PROGRESS IN TREATMENT

HW-79174

UC-70, Waste Disposal and Process ing

(TID-4500, 24th E d . )

PROGRESS IN TREATMENT

OF A RADIOACTIVE CONDENSATE WASTE

BY

J. M . Skarpelos

P r o c e s s Demonstration and Analysis Chemical Effluents Technology

Hanf o r d Lab o r at o r ie s

This document is October 1963 P&IBLICLY RELEASABLE

DEC 2 3 '63 Authorizing Official FIRST UNRESTRICTED ( - I ( - 0 7 DISTRIBUTION MADE

Date:

HANFORD ATOMIC PRODUCTS OPERATION RICHLAND, WASHINGTON

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

Printed in USA. Price $2.00 Available f rom the Office of Technical Services Department of Commerce Washington 2 5 , D . C .

DISCLAIMER

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- 2 - HW -7 9 174

TABLE O F CONTENTS

INTRODUCTION *

Page

3

c 1

i

.

SUMMARY. 4

DISCUSSION 4

Purpose of Study 4

Waste Pre t rea tment 7

Cesium Removal 8

Strontium, Cerium, and Zirconium Removal 9

Ruthenium Removal 9

Integrated Treatment P r o c e s s a 10

Trea tment Costs 0 1 2

Future Work 0 13

Radioisotope F o r m s Present in Waste a 8

DESCRIPTION OF PUREX TANK FARM CONDENSATE WASTE 0 14 Source of Waste 0 14

Radioisotopes P resen t in Purex Tank Fa rm Condensate. , 1 6

Nonradioactive Substances Present in Purex Tank Farm Condensate ” 1 7

EXPERIMENTAL PROGRAM a ~ 18

Description of Experimental Equipment . 18

Waste Pre t rea tment Experiments a 1 9

Radioisotope Adsorption Without Steam Stripping . a 2 1 Radioisotope Adsorption Following Steam Stripping . 24

Thin Bed Adsorption Studies . o

REFERENCES 0 - 31

APPENDIX A -- Adsorbents Used In Micro Pilot Plant T e s t s . D 32

APPENDIX B -- Summary of Micro Pilot Plant T e s t s e 35 APPENDIX C -- Clinoptilolite Beneficiation . 6 1

APPENDIX D -- Crushing Character is t ics of Clinoptilolite 65

APPENDIX E - - P r o c e s s Economics a0

a 30

-3- HW-79174

PROGRESS IN TREATMENT

OF A RADIOACTIVE CONDENSATE WASTE

INTRODUCTION

This report describes the experimental evaluation of a radioactive

condensate waste decontamination process on a smal l engineering scale .

The management of wastes in nuclear fuels reprocessing plants requires consideration be given to six waste s t r eams . These a r e the high-

level wastes, the process condensates, the s team condensates, the cooling

water, the cell drainage, and the laboratory wastes. Since the cell drainage and laboratory wastes a r e low volume but highly contaminated s t r eams ,

they w i l l probably be combined with the high level wastes. The resulting

dilution of the high-level waste w i l l be overcome by evaporation, and the

volumes of the process condensate and s team condensate s t r eams will be

increased accordingly.

be segregated, discharged to holding basins for monitoring, and then either

discharged to the environment o r combined with the process condensate if

excessive radiocontaminants a r e present; the most likely one to be contami-

nated is the s team condensate which is s imi la r in composition to the process

condensate. Thus, only the high-level wastes and process condensate waste

w i l l require routine treatment.

The cooling water and s team condensate wastes will

P rocess condensate is an intermediate-level waste both in volume

and radionuclide content.

decontamination factor requirements of 100 a r e ordinary and 1000 a r e not

unusual. achieved on a volume of waste which is grea te r than 95% of the total t reat-

able volume f rom a plant.

To dispose this waste safely to the environment,

These decontamination factors must be routinely and economically

Research and development. studies at Hanford and Oak Ridge indicated

that one way to obtain high capacity and high decontamination is by ion-

exchange. These studies, generally conducted on wastes spiked with selected

radionuclides, revealed many potential ion-exchange mater ia ls for a decon-

tamination process . Q If actual waste was used, the samples were not of 9

-4- HW-7 91 7 4

sufficient s ize o r the experiments were not conducted on a scale large

enough to evaluate potential processes .

g ram was considered necessary in which a condensate s t r eam from a reproc-

essing plant would be used a s feed for process studies.

To provide this information a pro-

SUMMARY

A waste s t r eam decontamination process based on ion-exchange was

selected for development. nology developed during recent years in the Hanford Laboratories and other

atomic energy r e sea rch centers .

application of ion-exchange technology resulted i n l e s s than satisfactory

resul ts when compared to laboratory data.

nonradioactive impurit ies in the wastes. cessfully removed these impurities, and excellent decontamination of all

significant isotopes except ruthenium w a s achieved by ion-exchange.

factory ruthenium decontamination was demonstrated on waste volumes up

to about 1000 column volumes, and the capacity for other isotopes ranged

f rom 10 ,000 to 20, 000 column volumes.

tamination is needed to simplify operations and to improve economics.

The process is centered on ion-exchange tech-

Early attempts at small engineering scale

The difficulties were traced to

Steam stripping and filtering suc-

Satis-

Improvement in ruthenium decon-

Although a large scale integrated process is yet to be demonstrated,

a cost es t imate of an ion-exchange process was made.

$ 7 . S O / l O O O gal was based on a 2 ton/day fuels reprocessing plant which pro-

duces about 30, 000 gal/day of condensate requiring treatment. The estimate was based on a process f o r alkaline condensate and i t was assumed a pro-

ce s s f o r acid condensate would cost about the same .

$10/1000 gal l e s s than the estimated cost for reevaporation.

The estimate of

This estimate i s about

DISCUSSION

L'

Purpose of Study

Figure 1 il lustrates a nuclear process waste s t r eam flow plan and highlights the fact that two waste treatment processes a r e required-one f o r

the high-level wastes and one for the low-level wastes. The high-level

waste is characterized by a high radionuclide content, a high sal t content, and a relatively smal l volume.

HW

-7 91 74

-6- HW-79174

The low-level waste is of large volume and generally contains less

than 0. 01% of the fission products.

about to pcuries of beta and gamma emit ters per ml . This waste

is mostly condensate and is formed when high-level solutions a r e concen-

t ra ted in the reprocessing plant and when high-level wastes self boil in

underground tanks.

copious volumes of condensate that will require treatment even though much

effort will be made to suppress radionuclide carryover .

The radioisotope concentration is

Waste solidification processes a lso will produce

Some condensate problems can be minimized, Reducing chemicals, such a s NaNOZ can be added to boiling, acidic solutions to suppress the

formation of volatile ruthenium tetroxide,

condensate for reevaporation o r for dilution of a high-salt content s t ream is another possibility; however, use of condensate as a diluent may recycle

t race quantities of troublesome chemicals such a s degraded organic material .

Even though condensate treatment requirements w i l l be lowered by such

techniques, a large volume w i l l s t i l l have to be decontaminated before the

waste can be released to the environment, and the decontamination must fit

economically into the fuel cycle.

Recycle of a highly contaminated

Multiple effect evaporation is one processing technique that can be

used for waste t reatment ,

assured and information i s available to predict the cost of the process . The technique is flexible and simple; the potential of any other treatment process

may be measured against reevaporation,

alternate processes is primarily economics

to 15 ,000 gal of condensate a r e produced p e r ton of fuel reprocessed by

conventional aqueous processes , appreciable savings can be achieved by

lowered unit processing costs .

The success of a reevaporation process is

The incentive for developing Since approximately 10, 000

Application of ion-exchange technology developed at Hanford and

other Atomic Energy Commission s i tes appeared to be a method of lowering

unit waste processing costs , on the removal of radioisotopes from waste s t r eams was directed to a

better understanding of the ion-exchange and other processes that occur in

the soils at Hanford,

Technology developed at Hanford before 1959

An outgrowth of this work was the discovery that

V

- 7 - HW-79174

.,

( 1 , 2 ) cer ta in minerals can selectively remove radioisotopes from wastes,

Laboratory work was initiated to evaluate one of the minerals, clinoptilo-

lite, for removing radiostrontium and radiocesium f rom condensate wastes At the same time, the need to study a treatment process on a smal l engi-

neering sca le was recognized and the design and installation of appropriate

equipment was s ta r ted .

( 3 )

Waste Pretreatment

Organic mat ter in the waste, especially in emulsified form, tends

to be mechanically removed by the ion-exchange beds. The emulsion glob-

ules fill the void spaces in the bed and cause excessive p re s su re drop af te r

only a fraction of the adsorption capacity of the bed i s used,

the bed by organic mater ia l is characterized by the formation of a distinct layer of an orange colored, wax-like mater ia l in the top inch of the bed.

Plugging of

Significant quantities of NH+* reduce the efficiency of cesium removal because Cs' is s imi l a r to NH4. Ear ly during the waste treatment

experiments, the presence of N H 4 had not been recognized; consequently,

much work was done on removing only the organic mat ter , Two methods

were tr ied: activated carbon adsorption and membrane separation.

The first method successfully removed both soluble and emulsified organic,

although there were severa l limitations to i ts use. Membrane separation was expected to remove only emulsified organic. The method w o r k e d w i t h

synthetic o r simulated waste, but the emulsion in the actual waste was too stable fo r separation. stituent of the condensate waste, i t was realized that a method for remov-

+ ing both organic mat ter and N H 4 was necessary to increase the life of

ion-exchange beds, Steam stripping had been used for removing organic

mater ia l f rom plutonium and uranium s t ream, (5' 6, but only with concen-

trations where large evaporation factors were used. NH removal has

been demonstrated with conventional deaerators f rom boiler feed waters

using a s imi la r technique.

4 +

f

d 4)

+ 4 When it was determined that NH was also a con-

+ 4

( 7 )

:F It is recognized that e i ther NH depending on the pH and the stoichiom&ry of the s t ream. NH; has been used throughout this report f o r consistency.

o r NH+ will exist in the waste sys tem 3.

-8 - HW-79174

+ A s team s t r ipper for the removal of gross amounts of NH4 and

organic impurities f rom condensate waste was designed and fabricated.

The unit was operated at a boil-off ra te of about 57'0 of the feed flow rate .

In general, the s t r ipper removed > 97% of the NH4 and organic impurities.

Some of the radioiodine and radioruthenium a r e volatilized and t ravel with the overhead s t ream.

the aqueous phase can be released to the environs without any fur ther special

treatment

+

These isotopes concentrate in the organic phase, and

Although the s team s t r ipper bottom s t r eams a r e very c lear , residual organic mat te r is present a s a filterable particulate.

is considered necessary to protect ion-exchange beds that a r e to be regen-

erated and reused.

R filtering step J

Radioisotope F o r m s P resen t in Waste

With nonradioactive impurities reduced to relatively low concentrations in the s team s t r ipper bottoms, the waste can be decontaminated by

ion-exchange adsorption.

forms of the radioisotopes,

entirely a s C s

a pH of 5 to 7 .

mari ly positively charged cations; however, 1 to 37'0 a r e nonionized,

pH must be reduced to l e s s than 4 to ionize these elements more completely.

Ruthenium is present pr imari ly in complexed forms.

ruthenium a r e chiefly anions,

Choice of adsorbent is dependent upon the ionic

The cesium in the waste i s present almost + The waste leaving the s t r ipper in the bottom s t r e a m has

At this pH the strontium, cerium, and zirconium a r e pri-

The

These complexes of

Cesium Removal

C s + can be removed f rom s team s t r ipper bottoms by conventional

cation exchange res ins ,

moving cesium from this waste s t r e a m is dependent upon the residual N a

and NHqo ford and has been u s e d to remove cesium from the s team s t r ipper bottom

s t r eam. In general, more waste can be treated by clinoptilolite than by a

The capacity of a strong acid cation resin for r e - +

+ The mineral clinoptilolite has been studied for some time at Han-

-

strong acid cation res in before Cs137 concentration in the effluent s t r eam

increases . The grea te r capacity of clinoptilolite is due to i ts crystal

-9- HW-79174

a T

st ructure . cesium removal even when la rger amounts of NH' and Na

Little work was done with synthetic alumino-silicate materials, but it is

believed that they have cesium capacities comparable to clinoptilolite

although they may not be a s selective.

near neutral solutions, since high o r low pH degrades most of the alumino-

si l icate zeolites.

The crystal s t ructure is near optimum dimensions for selective + a r e present. 4

These materials a r e limited to

Strontium, Cerium, and Zirconium Removal

The radioisotopes of strontium, cerium, and zirconium can also be

removed by cation exchange. The efficiency of removal, however, is sig-

nificantly related to the pH of the feed. Strontium, for example, can be

removed with a decontamination factor of 500 when the s team stripped waste

at a pH of 6 to 7 is passed through a bed of strong acid cation res in .

ever , if the pH is reduced to 4 o r l ess with HN03, the decontamination fac-

t o r is increased to 5000.

removed under the conditions which remove strontium effectively.

How-

Cerium and zirconium radioisotopes a r e a lso

Rut hen iu m Re mova 1

Ruthenium removal is difficult by an adsorption process .

of the complex chemistry of ruthenium this is not without expectation.

a separations plant, ruthenium is present in solutions of high H'NOQ concentration and significant nitr i te and nitrate complexes of the element a r e

formed. When the acid solutions a r e neutralized with caustic, water-,

soluble o r colloidal complexed polymeric species of ruthenium may be

formed. exact form in which the ruthenium is present. Adsorption studies showed,

however, that 10 to 2070 of the ruthenium was removed when the waste was

passed through a bed of strong acid cation resin. When waste was passed

through a bed of strong base anion exchange resin, ruthenium removal

was 80 to 9070.

in mixed beds, >9970 of the ruthenium was removed during the ear ly part

of an experiment. While the initial removal efficiency for ruthenium was

good, the capacity of the two bed system for ruthenium was relatively low. The

In view

In

It is exceedingly difficult and time consuming to determine the

When the two types of res in were used in s e r i e s o r together

-10- HW -7 91 7 4

reduction i n efficiency of ruthenium removal appears to be a function of nonradioactive anion concentrat ion.

Integrated Treatment P rocess

A possible process for treating a waste such as Purex tank f a rm + condensate is illustrated in Figure 2.

mater ia l along with a number of radioisotopes is fed to a s team str ipper

tower. The overhead vapors, representing about 570 of the waste, contain

most of the NH4 and organic impurities.

nium a r e a lso present.

of the waste, contains most of the ruthenium and iodine in the overhead

s t ream, and fur ther processing may be necessary.

tains most of the NH, and almost none of the radioisotopes; it can be disposed to the environment without further treatment.

The waste containing NH4 and organic

+ Some radioiodine and radioruthe-

The organic phase, which represents about 0.0270

The aqueous phase con- +

The bulk of the waste leaves the stripping tower a s bottoms. This s t r e a m is cooled and is passed through a precoated fi l ter .

cesium-selective adsorbent such as clinoptilolite o r Decalso is used as a

f i l ter aid.

A 100 x 400 mesh

This filtering s tep removes particulate mat ter and radiocesium.

.’

The adsorbent cake is discharged for burial whenever i ts cesium capacity

is exhausted o r whenever the p re s su re drop ac ross the f i l ter reaches a pre-

determined point.

anion bed which removes an appreciable amount of the ruthenium along with

NO; and N O i o Periodically this bed is regenerated with caustic.

erant solution is discharged to underground storage. Since alkali in excess

of the stoichiometric amount must be used, the regenerant solution could be

used fo r neutralizing high-level acid waste. The waste leaving the anion bed is acidified to a pH of 4 before it enters the cation bed which removes stron-

tium, cerium, zirconium, residual cesium, and other cationic radioisotopes e

The cation resin has an extremely high capacity for these radioisotopes, and can economically be discharged for burial.

ciently decontaminated that i t can be safely discharged to the environment.

If the residual acid needs to be neutralized, the effluent can be combined with

the aqueous overhead s t r e a m containing NH4.

The fi l tered waste is then passed through a strong base

The regen-

The cation bed effluent is suff i -

A +

k

G

F l o w = 0.02

c 3

r 7

C o n d e n s e r

D e c a n t e r

- Condensate Waste

Nonradioactive I mpurities:

Organic. 200 ppm

Radioactive Impuri t ies:

~ r 9 0 10-4 pc /m i ~ ~ 1 3 7 10-2 pc/ml ~ ~ 1 0 6 10-3 p c / m l C e 1 4 10-3 p c / m l ~ r 9 5 io-2 p c / m l 1131 10-5 p c / m l

u

N$ 150ppm

Organic Phase TO Pur i f i ca t ion Or Inc ine ra t i on

1131 10-3 pc/ml

~ ~ 1 0 6 10-4 pc/ml

F e e d T a n I(

", Y

%3- F l o w = I

S t e a m S t r i p p e r

F l o w 5 - I ] C a u s t i c (

To Environment

NH4 3000 ppm

Radioisotopes

P r e c o a t 3 Z e o l i t e

F i l t e r L

b 1 -

4 - A c i d

E f f l u e n t To E n v i r o n m e n t

R a d i o i s o t o p e s < I 1 1 0 MPC,

'I v

R e g e n e r a n t S o l u t i o n To

U n d e r g r o u n d S t o r a g e

1 E x h a u s t e d I C a t i o n O r D e g r a d e d A d s o r b e n t

C o o l e r ~ l 0 , = 9 5

Condensa te Decontaminat ion F l o w D i a g r a m FIGURE 2

I P F

I

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Treatment C os t s

Evaporation is an available method for the treatment of condensate

s t r eams ; the pr imary incentive for research and development of other t reat-

ment processes is economics.

service at several s i tes a r e available;‘8’ and, since evaporative processes

a r e widely used, cost estimates can be made with reasonable accuracy for

proposed evaporative processes .

data (Appendix E, Figure E-1) reflects that as the capacity of an evaporative system increases , the cost levels-off at $15 to $20 pe r 1000 gal treated. These numbers simply reflect the basic cost of the heat load and, unless the

cost of heat can be reduced markedly, little can be done to lower the costs

of evaporative plants.

Unit costs for evaporative processes in

Table I, l i s ts these costs ; a plot of these

TABLE I EVAPORATOR COST COMPARISON

Volume Treated/ Day, cos t , Site gal $ / l o 0 0 gal*

Bsookhaven 1000 103

Knolls 3000 65

Bettis 4600 38

Hanford Study b 30 ,000 1 7 ( e s t . )

8 A l l costs normalized by amortizing the capital investment over 20 years .

The price for s team alone at Hanford is $1/1000 lb or $8. 30/1000 gal of waste evaporated i f a 1 to 1 conversion is attained.

probably 2 lb of s team consumed for every 1 . 2 5 lb of water evaporated.

Actual conversion i s

Costs for flocculation and precipitation treatment processes at Rocky

Fla t s and Los Alamos were estimated at $9 and $12 per 1000 gal treated, respectively (adjusted for a 20 year amortization) a ‘8p An estimate for a

15, 000 gal/day flocuulation plant at Hanford indicated costs would be about

$9 per 1000 gal. level wastes which contain appreciable amounts of inorganic sal ts ; in fact ,

These chemical treatment processes a r e applicable to low-

n

-13- HW-79174

4

I

successful decontamination depends on the presence of these sal ts .

processes would not be useful to condensate s t r eams unless additional chem-

icals were added; however, their costs a r e included in this discussion for comparison purposes. )

(These

The estimated cost for the process shown in Figure 2 is $7 .50 /1000

gal of waste treated which is less than one-half of that estimated for an

evaporative process . The $7 .50 /1000 gal figure includes utilities, chemicals,

adsorbents, labor, a d s o d e n t burial, maintenance, and plant amortization.

Labor costs a r e based on using one operator half t ime (84 hr/wk, 5 2 wk/yr). It is assumed that he can be productively used elsewhere the other half t ime,

Maintenance is estimated at 570/yr of the $359, 000 investment, and amort i - zation of this capital over 20 y r adds another 5,70/yr.

3 3 of precoat zeolite adsorbent and 1 ft It is assumed that 2 f t of cation

Anion res in loss is res in w i l l be used for each 150, 000 gal of waste treated.

estimated to be about 27'0 per cycle.

be acidified with H N 0 3 to a pH of 3 . 5 to 4 before being fed to the cation resin

bed.

the effluent f rom the cation bed.

requires a large excess of caustic soda; consequently, the anion bed regenerant can be used for neutralizing high-level wastes. Therefore, no charge

w a s made fo r disposing of the regenerant solution.

assigned for burial of used adsorbents; this includes a storage container and burial space.

The effluent f rom the anion resin is to

Caustic soda w i l l be used to regenerate the anion bed and to neutralize

The regeneration of s t rong base anion resins

3 A charge of $ 3 . 2 0 / f t w a s

Appendix E contains a summary of cost information.

Future Work

Future effort w i l l be directed toward demonstrating an integrated process for decontaminating alkaline tank f a r m condensate by combining the

techniques described in this report . Additional demonstration r u n s of t reatment processes for other type wastes w i l l follow along with the evaluation of

other process techniques. The pilot scale demonstration r u n s w i l l be based on chemical flow sheets and on supporting information f rom laboratory studies

The long t e r m objective of this development effort is to provide integrated

waste treatment processes s o that most low- and intermediate-level wastes

can be safely and economically disposed to most environs.

9 Y

-14- HW-79174

Research effort is being directed toward studying ruthenium and improving removal of ruthenium f rom wastes. Ruthenium removal is especially difficult due to i ts many species and their interactions with

other constituents in the w a s t e s . exchangers that may improve ruthenium's decontamination factor, o r that

may have a high capacity for NO; and NO- which appear to limit ruthenium 2 capacity. Adsorption of ruthenium on preformed flocs, minerals, charcoal,

and metal sur faces w i l l a lso be examined.

Studies are aimed a t selection of ion-

Electrochemical reactions of ruthenium in wastes a r e a lso being

examined, particularly electrodialysis data obtained with a laboratory elec-

trodialysis unit indicate that ruthenium can be separated and concentrated.

An engineering scale unit is being installed in the Waste Treatment Pilot Plant and w i l l be used with other processing equipment to study ways of

decontaminating low- and intermediate-level wastes.

*

DESCRIPTION OF' PUREX TANK FARM CONDENSATE WASTE

Source of Waste

A simplified flow diagram of a Purex tank farm waste facility a t Han-

ford is shown in Figure 3 . Neutralized high-level radioactive wastes and

organic wash wastes a r e pumped f rom the Purex Plant to a diversion box f rom which they can be routed to any of s ix underground s torage tanks.

Vapors produced by radioactive decay heat in the s tored waste a r e routed

to an entrainment removal vessel and then to one of three surface condensers.

The liquid collected in the entrainment vessel drains to one of the storage

tanks.

underground retention tank.

(surface disposal pond); the condenser is vented through a deentrainment

tower and then to a local stack; any deentrained liquid is discharged to a c r ib

(a subsurface excavation filled with gravel and covered by ear th) .

The vapor condensate f rom the condenser is routed to a 40 ,000 gal

The condenser cooling water is sent to a swamp

Most of the aqueous condensate collected in the 40, 000 gal tank is

returned to the high-level waste storage tanks for volume control. Pumps a r e provided to allow future recycling of condensate to %the Purex P l a n t , if desired.

ically overflowed through a proportional sampler pit to a cr ib .

Much of the aqueous condensate and any organic mat te r is period-

3

Q -1

5-

H 14' - 7 9 1 7 4

a

a

E 3

a

c 0

c

.- a a E

3

Q

2m

J .I

.- =,"

Y.

LL

CL

a

I

II

a

- 1 6 - HW-7 9 174 n

T h e w a s t e u sed in the s tudy d e s c r i b e d in th i s r e p o r t is the aqueous

phase obtained f r o m the lower p a r t of the r e t en t ion tank (241-A-417) .

Radio iso topes P r e s e n t in P u r e x T a n k Farm Condensa te

T h e s ignif icant r ad io i so topes found in the P u r e x tank farm aqueous

A l s o l i s t ed is the m a x i m u m p e r - condensa te was te a r e l i s t ed in T a b l e 11.

m i s s i b l e concen t r a t ion of e a c h rad io iso tope al lowable in potable waters (MPC,) (only one r ad io i so tope p r e s e n t ) . T h e last co lumn in T a b l e I1 lists

the decontaminat ion f a c t o r r e q u i r e d of a t r e a t m e n t p r o c e s s t o produce the

MPC, va lue .

S r g O a n d C s . I so topes r e q u i r i n g the h ighes t decontaminat ion f a c t o r s a re

137

TABLE I1

RADIOISOTOPES PRESENT

IN P U R E X TANK FARM AQUEOUS CONDENSATE WASTE

Decontaminat ion F a c t o r (b)

Typ ica l

Radio iso tope Hal f -Li fe (a) i J . cu r i e s /ml p c u r i e s / m l R e q u i r e d Concent ra t ion , M F C w ,

28 y r 1 x >loo 90

137

95

106

S r

cs Z r

Ru

30 y r 2 >5 0

65 d 6 x >17

1 Y' 1 >10

50 d 1 '1 0

~e~~~ 285 d 1 >10

Nbg5 35 d I >10

Y 91 59 d 3 >3 1131 8 d 2 I O - ~ --

89 S r

95 (a) Half - l ives given a re for pa ren t s u b s t a n c e s only except f o r Nb which is l i s t e d s e p a r a t e l y . i so tope p r e s e n t i n suf f ic ien t concent ra t ion and with long enough half- l i fe t o b e c o n s i d e r e d i n th i s s tudy .

(b) Max imum P e r m i s s i b l e Concen t r a t ion in W a t e r for Occupat iona l E x p o s u r e (168 h r wk) f rom National B u r e a u of S t a n d a r d s Hand- book 69 (June 5, 1959).

Nb95 w a s the only daugh te r r ad io -

c a

-17- HW-79174

Nonradioactive Substances Present in Purex Tank F a r m Condensate

The significant nonradioactive substances found i n the Purex tank

F a r m condensate during normal operation a r e listed in Table 111.

organic mat ter present in solution a s a very stable emulslon does not

change the decontamination ability of ion exchange materials noticeably:

however, i t does plug packed ion exchange beds. similari ty toCs , reduces ion exchange removal of C S ~ ~ ~ .

f o r m complexes with ruthenium and inhibit i ts removal.

The

+ NH4, because of its + NO; and NO;

TABLE I11

NONRADIOAC TIVE SUBSTANCES PRESE NT

PUREX TANK FARM AQUEOUS CONDENSATE WASTE, pH 9-10

Typical Concentrations, mp/l i ter

Butyl Phosphates 30 to 200

Hydrocarbons 10 to 70

NH;

Na+

NO3

35 to 200

1 to 2

1 to 5 NO: 5 to 10

Periodic, but infrequent, addition of unneutralized waste to the high- levef waste tanks resul ts in H N 0 3 and HN02 in the vapors and condensate. Spot samples of condensate taken abou't. a day af ter unneutralized waste add i -

t ion had a pH of 2 . 7 , an iron c'oncentrat'ion of 3 mg/l i ter (the collection tank

is made of carbon steel), NO- concentration of 260 mg/li ter, and NO- con-

centration of'1100 mg/l i ter . Normal practice when this occurs is to add an excess of caustic to the storage tank to minimize corrosion.

3 2

-18- HW-79174

EXPERIMENTAL PROGRAM

Description of Experimental Equipment

Waste for the experimental program w a s taken f rom the Purex tank f a r m to a waste treatment pilot plant in stainless s tee l d rums o r in an 1800

gal tank truck.

Pyrex glass pipe having nominal 1, 2, and 4 in. diameters w a s used

The 4 in. glass pipe The glass pipe columns

to contain adsorbents for fixed bed adsorption studies.

w a s used only for an activated carbon pretreatment.

were provided with shop fabricated end fittings that held 24 by 110 twilled

Dutch weave stainless s tee l f i l ter cloth in the lower fittings to support the

adsorbent beds. the columns to be filled with or emptied of adsorbent.

in a 75 gal stainless steel feed tank and was pumped by a positive displace-

ment diaphragm pump through columns.

out the column bottom to a local crib.

ments to measure temperature, flow, and pressure drop ac ross adsorbent

beds

Ball valves on both the upper and lower end fittings allowed

The waste was stored

The column effluent w a s discharged The sys tem w a s provided with instru-

+ 4 The removal of NH and organic mat te r f rom the bulk of the w a s t e w a s

found necessary, s o a sma l l s team s t r ipper w a s designed and fabricated.

stripping column w a s fabricated f rom an 8 ft length of 2 in. stainless s teel (SS) pipe packed with 1 /4 in. SS Raschig rings.

2 ft length of 4 in. SS pipe containing a s t eam coil made f rom 10 ft of 3 / 8 in.

SS tubing. to pump waste to the s t eam str ipper , the overhead and bottom s t r eams would drain to receiver tanks below.

bottom s t r e a m w a s routed to the 75 gal feed tank.

A

A reboiler w a s fabricated f rom a

A 400 gal SS feed tank w a s added as w a s a second diaphragm pump

The s t r ipper w a s elevated so that both

The

J

The adsorbents used in the waste treatment experiments a r e listed i n

Appendix A, and a summary of the 35 experiments is listed in Appendix B.

-19- 0

HW-79174

.

Waste Pretreatment Experiments

+ . Before the detection of NH4 in the condensate and the use of the

s team str ipper , activated carbon adsorption was used to reduce the organic

content of the waste for long t e rm evaluation of ion exchange mater ia ls .

The effectiveness of the carbon was studied i n various sized columns at ~

2 column volume min waste flow rates of 0 . 25 to 10 gpm/ft (0 . 01 to 0. 4

The activated carbon reduced the butyl phosphate concentrations to <O. 1 mg/l i ter . Removal of hydrocarbons was not a s efficient; their effluent

concentrations varied from 0 . 5 to 4 mg/li ter, with the higher values occurring at higher flow ra tes . Indications a r e that activated carbon can remove

about 0 . 2 g of organic matter per gram of activated carbon.

100 mg organic per l i ter in the condensate, about 1000 column volumes

could be treated by a bed of activated carbon.

organic mat ter successfully reduced the ion exchange bed hydraulic problems,

but there were excessive pressure drops ac ross the carbon beds.

With about

Activated carbon removal of

In an attempt to reduce the separation necessary i n any pretreatment

step, a c.ommercia1 membrane separator" for removing emulsified organic

mat ter was evaluated. The separator was designed (1) to remove entrained

liquid contaminants f rom liquid systems and ( 2 ) to se,parate immiscible liq-

uids. The separator consisted of porous membranes which coalesce liquids and sepa ra t e light and heavy phases for discharge.

emulsion character is t ics of the Purex tank f a rm condensate was prepared

from tri-n-butyl phosphate (TBP), hydrocarbon diluent, and distilled water. The concentration of the settled.but cloudy mixture was about 150 mg of

TBP ,per l i t e r and 20 mg of hydrocarbon p e r l i ter .

passed through the membrane system, a very c lear effluent which had about

140 ppm TBP and 8 ppm hydrocarbons w a s ,produced.

not removed from Purex tank -farm condensate af ter passage through a s imi-

l a r membrane system.

A waste simulating the

When the emulsion was

Organic matter was

* Selas Liquid - - Liquid Separator manufactured by the Selas Corporation of America, Dresher , Pennsylvania.

'-. -

-20- HW-79174

+ The s team str ipper , which was used to reduce the NH4 and organic

matter concentration in the bulk of the Purex tank f a rm condensate waste,

was operated continuously for over 2500 h r without difficulty.

of 96 ml/min to the s t r ipper and an overhead distillate ra te of 6 ml/min,

the NH concentration in the bottoms ranged from 1 to 4 mg/li ter, the butyl

phosphate concentration was l e s s than 1 mg/l i ter and the hydrocarbon con-

centration varied from 1 to 4 mg/l i ter . Thus, the s t r ipper removed >977'0

of the N H 4 and organic impurit ies.

sisted of two phases. and aqueous phases a r e shown in Table IV.

very low i n the overheads, even though it is present in the feed in concen-

trations grea te r than any other isotope, entrainment of the aqueous feed is minor.

At a feed rate

+ 4

+ The condensed overhead s t r eam con- The concentrations of radioisotopes in the organic

Since C s 137 concentration i s

TABLE IV

RADIOISOTOPES PRESENT IN STEAM STRIPPER OVERHEADS

C onc ent ra t ion Concentration In Organic Phase in Aqueous Phase

Radioisotope ( pc u r ie s / ml) (pcuries/ml)

5 . 9 x 2 . 7

5 . 6 x 3 . 4

cs137 < 1 . 3 x <I. 3

1131

Ru

Zr-Nb

106

9 . 4 c 7 . 8 x 95

+ After the s team stripping process to remove NH4 and organic mat ter

f rom the condensate waste was successfully demonstrated, use of activated

carbon was continued for some time to remove residual organic mat ter in the s t r ipper bottom s t r eam. During severa l r u n s when the organic mat ter in the s t r ipper bottoms averaged about 2 mg/l i ter , the effluent f rom the activated

carbon bed averaged about 1 mg/li ter, indicating ra ther limited adsorption.

The pressure drop ac ross the carbon bed began to increase af ter about 2000

column volumes. Up-flow of 250 F s team at atmospheric pressure through

the activated carbon bed removed about 25% of the hydrocarbons and a negli-

gible amount of butyl phosphates. It is probable that the organic mater ia l

- s

63 removed by the s team

and had been removed

- 2 1 - HW-79174

treatment was present in the interstices of the bed

from the condensate by filtration ra ther than by

adsorption. Higher s team temperatures would have to be used to remove the adsorbed organic mater ia l effectively. After the s team regeneration

step, the bed was effective in removing organic matter, but the pressure drop ac ross the bed increased at a much higher ra te than before,

regeneration procedure apparently created enough fines to impair the hy-

draulic character is t ics of the bed,

The

Granular anthracite coal ("Anthrafilt'l-- which is often used in

conventional water treatment fi l ters) failed to prefil ter the s team s t r ipper

bottom s t ream. The fi l ter bed was able to remove particulate mat ter present in the waste, but excessive pressure drops were encountered af ter only a relatively smal l volume of waste was processed.

More recent experiments using smal l particle ion exchange adsor-

bents a s a precoat mater ia l indicate that filtration and some radioisotope

removal can be accomplished without ser ious hydraulic problems e

Radioisotope Adsorption Without Steam Stripping

The wide interest in the use of minerals for waste treatment and

disposal has led to much laboratory work at Hanford on the mineral clinop-

tilolite. ability of clinoptilolite to decontaminate Purex tank fa rm condensate. P a r a m e t e r s studied include clinoptilolite particle size, feed f l o w rate,

temperature, ,pretreatment of the waste to remove organic material , and

pretreatment of clinoptilolite to -remove associated clay.

The f i rs t six experiments in this s tudy were to determine the

The resul ts of these experiments showed that clinoptilolite has an

excellent ability to remove cesium from Purex tank f a rm condensate waste.

Cesium removal efficiency was enhanced by sma l l mineral particle s i ze ,

In general, the kinetics were so poor when +20 mesh* mater ia l was used

that this particle s ize is probably the upper limit for fixed bed adsorption

applications. The lower limit was fixed by the hydraulics of the system.

- * Mesh designation in this report re fe rs to standard sieve s i zes used in

sc reen analyses a s recommended by U, S . National Bureau of Standards. (The resul ts of the work done at the University of CalifGrnia reported in Appendix D includes Tyler Sieve designa.tion. )

s, 1

-22- HW-7 9 174

3 Flow rates of l e s s than 2 gpm/ft

cient cesium removal; however, increased temperature permits higher

flow rates without impairing cesium removal efficiency.

were necessary to obtain the most effi-

Clinoptilolite removed some strontium from the condensate, but the

decontamination factor was too low for radiostrontium concentrations less

than i ts MPCw. temperature did not a l te r the strontium decontamination efficiency s ignif i-

c antly. Cerium, zirconium, and ruthenium were not appreciably removed

by the mineral .

Variations in flow rate, clinoptilolite particle size, and

Strontium, zirconium, and cerium apparently a r e present a s nonionic

forms in Purex tank f a rm condensate, which is normally alkaline, and thus

ion exchange is not possible. conditions by activated carbon is probably due to physical adsorption o r filtration.

Some removal of these isotopes under alkaline

Removal of the organic impurities by activated carbon pretreatment

did not improve the decontamination efficiency of clinoptilolite. The use of

the activated carbon did improve the overall strontium decontamination be-

cause the carbon removed some strontium.

removed by the activated carbon minimized the hydraulic problems in the ion

exchange beds, these problems were merely t ransfer red to the carbon column.

Another problem with the activated carbon was the leaching of aluminum ash

present in the carbon by the alkaline solution; la ter , the aluminum precipi-

tated and tended to plug downstream beds.

Although organic mater ia l

Hydraulic problems also were met with clinoptilolite because the

mineral contained clay particles which tended to break down into fines when

contacted with water. The clay had to be removed before column operation.

The clinoptilolite beneficiation work is reported in Appendix C, and a study

made at the University of California on crushing character is t ics of clinopti-

lolite is included in Appendix D.

.

t

-23- HW-7 91 74

t

I'

Two extended experiments (11 and 1 2 ) were performed to measure

the capacity of clinoptilolite for removing cesium efficiently.

experiment using two beds in se r i e s was not valid for measuring capacity because one of the beds became plugged about half way through the r u n .

The plugging w a s caused by precipitate f rom the leached aluminum ash

from the activated carbon pretreatment step.

that the clinoptilolite could t reat about 5800 column volumes of waste before

the Cs137 concentration in the effluent would exceed its MPC decontamination factor varied from 1000 at the s t a r t to 100 at the er,d of

the r u n s even though about 1 6 0 mg of NH4 per l i ter was present in the waste.

The first

The second r u n indicated

value. The W

+

An attempt to use a calcite-phosphate replacement reaction for en-

hanced strontium removal during Experiment 1 2 w a s only slightly success-

f u l .

removed to obtain an effluent S r g O concentration less than its MPCwo

Some additional strontium removal was observed, but not enough was

Two experiments were performed to study the cesium removal effi-

ciency of two synthetic zeolites. :: Decalso removed cesium at a decontami-

nation factor of 850 to 1000 f rom a waste that contained NH4.

had little effect on the cesium decontamination factor. Some strontium was

removed; cerium, zirconium, and ruthenium were not appreciably removed.

+ Flow rate

Molecular Sieve 4A i n the form of 1/16 in. pellets was used to t reat A s l o w f l o w ra te was required w i t h the re la - P u r e x tank f a rm condensate.

tively large adsorbent particles, but the cesium decontamination factor

improved from 350 at the beginning of the run to 2000 when the r u n was

terminated af ter 500 column volumes of waste were treated. Strontium

w a s only partially removed.

Because strontium was not removed efficiently f rom the condensate

by natural or synthetic zeolites or by the calcite-phosphate replacement reaction, it was decided to evaluate strontium removal by a conventional

zg The t e r m zeolite was first applied to a c lass of naturally occurring c rys - talline minerals (such a s clinoptilolite) having cation exchange propert ies ~

Molecular sieves a r e synthetic counterparts of these minerals . The t e rm was used to describe alumino-silicate mater ia ls having cation exchange properties which were used for water softening. extended the t e rm to synthetic organic cation resins . The t e rm a s used i n this report re fe rs to inorganic alumino-silicate cation exchange mate- r ia l s (gel or crystalline) *

Popular usage has

-24- HW-79 1 7 4

strong acid cation resin.

that a feed pH of 2 . 5 would be most effective.

tempted with the acidified waste was terminated after only brief operation.

The acidified waste leached iron and aluminum ash impurities from the

activated carbon bed. A s the waste progressed through the bed, the pH began to r i s e a s the acid was depleted. The higher pH resulted in down-

s t r e a m precipitation of these elements a s iron and aluminum hydroxides.

The precipitate very quickly plugged the ion exchange resin bed.

Ion exchange studies in the laboratory indicated

The first experiment a t - .

A second attempt was made with a new bed of strong acid cation res in

af ter the activated carbon bed was treated with HN03 to preleach the ash

impurit ies. The test had to be stopped again because NH; in the waste was

neutralized by HNO ammonium nitrate provided a significant nonradioactive cation load on the

res in bed. Breakthrough of cesium occurred before the first sample was taken.

+ . were performed, the presence of NH in the waste was unsuspected. In the 4 concentrations encountered, an ammonia odor should have been a clue to its presence, but the odor given off by the organic mater ia l completely masked

the ammonia odor. The high pH of the condensate was believed to be due to

v

when the feed was acidified; at the low pH, ionized 3

Other isotopes were removed only s Lightly. Until these experiments

entrained caustic soda present in the high-level waste.

After significant quantities of NH: were noted, the s team stripping

process previously described was used. Thus, the la te r adsorption experi-

ments were performed on steam-stripped Purex tank f a r m condensate.

vated carbon used in these la te r experiments was commercial acid-leached

mate r ia l

Radioisotope Adsorption Following Steam Strip,ping

Acti-

After the s team stripping unit process was used, further adsorption studies were made with clinoptilolite, s t rong acid cation resins , strong base anion resins , a weak base anion resin, and an acid-leached activated carbon. Some of the experiments involved combinations of these adsorbents either a s separate beds in s e r i e s o r mixed in one bed. The activated carbon acted a s

-25 - HW - 7 9 174

i

a prefil ter-adsorber to remove residual organic mat ter that remained in

the s t eam s t r ipper bottoms. Although the activated carbon did i ts task

adequately, i ts use did not appear practical for large scale application.

La ter experiments omitted the activated carbon prefilter-adsorption step.

When used, however, the activated carbon bed often removed significant

amounts of strontium, cerium, zirconium, and ruthenium. The resul ts

were not always reproducible. Small changes in pH affected adsorption efficiency for these radioisotopes, an indication that par t ia l removal by the carbon might be due to filtration o r colloid adsorption.

Strong acid cation resins used to t reat s team stripped condensate were quite effective in removing cesium with decontamination factors >1000.

These res ins a r e effective in removing all cations present .

for cesium, therefore, is dependent upon the concentration of nonradio-

active cation impurit ies. F o r example, when steam-stripped waste with a

pH of 6 to 7 and about 0 , 5 0 meq cations/l i ter was passed through a bed of

Amberlite IR-120 in the hydrogen form, about 6000 column volumes of waste

were t reated before the C s

MPC, value. In a s imi la r tes t with the resin in the sodiumform and the

feed with a pH of 4 and about 0. 27 meq cat ions/ l i ter , the res in bed could

t rea t 11 ,000 column volumes to the same end point, The cesium break-

through curves for these experiments a r e shown in Figure 4.

The capacity

concentration in the effluent reached its

The pH of the feed did not affect the cesium removal efficiency of strong acid cation resins , but the pH was significant for strontium removal.

In general, when the pH of the s team stripped waste was lowered f rom 6

o r 7 to 3 o r 4, the strontium decontamination factor was increased ten-fold.

The pH effect was l e s s obvious when the hydrogen form of the res in was

used, because the exchanged hydrogen ions lowered the pH of the waste. The efficiency of strontium removal by a s t rong acid cation res in in the

hydrogen form with acidified feed is shown in Figure 5 , form of the cation res in was used, the pH effect was quite definite.

When the sodium

- 2 6 -

1 0 - 6

10 -7 ,

c HW-7 9 1 7 4

I C u r v e A : A m b e r l i t e I R - 1 2 0 B e d E f f l u e n t w i t h - 0 .50 m e q C a t i o n s / L i t e r o f F e e d

- C u r v e B: A m b e r l i t e I R - 1 2 0 B e d E f f l u e n t w i t h 0.27 m e q C a t i o n s / L i t e r o f F e e d

- C u r v e C: C l i n o p t i l o l i t e B e d E f f l u e n t w i t h - 0 .44 m e q C a t i o n s / L i t e r o f F e e d

I I I I I I I I I I I I I I I I I I

- -

-

A

Cs137 I n F e e d

B C

1 0 - z

1 0 - 3

1 0 - 4

1 0 - 5

C o l u m n V o l u m e s

FIGURE 4

Cs137 R e m o v a l f r o m S t e a m S t r i p p e r Bo t toms

* .

t

-27- HW-79174

h - E \

u I Y

S 0 + co L +

.-

t W u t 0 0

1 0 - 3

1 0 - 4

1 0 - 5

1 0 - 6

10-7

r i S r 9 0 i n F e e d

0 B e d E f f I u en t

A

0 5 0 0 0 10000 1 5 0 0 0 20000

Co lumn Volumes

FIGURE 5 90 S r Removal from Acidif ied Steam StrLpper Bottoms

A F C G E R I C H L A R D W A S H

-28- HW -7 9174

The efficiency of removal for cer ium and zirconium was s imi la r to

In general, when the pH was reduced to <4, the effluent that of strontium.

concentrations of these radioisotopes was l e s s than their respective MPC W

values. The decontamination factors were not high, however, because of the relatively low concentration of the isotopes in the feed. feed f o r these experiments was acidified with HN03.

the addition of C 0 2 to the feed lowered the pH sufficiently to reduce the

effluent strontium concentration.

ever, because the C 0 2 tended to escape while the feed was stored in the

vented feed tank.

Most of the In one experiment,

The low pH was difficult to maintain; how-

Clinoptilolite was also effective in removing cesium f rom s team

stripped condensate. and a capacity grea te r than that attained w i t h s t rong acid cation resins w a s

measured.

a bed of clinoptilolite, about 15, 000 column volumes of waste were treated

before the The breakthrough curve fo r this experiment is a l so shown i n Figure 4.

Cesium decontamination factors of >lo00 were obtained,

When feed containing 0 . 4 4 meq cations/l i ter was passed through

concentration in the effluent reached i ts MPC value,

With the feed at a pH of about 3, clinoptilolite initially removed s t ron- tium with a decontamination factor comparable to that measured with s t rong

acid cation res ins . S r g O in the effluent reached i ts MPCw value af ter 6000

column volumes of waste were treated.

an additional 10, 000 column volumes, however.

illustrated in Figure 5

Some strontium was removed from

The breakthrough curve is

f

Both types of cation exchange adsorbents removed only a smal l amount

Strong base anion resins removed about 70 to 8070

of ruthenium f rom the waste.

a strong acid cation res in ,

of the ruthenium. With a strong acid cation res in bed in se r i e s with a strong base anion bed, over 99% ruthenium removal from about 600 column volumes

of waste was accomplished. The capacity of such a system is dependent upon

the concentration on anionic impurities in the waste feed, When NO; and NO; appear i n the effluent, the efficiency of ruthenium removal decreases

(Figure 6).

bed a l so removed ruthenium, but not with the same efficiency a s the strong

base, strong acid s e r i e s .

About 10 to 207’0 removal was observed ac ross

A weak base anion resin bed following a s t rong acid cation res in

-29- HW- 7 9 1 7 4

10-3

/ E f f l u e n t From An ion Red Only

MPC, Ru106

10-6 t I ~ I I I l I I I I I I I l l l l ~ l I

0 5 0 0 1 0 0 0 1500 2 0 0 0

Column Volumes

FIGURE 6

Ru106 Removal from Steam Stripper Bottoms

The s team s t r ipper bottoms a r e very c lear but residual organic

mat ter is present a s a filterable particulate.

of 1 gpm/ft , the initial p ressure drop across an 11 in. deep strong acid

cation resin bed was about 0 . 1 p s i .

column volumes when the pressure drop across the bed had increased to

about 4 . 9 psi .

1 in. layer at the top of the bed (some organic mat ter was dispersed

throughout the bed).

which caused considerable resin particle agglomeration, mechanical

means were used to break u p the agglomerate, and solvent treatment was

necessary to dissolve the organic mat ter adhering to the res in beads before

rege ne rat ion.

In one r u n at a flow rate 2

The r u n was stopped after 6000

Most of the filterable organic material was removed in a

Since the organic mat ter had adhesive properties

-30- HW-7 9 1 7 4

Thin Bed Adsorption Studies

The organic mater ia l remaining in the s team s t r ipper bottoms is not

easily removed by normal backwashing and regeneration techniques; there-

fore, filtering is necessary to protect ion exchange beds which a r e to be

re gene ra t e d

The use of a precoated fi l ter with a smal l particle cation exchange

f i l ter aid was considered so that both filtering and cation exchange adsorp-

tion could be handled by one unit operation.

expected with natural zeolites such a s clinoptilolite in the smal le r particle

size, and more of the adsorptive capacity of the f i l ter aid mater ia l would

probably be used before hydraulic problems would be encountered.

Improved kinetics would be

T w o experiments were performed with s team stripped condensate to

evaluate the decontamination ability of thin precoat beds of cation exchangers

During one experiment the condensate was acidified with RNOQ to a pH of 3. 2

and was passed through 1 . 7 c m of 200 x 400 mesh strong acid sulfonated poly-

styrene cation resin at a flow ra te of 5 gpmjft

A strontium decontamination factor > 1000 was maintained with >5000 column

volumes of waste, The cesium decontamination factor varied f rom 700 at the

beginning of the test to 70 when its MPCw value was reached. The MPCw of

cesium in the effluent was reached a f t e r 2250 column volumes.

drop ac ross the bed increased from 2 . 1 psi at the s t a r t of the test to 3. 3 p s i

at the end,

2 (10 column volumes/min).

P r e s s u r e

During the other experiment the feed was acidified to a pH of 4 and

passed through 2 . 0 cm of P O 0 x 230 mesh acid-washed clinoptilolite in the

sodium form at a flow rate of 5 gpm/ft

tamination factor for strontium and cesium ranged from 100 to 400 through

4500 column volumes,

the effluent d id not exceed their respective MPCw values. a c r o s s the bed did not exceed 2 psi.

2 (10 column volumes/min), The decon-

Concentrations of radiostrontium and radiocesium in

P r e s s u r e drop

APPENDIX A

-31- HW-79174

R E F E R E NCES

1.

2.

3 .

4.

5 .

6 ,

7 ,

8.

L. L. A m e s . The R e m o v a l of Radio iso topes from W a s t e S t r e a m s by M i n e r a l Reac t ion . BNL-546, pp. 80 t o 84. J a n u a r y 8, 1959. (SECRET)

L. L. A m e s . T h e Zeo l i t e E x t r a c t i o n of C s from Aqueous Solution, HW-62607. S e p t e m b e r 30, 1959.

B. W. M e r c e r , T h e R e m o v a l of C e s i u m and S t r o n t i u m from Conden- s a t e W a s t e s with Clinopt i lol i te , HW-66276. J u l y 29, 1960.

Selas Liquid S e p a r a t o r , Bul le t in LS-1 Selas C o r p o r a t i o n of A m e r i c a , D r e s h e r , P e nns y lva n ia

F. W. Woodfield. P u r e x T e c h n i c a l Manual , HW-31000. M a r c h 25, 1955. (SECRET)

B o T . Bell. Capac i ty , C o n t r o l a n d TBP S t r ipp ing - -Tr i a l s on a S m a l l E v a p o r a t o r , AERE-R-3508. Atomic E n e r g y R e s e a r c h E s t a b l i s h m e n t , H a r w e l l , Eng land . 1960.

A. E . Ki t t r edge . The R e m o v a l of Di s so lved G a s e s f rom B o i l e r F e e d I f

I f W a t e r , pp. 38-42, S e p t . , pp. 43-44. 1941.

M o d e r n P o w e r & E n g . , vol. 35, July, pp. 42-44, A u g . ,

A. B. J o s e p h . Radioac t ive W a s t e D i s p o s a l P r a c t i c e s in the Atomic E n e r g y Indus t ry- -A Survey of t h e C o s t s , NYO-7830, D e c e m b e r 31, 1955,

-32 - HW-79174

APPENDIX A

ADSORBENTS USED IN WASTE TREATMENT PILOT PLANT TESTS

Activated Carbon, Type CAL

An activated carbon having a 1 2 x 40 mesh particle s ize produced by

the high temperature s team activation of bituminous coal.

Pittsburgh Chemical Company, Pittsburgh, Pennsylvania. Manufacturer:

Activated Carbon, Type SGL

Same a s activated carbon Type CAL except particle s ize is 8 x 30

mesh,

Amberlite IR-120

A sulfonated polystyrene strong acid cation resin. Manufacturer: Rohm and Haas Company, Philadelphia, Pennsylvania.

Ambe rlit e IR - 1 2 0 L

Same a s Amberlite IR-120 except screened to give a slightly l a rge r effective particle s ize .

Amberlite 200

A sulfonated polystyrene strong acid cation res in having a macro- re t icular bead s t ruc ture . Manufacturer: Rohm and Haas Company, Phila-

delphia, Pennsylvania

Amberlite XE-150

A nuclear grade mixture of sulfonated polystyrene s t rong acid cation resin i n the hydrogen form with Type I quaternary ammonium polystyrene

s t rong base anion res in in the hydroxide form uniformly mixed in the pro-

portion of 1 equivalent hydrogen ion to 1 equivalent hydroxide ion. Manu-

facturer : Rohm and Haas Company, Philadelphia, Pennsylvania.

Apatite, Canadian

A naturally occurring calcium hydroxyphosphate mineral .

- 3 3- .

@ HW-79174

Apatite, Synthetic

A synthetic calcium hydroxphosphate made by reacting calcite par - t icles with a hot tr isodium phosphate solution.

Calcite

A calcium carbonate mineral .

C linoptilolite

A naturally occurring alumino-silicate zeolite mineral having a si l ica to alumina rat io of 8-10:l.

by the Baroid Division of National Lead Company, Hector, California. The material used in this study w a s mined

t

Decalso

A synthetic alumino-silicate gel having 6 : l silica to alumina ratio.

Manufacturer: Permut i t Company, New York, New York.

Dowex 50W

A sulfonated polystyrene strong acid cation resin. Manufacturer: Dow Chemical Company, Midland, Michigan.

111~0 NR- 1

A nuclear grade sulfonated polystyrene s t rong acid cation res in in the

hydrogen fo rm marketed by the Illinois Water Treatment Company, Rockford,

Illinois.

111~0 NR-2

A nuclear grade Type I quaternary ammonium polystyrene s t rong base

anion res in in the hydroxide form marketed by the Illinois Water Treatment

Company, Rockford, Illinois.

'1

-34- HW-79174

111~0 TM-1

A commerc ia l grade mixture of sulfonated polystyrene s t rong acid

cation res in in the hydrogen form with Type I quarternary ammonium poly-

styrene s t rong base anion r e s i n in the hydroxide f o r m uniformly mixed in

the proportion of 1 equivalent hydrogen ion to 1 equivalent hydroxide ion.

It is marketed by the Illinois Water Treatment Company, Rockford, Illinois.

Molecular Sieve 4A

A synthetic alumino-silicate crystalline zeolite having a 2: 1 silica

to alumina ratio. Manufacturer: Line Company, Tonawanda, New York.

,-

APPENDIX B

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APPENDIX B

HW-79174

SUMMARY OF WASTE T R E A T M E N T P I L O T P L A N T T E S T S

EXPERIMENT 1

OBJECTIVES T o t e s t Was te T r e a t m e n t P i lo t P l an t equipment r e l i ab i l i t y and develop o p e r a t i n g p r o c e d u r e s

-

CONDITIONS ~~ ~

F e e d Dis t i l l ed w a t e r a t 2 0 t o 25 C

A d s o r b en t s Mesh Bed B e d

Bed Siz e Volume, D i a m e t e r , Flow, No. TJ’P e USBS c m in . g p m / f t

1 Clinopt i lol i te 1 2 x 30 -250 1 - 6

3

(un t r ea t ed )

RESULTS AND CONCLUSIONS

Equipment o p e r a t e d cont inuously for 124 h r . def ic ienc ies w e r e o b s e r v e d and c o r r e c t e d . w a s u s e d as feed, p r e s s u r e d rop a c r o s s t h e bed i n c r e a s e d 5070 dur ing t h e r u n . P r e s s u r e d rop i n c r e a s e w a s probably c a u s e d by degrada t ion of c l a y p a r t i c l e s a s s o c i a t e d with t h e cl inopt i lol i te .

S e v e r a l equipment Although d i s t i l l ed w a t e r

OBJECTIVES

CONDITIONS

EXPERIMENT 2

To t e s t W a s t e T r e a t m e n t Pilot P l a n t equ ipmen t r e l i ab i l i t y and develop ope ra t ing p r o c e d u r e s us ing ac tua l PTFC w a s t e

F e e d P u r e x tank farm condensa te a t 1 2 to 22 C

A d s o r b en t s

Mesh Bed Bed B e d S ize Volume, D i a m e t e r , Flow, - No. TYP e USBS c m in . gpm / f t

1 Clinopt i lol i te 1 2 x 30 - 250 1 3 to 6

3

(un t r ea t ed )


F low and t e m p e r a t u r e con t ro l w a s inadequate , s y s t e m w a s f u r t h e r modi f ied .

- 3 6 - HW-79174

EXPERIMENT 3

OBJECTIVES To measu re the decontamination efficiency of clinoptilolite at severa l flow ra t e s

CONDITIONS

Feed

Adsorbent s P u r e x tank f a r m condensate at 25 C

Mesh Bed Bed

in. USBS c m

1

Volume Diameter, Bed Siz e 3 - No Type

1 Clinoptilolite 3 0 x 40 - 180

(untreated)

Flow, gpm I ft 1 to 6


(1) Cesium decontamination factor > 1000 at all flows. (2 ) Strontium decontamination factor decreased from 25 to 11 as

(3) Cerium, zirconium, and ruthenium decontamination factor < 2 at

(4) Clay par t ic les associated with clinoptilolite created fines which

(5) Emulsified organic in waste was being fi l tered out causing

flow was increased.

all flows.

caused hydraulic problems

additional hydraulic problems

EXPERIMENT 4A OBJECTIVES To measu re the efficiency of activated carbon for

decontaminating the waste, and for removing organic impurit ies in the waste

CONDITIONS

Feed

Ads o r b ent s

Purex tank farm condensate at 25 C -

Mesh Bed Bed

USBS cm 1 Activated Carbon 8 x 30 ,500

Volume, Diameter, Flow

1 to 6 1

in gpm/ft Bed Size 3 - No TYP e

(type SGL) RESULTS AND CONCLUSIONS

(1) Activated carbon removed only strontium, decontamination factor

(2) Activated carbon removed over 98% of butyl phosphates and hydro- decreased f r o m 7 to 1 . 5 as flow ra t e was increased

carbons f rom the waste c

n -37- HW-791.74

EXPERIMENT 4B

OBJECTIVES To measu re the efficiency of a column of clinoptilolite for decontaminating after the waste had been pretreated for organic removal by passage through activated carbon.

CONDITIONS

Feed Purex tsnk f a r m condensate at 2 5 C

Adsorbente TWO beds in s e r i e s

Mesh Bed Bed Volume. Diameter, Flow,

in. gpm / ft 3 Bed Size No. Type USBS c m

~

1 Activated carbon 8 x 30 -500 1 1 to a (type SGL used during Run 4A)

(unt r eat e d) 2 Clinoptilolit e 1 6 x 20 -450 1 1 to a


Cesium decontaminztion factor increased f rom 25 to 100 as f low rate, w a s increased. Strontium decontamination factor ac ross both beds decreased f rom 35 to 7 a s flow r a t e w a s increased. Zirconium decontamination fsc tor ac ross both beds decreased from 10 to 7 a s flow r i t e w a s increased. Cerium and ruthenium dccontamination factor across both beds was < 2 at all flow ra t e s . Par t ic le s i ze of clinoptflolite w a s too la rge for efficient cesium removal at. fl.ows studied.

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EXPERIMENT 5A

OBJECTIVES To measu re the efficiency of clinoptilolite having a smaller par t ic le s i ze than that used in Run 4B for removing cesium and strontium after the waste had been pretreated fo r organic removal by passage through activated carbon.

CONDITIONS

Feed Purex tank farm condensate at 25 C

Adsorbents Three beds in series Mesh

Bed Size No TYP e USBS

1 Activated carbon 8 x 30

2 Activated carbon 8 x 30

3 Clinoptilolite 20 x 40

-

(type SGL)

(type SGL)

(untreated)


Bed Volume

0 3

- 460

- 460

N 410

Bed Diameter Flow,

in gpm / ft 1 0.25 to 6

1 0.25 to 6

1 0 . 2 5 to 6

(1) Cesium decontamination factor ac ross all t h ree beds decreased f rom 3000 to 720 as flow ra t e was increased.

( 2 ) Strontium decontamination factor ac ross all th ree beds decreased f rom 30 to 11 as flow rate was increased,

(3) Cerium, zirconium and ruthenium decontamination factors not measured because of poor resu l t s in earlier runs.

(4) Fines result ing f rom clay par t ic les in clinoptilolite caused increased p r e s s u r e drop ac ross the mineral bed.

EXPERIMENT 5B

OBJECTIVES

CONDITIONS Feed

Adsorbents

Same as Run 5A but at a higher feed temperature

Purex tank farm condensate at 45 C

Same beds used in Run 5A.


(1) Cesium decontamination factor ac ross all t h ree beds decreased 2900 to 1300 as flow r a t e was increased.

(2) Strontium decontamination factor ac ross all th ree beds decreased f rom 28 to 15 as flow ra t e was increased.

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EXPERIMENT 5B (Contd. )

(3) Higher feed tempera ture improved decontamination efficiency for cesium and strontium at higher flow ra tes .

(4) Butyl phosphate appeared in the effluent f rom the first activated carbon column af ter about 1000 l i t e rs of waste were t reated.

EXPERIMENT 6

OBJECTIVES To measu re the decontamination efficiency of clinop - tilolite which was t reated for clay removal at various flow rates af ter the waste had been pretreated for organic removal by passage through activated carbon.

CONDITIONS

Feed

Adsorbents Two beds in series Purex tank f a r m condensate at 25 C

Mesh Bed Bed

2 Bed Size Volunje, Diameter, Flow, No TYP e USBS cm in. gpm/ft

1 Activated carbon 8 x 30 -460 1 0.25 to 10

2 Clinoptilolite 20 x 25 -460 1 0 . 25 to 1 0 (type SGL)

(caustic soda t rea ted and water washed)


(1) Cesium decontamination factor decreased f rom 1000 to 200 a s flow rate w a s increased.

(2) Strontium decontamination factor ac ross both beds decreased from 20 to 1 0 a s flow rate was increased.

(3) Cerium, zirconium and ruthenium decontamination factors var ied from 2 to 4 ac ross both beds at all flow rates.

(4) Pretreatment of the clinoptilolite by immersion in hot 5% caustic soda for about 1 h r followed by a distilled water wash improved the hydraulics of the mineral column.

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EXPERIMENT 7

HW-79174

OBJECTIVES To measu re the decontamination efficiency of a synthetic apatite

CONDITIONS

Feed Adsorb ents


Mesh Bed Bed Bed Size Volurge, Diameter, Flow , No Type USBS cm in. gpm/ft 1 Apatite (made by 20 x 30 -440 1 1 -

reacting calcite with a hot sodium phosphate solution)

RESULTS AND CONCLUSIONS (1) No radioisotope removal was observed.

EXPERIMENT 8

OBJECTIVES To measu re the decontamination efficiency of a synthetic alumino -sil icate gel

CONDITIONS

Feed

Adsorbents Two beds in s e r i e s

P u r e x tank farm condensate at 25 C

Mesh Bed Bed Size Volume, Diameter, Flow,

No. TYP e USBS c m 3 in e gpm/ft2 Bed - 1 Activated carbon, 8 x 30 5 00 1 1 to 1 0

2 Decals o 1 6 x 50 400 1 1 to 1 0 (type SGL)


(1) Cesium decontamination factor varied f rom about 850 to 1000 at the beginning of the run to about 300 after about 150 liters of waste were t reated. Changes in flow rate did not appreciably effect the cesium decontamination factor.

(2) Strontium decontamination factor ac ross both beds var ied f rom 15 to 30 during the run. strontium decontamination factor e

Changes in flow rate did not appreciably effect the

9 (3) Cerium, zirconium and ruthenium were not removed significantly.

-41 -

EXPERIMENT 9

HW-79174

OBJECTIVES

CONDITIONS

Feed

Adsorbent s

To measu re the decontamination efficiency of a naturally occuring apatite mineral af ter passage of the waste through activated carbon for organic removal

Purex tank f a r m condensate at 25 C

Two beds in s e r i e s

Mesh Bed Bed Bed Siz e Volume, Diameter, Flow, No 'TYP e USBS em 3 in gpm/ft 1 Activated carbon, 8 x 30 500 1 1 to 1 0

1 Canadian Apatite 1 0 x 40 400 1 1 to 10 (type SGL)


(1) Strontium was removed with a decontamination factor of about 6 ac ross both beds.

(2) No other isotope removal was observed.

EXPERIMENT 10

OBJECTIVES To measu re the decontamination efficiency of a synthetic crystall ine zeolite after passage of the waste through activated carbon for organic removal.

CONDITIONS

RES

Feed Purex tank f a r m condensate at 2 5 C

J -

Bed No

1

2

JTS A

Adsorbents Two beds in s e r i e s -~ Mesh Bed Bed Siz e Vo luye Diameter Flow,

- Type USBS cm in a gpm/ft Activated carbon, 8 x 30 5 00 1 2 (type SGL) Molecular s ieve 1 / 1 6 in. 400 1 2 4A, pellets

JD CONCLUSIONS

(1) Cesium decontamination factor increased f rom about 350 at the start of the run to about 2000 after about 200 l i t e r s of waste w e r e t reated,

( 2 ) Strontium decontamination factor ac ross both beds var ied from 15 to 20 during the enti- e run.

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EXPERIMENT 11

OBJECTIVES To measu re the decontamination efficiency of clinoptilolit e after the w a s t e was pretreated for removal of organic mat te r

CONDITIONS

Feed P u r e x tank f a r m condensate at 25 C

Adsorbents Three beds in s e r i e s

Bed Size - No. TYP e USBS

Mesh Bed Bed Volume, Diameter, Flow,

in. gpm/ft 3 c m 1 Activated carbon, 8 x 30 10, 000 4 1 to 2

(type SGL) 1 4 2 Clinoptilolit e 18 x 20 250

(caustic soda treated and water washed)

3 Clinoptilolite 20 x 40 (caustic soda t rea ted and water washed)

250 1 4


Cesium decontamination factor var ied f rom 1000 at start of run to 100 when the concentration of Cs137 in the effluent reached its MPC,. value af ter about 1800 l i t e r s of waste were t reated. Strontlum decontamination factor ac ross the activated carbon bed var ied f rom 5 to 10 and ac ross the clinoptilolite beds var ied f rom 4 to 8 fo r an overall decontamination factor of 20 to 80. concentration in the effluent exceeded i t s MPC, during most of t h e run. Cerium, zirconium and ruthenium radioisotopes were only slightly removed. The high ammonia concentration in the feed leached aluminum ash impurit ies f r o m the activated carbon. Precipitation of aluminum hydroxide in the sys tem downstream f rom the activated carbon bed caused plugging of the first mineral bed.

Sr90

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EXPERIMENT 1 2

HW-79174

OBJECTIVES To m e a s u r e t h e decontaminat ion eff ic iency and capac i ty of c l inopt i lol i te f o r r emov ing c e s i u m and s t r o n t i u m and f o r m e a s u r i n g t h e eff ic iency with which s t r o n t i u m is r e m o v e d us ing a ca l c i t e -phospha te r e p l a c e m e n t r e a c t i o n

CONDITIONS

F e e d P u r e x tank farm condensa te containing about 1 6 0 m g l l i t e r a m m o n i a at 25 C; 200 m g / l i t e r NaOH and 173 mg/li ter N a 3 P 0 4 w e r e added t o w a r d s l a t t e r p a r t of r u n a f t e r C s 137 b reak th rough o c c u r r ed .

Adsorben t s T h r e e beds in series

M e s h Bed Bed Bed S ize Vo lume D i a m e t e r Flow, No. TYP e USBS c m in . g p m / ft 1 Act ivated c a r b o n 8 x 30 1 0 , 0 0 0 4 0 . 5 t o 1 . 3

3

( type SGL)

( c a u s t i c s o d a hea ted and w a t e r washed)

2 Cl inopt i lol i te 20 x 40 250 1 4

3 C a l c i t e 2 0 x 40 250 1 4


(1) C e s i u m decontaminat ion f a c t o r v a r i e d f r o m 1000 at s t a r t of r u n t o 1 0 0 when t h e concent ra t ion of i n t h e effluent r e a c h e d i t s MPC, va lue a f t e r about 1450 l i t e r s of w a s t e w e r e t r e a t e d .

( 2 ) S t ron t ium decontaminat ion f a c t o r a c r o s s t h e ac t iva t ed c a r b o n bed v a r i e d from 4 t o 1 0 and a c r o s s t h e m i n e r a l beds v a r i e d f r o m 5 t o 8 f o r a n o v e r a l l decontaminat ion f a c t o r of 2 0 to 80. w a s added to t h e f e e d t h e o v e r a l l decontaminat ion f a c t o r i n c r e a s e d t o 100. t h e e n t i r e r u n .

When phospha te

S r g O concen t r a t ion in t h e effluent exceeded i t s MPC, du r ing

-44- HW- 791 74

EXPERIMENT 13

OBJECTIVES To measure the efficiency of cesium and strontium decontamination by clinoptilolit e with and without activated carbon pretreatment of the waste for organic removal

CONDITIONS

Feed

Adsorbents

P u r e x tank farm condensate at 25 C.

During par t A of run two beds in s e r i e s . B one new clinoptilolite bed used.

During par t

Mesh Bed Bed Bed Size VoluTe, Diameter, Flow, No a TYP e USBS cm in. gpm / ft

1 Activated carbon 8 x 30 10,000 4 - 0 . 5

Part A

(type SGL) 2 Clinoptilolite 20 x 40 250 1 1 to 6

(caustic soda t rea ted water washed)

Part B

1 Clinoptilolite 20 x 40 (caustic soda t r ea t ed w at e r washed)

250 1 1 to 6


(1) Cesium decontamination factor var ied f rom 200 to 300 in both cases . (2 ) Strontium decontamination factor ac ross activated carbon was 15

and ac ross clinoptilolite was 6 for an overall decontamination factor of 90. was 45.

( 3 ) Activated carbon pretreatment of purex tank farm condensate did not affect cesium decontamination but improved the overall strontium removal by a factor of 2 .

When clinoptilolite was used alone, the decontamination factor

-45- HW-79174

EXPERIMENT 14

OBJECTIVES To measure the efficiency of a strong acid cation res in for decontaminating acidified waste

CONDITIONS

Feed P u r e x tank f a r m condensate at 25 C acidified to pH 3 with nitric acid


Mesh Bed Size No Type USBS - 1 Activated carbon 8 x 30

2 Amberlit e 1 6 x 50 (type SGL!

':R-120 (in hydrogen form)


Bed Bed Volurge, Diameter, Flow,

cm in gpm/ ft 1 0 , 0 0 0 4 0 . 3

250 1 4

Tes t was prematurely terminated. Acid in the feed leached i ron and aluminum ash impurit ies f rom the activated carbon bed, these elements then precipitated in the effluent s t r e a m resulting in plugging of the downstream res in bed,

EXPERiMENT 15

OBJECTIVES To measu re the efficiency of a strong acid cation res in fo r decontaminating acidified waste using an acid leached aetivated carbon bed f o r organic removal.

CONDITIONS

Feed


P u r e x tank farm condensate at 25 C acidified to pH 2 . 3 with nitric acid

Mesh Bed Bed

3 in gpm/ft2 USBS cm Volume, Diameter, Flow, Bed Size

No TYP e -- ~

1 Activated carbon 8 x 30 10, 000 4 0 . 3

2 Amberlite 16 x 50 250 1 4 (acid leached)

IR-120 (in hydrogen form)

HW- 791 74 -46-

EXPERIMENT 15 (Contd. )


Radioisotope breakthrough occurred after only a few liters of waste were treated. feed w e r e the cause of the ear ly run termination. P r i o r to this run, the presence of ammonia in the waste was not suspected.

Excessive ammonium ions and hydrogen ions in the

EXPERIMENT 16

OBJECTIVES To measu re the efficiency and capacity of a sulfonated polystyrene cation res in in the hydrogen fo rm for decontaminating s team stripped waste after passage through acid leached activated carbon.

CONDITIONS Feed Adsorbents Two beds in s e r i e s

Steam stripped Purex tank farm condensate at 25 C

Mesh Bed Bed Bed Siz e Volume, Diameter, Flow, - No. TYP e USBS cm3 in. gpm/ft 1 Activated carbon 12 x 40 10, 000 4 0 .3

(type CAL, acid 1 eached)


2 Amb er l i t e 16 x 50 250 1 4


(1) Cesium was removed by the res in bed only. Cesium decontamination factor was grea te r than 1000 until breakthrough. in the effluent reached its MPC, after 1500 liters of waste were t reated.

(2) Strontium decontamination factor ac ross the activated carbon bed var ied f r o m 100 to 10 and across the res in bed remained at about 100 fo r a38verall decontamination factor varying f rom 10, 000 to 1000. Sr in the effluent did not exceed its MPC, during the run treating 3000 liters of waste.

(3) The activated carbon bed removed cer ium with a decontamination factor of 50 to 1000, zirconium with a decontamination factor of 40 and ruthenium with a decontamination factor of about 20. l i t t le additional removal of these radioisotopes was observed ac ross the res in bed.

Cs137

Very

-47- HW-79174

EXPERIMENT 1 7

OBJECTIVES To measu re the efficiency and capacity of a sulfonated polystyrene cation res in previously used in Run 1 6 and regenerated with 1500 ml of 4 N HN03 f o r deeontami- nating s t eam stripped waste afFer passage through acid leached activated carbon.

CONDITIONS

Feed

Adsorbents .Two beds in s e r i e s


Mesh Bed Bed Bed Siz e Volume, Diameter, Flownr, No TYP e USBS cm 3 in g p m d I__

1 Activated carbon 1 2 x 40 10, 000 type CAL (acid leached and previously used for Run 1 6 )

IR-120 (acid r eg en e r at ed bed f rom Run 1 6 )


2 Amberlit e 1 6 x 50 250

4 0 .3

1 4

Cesium was removed by the res in bed only Cesium decontamination factor was 300 until breakthrough when Cs137 in the effluent reached its MPC, af ter 2200 l i t e r s of waste w e r e t reated. Strontium decontamination factor ac ross the activated carbon bed w a s about 4, decontamination factor of about 400. exceed its MPC, during the run treating 3700 l i t e r s of waste. The activated carbon bed removed cer ium with a decontamination factor of 10, zirconium with a decontamination factor of 10 and ruthenium with a decontamination factor of 25. additional removal of these radioisotopes was observed ac ross the res in bed,

and across the resin bed was about 100 for an overal l SrgO in the effluent did not

Very l i t t le

-48-

EXPERIMENT' 18

HW- 7 9 1 74

@

OBJECTIVES To measu re the efficiency and capacity of clinoptilolite in the hydrogen form for decontaminating s t eam stripped waste acidified to pH 3 and passed through an activated carbon bed.

CONDITIONS

Feed

Adsorbents Two beds in se r i e s

Steam s t r ippedpurex tank farm condensate at 25 C acidified with nitric acid to pH 3.

Mesh Bed Bed Bed Siz e VoluTe, Diameter, Flow, No. Type USBS c m in e gpm / ft 1 Activated carbon, 1 2 x 40 10, 000 4 0 .3 -

type CAL (acid 1 eached previously used fo r Runs 1 6 and 1 7 )

2 Clinoptilolit e 1 6 x 30 250 (caustic soda treated, water r insed ,nitric acid treated, water r insed)

1 4


(1) Cesium was removed by the clinoptilolite with a decontamination factor of 1000 to 10, 000 during the ear ly par t of the run. Cs137 in the effluent reached its MPC, after 3700 liters of waste were t reated. about 0. 44 meq/ l i te r during the run.

(2) Strontium was removed by the clinoptilolite with a decontamination factor of 10, 000 during the ear ly par t of the run. effluent reached its MPC, after 1300 liters of waste were treated. Strontium removal continued for an additional 2500 liters with a decontamination factor grea te r than 50,

Nonradioactive ionic impurit ies in the feed averaged

SrgO in the

(3) Cerium, zirconium and ruthenium decontamination factors:

Cerium DF Zirconium DF Ruthenium DF a. Across activated 50 40 10

carbon bed b. Across Clinoptilolite 2 10

bed 5

c. Overall 250 400 50

-49-

EXPERIMENT 19

HW- 791 74

OBJECTIVES 'To measu re the efficiency anc capacity of a bed of s t rong acid cation resin in s e r i e s with a bed of clinoptilolite for decontaminating s team stripped waste at a low pH and at nea r neutral pH.

CONDITIONS

Feed

Ads o r b en t s

Bed No.

Steam s t r ippedpurex tank farm condensate at 25 C acidified with nitric acid to pH 2 . 4 at the s t a r t of the run and nonacidified (pH 6 , 5) nea r the end of the run.

Three beds in s e r i e s Mesh Bed Bed Size Volume, Diameter, Flow,

TYP e USBS c rll in. gp rn / ft 3 - 1 Activated carbon, 1 2 x 40 1000 4 0 . 3

type CAL (acid leached)

(in hydrogen form)

(caustic soda treated, water rinsed, nitr ic acid t r eat ed, w at e r r insed)

2 Amberlite 1R-120 1 6 x 50 250 1 4

3 Clinoptilolit e 1 6 x 30 250 1 4

R E S U L T S AND CONCLUSIONS Decontamination Factor

Cei ium Strontium Cerium Zirconium Ruthenium a. Across 1 6 3 1 3

activated carbon bed

b. Across res in 1-100 100-2000 1 0 1 0 1

c . Across 40-100 nil 10 2 1 bed

Clinoptilolit e bed

d. Overall 200-2000 600-12000 300 20 3

1 -

-50-

EXPERIMENT 1 9 (Contd.)

HW-79174

Variations in cesium and strontium decontamination factors a r e a result of varying the pH of the feed. when the pH was near neutral, but the greatest strontium removal was observed when the pH was low (2 .5) . these two isotopes is between 3. 5 and 4.5.

Greater cesium removal was observed

The optimum pH fo r removing

EXPERIMENT 20

OBJECTIVES To measure the efficiency and capacity of an alumino- si l icate gel cation exchange adsorbent fo r decontaminating s t eam stripped waste.

CONDITIONS

Feed Adsorbents Two beds in s e r i e s

Steam stripped Purex tank f a r m condensate at 25 C.


in. gpm/ft2 3 Bed Size No TYP e USBS cm - 1 Activated carbon, 1 2 x 40 1000 2 1


2 Decalso 1 6 x 30 250 1 4


Malfunction of steam s t r ipper resulted in termination and cancellation of run.

EXPERIMENT 21

Feed Purex tank farm condensate

Adsorbents None

OBJECTIVES To study the operation of the s team s t r ipper and measu re the efficiency with which ammonia is steam stripped at varying feed flow ra tes .

CONDITIONS

RESULTS AND CONCLUSIONS ~~

Holding all other sys tem parameters constant, the feed r a t e to the s team s t r ipper was var ied f rom 60 ml /min to 9 0 ml /min resulting in a change of overhead flow r a t e f rom 1 2 ml /min to 6 ml /min . The ammonia in the steam s t r ipper bottom s t r e a m remained fairly constant a t 2 .3 mg/ l i t e r .

-51-

EXPERIMENT 22

HW-79174

OBJECTIVES To measu re the efficiency and capacity of a s t rong acid cation res in in the sodium form for decontaminating s team stripped waste acidified to a pH of about 4 and passed through an activated carbon bed.

CONDITIONS

Feed

Adsorbents

Steam stripped Purex tank f a r m condensate at 25 C acidified with nitric acid to a pH of 4 . 3.

Mesh Bed Bed Bed Size Voluye, Diameter, No. TYP e USBS cm in ~ - 1 Activated carbon, 1 2 x 40 1000 2


2 Amberlit e 1 6 x 50 250 1 IR-120 (in sodium form)


Flow gpm/ft2

1

4

Decontamination Factor Cesium Strontium Cerium Zirconium Ruthenium

a. Across 1 1 20 1 0 4-10 activated carbon bed

b. A c r o s s res in 1000 2000 5-10 2 1 0

c . Overall 1000 2000 100-200 20 40-100 bed

(2) Cs137 in the effluent exceeded its MPC, after 2800 l i t e r s were Concentrations of all other isotopes in the effluent did t reated.

not exceed the i r respective MPC, values e

n

,

-52-

EXPERIMENT 23

HW-79174

OBJECTIVES To measure the efficiency of a s team regenerated activated carbon bed for removing organic mat te r f rom waste.

CONDITIONS

Mesh Bed Bed Bed Siz e Volume, Diameter, Flow, - No a Type USBS 0 3 in - gpm/ft 1 Activated carbon, 1 2 x 40 1000 2 1

type CAL (acid 1 eac he d previously used in Run 2 2 )

Feed Adsorbents



The activated carbon bed used in Run 2 2 was regenerated by passing 250 F steam at atmospheric p r e s s u r e upflow through the bed. About 2570of the hydrocarbons and a negligible amount of the butyl phosphates w e r e removed by this technique. removed by s t eam regeneration was pr imari ly present in the inter- s t ices of the bed and had been removed f rom the condensate by filtration r a the r than by adsorption. s a r y to remove adsorbed organic.

After the regeneration step the bed was effective in removing organic, but the p r e s s u r e drop ac ross the bed increased during the run at a higher rate than was previously observed. The regeneration procedure apparently created enough fines to impair the hydraulic character is t ics of the bed when reused.

Probably the organic mater ia l

Higher s team tempera tures a re neces-

-53- HW-79174

EXPERIMENT 24

OBJECTIVES To evaluate the use of a bed of granular anthracite coal for filtering s team stripped waste before passage through ion exchange beds

CONDITIONS

Feed



Mesh Bed Bed Bed Size V o l u y , Diameter, Flow, No. Type USBS c m in gpm/ft2 1 Anthrafilt - 1 6 x 50 1500 2 1

2 Amberlit e 16 x 50 25 0 1 4

-

IR-120 ( res in f rom Run 2 2 regenerated with caustic soda)


The bed of granular anthracite coal was effective in fi l tering par t ic- ulate mat te r f rom the waste, but p re s su re drop ac ross the bed became excessive after only a few hundred l i t e r s of waste w e r e t reated. valve opened.

The run was terminated when the column p r e s s u r e relief

EXPERIMENT 25

OBJECTIVES 1 To measu re the efficiency of decontamination and hydraulic character is t ics of a s t rong acid cation r e s i n fo r t reat ing steam stripped waste without an activated carbon pretreatment step. 2 , To study the acid regeneration of this cation res in

CONDITIONS

Feed

Adsorbent s Steam str ipped P u r e x tank f a r m condensate at 24 C

Mesh Bed Bed Bed Siz e Voluye, Diameter, Flow, No TYP e USBS cm in* gpm/ft2 - 1 Amberli te 200 1 6 x 50 5 00 2 1

(in hydrogen form)

-54-

EXPERIMENT 25 (Contd.)

HW-79174


(1) Decontamination efficiency: Cesium - 1000; strontium - 1000; cer ium - 5; zirconium - 5-10; ruthenium - 1. waste were t rea ted with only Ru106 exceeding i t s MPC, in the effluent

Over 3000 l i t e r s of

( 2 ) P r e s s u r e drop ac ross the bed at the end of the run was 20 t imes higher than it was at the beginning of the run. Organic matter in the waste caused the agglomeration of a 1 in. l ayer of res in at the top of the bed. entire bed. Backwashing the bed with water was only partially effective in removing the organic. the organic, it was necessary to mechanically break up the agglomerated mat which had sett led to the bottom of the column during the backwash operation; in addition a smal l amount of acetone was used to remove residual organic adhering to the individual particles of resin.

Some organic mat ter was dispensed through the

To obtain maximum removal of

EXPERIMENT 26

OBJECTIVES To measu re the efficiency of decontamination and hydraulic character is t ics of a regenerated s t rong acid cation r e s in f o r treating acidified s t eam stripped waste without an activated carbon pretreatment s tep.

CONDITIONS

Feed Steam stripped P u r e x tank f a r m condensate waste at 24 C acidified with nitric acid to a pH that var ied f rom 3 . 4 to 4 .1 .

Adsorbent s Mesh Bed Bed

Volume, Diameter, Flow, 3 in gpmlft

Bed Siz e No. Type USBS c m - 1 Amberlite 200 1 6 x 50 5 00 2 1

(in hydrogen form, reg en e r at e d r e s in used in Run 25)


(1) Decontamination Efficiency: Cesium 2000 Strontium 1000 Cerium 40 Zirconium 10 Ruthenium 1.1 (-1 0% removal)

-55- HW- 791 74


Over 3000 l i t e r s of waste were t reated with only Ru106 exceeding its MPCw in the effluent.

appreciably increase during the run. (2) With the feed acidified p r e s s u r e drop ac ross the bed did not

EXPERIMENT 27

OBJECTIVES To measu re the efficiency of a two bed demineralizer followed by a mixed bed demineralizer fo r decontaminating acidified steam stripped waste

CONDITIONS

Feed

Adsorbents Three beds in seri.es

Steam stripped Purex tank farm condensate at 24 C acidified with ni.tric acid to pH 3. 7 .

Mesh Bed Siz e Volurng, Diameter, No, Type USBS c m in.

1 Amberlit e 1 6 x 50 500 2 -


(in hydrogen form)

2 111~0 NR-2 1 6 x 50 500 2

3 Amb e r l it e 1 6 x 50 500 2 XE-150


Decontamination Efficiency Decontamination Facto r

Flow, gpm / ft

1

1

1

Cesium Strontium Cerium Zirconium Ruthenium a. First part of run

Across Beds 2500 2500 2 0 0 18 200 1 and 2 Across Bed 3 2 1 3 2 1 Overall 5000 2500 600 36 2-0 0

Across Beds 2500 2500 200 30 10 1 and 2 Across Bed 3 1 , 2 1 3 1 2 Overall 3 000 2500 600 30 20

b. Last par t of run

! =

-56- HW-79174


Over 1500 l i t e r s of waste were t reated during the run. ruthenium the concentration of all radioisotopes in the effluent was l e s s than their respective MPC, values. Ruthenium was removed effectively by both the two beds and mixed bed sys tems during the ear ly par t of the run. The increase in effluent concentration in both cases coincided with the breakthrough of ni t r ic acid. Even after the nitric acid breakthrough, however, removal of over 5070 of the ruthenium was still ac hi ev ed .

Except for

OBJECTIVES

EXPERIMENT 28

To measu re the efficiency of a s t rong acid cation res in having a l a r g e r particle, s i ze for decontaminating s team stripped waste when used in the as-received sodium form.

CONDITIONS Feed Steam stripped Purex tank f a r m condensate at 25 C acidified

during latter part of the run with ni t r ic acid to pH 3 . 8.


Bed Siz e Volupe, Diameter, Flow, - No. TYP e USBS c m in gpm / ft 1 Amber lit e 1 6 x 40 1000 2 1

IR-120L (in sodium fo rm as-received)


Decontamination Efficiency: Cesium 5500 Strontium 3 000 Cerium 10 Zirconium 2 Ruthenium 1.1 (- 1070 removal)

-57-

EXPERIMENT 29

HW- 791 74

OBJECTIVES To measu re the efficiency of a strong acid cation res in in the sodium f o r m for decontaminating acidified s t eam stripped waste

CONDITIONS

Feed Steam stripped Purex tank farm condensate at 24 C acidified to pH 4 with nitric acid addition


Bed Siz e Volume, Diameter, Flow, - No Type USBS cm3 in. gpm/ft2 1 Amberlite 1 2 0 1 6 x 50 1000 2 1

(in sodium form)


Decontamination Efficiency : Cesium 4000 Strontium 10 Cerium 3 Zirconium 2 Ruthenium 1 2 (-20% removal)

EXPERIMENT 30

OBJECTIVES To measu re the efficiency of a strong base anion res in for removing ruthenium

CONDITIONS

Feed Steam stripped P u r e x tank farm condensate at 25 C


Bed Siz e Volurqe, Diameter, Flow, No. Type USBS c m in. gpm/ft - 1 111~0 NR-2 16 x 50 1000 2 1


About 2000 liters of waste w e r e t reated. ruthenium was removed with a decontamination factor of 7 (-85% removal) and during the last half of the run the radioisotope was removed with a decontamination factor of about 3 . 3 ( -70% removal). The decrease in removal efficiency coincided with ni t ra te and ni t r i te saturation of the bed.

During the f i r s t half of the run

-58-

EXPERIMENT 31

HW-79174

OBJECTIVES To measu re the decontamination efficiency and capacity of a commercial grade mixed bed ion exchange res in

CONDITIONS

Feed Steam stripped P u r e x tank farm condensate at 25 C


Bed Siz e Volume, Diameter, Flow , No. TYP e USBS cm 3 in. gpm/ft2 1 111~0 TM-1 1 6 x 50 500 2 1


Unexpected high concentrations of nonradioactive impurit ies in waste resulted in premature appearance of radioactivity in the t reated effluent. The run was terminated.

EXPERIMENT 32

OBJECTIVES To measu re the decontamination efficiency and capacity of a commercial grade mixed bed resin.

CONDITIONS

Feed Steam stripped P u r e x tank farm condensate at 25 C and pH 7.3. Na, 25 mg/ l i te r NO: and 32 mg/ l i te r NO;.

Feed contained 20 mg/ l i te r NH;, 5 mg/ l i t e r

Adsorb ents Mesh Bed Bed

Bed Siz e Voluqje, Diameter, Flow, - No. Type USBS c m in. gpm/ft 1 111~0 TM-1 1 6 x 50 1500 2 1


(1) Cesium decontamination factor was > 1000 for the first 800 liters of waste treated. and sodium ion saturation of the bed.

( 2 ) Strontium decontamination factor was 35 during most of the run. Reduction of the feed pH towards the end of the run to about 4 . 5 increased the strontium decontamination factor to 350.

(3) About 99% (decontamination factor of 100) of the ruthenium was removed by the bed during the ear ly par t of the run. and ni t r i te ions saturated the bed, ruthenium removal efficiency decreased, but 90% (decontamination factor of 10) continued to be removed fo r the remainder of the run (2400 l i t e r s ) .

Cs137 breakthrough coincided with ammonium ion

When ni t ra te

-59- HW-79174

EXPERIMENT 33

OBJECTIVES To measu re the ruthenium decontamination efficiency of a strong acid cation res in followed by a weak base anion res in

CONDITIONS

Feed Steam stripped Purex tank f a r m condensate at 25 C with carbon dioxide gas added to reduce the pH which var ied f rom

Adsorbents Two beds in

Bed No e Type 1 111~0 NR-1

(in hydrogen fo rm)

2 Nalco WBR (in hydrogen form)

4 .3 to 5, 8

s e r i e s Mesh Bed

USBS c m

1 6 x 50 250

Size Volums ,

1 6 x 50 50 0

Bed Diameter, Flow,

2 1

in. gpm/ft2

2 1


Ruthenium decontamination factor across the cation res in bed averaged over 1 .1 (-12770 removal) and ac ross the weak base anion bed varied f rom 3 to 15 (67 to 9370 removal) with the average overall decontamination factor of 6 . 8 (857'0 removal).

I .

OBJECTIVES

EXPERIMENT 34

T o measure the cesium and strontium decontamination efficiency of a thin precoat bed of smal l par t ic le s i ze s t rong acid cation r e s in

CONDITIONS

Feed

Adsorbents

Steam stripped P u r e x tank f a r m condensate at 25 C and acidified with ni t r ic acid to pH 3. 2


in. gpm / ft 2 3 Bed Size No TYP e USBS cm - 1 Dowex 50W 200 x 400 40 2 5

(in hydrogen form)

-60-

EXPERIMENT 34 (Contd.)

HW- 791 74


(1) Cesium was removed with a decontamination factor of 700 during the ear ly par t of the run. Cs137 in the effluent reached its MPC, after 2250 column volumes of waste were treated.

(2) Strontium was removed with a decontamination factor > l o 0 0 while treating over 5000 column volumes of waste.

(3) P r e s s u r e drop ac ross the bed increased f rom 2 . 1 psi t o 3 . 3 ps i when the run was completed.

EXPERIMENT 35

OBJECTIVES To measure the cesium and strontium decontamination efficiency of a thin precoat bed of small par t ic le s i ze clinoptilolit e

CONDITIONS

Feed

Adsorbents

Steam stripped Purex tank farm condensate at 25 C and acidified with nitric acid to pH 4

Mesh Bed Bed Bed Siz e , Volume, Diameter, Flow, - No. Type USBS c m 3 in. gpm/ft2 1 Clinoptilolite 100 x 230 40 2 5

(acid washed, so dium r eg en e r at e d and rinsed)


(1) Cesium and strontium decontamination factors var ied f rom 100 to 400 while treating over 4600 column volumes of waste. SrgO concentrations in the effluent did not exceed the i r respective MPC, values during the entire run.

(2) P r e s s u r e drop ac ross the bed did not exceed 2 psi during the run.

Cs137 and

- I

APPENDIX C

l -

-61 -

APPENDIX C

HW-79174

C LINOPTILOLITE BEIVXFICIATION

Because the zeolite mineral clinoptilolite has properties which allow it to adsorb cesium f rom solutions containing much higher concentrations of

other cations, research was directed at using this mater ia l for the removal

of radiocesium from waste s t r eams . The laboratory work exploring the

ion-exchange properties of this mineral was done on selected samples of

unweathered clinoptilolite which was crushed and screened in laboratory

equipment.

A l l of the mater ia l used i n the Waste Treatment Pilot Plant studies

was obtained from deposits owned by the Baroid Division of the National

Lead Company in Hector, California.

lolite were obtained for the initial experiments.

and screened by a Seattle, Washington, commercial f i rm which rented sma l l

crushing and screening equipment at a local university. The screening oper-

ation produced two fractions: one was 1 2 x 40 mesh (USBS), and the other

was -40 mesh (USBS).

at Hanford.

trouble. When we t , the clay particles disintegrated to produce fines. caused hydraulic problems when the mineral was used in fixed bed adsorption experiments.

Two tons of crude mine r u n clinopti-

This mater ia l was crushed

This mater ia l was further screened in sma l l batches

Par t ic le degradation in the wet mater ia l caused considerable

A large amount of the granular mineral consisted of clay particles.

These fines

To permit testing, fur ther treatment of the mater ia l was necessary.

The mineral was dry screened to the desired particle s ize range and im- mersed in hot caustic soda solution to peptize the clay.

i n a 2 in. glass pipe column and washed (upflow) with hot distilled water. 2 flow ra te of about 50 gpm/ft , fluidizing the bed fo r 8 h r was used.

allowed to sett le, most of the mater ia l in the bed had the character is t ic green color of Hector clinoptilolite.

contained brown clay par t ic les .

It was then placed

A When

The lower 10 to ,207' of the bed still

The clay mater ia l was discarded.

-62 - HW -7 91 7 4

Discussions were held with personnel of the National Lead Company

about the impurities present.

the exposed face of the deposit and did contain high clay and calcium c a r -

bonate impurit ies. tilolite to have a low clay content and l e s s than 1% calcium carbonate.

Except for 400 lb of crude which was sent directly to Hanford, this mater ia l

was sent to the University of California for crushing and screening experi-

ments. crushed and screened mater ia l was shipped to Hanford for fur ther testing.

Various samples were analyzed for carbonates and it was determined that

the crushed and screened mater ia l cont+ned an average of 3. 770 calcium carbonate (determined by the acid release and measurement of CO ) o r a l m o s t f o u r t i m e s that expec ted by the Nat iona l L e a d Company. Although

fewer impurities were present i n the second batch, further treatment was

necessary before the mater ia l could be used in fixed bed column experiments.

Experimental work showed that a simple crushing and screening proc-

The 2 ton batch of the mineral was mined at

An order was placed for an additional 2 tons of clinop-

The resul ts of these experiments a r e reported in Appendix D. The

2

e s s is not adequate for producing a granular clinoptilolite mater ia l suitable

f o r fixed bed application, A conceptual beneficiation process for preparing

clinoptilolite for fixed bed use is shown in Figure C-1.

tilolite is fed to a jaw crusher to produce an appropriate s ize feed for a rol l

mill. an appropriate particle s ize separation is made.

the oversize mater ia l is returned to the rol l mill and the intermediate prod-

uct enters a Dorr c lass i f ier where the classi f ier rakes aid in breaking up

clay particles and water removes the resultant clay and clinoptilolite fines.

The clinoptilolite is then contacted with hot 5 to 10% HN03 solution which is

followed by a 5 to 10% caustic soda wash. The acid dissolves calcium c a r -

bonate impurities, and the caustic soda peptizes and removes the las t t races of clay and neutralizes any residual acid in the mater ia l . If the clinoptilolite is not going to be used with acidic solutions, the acid treatment can be omit-

ted. mineralized water in a Dorr c lass i f ier to remove the fines created in the

chemical treatment steps, dewatered with a vibrating screen separator , and

The mine run clinop-

The milled clinoptilolite is fed to vibrating sc reen separa tors where

The fines a r e discarded,

The mineral leaving the hot caustic soda treatment is washed with de-

0

- 6 3 -

Jaw C r u s h e r

H W - 7 9 1 7 4

b

, Vibra t ing

S c r e e n S e p a r a t o r

T a p W a t e r

D isca r d F i n e s

Vibra t ing S c r e e n S e p a r a t o r

D i s c a r d F i n e s

D i s c a r d - F i n e s and W a t e r L

1 . Ni t r i c Acid 2 . C a u s t i c Soda C he m 1 c a 1 T r e at m e nt

De In i n e ra 1 i z e d W a t e r

D is ea r d D o r r C l a s s i f i e r Fines

t’ -

I P r o d u c e 20 x 50 M e s h )

I - 40% Yield I FIGURE C - 1

Conceptua l Flow s h e e t to P r e p a r e C l inopt i lol i te for F i x e d B e d Applicat ion

-64- HW-7 9 1 7 4

packaged for storage.

is 4070 for a 20 x 50 mesh product.

The best yield that can be expected for this process

A conceptual flowsheet for preparing clinoptilolite to be used in a

precoated zeolite f i l ter is similar to Figure C - l with the exception that the

chemical treatment to remove the fines w i l l be l e s s demanding.

product required is about 100 x 400 mesh, the yield may be > 6070.

Since the

The approximate cost of crude clinoptilolite is $125/ton in less than carload quantities and $80/ton in carload amounts.

ton batch of hand picked mater ia l w a s $140/ton. If the lowest pr ice is con- 3 3 sidered, the r a w clinoptilolite cost would be $2/ft ($80/ton 5 40 ft /ton).

An estimated cost for crushing and screening the r a w mater ia l in carload

quantities is $100/ton o r $2.50/ft .

The price of a 2

3

Table C-I compares costs of inorganic ion-exchangers, The costs

fo r clinoptilolite were corrected to a 4070 yield on the 20 x 50 mesh and a a’

60% yield on the 100 x 400 mesh.

TABLE C-I

APPROXIMATE COST O F INORGANIC ION-EXCHANGERS

(Excluding Shipping Costs)

$/f t3 of Product

n

C linop t il oli t e 20 x 50 Mesh 100 x 400 Mesh

Ore (Crude at $2/ft3) 5 3 Crush and Screen 6 4

2 - Chemical Treatment 3

Total 14 10

Decalso 25 Synthetic Zeolites 80

F o r cost es t imates of the ion-exchange process, $25/ft 3

The higher

of exchanger w a s used despite the apparent cost advantage of clinoptilolite.

cost w a s chosen because of the uncertainties in the cost es t imate fo r clinop-

tilolite, since prepared clinoptilolite is not currently a commercial product.

-

APPENDIX D

-65- HW-79174

APPENDIX D

CRUSHING CHARACTERISTICS OF CLINOPTILOLITE* J. A. P a s k and D. W. Fuerstenau

The objective of this brief report is to present the resul ts of work

done in preparing 10 x 50 mesh clinoptilolite particles and a l so to discuss

the resul ts of a brief investigation of the crushing character is t ics of clinop-

t ilolite . The major work concerned preparation of 10 x 20, 20 x 50, and

-50 mesh fractions f rom lump clinoptilolite (about 3 to 6 in. pieces).

Crushing and screening were ca r r i ed out s o as to obtain the maximum r e -

covery of 10 x 50 mesh mater ia l .

Clinoptilolite, which w a s obtained f rom the Baroid Division of

National Lead Company, w a s crushed in a j aw c rusher to prepare the mate-

rial as feed for the rol l mill.

the ro l l mill, it w a s screened dry on a tr iple deck screen containing 10,

20, and 50 mesh screens .

mater ia l w a s recycled to the rol l mill.

products :

After the clinoptilolite w a s passed through

Three products were collected and the oversize The procedure produced the following

Size Fract ion Weight, lb Weight Distribution, 70

10 x 20 mesh 1 6 7 7 4 7 . 1

20 x 50 mesh 823 23. 1

Minus 50 mesh 1061 29. 8 3561 100.0

Size distribution data of each of these three products a r e presented

in Table D-I . each of the products.

These s ize distribution data were obtained by dry sieving

:k The work reported in Appendix D w a s performed a t the University of California under Consultant Agreement CA-330 with the General Elec t r ic C ompany a

- 6 6 -

TABLE D-I

. HW -7 9 174

SIZE DISTRIBUTION OF CRUSHED AND SCREENED CLINOPTILOLITE Weight, Yo

Size Fraction, 10 x 20 mesh 20 x 50 mesh Minus 50 mesh Tyler Mesh fraction fraction fraction

10 x 14 6 0 . 1 0 . 0

14 x 20 3 5 . 7 0 . 4

20 x 2 8 3 . 4 42. 1

2 8 x 35 0 . 2 3 8 . 4 0 . 0

35 x 48 0 . 1 1 8 . 0 8 . 4

48 x 65 0 . 1 0 . 6 2 1 . 5

65 x 100 0 . 1 0 . 2 2 1 . 2

100 x 150 0 . 1 0 . 1 13 . 5

150 x 200 0 . 0 0 . 1 1 5 . 6

200 x D 0 . 2 0 . 1 1 9 . 8

1 0 0 . 0 1 0 0 . 0 1 0 0 . 0

To ascer ta in the optimum size distribution that can be obtained in

crushing clinoptilolite, a s e r i e s of tests was made grinding the mater ia l in a

laboratory rod mill in a simulated closed-circuit with a 10 mesh sieve.

Because coarse particles protect f iner particles by wedging the rods apart ,

rod milling produces a product that possesses fine particles characterist ic

of the material . This wedge-action in a rod mill produces particles with a

minimum amount of fines. In the rod mill experiments, 1 kg of 4 x 8 mesh

clinoptilolite was ground f o r a 2 min period, screened on a 10 mesh sieve,

and the oversize returned to the mill with enough new feed to make a 1 kg

charge in the mill.

these conditions the circulating load was 11070.

was r u n in 4 min cycles, giving a circulating load of 2370.

ucts f r o m the two different rod milling experiments were identical, the results of only the 4 min test w i l l be given.

tes t should yield a s ize distribution that is a straight line when the cumulative percent passing a certain s ize is plotted on log-log p a p e r versus the

This was repeated u n t i l steady state was reached. Under

A s imi la r s e r i e s of tes ts Since the prod-

The product f rom this type of

8

- 6 7 - HW - 7 9 1 7 4

I

size . Since the sieve se r i e s is logarithmic ( t o the basef i ) , a semilog

plot of cumulative percent f iner versus s ize in mesh should yield the

straight line ( see Figure D-1).

0 4 m i n rod m i l l cyc le t e s t -

FIGURE D-1

Cumulative Size Distributions of Clinoptilolite f rom Crshing Tes t s

-68- HW-79174 n

F o r a s ize distribution to follow the straight line perfectly, the

sieving should be done wet on a 400 mesh sieve first to wash the fine par-

t icles adhering to the coarse particles through the 400 mesh sieve. After

the + 400 mesh mater ia l has been dried, it should then be sieved in the u s u a l manner. Without the wet sieving step, deviations w i l l exist in the - 200 mesh

material . ticles when the mater ia l w a s screened, only d r y sieving resul ts w i l l be

reported here

Since there appeared to be a degradation of the clinoptilolite par-

In Table D-11, cumulative s ize distributions a r e tabulated for the 4 min, closed-circuit, rod milling test; the open-circuit, rol l mill, crushing

test; and the composite of the crushed 3600 lb sample (this w a s calculated

f rom weight distributions and the data in Table D-I).

TABLE D-I1

CUMULATIVE SIZE DISTRIBUTIONS OF PRODUCTS

FROM CRUSHING TESTS

Size, 4 min Open-C ire u i t Tyler Mesh Rod Mill Cycle Test , 71 Roll Mill Test , 70

8

10

1 4

20

28

35

48

65

100

150

200

270

400

1 0 0 . 0

9 9 , s

74. 6

5 5 . 7

43. 6

3 5 " P 26* 2

2 0 . 0

1 3 . 8

1 0 , o

7 # 0

0 . 5

0 . 2

1 0 0 , o

88. 2

72. 6

5 4 . 4

4 0 . 0

3 0 . 4

23 . 6

1 7 . 8

1 2 . 5

8 , 9

6. 8

3 . 2

1 . 5

3600 lb Composite, 70

1.00.0

9 9 . 7

7 1 . 4

54. 6

4 3 . 3

3 4 . 3

27 . 6

21 .0

14 . 6

E O . 6

5 . 9

1.1

0 . 3

.

-69- HW -7 9 174

In Figure D-1, a cumulative s ize distribution plot is presented,

This figure indicateg that a l l the products a r e quite s imilar ; that is , the

ro l l mill operated in closed and open circuit and the rod mill in closed

circui t yield s imi la r particles A s mentioned above, the sharp deviation

of the s ize distribution plot below 200 mesh is probably not r ea l but resul ts

form the dry screening procedure that was used. The equation of this line

i s

where x is the size in microns and y is the cumulative percent of material f iner than s ize x.

F r o m this plot, it can be seen that the maximum recovery of mate-

r i a l in the 10 x 20 mesh fraction might be expected to be about 4470~ about

31% in the 20 x 50 mesh fraction, and about 25% in the - 50 mesh fraction,

The closed-circuit ro l l crushing of the 3600 lb sample produced 47, 23, and 30% recovery in the respective fractions

It is surpr is ing that the slope of the s ize distribution curve for clinoptilolite is a s large a s 0 . 78.

tributions with excessive quantities of fines which then yields an exponent of

about 0 . 4 instead of 0. 78. This may result f rom the tendency of the clinop-

tilolite to break into two pieces ra ther than into fragments having a complete s ize distribution.

with a hammer, the fragments w i l l have a s ize distribution s imi la r to t,he

equation given above. If a piece of clinoptilolite is s t ruck with a hammer,

it s eems to tend to break into a few coarse pieces together with a distribu-

tion of fine fragments,

g rea te r slope,

would take advantage of this f racture mechanism and would result in the pro- duction of slightly l e s s fine material .

Usually mater ia ls of this nature give s ize dis-

F o r example, i f a piece of quartz is s t ruck a single blow

This would give r i s e to the s i ze distribution with the

Possibly higher circulating loads in the crushing device

APPENDIX E

-70-

APPENDIX E

PROCESS ECONOMICS

T-\ULE E-1

C.APIT-\L COST ESTIXATE FOR IOX E S C H A X G L

(Basis. 30, 000 gal /day,

Equi j iment and Cons t ruc t ion C o s t s

Feed, Condensate i r o m Stored I’urei \Vasle)

Feed P u m p s , 2, 3 HI’ a t S i f l O j H P

T a n k s , 2 , 10, 0 0 0 gal carbon sieel a t S2 /ga l

Str ipper Fcetl P u m p s . 2 , 2 HI’ a i S100iHP Str1ppc.r Kcbo i l e r , carbon s t ee l slicll, stn in lcss s iee1 , tube bundle , 50 i t 2 ,

S t r i p p e r Tower, 10 It oi I:! i n . schedule 40 p ~ p e

1, 400. 000 13tu/hr.

Feed Prelie.iter, carbon steel shell, s ta inless s teel tube bundle, 18 it?, 7 5 0 , 000 H t u / h r

HW-79174

Dollars

GO0

40, 0 0 0

400

4, nnn 2 , 500

2 , on0

3 , non 250

4, n o 0

E m 8 , 0 0 0

3 , 0 0 0

1 , 1 2 0

1 , 2 0 0

I50

40

3 , 550

2 , i o 0 2 , 0 0 0

G , 600

8 6 , 0 0 0

8 6 , 000

___

13, nnn 17, on0

iiti, o n n 3 5 , on0

2 3 1 , non 3 5 , 0 0 0

0 3 . 0 0 0

__

8 0 , 0 0 0

-360, 000

$Ida>-

1. 10

46.118

1 1 . 5 2

9n.00

51 .50

4 . 3 3

5. 70

5 . no 3 . 2 0

G . 00

-225. 00

- 7 1 - 13 W - 7 9 1 7 4

T A B L E E-I1

C A P I T A L COST E S T I M A T E F O R CONDENSATE EVAPOR-4TION

F e e d , C o n d e n s a t e f r o m S t o r e d P u r e x Was te ) ( B a s i s , 30, 000 @ / d a y ;

E au inmen t and C o n s t r u c t i o n C o s t s D o l l a r s

(1) P u m p s ; 1, 2HP a t $ 1 0 0 / H P

( 2 ) T a n k s ; 2 , 10, 000 gal, c a r b o n s t e e l a t $ 2 / g a l

(3) F e e d P u m p s ; 2, 2HP a t $ 1 0 0 / H P

(4) C o n c e n t r a t o r ; 2, c a r b o n s t e e l she l l , s t a i n l e s s s t e e l tube bundle, 220 ft2, 6, 000, 000 B t u / h r

(5) C o n d e n s e r s ; 2, c a r b o n s t e e l she l l , s t a i n l e s s s t e e l tube bundle, 200 ft2, 6, 000, 000 B t u / h r

( 6 ) C o n d e n s a t e T a n k ; 2, 2000 gal , c a r b o n s t e e l a t $ 2 / g a I

(7) B o t t o m s T a n k ; 1, 250 g a l s t a i n l e s s s t e e l a t $ 1 5 / g a l

(8) C o n d e n s a t e P u m p s ; 3, 2HP at $ 1 0 0 / H P

(9 ) I n s t r u m e n t s ; 18 poin ts a t $300/point

T O T A L

Ins t a l l a t ion ; 1570 equ ipmen t c o s t s

C o n t r a c t o r s M a r k u p ; 207'0 equ ipmen t cost B i d Price

P iping; 30% bid p r i c e

Building; 40 x 40 x 20 ft a t $2 / f t3 T O T A L EQUIPMENT AND INSTALLATION COST

Des ign ; 15% t o t a l equ ipmen t a n d in s t a l l a t ion c o s t s

c o n t i n g e n c i e s ; 4070 T O T A L ESTIMATED COST

E s t i m a t e d O p e r a t i n g C o s t s

(1) Bu i ld ing A m o r t i z a t i o n ; 57'0/yr

( 2 )

(3)

(4)

(5)

( 6 ) ( 7 ) U t i l i t i e s

D e p r e c i a t i o n ; 20% of m a j o r equ ipmen t p e r y e a r

Main tenance ; 5% of m a j o r equ ipmen t p e r y e a r

L a b o r ; 1 2 m a n - h r / d a y a t $ 7 . 5 0 / m a n - h r ( inc ludes d i r e c t and i n d i r e c t )

S t e a m ; 1 2 , 000 l b / h r a t $ 1 . 0 0 / 1 0 0 0 l b (1$ l b s t e a m r e q u i r e d f o r 1 lb evapora t ion )

W a t e r ; 400, 000 &/day at $90/106 gal

TOTAL,

200

40,000

400

50, 000

2 0 . 0 0 0

8,000

3, 750

600

5, 400 128, 350

1 9 , 0 0 0

2 6 , 000

173, 350

52, 000

80. 000

305, 350

45, 650

1 2 2 , 0 0 0

-473 ,000 $ day

1 . 1 0

70. 32

24. 70

9 0 . 0 0

2 8 8 . 0 0

36. 00

1 . 0 0

-511 .00

E s t i m a t e d C o s t = $ 5 1 1 / 3 0 , 0 0 0 gal = $17 /1000 g a l

* I C - G E R I C H L A N D . W A S H

- 7 2 -

TABLE E-I11

HW-79174

d-

c OST c OMPARISON”’ LOW-LEVEL WASTE TREATMENT PROCESSES

Es t imates $ / l o 0 0 gal

Ion-E xchange P r o c e s s 3 0 , 0 0 0 gal/day 7 . 50

Reevaporation (HAPO) 30 ,000 gal/day 1 7 . 0 0

9 -00 Chemical Flocculation (HAPO) 15, 000 gal/day ;M (a)

Actual Costs

.

(1) Evaporation B N L 1, 000 gal/day 103.00

KAPL 3 , 000 gal/day 65,OO

Bettis 4, 600 gal/day 3 8 . 0 0

(2 ) Chemical Flocculation Rocky Fla t s 4, 300 gal/day 9.00

LAS L 38, 000 galjday 12.00

~~ ~

:k A l l costs normalized to 20 yea r building and equipment amortization

** Actual costs were not corrected for increases f rom 1955 to present.

Atomic Energy Industry--A Survey of Costs, NYO-7830, December 31, 1955.

(a) A . Bo Joseph , Radioactive W a s t e Disposal P r a c t i c e s in the

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