Solvent extraction of Tc(VII) by the mixture of TBP and 2-nitrophenyl octyl ether

The extraction of Tc(VII) by the mixture of tri-n-butyl phosphate (TBP) and 2-nitrophenyl octyl ether (NPOE) has been studied. 0.2M NPOE-TBP can extract Tc(VII) effectively from 1M HNO₃ and 1M NaOH solutions with distribution ratios of 57.1 and 12.3, respectively. The distribution ratio of Tc(VII) decreases with increasing (>0.5M) HNO₃ concentration but increases with the increase of NaOH concentration. A pH 9 NaOH solution has proven to be suitable for Tc(VII) stripping. A simple extraction-stripping cycle can remove Tc(VII) from a sodium hydroxide solution. A more sophisticated extraction process is proposed to remove Tc(VII) from nitric acid solution because the co-extracted HNO3 prevents the direct stripping of Tc(VII) by NaOH solution of pH 9.     

Technetium-99m extraction and transport across tri-n-octylamine-xylene based supported liquid membranes

The nuclear properties of^99mTc radionuclide are ideal for organ imaging. Study of the technetium transport across supported liquid membranes has been performed to get data for its separation from other elements. Tri-n-octylamine diluted in xylene was used to constitute the liquid membranes, supported in polypropylene microporous films. Stripping on the product solution side was performed with dilute NaOH solutions. The effect of sulphuric acid, nitric acid and hydrochloric acid in the feed on transport of^99mTc as TcO ₄ ^– ions has been studied. The permeability of the given ions determined from kinetic activity data has been found to be in the order of PH₂SO₄>PHCl>PHNO₃. The flux values have been calculated based on this permeability data. The increase in carrier concentration has shown an increase in flux and permeability values to a given optimum concentration. The increase in temperature has been found to reduce the transport of Tc ions. The optimum conditions for transport of^99mTc for the given acid concentration have been determined. Mechanism of Tc ion transport has also been provided based on chemical reactions involved at the membrane interfaces and uptake of Tc ions by the membrane. MoO ₄ ^2– ions do not permeate through membrane under optimum conditions of transport for TcO ₄ ^2– ions from H₂SO₄ solution.     

Transport study of V(V), Zn(II) and Be(II) using supported liquid membranes

V(V), Zn(II) and Be(II) have been studied to test oxine and tri-n-butylphosphate (TBP) as carriers for transport through supported liquid membranes in polypropylene film. All the three types of ions can be passed through such membranes using oxine in case of V(V) and TBP in case of Zn(II) and Be(II). Maximum flux of metal ions has been observed from 0.01M H₂SO₄ for V(V) (3.22·10^–6 mol·m^–2·s^–1) and 2M HCl containing 3M CaCl₂ for Zn(II) solution (1.4·10^–6 mol·m^–2·s^–1). Low flux was observed in case of Be(II) since the membrane was affected by sulphocyanide group and did not remain hydrophobic. Mechanism of transport for these metal ions have been proposed separately. Distribution coefficient data for V(V) have also been evaluated to determine theoretical values of the permeability coefficient, and compared with experimental values.     

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.     

Nitric acid transport across TBP—Kerosene oil supported liquid membranes

HNO₃ transport across tri-n-butyl phosphate kerosene oil supported liquid membrane with or without uranyl ion transport has been studied. Parameters studied are the effect of TBP in the membrane, nitric acid in the feed solution and nitrate ion concentration in the feed solution. The flux of protons for 1 to 10 mol·dm^–3 HNO₃ solution is in the range of (0–25)·10^–4 mol·m^–2·s^–1 and for the TBP concentration range of 0.359 to 3.59 mol·dm^–3, the flux determined is (8.9 to 22)·10^–4 mol·m^–2·s^–1. From the experimental data and using theoretical equations the complex under transport through the membrane appears to be 2TBP·HNO₃ both in the presence and absence of uranyl ions. The diffusion coefficient for H⁺ ions through the membrane as a function of TBP concentration varies from (53 to 6)·10^–12 m²·s^–1, based on experimental flux and permeability data. The values of this coefficient supposing 2TBP·HNO₃ as diffusing species, based on viscosity data and theoretical estimation varies from (82.50 to 3.30)·10^–12 m²·s^–1. The value of distribution coefficient varies in the reverse direction from 0.06 to 1.46 at the same TBP concentration.     

Extraction of Pd(II) ions using tri-n-octylamine xylene base supported liquid membranes

Membranes, based on tri-n-octylamine (TOA) xylene liquid, supported in hydrophobic microporous films have been used to study the transport of Pd(II) ions, after extraction into the membrane. Various parameters, such as the effect of hydrochloric acid concentration in the feed solution, TOA concentration in the membrane phase, effect of stripping agent like nitric acid concentration, and temperature on the flux of Pd(II) ions across the liquid membranes have been investigated. The optimum conditions of transport for these metal ions determined are, TOA concentration, 1.25 mol·dm^–3, HCl concentration in the feed solution, 5 mol·dm^–3, and concentration of nitric acid used as a stripping, agent 5 mol·dm^–3. The maximum values of the flux and permeability determined under the optimum condition are 23·10^–6 mol·m^–2·s^–1 and 2.40·10³ m²·s^–1 at 25°C. The results obtained have been used to elucidate the mechanism of palladium transport.     

Separation of Cd(II) and Ni(II) ions by supported liquid membrane using D2EHPA/M2EHPA as mobile carrier

The separation of Cd(II) and Ni(II) ions was studied in an aqueous sulphate medium using supported liquid membrane (SLM). D2EHPA/M2EHPA was used as a mobile carrier, microporous hydrophobic PTFE film was used as a solid support for the liquid membrane, and the strip phase was sulphuric acid. The effects of different parameters such as feed concentration, carrier concentration, feed phase pH, and strip phase pH on the separation factor and flux of Cd(II) and Ni(II) ions were studied. The optimum values obtained to achieve the maximum flux were 5.0 for feed pH, 40 vol. % for D2EHPA/M2EHPA concentration in the membrane phase, 0.5 for strip pH, and 0.012 mass % for feed concentration. Under these optimum conditions, the flux values of Cd(II) and Ni(II) were 15.7 × 10^?7 kg m^?2 s^?1 and 2.6 × 10^?7 kg m^?2 s^?1, respectively. The separation factors of Cd(II) over Ni(II) were studied under different experimental conditions. At a carrier concentration of 10 vol. % and feed concentration of 0.012 mass %, the maximum value of 185.1 was obtained for the separation factor of Cd(II) over Ni(II). After 24 h, the percentages of the extracted Cd(II) and Ni(II) were 83.3 % and 0.45 %, respectively.     

Separation study of cadmium through an emulsion liquid membrane

A study of the transport of Cd(2+) ions through a tri-ndashoctylamine(TOA)-sorbital monooleate (Span 80)-oxylene liquid membrane has been performed with varying concentrations of HCl, KI, TOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed at 0.01 M KI, 0.025 M HCl, 0.015 M TOA, 3% (w/v) Span 80 and 0.025 M NaOH. With this system, cadmium could be completely separated from Zn(2+), Fe(2+), Co(2+), Ni(2+), Cr(3+) and Mn(2+). The transport mechanism of this metal ions through the membrane has been discussed.     

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.     

Formation of Tc metal in 12 M HCl using Zn as a reductant

Amorphous TcO₂ and NH₄TcO₄ solubilized into 12 M HCl will spontaneously convert to hexachlorotechnetate (TcCl₆ ^2?). This process is accelerated upon heating but species lower than Tc(IV) are not generated by this action. TcCl₆ ^2? is kinetically unstable with regards to formation in solutions of low concentrations of HCl and will spontaneously convert back to soluble and insoluble forms of Tc(IV) in water. TcCl₆ ^2? in 12 M HCl placed in contact with the reducing metal Zn at elevated temperatures (90 °C) forms a black precipitate that contains amorphous Tc metal, TcO₂, and oxy-chlorides of Tc. Powder X-ray diffraction indicates the presence of Tc metal after thermal treatment where X-ray absorption fine structure spectroscopy indicates the presence of hexagonal Tc metal and amorphous TcO₂ in the precipitate after rinsing with 12 HCl but before thermal treatment. The resulting solution contains a mixture of Tc chlorides and oxy-chlorides following reduction where TcCl₆ ^2? is completely consumed resulting primarily in Tc₂OCl₁₀ ^4? dominating the UV–visible spectra. Reducing the solution volume and reconstituting the products into 12 M HCl while boiling the mixed solution (>24 h) will slowly convert all soluble Tc back to TcCl₆ ^2?. Expanding on previous efforts made in this laboratory to recover Tc metal from aqueous solution, we investigate its synthesis when Tc(IV) and Tc(VII) in 12 M HCl is placed in contact with the reducing metal (i.e., Zn) at elevated temperatures.     

Separation study of cadmium through an emulsion liquid membrane using triisooctylamine as mobile carrier

A study of the transport of Cd(2+) ions through a triisooctylamine (TIOA)-sorbitan monooleate (Span 80)-dimethylbenzene liquid membrane has been performed with varying concentrations of HCl, KI, TIOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed with 0.025 M HCl, 0.01 M KI, 0.02 M TIOA, 3% (w/v) Span 80 and 0.05 M NaOH. With this system cadmium could be completely separated with Cu(2+), Zn(2+), Fe(2+), Co(2+), Ni(2+), Mn(2+), Cr(3+) and Al(3+). The transport mechanism of this metal ions through the membrane has been discussed.     

Separation of carrier-free 90Y from high level waste by supported liquid membrane using KSM-17

A generator system has been developed for the preparation of carrier-free ⁹⁰Y from ⁹⁰Sr present in the high level waste (HLW) of the Purex process by employing a supported liquid membrane (SLM) using 2-ethylhexyl-2-ethylhexyl phosphonic acid (KSM-17 equivalent to PC 88A) supported on a polytetrafluoro ethylene (PTFE) membrane. When uranium depleted Purex HLW at appropriate acidity is passed sequentially through octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) sorbed on chromosorb-102 (abbreviated as CAC) and Zeolite AR1 (synthetic mordenite) columns, all the trivalent, tetravalent and hexavalent metal ions and monovalent ¹³⁷Cs ions are sorbed. After adjusting to pH 2 with NaOH the resulting effluent is used as feed in a single stage membrane cell partitioned with a PTFE membrane impregnated with KSM-17 and having a feed and receiver compartment with 5.0 ml capacity each. The receiver compartment was filled with a 0.5M HNO₃ or 0.5M HCl stripping solution. ⁹⁰Y alone is preferentially transported across the membrane leaving behind all the impurities viz. ⁹⁰Sr, ¹²⁵Sb, ¹⁰⁶Ru, ¹⁰⁶Rh, etc. in the feed compartment. This technique can yield ⁹⁰Y in mCi levels in a pure and carrier-free form for medical applications. The feed can be reused repeatedly after allowing for ⁹⁰Y buildup.     

Separation study of mercury through an emulsion liquid membrane

A study of the transport of Hg(II) ions through a tri-n-octylamine (TOA) - sorbital monooleate (Span 80) -toluene liquid membrane has been performed with varying concentrations of HCl, KCl, TOA, Span 80 and NaOH in the feed, membrane and stripping solutions. Maximum transport was observed with 0.01 M KCl, 2.5 x 10(-2) M HCl, 1.5 x 10(-2) M TOA, 3% (w/v) Span 80 and 0.05 M NaOH. With this system, mercury could be completely separated from Cu, Zn, Fe, Co, Ni, Pb, Mn and Cd. The transport mechanism of this metal ion through the membrane is based on the association of metal anions (HgCl(4)(2)) with protonated TOA molecules at the feedside interface, diffusion through the membrane, decomposition of the complex at the strip-solution-side membrane interface under alkaline conditions, and backdiffusion of TOA molecules. Transport with the membrane is dependent on the concentration gradient but in the surrounding solutions it is inversely related to the concentration gradient.     

Nitrate ion transport across TBP-kerosene oil supported liquid membranes coupled with uranyl ions

The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO₃ and NaNO₃ has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO₃ · TBP, in addition to as UO₂(NO₃)₂ · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10^–3 mol · m^–2 · s^–1 compared to that of uranium ions (4.56 · 10^–6 mol · m^–2 · s^–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10^–10 m^–2 · s^–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction.     

Transport of Tb3+in Dispersion Supported Liquid Membrane System with Carrier P507

The Tb³⁺ transport in dispersion supported liquid membrane (DSLM) consisting of polyvinylidene fluoride membrane (PVDF) as the liquid membrane support and dispersion solution including HCl solution as the stripping solution and 2‐ethyl hexyl phosphonic acid‐mono‐2‐ethyl hexyl ester (P507) dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb³⁺ and different ionic strength in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on transport of Tb³⁺ has also been investigated, respectively. As a result, the optimum transport conditon of Tb³⁺ was that concentration of HCl solution was 4.0 mol/L, concentration of P507 was 0.10 mol/L, and volume ratio of membrane solution and stripping solution was 1.0 in the dispersion phase, and pH value was 5.2 in the feed phase. Ionic strength had no obvious effect on transport of Tb³⁺. Under the optimum condition studied, when initial concentration of Tb³⁺ was 1.0×10^?4 mol/L, the transport rate of Tb³⁺ was up to 95.2% during the transport time of 95 min. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The results were in good agreement with the literature data.     

Extraction and stripping study of strontium ions across D2EHPA-TBP-kerosene oil based supported liquid membranes

A Sr ion transport study across D2EHPA-TBP kerosene oil based liquid membranes supported on microporous polypropylene film has been performed. The parameters studied were the effect of di(2-ethylhexyl)phosphoric acid (D2EHPA) and TBP concentration variation in the membrane liquid, HNO₃ concentration variation in the stripping phase and citric acid concentration variation in the feed solution. The optimum conditions of transport are 0.3 mol/dm³ D2EHPA, 0.1 mol/dm³ TBP, 0.01 mol/dm³ citric acid in feed and 2 mol/dm³ HNO₃ in the stripping phase. The mechanism of transport observed is counter-ion coupled transport. The coupling ions are protons. The maximum flux for Sr ion transport observed is 5.33·10^–5 mol·m^–2·s^–1 and maximum permeability under optimum conditions observed is 8.08·10^–11 m^–2·s^–1.     

Continuous Transport of Zn(II) by Ammonium Chloride Media via Supported Liquid Membrane System

With the gradual depletion of traditional zinc resources, the full use of various non-traditional zinc-containing resources has received intensive attention. However, the efficient recovery of zinc ions with low concentrations remains challenging. Here efficient and continuous recovery of zinc ions in ammoniacal chloride media by a flat supported liquid membrane system is achieved, using Cyanex923 and TBP mixed extractant as the membrane phase. This article discusses the synergistic effect between Aliquat336, Cyanex923 and TBP, the effects of feed pH, total ammonia concentration, Cl⁻ concentration and temperature on Zn(II) transport.     

Cr(VI) ion removal from artificial waste water using supported liquid membrane

In this study, a novel flat-type synergic-supported liquid membrane was evaluated with a mixture of N-methyl-N,N,N-trioctylammonium chloride (Aliquat 336) and tributyl phosphate (TBP) as the carrier and kerosene as the diluent to remove Cr(VI) from synthetic waste water. The main parameters involved in the process were identified and optimised. The parameters were divided into two groups, those that were independent and those having an interaction. The parameters of the carrier/kerosene volumetric proportion and stirring rate were optimised individually due to their nature. The optimal values of these parameters were 0.5 and 500 min^?1, respectively, for a constant carrier/kerosene ratio and stirring rate in the designed experiments using the response surface method (RSM). The four parameters of TBP/Aliquat 336, chromium concentration in the feed phase, feed and product pH were optimised using RSM; it was observed that the TBP/Aliquat 336 ratio, feed pH, pH of the stripping phase and interaction of this parameter with feed concentration have the most important effects on the removal of Cr(VI). The optimal levels of these parameters were 0.61, 71.75 mg L^?1, 3.5 and 12.66 for the ratio of TBP/Aliquat 336, feed chromium concentration, pH of the feed and pH of the product, respectively. An experimental removal rate of 94.63 % at the optimized levels was obtained.     

Separation of 99mTc from 99Mo by Using TOPO — Kerosene Supported Liquid Membrane

Transport of ^99mTcO₄ ^– ions across TOPO-kerosene based supported liquid membrane was investigated at different concentrations of phosphoric acid as a feed solution and different concentrations of TOPO in the membrane, where 0.9% NaCl aqueous solution was used as a stripping solution. The flux of TcO₄ ^– ions across this liquid membrane varied with the concentration of both H₃PO₄ and TOPO. The best permeability coefficient was obtained at concentrations, [H₃PO₄] = 3 mole·l^–1 and [TOPO] = 0.5 mole·l^–1 (P = 2.08·10^–9 m²·s^–1). The results were utilized for the separation of ^99mTc from ⁹⁹Mo, where a selective and effective separation was obtained since no ⁹⁹Mo transport across this liquid membrane was noticed while a high rate of ^99mTc transport took place.     

Radiochemical solvent extraction of molybdenum/VI/ using99Mo tracer

A radiochemical solvent extraction method has been developed for the micro determination of Mo/VI/ using⁹⁹Mo tracer. It involves removal of^99mTc by ethyl methyl ketone /EMK/ and extraction of Mo with tri-n-butyl phosphate /TBP/ from 5M HCl. Different parameters affecting the extraction such as pH dependence, nature of solvent and interferences due to other radionuclides have been studied. The method can be used up to 2 g of Mo.