Alternatives to HDEHP and DTPA for simplified TALSPEAK separations / Jenifer C. Braley in Industrial & engineering chemistry research, Vol. 51 N° 2 (Janvier 2012)  

Public ISBD [article]  inIndustrial & engineering chemistry research > Vol. 51 N° 2 (Janvier 2012) . - pp. 629-638 Titre : Alternatives to HDEHP and DTPA for simplified TALSPEAK separations Type de document : texte imprimé Auteurs : Jenifer C. Braley, Auteur ; Travis S. Grimes, Auteur ; Kenneth L. Nash, Auteur Année de publication : 2012 Article en page(s) : pp. 629-638 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Talspeak process Résumé : The TALSPEAK process is an established option for lanthanide/minor actinide separations using solvent extraction. In this process, selective extraction of lanthanides is achieved by contacting a water-soluble aminopolycarboxylate complexant in a concentrated carboxylic acid buffer with a liquid cation exchanging extractant in an immiscible organic diluent. Although TALSPEAK process development has been successful on several levels, studies of the detailed fundamental chemistry have revealed undesirable complex interactions between aqueous and organic solute species. These complications threaten to impair process modeling and could impact engineered operations. In the present work, results are reported describing equilibrium partitioning and phase transfer kinetics trends for trivalent lanthanide ions and americium into bis-2-ethyl(hexyl) phosphoric acid (HDEHP) or structural analog 2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) organic phases from aqueous lactate solutions containing diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid (DTPA), triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid (TTHA), or N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid (HEDTA). The undesirable partitioning of Na+, lactic acid, and water into the organic phase is greatly reduced when HEH[EHP] replaces HDEHP as the extractant. TTHA appears to offer little advantage over DTPA in conventional TALSPEAK, but both DTPA and TTHA are too strong for use in combination with HEH[EHP]. The combination of HEDTA with HEH[EHP] achieves good balance and exhibits a nearly flat pH dependence between 2.5 and 4.5, in contrast with conventional TALSPEAK. The latter combination demonstrates more predictable performance than is seen in conventional TALSPEAK, while providing acceptable americium/lanthanide separation factors. The HEDTA/HEH[EHP] combination offers the additional advantage of more rapid phase transfer kinetics for the heavier lanthanides without the need for high concentrations of a lactate buffer. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie200285r [article] Alternatives to HDEHP and DTPA for simplified TALSPEAK separations [texte imprimé] / Jenifer C. Braley, Auteur ; Travis S. Grimes, Auteur ; Kenneth L. Nash, Auteur . - 2012 . - pp. 629-638. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 2 (Janvier 2012) . - pp. 629-638 Mots-clés : Talspeak process Résumé : The TALSPEAK process is an established option for lanthanide/minor actinide separations using solvent extraction. In this process, selective extraction of lanthanides is achieved by contacting a water-soluble aminopolycarboxylate complexant in a concentrated carboxylic acid buffer with a liquid cation exchanging extractant in an immiscible organic diluent. Although TALSPEAK process development has been successful on several levels, studies of the detailed fundamental chemistry have revealed undesirable complex interactions between aqueous and organic solute species. These complications threaten to impair process modeling and could impact engineered operations. In the present work, results are reported describing equilibrium partitioning and phase transfer kinetics trends for trivalent lanthanide ions and americium into bis-2-ethyl(hexyl) phosphoric acid (HDEHP) or structural analog 2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) organic phases from aqueous lactate solutions containing diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid (DTPA), triethylenetetramine-N,N,N′,N′′,N′′′,N′′′-hexaacetic acid (TTHA), or N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid (HEDTA). The undesirable partitioning of Na+, lactic acid, and water into the organic phase is greatly reduced when HEH[EHP] replaces HDEHP as the extractant. TTHA appears to offer little advantage over DTPA in conventional TALSPEAK, but both DTPA and TTHA are too strong for use in combination with HEH[EHP]. The combination of HEDTA with HEH[EHP] achieves good balance and exhibits a nearly flat pH dependence between 2.5 and 4.5, in contrast with conventional TALSPEAK. The latter combination demonstrates more predictable performance than is seen in conventional TALSPEAK, while providing acceptable americium/lanthanide separation factors. The HEDTA/HEH[EHP] combination offers the additional advantage of more rapid phase transfer kinetics for the heavier lanthanides without the need for high concentrations of a lactate buffer. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie200285r

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