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1.
Solvent extraction and supported liquid membrane transport studies on Y(III) and Sr(II) were carried out using both nitric as well as hydrochloric acid feed conditions using N,N,N′,N′-tetra-octyldiglycolamide (TODGA) in several organic diluents. The solvent extraction studies indicated extremely large separation factor (SF) values with chloroform, carbon tetrachloride, 1-decanol and hexone when 6 M HNO3 was used as the feed. On the other hand, the SF values were 1–2 orders of magnitude lower when the nitric acid concentration was 3 M HNO3. Significantly large SF values were also obtained from 6 M HCl when xylene, carbon tetrachloride, n-dodecane and hexone were used as the diluent. Though mass transfer was not very promising in the supported liquid membrane studies with most of the diluent systems, quantitative Y(III) transport was observed with 0.1 M TODGA in xylene with negligible Sr(II) transport suggesting possibility of obtaining carrier free 90Y. The purity of the radiotracer was checked by half-life method.  相似文献   

2.
This paper describes a method for the separation and purification of 90Sr from PUREX–HLLW employing solvent extraction and precipitation techniques. 30 % TBP in n-dodecane was used for the removal of residual uranium, plutonium and neptunium from HLLW. Trivalent actinides and lanthanides were subsequently removed using N,N,N’,N’-tetra(2-ethylhexyl) diglycolamide (TEHDGA, 0.20 M in 30 % isodecyl alcohol and n-dodecane). 90Sr was selectively extracted from actinides and lanthanides depleted HLLW using 0.3 M TEHDGA in 5 % isodecyl alcohol and dodecane. Loaded strontium was stripped using 0.01 M HNO3 and further purified by radiochemical precipitation technique after adding Fe and natural strontium as carriers. Based on the experimental results, a flow-sheet was formulated and mCi levels of 90Sr recovered.  相似文献   

3.
Facilitated transport of Am(III) in nitric acid medium using tetra(2-ethyl hexyl) diglycolamide (TEHDGA) in n-dodecane as carrier was studied. It was aimed at finding out the physico-chemical model for the transport of Am(III) using TEHDGA/n-dodecane as carrier under various experimental parameters like feed acidity, carrier concentration, varying strippant, varying membrane pore size, etc. The feed acidity and carrier concentrations were varied from 1 M to 6 M HNO3 and 0.1 M to 0.3 M TEHDGA/n-dodecane, respectively. The transport of Am(III) increased with increase in feed acidity and carrier concentration reaching maximum at 3 M HNO3 and 0.2 M TEHDGA/n-dodecane, respectively. Several stripping agents were tested and 0.1 M HNO3 was found to be the most suitable stripping agent for this system. Almost quantitative transport of Am(III) was observed at about 180 min with feed acidity of 3 M HNO3, 0.1 M HNO3 as strippant and 0.2 M TEHDGA/n-dodecane as carrier. The pore size of the membrane support was varied from 0.20 μm to 5 μm and the permeation coefficient increased with increase in pore size up to 0.45 μm (2.43 × 10−3 cm/s), and then decreased with further increase in pore size. The plot between permeation coefficient vs. (membrane thickness)−1 was linear which showed that the Am(III) transport was membrane diffusion limited. The membrane diffusion coefficient calculated from the graph was found to be 1.27 × 10−6 cm2/s and its theoretical value was 1.22 × 10−6 cm2/s. The stability of the carrier against leaching out of the membrane support as well as the integrity of membrane support was studied over a period of 30 days and was found to be satisfactory within the studied time period.  相似文献   

4.
Polyvinylpolypyrrolidone (PVPP) is a resin with adsorption selectivity for U(VI) in HNO3 media. The stability of this resin has been examined against gamma-ray irradiation using HNO3 solutions of various concentrations. Samples of PVPP immersed in HNO3 solutions up to 6 mol·dm?3 (=M) were irradiated by a 60Co source at 3.6 kGy·h?1 to reach 0.90 MGy at room temperature under ambient atmosphere. As a result, no clear decrease in the capacity for U(VI) when added in 3 M HNO3 was observed for any samples, or rather the capacity was found to increase by approximately 50 % for PVPP irradiated in 6 M HNO3. It was indicated from some spectroscopic analyses of the irradiated samples that the irradiation causes the cleavage of the pyrrolidone ring of PVPP. This occurs by the addition of an oxygen atom originating from HNO3, followed by the formation of straight-chain groups with multiple coordinative atoms by the successive addition of oxygen, finally leading to the generation of a primary-amine-type weakly-basic anion exchange resin. The increase in the U(VI) capacity would be due to the formation of the straight-chain groups. However, such structural changes were not observed by heating at 323 K in up to 6 M HNO3 for 20 days. Thus, it was shown that PVPP is a heat-resistant resin.  相似文献   

5.
Abstract

Five diglycolamide-appended calix[4]arene (C4DGA) ligands, viz. C4DGA with no substituent (L-I), n-propyl (L-II), 3-pentyl (L-III), n-octyl (L-IV) and both side (L-V) substituents were evaluated for the separation of carrier free 90Y from a 90Y–90Sr mixture using the flat sheet supported liquid membrane technique. Based on the results of earlier batch studies, the transport properties of the C4DGA ligands towards Y(III) and Sr(II) were monitored at two different feed acidities. The transport rates were significantly lower for 6 M HNO3 as compared to 3 M HNO3 as the feed. After 6 h, the observed trend of Y(III) transport with the C4DGA ligands using a feed of 3 M HNO3 was: L-I ~ L-III > L-V > L-IV > L-II which changed to L-III > L-I > L-IV > L-V > L-II for 6 M HNO3 as the feed. With 3 M HNO3 as feed, >97% Y(III) transport was obtained with L-I and L-III in 6 h. Comparative Sr(II) transport was negligible resulting in high decontamination factors. In a one-step separation process, using L-I as the carrier ligand, pure 90Y was obtained as the respective complex with either EDTA or DOTA. The highlights of this liquid membrane-based separation method comprise: its easiness, one-step separation, low ligand inventory, relatively pure product and continuous method.  相似文献   

6.
The radiolytic degradation of N,N-di-dodecyl-N′,N′-di-2-ethylhexyl-3-oxapentane-1,5-diamide (D3DEHDGA) was studied at various absorbed doses of γ-radiation. The degradation was assessed by measuring the variation in the extraction behavior of Am(III) in irradiated solvent systems composed of neat D3DEHDGA or 0.1 M D3DEHDGA/n-dodecane in the presence and absence of nitric acid. The distribution ratio of americium (D Am(III)) decreased with increase of absorbed dose. The presence of n-dodecane and nitric acid enhanced the radiolytic degradation of the solvent. The third phase formation behavior of Nd(III) decreased with increase of absorbed dose and the third phase was not observed at absorbed doses above 100 kGy. The recovery of Am(III) from the irradiated system was near quantitative in five contacts. The study revealed that the extraction and stripping behavior of the irradiated solvent was quite satisfactory for partitioning of minor actinides from real wastes.  相似文献   

7.
The radiation stability of N,N-di-dodecyl-N′,N′-di-octyl-3-oxapentane-1,5-diamide (D3DODGA) was studied by γ-irradiation of the solvent up to a absorbed dose of 1,000 kGy. The effect of γ-irradiation on the radiolytic degradation of D3DODGA was assessed by measuring the distribution ratio of Am(III) (D Am(III)) as well as the third phase formation in the irradiated D3DODGA-n-dodecane solution. The D Am(III) in the irradiated solution decreased with increase of absorbed dose. The critical aqueous concentration of Nd(III) above which the third phase forms, increased with increase of absorbed dose. However, the limiting organic concentration of Nd(III) remained at ~25 mM irrespective of the absorbed dose. Recovery of Am(III) from the radiolytically degraded organic phase showed that back extraction of Am(III) was quantitative in a few contacts using dilute nitric acid. Our studies clearly indicated that radiolytic degradation of D3DODGA in n-dodecane is marginal even at the absorbed dose of 1,000 kGy, and therefore D3DODGA is a potential candidate for minor actinide partitioning.  相似文献   

8.
Thermal stability of neat octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (OΦD[IB]CMPO) and TRUEX solvent composition (0.2M OΦD[IB]CMPO-1.2M tri n-butyl phosphate-in n-dodecane) in the presence and absence of nitric acid has been studied in ambient air in a closed vessel, employing an adiabatic calorimeter. Enthalpies and kinetic parameters for the decomposition reaction were derived wherever possible and are reported for the first time. Neat OΦD[IB]CMPO was found to be thermally stable up to 633 K and exhibited an exothermic decomposition later. It decomposed at lower temperatures (376–386 K) depending on the nitric acid concentration. The exothermic rise in temperature and pressure increased exponentially, while activation energies exhibited exponential decrease for the decomposition reactions with increase in nitric acid content. TRUEX solvent was found to be stable up to 661 K in the absence of nitric acid while in the presence of 8 and 4M HNO3, it decomposed between 387 and 413 K. All these samples on decomposition formed incompressible gases and viscous black liquids. The results also indicate that the neat OΦD[IB]CMPO and the TRUEX solvent are thermally more stable than neat tri n-butyl phosphate (TBP), PUREX solvent (1.1M TBP/n-DD), neat diamyl amyl phosphonate (DAAP) and 1.1M DAAP/n-DD, triisoamyl phosphate (TiAP) and 1.1M TiAP/n-DD.  相似文献   

9.
The radiolytic stability of a branched diglycolamide extractant, namely N,N,N′,N′-tetra-2-ethylhexyl diglycolamide (T2EHDGA) dissolved in n-dodecane containing several phase modifiers, viz. N,N-dihexyloctanamide (DHOA), tri-n-butyl phosphate (TBP), 1-decanol and iso-decanol has been investigated. The distribution ratio of Am(III) decreased with increased radiation dose studied up to 1000 kGy. Nevertheless, all the composition of extractants showed satisfactory results up to 500 kGy, beyond which the extractants degraded drastically. The stripping behaviour of Am(III) with 0.2 M HNO3 was found to be unaffected even with the ligand solution irradiated up to 1000 kGy. Extraction of fission product and structural elements was also investigated using the irradiated solvents and was found to be not significantly affected with increasing absorbed dose with the exception of Mo which showed sharp rise in the distribution coefficient values. Loading of Nd in the organic phase decreased with the irradiated solvent due to degradation of the carrier. The effect of the absorbed dose on physical parameters such as density, viscosity and interfacial tension of the solvents has also been investigated.  相似文献   

10.
The chemical and electrochemical properties of technetium metal were studied in 1–6 M HX and in 1 M NaX (pH 1 and 2.5), X = Cl, NO3. The chemical dissolution rates of Tc metal were higher in HNO3 than in HCl (i.e. 8.63 × 10?5 mol cm?2 h?1 in 6 M HNO3 versus 2.05 × 10?9 mol cm?2 h?1 in 6 M HCl). The electrochemical dissolution rates in HNO3 and HCl were similar and mainly depended on the electrochemical potential and the acid concentration. The optimum dissolution of Tc metal was obtained in 1 M HNO3 at 1 V/AgAgCl (1.70 × 10?3 mol cm?2 h?1). The dissolution potentials of Tc metal in nitric acid were in the range of 0.596–0.832 V/AgAgCl. Comparison of Tc behavior with Mo and Ru indicated that in HNO3, the dissolution rate followed the order: Mo > Tc > Ru, and for dissolution potential the order: E diss(Ru) > E diss(Tc) > E diss(Mo). The corrosion products of Tc metal were analyzed in HCl solution by UV–Visible spectroscopy and showed the presence of TcO4 ?. The surface of the electrode was characterized by microscopic techniques; it indicated that Tc metal preferentially corroded at the scratches formed during the polishing and no oxide layer was observed.  相似文献   

11.
Tridentate ligand N,N,N′,N′-tetraoctyl-4-oxaheptanediamide(TOOHA) and other three analogous diamides have been prepared and characterized by using NMR spectra and element analysis. The extraction of UO2 2+ and Th4+ with the present extractants was investigated at 293 ± 1 K from nitric acid solutions. n-Octane was found to be the most suitable diluent in the present study compared with other diluents tested. Extraction distribution ratios (D) of U(VI) and Th(IV) have been studied as a function of aqueous concentrations of HNO3, extractant concentrations. The results indicated that U(VI) is mainly extracted as UO2(NO3)2·2TOOHA. In the case of Th4+ ion, the possible compositions of extracted species in organic phase were presumed to be Th(NO3)4·2TOOHA and Th(NO3)4·3TOOHA. In addition, the influence of concentration of sodium nitrate as salting-out agent on the distribution ratio of U(VI) and Th(IV) with TOOHA was also evaluated.  相似文献   

12.
A natural silver foil was bombarded by 30 MeV α-particles which produced 111In, 109Cd and 106mAg in the target matrix. 111In and 109Cd were separated from the Ag target matrix employing ion-exchange chromatography and liquid–liquid extraction (LLX). In the chromatographic separation, the active solution containing the NCA products were adsorbed in the column containing Dowex 50 and were eluted with HNO3. Bulk silver and 109Cd were sequentially eluted with 1 M HNO3. After complete elution of 109Cd and the bulk, 111In was eluted with 1.5 M HNO3. In the LLX, the NCA 111In was extracted to 1 % HDEHP (di-2(ethylhexyl)phosphoric acid) from 10?2 M HNO3 solution, leaving cadmium and bulk silver quantitatively in the aqueous phase. The NCA 109Cd was separated from the bulk Ag by precipitating Ag as AgCl. NCA 111In was stripped back quantitatively from HDEHP phase using 8 M HNO3.  相似文献   

13.
To separate minor actinides from high level liquid waste (HLLW) of PUREX reprocessing, a silica-based macroporous isobutyl-BTP/SiO2-P adsorbent was synthesized by impregnating isobutyl-BTP (2,6-di(5,6-diisobutyl-1,2,4-triazin-3-yl)pyridine) extractant into the macroporous SiO2-P support with a mean diameter of 60 μm. A partitioning process using extraction chromatography for the treatment of HLLW was designed consisting five separation columns. As a partly work focused on isobutyl-BTP/SiO2-P separation column, adsorption behavior of 241Am and trivalent rare earth (RE) from simulated HLLW onto silica-based isobutyl-BTP/SiO2-P adsorbent was investigated by batch method. Meanwhile, the chemical and radiolytic stabilities of isobutyl-BTP/SiO2-P adsorbent against 0.01 M HNO3 solution and γ-ray irradiation were studied. It was found that isobutyl-BTP/SiO2-P adsorbent exhibited good adsorption selectivity for 241Am over RE(III) in 0.01 M HNO3 solution and showed weak or no adsorption affinity to light and middle RE(III) groups. In addition, in stability experiments, isobutyl-BTP adsorbent showed excellent stability against 0.01 M HNO3 solution and γ-ray irradiation over 4 months contact time.  相似文献   

14.
The distribution of nitric acid between an aqueous phase and a solution of THPO, TcHPO and TOPO in benzene was measured at 25°. The apparent stability constants K1' were found to be 17.2±1.0 (M)-2 for THPO.HNO3, 7.0±0.8 (M)-2 for TcHPO.HNO3 and 15.2 ± I.I (M)-2 for TOPO.HNO3. The stoichionetry of the last complex was confirmed in n-octane solution at constant ionic strength in the aqueous phase.  相似文献   

15.
The unsymmetrical diglycolamides (DGAs) such as N,N-dihexyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (DHDODGA), N,N-didecyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (D2DODGA), N,N-didodecyl-N′,N′-dioctyl-3-oxapentane-1,5-diamide (D3DODGA), were synthesized, and characterized by IR, NMR, and mass spectroscopic techniques. The extraction behaviour of Am(III), Eu(III), and Sr(II) by the solutions of these unsymmetrical DGAs in n-dodecane was studied as a function of concentration of nitric acid and DGA. The distribution ratio of Am(III) and Eu(III) increased with increase in the concentration of nitric acid; whereas, the distribution ratio of Sr(II) reached a maximum at 4 M nitric acid followed by decrease at higher acidities. The extraction of Am(III) and Eu(III) in 0.1 M DGA/n-dodecane decreased in the order DHDODGA > D2DODGA > D3DODGA. However, the order changed upon lowering the concentration of DGA. The third-phase formation behaviour of nitric acid and neodymium(III) in 0.1 M DGA/n-dodecane was studied as a function of concentration of nitric acid. The limiting organic concentration of nitric acid and neodymium increased with increase in the chain length of alkyl group attached to amidic nitrogen. Near stoichiometric amount of neodymium(III) was loaded in 0.1 M D3DODGA/n-dodecane without the formation of third-phase from 3 to 4 M nitric acid medium. The study revealed that the unsymmetrical diglycolamides D2DODGA and D3DODGA are superior candidates for partitioning the minor actinides from high-level liquid waste.  相似文献   

16.
Low plutonium content acidic waste is generated in nuclear chemical facilities. Study was initiated to develop hollow fiber supported liquid membrane (HFSLM) technique for quantitative separation and recovery of plutonium (Pu) from such wastes using tri-n-butyle phosphate (TBP) in dodecane as carrier. Hollow fiber test module was fabricated using 20 lumens of 33.91 cm2 surface area and 9 cm length. After satisfactory testing of the hydrodynamic condition of the module, it was operated at a flow rate of 3 ml min−1 on recycling mode with acidic waste solution containing Pu=8 mg dm−3, uranium=15 dm−3, gross β=49.33 mCi dm−3, gross γ=15.73 mCi dm−3 and acidity 3 M HNO3. In presence of various fission products, selective permeation of Pu(IV) through the bundle of hollow fiber test module was observed to be more than 90% into a stripping phase consisting 0.1 M NH2OH·HCl in 0.3 M HNO3. A model is presented to describe the transport mechanism and to evaluate the mass transfer coefficient. The radiation stability was also tested by exposing the membrane upto irradiation level of 1 M rad. Potentiality of the method for the selective separation of plutonium from acidic waste is, thus, clearly seen.  相似文献   

17.
The macrocycle-mediated flux of Hg2+ individually and of Hg2+ and Mn+ (Mn+ = K+, Tl+, Ag+, Sr2+, Cd2+, or Pb2+) in cation mixtures has been measured at 25°C in a I M HNO3CHCl31 M HNO3 liquid membrane system. Of the ten macrocycles used, 18-crown-6(18C6), dicyclohexano-18-crown-6(DC18C6), and 21-crown-7(21C7)were most effective in transporting Hg2+ individually. Relative cation fluxes in the metal ion mixtures correlated well with relative log K values for cation--macrocycle interaction and with relative partition coefficients for the distribution of the resulting complex between the aqueous and organic phases  相似文献   

18.
The novel ligand N,N,N′′′′,N′′′′-tetrabutyl-N′′′,N′′′-(N″,N″-diethyl)-ethidene bisdiglycolamide (TBEE-BisDGA) and other eight analogous extractants have been synthesized and characterized by NMR and HRMS. The solvent extraction of Th4+, UO2 2+ and Eu3+ from nitric acid solution using the above BisDGA extractants was investigated in 1-dodecanol at 30 ± 1 °C. The extractants exhibited higher affinity toward Th4+ than UO2 2+ and Eu3+ in the present system. The maximum value of separation factor SF Th(IV)/U(VI) and SF Th(IV)/Eu(III) is 78.5 and 53.3 respectively for TBEE-BisDGA, 88.1 and 69.5 respectively in the case of TB i-PE-BisDGA at 3 M HNO3 solution.  相似文献   

19.
Thermal decomposition of neat TBP, acid-solvates (TBP·1.1HNO3, TBP·2.4HNO3) (prepared by equilibrating neat TBP with 8 and 15.6?M nitric acid) with and without the presence of additives such as uranyl nitrate, sodium nitrate and sodium nitrite, mixtures of neat TBP and nitric acid of different acidities, 1.1?M TBP solutions in diluents such as n-dodecane (n-DD), n-octane and isooctane has been studied using an adiabatic calorimeter. Enthalpy change and the activation energy for the decomposition reaction derived from the calorimetric data wherever possible are reported in this article. Neat TBP was found to be stable up to 255?°C, whereas the acid-solvates TBP·1.1HNO3 and TBP·2.4HNO3 decomposed at 120 and 111?°C, respectively, with a decomposition enthalpy of ?495.8?±?10.9 and ?1115.5?±?8.2?kJ?mol?1 of TBP. Activation energy and pre exponential factor derived from the calorimetric data for the decomposition of these acid-solvates were found be 108.8?±?3.7, 103.5?±?1.4?kJ?mol?1 of TBP and 6.1?×?1010 and 5.6?×?109?S?1, respectively. The thermochemical parameters such as, the onset temperature, enthalpy of decomposition, activation energy and the pre-exponential factor were found to strongly depend on acid-solvate stoichiometry. Heat capacity (C p ), of neat TBP and the acid-solvates (TBP·1.1HNO3 and TBP·2.4HNO3) were measured at constant pressure using heat flux type differential scanning calorimeter (DSC) in the temperature range 32?C67?°C. The values obtained at 32?°C for neat TBP, acid-solvates TBP·1.1HNO3 and TBP·2.4HNO3 are 1.8, 1.76 and 1.63?J?g?1?K?1, respectively. C p of neat TBP, 1.82?J?g?1?K?1, was also measured at 27?°C using ??hot disk?? method and was found to agree well with the values obtained by DSC method.  相似文献   

20.
Macro-porous cation exchange resin Diaion CPK-08 and gel type cation exchange resin Dowex 50WX8 were irradiated with γ-rays from60Co, while soaked in distilled water, 0.5M HNO3 or 4M HNO3, and the ion-exchange properties, such as strong- and weak-acid capacities, moisture content and wet resin volume, were examined in relation to absorbed dose. There was no appreciable difference between the radiation stabilities of the two cation exchangers. Increase of HNO3 concentration reduced the loss of strong-acid capacity and increased the decross-linkage and the weak-acid capacity. Elution characteristics of137Cs and90Sr from columns packed with γ-irradiated resin were examined and the column distribution ratio of these radionuclides and the theoretical plate number were calculated. These values decreased with the increase of absorbed dose. Diaion CPK-08 was packed into a pressurized column and irradiated with γ-rays at a dose rate of 2·106 R/hr, while water was passed through the column at a constant flow rate. The greatest change of the resin properties was observed at an upper stream position from the position of the highest radiation dose of 2·106 R/hr.  相似文献   

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