fluorinated diluents for hlw processing – … diluents for hlw processing – techological point...
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Fluorinated Diluents for HLW Processing –
techological point of view
V.A.Babain
Khlopin Radium Institute, St-Petersburg, Russia
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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
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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
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Diluents for TBP -
Hexachlorobutadiene CCl2=CClCCl=CCl2
DisadvantagesHigh toxicity
Hydrocarbons
DisadvantagesRadiation products
Decision CHON conception
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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
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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
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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
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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)
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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
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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
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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
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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
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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
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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
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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 ?
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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
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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
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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
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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.
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Spent solvent utilization
Plasma chemical methodSolvent is converted to inorganic salts ( CaF2)Energy-consuming
Conversion to plastic
Low volume of low-level wasteEnergy save
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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.
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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
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NO
NN
O
CH3 CH3
NO
NN
O
EtPhDPAEtTDPA
DQDPA
N,N’-diaryl-N,N’-dialkyl diamides ofdipicolinic acid
PhMDPA