Supercritical fluid extraction of rare earth elements from luminescent material in waste fluorescent lamps

Abstract Rare earth elements were extracted from luminescent material in waste fluorescent lamps using supercritical carbon dioxide (SF-CO 2 ) containing tri- n -butyl phosphate (TBP) complexes with HNO 3 and H 2 O. The determined Y, Eu, La, Ce and Tb in the employed luminescent material were 29.6, 2.3, 10.6, 5.0 and 2.6 wt.%, respectively. Aqueous droplets were generated in an extraction experiment from a reaction with metal oxides and a complex prepared from vigorous mixing of TBP with concentrated nitric acid (15.5 mol dm −3 (M)). These droplets were generated because the complex was saturated with water and the excess water separated, leading to low recovery yields. The molecular ratio of TBP:HNO 3 :H 2 O in the complex was 1.0:1.8:0.6. When the ratio was changed to 1.0:1.3:0.4 by dilution with TBP anhydrate, the separation of water was prevented. Using this complex, extraction efficiencies for Y and Eu increased to over 99% after the static extraction for 120 min at 15 MPa, 333 K.

[1]  J. Ferraro,et al.  Third Phase Formation Revisited: The U(VI), HNO3–TBP, n‐Dodecane System , 2003 .

[2]  C. Wai,et al.  Extraction of Toxic Heavy Metals Using Supercritical Fluid Carbon Dioxide Containing Organophosphorus Reagents , 1997 .

[3]  Z. Yoshida,et al.  Dissolution Behavior of Uranium Oxides with Supercritical CO2 Using HNO3-TBP Complex as a Reactant , 2001 .

[4]  Z. Yoshida,et al.  Solubility of Organophosphorus Metal Extractants in Supercritical Carbon Dioxide , 1998 .

[5]  M. Baaden,et al.  TBP at the Water−Oil Interface: The Effect of TBP Concentration and Water Acidity Investigated by Molecular Dynamics Simulations , 2001 .

[6]  M. Shamsipur,et al.  Extraction of uranium from solid matrices using modified supercritical fluid CO2 , 2001 .

[7]  Z. Yoshida,et al.  New Method for the Removal of Uranium from Solid Wastes with Supercritical CO2 Medium Containing HNO3-TBP Complex , 2001 .

[8]  Y. Enokida Extraction of uranium and lanthanides from their oxides with a high-pressure mixture of TBP-HNO_3-H_2O-CO_2 , 2003 .

[9]  Chien M. Wai,et al.  Supercritical fluid extraction of lanthanides and actinides from solid materials with a fluorinated [beta]-diketone , 1993 .

[10]  Chien M. Wai,et al.  Ultrasound-enhanced dissolution of UO2 in supercritical CO2 containing a CO2-Philic complexant of tri-n-butylphosphate and nitric acid , 2002 .

[11]  W. W. Schulz,et al.  Science and technology of tributyl phosphate , 1987 .

[12]  Ichiro Yamamoto,et al.  Cleaning of materials contaminated with metal oxides through supercritical fluid extraction with CO2 containing TBP , 2000 .

[13]  C. Erkey Supercritical carbon dioxide extraction of metals from aqueous solutions: a review , 2000 .

[14]  Wai,et al.  On-line time-resolved laser-induced fluorescence of UO2(NO3)2.2TBP in supercritical fluid CO2 , 2000, Analytical chemistry.

[15]  C. Wai,et al.  Evaluation of dithiocarbamates and beta-diketones as chelating agents in supercritical fluid extraction of Cd, Pb, and Hg from solid samples. , 1996, Talanta.

[16]  Y. Enokida,et al.  Selective recovery of neodymium from oxides by direct extraction method with supercritical Co2 containing TBP–HNO3 complex , 2002 .