Nuclear Waste and Vitrification. Estremoz 2007 PDF

Marie Curie Summer School on Knowledge based Material
Estremoz Portugal 2007
Nuclear waste and vitrification

in France
Dr. Etienne Y. Vernaz,
Director of Research,
CEA / Nuclear Energy Division
Marcoule
Summary
Nuclear Energy
Fuel cycle
Fuel fabrication
Nuclear Reactor
Spent Fuel processing
Nuclear Waste
Waste treatment
Vitrification of nuclear waste
Waste Storage and Disposal
Etienne Y. Vernaz Nuclear waste and vitrification
Marie Curie Summer School Estremoz Portugal 2007,
Electricity production in France

78% nuclear
58 Pressurized Water Reactors (PWRs)
63 GWe installed
11% hydroelectric
10% thermal
<1% other
Very low greenhouse gas emission
Abundant electricity, stable cost, mature technology
French energy self-sufficiency: 50%
(DGMP figures: 2005)
Specific feature of nuclear power: concentrated energy

Energy produced by combustion of fossil fuel:
C + O2 CO2
H2 + O2 H2O
4.0 eV per atom of C

1.4 eV per atom of H
A few eV per atom of H or C

Energy produced by burnup of nuclear fuel (fission)
200 MeV per heavy atom
For the same mass, nuclear energy releases about one million times
more energy than chemical energy.
1 kg of oil (or 1 m3 of gas)
1 kg of natural uranium:
Power plant with U alone
Power plant with MOX
Fast breeder reactor
6 kWh
50 000 kWh
100 000 kWh
5 000 000 kWh
Specific feature of nuclear power: concentrated energy

The resulting waste mass is also reduced by the
same order of magnitude:
About 80% of French electricity is generated by nuclear
reactors, producing 1 kg of radioactive waste per person per
year, of which only 10 g consist of high-level long-lived waste.
This quantity can be compared with 10 000 kg of agricultural,
industrial or household waste produced per person per year in
France, about 100 kg of which are highly toxic.
In other words, the high-level waste arising from the electrical
consumption of one person throughout her entire life would fit
in a bottle of beer.
Advantages and drawbacks of concentrated energy
Concentrated energy production favors:

Competitiveness
Small volumes (materials, waste, transportation, etc.)
Controlled waste: insignificant release into the
environment (contrary to greenhouse gases)
But concentrated energy requires:

Intrinsically safe and controlled reactors
Highly processed nuclear fuel
High tech waste treatment
Each year a 1 GWe plant requires
GAS 1,8 billion m3

30 LNG tankers
OIL 1 300 000 metric tons

15 to 45 oil tankers
COAL 2 000 000 metric tons

600 trains
URANIUM (PWR) 150 t natural U

(20 t U enriched to 4%)
6 semisemi-trailers
Nuclear Fuel Cycle
Uranium Resources
An abondant resource
Largely spread on the earth ( 2 - 3 g/t )
Mainly two natural isotopes :
238 (99,28 %) fertile material
235 (0,718 %) fissile material
distributed well around the

world
Ultimate Resource ( < 130 $ / kg)

estimated at about 15 millions
tons
Uranium 2005 : Ressources, production et demande
World consomation ~68 000 t

Static reserves evaluated at 200 years
Mining and milling

Uranium is usually mined by
either surface or underground
mining techniques
the mined uranium ore is sent to
a mill which is usually located
close to the mine. At the mill the
ore is crushed and ground to a
fine slurry which is leached in
sulfuric acid to allow the
separation of uranium from the
waste rock. It is then recovered
from solution and precipitated as
uranium oxide concentrate
known as yellow cake ,
(ammonium diuranate(NH4)2 U2 O7)
10
Conversion and enrichment

The vast majority of all nuclear power reactors in operation and under
construction require enriched uranium fuel in which the proportion
of the U-235 isotope has been raised from the natural level of 0.7% to
about 3.5% or slightly more.
Because all the enrichment process work with gaseous uranium , the
first step is the conversion of yellow cake , into the uranium
hexafluoride (UF6), that is a gaz.
Two processes are used in the world for uranium enrichment :
Gazeous diffusion
Ultracentrifugation
1 kg of enriched Uranium (3.5%)

8kg of natural Uranium (0.7%)
7 kg of depleted uranium(0.25%)
11
Fuel fabrication
1.
Enriched UF6 is
converted to uranium
dioxide (UO2) and
pressed into small
pellets fritted at
1700C
2.
These ceramic pellets

are inserted into thin
tubes, of a zirconium
alloy (zircalloy) to form
fuel rods
3.
The rods are then

sealed and assembled in
clusters to form fuel
assemblies
Assemblage
FRAMATOME
12
Nuclear reactor
13
What is the difference between a nuclear

or a thermal power plant ?
Nuclear power plant (LWR)
Coal power plant in

Gardanne (France)
14
The major come of the way heat is produced to

make steam.
Steam Production
Electricity
Nuclear Reactor Heat Production

15
A nuclear reactor releases extremely small

amounts of radioactivity into the environment
Dismantling
Gaseous release
(about 100 times less radioactivity
than a coal-fired plant
of equivalent power ! ).
More than 99% of the

activity generated is
confined in the spent fuel
Solid waste
Reprocessing
< 100 m3 per year of LLW

ILW and HLW
16
What Nuclear material is produced in the reactor ?

Nuclear fission : A slow-moving
neutron is absorbed by the nucleus
of a uranium-235 atom, which in
turn splits into fast-moving lighter
elements (fission products) and
free neutrons.
Produce Fission Products ,

the main ultimum waste from
nuclear energy
Nuclear capture
For instance uranium-238 can
capture a neutron, transforms
into uranium-239, which
transform into plutonium-239
by 2 disintegrations
Produce Plutonium , and some

minor actinides that can be
consider as waste or as resources !
17
SPENT NUCLEAR FUEL

After 4 years in the reactor,
spent fuel contains:
94% uranium
1% plutonium
5% other
(Fission products
and minor actinides)
18
Elements formed in the spent fuel (burn-up 33 GWj/t)

U : 955 kg.t-1
Pu : 9.6 kg.t-1
AM : 0.8 kg.t-1
PF : 34 kg.t-1
H
3
Li
11
Be
12
Na Mg
19
K
37
Rb
55
20
Fr
22
Ca Sc
38
39
Sr
Y
Ln
57
La
89
ACTINIDES
Hf
104
Ra An
LANTHANIDES
Zr
72
88
Ac
23
Ti
40
56
Cs Ba
87
21
Rf
58
Ce
90
Th
24
V
41
25
Ta
105
27
Cr Mn Fe
42
43
Nb Mo Tc
73
26
74
W
106
75
44
Pr
91
Pa
60
Co
61
Ni
29
30
108
78
Ir
109
62
Pt
31
93
N
15
P
33
48
79
80
Au Hg
49
50
In
81
51
Sn Sb
82
Tl
Pb
83
Bi
F
17
S
34
Se
52
Cl
35
Po
A
36
Br
53
Te
84
Ne
18
Kr
54
Xe
85
86
At
Rn
110
64
65
95
96
97
Np Pu Am Cm Bk
66
67
68
98
Cf
99
69
70
Er Tm Yb
100
101
102
Es Fm Md No
URANIUM
AND
URANIUM
ETTRANSURANIC
LMENTS ELEMENTS
TRANSURANIENS
ACTIVATION PRODUCTS
PRODUITS
DACTIVATION
FISSION
PRODUCTS
PRODUITS
DE FISSION
FISSION AND DE
ACTIVATION
PRODUITS
FISSIONPRODUCTS
et DACTIVATION
10
O
16
Cu Zn Ga Ge As
47
Mt Uun
63
94
Si
32
Nd Pm Sm Eu Gd Tb Dy Ho
92
14
Al
46
77
13
Ru Rh Pd Ag Cd
76
Db Sg Bh Hs
59
He
5
28
45
Re Os
107
71
Lu
103
Lr
19
The Spent Fuel is store in a pool a few year

before processing
20
10
Spent fuel is reprocessed in the La Hague plants
UP2: EDF fuel:

800 t/year
UP3: Foreign fuel: 800 t/year
21
Main steps in reprocessing nuclear fuel

Cutting the fuel
assemblies
Disolving the fuel in nitric
acid
Liquide / liquide extraction

by TBP .
Uranium et Plutonium
recovered at 99,9 % !
dissolveur
roue
godets La
Hague
22
11
Reprocessed Uranium
The 235U content of

reprocessed uranium
is about the same as
natural uranium.
One part is recycled
in some nuclear
plants
One part is stored
as stratgic stock
waiting to be used in
fast breeder reactor
23
The recovered plutonium is recycled in MOX fuel
MOX fuel is a mixture

of plutonium oxide and
depleted uranium oxide
The MELOX plant at Marcoule
Recycling saves about 10% of the natural uranium
24
12
Nuclear Waste conditionning
25
Fission products solution vitrification :

a 50 years story !
The first part of the story is
solidification:
from a dispersible liquid to an
inert solid
First processes
developed in France
(1957), England and
USA were batch
processes
The first industrial
process (AVM) started
in Marcoule (France)
on 1978
Glass pouring in AVM
26
13
Why to vitrify the waste ?

The mission : Create a new material with a waste
9 Atomic scale containment (not a
coating)
9 Chemical flexibility
9 Stability, Durability (leaching
resistance)
Na
Al
Si
Zr
9 Volume reduction
9 Organic destruction
27
Complexity of fission products solutions

from LWR reprocessing
more than 40 different chemical elements !
Fission Products = 42.33 g/l

Se
Te
Ba
Ce
Rh
Sm
Cd
Rb
Y
Nb
Tc
Pd
Eu
In
Dy
Sb
Cs
La
Pr
Nd
Gd
Sn
Sr
Zr
Mo
Ru
Pm
Ag
Tb
Metallic Alloys = 4.69 g/l

Ru
Rh
Pd
Sn
Sb
Tc
Actinides = 3.37 g/l

U
Np
Am
Pu
Cm
Corrosion products and additives =

27.33 g/l
Fe
Mo
Na
Cr
Ni
28
14
How to formulate a HLW glass

Elaborate a glass from waste is a compromise
Ability to accomodate the waste
Solubility (Cr, Ru, Rh, Pd, Ce, Pu, SO4, Cl)
Phase separation (Mo, SO4, Cl, P)
Devitrification (Mo, P, F, Mg, )
Maximize the waste loading
Formulation
Process / Technology
Glass performance
Ease of processing
Melting temperature
Viscosity, reactivity, residence time,
Electrical cond., thermal cond.
Additives needed
Properties for storage/disposal

Thermal stability
Chemical durability
Resistance to self irradiation
Mechanical properties
29
GLASS FORMULATION MUST BE

TAILORED TO EACH APPLICATION
Oxide
France
R7/T7
SiO2
Na2O
Li2O + K2O
B2O3
CaO
Al2O3
Fe2O3 + NiO + Cr2O3
FP2O3 + Act
P2O5
ZrO2
45
10
2
14
4
5
4
15
0.3
1
47.0
8.5
4.0
17.2
Remainder
ZnO : 2.5
5.4
UK
0.9
14.9
USA
DWPF
WVDP
55.3
11.9
3.1
0.9
0.7
18.6
1
41.0
8.0
8.7
12.9
5.7
2.1
6.0
12.0
5.1
Hanford
AZ blend
50.3
13.2
1.6
10.4
0.2
7.4
10.7
1.0
0.5
20.0
1.3
5.0 incl.
2.8 incl.
2.7 incl.
ThO2 : 3.6
U3O8 : 2.3
U3O8 : 0.8
U3O8 : 0.6
Russia
Mayak
25
15
7
52
30
15
HLW-Glass formulation
The goal Solubilisation of all radionuclides in an ionic and covalent network by
chemical reactions at the molten state
Zr
Si
B
Na
A
l
Glass formulation = a mix of calculations and experimental measurements of

the basic properties to find the best compromise between contradictory
properties :
Homogeneity,
Viscosity
Electrical resistivity
Thermal conductivity
Devitrification sensitivity
Melting temperature,Tg, Tl,
Chemical durability, R0, Rf,
The design of an operational glass domain (for the industrial scale) is based on a
statistical design approach implemented at the lab scale and checked at scale
one on large pilots.
31
The R7T7 glass developed in France for LWR waste

Nominal
Composition
Specified
Interval
Mass (%)
min
max
SiO
45,1
42,4
51,7
B 2O
13,9
12,4
16,5
4,9
3,6
6,6
9,8
8,1
11,0
4,0
3,5
Al
Na
CaO
Fe
2,9
<4,5
0,4
<0,5
0,5
<0,6
NiO
Cr
P 2O
Li
4,8
0,3
ZnO
Ox(PF + Zr + actinides)
<1,0
2,0
1,6
2,5
2,2
2,4
2,8
12,8
4,2
18,5
+ Suspension de fines
Actinides Oxydes
SiO
+B
O 3 +Al
0,9
2
>60
32
16
Vitrification Principle
Solution
Objectif = Verre Final

45% SiO2
14% B2O3
10% Na2O
15% Ox. (PF+Act.)
Etc.
Calcination
Glass Frit
45% SiO2
18% B2O3
15% Na2O
Etc.
Calcinat
15% Ox. (PF+Act.)
FUSION
Verre Final
45% SiO2
14% B2O3
10% Na2O
15% Ox. (PF+Act.)
33
Chemical reactivity during melting

Glass Frit
Calcine
Impregnation
of the
Calcine
REE silicates
(Si, Ca, Nd, La,
Ce)
Partial dissolution
Local saturation
Crystal precipitation
Agitation
Pd
RuO2
Dilution
Crystal dissolution
(Ce,Zr)O2
Spinelles (Fe,
Ni, Cr, Mn)
Homogenization of
the molten liquid
GLASS
HT melting = RN solubilisation in a ionic and covalent network by chemical reactions at the molten state
34
17
The French Vitrification process

Liquid waste
Recycling
Additives
Calciner
Glass
frit
Glass
melter
Dust scrubber
Container
Two-step calciner / hot crucible vitrification process

35
La Hague Vitrification Plants
Hot cells vitrification lines
36
18
The Glass Container

Glass Volume
150 litres
Internationally
approved
Glass Mass
400 kg
Height
1,3 m
Thermal Power
~ 2 kw
Diameter
0,43 m
37
La Hague Glass interim storage

( air cooling )
air ambiant 25C
110C
45C
chemine 100C
stockage chaud
40C
38
19
Vitrified wasteforms are currently stored

at the production site
Marcoule
La Hague
Total number of glass containers produced in France > 13000

(18 000 t spent fuel)
39
The Near Term Future of Radwaste Vitrification

Increasing waste loading
Increasing glass throughputs
New matrix (glass-ceramics)
Higher Temprature, Corrosives glass compositions
Cold Crucible Induction Melter Technology

Cold
Cap
CCIM
Cold glass
layer
Inductor
Molten glass
40
20
Cold Crucible in Operation
41
The Emerging processes :

Plasma combustion & Vitrification
This process is a novel combination
of two innovative technologies:
Waste
+
Glass
precursor
Oxygen
Oxygen
VITRIFICATION:
Cathode
Anode
Glass melting by direct induction

in a metal cold crucible
COMBUSTION:
Oxygen arc plasma transferred
between two aerial torches above
the molten glass.
Burned
gases
exhaust
Metallic
Cooled
Plasma
walls
Molten
glass
HF
Current
Inductor
42
21
The EMERGING PROCESSES :

PLASMA COMBUSTION & VITRIFICATION
Ar/O2
Three Operations in one

Apparatus :
Waste
Ar/O2
Gas
treatment
Combustion/incineration.
Vitrification.
Gas postcombustion.
Glass
43
The three main waste conditionning

processes
1. Vitrification of Fission
product solution
2. Compaction
of cladding wastes (Hulls)
3. Cimentation of
technological waste
44
22
Cladding waste is compacted
45
Technological wastes are cemented

Most technological waste is LLW suitable for surface disposal
Some ILW is placed in interim storage at the production sites
1088
974
Heterogeneous solid waste
Homogeneous liquid or powdered waste
46
23
Ultimate reprocessing waste forms

The fission product solution, which
also contains the minor actinides
and about 0.1% U and Pu, is vitrified
The hulls and end pieces are rinsed

and then compacted
Technological waste is grouted

in cement
Today, the volume of

reprocessing waste produced
each year by a 1 GWe reactor is:
2.5 m3 HLW (glass)
5 m3 ILW (mainly compacted hulls)
12 m3 LLW (cemented)
47
Classification of solid nuclear waste in France

Nuclear waste are sorted over the period and the activity
Very low activity

(VLLW)
Short live
Longue Live
Period < 30 ans
Priode > 30 ans
1Dedicated surface
disposal (Morvilliers)
Mine residues
Low Activity (LLW)

Intermediate level
waste (ILW)
Stockage ddi
ltude pour les dchets
radifres et graphites
A - Waste
1Dedicated surface
disposal ( Soulaine )
High Activity (HLW)
B - waste :
Interim storage Interim

storage
C - Waste
Interim storage
48
24
Waste distribution by volume and activity
Type
vol%
Activity
Cumulative volume
(m3) until 2020
LLW
95%
<0.1%
1 200 000
ILW
4%
3%
55 000
HLW
0.3%
97%
3 600
A definitive industrial management route already exists

for about 95 % of the total waste volume produced.
49
LLW Disposal
Low-level waste is placed in surface storage
by ANDRA at the Soulaines center
in Northern France
The waste is compacted and packaged in drums
or metal containers, then immobilized in concrete
1.1 million m3
m3
With a capacity of 1 million

the Soulaines surface
repositoryinitially designed for 30 yearsis already
expected to last 60 years as a result of the two-fold volume
reduction of incoming waste over the last 15 years.
50
25
HLW and ILW Disposal

In France geological disposal is retained as reference solution
for the management of long life waste (ILW and HLW)
( french policy act n 2006-739 of June 29 ,2006)
Calendar :
2015 : safety assessment
deposit for a geological
disposal site
2020 : starting a prototype
reactor for transmutation
2025 : industrial opening of
underground disposal
51
Underground laboratory
An underground laboratory was built at at Bure (Northern France),
at a depth of 500 m in a clay formation
The clay layer investigated here has favorable properties for radioactive
waste containment:
- highly stable for the last 150 million years, unfractured
- very low permeability
- transport of chemical elements controlled by diffusion at an extremely low rate
52
26
Final conclusions
We know what to do with nuclear waste !
High tech processes have been developed and optimized
for each waste category
Vitrification of PF solution is a major step in this process
They are available today at affordable cost for society
This cost is taken into account in the price per kWh
and EDF has already constituted reserves
French and international studies have demonstrated
that with suitable processing the environmental impact of
nuclear waste will remain negligible, even over the long term
The CEAs considerable research potential ensures that
further progress will be made in the futur.
53
27

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Marie Curie Summer School on Knowledge based Material

Estremoz Portugal 2007

Nuclear waste and vitrification

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

Electricity production in France

Marie Curie Summer School Estremoz Portugal 2007,

Specific feature of nuclear power: concentrated energy

4.0 eV per atom of C

A few eV per atom of H or C

Marie Curie Summer School Estremoz Portugal 2007,

Specific feature of nuclear power: concentrated energy

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

Advantages and drawbacks of concentrated energy

Concentrated energy production favors:

But concentrated energy requires:

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

Each year a 1 GWe plant requires

GAS 1,8 billion m3

OIL 1 300 000 metric tons

COAL 2 000 000 metric tons

URANIUM (PWR) 150 t natural U

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

Nuclear Fuel Cycle

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

distributed well around the

Ultimate Resource ( < 130 $ / kg)

World consomation ~68 000 t

Marie Curie Summer School Estremoz Portugal 2007,

Mining and milling

Marie Curie Summer School Estremoz Portugal 2007,

Conversion and enrichment

1 kg of enriched Uranium (3.5%)

Marie Curie Summer School Estremoz Portugal 2007,

These ceramic pellets

The rods are then

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

Etienne Y. Vernaz Nuclear waste and vitrification

Marie Curie Summer School Estremoz Portugal 2007,

What is the difference between a nuclear

Nuclear power plant (LWR)

Etienne Y. Vernaz Nuclear waste and vitrification

Coal power plant in

Marie Curie Summer School Estremoz Portugal 2007,

The major come of the way heat is produced to

Nuclear Reactor Heat Production

Marie Curie Summer School Estremoz Portugal 2007,

A nuclear reactor releases extremely small

More than 99% of the

< 100 m3 per year of LLW

Marie Curie Summer School Estremoz Portugal 2007,

What Nuclear material is produced in the reactor ?

Produce Fission Products ,

Produce Plutonium , and some

SPENT NUCLEAR FUEL

Marie Curie Summer School Estremoz Portugal 2007,

Elements formed in the spent fuel (burn-up 33 GWj/t)