Solvent Extraction and Ion Exchange最新文献

{"title":"Novel Bis(diphenylcarbamoylmethylphosphine oxide) Ligand for Effective Extraction of Actinides and Lanthanides from Nitric Acid Solutions","authors":"А. N. Turanov, V. Karandashev, A. N. Yarkevich","doi":"10.1080/07366299.2021.2001973","DOIUrl":"https://doi.org/10.1080/07366299.2021.2001973","url":null,"abstract":"ABSTRACT A novel polydentate neutral organophosphorus ligand N,N’-dicyclohexyl-N,N’-bis(diphenylphosphinoylacetyl)urea 1 containing two Ph2P(O)CH2C(O)N(cyclo-Hex)- bidentate moieties connected by a carbonyl group through amide nitrogen atoms was studied as an extractant for U(VI), Th(IV) and lanthanides(III) ions from HNO3 solutions into molecular diluents and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. The influence of composition of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Slope analysis indicates that the ligand 1: metal ratio in the extracted complexes in ionic liquid is less than that in 1,2-dichloroethane. The extraction efficiency of bis-CMPO 1 towards U(VI), Th(IV) and lanthanides(III) increased significantly in the presence of ionic liquid. Bis-CMPO ligand 1 in ionic liquid was found to possess a higher extraction efficiency towards U(VI), Th(IV) and lanthanides(III) ions than its mono analog diphenyl-(N,N-dibutylcarbamoylmethyl)-phosphine oxide 2. The role of Tf2N− anions in increasing the efficiency of Ln(III) extraction in the presence of an ionic liquid is discussed.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"493 - 517"},"PeriodicalIF":2.0,"publicationDate":"2021-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47460143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Separation of uranium(VI) and americium(III) by Extraction from Na2CO3–H2O2 solutions using methyltrioctylammonium carbonate in toluene","authors":"Alexander Valentinovich Boyarintsev, Galina Valerievna Kostikova, Sergey Illarionovich Stepanov, Andrei Аleksandrovich Shoustikov, Alexander Mihailovich Chekmarev, Aslan Yusupovich Tsivadze","doi":"10.1080/07366299.2021.1876993","DOIUrl":"https://doi.org/10.1080/07366299.2021.1876993","url":null,"abstract":"ABSTRACT Liquid–liquid extraction of carbonate and mixed peroxo-carbonate compounds of U(VI) and Am(III) from Na2CO3 aqueous solutions by methyltrioctylammonium carbonate in toluene has been studied. The main patterns of effect of extractant, Na2CO3, and H2O2 concentration on distribution and separation of U(VI) and Am(III) have been established. Using slope analysis and UV–vis spectroscopy, the compositions of U(VI) and Am(III) extractable compounds are established as (R4N)4[UO2(CO3)3], (R4N)4[UO2(О2)(CO3)2], and (R4N)6[(UO2)2(O2)(CO3)4] for U(VI); R4N[Am(CO3)2] and (R4N)3[Am(CO3)3] for Am(III), where R4N is the quaternary ammonium cation. The obtained data showed high efficiency of the studied carbonate system for extraction of U(VI) and its purification from Am(III). The maximum separation factor of U(VI) and Am(III) was 25.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"39 1","pages":"745 - 763"},"PeriodicalIF":2.0,"publicationDate":"2021-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41986276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stoichiometry of the Nickel Complex Formed with LIX 63 Hydroxyoxime under Acidic Chloride Conditions","authors":"K. R. Barnard, L. Zeng, D. Shiers","doi":"10.1080/07366299.2021.1992891","DOIUrl":"https://doi.org/10.1080/07366299.2021.1992891","url":null,"abstract":"ABSTRACT The extraction of nickel by LIX® 63 hydroxyoxime (‘hydroxyoxime’) under acidic (10–100 g/L hydrochloric acid) chloride conditions was investigated with the intent of determining the stoichiometry of the resulting complex in solution. Maximum loading and continuous variation tests indicate that nickel is extracted as a cationic salt with chloride counter-ions, the resulting complex exhibiting octahedral coordination with 1:3:2 nickel:hydroxyoxime:chloride stoichiometry. This species is also observed to readily form under mildly acidic (pH 1–4) chloride conditions, with the extent of formation being independent of pH. Nickel extraction kinetics were moderately fast, equilibrium being reached in 10 minutes. The behaviour of this system helps to provide clarity in relation to complex stoichiometry and the role of different ligands in synergistic systems utilising LIX 63 and an organic acid such as Versatic 10, opening up the possibility of nickel extraction from acidic chloride media using LIX 63.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"477 - 492"},"PeriodicalIF":2.0,"publicationDate":"2021-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48299692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Special Issue on Hierarchical Organization in Solvent Extraction","authors":"T. Zemb, A. Clark","doi":"10.1080/07366299.2021.1972562","DOIUrl":"https://doi.org/10.1080/07366299.2021.1972562","url":null,"abstract":"Amongst the multitude of papers that report the phenomenological behavior of liquid–liquid extraction, a significant fraction are associated with the separation, purification, and recycling of metals (both for industrial metal production as well as energy portfolios – as in nuclear energy applications). Over the last decade, an exponential increase in publications has been supported by fundamental advances to the science of phase transfer in multiphase systems, which has evolved to include predictive capabilities that finally exceed rough apparent “stoichiometry” determinations. The trend was clearly articulated within the latest issue of the series edited by Bruce Moyer (Moyer, B. A., Ed. Changing the Landscape in Solvent Extraction. Ion Exchange and Solvent Extraction, A Series of Advances, Vol. 23, CRC Press: Philadelphia, PA, 2019.). There it was noted that, for carefully designed systems, distribution ratios can be directly related to the reaction free energy of transfer in a simple exact and unique formula. Further, any theory that predicts the energetic characteristics of phase transfer without fitting distribution ratios variation with temperature, mole ratios, solvent additives will help to design the separation processes of the future (Sholl, David S.; Lively, Ryan P. Seven chemical separations to change the world. Nature 2016, 532, 435–437.). In this special issue, we have assembled seven specially focused papers that emphasize the structure, function, and thermodynamic characteristics of the many interactions that contribute to this radically new approach toward the fundamental science of liquid–liquid phase transfer. Collectively, these works beautifully demonstrate how the organization and distribution of local and extended chemical environments at the interface and the organic phase can be used to re-interpret the traditional paradigms of liquid–liquid extraction. They also consolidate the simultaneous molecular, supramolecular and colloidal approach that moves towards predictive theories that are useful for the chemical engineer in charge of designing effective plants.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"1 - 5"},"PeriodicalIF":2.0,"publicationDate":"2021-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43184951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polyoxometalates in Extraction and Sorption Processes","authors":"L. Jelínek, Eva Mištová, M. Kubeil, H. Stephan","doi":"10.1080/07366299.2021.1874107","DOIUrl":"https://doi.org/10.1080/07366299.2021.1874107","url":null,"abstract":"ABSTRACT Polyoxometalates (POMs) represent a fascinating class of inorganic cluster compounds. Due to the almost unlimited possibilities to tailor size, shape and charge of this compound class and to perform various surface functionalization, they are discussed for different applications, especially in the fields of catalysis, material sciences, and biomedicine. In contrast, the systematic study of extraction and sorption properties of POMs has received relatively little attention so far. This review article provides a brief overview of relevant POM structures used for effective and selective phase transfer of metal ions from aqueous into organic media as well as for the development of efficient sorption processes. The use of inorganic-organic POM-based hybrid materials for extraction and sorption processes is also discussed.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"39 1","pages":"455 - 476"},"PeriodicalIF":2.0,"publicationDate":"2021-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1080/07366299.2021.1874107","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49099908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Behaviors of ALSEP Organic Extractants: an Atomic Perspective Derived from Molecular Dynamics Simulation","authors":"An T. Ta, Julian V. A. Golzwarden, M. Jensen, Shubham Vyas","doi":"10.1080/07366299.2021.1956104","DOIUrl":"https://doi.org/10.1080/07366299.2021.1956104","url":null,"abstract":"ABSTRACT Molecular dynamics simulations were performed on mixtures of N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA) and 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester (HEHEHP) extractants in a dodecane-water system in order to understand the organization and interfacial behavior of extractants in the Actinide-Lanthanide Separation (ALSEP) process. The dynamic behavior and coordination environments of these extractants near the interface were investigated as a function of aqueous nitric acid concentration in the range 0–6 M HNO3. To gain a complete molecular picture of the extractants’ interfacial behaviors, the effects of varying acidity were scrutinized in the context of spatial distributions of extractants within a given phase, chemical interactions, interfacial orientation, and extractant conformation. While the composition of the interfacial solvent mixing region changed with increasing acidity, the behavior of both extractants exhibited very little response to the varying acid levels, but in their own distinct manner. HEHEHP was found to express a specific interfacial behavior marked by a stronger affinity for the interface, with the polar POOH head group being oriented toward the interface and the alkyl chains residing in a constrained conformation. The larger and more flexible extractant, T2EHDGA, is less strongly associated with the interfacial region, on average dwells deeper into the organic phase, and displays orientations and conformations that are more like those of bulk organic phase T2EHDGA molecules than the ordered HEHEHP molecules.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"140 - 164"},"PeriodicalIF":2.0,"publicationDate":"2021-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46038388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrodynamic Properties of Tris(2-methylbutyl) Phosphate and Tri-n-alkyl Phosphates in n-Dodecane – A Comparative Investigation between Unirradiated and Gamma Irradiated Solvent Systems","authors":"Subramee Sarkar, S. Rajeswari, A. Suresh, N. Sivaraman","doi":"10.1080/07366299.2021.1972648","DOIUrl":"https://doi.org/10.1080/07366299.2021.1972648","url":null,"abstract":"ABSTRACT The physicochemical parameters of tris(2-methylbutyl) phosphate (T2MBP), a molecule possessing the essential characteristics required to be considered as a promising extractant in the solvent extraction stage of fast reactor fuel reprocessing, have been evaluated in the present study. In this context, the density, viscosity and interfacial tension (IFT), which are considered to be few among the important solvent selection criteria prior to its deployment in the plant scale have been measured for T2MBP in n-dodecane (n-DD) based systems. Similar studies have been performed with its straight chain isomer, tri-n-amyl phosphate (TAP) as well as the widely utilized commercial extractant, tri-n-butyl phosphate (TBP) so as to emphasize on the structural effects. Though the trends on the physicochemical behaviour of TBP based systems (temperature and ligand concentration effects) are well known in the literature, the data on TBP have been generated in the present work for comparison with the T2MBP results under similar experimental conditions. Solutions of trialkyl phosphates (TalP) in n-DD of different concentrations have been used to generate the data on the variation of density, IFT and viscosity with the change in the ligand concentration. In addition, the transformation in their properties has been assessed after subjecting the solvents to various levels of gamma absorbed doses. Overall, it has been observed that there was no significant variation in the density of the irradiated TalPs; however, there was a significant rise in the viscosity and reduction in the IFT of the TalP samples upon irradiation. The data on the Gibbs energy change of activation of various 1.1 M TalP/n-DD solutions have been generated by fitting their respective dynamic viscosity value as a function of temperature using Andrade’s equation. Moreover, from the IFT value, the parameters relating to the interfacial activity of TalP/n-DD solutions have been determined using the Szyszkowski adsorption isotherm.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"455 - 476"},"PeriodicalIF":2.0,"publicationDate":"2021-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48218799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials","authors":"Ramedy Flores, M. A. Momen, M. Healy, S. Jansone‐Popova, K. Lyon, Benjamin J. Reinhart, M. Cheshire, B. Moyer, V. Bryantsev","doi":"10.1080/07366299.2021.1956121","DOIUrl":"https://doi.org/10.1080/07366299.2021.1956121","url":null,"abstract":"Industrial rare earth element (REE) separations predominantly utilize solvent extraction processes tailored toward conventional resources such as bastnäsite, monazite, and ion adsorption clays. Advances in diglycolamide (DGA) chemistry have shown effective extraction characteristics for REE separations. However, limitations associated with traditional DGA solvent extraction techniques, such as third-phase formation and gelling, have hindered commercial viability. By supporting DGA extractants on porous resins such as polystyrene divinyl benzene (PS-DVB), the desirable combination of solvent extraction selectivity and ease of operation of sorbent columns can be achieved. To design a low-cost model for such solid-supported DGAs, extraction characteristics as influenced by the underlying coordination chemistry must be explored to achieve efficient functional systems. Within this study, we report novel DGA resin materials, each incorporating one of the DGAs N,N,N’,N’-tetra-(1-octyl)-3-oxapentane-1,5-diamide (TODGA), N,N′-dimethyl-N,N′-dioctyl-3-oxapentane-1,5-diamide (DMDODGA), and 2,2ʹ-oxybis(1-(3-(((2-ethylhexyl)thio) methyl)-4-methylpyrrolidin-1-yl)ethan-1-one) (DEHPDGA). The affinity of DGAs across the lanthanide (Ln) series was evaluated for both hydrochloric acid and nitric acid media with varying Ln feed concentrations to study distribution ratios and loading characteristics. Focusing on dysprosium, extended X-Ray Absorption Fine Structure (EXAFS) and density functional theory (DFT) calculations were also utilized to explore coordination chemistry and their effects on ligand performance. The general trend for both acid media resulted in DMDODGA having the highest extraction strength of all three DGAs at varying acid concentrations. Coordination-chemistry analysis supported by loading data, DFT calculations, and EXAFS results under forced loading conditions posited less than the expected 3:1 ligand-to-metal coordination.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"1 1","pages":""},"PeriodicalIF":2.0,"publicationDate":"2021-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41374183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evidence of Supramolecular Origin of Selectivity in Solvent Extraction of Bifunctional Amidophosphonate Extractants with Different Configurations","authors":"Alexandre Artese, S. Dourdain, N. Boubals, T. Dumas, P. Solari, D. Menut, L. Berthon, P. Guilbaud, S. Pellet-Rostaing","doi":"10.1080/07366299.2021.1961433","DOIUrl":"https://doi.org/10.1080/07366299.2021.1961433","url":null,"abstract":"ABSTRACT Extraction mechanisms of two bifunctional extractants which differ only by the grafting of an alkyl chain between their two functions were investigated at molecular and supramolecular scales to investigate the origin of their very different separation factors toward uranium and zirconium. Investigation of the complex structure with spectroscopic analysis (Fourier Transform Infra-Red (FTIR), ElectroSpray Ionization Mass Spectroscopy (ESI-MS) and Extended X-Ray Absorption Fine Structure (EXAFS)) demonstrated that alkylation does not affect the chelation mechanism of uranium and zirconium. Stoichiometries of complexes remain identical for both extractants: UO2L2(NO3)2 and zirconium polynuclear complexes are formed after extraction into the organic phase. The origin of selectivity was therefore investigated by considering the supramolecular self-assembly of the two bifunctional molecules. Small-Angle X ray and Neutrons Scattering (SAXS and SANS) showed that the highest separation factors between U and Zr are obtained when smaller aggregates are formed. The results of this study therefore suggests that the selectivity is controlled by the supramolecular self-assembly of the two extractant molecules. Thanks to a smaller packing parameter, the non-alkylated molecule forms bigger aggregates analogous to reverse micelles that can extract additional polar species in their polar core through a solubilization effect, thus decreasing the separation factor between uranium and zirconium.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"431 - 453"},"PeriodicalIF":2.0,"publicationDate":"2021-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46861818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effective Removal of Cesium by New Functionalized 1,3-Alternate Calixcrown Materials Immobilized on a Silica Carrier","authors":"A. Zhang, Rongrong Chen, Zheng Wang, Jiatian Su, Wenwen Zhang","doi":"10.1080/07366299.2021.1961424","DOIUrl":"https://doi.org/10.1080/07366299.2021.1961424","url":null,"abstract":"ABSTRACT Removal of Cs isotopes, one of the heat generators present in used fuel/reprocessing waste, is one of the most challenging obstacles in the disposal of these materials. For this purpose, a new silica-calix[4]crown material, CBisC6@SiO2, has been prepared. The material was created coupling a symmetric calixcrown derivative CBisC6 into the pores and channels of the SiO2-P particles through vacuum hybridization and immobilization. SEM, 29Si solid-state CP/MAS NMR, N2 adsorption-desorption isotherms, TGA-DSC and XPS were used to characterize the structure of the final material. The adsorption of Cs and some representative metals onto CBisC6@SiO2 has been investigated in the range of 0.4 to 6.0 M HNO3. CBisC6@SiO2 showed strong adsorption ability and selectivity for Cs over all of others except for Rb in 3.0 M HNO3. The adsorption mechanism of Cs was verified using XRD and FT-IR spectra. The separation of Cs from other waste materials by CBisC6@SiO2 was performed through six adsorption-desorption cycles. The removal efficiency of Cs was 99.5%, while other fission products were weakly absorbed except for Rb with the removal efficiency of 85.3%. A nearly quantitative removal of Cs by CBisC6@SiO2 was achieved.","PeriodicalId":22002,"journal":{"name":"Solvent Extraction and Ion Exchange","volume":"40 1","pages":"412 - 430"},"PeriodicalIF":2.0,"publicationDate":"2021-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42176910","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}