Influence of the Extractant on Strontium Transport from Reprocessing Concentrate Solutions through Flat-Sheet Supported Liquid Membranes

Abstract

The influence of the extractant on strontium transport through a flat-sheetsupported liquid membrane from nuclear fuel reprocessing concentrate solutions to demineralized water has been studied using two crown ethers of different lipophilicity: dicyclohexano-18-crown-6 (DC18C6) and di-tert-butylcyclohexano-18-crown-6 (DtBuC18C6). The distribution coefficients of strontium showed that DC18C6 is a better strontium extractant than DtBuC18C6 in the entire range of crown-ether concentration studied. No effect of association between the DC18C6 molecules was observed even at high concentrations. However, the strong lipophilic character of DtBuC18C6 led to a distribution coefficient of this extractant 10 times higher than the distribution coefficient of DC18C6. Thus, the membrane concentration of DtBuC18C6 was approximately 10 times higher than that of DC18C6. This leads to greater strontium permeability for DtBuC18C6, even though DC18C6 had a greater capacity for strontium extraction and a higher diffusion coefficient in the membrane due to the smaller molar volume of this crown ether. The precipitation of a white solid was observed when the synthetic concentrate was mixed with an organic phase containing DtBuC18C6 dissolved in n-hexylbenzene (0.7 mol·L^?1 isotridecanol), causing a decrease of strontium permeability. In this case, DC18C6 had the greatest strontium permeability.     

Some Aromatic Amine Transport through Emulsion Liquid Membranes

Abstract

This paper reports the permeation of 10 aromatic amines through emulsion liquid membranes and estimates of the apparent diffusion coefficients and apparent moving rates.     

Strontium Separation with Ultrafiltration Membranes from Dilute Aqueous Solutions

Abstract

The separation of Sr²⁺ from dilute and trace solutions of low activity by means of hollow fiber Amicon ultrafiltration membranes is studied. The cation is absorbed on colloidal particles of titanium oxide formed directly in solution, and the colloidal dispersion is filtrated. The method has been studied under several different operative conditions (pH, Ti/Sr ratio, the presence of interfering ions, colloid formation time) with the aim of determining the optimum conditions to develop a separation process.     

Quantitating the Effect of Solvent Type on Neutral Macrocycle-Mediated Cation Transport in Liquid Membranes

The recently confirmed diffusion-limited transport model for neutral macrocyle-mediated cation transport in membranes has been used to quantify the membrane solvent effects on the fundamental parameters in the model and their relative importance. The fundamental parameters involved are the extraction equilibrium constant, macrocycle partition coefficient, and diffusion coefficient. Experimental measurements and predictive correlation calculations have been made to quantify these fundamental parameters. Membrane stability has also been quantified by looking at solvent solubilities and solvent compatibility with various membrane types. It was found that membrane stability vs. rapid transport is the major choice to be made in choosing a membrane solvent. Retention of the macrocycle in the membrane and diffusion coefficients are greatest with short carbon chain solvents containing few chlorine atoms. On the other hand, high boiling points and low water solubility are obtained with long carbon chain solvents containing increasing numbers of chlorine atoms. Extraction equilibrium constants also decrease with increasing carbon chain lengths and increasing chlorination, but the decrease is not uniform like the changes in the other parameters. Little effect of solvent type on membrane selectivity was observed. The transport model and quantification of these fundamental parameters should allow for accurate predictions in the choice of solvent in designing stable membranes with optimal transport properties.     

Carrier-Mediated Transport of Rare Earth Ions through Supported Liquid Membranes

Abstract

Fluxes of rare earth ions (Sc³⁺, Y³⁺, La³⁺, Sm³⁺, and Lu³⁺) across supported liquid membranes using mixtures of nitrophenyl octyl, heptyl, or phenyl ethers and tris(2-n-butoxyethyl) phosphate (TBEP) as solvents and some β-diketones as carriers were determined. The effects of membrane composition, pH of the source phase, and carrier concentration on the flux are demonstrated. The effect of membrane composition is further discussed from the values of the membrane potential and the viscosity and electrical conductivity of the solvents. A maximal flux of lanthanum is observed for the membranes by using mixtures consisting of equal volumes of the nitrophenol derivative and TBEP. The fluxes of the rare earths, except scandium, decrease rapidly with decreasing pH difference between the source and receiving phases. The difference in flux among the rare earths, except scandium, is small. The flux increases in the carrier order benzoyl- > thenoyl- > furoyltrifluoroacetones. The lanthanum flux is proportional to the carrier concentration.     

Flux and Characteristic Parameters in Mediated Transport through Liquid Membranes. II. A Model for Co-transport and Experimental Study of Kl Transport through a Bulk Liquid Membrane

Abstract

In this article we establish a steady-state theoretical model for cotransport through liquid membranes. Integration of the flux equation gives the concentration in the receiving phase as a linear function of time under certain conditions. From this, an expression for the relative permeability of the carrier-permeant complex with respect to the carrier is obtained; this permeability depends on the equilibrium constant of the interphases reaction and on another parameter related to the initial concentration of permeant in extramembrane phases. An experimental study of the variation of permeant concentration in the receiving phase allows determination of several characteristic transport parameters.     

Selective Transport of Bismuth Ions through Supported Liquid Membrane

A new supported liquid membrane (SLM) system was prepared for the selective transport of bismuth ions from the aqueous feed into the aqueous permeate phase. The support of the SLM was a thin porous polypropylene or polyvinylidene fluoride membrane impregnated with diisooctyldithiophosphinic acid (Cyanex 301) as mobile carrier in 4‐chloroacetophenon as organic solvent. Cyanex 301 acts as a highly selective carrier for the uphill transport of bismuth ions through the SLM. In the presence of HNO₃ as a metal ion acceptor in the strip solution, the transport of bismuth ions into the strip side reached 70 % of the initial feed concentration after 3.5 hours. The selectivity and efficiency of bismuth transport from aqueous solutions containing different mixtures of cations were investigated. In the presence of P₂O₇^2– ions as suitable masking agent in the feed solution, the interfering effects of other cations were completely eliminated. The selective transport of bismuth through SLM is superior to liquid‐liquid extraction or through bulk liquid membranes. This is due to the high efficiency. The SLM reduces the solvent requirements, combines extraction and stripping operations in a single process and allows the use of highly selective extractants. The system may be applied to samples containing very low bismuth concentrations.     

Studies in Facilitated Transport of Nitric Oxide through Immobilized Liquid Membranes

Abstract

An experimental technique for studying facilitated transport through immobilized liquid membranes in a batch mode is presented along with its mathematical analysis. Results obtained with two carrier ions [Fe(II) and Zn(II)] in the solvent N-cyclohexyl-2-pyrrolidone are compared. The effects of carrier ion concentration and of initial pressure difference are studied. Facilitation factors (ratio of facilitated flux to the flux without any carrier ion) up to 8.1 were observed.     

Carrier-Mediated Transport of Molybdenum(VI) through Supported Liquid Membranes

Abstract

The liquid membrane transport of Mo(VI) from an acidic solution into an alkaline stripping solution was carried out by using a mobile carrier, 5,8-diethyl-7-hydroxy-dodecan-6-one oxime (LIX 63). Further transport of MoO₄ ^2? from the alkaline solution was performed by using another carrier, trioctylmethylammonium chloride (TOMAC). Molybdenum(VI) was effectively transported through double membranes composed of LIX 63/dilute NaOH solution/TOMAC from a feed solution (10^?3 M HNO₃) into a product solution (1 M NaOH). Molybdenum(VI) was concentrated with high recovery into a small volume of product solution. The separation of Mo(VI) from several ions was performed by means of the double membranes.     

Transport of Palladium(II) through Trioctylamine Liquid Membrane

Abstract

The permeation behavior of palladium(II) through a supported liquid membrane (SLM) impregnated with trioctylamine (TOA) in kerosene has been investigated. By selecting perchloric or nitric acid as a stripping agent, Pd(II) was transported through the SLM containing 0.5 M TOA and 20% 1-octanol without remaining in the liquid membrane. The permeation rate (k _{f. obs}) of Pd(II) for HNO₃ was faster than that for HClO₄. Palladium(II) was concentrated across the SLM from the 0.5 M CHI solution into the HClO₄ or HNO₃ solution.     

Coupled Transport of Zr(IV) through Tri-n-butylphosphate-Xylene-Based Supported Liquid Membranes

Abstract

The transport of Zr(IV) through tri-n-butylphosphate-xylene-based liquid membranes, supported in a polypropylene hydrophobic microporous film, has been studied. The concentration of HNO₃ in the feed solution and tri-n-butylphosphate (TBP) carrier in the membrane were varied, and the flux and permeability coefficients were determined. The optimum conditions found for maximum flux were determined to be 10 mol/dm³ HNO₃ and 2.93 mol/dm³ TBP with a flux value of 12.9 × 10^?6 mol · m^?2 · s^?1. The solvent extraction study revealed that 1.25 to 3.5 protons are involved in zirconium transport, and that two molecules of TBP are involved in the complex formation. The value of protons involved varies with acid concentration. The zirconium ion transport is coupled with nitrate ions transport.     

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.     

Bathocuproine-Mediated Copper Transport through Liquid Membrane Driven by Redox Potential

Abstract

A new type of carrier-mediated copper transport system driven by redox potential was studied. The two aqueous solutions of different redox potentials were separated by a polymer-supported organic liquid membrane in which Bathocuproine (L) was dissolved as a “carrier”. Copper(II) was reduced in the reducing phase to form [Cu¹L₂]⁺·X^? type complex at the membrane interface and extracted. The copper complex diffused to the other side of the membrane and decomposed to form the copper(II) species in the oxidizing phase, leaving the carrier in the membrane phase. The nature of the system under various operational conditions (pH, redox agents, pairing anions X^?, coexisting metals, etc.) was studied and compared with the metal transport system which can take place without the intervention of redox reaction. An extension of these transport reactions to water-in-oil-in-water type emulsion system was studied.     

Analysis of Transport Rate of Zinc Extraction through Liquid Surfactant Membrane

Abstract

Analysis of the transport rate of a metal ion through a liquid surfactant membrane is important for understanding an extraction system. A facilitated transport model for zinc extraction through a liquid surfactant membrane is proposed for the analysis of the transport rate. Based on the model, the transport rates, including the interfacial reaction rates and the diffusion rate of the zinc ion, are analyzed. From an analysis of the model, it is shown that the reactions at both interfaces are not in equilibrium before extraction is complete. It is also shown that the transport rates are not equal value in the early stage of a run. Parametric effects on the transport rates are also illustrated.     

Transport of Europium through Supported Liquid Membrane Containing Dihexyl-N,N-diethylcarbamoylmethylphosphonate

Abstract

The transport of europium has been studied through a supported liquid membrane (SLM) impregnated with dihexy-N,N-diethylcarbamoylmethylphosphonate (CMP). Europium was effectively extracted from the perchlorate solution into SLM, but was insufficiently stripped to a dilute acid solution. The addition of 1-decanol improved the stripping process, and quantitative transport of europium was achieved. By the combination of two SLM systems consisting of diiso-decylphosphoric acid and CMP, europium was transported from the feed solution (0.1 M HNO₃) through the intermediate solution (1 M HclO₄ + 4 M NaClO₄) to the product solution (0.1 M HNO₃) and effectively concentrated by a factor of about 20.     

Selective Transport of Copper through Liquid Membranes Using LIX 860 as Mobile Carrier

Abstract

Copper has been selectively extracted from aqueous solutions containing metal ions (Cu²⁺, Co²⁺, Ni²⁺, Fe²⁺, Fe³⁺, Mg²⁺, and Zn²⁺) by a liquid membrane technique. Experiments were carried out in a beaker equipped with a baffle, and the system was stirred by a variable-speed mixer equipped with a turbine impeller; the mixing speed was 300 rpm. A typical membrane formulation was 2.0% Span 80, 4.0% LIX 860, and 94.0% of commercial kerosene, all values being by weight. Copper was selectively separated and concentrated from both synthetic and natural aqueous mine solutions containing various metal ions.     

The Transport of Copper(II) through Hollow Fiber Renewal Liquid Membrane and Hollow Fiber Supported Liquid Membrane

Abstract

In this paper, hollow fiber renewal liquid membrane (HFRLM) and hollow fiber supported liquid membrane (HFSLM) were used to simultaneously remove and recover copper(II) from aqueous solutions, and the transport performance of these two techniques were compared under the similar conditions for the system of CuSO₄ +D2EHPA in kerosene +HCl. The results showed that the HFRLM process was more stable than the HFSLM process. The HFRLM process had a higher overall mass transfer coefficient than that of HFSLM process in single-pass experiments. These were because the renewal effect of the liquid membrane layer could reduce the mass transfer resistance of the lumen side and replenish the loss of the membrane liquid in the HFRLM process. The transport results were better in the HFRLM process than that in the HFSLM process with recycling experiments. Therefore, HFRLM technique is a promising method for simultaneous removal and recovery of heavy metal from aqueous solutions.     

Studies of Ion Transport through a Liquid Membrane by Using Crown Ethers

Abstract

Studies on ion transport through a liquid membrane system composed of two extraction processes have been carried out. Kinetic models based on extraction processes with consideration of the controlled parameters were developed for mediated ion transport through liquid membranes, especially those using crown ethers as the ion carrier. A study of the concentration change in the receiving or source phase envisages the determination of the equilibrium constant by a kinetic method corresponding to the chemical reaction at the interface as well as the maximum initial flux through the membrane. The equilibrium constant values determined by the kinetic process were checked by the solvent extraction method.     

Transport Behavior of Basic Amino Acids through an Organic Liquid Membrane System

Abstract

The transport behavior of basic amino acids (BAA), such as arginine (Arg), histidine (His), and ornithine (Orn), through an organic liquid membrane system (LMS) was investigated. The LMS was composed of two aqueous phases (Phases I and II) separated by an organic phase of chloroform containing sodium di-(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT). The amount of BAA that moved from Phase I at pH 3 into the organic phase increased with increasing AOT concentration (2–10 mM). The relative amount of extracted BAA was in the following order: Arg > His > Orn. On the other hand, the release of BAA from the organic phase into Phase II at pH 10 did not depend upon their amount in the organic phase. Arg was difficult to release. The relative amount of released BAA was in the following order: Arg = His > Orn. BAA were extracted from Phase I at pH 5 into the organic phase containing 4 mM AOT because they exist as cationic species. Other amino acids possessing nonionic residues were untransportable under these conditions except leucine, tryptophan, and phenylalanin, which have highly hydrophobic residues. However, they were transportable in their cationic forms at pH 1. These transport phenomena are essentially controlled by the interaction of the anionic group of AOT and a cationic form. These results suggested that BAA can be separated from most amino acids under an appropriate pH by using AOT.