lj-I I I I - IPEN
Transcript of lj-I I I I - IPEN
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
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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
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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 .
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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
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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
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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 ,
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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
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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)
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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 .
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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
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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
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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
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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
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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-
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HW-79622
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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
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UC-70 WASTF DISPOSAL AND PROCESSING
TKD-4500 (26th E d . ) ' @
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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 .