Studies on Separation of Actinides And Lanthanides by - - PowerPoint PPT Presentation

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May 23, 2023 169 likes •460 views

Studies on Separation of Actinides And Lanthanides by Extraction Chromatography Using 2,6-BisTriazinyl Pyridine P. Deepika, K. N. Sabharwal, T. G. Srinivasan and P. R. Vasudeva Rao Fuel Chemistry Division, Chemistry Group, Indira Gandhi

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Studies

  • n

Separation

  • f

Actinides And Lanthanides by Extraction Chromatography Using 2,6-BisTriazinyl Pyridine

  • P. Deepika, K. N. Sabharwal, T. G. Srinivasan and P.
  • R. Vasudeva Rao

Fuel Chemistry Division, Chemistry Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102 India

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OECD 2008, Japan 2

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OECD 2008, Japan 3

Stage Stage – – I PHWRs I PHWRs

  • 12

12-

  • Operating

Operating

  • 6

6 -

  • Under construction

Under construction

  • Several others planned

Several others planned

  • Scaling to 700 MWe

Scaling to 700 MWe

  • Gestation period being

Gestation period being reduced reduced

  • POWER POTENTIAL

POWER POTENTIAL ≅ ≅ 10,000 MWe 10,000 MWe

LWRs LWRs

  • 2 BWRs Operating

2 BWRs Operating

  • 2 VVERs under

2 VVERs under construction construction

81 91 85 82 80 75 71 67 60 90 86 84 84 79 75 69 72 90

50 55 60 65 70 75 80 85 90 95

1995-96 1996-97 1997-98 1998-99 1999-00 2000-01 2001-02 2002-03 2003-04 Availability /Capacity Factor (%) ----->

THREE STAGE NUCLEAR POWER PROGRAM THREE STAGE NUCLEAR POWER PROGRAM

Stage Stage -

  • II

II Fast Breeder Reactors Fast Breeder Reactors

  • 40 MWth FBTR

40 MWth FBTR -

  • Operating since 1985

Operating since 1985 Technology Objectives Technology Objectives realised realised

  • 500 MWe PFBR

500 MWe PFBR-

  • Under Construction

Under Construction

  • POWER POTENTIAL

POWER POTENTIAL ≅ ≅ 530,000 MWe 530,000 MWe Stage Stage -

  • III

III Thorium Based Reactors Thorium Based Reactors

  • 30 kWth KAMINI

30 kWth KAMINI-

  • Operating

Operating

  • 300 MWe AHWR

300 MWe AHWR-

  • Under Development

Under Development POWER POTENTIAL IS POWER POTENTIAL IS VERY LARGE VERY LARGE Availability of Availability of ADS ADS can enable early can enable early introduction of Thorium on introduction of Thorium on a large scale a large scale

DAE Presentation on 24-06-04

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Fast Breeder Test Reactor Kalpakkam

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Radiochemistry Laboratory

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Hot Cells

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Minor Actinides

104 105 106 107 108 109

The Chemist's Playground

H Li Be Na Mg K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Al Si P S Cl Ar B C N O F Ne He

Man-made Radioactive Elements Naturally Radioactive Elements

92 93 94 95 96 97 98 99 100 101 102 103

Cs Ba (Ln) Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra (An) Rf Db Sg Bh Hs Mt 110 111 112 113 114 116 118

Minor actinides

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Minor Actinides DIDPA TALSPEAK TRUEX TPTZ TRPO CYANEX 301 SASME HDEHP

Separation of MINOR actinides by various techniques

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Extractants used in our Laboratory

for Co extraction of lanthanides and actinides

Truex process ---- CMPO ------ Solvent Extraction

Diamides ----- DMDBMA ------- Solvent Extraction [Dimethyl Dibutyl Malonamide]

TEHDGA --- Tetraethyl Hexyl Diglycoamide -- Solvent Extraction

DMDOHEMA ---- Solvent Extraction [DimethylDioctylHexylEthoxyMAlonamide]

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Other Techniques

  • Extraction Chromatography
  • Room Temperature Ionic Liquids
  • Supercritical Fluid Extraction
  • High Performance Liquid Chromatography
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Actinide – Actinide – Lanthanide Lanthanide Separation Separation

  • Bis

Bis Triazinyl riazinyl Pyridine Pyridine (BTP) (BTP)

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Outline

  • Introduction

– Lanthanide-Actinide Separation. – Bis Triazinyl Pyridines (BTPs). – Advantages of Extraction Chromatography over Solvent Extraction.

  • Experimental Work

– Synthesis

  • f

2,6-bis(5,6-dipropyl-1,2,4-triazin-3- yl)pyridine. – Preparation of the Extraction Resin. – Extraction Studies

  • f

Am (III) and trivalent lanthanides by XAD-7 impregnated with 2,6- bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine.

  • Conclusions
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  • Need

– Partitioning and Transmutation ( to reduce long-

term radiological risks to the environment by transmutation of the minor actinides).

  • Difficulty

– Lanthanides and actinides have similar chemical properties due to similar ionic radii.

Lanthanide – Actinide Separation Introduction

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Bis Triazinyl Pyridines (BTPs)

First reported in 1999 by Kolarik, Mullich and Gassner that 2,6-di(5,6-dialkyl-1,2,4-triazin-3-yl)pyridines extract and separate Am(III) and Eu(III) very efficiently as nitrates.

(Solvent Extraction and Ion Exchange, 17(1), 23-22, 1999)

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Advantages of Extraction Chromatography

  • No third phase formation,
  • No need for a modifier,
  • Reusability of the synthesized resin,
  • Simple and compact equipment,
  • Minimal loss of organic solvent.

Limitations of solvent extraction –

  • Third Phase formation,
  • Need for phase-modifiers,
  • Disposal of large volumes of extractants and diluents,
  • Tedious multi-stage extraction procedures.
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Synthesis of 2,6-bis(5,6-dipropyl-1,2,4-triazine-3-yl)-pyridine

N C C

N N H 2

N N H 2 N H 2 N N N N N N N

N H 2

O O

2 , 6 - b is ( 5 , 6 - d ip r o p y l- 1 , 2 , 4 - t r ia z in e - 3 - y l) p y r id in e

+

2 , 6 - p y r id in e d ic a r b o x a m id e d ih y d r a z o n e

O c t a n e - 4 , 5 - d io n e

Experimental Work

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Preparation of the Extraction Resin

Resin Impregnation

XAD-7 particles Washing Air-drying Impregnation in rotary evaporator Removing Diluent Air-drying Extraction resin (nPr-BTP/XAD-7)

Extractant: nPr-BTP Diluent: dichloromethane (Methanol, Acetone) (298K, 2h) (323K)

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“ Extraction Studies of Am (III) and trivalent lanthanides by XAD-7 impregnated with 2,6- bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine”

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Figure : Kinetics of the uptake of Am (III) by nPr-BTP/XAD-7 resin (0.25g nPr- BTP/XAD-7, 0.1M HNO3, 2M NH4NO3, 303K)

5 1 0 1 5 2 0 2 5 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0

K

d

T i m e , h r

  • Distribution

coefficient (Kd) values increased with increasing time of equilibration and equilibrium is reached in 24 hours.

  • For Kd measurements, we have equilibrated for 3 hours.
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0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0

K

d

[H N O 3], M

W ith o u t N H 4N O 3 W ith N H 4N O 3

Figure: Effect of nitric acid concentration on the uptake of Am(III) by nPr-BTP/XAD-7 resin with and without 2M NH4NO3 (0.25g nPr-BTP/XAD-7, 303K, 3h).

  • Kd values for the extraction of Am(III) from nitric acid with ammonium nitrate are

significantly higher.

  • The increase of Am(III) adsorption with increasing nitrate concentration can be

explained by the following adsorption equilibrium represented by Equation (1), M3+ + 3NO3

  • + n(nPr-BTP) = M(NO3) 3 (nPr-BTP)n

(1)

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Figure : Effect of nitric acid concentration on the uptake of Am(III) and lanthanides by nPr-BTP/XAD-7 resin (0.25g nPr-BTP/XAD-7, 2 M NH4NO3, 303K, 3h)

1 2 3 4 3 0 0 4 0 0 5 0 0 6 0 0 7 0 0 8 0 0

A m ( I I I ) K

d

[ H N O

3 ] , M

1 2 3 4 2 4 6 8 1 0 1 2 1 4 1 6 1 8 2 0

L a ( I I I ) C e ( I I I ) N d ( I I I ) E u ( I I I ) G d ( I I I ) K

d

[ H N O

3 ] , M

  • The lanthanides are not extracted by the resin at any acidity.
  • Kd value for the extraction of Am(III) is maximum at 0.1M nitric acid in the

presence of ammonium nitrate.

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Figure : Effect of nitrate concentration on the uptake of Am(III) and Lanthanides by nPr-BTP/XAD-7 resin (0.25g nPr-BTP/XAD-7, 0.1M HNO3, 303K, 3h)

1 2 3 4 5 6 7 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0

A m ( I I I ) K

d

[ N H 4 N O 3 ] , M

1 2 3 4 5 6 7

  • 2 0

2 0 4 0 6 0 8 0 1 0 0 1 2 0 1 4 0

L a ( I II ) G d ( I II ) N d ( I I I ) C e ( I I I ) E u ( I I I ) K

d

[ N H 4 N O 3 ] , M

The distribution coefficient (Kd) value of Am (III) increases with increase in NH4NO3 concentration, which can be explained by equation (1), M3+ + 3NO3

  • + n(nPr-BTP) = M(NO3) 3 (nPr-BTP)n

(1)

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[NH4NO3] M Separation Factor (Kd Am / Kd Ln) La Ce Nd Eu Gd 192 173 173 173 173 1 2730 5187 5187 66 451 2 2471 7638 1400 43 296 3 8925 8926 8926 27 246 4 1412 937 347 14 92 6 770 465 117 7 52

Table: Separation Factors for Americium-Lanthanide Separations ( 0.25g nPr- BTP/XAD-7, 0.1M HNO3, 303K, 3h)

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Figure : Loading of Am (III) and Eu (III) on to a column of nPr-BTP/XAD-7 resin.

1 0 2 0 3 0 4 0 5 0 6 0 7 0 0 .0 0 .2 0 .4 0 .6 0 .8 1 .0

C/C V o lu m e , m L

E u ( III) A m ( III)

Europium was not retained in the column and up to 99.4% of it was recovered at the loading stage itself. Up to 90% of the Am was retained in the column.

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Figure : Elution of Am (III) from nPr-BTP/XAD-7 column with 0.3M DTPA.

5 1 0 1 5 2 0 2 5 3 0 1 2 3 4 5 6

C/Co V o lu m e , m L A m ( I I I ) e lu t io n w it h 0 . 3 M D T P A

  • Loaded Am(III) was recovered by passing 0.3 M DTPA solution (pH=4.0).
  • 60% of Am was recovered within the first three column volumes.
  • Further tailing was observed.
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  • nPr-BTP impregnated

XAD-7 resin displayed high selectivity for americium and good separation-factors for the separation of other lanthanides from the same.

  • Column runs for the separation of americium from

europium gave good results with 99.4% Europium being removed in the loading stage itself.

  • The elution of Am from the column using DTPA was

found to be 60% and efforts are on to improve the same.

Conclusions -

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Thank You…..