could we recycle the critical raw materials which are ... · could we recycle the critical raw...
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www.cea.fr
Could we recycle
the critical raw materials
which are present within
spent nuclear fuels?
| PAGE 1
Prof. Christophe POINSSOT (*), Stéphane BOURG CEA Marcoule / Nuclear Energy Division,
RadioChemistry & Processes Department,
(*) Head of the Department
Professor at the National Institute of Nuclear Science and Technology
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
A very large growing of raw materials
consumption at the world scale
Evolution of the production in Metric tons of 14 raw materials:
Al, Au, Ba, Co, Cr, Cu, Fe, K2O, Mn, Ni, (PO4)n, Pb, Pt, Zn
Drivers are:
• Population
growth
• Economic
Development
• New
technology
(courtesy of P.Landais, BRGM)
2
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
An increasing materials demand
• crucial for the sustainable
functioning of the economy.
• Used in microprocessors,
smartphones, LCD screens,
batteries and low energy light
bulbs,
• intrinsic part of today life
Strategic economic sectors in Europe, such as automotive, aerospace and
renewable energy industries, highly depend on a few raw materials
industry demand is
growing at impressive rates.
For REO, the demand has
doubled every 8 years
3
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
A very strong diversification of the raw materials
used: From XXth …
Elements used in early 1900's
Frequently used
Slightly used
4
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Lanthanides
(Rare Earth)
Actinides
Stockage de l'énergie Production et transport de l'électricité Eclairage
Connectique Supraconducteurs
Economies d'énergie
Compilation: P. Christmann, BRGM
Les symboles chimiques des éléments semi-conducteurs sont indiqués en lettres rouges
Catalyse (automobile, piles à
combustible)
Industrie électrique nucléaire
Photovoltaïque
Aimants permanents (véhicules
électriques, éoliennes, TGV...)
NoMdTh Pa U LrCm Bk Cf Es FmNp Pu Am
Dy Hm Er Tm Yb Lu
Uuo
Ce Pr Nd Pm Sm Eu Gd Tb
Rg Uub Uut Uuq Uup UuhDb Sg Bh Hs Mt DsAc RfFr Ra
Tl Pb Bi Po At RnRe Os Ir Pt Au HgLa Hf Ta WCs Ba
Sb Te I XeRh Pd Ag Cd In SnRb Sr Y Zr Nb Mo Tc Ru
Ga Ge As Se Br KrMn Fe Co Ni Cu ZnK Ca Sc Ti V Cr
Si P S Cl Ar
C N O F Ne
Al
He
Li Be B
H
Na Mg
Energy storage
Connections
Energy savings
Catalysts (automotive,
fuel cells)
Electricity production and transport
Nuclear energy industry
Photovoltaics
Permanent magnets (cars, wind
turbines…)
Lighting
supraconductors
Elements used in energy sector in 2014
A very strong diversification of the raw materials used:
… to early XXIst !
In red: semi-conductor elements
5
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
The overall economic and industrial
challenges are very high
An
nu
al w
orl
d p
rod
uct
ion
(th
ou
san
ds
t/y
ear)
Par
t o
f E
U p
rod
uct
ion
wit
hin
the
wo
rld
pro
du
ctio
n
- Since the mid-2000s, EU and countries as France realized how
dependent they are on foreign imports to access non energetic raw
materials
- Threat to Europe’s industrial network and global competitiveness.
- Needs for developing EU resources: primary mines, recycling of
end-of-life products, byproducts valorization
6
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
More generally, most of the raw materials resources are located out of
Europe - Consequences of the EU de-industrialization during previous decades
- Most of primary industry left Europe driven both by manpower cost and
environmental concerns
Most of the raw material natural resources are
located out of Europe
Where can we find the 52
materials
of BGS Risk List ?
(source BGS 2011)
7
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
The 20 Critical Raw Materials for Europe - 2014
8
Antimony Gallium Magnesite
Beryllium Germanium Niobium
Borates Graphite PGMs
Chromium HREE Phosphate rock
Cobalt LREE Silicon metal
Coking coal Indium Tungsten
Fluospar Magnesium
The rare earth crisis 2008
The European Innovation Partnership on Raw Materials (EIP-RM)
The CRM list (2010 and update in 2014 – next one in 2017)
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Towards the development of a clean and safe
mining and recycling industries in Europe
Mine tailings
Low
grade
ores
Waste Electrical and
Electronic Equipment
(WEEE)
Economic growth
in Europe Own mineral
resources
Primary resource: ore mining
Secondary resource: urban
mines
Recycling manufacturing
waste and end-of-life products
From E.Pirard, KU Leuven
Secondary resource: industrial waste
Solving environmental issues and valorizing byproducts
Slags
9
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Spent nuclear fuel contains some critical raw
materials !
1 H
3 Li
11 Na
19 K
37 Rb
55 Cs
87 Fr
4
Be
12 Mg
20 Ca
38 Sr
56 Ba
88 Ra
21 Sc
39 Y
Ln
An
22 Ti
40 Zr
72 Hf
104 Rf
23 V
41 Nb
73 Ta
105 Db
42 Mo
74 W
106 Sb
25 Mn
43 Tc
75 Re
107 Bh
26 Fe
44 Ru
76 Os
108 Hs
45 Rh
77 Ir
109 Mt
28 Ni
46 Pd
78 Pt
29 Cu
47 Ag
79 Au
30 Zn
48 Cd
80 Hg
5 B
13 Al
31 Ga
49 In
81 Tl
6 C
14 Si
32 Ge
50 Sn
82 Pb
7 N
15 P
33 As
51 Sb
83 Bi
8 O
16 S
34 Se
52 Te
84 Po
9 F
17 Cl
35 Br
53 I
85 At
57 La
89 Ac
58 Ce
90 Th
91 Pa
60 Nd
92 U
61 Pm
93 Np
62 Sm
94 Pu
63 Eu
95 Am
64 Gd
96 Cm
65 Tb
97 Bk
66 Dy
98 Cf
67 Ho
99 Es
68 Er
100 Fm
69 Tm
101 Md
70 Yb
102 No
71 Lu
103 Lr
2
2 He
10 Ne
18 Ar
36 Kr
54 Xe
86 Rn
ACTINIDES
LANTHANIDES 59
Pr
Actinides
Fission
products
Critical
material at the
world level
Mendeleiev table
10
1
H
37
Rb
55
Cs
38
Sr
56
Ba
39
Y
Ln
40
Zr 41
Nb 42
Mo 43
Tc 44
Ru 45
Rh 46
Pd 47
Ag 48
Cd 49
In
32
Ge
50
Sn
33
As
51
Sb
34
Se
52
Te
35
Br
53
I
57
La 58
Ce 60
Nd 61
Pm 62
Sm 63
Eu 64
Gd 65
Tb 66
Dy
36
Kr
54
Xe
59
Pr
An
92
U 93
Np 94
Pu 95
Am 96
Cm
Critical
material at the
EU level
24 Cr
27 Co
4
Be
12
Mg
41
Nb
74
W
5
B
31
Ga
49
In
9
F
57
La 58
Ce 60
Nd 61
Pm 62
Sm 63
Eu 64
Gd 65
Tb 66
Dy 59
Pr
44
Ru
76
Os
45
Rh
77
Ir
46
Pd
78
Pt
32
Ge
51
Sb
67
Ho 68
Er 69
Tm 70
Yb 71
Lu
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016 11
Could we recycle
the critical raw materials which
are present within spent
nuclear fuels?
Is there any interest to recover
CRM from spent fuel?
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Aim of this study: assess whether critical materials
from SNF are worth to be recycled?
1st step: Identify the elements of interest based on the available
inventory in SNF compared to the industrials needs: − Accessible critical materials inventory is calculated based on the current French recycling strategy:
Recycling of the 1150t of UOX SNF yearly discharged in France, with an average
burnup of 47,5 GWd/t and after 10y. of cooling time.
Inventory calculated based on the DARWING2.3 code with the JEFF3.1.1
database
− World critical material needs based on the 2013 annual production − French critical material need derived from the world need based on the French contribution to the World GDP (IMF, 2009)
2nd step: Identify their residual radioactivity activity as a function
of time: − Identification of the various isotopes and calculations of their decay chain
3rd step: Checking the feasibility of their chemical separation: − Assessment of the feasibility of the critical materials separation based on the current available knowledge
Description of the methodology
12
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
1st potential target: rare earth elements
(REE)
13
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Are the REE resources in SNF relevant?
REE are present in significant inventory (16,5t) …
but this inventory is not relevant with the French or World need
(< 0,1 %)
Light REE
are the most
abundant …
but the less
critical!
Rare earth oxide 2013
demand (t)
Annual flux* (annual flux stable
isotopes) (kg)
Lanthanum 31700 2030 (2030)
Cerium 39850 3930 (2036)
Praséodymium 6075 1810 (1810)
Néodymium 18925 6720 (3562)
Samarium 730 1310 (673)
Europium 330 215 (193)
Gadolinium 1360 222 (219)
Terbium 255 238 (238)
Dysprosium 780 5 (5)
Total 100005 16480 (10765)
(* for UOX 47GWd/t)
14
% world demand (based on stable
isotopes)
"% French Demand
estimate based on GDP"
0.006% 0.138
0.005% 0.110
0.030% 0.642
0.019% 0.406
0.092% 1.987
0.058% 1.260
0.016% 0.347
0.093% 2.011
0.001% 0.014
0.011% 0.232
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
isotope abundances of the elements and associated
contribution to the actitivy
15
Weight % Activity % Weight % Activity % Weight % Activity %
Cerium Europium Galodinium
Ce140 51.738% Eu151 0.6% Gd153 1.8E-8% 96%
Ce142 48.260% Eu152 4E-3% Gd154 12.4%
Ce144 2E-3% 100% Eu153 89.2% Gd155 4.6%
Eu154 8.8% 77% Gd156 66.7%
Praseodimium Eu155 1.4% 23% Gd157 0.1%
Pr141 100.0% Gd158 14.7%
Pr144F 1.4E-7% 99% Neodymium Gd159 1.4E-12% 2%
Pr144M 7.9E-10% 1% Nd142 0.6% Gd160 1.4%
Nd143 18.6%
Samarium Nd144 33.5% Dysprosium
Sm147 28.7% Nd145 16.3% Dy160 12.3%
Sm148 18.5% Nd146 17.6% Dy161 28.4%
Sm149 0.3% Nd147 1.7E-11% 36% Dy162 29.7%
Sm150 35.2% Nd148 9.2% Dy163 22.7%
Sm151 1.2% 100% Nd149 1e-13% 33% Dy164 6.8%
Sm152 11.7% Nd150 4.3% Dy165 3.9E-13% 51%
Sm154 4.5% Nd151 5.3E-15% 14% Dy165M 9.3E-17% 1%
Sm155 26.8% Nd152 3.3E-15% 9% Dy166 7.3E-12% 27%
Nd153 9.6E-17% 6% Dy167 4.5E-15% 13%
Nd154 3.0E-17% 2% Dy168 2.7E-15% 6%
Dy169 5.7E-17% 2%
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
What about their radioactivity?
REE radioactivity:
− All the REE have radioactive isotopes, often at trace concentrations −However, residual specific activity remains high:
o 0,0016% 144Ce (T1/2=284 d.) activity of Ce: 2 TBq/kg after purification
o 1.15% 151Sm (T1/2=88 y.) responsible for the activity of Sm
Separation : − separation processes could be easily developed thanks to the R&D conducted for the separation of the minor actinides for P&T
Activities, Bq per g of critical materials (and % of the French need)
La
(0,1%)
Ce
(0,2%)
Pr
(0,7%)
Nd
(0,7%)
Sm
(1,1%)
Eu
(0,9%)
Gd
(0,2%)
t0 2.104 2.109 4.109 1,5 103 1.1010 2.1012 2,4.1004
10 y. 1,7 102 5.105 10-3 4.10-1 1.1010 4,6.1011 6,6.10-1
20 y. 1,7 102 70 10-4 5 10-2 9,6.109 2.1011 1,9.10-5
30 y. 1,7 102 9.10-3 7.10-6 1,7 10-2 8,9.109 8,6.1010 5,4.10-10
40 y. 1,7 102 1.10-6 5.10-7 1,5 10-2 8,2.109 3,8.1010 << 10-10
50 y. 1,7 102 2 10-10 3.10-8 1,5 10-2 7,6.109 1,7.1010 << 10-10
16
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
2nd potential target: Platinoids groupe
metals (PGM)
http://www.platinum.matthey.com/
services/market-research/
17
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Are the PGM resources in SNF relevant?
PGM resources are relevant compared to the world need
World production
2008 (t)
Annual flux* (stable
isotopes) (kg)
% world production
2008
% French production
derived from GDP ratio
Palladium 200 2393 (1938) 1,2% ~25%
Ruthénium 17 3678 (3677) 21,6% ~450%
Rhodium 21,5 730 (730) 3,4% ~75%
http://www.platinum.matthey.com/services/
market-research/market-data-
charts/palladium
* For UOX 47GWd/t
18
YES !
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Are the PGM resources in SNF relevant?
Radiological specific activities:
−Rh : 35.10-6 % of 102Rh (T1/2=209 d.)
−Ru : 0,007 % of 106Ru
−Pd : 15 % of long-lived 107Pd
106Ru ~1014 Bq/g
106Rh ~1020 Bq/g
106Pd Stable
T1/2=29s T1/2=1 y.
107Pd ~107 Bq/g
T1/2=6,106a 107Ag stable
Only Ru and Rh are of potential interest although radioactive
Activités, Bq per g of critical material
Pd Rh Ru
t0 3.106 4.1010 8.109
10 y. 3.106 2.104 2.106
20 y. 3.106 2.103 2.103
30 y. 3.106 102 2
40 y. 3.106 101 2.10-3
50 y. 3.106 1 2.10-6
http://www.platinum.matthey.com/services/
market-research/market-data-
charts/palladium
19
Weight % Activity % Weight % Activity % Weight % Activity %
Palladium Ruthenium Rhodium
Pd104 17.3% Ru100 4.8% Rh103 100.0%
Pd105 28.3% Ru101 35.0% Rh106 3.1E-8% 100%
Pd106 25.0% Ru102 35.7%
Pd107 15.4% 100% Ru104 24.4%
Pd108 10.3% Ru106 6.7E-3% 100%
Pd110 3.6%
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Could we easily separate them from SNF?
2 main issues are associated to the PGM separation:
− Their specific location within SNF pellets:
− mainly located in metallic precipitates (epsilon particles) requires specific digestion processes to have access to them:
− Separation: no dedicated separation processes currently available for these elements in nitric media
− Highly complex aqueous chemistry (in particular for Ru) − For metallic fines, both pyro or hydro processes could be of interest, but much wider experience available for hydro. − For hydro separation processes,
− selective extracting molecules already available: organophosphines (Cyanex), quaternary ammonium salts … − very efficicient processes able to reach high decontamination level (FD > 108).
20
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
What about their potential declassification and
subsequent use?
Using critical materials from SNF requires their possible declassification
from nuclear materials
o No existing threshold in France
o Limited industrial experiences
• Pb recycling (D'Huart Industrie) : threshold = 0,5 Bq/g (U)
• Metals recycling (Feursmetal) : threshold = 1 Bq/g (U)
Declassification threshold proposed by IAEA (Tecdoc-1000, 1998) :
REE threshold
(Er, Pm)
~104 Bq/g
Transition metals
threshold (Mo, Tc)
~102 - 104 Bq/g
21
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
Conclusion on the French case
The recycling of 3 potential metals can be of interest :
− Ruthenium : potentially usable after ~ 25 years of decay storage,
production of 3,7 t/y. (19 % of annual world production), very fluctuating
price: from 50 to 500 k€/kg
Potential interest (resource, cost…) but separation processes to be
developed + decay storage to be organised.
− Rhodium : potentially usable after ~ 20 years of decay storage,
production of 740 kg/y. (~ 3 % of annual world production), price ~60 k€/kg
Potential interest
− Light REE: inventory very low compared to the industrial need
separation costs >> economic values (25 €/kg)
No interest
One of the major issue = accepting to use materials coming from past SNF in
non-nuclear activities ensure the traceability and the safety
22
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
What about the critical materials inventory
available in SNF at the EU level?
In Western Europe, it is
estimated that 30000
tons of SNF will have
been produced in 2020
(Based on average
burn-up of 33MWd/t)
World
production
2008 (t)
From 30kton
of SNF
% world
production
2008
Palladium 200 35503 18%
Ruthénium 17 67361 396%
Rhodium 21.5 13371 62%
Rare earth
oxide 2013
demand (t) From 30kton of
SNF (kg) % world
demand
Lanthanum 31700 37178 0,12% Cerium 39850 37287 0,09% Praséodymium 6075 33152 0,55% Néodymium 18925 65235 0,34% Samarium 730 12333 1,69% Europium 330 3536 1,07% Gadolinium 1360 4007 0,29% Terbium 255 4360 1,71% Dysprosium 780 91 0,01% Total 100005 197181 0,20%
23
REE
PGM
Inventory
available in SNF
may allow us to
overcome any
potential crisis the
EU level
Nuclear Energy Division – Marcoule -
RadioChemistry & Processes Department
TM on AFC for WBM,
Vienna, 2016
But…
recovering these elements would only be worth to be
implemented if uranium and plutonium are also recycled for
nuclear electricity production in order to share the treatment cost.
It is hence mainly relevant for countries which already recycle or
plan to recycle nuclear materials, such as France, UK, Japan,
and in the future China.
Apart of the residual radioactivity of the recovered elements and
whatever the dose rate, re-using materials produced by the
nuclear industry in non-nuclear applications will always remain a
political issue, driven by rules or laws, sometimes irrational, but
this is another debate.
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