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![Page 1: New Extraction Chromatographic Resins or New Tools for the Tool Box E. Philip Horwitz and Daniel R. McAlister PG Research Foundation, Inc. 8205 South Cass.](https://reader036.fdocuments.us/reader036/viewer/2022062322/5697bfaf1a28abf838c9d0ed/html5/thumbnails/1.jpg)
New Extraction Chromatographic Resins or New Tools for the Tool Box
E. Philip Horwitz and Daniel R. McAlister
PG Research Foundation, Inc.8205 South Cass Avenue, Suite 111
Darien, IL 60561
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Contents
1. Tetraalkyl diglycolamide (DGA) resins: DGA resins have unique actinide retention properties.
2. PSM 125 sterically hindered neutral phosphonate [di(4-methylpentyl-2-oxy) isobutylphosphonate]DMPe(iBuP) resin: PSM 125 is similar to UTEVA but has improved uranium selectivity.
3. UTEVA-2: A robust tetra- and hexavalent actinide selective resin designed for waste treatment or the isolation of Th and U from large volumes of solutions.
4. LN2 Resin: A new high resolution resin designed to separate heavy lanthanide pairs.
5. MnO2 Resin: A resin fabricated for use in columns to remove Ra from water samples. (To be presented by Bill Burnett)
6. Sr2 Resin: A more robust strontium selective resin capable of separating Ra from Ba.
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Diglycolamide (DGA) Resin
RN
ON
R
R R
O OExtractant:
Extraction Equilibrium:
N,N,N’,N’-tetra-n-alkyl-3-oxopentanediamide (TN-DGA)
N,N,N’,N’-tetra-(branched-alkyl)-3-oxopentanediamide (TB-DGA)
M(NO3)3 E3
M = Ln, An
M3+ + 3NO3- + 3E
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10-2 10-1 100 101
10-1
100
101
102
103
104
105
106TN-DGA ResinTRU Resin
Np(V)
Am(III)
Np(IV)
U(VI)
Comparison of TRU and DGA Resinsk'
[HNO3]
10-2 10-1 100 10110-1
100
101
102
103
104
105
106
Am(III)
U(VI)
Th(IV)
Th(IV)
Pu(IV)
[HNO3]
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10-2 10-1 100 101
10-1
100
101
102
103
104
105
106
Ce(III) Eu(III) Y(III) Am(III)
50-100 m, 1 h Contact Time, 25(2) oC
Dw vs. HNO
3 for TN-DGA Resin
Dw
[HNO3]
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10-2 10-1 100 101
10-2
10-1
100
101
102
103
104
105
106TN-DGA ResinTRU Resin
Am(III)
Np(IV)
U(VI)
Comparison of TRU and DGA Resinsk'
[HCl]10-2 10-1 100 101
10-2
10-1
100
101
102
103
104
105
106
Am(III)
U(VI)
Th(IV)
Th(IV)
Pu(IV)
[HCl]
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10-2 10-1 100 101
10-1
100
101
102
103
104
105
106
TN-DGA
TB-DGA
Comparison of TN-DGA and TB-DGA ResinsD
w f
or A
m
[HNO3]
10-2 10-1 100 10110-1
100
101
102
103
104
105
106
TN-DGA
TB-DGA
[HCl]
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Elution Behavior of Selected Cations
on TN-DGA Resin*
Percent of Total Fraction Bed
Volume Al(III) Y(III) Th(IV) U(VI)
Load (0.5 M HNO3)
2.0 66 0 0 0
Rinse 2.0 28 0 0 75 (0.1 M HNO3) 2.0 0 0 0 8.4 2.0 0 0 0 0 2.0 0 0 0 0 2.0 0 0 0 0 Strip 2.0 0 24 78 0 (0.1 M HCl) 2.0 0 76 16 0 2.0 0 0 0 0 2.0 0 0 0 0 2.0 0 0 0 0
*Bed volume = 0.5 mL; Flow rate = 0.1 mL/minute for load, rinse, and strip
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Elution of selected cations on TN-DGA resin.
Percent of Total Fraction Bed
Vols. Ba(II) Cd(II) Cu(II) Fe(III) Y(III) Zr(IV)
Load (4 M HNO3)
20 90 93 95 92 0 0.9
Rinse 2.0 10 7 3.5 7 0 0.2 (0.5 M HNO3)
2.0 < 0.1 < 0.1 0.4 0.6 0 0
2.0 < 0.1 0 0.4 < .1 0 0 2.0 0 0 0.4 0.4 0 0 2.0 0 0 < 0.1 0 0 0 Strip 2.0 0 0 0 0 71 5 (0.01 M HCl)
2.0 0 0 0 0 27 10
2.0 0 0 0 0 1 11 2.0 0 0 0 0 0.7 10 2.0 0 0 0 0 0.3 10 Column bed volume = 0.5 mL, flow rate = 0.5 mL/minute for
load and
0.25 mL/minute for wash and strip
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0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
10-2
10-1
100
101
102
103
104
105
99% 241Am
in 1 BV
96% Th(IV)
in 4 BV97% U(VI)
in 2 BV
Rinse0.1 M HNO
3
241Am(III)
U(VI)
Background
Rinse3.0 M HNO
3
Load 1 mg U(VI), 1 mg Th(IV)
and 241Am in 10 mL of 3.0 M HNO3 Strip
0.10 M HCl
2.0 mL Bed of TN-DGA Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) oC
ppm U and Th, cpm/mL 241Am vs. Bed Volumes of Eluate
pp
m U
an
d T
h
cpm
/mL
241 A
m
Bed Volumes
Th(IV)
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0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
100
101
102
103
104
105
106
226Ra(II)
225Ac(III)
Background
Rinse6.0 M HNO
3
Load 5.0 mL 6.0 M HNO3 spiked
with 226Ra(II) or 225Ac(III) Strip0.10 M HCl
0.50 mL Bed of TN-DGA Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) oC
cpm/mL vs. Bed Volumes of Eluate
cpm
/mL
Bed Volumes
96% 225Acin 3 BV
91% 226Ra
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10-2 10-1 100 101
10-1
100
101
102
103
104
Dw for Mg(II) < 1 for all concentrations of HNO
3
Ca(II)
Sr(II)
Ba(II)
Ra(II)
50-100 m, 1 h Contact Time, 25(2) oC
Dw vs. HNO
3 for TN-DGA Resin
Dw
[HNO3]
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0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 3410-3
10-2
10-1
100
101
102
103
99% Ca in 1 BV99% Sr
in 5 BV99% Mg and Ba
Rinse0.25 MHNO
3
Mg
CaStrip0.1 MHCl
Background
Sr
Ba
Rinse4.0 MHNO
3
Load 25 ppm Mg, Ca, Sr and Bain 25.0 mL of 4.0 M HNO
3
2.0 mL Bed of TN-DGA Resin, S-grade, gravity flow 1.0 mL/min, 25(2) oC
ppm vs. Bed Volumes of Eluate
pp
m
Bed Volumes
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0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 3410-3
10-2
10-1
100
101
102
103
99% Ca in 5 BV
99% Sr in 5 BV99% Mg and Ba
Rinse0.25 MHNO
3
Mg
Ca
Strip0.1 MHNO
3
Background
Sr
Ba
Rinse4.0 MHNO
3
Load 25 ppm Mg, Ca, Sr and Bain 25.0 mL of 4.0 M HNO
3
2.0 mL Bed of TN-DGA Resin, S-grade, gravity flow 1.0 mL/min, 25(2) oC
ppm vs. Bed Volumes of Eluate
pp
m
Bed Volumes
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PSM 125 Uranium Selective Resin
Di (4 methylpentyl-2-oxy) isobutylphosphonate
O
= O
P
O
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10-2 10-1 100 101
10-2
10-1
100
101
102
103
104
10-2 10-1 100 101 10-2 10-1 100 101
U(VI) Th(IV) Pu(IV)
k'
[HNO3]
U(VI) Th(IV) Pu(IV)
[HNO3]
0.1 M Acetohydroxamic Acid
U(VI) Th(IV) Pu(IV)
[HNO3]
40% loading of DMPe[iBuP], 100-150 m, 1 h contact time, 25(2) oC
k' vs. [HNO3] on Sterically Hindered Phosphonate Resin
0.05 M Acetohydroxamic Acid
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Acetohydroxamic Acid (AHA)
H
CH3 – C – N – OH
=
O
CH3 C – NH
= –
O
OM
4
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0 2 4 6 8 10 12 14 16 18 20 22 24 26 2810-2
10-1
100
101
102
103
104
105
97% Pu(IV) recoveredin 2 BV
239Pu(IV)
Rinse1.0 M HNO
3
0.1 M AHA
QuantitativeElution
of Th(IV)
Strip0.05 MHNO
3
Background
U(VI)
Th(IV)
99% U(VI) recoveredin 4 BV
Rinse1.0 M HNO
3
Load 1.0 mg U(VI) and 10 mg Th(IV)
+ 239Pu(IV) in 10 mL of 1.0 M HNO3
1.8 mL Bed of 40% (w:w) DMPe[iBuP], S=grade , Flow Rate 1.0 mL/min, 25(2) oCppm U and Th, cpm/mL 239Pu vs. Bed Volumes of Eluate
pp
m U
an
d T
h
cpm
/mL
239 P
u
Bed Volumes
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(UTEVA-2) An Improved Extraction
Chromatographic Resin for the Uptake
and Recovery of Uranium from a Wide
Range of Acidic Nitrate Media
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Element Number of free column volumes (1 FCV = 0.66 mL)Portion eluting (%)
2 M nitric acid 0.1 M oxalic acid1-5 6-10 11-15 16-20 21-25 26-30 31-35 36-40
Na 94 4.3 2.7 2.7 1.9 1.8 1.1 <1.0Mg 113 6.5 9.7 - - - - -Al 92 2.5 - - - - - -Ca 100 - - - - - - -Cr 97 1.7 0.6 - - - - -Mn 96 1.1 - - - - - -Fe 94 3.0 1.2 <0.1 - - - -Ni 101 - - - - - - -Cu 91 2.1 3.1 - - - - -Sr 95 1.1 - - - - - -Y - 25.5 51.1 19.1 - - - -Zr 2.2 1.3 - - - - 58.9 -Mo 40.4 - - - - - - -Ru 81.5 5.4 1.1 0.5 0.5 0.5 0.1 0.2Rh 91.7 1.9 0.2 - - - - -Pd 36.0 36.8 1.7 2.4 1.1 0.7 0.7 -Ag 18.2 - 45.5 - - - - -Cd 100 - - - - - - -Ba 84.7 17.0 - - - - - -La 100 - - - - - - -Ce 55.7 34.6 - - - - - -Pr 20.6 45.5 <7.4 9.5 <7.4 <7.4 8.8 <7.4Nd 20.8 71.2 5.4 - - - - -Sm - 54.2 39.4 - - - - -Eu - - 96.8 - - - - -U - - - - - - - -
Elution Behavior of Selected Elements on a U/TEVA-2 Chromatrographic Column
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Characteristics of the UTEVA-2 Extraction Chromatographic Resin and Packed Columns
Bulk Material
Stationary phase 1:1 molar mixture of DA[AP]
and Cyanex 923
Stationary phase density 0.902 g/mL
Preferred support silanized silica
Particle diameter (m) 90-130
Extractant loading 40% (w/w)
Density of loaded beads 1.216 g/mL
Capacity (mg U / mL bed) 59.4 (calculated); 49.2 (measured)
Packed Columns
Bed density 0.416 g/mL
Vs 0.185 mL / mL of bed
Vm 0.658 mL / mL of bed
Vs/Vm 0.281
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(LN2) A new EXC resin for the
separation of heavy lanthanide pairs
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Separation of Lu from Yb Using LN-2 Resin
0 5 10 15 20 25 30 35
5.0x100
1.0x101
1.5x101
2.0x101
2.5x101
90.5%
99.7%
Lu
Yb = 2.2
Lu(III), 0.5 mg
Yb(III), 5 mg
EluantLoad
ppm/mL vs. Bed Volumes of Eluate
pp
m/m
L
Bed Volumes
Note: scale on left is linear and scale on right is logarithmic
0 5 10 15 20 25 30 35
10-4
10-3
10-2
10-1
100
101
102
103
90.5%
99.7%
Flow Rate = 5 mL/min
= 5.3 mL/cm2/min = 3.8 min/Bed VolumePressure = 5 psi
Lu
Yb = 2.2
Lu(III), 0.5 mg
Yb(III), 5 mg
Eluant1.5 M HNO
3
Load0.10 M HNO
3
Slurry Packed 25-53 m LN2 Resin, Preequilibrated with 0.50 M HNO3, 50(1) oC
ppm/mL vs. Bed Volumes of Eluate
ppm
/mL
Bed Volumes
9-14 BV 90% Lu 0.1% Yb
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(Sr2) Super Strontium Resin
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0 2 4 6 8 10 12 14 16 18 20 22100
101
102
103
104
105
106
97% 226Rain 4 BV
<<1% 226Ra 98% 133Ba
in 3 BV
Strip0.01 M HNO
3
Background
226Ra
133Ba
Rinse1.0 M HNO
3
Load 133Ba and 226Rain 2.0 mL of 1.0 M HNO
3
2.0 mL Bed of Super Sr Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) oC
cpm vs. Bed Volumes of Eluate
cpm
Bed Volumes