Extraction of molybdenum and technetium with diamides of dipicolinic acid from nitric acid solutions

The concentration of molybdenum(VI) in dissolved spent nuclear fuel is comparable with the concentrations of Tc, and the minor actinides (Np, Am). Therefore it is of great interest to understand its behavior under conditions imposed by separation processes. The simultaneous extraction ability of ortho, meta, and para isomers of N,N′-diethyl-N,N′-ditolyl-dipicolinamide (EtTDPA) for molybdenum and technetium were investigated in a large range of nitric and hydrochloric acid conditions. Molybdenum shows no increase in extraction at higher concentrations of nitric acid giving a solvate number n=0 with all isomers of EtTDPA, while Mo shows great extractability from HCl. Technetium distribution ratios decrease with increasing concentrations of nitrate showing indication of ion exchange occurring between TcO₄ ⁻ and NO₃ ⁻ anions. Et(m)TDPA and Et(p)TDPA show the greatest extractability, with 60% of the total technetium extracted into the organic phase at 1M HNO₃.     

Novel diamides of 2,2′-dipyridyl-6,6′-dicarboxylic acid: synthesis, coordination properties, and possibilities of use in electrochemical sensors and liquid extraction

The procedure was proposed for the synthesis of various dipyridyldiamides. Their various properties in the series of rare-earth elements were studied. The possibility to use the synthe-sized compounds in polymer membranes of electrochemical sensors for the development of novel types of sensors was shown. A comparison of the influence of the ligand structure on the extraction and sensor characteristics was performed.     

Calixarenes functionalized with phosphine oxide and diamide functions as extractants and ionofores for rare-earth metals

Calixarene-based ligands with phosphine oxide and diamide functions at wide and narrow rims are synthesized and studied as extracting agents for liquid extraction and ionophores for polymeric electrochemical ion sensors. Calixarene ligands are compared with corresponding phosphine oxide and diamide ligands which are not attached to the calixarene platform. Extraction and sensor properties of the ligands were studied in different metal ion solution with special attention paid to rare-earth metals. Attachment of phosphine oxide groups to the calixarene platform leads to the sharp increase of both extraction and sensing ability of the corresponding systems comparing to non-bonded phosphine oxide. In case of the diamide derivatives attached to the calixarene performance of corresponding ligands was similar to those of non-bonded diamides.     

Extraction of americium and europium from perchloric acid solutions with N,N′-dialkyl-and N,N,N′,N′-tetraalkylpyridine-2,6-dicarboxamides

Extraction of americium and europium from perchloric acid solutions with pyridine-2,6-dicarboxamides was studied. The solvate numbers and Am/Eu separation factors were determined.     

Various flowsheets of actinides recovery with diamides of heterocyclic dicarboxylic acids

Solvents on the base of diamides of heterocyclic dicarboxylic acids are promising alternatives for studied Grouped ActiNide EXtraction (GANEX) solvents. Advantage of these ligands is the possibility of simultaneous extraction not only of residual uranium and plutonium, but also minor actinides—neptunium, americium and curium. Two flowsheets on the base of diamides of heterocyclic dicarboxylic acids for separation of actinides form acidic solutions were developed, tested in laboratory scale and compared. Both flowsheets allow separation of more than 99.95% of actinides from raffinates with high content of lanthanides.     

2,2′-Dipyridyl-6,6′-dicarboxylic acid diamides: Synthesis,complexation and extraction properties

New ligands for complexing of the post-transition metals – diamides of 2,2′-bipyridyl-6,6′-dicarboxylic acid were developed, synthesised and characterised. They were proposed to be effective extractants towards americium. The structures of the amides were studied in solid as well as in solution. The extraction of Am and lanthanides depending on diamide structure, chlorinated cobalt dicarbollide (CCD) – diamide ratio, type of diluent was studied. The optimal conditions for Am/REE separation were determined. The properties of new potentiometric sensors on the base of 2,2′-dipyridyl-6,6′-dicarboxylic acid diamides were studied. The correlation structure vs. properties of ionophores (i.e. extractants), their sensitivity and selectivity in sensor analysis and extraction are discussed.     

Separation of americium and europium from solutions of nitric and perchloric acid using dipicolinic acid diamides

Extraction of nitric acid, perchloric acid, americium, and europium with dialkyldiarylamides of 2,6-pyridinecarboxylic (dipicolinic) acid in polar fluorinated solvents (diluents) was analysed. Among the extractants studied N, N′-diethyl-N, N′-ditolylamide dipicolinate is characterized by the best extraction properties. On passing from nitric to perchloric acid solutions extraction of metals sharply increases. Extraction of americium from nitric acid solutions is significantly greater as compared with europium (separation coefficient reaches 6), whereas extraction of americium and europium from perchloric acid solutions is nearly similar. The effect of diluent on the extraction was analyzed; for different diluents the maximum of extraction from perchloric acid solutions shifts form 3 to 6 M.     

Polymeric sensors for determination of rare-earth metal ions, based on diamides of dipicolinic acid

New polymeric sensors with high sensitivity to cations of transition metals and lanthanides in acid media are suggested. The role of active substances in the polymeric membranes of the sensors is played by diamides of dipicolinic acid with various structures, which are compounds exhibiting a high extraction capacity for various metals.     

Separation of f-elements by resins impregnated with amides of pyridine-2,6-dicarboxylic acid

Chemistries of trivalent lanthanides and actinides under aqueous processing conditions are so similar that their satisfying separation is extremely challenging. Preparation of a functionalized solid material by impregnation of a support resin with an organic extraction phase is one of possible routes for novel materials development. The ortho- and para-dialkyl-diaryl-pyridine-2,6-dicarboxyamides were impregnated into two macroporous matrices (PS-DVB and PMA). Influence of the diamide structure, matrix type and conditions for effective extraction chromatography separation of Am(III) from Eu(III) was studied in dynamic conditions. The prepared sorbents exhibited more strong adsorptions of Am(III) to compare with Eu(III). Maximal separation factor (~ 90) was achieved with use of citrate ion as complexing eluent.