lj-I I I I RESEARCH AND

iLOPMENT REPORT 1 ,

HW-79622

R. C. FORSMAN and 6. 6. OBERG

OCTOBER 1963

ROCESSING

HANFORD ATOMIC PRODUCTS OPERATION RICHLAND, WASHINGTON

G E N E R A L

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 responsibility 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. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, 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.

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

L E G A L NOTICE

This report was prepared os an occount of Government sponsored work, Neither the United States,

A. Makes any warranty or representotion, expressed or implied, with respect to the accuracy, com- pleteness, or usefulness of the information contained in this report, or thot the use of any informotion, apparatus, method, or process disclosed in this report may not infringe privately owned rights; 3r

nor the Commission, nor ony person acting on beholf of the Cdmmission:

B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apporotus, method, or process disclosed in this report.

As used in the above, "person acting on behalf of the Commission" includes any employee or contractor of the Commission, or employee of such contractor, to the extent that such employee or con- tractor of the Commission, or employee of such controctor prepares, disserninotes, or provides occess to, any information pursuant to his employment or contract with the Commission, or his employment with such controctor.

A i C . G I R I C W L A I I D . W I S H

A HW-79622

UC-70, Waste Disposal and P rocess ing

(TID-4500, 26th Ed. )

P \

FORMALDEHYDE TREATMENT

OF PUREX RADIOACTIVE WASTES

R . C. F o r s m a n and G. C. Oberg

P u r e x P r o c e s s Engineering Resea rch and Engineering Operation

Chemic a1 P rocess ing Department

October 1963

HANFORD ATOMIC PRODUCTS OPERATION RICHLAND, WASHINGTON

Work performed under Contract No. AT(45-1)-1350 between the Atomic Energy Commission and Genera l E lec t r i c Company

Printed by/ for the U. S. Atomic Energy Commission

Pr in ted in USA. Price 75 cents . Available f rom the Office of Technical Serv ices Department of Commerce Washington 25, D . C .

- 2 - HW-79622

TABLE O F CONTENTS

I. INTRODUCTION . . 3

11. SUMMARY AND CONCLUSIONS . . 4

111. PUREX PLANT OPERATION . . 4

IV. EARLY LABORATORY WORK ON THE HN03- FORMALDEHYDE REACTION . . 6

V. SEMIWORKS DEVELOPMENT DATA . . 7

VI. APPLICATION TO THE PUREX PLANT. . 8

VII. PUREX PLANT EQUIPMENT DESIGN . . 9

A . P r o c e s s Equipment Description . . 9

B. Instrumentation . 10

1. P r o c e s s Control . . 10

2 . Safety Instrumentation . . 11

C . Remote Maintenance Concept . VIII. DEMONSTRATION O F PLANT-SCALE OPERATION

A . E a r l y Plant Experience . B. Scale Model Operation . C. Successful Plant Operation

IX. ADVANTAGES OF FORMALDEHYDE TREATMENT

A . Reduced Essent ia l Mater ia l s Cos ts . B. improved Waste Storage Capability . C . Increased Plant Flexibil i ty ,

REFERENCES . FIGURES

. 12

. 13

. 13

. 14

. 1 6

. 18

. 20

. 20

. 2 1

. 23

. 24

- 3- HW-79622

n

FORM ALD EH YD E TR E ATM E N T

OF PUREX RADIOACTIVE WASTES

I. INTRODUCTION

Denitration of high-level radioactive wastes with formaldehyde has

been successfully accomplished on a full plant scale at Hanford's P u r e x

chemical separat ions plant. In the Purex plant, plutonium, neptunium,

and uranium are recovered f rom irradiated fuel e lements by dissolving

the elements in H N 0 3 and subjecting the result ing solution to a mult is tep

solvent-extraction process . The plutonium, neptunium, and uranium

a r e decontaminated f rom radioactive fission products and recovered as

separated ni t ra te product solutions. The bulk of the fission products is contained in a single waste-raffinate s t r eam which is processed for

recovery of special mater ia l s and by-products, neutralized with NaOH

and t r ans fe r r ed to s torage in la rge underground tanks.

A key s tep in the economics of waste handling and s torage is

removal of HNO

tion to a minimum volume before neutralization. The rma l concentration

of the waste involves volatilization of the HNO and s e r v e s as the main

volume reduction p rocess .

r e su l t s in formation of gaseous denitration products and w a s found to be an effective supplement for plant operations, This repor t desc r ibes the

labora tory work, semiworks s tudies , and the design and successful opera-

tion of ful l -scale plant equipment using formaldehyde fo r the removal of

HNO

from the fission product waste s t r e a m and concentra- 3

3 The reaction between formaldehyde and H N 0 3

f rom a highly radioactive waste solution, 3 Denitration p rocesses using chemicals other than formaldehyde are

a l so being studied at Hanford on a batch and continuous operation bas is .

Relative effectiveness and cos ts , however, a r e not yet f i r m . F ina l choice

of the p rocess to be used f G r continued PAW denitration in P u r e x w i l l be

dictated by relative p rocess and economic effects of integrating the

denitration s tep into the overal l plant sys tem.

Y

- 4 -

11. SUMMARY AND CONCLUSIONS

HW-79622

Continuous denitration of Purex acid waste ( P A W ) with formaldehyde

has been successfully demonstrated in a full-scale plant prototype unit in

the Hanford Purex plant. The reaction is smooth and is easi ly and safely

controlled. Because seve re foaming can occur in the react ion vesse l , the

use of an antifoam agent is required to attain acceptable plant processing

r a t e s . Extensive laboratory and pilot plant work, proper equipment design,

and sat isfactory operating procedures were the bases fo r developing

adequate safeguards that a s s u r e complete control of the reaction at all

t imes .

During operation, the formaldehyde and the preheated P A W s t r e a m

(with 50 to 100 parts antifoam per million pa r t s PAW) a r e added continu-

ously to the r eac to r which is maintained at 95 C. concentration of approximately 6 . l M , - the f r ee acid is reduced to 0 . 5 to

1, OM in the t reated waste. About 2 . 5 moles of f r e e acid are destroyed

p e r mole of formaldehyde added to the unit for a 60% reaction efficiency.

A decontamination factor of 10

which means that the ra t io of radioactivity to H N 0 3 in the recovered acid has been reduced by a factor of 1 0 , 0 0 0 when compared to the same ra t io

in the high activity waste ( P A W ) .

F r o m an initial feed

-

4 f rom feed to recovered acid is typical,

Formaldehyde denitration of the Purex acid wastes reduce the

chemical cos ts of waste t reatment and s torage.

i nc reases the s torage capacity of underground tanks because of l e s s s a l t s

in the w a s t e , i nc reases the flexibility of waste t reatment equipment, and

improves the quality of feed for fission product recovery.

denitration is a safe and economical process f o r supplementing normal

waste t rea tment operations in a Purex-type radiochemical plant,

In addition, the process

Formaldehyde

111. PUREX PLANT OPERATION

The Purex plant process flow is shown in F igure 1 and is descr ibed

in References (1) and ( 2 ) . The key s teps involve feed preparation; solvent

extraction separat ion of the des i red products: and subsequent t reatment of

the separa ted products , the sclvent, and the waste s t r e a m s ,

- 5 - HW-79622

In the first s tep, caustic solution is used to remove the aluminum

The metal l ic jacket surrounding the uranium in the i r radiated fuel e lement .

uranium is dissolved in HNO

containing plutonium, neptunium, and fission products. The feed solution

is then contacted by an organic base (30 v0170 tributylphosphate, 70 v0170

diluent similar to kerosene) in a pulsed solvent extraction column under

the proper chemical and flow conditions s o that the plutonium, neptunium,

and uranium t r ans fe r into the solvent leaving the fission products in the

aqueous phase. Subsequent processing sepa ra t e s the plutonium and nep-

tunium f rom the uranium in the Parti t ioning and Second Uranium Extrac-

tion Columns by proper adjustment of the plutonium and neptunium valence

states. The th ree products leave the First Cycle as aqueous s t r e a m s

and each is subjected to a second t r ans fe r into the solvent (leaving the

fission products in the aqueous phase) for additional f ission product decon-

tamination.

t h ree Second Cycle operations a r e combmed, concentrated and introduced

into the f i r s t column to recover any plutonium, neptunium and uranium

that m a y have remained with the fission products,

the fission products (g rea t e r than 99 . 9Oj0) leave the separat ions equipment

in the HN03 effluent f rom the f i r s t column.

to fo rm an acid-uranium ni t ra te solution 3

The fission product s t r e a m s f rom the First Cycle and the

Thus virtually all of

The raffinate waste s t r e a m , Purex high-activity waste (PAW), is thermal ly concentrated to recover HN03 and reduce the volume; about

90 to 9570 of the HNO

5 to 10% of the H N 0 3 is neutralized during and immediately a f te r the

waste is processed for recovery of desirable fission products.

zation of acid is required to permit s torage of the waste in carbon steel- lined concrete tanks.

such that the solution is self-boiling and requi res that the ma te r i a l be

adequately contained fo r hundreds of yea r s . Consequently, construction

of suitable s torage space is costly and the incentive is great to reduce the

s tored waste volume to a minimum compatible with safety and the required

high s torage integrity.

in the waste s t r e a m is recovered . The remaining 3

Neutrali-

The radioactivity content of th i s waste s t r e a m is

P V

63 - 6- HW-79622

IV , EARLY LABORATORY WORK ON THE HN03-FORMALDEHYDE

R E ACTION

The reaction of formaldehyde and HNOQ has been known f o r years as a method of reducing the concentration of H N 0 3 and n i t ra tes f r o m solu-

t ions without adding undesirable nonvolatile ma te r i a l s t o the sys tem.

e v e r , the reaction was pictured a s violent and difficult to control mainly

because of i t s induction period. Very l i t t le information w a s reported in

the l i t e ra ture until T. V. Healy of the United Kingdom Atomic Energy

Resea rch Establishment published his work in 1957. ( 3 ) H i s studies of the

react ion were conducted at 100 C , and demonstrated that at this elevated

t empera tu re , the induction period is negligible. H i s w o r k a l so included

a laboratory demonstration of the feasibility of using a continuous formal -

dehyde addition to a vesse l containing H N 0 3 ( 3 to 2OM) at 100 C .

How-

-

The reaction was represented by Healy a s different equations depend-

ing upon concentration of H N 0 3 react ing. The equations a r e :

Nitr ic Acid C oncent r a t ion

4HN03 .+ C H 2 0 4N02 + co2 + 3H20 8M

2 to 8M

-

-

2 H N 0 3 + C H 2 0 -+ HCOOH + 2 N 0 2 + H 2 0 2M -

If formaldehyde is added to concentrated H N 0 3 , initially 4 moles of H N 0 3 are destroyed p e r mole of formaldehyde; but, a s the acid concentration

dec reases , the react ion finally approximates a one-for-one ra t io with

formic acid and NO2 a s the products,

Barton tes ted in the Han-Cord Labora tor ies the feasibil i ty of applying

the formaldehyde react ion as a means of reducing the H N 0 3 concentration

in the high-activity waste ( P A W ) f rom the P u r e x separat ions plant.

The react ion between formaldehyde and the H N 0 3 in synthetic PAW proceeded

smoothly when formaldehyde was added t o the solution at a t empera tu re

greater than 80 C . Up to 7570 of the formaldehyde w a s utilized at the stoichio-

m e t r i c ra t io of 4 moles of H N 0 3 destroyed pe r mole of formaldehyde added.

(4)

\

7 - HW-79622

Volatilization of fission products did not appear to be a problem.

synthetic acid waste could be concentrated by a factor of t h ree or m o r e

before sol ids began to precipitate.

Trea ted

V. SEMIWORKS DEVELOPMENT DATA ~~ ~ ~

When laboratory studies showed potential application f o r the reaction between formaldehyde and H N 0 3 in the Purex high-acitivty w a s t e , pilot plant studies were initiated to confirm and extend existing laboratory

information. (5 ) Equipment design, operational behavior, formaldehyde

utilization efficiency and safety considerations were the par t icu lar subjects of study. F igure 2 is a process flow chart showing the different equipment

pieces .

The r e su l t s f rom these studies confirmed the feasibil i ty of con-

Specific information tinuous denitration of synthetic Purex plant PAW. obtained f rom these studies included:

( 1) The efficiency of formaldehyde utilization depended pr imar i ly on

the tempera ture a t which the acid feed was introduced into the

sys tem; a tempera ture nea r boiling w a s required t o obtain good

efficiency . ( 2 ) Over 95% of the free acid" w a s removed at a ra t io of about 3 moles

of f r e e acid pe r mole of formaldehyde added. ( 3 ) The res idua l free acid must be g rea t e r than 0. 3M - to prevent

sol ids precipitation.

(4) Discharge of the formaldehyde ei ther above or below the su r face

of the liquid was immater ia l t o the efficiency of the react ion.

Pa r t i cu la r attention was given to studies involving pressurizat ion

of the equipment due to possible inadvertent addition of formaldehyde to

H N 0 3 at low tempera tures followed by heating. T e s t s showed that when

cold H N 0 3 and formaldehyde were mixed and heated, the subsequent

p r e s s u r e increased with HNOQ concentration until 47 in . H 2 0 p r e s s u r e

ab Free acid (dissociated hydrogen ions) analysis is determined by a coulo- m e t r i c t i t ra t ion that generates a f r e e base by the constant cur ren t e lec t ro lys i s of a dilute sodium bromide solution. The r e su l t s a r e repor ted a s f r e e acid molar i ty .

.8- HW-79622

w a s generated at 5M H N 0 3 .

usually s ta r ted before the mixture w a s heated or before the concentration

of formaldehyde could be increased sufficiently to produce a p r e s s u r e above

47 in. of water .

At higher acid concentrations, the reaction -

VI, APPLICATION TO THE PUREX PLANT

Successful pilot plant denitration of simulated Purex plant P A W

prompted fur ther evaluation as to the application of the reaction to the

P u r e x plant. (6 ) A reduction in the H N 0 3 concentration of the P A W before

neutralization would reduce the amount of NaN03 in the final waste in

proportion, and thus the volume of the final s tored w a s t e could be reduced

significantly without precipitating additional sol ids ,

reduced volume contribute to reduced waste s torage cos t s , but sludge

tempera ture control problems produced by precipitated sludge would be

reduced.

recovered and the savings f rom reduced caust ic consumption would result in a net essent ia l ma te r i a l saving of approximately $2/ ton of uranium

processed through the Purex plant. ‘I.

Not only would the

In addition, at normal production r a t e s , the value of the H N 0 3

..t,

The react ion between formaldehyde and H N 0 3 w a s recognized a s

The use of this reaction to t r e a t high-

an exothermic reaction with a possible induction period, and under cer ta in

conditions could be quite violent. activity waste in the processing plant meant that the reaction must be

under control at a l l t imes .

products , l o s s of control cannot be tolerated.

and the r e su l t s of the semiworks t e s t s , control could be assured under

proper operating conditions,

install formaldehyde denitration equipment as a prototype sys tem with all

the n e c e s s a r y safety fea tures engineered into it which would prevent losing

control of the reaction.

nized the need fo r in-plant t e s t s tudies to develop and establ ish f inal

p rocess and safety controls before placing the unit into routine operational

use .

When handling highly radioactive fission

Based on laboratory work

Accordingly, the decision w a s made to

Installation of one sys tem as a prototype recog-

:k A l l ma te r i a l s cos t s and flowsheet volumes are stated in t e r m s of do l la rs o r gallons pe r ton of uranium processed through the Purex plant.

- - 9 -

’ Q VII. PUREX PLANT EQUIPMENT DESIGN

HW-79622

A . P r o c e s s Equipment Description

The plant process flow sheet and prototype equipment design(7) were patterned af te r that developed f o r the semiworks studies a s shown in

F igure 3 .

Overflow Tank through a preheater into a packed tower mounted above the

r eac to r .

cur ren t to the hot gaseous products f rom the react ion and is at o r n e a r the

boiling point when i t drops into the r eac to r .

into the r eac to r and is discharged onto the surface of the liquid.

A controlled flow of P A W is pumped f rom the Concentrator

The heated PAW t r ave l s downward through the tower counter-

Formaldehyde is metered

The products of the react ion, C 0 2 , H 2 0 and oxides of nitrogen, t r ave l upward through the packed tower and a r e deentrained in the packed

section above the P A W inlet and by the tantalum m e s h deentrainment

pad mounted above the packed section of the tower.

gases a r e blended with air to oxidize the N O to NO2 and routed into the

bottom portion of a packed tube and sheet condenser provided with a

downward flow of reflux water .

outside of the tubes and the oxides of nitrogen, except NO, are absorbed

by the condensed vapor and reflux water to form recovered H N 0 3 .

60% of the oxides of nitrogen present a r e recovered in th i s s tep.

The deentrained off-

The water vapor is condensed on the

About

Depending upon i t s radioactivity content, the recovered acid can

be recycled to the Purex Acid Waste Concentrator for additional decon-

tamination by evaporation, or i t can be routed direct ly into the P u r e x

plant recovered acid sys tem.

throughout the plant.

The recovered acid. is used in the p rocess

The formaldehyde is s tored outside in a 5000 gal tank and is pumped

f rom the tank through an all-welded line and a flow control sys tem direct ly into the r eac to r by a canned motor pump. This design el iminates the hazards of s tor ing formaldehyde inside the building with the accompanying

special requi rements fo r fire and ventilation control.

n

- 10- HW-79622

Safety considerations were designed into the equipment wherever

To locate the denitration equipment adjacent to the vessels possible.

handling the P A W , the reaction vesse l was inser ted inside a 5000 gal tank

and the additional equipment w a s mounted on or above the tank. The tank-

within-a-tank concept provides a safety feature which w a s not included

as a design requirement but which could provide an additional margin of

safety.

high) w a s selected to limit the amount of formaldehyde and PAW reacting

at one t ime on the p remise that a la rge tankful of react ing formaldehyde

and H N 0 3 out of control would be m o r e hazardous than a s m a l l tankful.

Other safety controls a r e described in the section concerning safety

in st rument at ion.

The sma l l s i ze of the reaction vesse l ( 2 0 in. d iameter by 8 f t

B. Inst rumentation

1. P r o c e s s Control

P r o c e s s control instrumentation cen te r s mainly around flow and

tempera ture of the reacting solutions. The PAW flow is controlled by a

flow pot that is a piece of 5 in , pipe 24 in. long having an inlet and an

outlet chamber separated by a baffle containing two or i f ices located at different heights.

a s measu red by a s ta t ic p r e s s u r e instrument (weight fac tor ) , the flow through the orifice inc reases . Eventually the liquid level reaches the

second or i f ice and at this point the flow inc reases appreciably with a

minor inc rease in liquid height within the pot.

is controlled by a diaphragm-operated valve, actuated by the weight

factor control ler set to control the pot liquid level at a height which w i l l

del iver the prescr ibed flow.

of a ro t ame te r to avoid plugging problems associated with the fine solids

suspended in the PAW.

electronic ro tameter actuating a diaphragm-operated valve through a recorder -cont ro l le r .

As the hydrostatic head on the lower orifice i n c r e a s e s ,

The PAW flow into the pot

This type of control w a s selected instead

Formaldehyde flow control is accomplished by an

-11- HW-79622

The tempera tures of the preheated PAW, the reaction vesse l con-

tents and the recovered acid rece iver a r e measured by thermohms. The

measured tempera ture is recorded by a recorder -cont ro l le r which actu-

a t e s a steam control valve to maintain the des i red tempera ture . The

p r e s s u r e within the r eac to r and the differential pressures across the r eac to r tower and the packed condenser a r e measured and recorded.

2. Safety Instrumentation (Figure 4)

The condition that mus t be avoided during the operation of the formal -

dehyde unit is the addition of formaldehyde to the reaction vesse l before

the solution tempera ture in the vesse l reaches 80 C. interlock ex is t s between the tempera ture recorder -cont ro l le r fo r the

reaction vesse l and the e lec t r ica l c i rcui t for formaldehyde pump.

pot tempera ture falls below 90 C, the control ler shuts off the formaldehyde

pump i f it is running or prevents its being s ta r ted if i t is not running.

e i ther case , the pot tempera ture must exceed 90 C before the pump can be

s ta r ted .

sufficiently high to prevent an induction period which could resu l t in a

delayed reaction and pressurizat ion within the equipment. If f o r any

reason a vigorous reaction takes place in the react ion pot, and the operat-

ing p r e s s u r e in the pot which is normally negative becomes positive and

exceeds 2 in. w a t e r p r e s s u r e , an interlock shuts off the formaldehyde pump automatically to prevent fur ther formaldehyde addition to the react ing mix-

tu re . the pump m a y be res ta r ted .

Fo r th i s r eason , an

If the

In

Thus a t all t i m e s of formaldehyde addition, the tempera ture is

After a negative p re s su re has been reestabl ished and not before ,

The solvent used in the Purex process m a y become degraded and

nitrated if allowed to remain in contact with concentrated HN03 solutions at elevated tempera tures , The most likely location for forming ni t ra ted, degraded solvent is in the w a s t e concentrator, where the HN03 concentra-

tion ranges f rom 5 to 7M and the holdup time is g rea t e r than 50 h r .

Nitrated solvent is unstable and could produce a violent chemical react ion -

i f heated to a tempera ture g rea t e r than 130 C in the presence of heavy

meta l s a l t s o r if heated to g rea t e r than 150 C in the presence of PAW. (8) Q

1 2 - HW-79622

To insure a tempera ture of less than 150 C at a l l t imes (in case some

degraded solvent should en ter the denitration equipment), the s team p r e s -

s u r e to the coi ls of the PAW preheater and the reaction vesse l is limited to

a maximum p r e s s u r e of 39 lb / in .

control and p res su re relief valves.

by the installation of properly selected

Since heavily nitrated and degraded solvent is heavier than the

aqueous phase, it accumulates on the bottom of vesse ls .

introduction of degraded solvent and solids into the formaldehyde deni t ra-

tion r eac to r , the suction of the pump in the feed tank is located 12 in. off

the bottom. Possible accumulations of nitrated solvent and sol ids are

periodically purged f rom the feed tank by s team e jec tor t r ans fe r of the

bottoms direct ly into the neutral izer tank, bypassing the denitration

e qu ipm ent .

To prevent the

C. Remote Maintenance Concept

P rocess ing highly radioactive ma te r i a l s not only r equ i r e s remote

operation of the equipment, but a lso dictates remote maintenance capabili-

t i e s if failed equipment is to be replaced or repaired within a reasonable

t ime . Usually, failed equipment must be replaced because high radiation

dose r a t e s prevent maintenance personnel f rom approaching and repair ing

it. Cer ta in types of equipment pieces have sufficient value or requi re long enough del ivery t ime to warrant the i r decontamination and repair;

however, th i s is a lengthy procedure.

In any event, replacement or r epa i r r equ i r e s removal of the equip-

ment piece f rom the processing a r e a remotely. At Hanford, remote

maintenance is accomplished by a shielded-cab crane that has appropriate

hooks and electr ical ly operated impact wrenches attached to cables on

drums.

through a monocular periscope.

fabricated with connector nozzles which can be ' 'made up" by turning the

head of a single bolt.

The operator views the work a r e a f rom inside the shielded cab

Equipment pieces and piping sections a r e

These connector heads a r e used on piping called

jumpers" to t ranspor t s team, water , p rocess solutions, condensate, I I

- 13- HW-79622

p rocess and instrument a i r , instrument s ignals , e lec t r ica l power, and any

other kind of s e rv i ces required to operate the plant within the remotely

maintained process a r e a s . Design and construction are based on tolerances of 61 / 1 6 in. to insure reproducibility of location and a tight fit.

complete flexibility, a l l p rocess piping and equipment pieces can be

replaced remotely.

To provide

F igu res 5 , 6 , 7 , and 8 show the process vesse ls in the formalde-

Each vesse l is equipped with special nozzles to hyde denitration sys tem.

accept the connector heads attached to the piping jumpers . The react ion

vesse l bolts t o the ring flange of the tank into which it f i t s , while the tower

bolts to the reaction vesse ls . A total of 40 jumpers connect the var ious

equipment pieces to each other or to adjacent tanks and serv ice connec-

t ions.

schedule of installation to avoid interferences.

The equipment and piping were designed to permit a sequence

VI11 . DEMONSTRATION OF PLANT -SC ALE OPERATION

A . E a r l y Operating Experience

E a r l y operating experience with the prototype sys tem in the plant

demonstrated that safe control of the reac tor operation w a s pract ical .

The response of the safety features and the individual capacit ies of the

sys tem components were established during a s e r i e s of pre l iminary operabili ty t e s t s and initial t e s t operation with plant solutions.

tion was found to s t a r t within 1 to 3 min af ter the initial addition of formal -

dehyde to the heated P A W solution.

controllable although mechanical equipment difficulties did not permi t

good operating continuity.

The reac-

Operation appeared smooth and

P r o c e s s efficiencies real ized during e a r l y t e s t operations with the

prototype unit , however, were disappointingly low Allowable throughput

r a t e s and denitration efficiencies appeared to be l e s s than half that

expected on the bas i s of seimworks data.

at less than half the design r a t e , the p r e s s u r e drop a c r o s s the react ion

tower frequently exceeded 50 in. of wa te r , which caused the r eac to r t o

Although the unit w a s operated

- 14- HW-79622

operate slightly pressur ized . During initial operation, instrumentation

showed that the reac tor liquid level dropped off rapidly until only 10 to 20%

of the normal level remained. Even so , the pot contents continued to over-

flow into the rece iver tank. In addition, the radioactivity in the recovered

acid was thousandfold higher than desired.

o r both of two probable conditions were occurring:

formaldehyde were reacting in the tower, and ( 2 ) excessive foaming in

the react ion vesse l extended into the tower.

The behavior indicated that one

(1) the H N 0 3 and

Mechanical difficulties were also encountered, such as: (1) the

formaldehyde flow w a s frequently two to three t imes the flow sheet value

because of an oversized ro tameter ; ( 2 ) a failed thermohm erroneously

indicated the maximum obtainable reac tor tempera ture to be 95 to 100 C

when the tempera ture w a s actually higher; (3) the gasket between the

react ion vesse l and the tower did not s e a l tightly and allowed highly

radioactive vapor and liquid to leak into the ce l l i f the sys tem w a s slightly

pressur ized; and (4 ) a section of the t r ans fe r line between the PAW feed

tank and the r eac to r plugged during a shutdown period.

By proper maintenance and equipment modifications plus continued

the equipment difficulties w e r e resolved. operation of the plant prototype

However, because remote operation of the unit prevented a diagnosis and

because experimental operations interfered with production requi rements ,

a rapid and exact definition of the p rocess problem was impossible in the

plant unit. Consequently, fur ther laboratory and semiworks studies were

initiated.

B. Scale Model Operation (9)

Construction and operation of a one-tenth scale g lass model deni-

t ra t ion unit showed that the principal difficulty observed with the plant

prototype unit w a s associated with severe foaming in the r eac to r pot.

Two ma jo r t e s t study a r e a s were investigated in the scale model; opera-

tion without organic ma te r i a l s in the feed and operation with organic

ma te r i a l s in the feed.

tower w a s evaluated and batch ve r sus continuous operation w a s tes ted.

In addition, the probability of prereac t ion in the

-15- H W - 7 9 6 2 2

The operating difficulties that had been experienced in the plant

unit were not encountered in scale model operation during init ial t e s t s

using synthetic PAW that had not been contacted with solvent.

operated smoothly and the reaction was easi ly controlled. The p r e s s u r e

drop a c r o s s the tower was l e s s than 1 in. of water at a l l flows tes ted and

no difficulty was experienced in maintaining 10 to 20 in. of vacuum in the

react ion pot.

observed even at r a t e s equivalent to the plant flowsheet ra te .

The unit

N o flooding or excess reaction in the tower packing was

Plant operating difficulties were closely duplicated when seve re

foaming w a s induced in the g lass sca le model by the addition of solvent

degradation product (dibutyl phosphate) to the synthetic PAW. formaldehyde r a t e s , operation was essentially unchanged f rom e a r l i e r

runs conducted without dibutyl phosphate present . At flow sheet r a t e s ,

however, foam rose 7 6 in. above the overflow and 14 in. into the

packed tower.

the bottom of the tower, the p re s su re drop a c r o s s the tower rose (up to

2 3 in. of water ) and pot p re s su re increased (up to 15 in. of w a t e r ) .

At low

Whenever the foam layer covered the p r e s s u r e tap at

The foam problem was alleviated in the scale model by the addi-

tion of antifoam agents to the synthetic PAW. Of the th ree antifoam

agents tes ted , antifoams containing silicone in an emulsifying agent

were the most effective. height was reduced by a factor of two, and the tower differential p r e s -

s u r e dropped from 2 3 to 5 in. of water . In addition, the appearance of

the foam and solution in the reaction pot at normal flowsheet r a t e s w a s

changed when antifoam agents were added to PAW. The definite interface

between the foam layer and react ing liquid ordinar i ly seen nea r the over-

flow disappeared but s t r e a m s of foam permeated the liquid in the pot t o

within 2 8 in. of the bottom. After the addition of an antifoam agent, the

maximum foam height w a s 37 in. and maximum differential p r e s s u r e

a c r o s s the tower was only 5 in. of wa te r , compared to 7 6 in. and 2 3 i n . ,

respect ively, at the s a m e r a t e s without antifoam.

When antifoam was added to the P A W , foam

- 1 6 - HW-79622

T e s t runs with the formaldehyde added below the surface of the

liquid in the reac tor (vice vapor space addition) did not show any change

in operating charac te r i s t ics of the tes t unit.

Although operation of the sca le model unit during batch denitration

t e s t s was comparable to continuous operation, the formaldehyde uti l iza-

tion was lower ,

pe r mole of formaldehyde added to t e s t batches vs . 2 . 0 to 2 . 4 moles of

ni t ra te destroyed per mole of formaldehyde added to P A W on a continuous

bas is .

Approximately 1 . 4 to 2 . 0 moles of ni t ra te were destroyed

C. Successful Plant Operation

After the scale model t e s t s , continuous denitration of Purex high

level waste with formaldehyde was successfully demonstrated in the plant

prototype unit. Operation of the prototype unit is based upon the F o r m a l -

dehyde Denitration Flowsheet outlined in F igure 9 .

p rehea ter and reaction vesse l a r e maintained at 95 C by automatic

control lers during the ent i re operating period.

contains approximately 6. 1M - H N 0 3 is pumped at a controlled r a t e through

the flow pot through the preheater and into the packed section of the r eac to r

tower.

P A W in the flow pot to control foaming during the reaction. formaldehyde solution stabilized with 6. 5 to 7. 5% methanol is pumped at

a controlled r a t e into the vapor space of the reaction vessel .

dehyde-treated waste continuously overflows into the receiving vesse l .

The off-gases containing oxides of nitrogen, water vapor , and carbon

dioxide a r e deentrained in the tower, and then mixed with air before

enter ing the updraft condenser where H N 0 3 is recovered for r euse in the Purex plant.

Tempera tu res of the

The PAW feed which

An antifoam (10% silicone in an emulsifying agent) is added to the

A 37 w t %

The formal -

When antifoam is used to minimize foaming in the reaction vesse l , the react ion is smooth and easi ly controlled at flow sheet r a t e s .

antifoam addition, the formaldehyde flow ra te must be l imited to 50% of

flowsheet r a t e to prevent the foam created in the reac tor f rom enter ing

Without

17- HW-79622

the tower and pressurizing the unit.

into the PAW s t r eam at concentrations of 50 to 100 ppm reduces reactor foaming sufficiently to allow processing at flow sheet r a t e s .

Addition of the antifoam agent direct ly

Acid concentrations of the PAW s t r eam va ry somewhat depending

upon operating conditions in the plant solvent extraction section and waste

concentrator; however, concentrations a s determined by the f r e e acid

analysis cur ren t ly average 6. 1M HNO

F r e e acid concentratioris of formaldehyde-treated waste ranged between

0. 5 and 1. OM."' Calculations indicate 2 . 5 moles of acid are destroyed per mole of formaldehyde fed to the unit. Complete destruction of any residual

formaldehyde in the waste is assured by a res idence t ime in excess of 1 h r

at 95 C in the reaction vesse l and an additional res idence t ime in excess

of 24 h r at 70 to 90 C in the waste batch collection tank,

a s shown in the flowsheet, F igure 9. 3 -

.b

-

A gamma activity decontamination factor of l o 4 has been obtained

between the PAW and the recovered acid. This means that the ra t io of

fission product activity to HNO concentration in the recovered acid is

a factor of 10 , 000 sma l l e r than the s a m e rat io in the PAW. However,

under cur ren t operating conditions, the radioactivity is a factor of 10

g rea t e r than that acceptable for d i rec t reuse in the Purex plant; thus,

r e tu rn of the acid to the waste concentrator for additional decontamina-

tion by evaporation is required before plant usage. Approximately 4070

of the acid destroyed by the formaldehyde is recovered as 2 0 w t % H N 0 3

in the condensate rece iver tank.

escapes f rom the denitration prototype unit via the condenser vent

sys tem is recovered in the plant backcycle waste sys tem.

scheduled to determine the optimum a i r flow needed for oxidation of

the n i t r ic oxide and the optimum reflux water flow required to produce

maximum acid absorption at a reasonable concentration. Recovery in

3

Ar, estimated 5070 of the acid that

T e s t s a r e

:: In th i s range , the coulometric method used to date for determining free acid (disassociated hydrogen ion concentration reported as f r e e acid) produces higher resu l t s than pH measurements of the denitrated wastes . Plant experience indicates the f r e e acid is actually l e s s than reported; hence, efficiency calculations a r e biased low.

-18- HW-79622

the prototype condenser is expected to increase to a nominal 55 to 6070 of

the H N 0 3 destroyed by the reaction,

w i l l be recovered in the no rma l plant condenser vent sys tem.

Approximately 15% additional acid

Every precaution is taken to insure complete control of the react ion

by equipment design and administrative procedures .

diagram (Figure 4 and Section VII. B. 2 ) locate and descr ibe the p r i m a r y

equipment controls installed to a s su re safe operation of the prototype

unit.

values, the PAW is s tar ted and maintained at 95 C for a minimum of

30 min before the formaldehyde flow is s ta r ted at 10 to 207’0 of the flowsheet

value.

is stopped until the reason for nonreaction can be determined.

experience has shown the reaction s t a r t s within 1 to 3 min and is easi ly

detected by fluctuations in the reac tor liquid level and specific gravity

readings in the r eac to r and increased off-gas tempera tures .

The Hazards Control

After tempera tures and liquid levels a r e adjusted to runsheet

If the react ion does not begin within 3 min , the formaldehyde flow

Plant

After s t a r t of the reaction is a s su red , the formaldehyde flow is A s the reaction becomes increas- slowly increased to flowsheet r a t e .

ingly vigorous, the r eac to r p r e s s u r e r eco rde r and the r eac to r tower

differential p r e s s u r e r eco rde r indicate the extent of the reaction.

no rma l operation, the tower differential r eco rde r r e g i s t e r s 40 t o 45 in.

of water vacuum when the condenser vent sys tem r e g i s t e r s 50 in. of water vacuum.

a vacuum of g rea t e r than 15 in , of water .

During

The reaction vesse l p r e s s u r e r eco rde r usually indicates

IX. ADVANTAGES OF FORMALDEHYDE TREATMENT

Formaldehyde t reatment of Pu rex radioactive wastes offers

economic and operational advantages in t e r m s of reduced essent ia l

ma te r i a l s cos t s , improved waste s torage capability and increased plant

flexibility.

was tes with formaldehyde a r e summarized in Tables I and 11. The relative effects of t reat ing and not t reat ing Purex acid

- 19-

TABLE I

HW - 7 9 62 2

E F F E C T O F DENITRATION O F VOLUME AND CHEMICAL CONSUMPTION

(The comparative information given in th i s table i s based upon the chemicals a n d / o r volume required p e r ton of uranium

processed in the plant. )

Without With F o r m aldehyde F o r m aldehyde

T r e atm ent T rea tmen t

Volume of P A W f rom Concentrator , gal 40 40 104 83

Amount of HN03 Removed, lb Amount of H N 0 3 Recovered, lb Amount of "03 in F ina l W a s t e , lb 124 20 NaOH Required to Neutralize Waste , lb 78.7 1 2 . 7 Amount of Sodium Added, lb 45.2 7 . 3

fo r Sodium Added, gal 29.5 4 . 8

_ _ _ -

Minimum Safe Storage Volume Required

TABLE I1

D EN I TR ATION ECONOMICS

(To determine the economic value of the formaldehyde deni- t ra t ion p r o c e s s , the following bas i s w a s used f o r delivered

cos t s of chemicals as 100% usable m a t e r i a l s . )

Assumed Cost"

NaOH HN03 F o r m aldehyde Underground Tank Storage"":'

Direct Neutralization

2 .96 C/lb 2. 64 C/lb

10.05 C/lb 45.00 $ / g a l

Cost of NaOH $ 2 . 3 2 / T Net Cost $ 2 . 3 2 / T

Formaldehyde Trea tmen t P l u s Neutralization Cost of Formaldehyde U s e d 2 . 0 8 / T Cost of Antifoam 0 . 0 2 / T Cost of NaOH 0 . 3 8 / T

Tota l Cost $ 2 . 4 8 / T Value of HNO3 Recovered

Net Cost

2 . 2 0 / T

$ 0 . 2 8 / T

Savings

Chemical $ 2 . 0 4 / T Waste Storage 2 4 . 7 gal ( F r o m Table I )

x 45 C/gal 1 1 . 1 2 / T

Total Savings $13. l 6 / T

::: A flowsheet value of 40 gal of PAW/ton of uranium produced w a s assumed f o r calculating the cos t s of m a t e r i a l s and s torage . If underground s torage tank replacement cos t s w e r e used , s torage cos t s would be approximately a factor of t w o g r e a t e r than the figures in th i s table.

.I_ .I, <,. ,/.

- 2 0 - HW- 79622

A . Reduced Essent ia l Mater ia ls Costs

A

Denitrating the wastes with formaldehyde reduces the J a 0 I required

for neutralization of the P A W solution before t r ans fe r to underground s to r -

age f rom 78. 7 lb / ton to 1 2 . 7 lb/ton of uranium processed.

cos ts of 2 . 9 6 C/lb, this reduces the flowsheet chemical cost by $1. 94/ton

of uranium processed,

Assuming caustic

Approximately 83 lb of H N 0 3 per ton of uranium processed a r e

Acid is

Assuming

recovered f rom the P A W solution by formaldehyde t rea tment .

re turned to the recovered acid system of the plant for reuse .

acid values of 2 . 64 C/lb, the flowsheet re turn is $ 2 . 20/ton of uranium

processed.

After deducting the formaldehyde cos ts f rom the combined savings

result ing f rom reduced caustic consumption and increased acid recovery ,

formaldehyde t reatment offers a net savings in chemical cos t s of $2.04/ ton

of uranium processed through the plant.

B. Improved Waste Storage Capability

Treatment of acid in PAW solution with formaldehyde reduces the

sodium salt content of the neutralized waste during i t s s torage in under-

ground tanks and thereby improves waste sludge control.

heat generating fission products in the waste precipi ta tes in alkaline solutions and tends to sett le on the bottom of the tanks in a layer of sludge. Dissipation of heat generated in the sludge is affected by the amount of

solids deposited which is influenced by the circulation r a t e and sal t content of the supernatants. Uncontrolled precipitation and sett l ing out of sol ids

could resu l t in tempera tures considerably exceeding the control l imit of

300 F. The sodium sal t concentration in the tank is therefore l imited to

less than 8M to prevent excess sal t precipitation and sludge tempera ture

inc reases ,

The bulk of the

-

Removal of H N 0 3 before neutralization by formaldehyde reduces

the sodium added during neutralization from 45.2 to 7 . 3 lb/ ton of uranium

processed. The minimum waste s torage volume of the NaOH added during

, 2 1 - HW- 7 9 62 2

neutralization is therefore reduced from 29.5 to 4 . 8 gal / ton of uranium

processed.

equivalent to s torage space savings of $11. 12/ton of uranium processed.

Since construction cos ts a r e continually increasing, savings based upon

cur ren t or future tank replacement cos ts would be significantly higher.

A s indicated in Tables I and 11, this volume reduction is

(10)

C. Improved Plant Flexibility

Experience has shown that the recovery efficiency of the acid

abso rbe r in the Purex plant waste t reatment sys tem m a y be increased by

minor changes in the operating procedure. adjusting the r a t e of waste solution boil-off so a s to provide a nea r opti-

mum absorber vapor throughput; thus, the overhead acid lo s ses are

reduced. However, to provide minimum neutralized waste s torage

volumes, the r a t e of waste solution boil-off in the past has been controlled

to minimize the bottoms acid concentration r a the r than to optimize absorber

acid overheads efficiency.

recover HNOQ f r o m the PAW solution, absorber efficiency m a y be

increased with no increase in neutralized waste s torage requirements .

One such change involves

With formaldehyde t reatment available to

A lower acid concentration in the formaldehyde-treated PAW

reduces the amount of caustic required during acidity adjustments in the

F iss ion Product Recovery process . (I1) The lower salt content improves

the feed quality and the sma l l e r overal l volume reduces both the chemical

consumption and the processing t ime cycle. Some difficulties have been

noted in the plant in maintaining stable precipi ta te-free solutions of the

low free acid concentrations possible with formaldehyde denitration.

Curren t plans for long-term management of high level waste at

Hanford a r e based on processing the raffinate solutions for removal of

long-lived isotopes and in te r im storage of the short-l ived and iner t res idues until the ma te r i a l can be immobilized a s a sal t cake. ( I 2 ) The

process flowsheets developed fo r waste extraction require a slightly acid solution for good separation and benefit by a low salt content. Thus

n

- 2 2 - HW-79622

denitration with formaldehyde provides a feed mater ia l bet ter suited to

waste extraction than neutralization with caust ic ,

Other waste management plans under consideration for off- s i te

Pu rex type plants include calcination and long-term storage as an acid

solution.

tion process ; the fo rmer in t e r m s of a m o r e suitable feed stock and the

la t te r in t e r m s of lower tank corrosion.

Both types of s torage would benefit by a formaldehyde deni t ra-

, 2 3 - HW-79622

REFERENCES

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

I I V. R . Cooper and M . T. Walling, Jr . tion and Decontamination of I r rad ia ted Fue l s , ' I Proceedings of the Second United Nations International Conference on the Peacefu l U s e s of Atomic Energy, vol. 1 7 , pp. 291-323. United Nations, Geneva, 1958.

Aqueous Processes f o r Separa-

M. K . Harmon. Cur ren t Status of Solvent Extract ion Processing of I r r ad ia t ed Uranium Fue l s , HW-YA-2458. F e b r u a r y 22, 1962.

T. V. Healy. w i t h F o r m i c Acid and Its Application to the Removal of Ni t r ic Acid from M i x t u r e s , " J . Appl. C h e m . , vol. 8 , pp. 553-561. 1958.

G. B. Barton. The Removal of Ni t r ic Acid from P u r e x Plant First Cycle Acid Waste (IWW) by Reaction w i t h Formaldehyde, HW-55941. M a y 2 , 1958. (C onf i de nt ial)

T. F. Evans. The Pilot Plant Denitration of P u r e x Wastes with Formaldehyde, HW-58587. F e b r u a r y 23, 1959.

G. C . Oberg. Denitration of P u r e x Plant IWW, HW-60161. May 1, 1959. (Secret)

C . W. Smith. Scope Design - Denitration of P u r e x High Level Wastes , HW-63024. December 28, 1959. (C onf ident ial)

R . G. Ge ie r . Process Specifications fo r Chemical Hazards Control - P u r e x Plant, HW-67757. March 6 , 1961.

"The Reaction of Ni t r ic Acid w i t h Formaldehyde and

E. A. Coppinger. Unpublished Data . Genera l Electric Company, Richland, Wash. Februa ry 11, 1963.

B. F. Campbell , E. Doud, and R . E. Tomlinson. Management of High-Level Wastes - Cur ren t P r a c t i c e , HW-SA-2478. 1962. R . E. Burns , R . L. M o o r e , A. M. Platt, and W. H . S w i f t . Recovery and Purif icat ion of Megacurie Quantit ies of Strontium-90, HW-SA-2297. September 20, 1961.

R . E. Tomlinson. The Hanford P r o g r a m fo r Management of High- Level Waste , HW-SA-2515 REV. F e b r u a r y 4 , 1963.

F e b r u a r y 5 ,

First Cyle Part i t ion Cycle Second Uranium Cycle

S c r u b I

Scrub Scrub

f l

FIGURE 1

P u r e x Process Flowsheet

Str ip

Stripped Solvent To Recovery

A c i d F e e d

- 2 5 -

Vent

FIGURE 2

HW-79622

k Q, D k 0 v) D

C o n d e n s a t e A b s o r b e r

=L A c i d

Semiworks Denitration Flow sheet

r

NON-CONDENSABLES TO CONDENSER VENT

COOLING WATER

FROM TK-F7

TO NEUTRALIZER TK- F 16 REACTION L

VESSEL

WASTE SAMPLER TK- F15

FIGURE 3

TO CONCENTRATOR O R FEED TK

Form aldehyde D enit ration Equipment

ACID RECEIVER

20 %

I to G3 I

cu cu tD m r-

I

9 692- 51

I r- cu

I

.ZZI -3

I I_)

---- 3aAH30lVW109 I MVd - I

I I I I

L13MOd dWnd MVd (6

MOlj MVd M07 (E

13SS3A NOl13W NI alry3lMOl (2

13SS3A NOll3V3Zl NI 3WISS3Zld H31H (I

3AlVA 3S013 QNV dWnd 3aAH -3aivwaoj Ado inHs iitM swula -NO3 ONIMOTIOd 3HI do 3NO ANV Ai

!sd 6E 01 a3 -II w1132lv SI103

3013V321 01 31JflSS3Eld WV3J.S

..

-28 - HW- 79 62 2

FIGURE 5

Formaldehyde R e act o r 2 6 4 3 7 - 2 A E C - C E I I C H L A I I D . W A S H

A -29- HW-79622

A

2 6437 - 7 AEC.GL r ) l C H L I " D . WAS"

FIGURE 6

Formaldehyde Reactor

-30- HW-79622

FIGURE 8

A Formaldehyde Reaction Tower 26437-9

*EC.CE n I C H L I " 0 . W A S H

-31- HW - 7 9 6 2 2

FIGURE 8

Updraft Condenser 26437- 10 AEC.CE R I C H L A H O W A S H .

.

. 4

Ant i f o a m 50 t o 100 p a r t s antifoam p e r mi l l ion p a r t s P A W

F o r m a ldehyde Nl -

2 0 HCOH 1 3 . 5

1 Flow - 4 L

Flow 1 6 . 5 S p . G r . 1. 11 T e m p . 20 C

P A W F e e d t o R e a c t o r

6. 1 0 . 4 0 . 1 0 . 0 2 0. 03 0 . 7 6 . 7

0 . 8

0 . 0 2

0 . 0 2 0 . 0 0 3

Flow Sp. G r . T e m p .

100 1 . 3 7 50 C

C o n d e n s e r Vent; C o n d e n s e r

I , -7

-.

R e c o v e r e d Acid

F o rin a 1 de h yd e R e a c t o r

----ta

T e m p . 95 c

M - H 2 0 H+ 3 . 5

Flow 9 0 . 5 Sp. G r . 1. 1 T e m p . 30 C

Forma ldehyde T r e a t e d Was te

2 0

N i++ ~ r + 3 N a+ NO2 + NO:

so,- PO4 -

SiOQ- F-

0 . 5 0 . 4 0 . 1 0 . 0 2 0 . 03 0.. 7 1 . 1

0 . 8

0 . 0 2

0 . 0 2 0 . 0 0 3

Flow Sp. G r T e m p .

100 1 . 3 7

-75 c

FIGURE 9

Form aldehyde D enit ration F l o w she e t

T o P l a n t Backcyc le I Waste System

1 122 Flow M o l e s Acid I

I W w I

-33-

INTERNAL DISTRIBUTION

HW-79622

Copy Number

1 2 3 4 5 6 7 8 9 - 24

25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 - 55 56 57

S. J . Beard 0. F. Beaulieu L. A. B r a y R. E. Burns T. R . Clark E. A . Coppinger J . P. Duckworth J . B. Fecht R . C . F o r s m a n W. S. F rank K . G . Gr imm K . Nl. Harmon M. K. Harmon W. M. Har ty 0, F. Hill E. R . I r i s h R . E. Isaacson B. F. Judson J . B. Kendall J . R. LaRiviere R . W. M cCullugh L. R . Michels R . L. Moore G. C . Oberg A. M . Platt W. H. R e a s H . P. Shaw R . J . Sloat S. G. Smolen W. H. S w i f t R . E. Tomlinson A. J . Waligura M. T. Walling J . H. W a r r e n Technic a1 Public ations E x t r a 300 F i l e s Record Center

EXTERNAL DISTRIBUTION (Special)

Number of Copies

1 Atomic Energy Commission, Washington Mil i tary Liaison Commit tee

Attn: Captain D. E. McCoy, Staff Assistant to the Chai rman

1 RLOO Technical Information L i b r a r y 2 Genera l Elec t r ic Technical Data Center , Schenectady

c

UC-70 WASTF DISPOSAL AND PROCESSING

TKD-4500 (26th E d . ) ' @

Ptd.

4

1

1

1

1

1

1

1

1

Standard Distribution

BROOKHAVEN NATIONAL LABORATORY

P t d Standard Distribution

3 ABERDEEN PROVINGGROUND

1 AEROJET-GENERAL CORPORATION

1 AEROJET-GENERAL NUCLEONICS

BUREAU OF MEDICINE AND SURGERY

BUREAU OF MINES, ALBANY

4 AERONAUTICAL SYSTEMS DIVISE)N

AIR FORCE CAMBRIDGE RESEARCH LABORATORIES

BUREAU OF MINES, SALT L A K E CITY

BUREAU OF MINES, WASHINGTON

BUREAU OF SHIPS (CODE 1500) AIR FORCE INSTITUTE OF TECHNOLOGY

AIR F9RCE SURGEON GENERAL B U R E A U O F Y A R D S A N D D O C K S

BURNS AND ROE, INC. (EROL)

CAL IFORNIA INSTITUTE OF TECHNOLOGY (ROSSANO)

CHANCE VOUGHT CORPORATION

AIR FORCE WEAPONS LABORATORY

ALLIS-CHALMERS MANUFACTURtNG COMPANY

ALLIS-CHALt,(,EHS U.ANUFACTURING COMPANY, WASHINGTON

ALLISON DIVISION-GMC

ARGOtiNE NATIONAL LABORATORY

CHICAGO PATENT GROUP 1

10

1

COMBUSTION ENGINEERING, INC.

COMMITTEE ON THE EFFECTS OF ATOMIC RADIATION

DEFENCE RESEARCHMEMBER

ARMED FORCES RADIOBIOLOGY RESEARCH INSTITUTE

ARMY CHEMICAL CENTER (TARAS) DIVISION OF RAW MATERIALS, WASHINGTON

DOW CHEMICAL COMPANY, ROCKY FLATS ARMY CHEMICAL CORPS

ARMY CHEMICAL SESEARCH A N L CEVELGPMENT LARCRATOSIES DU PONT COMPANY, A lKEN

DU PONT COMPANY, WILMINGTON ARMY ENVIRONMENTAL HYGIENE AGENCY

ARM,Y MATERIALS XESELRCH AGENCY

ARMY MlSSlL& COMMAND

EDGERTON, GERMESHAUSEN A N 0 GRIER, INC., GOLETA

FRANKFORD ARSENAL

FRANKLIN INSTITUTE OF PENNSYLVANIA ARMY NUCLEAR DEFENSE LABORATORY

ARMYSIGNAL RESEARCH ANDDEVELOPMEN1 LABORATORY GENERAL ATOMIC DIVISION

GENERAL DYNAMICS/FORT WORTH

GENERAL ELECTRIC COMPANY, CINCINNATI

3

1

1

1

1

3

4

4

2

2

1

ARMY SURGEON GENERAL

ATOMIC BOMB CASUALTY COMMISSION

ATOMIC ENERGY COMMISSION, BETHESDA

GENERAL ELECTRIC COMPANY, SAN JOSE

GENERAL INSTRUMENT CORPORATION

GlBBS AND COX, INC.

COODYEAR ATOMIC CORPORATION

GRAND JUNCTION OFFICE

t ;AZLETOh NUCLEAR SCIENCE CORPORATION

HUGHESAIRCRAFTCOMPANY

IOWA STATE UNIVERSITY

AEC SCIENTIFIC REPRESENTATIVE, FRANCE

AEC SCIENTIFIC REPRESENTATIVE, JAPAN

'ATOMIC ENERGY COMMISSION, WASHINGTON

ATOMIC ENERGY OF CANADA LIMITED

ATOMICS INTERNATIONAL

BABCOCK AND WlLCOX COMPANY

B A T T E L L E MEMORIAL INSTITUTE

BRIDGEPORT BRASS COMPANY

TID-4500 (26th Ed. ) Ptd.

1

(IC-70 WASTE DISPOSAL AN0 PROCESSING

Standard Distribution

J E T PROPULSION LABORATORY

Pld.

1

2

2

Standard Distribulion

POWER REACTOR DEVELOPMENT COMPANY

PRATT AND WHITNEY AIRCRAFT DIVISION

PUBLIC H E A L T H SERVICE

PUBLIC H E A L T H SERVICE, CINCINNATI

PUBLIC H E A L T H SERVICE, L I S VEGAS

PUBLIC H E A L T H SERVICE, MONTGOMERY

PURDUE UNIVERSITY

1 K E L L Y AIR FORCE BASE

2 KNOLLS ATCMIC POWER LABGHATCRY

LOCKHEED-GEORGIA COMPANY 1

1 LOCKHEED MISSILES AND SPACE COMPANY (NASA)

LOS ALAMOS SCIENTIFIC LABORATORY

M 8, C NUCLEAR, INC.

MALLINCKRODT CHEMICAL WORKS

MARITIME ADMINISTRATION

MARTIN-MARIETTA CORPORATION

MASSACHUSETTS INSTITUTE OF TECHNOLOGY

MOUND LABORATORY .

NASA LEWIS RESEARCH CENTER

RADIATION APPLICATIONS, INC.

RENSSELAER POLYTECHNIC INSTITUTE

REYNOLDS ELECTRICAL AND ENGINEERING COMPANY, INC.

SANDIA CORPORATION, ALBUQUERQUE

SCHENECTADY N A V A L REACTORS OFFICE

SECOND AIR FORCE (SAC)

SPACE TECHNOLOGY LABORATORIES, INC. (NASA)

c NASA SCIENTIFIC AND TECHNICAL INFORMATION FACIL ITY

2 NATIONAL BUREAU OF STANDARDS STANFORD RESEARCH INSTITUTE

NATIONAL L E A D COMPANY OF OHIO

N A V A L C I V I L ENGINEERING LABORATORY

N A V A L POSTGRADUATE SCHOOL

TENNESSEE V A L L E Y AUTHORITY

TODD SHIPYARDS CORPORATION

UNICN CARBIDE CORPORATICN (ORGDP)

UhlGEi CARBIDE COkPCkATICN (ORNL)

UNION CARBIDE CCRPCRATICN (GRNL-Y-12)

UNION CbRBlDF CCEPCRATION (PAOUCAH P L A N T )

UNITED NUCLEAR CORPORATION (NDA)

U. 5. GEOLOGICAL SURVEY, ALBUQUERQUE

U. 5 . GEOLOGICAL SURVEY, DENVER

U. 5 . GEOLOGICAL SURVEY, MENLO PARK

U. 5. GEOLOGICAL SURVEY (NOLAN)

U. S. GEOLOGICAL SURVEY, WASHINGTON

U. 5 . GEOLOGICAL SURVEY, WR DIVISION

U. 5 . WEATHER BUREAU, WASHINGTON

UNIVERSITY OF CALIFORNIA, BERKELEY

UNIVERSITY OF CALIFORNIA, D4VIS

U N IV E RSI TY 0 F C.4 L I FO R N I A, L IVE RMO R E

UNIVERSITY OF CALIFORNIA, LOS ANGELES

1

N A V A L RADIOLOGICAL DEFENSE LABORATORY

N A V A L RESEARCH LABORATORY

NEVADA OPERATIONS OFFICE

NEW JERSEY STATE DEPARTMENT O F HEALTH

1

1

1

1

1

1

1

1

1

2

1

2

1

NEW YORK OPERATIONS OFFICE

NEW YORK UNIVERSITY (EISENBUD)

NUCLEAR MATERIALS AND EQUIPMENT CORPORATION

NUCLEAR METALS, INC.

OFFICE OF ASSISTANT GENERAL COUNSEL FOR PATENTS (AEC)

OFFICE OF INSPECTOR GENERAL

OFFICE OF NAVAL RESEARCH

OFFICE OF NAVAL RESEARCH (CODE 422)

OFFICE OF THE CHIEF OF ENGINEERS

OFFICE OF THE CHIEF OF NAVAL OPERATIONS

PHILL IPS PETROLEUM COMPANY (NRTS)

11 G70 WASTE DISPOSAL AND PROCESSING

Ptd. Standard Distribution

1

1 UNIVERSITY O F HAWAII

UNIVERSITY OF CALIFORNIA, SAN DIEGO

1 UNIVERSITY OF PUERTO RlCO

1 UNIVERSITY OF ROCHESTER

1 WALTERREEDARMYMEDICALCENTER

2 WESTINGHOUSE BETTIS ATOMIC POWER LABORATORY

Ptd.

1

1

1

325

75t

TID-4500 (26th Ed. )

Standard Distribution

WESTINGHOUSE ELECTRIC CORPORATION

WESTINGHOUSE ELECTRIC CORPORATION (NASA)

YANKEE ATOMIC ELECTRIC COMPANY

DIVISION OF TECHNICAL INFORMATION EXTENSION

OFFICE OF TECHNICAL SERVICES, WASHINGTON

*New listing or change in old l isting. flhese c o p i e s should b e shipped directly t o the Office of Technical

Services , Department of Commerce, Washington 25, D. C .