A POSSIBILITY OF NUCLIDES SEPARATION BY SUPER

HIGH TEMPERATRUE TREATMENT METHOD OF HLLW

H. HORIE and M. YONEYA

PNC, Japan

271

PROCEDURE

CALCINATION ; HLLW IS HEATED, WATER IS VAPORIZED AND FP NITRATES DECOMPOSE

TO OXIDES.

SUBLIMATION ; OXIDES ARE HEATED AT 700°C AND CS IS REMOVED BY VAPORIZATION.

MELTING ; NOBLE METALS ARE REDUCED TO METALS DURING MELTING, SEPARATES

FROM OXIDE PHASE AND MELT DOWN

SOLIDIFICATION ; NOBLE METALS AND OXIDE RESIDUE

CONTAINS ALKALI EARTH ELEMENT,

ACTINIDES.

AT THE CRUCIBLE BOTTOM.

ARE SOLIDIFIED. SOLIDIFIED OXIDE

RARE EARTH ELEMENTS, Zr AND

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273

BOILING & MELTING POINTELEMENT

SERbSrYZr

M oTcRuRhP dAgCdInSnSbTeCsBaLaCePrN dP mSmEuG dTb

,DyuNpPuA mC m

BP(”C) I MP~C) I ORIGEN C O D E

METAL

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:,. L ,, .. .141s :,,.. , ‘ ! .’l., . . ’ . ;}., ‘ . .

,,:,

, ,’:; -;-..,,,,.., :, ,

MAIN ELEMENTS

FP MORE THAN lg/MtU IS LISTED UP

1. ALKALI METAL MAY BE REMOVED AT TEMPERATURE BELOW 1000”C.

2. ALKALI EARTH METALS HAVE TO BE. REDUCED, BECAUSE THESE OXIDE’S bp ARE VERY HIGH.

3. HIGH TEMPERATURE TREATMENT IS NECESSARY TO MELT TRANSITION METALS, NOBLE

METALS AND RARE EARTH OXIDES TO SEPARATE METALS FROM OXIDES.

FREE

FREE ENERGY OF OXIDE FORMATION AT 2000K

ENERGY

‘EL DT6NSHJSruyrnddrna r

(kj/atom-0]■ ALKALI

EARTH

❑ RAREEARTH

■ AcTINoID

■ oTHERs

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ELEMENT

THE CONCEPT OF HIGH LEVEL WASTE TREATMENT

1. CONCENTRATION

THIS AIMS TO VITRIFY ALL FP IN HLLW AND TO RELEASE ONLY MINIMUM” VLLW “INTO

ENVIRONMENT. BUT, MLLW SUCH AS BITUMEN OR CEMENT MATERIALS IS PR6DU&D IN

REPROCESSING PLANT. THE EFFORT OF Ml+LW TREATMENT TO SEPARATE INTO HLLW AND

VLLW IS CONTINUED.

2. SEPARATIONN-JU’J

THE SEPARATION OF ALKALI METAL(Cs), ALKALI “EARTH METAL(Sr), NOBLE ‘$?lk~~~(~u, Rh,

P a l ) , .AND TRU IN” HLLW IS IN V E S T I G A T E D F O R L O N G T I M E . THE ADAP~AT:lOti’ ““.~F THIS

PROCESS IS NOT YET SUCCEEDED AT ANY PREPROCESSING PLANT.

3. RATIONALIZATION

THIS IS OUR CONCEPT FOR HLLW TREATMENT.

WE ATTEMPT TO OBTAIN THE MOST COMPACT HIGH LEVEL WASTES AND TO SEPARATE

MANY ELEMENTS IN HLLW AS BY PRODUCTS.

L

ISSUES OF THESE CONCEPT

1. CONCENTRATION – VITRIFICATION

1) LARGE VOLUME ; THIS HAW CAN NOT CONTAIN FP BEYOND

CONCENTRATION IS LIMITED BASED ON FP VOLUBILITY

MATERIAL THERMAL STABILITY.

2) THERMAL POWER ; THE THERMAL POWER OF VITRIFIED

COOLING TIME TO DISPOSE INTO THE EARTH.

2. SEPARATION _– UTILIZATION OF cs AND NOBLE METALS

1) HIGH COST ; THE PRICE OF RECOVERED ELEMENTS = PLANT. . . . ,,. \ ,.

ABOUT 10%, BECAUSE OF FP

IN THIS MATRIX AND THIS

HAW REQUIRES 30–50 YEAR

C O N S T RU CTION & oFJERATIoN

COST/RECOVERED E L EM EN T S s T H E S E P R I C E O N T H E M A R K E T. f?].,. . . . . . . . ,’. . :,. . !!.,..... .,, ,,.2) 2nd WASTE GENERATION ; NEW SOLVENT WASTE AND/OR ION EXCHANGE RESIN WASTE IS

GENERATED. THESE ARE NOT PRODUSED IN PUREX REPROCESSING PLANT.

3. RATIONALIZATION – VERY COMPACT SOLIDIFICATION & SEPARATION AS BY PRODUCTS— —. —..—

OUR CONCEPT MUST ANSWER THE ABOVE MENTIONED ISSUES.

RATIONALIZATIONVOLUME REDUCTION

WASTE MATRIX FP CONTENTVOLUME of WASTE

1 I . . . . . . LZ ,,.. ,. >\,. .,.., .> , . . . . . . !. -, ..., . . . . . ...,.”.,, ,., ,., ,,, , ., !..,- .,, ,,, ,, .’.,

PJJCLEAR RARE EARTH WASTE CERAMICS—

VITRIFICATION OUR METHOD

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COST OF SEPARATION

1.

2.

1.

2.

REPORT BY EXXON NUCLEAR COMPANY(1 978)

REPROCESSING PLANT

,.

PLANT CONSTRUCTION

Cs RECOVERY

Sr RECOVERY

Cs + Sr RECOVERY

REPORT BY PNL(1977)

REPROCESSING PLANT

C A P A C I T Y ;’,5t/d. .PLANT CONSTRUCTION

Cs RECOVERY

Sr RECOVERY

Cs -t- Sr RECOVERY

PLANT

PLANT

PLANT

“ 48M$

95

1’12

CAPACITY ; 2100t/y, BURN UP ; 33,000 Mwd/t

IT DIFF CULT TO OBTAIN USEFUL

PLANT

PLANT

PLANT

THIS HIGH PLANT CONSTRUCT ON.,COST

IN HLLW AT REASONABLE FEE.

SO, USEFUL ELEMENTS IN HLLW MUST BE

PROCESS.

37M$

37

51

MAKES

RECOVERED AS BY–PRODUCT IN ANY

ELEMENT

ANOTHER

E X P E R I M E N T

1. SPENT FUEL CALCULATION

CODE ORIGEN 2

SPENT FUEL

BURN UP 45,000 Mwd/MtU

COOLING TIME 5y

2., SIMULATED HLLW

‘ E L E M E N T ‘“ >1 g/MtU

‘Tc’ IS REPLACED BY Re.

Pm IS REPLACED BY Ce.

3. CALCINATION OF HLLW

TEMPERATURE 700”C

4.SUBLIMATION OF CALCINED HLLW

TEMPERATURE ?00 ,,- 1000”C

ATMOSPHERE ,~.r &i&~

5. MELTING

TEMPERATURE 1800°C

A T M O S P H E R E ~ Ar GAS

SOLUTION : NITRIC ACID SOLUTIN

IQcoN

SUBLIMATION EXPERIMENTS

SEMIVOLATILE FP SUBLIMATION (1 OOO)

-IlkSe Rb

1.

2.

3.

4.

JAg Cd Sn

ELEMENT(OXIDE)

1Te

L-s

❑ Oh

❑ lh• l 2h

OF SIMULATED CALCINED HLLW

1

0

SEMIVOLATILE FP SUBLIMATION (900)

I-1

LiIlllSe Rb

_dl_lAg Cd Sn Te

ELEMENT(OXIDE)

1->

khlie

❑ Oh

❑ lh

❑ 2h

Rb, Ag, Cd, Cs, AND Re SUBLIMED.

Se, Ru, Sn AND Te DID NOT SUBLIME.

Ru IS THE MOST SUBLIMABLE ELEMENT AS THE CHEMICAL FORM Ru04 IN VITRIFICATION

EXPERIMENTS CARRIED OUT UNDER Ar GAS, Ru WAS NOT OXIDIZED ANDPROCESS. IN THIS

NOT VAPORIZED.

THIS EXPERIMENT

BE SEPARATED.

THAT Cs, THE H GHEST

11

THERMAL POWER ELEMANT, S ABLE TO

VAPORIZED

[%)

100

90

Elo

70

60

Cs 50

40

30

20

10

0

Cs VAPORIZATION

rt–800

–900

–1000

o 1 2 3 4. 5 6

TIME(hr]

THE EFFECT

Cs VAPORIZATIONA

OF Cs SEPARATION

THE RATlO OF THERMAL POWER(HLw OF 50Y COOLING TIME= 100%)

400

$ h

-a-9oo

i=:100 -

nl t

o 1 2 3 4 5 6 ‘O 10 20 30 40 50 60 70 80 90100

1.

2.

3.

TIM E(hr) COOLING TIME(Y)

THIS FIGURE SHOWS THERMAL POWER RATlO ON THE BASIS OF 50y COOLING HLLW’S

THERMAL POWER.

THE 23y COOLING HLLW SEPARATED cs HAS EQUAL VALUE TO 50y COOLING HLLW.

IT IS SAID THAT 30–50 STORAGE IS NECESSARY TO LOWER HAW THERMAL POWER TO

PREVENT HEATING UP THE ROCK AROUND DISPOSAL PIT.

cs SEPARATION FROM HAW BY OUR METHOD SHORTENS ABOUT 25Y OF THE STORAGE

TIME.

MELTING EXPERIMENT OF CALCINED HLLW

Oxide

1. THIS FIGURE ILLUSTRATES THE SECTION OF CRUCIBLE AFTER MELTING OF CALCINED

HLLW.

2. THIS IS A PHOTOGRAPH OF THE METAL OBTAINED BY MELTING OF CALCINED HLLW.

3. THUS, CALCINED HLLW WAS SEPARATED TO METAL PHASE AND OXIDE PHASE DURING

METLTING PROCESS.

n

Iii

286

Nco%1

RED~CTION OF NOBLE METALsSTANDARD FREE ENEGY OF OXIDE FORMATION

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——

FREE ENERGY OF MAIN ELEMENT IN HLLW(1800”C)

,,,,,. ,\ .’,’ ,,. ,

NO”:B,iE ,>ME~AL “ ~,:RU’ ‘;.”. ‘,’: :; “Rh ~~ ‘:

“MO “Tc

ALKALI EARTH” METAL

SrBa.’

RARE EARTH METAL

TRU ‘

OUR EXPERIMENT CONDITION, ELEMENTS WHICH HAVE FREE ENERGY MORE THAN THAT

Mo ARE REDUCED.

1.

2,

3.

NOBLE METAL RECOVERY

NOBLE METAL RECOVERY(ANALYSIS)

ELEMENT I ‘YIELD

Ru

Rh

Pd

Mo

:::;. .’ .,;’! ... .1;,.,, ...; ., ..,...;

““”:’ ““101 :’7% “’r

HIGH RECOVERY YIELD OF NOBLE METAL IS

CARRIED OUT.”

RECOVED NOBLE METAL. IS ALLOY W

ANOTHER TRANSITION METAL.

THIS ALLOY IS BETTER FORM FOR SAV

TH

NG

IT FOR EMERGENCY BECAUSE OF IT’S LOW

RADIO ACTIVITY.

FEATURE IN NOBLE METAL RECOVERY

FORMER METHOD N E W METtjOD

N. M. PRODUC

METHOD

REAGENT

WASTE

OTHER

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15

10

CONTENT (%] O

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:

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uxlut COMPOSITION

BNa P CrFe NiSe RbSr YZr MoHu HhPd AgCd In SnSb TeCs BaLa CePr NdSrn EuGd TbDy HReELEMENT (oxIOE)

X-RAY D FFRACTION SPECTRA

I 1 I I I

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** * RESULTS OF 2nd SEARCH MATCH * * *Sample Name J BN-1-M1800 (File name : BN-11OO)

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t )0611 Po

I 111882 [Rul e!)

I 181141 (llu Z R )

I 1“?Sllcc (MO1 N)

t I

X-RAY DIFFRACTION SPECTRA FOR OXIDE PHASE X-RAY DIFFRACTION SPECTRA FOR METAL PHASE

1. THE SHARP PEAK OF OXIDE PHASE SHOWS THAT THIS PHASE IS CRYSTAL AND NOT

GLASS. THIS PHASE CONSISTS IN THREE PHASE, ALKALI EARTH OXIDE, ZIRUKONIA AND RARE

EARTH OXIDE. DETAIL ANALYSIS

2. METAL PHASE CONSISTS IN NOB

IS UNDER INVESTIGATION.

.E METAL AND TRANSITION METAL. X–RAY DIFFRACT ON

RuANALYSIS INDICATES Ru IS METAL FORM AND DIOXIDE. IN THE VITRIFICATION

PRECIPITATES AS DIOXIDE. AS ABOVE MENT

PROCESS, Ru MAY BE EASILY REDUCED.

ONED, Ru IS NOT VAPORIZED. IN OUR

COMPOSITION OF NEW CERAM

UDSr Y

MAIN ELEMENT

r Ag Sn Sb Ba La Ce Pr

IN NEW CERAM

1I

LId Pm Sm Eu Gd U Np Pu AM Cm

ELEMENT(OXIDE)

COMPOSITION OF NEW CERAM

ELEMENT CONTENT

Zr

RARE EARTH

, TRU

TOTAL

1. FIGURE AND TABLE SHOW THE COMPOSITION OF NEW HAW OXIDE ON THE BASE OF

CALCULATION USING ORIGEN CODE.

2. COMPOSITION OF NEW HAW OXIDE IS SIMPLIFIED AS SHOWED IN TABLE.

3. THE MAJOR ELEMENT OF NEW HAW OXIDE IS RARE EARTH ELEMENT. SO IT IS NAMED NEW

CERAM(tjUCLEAR RARE EARTH WASTE CERAMIC).—

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+

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+

CONCLUSION

WE INVESTIGATED NEW HLLW TREATMENT METHOD AND FOUND NEXT.

(1) Cs SUBLIMES ALMOST PERFECTLY AT 1000”C.

(2) NOBLE METAL (AND TRANSITION METAL) IS REDUCED TO METAL AND RECOVERED.

(3) RESIDUAL OXIDE IS THE MOST COMPACT HAW.

(4) ALMOST FPs BEHAVE AS EACH SINGLE OXIDE AND COMPLICATED BEHAVIOR BY

FORMATION OF THESE COMPLEX OXIDES DOES NOT BE OBSERVED IN THIS PROCESS.

(5) IT MAY BE ABLE TO SAY THAT ACTINOID, ALKALI EARTH AND RARE EARTH ACT

IN ACCORDANCE WITH EACH THERMOCHEMICAL DATA AT REDUCTION AND SUBLIMATION.

(0 So, THESE ELEMENT GROUP MAYBE SEPARATED EACH OTHERS.