EXTRACTION OF RARE EARTHS FROM CHLORIDE

SOLUTIONS TO A NITRATE IONIC LIQUID BY THE NEUTRAL

EXTRACTANT CYANEX 923
Mercedes Regado1, Koen Binnemans1
1KU

Leuven, Dept of Chemistry, Celestijnenlaan 200F, 3001 Heverlee. Belgium

Mercedes.Regadio@kuleuven.be

The rare-earth elements (REEs) are listed as critical metals in Europe due to
their high economic value (increasing demand in motors, electronics, renewal
energy and catalysts) and supply risks (>95% sourced from China) (1). Solvent
extraction (SX) is currently the most important process for separating and
obtaining REEs. First, a leaching solution with the dissolved elements (aqueous
feed phase) is intensively mixed with a solvent (organic phase), which
selectively extracts only the desired element/s. Then, the process is reversed by
contacting the loaded organic phase with an acidic aqueous strip solution that
recovers the desired element/s back out of the solvent. For this purpose, large
amount of organic solvent and acids are required. In the present work, a more
environmentally friendly approach is tested using split-anion extraction (2).
The organic phase consisted of Cyanex 923 (extractant) added to the
quaternary phosphonium ionic liquid (IL) Cyphos IL-101 in its nitrate form
(diluent). The aqueous phase consisted of a synthetic feed solution that
simulates the composition of a HCl releachate originated from Kringlerne REE
deposit in Greenland (77 g/L of REE chlorides) in a 2.5 M CaCl2 matrix. Addition
of Cyanex 923 to the nitrate IL has two major advantages. Firstly, the loading
capacity of the organic phase substantially increased due to the strong
interactions of the phosphine oxides in Cyanex 923, with the Lewis acidic REE.
Secondly, the extraction sequence across the lanthanide series was changed
from a negative one (La more extracted than Lu) to a positive one (La less
extracted than Lu), with Y behaving similarly to Pr-Nd. This is convenient since
La, Ce, Pr, Nd and Y make up the 77 w% of the total REE, and they will remain
in the aqueous phase after SX, what reduces the organic phase consumed and
the extraction stages needed for their full separation from the rest of heavier
REE. For completing such a separation at a volume ratio aqueous:organic 1:1
and room temperature, the extraction isotherm/McCabeThiele diagram
predicted five theoretical stages and 35-40 g/L of loading capacity. Finally,
stripping the loaded organic phase with water (1:1 v:v) is possible, with almost
100% recovery of the previously extracted REE (Sm to Lu), after one stage.
Using ILs instead of molecular organic diluents (volatile, flammable and nonelectrically conductive) and stripping with water instead of acids leads to safer
and environmentally friendlier solvent extraction processes.
Acknowledgements: These results has received funding from the European Communitys
Seventh Framework Programme ([FP7/ 2007-2013]) under grant agreement n309373. This
work reflects only the authors view, exempting the Community from any liability.
References
1. European Commission (2010). Report of the Ad hoc Working Group on defining critical raw
materials. Critical raw materials for the EU.
2. K. Larsson, K. Binnemans, Hydrometallurgy, 156(2015)206214.