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Sample records for cmpo

  1. Novel types of tripodal CMPO ligands: synthesis and extraction

    Energy Technology Data Exchange (ETDEWEB)

    Janczewski, D. [Twente Univ., Enschede (Netherlands). Lab. of Supramolecular Chemistry and Technology; Inst. of Materials Research and Engineering, Research Link (Singapore); Rawdanowicz, M.; Reinhoudt, D.N.; Verboom, W. [Twente Univ., Enschede (Netherlands). Lab. of Supramolecular Chemistry and Technology; Hill, C.; Martinez, I. [Commissariat a l' Energie Atomique, CEA-Valrho, DRCP/SCPS/LCSE, Bagnols-sur-Ceze (France)

    2008-07-01

    Novel tripodal CMPO ligands having either aryl groups at the N-atom or alkyl groups at the CMPO methylene bridge were prepared in good yields. In the latter case one alkyl group per CMPO moiety was selectively introduced. Extraction studies with Am{sup 3+} and Eu{sup 3+} show that there is an influence of the electronic character of the aryl groups on the extraction. Alkylation of the CMPO methylene group gives rise to a considerable decrease of the D-values (about 100-1000 times), dependent on the bulkiness of the alkyl substituent. (orig.)

  2. Lanthanides and actinides extraction by calixarenes containing CMPO groups

    International Nuclear Information System (INIS)

    Garcia Carrera, A.

    2001-01-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  3. Experimental study on the basic characteristics of a novel silica-based CMPO adsorbent

    International Nuclear Information System (INIS)

    Wei, Yuezhou; Arai, Tsuyoshi; Zhang, Anyun; Hoshi, Harutaka; Koma, Yoshikazu; Watanabe, Masayuki

    2002-01-01

    In order to establish the extraction chromatography process for recovery of minor actinides from HLLW with a novel silica-based CMPO (octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide) adsorbent, some basic characteristics, such as dissolving behavior of CMPO from the adsorbent, thermal decomposition of the adsorbent and treatment method of organic wastes, were examined. It was found that the leakage of CMPO from the adsorbent in contact with an aqueous solution is the result of the solubility of CMPO in the solution. About 40-50 ppm of CMPO constantly leaked into the effluent from the adsorbent packed column using 0.01 M (M=mol/dm 3 ) HNO 3 as a mobile phase. The leakage of CMPO from the adsorbent could be effectively depressed with the utilization of the aqueous solution saturated by CMPO. TG-DTA thermal analysis results indicate that CMPO in the adsorbent decomposed at 20degC and the SDB-polymer at 290degC. The impregnated CMPO could be completely dissolved out from the support with acetone. Furthermore, the organic wastes such as CMPO, oxalic acid and DTPA those come from the elution procedure could be effectively decomposed with the Fenton reagent. (author)

  4. A comparison of the alpha and gamma radiolysis of CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher; Stephen P. Mezyk; Gary Groenewold; Gracy Elias

    2011-06-01

    The radiation chemistry of CMPO has been investigated using a combination of irradiation and analytical techniques. The {alpha}-, and {gamma}-irradiation of CMPO resulted in identical degradation rates (G-value, in {mu}mol Gy{sup -1}) for both radiation types, despite the difference in their linear energy transfer (LET). Similarly, variations in {gamma}-ray dose rates did not affect the degradation rate of CMPO. The solvent extraction behavior was different for the two radiation types, however. Gamma-irradiation resulted in steadily increasing distribution ratios for both forward and stripping extractions, with respect to increasing absorbed radiation dose. This was true for samples irradiated as a neat organic solution, or irradiated in contact with the acidic aqueous phase. In contrast, {alpha}-irradiated samples showed a rapid drop in distribution ratios for forward and stripping extractions, followed by essentially constant distribution ratios at higher absorbed doses. These differences in extraction behavior are reconciled by mass spectrometric examination of CMPO decomposition products under the different irradiation sources. Irradiation by {gamma}-rays resulted in the rupture of phosphoryl-methylene bonds with the production of phosphinic acid products. These species are expected to be complexing agents for americium that would result in higher distribution ratios. Irradiation by {alpha}-sources appeared to favor rupture of carbamoyl-methylene bonds with the production of less deleterious acetamide products.

  5. CMP(O) tripodands: synthesis, potentiometric studies and extractions

    Energy Technology Data Exchange (ETDEWEB)

    Reinoso-Garcia, M.M.; Jaczewski, D.; Reinhoudt, D.N.; Verboom, W. [Twente Univ., Lab. of Supramolecular Chemistry and Technology, Mesa Research Institute for Nanotechnology, Enschede (Netherlands); Malinowska, E.; Pietrzak, M. [University of Technology, Dept. of Analytical Chemistry, Faculty of Chemistry, Warsaw (Poland); Hill, C. [CEA Valrho Site de Marcoule, Dept. Radiochimie et Procedes, 30 (France); Baa, J.; Gruner, B. [Institut of Organic Chemistry, Academy of Sciences of the Czech Republic, Prague (Czech Republic); Selucky, P. [Nuclear Research Institute REZ, CZ (Czech Republic); Gruttner, C. [Micromod Partikeltechnologie GmbH, Rostock (Germany)

    2006-10-15

    Ligand systems containing three carbamoyl-methyl-phosphonate (CMP) or -phosphine oxide (CMPO) moieties attached to a tripodal platform have been synthesized for metal complexation and subsequent extraction from HNO{sub 3} solutions. The incorporation into ion selective electrodes (ISE) and picrate extractions with Na{sup +}, K{sup +}, Ag{sup +}, Ca{sup 2+}, Cd{sup 2+}, Hg{sup 2+}, Pb{sup 2+}, Cu{sup 2+}, Eu{sup 3+} and Fe{sup 3+} shows that CMPO tripodand 3 is very selective for Eu{sup 3+} and forms a very stable complex (log{beta}{sub ML} = 28.3). Liquid-liquid extractions performed with Eu{sup 3+} and Am{sup 3+} show reasonable extraction properties of the CMP(O) tripodands 3, 11 and 13 in 1,1,2,2-tetra-chloro-ethane, while in 1-octanol for all tripodands studied the distribution coefficients are low. Upon addition of the synergistic agent hexa-brominated cobalt bis(dicarbollide) anion (bromo-COSAN) the distribution coefficients for Am{sup 3+} and Eu{sup 3+} extraction increase considerably for CMP(O) tripodands 3 and 4. Covalently linked COSAN only enhances the extraction of Am{sup 3+} and Eu{sup 3+} at 0.001-0.01 M HNO{sub 3}. The functionalization of dendrimer coated magnetic silica particles with CMP(O) tripodands led to very effective particles (31 and 32) for Am{sup 3+} and Eu{sup 3+} removal from 0.01 M HNO{sub 3} solutions. (authors)

  6. The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

    International Nuclear Information System (INIS)

    Mincher, B.J.; Groenewold, G.S.; Mezyk, S.P.

    2016-01-01

    The organophosphorus amide octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) is proposed for use in fuel cycle separations as a group actinide/lanthanide extractant. Alternative compounds such as the mono-amides and diglycol amides (DGAs) proposed for actinide and/or actinide/lanthanide extraction also contain the amidic functional group, but do not contain the CMPO aromatic or phosphoryl groups. Their radiation stability is in the order mono-amides > CMPO > DGA for irradiation under similar conditions. Although they produce similar radiolysis products, the kinetics of degradation for CMPO are completely different than for the other amides. CMPO degradation occurs in a zero-order fashion, and the -G-value for the change in [CMPO] is much lower when in the presence of acid. The DGAs and mono-amides degrade with pseudo-first-order kinetics and are not protected by acidity. Possible mechanistic reasons for the differences between CMPO and the other amides are discussed, as are the effects of the diluent and metal complexation on CMPO free radical reaction rates. Finally, it is also shown that α-irradiation has much less adverse effects on CMPO degradation than β/γ irradiation, both with respect to -G-values, and radiolysis product generation. (authors)

  7. The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, B.J.; Groenewold, G.S. [Idaho National Laboratory, PO Box 1625, Idaho Falls, ID 83415 (United States); Mezyk, S.P. [California State University at Long Beach, Long Beach, CA 90840 (United States)

    2016-07-01

    The organophosphorus amide octyl(phenyl)-N,N-diisobutyl-carbamoylmethyl phosphine oxide (CMPO) is proposed for use in fuel cycle separations as a group actinide/lanthanide extractant. Alternative compounds such as the mono-amides and diglycol amides (DGAs) proposed for actinide and/or actinide/lanthanide extraction also contain the amidic functional group, but do not contain the CMPO aromatic or phosphoryl groups. Their radiation stability is in the order mono-amides > CMPO > DGA for irradiation under similar conditions. Although they produce similar radiolysis products, the kinetics of degradation for CMPO are completely different than for the other amides. CMPO degradation occurs in a zero-order fashion, and the -G-value for the change in [CMPO] is much lower when in the presence of acid. The DGAs and mono-amides degrade with pseudo-first-order kinetics and are not protected by acidity. Possible mechanistic reasons for the differences between CMPO and the other amides are discussed, as are the effects of the diluent and metal complexation on CMPO free radical reaction rates. Finally, it is also shown that α-irradiation has much less adverse effects on CMPO degradation than β/γ irradiation, both with respect to -G-values, and radiolysis product generation. (authors)

  8. Lanthanides and actinides extraction by calixarenes containing CMPO groups; Extraction des lanthanides et des actinides au moyen de calixarenes portant des groupements CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Carrera, A

    2001-07-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  9. The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold

    2016-05-01

    Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. It was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.

  10. CMPO, a new extractant for actinides: A review of the currently available literature

    International Nuclear Information System (INIS)

    Wei Liansheng; Gasparini, G.M.

    1989-05-01

    The extractive properties of dialkyl-N,N-dialkyl carbamoyl methyl phosphinoxides, a series of extractants for liquid-liquid extraction techniques, suitable for actinides separation in any valence state, are described. These extractants have been especially studied to treat effluents contaminated with alpha emitters. The technical reasons because n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO) and its best experimental conditions have been chosen are examined. CMPO is the extractant utilized to treat the alpha contaminated effluents of the CRE Casaccia Plutonium Laboratory by means of the TESEO Process, studied and verified in our laboratories. (author)

  11. CMPO, a new extractant for actinides: A review of the currently available literature

    Energy Technology Data Exchange (ETDEWEB)

    Liansheng, Wei [Institute of Atomic Energy of Beijing (China); Gasparini, G M [ENEA - Dipartimento Ciclo del Combustibile, Centro Ricerche Energia, Casaccia (Italy)

    1989-05-15

    The extractive properties of dialkyl-N,N-dialkyl carbamoyl methyl phosphinoxides, a series of extractants for liquid-liquid extraction techniques, suitable for actinides separation in any valence state, are described. These extractants have been especially studied to treat effluents contaminated with alpha emitters. The technical reasons because n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO) and its best experimental conditions have been chosen are examined. CMPO is the extractant utilized to treat the alpha contaminated effluents of the CRE Casaccia Plutonium Laboratory by means of the TESEO Process, studied and verified in our laboratories. (author)

  12. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  13. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    International Nuclear Information System (INIS)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660±0.092 at 25 C, and extraction enthalpy is -5. 46±0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 x 10 6 ±3.56 x 10 4 at 25 C; reaction enthalpy was -9.610±0.594 kcal/mol. Nitration complexation constant is 8.412±0.579, with an enthalpy of -10.72±1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured

  14. Polyacrylonitrile based composite materials with extracting agents containing chemically bonded CMPO groups for separation of actinoids

    Czech Academy of Sciences Publication Activity Database

    Kameník, Jan; Šebesta, F.; John, J.; Böhmer, V.; Rudzevich, V.; Grüner, Bohumír

    2015-01-01

    Roč. 304, č. 1 (2015), s. 313-319 ISSN 0236-5731 Institutional support: RVO:61388980 ; RVO:61389005 Keywords : actinoids * CMPO * Calix[4]arene * cobalt bis(dicarbollide) * polyacrylonitrile * composite material Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 0.983, year: 2015

  15. Structural investigation of the complexation of uranyl and lanthanide ions by CMPO-functionalized calixarenes

    International Nuclear Information System (INIS)

    Cherfa, S.

    1998-12-01

    A way to reduce the volume of nuclear wastes is to make a simultaneous extraction of actinides and lanthanides for their ulterior separation. Historically, the two first series of extractants used for the reprocessing of these wastes are the phosphine oxides and the CMPO (carbamoyl methyl phosphine oxide). In order to better know the type of complexes formed during the extraction, have been carried out structural studies concerning these two series (uranyl complexes and lanthanide nitrates). These studies have been carried out by X-ray diffraction on monocrystals. More recently, a new series of extracting molecules of lanthanides (III) and actinides (III) have been developed. It has been shown that in functionalizing an organic macrocycle of calixarene type (cyclic oligomer resulting of the poly-condensation of phenolic units) by a ligand of CMPO type, the extracting power of these molecules in terms of yield and selectivity towards the lighter lanthanides was superior to those of the CMPO alone. This study, carried out by X-ray diffraction on monocrystals of complexes formed between these ligands calix[4]arenes-CMPO (with 4 phenolic units) with uranyl and lanthanides nitrates, has allowed to define the type of the formed complexes, that is to say to establish the stoichiometry and the coordination mode (monodentate or bidentate) of the CMPO functions. These different steps of characterization have allowed too to determine the correlations existing between the complexes structures in the one hand and the selectivity and the exacerbation of the extracting power measured in liquid phase on the other hand. (O.M.)

  16. Recovery of plutonium from oxalate bearing solutions using a mixture of CMPO and TBP

    International Nuclear Information System (INIS)

    Mathur, J.N.; Murali, M.S.; Rizvi, G.H.; Iyer, R.H.; Badheka, L.P.; Banerji, A.; Michael, K.M.; Kapoor, S.C.; Dhumwad, R.K.

    1993-01-01

    A simple and efficient procedure has been developed to quantitatively recover Pu from oxalate bearing solutions using a mixture of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane. Pu(IV) in the range of 6.9 to 34.6 mg/1 was quantitatively extracted into 0.2 M CMPO+ 1.2 M TBP in dodecane from an aqueous solution containing 3.0 M HNO 3 and 0.1 M H 2 C 2 O 4 . At such low concentrations of Pu, the distribution ratio (D) did not change but the increase in oxalic acid concentration drastically reduced these values. The variation in HNO 3 concentration at a fixed concentration of 0.2 M CMPO + 1.2 M TBP has shown a dramatic increase in the D values, being 0.3 at 1.0 M and > 10 4 at 7.5 M. The extraction was almost quantitative even at the aqueous to organic ratio of 10:1. Plutonium could be quantitatively recovered (i) by stripping with 0.5 M acetic acid and (ii) by coprecipitating it directly from the organic phase with 0.3 M oxalic acid + 0.3 M calcium nitrate + sodium nitrite. ∼ 92% of the Pu was found in the precipitate and ∼7% in the supernatant. Using this procedure Pu, in a concentrated form (∼50 times), could be recovered from the oxalate bearing solutions without recourse to the destruction of oxalate ion. The slope of 2 from the nitrate ion as well as CMPO variation experiments suggest the species in the organic phase to be PuC 2 O 4 (NO 3 ) 2 .2CMPO. The absorption spectral study of Pu(IV) confirmed the above species in the organic phase. (author). 19 refs., 5 figs., 9 tabs

  17. Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Cherfa, S

    1998-12-10

    In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

  18. Extraction behaviour of Am(III) and Eu(III) from nitric acid medium in CMPO-HDEHP impregnated resins

    Energy Technology Data Exchange (ETDEWEB)

    Saipriya, K.; Kumar, T. [Bhabha Atomic Research Centre Facilities (India). Kalpakkam Reproscessing Plants; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Center for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2016-05-01

    Chromatographic resin containing extractants such as octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) or bis-(2-ethylhexyl)phosphoric acid (HDEHP) or mixture of extractants (CMPO + HDEHP) in an acrylic polymer matrix was prepared and studied for the extraction of Am(III) and Eu(III) over a range of nitric acid concentration. The effect of various parameters such as concentration of nitric acid in aqueous phase and the concentration of CMPO and HDEHP in the resin phase was studied. The distribution coefficient of Am(III) and Eu(III) in the impregnated resin increased with increased in the concentration of nitric acid for CMPO-impregnated resin, whereas a reverse trend was observed in HDEHP impregnated resin. In case of resin containing both the extractants, synergism was observed at low nitric acid concentration and antagonism at high nitric acid concentration. The mechanism of extraction was probed by slope analysis method at 0.01 and 2 M nitric acid concentrations. Citrate-buffered DTPA was used for the selective separation of Am(III), and a separation factor of 3-4 was obtained at pH 3.

  19. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    Energy Technology Data Exchange (ETDEWEB)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W. [Twente Univ., Lab. of Supramolecular Chemistry and Technology, Mesa Research Institute for Nanotechnology, Enschede (Netherlands); Malinowska, E.; Pietrzak, M. [Warsaw Univ. of Technology, Dept. of Analytical Chemistry, Faculty of Chemistry (Poland); Hill, C.; Allignol, C. [CEA Valrho, 30 - Marcoule (France)

    2007-01-15

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am{sup 3+} and Eu{sup 3+} show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, and K{sup +} salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO{sub 2}{sup 2+} among all examined cations (Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, K{sup +}). (authors)

  20. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    International Nuclear Information System (INIS)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W.; Malinowska, E.; Pietrzak, M.; Hill, C.; Allignol, C.

    2007-01-01

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am 3+ and Eu 3+ show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , and K + salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO 2 2+ among all examined cations (Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , K + ). (authors)

  1. Numerical simulation of extraction behavior of major components in the CMPO-TBP-HNO3 system

    International Nuclear Information System (INIS)

    Takanashi, M.; Koma, Y.; Koyama, T.; Funasaka, H.

    2000-01-01

    A numerical simulation code was developed in order to find the optimum condition for separation and the recovery of TRU (TRansUranium) elements in the octyl(phenyl)-N,N-di-isobutyl-carbamoyl-methyl-phosphine oxide (CMPO) - tri-butyl phosphate (TBP) - HNO 3 solvent extraction system. This code is able to predict the extraction behavior of americium and europium in the system containing many components. Calculations of concentration profiles of americium and lanthanides were carried out for a counter current experiment with laboratory scale mixer-settlers. The calculated profiles were in agreement with the experimental ones. The effect of oxalic acid was also included in the calculation and was discussed. (authors)

  2. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides

    International Nuclear Information System (INIS)

    Belair, S.

    2003-01-01

    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO 3 ) 3 -HNO 3 -H 2 O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  3. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Belair, S

    2003-07-01

    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  4. Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

    International Nuclear Information System (INIS)

    Chitnis, R.R.; Dhami, P.S.; Gopalkrishnan, V.; Wattal, P.K.; Ramanujam, A.; Murali, M.S.; Mathur, J.N.; Bauri, A.K.; Chattopadhyay, S.

    2000-10-01

    A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

  5. Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption

    Energy Technology Data Exchange (ETDEWEB)

    De Decker, Jeroen [Department of Inorganic and Physical Chemistry, Center for Ordered Materials, Organometallics, and Catalysis (COMOC), Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Folens, Karel [Laboratory of Analytical Chemistry and Applied Ecochemistry, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); De Clercq, Jeriffa [Department of Materials, Textiles, and Chemical Engineering, Industrial Catalysis and Adsorption Technology (INCAT), Ghent University, Valentin, Vaerwyckweg 1, 9000 Ghent (Belgium); Meledina, Maria; Van Tendeloo, Gustaaf [EMAT, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium); Du Laing, Gijs [Laboratory of Analytical Chemistry and Applied Ecochemistry, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Department of Inorganic and Physical Chemistry, Center for Ordered Materials, Organometallics, and Catalysis (COMOC), Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2017-08-05

    Highlights: • Highly stable metal-organic framework, MIL-101(Cr), for uses in aqueous, acidic adsorption. • Uranium recovery from low concentration acidic solutions. • One-step ship-around-the-bottle synthetic approach to incorporate CMPO in MIL-101(Cr). • Highly selective U(VI) adsorbent in competition with a high variety of metals, incl. rare earths and transition metals. • Regenerable and reusable adsorbent via 0.1 M nitric acid stripping. - Abstract: Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32 mg U/g (pH 3) and 27.99 mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375 min. The adsorbed U(VI) is easily recovered by desorption in 0.1 M HNO{sub 3}. Three adsorption/desorption cycles were performed.

  6. Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption

    International Nuclear Information System (INIS)

    De Decker, Jeroen; Folens, Karel; De Clercq, Jeriffa; Meledina, Maria; Van Tendeloo, Gustaaf; Du Laing, Gijs; Van Der Voort, Pascal

    2017-01-01

    Highlights: • Highly stable metal-organic framework, MIL-101(Cr), for uses in aqueous, acidic adsorption. • Uranium recovery from low concentration acidic solutions. • One-step ship-around-the-bottle synthetic approach to incorporate CMPO in MIL-101(Cr). • Highly selective U(VI) adsorbent in competition with a high variety of metals, incl. rare earths and transition metals. • Regenerable and reusable adsorbent via 0.1 M nitric acid stripping. - Abstract: Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32 mg U/g (pH 3) and 27.99 mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375 min. The adsorbed U(VI) is easily recovered by desorption in 0.1 M HNO 3 . Three adsorption/desorption cycles were performed.

  7. CMPO-calix[4]arenes and the influence of structural modifications on the Eu(III), Am(III), Cm(III) separation

    International Nuclear Information System (INIS)

    Peters, C.; Braekers, D.; Desreux, J.F.; Kasyan, O.; Miroshnichenko, S.; Rudzevich, V.; Boehmer, V.

    2008-01-01

    The syntheses of new calix[4]arenes featuring CMPO groups on the wide rim are reported and the extraction of Am(III) and Eu(III) from concentrated HNO 3 aqueous phases are discussed with reference to the properties of the symmetric tetra-CMPO derivative 1. All extraction studies were conducted in the same experimental conditions which allows to directly compare the dependence of the distribution coefficients of various calixarenes on the acid concentration (0.1 M 3 ] < 5 M). Calix[4]arene 1 becomes a very poor extractant if the length of the aliphatic chain between the amide and phosphine oxide groups of CMPO is increased, if the bridging methylene groups are replaced by sulfur atoms or if the macrocyclic cavity size is increased. By contrast, mixed amide - CMPO calix[4]arenes are nearly as effective than 1. Moreover, Am(III)/Cm(III) separation coefficients between 1.5 and 3 have been obtained with unsymmetrical calix[4]arenes of type 1 with different aliphatic chains grafted on the narrow rim. Guidelines to anticipate the extraction ability of calix[4]arenes remain elusive because of the intricate solution behavior of these compounds. (orig.)

  8. Partitioning of actinide from simulated high level wastes arising from reprocessing of PHWR fuels: counter current extraction studies using CMPO

    International Nuclear Information System (INIS)

    Deshingkar, D.S.; Chitnis, R.R.; Wattal, P.K.; Theyyunni, T.K.; Nair, M.K.T.; Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Rao, M.K.; Mathur, J.N.; Murali, M.S.; Iyer, R.H.; Badheka, L.P.; Banerji, A.

    1994-01-01

    High level wastes (HLW) arising from reprocessing of pressurised heavy water reactor (PHWR) fuels contain actinides like neptunium, americium and cerium which are not extracted in the Purex process. They also contain small quantities of uranium and plutonium in addition to fission products. Removal of these actinides prior to vitrification of HLW can effectively reduce the active surveillance period of final waste form. Counter current studies using indigenously synthesised octyl (phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) were taken up as a follow-up of successful runs with simulated sulphate bearing low acid HLW solutions. The simulated HLW arising from reprocessing of PHWR fuel was prepared based on presumed burnup of 6500 MWd/Te of uranium, 3 years cooling period and 800 litres of waste generation per tonne of fuel reprocessed. The alpha activity of the HLW raffinate after extraction with the CMPO-TBP mixture could be brought down to near background level. (author). 13 refs., 2 tabs., 12 figs

  9. Partitioning of actinide from simulated high level wastes arising from reprocessing of PHWR fuels: counter current extraction studies using CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Deshingkar, D S; Chitnis, R R; Wattal, P K; Theyyunni, T K; Nair, M K.T. [Bhabha Atomic Research Centre, Bombay (India). Process Engineering and Systems Development Div.; Ramanujam, A; Dhami, P S; Gopalakrishnan, V; Rao, M K [Bhabha Atomic Research Centre, Bombay (India). Fuel Reprocessing Group; Mathur, J N; Murali, M S; Iyer, R H [Bhabha Atomic Research Centre, Bombay (India). Radiochemistry Div.; Badheka, L P; Banerji, A [Bhabha Atomic Research Centre, Bombay (India). Bio-organic Div.

    1994-12-31

    High level wastes (HLW) arising from reprocessing of pressurised heavy water reactor (PHWR) fuels contain actinides like neptunium, americium and cerium which are not extracted in the Purex process. They also contain small quantities of uranium and plutonium in addition to fission products. Removal of these actinides prior to vitrification of HLW can effectively reduce the active surveillance period of final waste form. Counter current studies using indigenously synthesised octyl (phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) were taken up as a follow-up of successful runs with simulated sulphate bearing low acid HLW solutions. The simulated HLW arising from reprocessing of PHWR fuel was prepared based on presumed burnup of 6500 MWd/Te of uranium, 3 years cooling period and 800 litres of waste generation per tonne of fuel reprocessed. The alpha activity of the HLW raffinate after extraction with the CMPO-TBP mixture could be brought down to near background level. (author). 13 refs., 2 tabs., 12 figs.

  10. CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonding: Effect of local rigidification on solvent extraction toward f-block elements

    International Nuclear Information System (INIS)

    Chu, Hongzhu; He, Lutao; Jiang, Qian; Fang, Yuyu; Jia, Yiming; Yuan, Xiangyang; Zou, Shuliang; Li, Xianghui; Feng, Wen; Yang, Yuanyou; Liu, Ning; Luo, Shunzhong; Yang, Yanqiu; Yang, Liang; Yuan, Lihua

    2014-01-01

    Highlights: • Three CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonds were designed and synthesized. • The influence of local rigidification caused by intramolecular hydrogen bonds upon extraction of f-elements was investigated. • Selective extraction is realized via tuning local chelating surroundings by aid of intramolecular hydrogen bonds. -- Abstract: To understand intramolecular hydrogen bonding in effecting liquid–liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a–5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La 3+ , Eu 3+ , Yb 3+ , Th 4+ , and UO 2 2+ has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La 3+ more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La 3+ and Yb 3+ (or Eu 3+ ) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log–log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La 3+ , Th 4+ , UO 2 2+ , respectively. Additionally, their corresponding acyclic analogs 7a–7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding

  11. Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption.

    Science.gov (United States)

    De Decker, Jeroen; Folens, Karel; De Clercq, Jeriffa; Meledina, Maria; Van Tendeloo, Gustaaf; Du Laing, Gijs; Van Der Voort, Pascal

    2017-08-05

    Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32mg U/g (pH 3) and 27.99mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375min. The adsorbed U(VI) is easily recovered by desorption in 0.1M HNO 3 . Three adsorption/desorption cycles were performed. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Upper-rim CMPO-substituted calix[6]- and calix[8]arene extractants for the An3+/Ln3+ separation from radioactive waste

    International Nuclear Information System (INIS)

    Sansone, F.; Ungaro, R.; Casnati, A.; Galletta, M.; Macerata, E.; Trivellone, E.; Giola, M.; Mariani, M.; Boehmer, V.

    2008-01-01

    Two new ligands (1 and 2) for actinide/lanthanide separation derived from calix[6]- and calix[8]arenes functionalised at the upper rim with six or eight CMPO binding units were synthesised. These ligands, having a methoxy group at the lower rim, are conformationally mobile in solution at room temperature. Extraction data from water to a NPHE/n-octanol (90/10) solution of ligands 1 and 2, in the presence of bromo-cosan as synergist, show that these derivatives are less efficient and selective than the previously reported homologues derived from calix[4]arenes or from the lower rim CMPO calix[6]- and calix[8]arenes, especially at high nitric acid concentrations. However, although compound 1 and 2 do not appear promising for the actinide/lanthanide separation from high acidity radioactive waste, the results obtained in this work disclose some important structural results which can be useful for the design of new efficient and selective polytopic ligands. (orig.)

  13. Comparative evaluation of DHDECMP [dihexyl-N,N-diethylcarbamoyl-methylphosphonate] and CMPO [octylphenyl-N,N,-diisobutylcarbamoylmethylphosphine oxide] as extractants for recovering actinides from nitric acid waste streams

    International Nuclear Information System (INIS)

    Marsh, S.F.; Yarbro, S.L.

    1988-02-01

    Certain neutral, bifunctional organophosphorous compounds are of special value to the nuclear industry. Dihexyl-N,N-diethylcarbomoylmethylphosphonate (DHDECMP) and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) are highly selective extractants for removing actinide and lanthanide elements from nitric acid. We obtained these two extractants from newly available commercial sources and evaluated them for recovering Am(III), Pu(IV), and U(VI) from nitric acid waste streams of plutonium processing operations. Variables included the extractant (DHSECMP or CMPO), extractant/tributylphosphate ratio, diluent, nitrate concentration, nitrate salt/nitric acid ratio, fluoride concentration, and contact time. Based on these experimental data, we selected DHDECMP as the perferred extractant for this application. 18 refs., 30 figs

  14. CMPO-calix[4]arenes with spacer containing intramolecular hydrogen bonding: effect of local rigidification on solvent extraction toward f-block elements.

    Science.gov (United States)

    Chu, Hongzhu; He, Lutao; Jiang, Qian; Fang, Yuyu; Jia, Yiming; Yuan, Xiangyang; Zou, Shuliang; Li, Xianghui; Feng, Wen; Yang, Yuanyou; Liu, Ning; Luo, Shunzhong; Yang, Yanqiu; Yang, Liang; Yuan, Lihua

    2014-01-15

    To understand intramolecular hydrogen bonding in effecting liquid-liquid extraction behavior of CMPO-calixarenes, three CMPO-modified calix[4]arenes (CMPO-CA) 5a-5c with hydrogen-bonded spacer were designed and synthesized. The impact of spacer rotation that is hindered by introduction of intramolecular hydrogen bonding upon extraction of La(3+), Eu(3+), Yb(3+), Th(4+), and UO2(2+) has been examined. The results show that 5b and 5c containing only one hydrogen bond with a less hindered rotation spacer extract La(3+) more efficiently than 5a containing two hydrogen bonds with a more hindered rotation spacer, demonstrating the importance of local rigidification of spacer in the design of extractants in influencing the coordination environment. The large difference in extractability between La(3+) and Yb(3+) (or Eu(3+)) by 5b (or 5c), and the small difference by 5a, suggests intramolecular hydrogen bonding do exert pronounced influence upon selective extraction of light and heavy lanthanides. Log-log plot analysis indicates a 1:1, 2:1 and 1:1 stoichiometry (ligand/metal) for the extracted complex formed between 5b and La(3+), Th(4+), UO2(2+), respectively. Additionally, their corresponding acyclic analogs 7a-7c exhibit negligible extraction toward these metal ions. These results reveal the possibility of selective extraction via tuning local chelating surroundings of CMPO-CA by aid of intramolecular hydrogen bonding. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Energy Technology Data Exchange (ETDEWEB)

    Selucky, P.; Rais, J.; Lucanikova, M. [Nuclear Research Inst. plc., Rez near Prague (Czech Republic); Gruener, B.; Kvicalova, M. [Inst. of Inorganic Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Husinec-Rez near Prague (Czech Republic); Fejfarova, K. [Inst. of Physics, Academy of Sciences of the Czech Republic, Prague (Czech Republic); Cisarova, I. [Charles Univ., Prague (Czech Republic). Dept. of Chemistry

    2008-07-01

    Compounds were synthesized with the aim to develop efficient extraction agents for liquid-liquid extraction of polyvalent cations, i.e. lanthanides and actinides from high-level activity nuclear waste. Compounds of general formulation [(8-CMPO-(CH{sub 2}-CH{sub 2}O){sub 2}-1,2-C{sub 2}B{sub 9}H{sub 10})(1',2'-C{sub 2}B{sub 9}H{sub 11})-3.3'-Co(III)] with different phosphorus and nitrogen substitution (CMPO={sup 2}R,{sup 3}R P(O)-(CH{sub 2}){sub n}C(O)N{sup 1}R, {sup 1}R = t-octyl, H, Ph, {sup 2}R=Ph, n-octyl, {sup 3}R=Ph, n = 1,2)-(4a to 4e), were prepared and characterized by combination of {sup 11}B NMR, {sup 1}H high field NMR, ESI-M.S., HPLC and other techniques. Molecular structure of the sodium complex of ligand 4a ({sup 1}R = t-octyl, {sup 2}R = {sup 3}R = Ph, n = 1) was determined by single crystal X-ray diffraction analysis. Effect of several modifications in the structure of 4a-4e on the extraction properties was outlined. The study resulted in the definition of ionic ligand with enhanced extraction efficiency for 4a,b (t-octyl and H on the amidic nitrogen atom) and a better solubility of 4a and 4d ({sup 1}R = t-octyl, {sup 2}R = n-Oct, {sup 1}R=Ph, n = 1) in less polar solvents. Low polar mixtures of hydrogenated tetrapropylene (TPH) hexyl methyl ketone (HMK) can be applied as an auxiliary solvent for 4a, selected for detailed studies, replacing thus the polar and less environmentally friendly nitro-, fluoro- and chloro- solvents used in the current dicarbollide liquid-liquid extraction process. Results of the fission products separation from the simulated PUREX feed using 4a are presented inclusive procedures for Eu{sup 3+} stripping. (orig.)

  16. CMPO-functionalized C{sub 3}-symmetric tripodal ligands in liquid/liquid extractions : efficient, selective recognition of Pu(IV) with low affinity for 3+ metal ions.

    Energy Technology Data Exchange (ETDEWEB)

    Matloka, K.; Sah, A. K.; Peters, M. W.; Srinivasan, P.; Gelis, A. V.; Regalbuto, M.; Scott, M. J.; Univ. of Florida

    2007-12-10

    Structural modifications of carbamoylmethylphosphine oxide (CPMO)-functionalized triphenoxymethane platforms are described, and the influence of these changes on the ability of the ligand to extract actinides from simulated acidic nuclear waste streams has been evaluated. The ligand system has been shown to have excellent binding efficiency and a selectivity for An(IV) in comparison to the a simple monomeric CMPO ligand under analogous conditions. Both the extraction efficiency and selectivity are strongly dependent on the flexibility and electronic properties of the ligating units in the triphenoxymethane construct. The Tb(III) and Bi(III) nitrate complexes of tris-CMPO derivatives have been isolated, and their structures were elucidated by NMR, ESI FT-ICR MS, and X-ray analysis, providing information on the interactions between metal ions and the tris-CMPO molecules.

  17. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  18. Partitioning of actinides from high level waste of PUREX origin using octylphenyl-N,N'-diisobutylcarbamoylmethyl phosphine oxide (CMPO)-based supported liquid membrane

    International Nuclear Information System (INIS)

    Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Dudwadkar, N.L.; Chitnis, R.R.; Mathur, J.N.

    1999-01-01

    The present studies deal with the application of the supported liquid membrane (SLM) technique for partitioning of actinides from high level waste of PUREX origin. The process uses a solution of octylphenyl-N,N'-diisobutylcarbamoylmethyl phosphine oxide (CMPO) in n-dodecane as a carrier with a polytetrafluoroethylene support and a mixture of citric acid, formic acid, and hydrazine hydrate as the receiving phase. The studies involve the investigation of such parameters as carrier concentration in SLM, acidity of the feed, and the feed composition. The studies indicated good transport of actinides like neptunium, americium, and plutonium across the membrane from nitric acid medium. A high concentration of uranium in the feed retards the transport of americium, suggesting the need for prior removal of uranium from the waste. The separation of actinides from uranium-lean simulated samples as well as actual high level waste has been found to be feasible using the above technique

  19. CMP(O) tripodands: synthesis, potentiometric studies and extractions

    Czech Academy of Sciences Publication Activity Database

    Reinoso-García, M.M.; Janczewski, D.; Reinhoudt, D.N.; Verboom, W.; Malinowska, E.; Pietrzak, M.; Hill, C.; Báča, Jiří; Grüner, Bohumír; Selucký, P.; Grűttner, C.

    2006-01-01

    Roč. 30, č. 10 (2006), s. 1480-1492 ISSN 1144-0546 Grant - others:EEC(PL) FIKW-CT-2000-00088; EEC(PL) F16W-CT-2003-508854 Institutional research plan: CEZ:AV0Z40320502 Keywords : assisted chemical-separation * complex-formation constants * solvent-extraction Subject RIV: CA - Inorganic Chemistry Impact factor: 2.647, year: 2006

  20. Application of the CMPO extractant (supported liquid membrane) for the alpha decontamination of marcoule reprocessing concentrate

    International Nuclear Information System (INIS)

    Dozol, J.F.

    1990-01-01

    Reprocessing operations produce medium activity liquid wastes, in which the main components are sodium nitrate and nitric acid. These wastes are treated by evaporation, the distillate is discharged in the environment and all active and inactive salts are concentrated, leading to an important volume of wastes. The overall objective of this work, carried out within the framework of an CEC contract is to separate long life radionuclides (actinides and Cs - Sr) into a small volume from the large volume of the concentrate

  1. Two-stage supported liquid membrane method for the separation of carrier-free {sup 90}Y from {sup 90}Sr using KSM-17 and CMPO as carriers

    Energy Technology Data Exchange (ETDEWEB)

    Dhami, P S; Naik, P W; Dudwadkar, N L; Kannan, R; Achuthan, P V; Dakshinamoorthy, A; Jambunathan, U; Munshi, S K; Dey, P K [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai (India); Pandey, Usha; Venkatesh, Meera [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai (India)

    2007-07-01

    A two stage supported liquid membrane system is developed for the separation of carrier free {sup 90}Y from {sup 90}Sr for therapeutic applications. The feed containing {sup 90}Sr-{sup 90}Y in nitric acid solution at pH 2 is placed in the feed compartment and transported across a polytetrafluoroethylene membrane containing 2-ethyhexyl2ethylhexyl phosphonic acid to a 4M HNO{sub 3} receiver phase. This is then transported across another polytetrafluoroethylene membrane containing octyl phenyl N,N-diisobutylcarbamoyl methylphosphene oxide to another receiving phase, 1 M acetic acid. This has been implemented on simultaneous and sequential modes with very good yield. The second stage will act as a barrier for {sup 90}Sr, and will improve the product purity. (author)

  2. Halogen protected cobalt bis(dicarbollide) ions with covalently bonded CMPO functions as anionic extractants for trivalent lanthanide/actinide partitioning

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Švec, Petr; Selucký, P.; Bubeníková, M.

    2012-01-01

    Roč. 38, č. 1 (2012), s. 103-112 ISSN 0277-5387 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * CMPR * liquid-liquid extraction * lanthanides * actinides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.813, year: 2012

  3. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Plešek, Jaromír; Báča, Jiří; Císařová, I.; Dozol, J. F.; Rouquette, H.; Vinas, C.; Selucký, P.; Rais, J.

    2002-01-01

    Roč. 26, č. 10 (2002), s. 1519-1527 ISSN 1144-0546 R&D Projects: GA ČR GA104/99/1096; GA ČR GA104/01/0142; GA ČR GA203/99/M037; GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : LIQUID-CHROMATOGRAPHIC SEPARATIONS * BORON-CLUSTER COMPOUNDS * CALIXARENES Subject RIV: CA - Inorganic Chemistry Impact factor: 2.060, year: 2002

  4. Extraction complexes of Pu(IV) with carbamoylmethylphosphine oxide ligands. A relativistic density functional study

    International Nuclear Information System (INIS)

    Wang, Cong-Zhi; Lan, Jian-Hui; Feng, Yi-Xiao; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun; Wei, Yue-Zhou

    2014-01-01

    The extraction complexes of Pu(IV) with n-octyl(phenyl)-N,N-diisobutyl-methylcarbamoyl phosphine oxide (CMPO) and diphenyl-N,N-diisobutyl carbamoyl phosphine oxide (Ph 2 CMPO) have been studied by using density functional theory (DFT) combined with relativistic small-core pseudopotentials. For most complexes, the CMPO and Ph 2 CMPO molecules are coordinated as bidentate chelating ligands through the carbonyl oxygen and phosphoric oxygen atoms. The metal-ligand bonding is mainly ionic for all of these complexes. The neutral PuL(NO 3 ) 4 and PuL 2 (NO 3 ) 4 complexes are predicted to be the most thermodynamically stable molecules according to the metal-ligand complexation reactions. In addition, hydration energies may also play a significant role in the extractability of CMPO and Ph 2 CMPO for the plutonium cations. In most cases, the complexes with CMPO possess qualitatively similar geometries and electron structures to those with Ph 2 CMPO, and they also have comparable metal-ligand binding energies. Thus, replacement of alkyl groups by phenyl groups at the phosphorus atom of CMPO seems to have no obvious influence on the extraction of Pu(IV). (orig.)

  5. Cobalt bis(dicarbollide) ions functionalized by CMPO-like groups attached to boron by short bonds; efficient extraction agents for separation of trivalent f-block elements from highly acidic nuclear waste

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Kvíčalová, Magdalena; Plešek, Jaromír; Šícha, Václav; Císařová, I.; Lučaníková, M.; Selucký, P.

    2009-01-01

    Roč. 694, č. 11 (2009), s. 1678-1689 ISSN 0022-328X R&D Projects: GA MŠk LC523; GA AV ČR IAA400310613 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallacarbaboranes * liquid-liquid extraction Subject RIV: CA - Inorganic Chemistry Impact factor: 2.347, year: 2009

  6. Separation of lanthanides (III) and actinides (III) by calixarenes containing acetamide-phosphine oxides functions

    International Nuclear Information System (INIS)

    Garcia Carrera, A.; Dozol, J.F.; Rouquette, H.

    2001-01-01

    The carbamoyl methyl phosphine oxide CMPO is the well known extractant of the TRUEX process for extraction of actinides from highly salted acidic wastes. In the framework of an European research contract coordinated by CEA/DDCC. V. Boehmer (Mainz, Germany) synthesized calix(4)arenes bearing CMPO moieties either on the wide rim, or on the narrow rim. Some of these calixarenes used at a concentration 10 -3 M are more efficient than CMPO used at a two hundred fifty fold higher concentration. Moreover, calixarene skeleton leads to a strong selectivity among lanthanides, this selectivity is much less obvious for CMPO. Selectivity order is reversed according to whether CMPO unit is borne by the wide rim or the narrow rim. The most efficient calixarenes allow actinides to be separated from most of the lanthanides except the lightest ones. (authors)

  7. Extraction of cerium (III) by polymer gels swollen with bidentate organophosphorus compounds

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Takashima, Yoichi; Matsumoto, Shiro; Yamanaka, Hiromitsu.

    1995-01-01

    The extraction of Ce (III) from aqueous solutions containing Al (NO 3 ) 3 was examined by using styrene-divinylbenzene copolymer (SDB) gels swollen with dihexyl-N, N-diethylcarbamoylmethylphosphonate (CMP), octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and an equimolar mixture of CMP and CMPO. The extraction constants (K ex ) for the gels with CMP and CMPO were evaluated. The distribution ratio of Ce (III) for the gel with an equimolar mixture of CMP and CMPO was described as K d = (K ex CMP [CMP] 3 + K ex CMPO [CMPO] 3 ) [NO 3 - ] 3 by using these extraction constants. The extraction rate was found to be controlled by diffusion of Ce-complex [Ce(NO 3 ) 3 (CMPO) 3 or Ce(NO 3 ) 3 (CMP) 3 ] through the gel. The diffusion coefficient (D s ) was inversely proportional to the viscosity of extractant (η) and represented by an expression similar to the Stokes-Einstein equation, D s η/T = constant. A decrease in the viscosity of extractant was effective for increasing the extraction rate. (author)

  8. Influence of the platform in multi coordinate ligands for actinide partitioning

    International Nuclear Information System (INIS)

    Dam, H.H.; Reinhoudt, D.N.; Verboom, W.

    2007-01-01

    Multi-coordinate ligands based on the trityl, C-pivot, and CTV platforms and the ligating groups CMPO, DGA, PICO, and MPMA were synthesized and studied for their extraction properties. The extraction efficiencies of these multi-coordinate ligands are largely influenced by the properties of the platform. The D Am values follow the order CTV6 ≥ trityl ∼ C-pivot ≥> CTV3 ≥ CTV0 with a maximum for CTV6CMPO of D Am = 30 (S Am/Eu 1.4, c L = 10 -4 M, 3 M HNO 3 ). There is a strong relationship between the D Am values, increasing in the order of CTV0CMPO ≤ CTV3CMPO ≤ CTV6CMPO, and the mobility of their CMPO groups. The S Am/Eu values are less influenced by the platform and range between 0.2 and 2.0, though they can reverse under the influence of the HNO 3 concentration (CTV6PICO S Am/Eu 0.7 at 0.001 M HNO 3 to 1.2 at 0.01 M HNO 3 ) or by changing the platform (CTV(0, 3 or 6)MPMA from S Am/Eu = 0.4 to 1.6 for tritMPMA both at 0.001 M HNO 3 ). For the CMPO derivatives the S Am/Eu values are most consistent, ranging from 1.4 to 1.8. (authors)

  9. Radical Cations and Acid Protection during Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-09-09

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  10. Radical Cations and Acid Protection during Radiolysis

    International Nuclear Information System (INIS)

    Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.

    2016-01-01

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  11. Carbamoyl methylphosphine oxide derivatives of adamantane as americium and europium extractants

    International Nuclear Information System (INIS)

    Babain, V.A.; Alyapyshev, M.Yu.; Novakov, I.A.; Orlinson, B.S.; Savel'ev, E.N.; Shokova, Eh.A.; Serebrayannikova, A.E.; Kovalev, V.V.

    2007-01-01

    Adamantane di-1,3-carbamoyl methylphosphine oxide (CMPO) derivatives, where CMPO-groups connect with 1,3-positions of rigid adamantane platform by methylene and ethylene bridges, are synthesized, and their efficiency as extractants of americium(III) and europium(III) from nitric acid solutions is demonstrated. Distribution function of Am 3+ and Eu + during extraction from 3M HNO 3 are measured in the investigation of extraction properties. It is noted that first synthesized adamantane CMPO derivatives are more effective for the extraction of americium(III) and europium(III) from 3MHNO 3 [ru

  12. The TRansUranium EXtraction (TRUEX) process: A vital tool for disposal of US defense nuclear waste

    International Nuclear Information System (INIS)

    Horwitz, E.P.; Schulz, W.W.

    1990-01-01

    The TRUEX (TRansUranium EXtraction) process is a generic actinide extraction/recovery process for the removal of all actinides from acidic nitrate and chloride nuclear waste solutions. Because of its high efficiency and flexibility and its compatibility with existing process facilities, TRUEX has now become a vital tool for the disposal of certain US defense nuclear waste. The development of TRUEX is closely coupled to the development of bifunctional extractants belonging to the carbamoylphosphoryl class and CMPO in particular. A brief review of the development of CMPO and its relationship to other bifunctional and monofunctional extractants is presented. The effect of TBP on CMPO, the selectivity of CMPO for actinides extracted from acidic nitrate media, the influence of diluents on CMPO behavior and 3rd phase formation, and the radiolysis/hydrolysis of CMPO and subsequent solvent cleanup will be highlighted. Application of TRUEX in the chemical pretreatment of specific nuclear waste streams and a summary of the current status of development and deployment of TRUEX is presented. 15 refs., 10 figs., 3 tabs

  13. Anionic tert-butyl-calix[4]arenes substituted at the narrow and wide rim by cobalt bis(dicarbollide)(1-) ions and CMPO-groups. Effect of stereochemistry and ratios of the functional groups on the platform on the extraction efficiency for Ln(III)/An(III)

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Böhmer, V.; Dordea, C.; Selucký, P.; Bubeníková, M.

    2013-01-01

    Roč. 747, december (2013), s. 155-166 ISSN 0022-328X R&D Projects: GA ČR GA104/09/0668 Institutional support: RVO:61388980 Keywords : Actinides * Calixarenes * Carboranes * Lanthanides * Liquid-liquid extraction Subject RIV: CA - Inorganic Chemistry Impact factor: 2.302, year: 2013

  14. Synthesis and application of a macroporous silica-based polymeric octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide composite for the chromatographic separation of high level liquid waste

    International Nuclear Information System (INIS)

    Zhang, A.

    2006-01-01

    The Minor Actinides Recovery from HLW by Extraction Chromatography (MAREC) process was used mainly for the separation of minor actinides (MAs) and some specific fission products (FPs) from highly active liquid waste (HLW) by the composite CMPO/SiO 2 -P of the macroporous silica based polymeric octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide (CMPO) and others. In this study a cascade of chromatographic separation was performed on a 3.0M HNO 3 solution containing 5.0 x 10 -3 M of 13 elements, at 323 K. The cascade consisted of three columns the first and second ones were packed with CMPO/SiO 2 -P and the third with SiO 2 -P particles. The first column was employed to prepare various eluents containing saturated CMPO. The second column was used for separation into groups. The CMPO of CMPO/SiO2-P was recovered from the effluent by the third column and a CMPO-free effluent containing minor actinides was obtained. The elements contained in the simulated HLW of 3.0M HNO 3 were separated into (1) a non-adsorption group (Sr, Cs, and Ru etc.), (2) a MA-hRE (heavy rare earth)-Mo-Zr group, and (3) a lRE (light rare earth) group by eluting with 3.0M HNO 3 , 0.05M DTPA (diethylenetriaminepentaacetic acid) (pH 2.0) and HNO 3 (pH 3.5), respectively. The resultant MA-hRE-Mo-Zr mixture containing minor actinides was then separated into the groups (1) Pd-Ru, (2) MA-hRE, and (3) Mo-Zr by utilizing 3.0M HNO 3 , distilled water, and 0.05M DTPA (pH 2.0) as eluents. More than 92% of CMPO in the MA-hRE containing effluent was adsorbed by SiO 2 -P particles. The effectivity and technical feasibility of MAREC process were demonstrated. (author)

  15. Removal of plutonium from real time waste using supercritical fluid extraction

    International Nuclear Information System (INIS)

    Sujatha, K.; Sivaraman, N.; Kumar, R.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2010-01-01

    Supercritical fluid extraction (SFE) technique was carried out for the recovery of plutonium from cellulose waste matrix using supercritical carbon dioxide (SC-CO 2 ) modified with suitable ligands such as octylphenyl N,N-diisobutyl carbamoylmethyl phosphine oxide (φCMPO), tri-n-butyl phosphate (TBP), acetyl acetone, trifluoro acetyl acetone and theonyltrifluoroacetyl acetone (TTA). The maximum plutonium recovery was found to be 99.8% when SC-CO 2 modified with CMPO was employed. About 15mg of plutonium was recovered from waste. (author)

  16. Plutonium and americium extraction studies with bifunctional organophosphorus extractants

    International Nuclear Information System (INIS)

    Navratil, J.D.

    1985-01-01

    Neutral bifunctional organophosphorus extractants, such as octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP), are under study at the Rocky Flats Plant (RFP) to remove plutonium and americium from the 7M nitric acid waste. These compounds extract trivalent actinides from strong nitric acid, a property which distinguishes them from monofunctional organiphosphorus reagents. Furthermore, the reagents extract hydroytic plutonium (IV) polymer which is present in the acid waste stream. The compounds extract trivalent actinides with a 3:1 stoichiometry, whereas tetra- and hexavalent actinides extract with a stoichiometry of 2:1. Preliminary studies indicate that the extracted plutonium polymer complex contains one to two molecules of CMP per plutonium ion and the plutonium(IV) maintains a polymeric structure. Recent studies by Horwitz and co-workers conclude that the CMPO and CMP reagents behave as monodentate ligands. At RFP, three techniques are being tested for using CMP and CMPO to remove plutonium and americium from nitric acid waste streams. The different techniques are liquid-liquid extraction, extraction chromatography, and solid-supported liquid membranes. Recent tests of the last two techniques will be briefly described. In all the experiments, CMP was an 84% pure material from Bray Oil Co. and CMPO was 98% pure from M and T Chemicals

  17. Boron(8) substituted nitrilium and ammonium derivatives, versatile cobalt bis(1,2-dicarbollide) building blocks for synthetic purposes

    Czech Academy of Sciences Publication Activity Database

    Šícha, Václav; Plešek, Jaromír; Kvíčalová, Magdalena; Císařová, I.; Grüner, Bohumír

    -, č. 5 (2009), s. 851-860 ISSN 1477-9226 R&D Projects: GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : nuclear waste solutions * cluster compounds * CMPO groups Subject RIV: CA - Inorganic Chemistry Impact factor: 4.081, year: 2009

  18. Synthesis of [B12H12](2-) based extractants and their application for the treatment of nuclear wastes

    Czech Academy of Sciences Publication Activity Database

    Bernard, R.; Cornu, D.; Grüner, Bohumír; Dozol, J. F.; Miele, P.; Bonnetot, B.

    2002-01-01

    Roč. 657, 1-2 (2002), s. 83-90 ISSN 0022-328X R&D Projects: GA ČR GA104/99/1096 Institutional research plan: CEZ:AV0Z4032918 Keywords : hydrododecaborate * oxonium * CMPO Subject RIV: CA - Inorganic Chemistry Impact factor: 1.901, year: 2002

  19. Separation of trivalent actinides and lanthanides from simulated high-level waste using cobalt bis(dicarbollide) ion derivate substituted with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide

    Czech Academy of Sciences Publication Activity Database

    Selucký, P.; Lučaníková, M.; Grüner, Bohumír

    2012-01-01

    Roč. 100, č. 3 (2012), s. 179-183 ISSN 0033-8230 R&D Projects: GA MŠk LC523; GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : dicarbollide * CMPO * liquid-liquid extraction * actinides * lanthanides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.373, year: 2012

  20. Supercritical fluid extraction of uranium and thorium using modifier free delivery of ligands

    International Nuclear Information System (INIS)

    Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2009-01-01

    The modifier free controlled delivery of octyl (phenyl)-N,N-diisobutylcarbamoylmethy phosphineoxide (CMPO) using supercritical carbon dioxide was established for the extraction of uranyl nitrate as well as uranyl nitrate sorbed on tissue paper matrix and the results were compared with modifier method. The preferential extraction of uranium over thorium was also demonstrated using di (2-ethylhexyl)isobutyramide (D2EHIBA). (author)

  1. Bleeding evaluation of the stationary phase from a few novel macroporous silica-substrate polymeric materials used for radionuclide partitioning from HLLW in MAREC process

    International Nuclear Information System (INIS)

    Zhang, A.; Wei, Y.; Kumagai, M.

    2005-01-01

    To separate minor actinides from HLLW by extraction chromatography, a few novel silica-based di(2-ethylhexyl)phosphoric acid (HDEHP), 4,4',(5')-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption materials (HDEHP/SiO 2 -P, DtBuCH18C6/SiO 2 -P, CMPO/SiO 2 -P, and TODGA/SiO 2 -P) were synthesized by impregnating HDEHP, DtBuCH18C6, CMPO, and TODGA into the pores of porous SiO 2 -P particles, which were the new kind of inorganic/organic composites consisted of macroporous SiO 2 and copolymer. The bleeding behavior of these composites was investigated by examining the effect of contact time and HNO 3 concentration. It was found that in the tested HNO 3 concentration range, a noticeable quantity of DtBuCH18C6, at least 600 ppm, leaked out from DtBuCH18C6/SiO 2 -P because of the protonation of DtBuCH18C6 with hydrogen ion, while the others were lower and basically equivalent to the solubility of HDEHP, CMPO, or TODGA in corresponding acidities solutions. Based on the batch experiment, the bleeding of CMPO/SiO 2 -P and TODGA/SiO 2 -P, the main adsorbents used in MAREC process for HLLW partitioning, was evaluated by column operation in 0.01M HNO 3 and 3M HNO 3 . The quantity of CMPO leaked was ∼48 ppm in 0.01M HNO 3 and ∼37 ppm in 3.0M HNO 3 . The bleeding of TODGA decreased from 23.2 ppm to 7.27 ppm at the initial stage and then basically kept constant. An actual bleeding of TODGA was evaluated by the separation of Sr(II) from a 2.0M HNO 3 solution containing 5.0 x 10 -3 M of 6 typically simulated elements. (author)

  2. Use of liquid membranes for treatment of nuclear wastes

    International Nuclear Information System (INIS)

    Dozol, J.F.

    1988-01-01

    The reprocessing operations produce liquid wastes in which the main components are nitric acid and sodium nitrate. The goal of the experiments is to separate trace amounts of radioactive elements from these acidic and high sodium nitrate content solutions. CMPO, a neutral bifunctional organophosphorus compound, and crown compounds (DC18 C6 - B21 C7) are able to extract respectively actinides, strontium and cesium from these high salinity solutions. The supported liquid membrane (SLM) render the use of expensive tailor-made extractant molecules like CMPO or crown ethers possible. The results obtained for the extraction of actinides and strontium are promising, but research must now be oriented towards improving the stability of the membrane

  3. Is the stoichiometry of the europium nitrate complexes with neutral organophosphorus extractants be anticipated?

    International Nuclear Information System (INIS)

    Beudaert, Ph.; Lamare, V.; Wipff, G.

    2001-01-01

    Molecular dynamics simulations have been performed in water on europium nitrate complexes with three neutral organophosphorus extractants (TBP, TPPO and CMPO) in order to determine on what criteria it is possible to obtain by simulations the experimental 1:3 stoichiometry in organic solution. This stoichiometry was investigated by progressive saturation of the cation coordination sphere. When the nitrate counter-ions are bidentate, the 1:3 stoichiometry corresponds to the degree of saturation where the interaction energy between europium and water becomes repulsive. Beyond this stoichiometry, complexes with TPPO and CMPO are unstable, although a 1:4 complex with TBP may exist but its formation appears to be energetically unfavored. (author)

  4. Using solvent extraction to process nitrate anion exchange column effluents

    International Nuclear Information System (INIS)

    Yarbro, S.L.

    1987-10-01

    Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), a new organophosphorous extractant, and a new centrifugal mixer-settler both recently developed at Argonne were evaluated for their potential use in the recovery of actinides from nitrate anion exchange column effluents. The performance of the extractant was evaluated by measuring the extraction coefficient values as a function of acid and salt concentration. Additional performance parameters include extraction coefficient behavior as a function of the total metal concentration in the organic phase, and comparison of different stripping and organic scrubbing techniques. A simulated effluent stream was used to evaluate the performance of the centrifugal mixer-settlers by comparing experimental and calculated interstage concentration profiles. Both the CMPO extractant and the centrifugal mixer-settlers have potential for processing nitrate column effluents, particularly if the stripping behavior can be improved. Details of the proposed process are presented in the flowsheet and contactor design analyses

  5. Using solvent extraction to process nitrate anion exchange column effluents

    Energy Technology Data Exchange (ETDEWEB)

    Yarbro, S.L.

    1987-10-01

    Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), a new organophosphorous extractant, and a new centrifugal mixer-settler both recently developed at Argonne were evaluated for their potential use in the recovery of actinides from nitrate anion exchange column effluents. The performance of the extractant was evaluated by measuring the extraction coefficient values as a function of acid and salt concentration. Additional performance parameters include extraction coefficient behavior as a function of the total metal concentration in the organic phase, and comparison of different stripping and organic scrubbing techniques. A simulated effluent stream was used to evaluate the performance of the centrifugal mixer-settlers by comparing experimental and calculated interstage concentration profiles. Both the CMPO extractant and the centrifugal mixer-settlers have potential for processing nitrate column effluents, particularly if the stripping behavior can be improved. Details of the proposed process are presented in the flowsheet and contactor design analyses.

  6. Recovery of plutonium and americium from chloride salt wastes by solvent extraction

    International Nuclear Information System (INIS)

    Reichley-Yinger, L.; Vandegrift, G.F.

    1987-01-01

    Plutonium and americium can be recovered from aqueous waste solutions containing a mixture of HCl and chloride salt wastes by the coupling of two solvent extraction systems: tributyl phosphate (TBP) in tetrachloroethylene (TCE) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in TCE. In the flowsheet developed, the salt wastes are dissolved in HCl, the Pu(III) is oxidized to the IV state with NaClO 2 and recovered in the TBP-TCE cycle, and the Am is then removed from the resultant raffinate by the CMPO-TCE cycle. The consequences of the feed solution composition and extraction behavior of these species on the process flowsheet design, the Pu-product purity, and the decontamination of the aqueous raffinate from transuranic elements are discussed. 16 refs., 6 figs

  7. Synergistic extraction of hexavalent plutonium by HTTA and HPMBP using mono- and bi- functional neutral donors: a comparative study

    International Nuclear Information System (INIS)

    Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.

    1997-01-01

    Thermodynamics and synergistic extraction of hexavalent plutonium were studied from HNO 3 medium (0.05M) with HTTA and HPMBP and various neutral donors viz. DPSO, TBP, TOPO (monofunctional) and DBDECMP, DHDECMP, CMPO (bifunctional) using benzene as a diluent. The net enthalpy and entropy changes were interpreted in terms of different organic phase adduct formation reaction mechanisms i.e. substitution in HTTA vs addition in HPMBP. (author). 4 refs., 2 figs

  8. Application of IC and HPLC as an analytical tool in solvent extraction studies

    International Nuclear Information System (INIS)

    Das, Debasish; Sureshkumar, M.K.; Mohapatra, P.K.; Manchanda, V.K.

    2010-01-01

    Ion chromatography and HPLC was used for analyzing the concentration of various metal ions present in the aqueous phase after solvent extraction using a number of novel organic extractants such as CMPO, DMDBTDMA and TODGA. Calibration plots were obtained for each of the metal ions studied. Interference of one group of metal ions on the other was investigated. The error in the expected values was within the < 10% even in the presence of interfering elements. (author)

  9. Complexation of amidocarbamoyl phosphine oxides with Ln{sup +3} (Ln = La, Nd, Pm, Sm and Eu) cation series: structural and thermodynamical features

    Energy Technology Data Exchange (ETDEWEB)

    Hosseinnejad, Tayebeh; Kazemi, Tayebeh [Alzahra Univ., Tehran (Iran, Islamic Republic of). Dept. of Chemistry

    2016-05-01

    In the present study, we have mainly investigated the nature of interactions in Ln{sup 3+} (Ln = La, Nd, Pm, Sm, Eu) complexes with amidocarbamoyl methyl phosphine oxide (CMPO) and amidocarbamoyl propyl phosphine oxide (CPPO) ligands based on density functional theory (DFT) approaches. In the first step, thermodynamical properties for complexation of CMPO and CPPO ligands with Ln{sup 3+} cation series have been determined in the gas phase and with the presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) computations. The trend of metal-ligand interaction strength has been analyzed and compared with the trend of ionic hardness within the series of lanthanide cations and different size of alkyl chain of amidocarbamoyl phosphine oxide ligand. The calculated thermochemical results in the gas and solution phases reveals that there is a consistency between increasing trend in the hardness of Ln{sup 3+} cation series and also electron-donating property of alkyl chain with increasing in thermodynamical stability of [Ln-CMPO]{sup 3+} and [Ln-CPPO]{sup 3+} complex series. We have also demonstrated that in the complexation reaction of all complex series, using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene. It should be stated that this issue has been observed in many experiments. Finally, analysis of calculated deformation energies and also the variation in bond order of some selected key bonds in CMPO and CPPO ligands and their corresponded Ln{sup 3+} complexes series show a similar trend with increasing in the hardness of Ln{sup 3+} cation series and electron-donating of alkyl chain of amidocarbamoyl phosphine oxide ligand.

  10. Complexation of amidocarbamoyl phosphine oxides with Ln+3 (Ln = La, Nd, Pm, Sm and Eu) cation series: structural and thermodynamical features

    International Nuclear Information System (INIS)

    Hosseinnejad, Tayebeh; Kazemi, Tayebeh

    2016-01-01

    In the present study, we have mainly investigated the nature of interactions in Ln 3+ (Ln = La, Nd, Pm, Sm, Eu) complexes with amidocarbamoyl methyl phosphine oxide (CMPO) and amidocarbamoyl propyl phosphine oxide (CPPO) ligands based on density functional theory (DFT) approaches. In the first step, thermodynamical properties for complexation of CMPO and CPPO ligands with Ln 3+ cation series have been determined in the gas phase and with the presence of three solvents: n-hexane, chloroform and toluene, via polarized continuum model (PCM) computations. The trend of metal-ligand interaction strength has been analyzed and compared with the trend of ionic hardness within the series of lanthanide cations and different size of alkyl chain of amidocarbamoyl phosphine oxide ligand. The calculated thermochemical results in the gas and solution phases reveals that there is a consistency between increasing trend in the hardness of Ln 3+ cation series and also electron-donating property of alkyl chain with increasing in thermodynamical stability of [Ln-CMPO] 3+ and [Ln-CPPO] 3+ complex series. We have also demonstrated that in the complexation reaction of all complex series, using n-hexane as solvent is more favorable thermodynamically than chloroform and toluene. It should be stated that this issue has been observed in many experiments. Finally, analysis of calculated deformation energies and also the variation in bond order of some selected key bonds in CMPO and CPPO ligands and their corresponded Ln 3+ complexes series show a similar trend with increasing in the hardness of Ln 3+ cation series and electron-donating of alkyl chain of amidocarbamoyl phosphine oxide ligand.

  11. Removal of radioactive and other hazardous material from fluid waste

    Science.gov (United States)

    Tranter, Troy J [Idaho Falls, ID; Knecht, Dieter A [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Burchfield, Larry A [W. Richland, WA; Anshits, Alexander G [Krasnoyarsk, RU; Vereshchagina, Tatiana [Krasnoyarsk, RU; Tretyakov, Alexander A [Zheleznogorsk, RU; Aloy, Albert S [St. Petersburg, RU; Sapozhnikova, Natalia V [St. Petersburg, RU

    2006-10-03

    Hollow glass microspheres obtained from fly ash (cenospheres) are impregnated with extractants/ion-exchangers and used to remove hazardous material from fluid waste. In a preferred embodiment the microsphere material is loaded with ammonium molybdophosphonate (AMP) and used to remove radioactive ions, such as cesium-137, from acidic liquid wastes. In another preferred embodiment, the microsphere material is loaded with octyl(phenyl)-N-N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) and used to remove americium and plutonium from acidic liquid wastes.

  12. Americium removal from nitric acid waste streams

    International Nuclear Information System (INIS)

    Muscatello, A.C.; Navratil, J.D.

    1986-01-01

    Separations research at the Rocky Flats Plant (RFP) has found ways to significantly improve americium removal from nitric acid (7M) waste streams generated by plutonium purification operations. Partial neutralization of the acid waste followed by solid supported liquid membranes (SLM) are useful in transferring and concentrating americium from nitrate solutions. Specifically, DHDECMP (dihexyl-N,N-diethylcarbamoylmethylphosphonate) supported on Accurel polypropylene hollow fibers assembled in modular form transfers >95% of the americium from high nitrate (6.9M), low acid (0.1M) feeds into 0.25M oxalic acid stripping solution. Maximum permeabilities were observed to be 0.001 cm/sec, consistent with typical values for other systems. The feed:strip volume ratio shows an inverse relationship to the fraction of metal ion transferred. Cation exchangers may be used to concentrate americium from the strip solution. Furthermore, O0D (iB)CMPO (or CMPO) (octylphenyl-N-N-diisobutylcarbamoylmethylphosphine oxide) has been tested in an extraction chromatography mode. Preliminary results show CMPO to be effective in removing americium if the feed is neutralized to 1.0M acidity and iron(III) is complexed with 0.20M oxalic acid. 3 figs

  13. Design, synthesis and evaluation of carbamoyl-methyl-phosphine sulfide (CMPS)-based chelates for separation of lanthanides and actinides

    Energy Technology Data Exchange (ETDEWEB)

    Matlokaa, K.; Saha, A.K.; Srinivasan, P.; Scott, M.J. [Florida Univ., Dept. of Chemistry, FL (United States)

    2007-10-15

    C{sub 3}-symmetric tri-phenoxy-methane platforms were substituted with carbamoyl-methyl-phosphine sulfide arms and these tris-CMPS compounds were evaluated as extractants for f-element metal ions from 1 M nitric acid solution. Their properties were compared to the carbamoyl-methyl-phosphine oxide derivatives on the same tri-phenoxy-methane platform (tris-CMPO). The terbium complex of tris-CMPS was crystallized and examined via X-ray structural analysis to provide valuable insight into the binding properties of the soft tripodal chelate. (authors)

  14. Sigma Team for Minor Actinide Separation: PNNL FY 2011 Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Levitskaia, Tatiana G.; Carter, Jennifer C.; Warner, Marvin G.; Pittman, Jonathan W.

    2011-08-13

    This report summarizes work conducted in FY 2011 at PNNL to investigate new methods of separating the minor actinide elements (Am and Cm) from the trivalent lanthanide elements, and separation of Am from Cm. For the former, work focused on a solvent extraction system combining an acidic extractant (HDEHP) with a neutral extractant (CMPO) to form a hybrid solvent extraction system referred to as TRUSPEAK (combining the TRUEX and TALSPEAK processes). For the latter, ligands that strongly bing uranyl ion were investigated for stabilizing corresponding americyl ion.

  15. Synergistic extraction of europium(III) in ammonium ionic liquid

    International Nuclear Information System (INIS)

    Rout, Alok; Venkatesan, K.A.; Antony, M.P.

    2016-01-01

    Room temperature ionic liquids have been receiving increased attention for possible applications in the area of nuclear fuel reprocessing and waste management due to their fascinating properties such as good ionicity, high solvation capability, properties tunable etc. Most of the studies in the literature on the extraction of metal ions with molecular extractants dissolved in ionic liquid diluents are making use of the hydrophobic ionic liquids containing imidazolium cations such as the 1-alkyl-3-methylimidazolium ion. From an environmental point of view, such ionic liquids are not suitable as the primary mode of the metal extraction is by cation exchange mechanism wherein ionic liquid cation is lost to the aqueous phase leading to aqueous contamination and issue of recyclability of organic phase. However, there are some hydrophobic ionic liquids such as trioctylmethylammonium chloride ((N 1888 )(Cl)), and trihexyl(tetradecyl)phoshonium chloride (Cyphos IL 101) that exhibit no cation exchange in the aqueous phase during extraction. In this context, the extraction behavior of europium(III) using a neutral extractant, octyl, phenyl-N.N-diisobutylmethylcarbamoylphophinoxide (CMPO) and/or an acidic extractant bis(ethylhexyl)phosphoric acid (D2EHPA) dissolved in the ammonium ionic liquid diluent, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, (N 1888 )(NTf 2 ). The extraction behavior of CMPO (or D2EHPA)/(N 1888 )((Tf 2 ) system was investigated as a function of different extraction parameters such as feed acidity, extractant concentration, equilibration time etc.

  16. Double liquid membrane system for the removal of actinides and lanthanides from acidic nuclear wastes

    International Nuclear Information System (INIS)

    Chiarizia, R.; Danesi, P.R.

    1985-01-01

    Supported liquid membranes (SLM), consisting of an organic solution of n-octyl-(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl-phosphate (TBP) in decalin are able to perform selective separation and concentration of actinide and lanthanide ions from aqueous nitrate feed solutions and synthetic nuclear wastes. In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of nitric acid which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO 3 from the strip solution. In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HNO 3 concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion. 15 refs., 10 figs., 1 tab

  17. Decontamination of radioruthenium from TRUEX Solvent

    International Nuclear Information System (INIS)

    Kumaresan, R.; Nayak, Prasant; Venkatesan, K.A.; Antony, M.P.; Rao, P.R. Vasudeva

    2012-01-01

    A procedure has been developed for the decontamination of radioruthenium from the lean organic phase composed of a solution 0.2 M n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylyphosphineoxide (CMPO) and 1.2 M tri-n-butylphosphate (TBP) in n-dodecane (n-DD), which was used for the partitioning of minor actinides from actual high active waste solution (155 GWd/Te). For this purpose, the stripping behavior of radioruthenium from 0.2 M CMPO-1.2 M TBP in n-DD was studied at 298 K by using various aqueous reagents and adsorbents. Among the different reagents investigated, the aqueous solution of sodium hydroxide and sodium carbonate and adsorbents such as neutral alumina and anion exchange resin (OH - form) were identified as the promising candidates. Nearly 90-95% of radioruthenium was removed from the lean organic phase in seven contacts using sodium carbonate or sodium hydroxide solution. The residual radioactivity in the organic phase was removed by treatment with neutral alumina or anion exchange resin. The quality of the organic phase was ascertained by 241 Am(III) retention test. (orig.)

  18. Crystal structure of a samarium(III nitrate chain cross-linked by a bis-carbamoylmethylphosphine oxide ligand

    Directory of Open Access Journals (Sweden)

    Julie A. Stoscup

    2014-10-01

    Full Text Available In the title compound poly[aquabis(μ-nitrato-κ4O,O′:O,O′′tetrakis(nitrato-κ2O,O′{μ4-tetraethyl [(ethane-1,2-diylbis(azanediylbis(2-oxoethane-2,1-diyl]diphosphonate-κ2O,O′}disamarium(III], [Sm2(NO36(C14H30N2O8P2(H2O]n, a 12-coordinate SmIII and a nine-coordinate SmIII cation are alternately linked via shared bis-bidentate nitrate anions into a corrugated chain extending parallel to the a axis. The nine-coordinate SmIII atom of this chain is also chelated by a bidentate, yet flexible, carbamoylmethylphoshine oxide (CMPO ligand and bears one water molecule. This water molecule is hydrogen bonded to nitrate groups bonded to the 12-coordinate SmIII cation. The CMPO ligand, which lies about an inversion center, links neighboring chains along the c axis, forming sheets parallel to the ac plane. Hydrogen bonds between the amide NH group and metal-bound nitrate anions are also present in these sheets. The sheets are packed along the b axis through only van der Waals interactions.

  19. Decontamination of evaporator concentrated for cesium, strontium and transuranium elements

    International Nuclear Information System (INIS)

    Dozol, J.F.; Eymard, S.; Gambade, R.; La Rosa, G.; Casas i Garcia, J.

    1992-01-01

    Reprocessing produces medium activity liquid wastes. These wastes are evaporated, the distillate is discharged into the environment and all active and inactive salts are concentrated, leading to an important volume of wastes. The objective of this work is to separate long-lived radionuclides into a small volume addressed to a geological formation from the large volume of the concentrate, this concentrate after embedding is disposed on surface site. Supported liquid membranes (S.L.M.s) are used because they enable us to use low inventory of organic phase, hence to use very sophisticated and expensive extractants. To confirm the results obtained with simulated wastes, tests were carried out with genuine concentrate using two S.L.M.s: the first one with CMPO/TBP diluted in decalin, the second one impregnated by the mixture DC18-C-6/decanol/hexylbenzene. The decontamination factor (DF) achieved for actinides is about 100 with the CMPO/TBP SLM. The DF is increased by the second membrane: after treatment with crown ether SLM, the total DF is higher than 400

  20. A comparative study of thermodynamics in synergistic extraction of hexavalent plutonium by HTTA and HPMBP using mono- and bi-functional neutral donors

    International Nuclear Information System (INIS)

    Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.

    1996-01-01

    Synergistic extraction of hexavalent plutonium was studied from HNO 3 medium (0.05 M) with HTTA and various neutral donors viz. DPSO, TBP, TOPO (monofunctional) and DBDECMP, DHDECMP, CMPO (bifunctional) using benzene as a diluent. Thermodynamic parameters (Δ G, Δ H, Δ S) were evaluated at 298 K from the experiments performed at four fixed temperatures in 288 to 318 K range. These were compared with the corresponding values reported earlier for Pu(VI) + HPMBP + neutral donor system. The net negative enthalpy changes with HTTA were observed to be low as compared to those with HPMBP. The net entropy changes were found to be either negligibly small (in cases of DPSO, TBP, DBDECMP, DHDECMP) or positive (in cases of CMPO, TOPO) with HTTA in comparison to large negative values with HPMBP. These results were interpreted in terms of different organic phase adduct formation reaction mechanisms i.e. substitution in HTTA vs. addition in HPMBP. Further, the lower net enthalpy changes with HTTA were explained due to a part of the energy used in release of water molecules bonded to plutonium in the plutonium chelate. (orig.)

  1. Advanced Extraction Methods for Actinide/Lanthanide Separations

    International Nuclear Information System (INIS)

    Scott, M.J.

    2005-01-01

    The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

  2. Advanced Extraction Methods for Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.

    2005-12-01

    The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

  3. Thermodynamics of synergistic extraction of hexavalent plutonium with HPMBP and neutral donors: monodentate versus bidentate

    International Nuclear Information System (INIS)

    Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.; Jain, H.C.

    1996-01-01

    Synergistic extraction of hexavalent plutonium was studied from HNO 3 medium (0.05 M) with 1-phnyl, 3-methyl, 4-benzoyl, pyrazolone-5 (HPMBP) and different monodentate neutral donors viz. diphenyl sulphoxide (DPSO), tri-n-butyl phosphate (TBP) and tri-n-octyl phosphine oxide (TOPO) using benzene as a diluent. Thermodynamic parameters (ΔG, ΔH, ΔS) evaluated by performing the experiments at various fixed temperatures (288 K to 318 K) were compared with those reported previously for the bidentate neutral donors (DBDECMP, DHDECMP and CMPO). The net enthalpy changes were negative and comparable. The monodentate neutral donors, however, showed a larger decrease in the entropy values. Further, the negative values of enthalpy and entropy changes indicated that the organic adduct formation is an addition reaction as reported ealier for the bidentate donors. (orig.)

  4. Malonamides as new extractants for nuclear waste solutions

    International Nuclear Information System (INIS)

    Cuillerdier, C.; Musikas, C.; Hoel, P.; Nigond, L.; Vitart, X.

    1989-01-01

    Substituted malonamides are able to extract α emitters from radioactive solutions in nitric acid, all the actinides (III, IV, VI) are well extracted and can be easily back extracted. Some problems remain with neptunium and technetium. These solvents are not expensive. For an industrial purpose, synthesis has been optimized, and a proper choice of commercial basic products can decrease the cost. The solvent obtained on a pilot scale (1 kg) was found to be pure enough, it didn't need any additional treatment. Degradation under hydrolysis or radiolysis is not important in the conditions of practical experiment (t 0 C). Degradation products can be washed with NaOH (carboxylic acids) they don't give precipitates or emulsions. Efficiency of the solvent is good compared to CMPO, taking into account the lack of extensive industrial development. Further researches are undertaken in two main directions: optimizing the synthesis and use of aliphatic diluents

  5. Analytical methods and problems for the diamides type of extractants

    International Nuclear Information System (INIS)

    Cuillerdier, C.; Nigond, L.; Musikas, C.; Vitart, H.; Hoel, P.

    1989-01-01

    Diamides of carboxylic acids and especially malonamides are able to extract alpha emitters (including trivalent ions such as Am and Cm) contained in the wastes solutions of the nuclear industry. As they are completely incinerable and easy to purify, they could be an alternative to the mixture CMPO-TBP which is used in the TRUEX process. A large oxyalkyl radical enhances the distribution coefficients of americium in nitric acid sufficiently to permit the decontamination of wastes solutions in a classical mixers-settlers battery. Now researches are pursued with the aim of optimizing the formula of extractant, the influence of the structure of the extractant on its basicity and stability under radiolysis and hydrolysis is investigated. Analytical methods (potentiometry and NMR of C 13 ) have been developed for solvent titration and to evaluate the percentage of degradation and to identify some of the degradation products

  6. Summary of TRUEX Radiolysis Testing Using the INL Radiolysis Test Loop

    Energy Technology Data Exchange (ETDEWEB)

    Dean R. Peterman; Lonnie G. Olson; Rocklan G. McDowell; Gracy Elias; Jack D. Law

    2012-03-01

    The INL radiolysis and hydrolysis test loop has been used to evaluate the effects of hydrolytic and radiolytic degradation upon the efficacy of the TRUEX flowsheet for the recovery of trivalent actinides and lanthanides from acidic solution. Repeated irradiation and subsequent re-conditioning cycles did result in a significant decrease in the concentration of the TBP and CMPO extractants in the TRUEX solvent and a corresponding decrease in americium and europium extraction distributions. However, the build-up of solvent degradation products upon {gamma}-irradiation, had little impact upon the efficiency of the stripping section of the TRUEX flowsheet. Operation of the TRUEX flowsheet would require careful monitoring to ensure extraction distributions are maintained at acceptable levels.

  7. A radiochemical procedure for a low-level measurement of ''241 Am in environmental samples using a supported functional organo phosphorus extractant

    International Nuclear Information System (INIS)

    Gasco, C.; Anton, M.A.; Alvarez, A.; Navarro, N.; Salvador, S.

    1994-01-01

    The transuranides analysis in environmental samples is carried out by CIEMAT using standardized methods based on sequential separation with ionic-exchange resins. The americium fraction is purified through a two-layer ion exchange column and lately in an anion-exchange column in nitric acid methanol medium. The technique is time-consuming and the results are not completely satisfactory (low recovery and loss of alpha-resolution) for some samples. The chemical compound CMPO (octyl(phenyl).N,N-diisobutyl carbomoylmethyiphosphine oxide) dissolved in TPB (tributyl phosphate) and supported on an inert substrate has been tested directly for ''241 Am analysis by a large number of laboratories. A new method that combines both procedures has been developed. The details of the improved procedure are described in this paper. The advantages of its application to environmental samples (urine, faeces and sediments) are discussed. The utilization of standard, with americium certified concentrations confirms the reliability of our measurements

  8. A radiochemical procedure for a low-level measurement of ''241Am in environmental samples using a supported functional organo phosphorus extractant

    International Nuclear Information System (INIS)

    Gasco, C.; Anton, M. P.; Alvarez, A.; Navarro, N.; Salvador, S.

    1994-01-01

    The transuranides analysis in environmental samples is carried out by CIEMAT using standardized methods based on sequential separation with ionic-exchange resins. The americium fraction is purified through a two-layer ion exchange column and lately in an anion-exchange column in nitric acid methanol medium. The technique is time consuming and the results are not completely satisfactory (low recovery and loss of a-resolution) for some samples. The chemical compound CMPO (octyl(phenyl)-N,N-diisobutyl carbomoylmethyiphosphine oxide) dissolved in TPB (tributyl phosphate) and supported on an inert substrate has been tested directly for ''241Am analysis by a large number of laboratories. A new method that combines both procedures has been developed. The details of the improved procedure are described in this paper. The advantages of its application to environmental samples (urine, faeces and sediments) are discussed. The utilization of standard samples, with americium certified concentrations confirms the reliability of our measurements. (Author) 8 refs

  9. Extraction Chromatography for Am and Cm Recovery in Engineering Scale

    International Nuclear Information System (INIS)

    Koma, Y.; Watanabe, S.; Sano, Y.; Asakura, T.; Morita, Y.

    2008-01-01

    The Japan Atomic Energy Agency (JAEA) has been developing the extraction chromatography for Am and Cm (An(III)) recovery from HLLW aiming at an engineering scale application. For process development, we started to assess the characteristics of adsorbents with some extractants by laboratory scale experiments. The experimental results with HDEHP/SiO 2 -P adsorbent suggested that An(III) is separated from other fission products by adjusting the pH of a feed solution and/or an eluent containing DTPA to be an appropriate value. The durability of CMPO/SiO 2 -P and HDEHP/SiO 2 -P adsorbents for gamma-ray irradiation were estimated to be 1 and 0.5 MGy, respectively. In the system development, system experiments for fluid flow, safety and durability using engineering scale column as well as studies on remote control/maintenance are now under progress. (authors)

  10. Chromatographic decontamination of medium-activity waste concentrates

    International Nuclear Information System (INIS)

    Faubel, W.; Menzler, P.M.; Sameh, A.A.

    1988-01-01

    The chromatographic decontamination of a MAW concentrate was carried out in a laboratory plant in 1-l-batches in the following way: In order to purify the nitric MAW concentrate from its solid and organic contamination products, it is passed through a filter and an absorber (SM7) for organic species. Subsequently the purified solution runs on-line through all following columns. First the main activity carrier cesium ( 137 Cs, 134 Cs) is transferred to ammonium molybdate phosphate (AMP-1) by means of a newly developed fluidized bed process. In the further course, 125 Sb is separated on metal oxides (Sb 2 O 5 , MnO 2 ) and the three-valued actinides/lanthanides on an extraction-chromatographic CMPO column. Finally the remaining 106 Ru and 60 Co activities are separated on dimethylglyoximes (DMG) coated on active carbon. (orig./RB) [de

  11. Experiments comparing the uptake of americium from chloride media using extraction chromatography

    International Nuclear Information System (INIS)

    FitzPatrick, J.R.; Schake, B.S.; Schulte, L.D.; Martinez, B.T.; Salazar, R.R.

    1995-01-01

    Clean-up of actinide effluent waste steams is of increasing importance at the Los Alamos Plutonium Facility, TA-55, and removing the actinide elements to very low levels allows less radioactivity to go the Los Alamos National Laboratory Water Treatment Facility, TA-50, thus reducing the number of drums of TRU waste. Americium (Am) is a difficult element to remove from chloride media because the +3 state is difficult to oxidize and chelating resins work better with elements such as plutonium which are more readily oxidized to the +4 and/or +6 state. Currently in hydrochloric acid (HC1) media, the acidic liquid waste is neutralized with potassium hydroxide to precipitate the metal hydroxides, before disposal to TA-50. This process is not very efficient. The removal of Am from chloride media was compared using a series of resins, some commercial and some made in our laboratory, using different percentages by weight of octyl(phenyl)-N,N-diiso- butylcarbamoyl-methylphosphine oxide (CMPO ) along with diamyl amylphosphonate (DAAP) or tributyl phosphate (TBP) as diluents. Resins were also made with no added diluent. Early comparisons using small-scale contact studies with 0.5 grams of resin in 0.1M-12M HC1, and subsequent small-scale flow experiments show a trend in which Am uptake is proportional to the amount of CMPO on the resins and the diluent plays a minor role in the uptake of Am from these solutions. Redox chemistry effects were also investigated. From these studies, it is possible to determine the best conditions for the removal of Am from HC1 media thus reducing the gross alpha content of the waste stream by a factor of 10-100 which reduces the number of barrels of waste produced at the Water Treatment Facility

  12. Separation of actinide elements by solvent extraction using centrifugal contactors in the NEXT process

    International Nuclear Information System (INIS)

    Nakahara, Masaumi; Sano, Yuichi; Koma, Yoshikazu; Kamiya, Masayoshi; Shibata, Atsuhiro; Koizumi, Tsutomu; Koyama, Tomozo

    2007-01-01

    Using the advanced aqueous reprocessing system named NEXT process, actinides recovery was attempted by both a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery and the SETFICS process for Am and Cm recovery from the raffinate. In U, Pu and Np co-recovery experiments a single cycle flow sheet was used under high nitric acid concentration in the feed solution or scrubbing solution. High nitric acid concentration in the feed solution aided Np oxidation not only in the feed solution, but also at the extraction section. This oxidation reaction accomplished Np extraction by TBP with U and Pu. Most of Np could be recovered into the product solution. In the SETFICS process, a TRUEX solvent of 0.2 mol/dm 3 CMPO and 1.4 mol/dm 3 TBP in n-dodecane was employed instead of 0.2 mol/dm 3 CMPO and 1.0 mol/dm 3 TBP in n-dodecane in order to increase the loading of metals. Instead of sodium nitrate, hydroxylamine nitrate was applied to this experimental flow sheet in accordance with a 'salt-free' concept. The counter current experiment succeeded with the Am and Cm product. On the high-loading flow sheet, compared with the previous flow sheet, the flow of the aqueous effluents and spent solvent were expected to decrease by about one half. Two solvent extraction experiments for actinides recovery demonstrated the utility of the flow sheet of these processes in the NEXT process. (author)

  13. Supercritical fluid extraction of uranium and thorium from nitric acid medium using organophosphorous compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pitchaiah, K.C.; Sujatha, K.; Rao, C.V.S. Brahmmananda; Subramaniam, S.; Sivaraman, N.; Rao, P.R. Vasudeva [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

    2015-06-01

    In recent years, Supercritical Fluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

  14. High linear energy transfer degradation studies simulating alpha radiolysis of TRU solvent extraction processes

    Energy Technology Data Exchange (ETDEWEB)

    Pearson, Jeremy [Department of Chemical Engineering and Materials Science - University of California Irvine, 916 Engineering Tower, Irvine, CA, 92697 (United States); Miller, George [Department of Chemistry- University of California Irvine, 2046D PS II, Irvine, CA, 92697 (United States); Nilsson, Mikael [Department of Chemical Engineering and Materials Science - University of California Irvine, 916 Engineering Tower, Irvine, CA, 92697 (United States)

    2013-07-01

    Treatment of used nuclear fuel through solvent extraction separation processes is hindered by radiolytic damage from radioactive isotopes present in used fuel. The nature of the damage caused by the radiation may depend on the radiation type, whether it be low linear energy transfer (LET) such as gamma radiation or high LET such as alpha radiation. Used nuclear fuel contains beta/gamma emitting isotopes but also a significant amount of transuranics which are generally alpha emitters. Studying the respective effects on matter of both of these types of radiation will allow for accurate prediction and modeling of process performance losses with respect to dose. Current studies show that alpha radiation has milder effects than that of gamma. This is important to know because it will mean that solvent extraction solutions exposed to alpha radiation may last longer than expected and need less repair and replacement. These models are important for creating robust, predictable, and economical processes that have strong potential for mainstream adoption on the commercial level. The effects of gamma radiation on solvent extraction ligands have been more extensively studied than the effects of alpha radiation. This is due to the inherent difficulty in producing a sufficient and confluent dose of alpha particles within a sample without leaving the sample contaminated with long lived radioactive isotopes. Helium ion beam and radioactive isotope sources have been studied in the literature. We have developed a method for studying the effects of high LET radiation in situ via {sup 10}B activation and the high LET particles that result from the {sup 10}B(n,a){sup 7}Li reaction which follows. Our model for dose involves solving a partial differential equation representing absorption by 10B of an isentropic field of neutrons penetrating a sample. This method has been applied to organic solutions of TBP and CMPO, two ligands common in TRU solvent extraction treatment processes. Rates

  15. Multidisciplinary approach and multi-scale elemental analysis and separation chemistry

    International Nuclear Information System (INIS)

    Mariet, Clarisse

    2014-01-01

    The development of methods for the analysis of trace elements is an important component of my research activities either for a radiometric measure or mass spectrometric detection. Many studies raise the question of the chemical signature of a sample or a process: eruptive behavior of a volcano, indicator of pollution, ion exchange in vectors vesicles of active principles,... Each time, highly sensitive analytical procedures, accurate and multi-elementary as well as the development of specific protocols were needed. Neutron activation analysis has often been used as reference procedure and allowed to validate the chemical lixiviation and the measurement by ICP-MS. Analysis of radioactive samples requires skills in analysis of trace but also separation chemistry. Two separation methods occupy an important place in the separation chemistry of radionuclides: chromatography and liquid-liquid extraction. The study of extraction of Lanthanide (III) by the oxide octyl (phenyl)-n, N-diisobutyl-carbamoylmethyl phosphine (CMPO) and a calixarene-CMPO led to better understand and quantify the influence of operating conditions on their performance of extraction and selectivity. The high concentration of salts in aqueous solutions required to reason in terms of thermodynamic activities in relying on a comprehensive approach to quantification of deviations from ideality. In order to reduce the amount of waste generated and costs, alternatives to the hydrometallurgical extraction processes were considered using ionic liquids at low temperatures as alternative solvents in biphasic processes. Remaining in this logic of effluent reduction, miniaturization of the liquid-liquid extraction is also study so as to exploit the characteristics of microscopic scale (very large specific surface, short diffusion distances). The miniaturization of chromatographic separations carries the same ambitions of gain of volumes of wastes and reagents. The miniaturization of the separation Uranium

  16. The chemistry of separations ligand degradation by organic radical cations

    International Nuclear Information System (INIS)

    Mezyk, S.P.; Horne, G.P.; Mincher, B.J.; Zalupski, P.R.; Cook, A.R.; Wishart, J.F.

    2016-01-01

    Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexing agents and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R"."+), carbon-centered radicals (R".), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R"."+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with 2 ligands: CMPO and TODGA. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved. (authors)

  17. Radiochemistry Division annual progress report: 1993

    International Nuclear Information System (INIS)

    Natarajan, V.; Godbole, S.V.; Iyer, R.H.

    1995-01-01

    The research and development activities of the Radiochemistry Division of BARC during the year 1993 are briefly described under the headings: (i) nuclear chemistry; (ii) actinide chemistry; (iii) spectroscopy and (iv) instrumentation. Nuclear chemistry work deals with areas of nuclear reactions, nuclear fission, nuclear spectroscopy, nuclear data measurements and synthesis of transplutonium isotopes. The research programme in actinide chemistry deals mainly with the complexation of actinides, lanthanides and fission products from aqueous media with organic reagents such as amides, diamides, CMPO, crown ethers and macrocyclic ligands. Spectroscopic studies include electron paramagnetic resonance and optical investigations to probe phase transitions in actinide and other compounds, investigation of role of radiation induced radical ions in the thermoluminescence of actinide doped phosphors, photoacoustic spectra of uranium compounds and development of analytical methods for the determination of silver and rare earths from uranium and thorium oxide matrices. The instrumentation group has developed electronic circuitry and software support for installing a pilot plant for the preparation of dry gel microspheres of UO 2 and (U, Pu)O 2 . A list of publications by the scientific staff of the Division is also included. (author). refs., 38 figs., 26 tabs

  18. A comparative evaluation of synergistic extraction behaviour of hexavalent uranium with thenoyl tri-fluoro-acetone (HTTA) and 1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) using mono-functional and bi-functional neutral donors

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    2002-01-01

    Synergistic extraction of hexavalent uranium was studied using acidic extractants HTTA/HPMBP with two different bifunctional neutral donors, DHDECMP and CMPO, from HNO 3 medium at various fixed temperatures. The equilibrium constants for the organic phase addition reaction (log K s ) were correlated with the basicity (K h ) of the neutral donors. The data reported earlier for monofunctional neutral donors (DPSO, TBP, TOPO) were used for the comparison. A linear correlation between log K s and log K h was observed for U(VI)/HTTA/S (S = neutral donor) system. However, in U(VI)/HPMBP/S system, the observed log K s values for bifunctional neutral donors were much lower than those expected from linear correlation. This was attributed to the different mechanisms operative in the synergistic extraction i.e. substitution in the former vs. addition in the latter. These conclusions are also supported by the thermodynamic data obtained in the present studies. Nevertheless, it is seen that bifunctional neutral donors act only as monofunctional with both HTTA and HPMBP. (orig.)

  19. Solvent extraction of uranium(VI), plutonium(VI) and americium(III) with HTTA/HPMBP using mono- and bi-functional neutral donors. Synergism and thermodynamics

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    2000-01-01

    Synergistic extraction of hexavalent uranium and plutonium as well as trivalent americium was studied in HNO 3 with thenoyl, trifluoro-acetone (HTTA)/1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) in combination with neutral donors viz. DPSO, TBP, TOPO (mono-functional) and DBDECMP, DHDECMP, CMPO (bi-functional) with wide basicity range using benzene as diluent. A linear correlation was observed when the equilibrium constant log Ks for the organic phase synergistic reaction of both U(VI) and Pu(VI) with either of the chelating agents HTTA or HPMBP was plotted vs. the basicity (log Kh) of the donor (both mono- and bi-functional) indicating bi-functional donors also behave as mono-functional. This was supported by the thermodynamic data (ΔG 0 , ΔH 0 , ΔS 0 ) obtained for these systems. The organic phase adduct formation reactions were identified for the above systems from the thermodynamic data. In the Am(III) HTTA system log K s values of bi-functional donors were found to be very high and deviate from the linear plot (log K s vs. log K h ) obtained for mono-functional donors, indicating that they function as bi-functional for the Am(III)/HTTA) system studied. This was supported by high +ve ΔS 0 values obtained for this system. (author)

  20. Immunophenotypes and Immune Markers Associated with Acute Promyelocytic Leukemia Prognosis

    Directory of Open Access Journals (Sweden)

    Fang Xu

    2014-01-01

    Full Text Available CD2+, CD34+, and CD56+ immunophenotypes are associated with poor prognoses of acute promyelocytic leukemia (APL. The present study aimed to explore the role of APL immunophenotypes and immune markers as prognostic predictors on clinical outcomes. A total of 132 patients with de novo APL were retrospectively analyzed. Immunophenotypes were determined by flow cytometry. Clinical features, complete remission (CR, relapse, and five-year overall survival (OS rate were assessed and subjected to multivariate analyses. The CD13+CD33+HLA-DR-CD34− immunophenotype was commonly observed in patients with APL. Positive rates for other APL immune markers including cMPO, CD117, CD64, and CD9 were 68.7%, 26%, 78.4%, and 96.6%, respectively. When compared with patients with CD2− APL, patients with CD2+ APL had a significantly higher incidence of early death (50% versus 15.7%; P=0.016, lower CR rate (50% versus 91.1%; P=0.042, and lower five-year OS rate (41.7% versus 74.2%; P=0.018. White blood cell (WBC count before treatment was found to be the only independent risk factor of early death, CR failure, and five-year mortality rate. Flow cytometric immunophenotype analysis can facilitate prompt APL diagnosis. Multivariate analysis has demonstrated that WBC count before treatment is the only known independent risk factor that predicts prognosis for APL in this study population.

  1. Development of 90Sr/90Y Generator Systems Based on SLM Techniques for Radiolabelling of Therapeutic Biomolecules with 90Y. Chapter 14

    International Nuclear Information System (INIS)

    Thu, N.T.; Van Dong, D.; Van Cuong, B.; Van Khoa, C.; Cam Hoa, V.T.

    2015-01-01

    Yttrium-90 is one of the most useful radionuclides for radioimmunotherapeutic applications, especially for labelling peptides and antibodies. Studies were carried out to develop a 90 Sr/ 90 Y generator system based on the SLM technique. Two stages of 90 Sr/ 90 Y generator systems were developed at different activity levels of 5, 20, 50 and 100 mCi and operated with semiautomation in sequential mode. In the first stage of the system, PC88A based SLM was used, which transported 90 Y from a nitric acid medium containing 0.01–4M HNO 3 . In the second stage, the 90 Y from the first stage was transferred to the first compartment of the second stage using carbamoylmethyl phosphine oxide (CMPO) based SLM where 1M acetic acid was used as the receiving phase for 90 Y. Quality control was carried out for the products of 90 Y using EPC with paper chromatography and Tec control chromatography. Peptides and antibodies were labelled using the 90 Y product obtained from the generator developed in house. (author)

  2. Metals separation using solvent extractants on magnetic microparticles

    International Nuclear Information System (INIS)

    Nunez, L.; Pourfarzaneh, M.

    1997-01-01

    The magnetically assisted chemical separation program was initially funded by DOE EM-50 to develop processes for the efficient separation of radionuclides and other hazardous metals. This process has simulated the partnership between industry and ANL for many applications related to hazardous metal problems in industry. In-tank or near-tank hazardous metals separation using magnetic particles promises simple, compact processing at very low costs and employs mature chemical separations technologies to remove and recover hazardous metals from aqueous solutions. The selective chemical extractants are attached to inexpensive magnetic carrier particles. Surfaces of small particles composed of rare earths or ferromagnetic materials are treated to retain chemical extractants (e.g., TBP, CMPO, quaternary amines, carboxylic acid). After selective partitioning of contaminants to the surface layer, magnets are used to collect the loaded particles from the tank. The particles can be regenerated by stripping the contaminants and the selective metals can be recovered and recycled from the strip solution. This process and its related equipment are simple enough to be used for recovery/recycling and waste minimization activities at many industrial sites. Both the development of the process for hazardous and radioactive waste and the transfer of the technology will be discussed

  3. Synergism in the sorption of europium on chromatographic supports impregnated with dicarbollide acid and bidentate phosphororganic extractant

    International Nuclear Information System (INIS)

    Svoboda, K.; Kyrs, M.; Vanura, P.

    1997-01-01

    Extraction chromatographic supports (XAD-7) impregnated with binary mixtures of cobalt dicarbollide and one of the two phosphororganic extractants (dibutyl-N,N-diethylcarbamoylmethyl phosphonate, DBDECMP, or octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide, (CMPO) were prepared using methanolic solutions of the extractants and subsequent evaporation of methanol at room temperature. The molar ratios (x) in isomolar series of the two extractants were 0.025, 0.5, 0.75, and 1. The sorbents were used for investigating Eu capture from 0.1 and 1M HNO 3 solutions under static conditions (24 hours shaking, 2 cm 3 aqueous phase with 0.2 g sorbent, Eu initial concentrations 3 * 10 -9 , 0.0001, 0.001, 0.01 and 0.1M). The sorbents containing mixtures of extractants corresponding to the interpolated value x=0.45 (phosphororg./dicarb.) exhibited the highest values of the distribution ratios of Eu. A synergic effect of three orders of magnitude for low concentrations of Eu was observed. A tentative determination is given of the nature and the equilibrium constants of the chemical reactions assumed. (author)

  4. Mercury extraction by the TRUEX process solvent. II. Selective partitioning of mercury from co-extracted actinides in a simulated acidic ICPP waste stream

    International Nuclear Information System (INIS)

    Brewer, K.N.; Herbst, R.S.; Tranter, T.J.; Todd, T.A.

    1995-01-01

    The TRUEX process is being evaluated at the Idaho Chemical Processing Plant (ICPP) as a means to partition the actinides from acidic sodium-bearing waste (SBW). The mercury content of this waste averages 1 g/l. Because the chemistry of mercury has not been extensively evaluated in the TRUEX process, mercury was singled out as an element of interest. Radioactive mercury, 203 Hg, was spiked into a simulated solution of SBW containing 1 g/l mercury. Successive extraction batch contacts with the mercury spiked waste and successive scrubbing and stripping batch contacts of the mercury loaded TRUEX solvent (0.2 M CMPO-1.4 M TBP in dodecane) show that mercury will extract into and strip from the solvent. The extraction distribution coefficient for mercury, as HgCl 2 , from SBW having a nitric acid concentration of 1.4 M and a chloride concentration of 0.035 M was found to be 3. The stripping distribution coefficient was found to be 0.5 with 5 M HNO 3 and 0.077 with 0.25 M Na 2 CO 3 . Because experiments described here show that mercury can be extracted from SBW and stripped from the solvent, a process has been developed to partition mercury from the actinides in SBW. 10 refs., 3 figs., 10 tabs

  5. Radiochemistry Division annual progress report: 1994

    International Nuclear Information System (INIS)

    Babu, Y.; Seshagiri, T.K.; Iyer, R.H.

    1996-01-01

    The research and development activities of Radiochemistry Division during 1994 are briefly described under the headings: (i) nuclear chemistry; (ii) actinide chemistry; (iii) spectroscopy and (iv) instrumentation. Nuclear chemistry work deals with the areas of nuclear reactions, nuclear fission, nuclear spectroscopy, nuclear data measurements, neutron activation analysis and positron annihilation spectroscopy. The research programme in actinide chemistry deals mainly with the complexation of the actinides, lanthanides and fission products from aqueous media with organic reagents such as amides, diamides, HTTA, CMPO, BEHSO and macrocyclic ligands. Spectroscopic studies include electron paramagnetic resonance investigations of actinide and other compounds, investigation of role of radiation induced radical ions in the thermoluminescence of actinide/lanthanide doped phosphors and development of analytical methods for the determination of metallic impurities in plutonium, uranium, thorium oxide and yttrium aluminium garnet matrices. A sinusoidal waveform generator for facilitating electrochemical etching of nuclear tracks and an IBM PC/AT based data station for the IR spectrophotometer were developed by the instrumentation group. A list of publications, numbering 107, by the Scientific staff of the Division is also included in the report. (author). refs., 32 tabs., 31 figs

  6. Separation of actinides and lanthanides from acidic nuclear wastes by supported liquid membranes

    International Nuclear Information System (INIS)

    Danesi, P.R.; Chiarizia, R.; Rickert, P.; Horwitz, E.P.

    1985-01-01

    Supported liquid membranes, SLM, consisting of a solution of 0.25 M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 0.75 M tributylphosphate (TBP) in decalin absorbed on thin microporous polypropylene supports, have been studied for their ability to perform selective separations and concentrations of actinide and lanthanide ions from synthetic acidic nuclear wastes. The permeability coefficients of selected actinides (Am, Pu, U, Np) and of some of the other major components of the wastes have been measured using SLMs in flat-sheet and hollow-fiber configurations. The results have shown that with the thin (25 μm) flat-sheet SLMs, using Celgard 2500 as support, the membrane permeation process is mainly controlled by the rate of diffusion through the aqueous boundary layers. With the thicker (430 μm) hollow-fiber SLMs, using Accurel hollow-fibers as support, the membrane permeation process is controlled by the rate of diffusion through both the SLM and the aqueous boundary layers. Hollow-fibers SLMs exhibited lower permeability coefficients and longer life-times. The experiments have shown that the actinides can be very efficiently removed from the synthetic waste solutions to the point that the resulting solution could be considered a non-transuranic waste (less than 100 mCi/g of disposed form). The work has demonstrated that actinide removal from synthetic waste solutions is a feasible chemical process at the laboratory scale level

  7. Selective partitioning of mercury from co-extracted actinides in a simulated acidic ICPP waste stream

    International Nuclear Information System (INIS)

    Brewer, K.N.; Herbst, R.S.; Tranter, T.J.

    1995-01-01

    The TRUEX process is being evaluated at the Idaho Chemical Processing Plant (ICPP) as a means to partition the actinides from acidic sodium-bearing waste (SBW). The mercury content of this waste averages 1 g/l. Because the chemistry of mercury has not been extensively evaluated in the TRUEX process, mercury was singled out as an element of interest. Radioactive mercury, 203 Hg, was spiked into a simulated solution of SBW containing 1 g/l mercury. Successive extraction batch contacts with the mercury spiked waste simulant and successive scrubbing and stripping batch contacts of the mercury loaded TRUEX solvent (0.2 M CMPO-1.4 M TBP in dodecane) show that mercury will extract into and strip from the solvent. The extraction distribution coefficient for mercury, as HgCl 2 from SBW having a nitric acid concentration of 1.4 M and a chloride concentration of 0.035 M was found to be 3. The stripping distribution coefficient was found to be 0.5 with 5 M HNO 3 and 0.077 with 0.25 M Na 2 CO 3 . An experimental flowsheet was designed from the batch contact tests and tested counter-currently using 5.5 cm centrifugal contactors. Results from the counter-current test show that mercury can be removed from the acidic mixed SBW simulant and recovered separately from the actinides

  8. A radiochemical procedure for a low-level measurement of ''241Am in environmental samples using a supported functional organo phosphorus extractant; Metodo analitico para la determinacion de ''241Am en muestras biologicas y sedimentos marinos mediante uso de una columna con extractante organico

    Energy Technology Data Exchange (ETDEWEB)

    Gasco, C.; Anton, M. P.; Alvarez, A.; Navarro, N.; Salvador, S.

    1994-07-01

    The transuranides analysis in environmental samples is carried out by CIEMAT using standardized methods based on sequential separation with ionic-exchange resins. The americium fraction is purified through a two-layer ion exchange column and lately in an anion-exchange column in nitric acid methanol medium. The technique is time consuming and the results are not completely satisfactory (low recovery and loss of a-resolution) for some samples. The chemical compound CMPO (octyl(phenyl)-N,N-diisobutyl carbomoylmethyiphosphine oxide) dissolved in TPB (tributyl phosphate) and supported on an inert substrate has been tested directly for ''241Am analysis by a large number of laboratories. A new method that combines both procedures has been developed. The details of the improved procedure are described in this paper. The advantages of its application to environmental samples (urine, faeces and sediments) are discussed. The utilization of standard samples, with americium certified concentrations confirms the reliability of our measurements. (Author) 8 refs.

  9. Development of a chromatographic micro-system for radionuclides analysis in nitric acid media

    International Nuclear Information System (INIS)

    Losno, Marion

    2017-01-01

    Radionuclides analysis is a key point for nuclear waste management and nuclear material control. Several steps of sample modification have to be carried out before measurements in order to avoid any interferences and improve measurement precision. However those different steps are long, irradiating and difficult to achieve in gloveboxes. Moreover they produce liquid and solid waste. The goal of the study is to offer a new alternative to the use of solid phase extraction column for radionuclides separation in hard nitric acid medium. The system will decrease the amount of nuclear waste due to the analysis and automatize the different steps of the analysis. A plastic device made of COC containing a micro solid phase extraction column is first designed. Stationary phase is a poly(AMA-co-EDMA) monolith synthesized in situ. Its structure is adjustable and its functionalization versatile with a high resistance to nitric acid medium. Exchange capacity is 150 mg/g of monolith for TBP and TBP/CMPO column and up to 280 mg/g of monolith in case of DAAP. Exchange coefficients are determined for U(VI), Th(IV), Eu(III) and Nd(III) for 3 different extractants (and Pu(IV) in case of TBP column). Monolith synthesis is transferred in centrifugal device and hydrodynamic behavior studied. U,Th/Eu separation was finally carried out in both classic and centrifugal micro-system on TBP column. (author) [fr

  10. The chemistry of separations ligand degradation by organic radical cations

    Energy Technology Data Exchange (ETDEWEB)

    Mezyk, S.P.; Horne, G.P. [California State University at Long Beach, Long Beach, CA 90840 (United States); Mincher, B.J.; Zalupski, P.R. [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Cook, A.R.; Wishart, J.F. [Chemistry Department, Brookhaven National Laboratory, New York, 11973 (United States)

    2016-07-01

    Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexing agents and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R{sup .+}), carbon-centered radicals (R{sup .}), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R{sup .+} as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with 2 ligands: CMPO and TODGA. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved. (authors)

  11. Magnetically assisted chemical separation (MACS) process: Preparation and optimization of particles for removal of transuranic elements

    International Nuclear Information System (INIS)

    Nunez, L.; Kaminski, M.; Bradley, C.; Buchholz, B.A.; Aase, S.B.; Tuazon, H.E.; Vandegrift, G.F.; Landsberger, S.

    1995-05-01

    The Magnetically Assisted Chemical Separation (MACS) process combines the selectivity afforded by solvent extractants with magnetic separation by using specially coated magnetic particles to provide a more efficient chemical separation of transuranic (TRU) elements, other radionuclides, and heavy metals from waste streams. Development of the MACS process uses chemical and physical techniques to elucidate the properties of particle coatings and the extent of radiolytic and chemical damage to the particles, and to optimize the stages of loading, extraction, and particle regeneration. This report describes the development of a separation process for TRU elements from various high-level waste streams. Polymer-coated ferromagnetic particles with an adsorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted with tributyl phosphate (TBP) were evaluated for use in the separation and recovery of americium and plutonium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles, which can then be recovered from the solution by using a magnet. The partition coefficients were larger than those expected based on liquid[liquid extractions, and the extraction proceeded with rapid kinetics. Extractants were stripped from the particles with alcohols and 400-fold volume reductions were achieved. Particles were more sensitive to acid hydrolysis than to radiolysis. Overall, the optimization of a suitable NMCS particle for TRU separation was achieved under simulant conditions, and a MACS unit is currently being designed for an in-lab demonstration

  12. Safety confirmation study of TRUEX solvent by accelerating rate calorimeter (ARC)

    International Nuclear Information System (INIS)

    Sato, Yoshihiko; Hirumachi, Suguru; Takeda, Shinso; Kanazawa, Yoshito; Sasaya, Shinji

    1999-02-01

    In order to confirm the engineering safety on the TRUEX solvent (mixed solvent of CMPO/TBP/n-dodecane) for separating the transuranics from high-level activity liquid waste in advanced nuclear fuel recycling technological R and D, thermal behavior and pressure behavior in heating PUREX solvent (mixed solvent of 30% TBP-n-dodecane), TRUEX solvent and in the exothermic reaction of TRUEX solvent etc. and nitric acid in sealed adiabatic system which was severer condition than actual plant were measured by using accelerating rate calorimeter (ARC). The Arrhenius parameters (activation energy and frequency factor) which are necessary for the evaluation of reaction rate was examined from the measurement data in ARC. Analytical method and analysis condition of reaction products were examined in order to clarify chemical form of reaction products in exothermic reaction between solvent and nitric acid in ARC, and the qualitative evaluation was carried out. Main results are shown in the following. 1) TBP, CMPO, n-dodecane and 10 M nitric acid hardly exothermed in the simple substance. 2) On the solvent phase after the solvent contacted with 10 M nitric acid and the equilibrium has been attained (single-phase sample), the heat quantity per unit sample weight of the TRUEX solvent tended to be bigger than that of the PUREX solvent when heat quantity was evaluated in ARC. However, on the mixed sample of solvent and 10 M nitric acid enclosed in a sample container simultaneously (two phase system sample), the heat quantity per unit solvent weight was almost equivalent for PUREX solvent and TRUEX solvent. 3) The kinetic analysis was carried out, and on the TBP-10 M nitric acid single-phase sample, the activation energy of the reaction was evaluated to be 118 kJ/mol. Its activation energy was approximately equal to 112 kJ/mol by Nichols. The reaction rate constant was calculated, and it was shown that reaction rate constants of PUREX solvent-10 M nitric acid single-phase sample and

  13. Selective decontamination of cesium and strontium from evaporation concentrates of spent fuel reprocessing plants with crown ethers by transport through supported liquid membranes

    International Nuclear Information System (INIS)

    Casas i Garcia, J.

    1993-01-01

    Reprocessing operations lead to the production of radioactive medium activity liquid waste which is treated by evaporation and solutions of very high salinity are thus formed. The concentrates from reprocessing plant evaporators have to be stored in geological storage sites in view of their strong caesium, strontium and actinides activity. These elements, contained in acid and high sodium nitrate content liquid waste, are removed by means of selective extractants, using the supported liquid membrane technique (SLM), which allows them to be stored in surface sites, the actinides and long-life fission products being respectively recycled and concentrated into reduced volumes. The removal of the actinides is done by means of an Octyl N.N Diisobutyl Carbamoyl Methyl Phosphine Oxide (C.M.P.O.) based liquid membrane, whereas the removal of the caesium and strontium involves crown ethers. Supported liquid membranes (S.L.M.s) have the advantage of implementing very small quantities of extractant, but they generally have poor stability. The extractant, the diluent and the phase modifier impregnating the membrane play a vital role in SLM stability; the support also affects stability by its nature and geometry. For the extraction of strontium, the most lipophilic extractant, DtBu 18 C 6, enables higher strontium transfer kinetics to be attained. As regards caesium, the extremely lipophilic nDec B21 C7 is the most efficient. Caesium cannot be quantitatively removed, due to the competition of the very high content of sodium ions in the concentrate. Stable membranes are obtained with DC18 C6 or DtBu18 C6 diluted in alkylbenzenes with an added phase modifier such as decanol or especially isotridecanol

  14. Process chemistry for the pretreatment of Hanford tank wastes

    International Nuclear Information System (INIS)

    Lumetta, G.J.; Swanson, J.L.; Barker, S.A.

    1992-08-01

    Current guidelines for disposing radioactive wastes stored in underground tanks at the US Department of Energy's Hanford Site call for the vitrification of high-level waste in borosilicate glass and disposal of the glass canisters in a deep geologic repository. Low-level waste is to be cast in grout and disposed of on site in shallow burial vaults. Because of the high cost of vitrification and geologic disposal, methods are currently being developed to minimize the volume of high-level waste requiring disposal. Two approaches are being considered for pretreating radioactive tank sludges: (1) leaching of selected components from the sludge and (2) acid dissolution of the sludge followed by separation of key radionuclides. The leaching approach offers the advantage of simplicity, but the acid dissolution/radionuclide extraction approach has the potential to produce the least number of glass canisters. Four critical components (Cr, P, S, and Al) were leached from an actual Hanford tank waste-Plutonium Finishing Plant sludge. The Al, P, and S were removed from the sludge by digestion of the sludge with 0.1 M NaOH at 100 degrees C. The Cr was leached by treating the sludge with alkaline KMnO 4 at 100 degrees C. Removing these four components from the sludge will dramatically lower the number of glass canisters required to dispose of this waste. The transuranic extraction (TRUEX) solvent extraction process has been demonstrated at a bench scale using an actual Hanford tank waste. The process, which involves extraction of the transuranic elements with octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), separated 99.9% of the transuranic elements from the bulk components of the waste. Several problems associated with the TRUEX processing of this waste have been addressed and solved

  15. Influence of ionic liquids on actinides extraction by diphenyl(dibutyl)carbamoylmethylphosphine oxide in different solvents from nitric acid solution

    International Nuclear Information System (INIS)

    Pribylova, G.A.

    2011-01-01

    Influence of ionic liquids (ILs) addition (1-50 wt%) on extraction efficiency of actinides by diphenyl(dibutyl)carbamoylmethylphosphine oxide (Ph 2 Bu 2 ) from 3 M HNO 3 has been studied. Am(III) distribution ratios in two-phase systems 0.1 M Ph 2 Bu 2 in either DCE or CHCl 3 -3 M HNO 3 depending on the nature of additional ionic liquids: imidazolium-based ILs: [C 4 mim][PF 6 ], [C 4 mim][BF 4 ] and phosphonium-based ILs: PPF 6 , PBF 4 and PCl were determined. The highest value of Am(III) extraction ratio change (1040) was found on addition of PPF 6 to Ph 2 Bu 2 in CHCl 3 . Extraction of Pu(IV) and U(VI) by 0.001 M Ph 2 Bu 2 in the presence of [C 4 mim][PF 6 ] in DCE, CHCl 3 or meta-nitrobenzotrifluoride (NBTF) have been investigated. The greatest enhancement of extraction efficiency was observed using CHCl 3 , the least polar studied solvent. Using a mixture of conventional solvent and ionic liquid as a solvent for extractant enables one to increase distribution ratios and reduce viscosity of organic phase as compared with ionic liquid viscosity. The marked increase of Am(III), Pu(IV) and U(VI) extraction extent by Ph 2 Bu 2 on addition of ionic liquids to the extent of 10 wt% permit one essentially to diminish amounts considerably more expensive carbamoylmethylphosphine oxide(the general name is CMPO) used in TRUEX process. (author)

  16. Actinide separation of high-level waste using solvent extractants on magnetic microparticles

    International Nuclear Information System (INIS)

    Nunez, L.; Buchholz, B.A.; Kaminski, M.; Aase, S.B.; Brown, N.R.; Vandegrift, G.F.

    1994-01-01

    Polymeric-coated ferromagnetic particles with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted by tributyl phosphate (TBP) are being evaluated for application in the separation and the recovery of low concentrations of americium and plutonium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles, which can be recovered from the waste solution using a magnet. The effectiveness of the extractant-absorbed particles at removing transuranics (TRU) from simulated solutions and various nitric acid solutions was measured by gamma and liquid scintillation counting of plutonium and americium. The HNO 3 concentration range was 0.01 M to 6M. The partition coefficients (K d ) for various actinides at 2M HNO 3 were determined to be between 3,000 and 30,000. These values are larger than those projected for TRU recovery by traditional liquid/liquid extraction. Results from transmission electron microscopy indicated a large dependence of K d on relative magnetite location within the polymer and the polymer surface area. Energy disperse spectroscopy demonstrated homogeneous metal complexation on the polymer surface with no metal clustering. The radiolytic stability of the particles was determined by using 60 Co gamma irradiation under various conditions. The results showed that K d more strongly depends on the nitric acid dissolution rate of the magnetite than the gamma irradiation dose. Results of actinide separation from simulated high-level waste representative of that at various DOE sites are also discussed

  17. Research program on development of advanced treatment technology for americium-containing aqueous waste in NUCEF

    Energy Technology Data Exchange (ETDEWEB)

    Mineo, Hideaki; Matsumura, Tatsuro; Tsubata, Yasuhiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1996-10-01

    A research program was prepared on the development of an advanced treatment process for the americium-containing concentrated aqueous waste in NUCEF, than allows americium recovery for the reuse and the reduction of TRU waste generation. A preliminary analysis was conducted on the separation requirements based on the components estimated for the waste. An R and D strategy was proposed from the view to reduce TRU waste generated in the processing that the highest priority is given on the control of TRU leakage such as americium into the effluent stream after americium recovery and the minimization of salt used in the separation over the decontamination of impurities from americium. The extraction chromatographic method was selected as a candidate technology for americium separation under the principle to use reagents that are functional in acidic conditions such as bidentate extractants of DHEDECMP, CMPO or diamides, considering the larger flexibilities in process modification and possible multi-component separation with compact equipment and the past achievements on the recovery of kg quantities of americium. Major R and D items extracted are screening and evaluation of extractants for americium and plutonium, optimization of separation conditions, selection of denitration method, equipment developments and development of solidification methods of discarded americium after reuse and of various kinds of separation residues. In order to cope these items, four steps of R and D program were proposed, i.e., fundamental experiment in beaker-scale on screening and evaluation of extractants, flowsheet study in bench-scale using simulated and small amount of americium aqueous waste solution to evaluate candidate process, americium recovery test in iron-shielded cell to be installed in NUCEF. It is objected to make recovery of 100g orders of americium used for research on fundamental TRU fuel properties. (J.P.N.)

  18. Selective decontamination for cesium and strontium in evaporation concentrates from reprocessing plants with crown ethers by transport through supported liquid membranes

    International Nuclear Information System (INIS)

    Casas i Garcia, J.

    1991-01-01

    Reprocessing operations lead to the production of radioactive medium activity liquid waste which is treated by evaporation. The concentrates from reprocessing plant evaporators have to be stored in geological storage sites in view of their strong caesium, strontium and actinides activity. These elements, contained in acid and high sodium nitrate content liquid waste, are removed by means of selective extractants, using the supported liquid membrane technique (SLM), which allows them to be stored in surface sites, the actinides and long-life fission products being respectively recycled and concentrated into reduced volumes. The removal of the actinides is done by means of an Octyl N.N Diisobutyl Carbamoyl Methyl Phosphine Oxyde (C.M.P.O.) based liquid membrane, whereas the removal of the caesium and strontium involves crown ethers. Supported liquid membranes (S.L.M.s) have the advantage of implementing very small quantities of extractant, but, they generally have poor stability. The extractant, the diluent and the phase modifier that constitute the organic phase impregnating the membrane play a vital role in SLM stability; the support also affects stability by its nature and geometry. For the extraction of strontium, DtBu 18 C6 enables higher strontium transfer kinetics to be attained than with DC18 C6. As regards caesium, nDec B21 C7 is the most efficient. Unlike strontium, caesium cannot be quantitatively removed, due to the competition of sodium ions in the concentrate. Stable membranes are obtained with DC18 C6 or DtBu18 C6 diluted in alkylbenzene with an added phase modifier such as decanol or isotridecanol. The highest strontium transfer kinetics were obtained with the DC18 C6/hexylbenzene/isotridecanol mixture

  19. Country report: Vietnam. Setting Up of a {sup 90}Sr/{sup 90}Y Generator System Based on Supported Liquid Membrane (SLM) Technique and Radiolabeling of Eluted {sup 90}Y with Biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Thu, Nguyen Thi; Dong, Duong Van; Cuong, Bui Van; Khoa, Chu Van [Vietnam Atomic Energy Commission (VAEC), Nuclear Research Institute, Dalat (Viet Nam)

    2010-07-01

    In the course of participating in the IAEA-CRP during the last two years, Vietnam has achieved the goal of setting up a {sup 90}Sr/{sup 90}Y generator system based on Supported Liquid Membrane (SLM) technique and also radiolabeling of the eluted {sup 90}Y with antibody, peptides and albumin. A two stage SLM based {sup 90}Sr-{sup 90}Y generator was set up in-house to generate carrier-free {sup 90}Y at different activity levels viz. 5, 20, 50 mCi. The generator system was operated in sequential mode in which 2-ethylhexyl 2-ethylhexyl phosphonic acid (PC88A) based SLM was used in the first stage for the transport {sup 90}Y in 4.0 M nitric acid from source phase where {sup 90}Sr-{sup 90}Y equilibrium mixture is placed in nitric acid medium at pH to 1-2. In the second stage, octyl (phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) based SLM was used for the transport of {sup 90}Y selectively to 1.0 M acetic acid which is the best medium for radiolebeling. The eluted {sup 90}Y from the generator was tested for the presence of any traces of {sup 90}Sr using the Extraction Paper Chromatography (EPC) and was found suitable for radiolabeling. The generator system could be upgraded to 100 mCi level successfully due to an expert mission from India through IAEA. The {sup 90}Y product obtained from the generator system was used for radiolabeling of antibody and peptides viz. Rituximab, DOTATATE and albumin particles under different experimental conditions. A new chromatography system could be developed for analyzing {sup 90}Y labeled albumin using the TAE buffer as mobile phase in PC and ITLC.

  20. Country report: Vietnam. Setting Up of a 90Sr/90Y Generator System Based on Supported Liquid Membrane (SLM) Technique and Radiolabeling of Eluted 90Y with Biomolecules

    International Nuclear Information System (INIS)

    Nguyen Thi Thu; Duong Van Dong; Bui Van Cuong; Chu Van Khoa

    2010-01-01

    In the course of participating in the IAEA-CRP during the last two years, Vietnam has achieved the goal of setting up a 90 Sr/ 90 Y generator system based on Supported Liquid Membrane (SLM) technique and also radiolabeling of the eluted 90 Y with antibody, peptides and albumin. A two stage SLM based 90 Sr- 90 Y generator was set up in-house to generate carrier-free 90 Y at different activity levels viz. 5, 20, 50 mCi. The generator system was operated in sequential mode in which 2-ethylhexyl 2-ethylhexyl phosphonic acid (PC88A) based SLM was used in the first stage for the transport 90 Y in 4.0 M nitric acid from source phase where 90 Sr- 90 Y equilibrium mixture is placed in nitric acid medium at pH to 1-2. In the second stage, octyl (phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) based SLM was used for the transport of 90 Y selectively to 1.0 M acetic acid which is the best medium for radiolebeling. The eluted 90 Y from the generator was tested for the presence of any traces of 90 Sr using the Extraction Paper Chromatography (EPC) and was found suitable for radiolabeling. The generator system could be upgraded to 100 mCi level successfully due to an expert mission from India through IAEA. The 90 Y product obtained from the generator system was used for radiolabeling of antibody and peptides viz. Rituximab, DOTATATE and albumin particles under different experimental conditions. A new chromatography system could be developed for analyzing 90 Y labeled albumin using the TAE buffer as mobile phase in PC and ITLC

  1. Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste.

    Science.gov (United States)

    Stockmann, T Jane; Zhang, Jing; Montgomery, Anne-Marie; Ding, Zhifeng

    2014-04-22

    A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P66614(+)) and tetrakis(pentafluorophenyl)borate anion (TB(-)) was employed within a water|P66614TB (w|P66614TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. (137)Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N'-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6×10(11) at the w|P66614TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ(α), with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ(α) of 2 and 8.2×10(7), respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water-organic solvent mixture into an electron spray ionization mass spectrometer. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Recovery of minor actinides from spent fuel using TPEN-immobilized gels

    International Nuclear Information System (INIS)

    Koyama, S.; Suto, M.; Ohbayashi, H.; Oaki, H.; Takeshita, K.

    2013-01-01

    A series of separation experiments was performed in order to study the recovery process for minor actinides (MAs), such as americium (Am) and curium (Cm), from the actual spent fuel by using an extraction chromatographic technique. N,N,N',N'-tetrakis-(4-propenyloxy-2-pyridylmethyl) ethylenediamine (TPPEN) is an N,N,N',N'-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN) analogue consisting of an incorporated pyridine ring that acts as not only a ligand but also as a site for polymerization and crosslinking of the gel. The TPPEN and N-isopropylacrylamide (NIPA) were dissolved into dimethylformamide (DMF, Wako Co., Ltd.) and a silica beads polymer, and then TTPEN was immobilized chemically in a polymer gel (so called TPEN-gel). Mixed oxide (MOX) fuel, which was highly irradiated up to 119 GWD/MTM in the experimental fast reactor Joyo, was used as a reference spent fuel. First, uranium (U) and plutonium (Pu) were separated from the irradiated fuel using an ion-exchange method, and then, the platinum group elements were removed by CMPO to leave a mixed solution of MAs and lanthanides. The 3 mol% TPPEN-gel was packed with as an extraction column (CV: 1 ml) and then rinsed by 0.1 M NaNO 3 (pH 4.0) for pH adjustment. After washing the column by 0.01 M NaNO 3 (pH 4.0), Eu was detected and the recovery rate reached 93%. The MAs were then recovered by changing the eluent to 0.01 M NaNO 3 (pH 2.0), and the recovery rate of Am was 48 %. The 10 mol% TPPEN-gel was used to improve adsorption coefficient of Am and a condition of eluent temperature was changed in order to confirm the temperature swing effect on TPEN-gel for MA. More than 90% Eu was detected in the eluent after washing with 0.01 M NaNO 3 (pH 3.5) at 5 Celsius degrees. Americium was backwardly detected and eluted continuously during the same condition. After removal of Eu, the eluent temperature was changed to 32 Celsius degrees, then Am was detected (pH 3.0). Finally remained Am could be stripped from TPPEN-gel by

  3. Radiation chemistry in solvent extraction: FY2010 Research

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk

    2010-09-01

    This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR&D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: • Development of techniques to measure free radical reaction kinetics in the organic phase. • Initiation of an alpha-radiolysis program • Initiation of an effort to understand dose rate effects in radiation chemistry • Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the •NO3 radical with solvent extraction ligands in organic solution, and the method to measure •OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with •NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry

  4. Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Wall, Nathalie [Washington State Univ., Pullman, WA (United States); Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Washington State Univ., Pullman, WA (United States)

    2017-03-17

    In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste. As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the

  5. Radiation chemistry in solvent extraction: FY2010 Research

    International Nuclear Information System (INIS)

    Mincher, Bruce J.; Martin, Leigh R.; Mezyk, Stephen P.

    2010-01-01

    This report summarizes work accomplished under the Fuel Cycle Research and Development (FCR and D) program in the area of radiation chemistry during FY 2010. The tasks assigned during FY 2010 included: (1) Development of techniques to measure free radical reaction kinetics in the organic phase. (2) Initiation of an alpha-radiolysis program; (3) Initiation of an effort to understand dose rate effects in radiation chemistry; (4) Continued work to characterize TALSPEAK radiation chemistry Progress made on each of these tasks is reported here. Briefly, a method was developed and used to measure the kinetics of the reactions of the NO3 radical with solvent extraction ligands in organic solution, and the method to measure OH radical reactions under the same conditions has been designed. Rate constants for the CMPO and DMDOHEMA reaction with NO3 radical in organic solution are reported. Alpha-radiolysis was initiated on samples of DMDOHEMA in alkane solution using He ion beam irradiation and 211At isotope irradiation. The samples are currently being analyzed for comparison to DMDOHEMA ?-irradiations using a custom-developed mass spectrometric method. Results are also reported for the radiolytic generation of nitrous acid, in ?-irradiated nitric acid. It is shown that the yield of nitrous acid is unaffected by an order-of-magnitude change in dose rate. Finally, recent results for TALSPEAK radiolysis are reported, summarizing the effects on solvent extraction efficiency due to HDEHP irradiation, and the stable products of lactic acid and DTPA irradiation. In addition, results representing increased scope are presented for the radiation chemistry program. These include an investigation of the effect of metal complexation on radical reaction kinetics using DTPA as an example, and the production of a manuscript reporting the mechanism of Cs-7SB radiolysis. The Cs-7SB work takes advantage of recent results from a current LDRD program to understand the fundamental chemistry of

  6. An Overview of the Production, Quality Control and Feasibility of Using 90Y as a Therapeutic Radionuclide

    International Nuclear Information System (INIS)

    Venkatesh, M.

    2009-01-01

    90 Y is increasingly accepted world wide as a radionuclide for in-vivo therapy owing to attractive decay features (T1/2 2.67 d; Eβ max 2.28 MeV) and viable production feasibility in high specific activities. 90 Y is most often recommended for treatment of large tumour lesions as the hard β rays are effective in delivering therapeutic dose to large volume. However, possibility of high radiation dose to the critical organs such as bone marrow and kidneys is an important concern that is given due weightage while designing therapy using 90 Y. The best route to avail 90 Y for therapy applications is from 90 Sr, though neutron actiation of natural 89 Y(100% abundance) is feasible. The absorption cross section σ is barely 1.38 b, resulting in low specific activity 90 Y which is useful for limited applications. The possibility of obtaining 90Y through a radionuclide generator as the daughter of a long lived parent 90 Sr (T1/2 28.9 y) is a major advantage that enables access to high specific activity 90 Y. Transporting the 90Y activity to a user institution from a centralized production facility is reasonably feasible and this facilitates its wide spread use. Several generator designs have been developed and reported to access 90 Y. Solvent extraction using a chelating molecule in an organic solvent (0.3M HDEHP/n-dodecane), column chromatography using ion exchange resins (cationic as well as anionic; Dowex-50x8; AG 50x16; Aminex-A5) or inorganic exchanger, membrane based separation using chelating ligand impregnated membranes (CMPO in electrochemical separation are some of the methods reported. Limitations such as elution of 90 Y after initial elution of 90 Sr, availability of 90 Y as a chelated complex which then has to be treated to enable labeling the molecule of interest, possibility of obtaining small quantities of 90 Y owing to radiolytic damages to the separation system components, paucity of special automation gadgets for handling the high activities remotely