ML19321A477

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Technical Rept on Urea Formaldehyde. Marked-up Amefco Rept on Procedure for Onsite Solidification of Low Level Radwaste at Facility Encl
ML19321A477
Person / Time
Site: Sequoyah  Tennessee Valley Authority icon.png
Issue date: 07/18/1980
From:
ANEFCO, INC.
To:
Shared Package
ML19321A475 List:
References
NUDOCS 8007230483
Download: ML19321A477 (45)


Text

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                         ,                                                             TECHNICAL REPORT ON UREA FOP.%LDEHYDE
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3 PRE'?ARED BY: I

                                                               .                                                                                                                        ANIFCO, INC.                                                                            -

227 MAMARONECK AVENUE WH11T PLAINS, NEW YORK 10605 l 4 (914) 946-4631 t g 800723oy.(j

                                                                                                                                                                                            ~         '

Amanccs, INC.

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                                                                                                          -                                  INDEX.                                                                                            '
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Chemical Reaction (Polymerization)

                                                              . . Electron Microscopic Examination                                                                                                     -
                                          , ,                           Physical Properties of Urea Formaldehyde                                                                                                       .

Page 1 '

                                                            .                   Page 2
  • i .

t Fire Test , ,

               .                                                        Data Applicable to Storage and Pumping                                                                                        -

Appendix A o .

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r s 8 w - CHEMICAL REACTION (POLYMERIZATION)

        ;

Urea has the formula CO (NH).~ It is produced by the -

  , li                                                           reaction of ammonia and carbon dioxide. Formaldehyde has the basic formula of HCHO.

The first step of"the reaction urea molecules link to the - .

              -                                                 methylene marks, (,,CH 2 -).

bridge, marked on the schemitic drawing with red

       .                                                                                                                 These bridges form by the spliting off of                                                                                         ';
      '.,                                                       molecules of water, the oxygen coming from the formaldehyde and the bydrogen atoms from each of two urea molecules.                                                                                                                       .

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                                                        ~       During the reaction, other formaldehyde adds on-to various                                                                                                                                         -
      ;.                                                        urea molecules to form dangling methylol, - CHgOH, groups.                                                                                                                        ~t~

1: Thus, the following urea-formaldehyde formul.t is derived . Four molecules of urea condense and polymeri=e with six -

      ;                                                         =olecules of formaldehyde. The for=aldeh 9                             .

is 1.5:1 and typical of the amino group. yde to urea ratio Additives are used to provide a wetting agent and form and azeotropic mixture with the alcohol groups (R-0-Rl). This j 'also affords additional strength'to the compound and elimi-I, nation of the water of condensation by reaction.

  • H .
                                                                              'N'H                                        2 OH                         CH2OJ H')[CH                                      N 1

C=0 1 C=0

                                                                                                                                               'I         'CHd' i- N -2CH --*. -

t-C=0 C=0

                                                                .              J.,s                              1       . , ~                       l                     I 4-- N           gCH ' - N - ICH l -                                                                                             #
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H g . ,, o. . ' ,

                                                                                              ' UREA. FORMALDEHYDE                                                                                                            -
   '                                                                    H H                                                                                     .
                                                                        \fN e--        ,                        -                    .

B l _a u _ RIDGE'

                              ,                                           C=0                            . s            .

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  '- .                                                              H          H UREA                                                                                                                                           .                    .
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ELECTRON MICROSCOPIC EXAMINATION l 4 i* In order to ' demonstrate the cross linkage and bonding of I U-F, ANEFCO,.INC.. retained Arthur D. Little to perform i 1 ,. electron microscopic examination of U-F samples with resin (ion-exchange) materials solidified in the media.

        !                                               Two distinctly different. samples were prepared. One with                                                                                                                           ~

1

                                               '        proper pH control and the proper amount of hydrogen ion                                                                                                                            .

l to produce the cross linkage and the second Cth insuffi- - '

        '                                               cient quantities of hydrogen ion.                                                         The latter was done in                                                  s order to show the two phase reaction and the bonding of the resin beads to the final phase.

l i The results may be seen in the photographs by observing the i-two shaded areas with the complete surrounding and coupling l* - of the U-F and its tentacles to the resin heads. The various magnifications are shown on the back of each film. Copies of these photograp'hs are attached at the end of this t section. Appendix A. ' - l l l

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M e r. t' , PHYSICAL PROPERTIES OF UREA FORMALDEEYDE t

 'i'                    -
  • density, Ib/ft 3 '

i 1.8 i' i Mechanical properties ,

                                                                                                                                                                                                                                                                 .t-,

i .. , compression strength, psi. 8 ' -

                                                                                                                                                                                                                                                                             ':/

flexural strength, psi.

   !                                                                                                                                                                             17                                        .
                                                                                                                                                                                                                                                  ,;               ,,,. .:,,

flexural mod us, .c ., ~ ..V , i psi. x 10- 0.7 '

                                                                                                                                                                                                                                                    -  4
   !                                                      Thermal properties flammability, SE
                                                                                                                                                                                                                            - ' N ! I '.t~
                                                                                                                                                                                                                                                                    .      i-
                                                                                                                                                                                                                                                                                 '.C
                                                    . .                  specific heat, Btu /lb.                                                                             0.40              -                                                  ~                      -

Absorption t, . . water, 1b/ft2 (10 ft. head) -- f-water, vol.% - - * . - moisture-vapor transmission rate, perin-in. -- r . SE - self extinguishing - a

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  .;                                                                      PHYSICAL PROPERTIES OF UREA FORMALDEHYDE 4

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  • ASTM
  • l test method DATA 4, .

C. Compression ratio ' I Mold (linear) . shri.nkage, in./in. .

                                                                                                                                                                -             t                   2.1 + 4.4
                                                                                                                                                                                                  .004 - 0.010 .:

, l' ' Specific gravity (density) D792 1.5 - 1.7 .,

                                 '                Specific volume, cu.in./lb.                                                                 D792                                                20.9 - 17.8
? Tensile strength, p.s.i.  : D638
                                                                                                                                                                                             ' 6000 - 8000 Elongation, t .                                                     -

D638 0.4 - 0.8 5 -

            ',                                    Tensile elastic modulus, 10 p.s.i.                                                         D638             ,

8.0 '17.0 Compressive strensth,.p.s.i. D695 26000 - 30000 5

       .;                                         Flexural yield strength,-p.s.i.                                                            D790                                                 8000 - 10000                                      l
        '                                    ' Impact strength, ft.lb./in. of notch
  • I (1/2 x 1/2 in. notch bar, i=od test) D256 0.27 - 0.'38 l Hardness, Rockwell . D785 E95 - 100
i Flexural elastic modulus, p.s.i.5 ' * ~
    ;-                      .
                                               'Co=pressive modulus, p.s.i. x 10                                                             D695                                                --
  ~/                           ~

Ther=al conductivityr 10-4 . cal /sec/ .

                                                                                                                                                                                                                                  ~

sq.cm.,/1 (*C./cm) '

                                                                                                                                   .         Cll7                                                4.0 - 7.0 Specific heat, cal /*C/p                                                                   -- -

0.35 - 0.40 l l Ther=al expansion, 10-3 in./in./*C 'D696 1.0 - 4.0 Resistance to heat.*F (continuous) 1- -- 275 - 325

   ?

Deflection temp., 'F ~ '

   }-

0264 p.s.i. fiber stress O 66 p.c.i. fiber stress

                                                                                                                                           , D648
                                                                                                                                                                                           ~

285 - 310

                                                                                                                                                                                                                            ,~
                                              ' Volu=e resistivity, ohn-cm.                                                                                                   ,
                                            ,           (50% RH and 23*C).                                                                   D257                                              --

Dielectric strength, short-time,

       ,'                                              1/8 in, thickness, volts / mil.                                                       D149                                               220-325
                                        .         Dielectric strength, step-by-step,                                                                                                         -                    -

iL 1/8 in. thickness, volts / mil. D149 -- Dielectric constant, 60,cyc D150 7.0 - 7.7

       '                                          Dielectric constant, 10jcyc Dielectric constant, 10 D150                                              --           .

cyc D150 5.2 - 6.0 Dissipation (power) factor,'60 cyc D150. 0.02 - 0.04 Dissipation (power) fact cyc D150

  ;'.'                  .

Dissipation (factor).,10gr,10 cyc D150 0.04 - 0.06 1 Arc resistance,'sec. .

                                                                                                                            .              .D495                                               130 - 180                        .

Water.absorp., 24 hr., 1/8 in. thick,% D570. 5 0.03 ' b ' Burning rate (flammability)., in./ min. D635 ' self ext.

                                                                                                                    ~                                                                                                                               l Effect of sunlight                                                                        --

nil. l Y~ Effect of weak. acids

  • D543 none .

l Effect of strong acids - D543 mild  ;

  '.,                                             Effect of. strong alkalies                                                                D543                                              none
  • Effect of organic solvents D543 none Effect of weak alkalies ,

D543 none

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      ;                                                FIRE TEST
  • s In order to categorically prove that U-F is not only
, fire proof', but self extinguishing, ANEFCO, INC. con- ,

i ducted a field fire test in a quarter scale polyethylene liner. The flammable material used was gasoline in order -

     !-                                                 to simulate a maximum credible accident' nominal to high-way transport.                  The photographs and motion picture film i                                                 demonstrate graphically that the material is not pyro-foric.

The need to more dramatically demonstrate th'ese facts,, . ,

     ,                                                 ANEFCO attempted to burn the U-F with an acetylene j-                                                torch and again could not produce burning.

The chemical reason for the abohe is best explained by' #, I. the following senus of reactions which show the pro- .l

                                .                      duction of carbon dioxide (CO 2) which extinguishes the                                                                                                                !

flame and insulates the remaining mass. ' H H , O l l R-- , , H-C-O-H --* H-C=0, r H-C-O-H ---* O=C=0 *

                                                                                                                                                                                                  ~

l . H _ .~. 4;: - Methyl Alcohol Formaldehyde Formic Acia Carbon Dioxide ,

                                                                                 ~
 '{                                                        CH3 - + H 2 0--* CH3 0H + 2H++ 2e#                           -

0.58 Volts 25' CH 3, 0H - HCHg 4 2Hb 2e -. 'O.24 Volts 25' ,

                                     '                                             '                   ~

{... . . HCHO + H2 0 --* HCOOH + 2H++ 2e + 0. 01 Volts 25' .

              ..-                                         HCOOH         : CO2 + 2H++ 2e + 0.14                                 Volts 25*

The half reactions involved in these oxidation reactions

                               '                       and their approximate potentials in water solution are snosm.                                                                                              '

The couples are not reversable at room temperature. Thus, one may observe that the' reaction in' fire conditions p- shows the production of CO2 making it a self extinguishing ~ i fire proof material.

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                                                                                                                                                                       '1 DATA APPLICABLE TO STORAGE AND PUMPING OF                                                                                 !
  .                                                                            A-SET RESDI
    '                                          PHYSICAL PROPERTIES (at time' of manufacture) :                                                                              ,

l

,                                                        pH                                               7.2-7.5
  • Viscosity 0 250C., cps I
 "                                 ~

P-500-700 l Specific Gravity #25/25 C. 1.295-1.300 - Solids % . ,66 i 1 t

      '                                                 Free Formaldehyde %                               3 max.
                                                    , Storage Life, Months 8 50*F                                            .        .
       .,                                                                                                                                                                   l
                                                                                                        18                                                 .       -

O 70'F ' 2

-.                                                             O'. 9 0 *F                     ,              'l e-
  • Brookfield RVF, 1/10 t -

f' , 8*

  • ROGR_KS.:

{ The degree of'reactivi.ty of the resin can be  % i controlled by varying the amount and makeup of a catalyst. This product ahs the desirable characteristic of being very stable. i, -

  • A-SET FOAM
              ,                                  PHYSICAL PROPERTIES                                                                                                        ,
                                                                                                                      ..                                                     l
                                                                                                                       ~

Density , . ' '. Ash content .' 0.8 lbs./cu-ft '- O.7 % Free Formaldehyde l'% Setting Time ~ 10-30 Seconds Electric Resistivity 5.00 ohms /cm  !

  • WICKING' i

Water Absorption 3.8 hrs.' 0 15% by weight. - l ASTM Method 6.2/6'9 b . 1 1 O a

s . g,-..< f '%..

                                     ?'

[ . Storage of Urea Formaldehyde Urea Formaldehyde is stable for at least six months under normal storage conditions. At 35 0C (950F)

        '                                         . viscosity will increase rapidly upon storage. For
       '                                            this reason, storage tanks should not be exposed to.

direct summer sunlight. Extended storage at temper-

  • atures as low as -200C (-40F) has no permanent deleterious effect on Urea Formaldehyde, but to .

maintain the proper viscosity it is recommended that Urea Formaldehyde be stored at 20 to 300C (68-860F). If low ambient temperatures are anticipated, indoor

                                '                 or insulated storage tanks should be used, with provisions for heating.and recirculation or agitation.                                                         C Aheatingcoh.1'issometim'esneededonlynearthe outlet of small tanks; this can be used to avoid having to heat the entire contents of the tank.                                        -

Water heated about 50 C (1220F) should be used in-stead of steam for heating stored Urea Formaldehyde, I since localized overheating could deteriorate t'a

                                                                                         ~

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o Table 1: pit Measurements by mis. of Catalyst for .-

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                                                                                           -200 ml. Slurries of Water /h -SET
     !                                                             X                                           Y M1. of 252 we.

Sodium Bisulfste pit of Slurry 0 700 F. Estimated pH

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2.4 2 . 2.4 4 1.7 1.7 6 1.5 1.5

                                  .                                8                        .

1.4 1.4 10 1.3 1.3 i ' Equation for cury.111near fit of raw data. Shown in Figure 1. - Y = 1.02522 + (.0415589X) Index of Jetermination = .99724

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t' . i X Y . M1. of 3N H3506 pH of Slurry 0 70 0F. Estimated oH ( O . 1 2.7 2.7

                 .                                                 2                                        1.9                                         1.9 3

1.6 1.6 4 . 1.4 1.5 6 1.4 1.3 10* 1. 2- 1.2

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   .r                                                                                                     -

T = 1.05443 + (1.64827/X) Index of Determination = .99304 -

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' i - Table 2. 700 and 90 F. Cel Times by pit of Water / SlurriesCatalyzedwith25%SodiumBisulhgg... ate . X Y Slurry pH G 70*F. Using 25% we. Cel Time G 70 F. Estimated Sodium Bisulfate Solution (mins.) Cel Time G 700 F. 2.4 19 - 19.4 1.7 ' 11 9.3 1.5 5 . 5.7 1.4 4 5.0 1.3 4 3.5

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Equation, for curvilinear fit of raw data. Shown in Figure 2. - Y = -15.2101 + (14.43')4X) Index of Determination = .97226  ; i i - X ' Y Slurrf pH G 70 F. . f .. g Using 25% we. Cel Time G 900F. Estimated l j Sodium 31 sulfate Solution (mins.) Cel Time 0 900F. . i .

     ,                                                        2.4                                           16                                               15.3
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s 1.3 3 1.9 t Equation for curvilinear fit of raw data. Shown in Figure 2. I

    ;.                                       Y = -13.8506 + (12.1519X) Index of Determination = .94999                                                                        -

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l Table ~3. 700 and 90 F. Gel Times by pH of Water / A-SET . . Slurrics Cataly:cd with 3N Sulfuric Acid - X Y Estimated

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Slurry pH 0.70 0F. Gel Time 0 70 F. Gel Time 0 70 F.

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Usine 3N H SO, ___ (mins.) , (mins . ) .

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2.7 118 . 133.7 1.9 24 21.1 1.6 9 8.5 1.4 6 - 4.2

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                                                       .X                                             Y                                 Estimated
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                              .                          1.9                .                       13                                                   12.9                                                                              '

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   .                                          Y = -18.9736 + (16.7857X)                          Index of Determination = .982(J
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  '                                          ANEFCO INC. ECOPAC SYSTEM                                             .
                                                                                                                                          ;
                                                                                                                      ~

l PROCEDURE FOR ON-SITE SOLIDIFICATION OF LOW-LEVEL RADIOACTIVE WASTE j , AT SEQUOYAH NUCLEAR PLANT . 1 i . 1 l l CONTRACT 80P68-161957 ' l t ANEFCO CODE B-123 i l l

 .                                                                                                                                        1 I                                                                                                                                        l i                                                                                           -

i l l

;                                  This Procef.ure describes general operation                                  .                          l of the ECOPAC system and the necessary                                     ,

interfacing with Sequoyah Nuclear Plant systems. l i

                                                -                                                                                         I
                                                                                               .                                          l
                                                                                                                         ..s              j 1/31/p0 .Rev.                O 7                           ,

tNEFCO _ m_ ,

                     ~ ;..

s SCOPE:

       ,                        1.0  The purpose of this procedure is to describ(~the general                        ~

j \

      ;                              operations, precautions, and interfacing for the removal and packaging of :esin and liquid radwaste from the                          ,

I Sequoyah Nuclear Plant (SNP), I PREREQUISITES : - 2.0 All radiation protection standards will be in acccrdance with the Radiological Safety Policy and Program of Sequoyah Huclear Plant, and Code of Federal hegulations, l Title 10, ENERGY; Part 20, Standards for Protectio.n Against Radiation. I 2.1 All ECOPAC equipment will be checked prior to this operation by the ANEFCO field supervisor. . 2.2 Radiation work permit must be completed. i l. PRECAUTIONS:. . 3.0 Traumatic safety is of primary concern throughout the entire

                                                                                                          ,               )

i operation. * ' 3.1 Radiation limits established by Health Physics section and

                                                                                            .                             I 10 CFR 20, will be monitored.
                           .                                              .                                               ;

3.2 The limiting radiation factors, as applied to this procedure, are the readings on the side of the transfer vehicle. Dose rates on shielded container will be limited to DOT regulations for sole use vehicle, 200 mr/hr. contact an.d 10 mr/hr at six l feet ' rom truck body, 3.3 Area barriers (i.e. padiation signs} will be posted per

                                                                               ~

10 CFR 20.

                                                                                                     #^

1 l l

                                                                                     ,  ANEFCC.4 m

3.4 Wipe tests (i.e. smearable loose contamination) will be performed prior to work and at the finish c2 the job to _ establish that this area is within the linits as prescribed

      ,                           by the applicable regulation.

I 3.5 Waste transfer piping and hose will be blown free when l . l transfer is completed to prevent subsequent plugging, i contamination buildup within the lines, and to reduce area

l. background radiation levels.

3.6 All ECOPAC connecting hoses will be disconnected and stored when operations are completed. - OPER\TIONAL PROCEDURE (Utilize 4.0 thru 4.8 for both Resin and Boric Acid solidification) 4.0 Position cask with empty' disposable liner inside auxiliary building access bay alongside the AMEFCO ECOPAC solidification

                                                                    ~

g , system. - 1 l 4.1 Attach ECOPAC loading arm to th'e liner 2" male dry-break i

  ;                              connector. Verify that the ultra-sonic level detector fits properly into liner port and seal OPW quick disconnect.

4.2 Connect the loading arm acid line to the liner 1/2" male dry , t . . break connector. - 4.0 Connect the dewatering system hose to the ECOPAC system air 8 compressor outlet.

4.4 Connect two air hoses from plant service' air to the ECOPAC

. system, 4.5 Connect both electrical supplies to ECOPAC system. (110 VAC,

, .

60 hz; 220 VAC 3 phase, 60 hz). - 4.6 Couple U-F ta'nk to the 1 A l2" Sandpiper pump using 4' double OPtf female quick-disconnect hose. - jfilNEFCO

.. 4.7 Couple U-F Sandpiper pump to ECOPAC system using 25' double ,

  !                                   OPW female quick-disconnect hose.

f 4.8 Attach air supply from ECOPAC system outlet to the U-F i . Sandpiper pump. .

 ,!                             RESIN SOLIDIFICATIOff           .

5.0 Slide hose containment over resin-transfer hose prior to f f . i attaching hose to SNP ',ischarge fitting FCV 5 004 5.0.1 Tape hose containment to hose, add (3) three.absorbant pads

 !                                    into the containment, then tape and seal she containment to SNP pipe (refer to draw'ing SNP-1) .                                                               -
                                                                                                                                           )

5.1 Connect the SNP resin's outlet hose to the catch tank top j b 1

 .                                    inlet quick-disconnect and contain per drawing SNP-1.

5.2 Connect the resin catch tank discharge pump outlet (Moyno) i to the ECopAC. system utilizing the 25' female quick disconnect' flanged hose an'd contain per drawing SpiP-1

                                                        '                                                                                  l 5.3   Connect the resin catch tank well potnt to the dewatering pump and contain per drawing SNP-1.
+

5.4 Attach dewatering pump discharge hose to SNP valve number f43/17 40, i . o n e. complete. 5.5 ANEFCO will indicate when -g 11c.7 batch of resin can,be pumped by SNP to the catch tank. 5.6 SNP should flush / clear resin hose prior to step 5.7 to lower the dose rate as low as reasonably achievable, ,

  • . l

5.7 Supply 110 vac to the dewatering pump and dewater resir,. .-

                                                                                                                   ,-     through .        i SNP valve (Raf-TFyCy Water recovered by dewatering JSteg ' rom

. . ..e - i catch tank will be pumped to SNP rece$.ving  ;.

                                                                                             .~ $$ne, j                                                                              ., 3 . .            ;.

~ 5.8 Supply 220 vac, 3 phase 60 hp

                                                    ,                     to resig forwayding go no pump     ,- ..

from ECOPAC system. ._ a g

                                                                   .                                    NEFCO~

l

(.,

  !                                                                                                                 I

( 5.9 Connect air sparge hose from ECOPAC system to resin catch l tank and sparge for a minimum of 30 minutes prior to transfer f for solidification.  !

 !                  5.10     ANEFCO personnel to solidify the dewatered resin according
  • i to the ANEFCO ECOPAC process control plan. When resin
 !                           solidification is completed, disconnect the SNP ' resin outlet hose to the catch tank top inlet and contain per drawing S NP -1.'   Store hose in assigned location.

5.11 Disconnect the catch tank discharge pump (Moyno) outlet' hose to the ECOPAC system and contain per drawing SNP-1, Store . { hose in proper location. 5.12 Disconnect loading arm waste dry-brea}c connector, acid dry-

 ;                                                                                               -

break connector, and ultra-sonic le. vel. det,ector.. Contain,

                                       ,                                .  - ;                .-

opening with safety drip' bags. '

!                  5.13      Health Physics Technician will monitor radiation levels and 4
.                            condition of solidified waste in the liners,                   -

t i 5.14 Seal full liners. Paint one liner cap with temporary sealed cap for indentification at burial site for subsequent inspection.. Seal other liner caps with lock-cement (permanent) . 5,.15 Seal cash' cover , BORIC ACID / EVAPORATOR BOTTOMS (Liquid Wastes) 6.0 Slide hose containment over boric acid-transfer hose prior to attaching hose to SNP discharge line number 6.1 Tape hose cont'ainmen~c to hose, add (3) th$ee absorbant pads I into the containment then tape and seal the containment to l SNP pipe (refer, to drawing SNP-1) . I 6.2 Connect the boric acid transfer hose to the ECOPAC system waste inlet and contain per drawing SNP-1. . J

                                                                           /1NEFCC3l
                                                                               *    , .:.; i. ." . . ;;- ~~
                                                                                                              ~
        ;

9 j 6.3 ANEFCO will notify SNP when ECOPAC system isfready to receive, liquid wastes. \ pc'v 77- 90 2 6.4 S?iP to open valve number A for transfer of waste to ECOPAC i system.

  • 6.5 AMEFCO personnel will solidify the liquid wastes according to the ANEFCO ECOPAC Process Control -Pten. Proyar., .

6.6 ANEFCO will verbally notify SNP upon receipt of one complete

     .                        batch of beric acid so that SNP can terminate pumping waste
                     ,        by closing valve number FCV 40 Z ,                                     ,

6.7 After notifying SNP operator, ANEFCO will flush ECOPAC system l

     ,                        using SNP demin wate        S IP valve number FCV-77-4gh .

l 6.8 Disconnect the boric acid transfer hose from both the ECOPAC

                                        ~

i VALv6 F<N-TT-9 02  !

     ,                        waste inlet and the SNP discharge line4 number A using the containment method illustrated in drawing SUP-1.            Store hoses in proper location.

6.9 Disconnectloadingarmwastedry-breakconnebor, acid' dry-break connector, and ultra-sonic level detector. Contain op'enings with safety drip bags.

                                                                                                  ~

6.10 Health Physics technicianswill monitor radiation levels,: -

                              ....   .-       , . _ ._-    - > .                                             l 6.11 Seal full liners. Paint one liner cap with temporary seal for identification at the burial site for' subsequent inspection.
i l Seal other liner caps with lock-ccment (permanent) .

6.12 Seal cask cover. ,

   !                                                                                                         l
   ;                                                                                                         1 I                                           .

LAN EFCD l

UrGO-formaldchyds - -

                                                                            *                              .                                           Storage Tank j                                                                                                                                                                                      ..

i_ =

                                                                                                                                                                                                                   \.
     ;                                -A                                                                               .
    !                     Resin Slurry IN                                                                                                                       c                  \.'
                                                                                                                                                       -O                                                      "*"i" C^t h T*"k g                                                                                                                                                                                i Water OUT        -
                                                                                                             ~_~-          .
    .,        y* SNP Valve # /C/-4400                                                                                        g-                                   -

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                                                                                                           . RESIN SOLIDIFICATION SCHIMATIC                                                                                                                                              . .                                                              l
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                                                                                                                                               .                         Urac-formaldshydo                                                                                                           '
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        ;
        ,                         .i                                                                                                                      f                                             /                                                                                                                                           -                               -

n, . . g3 . .  : ; ... . 8FA ShP. Valvei FCV-77 .400-

                                                                                                                                                                                                                                                                                                                                                                            .s.:...-    ..: > . . .
. . . . .s-. . . . .
l. .* ' , ..E.COPAC SYSTDi
                                                                                                                                                                                                                                                                                                                                                                        .#- .*I.I.                   .'~-  *-
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  • BORIC ACIb .

SOLIDIFICATION SCHEMATIC

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EXPERIMENTAL SIMULATIONS OF RAbIOACTLVE i

                                                   , WASTP, AND A-SET RESIN
  • FORMULAT.T. OMS * -

l .

      ;                                                                                                                                   '

l-Experimental formulations for the solidification of selected i simulated wastes with A-Set Resin has been, determined. These formulations, , attempt; to  ! l incorporate. a relatively maximum quantity of waste while i consistently producing a solidified product. Solidified products

    !                     were obtained for all waste types tested although some difficulties were encountered at high waste to solidification agent ratios for                                               ;

sulfate wastes to UF. The addition of sufficient , acid catalyst  ! I to waste-UF mixtures to achieve a pH of 1.5 0.5 was found to produce a more rapid and consistant polymedzation and also permit 1 J a higher waste to UF ratio for most wastes. Care should be exercised te assume that a thorough homogeneous blend is achieved. - Mixing equipment must be kept free from foreign matter and cured ~-l l a d h e s'i v e b u i l d - u p . i -2 The free standing water in simulated wastes solidified with UF was l

   .                      measured and found to vary from zero to 25.4 wt.%. Adjustment,of                                                !

the waste to UF mixture pH to 1.St 0.5 by the addition of sufficient acid catalyst resulted in a significant reduction in the quantity , of free standing water. The free standing water was found to )

   ,                      have a pH approximating that of the water to UF mixture after                                                   )

I addition of the catalyst.

  • The polymedzation reaction is acid catalyzed and is both temperature and pH dependent. Low waste to UF mixture pH and high ambient temperature decrease the time required for solidification. A pH of 1.5 0.5 in the waste-UF mixture is desirable; however, the amount of catalyst needed must be determined for each'17dEt'e. Such m.ixturcs will begin to gel _.in several minutes and are generally well solidified within thi'rty minutes. Dilute solutions of. strong acids maybe used to adjust the pH of highly buffered waste-UF mixtures. The use of strong acid solutions must be done with care to avoid premature gelling of the mixture.
         .                Concentyaf5dsoduimsulfatewastesmaycauseerraticsettinginUF.

Additions of less than ten weight percent sodium sulfate or small amounts of calcium chloride are reported to eliminate this problem.1 sodium The addition of 2 wt.% calcium chloride to UF containing l Heacock, H.W. and Riches, J.W., Waste Solidification-Cement or _Ureaformaldehyde, American Society of Mechanical Engineers, 74-WA/NE-9, 1974.

  • Registered Trademark
                                                                                                   ~~         ~
                                                                                                  ,1          < ? - *&. 7 ;_1 " ,,
                                                                                                .' h* .~.. \: .e ' .5 .~ '; .' W. ' 
             .      . s .,                                                                                                                         .

sulfate wastes'was found to increase the permissi le waste /A-set Resin

          !                ratio.. The addition .of sufficient cataly'st to produce a pH of                                               ,
          !                1.5* 0.5 in the waste-UF mixture allows an~ increase in the                                            *
      'I                  waste /UF ratio for most wastes.                                          .

1 l e

                                                                                , .a i                                                                   TABLE 1 Simulated' Waste Tvoes Included in the_ Experimental Program
        ;
        ?
        ;                               1. Bead Rosin Waste I
    '!                                  2. BWR Precoat Filter Cake
       ,                                              a.        Powdered Resin                                                       .
b. Diatomaceous Earth I' I

I 3. Forced Recirculation Evaporator Concentrates ,

a. BWR Chemical Regenerative Waste
b. .PWR Chemical Regenerative Waste
c. Boric Acid Waste -
d. Decontamination Waste -

I a

4. Thin Film Evaporator Concentrates I
                                                               'BWR Chemical Regenerative Waste a.
                                                    .b.        PWR Chemical Regenerative Waste                                  -
c. Bor.ic Xcid Waste
                              .                       d.       Decontamination Waste s

S

                                      ~

f l' a f f'

                                                                                                                     . . . , , .    .a         ,    ,.
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        !                                                                         TABLE 2                                                      -
  • I .
      .                                                                 Simulated Vaste Formulations i                                  .                                               .
   -4
1. BEAD KESIN WASTE
                 **                                                                                          Weight Percent, t Material 8

Water 50.

              *   .                                               Bead Resin (IEN-150)a                                     50.

Teanpera ture 700F pH l' 2a. BWR PRICOAT FILTER CAXE (WI'Dt POWDERID RESIN) Weight Percent Material in Filter Cake, s Wa't er 50. Anion Powdered Rcsin (FAO)b 20. l Cation Powdered Resin (PCH)D 20. 3 , Crudo

  • 5.

Sodium Chloride ~ 5. Temperature . 7COF

  • pH 7 i

2b. BhR FRECOAT FILTER CAXE (WInt DIATCMACF.OUS EAR'DI) ,..

     ;                                                                                                                                       .           .

Weight Percent Material in Filter Cake, s

  .I                                                                                                                                                                                1 l

Water 50.  ;

    ;                                                     .       Diatomaceous Earth                                        40.                                                     '

I Crude . 10.

                                                               - Temperature 70*T                     -

pH ] 3a. BWR ChTatICAI. TECENERATIVE WASTE CF A FORCED RECIRCULtTIOr3 EVAPORATOR Weight Percent Material in reaoorator sottons, t

    .                                                             Wates                                                     75.                  '

Sodiurs Sulfate 22.9

                      .                                           Sodium Chloride                                            2.0 Crude                                       .,

y . 0.1 0 Temperature 170 r PK 6 ,

   ;                                                                                                                                                                                 l l

i

                                                                                   - 3. -

l

                                                                                                                                                                                     \
m. _ l
          *           *                                          ~

J = ' I \ *

 .t
   !                          3b. PWR CHr.MICAL RECEF!ERATIVE WASTE OF A FORCED RECIRCULATIOtt EVAPOR.11 Weight Percent 1                                                                                  .
in Evaporator Bottoms, s Material .
                                                                                                      ~r*

i - .; 73.4

   '                                                   Water                                                        14.9 Sodiura Sulfate                                               9.6 l                                                    Ac.noniura Sulfate
  • j 2.0 Sodlurn Chloride 0.1
  • CndC 1700F Tcmperatura 2.5 to 4.0 3c. BOR3C _ ACID WASTE OF A TORCED RECIRCUuTICN EVAPCAAMR .

Weight Percent , in Evaoorator Bottoms, s Material _ . , 87.9 Water 12.0 . soric Acid 0.1 Caud C l~ 17C0 7 . Tecperature *

  • 3.5 pH 3d. DECot4TAMI!:ATICN WASTE OF A FOR_CED RECIRCUMTION EVAPORAMR Weight percent
 *                                                                                          -           in Evaporator Botto.ms, s Material _                                                                 ,

80. Water g,4 WrEK-700d ) 5. EDTA b. Citric Acid 0.7

  • Crud C 0.2 Hydzaulic Oil No. 2 0.2 - 1 Lubrica, ting 011 No. 20 170 70 )

Tc.mperature 5 l 1 pH . I l j

  • 44. EWR CEEMICAL FICD ERATIVE WASTE OF A THIN TII.M C/APORATR 1
  • Weight Percent in Evaoorator Bottoms, s
                              -                                 Material 8                                                                                                                                            .

50.

                   ~

Water

      .                                                                                                                45.8
  • Sodium sulfate 4.0 Sodium Chloride 0.2 )

C Cnd Temperature - 150 to 25007 6 ' .PR . g . . 0

                                                                                      -4 e

l

          .
  • 1. .

l 4b. PWR CHEF".1 CAL RECEF:ERATIVE WASTE _CF A 1 MIN, F11M EVAPOEA1CR_ . I g_ Weight Percent i Mat errial in Evaporator Pottoms, t Water 50

    ;

Sodium Sulfate

  • 29.

Ar:monium Sulfate 16.8 l Sodium Chloride - 4.0

                         .                                     Crud C                                                             0.2 Temperature                                              150 to 2500F            .

pH 1.8 to 4.0 l t 4c. BORTC ACID WASTE CF A 11 TIN FIIM EVAPOPA1DR

    ;

a weight Percent Material in Evaporator Bottems, t . Water 50. Boric Acid 49.8 C Czvd 0.2 l Temperature 150 to 250 0 F l pH . 2.5 to 3 5 . 4d. D,ECONTAMINATICN WASTE OF A THIN FIIM EVAPORA1CR ,

                                                                                                                   . Weight Percent gterial                                   , in Evaoorator Bottoms, t Water                                                           50.

hTTEK-700d 20. EDTA 9.8 . I citric Acid 19.

   !                                                           CamdC                                                             0.2 Hydraulic 011 No. 2                                               0.5
  ,                   ,                                        Luhricating 011 No. 20                                            0.5                           l Temperature         -

150 to 2500 F -

                                                                              ~ '

pH 5 l l a RoNa ar.d Maas Co., Philadelphia, Pa.19105 '

              .                             b Ecodyne Corp., Union, N.J. 07083 e fine air cleaner test dust no. 1543094, AC Spark Plug Divisicn, General
 !.                 ;

Motors Corp., Flint, Michigan 48556 d cocpound for the dissolution of calcium sulfate scale, Nuclear Technology Corp., Amston, Conn. 06231 ,

                                                                                                                                                               )

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       ;                                                                                                                                                                                 . .

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       !-                                                         ,                    _              TABLE 5                                       .
Formulations for the Solidification of 3V8 and Pk'R Wastes Using
      ;                                                   A-5'et Resin.                      Sufficient 25 Ut.Z Sodium Bisulfate (Anhydrous)
      ;                                         .A,c,ueous o            CataA st Solution Added to Achieve pH = 1.5 0.5 in the Waste-UF Mixture
      ?.
                                              ~

WekghtRatio Approxicate Volume %

      ,                                          . Msje_ Type,                           Waste to UF           Solidifi_ca, tion Time            FaHS0t Solution Added
1. Nad Resin 2.2 15 minutes , ' 1.8 i .
2. SVR Precoac Filter Cake
a. Fowdered Resia 2.0 15 minutes ,- . 1.9 -
      !                                    b.       Diate aceous Earth                         2.0                 15 minutes                                           3.0 t                                                                                                                                             *
3. Forced Recirculatio'n' -

Evaporator Concentrates *-

a. 3kA Chenical 1.3 15 minutes 3.1
     ;                                             Regenerative Waste
b. F'R Chemical' 1.3 15 minutos 2.9 Regenerative Waste
c. Boric Acid Waste 1.2 10 minutes 0.8 4
d. Decontamination Waste 1.2 30 c,inute's 10.5
     ,! .                          4. 'T.iin Film Evaporator i                                      Concentrates                                                                                 -

I a. 3VR Chemical 1.5 20 minutes 1.5

 -l                                               Regenerative Waste
b. - FWR Chemical
  • 1.0 20 minutes 1.7 Regenerative Waste- ,
c. Boric Acid Waste , 1.2 20 minutes
  • 3
                                         .d.      Decontamination Waste                       1.5                  30 minutes                                        13.3         .

g . t O

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                                                                                                                                                                                    .m n                   --
                                        -k           y%
                                                                                                                                                                                                      -9 i                                                                                           Techniedl Service Report
               '.~                                                                                                                                                                     .

i . l Data and' Discussion.:- Tabics 1 through 3 as described below show the raw data I 3 _. _obtained in these catalyst studies of A-Set Pesin 2 as well as their conversion to a curvilinear fit in graphing. ,

     ;                    Table 1:           p!! icasurements by mis. of Catalyst for 200 ml. Slurrics of Ifater/CASCO-RESIN 2 l-table 2:           700 and 900F. Cel Times by pit of flater/A-Set Fasin' 2 Slurries                                                                                                 I Catalyzed with 25% Sodiu:2 31 sulfate                                           ,

Table 3: 700 and 900F. Cel Times by pH of' Water /A-Fet Desin' 2 Slurries i Catalyzed with 3N Sulfuric Acid l g l

    ,             Figures 1 through 3 actas:hed are graphical portrayals of Tables 1 through 3 and                                                                                                            l need no further description.                                                                                                                                          *
                                                                                                                                                                                                       . H
                               .                                                                                                 y n                                .
                                                                                                                                                           .Y
                .                                                                                                                                                            .   ~
                                                                                    .                          8                                    .

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e  % [.) *

                                                                                                                               .                                                                        f.

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  • m g - # . .
                  *                                                                                                                    *                                             . e
                                              '                                                                    -                                 Technical Snevice Ecport'                                 -
             ;                                                                                                                                                                             ,
                                                           -                                    Table 1:                   pit Measurements by mis. of Catalyst for                                       .-
             !                                                                                                             200 n.1. Slurries of Water /A , Set Resin 2 A
                                                                                  ,X                                                            Y M1. of 25% vt.

Sodium Bisulface_ pil of Sierry 0 70 F. 0 Estimated ol! 2 2.4 , 2.4

                                    -                                               4                                                          1.7        .

1.7 g. 6 1.5 1.5 8 1.4 1.4

            ,                                                                     10                                                           1.3                                   ~1.3 Equation for curv.ilinear fit of raw data. Shown in Figure 1..

t

- Y = 1.02522 + (.0415589X) Inde:c of Determination = .99724 X Y '

0 Estimated pK M1. o f 3N H,50t. pH o f SI :r n 0 70 F. O - _ 1 2.7 2.7 >

                    .                                                               2                                                           1.9                                   1.9 3                                                    -     1.6                                   1.6 4                           .                              1.4                                   1.5 6                              ~

1.4

  • 1.3 -
1. 2* 1,2 10

Equation for curvilinear fit of raw data. Shown in Figure 1. Y = 1.05443 + (1.64827/X) Index of Determination = .99304 . 9 O e D e 9 e e

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           ;

Technicar Service Report

    ;             -
    *                                                                                                                         ,1
    ;

Table 2. 700 and 90'F. Cel Times by pit of yater/A-Set Pasin 2

  • Slurries Catalyzed with 25% Sodium' Bisulfate .
  !                                                      X                                                        Y
  !                                     Slurry bl! G 70 F.                                                                                    '

I Using 257. we. Cel Time G 70 F. Estimated Sodium Eisulfate Solution _ (mins.) Cel Time 0 700F. l

                                                 .                                                                                   .                                                                   I i                                                   2.4                                                          19                                            19.4 l                                                   1.7 11       -

9.3 1.5 5 5.7 l 1.4 4 . 5.0 .!

  .                                                   1.3                                                           4                                             3.5                                  -

s *

  • Equation, for curvilinear fit of rau data. Shown in Figure 2.

{

Y = -15.2101 + (14.4304X) . . Index of Determination = .97226 j . l X Y .
 ,.                                                                o                                                                            . .

Slurry pH G 70 F.

  • s Using 25% wt. Cel ".imei G 90 F. Estimated  !
 ;j                            Sodit. i 31 sulfate Solution (mins.)                                     Cel Time G 90 0 F__ ,

2.4 16 , 15.3 . 1.7 5 6.8

  • 1.5 ,3 " ' 3.8 . -
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3.2 14 . ,4 . , 1.3 3 1.9 Equation for curvilinear fit of raw data. Shown in Figure 2. Y = -13.8506 + (12.1519;O Index of Determination = .94999 . e l

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VII. APPENDIX

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( ( LIllER READY KEY IDCK POWER AND ( EMERGENCY SIIUT DOWN IllTERLOCK START FILL CAFETY SWITCll [ CIRCUITS & SWITCll ( ( SWITClf I ds I 8

                                                                                                                                .                                                                                                        i I

MANUAL 'I AUTO *.tADWASTE 'I SYSTEM FLUSH 8

         .                                                              FILL                      .
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BINDER i. MANUAL. l FLUSII VALVE l . LOW.  % g Sf-CATALYST N-C 4ASTE VALVE ( TURN OFF WASTE g WASTE l l [1  ; 7 ( VALVE FMSH RADIATION . I VALVE i LEVEL h .  !

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LINER AUTO REF . I LEVEL .>. - MANUAL _..  ! I - - l

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I FIDW RATE --

  • WASTE / FLUS!!:

A-SET A-SET ,

                                                               *'                                                 >    CONTROL                                                         O 1

FIDW RATE VALVE

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  • CATALYST
  • CATALYST  ;-

D- CONTROL  !

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