Uranium Permeation from Nitrate Medium Across Supported Liquid Membrane Containing Acidic Organophosphorous Extractants and their Mixtures with Neutral Oxodonors
05 Jul 2011-Separation Science and Technology (Taylor & Francis Group)-Vol. 46, Iss: 13, pp 2110-2118
TL;DR: In this paper, the authors studied the transport of U(VI) from nitric acid solution 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.
Abstract: 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...
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TL;DR: In this article, a carrier facilitated transport of U(VI) from nitric acid medium across supported liquid membrane (SLM) has been studied under varying experimental conditions, namely feed, carrier, receiver phase compositions, pore size and membrane thickness etc.
Abstract: Carrier facilitated transport of U(VI) from nitric acid medium across supported liquid membrane (SLM) has been studied under varying experimental conditions, namely feed, carrier, receiver phase compositions, pore size and membrane thickness etc Microporous polytetrafluoroethylene (PTFE) membranes were used as a solid support and dinonyl phenyl phosphoric acid (DNPPA) either alone or in combination with neutral donors dissolved in n -paraffin was used as carrier Receiver phases like H 2 SO 4 , Oxalic acid, Citric acid and Na 2 CO 3 were evaluated 2 M H 2 SO 4 appeared to be most effective as receiver for U(VI) transport across SLM under the conditions of these studies The permeability coefficient ( P ) evaluated for 01 M DNPPA in combination with 005 M neutral donors showed the U(VI) transport order: Cyanex 923 ~ TOPO > TBP > TEHP The permeability ( P ) of U(VI) decreased with increase in HNO 3 concentration and with metal ion concentration in feed solution The variation of Cyanex 923 concentration at fixed DNPPA concentration (01 M) revealed that U(VI) permeation across SLM was maximum at 1:25 mole ratio The synergistic mixture of 01 M DNPPA + 005 M Cyanex 923 was used for uranium recovery from uranyl nitrate raffinate (UNR) solution
32 citations
Cites background from "Uranium Permeation from Nitrate Med..."
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TL;DR: Tian et al. as discussed by the authors performed spectrophotometric and microcalorimetric studies of U(VI) complexation with sulfate at 25-70 o C and determined the equilibrium constants and enthalpy of complexation at 25 - 70 o C.
Abstract: Spectrophotometric and Calorimetric Studies of U(VI) Complexation with Sulfate at 25-70 o C Guoxin Tian, Linfeng Rao * Lawrence Berkeley National Laboratory, Berkeley, CA 94720, U.S.A. ABSTRACT Sulfate, one of the inorganic constituents in the groundwater of nuclear waste repository, could affect the migration of radioactive materials by forming complexes. Spectrophotometric and microcalorimetric titrations were performed to identify the U(VI)/sulfate complexes and determine the equilibrium constants and enthalpy of complexation at 25 – 70 o C. Results show that U(VI) forms moderately strong complexes with sulfate, i.e., UO 2 SO 4 (aq) and UO 2 (SO 4 ) 22- , in this temperature range and the complexes become stronger as the temperature is increased: 2- fold and 10-fold increases in the stability constants of UO 2 SO 4 (aq) and UO 2 (SO 4 ) 22- , respectively, when the temperature is increased from 25 o C to 70 o C. The complexation is endothermic and entropy-driven, showing typical characteristics of inner-sphere complexation and “hard acid”/”hard base” interactions. The thermodynamic trends are discussed in terms of dehydration of both the cation (UO 22+ ) and the anion (SO 42- ) as well as the effect of temperature on the structure of water. Key Words: Uranium, sulfate, complexation, temperature effect Corresponding author. E-mail address: LRao@lbl.gov
19 citations
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TL;DR: In this article, the authors applied the results from central composite design (CCD) experiments, further optimization experiments were carried out using response surface methodology (RSM), and validation tests revealed optimum performance at 0.1m Cyanex 272 and 0.05m TOPO, 4m HNO3 as the stripping solution and flow rates of both feed and stripping solutions were 100mL/min.
Abstract: The extraction of neodymium ions from monazite leach solution was achieved by synergistic extraction via hollow fiber supported liquid membrane (HFSLM). Applying the results from central composite design (CCD) experiments, further optimization experiments were carried out using response surface methodology (RSM). Validation tests revealed optimum performance at 0.1 M Cyanex 272 and 0.05 M TOPO, 4 M HNO3 as the stripping solution and flow rates of both feed and stripping solutions were 100 mL/min. The extraction of neodymium ions reached a maximum of 98%. Results indicated that the highest fractional resistance was a chemical reaction. This showed that mass transfer resistance due to chemical reaction was dominant for transport of neodymium ions through the hollow fiber supported liquid membrane system.
15 citations
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TL;DR: In this paper, the authors reported the U(VI) from nitric acid medium across polytetrafluoroethylene (PTFE) membrane impregnated with dinonyl phenyl phosphoric acid (DNPPA) as carrier.
Abstract: This paper reports the permeation of U(VI) from nitric acid medium across polytetrafluoroethylene (PTFE) membrane impregnated with dinonyl phenyl phosphoric acid (DNPPA) as carrier. The effects of various parameters such as nature and concentration of receiver phases, feed acidity, carrier/uranium concentration and membrane thickness were evaluated. 6 M H2SO4 was identified as receiver phase. Experimental data were fitted to a kinetic model to calculate the diffusion coefficient D(o) and mass transfer coefficients Δ ( a ) − 1 . The optimized conditions were applied for recovery of uranium from uranyl nitrate raffinate (UNR) waste solution generated during the purification of uranium through U(VI)–HNO3–TBP route.
13 citations
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TL;DR: In this article, the mass transfer of synergistic extraction of uranium ions from monazite leach solution via HFSLM was examined and the optimum conditions were found to be pH 5 in the feed solution, 0.1m TOPO in the liquid membrane and 2m H2SO4 in the stripping solution at 30°C.
Abstract: The mass transfer of synergistic extraction of uranium ions from monazite leach solution via HFSLM was examined. Optimum conditions for synergistic extraction were found to be pH 5 in the feed solution, 0.1 M Cyanex 272 + 0.1 M TOPO in the liquid membrane and 2 M H2SO4 in the stripping solution at 30 °C. After a fourth cycle, the cumulative extraction and stripping of uranium ions reached 95% and 90%. Fractional resistance due to extraction reaction proved to be the highest value. This indicated that mass transfer resistance from the extraction was dominant. The controlling step is the chemical reaction.
12 citations
References
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TL;DR: In this article, a review of the works performed in the Separation Chemistry Group of the Chemistry Division of Argonne National Laboratory on the transport and separation properties of supported liquid membranes (SLM) is presented.
Abstract: The works performed in the Separation Chemistry Group of the Chemistry Division of Argonne National Laboratory on the transport and separation properties of supported liquid membranes (SLM) are reviewed. The models and equations which describe the permeation through SLMs of metal species are described. These models have been tested with various carriers absorbed on flat-sheet and hollow-fiber SLMs by measuring the permeation of several metal species of hydrometallurgical and nuclear interest. An equation for the separation factor of metal species in SLM processes and examples of separations of metal ions are reported. The possibility of bypassing the single stage character of SLM separations by using multilayer composite SLMs, arranged in series, is also analyzed. Finally, the factors which control the stability of SLMs are briefly discussed.
547 citations
"Uranium Permeation from Nitrate Med..." refers methods in this paper
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TL;DR: In this paper, the authors present a survey of Membrane applications in the chemical and pharmaceutical industries and discuss the current state of the art and future directions of the application of these materials.
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275 citations
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TL;DR: In this article, the development of the range of Cytec extractants and their application for the separation of cobalt from nickel is described. But it was not until the dialkyl phosphinic acid reagent, CYANEX 272, and its dithio analogue, CyANEX 301, became available that liquors containing very low Co:Ni ratios of at least 1:40 to even > 1:100 could be treated.
Abstract: Solvent extraction (SX) has come to be one of the most important separation processes in hydrometallurgy. Phosphorus-based extractants have proved to be of particular importance, especially for the separation of cobalt from nickel. However it was not until the dialkyl phosphinic acid reagent, CYANEX 272, and its dithio analogue CYANEX 301, became available that liquors containing very low Co:Ni ratios of at least 1:40 to even >1:100 could be treated. This has opened the way to the direct application of SX for the separation of Co from Ni in liquors derived from the leaching of nickel mattes from the smelting of nickel sulphide ores and from the pressure acid leaching of nickel laterite ores. This paper describes the development of the range of Cytec extractants and, in particular, discusses the development of their application for the separation of cobalt from nickel. Examples of actual industrial operating plants will also be given and individual flowsheets discussed.
212 citations
"Uranium Permeation from Nitrate Med..." refers background in this paper
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TL;DR: In this paper, current status on the chemical aspects of nuclear fuel reprocessing is presented with special emphasis on the Purex process which continues to be the process of choice for the last four decades.
Abstract: Current status on the chemical aspects of nuclear fuel reprocessing is presented with special emphasis on the Purex process which continues to be the process of choice for the last four decades. Better decontamination from fission products, new methods for uraniumplutonium partitioning and removal of actinides from high active waste are challenging areas in process chemistry. The development work on TRUEX and DIAMEX process for treating high active waste is briefly described. An overview of pyrochemical processes, which are important for Integral Fast Reactor Concept, is presented.
175 citations
"Uranium Permeation from Nitrate Med..." refers background in this paper
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TL;DR: In this paper, a new reagent, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol, is described for the spectrophotometric determination of uranium(VI).
Abstract: A new reagent, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (bromo-PADAP), is described for the spectrophotometric determination of uranium(VI). This reagent is highly sensitive towards uranium, the uranyl complex having a molar absorptivity of 74,000 at 578 nm and pH 7.6. In the presence of a mixed masking solution only a few ions interfere seriously, and the method can be made specific for uranium by a preliminary extraction of uranium into tri-n-octylphosphine oxide, and direct development of the bromo-PADAP colour in the organic phase. Details are given for the determination of uranium in waters, ores, phosphoric acid and phosphate rocks, thorium oxide, and zirconium oxide.
166 citations
"Uranium Permeation from Nitrate Med..." refers methods in this paper
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