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