could we recycle the critical raw materials which are ... · could we recycle the critical raw...

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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,

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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)

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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

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A very strong diversification of the raw materials

used: From XXth …

Elements used in early 1900's

Frequently used

Slightly used

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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

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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

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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)

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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)



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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

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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



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Could we recycle

the critical raw materials which

are present within spent

nuclear fuels?

Is there any interest to recover

CRM from spent fuel?



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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

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1st potential target: rare earth elements

(REE)

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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



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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%



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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

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2nd potential target: Platinoids groupe

metals (PGM)

http://www.platinum.matthey.com/

services/market-research/

17



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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 !



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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%



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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).

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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

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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

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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



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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.

24

Christophe POINSSOT, CEA Marcoule / Nuclear Energy Division (DEN)

Head of the RadioChemistry & Processes Department (DRCP)

Professor in Nuclear Chemistry, National Institute of Nuclear Science &

Technology (INSTN)

25

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