Fluorinated Diluents for HLW Processing –

techological point of view

V.A.Babain

Khlopin Radium Institute, St-Petersburg, Russia

Advanced Aqueous Processing of HLW

• Aqueous solvent extraction process is the reference method being developed for treatment of HLW

• High degree of technological maturity; industrial practice in France, USA, Russia, Japan and UK,

• Capable of achieving high decontamination factors for separated products

• Provides flexibility in degree of partitioning of radionuclides present in spent fuel

Ideal diluent

• Good solubility of extractant • No third phase danger ( high metal concentration

in organic phase)• Good hydrodynamic properties of solvent• High radiation stability• Fire and explosive – safety• Non-toxic, cheap

Diluents for TBP -

Hexachlorobutadiene CCl2=CClCCl=CCl2

DisadvantagesHigh toxicity

Hydrocarbons

DisadvantagesRadiation products

Decision CHON conception

Polar diluents for polar extractants:fluorinated dilients

• High chemical and radiolytic stability• High density, non - flammable • High solvate solubility• High extraction ability

Disadvantages • High price• Problem of utilization

Advantages

Clorinated cobalt dicarbollide

NB/CCl4J. Rais, et al. J I N C, 38, 1376, (1976)

Bis- tetrafluoropropoxy etherof diethyleneglycolV.Babain et al., Radiochemistry, 35, 81 (1993)

N+O

O

CCD diluents

N+O

OFF

F

OO

O CH2CF2CF2H

CH2CF2CF2H

S FF

FO

O

NitrobenzotrifluorideL.N.Lazarev et al.,RF Pat № 1603552

PhenyltrifluoromethylsulfoneRomanovskiy et al., RF Pat № 2163403US Pat № 6,258,333 B1US Pat №6,468,445 B2

F-8

FS-13

F-3

Extraction of cesium by 0,06 M CCD solution

F-3

NB

FS-1

3

Dch

E

F-8

chlo

rex

3M HNO3

0,01

0,1

1

10

100

D Cs3M HNO33M NaNO3

Crown ethers ( Sr extraction)

OO

O

OO

O

Fluorinated alcoholsI.V.Mamakin et.al.

RF pat 1706661 (1992)

OktanolTBP - isopar L (SREX)

OO

O

OO

O

RR

Crown ethers ( Cs extraction)

I.Smirnov, V.BabainRFpat № 1.695.547 ( 1994)

Crown ethers ( common Cs + Sr extraction)

Glagolenko J. V., et al.// Patent WO2006036083 (2006).

H(CF2)6CH2OH + aliphatic alcohols

O

OO

O

O O

O

O

O

O

O

O

O

DCH18C6DB21C7

O

OO

OOO

OOO

O O O

O

OCH2CF2CF2H

OH

Modificator Cs7B

BOBCalixC6

Riddle, C.L., Baker, J.D., Law, et al., //Solv. Extr. Ion Exch., 2005, v.23 (3), 449

FPEX process. Cs and Sr exractionFPEX process. Cs and Sr exraction

4,4’,(5’)-di-(t-butyldicyclohexano)-18-crown-6

(DtBuCH18C6),

OO

O

OO

O

PN

OktO O

CH3

CH3

CH3CH3

PN

O O

CH3

CH3

Carbamoyl-phosphineoxides

NN

O O

RNN

O OO

Okt

Okt Okt

Okt

Malonic acid diamides Diglycolic acid diamides.

Ph2Bu2 PhOkt(iBu)2

TBP + hydrocarbons or polar diluents

Hydrocarbons or hydrocarbones + monoamidesas a diluents

Actinides extractionActinides extraction

PN

O O

CH3

CH3

Shadrin et al.,.Radiochemistry, 35, 86,(1993)

Fluorinated ethers

Formula d204,

g/sm3

η20,mPa

.sn20

D ε

T-24 Н(CF2)4CH2OCF2CF2H 1,648 3,5 1,3025 15

T-26 Н(CF2)4CH2OCF2CFHСF3 1,679 2,6 1,2976 12

F-8 [Н(CF2)2CH2OCН2СН2]2О 1,374 8,9 1,3610 24

F-3 ≥ FS-13 ≥ F-8 > T-24,T-26, СHСl3> C6H6

Ph2Bu2Ph2Bu2

Am extractionby 0.1 M Ph2Bu2 from 3M nitric acid

0,1

1

10

100

1000

F-3 F-8 T-24 DChET-26

F-14 Anisole

D Am

CF3

NO2F-3

Modified TRUEX (SETFICS)

Ph2CMPO

TBP

PN

O

C8H15

O

0.4M CMPO ++

(C4H90)3PO

F-3

CF3

NO2

P NOO

CH3

CH3

Myasoedov B., Dzekun E., Chmutova M., Babain V., Pribylova G., Shadrin A . SU Pat N1524519

Ozawa M., Babain V., Fedorov Y., Shadrin A., Romanovsky V., Zilberman BRU Pat 2273507; JP2009008688; US7491345; FR2874281

ORGA

NN

O OO

Okt

Okt Okt

Okt

Actinides extraction by TODGA solutions

Solution in hydrocarbonsVery good extraction properties

Low capacity

Modificators: Monoamides - CHON

TBP – CHON ?

0,01

0,1

1

10

100

1000

0 1 2 3 4 5 6 7

[HNO3], M

D A

m

DDFHMEDDFHAFormal-2F-3

DDFHME H(CF2)6CH2OCH3 DDFHA H(CF2)6CH2OOCCH3 Formal-2 [H(CF2)4 CH2O]2CH2F-3 CF3C6H4NO2

Am extraction by 0.01 M TODGA solutions

Complexants for Am-Ln Separation

NN N

NNN

NN N

NNN

NN

NNR

R

R

R

2,6-bis-triazinyl-pyridines

N N

ON

O R

R'R'

R

Diamides of 2,2’ dipyridyl-6,6’-dicarboxylic acid

2,6-bis(1-aryltetrazol-5-yl)-pyridines

triazinyl-bipyridine

NN

NN

N R

R

NN

O

N

OR"

R'R'

R"

Diamides of dipicolinic acid

0,01

0,1

1

10

100

1000

0 1 2 3 4 5 6 7[HNO3], M

DU

Am

Eu

U, Am, Eu extractionby 0.2 M EtTlDPA in F-3

N+O

OFF

F F-3EtTlDPA

Corrosion problem

Majority of fluorinated diluents are very stable to radiolysis

Yields of F-ions 1.5 -2.5 /100 eV

Mayak experience shows, that stainless steel corrosion problem

Is not really serious.

Spent solvent utilization

Plasma chemical methodSolvent is converted to inorganic salts ( CaF2)Energy-consuming

Conversion to plastic

Low volume of low-level wasteEnergy save

ConclusionPolar fluorinated diluents increase the extraction ability of polydentate extractantsOrganic phase capacity also increases

Solvents on the base of polar diluents are promising for new HLW processing technologies.

C8H17N O N C8H17

O O

C8H17C8H17

TODGA

N N

ONN

O

Dyp-1

0.1

1

10

100

TODGA Et(p)TDPA Dyp-1

D

AmEu

NN

O O

N

Et(p)TDPA

Am/Eu separation by diamide – CCD mixture

NO

NN

O

CH3 CH3

NO

NN

O

EtPhDPAEtTDPA

DQDPA

N,N’-diaryl-N,N’-dialkyl diamides ofdipicolinic acid

PhMDPA