Pretreatment Methods for Rare Earth Element Extraction in Supercritical Carbon Dioxide

"In this study, rare earth elements were recovered from bastnasite concentrate and waste fluorescent lamp phosphors using supercritical carbon dioxide extraction with a nitric acid/tributyl phosphate adduct. Several pretreatment methods were used to alter the crystal structure of the source materials, and thus improve rare earth element recovery. Pretreatment methods included 1) dry roasting of the source material at 730oC, 2) decomposition with 50% sodium hydroxide solution at 150oC for 4 hours, and 3) decomposition with 12 M sulfuric acid at 300oC for 4 hours. Treated and untreated samples underwent supercritical extraction at 24 MPa and 65oC for 1 hour. Untreated bastnasite and phosphor samples showed <10% rare earth element recovery, but sodium hydroxide digestion resulted in >60% recovery for most rare earth elements. Dry roasting of the bastnasite concentrate was also effective, resulting in >60% recovery for cerium.INTRODUCTIONRare earth elements (REEs) consist of the 15 lanthanides, scandium, and yttrium. Scandium and yttrium are included because they are in the same group as lanthanum, appear in many of the same ore deposits as the rest of the lanthanides, and exhibit many similar chemical properties. REEs are used in a wide array of applications including electronics, magnets, catalysts, glass, and solid-state lighting (Xie, Zhang, Dreisinger, & Doyle, 2014). Because of China’s continued dominance of worldwide REE production, the United States Department of Energy has sought to diversify domestic supplies of REEs (United States Department of Energy, 2011). A key part of this strategy is the development of improved extraction methods for both ores and recycled sources.Supercritical fluid extraction (SFE) is a promising technology for extraction and separation of rare earth elements. Contact with an acid adduct dissolved in supercritical carbon dioxide allows for the rapid extraction of REEs from solid matrices. Supercritical CO2 has several potentially useful properties as a solvent, including high diffusivity and the ability to tune solvation properties by adjusting pressure. Such tunability may have applications in separating the REEs once they have been extracted from the solid phase. Tributyl phosphate/nitric acid adducts (TBP:HNO3) are a particularly promising class of adducts for SFE extraction of rare earth elements. Using TBP:HNO3 adducts in supercritical CO2, several researchers have successfully extracted REEs from their oxides (Wuhua, Pijia, & Yongjun, 2010; Zhu, Duan, Xu, & Zhu, 2009). However, there is a complication in applying this technique to many types of ores and recycled sources: REEs are often locked in refractory minerals which are resistant to acid attack, resulting in limited recovery in supercritical extraction."