Spent Fuel Treatment Options- An Indian PerspectiveP.M. GandhiFuel Reprocessing DivisionBhabha Atomic Research CentreTrombay, Mumbai, INDIA

Three stage nuclear power programme

&

Pivotal role of fuel reprocessing

India has large deposits of thorium and modest deposits of uranium. The nuclear power programme has three stages

1. Series of PHWRs fuelled by Nat. U for producing power and Pu.

2. Use of Pu from the first stage in fast breeder reactors to produce power, more Plutonium and for conversion of Th to 233U.

3. Third stage will be based on Thorium/233U reactors.

Thus reprocessing forms the main link between these stages.

Power Reactors

Operating Reactors Nos x MWe Total MWeBWRs2 x 160320PHWRs 1 x 1001 x 1701 x 2001 x 5409 x 220

2450 Reactors under ConstructionPHWRs 1 x 5404 x 220 1420 PWRsPFBR2 x 10001 x 5002500 Reactor under PlanningAHWR 1 x 300 300

THE STATUS TODAY TECHNOLOGY

EXPERTISE IN PUREX TECHNOLOGY FOR REPROCESSING OF SPENT FUEL FROM RESEARCH AND POWER REACTORS

EXPERTISE IN REPROCESSING OF IRRADIATED THORIUM FOR SEPARATION OF 233U

EXPERTISE IN EFFICIENT WASTE MANAGEMENT

Reprocessing Facilities

FacilitySpent fuel TypeStatusTrombayResearch ReactorIn Operation TarapurPHWRKalpakkamPHWRTrombayIrradiated ThoriaDemonstration FacilityTarapurPHWRUnder Construction

KalpakkamPHWRKalpakkamFBRDesign

Constituents of spent PHWR fuelClosed fuel cycle with partitioning makes senseMost of the U and Pu can be usefully recycledMost of the heat is produced by 90Sr and 137Cs decay in 300 yrsMost of the radiotoxicity is associated with the LLFPs and the MAs and can be transmuted or conditioned in small packages

1 metric ton of SNF* contains (In grams)Uranium 989300Plutonium 3754Minor Actinides237Np 23.96Am 40.72Cm 0.07Long-lived Fission Products129I 36.9699Tc 168.8093Zr 146.30135Cs 20.72Short-lived Fission Products137Cs 221.5090Sr 97.32OthersRare earths 1751.80Remaining 4460.73*6600 MWD/T, 5 year cooling

Chart1

989300

3754

64.7514

318.82

372.78

1751.8

4460.73

Sheet1

Actinide Concentration/THMFission Products Concentration

NuclidegramsNuclideCiHalf LifeunitNuclidegramsNuclideCi

TH2310.00TH2310.0125.5HoursH 30.01H 387.6912.323years

TH2340.00TH2340.3324.1daysGE 730.01GE 730.00

PA2330.00PA2330.0227daysGE 740.01GE 740.00

PA234M0.00PA234M0.331.17mAS 750.03AS 750.00

U23443.95U2340.272.46E+05yearsGE 760.09GE 760.00

U2352510.00U2350.017.04E+08yearsSE 770.19SE 770.00

U236694.40U2360.042.34E+07yearsSE 780.47SE 780.00

U2370.00U2370.356.75daysSE 791.17SE 790.086.50E+04years

U238986100.00U2380.334.47E+09yearsSE 802.75SE 800.00

NP23723.96NP2370.022.14E+06yearsBR 814.56BR 810.00

NP2390.00NP2390.232.36daysSE 826.80SE 820.00

PU2382.88PU23849.3587.74yearsKR 820.08KR 820.00

PU2392674.00PU239166.302.41E+04yearsKR 837.89KR 830.00

PU240899.80PU240205.106563yearsKR 8422.74KR 840.00

PU241138.60PU24114280.0014.35yearsKR 853.65KR 851434.0010.76years

PU24237.98PU2420.153.75E+05yearsRB 8520.67RB 850.00

AM24139.56AM241135.80432.2yearsKR 8637.82KR 860.00

AM242M0.01AM242M0.09141yearsSR 860.03SR 860.00

AM2420.00AM2420.0916HoursRB 8748.61RB 870.00

AM2431.15AM2430.237370yearsSR 8869.66SR 880.00

CM2420.00CM2420.62162.94daysY 8991.29Y 890.00

CM2430.00CM2430.1829.1yearsSR 9097.32SR 9013280.0028.64years

CM2440.07CM2445.4318.1yearsY 900.02Y 9013280.0064.1hours

TOTAL993166.36TOTAL14845.28ZR 9013.81ZR 900.00

Actinide Concentration/THMZR 91118.50ZR 910.00

NuclidegramsNuclideCiZR 92128.30ZR 920.00

HE0.03HE0.00ZR 93146.30ZR 930.371.50E+06years

TH0.00TH0.34NB 93M0.00NB 93M0.0916.13years

PA0.00PA0.35ZR 94150.00ZR 940.00

U989300.00U1.01MO 95158.10MO 950.00

NP23.96NP0.25ZR 96162.50ZR 960.00

PU3754.00PU14700.00MO 962.03MO 960.00

AM40.72AM136.20MO 97161.70MO 970.00

CM0.07CM6.23MO 98167.40MO 980.00

TOTAL993118.78TOTAL14844.37TC 99168.80TC 992.862.10E+05years

989300.00UMO100190.60MO1000.00

SR 9097.323754.00PuRU1007.49RU1000.00

CS137221.5064.75MARU101159.80RU1010.00

318.8290Sr+137CsRU102150.80RU1020.00

ZR 93146.30372.78LLFPsRH103118.90RH1030.00

TC 99168.801751.8RERU104110.30RU1040.00

I12936.964460.73OthersPD10423.05PD1040.00

CS13520.72PD10568.44PD1050.00

RE1751.80RU1061.59RU1065315.00373.6days

Others4460.73RH1060.00RH1065315.0030seconds

PD10681.93PD1060.00

PD10744.95PD1070.026.50E+06years

PD10831.07PD1080.00

AG10917.72AG1090.00

PD1109.45PD1100.00

AG1100.00AG1100.0324.6seconds

AG110M0.00AG110M2.10249.9days

CD1102.92CD1100.00

CD1114.88CD1110.00

CD1122.65CD1120.00

CD1130.03CD1130.00

CD113M0.03CD113M6.0114.6years

IN1130.01IN1130.00

CD1143.47CD1140.00

IN1150.80IN1150.00

SN1150.05SN1150.00

CD1161.24CD1160.00

SN1160.60SN1160.00

SN1171.26SN1170.00

SN1181.28SN1180.00

SN1191.27SN1190.00

SN1201.30SN1200.00

SN121M0.00SN121M0.0450years

SB1211.34SB1210.00

SN1221.44SN1220.00

TE1220.02TE1220.00

SB1231.64SB1230.00

SN1242.03SN1240.00

TE1240.02TE1240.00

SB1250.87SB125897.302.77years

TE1252.48TE1250.00

TE125M0.01TE125M218.9057.4days

SN1265.04SN1260.141.00E+05years

SB1260.00SB1260.0212.4days

SB126M0.00SB126M0.1419minutes

TE1260.13TE1260.00

TE1270.00TE1270.069.35hours

TE127M0.00TE127M0.06109days

I12711.42I1270.00

TE12822.01TE1280.00

XE1280.15XE1280.00

I12936.96I1290.011.57E+07years

TE13072.17TE1300.00

XE1301.97XE1300.00

XE131107.30XE1310.00

XE132200.30XE1320.00

CS133249.30CS1330.00

XE134299.10XE1340.00

CS1342.27CS1342943.002.06years

BA13411.28BA1340.00

CS13520.72CS1350.022.00E+06years

XE136515.70XE1360.00

BA1362.17BA1360.00

CS137221.50CS13719270.0030.17years

BA13729.85BA1370.00

BA137M0.00BA137M18230.002.55minutes

BA138257.00BA1380.00

LA139245.50LA1390.00

CE140253.80CE1400.00

PR141226.60PR1410.00

CE142230.70CE1420.00

ND1423.63ND1420.00

ND143149.00ND1430.00

CE1441.56CE1444967.00284.8days

PR1440.00PR1444967.0017.3minutes

PR144M0.00PR144M59.607.2minutes

ND144277.20ND1440.00

ND145141.80ND1450.00

ND146130.80ND1460.00

PM14715.31PM14714190.002.62years

SM14749.23SM1470.00

ND14874.55ND1480.00

SM14821.26SM1480.00

SM1490.98SM1490.00

ND15035.45ND1500.00

SM15054.15SM1500.00

SM1511.27SM15133.3993years

EU1510.05EU1510.00

SM15236.59SM1520.00

EU1520.00EU1520.1613.33years

EU15317.16EU1530.00

GD1530.00GD1530.01239.47days

SM1547.56SM1540.00

EU1542.82EU154762.608.8years

GD1541.51GD1540.00

EU1550.86EU155398.804.761years

GD1550.87GD1550.00

GD15612.20GD1560.00

GD1570.02GD1570.00

GD1583.82GD1580.00

TB1590.49TB1590.00

GD1600.23GD1600.00

DY1600.02DY1600.00

DY1610.07DY1610.00

DY1620.08DY1620.00

DY1630.04DY1630.00

HO1650.02HO1650.00

TOTAL6904.54TOTAL105661.50

H0.01H87.69

GE0.11GE0.00

AS0.03AS0.00

SE11.37SE0.08

BR4.56BR0.00

KR72.19KR1434.00

RB69.28RB0.00

SR167.00SR13280.00

Y91.32Y13280.00

ZR719.40ZR0.37

NB0.00NB0.09

MO679.80MO0.00

TC168.80TC2.86

RU430.00RU5315.00

RH118.90RH5315.00

PD258.90PD0.02

AG17.72AG2.13

CD15.21CD6.01

IN0.81IN0.00

SN14.24SN0.57

SB3.85SB897.50

TE96.84TE219.10

I48.38I0.01

XE1124.00XE0.00

CS493.80CS22220.00

BA300.30BA18230.00

LA245.50LA0.00

CE486.10CE4967.00

PR226.60PR5027.00

ND812.50ND0.00

PM15.31PM14190.00

SM171.00SM33.3936.96

EU20.90EU1162.00168.8

GD18.66GD0.01146.3

TB0.49TB0.0020.72

DY0.22DY0.00221.5

HO0.02HO0.0097.32

ER0.01ER0.001751.80

TOTAL6904.13TOTAL105669.834460.73

6904.131793

Sheet1

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0

0

0

0

0

0

Sheet2

Sheet3

Spent fuel Treatment - PUREX ProcessMajor Chemistry ModificationsCo-decontamination and partitioning cycles combined into one cyclePartitioning agent was changed from ferrous to uranousSalt free reagents for feed conditioningFeed filtration step introduced Waste volume reduction by acid killingTrombay Plant (1964)

Major Engineering ModificationsOptimised column designChange from mechanical pulsing to air pulsingIntroduction of air lifts for meteringAutomation and Remote maintenance for Head-endElaborate interlock systems for safetyEfficient off-gas managementUse of thermosyphon evaporators Use of special grade alloys for construction

AchievementsRecovery of Pu and U > 99.5%Product Decontamination from Fps > 106 Plutonium and uranium recovered are recycled with minimum shieldingHigh Level Waste volume brought down to ~600 liters per ton of spent fuelExposure and discharges are with in the international stipulated values

Spent Fuel Reprocessing - TodaySpent FuelDecladding & DissolutionPurex ProcessHLW containing Fps and MAsUPuVitrificationRepository

Developments in process ChemistryImprove the recovery of Pu and U to 99.9%In-situ partitioning of PuCo-processing and co-conversion for MOXCrystallisation for purificationSeparation of long lived minor actinides and fission products from short lived fission products for efficient waste managementRecovery of useful nuclides like 90Sr, 90Y, PGM, 137Cs etc.Development of new solvents/ sorbentsReduction in environmental discharges

Engineering DevelopmentsReduced Number of cycles with waste volume reduction Head End ModificationsLaser Assisted Single Pin Chopper System Feed ClarifiersRotary Semi-Continuous DissolverFIBRE OPTICCABLE3 Axis CNC for Laser Nozzle & Bundle Gripper Single Pin Hydraulic Chopper

Development of contacting Equipments Columns, electro-pulse columns, Centrifugal Contactors, Mixer Settlers 2. On-line monitoring and control3. Material Development to deal with fluorideEngineering Developments (contd.)CAL-MIX Mixer Settler Centrifugal Contactors

Thorex ProcessPilot Plant facilities for Recovery of 233U from irradiated thoria from research reactors operated in the early 1970s.An Engineering scale facility operated in this domain on a campaign basis for Research Reactor thoria treatment.Another facility is expected to be on stream for 233U recovery from PHWR irradiated thoria bundles used in the initial flux flattening.Facility to treat the spent fuels from AHWR reactor, a hybrid reactor using both (Th-Pu) and (Th-233U) oxide spent fuels is under planning

THOREX Process Flow Sheet

The Future strategy Extending the capability of PUREX to tackle 129I, 99Tc and 237NP

Partitioning the HLLW to extract MAs

Extensive Experimentation with new solventsOctyl(phenyl)N,N-diisobutylcarbamoylmethyl phosphine oxide(CMPO)Tetraethylhexyldiglycolamide(TEHDGA)Tetraoctyldiglycolamide(TODGA) Extracts both trivalent actinides and lanthanides together Actinide-Lanthanide Separation Di-2-ethylhexyl phosphoric acid(HDEHP) TALSPEAK Ethylhexyl(ethylhexyl)hydrogen phosphonate(KSM-17)

The Future strategy (contd.) Am- Cm Separation Oxidation followed by Extraction Separation of 137Cs and 90Sr Ammoniummolybdophosphate Dicyclohexano-18-Crown-6 and derivatives Recovery of useful nuclides 90Y, 147Pm, Pd etc Pyroprocessing for total actinide recycling Laboratory scale studies on molten salt electrolysis using cost effective electrolytes.Injection casting set up inside glove box

ADVANCED FUEL CYCLE

Challenges in AHWR Spent Fuel Reprocessing

Startup core (Pu,Th)O2Equilibrium Core (233U,Th)O2 and (Pu,Th)O2Burnable Poison dysprosium

Challenges

1. Segregation of fuel pins2. Three component 233U-Pu-Th separation3. High 232U content in the 233U product

(Th,Pu)O2

(233U,Th)O2

Burnable Dy+water rod

Thorium Fuel Cycle An Indian Fuel CycleThe advantages are

Abundant availabilityBetter neutronics of 233UBetter stabilityLower Minor Actinide Generation

Challenges

Slow dissolution rate of thoriaBetter dissolver material to combat fluorideDevelopment of Thorex to an industrial scaleThird phase problems with higher thorium loadingTackling of the gamma radiation from 232U daughter productsThree component separation for irradiated (Th,Pu)O2 spent fuel

PHWR Fuel Cycle Fully developedFBR Fuel cycle under Development1. Short Doubling time Metalic fuel 2. Reprocessing Pyro-metallurgical Process Total Recycle of Minor actinides and select FPs Reduced Repository load and Radiological HazardThorium Fuel Cycle Activities Initiated 1. Thorex Development 2. AHWR Fuel Cycle DevelopmentFuel Cycle Scenario