N

THE 4TH INTERNATIONAL TOPICAL MEETING ON

NUCLEAR THERMAL HYDRAULICS, OPERATIONS AND SAFETY
April 68,1994, Taipei, Taiwan

XA04NO644
A IGH-VOLUME-EF71CIENCY PROCESS

FOR SOLIDIFICATION OF BORIC ACID WASTES

Ching-Tsven Huang and Wen-yi Yang

Institute of Nuclear Energy Research
P. 0. Box 37
Lung-Tan, Taiwan 32500
Tel:(03)4711400 ext. 5980, FAX:(03)4711411

ABSTRACT its long term stability remains, however,

doubtful. Again, in the umen solidification
A novel process for the solidification of method, the volume efficiency is igh, the
radioactive liquid borate wastes is currently strength of the bitumen-solidified waste form is,
under development -in tl-x-- Institute of Nuclear nevertheless, low and the waste form is also
Energy Research (INER). The process using a flammable. The current solidification methods are,
special-recipe powder as the solidifying agent is therefore, still far fm perfection and in many
very useful for solidifying la-quid borate wastes areas need for irovements. 1 Judging fm the
generated -in PWR nuclear power plants. Under sme nature of these slidification methods t long-
unique conditions te blending of the solidifying term stability of the cementitious waste form
agent and the liquid borate waste is a highly comimnucates to the mind of people a very
fluidy slurry, which sets quickly within about 30 important security in relation to the storage
minutes forming a solidified product of high requiring a period over hundreds of years. Hence,
strength. Retardation such tat occurred in the it as become a very urgent task to improve the
solidification of borate waste with cement is not volume efficiency of the cement solidification
observed in this process. The volume efficier-Y of method for reducing the over-all cost the
the process is about 510 times that of the management of LLW.
conventional cementation process. Characterizatim
showed that te olidified product has qualities 2. DESCRIPrIGNS OF THE MMUD
far superior to the acceptance creteria of the US
NRC regulation. Smplicity being the oher feature In the alent-solidification method, the
of the process results in a low perating cost and caTentitious monolith formed by the hydratio of
a considerable decrease of the capital investiment cement components eapsulates the wastes. The
when the process is used. Possible uses of the components of ement, taking Portland cement as an
process to slidify other radioactive wastes example, principally consist of tricalcium
generated n W nuclear power plants are also silicate aO- SiO2 or C3S for abbreviation),
discussed in ts paper. dicalcium silicate (2CaO- SiO2 or C2S), tricalcium
aluninate (Cao- A1201 or CA), tetracalcium.
1. nfrRODUCTION aluminaferrate 4a0- AIA-FeP3 or CAF), and a
small amount of magnesium oxide, titanium oxide,
Low-level radioactive wastes (L-W) generated sodium oxide ad ferric oxide. The solidification
at nuclear power plants a solidified before of cement is essentially brought about by
transporting to the interim-storage or final- hydrations of the above mentioned principal
disposal site. The wastes are solidified so that components, the reaction being as follows:
they can be handled wth ease and their chemical
and physicAl stabilities can be maintained over a 2CS + 610 = 3aO-2M,-31 + 3Ca(OH), (1)
long period of time. Currently, ag the
solidification methods for LLW, the most 2CS + 40 3a0-2Si0,-3H2 + Ca(OH), (2)
frequently used are the three ethods of cement .12H2 3)
solidification, plastic solidification and bitumen C3S + 1210 + Ca(CH 2 = 3a0 AA-Ca(OH)2
solidification. Each of the three methods has its - Felol. 12H20 (4)
own advantages and disadvantages. Generally, the C4A +'OHIO 2Ca(OH)2 = 6aO.A1201
cementitious waste form possesses exoallent lng-
term stability; however, the cement solidification Equation (1) being UP lWdratim reaction of C3S
method has a low volume efficiery-y. On the other represents the fastest among the above mentioned
hand, while volume efficiaAW of the plastic four types of hydration reaction and therefore
solidification method is high and the plastic- constitutes the early hardening action, in which
solidified waste form possesses a high strength, the release of hydration heat is very obvious.

36-B-1
 (a) (b)

Figure 1: The hardenable mix and specimens

of solidified borate waste forms.

Equation 2) is the hydration reaction of C2S, in solidified product does not normally go beyond 0
which the rate is slower ad following the wt% and te addition of luTe increases the volume
reaction the strength gradually increases. The of the solidified product and thus reduces the
3CaO-2SiO,,3H20 gel produced in the reactions (1) volume efficiexr-y of the cement solidification.
and 2 possess cementation action capable of Through numerous experiments, we have now
solidifying other particulates. Equation 3 and discovered a special-recipe powder mixture which
(4) represent hydration reactions of CA and CAF, can react with sodium borate to form a high-
the calcium hydroxide required n the respective strength solid product under certain unique
reactions being produced In the hydration conditions, if sodium borate solution is mixed
reactions of Equations (1) and 2). with the powder mixture. The discovery of the
When cement is used for solidifying the liquid foregoing ardening phenomenon is a te(:tmcal
borate waste fom PWR, generally, the liquid waste breakthrough for te solidification of liquid
is frst neutralized with NaOH to have a pH in the borate wastes; in this process, borate is no
range of 711 and cncentrated t a solution longer just an encapsulated waste but a ain
obtaining 20,ODO to 40,000 ppm of bon, then, component of the solid form; it cnstitutes the
lime and cement are added to the solution a main part of solid structure and thus result
mixed, s that solidification takes place. in a very high volume efficiency of
In the presence of sodium borates, the solidification.
component of calcium oxide that is dissolved out Sodium borates have a water solubility largely
from the cement particulates Wll form with depending on the ratio of sodium to boron in the
borates into a crystal film of calcium borates solution; the maximum solubility can be obtained
(CaO- B203- nfO). This crystal film forms a coating by adjusting the Na/B ratio to 032. Under this
on the surfaces of the ement grains and prevents Portion, the solution may contain dissolved
the cment oaqcnents fom dissolving out, tereby sodium borates over 75 wt%- at 60 C 3 whiCh
slowing down the hydration action of cement and consequently results in a very high volume
thus retards the ardening ation 2 Therefore, when efficiency of solidification.
use cement to solidify liquid borate wastes, Concentrated sodium borate solution has low
calcium hydroxide is generally added to first viscosity, for example, the vscosity for a 73 wt%
react with borates to thereby decrease the sodium borate solution is ca. 70 cp at 4PC. When
formation on the surfaces of the cement grains of the special-recipe solidifying agent is blended
the crystalline film of calcium borates. Although with such a borate waste solution, the reaction
the method serves to reduce obstacles to the above between sodium borates and the powder takes place
mentioned solidification reaction of cement, it immediately, and the hardening action starts.
does not, hever, cpletely stop them and the Since the borate solution has low viscosity,
curing time required for cementation of liquid therefore, the mix is highly flowable before
borate wastes is still muc lnger than for other hardening and can I ly grout and pour Fig -
wastes. Besides, the method also presents some la). Depending on weight fractions of sodium
other drawbacks: the weight of borates n the borate, Solidifying agent and water in the mix ad

36-B-2
 Solidification of boric acid wastes

Solidifying agent Admixture

Boric acid
waste sol'n d pH adjustmei Mixing

Solidification of sodium sulfate and powdery r sin wastes

FN.OH I olidifying agent Admixture

I I

slurry pH adjustment

Fig-we 2- S&ematic fre diagram of te solidificaticn

of liquid borate wastes and other W

Test Item Compressive Radiation Leachability Immersion Thermal Free

Strength Stability Cycling Water

Test Method ASTM 039 ASTM108rads

After C39 ANS 16.1 ASTM C39 ASTM 553 ANS 55.1

Acceptance > kg/crr > kgIcn? Leachindex > 15 kg/cn? > 15 kg/ce 0.5 V%
Criteria I I I > After 90 D I to 60'C, 30 Cy.

Table 1: Standard med-cd of cbaracterizaticn and quality

acceptance riteria follaging te US Nr TqJmcal
Position on Waste Forms

the tperature, the imix will set within 10 special-recipe Solidifying agent to make
to 40 minutes forming a solid form of high hardenable ix, then pouring the hardenable mix
strength ig. lb) The hardening reaction of this 3-ntc) polyethylene mlds to form cylindrical S013-d-
method is So fast that the retardation of te for secimens having 10 cm in height and m in
solidification of borate waste is nt observed in diameter. The solid forms were cured in room,
this process. after that, five ieces of the specimens were
Fig 2 dxws the flow diagram of the process, tested for each property and the results reported
which is similar to the ementation process except are their averaged values.
that the borate waste solution to be solidified
need to be mre cncentrated. Comnressive strenorth

3. CMRACTERIZATIONS OF THE METHOD AND SOLIDIFIED The solid forms showed a rapid buildup of
PRDDL)= ocapressive strength n the early stage of curing;
usually over 70% of the desirable Compressive
A series of experiments have been conducted t Strength is established in a 24-hr curing.
optimize the omditicn of Solidifying liquid It was shown that for obtaining solid forms
borate wastes. with good compressive strength, the weight ratio
The characterizations of solid forms was of the solidifying agent to borate is preferably
conducted following the standard method given in between 0. 4 to 0 7 and water in the blending
US NEU Technical Position m Waste Form (Table 1). slurry should be lower than 3o wt-. The
The solid forms for testing were prepared by ompressive strength depending n the formulation
mixing simulative borate waste solutions, nely can be up to 100 kg/cm? after a 2-weeks curing in
solutions containing 70 t 75 wt-W of sodium the absence of any reifforoment additive for
borates with a Na/B ratio of 03, with the solid forms containing 50 wt% borate.

36-13-3
 solid-form spechm-is ontaining 52-W borate and
0.14% graphite fiber. The sVecimen showed an
Graphite content, wt.% 0 0. 14 0.35 average compressive strength of 125 kg/am? after
test; no significant effect of the t1nrmal cycling
Comp. strength, kg/an 2 56 112 155 test was observed.

Waste loading
Table 2 Effect of Graphite Fiber Cntent o te
compressive Strength of Solidified Products The total content of borate n the slidified
product may be up to 60 wt%; the specific gravity
Many aditives may be incorporated to iprove of the solidified poduct is about 17 g/ar?. Thus,
the quality Of the solid form. For example, 1 mP of solid form may contain as high as 135 kg of
graphite fiber is added to reinforce the solid boron. Therefore, the volume of waste form
form and to improve the dispersion of the obtained from teating of a borate waste
9013-d3-fying-agent pder the borate waste solution oiginally containing 21,000 ppm boron
solution and thus to improve the hoff"jeneity of using this process is about 016 , comparing to
quality- 2 mP of the conventional cementation process and
The compressive strength of the sid form 0 25 of the AC-prooess .4 In FIG. 3 the dry
increased significantly wth the adition of weights of various wastes tolerable in solid forms
graphite fiber as shown :in Table 2; the in LLW solidifications wem shown.
compressive strength for the solid forms
containing 035 wt% of chopped graphite fiber, 1300
Hercules 1900/AS, is as high as 205 kg/ca?. 1200-

Water immersion co 1100-

01 1000- this
The solid form showed a good dimensional. process
stability in the water-innersion test; no 900
significant mensional change was observed in the 800 - cementat ion
test. The test results showed that the mpressive 700 -
strength weaic in the water-1MMerS3.M 90 days) 600 -

test, however, the compressive strength after test 500 -

can be as high as 130 kg/cm?, which is still far
superior t the quality acceptance criteria of the 400 -
US NRC regulations. 300 -

Leachability 'a 200 -

The leachabilities were measured with 1000

solidified prmhicts containing Co-60 and Cs-137
following the procedures given in ANS 16.1. The
results swed tat the leach index was 12.5 for
Co-60 and 75 for Cs-137 for the solidified
products ontaining 50 wt% borate. Addition of
fume silica to the hardenable blending low-red the
leachability of the solidified products.
Eq:)erimental results showed tat the leach index
of Cs-137 can be as high as 10.2 when an adequate
amount of fume silica was icorporated. Thus, te
leachability of the solid forms was much lower
than the cement-solidified borate waste forms.
Irradiation tests
Irradiation tests showed that the solid form
has excellent irradiation resistance. Tis is riot
surprising because the solid form contains only
inorganic ponents. The solid form was not
weakened under irradiation, contrarily smetimes
it might even have higher compressive strength
after irradiation possibly due to the cing
effect of irradiation.
Thermal cycling test
The thermal cycling test was conducted wth
sodium sodium powdery
borate -Sulfate ion-exchange
resin
Figure 3 Comparison. of the tolerable waste
loading between the present process and
cementation
4. SOLIDIFRMTIONS OF OTHER RADIOACTIVE WASTES
The present process is not ny suitable for
solidifying liquid borate wastes, but also
suitable for solidifying LLWs generated at BR NPP
such as sodium. sulfate wastes, spent powdery ion-
exchange resins, and ircinerator ash. In the those
uses, the wastes t be solidified are blended with
the hardo-oble mix made from the special-recipe
powder nurture and sodium borate solutions. After
setting of the hardenable mix, solidified products
containing embeded waste a obtained.
Solidifications of sodium sulfate wastes
The performance of the solidificatio of
sodium sulfate wastes was tested following the
steps: (1 A hardenable mix was prepared fran the
solidifying agent and sodium borate solution 2)

36-B-4
sodium sulfate powders as smulative wastes were free fro EODEX. Also, it was observed that the
added to the IX graduately under agitation to broken pieces of the ECODEX waste forms after
make a paste, which is then poured into mlds to compression tests were not separated but connected
make cylinderical solid-form specimens, 3 after together, indicating that EODEX like graphite
a 24-hour curing at room temperature, these fiber strengthened the solidified product.
specdmens were characterized.
The variation of compressive strength with the 5. CONCLUSICNS
sodium sulfate content in the solid forms is shown
in Table 3 It is interesting that the pressive The solidification method described in this
strength increased wth the icreasing sodium paper is novel and suitable for solidifying liquid
borate waste. Beang the major reactant in the
hardening reaction, a large amount of boiate is
Sodium sulfate 30 wt% 40 wt% 50 wt% required in the reaction, thus, the volume
efficiency of the solidification is very high. In
Specific gravity 1.82 1.94 2.1 addition to the high volume efficiency, the method
also possesses the following merits: (1) use of
Comp sength 180 270 286 inexpensive solidifying agent, (2) all the
kg/CM2 components included in the solid form are
inorganic, 3 the equipment used is simple, 4)
the operation is easy, and (5) the quality of
Table 3 CaTpressive strength ad density of solid forms produced is far superior to the
solidified products under various sodium sulfate acceptance criteria of the US NRC regulations.
contents Solidifications of sodium sulfate and powdery
ion-exchange re in wastes using this process were
sulfate content and so did the density. Obviously, also demonstrated. Excellent volume efficiency and
the hardenable mx is hghly patible with solid forms with high mechanical strength were
sodium sulfate and thus benefits the formation of also obtairiDd showing the versatility of the
strong slid forms. The NaSO, content in the solid present process.
form may be as high as 60 wt% a ontent higher The method is pomising, because: (1) the
than this value may cause mixing problems. process is simple, the operating cost and capital
The large NaSO4 ontent and density of the investiment are low; 2 the volume efficiency of
solidified product result n a very hgh volume the method is so excellent that a tremendous
efficiency when this process is used to solidify reduction of the solidified-waste volume and
sodium sulfate wastes. consequently of the ttal disposal cost will be
Due t that the hardenable mix is highly resulted.
flowable, the solidificaticn can also be done in
such a way as that as been dne in the REFERENCES
pelletizing solidification process, 5 i.e. to
pelletize the sodium sulfate powder first, and 1. M. G. 9XILL, Comparison of Solidification
then pour the mix nto the container containing Media for the Stabilization of Icw-level
the pellets. By this way, the volume efficiency is Radioactive Wastes", DOE report, BNL-52304, Oct.
about the same as that of the aforesaid direct (1991).
blending method, but, with more complicated
operation for pelletizing the waste. 2. LEA, F. M., The Chemistry of Cement and
Concrete, Third Edition, Edward Arnold Ltd.,
Solidifications of ion-gj resin pgm!krg Glasgow 1970).

The solidification of powdery ion-excharxje 3. Kirk-Otbmer Encyclomdia of Chemical

resins using the present process was demonstrated Technology, 4th ed., vol 4 p 379 1978).
by blending the resin with the hardenable mix. The
resin, "ECODEX", used in this study was obtained 4. T. SHIMIZU, T. NAKASHIMA, K. SAUDA, F. TODD, S.
from the Chin-Shan NPP of Taipower's. It has been KITA, H. KURIBAYASHI, "High Voluie-Reduction
using as the filter precoat in the clean-up and Solidification of Radioactive Waste with Cement",
the liquid-radwaste-treatment systems. Because of Proceedings of the Joint International Waste
the low bulk density, dry ECODEX in the solidified Management Conference (Seoul, Korea, Oct. 1991)),
product is limited to a content of about 16 wt%, p 441-447 1991).
a higher content will have poor workability.
Solid forms containing 13.2 wt% dry BOODEX 5. S. HORIUCHI, M. KIKUCHI, K. CHINO, T. BABA H.
were prepared by blending dy BOODEX with the YUSA, Solidification of cement glass", J. Nucl.
hardenable mix. Characterizations sowed that the Sci. Tech., 26(9), 887-892 1989).
averaged ocirpressive strength was 127.5 kg/ar?,
this valve is higher tan that for the solid forms

36-B-5