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Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and preparative
scale separationsDan McAlister and Phil Horwitz
Eichrom Technologies and PG Research Foundation
Separation Toolbox
Precipitation
Solvent Extraction
Chromatography
(Selective) Dissolution
(Co)PrecipitationPreconcentration Matrix Removal Source Preparation
AgCl BaSO4 PbSO4 CaCO3 BaCO3
CeF3 Fe(OH)3 Calcium‐Phosphate MnO2
Hydrous Titanium Oxide Ca‐oxalate BiPO4
Separation Factors limited by non‐specific binding
S.L. Maxwell, B.K. Culligan, J.B. Hutchison, R.C. Utsey, D.R. McAlister, “Rapid Determination of Po‐210 in Water Samples,” Radioanalytical and Nuclear Chemistry, in press, (2013) DOI: 10.1007/510967‐013‐2644‐2.
Library.lanl.gov/radiochemistry/elements.html
Complete Recovery of analyte(s)
Compatibility with Matrix
Redissolve?
Compatibility with Separation Methods
Decontamination?
Additional ppt
Solvent Extraction
Chromatography
“Matrix and High Loading Effects on EXC Resins,” D.R. McAlister, E.P. Horwitz, Eichrom Workshop at 58th Annual Radiobioassay and Radiochemical Measurements Conference, Fort Collins, CO, October 29 to November 2, 2012.
Chromatography
Ion ExchangeExtraction
ChromatographyRelatively Cheap Reagents
Moderate Selectivity
Moderate Capacity
Resins more Expensive
Superior Selectivity
Limited Capacity
Solvent Extraction
Relatively Cheap Reagents
Higher Capacity/Throughput
Stage Efficiency Limited byEntrainment
Third phase, Interfacial CRUD, solvent degradation
Analytical
Sample
Load Solution
counting
TEVA
UTEVA
Load*
Tc, Np
Th,U
Waste
TRU Am, Pu
Sr Sr
35g Th Metal(2.3 x 1.0 x 1.3 cm)
Dissolve Th8M HNO3 + 0.01M HFComplex
Residual F-
with Boric acid
Raffinate from SX Process 3M HNO3
Th, Pa, U
Y, Sc, Ln(Z>Pm), Po
Ra, Ac, Ln, Y, Sc, Po
To Recycle Ra, Sr
Ac
La-Pm
Ac, La-Pm
Ac‐225 Production
Rare Earths?
Eu
Tb
Production
Production
http://geology.com/articles/rare-earth-elements/
Metal $/kg UsesLa 15 Batteries (10 kg La in a Prius)Ce 15 Catalytic Converter, PolishingPr 105 Alloys, Arc Lights, Welding GlassesNd 98 Magnets, LasersSm 40 MagnetsEu 4000 Phosphor (TV, CFLS)Gd 210 Phosphor, Neutron CaptureTb 2100 Phosphor, AlloysDy 1100 Lasers, LightingHo 1000 Lasers, MagnetsEr 275 Lasers, Glass ColorantTm 4600-13000 Lasers, Portable XRay SourcesYb 1000 Atomic Clocks, Stress GaugesLu 10000 Few (Catalyst)Y 68 Phosphors, Synthetic Garnets
Sc 15000 Alloys, Lamps, Dental LasersAu 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
Monozitemonazite‐Ce (Ce, La, Pr, Nd, Th, Y)PO4 monazite‐Nd (Nd, La, Ce, Pr)PO4monazite‐La (La, Ce, Nd, Pr)PO4 monazite‐Sm (Sm, Gd, Ce, Th)PO4
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
DyTb
GdEu
Sm
NdPrCe
k'
Rel
ativ
e to
La
on L
N2
= 1
Z
La
PO
OH
O
O
PO
OH
O
PO
OH
NR
R OO O
N RR
56 58 60 62 64 66 68 70 7210-1
100
101
102
103
104
105
Ac
Ac
Pm
Pm
Lu
Lu
Yb
YbTm
TmEr
ErHo
Ho
Dy
Dy
Tb
Tb
Gd
GdY
YEu
Eu
Sm
Sm
Nd
Nd
Pr
PrCe
Ce
La
0.05 M HNO3
0.50 M HNO3
TODGA
k'
Z
La
precipitates
Solvent Extraction
0 5 10 15 20 25 30 3510-4
10-3
10-2
10-1
100
101
102
103
Bed Volume = 19.4 mLBed Height = 20.4 cmColumn Diameter = 1.1 cmFlow Rate = 5.0 mL/min = 5.3 mL/cm2/min = 3.9 min/Bed Volume = 2.225-53 m
Lu(III), 0.5 mg
Yb(III), 5 mg
Eluant1.5 M HNO3
Load0.10 M HNO3
ppm
/mL
Bed Volumes
Lu/Yb Separation on LN2 Resin, 50oC, 5 mg Yb
0 5 10 15 20 25 30 3510-4
10-3
10-2
10-1
100
101
102
103
Bed Volume = 19.0 mLBed Height = 20.0 cmColumn Diameter = 1.1 cmFlow Rate = 5.0 mL/min = 5.3 mL/cm2/min = 3.8 min/Bed Volume = 3.425-53 m
Lu(III), 0.5 mg
Yb(III), 25 mg
Eluant1.5 M HNO3
Load0.10 M HNO3
ppm
/mL
Bed Volumes
Lu/Yb Separation on LN2 Resin, 50oC, 25 mg Yb
Displacement Chromatography
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 elementsfrom large stream
Add value to existingstream
Enable better analyticalresults
Cerium Removal (analysis)
10-3 10-2 10-110-1
100
101
102
103
104
k' Ce-139 on UTEVA-3 vs NaBrO3
0.75MY/Yb(NO3)3
Adjusted towith 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 4.0100
101
102
103
104
105
Dw Fe-55 from YCl3/Rare Earth Feed
1x8
WBEC
Dw
-Fe
[HCl], M
TEVA
HCl concentration achievedby adding 12M HCl to YCl3Rare Earth feed solution
2h, 21(1)oC, 30-60 mesh
Iron Removal (analysis)
Iron Removal (analysis)
10-1 100 10110-1
100
101
102
103
104
105
Dw Ni, Ca, Mg,Na, K, Al <1
Co
Cu
Bi
In
GaFe(III)
Pb
Zn
Dw on TEVA from HCl
Dw
[HCl], M
2h, 21(1)oC, 30-60 mesh
Cd
Heavy Lanthanide Separations (analysis)
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 HCl50-100 m, 21(1)oC, 2h
1.0 M LnCl3
La
Sc Separations (analysis)
10-1 100 10110-1
100
101
102
103
104
105
Sc Yb Y Eu La
k'
[HCl], M
UTEVA-3
10-1 100 10110-1
100
101
102
103
104
105
k'
[HNO3], M
UTEVA-3