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1.
Abstract

Conditions for the selective removal of uranium from high‐level waste solution have been optimized using tri‐n‐butyl phosphate (TBP) as the extractant. Various aqueous soluble reducing agents viz. hydroxylamine nitrate (HAN), hydrazine nitrate (HN), and diethyl hydroxylamine nitrate (DEHAN) as well as n‐dodecane soluble reductant viz. tert‐butyl hydroquinone (TBH) have been evaluated for the separation of U with respect to Pu and Np. The combination of DEHAN and TBH has been found to be most promising for the selective extraction of U from HLW. Extraction data of a few other metal ions expected to be present in high‐level waste solutions viz. Am(III), Eu(III), Zr(IV), Sr(II), and Cs(I) are also obtained.  相似文献   

2.
Suitable N.N'-tetraalkylmalonamldes for Am(III) extraction from concentrated HNO3 aqueous liquors have been selected. Extraction mechanisms of Eu(III) and Am(III) by NN'-dlmethyldioctylmalonamide (DMDOMA) have been investigated. The distributions ratios of Am(III) and Eu(III) between 1M DMDOMA in t-butylbenzene and per chloric acid are higher than those obtained In nitrate media. Extraction data for Pu)IV), U(VI), Fe(III), Zr(IV) are reported. From these results It can be concluded that the NN'-dlmethyldlal-kylmalonamldes are good extractants for the actinides contained in the radioactive wastes.  相似文献   

3.
Abstract

Room temperature ionic liquids (RTILs) containing β-diketonate anions have been prepared and studied for the extraction of 239Pu(IV), 233U(VI), and 241Am(III) from nitric acid medium. The ionic liquids such as alkylquaternaryammonium thenoyltrifluoroacetonate (R4NTTA), and 1-alkyl-3-methylimidazolium thenoyltrifluoroacetonate (amimTTA), with methyl, butyl, hexyl, heptyl, and octyl moieties have been prepared and characterized by 1H and 13C nmr and IR spectroscopy. The distribution ratio of plutonium(IV) (D Pu(IV)) in a solution of tri-n-octylmethylammonium thenoyltrifluoroacetonate (TOMATTA) present in tri-n-octylmethylammonium bis(trifluoromethylsulfonyl)imide (TOMANTf2) and amimTTA in amimNTf2 was studied as a function of various parameters. The unique property of β-diketonate ionic liquids, namely, the miscibility in molecular diluents, was exploited to elucidate the mechanism of Pu(IV) extraction in these ionic liquids.  相似文献   

4.
《分离科学与技术》2012,47(9):1384-1393
Two bisdiglycolamides (BisDGAs) of N,N,N′′′,N′′′-tetrabutyl-N?,N′′-ethidene bisdiglycolamide (TBE-BisDGA) and N,N,N′′′,N′′′-tetrabutyl-N?,N′′-m-xylylene bisdiglycolamide (TBX-BisDGA) were synthesized. Their extraction behaviors of Eu(III) and Am(III), as well as nitric acid were investigated from nitric acid medium by using n-octanol as diluent. Nitric acid is extracted as the form of HNO3·(BisDGAs)0.6 by BisDGAs and the conditional acid uptake constants of TBE-BisDGA and TBX-BisDGA were 0.26 and 0.10, respectively. The distribution ratios of Eu(III) and Am(III) increased with the increase of nitric acid and extractant concentration, whilst decreased with temperature rise. TBX-BisDGA had a stronger extraction power for Eu(III) and Am(III) than TBE-BisDGA. Both of the extractants displayed a higher affinity toward Eu(III) than Am(III). In the examination of the acidity range from 0.5 to 5.0 M, a maximum separation factor SFEu(III)/Am(III) can reach 8.0 at 3.0 M HNO3 for TBX-BisDGA; and 10 at 4.0 M HNO3 for TBE-BisDGA, respectively. Slope analyses showed that Eu(III) and Am(III) are extracted as di-solvated species by TBX-BisDGA or TBE-BisDGA. The extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addition, their Eu(III) complexes were analyzed by using infrared spectra.  相似文献   

5.
《分离科学与技术》2012,47(10):883-894
Abstract

Extraction behavior of plutonium(IV), uranium(VI), and some fission products from aqueous nitric acid media with di-n-octylsulfoxide (DOSO) has been studied over a wide range of conditions. Both the actinides are extracted essentially completely, whereas fission product contaminants like Zr, Ru, Ce, Eu, and Sr show negligible extraction. The absorption spectra of sulfoxide extracts containing either Pu4+ or UO2 2+ indicate the species extracted from nitric acid into the organic phase to be Pu(NO3)4. 2DOSO and UO2(NO3)2. 2DOSO, respectively. Extraction of these actinides decreases with increasing temperature, indicating the extraction to be exothermic. DOSO extracts plutonium and uranium better than di-n-hexylsulfoxide (DHSO) under all condition and is also more soluble in aromatic diluents than the latter. The effect of gamma radiation on the extraction properties of DOSO is found to be similar to that of DHSO.  相似文献   

6.
Actinide partitioning studies with improved N,N,N',N'-tetraoctyl diglycolamide (TODGA) solvent (0.05 M TODGA + 5% iso-decanol in n-dodecane) has been explored in order to achieve better decontamination from fission products. The distribution behavior of various metal ions, viz. Am, Pu, U, Eu, Sr, Pd, Cs, Tc, Fe, and Mo with improved TODGA solvent was investigated. Lower concentration of TODGA (0.05 M as compared to previously proposed 0.1 M or 0.2 M) exhibited required extraction properties for actinide partitioning from pressurized heavy water reactor high level waste (PHWR-HLW). Counter-current extraction studies with simulated PHWR-HLW spiked with different radio-tracers (viz. 241Am, 152Eu, 137Cs, 85,89Sr, 59Fe, 106Ru, 109Pd, 95Zr, and 99Mo) suggested that > 99.9% of the trivalent actinides and lanthanides could be extracted in six stages and stripped in four stages. The decontamination factor for various fission products with respect to Am was: 3918 (Cs), 2990 (Sr), 1150 (Zr), 1407 (Ru), 1185 (Pd), and 3250 (Mo). The counter-current extraction studies with the irradiated solvent (500 kGy) reflected a significant amount of Mo extraction.  相似文献   

7.
The unsymmetrical diglycolamide, di-dodecyl-di-octyl diglycolamide (D3DODGA) is a modifier-free extractant proposed for partitioning of trivalent actinides from nitric acid medium. D3DODGA has been evaluated for the feasibility of using it in the absence of a phase modifier, for the partitioning of minor actinides from fast reactor high-level liquid waste (FR-HLLW). The extraction behavior of various metal ions present in the simulated FR-HLLW was studied in a solution of 0.1 M D3DODGA/n-dodecane from nitric acid medium. The distribution ratio of about 20 metal ions was measured as a function of concentration of nitric acid and other interfering ion. The extraction was found to be strongly dependent on the oxidation state of the metal ion. The extraction of Am(III) from 3–4 M nitric acid medium was quantitative in a single contact. However, it was accompanied by the quantitative extraction of fission products such as trivalent lanthanides (Ln(III)), Y(III), and Zr(IV). The extraction of Sr(II), Pd(II), and Ru(III) in 0.1 M D3DODGA/n-dodecane was not insignificant, but quite low. The extraction of Ba(II), Ni(II), Mo(VI), and Fe(III) was marginal and the extraction of Co(II), Sb(III), Mn(II), and Cs(I) in 0.1 M D3DODGA/n-dodecane was negligible. Our results indicated that 0.1 M D3DODGA/n-dodecane is a promising candidate for the separation of trivalent actinides from fast reactor high-level liquid waste containing significant quantities of trivalent lanthanides and actinides.  相似文献   

8.
《分离科学与技术》2012,47(10):2111-2127
Abstract

The extraction properties of diamide derivatives of dipicolinamide (2,6‐pyridinedicarboxylamide or DPA, (R′R″NCO)2C5NH3) in mixtures containing chlorinated cobalt dicarbollide in the acid form (HCCD), with and without a substituted polyethylene glycol (PEG), have been investigated. Distribution ratios of Cs, Sr, U, Eu and Am have been measured for various concentrations of diamide, PEG, aqueous phase nitric acid, with various HCCD:diamide ratios, and using different organic diluents. In the absence of HCCD, the diamides show little affinity for the extraction of Am or Eu from nitric acid solutions (distributions typically <1). Addition of HCCD with the diamide extractants indicates a pronounced synergistic effect with regard to actinide and lanthanide extraction; the observed Am and Eu distribution ratios typically increase by several orders of magnitude. Cesium is also appreciably extracted by the HCCD in the presence of the various diamides. Addition of PEG (to simultaneously extract Sr) with HCCD and diamide has minimal impacts on the Eu and Am distribution ratios. The initial data indicate that alkyl substituted DPA derivatives weakly affect the extraction properties with regard to actinides and lanthanides, while aryl substituents decrease extraction ability of the mixture. The results of this preliminary work indicate that numerous HCCD‐PEG‐DPA systems are promising and effective for the simultaneous extraction Cs, Sr, Am, and Eu from acidic solutions.  相似文献   

9.
Interactions of 134Cs(I), 152,154Eu(III), and 60Co(II) ions from HCl acid solutions with tungstocerate(IV) gel matrices, dried at 50°C, have been individually investigated by the batch equilibration method. The selectivity sequence was found to be in the order: Cs(I) >Eu(III) >Co(II). The breakthrough capacities of 12‐tungstocerate(IV) for Cs(I), Eu(III), and Co(II) were found to be 1.00, 0.55, and 0.26 mmol/g of the sorbent, respectively. In addition, a mixture of these radionuclides [6.20 × 10?3 M Cs(I), 3.53 × 10?3 M Eu(III), and 1.4 × 10?3 M Co(II)], in 150 ml of 0.02 M HCl solution was passed through 1‐g 12‐tungstocerate(IV) chromatographic column. Quantitative uptake of both 134Cs(I) and 152,154Eu(III) has been achieved, while only ?22% of 60Co(II) has been retained. Then, quantitative elution of the retained fraction of Co(II) was achieved with 14 ml of 0.1 M HCl acid solution leaving Eu(III) and Cs(I) strongly retained onto the column. Quantitative elutions of Eu(III) and Cs(I) were achieved by passing 20 ml of 0.3 M HCl and 16 ml of 2 M HCl acid solutions, respectively.  相似文献   

10.
《分离科学与技术》2012,47(17):2576-2581
An Aliquat-336 based ionic liquid, namely, tri-n-octylmethylammonium bis(2-ethylhexyl)phosphate ([A3636]+[DEHP]?) was prepared and studied for the extraction of U(VI), Pu(IV), and Am(III) from nitric acid medium. Since the ionic liquid, [A336]+[DEHP]? was miscible in n-dodecane (n-DD), the extraction of these actinides in the PUREX solvent, 1.1 M tri-n-butylphosphate (TBP) in n-dodecane (n-DD), was investigated in the presence of small concentrations of ionic liquid. The distribution ratio of U(VI) and Am(III) in 0.03 M [A336]+[DEHP]?/n-DD decreased with increase in the concentration of nitric acid; whereas the extraction of Pu(IV) initially increased, it reached a maximum at 4 M nitric acid followed by the decrease. The extraction of actinides in ionic liquid medium decreased in the order Pu(IV) > U(VI) >> Am(III), indicating the feasibility of modifying the extractive properties of TBP/n-DD to favor Pu(IV) extraction. Therefore, the extraction of Pu(IV) in a solution of TBP – [A336]+[DEHP]? in n-DD was also studied. The distribution ratio of Pu(IV) increased with increase in the concentration of ionic liquid and decrease in the concentration of TBP in organic phase. The distribution ratio of Pu(IV) determined in the presence of small concentration of ionic liquid in 1.1 M TBP/n-DD was always much higher than that observed in 1.1 M TBP/n-DD. In contrast to this, the distribution ratio of U(VI) decreased by the addition of ionic liquid and Am(III) was inextractable even in the presence of ionic liquid.  相似文献   

11.
Various diglycolamides (DGAs), N,N,N’,N’-tetraoctyl diglycolamide (TODGA), N,N-di-2-ethylhexyl-N’,N’-di-octyl diglycolamide (DEHDODGA), N,N,N’,N’-tetra-2-ethylhexyl diglycolamide (TEHDGA), N,N-di-decyl-N’,N’-di-hexyl diglycolamide (D2DHDGA), N,N-di-butyl-N’,N’-di-dodecyl diglycolamide (DBD3DGA), N,N,N’,N’-tetra-hexyl diglycolamide (THDGA), and N,N,N’,N’-tetradecyl diglycolamide (TDDGA) have been synthesized and studied for the extraction of Am(III) and Eu(III) from nitric acid medium. An attempt was made to understand the extraction and third phase formation behavior of trivalent metal ions in these DGAs. Our results revealed that despite having the same carbon to oxygen ratio in these DGAs, the third phase formation behavior and extractions achieved in these DGAs are significantly different.  相似文献   

12.
《分离科学与技术》2012,47(18):2927-2932
A malonamide based extractant, i.e., N,N′-dimethyl-N,N′-dicyclohexyl-malonamide (DMDCMA) was synthesized in a single step and tested for the extraction of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV), Pu(VI), etc., from nitric acid medium. The extractant was soluble in phenyltrifluoromethylsulphone (PTMS or FS-13) unless stated otherwise. The effect of various experimental parameters, such as the aqueous phase acidity (0.01–3 M HNO3), nature of the acid, oxidation states of the metal ions, ligand concentration, nature of the diluent and temperature on the extraction behavior of metal ions was studied. The extracted Am(III) species was determined from slope analysis method as [Am(NO3)3(DMDCMA)2]. The extraction of the metal ions was found to increase with the aqueous phase acidity. The temperature variation studies allowed the calculation of the heat of the two-phase extraction reaction as well as the corresponding extraction constants. These studies revealed that DMDCMA showed good extraction for all the actinide metal ions investigated, and have the advantage of single stage synthesis and easier purification protocol.  相似文献   

13.
Extraction properties of N,N-di(2-ethylhexyl)-2,2-dimethylpropanamide (DEHDMPA) for nitric acid, U(VI), and Pu(IV) were studied by a batch method using various nitric acid concentrations. The distribution ratio equations for nitric acid, U(VI), and Pu(IV) were derived. A continuous counter-current experiment was performed using mixer-settler extractors to determine the performance of a process that uses two types of monoamides, DEHDMPA and N,N-di(2-ethylhexyl)butanamide (DEHBA), as extractants. This process consisted of two cycles: one dedicated to extraction of U(VI) by DEHDMPA, and the other dedicated to the co-extraction of U(VI) and Pu(IV) by DEHBA. The feed solution used for the continuous counter-current experiment was 4 mol/dm3 nitric acid containing U(VI), Pu(IV), and simulated fission products. DEHDMPA exclusively extracted U(VI) from the feed at the 1st cycle, and the ratio of U recovered in the U fraction stream was 99.93%. The residual U and almost all Pu were extracted by DEHBA in the 2nd cycle, and the recovery of Pu in the U-Pu fraction stream was 99.94%. Concentration profiles of U and Pu in mixer-settlers were calculated using a simulation code, which confirmed that the calculation was effective for estimating the U concentration in the U fraction stream, and the U and Pu concentrations in the U-Pu fraction stream.  相似文献   

14.
Iron oxide (Fe3O4) particles functionalized with diglycolamic acid (Fe-DGAH) were synthesized and characterized by TG-DTA, X-Ray diffraction,1H NMR, and scanning electron microscopy (SEM). The extraction behavior of Am(III) and Eu(III) in Fe-DGAH was studied from dilute nitric acid medium to examine the feasibility for the mutual separation of trivalent actinides and lanthanides using Fe-DGAH. For this purpose, the effect of various parameters such as the duration of equilibration and concentrations of europium, nitric acid, and diethylenetriaminepentaacetic acid (DTPA) in the aqueous phase on the distribution ratio (Kd) of Am(III) and Eu(III) was studied. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized using DTPA. The distribution ratio of ?104 mL/g was obtained for both Am(III) and Eu(III) at pH 3, and it decreased with an increase in the concentration of nitric acid. However, a separation factor of Eu(III) over Am(III) of ?150 was achieved in the presence of DTPA. Rapid sorption of metal ions in the initial stages of equilibration followed by the establishment of equilibrium occurred within 2 h. The sorption data were fitted to the Langmuir adsorption model, and the apparent europium sorption capacity was determined to be ?50 mg/g. The study indicated the feasibility of using Fe-DGAH particles for magnetic separation of Eu(III) from Am(III) with high separation factors.  相似文献   

15.
《分离科学与技术》2012,47(10):1492-1497
Extraction behavior of neptunium has been compared for tri-n-butyl phosphate (TBP) and N,N-dihexyl octanamide (DHOA) extractants as a function of nitric acid concentration (0.5 ? 6 M HNO3), uranium loading (50 and 300 g/L relevant to Pu rich fast reactor and Pressurized Heavy Water Reactor, PHWR spent fuels, respectively), and in the presence of oxidizing and reducing agents. These studies suggest the possibility of co-recovery of U(VI), Pu(IV) and Np(IV) from spent fuel dissolver solutions (of Pu rich fuels) employing DHOA as extractant.  相似文献   

16.
Abstract

Extraction of Eu(III) and Am(III) from HNO3 into the organic solvents using N,N,N′,N′‐tetraoctyl‐diglycolamide (TODGA) was investigated in order to study the detailed extraction reaction. The chemical species: 1:2 for metal:TODGA complex is present in polar diluents. On the other hand, the metal complexes need three or more TODGA molecules to remain stable in non‐polar diluents. The HNO3 concentration dependence on the distribution ratio suggests that HNO3 participates in the metal extraction. Infrared spectra indicate that the carbonyl oxygen coordinates with Eu(III), and luminescence lifetimes suggest that there are no water molecules in the inner coordination sphere of the extracted Eu‐complex.  相似文献   

17.
ABSTRACT

Solvent extraction of Eu(III) and Am(III) from weakly acidic solutions with octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 2,6-bis((diphenylphosphino)methyl)pyridine N, P, P-trioxide (NOPOPO) in 1,2-dichloroethane was studied on a comparative basis. NOPOPO was found to exhibit unusually high extractability for Eu(III) and Am(III), probably due to its trifunctional nature, sufficient steric flexibility and basicity of the functional groups. Both CMPO and NOPOPO demonstrated synergistic effects in extraction of Eu(III) and Am(III) when used in combination with thenoyltrifluoroacetone (HTTA). However, the stoichiometry of the extracted species with CMPO/HTTA and NOPOPO/HTTA was different under similar experimental conditions. The extractant dependencies of the synergistic extractions suggest that the extracted species are the adduct complexes, M(ClO4)(TTA)2(CMPO)2 and M(ClO4)2(TTA)(NOPOPO)2, respectively. It was also observed that CMPO and CMPO/HTTA in dichloroethane extracted Eu(III) and Am(III) equally well, with very similar extraction constants. However, NOPOPO and NOPOPO/HTTA in dichloroethane demonstrated a slight preference for Eu(III) over Am(III), with the extraction constants for Eu(III) more than one order of magnitude higher than that for Am(III).  相似文献   

18.
《分离科学与技术》2012,47(13-15):1629-1639
Abstract

The extraction of Th(IV), UO2(II), Am(III), and Eu(III) from aqueous acid by a tetradentate extractant, 4,4′-nonanedioyl-bis(2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one), H2NDBP, has been studied and compared with two bidentate model compounds, 4-hexanoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HHMPP, and 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HBMPP. The distribution coefficients of UO2(II), Am(III), and Eu(III) were somewhat larger using H2NDBP relative to the model compounds under the conditions studied. However, the Th(IV) extraction using H2NDBP was greatly enhanced when compared to HBMPP or HHMPP. The distribution coefficient for Th(IV) from 0.5 M HNO3 was 11.6 using 3.0 × 10?3 M H2NDBP compared with values of D < 0.01 using 3.0 × 10?3 M HBMPP or HHMPP.  相似文献   

19.
Single-stage batch experiments to reveal the extraction properties of N,N,N’,N’-tetradodecyldiglycolamide (TDdDGA) for Y, La, Eu, Nd, and Am in nitric acid were carried out. The distribution ratios of Y, Eu, Nd, and Am exceeded 10 when the nitric acid concentration was 1–2 mol/dm3 (M), and the distribution ratio of La was 5.5 when the nitric acid concentration was 2 M. A continuous counter-current experiment using 0.1 M TDdDGA diluted with n-dodecane was performed using mixer-settler extractors installed in a hot cell. Nitric acid with a concentration of 2.1 M containing minor actinides (MAs: Am and Cm), rare earths (REs: Y, La, Nd, and Eu), and other fission products (Sr, Cs, Zr, Mo, Ru, Rh, and Pd) was fed to the extractor. TDdDGA effectively extracted MAs and REs from the feed, while other fission products were barely extracted. The extracted MAs and REs were back-extracted by bringing them in contact with 0.02 M nitric acid, and they were collected as the MA–RE fraction. The results indicated that more than 98% of Am and Cm in the feed were recovered in the MA–RE fraction. The proportions of Y, La, Nd, and Eu in the MA–RE fraction were 94.0%, 99.9%, 99.9%, and 86.9%, respectively.  相似文献   

20.
Abstract

The extraction of actinides, fission products, some non-nuclear elements, and nitric acid by N,N,N′,N′-tetraoctyl-3,6-dioxaoctanediamide (DOODA-C8) in dodecane was extensively studied. Also studied was the extraction of HNO3 and Nd(III) by the tetradodecyl analog of DOODA-C8 in dodecane. Both extractants contain two ether oxygen atoms in the backbone chain carrying the two amide groups and can thus act as tetradentate ligands. The extractability of actinides decreases in the order Pu(IV) > U(VI), Am(III) > Np(V) in the extraction from nitric acid and Pu(IV) > Am(III) >> U(VI) in the extraction from perchloric acid. Ions of di-, tri-, tetra-, hexa-, and heptavalent metals strongly differ in the extractability by DOODA-C8 but, except for lanthanides(III), there is no visible correlation of their distribution ratios with ionic radii. Due to the efficient extraction of actinides, weak extraction of fission products, and sufficient extraction capacity, DOODA-C8 is a promising extractant for the recovery of minor actinides from high-level radioactive wastes.  相似文献   

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