Post on 29-Jun-2018
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