utilizing combinations of co precipitation, extraction …...utilizing combinations of...
TRANSCRIPT
![Page 1: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/1.jpg)
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
![Page 2: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/2.jpg)
Separation Toolbox
Precipitation
Solvent Extraction
Chromatography
(Selective) Dissolution
![Page 3: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/3.jpg)
(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
![Page 4: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/4.jpg)
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.
![Page 5: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/5.jpg)
Chromatography
Ion ExchangeExtraction
ChromatographyRelatively Cheap Reagents
Moderate Selectivity
Moderate Capacity
Resins more Expensive
Superior Selectivity
Limited Capacity
![Page 6: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/6.jpg)
Solvent Extraction
Relatively Cheap Reagents
Higher Capacity/Throughput
Stage Efficiency Limited byEntrainment
Third phase, Interfacial CRUD, solvent degradation
![Page 7: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/7.jpg)
![Page 8: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/8.jpg)
![Page 9: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/9.jpg)
![Page 10: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/10.jpg)
![Page 11: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/11.jpg)
Analytical
Sample
Load Solution
counting
TEVA
UTEVA
Load*
Tc, Np
Th,U
Waste
TRU Am, Pu
Sr Sr
![Page 12: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/12.jpg)
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
![Page 13: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/13.jpg)
Rare Earths?
![Page 14: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/14.jpg)
Eu
Tb
![Page 15: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/15.jpg)
![Page 16: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/16.jpg)
Production
![Page 17: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/17.jpg)
Production
http://geology.com/articles/rare-earth-elements/
![Page 18: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/18.jpg)
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.
![Page 19: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/19.jpg)
C&E News, May 30, 2011 Volume 89, Number 22 p. 9 DOI:10.1021/CEN060211130455
![Page 20: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/20.jpg)
Bastnäsite(Ce, La)CO3F
(Y, Ce)CO3F
![Page 21: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/21.jpg)
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
![Page 22: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/22.jpg)
Ce(IV)
Eu(II)
Yb(II)
Sm(II)
![Page 23: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/23.jpg)
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
![Page 24: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/24.jpg)
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
![Page 25: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/25.jpg)
![Page 26: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/26.jpg)
precipitates
Solvent Extraction
![Page 27: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/27.jpg)
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
![Page 28: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/28.jpg)
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
![Page 29: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/29.jpg)
Displacement Chromatography
![Page 30: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/30.jpg)
![Page 31: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/31.jpg)
Application of EXC to Large Scale Separations
High cost of resins High Value Products
Limitation Consequence(s)
Resin Stability
Analytical Applications
![Page 32: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/32.jpg)
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
![Page 33: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/33.jpg)
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
![Page 34: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/34.jpg)
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)
![Page 35: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/35.jpg)
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
![Page 36: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/36.jpg)
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
![Page 37: Utilizing combinations of co precipitation, extraction …...Utilizing combinations of co‐precipitation, solvent extraction and chromatography to design efficient analytical and](https://reader030.vdocument.in/reader030/viewer/2022040917/5e92011ceff631067e0422cd/html5/thumbnails/37.jpg)
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