TRITIUM 2007

TRITIUM REMOVAL and APPLICATIONS

for WOLSONG HEAVY WATER REACTORS

Sep. 2007

S.H. Son*, K.M Song, Y.G Chung

Korea Electric Power Research Institute

K E P R I 1
 CONTENTS TRITIUM 2007

ƒ BACKGROUND
ƒ WOLSONG TRITIUM REMOVAL FACILITY
ƒ TRITIUM REMOVAL PROCESS
ƒ PERFORMANCE TEST
ƒ TRITIUM APPLICATION PROGRAM
ƒ SUMMARY

K E P R I 2
 BACKGROUND TRITIUM 2007

ƒ Wolsong Nuclear Power Plants in Korea

Four heavy water reactors

K E P R I 3
 BACKGROUND TRITIUM 2007

ƒ Tritium(3H or T) Production and Removal

ƒ Tritium production in PHWR : D(n,γ)T, ternary fission, 3He reconv.
ƒ Production rate : 2.4 MCi/Gwe·a
ƒ Emission of a beta particle to form 3He (3H → 3He + β-)
ƒ Half-life : 12.3 yrs
ƒ Maximum energy of β-particles from tritium : 18.6 keV
ƒ Tritium removal from reactor
ƒ Beta decay, heavy water loss & detritiation by tritium removal facility
Calandria Beta decay

Heavy water Heavy water loss

make-up D(n,γ)T
Tritium
Removal Detritiation
Facility
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 BACKGROUND TRITIUM 2007

ƒ Tritium Levels in Heavy Water Reactors

ƒ CPHT = 1.9 x [1 - exp(-0.0755 x t)] Ci/kg D2O (t : operating year)
ƒ CMOD = 88.0 x [1 - exp(-0.0624 x t)] Ci/kg D2O (t : operating year)
2 80

1.8
70
1.6
T ritiu m C o n c e n tra tio n ( C i/kg )

60

Tritium Concentration(Ci/kg)
1.4

1.2 50

1 40

0.8
30
Estimated
0.6 Estimated
W#1
20 W#1
0.4 W#2
W#2
W#3
10 W#3
0.2 W#4 W#4
0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Time(Operating year) Time(Operating year)

Tritium Levels in PHT Tritium Levels in Moderator

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 BACKGROUND TRITIUM 2007

ƒ Tritium Emissions at Wolsong Site

ƒ Tritium emissions are proportional to tritium concentrations
ƒ Large inventory of tritium in Moderator
ƒ Low leakage of heavy water from Moderator system
ƒ Fractional contributions of PHT and Moderator on
environmental emissions

D2O loss fraction Tritium emission

Vapor Liquid Vapor Liquid Total

PHT 0.95 0.86 0.39 0.22 0.36

MOD 0.05 0.14 0.61 0.78 0.64

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 WOLSONG TRTIUM REMOVAL FACILITY
TRITIUM 2007

ƒ Tritium Removal from Wolsong Heavy Water Reactors

ƒ To minimize operator' dose and site emissions
ƒ Alternative option of tritium management for plant life
extension and decommissioning
ƒ Construction Project of Tritium Removal Facility
ƒ Planning of construction project : 1998
ƒ Start of design and engineering : Nov. 2000
ƒ Designed by AECL, KI, KOPEC & KEPRI
ƒ Start of construction : Jan. 2003
ƒ Commissioning(PhaseⅠ- PhaseⅤ) completion : June 2007
ƒ Operation start : July 2007

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 WOLSONG TRTIUM REMOVAL FACILITY
TRITIUM 2007

ƒ Wolsong Tritium Removal Facility(WTRF)

30m x 40m x 24m(H)

ƒ Six level building

ƒ Service area
ƒ Operation area
ƒ Process area

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 WOLSONG TRTIUM REMOVAL FACILITY
TRITIUM 2007

ƒ Key Design Parameters of WTRF

WTRF DTRF
Tritium target level in PHT 0.5 Ci/kg -
Tritium target level in MOD 10 Ci/kg 10 Ci/kg
D2O processing rate 100 kg/hr 360 kg/hr
D2O feed tritium concentration < 60 Ci/kg -
Tritium extraction efficiency per pass 97% 97%
T2 product >99.0% T2 >99.0% T 2
Technologies LPCE + CD VPCE + CD

ƒ LPCE : Liquid Phase Catalytic Exchange

ƒ CD : Cryogenic Distillation
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 WOLSONG TRTIUM REMOVAL FACILITY
TRITIUM 2007

ƒ Effects of WTRF on Tritium Inventory and Emission

at Wolsong Site
70 100

Inventory w/o W TRF 90

60 Inventory w W TRF
80
Emission w/o W TRF
50 70
Tritium Inventory(MCi)

Emission w W TRF

Tritium Emssion(kCi)
60
40
50
30
40

20 30

20
10
10

0 0
2

0
'8

'8

'8

'9

'9

'9

'0

'0

'0

'0

'1

'1

'1

'2

'2

'2

'3
Time(Year)

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Tritium Removal and Immobilization Processes

ƒ Liquid Phase Catalytic Exchange of front-end process
ƒ Hydrogen isotope exchange between deuterium and tritiated heavy water
ƒ Korean-developed wetproofed catalyst
ƒ Cryogenic Distillation (CD) of back-end process
ƒ Separate D2 and T2 by distillation at ~25 K
ƒ Kinectrics design
ƒ Tritium Packaging and Storage
ƒ Measure quantity of T2 removed
ƒ Store T2 as a metal tritide for safe storage

DTO/D2O DT/D2
CANDU Front-end Back-end T2
Immobilization
Reactor Process Process
D2O D2
LPCE CD Metal tritide

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Liquid Phase Catalytic Exchange Process(LPCE)

ƒ LPCE reaction
ƒ Tritium transfer from tritiated heavy water to D2
ƒ Highly stable and active catalysts in the presence of water
ƒ DTO(v) + D2 ⇔ DT + D2O(v) on catalyst
ƒ DTO(l) + D2O(v) ⇔ DTO(v) + D2O(l) at vapor-liquid interface
ƒ Idea of isolating Pt from liquid water
ƒ Developed by Stevens, Rolston, etc. in Canada
ƒ Hydrophobic supports or wet-proof coating
ƒ Pt/carbon with Teflon coating : particles and structured packing
ƒ Korean-developed Hydrophobic Catalyst
ƒ Supported Pt catalyst : Pt/SDBC
ƒ Separated-bed type reactor for LPCE
ƒ Applied to Wolsong Tritium Removal Facility of KHNP

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ LPCE Column of Separated-bed Type

DTO(l) + D2O(v) ⇔ DTO(v) + D2O(l)

DTO(v) + D2 ⇔ DT + D2O(v)
Height :
600

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Korean-developed Hydrophobic Catalyst

ƒ Hydrophobic support : SDBC pellet (4mm x 4mm)
ƒ Polymerization with tubular reactor(80oC, 15hrs)
ƒ Impregnation with H2PtCl6
ƒ Reduction with H2 (230oC, 15hrs)
BET (m2/g) 450
Density(g/cc) 0.18
Pt loading(weight %) 0.8-1.0
Pt dispersion(%) 100
Mean pore radius(nm) 6.0

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ LPCE Column Modelling

DT/D2 Heavy Water
Purification Feed
Condenser
L=F+V, xN+1
zN yN’
Mass transfer
Nth stage α r / γ g − (α d / γ l ) M +1
zN yN yn − yn'
=
Catalytic exchange yn − xn +1 / α d 1 − (α d / γ l ) M +1

Mass transfer
2nd stage z2 y2 α r γ g Eff c γ Eff c '
yn = ( ) z n −1 + (1 − g ) yn −1
Catalytic exchange x2 αr + γ g αr + γ g
’
z1 y1
Mass transfer Eff c α r Eff c
z n = (1 − ) z n −1 + ( ) y n' −1
1st stage z1 y1 αr + γ g αr + γ g
Catalytic exchange
zo yo’ x1
Humidifier
DT/D2 Heavy Water
Purification G, zin L, xo Product

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ LPCE Column of WTRF

ƒ Design parameters for WTRF

Heavy water feed(moles/hr) 5,000

Deuterium gas feed(moles/hr) 10,000

Operating temperature(oC) 70 to 73

Operating pressure(kPa) 120 to 145

Number of stages 55(28/27)

Column Diameter 0.6m

Column Height(m) ~ 22m

Detritiation factor 35

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Cryogenic Distillation Column

ƒ Deuterium Gas Purification System
ƒ To remove water vapor and all condensable gases from the D2/DT
ƒ Major components : oxygen catalytic converter, molecular sieve dryer,
cryoadsorber, pumps
ƒ Cryogenic Distillation Columns
ƒ To separate D2, DT and T2 in distillation columns operated at ~24-26 K
ƒ D2 with reduced DT content is returned to LPCE column
ƒ T2 is produced and removed to Tritium Handling System for packaging.
ƒ Major components: high vacuum cold box, 4 distillation columns,
catalytic conversion equipment (for T2), pumping system, heat
exchangers, expansion tanks
ƒ Helium Refrigeration System
ƒ To provide cooling to the CD columns
ƒ Major components: compressor, He purification, He buffer tank,
refrigeration cold box containing the expansion engine
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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Cryogenic Distillation Column

He 35 kW, 1125 g/s
. Refrigerator

Helium H2
Full TM
Expansion Monitor vacuum
Tank
H2
TM Monitor

LT Cold Box
Expansion
HT Expansion
Tank Clean Up
Tank
127 m3 2 m3
TM

1m(D) x 2.5m(L)
T2
Diameter in the lower section : 1.3 m
Clean Up
Diameter in the upper section : 1.1 m
TM
Height : 25.7 m PM

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Cryogenic Distillation Design Parameters

CD1 CD2 CD3 CD4

Diameter(mm) 495.3 108 30.1 13.4

Height(m) 21.05 3.4 2.96 2.55

Gas flow rate(mole/h) 10,000 325 20 4

Condenser duty(W) 27,000 850 60 10

Detritiation factor 50

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Tritium Immobilization
ƒ To receive tritium(T2) in ~50,000 Ci batches(10 batches)
ƒ Limit heat generated during immobilization
ƒ Limit consequences of a malfunction
ƒ To determine tritium quantity by PVTc (pressure, volume,
temperature and concentration)
ƒ Tritium accountability
ƒ To store tritium as metal tritide
ƒ Low equilibrium tritium pressures at room temperature
ƒ Standard practice world wide
ƒ A high-integrity(dry N2) glove box, a glove box
atmosphere monitoring and control system, a getter-
based tritium recovery system, an air purged enclosure
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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Tritium Immobilization
Nitrogen Pure Gas to
Building Exhaust From Cryogenic
Vacuum
Distillation
Pump
System

To Purge Gas
& Recombiner
System Dry N2 Glove Box
Tritium
Metering
Pumping
Tank
System
He supply

Storage D2 Supply
Vessels
Ti Ti
Inert
Circulating
Blower U Glovebox
Nitrogen
Purge Gas
Air Purged enclosure Air
Closed-Loop Gas Analysis
Air
Glove Box system Purge
Exhaust
Cleanup System

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 TRITIUM REMOVAL PROCESS TRITIUM 2007

ƒ Tritium Storage Tank • Stainless steel 316L

• 6.5L in volume
1/2" VCR
CONNECTOR VALVE • 2µm porous SS filter
PROTECTOR

BELLOWS
SEALED
• Bellows sealed valve
VALVE
• 10–6 torr ~ 64 atm

• 0.5 MCi per vessel

89

• Titanium sponge : ~1 kg
POROUS
S.S. FILTER
2µ FILTER - 99.5% purity(Aldrich)
1/2" TUBE - Particle size : 2 - 12mm
308

OD
(12.7x2.1t) 6" SCH.40
(OD 168.3)
- Activation at 500oC

TITANIUM
SPONGE
89

PIPE CAP
6"SCH.40
168

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 PERFORMANCE TSET TRITIUM 2007

ƒ Performance Test Targets

ƒ Overall tritium extraction efficiency : 97%
ƒ Detritiation factor = 35
ƒ Tritium extraction efficiency of CD : 98%
ƒ Detritiation factor = 50
ƒ Tritium product : > 99% T2
ƒ Heavy water loss : 0.1 kg/day

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 PERFORMANCE TSET TRITIUM 2007

ƒ Overall Tritium Extraction Efficiency

= Tritium Extraction Efficiency of LPCE process
60 100

90
50
80
Tritium concentration(Ci/kg)

70
40

Detritiation factor
60

30 50

40
20 Feed Concentration(Ci/kg)
Product Concentration(Ci/kg) 30
Detritiation Factor(%) 20
10
Detritiation Factor
10

0 0
3:00 9:00 21:00 9:00 15:00 21:00 9:00 15:00 21:00
16 APR 07 17 APR 07 18 APR 07
Time

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 PERFORMANCE TSET TRITIUM 2007

ƒ Tritium Extraction Efficiency of CD process

Test Low tritium High tritium

Series no. 1 2 3 1 2 3
Detritiation
66.8 66.9 66.2 62.8 64.3 65.1
factor

ƒ Tritium Product
ƒ Tritium purity : 100% T2
ƒ Tritium product during commissioning : 2.2 MCi

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 TRITIUM APPLICATION PROGRAM TRITIUM 2007

ƒ To build-up Infrastructure to Support Tritium

Research Activities in Korea
ƒ Industrial applications : EXIT Signs, Runway landing lights for
remote airfields, Radio-luminous colors, Timepieces, etc
ƒ Research fields : fusion energy research, nuclear physics,
medical, chemical and geological research, especially as
tracer
ƒ To Support Tritium Control and Accountability
Systems
ƒ Exchange of Notes between the Government of the Republic of
Korea and the Government of Canada
ƒ Administrative Procedures established by the Ministry of Science
and Technology and the Canadian Nuclear Safety Commission
ƒ Nuclear Laws & Notice for Expert Permit in Korea

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 TRITIUM APPLICATION PROGRAM TRITIUM 2007

ƒ General Arrangement of KEPRI Tritium Laboratory

T
M

GC/MS
1 Air Lock
T T
M Glove Box 1 M
T 6 5
M
8
T
Glove Box Glove Box 2 M
T
3 7
M
2

ACS
Tritium
TRS Air Purged Enclosure Storage
PGRS
Dismantling
T T
Calorimeter
M M
1 9
T T
0
M M Glove Box Glove Box
3 4
5 4

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 TRITIUM APPLICATION PROGRAM TRITIUM 2007

ƒ Tritium Recovery System for KEPRI Tritium Lab.

1 2 3 4
STACK
1 1

HVAC
HV AC
GB1 TM
GB2 TM
TM
GB3 TM

TM

2 2

TFS TM
TRS
(2 TRS
trains) PGRS ACS
GB1 PGRS ACS
(2 trains) PGRS
GB2 GB1
GB3 GB2
GB3
TM
3 3

Glove Box
Glove Box

TFS GB1 GB2 GB3 GB1 GB2 GB3

4 4

1 2 3 4

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 TRITIUM APPLICATION PROGRAM TRITIUM 2007

ƒ Tritium Storage and Assay System

pirani P Vacuum
Gas
TRS
Chromatography

P T

T,P

P T

T,P

TM
T,P

Argon

Helium

T storage tank T storage/cleanup tank(U) T Metering Recirculation blower T storage tank(U or ZrCo)
from outside with cavity wall tank (Injection & recovery) (L, M, S, ITER)

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 SUMMARY TRITIUM 2007

ƒ The WTRF has been constructed to reduce tritium

levels in heavy water reactors at Wolsong site in Korea.
ƒ Minimize operator dose and site tritium emissions
ƒ The WTRF is based on the detritiation process of
[LPCE+CD] and removes tritium from the heavy water,
enriches it as T2 and stores recovered tritium in a safe
metal tritide.
ƒ Tritium produced from the WTRF will be used for
industrial applications and fusion energy research
ƒ Peaceful purposes only
ƒ Prior written consent of the Government of Canada
ƒ Infrastructure for tritium research activities and reliable
accountability in Korea

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