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On extracting and application of
noble metal fission product alloy
particles from spent fuel as
catalysts
Daqing Cui
Team: Y. Ouyang, S. Xiao, T. Li, L.Wang & G.Ye
China Institute of Atomic Energy
2017 10 17-19, IAEA Vienna
CIAE
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Content
Introduction 1
FP alloy particles charaterization, composition, size & structure
2
Charaterization of catalytical effect & β radiation 3
As electrolysis catalysts 4
As photo catalysts 5
Optimizing FP noble metal extracting methods
6
SNP generated per year in China t/a SNP accumulated in China, t
in the World
1. Direct disposal
2. Monorecycling Pu
3. Multirecycling Pu
4. Multirecycling Pu & An
5. Improved option4 with
separation of Cs, Sr
6. Transmutation of long
lived fission products
Nuclear Fuel Cycle Options
The best cleaner is who can both clean the house and sell the waste at a good price
SNF
SNF
reprocessing
Waste
U & Pu
SNF
reprocessing
Waste
U & Pu
FP alloy Particles as H2
catalysts
Sr +Cs
Minor An
235U + n → 138Ba + 95Mo + 3n + 6β- : 7.8 x 107KJ/g
• What are noble FP metals ?
1/ How much will be created in a spent fuel ?
2/ How will be their radio activities & toxicities ?
• How to Separate and Utilize?
a) Extracting FP noble metals from high level liquid Waste, by electro deposition
M. Ozawa, JAEA as Electrode catalysts for H2 production
b) Directly extracting as original particles
as catalysts for photocatalyst or electrolyse/fuel cell catalysts
2
RE, Y: 24% Mo,Ru, Tc, Rh, Pd: 29% Kr, Xe: 15% Zr, Nb: 14% Cs, Rb, I, Te: 11% Ba, Sr: 7%
Fission product yield from normal LWR 29%x6.5g/130g = 1.45% Particles / solid solution in UO2?
11
Periodic Table of the Elements
Group**
Period 1
IA
1A
18
VIIIA
8A
1
1
H1.008
2
IIA
2A
13
IIIA
3A
14
IVA
4A
15
VA
5A
16
VIA
6A
17
VIIA
7A
2
He4.003
2
3
Li6.941
4
Be9.012
5
B10.81
6
C12.01
7
N14.01
8
O16.00
9
F19.00
10
Ne20.18
8 9 10
311
Na22.99
12
Mg24.31
3
IIIB3B
4
IVB4B
5
VB5B
6
VIB6B
7
VIIB
7B
------- VIII -----
--
------- 8 -------
11
IB1B
12
IIB2B
13
Al26.98
14
Si28.09
15
P30.97
16
S32.07
17
Cl35.45
18
Ar39.95
419
K39.10
20
Ca40.08
21
Sc44.96
22
Ti47.88
23
V50.94
24
Cr52.00
25
Mn54.94
26
Fe55.85
27
Co58.47
28
Ni58.69
29
Cu63.55
30
Zn65.39
31
Ga69.72
32
Ge72.59
33
As74.92
34
Se78.96
35
Br79.90
36
Kr83.80
5
37
Rb85.47
38
Sr87.62
39
Y88.91
40
Zr91.22
41
Nb92.91
42
Mo95.94
43
Tc(98)
44
Ru101.1
45
Rh102.9
46
Pd106.4
47
Ag107.9
48
Cd112.4
49
In114.8
50
Sn118.7
51
Sb121.8
52
Te127.6
53
I126.9
54
Xe131.3
655
Cs132.9
56
Ba137.3
57
La*138.9
72
Hf178.5
73
Ta180.9
74
W183.9
75
Re186.2
76
Os190.2
77
Ir190.2
78
Pt195.1
79
Au197.0
80
Hg200.5
81
Tl204.4
82
Pb207.2
83
Bi209.0
84
Po(210)
85
At(210)
86
Rn(222)
787
Fr(223)
88
Ra(226)
89
Ac~(227)
104
Rf(257)
105
Db(260)
106
Sg(263)
107
Bh(262)
108
Hs(265)
109
Mt(266)
110
---()
111
---()
112
---()
114
---()
116
---()
118
---()
Lanthanide
Series*
58
Ce140.1
59
Pr140.9
60
Nd144.2
61
Pm(147)
62
Sm150.4
63
Eu152.0
64
Gd157.3
65
Tb158.9
66
Dy162.5
67
Ho164.9
68
Er167.3
69
Tm168.9
70
Yb173.0
71
Lu175.0
Actinide Series~
90
Th232.0
91
Pa(231)
92
U(238)
93
Np(237)
94
Pu(242)
95
Am(243)
96
Cm(247)
97
Bk(247)
98
Cf(249)
99
Es(254)
100
Fm(253)
101
Md(256)
102
No(254)
103
Lr(257)
Classification (Kleykamp, 1975)
1) Dissolved in the matrix: Rb, Sr, Y,
Zr, Nb, Te, Cs, Ba, La, Ce, Pr, Nd,
Pm, Sm, Eu
2) Partly precipitated at grain
boundaries (oxides): Rb, Sr, Zr,
Nb, Mo, Te, Cs, Ba
3) Metallic precipitates: Mo, Tc, Ru,
Rh, Pd, Ag, Cd, In, Sn, Sb, Te
4) Volatiles: Br, Kr, Rb, I, Xe, Cs
Particle size bigger in central part due to better diffusion at higher temrature. Contents differ due to Pu/U vary
Mo-Ru-Tc-Pd-Rh FP alloy particles formed in nuclear fuel
Results of North American palladium Ltd in Canada
1,4266,9886171,900~4,1502.4~7.4Pd
Estimate from PGM production results in main mine
6,6522,5431,527578~949(0.4~0.6)Rh
45
1.4
36
1.4
Ratio
(-)
634~842
102~251
4,021~6,059
50~98
Conc.(ppm)
LWR
113
5.8
84
7.1
Ratio
(-)
Remark
FBR
Metal
Estimated from Cu ore in Russia UGMK
(2004)1,840(3.6~29)Te
Results of Galmony mine in Ireland and Dikulushi mine in Congo
71546~201Ag
Results of Erdenet mine in Mongolia8,966140Mo
Estimated from Cu ore in Russia UGMK
(2004)140(12~92)Se
Conc.(ppm)
Contents(ppm)
Results of North American palladium Ltd in Canada
1,4266,9886171,900~4,1502.4~7.4Pd
Estimate from PGM production results in main mine
6,6522,5431,527578~949(0.4~0.6)Rh
45
1.4
36
1.4
Ratio
(-)
634~842
102~251
4,021~6,059
50~98
Conc.(ppm)
LWR
113
5.8
84
7.1
Ratio
(-)
Remark
FBR
Metal
Estimated from Cu ore in Russia UGMK
(2004)1,840(3.6~29)Te
Results of Galmony mine in Ireland and Dikulushi mine in Congo
71546~201Ag
Results of Erdenet mine in Mongolia8,966140Mo
Estimated from Cu ore in Russia UGMK
(2004)140(12~92)Se
Conc.(ppm)
Contents(ppm)
Spent Fuel as “ Nuclear Ore”
Richest ore
The mass of NRM generated in SNF worldwide is similar with the total production, Rh is even more, 2.5 time higher National Demands of PGM in Japan (FY2006);Ru:3.7t, Rh:2.7t, Pd:50.6t Ozawa: In estimating nuclear fuel cycle capacity in Japan can cover ca.100% of Ru, ca.40% of Rh and ca.7% of Pd against the demands.
Repository NRM particles H2 catalyst
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1. D. Cui* , J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, 2537-2545, DOI:10.1039/C0EE00582G
2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf , D. J. Wronkiewicz and K. Spahiu, “Charactorisation of alloy particles extracted from spent nuclear fuel”, Journal of Nuclear Materials 420, 1-3 (2012)328-33.
3. D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) 173–178
4. Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru-Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92(551-555) (2004)
5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001)
6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Manuscript to JNM,2017
Previous work
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1. D. Cui* , J. Low, K. Spahiu, Environmental behaviors of spent nuclear fuel and canister materials, Energy & Environmental Science 2011, 4, 2537-2545, DOI:10.1039/C0EE00582G
2. D. Cui, V.V. Rondinella, J. A. Fortner, A. J. Kropf , D. J. Wronkiewicz and K. Spahiu, “Charactorisation of alloy particles extracted from spent nuclear fuel”, Journal of Nuclear Materials 420, 1-3 (2012)328-33.
3. D. Cui, V.V. Rondinella, J. Low and K. Spahiu, Hydrogen catalytic effects of nanostructured alloy particles in spent fuel on radionuclide immobilization, Applied Catalysis B: Environmental 94 (2010) 173–178
4. Daqing Cui, Jeanett Low, C. Janzon, Kastriot Spahiu, Leaching of Spent Fuel Mo-Ru-Tc-Pd- Rh Aggregates under Anoxic Conditions Radiochimica Acta 92(551-555) (2004)
5. Daqing Cui, Trygve Eriksen and Ulla-Britt Eklund. On metal aggregates in spent fuel, synthesis and leaching of Mo-Ru-Pd-Rh Alloy, Material Research Society Symp. Proc Vol 663, Scientific Basis for Nuclear Waste Management XXXIV (2001)
6. D. Cui H. Yang,Y. Zhong, Y. Yun, W. Wan, S. Hovmöller, L. Eriksson, K. Spahiu On fission product alloy nanoparticles, important energy and environmental catalysts, Submitted to JNM,2015
Un Oxic extraction
Normal Reprocessing, oxic HNO3
oxidative corrosion of alloy particles
Conditions: UO2 soluble,but NRM alloy particles stable?
0
200
400
600
800
1000
1200
0 200 400 600 800 1000 1200 1400 1600 1800
pp
b
hours
Mo-100
Pd-105
Rh-103
1. Similar alloy without Tc
46Mo-29-Ru-21-Pd-4Rh.
~1800oC melte, Aging in Ar,
1511oC, 4oC/min.
2. Test (6 g, 4 cm2/g) in 25
mL .under gental conditions
in that UO2 dissolved easily
In deoxygenated H3PO4 113oC
Ru, Pd, Rh ≈0.5 ppb, Mo= 900ppb stabilized
BWR 23 MWd/KgU, rumped SNF
Dissolving
SNP in H3PO4 at 113 oC
(glass-fiber filter)
filterate
ICP-MS
Residue
wash & dry
Charaterising
-spectrometry
XRD
SEM-WDS
TEM-EDS-diffraction
EXAFS
Testing as catalyst
flashing Ar/Ar+10%H2
H2- U(VI) Np(V) Pu(V)
Se(IV)
pH3 and pH8.5
vs. 合成合金, Fe(0)
SEM
SEM
5nm —
TEM
TEM
50nm _____
24
Single crystal ED on nano-crystals
Rotation electron diffraction(RED)
Eward sphere
Reciprocal space
24 Zhang et al. Z. Kristallogr., 2010, 225, 94
Wan, et al. J. Appl. Cryst., 2013, 46, 1863
TEM - RED
Diffraction patterns from a 10 nm sized particle. D(Å)
calculated from distances
Scanning of XRD film, 0.5 mg alloy residue
(*trace UO2)
XRD on alloy residue
TEM-diffraction on a
nanoparticle
d(Å) Intensity d(Å) values measured
2.095 100 2.11, 2.09, 2.07, 2.05
2.38 20 2.39, 2.38
2.210 20 2.28, 2.24, 2.21, 2.18
1.168 20 1.16, 1.18, 1.19
1.149* 10
2.49 5 2.48, 2.49
1.045* 5
1.000* 5
a , nm c, nm
1) Residues nondestructicely, with
hexagonal symmetry
extracted from SF MoRuTcRhPaTe
0.2749 0.4386
2) Tc element 0.2740 0.4395
3)Ru element 0.2700 0.4277
4)synthesized Mo40Ru50Pd10 epsilon
alloy phase[Park 2000]
Park et al Korean Chem. Soc. 2000, 21, 1187-1192
0.2757 0.4427
TEM-diffraction
•0.5-0.7 mm particles + clusters (composed by
~10 nm sized nanoparticles):
•TEM-EDS & SEM-WDS: similar sized particles
have similar composition.
•nm particles outside cluster differ in
composition
•SEM-WDS on the biggest particles,0.5-
0.7µm
•TEM-EDS analysis on nanoparticles
•Calculated inventories, 23 MWd/kgU
•Literature data for comparison
fission products Mo Ru Tc Pd Rh Te
SEM_WDS average of 8
submicroparticles
± s
32.7
±1.9
40.5
±1.7
7.0
±0.8
11.7
±1.6
4.2
±0.4
3.8
±1.4
TEM-EDS average of 9
clustered nanoparticles
± s
26,5
±
4,4
32,7
±5,4
7,6
±3,0
23,1
±3,0
6,3
±3,9
4,9
±3,4
nanoparticle analysed
by TEM diffraction 23,2 38,9 4,26 19,2 7,49 6,85
particles from HNO3 SF
reprocessing 20
50–
60
0.5-
5.0 10 10 --
calculated fission yield
[Origen] 42.9 26.0 10.1 10.9 5.9 4.3
s= standard deviation
normalized at.%
Characterization of metal alloy particles
Spectral edges (Mo, Tc and Ru).
synthetic
particles
EXAFS : Mo in the residue is very well coordinated with other metals
EXAFS of 4d-metal particles
Fourier transform modulus
EXAFS: all elements are in similar conditions hemogenoius (true) alloy
Particles
extracted from
spent fuel
fine structure
Test NRM alloy particles: catalyst in 10 % H2 to reduce U(VI) Np(V) Pu(VI)?
25 mL 10NaCl 2mM NaHCO3 solution with U(VI) Pu(VI), Np(V) Tc(VII) Se(VI), flashing Ar+0.03%CO2+10% H2 mixture
pH3 (non sorption) & pH8.5
Study the fates of nuclides in following batch test,
• 5.5 mg NRM particles
• 1 cm2 similar synth alloy, but no Tc
• 1 cm2 similar synth alloy, 0.1 mm source (90Sr 370kBq) effects
• 1 cm2 iron metal,disposal canister material
0,10
1,00
10,00
100,00
1000,00
10000,00
0,00 5,00 10,00 15,00 20,00 25,00 30,00
day
pp
b
U
0,01
0,10
1,00
10,00
100,00
1000,00
0,00 5,00 10,00 15,00 20,00 25,00 30,00
daysp
pb
Pu
Np
0,01
0,10
1,00
10,00
100,00
1000,00
0,00 5,00 10,00 15,00 20,00 25,00 30,00days
pp
b
Experiments at pH 3.0, 5%H2: U(VI), Pu(VI), Np(V)
• H2 has no reducing effects • Synt alloy has some effect • Synt alloy + β much bigger
effects • Extracted alloy has highest
effcts
β radioisotopes in FP alloy particles
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Green energy, H2 & fuel cell need catalysts
Photocatalysis H2 from 4Gen. NPP Photolyzer, calalysis
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Hydrogen made by the electrolysis of water is now cost-competitive and gives us another building block for the low-carbon economy July 05, 2017 , https://www.carboncommentary.com More competitive if the low cost high efficient radcatalysts can be developed.
Wind power is over built night day
Electro-deposition of NRM in S-HLLW; HCl vs. HNO3 media (Masaki Ozawa)
16
HNO3-S-HLLW
HCl-S-HLLW
Electrolysis; Catholyte: 50cm3, 50℃, Cathode: Ptsmooth, 2cm2, Ic: 2.5mA/cm2(1hr)→75(2hr)→100(4hr), ICP Atomic Emission Spectrometry
★
★Pd; must be higher
Micro NRM Deposits by CEE of S-HLLWHCl-0.5M
Mixture of Dendrite and Coagulated fine sphere particles
Metal ; Ru,Pd,Rh, Oxide ; ReO3, TcO2, MoO2 Ru, Rh, Re > Pd, Mo・・・ by 17
SEM/EDS Analysis
S-HLLW-0.5M HCl
S-HLLW-0.5M HNO3-
Pdadded
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
-1.5 -1 -0.5 0 0.5 1 1.5
Pd:Ru:Rh:Re=3.5:4:1:1 *1 Pd:Ru:Rh:Re=1:1:1:1
Pd:Ru:Rh:Re=3.5:4:1:1 *2 Pd
Rh Pd-Ru
Pd-Rh Pd-Re
Ru-Rh
S-HLLW-0.5M
HNO3
Had →H+ + e-
H+ + e- →Had
CV on NRM-deposit
Electrodes
Catalytic Activity of various NRM deposits
for Electrolytic H2 Production in 1M NaOH soln.
19
1) Highest catalytic reactivity has been assigned to the quaternary deposit (Pd-Ru-Rh-
Re (3.5:4:1:1)) electrode, in electrolysis either in NaOH or artificial sea water
(Global2007).
2) Noblest φHinit. (>-1.05V) was observed on NRM deposit electrodes from S-HLLW
(HCl, HNO3)
3) Energy consumption of such electrodes on H2 production was about half of smooth
Pt electrode, specifically in artificial sea water (ibid.).
4) Those (including the deposit from S-HLLW) reactivity, better that of Pt-black
electrode as well as smooth Pt (ibid.).
5) A high reactivity would attribute to higher numbers of Ru and Rh atoms at the
surface (Global2007, 2009). Higher adsorption sites for H+ by them was responsible.
6) Tc showed higher reactivity than that of Re, in/off the combination with Rh (ibid.)
Due to its beta?
Utilization of NRM-deposit Electrodes (Masaki Ozawa)
• In reprocessing, FP alloy particles partly exist as residue in filters or filtrates
called as ”black shit” , often stop filter, or cause short cut during vatrification of HLW, deposite in glass. How to extract FP alloy particles?
H2 produced
• 3G NPP, the electrolzse water to H2 +O2 during nights, high cost catalyst?
H2 used by car or convert to electricity during the day.
• Sunshine photolyse water
Radioactive (Mo-Ru-Tc-Pd-Rh) - TiO2 ,combined photocatalyst
Study the machenism, how much and why beta radioactivity can
enhance the calalyst properties
3.2eV,λ<387nm ultra violet light
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Alloy catalyst Rh:Pd combined effect?
β accelerator
Experimental set up
Light
β accelerator
H2 gas analysis
• On quantitative structure-activity relationships between hydrazine derivatives and β irradiation,,Nuclear Science and Technology, 2017
• Quantitative Comparative Kinetics of hydrazine decomposition on platinum under the effect of β radiolysis,Manuskript to ACS catalysis
• Zeolite Y Encapsulated Cu(II) and Zn(II)-Imidazole-Salen Catalysis for Benzyl Alcohol oxidation,Journal of Catalysis,accepted
• Synthesis of amidoxime-grafted activated carbon fibers for efficient removal of uranium(VI) from aqueous solution,Chemical Engineering Journal, accpeted
Some positive effects of beta radiation On redox catalysed reactions by our group at CIAE
Control temperature and TiO2 structure
TiO2
coated NRM particles
Futural optimization of FP particle extraction
1)Extract nano particles from SNF reprocessing residue on the
filters, purification by HNO3 HF or H3PO4
in hot HNO3 FP alloy particles can be oxidatively dissolved
2) Electrodeposition noble metal elements from HLW
3) High temp., (release/collect I, Cs, enlarge FP alloy particles),
crush SNF, high voltage puls fragmentation of SNP to grain
size in water and separate FP alloy particles
The nonaqueous methods developed for reprocessing spent fuel: fluoride, molybdate, in melts of metals and chlorides, electrochemical, ,,,, A. V. Bychkov, O. V. Skiba, Review of Non-Aqueous Nuclear Fuel Reprocessing and Separation Methods, Chemical Separation Technologies and Related Methods of Nuclear Waste Management pp 71-98|
All nonaqueous method expensive and lack of knowledge
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