ProgressinNuclearEnergy, Vol. 37,No. 1-4,pp.393-397.

2000
Q 2000 Elsevier Science Ltd. All rights reserved
Pergamon
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LEACHING BEHAVIOR OF BORIC ACID AND COBALT

FROM PARAFFIN WASTE FORMS

JUYOULKIM, CHANGHYUN CHUNG

Department of Nuclear Engineering, Seoul National University

San56-1 Shinrim-dong, Gwanak-gu, Seoul, 15 l-742, Korea
Phone: +82-2-880-833 1, Fax: +82-2-889-2688, E-mail: kimjuyou@gong.snu.ac.kr

CHANG LAK KIM

Nuclear Environment Technology Institute, Korea Electric Power Corporation

150 Dukjin-dong, Yusong-gu, Taejon, 305-353, Korea

ABSTRACT

Ninety-day leaching test was performed to investigate the leaching

characteristics of paraffin waste forms that had been recently generated in large
quantities at Korean nuclear power plants(KNPPs). In the case where mixing
weight ratio of boric acid to paraflin was 78122, which was adopted in concentrate
waste drying system(CWDS) of KNPPs, the cumulative fraction leached(CFL) of
boric acid and cobalt was about 5 1% and 61%, respectively. The compressive
strengths of waste form before and after the leaching test exhibited
666psi(4,53MPa) and 232psi(1.58MPa), respectively. The CFLs of paraf?in waste
form were well expressed by diffision-controlled dissolution model such as
Gintsling-Brounshtein kinetics. The internal cross-sectional view of specimen
after the test demonstrated the applicability of this unreacted shrinking core model
to the leaching analysis of paraflin waste form. 0 2000 Elsevier Science Ltd. All
rights reserved.

393
394 .I. Z Kim and C. H. Chung

1. INTRODUCTION

Low- and intermediate-level radioactive wastes arising from the operation of nuclear power plants can be
immobilized by various solidification techniques prior to disposal. Liquid radioactive wastes have been
treated with filtration, ion exchange resin, evaporation, and so on. The remaining liquid concentrate wastes
from evaporator have been immobilized by solidifying agents such as cement, bitumen, and polymer, and
then they are filled and packaged in several kinds of containers. Because waste forms including
radionuclides are immobilized with solidifying agents and finally disposed of, they can be safely stored in
radioactive waste repository, isolated from biosphere for a long time. However, despite of engineered and
natural barriers of radioactive waste repository, the radioactive waste forms would eventually be in contact
with groundwater, and the release of radioactive species from the waste forms would occur by leaching
mechanism. Therefore, acceptance criteria of radioactive waste forms have been developed to guarantee the
long-term safety performance of radioactive waste repository (U.S. NRC, 1991).

Low-level liquid borate wastes have been recently converted to parafIin waste forms by utilizing the
concentrate waste drying system(CWLG) in Korean nuclear power plants(KNPPs) (Kim and Bae, 1997).
Paraffin waste forms could be classified as class A unstable. Nevertheless CWDS had the advantages of high
volume reduction, low cost, and simple manufacturing process. This study was performed to investigate the
leaching characteristics of pat&in waste forms.

2. EXPERIMENTAL PROCEDURES

Cylindrical waste forms with a diameter of 5cm and a height of 1Ocm were prepared. The operational
temperature was maintained within the range of 120-140°C and the speed of stirrer was 600 r.p.m. Paraffin
was physically mixed with boric acid and played a binding role within waste form. The mixing ratio of boric
acid to paraffin was very important in order to make a homogeneous waste form because it made a
difference between boric acid( 1.44) and paraffrn(0.933) in specific gravity. If the ratio of paraffin content
was less than 15%, it was difftcult to make a waste form due to a low fluidity, while the phenomenon of
stratification began to occur when the ratio of paraffin content was more than 25%.

The compressive strength test was performed to confirm the integrity of waste forms according to ASTM
C39-86 (1986). The test was applied to at least three specimens under each test condition of different mixing
ratios of boric acid to parafhn.

ANWANS-16.1 (1986) leaching standard procedure was used to investigate the leaching characteristics
of paraffin waste form. The test was developed by an American Nuclear Society Standards Committee for
the characterization of solidified low-level radioactive waste forms. This procedure uses demineralized water
as the leachant and is conducted at a temperature of (22.5*5)“C. Sufficient leachant is used to provide a ratio
of leachant volume to specimen external geometric surface area of (lOti.2)cm. The leachant is sampled and
replaced at the following frequency; 2, 7, and 24h from the initiation of the test, then at 24h intervals for the
next 4d, and then at 14, 28, and 43d intervals to extend the entire test to 90d. The paraBin waste form whose
mixing ratio of boric acid to pa&in is 78122, which had been adopted in CWDS of KNPPs, was chosen for
the leaching test. Non-radioactive species cobalt(I1) chloride hexahydrate whose amount corresponds to
0.24% of boric acid by weight was added to the specimen. The concentration of cobalt included in leachate
was measured by means of inductive coupled plasma-mass spectroscopy(ICP-MS) and that of boric acid
within leachate was analyzed by titration.
 Leaching behaviour of boric acid and cobalt 395

3. RESULTS AND DISCUSSION

The mixtures whose paraffin contents were within the range of 20-24% were easily poured into mold
owing to good workability, and the compressive strength tests resulted in similar values of
622-673psi(4.23-4.58MPa). It was desirable to keep a pa&Fin weight ratio within the range of 20-24% in
order to prepare a homogeneous waste form as the matters of fluidity and stratification were solved at a time.
For the par&n content was 22%, the compressive strength before and after the leaching test of ninety days
was 666psi(4.53MPa) and 232psi( lS8MPa), respectively.

It was observed that the cumulative fraction leached(CFL) of boric acid and cobalt was about 5 1% and
61%, respectively, after ninety days as shown in Fig. l(a). The effective diffisivities of boric acid and cobalt
were 1.5 X 1c6 cm’/sec and 5.7 X lo-* cm2/sec, respectively, which could be obtained from Eq. (1). They
indicated that the leaching rates of pa&in waste form were considerably higher than those of cement and
bitumen waste form with the effective difisivity of approximately 10-‘3-10-12 cm2/sec and l@‘*- IO-l7
cm’/sec, respectively, for cobalt. Fig. l(a) also showed that the CFL of cobalt was higher than that of boric
acid only by 10% although the solubility of cobalt(0.33Sg/cm3 at 20°C) was about seven times higher than
that of boric acid(0.0465g/cm3 at 20°C). These results could be explained by that the boric acid which
occupied a large portion of paraffin waste form was easily dissolved from the surface of waste form by
leachant, and the cobalt immobilized within paraffin waste form was leached out in company with boric acid.
The dissolution rates of boric acid and cobalt were not influenced by their concentration changes within the
leachant because of the sufficient supply and the periodical replacement of leachant. Accordingly, the
leaching of cobalt was thought to be mainly dependent on the dissolution of boric acid.

.I. I .I. I., I., , 1.

?? Boric Acid ?? Boric Acid
?? Cobalt

Time(day)

0 10 20 30 40 50 60 70 80 90 100
Time(day)

(c) (R is a correlation coefficient)

Fig. 1 Cumulative Fraction Leached of Boric Acid and Cobalt Plotted as a Function of Time(a),
Square Root of Time(b), and Gintsling-Brounshtein Kinetics as a Function of Time(c)
396 .I. Y. Kim and C. H. Chung

The leaching of paraffin waste form might appear to be controlled by conventional diffusion because the
CFL values had linear relation to square root of time in Fig. l(b). But the conventional diffusion model
which would have the maximum concentration at the center could not explain the photograph(Fig. 2)
showing the shrinking dissolution front.

Reacted Layer

Dissolution Front

Fig. 2 External Shape(left) and Internal Section(right) of Paraffin Waste Form

after the Leaching Test of 90 days

The reaction initially occurred at the external surface of waste form and the dissolution front gradually
moved inside leaving a reacted layer behind. The leaching rates of boric acid and cobalt were influenced by
reacted layer depth as the reaction progressed. It was revealed that this reacted layer decreased the diffusive
fluxes of leached boric acid and cobalt and controlled the overall dissolution rate. Therefore, the leaching
mechanism of paraffin waste form was well explained by the diffusion-controlled dissolution model such as
Gintsling-Brounshtein kinetics which was a kind of unreacted shrinking core model (Wen, 1968; Bamford
and Tipper, 1969).

l-3(1-X)2/3 +2(1-X)=KDt (I)

where, X was dissolved fraction, Ku overall reaction rate constant(day-‘), and t reaction time(day). This
unreacted shrinking core model assumed that the reaction between solid and fluid was noncatalytic and solid
particle was spherical. Although the specimen of this study was cylindrical, the above model could be
applied to the leaching analysis of paraffin waste form because the leaching rates were constant along the all
surfaces, i.e., top/bottom and lateral sides, of the cylindrical waste form. Fig. l(c) described the relation
between dissolved fraction and reaction time by Eq. (1). Model predictions were excellently agreed with test
data and overall reaction rate constants were obtained from the inclinations of each straight line.

4. CONCLUSIONS

The leaching test of paraffin waste form was carried out according to ANSI/ANS-16.1 test procedure. For
the waste form with the mixing ratio of 78122 between boric acid and paraffin, it was observed that about
51% and 61% of boric acid and cobalt, respectively, were released after ninety days. The compressive
strength of waste form before and after the leaching test resulted in 666psi(4.53MPa) and 232psi(1,58MPa),
respectively. The leaching rates of boric acid and cobalt were influenced by reacted layer depth as the
reaction progressed and this reacted layer controlled the overall dissolution rate. It was concluded that the
leaching mechanism of paraffin waste form was diffusion-controlled dissolution with the shrinking
dissolution front.
 Leaching behaviour of boric acid and cobali 397

REFERENCES

American National Standards Institute (1986), Measurement of the Leachability of Solidified Low-level
Radioactive Wastes by a Short-term Test Procedure, ANSVANS-16.1.
American Society for Testing Materials (1986), Standard Test Method for Compressive Strength of
Cylindrical Concrete Specimens, ASTM C39-86.
Bamford C.H. and Tipper C. F. H. (1969), The i%eo?y ofKinetics, Comprehensive Chemical Kinetics, Vol.II,
Elsevier Scientific Publishing Company, Amsterdam.
Kim H.G. and Bae H.I. (1997), Experiences for Concentrated Waste Drying System, Proceedings of
International Symposium on Radiation Safety Management.
U. S. Nuclear Regulatory Commission (1991), Low-level Waste Licensing Branch Technical Position on
Waste Form, Rev. 1.
Wen C.Y. (1968), Noncatalytic Heterogeneous Solid Fluid Reaction Models, Industrial and Engineering
Chemistry, 60, 34.