Multitracer studies on the permeation of various elements through a supported liquid membrane containing TBP

The permeation of various elements through a tributyl phosphate (TBP)-decalin membrane supported on a microporous polytetrafluoroethylene sheet was studied using a multitracer. Permeation rates of elements from feed solutions to distilled water as a receiving agent were determined by changing the HCl concentration in feed solutions. An increase in the transport was observed for most of the elements studied with increasing HCl concentration in the feed solutions. Among them, Fe, Zn, Se, Zr, Nb, Te, Hf and Re gave relatively high percentages of permeation from 4-12 mol^.dm^-3 HCl feed solutions. The permeability coefficients of these elements were determined.     

Carrier-mediated transport of rare earth elements through liquid membranes

Transport of tervalent REEs — Sc, Y, Ce, Eu, Gd, Tm, Yb — from nitrate medium through a liquid membrane containing TBP in n-dodecane, impregnated on a flat-sheet nucleoporous support, has been studied as a function of time and initial metal concentration, salting-out agent concentration and pH of the feed phase. Influences of various complexing agents dissolved in the strip phase was investigated, too. Adding a suitable amount of EDTA into the feed phase, separation of binary mixtures of REEs was experimentally achieved.     

Carrier-mediated transport of rare earth elements through liquid membranes

Transport of tervalent REEs–Sc, Y, Ce, Eu, Gd, Tm, Yb—from nitrate medium through flat-sheet SLM containing DEHPA in n-dodecane, supported on a nucleoporous filter, has been studied. Influences of both aqueous phase acidities, concentrations of metal and carrier were investigated. Transport courses of the metals in question had been obtained and their premeation coefficients or initial fluxes were evaluated. Separation of some binary mixtures Ce–Tm, Ce–Yb, Ce–Sc was experimentally achieved.     

Extraction of rare earth elements with organophosphorus extractants as carriers in supported liquid membranes

The membrane extraction of Y, Ce, Eu, Tm and their binary mixtures Ce–Y, Ce–Eu, Ce–Tm with supported liquid membranes containing TBP and HDEHP as carriers in decanedodecane hydrocarbon solvent, has been studied. Upon extraction with TBP aqueous nitrate solutions of rare earth elements (REE) were used as feed phase. In some cases they also contained EDTA or DCTA. In most cases, the receiving phase was an aqueous solution of EDTA. Extraction with HDEHP was performed from nitrate and chloride solutions and the receiving phase was the corresponding dilute acid. Pertraction of an element through a membrane was studied as a function of time and of initial composition of phases. The results are presented in the following forms: flux of metal through membrane, coefficients of permeability, separation factors and effective diffusion coefficients.     

Carrier-mediated transport of actinides and rare earth elements through liquid and plasticized membranes

The first works in this field were realized approximately 25 years ago, when BLOCK et al. reported^1,2 their studies about carrier-mediated transport (also called pertraction or membrane extraction) of uranium through plasticized membranes with neutral esters derived from phosphoric acid. At this time, the methodical principles of selective pertraction of ionic compounds through so-called bulk liquid membranes containing carriers were known.³ However, these membranes, similarly as plasticized membranes, have not achieved a broader use. This is probably because bulk liquid membranes are from a technical point of view fairly distant from the idea of a typical membrane system, and plasticized membranes (sometimes also called gel membranes) present great resistance. By the end of the 1960's and at the beginning of the 1970's, LI^4–7 and CUSSLER⁸ worked out the principles for two widely used pertraction techniques, called pertraction through emulsion liquid and supported liquid membranes (ELM and SLM). These two techniques not only have greatest significance in laboratory practice, but they also are interesting for technological aims because of the attainable large phase boundaries, e. g. 10³–10⁴ m²/m³. Many ways to arrange membrane systems are described in papers.^9,10 Recently, the significance of carrier-mediated transport through liquid membranes has grown to have (since 1980) separate section at the International Solvent Extraction Conference.This paper does not deal with mathematical models and the mechanism of pertraction in general, but it gives an overview of results obtained in publications referring to pertraction of two related element groups — actinoids and rare earth elements — using various membrane types.     

Carrier-mediated transport of rare earth elements through liquid membranes. Transport of Sc,Y, Ce,Eu, Gd,Tm, Yb through supported liquid membrane containing TOPO in n-dodecane

Transport of trivalent rare earth elements-REE (Sc, Y, Ce, Eu, Gd, Tm, Yb) from nitrate medium through SLM containing TOPO in n-dodecane, supported on a nucleoporous filter, into a strip solution with EDTA, has been studied. Permeability coefficients of metal transport decreased with increasing of their atomic number except for Ce and Tm. At higher concentration of TOPO in the membrane, metal transport was faster, but the differences among the transport rates of the investigated elements decreased. A good separation of Ce from its binary mixtures with other investigated REE was achieved using DTPA as masking agent, added the feed solution.     

Studies on phenol permeation through supported liquid membranes containing functionalized polyorganosiloxanes

In this study, the functionalized, linear, hydrophobic fluid organosiloxane polymers, namely, methylhydrosiloxane–dimethylsiloxane copolymers supported on a polypropylene microporous flat sheet membrane (Celgard 2502 and 2402) have been tested as supported liquid membranes (SLMs) for phenol recovery from aqueous phases into a 0.1 M NaOH phase. The functionalized polymers include, Me₃SiO[MeSi(OR)O]_x[Me₂SiO]_ySiMe₃ (containing x = 15–18, 25–35 and 50–55 mol% of R, where R is –(CH₂)_nNMe₂ (n = 3 or 4 or 6) or –(CH₂)₂OEt pendent organofunctional groups. The functionalities, R, tested were derived from the commercially available 3-dimethylamino-1-propanol and 2-ethoxyethanol as well as newly synthesized 4-dimethylamino-1-butanol and 6-dimethylamino-1-hexanol which have been made for the purpose of this study.

The study showed that phenol permeation expressed as permeate flux through the membranes increases with the larger number of carbon spacers in the alkyl chain of the aminoalcohol pendent, larger porosity of the polypropylene support films, higher mol% of the methylhydrosiloxane portion functionalized and faster flow rates of both the feed and the receiving phases. Phenol permeation was enhanced significantly when the mol% of the methylhydrosiloxane portion was 50–55 or 25–35 with 6-dimethylamino-1-hexanol functionality supported on Celgard 2502.     

Induction time in metal permeation processes through supported liquid membranes

The origin of the induction time observed in the permeation process of cadmium species through trilaurylammonium chloride in triethylbenzene supported liquid membranes is discussed. A model for the non-steady state transference process, where aqueous film diffusion coupled to an interfacial chemical reaction are the main rate determining processes, was developed. By comparison with experimental transference data, the rate constant of the interfacial reaction between cadmium chloride aqueous complexes and the membrane carrier, trilaurylammonium chloride, was evaluated. The time evolution of the concentration profiles through the aqueous diffusion film is also described.     

Distribution characteristics of rare earth elements in plants from a rare earth ore area

The contents of eight rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) in various plant species taken from a rare earth ore area were determined by instrumental neutron activation analysis. For a given plant, the REE patterns in root, leaf and host soil are different from each other. The REE distribution characteristics in roots of various species are very similar and resemble those in the surface water. The results of this study suggest that there is no significant fractionation between the REEs during their uptake by the plant roots from soil solution. However, the variation of the relative abundance of individual REE occurs in the process of transportation and deposition of REEs in plants.     

Polyphenylcyclopentadienyl complexes of rare earth elements

Reaction of LnCl₃(thf) _x (Ln = Y, La, Yb, Lu) with NaCp^Phn (Cp^Phn = 1,3-Ph₂C₅H₃, 1,2,4-Ph₃C₅H₂, Ph₄C₅H) leads to formation of monocyclopentadienyl dichloride complexes Yb(Ph₂C₅H₃)Cl₂(thf)₃ (1), Ln(Ph₃C₅H₂)Cl₂(thf)₃ (Ln = Y (2), Lu (3)), La(Ph₄C₅H)Cl₂(thf)₃ (4). Molecular structures of 1, 2 and the polynuclear complex [(Ph₃C₅H₂)₃Lu₄(Cl)₇(O)(thf)₃] (5), which is a partial hydrolysis product of 3, have been established by the X-ray method.     

Detailed study on simultaneous separation of rare earth elements by capillary electrophoresis

Separation of all rare earth elements (REEs) by capillary zone electrophoresis was investigated in a system of alpha-hydroxyisobutyric acid (HIBA) as a main complex reagent and acetic acid (HAc) as an assistant complex reagent. In the combined system, ligand Ac- plays an important role in improving separation of Eu and Gd, and Y and Dy. The calculated ratio of Ac- to HIB- concentrations was compared and demonstrated that Eu and Gd, and Y and Dy tend to be separated at lower, and higher ratio of the two free ligands, respectively. An operational buffer system was developed for a complete separation of all REE ions.     

Multitracer study on the behavior of various elements in atmosphere plant-systems

The direct absorption of atmospheric elements via soybean leaves has been studied using a radioactive multitra r technique. Soybean was cultivated until it bore seeds in a box under no-rain conditions and with introduction of multitracer-adsorbed cellulose powders. The radioactive nuclides of 40 elements were produced from Au target irradiated with¹⁴N, and the nuclides with relatively long half-life of the elements Sc, Mn, Co, As, Se, Rb, Sr, Y, Eu, Gd, Yb, Re, and Ir were dominantly observed in each part of soybean plant.     

Solvent extraction kinetics of rare earth elements

The kinetics of solid-liquid extraction of rare earth elements (RE) (La, Ce, Sm, Dy and Yb) were studied with 1-(2-pyridylazo)-2-naphthol (PAN) at 60 degrees C using paraffin wax as a diluent. The rate of extraction is first order with respect to metal ion and hydrogen ion in the aqueous phase and second order with respect to the extractant in the organic phase. The rate-determining step is the formation of an [RE(PAN)(2)](+) complex between RE(3+) and PAN in the aqueous phase. The rate constant for the extraction was found to be about 10(11) 1 mol(-1) s(-1). The temperature dependence of extraction rate was determined and the activation parameters were calculated.     

Behaviour of transplutonium and rare earth elements on TVEX

Behaviour of transplutonium and rare-earth elements on TVEX, containing TBP, HDEHP, mixture of TBPHDEHP (11), PAPNA and TOA has been studied. The analytical possibility of isolation and separation of tetravalent Pu and Bk from trivalent actinides and lanthanides from strong nitric acid solutions (1.0–12.0) on TVEX with TBP, POR, HDEHP and TOA has been demonstrated. The separation of trivalent Bk, Cf and Eu from Am and Cm is real on TVEX, containing HDEHP and mixture of TBPHDEHP.     

Production of a tracer packet of heavier rare earth elements

The paper describes the production of a tracer packet of heavier rare earth elements containing carrier-free radionuclides of ^153,155Tb, ^153,155,157Dy, ¹⁵⁹Ho, ^159,161Er, ¹⁶¹Tm produced by medium energy ⁷Li and ¹²C irradiation on an europium oxide target and the subsequent separation of bulk europium from the carrier-free products. This revised version was published online in July 2006 with corrections to the Cover Date.