RL- 4 4 DISCLAIMER

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsi- bility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Refer- ence herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recom- mendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

Cover Sheet for a Hanford Historical Document Released for Public Availability

Released 1994

Prepared for the U.S. Department of Energy under Contract DE-AC06-76RLO 1830

Pacific Northwest Laboratory Operated for the U.S. Department of Energy by Batteile Memorial Institute

DISCLAIMER

Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.

I

RL 4-3

Hanford Category C-65

- i -

Date 6-30-68

RICHLAND FIVE-YEAR 02 R&D P R O G R A M

TRANSPLUTON IUM

RICHLAND OPERATIONS OFFICE ATL,4NTIC RICHFIELD HANFORD COMPANY

BATTELLE-NORTHWEST DOUGLAS UNITED NUCLEAR, INC.

MC-RL R l C W M N L WASH.

R I C H L A N D F I V E - Y E A R

0 2 R & D P R O G R A M

T R A N S P L U T 0 N I U 14 P R 0 G R A M - M I S S I O N 3

June 30, 1968

RICHLAND OPERATIONS O F F I C E

ATLANTIC R I C H F I E L D HANFORD COMPANY

BATTELLE - NORTHWEST

DOUGLAS U N I T E D NUCLEAR, INC.

P L E A S E S I G N B E F O R E R E A D I N G

P.R. Files

I I

RL 4-3 Page 2

R I C H L A N D F I V E - Y E A R

' 0 2 R & D P R O G R A M

T R A N S P L U T O N I U M P R O G R A M - M I S S I O N 3

PRINCIPAL CONTRIBUTORS

G. F. Owsley DUN

M. Szu l insk i ARHCO

SUMMARY

B A S I C PRODUCTION M I S S I O N

COPRODUCT M I S S I O N

TRANSPLUTONIUM PROGRAM

P U - 2 3 8 PROGRAM

OTHER I S O T O P E S

ENRICIIED FUEL P R O C E S S I N G

TARGET S P A C E ENHANCEMENT

R L 4-3 Page 3

R I C H L A N D F I V E - Y E A R

0 2 R & D P R O G R A M

NUCLEAR SAFETY PROGRAM

WASTE MANAGEMENT

COLUMBIA R I V E R STUDIES

R L 4-0

R L 4-1

R L 4-2

R L 4-3

R L 4-4

RL 4-5

R L h-6

R L 4-7

R L 4-8

R L 4-9

RL- 4-10

RL 4-3 Page 4

TABLE OF CONTE2TS

SCOPE AJJD OBJECTIVE3

IBCE~~TIVES

PROGRESS D’dRIIIG THE REPORT PERIOD

EVKLJATZOEI SF WORK TO DATE

BUDGET PER103 PLATIS AN3 EXPECTED RESCZ?S

SCHE3USE 3F ACTIVITIES

STATISTIZAL SLJMbfARY SCHEDirLE

P R O G R A M S C r n r n -

5

6

7

8

12

15

16

TRANSPLUTONIUM PROGRAN - N I S S I O N 3

Introduction

This program is directed to the production of higher weight plutonium isotopes and transplutonium isotopes from the i r radiat ion of transuranic elements, par t icular ly plutonium. Np-237 and Am-241 is the subject of Mission 4, PU-238 Program, it is excluded from t h i s Mission. and plutonium containing a high concentration of e i ther the Pu-240 isotope or the Pu-242 isotope. sowce i n the 1970's, the main emphasis has been t o provide the capabili ty f o r producing t h i s isotope. I n support of t h i s program, irradiatZons have been performed t o obtain isotopic buildup ra tes , and a production and economic calculational model has been prepared for determining production methods and costs of producing Cm-24-4 i n the Richland complex+

Since production of PU-238 from t h e i r radiat ion of

Specific products which are of prime in te res t are Cm-244

Because of the poten t ia l in te res t i n Cm-244 as a heat

The Richland production reactors have par t icular advantages i n producing higher weight plutonium isotopes f rm the i r radiat ion of plutonium because of a desirable neutron flux spectrum and a high heat removal capability. high temperature thermal neutron flux maximizes the capture-to-fission r a t i o of the Pu-239 and Pu-241 isotopes; the high heat removal capabili ty provides f o r the large decrease i n heat generation i n the plutonium elements with minimum ef fec t on reactor power levels and efficiency.

Specifically, the

Based on the developed technology, a program for i r radiat ing 10 kg of plutonium t o produce higher weight plutonium isotopes, Am-243, and Cm-244, was recently authorized; preparation for t h i s i r rad ia t ion and fabricat ion of the elements is proceeding. program may require substant ia l plutonium irradiat ion by 1970, The authorized i r rad ia t ion w i l l serve t o demonstrate the capabili ty of the Richland production complex t o perform such large scale plutonium irradiat ions.

The Cm-24.h production program and possibly the f a s t reactor

This program also includes investigation of the attractiveness of producing '3-252 i n the reactor from the i r radiat ion of Cm-244 and Am-243.

Scopc and Objectives

The pr incipal objective of t h i s program is t o identif'y and t o provide the capabili ty f o r producing -large quant i t ies of Cm-244 and the intermediate plutonium and americium isotopes from the i r radiat ion of plutonium i n the Richland reactors

Reactor operation with an inventory of' us t o 150 kg t o plutonium i n C Reactor and up t o 300 kg i n the K and N Reactors is being examined. operabili ty problems and the economics of such i r radiat ions are being investi- gated. The cost and best methods w i l l be determined f o r me t ing poteut ia l customer requirements, whether they be for a plutonium fuel containing the heavier plutonium isotopes, f o r a sat isfactory feed material for the Cm-244 program, or

Safety and

t o obtain substant ia l t i on of the plutonium

quantit ies of cm-244 directly. w i t h other loadings which my be i n the reactor t o achieve

This a lso includes integra-

1

RL 4-3 Page 6

maximum u t i l i za t ion of the neutrons and provide smooth operational t rans i t ion a s the fissionable isotopes are consumed. Also, concentrated effort is required to predict isotopic buildup in the reactors. In-reactor i r radiat ions have been coxpleted which support the calculational model development. i r radiat ion w i l l provide more precise data for establishing effect ive neutron cross sections and w i l l a id i n developing fabrication and reprocessing technology. In the fue ls area, e f f ic ien t manufacturing p_rocesses w i l l be developed with prLmary emphasis, a t l ea s t i n i t i a l l y , on PuAl elements, but investigations w i l l be made of oxide fue ls and other ca r r i e r materqals. Investigation of the f e a s i b i l i t y and production capabili ty of producing Cf-252 from the i r radiat ion of Cm-244 w i l l be investigated. It is planned t h a t t h i s study w l ' l l include t e s t scale irradiations.

The scheduled

The plutonium recycle program in Pacif ic Morthwest Laboratories has provided mch of the needed separations technology. However, handling large quantit ies of plutonium ef f ic ien t ly requires the development of flow sheets t o u t i l i z e existing f a c i l i t i e s . i r radiated plutonium fuels of high kurnout i n Atlantic Richfield Hanford Company- operated f a c i l i t i e s , recovering not only the plutonium, but also the trans- plutonium elements, americium and curium, Also, the technology f o r processing americium ta rge ts for curium recovery and f o r purif icat ion of americium and curium products w i l l be provided.

Incentives

The technical bases w i l l be developed f o r processing

.

The incentives for Frradiating plutonium i n the reactor a re d i rec t ly dependent upon the market f o r the ashes of the irradiation. However, since the plutonium would be u t i l i zed as an enrichment for other irradiations, the reactor process- ing costs w i l l be re la t ive ly small. foreseen: reactor development program, ( f a s t breeder plutonium f u e l is included i n mission 1, Easic Production) and high Pu-240 plutonium for exploiting the Phoenix f u e l concept. heat producing isotope or as feed for producing Cf-252), t h i s program fs receiving prime emphasis. However, the developed technology is fully applicable t o plutonium processing f o r other purposes.

A t presen'c three poten t ia l markets are Cm-244, plutonium f u e l of specific isotopic content f o r the f a s t

Since the most promising market foreseen is for Cm-244 (e i ther a s a

In the Cm-244 program, the Richland reactors are ideal ly suited for producing the Pu-2k2, which is an intermediate isotope i n the production of Cm-244. advantages are as follows: The higher temperature thermal neutron flux of the graphite moderated reactors maximizes the quantity of feed Pu-239 converted t o Pu-242; second, %he high heat removal capabill ty of the Richland reactors permits burning of the fissionable isotopes, Pu-239 and Pu-241, i n a single i r rad ia t ion without requiring rmjor expense t o maintain full operating efficiency; third, the Richland reactors have a versa t i le capabili ty for u t i l i z ing the neutrons produced i n the plutonium f u e l a t the s t a r t of the i r rad ia t ion fo r producing a variety of products, and fo r adjusting the loading as the plutonium burns out without compromising reactor operating economics or neutron u t i l i za t ion efficiency.

These

Also, a substant ia l portion of the Pu-2b2 can be converted t o hi-2b3 and Cm-244 d i rec t ly vithout s n bnterxediate separation and fabrication step.

"he Richland reactors can also be utilized. t o obta.'n E vide range of assays by u t i l i z ing the wide ranges of plutonium assays available f o r i n i t i a l f u e l m t e r i a l , controlling the residence t i m e , and ta i lor ing the neutron energy spectrum by such means as varying the graphite moderator temperatme and the makeup of the plutoniurn eleinent.

The Phoenix fue 1 progrem would require plutonium containing a large concentration of Pu-240. u t i l i z e p lu toniw with a very hi& Pu-240 concentration, spectruq i n the Richland reactors can be macle par t icular ly e f f i c i en t for convert- ing Pu-239 t o Pu-2110 with a minimm amount of f i ss ions and f o r concentrating the Pu-24'3 with a rninimwi conversion t o Pu-241. Experimental r e su l t s have conPirmed t h a t Pu-240 concentrations i n plutonium i n excess of 60 percent could be attained. A plutonium irradiat ion pi-ogi-an also complements t'ne plan fo r considering Rich- land as a plutonium storsge center. Plutonim-having a wide range of isotopic assays would be available and could be obtained quickly f o r fabricating and i r radiat ing in . the reactors t o meet customer requirements.

Also, productive investigations i n the f a s t reactor program could Toe neutror, energy

The incentives f o r i r rediat ing Crii-244 t o produce Cf-252 i n the Hanford reactors are uncertain. high t o .ttIie such i r radiat ions a t t rac t ive ; however, the effect ive cross sections for these higher weight isotopes i n the HarSord f lux spectrum are unresolved. Consequently, a small scale Cn-241! i r rad ia t ion from VhLch the cross sections and hence the Cf-252 cepabili ty can be assessed is considered a desirable extension of the technology.

The flux l eve l i n the Hanford reactors nay not be suff ic ient ly

Progress During the Report Period

The i-esults of the small scale i r radiat ion completed i n Fy-1967 were subjected t o rigorous analysis t o assess -L;fie pertinent cross sections and t o determine the covTidence level t o assign t o the buildup predictions, r e l a t ive neutron cross-section values were derived from the analysis:

-- _c_

The following

.E14°/~29 =.166 + . 483 x 1 0 - 5 / ~ 4 0

a,41/0 a" 9 = . 965

a"" = . 503

d effective neutron mZcroscopic Ci-OSS section

a i capture-to-fission r a t i o

N40 E the concentration of the Pu-240 isotope i n units of atom/barn-Cm.

RL 4-3 Page 8

Based on these measured a Is, 9.5% of the or iginal Pu-239 would escape f i s s ion and thus be converted t o Pu-242, a value which matches ca lcu la t l ions. the Pu-242 absorption cross section was not possible because of uncertainties and apparent discrepancies i n the measured Am-243 concentrations i n the irradiated plutonium elements; re-measurements of the Am-243 concentrations are scheduled. However, measured concentrations of cm-244 were consistent with the predicted values.

Evaluation of

The fabrication, loading, and operating plans fo r i r radiat ing the recently authorized 10 kg of plutoni.um have been developed. The operating mode is designed t o maximize the plutonium conversion r a t e t o the higher weight isotopes i n an e f f ic ien t manner. obtained and fabrication of the plutonium f u e l elements has been ini t ia ted. Supporting stwlies and t e s t s were progressing sa t i s fac tor i ly t o meet a charge date i n September, 1968, code (CUPID) to more closely match the experimental data, f u l l y operational for planning and optimizing a generalized Cm-244 production program a t Richland.

Also, plutonium of a high Pu-240 content (- 20 percent) was

A major modification Was made t o the Cm-24.4 production The Cm-244 model is

The processes required t o decontaminate americium and curium from f i ss ion products and t o separate the americium from %he curium were developed and used t o recover an americium and curium product of high purity from the waste which resulted from processing the Shippingport blanket. d i (2-ethylhexyl) phosphoric acid (D2EXPA) solvent extraction purif icat ion of the Am-Cm-Rare Earth crude which had been collected by 5076 TBP extraction of the Shippingport waste; followed by chromatographic ion exchange using DTPA (diethylenetriaminepentaacetic acid) an8 NTA ( n i t r i l o t r i a c e t i c acid) as complexants for successive elutions. The function of the f irst elution was to separate the Am-Cm from the lathanide r a re earths and the second to separate the Am from the Cm. extraction process was refined, SAMRM vice PAMEX processes, such t h a t separation of the Am-Cm from most of the lanthanides is possible i n , t h i s step. Further work on separation of Am from Cm by simple solvent extraction technology appears less favorable a t t h i s time. technology applicable t o the recovery and purif icat ion of americium and curium was developed. The technologies used a re l i s t ed in Table I. Typical concentra- t i on curves during the DTPA and PITA elutions are given i n Figures I and 11. The developed techniques are powerful tools t h a t can be useful i n r a re earth-actinide processing, w i t h t he major unresolved problem being the path of the transcilr!ums, berkl'ium and californium, and the operating parmeters which could o p t i d z e the productive capacity of the process. It is l lxely also t h a t the process couui be adapted t o the recovery of products from irradiated plutonium; and it is proposed t h a t the plutonium currently planned fo r i r radiat ion a t Hanford be processed i n t h i s manner. process does not appear too favorable due t o the high energy output of the Cm-242, it appears t ha t yttrium w i l l follow curium and t h a t yttrium-curium-242 mixtures of reasonable heat output per gram of mixture could be processed successfully.

The processes used a t Hanford were a

Subsequent t o the recovery campaign, the D&A solvent

In the course of the recovery caqaign, considerable

Although the separation of Cm-242 from Am-241 by the chromatographic

These processes need fur ther development.

Evaluation of Work t o Date

The experimental r e su l t s have confirmed, with minor modifications t o neutron cross sections, the va l id i ty of the production model i n predicting isotope -

I TABLT: I

AMERICIUM-CURIUM TECHNOLOGY

B N W A R H C O L A B S C A L E P I L O T S C A L E P L A N T S C A L E

C R U D E R E C O V E R Y

. P O W E R R E A C T O R WASTE S U L F A T E P P T T B P EXT.

H A N F O R D P U R E X W A S T E S U L F A T E P P T D L E H P A EXT.

L A N T H A N I D E - A C T I N I DE REF I N I N G

D2EH P A

L A N T H A N I D E - A C T 1 N I DE S P L I T

C H R O M A T O G R A P H I C I O N E X C H A N G E

A C T I N I D E S E P A R A T I O N A N D P U R I F I C A T I O N

C H R O M A T O G R A P H I C I O N E X C H A N G E

)< X X

X X

X X

X X

X 0

@ T E C H N O L O G Y U S E D FOR S H I P P I N G P O R T A m - C m R E C O V E R Y

X X

c 0 N

C O L U M N EFFLUENT S O L U T I O N C O N C E N T R A T I O N ( c o u n t i n g rate -arbitrary scale)

Y 0

W

c 0

L 0 P VI

t

ll

Q ;P 0 0 c c) I .

PW 0

c. 0 0

C O L U M N E F F L U E N T S O L U T I O N C O N C E N T R A T I O N ( c o u n t i n g rate -arbi trary s c a l e )

c 0

01

R i 4-3 Page 12

formation r a t e s up t o Cm-244. A s noted above, the experimental r e su l t s confirm the advantages of the Hanford reactors i n maximizing the conversion of Pu-239. Development of i r radiat ion techniques, including flux ta i lor ing, haE txoceeded t o the point t h a t a p i l o t scale plutonium loading 2nd operating modes nave 3een designed which should maximize the transmutation r a t e of the plutonium and overal l reactor production efficiency.

Processes were devised and used t o recover and purify americium and curium from waste generated by recovering the plutonium and neptunium from the Shippingport reactor blanket. n i t r i c acid system which is compatible w i t h s ta in less s t ee l s normally used i n separations plants. Processes under development fo r use a t other s i t e s u t i l i z e solvent extraction i n a chloride system which requires exotic materials of construction, and a precipi ta t ion process for separation of Am and Cm, which is d i f f i c u l t t o operate with a high degree of separation. recovery campaign, the solvent extraction processes were improved (XAMREX vice PAMEX) t o the extent t h a t capacity and performance of the f i n a l ion exchange process is fur ther enhanced. Incidental t o the technology developed, the isotopic composition of the curium appears t o be very useful t o the atomic energy program, since the Cm-245 content is substantially higher than tha t of material which has been available. The isotopic composition is a s follows:

The s ignif icant achievement is t h a t these processes are i n a

Subsequent t o the

Cm-243 - 1.4% -244 - 93.91%

-246 - 0.62% -245 - 3 98%

Budaet Period Plans and Exxtected Results

The i r radiat ion of 10 kg of plutonium i n the K Reactors was recently arithorized. Fabrication has been in i t i a t ed and reactor charging w i l l take place ear ly i n FY-1969. Evaluation and optimization of the ta rge t fabr icat ion process w i l l be undertaken during the fabrication of the t e s t material. Pu-A1 ta rge t elements on a sustained program w i l l be studied during the present campaign.

Capability for fabricating

Although the i r radiat ion time f o r t h i s loading has not been defined, it is anticrpated t h a t an 18-month t o five-year period w i l l be selected, depending on the f i n a l use and scheduled need for the material, (- 6@) w i l l occur w i t h less than six-months i r radiat ion while the maximum Pu-242 content w i l l occur a f t e r about two years of irradiation. t o obtain curium i n a single i r radiat ion step, an i r radiat ion time of three t o f i ve years is more optimum. Based on previously estimated Pu-23g.burnout required pr ior t o t ransferr ing the material t o a Savannah River high f lux charge, and i r rad ia t ion time of nine montbs t o one year is minimum. the plutonium elements w i l l be discharged a t intermediate exposures t o assure sat isfactory element performance and accurate prediction of isotopic formation rates .

The maximum Pu-240 content

If it is desired

Mnitor columns Df

The detai led evaluation of the Pu-242 absorption cross section from re-measurement of the Am-243 content is scheduled t o be completed'early i n Fy-1969. Also, a comprehensive production and economic study of an optimized curium production

RL 4-3 Page 13

mode a t Richland w i t h current technology w i l l be performed i n response t o indicated needs fo r the information.

Fabrication of capsules containing small, tes t quantit ies of Cm-244 w i l l be completed for charging i n K Reactor l a t e in FY-1969. irradiation, which w i l l probably require two t o four years ' reactor residence time, w i l l be t o assess the buildup characterist ics of trans-curium isotopes i n the Hanford reactors.

The purpose of t h i s

No work i n the separations area is planned during FY-1969 due t o the lack of funds. implemented. solvent extraction and ion exchange processes indicated, and if possible, the path of the t r a n s c u r i w w i l l be determined. The processes w i l l be optimized and other complexing agents tested. these processes will be made.

In FY-1970, plans t o process the irradiated plutonium and Cm-244 w i l l be The irradiated plutonium w i l l be processed by the combination of

Engineering studies on the application of

RL 4-3 Page 14

Reports Issued

E. J. Wheelwright, F. P. Roberts, L. A. Bray, G. L. Ritter, A. L. Boldt, "Simultaneous Recovery and Purification of b, Am and Cm by the Use of Alternating DTPA and NTA Cation Exchange Processes, BNWL-SA-1492, March 6 , 1968 . L. A. Bray and G. L. Ritter, "Solvent Extraction Purification of Americium with Di( 2-ethylhexyl) Phosphoric Acid," Invention Report, CFDIR-142 , May 8, 1967 a

L. A. Bray, "Solvent Extraction Purification of Americium with Di( 2-ethylhexyl) Phosphoric Acid," BNWL-SA-l446A, October 2, 1967.

L. A. Bray, "Solvent Extraction of the Shippingport Transplutonium and Rare Earth Elements using Di ( 2-ethylhexyl) Phosphoric Acid ," BNWL-CC-1433, December 1, 1967.

G. L. Richardson, "Pilot Plant Demonstration of the SAMREX Process," BNWL-CC-1455, January 18, 1968.

RL 4-3 Page 15

Schedule of Activit ies

Complete fabrication and i n i t i a t e i r radiat ion of 1 0 kg of plutonium - September,

1968.

Complete capsule fabrication and i n i t i a t e i r radiat ion of s m a l l quantity of

Ch-244 - FY-1969,

Discharge and analyze first plutonium irradiat ion monitor column - complete

analysis September 1970.

Discharge 1 0 kg loading - FY-1970-72.

Discharge and analyze Cm-244 i r radiat ion - FY-1971 or FY-1972.

RL 4-3 Page 16

Dol la rs (in thousands)

DUN

ARHCO

Total

k n Years

DUN

ARHCO

Total

Equipment

DUN

ARHCO

Total

STATISTICAL SUMMARY SCHEDULE

Fiscal Year

0 0

100 0 - - - - 0 100 130 210

0 0

0 0.25 I_

0 0.25

0 0

0 - 0 - 0 0

I_ 1973

- 210

FY 68 c FY 69 FY 70 ’ FY 71 FY 72 FY 73

r I 1 1 --------- - FAB ELEMENTS FOR I 10 KG OF PU [ I

CM-244 CAPSULE FABR I CAT I ON CM-244 CAPSULE IRRADIATION - - - - - - - - -

DISCH. 8 ANALYZE FIRST CM-244

PFIOGRAI4 SCI IEDIJLE - TF7HNSf’LUTOI.J I Uf’i

RL 4-3 Page 18

DISTRIBUTION

RICHLAND OPERATIONS

1-24. D. G. Williams

ATLANTIC RICHFIELD W O R D COMPANY

25. 3. M. Dobbs/J. Christy 26. J. B. Fecht 27. B. B. Field 28. W. M. Harty 29. H. H. Hopkins 30. L. M. Knights 31. H. C. Rathvon

32. 33. H. F. Shaw 34. A. E. Smith 35. P. W. Smith 36. W. Go Smith 37. M. J. Szulinski 38. 39. ARHCO Fi les

L. M. Richards/R. P. Corlew

R. E. Tomlinson/R. E. Isaacson

40. F. W. Albaugh 41. J. M, Batch 42. C. A. Bennett 43. R. E. Burns 44. F. G. Dawson 45. D. R. deHalas 46. E, A. Eschbach 47. E. A. Bmns

BATTELLJ3-NORTHWEST

48. J. J. Fuqmy 49. R. L. Moore 50. H. M. Parker 51. A. M. P h t t 52. W. Do Richmond 53. C. A. Rohrmann 54. E. E. Voiland 55. D. C. Worlton

56. T. W. Ambrose 57. P. A. Carlson 58, D. W. Constable 59. D. H. Curtiss 60. G. C. Fullmer 61. R. G. Geier 62. C. D. Harrington 63. C. V. ,Kuhlman 64. M. Lewis 65. W. M. &this 66. J. M. Mcfihon

DOUGLAS UNITED NUCItEAR, INC.

67. N. R. Miller 68. W. S. Nechodom 69. R. Nilson 70. Go F, Owsley 71. R. W. Reid 72. J. W. Riches 73. R. K. Robinson 74. 0. C. Schroeder 75. C. H. Shaw 76. R. H. Shoemaker 77. J. T. Stringer