Dialkylphosphoric acids as carriers in separation of lanthanides and thorium on supported liquid membranes

Permeation of seven lanthanides (Ln) and thorium through a supported liquid membrane containing di-(n- octyl)phosphoric (DOPA) or di-(n-pentyl)phosphoric (DPPA) acid as a carrier has been studied as a function of the chemical composition of the system. The results have been compared with a previous study in which di-(2-ethylhexyl)phosphoric acid was used. Metal cations were transported from feed solutions of pH 1.1-4.8 (HNO(3)) into strip solutions of 0.015-0.1 mol l(-1) nitric acid. The ionic strength was kept constant at 0.1 mol l(-1) (HNO(3), KNO(3)). The initial lanthanide concentration and carrier concentration in the liquid membrane were varied from 0.5 to 500 mumol l(-1) and from 0.01 to 0.5 mol l(-1) respectively. To describe the mass transfer of metal cations, permeability coefficients have been determined by inductively-coupled plasma atomic emission spectroscopy or by on-line flow-injection analysis of metal concentrations in strip or feed solution. Probably as the result of a higher solubility of the carrier in aqueous media, transport of Ln with DPPA was not observed. By using DOPA, La, Ce, Pr, and Nd permeated through the membrane while transport of heavier Ln was partly or totally suppressed. This enables these four Ln (separation factor alpha = 3.0 for Nd and Sm) to be separated from the others. Furthermore, at a very low acidity gradient, only La (III) is transported over the membrane (alpha >/= 3.4 for La, Ce and next Ln). The seven elements from La to Tb can be separated from Th(IV) because no evidence of its permeation through the membrane was found under the conditions of Ln transport. In contrast to previous studies on Ln transport with dialkylphosphoric acid carrier, the possibility of participation of species other than Ln(AHA)(3) in the transport has been discussed. The decrease of permeability observed at higher Ln concentrations and higher pH of the feed solution has been explained as the result of formation of species, e.g. polymeric ones, that are unable to permeate through the membrane.     

Uphill transport of uranium across a liquid membrane

A liquid membrane was prepared by entrapping tributyl phosphate (TBP) in a cellulose triacetate (TAC) membrane matrix. The membrane was used to separate two aqueous solutions, one acidic and the other alkaline, which were saturated with TBP to prevent its loss from the membrane. Uphill transport of uranium was achieved with the TBP liquid membrane. Both solutions containing TBP were stirred magnetically. When the initial concentration of uranium in the two solutions was 3.5 mM, more than 50% of the uranium contained in the acidic solution was transported to the alkaline solution across the liquid membrane within 5 h. A transport mechanism is described in which the membrane-bound TBP acts as a mobile carrier for uranium.     

Studies on the partitioning of actinides from high level liquid waste solution employing supported liquid membrane with Cyanex-923 as carrier

The present paper deals with the studies on the partitioning of actinides from high level liquid waste solution of PUREX origin employing supported liquid membrane technique. The process uses solution of Cyanex-923 in n-dodecane as a carrier with poly tetra fluoro ethylene support and a mixture of citric acid, formic acid and hydrazine hydrate as a receiving phase. Transport studies are carried out for ²⁴¹Am under different experimental conditions to optimize the transport parameters such as feed acidity, carrier concentration, effect of uranium, trivalent metal ion and salt concentration in the feed. Studies indicated good transport of actinides across the membrane from nitric acid medium. Under the optimized conditions the transport of ²⁴¹Am is studied from a uranium depleted synthetic PHWR-HLLW and finally the technique has been used for the partitioning of alpha emitters from an actual research reactor-HLLW. High concentration of uranium in the feed is found to retard the transport of americium, suggesting the need for prior removal of uranium from the waste.     

Separation of Americium from Europium Using Liquid Membrane Impregnated with Organodithiophosphinic Acid

The selective transport of Am across a supported liquid membrane (SLM) has been investigated by using bis (2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301) as a mobile carrier. This extractant containing soft donor atoms exhibits strong affinity for actinoids, giving a large separation factor between trivalent Am and Eu. Separation of Am from Eu was achieved by an SLM containing highly purified Cyanex 301. Americium was preferentially transported across the SLM and concentrated in the product solution, while most of Eu remained in the feed solution.     

Liquid membrane transport of lanthanoid elements using organophosphinic acid

Transport of La, Nd, Eu, Tb, Tm and Lu through a supported liquid membrane (SLM) was investigated by using di(2,4,4-trimethylpentyl)phosphinic acid (DTMPPA) as a mobile carrier. Lanthanoid elements in the feed solution were quantitatively transported and concentrated into the product solution of mild acidity. The transport rates increased with increasing atomic number of lanthanoids in the low pH region of the feed solution. Separation factors evaluated from the transport rates for lanthanoids were close to those from the distribution ratios in liquid-liquid extraction.     

Coupled transport of Ag(I) ions through triethanolamine–cyclohexanone-based supported liquid membranes

Facilitated transport of silver(I) ions in acidic medium, across a supported liquid membrane (SLM) by using triethanolamine (TEA) as carrier, dissolved in cyclohexanone, has been investigated. The parameters studied are HNO₃ concentration variation in the feed, pH of the feed solution, carrier concentration in the membrane phase, silver(I) ions concentration in the feed phase and KCN concentration in the stripping phase. Increase in H⁺ concentration by increasing HNO₃ concentration from 0.5 to 1 M results into an increase in silver ions flux but a decrease in flux has been found beyond 1 M HNO₃ concentration in the feed, providing a maximum flux of 3.21 × 10⁻⁷ mol/m² s at 1 M HNO₃. Increase in TEA concentration inside the membrane enhances flux with its maximum value at 2.25 M TEA. Further increase in the concentration of TEA leads to a decreased rate of transport due to the increase in viscosity of membrane liquid. The optimum conditions for Ag(I) ions transport are 1 M HNO₃ (feed), 2.25 M TEA (membrane) and 1.5 M KCN in the stripping phase. It has been observed that Ag(I) flux across the membrane tends to increase with increase in Ag(I) ions concentration in the feed phase. Applying the studied conditions to silver plating waste solutions, Ag ions have been removed up to 99% in a time interval of 5 h.     

Hybrid liquid membrane (HLM) system in separation technologies

A novel liquid membrane system, denoted hybrid liquid membrane (HLM), was developed for the separation of solutes (metal ions, acids, etc.). It utilizes a solution of an extracting reagent (carrier solution), flowing between membranes. The membranes, which separate the carrier solution from feed and receiving (strip) solutions, enable the transport of solutes, but block the transfer of the carrier to the feed or to the strip. Blocking the carrier is achieved through membranes hydrophilic/hydrophobic or ion exchange properties, or through their rentention abilities, due to pore size.     

三正辛胺-仲辛醇-煤油组合液膜分离镉锌的研究

本文用萃取和膜迁移实验研究了镉、锌离子在三正辛胺-仲辛醇-煤油组合液膜体系中的迁移和分离的影响因素。实验证实,该组合液膜体系能从含镉、锌的料液中选择性地迁移镉,有效地实现镉、锌分离。理论分析表明,组合液膜的双固体膜可简化为具备两张固体膜厚度的单一固体支撑体的支撑液膜。测定了组合液膜因迁移而流失在料液相和反萃相中的三正辛胺含量,实验显示,组合液膜的两张固体支撑体可阻止三正辛胺的流失,增加膜稳定性,延长膜寿命。     

Recovery of acetaminophen from aqueous solutions using a supported liquid membrane based on a quaternary ammonium salt as ionophore

A flat sheet-supported liquid membrane (FSSLM) system, consisting of an ionic liquid, tricapryl-methylammonium chloride (Aliquat 336®) in octan-2-ol, is proposed as a means of recovering acetaminophen (Ac) from aqueous solutions; Ac is an active ingredient widely used in many pharmaceutical preparations. Several parameters which could affect the transport efficiency were examined, i.e., the strippant nature and concentration in the receiving solution, the diluent nature, carrier concentration, initial acetaminophen concentration in the feed solution, and the polymeric support type. A facilitated transport was obtained by impregnating the polymeric support with 10 vol. % of Aliquat 336® in octan-2-ol, 1 M NaOH as a receiving solution, and a feed solution of Ac dissolved in ultrapure water. The study was completed by using the FSSLM thus developed for extracting Ac from some drugs in frequent use in Tunisia (Analgan®, Doliprane®, and Fervex®).     

Zn(II), Cd(II) and Cu(II) separation through organic–inorganic Hybrid Membranes containing di-(2-ethylhexyl) phosphoric acid or di-(2-ethylhexyl) dithiophosphoric acid as a carrier

A membrane process for metal recovery from aqueous solutions was studied. Metal ions diffused from the feed solution to the stripping phase through an Hybrid Membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) and/or di-(2-ethylhexyl) dithiophosphoric acid (D2EHDTPA) as a carrier. Such membranes were prepared by a sol–gel route including cellulose triacetate and polysiloxanes. Transport behaviour was evaluated for both carriers under similar experimental conditions. The transport experiments reported here concerned transport at different cycles and selectivity towards different metal ions. Using D2EHPA the membrane provided a selective transport of zinc to the stripping compartment of the membrane cell, while copper and cadmium remained in the feed compartment. Whereas, using D2EHDTPA as carrier the transport rate increased and the selectivity profiles were inverted in relation with those of D2EHPA. With a mixture of both extracting agents it was observed an intermediate behaviour in selective transport, being possible to modulate it.     

Separation and concentration of cobalt from ammoniacal solutions containing cobalt and nickel by emulsion liquid membranes using 5,7-dibromo-8-hydroxyquinoline (DBHQ)

The separation and concentration of cobalt from ammoniacal solutions containing nickel and cobalt by an emulsion liquid membranes (ELMs) using 5,7-dibromo-8-hydroxyquinoline as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (Span 80), a modifier (tributylphosphate), and an extractant (DBHQ). Very dilute sulphuric solution containing EDTA as complexing agent, buffered at pH 5.0, has been used as a stripping solution. pH of ammoniacal feed solution containing cobalt and nickel was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt have been studied. These variables are membrane composition, pH of the feed solution, cobalt and nickel concentrations of the feed solution, mixing speed, surfactant concentration, extractant concentration, EDTA concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively extract 99.0% of cobalt from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt with respect to nickel, based on initial feed concentration, have experimentally found to be of as high as 247.5 for about equimolar Co–Ni feed solutions.     

Extraction and recovery of lignosulfonate from its aqueous solution using bulk liquid membrane

The paper presents an experimental study on the coupled transport of lignosulfonate (LS) through bulk liquid membrane (BLM) and thereby to identify the best set of solvent, operating conditions and mode of transport that would yield optimum performance of the BLM. Trioctylamine (TOA) is used as carrier. Among various solvents, tested for the above purpose, dichloroethane is found to be the best. The effects of operating condition, viz. pH, temperature, and carrier concentration, on the equilibrium distribution of LS are investigated. The effects of temperature, stirring of aqueous and organic phases, stirring speed, carrier concentration, initial feed and strip phase concentration on the separation of LS using BLM are also studied. It is observed that transport of LS can be enhanced by increasing the temperature and stirring speed of feed phase. Stirring of strip phase has no appreciable effects on the transport of LS. With increase in initial feed concentration the initial rate of the transport of LS is higher but continues for a longer time. Recovery of LS is much higher in co-transport mode in comparison to counter transport mode. Application of 1.25 M NaOH as stripping solution gives high recovery (70%) and high strip flux (70% of feed flux).     

Separation of yttrium(III) from iron(III) through liquid membrane impregnated with di(2-ethylhexyl)phosphoric acid

The selective transport of yttrium(III) in the presence of iron(III) through a supported liquid membrane (SLM) has been investigated by using di(2-ethylhexyl)phosphoric acid (DEHPA) as a mobile carrier. Yttrium(III) with fast kinetics was preferentially transported from the feed solution of dilute acid into the product solution of 1M H₂SO₄, while most of iron(III) with slow kinetics remained in the feed solution. The effective separation of yttrium(III) from a large amount of iron(III) was accomplished by the selective transport of yttrium(III) through the SLM.     

Carrier-facilitated liquid membrane extraction of penicillin G from aqueous streams

Kinetics and mechanism for the carrier-facilitated transport of penicillin G from aqueous solutions through a supported liquid membrane containing Amberlite LA-2 were investigated. The strip phase was either phosphate buffer or sodium carbonate solution. Experiments were performed as a function of the pH, the concentrations of penicillin G in the feed phase and of amine in the membrane phase. A transport model was proposed considering aqueous film diffusion, interfacial chemical reaction, and membrane diffusion. The calculated rates were found to agree with the measured ones (average standard error, 12%). Under the conditions investigated (feed pH 5.02–7.83, penicillin G concentration 10–500 mol/m³, amine concentration 50–1000 mol/m³), the present transport process was shown to be governed by combined interfacial chemical reaction and membrane diffusion.     

Transport and separation of carboxylic acids through bulk liquid membranes containing tributylamine

In this study, transport and separation of carboxylic acids (formic, acetic, propionic, and butyric acids) from their aqueous solutions through bulk liquid membrane (BLM) containing tributylamine (TBA) and the parameters affecting the transport were investigated. The influence of the parameters on the separation process such as the stirring of membrane phase, the stripping phase type and concentration, the feed phase type, and the feed:membrane:stripping phase ratio (F/M/S phase ratio) were examined. In the experiments, 10% (w/w) acid solutions (formic, acetic, propionic, and butyric acids) were used as the feed phase, different concentrations of NaOH solutions within the range of 0–2?N were used as the stripping phase, and 0.5?mol/lt TBA, dissolved in oleyl alcohol, was used as the membrane phase. It was determined that the stirring of the membrane phase increases the transport of acids. In the case of 2 N NaOH solution in the stripping phase and F/M/S phase ratio 1:2:1 gave the best recovery (96.75%) for butyric acid. It was observed that BLM was an effective technique for the separation of carboxylic acids from aqueous solutions.     

A study on separation and extraction of four main alkaloids in Macleaya cordata (Willd) R. Br. with strip dispersion hybrid liquid membrane

A technique based on strip dispersion hybrid liquid membrane was developed for the separation and extraction of four main alkaloids from fruits of Macleaya cordata (Willd) R. Br. A microporous polypropylene membrane impregnated with an organic membrane solution comprised the heart of the strip dispersion hybrid liquid membrane system. The membrane solution was made by dissolving a cationic carrier, di‐(2‐ethylhexyl) phosphoric acid in an inexpensive, less toxic membrane solvent, kerosene. The transport of alkaloids from an aqueous feed solution through the membrane to a strip dispersion phase was driven by the concentration gradient of H⁺ and facilitated by di‐(2‐ethylhexyl) phosphoric acid. The effects of the extraction time and reuse times of the membrane, the strip solution composition, the carrier concentration, the volume ratio of the aqueous strip solution to the organic membrane solution, and the flow rates of the feed solution and the strip dispersion phase on the transport of alkaloids were investigated. Under the optimal conditions, the permeability coefficients obtained for the four main alkaloids allocryptopine, protopine, sanguinarine, and chelerythrine were 1.66, 1.99, 2.98, and 3.06×10^?4 cm/s, and the transport efficiencies were as high as 68, 77, 83, and 85%, respectively.     

Carrier-mediated transport of yttrium(III) through a supported liquid membrane containing TOPO in n-dodecane

Transport of yttrium(III) from nitrate medium through liquid membrane containing tri-n-octyl-phosphine oxide (TOPO) in n-dodecane, supported on a nucleoporous filter, into a strip solution with ethylenediaminetetraacetic acid (EDTA) has been studied. The kinetic dependences of transport were obtained and compared with a model, resulting in calculation of permeability coeffients and initial fluxes of yttrium. The influence of salting-out agent, initial metal and nitric acid concentrations in the feed, and of concentration of carrier in membrane are discussed.     

Transport of U(VI) from sulphuric acid medium across supported liquid membrane (SLM) containing di-(2-ethylhexyl) phosphoric acid (D2EHPA)/n-dodecane as a carrier

This paper reports on the supported liquid membrane (SLM) based transport studies of U(VI) from sulphate medium using di-(2-ethylhexyl) phosphoric acid/n-dodecane as carrier. Polytetrafluoroethylene membrane was used as solid support and H₂SO₄ as receiver phase. The effects of various parameters such as receiver phase concentration, feed acidity, carrier concentration, U(VI) concentration, membrane thickness and membrane pore size on U(VI) transport had been investigated. With increase in H₂SO₄ concentrations and pH of feed solution there is an increase in U(VI) transport across the SLM. Similarly with increase in membrane thickness the U(VI) transport decrease whereas in case of pore size variation reverse results are obtained. The membrane thickness variation results showed that the U(VI) transport across the SLM is entirely diffusion controlled and the diffusion coefficient the D _(o) was calculated as 1.36 × 10^?7 cm² s^?1. Based on optimized condition, a scheme had been tested for selective recovery of U(VI) from ore leach solution containing a large number of other metal ions.     

反萃分散组合液膜分离提取氨基酸

建立了分离提取蛋氨酸、亮氨酸、苯丙氨酸和色氨酸的磷酸二（2-乙基己基）酯(D2EHPA) 煤油-HCl反萃分散组合液膜体系,考察了料液相pH值、载体D2EHPA浓度、液膜相与反萃相体积比、反萃相组成、料液相与反萃分散相流速、传输时间以及支撑膜重复使用次数对氨基酸渗透系数和传输效率的影响。 在优化的条件下,建立的反萃分散组合液膜体系对4种氨基酸均可以获得大于35%的传输效率,其中色氨酸和亮氨酸的传输效率超过了79%,且传输效率呈Et,Trp＞Et,Leu＞Et,Phe＞Et,Met的趋势。 支撑膜重复使用25次,对氨基酸的传输效率没有明显改变。建立的液膜体系对考察的氨基酸展示了较高传输效率和优越的传输选择性,是一种简单和环境友好的分离技术。     

The effect of chelating agent on the separation of Fe(III) and Ti(IV) from binary mixture solution by cation-exchange membrane

The competitive transport of Fe(III) and Ti(IV) ions and the effect of chelating agents on separation from binary mixture solutions through charged polysulfone cation-exchange membrane (SA3S) has been studied under Donnan dialysis conditions. The amount of chelating agent was taken as an equimolar of Fe(III) ion in the feed phase. In this process, the membrane separated two electrolyte solutions: the feed solution, initially containing metal salts (Fe, Ti), or metal salts solution, containing a chelating agent, and the other side (receiver solution) being HCl solution. An external potential field is not applied. It was observed that the chelating agents affect the metal transport; the transport of Fe(III) is decreased and the transport of Ti(IV) is increased.