Tritium isotope separation

1. TRITIUM ISOTOPE SEPARATIONTRITIUM ISOTOPE SEPARATION
GHEORGHE VASARUGHEORGHE VASARU
ALEEA TARNITA, NR. 7, APT. 11ALEEA TARNITA, NR. 7, APT. 11
400659, CLUJ NAPOCA, ROMANIA400659, CLUJ NAPOCA, ROMANIA
E-mail: [email protected]: [email protected]

2. OUTLINEOUTLINE::
SOURCES OF TRITIUMSOURCES OF TRITIUM
PROCESSES AND PLANTS FOR PROCESSES AND PLANTS FOR
TRITIUM ISOTOPE SEPARATIONTRITIUM ISOTOPE SEPARATION

3. I. SOURCES OF TRITIUMI. SOURCES OF TRITIUM
Natural Sources:Natural Sources:
- Cosmic ray neutrons- Cosmic ray neutrons
- Solar protons- Solar protons

Artificial Sources:Artificial Sources:
A. Thermonuclear DetonationsA. Thermonuclear Detonations
B. Fission Nuclear ReactorsB. Fission Nuclear Reactors
- Light Water Reactors (LWR)- Light Water Reactors (LWR)
- Heavy-Water Reactors (HWR)- Heavy-Water Reactors (HWR)
- Tritium Emissions from Reactors- Tritium Emissions from Reactors
- Fuel-Reprocessing Plants- Fuel-Reprocessing Plants
C. Fusion Nuclear ReactorsC. Fusion Nuclear Reactors

4. II. SOURCES OF TRITIUMII. SOURCES OF TRITIUM
In fission reactors:In fission reactors:
- By deuterium activation: - By deuterium activation:
D(n,D(n,gg))T and H(n,))T and H(n,gg)D(n,)D(n,gg)T,)T,
Production: PWR: 10 Ci/GWe.year; Production: PWR: 10 Ci/GWe.year;
HWR: 30 - 40 kCi/GWe.year HWR: 30 - 40 kCi/GWe.year
- By ternary fission, - By ternary fission,
Production: 12 - 15 kCi/GWe.yearProduction: 12 - 15 kCi/GWe.year
- By boron activation: - By boron activation:
1010
B(n,2B(n,2aa)T and )T and
1010
B(n,B(n,aa))
77
Li(n,nLi(n,naa)T,)T,
Production: PWR: 1 – 1.5 kCi/GWe.yearProduction: PWR: 1 – 1.5 kCi/GWe.year
- By lithium activation: - By lithium activation:

66
Li(n,Li(n,aa)T, with thermal neutrons and)T, with thermal neutrons and

77
Li(n,nLi(n,naa)T, with fast neutrons, )T, with fast neutrons,
Production: 10 Ci/GWe.yearProduction: 10 Ci/GWe.year

5. III. SOURCES OF TRITIUMIII. SOURCES OF TRITIUM
In nuclear fuel reprocessing:In nuclear fuel reprocessing:
- For a PWR reactor of 1,000 MWe: - For a PWR reactor of 1,000 MWe:
655 Ci/t for UO655 Ci/t for UO
22 (liquid); (liquid);
- - In nuclear power station exists:In nuclear power station exists:
- high active liquid waste: > 10- high active liquid waste: > 10
-4-4
Ci/kg Ci/kg
- low active liquid waste: > 10- low active liquid waste: > 10
-4-4
Ci/kg Ci/kg
- mean activity waste (HTO): 10- mean activity waste (HTO): 10
-4-4
– 10 Ci/kg – 10 Ci/kg
- by purification: 10- by purification: 10
-8-8
Ci/kg Ci/kg
Admitted activity in drink water: 10Admitted activity in drink water: 10
-10-10
Ci/kg Ci/kg

6. Tritium yields for a 3Tritium yields for a 3,,000 MW000 MW((tt))
reactor (Ci/day). reactor (Ci/day).
TThermal fission, hermal fission,
235235
U U 50 50
Reactivity control (chemical shims), PWR: Reactivity control (chemical shims), PWR: 10-60 10-60
Reactivity control (chemical shims), BWR: Reactivity control (chemical shims), BWR: 2-15 2-15
1 ppm Li impurity in primary system: 1 ppm Li impurity in primary system: 25 25
Deuterium in light water (assumes doubling of natural D Deuterium in light water (assumes doubling of natural D
content by n reactions with light water): content by n reactions with light water): 0.03 0.03
Heavy water moderated reactor, HWR: Heavy water moderated reactor, HWR: 80-150 80-150
Fast breeder reactor, FBR: Fast breeder reactor, FBR: 50-100 50-100
Controlled thermal fusion reactor, CTR: Controlled thermal fusion reactor, CTR: 106-107106-107
--------------------------
SourceSource: Burger, L.L., The separation of hydrogen isotopes, State-of-the art study,: Burger, L.L., The separation of hydrogen isotopes, State-of-the art study,
Battelle Pacific Northwest Labs., 1972Battelle Pacific Northwest Labs., 1972

7. I. BASIC FACTS ABOUT TRITIUMI. BASIC FACTS ABOUT TRITIUM
There are three isotopes of hydrogen:There are three isotopes of hydrogen:
- a protium nucleus has one proton and no neutrons- a protium nucleus has one proton and no neutrons
- a deuterium nucleus has one proton and one neutron- a deuterium nucleus has one proton and one neutron
- a tritium nucleus has one proton and two neutrons- a tritium nucleus has one proton and two neutrons
Tritium decays to Tritium decays to
33
He + beta + neutrinoHe + beta + neutrino
Half-Life:Half-Life:
(DOE 5630.9) = 12.323 ± 0.004 years = 4500.88 ± 1.46 days(DOE 5630.9) = 12.323 ± 0.004 years = 4500.88 ± 1.46 days
(Mound) = 12.3232 ± 0.0043 years = 4500.96 ± 1.57 days(Mound) = 12.3232 ± 0.0043 years = 4500.96 ± 1.57 days
1 year = 365.2425 days 1 year = 365.2425 days
Tritium Decay Factor = 0.99984601/dayTritium Decay Factor = 0.99984601/day
Energy of decay, dissociation, ionization:Energy of decay, dissociation, ionization:
(E(E
maxmax) = 18.6 keV) = 18.6 keV
(E(E
meanmean) = 5.69 keV) = 5.69 keV
Dissociation energy, TDissociation energy, T
22 to 2T = 4.59 eV to 2T = 4.59 eV
Ionization energy, T to TIonization energy, T to T
++
+ e + e
--
= 13.55 eV = 13.55 eV
Energy to break T bond = 3.858 eV/moleculeEnergy to break T bond = 3.858 eV/molecule

8. II. BASIC FACTS ABOUT TRITIUMII. BASIC FACTS ABOUT TRITIUM
MiscellaneousMiscellaneous
1 Ci T1 Ci T
22 gas at STP = 0.386 ml gas at STP = 0.386 ml
1 gram T1 gram T
22 gas at STP = 9,619 Ci gas at STP = 9,619 Ci
1 gram T1 gram T
22 gas at STP = 3.71579 liter gas at STP = 3.71579 liter
1 ml T1 ml T
22 gas at STP = 2.589 Ci gas at STP = 2.589 Ci
1 ml T1 ml T
22O (tritiated water) = 3,200 CiO (tritiated water) = 3,200 Ci
1 liter T1 liter T
22 gas at STP = 2,589 Ci gas at STP = 2,589 Ci
1 liter T1 liter T
22 gas at STP = 0.269122 gram gas at STP = 0.269122 gram
1 ppm of T1 ppm of T
22 gas at STP = 2.589 Ci/m gas at STP = 2.589 Ci/m
33
Atomic Weight = 3.01605Atomic Weight = 3.01605
Molecular Weight = 6.0321Molecular Weight = 6.0321
----------------------------
SourceSource: Internet: Internet
Boiling points:
H
2
: 20.39 K
HD: 22.14 K
HT: 22.92 K
D
2
: 23.66 K
DT: 24.38 K
T
2
: 25.04 K

9. TRITIUM ISOTOPE SEPARATIONTRITIUM ISOTOPE SEPARATION
General Purposes:General Purposes:
- Removal of tritium from Light Water Reactors (LWR)- Removal of tritium from Light Water Reactors (LWR)
- Removal of tritium from Heavy Water Reactors (HWR)- Removal of tritium from Heavy Water Reactors (HWR)
- Removal of tritium from reprocessing plants- Removal of tritium from reprocessing plants
- Purification of deuterium and tritium to be used as - Purification of deuterium and tritium to be used as
fuels in fusion reactorsfuels in fusion reactors

10. SEPARATION FACTOR FOR SOME SEPARATION FACTOR FOR SOME
METHODS FOR TRITIUM SEPARATIONMETHODS FOR TRITIUM SEPARATION

Methods Methods Separation factor Separation factor

Diffusion and membranes processes: Diffusion and membranes processes: ca. 1.6 2. ca. 1.6 2.
Ultracentrifuge and separation nozzle:Ultracentrifuge and separation nozzle: ? ?
Laser excitation: Laser excitation: 1010
4 4
Adsorption processes: Adsorption processes: ca. 1.4 ca. 1.4
HH
22S, NHS, NH
33 and methylamine exchange processes: and methylamine exchange processes: 0.3 - 3 0.3 - 3
Rectification (distillation) as HTO:Rectification (distillation) as HTO: 1.05. 1.05.
Catalytic exchange: Catalytic exchange:
– in the gas phase as HT: in the gas phase as HT: 4.50 4.50
– in the vapour phase as HTO: in the vapour phase as HTO: 0.40 0.40
– in the liquid phase as HTO: in the liquid phase as HTO: 0.20 0.20
Electrolysis as HTO: Electrolysis as HTO: ca. 10 ca. 10
Low-temperature rectification as HT: Low-temperature rectification as HT: 1.801.80
----------------------------
SourceSource: Specht, S. et al.,: Specht, S. et al., Kerntechnik, 54 4 263 1989Kerntechnik, 54 4 263 1989

11. I. ENRICHMENT OF TRITIUM FOR I. ENRICHMENT OF TRITIUM FOR
ANALYTICAL PURPOSESANALYTICAL PURPOSES

Water Electrolysis (Groningen)Water Electrolysis (Groningen)
Water DistillationWater Distillation
Thermal Diffusion (Los Alamos, Mainz, Heidelberg, Thermal Diffusion (Los Alamos, Mainz, Heidelberg,
Johannesburg, Darmstadt, Saclay, Marcoule)Johannesburg, Darmstadt, Saclay, Marcoule)
Permeation through Membranes (Chalk River)Permeation through Membranes (Chalk River)
Adsorption and Chromatography (Julich)Adsorption and Chromatography (Julich)

12. WWATER ELECTROLYSISATER ELECTROLYSIS
The enrichment of tritium by electrolysis of water is a relatively simple method. The enrichment of tritium by electrolysis of water is a relatively simple method.
The process requires little sample handling and supervision during enrichment. The process requires little sample handling and supervision during enrichment.
The simultaneous enrichment of a series of samples is easily feasible from a The simultaneous enrichment of a series of samples is easily feasible from a
technical point of view and has the advantage that standard and background technical point of view and has the advantage that standard and background
samples can be run together with the unknown samples under (almost) samples can be run together with the unknown samples under (almost)
identical conditions.identical conditions.
The enriched effect of the processThe enriched effect of the process
HTO HTO  HT + 1/2 O HT + 1/2 O
22
HT + HHT + H
22O O «« HTO + H HTO + H
22
is based on the higher precipitation velocity of the lighter hydrogen isotopes is based on the higher precipitation velocity of the lighter hydrogen isotopes
(protium and deuterium) as compared to tritium(protium and deuterium) as compared to tritium.. With smaller current densities With smaller current densities
the separation factor is determined solely by the equilibrium constant of thethe separation factor is determined solely by the equilibrium constant of the
exchange equilibrium, which adjusts itself to the catalytic electrode where the exchange equilibrium, which adjusts itself to the catalytic electrode where the
hydrogen is in equilibrium with the surrounding water.hydrogen is in equilibrium with the surrounding water.
Hydrogen, produced by electrolysis of water, is depleted in the heavy isotopes Hydrogen, produced by electrolysis of water, is depleted in the heavy isotopes
(D and T). Consequently, the tritium concentration in the residual water (D and T). Consequently, the tritium concentration in the residual water
increases. If we are able to express the ratio of final to initial tritium increases. If we are able to express the ratio of final to initial tritium
concentration, defined as enrichment factor E, in measurable quantities, we can concentration, defined as enrichment factor E, in measurable quantities, we can
calculate the initial specific activity of the sample by measuring the enriched calculate the initial specific activity of the sample by measuring the enriched
waterwater

13. WATER ELECTROLYSISWATER ELECTROLYSIS (CONT’D)(CONT’D)
Nominal enrichment runNominal enrichment run
Sample charge Sample charge 246 g 246 g
NaOH solution added NaOH solution added 3 ml 3 ml
water water 3 g 3 g
NaNa
22O: O: 1 g 1 g
Current: Current: 10 A 10 A
Time: Time: 4,038 min4,038 min
Cooling bath temperature: Cooling bath temperature: -2-2
oo
C C
Temperature of electrolyte: Temperature of electrolyte: 0 - 80 - 8
oo
C C
Removed water: Removed water:
- by decomposition:- by decomposition: 225 g 225 g
- by evaporation: - by evaporation: 2.58 g 2.58 g
- by spray: - by spray: 0.06 g 0.06 g
Volume concentration: Volume concentration: 11.7 11.7
Enrichment factor for tritium:Enrichment factor for tritium: 10.7 10.7
Recovery for tritium: Recovery for tritium: 0.93 0.93
------------------------
Source: Groeneveld, D.J., Thesis, Groningen, 1977Source: Groeneveld, D.J., Thesis, Groningen, 1977

14. II. METHODS FOR RECOVERY AND II. METHODS FOR RECOVERY AND
ENRICHMENT OF TRITIUM FROM ENRICHMENT OF TRITIUM FROM
NUCLEAR PLANTSNUCLEAR PLANTS

..Water Distillation (Nagoya, Sulzer - Switzerland),Water Distillation (Nagoya, Sulzer - Switzerland),
Hydrogen Distillation (Grenoble)Hydrogen Distillation (Grenoble)
Water ElectrolysisWater Electrolysis
Chemical Exchange (RIKEN - Tokyo)Chemical Exchange (RIKEN - Tokyo)
Vapour Phase Catalytic Exchange & Cryogenic Distillation (VPCE - CD)Vapour Phase Catalytic Exchange & Cryogenic Distillation (VPCE - CD)
(Sulzer Tritium Extraction Plant-Grenoble, Sulzer Tritium Removal Facility /TRF/ (Sulzer Tritium Extraction Plant-Grenoble, Sulzer Tritium Removal Facility /TRF/
- Ontario Hydro, Darlington - Canada)- Ontario Hydro, Darlington - Canada)
Liquid Phase Catalytic Exchange & Cryogenic Distillation (LPCE - CD)Liquid Phase Catalytic Exchange & Cryogenic Distillation (LPCE - CD)
(Chalk River - Canada)(Chalk River - Canada)
Combined Electrolysis Catalytic Exchange & Cryogenic Distillation (CECE - Combined Electrolysis Catalytic Exchange & Cryogenic Distillation (CECE -
CD), (Chalk River-Canada, Mound - Miamisburg, Karlsruhe)CD), (Chalk River-Canada, Mound - Miamisburg, Karlsruhe)
Direct Electrolysis & Cryogenic Distillation (DE - CD)Direct Electrolysis & Cryogenic Distillation (DE - CD)
Combined Electrolysis Catalytic Exchange (CECE), (Mound Laboratory, Combined Electrolysis Catalytic Exchange (CECE), (Mound Laboratory,
Miamisburg, ELEX Process in Belgium, Tsuruga, Karlsruhe,Miamisburg, ELEX Process in Belgium, Tsuruga, Karlsruhe,
Thermal Diffusion (Toyama, Nagoya)Thermal Diffusion (Toyama, Nagoya)
Liquid-Liquid Extraction (Osaka)Liquid-Liquid Extraction (Osaka)

15. WWATERATER D DISTILLATIONISTILLATION
Water distillation, (WD), exploits the vapour-liquid equilibrium,Water distillation, (WD), exploits the vapour-liquid equilibrium,
HTO(v) + HHTO(v) + H
22O (l) O (l) «« H H
22O(v) + HTO (l), O(v) + HTO (l),
by which tritium is enriched in the liquid phase. The separation factors for distillation can be taken by which tritium is enriched in the liquid phase. The separation factors for distillation can be taken
approximately as the ratio of the vapour pressures. Boiling point data and vapor pressures ratio for approximately as the ratio of the vapour pressures. Boiling point data and vapor pressures ratio for
isotopic species of interest are given in Table isotopic species of interest are given in Table 11
Table Table 11. Boiling point and vapor pressure of oxides of hydrogen isotopes.. Boiling point and vapor pressure of oxides of hydrogen isotopes.
H2O HDO D2O T2O HTOH2O HDO D2O T2O HTO
Boiling point (Boiling point (
oo
C): 100.00 101.42 101.51 100.8C): 100.00 101.42 101.51 100.8
Vapour pressure,: 23.76 22.12 Vapour pressure,: 23.76 22.12 20.6 20.6 19.8 19.8 21.7 21.7
(mmHg), at 25(mmHg), at 25
oo
CC
Water pressure ratios for isotopic water species P(H2O)/P(x) calculated using Van Hook's equation and Water pressure ratios for isotopic water species P(H2O)/P(x) calculated using Van Hook's equation and
data for three temperatures are given in Table data for three temperatures are given in Table 22
Table Table 22. Vapour pressure ratios for isotopic water species P(H2O)/P(x).. Vapour pressure ratios for isotopic water species P(H2O)/P(x).
Temperature,Temperature,
oo
C TC T
22O DTO DO DTO D
22O HTO HDOO HTO HDO
25 1.193 1.175 1.154 1.095 1.075 25 1.193 1.175 1.154 1.095 1.075
50 1.134 1.123 1.110 1.065 1.05350 1.134 1.123 1.110 1.065 1.053
100 1.064 1.060 1.052 1.030 1.026 100 1.064 1.060 1.052 1.030 1.026
----------------------------------
Source:Source: Burger L.L, Op. cit., 1972; Van Hook W.A., et al., J.Phys.Chem. 72, 1234, 1968 Burger L.L, Op. cit., 1972; Van Hook W.A., et al., J.Phys.Chem. 72, 1234, 1968

16. Operating data of a Sulzer plant for Operating data of a Sulzer plant for
tritium extraction from light watertritium extraction from light water
Quantity (l/h) Quantity (l/h) Concentration (Ci/mConcentration (Ci/m
33
))
Feed: 190 1 Feed: 190 1
Return: 189.875 0.5 Return: 189.875 0.5
Concentrate: Concentrate: 0.125 720 0.125 720
Operating pressure at top of column: 150 mbar Operating pressure at top of column: 150 mbar
Heating steam: 3,000 kg/h Heating steam: 3,000 kg/h
Cooling water: 160 mCooling water: 160 m
33
/h /h
Electric energy: Electric energy: 15 kW15 kW
A tritium emission to the environment of 80 Ci/year with a tritium A tritium emission to the environment of 80 Ci/year with a tritium
concentration of 1 Ci/mconcentration of 1 Ci/m
33
in the reactor cooling water would allow an in the reactor cooling water would allow an
admissible leakage rate of 80 m3/year (0.01 madmissible leakage rate of 80 m3/year (0.01 m
33
/h)./h).
--------------------------------
SourceSource: Damiani, M., et al., Sulzer Tech. Rev., Nuclex 75, 1975: Damiani, M., et al., Sulzer Tech. Rev., Nuclex 75, 1975

17. HYDROGEN DISTILLATIONHYDROGEN DISTILLATION
To use hydrogen distillation to recover tritium from water streams, it is To use hydrogen distillation to recover tritium from water streams, it is
necessary to couple it with a front-end transfer process that transfers the necessary to couple it with a front-end transfer process that transfers the
tritium from the water molecule to the hydrogen molecule. For heavy water tritium from the water molecule to the hydrogen molecule. For heavy water
application, the reaction is application, the reaction is
catalystcatalyst
DTO + DDTO + D
22  D D
22O + DT O + DT
Tritium recovery for HWR generally would consist of two separate processes: a Tritium recovery for HWR generally would consist of two separate processes: a
transfer process that moves tritium from tritiated heavy water to tritiated transfer process that moves tritium from tritiated heavy water to tritiated
hydrogen and a concentration process that separates and enriches the tritium hydrogen and a concentration process that separates and enriches the tritium
to high specific activity tritiated hydrogen (Tto high specific activity tritiated hydrogen (T
22))..
Since it is most economical to produce a small and highly concentrated tritium Since it is most economical to produce a small and highly concentrated tritium
stream for storage, CD of Dstream for storage, CD of D
22/DT/T/DT/T
22 is the most practical process available for the is the most practical process available for the
final enrichment of tritium. final enrichment of tritium.
The options of the transfer process are:The options of the transfer process are:
- - Vapour-phase catalytic exchange (VPCE) of tritiated DVapour-phase catalytic exchange (VPCE) of tritiated D
22O vapour with DO vapour with D
22, ,
producing a Dproducing a D
22/DT mixture /DT mixture
- Direct electrolysis (DE) of tritiated D- Direct electrolysis (DE) of tritiated D
22O, producing a DO, producing a D
22/DT mixture/DT mixture
- Combined electrolysis-chemical exchange CECE of the tritiated D- Combined electrolysis-chemical exchange CECE of the tritiated D
22O in the O in the
liquid phase with Dliquid phase with D
22/DT producing a D/DT producing a D
22/DT stream enriched in tritium/DT stream enriched in tritium
- Liquid-phase catalytic exchange LPCE of tritiated D- Liquid-phase catalytic exchange LPCE of tritiated D
22O with DO with D
22 producing a producing a
DD
22/DT mixture/DT mixture
Each of these transfer processes may be coupled with CD of hydrogen isotopes Each of these transfer processes may be coupled with CD of hydrogen isotopes
to provide a process for tritium recovery from heavy water. to provide a process for tritium recovery from heavy water.

18. HHYDROGEN DISTILLATION YDROGEN DISTILLATION (CONT’D)(CONT’D)
Unlike the isotopes of other elements, the relatively large mass differences of H, D, and T Unlike the isotopes of other elements, the relatively large mass differences of H, D, and T
cause appreciable differences in properties of these isotopes and their compounds. Table cause appreciable differences in properties of these isotopes and their compounds. Table
11 lists some physical properties of the isotopic forms of hydrogen lists some physical properties of the isotopic forms of hydrogen
Table Table 11. Physical properties of isotopic hydrogen species. . Physical properties of isotopic hydrogen species.
==========================================================================================================================
HH
22* HD * HD HT D HT D
22 DT T DT T
22
Molecular weight: 2.016 3.022 4.025 4.029 5.032 6.034 Molecular weight: 2.016 3.022 4.025 4.029 5.032 6.034
Boiling point (K): 20.39 22.14 22.92 23.67 24.38 25.04 Boiling point (K): 20.39 22.14 22.92 23.67 24.38 25.04
Triple point (K): 13.96 16.60 17.62 18.73 19.71 20.62 Triple point (K): 13.96 16.60 17.62 18.73 19.71 20.62
Triple point pressure (mmHg): 54.0 92.8 109.5 128.6 145.7 162.0 Triple point pressure (mmHg): 54.0 92.8 109.5 128.6 145.7 162.0
Critical tempe rature (K): 33.24 35.91 37.13 38.35 39.42 40.44 Critical tempe rature (K): 33.24 35.91 37.13 38.35 39.42 40.44
Critical pressure (mmHg): 9,736 11,134 11,780 12,487 13,300 13,878Critical pressure (mmHg): 9,736 11,134 11,780 12,487 13,300 13,878
Dissociation energy (eV): 4.476 4.511 4.524 4.553 4.588 Dissociation energy (eV): 4.476 4.511 4.524 4.553 4.588
Zero point energy (cm-1): 2,171.4 1,884.3 1,542.4Zero point energy (cm-1): 2,171.4 1,884.3 1,542.4
*/ The normal state (high temperature ortho-para composition) is used for this table. The */ The normal state (high temperature ortho-para composition) is used for this table. The
"equilibrium" state, the composition existing at the normal boiling point gives slightly "equilibrium" state, the composition existing at the normal boiling point gives slightly
different properties.different properties.
------------------------------------
SourceSource: Burger, L.L., Op. cit. 1972: Burger, L.L., Op. cit. 1972

19. WWATER ELECTROLYSISATER ELECTROLYSIS
Water electrolysis, has long been used to concentrate small Water electrolysis, has long been used to concentrate small
quantities of tritium for analyses. Electrolysis has a high separation quantities of tritium for analyses. Electrolysis has a high separation
factor. The tritium is concentrated in the electrolyte with the factor. The tritium is concentrated in the electrolyte with the
hydrogen depleted in the tritium. Several stages of electrolysis are hydrogen depleted in the tritium. Several stages of electrolysis are
required to achieve the required tritium separation and enrichment, required to achieve the required tritium separation and enrichment,
and energy costs are high. There is also an absence of commercial and energy costs are high. There is also an absence of commercial
cell designs that are sufficiently leak-free to enable processing the cell designs that are sufficiently leak-free to enable processing the
tritium- enriched water.tritium- enriched water.
The electrolysis technology is well developed, the process is The electrolysis technology is well developed, the process is
probably the simplest of all, the separation factor is the highest, the probably the simplest of all, the separation factor is the highest, the
capital costs would be small, and there is no doubt that an capital costs would be small, and there is no doubt that an
electrolytic separation plant would do the jobelectrolytic separation plant would do the job..

20. CCHEMICAL EXCHANGEHEMICAL EXCHANGE
Depending on the physicochemical form of tritium at the start of the Depending on the physicochemical form of tritium at the start of the
chemical exchange reaction, three procedures are possible:chemical exchange reaction, three procedures are possible:
HT(g) + HHT(g) + H
22O(l) O(l) «« H H
22(g) + HTO(l), (g) + HTO(l), ((11))
HTO(v) + HHTO(v) + H
22(g) (g) «« H H
22O(v) + HT(g), O(v) + HT(g), ((22))
HTO(l) + HHTO(l) + H
22(g) (g) «« H H
22O(l) + HT(g). O(l) + HT(g). ((33))
In order to achieve the minimum velocities necessary to obtain the In order to achieve the minimum velocities necessary to obtain the
chemical equilibria which are required for technical utilization, it is chemical equilibria which are required for technical utilization, it is
necessary to use catalyzers.These have to be hydrophobic wherever necessary to use catalyzers.These have to be hydrophobic wherever
an aqueous phase may prevent or impair the catalytic process. an aqueous phase may prevent or impair the catalytic process.
Advantages of catalytic exchange procedures are the small content, Advantages of catalytic exchange procedures are the small content,
compact construction and robust technology. A disadvantage is the as compact construction and robust technology. A disadvantage is the as
yet unproven long-term performance of hydrophobic catalysts. yet unproven long-term performance of hydrophobic catalysts.
Although at different levels of development, all three procedures are Although at different levels of development, all three procedures are
already at the industrial stage [4].already at the industrial stage [4].
Catalyzed chemical exchange always appear coupled with an another Catalyzed chemical exchange always appear coupled with an another
process. process.
------------------------
Source: Specht, S et al., Kerntechnik, 54 4 263 1989Source: Specht, S et al., Kerntechnik, 54 4 263 1989

21. VVAPOR-PHASE CATALYTIC EXCHANGEAPOR-PHASE CATALYTIC EXCHANGE
(VPCE) (VPCE) AND CRYOGENIC DISTILLATIONAND CRYOGENIC DISTILLATION (CD) (CD)
The high flux reactor in Grenoble (France) which was built as a result of The high flux reactor in Grenoble (France) which was built as a result of
Franco-German cooperation, is the first reactor installation in the world Franco-German cooperation, is the first reactor installation in the world
possessing a plant in operation for the simultaneous extraction of hydrogen possessing a plant in operation for the simultaneous extraction of hydrogen
and tritium from heavy water. and tritium from heavy water.
Tritium is formed here by neutron absorption into heavy water which surrounds Tritium is formed here by neutron absorption into heavy water which surrounds
the fuel element. Without removal of tritium, the heavy water would reach a the fuel element. Without removal of tritium, the heavy water would reach a
tritium content of about 84,000 Ci/mtritium content of about 84,000 Ci/m
33
(84 Ci/l), whereas with tritium extraction a (84 Ci/l), whereas with tritium extraction a
value of about 1,700 Ci/mvalue of about 1,700 Ci/m
33
(1.7 Ci/l) can be maintained. This requires an annual (1.7 Ci/l) can be maintained. This requires an annual
extraction of 16,000 Ci, equivalent to about 60 nl of pure tritium.extraction of 16,000 Ci, equivalent to about 60 nl of pure tritium.
The Grenoble tritium and hydrogen extraction plant is made up of two main The Grenoble tritium and hydrogen extraction plant is made up of two main
parts]:parts]:
a).Catalytic exchange between heavy water vapor and deuterium gas at 200a).Catalytic exchange between heavy water vapor and deuterium gas at 200
oo
C C
and ca 1.2 bar, which allows the mass transfer of hydrogen and tritium from and ca 1.2 bar, which allows the mass transfer of hydrogen and tritium from
heavy water to deuterium to reach equilibrium according to the following heavy water to deuterium to reach equilibrium according to the following
reactionsreactions::
DTO(v) + DDTO(v) + D
22(g) (g) «« D D
22O(v) + DT(g) O(v) + DT(g) K K
TT = 0.82= 0.82
HDO(v) + DHDO(v) + D
22(g) (g) «« D D
22O(v) + HD(g) KO(v) + HD(g) K
HH = 1.78 = 1.78
b).Low temperature rectification of the hydrogen isotopes HD/Db).Low temperature rectification of the hydrogen isotopes HD/D
22/DT/T/DT/T
22 at ca 1.5 at ca 1.5
bar in two column with extraction of HD at the top of the first column and pure bar in two column with extraction of HD at the top of the first column and pure
tritium at the bottom of the second column.tritium at the bottom of the second column.
----------------------------
Source: Damiani, M., et al., Op.cit. 1975Source: Damiani, M., et al., Op.cit. 1975

22. VPCE-CD ADVANTAGES VPCE-CD ADVANTAGES (CONT’D)(CONT’D)
The VPCE-CD process has been verified successfully, although is The VPCE-CD process has been verified successfully, although is
operated at high temperature, each stage requiring the evaporation, operated at high temperature, each stage requiring the evaporation,
superheating, vapour-phase exchange, and condensation of the superheating, vapour-phase exchange, and condensation of the
feedwater, it remained in attention as an important process. Thus, a feedwater, it remained in attention as an important process. Thus, a
decision was reached around 1980 by Ontario Hydro to construct a decision was reached around 1980 by Ontario Hydro to construct a
Tritium Removal Facility (TRF) in Canada, at the Darlington generating Tritium Removal Facility (TRF) in Canada, at the Darlington generating
station, near Toronto. This plant would reduce the tritium levels in the station, near Toronto. This plant would reduce the tritium levels in the
moderator and heat transport systems of both the Pickering, moderator and heat transport systems of both the Pickering,
Darlington and possibly the Bruce generating stations. Detritiation at Darlington and possibly the Bruce generating stations. Detritiation at
Pickering or Bruce would be accomplished by transporting heavy Pickering or Bruce would be accomplished by transporting heavy
water to and from the TRFwater to and from the TRF..
The TRF is also based on a VPCE front-end process followed by The TRF is also based on a VPCE front-end process followed by
concentration through CD. The contract for TRF, consisting of the concentration through CD. The contract for TRF, consisting of the
VPCE front-end, feed treatment and CD, was awarded to Sulzer VPCE front-end, feed treatment and CD, was awarded to Sulzer
Canada Inc. The Ontario Hydro TRF will produce 800 g/yr of tritium as Canada Inc. The Ontario Hydro TRF will produce 800 g/yr of tritium as
TT
22 at equilibrium, with a feed flow of 360 kg/h. In comparison, the at equilibrium, with a feed flow of 360 kg/h. In comparison, the
Grenoble plant has a feed rate of 25 kg/h. Grenoble plant has a feed rate of 25 kg/h.
--------------------------------------
SourceSource: Sood, S.K., et al., Fusion Technol. 8 2 2478 1985: Sood, S.K., et al., Fusion Technol. 8 2 2478 1985

23. Operating data and operating media of the Operating data and operating media of the
Grenoble tritium and hydrogen extraction Grenoble tritium and hydrogen extraction
plant.plant.
============================================================= =============================================================
..Intake: Intake: 16.7 litres/h 16.7 litres/h
Head product: Head product: 60 litres H60 litres H
22O/year O/year
Bottom product: 60 standard litres TBottom product: 60 standard litres T
22/year /year
(160000 Ci/year)(160000 Ci/year)
DD
22 consumption: consumption: 60 standard litres/h 60 standard litres/h
OO
22 consumption: consumption: 35 standard litres/h 35 standard litres/h
Electric power input: 800 Electric power input: 800 kW kW
Cooling water consumption: 25 Cooling water consumption: 25 mm
33
/h /h
Compressed air consumption: Compressed air consumption: 50 50 standard m3/h standard m3/h
DD
22O hold-up: O hold-up: 1 1,000 litres ,000 litres
DD
22 hold-up: hold-up: 85 standard m 85 standard m
33
TT
22 hold-up: hold-up: 60 standard l60 standard l
He hold-up: He hold-up: 35 standard m35 standard m
33
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
SourceSource: Damiani, M. et al., Sulzer Tech. Rev., Nuclex 72 41 1972: Damiani, M. et al., Sulzer Tech. Rev., Nuclex 72 41 1972

24. LLIQUIDIQUID-P-PHASE CATALYTICHASE CATALYTIC E EXCHANGEXCHANGE (LPCE) (LPCE)
AND CRYOGENICAND CRYOGENIC D DISTILLATIONISTILLATION (CD) (CD)
The discovery, at Chalk River Nuclear Laboratories (CRNL), Canada, of a simple The discovery, at Chalk River Nuclear Laboratories (CRNL), Canada, of a simple
method of wetproofing platinum catalysts has stimulated an extensive research method of wetproofing platinum catalysts has stimulated an extensive research
program for the development of hydrogen isotope separation and program for the development of hydrogen isotope separation and
hydrogen/oxygen recombination processes. Over 14 years of study has hydrogen/oxygen recombination processes. Over 14 years of study has
resulted in highly efficient catalysts which retain their activity while immersed resulted in highly efficient catalysts which retain their activity while immersed
in liquid water for periods of more 3 years..in liquid water for periods of more 3 years..
The catalysts, for example, as platinum or palladium on carbon, silica, or The catalysts, for example, as platinum or palladium on carbon, silica, or
alumina are rendered "wet-proof" by a special process in which a Teflon or alumina are rendered "wet-proof" by a special process in which a Teflon or
silicone coating is applied to the surface. The Teflon provides a hydrophobic silicone coating is applied to the surface. The Teflon provides a hydrophobic
surface that repels liquid water, but is permeable to gas and vapor, thus surface that repels liquid water, but is permeable to gas and vapor, thus
enabling isotope exchange to take place in the presence of a liquid. Wetproofed enabling isotope exchange to take place in the presence of a liquid. Wetproofed
catalysts are therefore capable of achieving reaction rates comparable to those catalysts are therefore capable of achieving reaction rates comparable to those
for conventional catalysts operating in dry environments.for conventional catalysts operating in dry environments.
The detritiation mechanism of the LPCE front end is similar to that of the VPCE The detritiation mechanism of the LPCE front end is similar to that of the VPCE
front end process except that the tritiated heavy water feed remains in the liquid front end process except that the tritiated heavy water feed remains in the liquid
phase. In this process, during the first stage, tritium is transferred by catalytic phase. In this process, during the first stage, tritium is transferred by catalytic
isotope exchange from the tritiated water into deuterium gas and the tritium-isotope exchange from the tritiated water into deuterium gas and the tritium-
depleted water is returned for reuse in the reactor. The heart of the process is a depleted water is returned for reuse in the reactor. The heart of the process is a
novel wet-proofed catalyst (of platinum crystallites deposited on carbon novel wet-proofed catalyst (of platinum crystallites deposited on carbon
powder), bounded to 6-mm diameter inert alumina spheres with powder), bounded to 6-mm diameter inert alumina spheres with
polytetrafluoroethylene (Teflon))polytetrafluoroethylene (Teflon))..
--------------------------
SourceSource: Seddon, W.A., et al., Report AECL 8293, 1984: Seddon, W.A., et al., Report AECL 8293, 1984
The LPCE process is simpler and require less energy because the reaction is The LPCE process is simpler and require less energy because the reaction is
conducted at ambient temperature in a single packed column [44]. This proces has conducted at ambient temperature in a single packed column [44]. This proces has
therefore been chosen for CRNL's proposed demonstration plant for tritium recovery therefore been chosen for CRNL's proposed demonstration plant for tritium recovery
from heavy water. The decision to build the CRNL tritium extraction plant (TEP) was from heavy water. The decision to build the CRNL tritium extraction plant (TEP) was
preceded by laboratory and pilot plant studies. A pilot plant was built at CRNL in 1979 preceded by laboratory and pilot plant studies. A pilot plant was built at CRNL in 1979
to demonstrate LPCE process, to measure catalyst activity for hydrogen isotope to demonstrate LPCE process, to measure catalyst activity for hydrogen isotope
exchange and to demonstrate the lifetime performance of the catalyst. The tests were exchange and to demonstrate the lifetime performance of the catalyst. The tests were
carried out to determine catalyst activity under typical TEP conditions and provided carried out to determine catalyst activity under typical TEP conditions and provided
essential design data [45]essential design data [45]
The CRNL TEP has been built to remove tritium from Atomic Energy of Canada Ltd The CRNL TEP has been built to remove tritium from Atomic Energy of Canada Ltd
(AECL) heavy water, to reduce operator dose and to reduce emmisions. A (AECL) heavy water, to reduce operator dose and to reduce emmisions. A
supplementary purpose of the plant is to demonstrate, in a full-scale environment, supplementary purpose of the plant is to demonstrate, in a full-scale environment,
LPCE-CD process technology [46]. A future option to increase plant capacity is LPCE-CD process technology [46]. A future option to increase plant capacity is
conversion of the LPCE front end to a Combined Electrolysis Catalytic Exchange conversion of the LPCE front end to a Combined Electrolysis Catalytic Exchange
(CECE) process.(CECE) process.

25. LLIQUID-PHASE CATALYTIC EXCHANGEIQUID-PHASE CATALYTIC EXCHANGE (LPCE) (LPCE)
AND CRYOGENIC DISTILLATION AND CRYOGENIC DISTILLATION (CONT’D(CONT’D))
Advantages:Advantages:
The LPCE process is simpler and require less energy because the reaction is The LPCE process is simpler and require less energy because the reaction is
conducted at ambient temperature in a single packed column. This proces has conducted at ambient temperature in a single packed column. This proces has
therefore been chosen for CRNL's proposed demonstration plant for tritium therefore been chosen for CRNL's proposed demonstration plant for tritium
recovery from heavy water. The decision to build the CRNL tritium extraction recovery from heavy water. The decision to build the CRNL tritium extraction
plant (TEP) was preceded by laboratory and pilot plant studies. A pilot plant plant (TEP) was preceded by laboratory and pilot plant studies. A pilot plant
was built at CRNL in 1979 to demonstrate LPCE process, to measure catalyst was built at CRNL in 1979 to demonstrate LPCE process, to measure catalyst
activity for hydrogen isotope exchange and to demonstrate the lifetime activity for hydrogen isotope exchange and to demonstrate the lifetime
performance of the catalyst. The tests were carried out to determine catalyst performance of the catalyst. The tests were carried out to determine catalyst
activity under typical TEP conditions and provided essential design dataactivity under typical TEP conditions and provided essential design data..
The CRNL TEP has been built to remove tritium from Atomic Energy of Canada The CRNL TEP has been built to remove tritium from Atomic Energy of Canada
Ltd (AECL) heavy water, to reduce operator dose and to reduce emmisions. A Ltd (AECL) heavy water, to reduce operator dose and to reduce emmisions. A
supplementary purpose of the plant is to demonstrate, in a full-scale supplementary purpose of the plant is to demonstrate, in a full-scale
environment, LPCE-CD process technologyenvironment, LPCE-CD process technology.. A future option to increase plant A future option to increase plant
capacity is conversion of the LPCE front end to a Combined Electrolysis capacity is conversion of the LPCE front end to a Combined Electrolysis
Catalytic Exchange (CECE) process.Catalytic Exchange (CECE) process.
----------------------------------
SourceSource: Seddon, W.A., Op. cit. 1984: Seddon, W.A., Op. cit. 1984
Holtslander, W.J., et al., Meet. T Technol. Toronto, 1988Holtslander, W.J., et al., Meet. T Technol. Toronto, 1988

26. DIRECT ELECTROLYSISDIRECT ELECTROLYSIS (DE) (DE) AND AND
CRYOGENIC DISTILLATIONCRYOGENIC DISTILLATION (CD)(CD)
Tritiated heavy water from the reactor units is fed to the electrolytic cells where Tritiated heavy water from the reactor units is fed to the electrolytic cells where
it is decomposed into an oxygen gas and a Dit is decomposed into an oxygen gas and a D
22/DT gas stream/DT gas stream::
electrolysiselectrolysis
2DTO 2DTO  2DT + O2DT + O
22
electrolysiselectrolysis
2D2D
22OO  2D2D
22 + O + O
22
The DThe D
22/DT stream is purified and fed to the CD system, as in the VPCE process. /DT stream is purified and fed to the CD system, as in the VPCE process.
The deuterium gas is recombined with the oxygen generated in the electrolytic The deuterium gas is recombined with the oxygen generated in the electrolytic
cells to form detritiated heavy water which is then returned to the reactor units. cells to form detritiated heavy water which is then returned to the reactor units.
Electrolysis has a high separation factor. The tritium is concentrated in the Electrolysis has a high separation factor. The tritium is concentrated in the
electrolyte. Several stages of electrolysis are required to achieve the required electrolyte. Several stages of electrolysis are required to achieve the required
tritium separation and enrichment, and energy costs are high. There is also an tritium separation and enrichment, and energy costs are high. There is also an
absence of commercial cell designs that are sufficiently leak-free to enable absence of commercial cell designs that are sufficiently leak-free to enable
processing of tritium enriched waterprocessing of tritium enriched water
------------------------------
SourceSource: Holtslander, W.J., et al., Op. cit. 1981: Holtslander, W.J., et al., Op. cit. 1981

27. CCOMBINEDOMBINED E ELECTROLYSIS LECTROLYSIS
CATALYTIC EXCHANGECATALYTIC EXCHANGE , (CECE), (CECE)
Tritium recovery from light water streams from reactors and plants operated by Tritium recovery from light water streams from reactors and plants operated by
the Department of Energy contractors in the U.S. is being demonstrated under a the Department of Energy contractors in the U.S. is being demonstrated under a
cooperative program on a laboratory scale at the Mound Laboratory, cooperative program on a laboratory scale at the Mound Laboratory,
Miamisburg, OH. This facility incorporates the CECE-HWP (Heavy Water Miamisburg, OH. This facility incorporates the CECE-HWP (Heavy Water
Process) with the AECL hydrophobic platinum catalyst as the preconcentration Process) with the AECL hydrophobic platinum catalyst as the preconcentration
step. Final enrichment to pure tritium is by CD of hydrogenstep. Final enrichment to pure tritium is by CD of hydrogen..
The The final goal of the final goal of the Mound pilot CECE-TRP system is to build a larger system Mound pilot CECE-TRP system is to build a larger system
which would be used to treat aqueous tritiated waste for the Department of which would be used to treat aqueous tritiated waste for the Department of
Energy (DOE).Energy (DOE).
The same CECE-TRP is also being developed independently in Belgium], Japan The same CECE-TRP is also being developed independently in Belgium], Japan
and Germany to detritiate light water streams from nuclear fuel reprocessing and Germany to detritiate light water streams from nuclear fuel reprocessing
plants. Thus, the Belgians are developing the ELEX process (an acronym for plants. Thus, the Belgians are developing the ELEX process (an acronym for
combined ELectrolysis chemical EXchange process) on behalf of the European combined ELectrolysis chemical EXchange process) on behalf of the European
Economic Community. In Japan the proces is apparently referred to as EXEL Economic Community. In Japan the proces is apparently referred to as EXEL
proces (an acronym for combined chemical Exchange Electrolysis process). proces (an acronym for combined chemical Exchange Electrolysis process).
Both the EXEL and ELEX processes are based on the Canadian invention of the Both the EXEL and ELEX processes are based on the Canadian invention of the
hydrophobic platinum catalysthydrophobic platinum catalyst..
--------------------------
Source: Butler, J.P., Sep. Sci. Technol., 15 3 371 1980Source: Butler, J.P., Sep. Sci. Technol., 15 3 371 1980
Bruggeman, A., et al., ANS Natl. Topical Meet., Dayton, 1980Bruggeman, A., et al., ANS Natl. Topical Meet., Dayton, 1980
Nakane, R., Report RIKEN, Tokyo, 1980Nakane, R., Report RIKEN, Tokyo, 1980
Fiek, H.J., et al., Nucl. Technol. Fusion, 3, 112, 1983Fiek, H.J., et al., Nucl. Technol. Fusion, 3, 112, 1983
In Germany, the Dornier System GmbH studied the possibilty to utilize the existing In Germany, the Dornier System GmbH studied the possibilty to utilize the existing
CECE-process, which is presently in pilot operation with tritium at CECE-process, which is presently in pilot operation with tritium at
Kernforschungszentrum, Karlsruhe, in order to recover the tritium from aqueous Kernforschungszentrum, Karlsruhe, in order to recover the tritium from aqueous
waste of nuclear fuel reprocessing plants, contaminated with tritium in the form of waste of nuclear fuel reprocessing plants, contaminated with tritium in the form of
HTO. HTO.
In order to recover tritium from light water, research and development was carried In order to recover tritium from light water, research and development was carried
out at RIKEN, concerning a tritium separation process based on the principle of out at RIKEN, concerning a tritium separation process based on the principle of
hydrogen-water isotopic exchange reaction. The performance and durability of unit hydrogen-water isotopic exchange reaction. The performance and durability of unit
operations for the process was studied. A pilot plant having a capacity of 1 ton/y (3.6 operations for the process was studied. A pilot plant having a capacity of 1 ton/y (3.6
l/d) was designed and fabricated based on the results of the tests and studies. Using l/d) was designed and fabricated based on the results of the tests and studies. Using
this plant, tritiated water could be concentrated to the order of magnitude of 104. this plant, tritiated water could be concentrated to the order of magnitude of 104.
Furthermore, the effect of the various operating conditions on the tritium Furthermore, the effect of the various operating conditions on the tritium
concentration factor was calculated by applying a data analysis program for the pilot concentration factor was calculated by applying a data analysis program for the pilot
plant. This study offered prospect of practical application of the process by hydrogen-plant. This study offered prospect of practical application of the process by hydrogen-
vapour isotopic exchange reactionvapour isotopic exchange reaction
At the Tritium process laboratory in the JAERI (Japan) an apparatus for the fuel At the Tritium process laboratory in the JAERI (Japan) an apparatus for the fuel
clean-up process was developed. This was designed, fabricated and installed for the clean-up process was developed. This was designed, fabricated and installed for the
experiments with up to 1 g of tritium. The function of the system is continuous experiments with up to 1 g of tritium. The function of the system is continuous
processing of a simulated plasma exhaust and separation of hydrogen isotopes and processing of a simulated plasma exhaust and separation of hydrogen isotopes and
impurity elements in it. Main components are palladium diffusers, catalytic reactors, impurity elements in it. Main components are palladium diffusers, catalytic reactors,
cold traps, an electrolysis cell and zirconium-cobalt beds. The apparatus was cold traps, an electrolysis cell and zirconium-cobalt beds. The apparatus was
installed in a glovebox and tested with hydrogen [55].installed in a glovebox and tested with hydrogen [55].

28. III. METHODS FOR RECOVERY AND III. METHODS FOR RECOVERY AND
ENRICHMENT OF TRITIUM FROM ENRICHMENT OF TRITIUM FROM
THERMONUCLEAR PLANTSTHERMONUCLEAR PLANTS
Fuel Cycle System for D - T Burning Fusion ReactorFuel Cycle System for D - T Burning Fusion Reactor
Roles of Stage Processes in Fuel Cycle SystemRoles of Stage Processes in Fuel Cycle System
Cryogenic Distillation of Hydrogen (Tritium System Cryogenic Distillation of Hydrogen (Tritium System
Test Assembly (TSTA), Los Alamos, The Isotope Test Assembly (TSTA), Los Alamos, The Isotope
Separation System (ISS), Los Alamos, Kyoto, JAERI Separation System (ISS), Los Alamos, Kyoto, JAERI
-Tokai Mura)-Tokai Mura)
Permeation through Porous Membranes (Kyoto, Permeation through Porous Membranes (Kyoto,
Nagoya)Nagoya)
Gas Chromatography (Karlsruhe, Canadian Fusion Gas Chromatography (Karlsruhe, Canadian Fusion
Fuel Technology Project - Ontario Hydro) Fuel Technology Project - Ontario Hydro)

29. TTRITIUM SYSTEM TEST ASSEMBLY RITIUM SYSTEM TEST ASSEMBLY
(TSTA) AND(TSTA) AND I ISOTOPESOTOPE S SEPARATIONEPARATION
SSYSTEMYSTEM (ISS) (ISS)
At TAt TRITIUM SYSTEM TEST ASSEMBLY (TRITIUM SYSTEM TEST ASSEMBLY (T STASTA), LANL, ), LANL, cryogenic fractional distillation is cryogenic fractional distillation is
being used for hydrogen isotope separation. The ISS is sized to handle the full flow being used for hydrogen isotope separation. The ISS is sized to handle the full flow
appropiate to ETF or INTOR. It has four principal duties. From a purified stream of 360 g appropiate to ETF or INTOR. It has four principal duties. From a purified stream of 360 g
mol/d of mixed hydrogen isotopes, consisting nominally of equimolar quantities of mol/d of mixed hydrogen isotopes, consisting nominally of equimolar quantities of
deuterium and tritium with low levels (1%) of hydrogen impurity, the ISS provides four deuterium and tritium with low levels (1%) of hydrogen impurity, the ISS provides four
product streams, namelyproduct streams, namely::
- an essentially tritium-free stream of H2 and HD wastes for disposal to the atmosphere- an essentially tritium-free stream of H2 and HD wastes for disposal to the atmosphere
- a high purity stream of D- a high purity stream of D
22, a stream needed by fusion reactors for, a stream needed by fusion reactors for refuelling and refuelling and pplasmalasma
heating by injection as a neutral beamheating by injection as a neutral beam
- a stream of basically pure DT for refuelling- a stream of basically pure DT for refuelling
- a high-purity stream of T- a high-purity stream of T
22 for refuelling and for studies on properties of tritium and effects for refuelling and for studies on properties of tritium and effects
of tritium on materialsof tritium on materials
Secondary duties of the ISS include: processing of the relative pure DSecondary duties of the ISS include: processing of the relative pure D
22 return from a return from a
simulated neutral beam line (simulated neutral beam line ( 275 g-mol of D 275 g-mol of D
22 per day) and processing of electrolytic per day) and processing of electrolytic
hydrogens generated in the fuel clean-up system. hydrogens generated in the fuel clean-up system.
The ISS must perform all of the above separations continuously and reliably over the long The ISS must perform all of the above separations continuously and reliably over the long
period of time typical of commercially operating power reactors.period of time typical of commercially operating power reactors.
--------------------------------
SourceSource: Bartlit, J.R., et al., Cryogenics, May 1979: Bartlit, J.R., et al., Cryogenics, May 1979
Anderson, J.L., LA-UR-80-1201, Los Alamos, 1980Anderson, J.L., LA-UR-80-1201, Los Alamos, 1980

30. KEY DESIGN PARAMETERS FOR THE AECL KEY DESIGN PARAMETERS FOR THE AECL
CECE DEMONSTRATION FACILITYCECE DEMONSTRATION FACILITY
In 1998, AECL began operation in upgrading mode of a CECE Upgrading and In 1998, AECL began operation in upgrading mode of a CECE Upgrading and
Detritiation (CECE-UD) Demonstration Facility at Chalk River using its Detritiation (CECE-UD) Demonstration Facility at Chalk River using its
wetproofed catalyst. The design rate ranged up to 25 Mg/year for 95 mol% Dwetproofed catalyst. The design rate ranged up to 25 Mg/year for 95 mol% D
22O O
feed water. Other key design parameters are given below:feed water. Other key design parameters are given below:
- Electrolysis cell: 7.2 kA; 2.7 l/h D- Electrolysis cell: 7.2 kA; 2.7 l/h D
22OO
- Electrolysis cell-max. conc.: 600 Ci/kg- Electrolysis cell-max. conc.: 600 Ci/kg
- Catalyst: 75 l, AECL random catalyst - Catalyst: 75 l, AECL random catalyst
- Catalyst column dia., operating temp.,- Catalyst column dia., operating temp.,
operating pressure: operating pressure: 0.05 m, 0.05 m,  50 50
oo
C, 100-120 kPa C, 100-120 kPa
- Detritiation capacity: 5 Mg/year- Detritiation capacity: 5 Mg/year
- Maximum tritium in deuterium conc.: 100 ppm DT in D- Maximum tritium in deuterium conc.: 100 ppm DT in D
22
- Storage method for recovered tritium: Titanium metal- Storage method for recovered tritium: Titanium metal
- Detritiation factors: Exceeding 50.000- Detritiation factors: Exceeding 50.000
------------------------
Source:Source: Sadhankar, R.R., and Miller, A.I., Preprint, 3 Sadhankar, R.R., and Miller, A.I., Preprint, 3
rdrd
Conf. on Isotopic and Conf. on Isotopic and
Molecular Processes, Cluj-Napoca, Romania, 25-27 Sept. 2003 Molecular Processes, Cluj-Napoca, Romania, 25-27 Sept. 2003

31. I. LASER ISOTOPE SEPARATION OF I. LASER ISOTOPE SEPARATION OF
TRITIUM- TRITIUM- GENERALGENERAL
Among many techniques for tritium isotope separation, Among many techniques for tritium isotope separation,
the one utilizing IR - laser- induced multiphoton dissociation the one utilizing IR - laser- induced multiphoton dissociation
(IRMPD) has been extensively investigated being given its high (IRMPD) has been extensively investigated being given its high
single-step enrichment factors. For this was necessary to find single-step enrichment factors. For this was necessary to find
suitable tritium - substituted molecules (working molecules or suitable tritium - substituted molecules (working molecules or
working substances) that have selective absorption bands in working substances) that have selective absorption bands in
the range of the IR wavelength. Then, from practical point of the range of the IR wavelength. Then, from practical point of
view, it was necessary to optimize the gas temperature and view, it was necessary to optimize the gas temperature and
irradiation wavelength, in order to obtain the best performance irradiation wavelength, in order to obtain the best performance
for a given working molecule. The major criteria of such for a given working molecule. The major criteria of such
optimization being operating pressure, selectivity and critical optimization being operating pressure, selectivity and critical
fluency, a great effort has been made to find the conditions to fluency, a great effort has been made to find the conditions to
yield to high - selectivity at high operating pressure and low-yield to high - selectivity at high operating pressure and low-
critical fluency for complete dissociation of tritiated molecule.critical fluency for complete dissociation of tritiated molecule.
Tritium isotope separation using laser method has been Tritium isotope separation using laser method has been
intensively investigated since 1979, especially by two groups: intensively investigated since 1979, especially by two groups:
at the Institute of Physical and Chemical Research, Wako, at the Institute of Physical and Chemical Research, Wako,
Saitama, Japan and at the Lawrence Livermore National Saitama, Japan and at the Lawrence Livermore National
Laboratory, Livermore, California, USA, at the laboratory scale.Laboratory, Livermore, California, USA, at the laboratory scale.

32. II. LASER ISOTOPE SEPARATION II. LASER ISOTOPE SEPARATION
OF TRITIUMOF TRITIUM
Principle of the methodPrinciple of the method
This method is based on isotopic selective laser - induced This method is based on isotopic selective laser - induced
photochemical reaction of a working substance.photochemical reaction of a working substance.
The working substance is tritiated by chemical exchange with tritium-The working substance is tritiated by chemical exchange with tritium-
containing effluent water. No enrichment is required in this section.containing effluent water. No enrichment is required in this section.
In a photochemical reactor, selective laser - induced dissociation of In a photochemical reactor, selective laser - induced dissociation of
tritiated working molecule occurs.tritiated working molecule occurs.
The product enriched in tritium is recovered and the tritium - depleted The product enriched in tritium is recovered and the tritium - depleted
working substance is recirculated and retritiated. working substance is recirculated and retritiated.
Steps for developmentSteps for development
Selection of the most suitable working substanceSelection of the most suitable working substance
Study of the reaction kinetics in batch irradiation experimentsStudy of the reaction kinetics in batch irradiation experiments
The design and experimentation of a continuous operation reactorThe design and experimentation of a continuous operation reactor
Pilot scale experimentsPilot scale experiments

33. III. LASER ISOTOPE SEPARATION III. LASER ISOTOPE SEPARATION
OF TRITIUMOF TRITIUM
Conditions for a performing working substanceConditions for a performing working substance
high selectivityhigh selectivity
high operating pressurehigh operating pressure
high reaction rate (low critical fluence)high reaction rate (low critical fluence)
rapid and easily tritium chemical exchangerapid and easily tritium chemical exchange
low costlow cost
The working substances surveyed till now for tritium laser The working substances surveyed till now for tritium laser
isotope separation areisotope separation are
halogenated methanes (particularly CTFhalogenated methanes (particularly CTF
33))
halogenated ethanes (CFhalogenated ethanes (CF
33CTClF, CCTClF, C
22TFTF
55))
chloroform (CTClchloroform (CTCl
33))
halogenated propanes (i-Chalogenated propanes (i-C
33TFTF
77))

34. IV. LASER ISOTOPE SEPARATION IV. LASER ISOTOPE SEPARATION
OF TRITIUM OF TRITIUM - RESULTS- RESULTS
From the certain halomethanes whose IRMPD have been From the certain halomethanes whose IRMPD have been
extensively studied for tritium LIS, the best results have been extensively studied for tritium LIS, the best results have been
obtained for CTFobtained for CTF
33, with selectivity of over 10, with selectivity of over 10
44
at 9P(8) line (1057 at 9P(8) line (1057
cmcm
-1-1
) at - 78) at - 78
oo
C for 85 - 205 Torr CHFC for 85 - 205 Torr CHF
33 and 1 and 1Torr CTFTorr CTF
33. By . By
addition of 100 Torr argon, as buffer gas, critical fluency of addition of 100 Torr argon, as buffer gas, critical fluency of
CTFCTF
33 was decreased from 136 J/cm was decreased from 136 J/cm
22
to 34 J/cm to 34 J/cm
22
..
Among halogenated ethanes, for which far lower threshold Among halogenated ethanes, for which far lower threshold
fluency for MPD is expected, CFfluency for MPD is expected, CF
33CTClF and CCTClF and C
22TFTF
55 has been has been
found to give both high selectivity (found to give both high selectivity ( 400) and moderated 400) and moderated
fluency (20 - 30 J/cmfluency (20 - 30 J/cm
22
) for C) for C
22TFTF
55 and 8 J/cm and 8 J/cm
22
for CF for CF
33CTClF at 973 CTClF at 973
cmcm
-1-1
..
The T/H separation using CThe T/H separation using C
22TFTF
55 has been performed with a has been performed with a
selectivity selectivity  500 for P(20) line at 944.2 cm 500 for P(20) line at 944.2 cm
-1-1
and later, T/D and later, T/D
separation with single step separation factors exceeding 3,000 separation with single step separation factors exceeding 3,000
for 10P(34) line at 931 cmfor 10P(34) line at 931 cm
-1-1
and – 78 and – 78
oo
C.C.

35. TRITIUM ISOTOPE SEPARATIONTRITIUM ISOTOPE SEPARATION
CRC PRESSCRC PRESS
Tritium Isotope Separation is the first book to present a current Tritium Isotope Separation is the first book to present a current
overview of the separation processes for tritium isotopes. overview of the separation processes for tritium isotopes.
The book consists of two parts. The book consists of two parts.
Part I explores the sources of tritium and the evolution of the world's Part I explores the sources of tritium and the evolution of the world's
tritium inventory. tritium inventory.
Part II describes the processes and plants used for tritium isotope Part II describes the processes and plants used for tritium isotope
separation, enrichment methods for tritium for analytical purposes, separation, enrichment methods for tritium for analytical purposes,
methods for recovering and enriching tritium from nuclear and methods for recovering and enriching tritium from nuclear and
thermonuclear plants, and the laser method. thermonuclear plants, and the laser method.
The book in general emphasizes applications, performance, The book in general emphasizes applications, performance,
characterization, laboratory experiments, pilot plants and industrial characterization, laboratory experiments, pilot plants and industrial
production, reliability,production, reliability,and cost. and cost.
An author index, subject index, list of acronyms and abbreviations, An author index, subject index, list of acronyms and abbreviations,
and glossary have been included to make the book an even moreand glossary have been included to make the book an even more
valuable reference. valuable reference.
Tritium Isotope Separation is an essential book for all nuclear energy Tritium Isotope Separation is an essential book for all nuclear energy
engineers, nuclear physicists, and others working with various engineers, nuclear physicists, and others working with various
aspects of isotope separation science. aspects of isotope separation science.