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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
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.
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
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]
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]
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]
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]
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
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
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)
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
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]
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
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
PSM 125 Uranium Selective Resin
Di (4 methylpentyl-2-oxy) isobutylphosphonate
O
= O
P
O
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
Acetohydroxamic Acid (AHA)
H
CH3 – C – N – OH
=
O
CH3 C – NH
= –
O
OM
4
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
(UTEVA-2) An Improved Extraction
Chromatographic Resin for the Uptake
and Recovery of Uranium from a Wide
Range of Acidic Nitrate Media
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
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
(LN2) A new EXC resin for the
separation of heavy lanthanide pairs
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
(Sr2) Super Strontium Resin
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