reducing agent, solvent extraction with Cyanex 921 and Cyanex 301 was investigated in the HCl concentration range from 1 M to 9 M. Addition of both SnCl₂ and ascorbic acid led to the selective extraction of rhodium by the two extractants, leaving Ir(III) in the raffinate. Since tin was selectively extracted over Rh(I) in the presence of SnCl₂, it is necessary to separate Rh(I) and tin by selective stripping from the organic phase. In the presence of ascorbic acid, the extraction percentage of rhodium by Cyanex 921 was much smaller than that in the presence of SnCl₂. UV spectra was analyzed to verify the reduction reaction of both metal ions. FT-IR was analyzed between fresh and loaded organic solution. The reduction of Ir(IV) and Rh(III) in the presence of ascorbic acid was explained. Selective stripping of Rh(I) over tin from the loaded Cyanex 921 was obtained by the mixture of HCl and (NH₂)₂CS.     

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.     

Separation of Zinc and Bismuth by Facilitated Transport through Activated Composite Membranes

Abstract

This paper reports the results on the further development of activated composite membranes (ACM) containing di‐2‐ethyhexyl‐dithiophosphoric acid (D2EHDTPA) as a carrier. The selectivity and transport properties of D2EHDTPA‐based ACMs towards different metal ions including bismuth and zinc appear to be interconnected with each other. It has been shown that unlike the liquid‐liquid extraction of bismuth, the use of D2EHDTPA‐ACM permits to recover and to concentrate bismuth from a highly saline medium without irreversible destruction of the carrier. The difference in the rates of bismuth and zinc transport through ACMs permits their separation since the former is concentrated in the stripping solution and the latter retains in the feed compartment of the membrane cell.     

Uranium Permeation from Nitrate Medium Across Supported Liquid Membrane Containing Acidic Organophosphorous Extractants and their Mixtures with Neutral Oxodonors

Permeation of U(VI) from nitric acid solution has been studied across supported liquid membrane (SLM) using bis[2,4,4 trimethyl pentyl] phosphinic acid (Cyanex 272) either alone or in combination with neutral donors like Cyanex 923 (a mixture of four trialkyl phosphine oxides viz. R₃PO, R₂R′PO, RR′₂PO, and R′₃PO where R: n-octyl and R′: n-hexyl chain), TBP (tri-n-butyl phosphate), and TEHP (tris-2-ethylhexyl phosphate) dissolved in n-paraffin as carriers. Effect of various other parameters such as nature and concentration of receiver phase, feed acidity, uranium concentration, pore size, and membrane thickness on U(VI) transport across SLM were investigated. Transport behavior of U(VI) was also compared with other derivatives of phosphoric acids like 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A), dinonyl phenyl phosphoric acid (DNPPA) under identical conditions and it followed the order: Cyanex 272 > PC88A > DNPPA. 2 M H₂SO₄ was suitable for effective U(VI) transport across SLM. Presence of neutral donors in carrier showed significant enhancement in U(VI) permeation in the order: Cyanex 923 > TBP > TEHP. U(VI) transport decreased with increased membrane thickness as well as decrease in pore size. The optimized conditions were tested for recovery of U(VI) from uranyl nitrate raffinate (UNR) waste generated during purification of uranium.     

The Effect of Porous Support Composition and Operating Parameters on the Performance of Supported Liquid Membranes

Abstract

Factors, such as porous support composition and operating parameters, that influence the performance of supported liquid membranes (SLMs) were investigated. SLMs of varying porous support compositions and structures were studied for the transport of metal ions. A microporous polybenzimidazole support was synthesized and prepared in the form of an SLM. This SLM, containing the selective extractant di-(2-ethylhexyl)phosphoric acid, was evaluated for the transport of copper and neodymium. Dramatically improved performance over that of commercially available membranes was found in tests for removing the metal ions from solution. Metal ion transport reaches near completion in less than 3 h, whereas Celgard-polypropylene and Nuclepore-polycarbonate reaches only 50% completion even after 15 h. The transport driving force for acidic extractants is a pH gradient between the feed and strip solutions. Polybenzimidazole, an acid- and radiation-resistant polymer, has two protonatable tertiary nitrogens per repeat unit that may help sustain the pH driving force. Another factor may be the ability of the polybenzimidazole to hydrogen bond with the extractant. Transport through the flat-sheet SLMs was tested by using a unique cell design. Countercurrent flow of the feed and strip solutions was established through machined channels in half-cell faceplates that are in a spiral, mirror-image pattern with respect to each other, with the flat-sheet SLM interposed between the two channeled solutions. Advantages comprised in the design of the two clamped half-cells (tangential entry, zero primary pressure, zero pressure differential, controlled flow regimes, no sharp turns, and channeled flow) give operating parameters that will not physically dislodge the liquid membrane from the porous support; consequently, the lifetime of the support is increased. Permeability coefficients remained unchanged after a month of daily use versus 20 to 100% declines for membranes in other cell configurations.