Transcript Slide 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 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-methylpentyl2-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
Extractant:
O
R
O
O
N
R
N
R
R
N,N,N’,N’-tetra-n-alkyl-3-oxopentanediamide (TN-DGA)
N,N,N’,N’-tetra-(branched-alkyl)-3-oxopentanediamide (TB-DGA)
Extraction Equilibrium:
3+
M
-
+ 3NO3 + 3E
M(NO3 )3 E3
M = Ln, An
Comparison of TRU and DGA Resins
10
6
10
5
TRU Resin
10
6
10
5
10
4
10
3
10
2
10
1
10
0
TN-DGA Resin
Pu(IV)
Np(IV)
Am(III)
10
4
Th(IV)
3
10
2
10
1
10
0
U(VI)
Th(IV)
k'
10
Am(III)
U(VI)
10
Np(V)
-1
10
10
-2
10
-1
10
[HNO3]
0
10
1
-1
10
-2
10
-1
10
[HNO3]
0
10
1
Dw vs. HNO3 for TN-DGA Resin
o
50-100 m, 1 h Contact Time, 25(2) C
6
10
Ce(III)
Eu(III)
Y(III)
Am(III)
5
10
4
10
3
Dw
10
2
10
1
10
0
10
10
-1
-2
10
10
-1
0
10
[HNO3]
10
1
Comparison of TRU and DGA Resins
10
TRU Resin
6
10
6
10
5
10
4
10
3
10
2
10
1
10
0
TN-DGA Resin
Pu(IV)
k'
Np(IV)
10
5
10
4
10
3
10
2
10
1
Th(IV)
U(VI)
Th(IV)
Am(III)
Am(III)
10
0
U(VI)
10
-1
10
-2
10
-2
10
-1
10
[HCl]
0
10
1
10
-1
10
-2
10
-2
10
-1
10
[HCl]
0
10
1
Comparison of TN-DGA and TB-DGA Resins
10
6
10
5
10
6
10
5
10
4
10
3
10
2
10
1
Dw for Am
TN-DGA
10
4
10
3
TN-DGA
TB-DGA
10
2
10
1
TB-DGA
10
10
0
10
-1
10
10
-2
10
-1
[HNO3]
10
0
10
1
0
-1
10
-2
10
-1
[HCl]
10
0
10
1
Elution Behavior of Selected Cations
on TN-DGA Resin*
Percent of Total
Al(III) Y(III) Th(IV)
Fraction
Bed
Volume
Load (0.5 M
HNO3)
2.0
66
0
0
0
Rinse
(0.1 M HNO3)
2.0
2.0
2.0
2.0
2.0
28
0
0
0
0
0
0
0
0
0
0
0
0
0
0
75
8.4
0
0
0
Strip
(0.1 M HCl)
2.0
2.0
2.0
2.0
2.0
0
0
0
0
0
24
76
0
0
0
78
16
0
0
0
0
0
0
0
0
*Bed volume = 0.5 mL; Flow rate = 0.1
mL/minute for load, rinse, and strip
U(VI)
Fraction
Elution of selected cations on
TN-DGA resin.
Percent of Total
Bed
Ba(II) Cd(II) Cu(II) Fe(III) Y(III) Zr(IV)
Vols.
20
90
93
95
92
0
0.9
Load
(4 M HNO3)
Rinse
2.0
10
7
3.5
7
0
(0.5 M
2.0
< 0.1 < 0.1
0.4
0.6
0
HNO3)
2.0
< 0.1
0
0.4
< .1
0
2.0
0
0
0.4
0.4
0
2.0
0
0
< 0.1
0
0
Strip
2.0
0
0
0
0
71
(0.01 M
2.0
0
0
0
0
27
HCl)
2.0
0
0
0
0
1
2.0
0
0
0
0
0.7
2.0
0
0
0
0
0.3
Column bed volume = 0.5 mL, flow rate = 0.5 mL/minute
load and
0.25 mL/minute for wash and strip
0.2
0
0
0
0
5
10
11
10
10
for
ppm U and Th, cpm/mL
241
Am vs. Bed Volumes of Eluate
o
10
2.0 mL Bed of TN-DGA Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) C
5
Load 1 mg U(VI), 1 mg Th(IV)
241
and Am in 10 mL of 3.0 M HNO3
10
ppm U and Th
241
cpm/mL Am
10
10
Strip
0.10 M
HCl
4
Rinse
0.1 M
HNO3
3
U(VI)
Rinse
3.0 M
HNO3
2
241
Am(III)
Th(IV)
96% Th(IV)
in 4 BV
97% U(VI)
99%
in 2 BV
10
1
10
0
10
241
Am
in 1 BV
-1
Background
10
-2
0
2
4
6
8
10
12
14
16
18
Bed Volumes
20
22
24
26
28
30
cpm/mL vs. Bed Volumes of Eluate
o
10
0.50 mL Bed of TN-DGA Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) C
6
Load 5.0 mL 6.0 M HNO3 spiked
with
10
226
Ra(II) or
Strip
0.10 M HCl
225
Ac(III)
5
225
Ac(III)
91%
cpm/mL
10
226
4
10
3
10
2
10
1
10
0
Ra
Rinse
6.0 M HNO3
225
96% Ac
in 3 BV
226
Ra(II)
Background
0
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20
Bed Volumes
Dw vs. HNO3 for TN-DGA Resin
o
50-100 m, 1 h Contact Time, 25(2) C
4
10
Ca(II)
Sr(II)
3
10
Ba(II)
Ra(II)
2
Dw
10
1
10
0
10
10
Dw for Mg(II) < 1 for all concentrations of HNO3
-1
-2
10
10
-1
0
10
[HNO3]
10
1
ppm vs. Bed Volumes of Eluate
o
2.0 mL Bed of TN-DGA Resin, S-grade, gravity flow 1.0 mL/min, 25(2) C
10
3
10
2
10
1
Load 25 ppm Mg, Ca, Sr and Ba
in 25.0 mL of 4.0 M HNO3
Rinse
4.0 M
HNO3
Ba
Ca
Rinse
0.25 M
HNO3
Sr
Strip
0.1 M
HCl
ppm
Mg
10
99% Ca
in 1 BV
0
99% Sr
in 5 BV
99% Mg and Ba
10
-1
10
-2
10
-3
Background
0
2
4
6
8
10
12
14
16
18
20
Bed Volumes
22
24
26
28
30
32
34
ppm vs. Bed Volumes of Eluate
o
2.0 mL Bed of TN-DGA Resin, S-grade, gravity flow 1.0 mL/min, 25(2) C
10
3
10
2
10
1
Load 25 ppm Mg, Ca, Sr and Ba
in 25.0 mL of 4.0 M HNO3
Rinse
4.0 M
HNO3
Ba
Rinse
0.25 M
HNO3
Sr
Ca
Strip
0.1 M
HNO3
ppm
Mg
10
0
99% Sr
in 5 BV
99% Mg and Ba
10
-1
10
-2
10
-3
99% Ca
in 5 BV
Background
0
2
4
6
8
10
12
14
16
18
20
Bed Volumes
22
24
26
28
30
32
34
PSM 125
Uranium Selective Resin
Di (4 methylpentyl-2-oxy) isobutylphosphonate
=
O
O
P
O
k' vs. [HNO3] on Sterically Hindered Phosphonate Resin
o
40% loading of DMPe[iBuP], 100-150 m, 1 h contact time, 25(2) C
10
10
3
10
2
k' 10
1
10
0
0.1 M Acetohydroxamic Acid
0.05 M Acetohydroxamic Acid
4
U(VI)
Th(IV)
Pu(IV)
U(VI)
Th(IV)
Pu(IV)
U(VI)
Th(IV)
Pu(IV)
-1
10
-2
10
-2
10
10
-1
0
10
[HNO3]
10
1
10
-2
-1
10
10
[HNO3]
0
1
10
-2
10
10
-1
0
10
[HNO3]
10
1
Acetohydroxamic Acid (AHA)
O
=
H
CH3 – C – N – OH
C – N
=
–
CH3
O
O
M
4
H
ppm U and Th, cpm/mL
239
Pu vs. Bed Volumes of Eluate
o
1.8 mL Bed of 40% (w:w) DMPe[iBuP], S=grade , Flow Rate 1.0 mL/min, 25(2) C
10
10
5
Load 1.0 mg U(VI) and 10 mg Th(IV)
239
+ Pu(IV) in 10 mL of 1.0 M HNO3
4
Th(IV)
ppm U and Th
239
cpm/mL Pu
10
Rinse
1.0 M
HNO3
3
10
2
10
1
10
0
10
-1
10
-2
Rinse
1.0 M HNO3
Strip
0.05 M
HNO3
0.1 M AHA
239
U(VI)
Pu(IV)
Quantitative
Elution
of Th(IV)
Background
0
2
4
99% U(VI)
recovered
in 4 BV
97% Pu(IV)
recovered
in 2 BV
6
8
10
12
14
16
Bed Volumes
18
20
22
24
26
28
(UTEVA-2) An Improved Extraction
Chromatographic Resin for the Uptake
and Recovery of Uranium from a Wide
Range of Acidic Nitrate Media
Elution Behavior of Selected Elements on a U/TEVA-2 Chromatrographic Column
Element
Na
Mg
Al
Ca
Cr
Mn
Fe
Ni
Cu
Sr
Y
Zr
Mo
Ru
Rh
Pd
Ag
Cd
Ba
La
Ce
Pr
Nd
Sm
Eu
U
Number of free column volumes (1 FCV = 0.66 mL)
Portion eluting (%)
2 M nitric acid
0.1 M oxalic acid
1-5
6-10
11-15 16-20
21-25 26-30
31-35
36-40
94
4.3
2.7
2.7
1.9
1.8
1.1
<1.0
113
6.5
9.7
92
2.5
100
97
1.7
0.6
96
1.1
94
3.0
1.2
<0.1
101
91
2.1
3.1
95
1.1
25.5
51.1
19.1
2.2
1.3
58.9
40.4
81.5
5.4
1.1
0.5
0.5
0.5
0.1
0.2
91.7
1.9
0.2
36.0
36.8
1.7
2.4
1.1
0.7
0.7
18.2
45.5
100
84.7
17.0
100
55.7
34.6
20.6
45.5
<7.4
9.5
<7.4
<7.4
8.8
<7.4
20.8
71.2
5.4
54.2
39.4
96.8
-
Characteristics of the UTEVA-2 Extraction
Chromatographic Resin and Packed Columns
Bulk Material
Stationary phase
Stationary phase density
Preferred support
Particle diameter (m)
Extractant loading
Density of loaded beads
Capacity (mg U / mL bed)
1:1 molar mixture of DA[AP]
and Cyanex 923
0.902 g/mL
silanized silica
90-130
40% (w/w)
1.216 g/mL
59.4 (calculated); 49.2 (measured)
Packed Columns
Bed density
Vs
Vm
0.416 g/mL
0.185 mL / mL of bed
0.658 mL / mL of bed
V s/ V m
0.281
(LN2) A new EXC resin for the
separation of heavy lanthanide pairs
Separation of Lu from Yb
Using LN-2 Resin
Note: scale on left is linear and scale on right is logarithmic
ppm/mL vs. Bed Volumes of Eluate
ppm/mL vs. Bed Volumes of Eluate
o
Slurry Packed 25-53 m LN2 Resin, Preequilibrated with 0.50 M HNO3, 50(1) C
2.5x10
1
10
Load
2.0x10
Load
0.10 M HNO3
Eluant
10
2
10
1
10
0
Eluant
1.5 M HNO3
1
1.0x10
1
Lu(III), 0.5 mg
ppm/mL
ppm/mL
1
9-14 BV
Yb(III), 5 mg
Yb(III), 5 mg
1.5x10
5.0x10
3
Lu

10
-1
10
-2
= 2.2
Yb
99.7%
99.7%
0
Flow Rate = 5 mL/min90% Lu
2
= 5.3 mL/cm0.1%
/min Yb
= 3.8 min/Bed Volume
Pressure = 5 psi
Lu
 Yb = 2.2
10
90.5%
-3
90.5%
Lu(III), 0.5 mg
10
0
5
10
15
20
Bed Volumes
25
30
35
-4
0
5
10
15
20
Bed Volumes
25
30
35
(Sr2) Super Strontium Resin
cpm vs. Bed Volumes of Eluate
o
2.0 mL Bed of Super Sr Resin, S-grade, Flow Rate 1.0 mL/min, 25(2) C
10
6
133
226
Load Ba and Ra
in 2.0 mL of 1.0 M HNO3
10
5
10
4
226
Ra
133
Ba
Rinse
1.0 M
HNO3
226
<<1% Ra
133
98% Ba
in 3 BV
cpm
226
10
3
10
2
10
1
Strip
0.01 M
HNO3
97% Ra
in 4 BV
Background
10
0
0
2
4
6
8
10
12
Bed Volumes
14
16
18
20
22