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铵金属氟化物在乙醇水溶液混合物中的溶解度——对通过反溶剂结晶回收钪的影响。

Solubility of ammonium metal fluorides in aqueous ethanol mixtures - implications for scandium recovery by antisolvent crystallization.

作者信息

Peters Edward Michael, Svärd Michael, Forsberg Kerstin

机构信息

MEAB Chemie Technik GmbH Dennewartstraße 25 52068 Aachen Germany.

KTH Royal Institute of Technology, Department of Chemical Engineering SE-100 44 Stockholm Sweden

出版信息

RSC Adv. 2023 Jan 5;13(2):1288-1294. doi: 10.1039/d2ra07516d. eCollection 2023 Jan 3.

Abstract

The recovery of scandium from waste streams of other mining and metallurgical processing industries is gaining research interest due to the scarcity of scandium-containing ores. Hydrometallurgical techniques such as leaching, solvent extraction and crystallization amongst others have been successfully applied to recover scandium salts from such waste streams. Scandium can be recovered as (NH)ScF by antisolvent crystallization from NHF strip liquors obtained after solvent extraction. The coextraction of metal impurities such as Fe, Al, Zr and Ti causes contamination of the final solid product. The extent of coprecipitation of ammonium metal fluorides depends on their initial concentration in the strip liquor and their solubility in the NHF-antisolvent mixtures. Here, the solubility of ammonium metal fluorides of Sc, Zr, Fe, Al and Ti is reported separately in 3 mol L NHF-ethanol mixtures at 25 °C as well as in a system containing all five solid phases. The solubility of (NH)ZrF is slightly higher than that of (NH)ScF, while the solubilities of (NH)FeF and (NH)AlF are significantly lower in comparison to (NH)ScF. The solubility of (NH)TiF is 1-2 orders of magnitude higher than those of other ammonium metal fluorides. When a mixture of ammonium metal fluoride salts is dissolved in the same 3 mol L NHF-ethanol mixture as for the individual salts, the resultant solubility of the ammonium metal fluorides of Sc, Zr and Fe decreases significantly, while the resultant solubility of ammonium aluminum hexafluoride increases. This is likely due to changes in solution speciation with increased NHF concentration and ionic strength.

摘要

由于含钪矿石的稀缺,从其他采矿和冶金加工业的废物流中回收钪正引起研究兴趣。诸如浸出、溶剂萃取和结晶等湿法冶金技术已成功应用于从此类废物流中回收钪盐。钪可通过反溶剂结晶从溶剂萃取后获得的NH₄F贫液中以(NH₄)₃ScF₆形式回收。金属杂质如Fe、Al、Zr和Ti的共萃取会导致最终固体产物受到污染。铵金属氟化物的共沉淀程度取决于它们在贫液中的初始浓度以及它们在NH₄F-反溶剂混合物中的溶解度。在此,分别报道了Sc、Zr、Fe、Al和Ti的铵金属氟化物在25℃下于3 mol/L NH₄F-乙醇混合物中的溶解度以及在包含所有五种固相的体系中的溶解度。(NH₄)₃ZrF₆的溶解度略高于(NH₄)₃ScF₆,而(NH₄)₃FeF₃和(NH₄)₃AlF₃的溶解度与(NH₄)₃ScF₆相比显著更低。(NH₄)₂TiF₆的溶解度比其他铵金属氟化物高1 - 2个数量级。当将铵金属氟化物盐的混合物溶解在与单个盐相同的3 mol/L NH₄F-乙醇混合物中时,Sc、Zr和Fe的铵金属氟化物的所得溶解度显著降低,而六氟铝酸铵的所得溶解度增加。这可能是由于随着NH₄F浓度和离子强度增加溶液形态发生了变化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2115/9813942/ada04e6665c3/d2ra07516d-f1.jpg

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