Advanced Nuclear Fuel Cycles

(Advanced) nuclear fuel cycles
© Thomas Cardinaels, academic year 2018-2019
• Reprocessing?
• PUREX?
• Partitioning?
• Transmutation?
• SANEX? GANEX? EXAm?
• Belgium?
© Thomas Cardinaels, academic year 2018-2019
Nuclear fuel cycle
3 © Thomas Cardinaels, academic year 2018-2019
Nuclear fuel

Nuclear fuel
 Nuclear fuel = fuel for nuclear reactors
 Specific per reactor type
 UO2 mostly used
 Pellet form
Fuel rods
 Pellets loaded into tubes (L = 4 m, D = 1 cm) called “cladding“

= fuel rod or fuel pin
 Spring inserted at end of fuel pin and put under ca. 20 bar He gas
Source: I. Crossland, “Nuclear Fuel Cycle Science and Engineering”

Fuel element
 Fuel element or fuel assembly = skeleton with fuel rods
 Fuel element contains few hundred fuel needles

(typically 17x17 for a PWR reactor)
Reactor core
 Reactor core
 ca. 100-200 fuel elements
 ca. 40 000 fuel rods
 ca. 16 000 000 fuel pellets
 ca. 100 tonnes of uranium dioxide (ca. 88% uranium)

Reactor
Nuclear fission reaction
 Fission energy ≈ 200 MeV

 2-3 energetic fragments created
 2-3 fast neutrons released
FISSION
Neutron
Nucleus
Deformed Fast
excited Highly neutrons
nucleus deformed
nucleus at Fission
saddle point products

Nuclear versus fossil fuels
1000 kWh is equivalent to
Factor 100 000!!
350 kg coal 250 L oil
1 pellet  7 g  2000 kWh

2 pellets  4000 kWh
300 m3 natural gas 3 g of 4% enriched U
Note: average annual household electricity consumption = ca. 3500 kWh!

Irradiation of nuclear fuel
1. Consumption of fissile nuclides:

235U and fissile Pu isotopes are “burned”
2. Formation of transuranium elements by neutron

absorption of 238U: Np, Pu, Am, Cm
3. Formation of fission products

Spent fuel
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 2
1
H He
3 4 5 6 7 8 9 10
2
Li Be B C N O F Ne
Heavy nuclei
11 12 13 14 15 16 17 18
3
Na Mg Al Si P S Cl Ar
Fission products
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 Long-living
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 radionuclides
5
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Activation products
55 56 57-71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Fission and activation
Cs Ba Ln Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89-103 104 105 106 107 108 109 110 111 products
7
Fr Ra An Rf Db Sg Bh Hs Mt Ds Rg
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ln
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
An
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Reprocessing

Reprocessing
 Chemical recycling of uranium and plutonium is very complex
 Main restrictions
 Cladding inert to most chemical reagents
 Very high radioactivity of spent nuclear fuel: special working conditions
 Large amount of fissile materials: special safety measures (criticality)
 Emission of radioactive materials: below legal criteria
Reprocessing
 Steps in reprocessing
1. Cladding removal (“decladding”) and fuel dissolution
2. Separation of U and Pu from fission products (FP) and minor actinides (MA)
3. Separation of U and Pu followed by purification
 PUREX = Plutonium Uranium Redox Extraction process

 Most applied process on industrial scale
 U and Pu recovered with industrial yield of ca. 99.9%
 La Hague: largest reprocessing plant in world with capacity of

ca. 1700 tonnes per year

PUREX process
 Basics = solvent extraction combined with redox reactions
 Organic extraction agent = 30% tri-n-butyl phosphate (TBP) in kerosene
 Water phase = HNO3
 High concentration of HNO3

 KD is high only for An(IV) and An (VI), not for An in other oxidation states
 KD < 0.01 for most FP
 U and Pu selectively extracted by TBP
 FP and MA remain in water phase
 Low concentration of HNO3

 KD < 1 for An in all oxidation states
 U and Pu back-extracted (= stripped) to water phase
PUREX process

PUREX process chemistry
 Lighter An (Ac-Pu) have multiple oxidation states available in

aqueous solution
 PUREX process makes use of this to separate U and Pu from
fission products and MA
Source: H.C. Aspinall, “Chemistry of the f-block Elements”

PUREX process chemistry
 TBP is neutral extractant and only electro-neutral complexes are

extracted into organic phase via solvation
 Equilibrium: Anx+ + xNO3- + nTBP ↔ An(NO3)x(TBP)n
 Equilibrium constant KE = [An(NO3)x(TBP)n]/[Anx+][NO3-]x[TBP]n
 Distribution constant KD = [An]org/[An]aq = KE[NO3-]x[TBP]n
 Extraction of An can be tuned by [NO3-] (“salting effect”)
 Only An(IV) and An (VI) are extracted

 An4+ + 4NO3- + 2TBP ↔ An(NO3)4(TBP)2
 AnO22+ + 2NO3- + 2TBP ↔ AnO2(NO3)2(TBP)2
 All other species are rejected: AnO2+and An3+

TBP
Mx+
Control of valence states of An
 U not problematic and exists in hexavalent state (UO22+)
 Pu brought to its most extractable tetravalent state via NaNO2

 PuO22+ + NO2- + 2H+ ↔ Pu4+ + NO3- + H2O
 Np exists mainly in (non-extractable) pentavalent state BUT

 Np(V)/Np(VI) equilibrium in nitric acid
 2Np5+ + NO3- + 3H+ ↔ 2Np6+ + HNO2 + H2O
 Np(V) oxidized into Np(VI) by nitrite (NO2-)
 Np5+ + NO2- + H+ ↔ Np6+ + NO + H2O
 Np(V) disproportionates in Np(IV) and Np(VI) in acid conditions
 Np5+ ↔ Np4+ + Np6+
 Np contamination in recycled U and Pu streams
 Am and Cm exist in (non-extractable) trivalent state

Distribution ratios
 Extraction of An by TBP dependant on [HNO3] due to salting out

effect (nitric acid = salting agent)
D high only for An(IV) and An(VI) U4+ < Np4+ < Pu4+ UO22+ > NpO22+ > PuO22+
Reduction of Pu
 To remove Pu from organic phase Pu(IV) is reduced to

(non-extractable) Pu(III) using reducing agent
 Reducing agents: ferrous sulfamate (Fe(NH2SO3)2) , uranium(IV),

hydroxylamine (NH2OH)
 Reduction via ferrous sulfamate

 Pu4+ + Fe2+ + NH2SO3- ↔ Pu3+ + Fe3+ + NH2SO3-
 Sulfamate is nitrite suppressor minimizing oxidation of Fe(II) and Pu(III)
 NH2SO3- + NO2- ↔ N2 + SO42- + H2O
 Fe2+ + NO2- + H+ ↔ Fe3+ + NO + H2O
 Pu3+ + NO2- + H+ ↔ Pu4+ + NO + H2O
 But: introduction of Fe into the system

Reduction of Pu
 Reduction via U(IV)

 2Pu4+ + U4+ + 2H2O ↔ 2Pu3+ + UO22+ + 4H+
 But: Pu(III) is unstable in HNO3 due to the presence of nitrite
 Hydrazine is added as stabilizer (HNO2 getter):
2HNO2 + N2H4 ↔ N2 + N2O + 3H2O
 Reduction via hydroxylamine

 Hydroxylamine is both reductant and nitrite suppressor
 4Pu4+ + 2NH3OH+ ↔ 4Pu3+ + H2O + N2O + 6H+
 NH3OH+ + NO2- ↔ N2O + 2H2O
 Pu(IV) reduction into Pu(III) leaves U(VI) unaffected

 Pu(III) can be selectively back-extracted to aqueous phase
PUREX step 1: extraction of U and Pu
UO22+ + 2NO3– + 2TBP → UO2(NO3)2 · 2TBP

Pu4+ + 4NO3– + 2TBP → Pu(NO3)4 · 2TBP

PUREX step 1: extraction of U and Pu
Scrubbing with 2 M HNO3

Extraction of U and Pu by TBP
to remove co-extracted FP
[HNO3] = 2-3 M
(e.g. Zr, Ru, Nb)
UO2 + 2NO3– + 2TBP → UO2(NO3)2 · 2TBP
2+
Pu4+ + 4NO3– + 2TBP → Pu(NO3)4 · 2TBP

PUREX step 2: separation of U and Pu
Scrubbing with Pu(IV) reduced to Pu(III)

TBP/kerosene to remove and back-extraction of
back-extracted U Pu to aqueous phase
Purification of Pu streams via

additional cycles of
solvent extraction & stripping

Stripping of U
Back-extraction of U
with 0.01 M HNO3 at
elevated
temperatures
Washing of solvent with

carbonate or hydroxide solution
to remove degradation
products
Purification of U streams via

additional cycles of
solvent extraction & stripping

Conversion of U and Pu
 Thermal denitration of uranyl nitrate into uranium trioxide

 UO2(NO3)2.6H2O  6H2O + UO3 + 2NO2 + ½O2 (T↑)
 Plutonium nitrate precipitated as oxalate or peroxide and

calcined to plutonium dioxide
 Plutonium oxalate route

 Pu4+ + 2H2C2O4 + 6H2O  Pu(C2O4)2.6H2O + 4H+
 Pu(C2O4)2.6H2O + O2  PuO2 + 6H2O + 4CO2 (T↑)
 Plutonium peroxide route

 2Pu4+ + 4H2O2  Pu2O7 + 8H+ + ½O2
 Pu2O7 + ½O2  2PuO2 (T↑)
Reprocessing plant in La Hague (France)
Mixed oxide (MOX) fuel

 PuO2 mixed with depleted UO2 (depleted stream enrichment

process) to form "Mixed OXide" (MOX) fuel
 Ca. 65% of plutonium is fissile  MOX fuel with 7-9% Pu is

equivalent to uranium fuel enriched to 3-5% 235U
 In reactor performance and behaviour of MOX fuel quite similar

to UO2 fuel
 Typically 1/3 of reactor core loaded with MOX fuel assemblies

Processing of radioactive waste
Processing of high-level waste
 High-level waste (HLW): FP + MA

 processed through vitrification
 Only 3% of total mass of spent fuel BUT accounts for 98-99% of

total radioactivity
 After processing intermediate storage for ca. 50 years before

final storage (cooling and decrease in radioactivity)

Vitrification process
CSD-V
Final disposal of radioactive waste

Belgian classification of conditioned
radioactive waste
CAT B: Heat production < 20 W/m3

CAT C: Heat production > 20 W/m3
t1/2 < 30 y
t1/2 > 30 y
Source: NIRAS
Final disposal of radioactive waste
 Storage should be safe in the long term:

“Isolate – Contain – Retard” principle
 CAT A
 Shielding from people and environment for
ca. 300 years = 10 x t1/2
 Surface disposal
 CAT B & CAT C

 Shielding for > 10 000 years
 Deep geological disposal
Source: NIRAS
Spent fuel in Belgium
 Nuclear energy in Belgium since 1975

 7 PWR reactors: 4 at Doel NPP, 3 at Tihange NPP
 Irradiated nuclear fuel
 < 1993: Reprocessing + reuse of Pu in MOX
 > 1993: No more reprocessing
 Projections at reactor EOL:
– 630 tHM irradiated fuel reprocessed ultimate
» 66 tHM irradiated MOX fuel waste
» 390 canisters (150 l) vitrified HLW
» 432 canisters (150 l) compacted MLW
– 4643 tHM irradiated UOX fuel (wet + dry storage)
 What to do with spent fuel?
 Management option has direct influence on amount and
radiotoxicity of final radioactive waste streams
Spent fuel management options
 Composition of SF after irradiation

 still high amount of fissile/fertile materials
 93.6% U
 1.0% Pu
 0.08% Np
 0.18% Am
 0.002% Cm
 Rest: ~5% fission and activation products
 Management options
 Direct disposal
 Classical reprocessing (partial or full)
 Reprocessing with advanced partitioning

Advanced nuclear fuel cycles
 Aim to improve sustainability of nuclear energy

 Reduce volume and long-term radioxicity of HLW
 Better use of natural resources (reduce footprint NE)
 Keep energy/electricity cost economically viable
 Societal acceptability
 Include advanced separation technologies (partitioning)

 Allow more optimal waste management policies
“Partitioning and Conditioning” (P&C)
 Allow burning of MAs (transmutation)
“Partitioning and Transmutation” (P&T)
Partitioning of MAs
250 000 y
Partitioning
MAs
10 000 y
FPs
300 y

Transmutation of MAs
 Nuclear transmutation: transformation of long-lived

radionuclides into short-lived/stable radionuclides nuclides by
irradiation
 Fast neutron spectrum required (no moderator)

 Fast reactors (FRs): critical reactors, no moderator; many concepts
 Accelerator Driven Systems (ADS): subcritical; accelerator +
spallation source
 P&T principle
 Partitioning = separation of MAs from spent fuel
 Transmutation = burning of MAs in FRs
Transmutation of MAs

MYRRHA
“Multi-purpose hYbrid Research Reactor for High-tech Applications”
Transmutation
Source: SCK•CEN
3 options for MA transmutation
 Europe is considering 2 approaches

 Via FR
 Via ADS
FR FR ADS
Heterogeneous Homogeneous
Driver fuel Fuel with MA Fuel with MA

Blanket with MA Blanket

Once-through fuel cycle
Source: OECD, “Advanced nuclear fuel cycles and radioactive waste management”
Twice-through fuel cycle

(conventional reprocessing)
Heterogeneous Am recycling
Double strata fuel cycle
Impact of advanced fuel cycles on
use of resources
 Natural U use for production of 1 TWh(e):
Fuel cycle A1 A2 A3 B1 B2
Nat. U consumption kg/TWh(e) 20723 18448 986 106 15766
normalised 1 0.89 0.048 0.0051 0.76
A1: open cycle PWR with UOX fuel

A2: mono-recycling of Pu as MOX in PWRs
A3: multi-recycling of Pu in Na-cooled FRs
B1: multi-recycling of Pu and MA in Na-cooled FRs
B2: double strata cycle of PWR’s and ADS
Source: Red-Impact comparative study


radiotoxicity (activity × dose factor ingestion)
 Radiotoxicity /10 if Pu is recycled (multi-recycling)

 Radiotoxicity /100 if Pu and MA are recycled

waste volumes
 Dimensions of waste packages as a basic overpack
TOTAL HLW (m3/TWhe) 3.86 2.13 1.27 1.21 1.41
relative TOTAL HLW (-) 1.00 0.55 0.33 0.31 0.37
TOTAL HLW + ILW (m3/TWhe) 3.86 4.62 6.57 6.50 4.75
relative HLW +ILW (-) 1.00 1.20 1.70 1.68 1.23
 Dimensions of waste packages as proposed by ONDRAF/NIRAS

(monoliths and supercontainers)
TOTAL HLW (m3/TWhe) 27.01 22.85 15.82 14.96 17.53
relative TOTAL HLW (-) 1.00 0.85 0.59 0.55 0.65
TOTAL HLW + ILW (m3/TWhe) 27.01 27.25 25.19 24.33 23.44
relative HLW +ILW (-) 1.00 1.01 0.93 0.90 0.87

repository footprint (HLW only)
 Only HLW considered (no ILW)
 Theoretical maximum disposal density
TOTAL HLW (m2/TWhe) 711 464 174 94 145
relative (-) 1.00 0.65 0.24 0.13 0.20
Factor ~10
 Variants of B1: Impact of separation of 137Cs and 90Sr:
 Hypotheses:
 Cs and Sr streams are individually vitrified (waste loading 60%)
 100 years decay storage
Fuel cycle B1.1 (40FP-60Cs-60Sr) B1.4 (60FP-60Cs-60Sr)
TOTAL HLW (m2/TWhe) 21.86 21.95
relative (-) 0.031 0.031

Factor ~30
Potential size reduction for Belgian geological repository
needed gallery length (km)
MA+FP P&T case based on extrapolations from Oigawa et al. 2006


environment
BACK-END
FRONT-END
Improve overall footprint  improve or reduce front-end activities

Source: C. Poinssot, Chair Roger Van Geen lectures
Main partitioning processes developed in EU
U,Np,
Pu,Am,
Cm U
PUREX
Pu
U GANEX 1
An(III) selective
stripping Am Cm
GANEX 2 (DIAMEX/SANEX)
Am selective
stripping Am
Np Pu Am Cm (EXAm)
Homogeneous recycling Heterogeneous recycling

= grouped separation = enhanced partitioning
GANEX DIAMEX/SANEX
Source: C. Poinssot, Chair Roger Van Geen lectures
Main partitioning processes developed in EU
 GANEX
 Homogeneous MA recycling route
 1st step: separation of U
 2nd step: co-extraction of TRU+Ln
 3rd step: selective stripping of TRU (transuranium elements)
 DIAMEX/SANEX
 Heterogeneous MA recycling route
 1st step (PUREX or COEX): separation of U+Pu
 2nd step (DIAMEX): co-extraction of MAs+Ln
 3rd step (SANEX): selective stripping of MAs
 EXAm
 Heterogeneous Am-only recycling route
 1st step (PUREX or COEX): separation of U+Pu
 2nd step: co-extraction of Am+light Ln
 3rd step: selective stripping of Am
DIAMEX/SANEX
heterogeneous recycling
An(III) + Ln(III) An(III)/Ln(III)

co-extraction separation Am Cm
(DIAMEX) (SANEX)
U,Np,
Pu,Am,
Cm
PUREX U Pu
DIAMEX chemistry
 “DIAMide Extraction” – processes using a diamide-based solvent

 Co-extraction of An(III) and Ln(III)
DMDBTDMA DMDOHEMA TODGA
Malonamides Diglycolamide

DIAMEX process
SANEX chemistry
 “Selective ActiNide EXtraction”

 Classic SANEX: extraction of Am(III) and Cm(III) from DIAMEX product
BTBP BTPhen BTP

 Innovative SANEX: integration of DIAMEX and SANEX into one process
SO3-Ph-BTP

SANEX process
GANEX
homogeneous recycling
U,Np,
Pu,Am,
Cm
U GANEX 1
GANEX 2
Np Pu Am Cm
GANEX 1 chemistry
 “Group ActiNide EXtraction”

 GANEX first cycle: uranium selective separation using N,N-
dialkylamide extractants
DEHiBA
GANEX 1 process

GANEX 2 chemistry
 GANEX second cycle: TRU group extraction

 Extraction
 TODGA: extracts An(III) and An(IV)
 DMDOHEMA: to avoid Pu precipitation (increase Pu loading
capacity)
 Stripping
 SO3-Ph-BTP: stripping of An(III)
 AHA (acetohydroxamic acid): stripping of Pu(IV), Np(IV), Np (VI)
extraction stripping
GANEX 2 process

References
 R. Taylor, “Reprocessing and Recycling of Spent Nuclear Fuel”

Advanced Nuclear Fuel Cycles

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Advanced Nuclear Fuel Cycles

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(Advanced) nuclear fuel cycles

© Thomas Cardinaels, academic year 2018-2019

• SANEX? GANEX? EXAm?

3 © Thomas Cardinaels, academic year 2018-2019

4 © Thomas Cardinaels, academic year 2018-2019

 Nuclear fuel = fuel for nuclear reactors

 Specific per reactor type

 UO2 mostly used

5 © Thomas Cardinaels, academic year 2018-2019

 Pellets loaded into tubes (L = 4 m, D = 1 cm) called “cladding“

Source: I. Crossland, “Nuclear Fuel Cycle Science and Engineering”

 Fuel element or fuel assembly = skeleton with fuel rods

 Fuel element contains few hundred fuel needles

7 © Thomas Cardinaels, academic year 2018-2019

8 © Thomas Cardinaels, academic year 2018-2019

9 © Thomas Cardinaels, academic year 2018-2019

Nuclear fission reaction

 Fission energy ≈ 200 MeV

10 © Thomas Cardinaels, academic year 2018-2019

1000 kWh is equivalent to

Factor 100 000!!

350 kg coal 250 L oil

1 pellet  7 g  2000 kWh

300 m3 natural gas 3 g of 4% enriched U

Note: average annual household electricity consumption = ca. 3500 kWh!

Irradiation of nuclear fuel

1. Consumption of fissile nuclides:

2. Formation of transuranium elements by neutron

3. Formation of fission products

12 © Thomas Cardinaels, academic year 2018-2019

13 © Thomas Cardinaels, academic year 2018-2019

14 © Thomas Cardinaels, academic year 2018-2019

 Chemical recycling of uranium and plutonium is very complex

15 © Thomas Cardinaels, academic year 2018-2019

 PUREX = Plutonium Uranium Redox Extraction process

 La Hague: largest reprocessing plant in world with capacity of

16 © Thomas Cardinaels, academic year 2018-2019

 Basics = solvent extraction combined with redox reactions

 Organic extraction agent = 30% tri-n-butyl phosphate (TBP) in kerosene

 Water phase = HNO3

 High concentration of HNO3

 Low concentration of HNO3

17 © Thomas Cardinaels, academic year 2018-2019

18 © Thomas Cardinaels, academic year 2018-2019

 Lighter An (Ac-Pu) have multiple oxidation states available in

Source: H.C. Aspinall, “Chemistry of the f-block Elements”

PUREX process chemistry

 TBP is neutral extractant and only electro-neutral complexes are

 Only An(IV) and An (VI) are extracted

20 © Thomas Cardinaels, academic year 2018-2019

21 © Thomas Cardinaels, academic year 2018-2019

Control of valence states of An

 U not problematic and exists in hexavalent state (UO22+)

 Pu brought to its most extractable tetravalent state via NaNO2

 Np exists mainly in (non-extractable) pentavalent state BUT

 Am and Cm exist in (non-extractable) trivalent state

22 © Thomas Cardinaels, academic year 2018-2019

 Extraction of An by TBP dependant on [HNO3] due to salting out

23 © Thomas Cardinaels, academic year 2018-2019

 To remove Pu from organic phase Pu(IV) is reduced to

 Reducing agents: ferrous sulfamate (Fe(NH2SO3)2) , uranium(IV),

 Reduction via ferrous sulfamate

24 © Thomas Cardinaels, academic year 2018-2019