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Analytical Separations for Rare Earth Elements and Impurities in Rare Earth
Concentrates
Dan McAlister and Phil Horwitz
Eichrom Technologies and PG Research Foundation
Utilizing combinations of co-precipitation, solvent extraction and chromatography to design efficient analytical and preparative
scale separations Dan McAlister and Phil Horwitz
Eichrom Technologies and PG Research Foundation
Application of EXC to Large Scale Separations
High cost of resins High Value Products
Limitation Consequence(s)
Resin Stability
Analytical Applications
Application of EXC to Large Scale Separations
Low Capacity High Value Products
Limitation Consequence(s)
Scavenge trace elements from large stream
Add value to existing stream
Enable better analytical results
Rare Earths?
Eu
Tb
Production
http://geology.com/articles/rare-earth-elements/
Metal $/kg Uses
La 15 Batteries (10 kg La in a Prius)
Ce 15 Catalytic Converter, Polishing
Pr 105 Alloys, Arc Lights, Welding Glasses
Nd 98 Magnets, Lasers
Sm 40 Magnets
Eu 4000 Phosphor (TV, CFLS)
Gd 210 Phosphor, Neutron Capture
Tb 2100 Phosphor, Alloys
Dy 1100 Lasers, Lighting
Ho 1000 Lasers, Magnets
Er 275 Lasers, Glass Colorant
Tm 4600-13000 Lasers, Portable XRay Sources
Yb 1000 Atomic Clocks, Stress Gauges
Lu 10000 Few (Catalyst)
Y 68 Phosphors, Synthetic Garnets
Sc 15000 Alloys, Lamps, Dental Lasers
Au 45000
DOE Critical Materials for Clean Energy
US DOE Critical Materials Strategy, December 2011.
C&E News, May 30, 2011 Volume 89, Number 22 p. 9 DOI:10.1021/CEN060211130455
Bastnäsite (Ce, La)CO3F
(Y, Ce)CO3F
Monozite monazite-Ce (Ce, La, Pr, Nd, Th, Y)PO4 monazite-Nd (Nd, La, Ce, Pr)PO4 monazite-La (La, Ce, Nd, Pr)PO4 monazite-Sm (Sm, Gd, Ce, Th)PO4
precipitates
Solvent Extraction
Ce(IV)
Eu(II)
Yb(II)
Sm(II)
56 58 60 62 64 66 68 70 7210
-3
10-2
10-1
100
101
102
103
104
105
106
107
108
LN
LN2
LN3
Pm
LuYb
Tm
ErHo
Dy
Tb
Gd
Eu
Sm
NdPrCe
k' R
elat
ive
to L
a on L
N2 =
1
Z
La
PO
OH
O
O
PO
OH
O
PO
OH
NR
R O
O O
N R
R
56 58 60 62 64 66 68 70 7210
-1
100
101
102
103
104
105
Ac
Ac
Pm
Pm
Lu
Lu
Yb
Yb
Tm
Tm
Er
ErHo
Ho
Dy
Dy
Tb
Tb
Gd
Gd
Y
YEu
Eu
Sm
Sm
Nd
Nd
Pr
Pr
Ce
Ce
La
0.05 M HNO3
0.50 M HNO3
TODGA
k'
Z
La
0 5 10 15 20 25 30 35
10-4
10-3
10-2
10-1
100
101
102
103
Bed Volume = 19.4 mL
Bed Height = 20.4 cm
Column Diameter = 1.1 cm
Flow Rate = 5.0 mL/min
= 5.3 mL/cm2/min
= 3.9 min/Bed Volume
= 2.2
25-53 m
Lu(III), 0.5 mg
Yb(III), 5 mg
Eluant
1.5 M
HNO3
Load
0.10 M
HNO3
ppm
/mL
Bed Volumes
Lu/Yb Separation on LN2 Resin, 50oC, 5 mg Yb
0 5 10 15 20 25 30 35
10-4
10-3
10-2
10-1
100
101
102
103
Bed Volume = 19.0 mL
Bed Height = 20.0 cm
Column Diameter = 1.1 cm
Flow Rate = 5.0 mL/min
= 5.3 mL/cm2/min
= 3.8 min/Bed Volume
= 3.4
25-53 m
Lu(III), 0.5 mg
Yb(III), 25 mg
Eluant
1.5 M
HNO3
Load
0.10 M
HNO3
ppm
/mL
Bed Volumes
Lu/Yb Separation on LN2 Resin, 50oC, 25 mg Yb
0.1 110
-1
100
101
102
103
104
0.70.40.2
Cf/Cm ~24
Cm/Am ~1.2
Am-241
Cm-244
Cf-252
50-100 m, 21(1)oC, 1 hr equil.
k' on LN Resin vs HNO3
k'
[HNO3], M
244Cm (xn, b-) 252Cf 252Cf 248Cm
10-1
100
101
100
101
102
103
104
105
106
Cf(III)
Am(III)
50-100 m, 1 h contact time, 22(1)oC
k' on TODGA Resin vs. HCl
k'
[HCl], M
Cm(III)
10-1
100
101
101
102
103
104
105
106
Cf(III)
Am(III)
50-100 m, 1 h contact time, 22(1)oC
k' on TODGA Resin vs. HNO3
k'
[HNO3], M
Cm(III)
0 50 100 150 200 250
101
102
103
104
105
106
252Cf
peak = 101mL
width = 34
cp
m/m
L
mL
241Am
peak = 9.6 mL
width = 3.0
Elution of Am and Cf on DGA Resin5 mL BV, 1.0 x 6.5 cm, 25-50 m, 21(1)
oC, 3mL/min
1M HCl
0 2 4 6 8 10 12 14 16 18 20
0
20
40
60
80
100
% C
f-2
52
mL
TODGA, 0.1M HCl
TODGA, 0.25M HCl
TODGA, 0.5M HCl
TODGA, 0.1M Biox.
TEHDGA, 0.5M HCl
Stripping Cf-252 from 2mL Cartridges of DGA Resins
50-100m, 21(1)oC, 2mL/min
Displacement Chromatography
Cerium Removal
10-3
10-2
10-1
10-1
100
101
102
103
104
k' Ce-139 on UTEVA-3 vs NaBrO3
0.75M
Y/Yb(NO3)3
Adjusted to
with HNO3
k'-C
e
[NaBrO3], M
100-150 m, 21(1)oC, 1h
1.0M HNO3
1.5 M HNO3
2.0 M HNO3
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.010
0
101
102
103
104
105
Dw Fe-55 from YCl3/Rare Earth Feed
1x8
WBEC
Dw
-Fe
[HCl], M
TEVA
HCl concentration achieved
by adding 12M HCl to YCl3
Rare Earth feed solution
2h, 21(1)oC, 30-60 mesh
Iron Removal
Iron Removal
10-1
100
101
10-1
100
101
102
103
104
105
Dw Ni, Ca, Mg,
Na, K, Al <1
Co
Cu
Bi
In
Ga
Fe(III)
Pb
Zn
Dw on TEVA from HCl
Dw
[HCl], M
2h, 21(1)oC, 30-60 mesh
Cd
Heavy Lanthanide Separations
1E-3 0.01 0.11
10
100
1000
NdPr
Ce
Y-90 as Heavy Ln analog
k'-Y
[HCl], M
k' Y-90 on LN2 from 1M LnCl3 vs HCl
50-100 m, 21(1)oC, 2h
1.0 M LnCl3
La
Sc Separations (analysis)
10-1
100
101
10-1
100
101
102
103
104
105
Sc
Yb
Y
Eu
La
k'
[HCl], M
UTEVA-3
10-1
100
101
10-1
100
101
102
103
104
105
k'
[HNO3], M
UTEVA-3
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