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Influence of KF and HF on the selectivity of Zr and Hf separation by fractional crystallization of K2Zr(Hf)F6 / Branken, Dawie J. in Industrial & engineering chemistry research, Vol. 49 N° 2 (Janvier 2010) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 49 N° 2 (Janvier 2010) . - pp 797–808 Titre : Influence of KF and HF on the selectivity of Zr and Hf separation by fractional crystallization of K2Zr(Hf)F6 Type de document : texte imprimé Auteurs : Branken, Dawie J., Auteur ; Lachmann, Gerhard, Auteur ; Krieg, Henning M., Auteur Année de publication : 2010 Article en page(s) : pp 797–808 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Crystallization  KF  Zirconium  meta  Nuclear  characteristics  Separation  method. Résumé : For nuclear applications, zirconium metal (Zr) must adhere to stringent specifications, where a low hafnium (Hf) content, i.e., <100 ppm, is one of the most important requirements due to the opposing nuclear characteristics of the two elements. Hf-purified Zr is however not easily obtained, as the two entities occur together in nature and they are exceptionally difficult to separate due to their close chemical and physical similarities. In this study, cooling crystallization of K2Zr(Hf)F6 from aqueous solutions, i.e., fractional crystallization, was investigated as a separation method. The influence of the solvent composition on the selectivity of fractional crystallization as separation method was studied, wherein KF and HF were used as additives. Using scanning electron microscopy and X-ray diffraction analysis of the product crystals, it is shown that crystallization from KF solutions resulted in a decrease in the crystal size leading to the formation of K3Zr(Hf)F7 with increasing KF concentration. These effects resulted in a decreased selectivity, which was suppressed by the addition of 2.5 mol/L HF to the crystallization solution. In addition, it is shown that selectivity improved with an increasing relative excess amount of solute with respect to the solubility at the lower crystallization temperature, which could be favorably regulated by adjusting the KF concentration of a 2.5 mol/L HF solvent solution. Consequently, the most efficient separation was obtained using a solution consisting of 0.45 mol/L KF and 2.5 mol/L HF. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie900747k [article] Influence of KF and HF on the selectivity of Zr and Hf separation by fractional crystallization of K2Zr(Hf)F6 [texte imprimé] / Branken, Dawie J., Auteur ; Lachmann, Gerhard, Auteur ; Krieg, Henning M., Auteur . - 2010 . - pp 797–808. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 2 (Janvier 2010) . - pp 797–808 Mots-clés : Crystallization  KF  Zirconium  meta  Nuclear  characteristics  Separation  method. Résumé : For nuclear applications, zirconium metal (Zr) must adhere to stringent specifications, where a low hafnium (Hf) content, i.e., <100 ppm, is one of the most important requirements due to the opposing nuclear characteristics of the two elements. Hf-purified Zr is however not easily obtained, as the two entities occur together in nature and they are exceptionally difficult to separate due to their close chemical and physical similarities. In this study, cooling crystallization of K2Zr(Hf)F6 from aqueous solutions, i.e., fractional crystallization, was investigated as a separation method. The influence of the solvent composition on the selectivity of fractional crystallization as separation method was studied, wherein KF and HF were used as additives. Using scanning electron microscopy and X-ray diffraction analysis of the product crystals, it is shown that crystallization from KF solutions resulted in a decrease in the crystal size leading to the formation of K3Zr(Hf)F7 with increasing KF concentration. These effects resulted in a decreased selectivity, which was suppressed by the addition of 2.5 mol/L HF to the crystallization solution. In addition, it is shown that selectivity improved with an increasing relative excess amount of solute with respect to the solubility at the lower crystallization temperature, which could be favorably regulated by adjusting the KF concentration of a 2.5 mol/L HF solvent solution. Consequently, the most efficient separation was obtained using a solution consisting of 0.45 mol/L KF and 2.5 mol/L HF. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie900747k